calculated vibrational wavenumbers: Topics by Science.gov

Sample records for calculated vibrational wavenumbers

Structural and vibrational spectroscopy investigation of the 5-[(diphenyl) amino] isophthalic acid molecule

NASA Astrophysics Data System (ADS)

Kurt, M.; Şaş, E. Babur; Can, M.; Okur, S.; Icli, S.; Demic, S.

2014-10-01

The molecular structure and vibrations of 5-(diphenyl) amino] isophthalic acid (DPIFA) were investigated by different spectroscopic techniques (such as infrared and Raman). FT-IR, FT-Raman and dispersive Raman spectra were recorded in the solid phase. HOMO-LUMO analyses were performed. The theoretical calculations for the molecular structure and spectroscopic studies were performed with DFT (B3LYP) and 6-311G(d,p) basis set calculations using the Gaussian 09 program. After optimizing the geometry of the molecule, vibration wavenumbers and fundamental vibrations wavenumbers were assigned on the basis of the potential energy distribution (PED) of the vibrational modes calculated with VEDA 4 program. The results of theoretical calculations for the spectra of the title compound were compared with the observed spectra.
Computational vibrational study on coordinated nicotinamide

NASA Astrophysics Data System (ADS)

Bolukbasi, Olcay; Akyuz, Sevim

2005-06-01

The molecular structure and vibrational spectra of zinc (II) halide complexes of nicotinamide (ZnX 2(NIA) 2; X=Cl or Br; NIA=Nicotinamide) were investigated by computational vibrational study and scaled quantum mechanical (SQM) analysis. The geometry optimisation and vibrational wavenumber calculations of zinc halide complexes of nicotinamide were carried out by using the DFT/RB3LYP level of theory with 6-31G(d,p) basis set. The calculated wavenumbers were scaled by using scaled quantum mechanical (SQM) force field method. The fundamental vibrational modes were characterised by their total energy distribution. The coordination effects on nicotinamide through the ring nitrogen were discussed.
An experimental and theoretical study of molecular structure and vibrational spectra of 2-methylphenyl boronic acid by density functional theory calculations

NASA Astrophysics Data System (ADS)

Hiremath, Sudhir M.; Hiremath, C. S.; Khemalapure, S. S.; Patil, N. R.

2018-05-01

This paper reports the experimental and theoretical study on the structure and vibrations of 2-Methylphenyl boronic acid (2MPBA). The different spectroscopic techniques such as FT-IR (4000-400 cm-1) and FT-Raman (4000-50 cm-1) of the title molecule in the solid phase were recorded. The geometry of the molecule was fully optimized using density functional theory (DFT) (B3LYP) with 6-311++G(d, p) basis set calculations. The vibrational wavenumbers were also corrected with scale factor to take better results for the calculated data. Vibrational spectra were calculated and fundamental vibrations were assigned on the basis of the potential energy distribution (PED) of the vibrational modes obtained from VEDA 4 program. The calculated wavenumbers showed the best agreement with the experimental results. Whereas, it is observed that, the theoretical frequencies are more than the experimental one for O-H stretching vibration modes of the title molecule.
Molecular structure, vibrational spectra, NBO, UV and first order hyperpolarizability, analysis of 4-Chloro-dl-phenylalanine by density functional theory.

PubMed

Govindarasu, K; Kavitha, E

2014-12-10

The Fourier transform infrared (4000-400cm(-1)) and Fourier transform Raman (3500-50cm(-1)) spectra of 4-Chloro-dl-phenylalanine (4CLPA) were recorded and analyzed. The equilibrium geometry, bonding features and harmonic vibrational wavenumbers were investigated with the help of density functional theory (DFT) method using B3LYP/6-31G(d,p) as basis set. The observed vibrational wavenumbers were compared with the calculated results. Natural bond orbital analysis confirms the presence of intramolecular charge transfer and the hydrogen bonding interaction. Predicted electronic absorption spectra from TD-DFT calculation have been analyzed comparing with the UV-Vis (200-800nm) spectrum. The effects of chlorine and ethylene group substituent in benzene ring in the vibrational wavenumbers have been analyzed. The HOMO-LUMO energy gap explains the charge interaction taking place within the molecule. The first order hyperpolarizability (β0) and related properties (β, α0 and Δα) of 4CLPA were calculated. The Chemical reactivity and chemical potential of 4CLPA is calculated. In addition, molecular electrostatic potential (MEP), frontier molecular orbital (FMO) analysis were investigated using theoretical calculations. Published by Elsevier B.V.
Vibrational spectroscopic studies, NLO, HOMO-LUMO and electronic structure calculations of α,α,α-trichlorotoluene using HF and DFT.

PubMed

Govindarajan, M; Karabacak, M; Periandy, S; Xavier, S

2012-08-01

FT-IR and FT-Raman spectra of α,α,α-trichlorotoluene have been recorded and analyzed. The geometry, fundamental vibrational frequencies are interpreted with the aid of structure optimizations and normal coordinate force field calculations based on density functional theory (DFT) B3LYP/6-311++G(d,p) method and a comparative study between HF level and various basis sets combination. The fundamental vibrational wavenumbers as well as their intensities were calculated and a good agreement between observed and scaled calculated wavenumbers has been achieved. The complete vibrational assignments of wavenumbers are made on the basis of potential energy distribution (PED). The effects due to the substitutions of methyl group and halogen were investigated. The absorption energy and oscillator strength are calculated by time-dependent density functional theory (TD-DFT). The electric dipole moment, polarizability and the first hyperpolarizability values of the α,α,α-trichlorotoluene have been calculated. (1)H NMR chemical shifts were calculated by using the gauge independent atomic orbital (GIAO) method with HF and B3LYP methods with 6-311++G(d,p) basis set. Moreover, molecular electrostatic potential (MEP) and thermodynamic properties were performed. Mulliken and natural charges of the title molecule were also calculated and interpreted. Copyright © 2012 Elsevier B.V. All rights reserved.
Experimental and DFT studies on the vibrational spectra of 1H-indene-2-boronic acid

NASA Astrophysics Data System (ADS)

Alver, Özgur; Kaya, Mehmet Fatih

2014-11-01

Stable conformers and geometrical molecular structures of 1H-indene-2-boronic acid (I-2B(OH)2) were studied experimentally and theoretically using FT-IR and FT-Raman spectroscopic methods. FT-IR and FT-Raman spectra were recorded in the region of 4000-400 cm-1, and 3700-400 cm-1, respectively. The optimized geometric structures were searched by Becke-3-Lee-Yang-Parr (B3LYP) hybrid density functional theory method with 6-31++G(d,p) basis set. Vibrational wavenumbers of I-2B(OH)2 were calculated using B3LYP density functional methods including 6-31++G(d,p) basis set. Experimental and theoretical results show that density functional B3LYP method gives satisfactory results for predicting vibrational wavenumbers except OH stretching modes which is probably due to increasing unharmonicity in the high wave number region and possible intra and inter molecular interaction at OH edges. To support the assigned vibrational wavenumbers, the potential energy distribution (PED) values were also calculated using VEDA 4 (Vibrational Energy Distribution Analysis) program.
Structure and vibrational analysis of methyl 3-amino-2-butenoate.

PubMed

Berenji, Ali Reza; Tayyari, Sayyed Faramarz; Rahimizadeh, Mohammad; Eshghi, Hossein; Vakili, Mohammad; Shiri, Ali

2013-02-01

The molecular structure and vibrational spectra of methyl 3-(amino)-2-butenoate (MAB) and its deuterated analogous, D(3)MAB, were investigated using density functional theory (DFT) calculations. The geometrical parameters and harmonic vibrational wavenumbers of MAB and D(3)MAB were obtained at the B3LYP/6-311++G(d,p) level. The calculated vibrational wavenumbers were compared with the corresponding experimental results. The assignment of the IR and Raman spectra of MAB and D(3)MAB was facilitated by calculating the anharmonic wavenumbers at the B3LYP/6-311G(d,p) level as well as recording and calculating the MAB spectra in CCl(4) solution. The assigned normal modes were compared with a similar molecule, 4-amino-3-penten-2-one (APO). The theoretical results were in good agreement with the experimental data. All theoretical and experimental results indicate that substitution of a methyl group with a methoxy group considerably weakens the intramolecular hydrogen bond and reduces the π-electron delocalization in the chelated ring system. The IR spectra also indicate that in the solid state, MAB is not only engaged in an intramolecular hydrogen bond, but also forms an intermolecular hydrogen bond. However, the intermolecular hydrogen bond will be removed in dilute CCl(4) solution. Copyright © 2012 Elsevier B.V. All rights reserved.
Structural, vibrational and nuclear magnetic resonance investigations of 4-bromoisoquinoline by experimental and theoretical DFT methods.

PubMed

Arjunan, V; Thillai Govindaraja, S; Jayapraksh, A; Mohan, S

2013-04-15

Quantum chemical calculations of energy, structural parameters and vibrational wavenumbers of 4-bromoisoquinoline (4BIQ) were carried out by using B3LYP method using 6-311++G(**), cc-pVTZ and LANL2DZ basis sets. The optimised geometrical parameters obtained by DFT calculations are in good agreement with electron diffraction data. Interpretations of the experimental FTIR and FT-Raman spectra have been reported with the aid of the theoretical wavenumbers. The differences between the observed and scaled wavenumber values of most of the fundamentals are very small. The thermodynamic parameters have also been computed. Electronic properties of the molecule were discussed through the molecular electrostatic potential surface, HOMO-LUMO energy gap and NBO analysis. To provide precise assignments of (1)H and (13)CNMR spectra, isotropic shielding and chemical shifts were calculated with the Gauge-Invariant Atomic Orbital (GIAO) method. Copyright © 2013 Elsevier B.V. All rights reserved.
Molecular conformational analysis, vibrational spectra and normal coordinate analysis of trans-1,2-bis(3,5-dimethoxy phenyl)-ethene based on density functional theory calculations.

PubMed

Joseph, Lynnette; Sajan, D; Chaitanya, K; Isac, Jayakumary

2014-03-25

The conformational behavior and structural stability of trans-1,2-bis(3,5-dimethoxy phenyl)-ethene (TDBE) were investigated by using density functional theory (DFT) method with the B3LYP/6-311++G(d,p) basis set combination. The vibrational wavenumbers of TDBE were computed at DFT level and complete vibrational assignments were made on the basis of normal coordinate analysis calculations (NCA). The DFT force field transformed to natural internal coordinates was corrected by a well-established set of scale factors that were found to be transferable to the title compound. The infrared and Raman spectra were also predicted from the calculated intensities. The observed Fourier transform infrared (FTIR) and Fourier transform (FT) Raman vibrational wavenumbers were analyzed and compared with the theoretically predicted vibrational spectra. Comparison of the simulated spectra with the experimental spectra provides important information about the ability of the computational method to describe the vibrational modes. Information about the size, shape, charge density distribution and site of chemical reactivity of the molecules has been obtained by mapping electron density isosurface with electrostatic potential surfaces (ESP). Copyright © 2013 Elsevier B.V. All rights reserved.
FT-IR, FT-Raman spectra, density functional computations of the vibrational spectra and molecular conformational analysis of 2,5-di-tert-butyl-hydroquinone

NASA Astrophysics Data System (ADS)

Subramanian, N.; Sundaraganesan, N.; Dereli, Ö.; Türkkan, E.

2011-12-01

The purpose of finding conformer among six different possible conformers of 2,5-di-tert-butyl-hydroquinone (DTBHQ), its equilibrium geometry and harmonic wavenumbers were calculated by the B3LYP/6-31G(d,p) method. The infrared and Raman spectra of DTBHQ were recorded in the region 400-4000 cm -1 and 50-3500 cm -1, respectively. In addition, the IR spectra in CCl 4 at various concentrations of DTBHQ are also recorded. The computed vibrational wavenumbers were compared with the IR and Raman experimental data. Computational calculations at B3LYP level with two different basis sets 6-31G(d,p) and 6-311++G(d,p) are also employed in the study of the possible conformer of DTBHQ. The complete assignments were performed on the basis of the potential energy distribution (PED) of the vibrational modes, calculated using VEDA 4 program. The general agreement between the observed and calculated frequencies was established.
DOE Office of Scientific and Technical Information (OSTI.GOV)

Mackeprang, Kasper; Kjaergaard, Henrik G., E-mail: hgk@chem.ku.dk; Salmi, Teemu

We describe the vibrational transitions of the donor unit in water dimer with an approach that is based on a three-dimensional local mode model. We perform a perturbative treatment of the intermolecular vibrational modes to improve the transition wavenumber of the hydrogen bonded OH-stretching transition. The model accurately predicts the transition wavenumbers of the vibrations in water dimer compared to experimental values and provides a physical picture that explains the redshift of the hydrogen bonded OH-oscillator. We find that it is unnecessary to include all six intermolecular modes in the vibrational model and that their effect can, to a goodmore » approximation, be computed using a potential energy surface calculated at a lower level electronic structure method than that used for the unperturbed model.« less
FT-Raman, FT-IR and UV-visible spectral investigations and ab initio computations of anti-epileptic drug: Vigabatrin

NASA Astrophysics Data System (ADS)

Edwin, Bismi; Joe, I. Hubert

2013-10-01

Vibrational analysis of anti-epileptic drug vigabatrin, a structural GABA analog was carried out using NIR FT-Raman and FTIR spectroscopic techniques. The equilibrium geometry, various bonding features and harmonic vibrational wavenumbers were studied using density functional theory method. The detailed interpretation of the vibrational spectra has been carried out with the aid of VEDA.4 program. Vibrational spectra, natural bond orbital analysis and optimized molecular structure show clear evidence for the effect of electron charge transfer on the activity of the molecule. Predicted electronic absorption spectrum from TD-DFT calculation has been compared with the UV-vis spectrum. The Mulliken population analysis on atomic charges and the HOMO-LUMO energy were also calculated. Good consistency is found between the calculated results and experimental data for the electronic absorption as well as IR and Raman spectra. The blue-shifting of the Csbnd C stretching wavenumber reveals that the vinyl group is actively involved in the conjugation path. The NBO analysis confirms the occurrence of intramolecular hyperconjugative interactions resulting in ICT causing stabilization of the system.
Structural investigation of a self-assembled monolayer material 5-[(3-methylphenyl) (phenyl) amino] isophthalic acid for organic light-emitting devices.

PubMed

Saş, E Babur; Kurt, M; Can, M; Okur, S; İçli, S; Demiç, S

2014-12-10

The molecular structure and vibrations of 5-[(3-methylphenyl) (phenyl) amino] isophthalic acid (MePIFA) were investigated by infrared and Raman spectroscopies, UV-Vis, (1)H and (13)C NMR spectroscopic techniques and NBO analysis. FT-IR, FT-Raman and dispersive Raman spectra were recorded in the solid phase. (1)H and (13)C NMR spectra and UV-Vis spectrum were recorded in DMSO solution. HOMO-LUMO analysis and molecular electrostatic potential (MEP) analysis were performed. The theoretical calculations for the molecular structure and spectroscopies were performed with DFT (B3LYP) and 6-311G(d,p) basis set calculations using the Gaussian 09 program. After the geometry of the molecule was optimized, vibration wavenumbers and fundamental vibration wavenumbers were assigned on the basis of the potential energy distribution (PED) of the vibrational modes calculated with VEDA 4 program. The total (TDOS), partial (PDOS) density of state and overlap population density of state (OPDOS) diagrams analysis were made using GaussSum 2.2 program. The results of theoretical calculations for the spectra of the title compound were compared with the observed spectra. Copyright © 2014 Elsevier B.V. All rights reserved.
Structural investigation of a self-assembled monolayer material 5-[(3-methylphenyl) (phenyl) amino] isophthalic acid for organic light-emitting devices

NASA Astrophysics Data System (ADS)

Saş, E. Babur; Kurt, M.; Can, M.; Okur, S.; İçli, S.; Demiç, S.

2014-12-01

The molecular structure and vibrations of 5-[(3-methylphenyl) (phenyl) amino] isophthalic acid (MePIFA) were investigated by infrared and Raman spectroscopies, UV-Vis, 1H and 13C NMR spectroscopic techniques and NBO analysis. FT-IR, FT-Raman and dispersive Raman spectra were recorded in the solid phase. 1H and 13C NMR spectra and UV-Vis spectrum were recorded in DMSO solution. HOMO-LUMO analysis and molecular electrostatic potential (MEP) analysis were performed. The theoretical calculations for the molecular structure and spectroscopies were performed with DFT (B3LYP) and 6-311G(d,p) basis set calculations using the Gaussian 09 program. After the geometry of the molecule was optimized, vibration wavenumbers and fundamental vibration wavenumbers were assigned on the basis of the potential energy distribution (PED) of the vibrational modes calculated with VEDA 4 program. The total (TDOS), partial (PDOS) density of state and overlap population density of state (OPDOS) diagrams analysis were made using GaussSum 2.2 program. The results of theoretical calculations for the spectra of the title compound were compared with the observed spectra.
Spectroscopic (FT-IR, FT-Raman, and UV-visible) and quantum chemical studies on molecular geometry, Frontier molecular orbitals, NBO, NLO and thermodynamic properties of 1-acetylindole.

PubMed

Shukla, Vikas K; Al-Abdullah, Ebtehal S; El-Emam, Ali A; Sachan, Alok K; Pathak, Shilendra K; Kumar, Amarendra; Prasad, Onkar; Bishnoi, Abha; Sinha, Leena

2014-12-10

Quantum chemical calculations of ground state energy, geometrical structure and vibrational wavenumbers of 1-acetylindole were carried out using density functional (DFT/B3LYP) method with 6-311++G(d,p) basis set. The FT-IR and FT-Raman spectra were recorded in the condensed state. The fundamental vibrational wavenumbers were calculated and a good correlation between experimental and scaled calculated wavenumbers has been accomplished. Electric dipole moment, polarizability and first static hyperpolarizability values of 1-acetylindole have been calculated at the same level of theory and basis set. The results show that the 1-acetylindole molecule possesses nonlinear optical (NLO) behavior with non-zero values. Stability of the molecule arising from hyper-conjugative interactions and charge delocalization has been analyzed using natural bond orbital (NBO) analysis. UV-Visible spectrum of the molecule was recorded in the region 200-500nm and the electronic properties like HOMO and LUMO energies and composition were obtained using TD-DFT method. The calculated energies and oscillator strengths are in good correspondence with the experimental data. The thermodynamic properties of the compound under investigation were calculated at different temperatures. Copyright © 2014 Elsevier B.V. All rights reserved.
Vibrational spectroscopic studies of Isoleucine by quantum chemical calculations.

PubMed

Moorthi, P P; Gunasekaran, S; Ramkumaar, G R

2014-04-24

In this work, we reported a combined experimental and theoretical study on molecular structure, vibrational spectra and NBO analysis of Isoleucine (2-Amino-3-methylpentanoic acid). The optimized molecular structure, vibrational frequencies, corresponding vibrational assignments, thermodynamics properties, NBO analyses, NMR chemical shifts and ultraviolet-visible spectral interpretation of Isoleucine have been studied by performing MP2 and DFT/cc-pVDZ level of theory. The FTIR, FT-Raman spectra were recorded in the region 4000-400 cm(-1) and 3500-50 cm(-1) respectively. The UV-visible absorption spectra of the compound were recorded in the range of 200-800 nm. Computational calculations at MP2 and B3LYP level with basis set of cc-pVDZ is employed in complete assignments of Isoleucine molecule on the basis of the potential energy distribution (PED) of the vibrational modes, calculated using VEDA-4 program. The calculated wavenumbers are compared with the experimental values. The difference between the observed and calculated wavenumber values of most of the fundamentals is very small. (13)C and (1)H nuclear magnetic resonance chemical shifts of the molecule were calculated using the gauge independent atomic orbital (GIAO) method and compared with experimental results. The formation of hydrogen bond was investigated in terms of the charge density by the NBO calculations. Based on the UV spectra and TD-DFT calculations, the electronic structure and the assignments of the absorption bands were carried out. Besides, molecular electrostatic potential (MEP) were investigated using theoretical calculations. Copyright © 2014 Elsevier B.V. All rights reserved.
Excitation of ground vibration due to the passage of trains over a track with trackbed irregularities and a varying support stiffness

NASA Astrophysics Data System (ADS)

Auersch, Lutz

2015-01-01

Train-induced ground vibration can be excited by wheel and track irregularities and by two kinds of irregularities of the soil, by geometric irregularities or by the spatially varying soil stiffness. For both types of irregularities, the effective track irregularity on top of the track is calculated in wavenumber domain and with wavenumber integrals. For a general multi-beam track model, the wavenumber integrals are solved numerically. The irregularities of the soil are filtered by the track when transferred from the bottom to the top of the track. The high-wavenumber irregularities are strongly reduced due to the bending stiffness of the track and the compliance of the support. In addition, soft track elements reduce directly the stiffness variation of the support. Therefore, the mitigation effect of elastic track elements for these excitation components seems to be important. For under-sleeper pads and slab tracks, calculation and measurements are presented including additional excitation components and the dynamic vehicle-track interaction, and the relevance of the excitation mechanisms is discussed based on the dynamic forces which are acting on the ground. Due to the restricted amplitudes, the parametric excitation by the stiffness variation seems to be less important than the geometric irregularities. The calculations yield the correct trends of the measurements and many details of the measured ballast, slab, and under-sleeper-pad tracks.
NMR, FT-IR, Raman and UV-Vis spectroscopic investigation and DFT study of 6-Bromo-3-Pyridinyl Boronic Acid

NASA Astrophysics Data System (ADS)

Dikmen, Gökhan; Alver, Özgür

2015-11-01

Possible stable conformers and geometrical molecular structures of 6-Bromo-3-Pyridinyl Boronic acid (6B3PBA; C5H5BBrNO2) were studied experimentally and theoretically using FT-IR and Raman spectroscopic methods. FT-IR and Raman spectra were recorded in the region of 4000-400 cm-1 and 3700-400 cm-1, respectively. The structural properties were investigated further, using 1H, 13C, 1H coupled 13C, HETCOR, COSY and APT NMR techniques. The optimized geometric structures were searched by Becke-3-Lee-Yang-Parr (B3LYP) hybrid density functional theory method with 6-311++G(d, p) basis set. Vibrational wavenumbers of 6B3PBA were calculated whereby B3LYP density functional methods including 6-311++G(d, p), 6-311G(d, p), 6-311G(d), 6-31G(d, p) and 6-31G(d) basis sets. The comparison of the experimentally and theoretically obtained results using mean absolute error and experimental versus calculated correlation coefficients for the vibrational wavenumbers indicates that B3LYP method with 6-311++G(d, p) gives more satisfactory results for predicting vibrational wavenumbers when compared to the 6-311G(d, p), 6-311G(d), 6-31G(d, p) and 6-31G(d) basis sets. However, this method and none of the mentioned methods here seem suitable for the calculations of OH stretching modes, most likely because increasing unharmonicity in the high wave number region and possible intra and inter molecular interactions at OH edges lead some deviations between experimental and theoretical results. Moreover, reliable vibrational assignments were made on the basis of total energy distribution (TED) calculated using scaled quantum mechanical (SQM) method.
FT-Raman, FT-IR and UV-visible spectral investigations and ab initio computations of anti-epileptic drug: vigabatrin.

PubMed

Edwin, Bismi; Joe, I Hubert

2013-10-01

Vibrational analysis of anti-epileptic drug vigabatrin, a structural GABA analog was carried out using NIR FT-Raman and FTIR spectroscopic techniques. The equilibrium geometry, various bonding features and harmonic vibrational wavenumbers were studied using density functional theory method. The detailed interpretation of the vibrational spectra has been carried out with the aid of VEDA.4 program. Vibrational spectra, natural bond orbital analysis and optimized molecular structure show clear evidence for the effect of electron charge transfer on the activity of the molecule. Predicted electronic absorption spectrum from TD-DFT calculation has been compared with the UV-vis spectrum. The Mulliken population analysis on atomic charges and the HOMO-LUMO energy were also calculated. Good consistency is found between the calculated results and experimental data for the electronic absorption as well as IR and Raman spectra. The blue-shifting of the C-C stretching wavenumber reveals that the vinyl group is actively involved in the conjugation path. The NBO analysis confirms the occurrence of intramolecular hyperconjugative interactions resulting in ICT causing stabilization of the system. Copyright © 2013 Elsevier B.V. All rights reserved.
Theoretical investigations on molecular structure, vibrational spectra, HOMO, LUMO, NBO analysis and hyperpolarizability calculations of thiophene-2-carbohydrazide.

PubMed

Balachandran, V; Janaki, A; Nataraj, A

2014-01-24

The Fourier-Transform infrared and Fourier-Transform Raman spectra of thiophene-2-carbohydrazide (TCH) was recorded in the region 4000-400 cm(-1) and 3500-100 cm(-1). Quantum chemical calculations of energies, geometrical structure and vibrational wavenumbers of TCH were carried out by DFT (B3LYP) method with 6-311++G(d,p) as basis set. The difference between the observed and scaled wavenumber values of most of the fundamentals is very small. Stability of the molecule arising from hyper conjugative interaction and charge delocalization has been analyzed using natural bond orbital (NBO) analysis. UV spectrum was measured in different solvent. The energy and oscillator strength are calculated by Time Dependant Density Functional Theory (TD-DFT) results. The calculated HOMO and LUMO energies also confirm that charge transfer occurs within the molecule. The complete assignments were performed on the basis of the potential energy distribution (PED) of vibrational modes, calculated with scaled quantum mechanics (SQM) method. Finally the theoretical FT-IR, FT-Raman, and UV spectra of the title molecule have also been constructed. Copyright © 2013 Elsevier B.V. All rights reserved.

Structural and vibrational spectroscopic analysis of anticancer drug mitotane using DFT method; a comparative study of its parent structure

NASA Astrophysics Data System (ADS)

Mariappan, G.; Sundaraganesan, N.

2015-04-01

A comprehensive screening of the density functional theoretical approach to structural analysis is presented in this section. DFT calculations using B3LYP/6-311++G(d,p) level of theory were found to yield results that are very comparable to experimental IR and Raman spectra. Computed geometrical parameters and harmonic vibrational wavenumbers of the fundamentals were found in satisfactory agreement with the experimental data and also its parent structure. The vibrational assignments of the normal modes were performed on the basis of the potential energy distribution (PED) calculations. It can be proven from the comparative results of mitotane and its parent structure Dichlorodiphenyldichloroethane (DDD), the intramolecular nonbonding interaction between (C1sbnd H19⋯Cl18) in the ortho position which is calculated 2.583 Å and the position of the substitution takeover the vibrational wavenumber to redshift of 47 cm-1. In addition, natural bond orbital (NBO) analysis has been performed for analyzing charge delocalization throughout the molecule. Stability of the molecule arising from hyperconjugative interactions leading to its bioactivity and charge delocalization has been analyzed. 13C and 1H nuclear magnetic resonance chemical shifts of the molecule have been calculated using the gauge independent atomic orbital (GIAO) method and compared with published results.
Vibrational analysis and quantum chemical calculations of 2,2‧-bipyridine Zinc(II) halide complexes

NASA Astrophysics Data System (ADS)

Ozel, Aysen E.; Kecel, Serda; Akyuz, Sevim

2007-05-01

In this study the molecular structure and vibrational spectra of Zn(2,2'-bipyridine)X 2 (X = Cl and Br) complexes were studied in their ground states by computational vibrational study and scaled quantum mechanical (SQM) analysis. The geometry optimization, vibrational wavenumber and intensity calculations of free and coordinated 2,2'-bipyridine were carried out with the Gaussian03 program package by using Hartree-Fock (HF) and Density Functional Theory (DFT) with B3LYP functional and 6-31G (d,p) basis set. The total energy distributions (TED) of the vibrational modes were calculated by using Scaled Quantum Mechanical (SQM) analysis. Fundamentals were characterised by their total energy distributions. Coordination sensitive modes of 2,2'-bipyridine were determined.
Characterization of 1,5-dimethoxynaphthalene by vibrational spectroscopy (FT-IR and FT-Raman) and density functional theory calculations.

PubMed

Kandasamy, M; Velraj, G; Kalaichelvan, S; Mariappan, G

2015-01-05

In this work, we reported a combined experimental and theoretical study on molecular structure, vibrational spectra and natural bond orbital (NBO) analysis of 1,5-dimethoxynaphthalene. The optimized molecular structure, atomic charges, vibrational frequencies and natural bond orbital analysis of 1,5-dimethoxynaphthalene have been studied by performing DFT/B3LYP/6-31G(d,p) level of theory. The FTIR, FT-Raman spectra were recorded in the region of 4000-400 cm(-1) and 3500-50 cm(-1) respectively. The scaled wavenumbers are compared with the experimental values. The difference between the observed and scaled wavenumber values of the most fundamentals is very small. The formation of hydrogen bond was investigated in terms of the charge density by the NBO analysis. Natural Population Analysis (NPA) was used for charge determination in the title molecule. Besides, molecular electrostatic potential (MEP), frontier molecular orbitals (FMO) analysis were investigated using theoretical calculations. Copyright © 2014 Elsevier B.V. All rights reserved.
Suppression of sound radiation to far field of near-field acoustic communication system using evanescent sound field

NASA Astrophysics Data System (ADS)

Fujii, Ayaka; Wakatsuki, Naoto; Mizutani, Koichi

2016-01-01

A method of suppressing sound radiation to the far field of a near-field acoustic communication system using an evanescent sound field is proposed. The amplitude of the evanescent sound field generated from an infinite vibrating plate attenuates exponentially with increasing a distance from the surface of the vibrating plate. However, a discontinuity of the sound field exists at the edge of the finite vibrating plate in practice, which broadens the wavenumber spectrum. A sound wave radiates over the evanescent sound field because of broadening of the wavenumber spectrum. Therefore, we calculated the optimum distribution of the particle velocity on the vibrating plate to reduce the broadening of the wavenumber spectrum. We focused on a window function that is utilized in the field of signal analysis for reducing the broadening of the frequency spectrum. The optimization calculation is necessary for the design of window function suitable for suppressing sound radiation and securing a spatial area for data communication. In addition, a wide frequency bandwidth is required to increase the data transmission speed. Therefore, we investigated a suitable method for calculating the sound pressure level at the far field to confirm the variation of the distribution of sound pressure level determined on the basis of the window shape and frequency. The distribution of the sound pressure level at a finite distance was in good agreement with that obtained at an infinite far field under the condition generating the evanescent sound field. Consequently, the window function was optimized by the method used to calculate the distribution of the sound pressure level at an infinite far field using the wavenumber spectrum on the vibrating plate. According to the result of comparing the distributions of the sound pressure level in the cases with and without the window function, it was confirmed that the area whose sound pressure level was reduced from the maximum level to -50 dB was extended. Additionally, we designed a sound insulator so as to realize a similar distribution of the particle velocity to that obtained using the optimized window function. Sound radiation was suppressed using a sound insulator put above the vibrating surface in the simulation using the three-dimensional finite element method. On the basis of this finding, it was suggested that near-field acoustic communication which suppressed sound radiation can be realized by applying the optimized window function to the particle velocity field.
Vibrational spectroscopic and quantum chemical calculations of (E)-N-Carbamimidoyl-4-((naphthalen-1-yl-methylene)amino)benzene sulfonamide.

PubMed

Chandran, Asha; Varghese, Hema Tresa; Mary, Y Sheena; Panicker, C Yohannan; Manojkumar, T K; Van Alsenoy, Christian; Rajendran, G

2012-02-15

FT-IR and FT-Raman spectra of (E)-N-Carbamimidoyl-4-((naphthalen-1-yl-methylene)amino)benzene sulfonamide were recorded and analyzed. The vibrational wavenumbers were computing at various levels of theory. The data obtained from theoretical calculations are used to assign vibrational bands obtained experimentally. The results indicate that B3LYP method is able to provide satisfactory results for predicting vibrational frequencies and structural parameters. The calculated first hyperpolarizability is comparable with reported values of similar derivatives and is an attractive object for future studies of non-linear optics. The geometrical parameters of the title compound are in agreement with that of similar derivatives. Copyright © 2011 Elsevier B.V. All rights reserved.
Crystal structure, vibrational spectra, optical and DFT studies of bis (3-azaniumylpropyl) azanium pentachloroantimonate (III) chloride monohydrate (C6H20N3)SbCl5·Cl·H2O.

PubMed

Ahmed, Houssem Eddine; Kamoun, Slaheddine

2017-09-05

The crystal structure of (C 6 H 20 N 3 )SbCl 5 ·Cl·H 2 O is built up of [NH 3 (CH 2 ) 3 NH 2 (CH 2 ) 3 NH 3 ] 3+ cations, [SbCl 5 ] 2- anions, free Cl - anions and neutral water molecules connected together by NH⋯Cl, NH⋯O and OH⋯Cl hydrogen bonds. The optical band gap determined by diffuse reflection spectroscopy (DRS) is 3.78eV for a direct allowed transition. Optimized molecular geometry, atomic Mulliken charges, harmonic vibrational frequencies, HOMO-LUMO and related molecular properties of the (C 6 H 20 N 3 )SbCl 5 ·Cl·H 2 O compound were calculated by Density functional theory (DFT) using B3LYP method with GenECP sets. The calculated structural parameters (bond lengths and angles) are in good agreement with the experimental XRD data. The vibrational unscaled wavenumbers were calculated and scaled by a proper scaling factor of 0.984. Acceptable consistency was observed between calculated and experimental results. The assignments of wavenumbers were made on the basis of potential energy distribution (PED) using Vibrational Energy Distribution Analysis (VEDA) software. The HOMO-LUMO study was extended to calculate various molecular parameters like ionization potential, electron affinity, global hardness, electro-chemical potential, electronegativity and global electrophilicity of the given molecule. Copyright © 2017 Elsevier B.V. All rights reserved.
Crystal structure, vibrational spectra, optical and DFT studies of bis (3-azaniumylpropyl) azanium pentachloroantimonate (III) chloride monohydrate (C6H20N3)SbCl5·Cl·H2O

NASA Astrophysics Data System (ADS)

Ahmed, Houssem Eddine; Kamoun, Slaheddine

2017-09-01

The crystal structure of (C6H20N3)SbCl5·Cl·H2O is built up of [NH3(CH2)3NH2(CH2)3NH3]3 + cations, [SbCl5]2 - anions, free Cl- anions and neutral water molecules connected together by Nsbnd H ⋯ Cl, Nsbnd H ⋯ O and Osbnd H ⋯ Cl hydrogen bonds. The optical band gap determined by diffuse reflection spectroscopy (DRS) is 3.78 eV for a direct allowed transition. Optimized molecular geometry, atomic Mulliken charges, harmonic vibrational frequencies, HOMO-LUMO and related molecular properties of the (C6H20N3)SbCl5·Cl·H2O compound were calculated by Density functional theory (DFT) using B3LYP method with GenECP sets. The calculated structural parameters (bond lengths and angles) are in good agreement with the experimental XRD data. The vibrational unscaled wavenumbers were calculated and scaled by a proper scaling factor of 0.984. Acceptable consistency was observed between calculated and experimental results. The assignments of wavenumbers were made on the basis of potential energy distribution (PED) using Vibrational Energy Distribution Analysis (VEDA) software. The HOMO-LUMO study was extended to calculate various molecular parameters like ionization potential, electron affinity, global hardness, electro-chemical potential, electronegativity and global electrophilicity of the given molecule.
Thiol-thione tautomeric analysis, spectroscopic (FT-IR, Laser-Raman, NMR and UV-vis) properties and DFT computations of 5-(3-pyridyl)-4H-1,2,4-triazole-3-thiol molecule.

PubMed

Gökce, Halil; Öztürk, Nuri; Ceylan, Ümit; Alpaslan, Yelda Bingöl; Alpaslan, Gökhan

2016-06-15

In this study, the 5-(3-pyridyl)-4H-1,2,4-triazole-3-thiol molecule (C7H6N4S) molecule has been characterized by using FT-IR, Laser-Raman, NMR and UV-vis spectroscopies. Quantum chemical calculations have been performed to investigate the molecular structure (thione-thiol tautomerism), vibrational wavenumbers, electronic transition absorption wavelengths in DMSO solvent and vacuum, proton and carbon-13 NMR chemical shifts and HOMOs-LUMOs energies at DFT/B3LYP/6-311++G(d,p) level for all five tautomers of the title molecule. The obtained results show that the calculated vibrational wavenumbers, NMR chemical shifts and UV-vis wavelengths are in a good agreement with experimental data. Copyright © 2016 Elsevier B.V. All rights reserved.
Resonant frequency function of thickness-shear vibrations of rectangular crystal plates.

PubMed

Wang, Ji; Yang, Lijun; Pan, Qiaoqiao; Chao, Min-Chiang; Du, Jianke

2011-05-01

The resonant frequencies of thickness-shear vibrations of quartz crystal plates in rectangular and circular shapes are always required in the design and manufacturing of quartz crystal resonators. As the size of quartz crystal resonators shrinks, for rectangular plates we must consider effects of both length and width for the precise calculation of resonant frequency. Starting from the three-dimensional equations of wave propagation in finite crystal plates and the general expression of vibration modes, we obtained the relations between frequency and wavenumbers. By satisfying the major boundary conditions of the dominant thickness-shear mode, three wavenumber solutions are obtained and the frequency equation is constructed. It is shown the resonant frequency of thickness-shear mode is a second-order polynomial of aspect ratios. This conforms to known results in the simplest form and is applicable to further analytical and experimental studies of the frequency equation of quartz crystal resonators.
Molecular structure and vibrational analysis of Trifluoperazine by FT-IR, FT-Raman and UV-Vis spectroscopies combined with DFT calculations.

PubMed

Rajesh, P; Gunasekaran, S; Gnanasambandan, T; Seshadri, S

2015-02-25

The complete vibrational assignment and analysis of the fundamental vibrational modes of Trifluoperazine (TFZ) was carried out using the experimental FT-IR, FT-Raman and UV-Vis data and quantum chemical studies. The observed vibrational data were compared with the wavenumbers derived theoretically for the optimized geometry of the compound from the DFT-B3LYP gradient calculations employing 6-31G (d,p) basis set. Thermodynamic properties like entropy, heat capacity and enthalpy have been calculated for the molecule. The HOMO-LUMO energy gap has been calculated. The intramolecular contacts have been interpreted using natural bond orbital (NBO) and natural localized molecular orbital (NLMO) analysis. Important non-linear properties such as first hyperpolarizability of TFZ have been computed using B3LYP quantum chemical calculation. Copyright © 2014 Elsevier B.V. All rights reserved.
Experimental and theoretical studies of (FT-IR, FT-Raman, UV-Visible and DFT) 4-(6-methoxynaphthalen-2-yl) butan-2-one.

PubMed

Govindasamy, P; Gunasekaran, S

2015-01-01

In this work, the vibrational spectral analysis was carried out by using FT-Raman and FT-IR spectroscopy in the range 4000-50 cm(-1) and 4000-450 cm(-1) respectively for 4-(6-methoxynaphthalen-2-yl) butan-2-one (abbreviated as 4MNBO) molecule. Theoretical calculations were performed by density functional theory (DFT/B3LYP) method using 6-311G(d,p) and 6-311++G(d,p) basis sets. The difference between the observed and calculated wavenumber value of most of the fundamentals were very small. The complete vibrational assignments of wavenumbers were made on the basis of potential energy distribution (PED). The UV-Vis spectrum was recorded in the methanol solution. The energy, wavelength and oscillator's strength were calculated by Time Dependent Density Functional Theory (TD-DFT) and matched to the experimental findings. The intramolecular contacts have been interpreted using natural bond orbital (NBO) and natural localized molecular orbital (NLMO) analysis. Thermodynamic properties of 4MNBO at different temperature have been calculated. The molecular electrostatic potential surface (MESP) and Frontier molecular orbital's (FMO's) analysis were investigated using theoretical calculations. Copyright © 2015 Elsevier B.V. All rights reserved.
Low-energy vibrations of the group 10 metal monocarbonyl MCO (M = Ni, Pd, and Pt): rotational spectroscopy and force field analysis.

PubMed

Okabayashi, Toshiaki; Yamamoto, Takuya; Okabayashi, Emi Y; Tanimoto, Mitsutoshi

2011-03-17

The rotational spectra of NiCO and PdCO in the ground and ν(2) excited vibrational states were observed by employing a source-modulated microwave spectrometer. The NiCO and PdCO molecules were generated in a free space cell by the sputtering reaction of nickel and palladium sheets, respectively, lining the inner surface of a stainless steel cathode with a dc glow plasma of CO and Ar. The molecular constants of NiCO and PdCO were determined by least-squares analysis. By force field analysis for the molecular constants of not only NiCO and PdCO but also of PtCO as previously reported, the harmonic force constants were determined for these three group 10 metal monocarbonyls. The vibrational wavenumbers derived for the lower M-C stretching vibrations were in good agreement with those obtained from the IR spectra in noble gas matrices and those predicted by several quantum chemical calculations published in the past. The bending vibrational wavenumbers derived by the force field analysis were also consistent with most quantum chemical calculations previously reported, but showed systematic discrepancies from the matrix IR values by about 40 cm(-1), even after reassignment (ν(2) band → 2ν(2) band) of the matrix IR spectra of PdCO and PtCO.
Vibrational assignment of aluminum(III) Tris-acetylacetone

NASA Astrophysics Data System (ADS)

Tayyari, Sayyed Faramarz; Raissi, Haydar; Ahmadabadi, Zahra

2002-10-01

The geometry, frequency and intensity of the vibrational bands of aluminum(III) Tris-acetylacetone Al(AA) 3 and its 1, 3, 5- 13C derivative were obtained by the Hartree-Fock (HF) and Density Functional Theory (DFT) with the B3LYP, B1LYP, and G96LYP functionals and using the 6-31G* basis set. The calculated frequencies are compared with the solid IR and Raman spectra. All of the measured IR and Raman bands were interpreted in terms of the calculated vibrational modes. Most computed bands are predicted to be at higher wavenumbers than the experimental bands. The calculated bond lengths and bond angles are in good agreement with the experimental results. Analysis of the vibrational spectra indicates a strong coupling between the chelated ring modes. Four bands in the 500-390 cm -1 frequency range are assigned to the vibrations of metalligand bonds.
Theoretical and Experimental Studies on the Nonlinear Optical Chromophore para Bromoacetanilide

NASA Astrophysics Data System (ADS)

Jothy, V. Bena; Vijayakumar, T.; Jayakumar, V. S.; Udayalekshmi, K.; Ramamurthy, K.; Joe, I. Hubert

2008-11-01

Vibrational spectral analysis of the hydrogen bonded non-linear optical (NLO) material para Bromo Acetanilide (PBA) is carried out using NIR FT-Raman and FT-IR spectroscopy. Ab initio molecular orbital computations have been performed at HF/6-31G(d) level to derive equilibrium geometry, vibrational wavenumbers, intensities and first hyperpolarizability. The lowering of the imino stretching wavenumbers suggests the existence of strong intermolecular N-H⋯O hydrogen bonding substantiated by the natural bond orbital (NBO) analysis. Blue shifting CH stretching wavenumbers, simultaneous activation of carbonyl stretching mode and the strong activation of low wavenumber H-bond stretching vibrations shows the presence of intramolecular charge transfer in the molecule.
Vibrational and electronic investigations, thermodynamic parameters, HOMO and LUMO analysis on Lornoxicam by density functional theory

NASA Astrophysics Data System (ADS)

Suhasini, M.; Sailatha, E.; Gunasekaran, S.; Ramkumaar, G. R.

2015-11-01

The Fourier transform infrared (FT-IR) and FT-Raman spectra of Lornoxicam were recorded in the region 4000-450 cm-1 and 4000-50 cm-1 respectively. Density functional theory (DFT) has been used to calculate the optimized geometrical parameters, atomic charges, and vibrational wavenumbers and intensity of the vibrational bands. The computed vibrational wave numbers were compared with the FT-IR and FT-Raman experimental data. The computational calculations at DFT/B3LYP level with 6-31G(d,p) and 6-31++G(d,p) basis sets. The complete vibrational assignments were performed on the basis of the potential energy distribution (PED) of the Vibrational modes calculated using Vibrational Energy Distribution Analysis (VEDA 4) program. The oscillator's strength calculated by TD-DFT and Lornoxicam is approach complement with the experimental findings. The NMR chemical shifts 13C and 1H were recorded and calculated using the gauge independent atomic orbital (GIAO) method. The Natural charges and intermolecular contacts have been interpreted using Natural Bond orbital (NBO) analysis and the HOMO-LUMO energy gap has been calculated. The thermodynamic properties like Entropy, Enthalpy, Specific heat capacity and zero vibrational energy have been calculated. Besides, molecular electrostatic potential (MEP) was investigated using theoretical calculations.
Structure analysis and spectroscopic characterization of 2-Fluoro-3-Methylpyridine-5-Boronic Acid with experimental (FT-IR, Raman, NMR and XRD) techniques and quantum chemical calculations

NASA Astrophysics Data System (ADS)

Alver, Özgür; Dikmen, Gökhan

2016-03-01

Possible stable conformers, geometrical molecular structures, vibrational properties as well as band assignments, nuclear magnetic shielding tensors of 2-Fluoro-3-Methylpyridine-5-Boronic Acid (2F3MP5BA) were studied experimentally and theoretically using FT-IR, Raman, (CP/MAS) NMR and XRD spectroscopic methods. FT-IR and Raman spectra were evaluated in the region of 3500-400 cm-1, and 3200-400 cm-1, respectively. The optimized geometric structures, vibrational wavenumbers and nuclear magnetic shielding tensors were examined using Becke-3-Lee-Yang-Parr (B3LYP) hybrid density functional theory method with 6-311++G(d, p) basis set. 1H, 13C NMR chemical shifts were calculated using the gauge invariant atomic orbital (GIAO) method. 1H, 13C, APT and HETCOR NMR experiments of title molecule were carried out in DMSO solution. 13C CP/MAS NMR measurement was done with 4 mm zirconium rotor and glycine was used as an external standard. Single crystal of 2F3MP5BA was also prepared for XRD measurements. Assignments of vibrational wavenumbers were also strengthened by calculating the total energy distribution (TED) values using scaled quantum mechanical (SQM) method.
Vibrational dynamics of hydrogen-bonded complexes in solutions studied with ultrafast infrared pump-probe spectroscopy.

PubMed

Banno, Motohiro; Ohta, Kaoru; Yamaguchi, Sayuri; Hirai, Satori; Tominaga, Keisuke

2009-09-15

In aqueous solution, the basis of all living processes, hydrogen bonding exerts a powerful effect on chemical reactivity. The vibrational energy relaxation (VER) process in hydrogen-bonded complexes in solution is sensitive to the microscopic environment around the oscillator and to the geometrical configuration of the hydrogen-bonded complexes. In this Account, we describe the use of time-resolved infrared (IR) pump-probe spectroscopy to study the vibrational dynamics of (i) the carbonyl CO stretching modes in protic solvents and (ii) the OH stretching modes of phenol and carboxylic acid. In these cases, the carbonyl group acts as a hydrogen-bond acceptor, whereas the hydroxyl group acts as a hydrogen-bond donor. These vibrational modes have different properties depending on their respective chemical bonds, suggesting that hydrogen bonding may have different mechanisms and effects on the VER of the CO and OH modes than previously understood. The IR pump-probe signals of the CO stretching mode of 9-fluorenone and methyl acetate in alcohol, as well as that of acetic acid in water, include several components with different time constants. Quantum chemical calculations indicate that the dynamical components are the result of various hydrogen-bonded complexes that form between solute and solvent molecules. The acceleration of the VER is due to the increasing vibrational density of states caused by the formation of hydrogen bonds. The vibrational dynamics of the OH stretching mode in hydrogen-bonded complexes were studied in several systems. For phenol-base complexes, the decay time constant of the pump-probe signal decreases as the band peak of the IR absorption spectrum shifts to lower wavenumbers (the result of changing the proton acceptor). For phenol oligomers, the decay time constant of the pump-probe signal decreases as the probe wavenumber decreases. These observations show that the VER time strongly correlates with the strength of hydrogen bonding. This acceleration may be due to increased coupling between the OH stretching mode and the accepting mode of the VER, because the low-frequency shift caused by hydrogen bond formation is very large. Unlike phenol oligomers, however, the pump-probe signals of phenol-base complexes did not exhibit probe frequency dependence. For these complexes, rapid interconversion between different conformations causes rapid fluctuations in the vibrational frequency of the OH stretching modes, and these fluctuations level the VER times of different conformations. For the benzoic acid dimer, a quantum beat at a frequency of around 100 cm(-1) is superimposed on the pump-probe signal. This result indicates the presence of strong anharmonic coupling between the intramolecular OH stretching and the intermolecular stretching modes. From a two-dimensional plot of the OH stretching wavenumber and the low-frequency wavenumber, the wavenumber of the low-frequency mode is found to increase monotonically as the probe wavenumber is shifted toward lower wavenumbers. Our results represent a quantitative determination of the acceleration of VER by the formation of hydrogen bonds. Our studies merit further evaluation and raise fundamental questions about the current theory of vibrational dynamics in the condensed phase.
Molecular structure, vibrational analysis (IR and Raman) and quantum chemical investigations of 1-aminoisoquinoline

NASA Astrophysics Data System (ADS)

Sivaprakash, S.; Prakash, S.; Mohan, S.; Jose, Sujin P.

2017-12-01

Quantum chemical calculations of energy and geometrical parameters of 1-aminoisoquinoline [1-AIQ] were carried out by using DFT/B3LYP method using 6-311G (d,p), 6-311G++(d,p) and cc-pVTZ basis sets. The vibrational wavenumbers were computed for the energetically most stable, optimized geometry. The vibrational assignments were performed on the basis of potential energy distribution (PED) using VEDA program. The NBO analysis was done to investigate the intra molecular charge transfer of the molecule. The frontier molecular orbital (FMO) analysis was carried out and the chemical reactivity descriptors of the molecule were studied. The Mulliken charge analysis, molecular electrostatic potential (MEP), HOMO-LUMO energy gap and the related properties were also investigated at B3LYP level. The absorption spectrum of the molecule was studied from UV-Visible analysis by using time-dependent density functional theory (TD-DFT). Fourier Transform Infrared spectrum (FT-IR) and Raman spectrum of 1-AIQ compound were analyzed and recorded in the range 4000-400 cm-1 and 3500-100 cm-1 respectively. The experimentally determined wavenumbers were compared with those calculated theoretically and they complement each other.
Molecular structure, electronic properties, NLO, NBO analysis and spectroscopic characterization of Gabapentin with experimental (FT-IR and FT-Raman) techniques and quantum chemical calculations

NASA Astrophysics Data System (ADS)

Sinha, Leena; Karabacak, Mehmet; Narayan, V.; Cinar, Mehmet; Prasad, Onkar

2013-05-01

Gabapentin (GP), structurally related to the neurotransmitter GABA (gamma-aminobutyric acid), mimics the activity of GABA and is also widely used in neurology for the treatment of peripheral neuropathic pain. It exists in zwitterionic form in solid state. The present communication deals with the quantum chemical calculations of energies, geometrical structure and vibrational wavenumbers of GP using density functional (DFT/B3LYP) method with 6-311++G(d,p) basis set. In view of the fact that amino acids exist as zwitterions as well as in the neutral form depending on the environment (solvent, pH, etc.), molecular properties of both the zwitterionic and neutral form of GP have been analyzed. The fundamental vibrational wavenumbers as well as their intensities were calculated and compared with experimental FT-IR and FT-Raman spectra. The fundamental assignments were done on the basis of the total energy distribution (TED) of the vibrational modes, calculated with scaled quantum mechanical (SQM) method. The electric dipole moment, polarizability and the first hyperpolarizability values of the GP have been calculated at the same level of theory and basis set. The nonlinear optical (NLO) behavior of zwitterionic and neutral form has been compared. Stability of the molecule arising from hyper-conjugative interactions and charge delocalization has been analyzed using natural bond orbital analysis. Ultraviolet-visible (UV-Vis) spectrum of the title molecule has also been calculated using TD-DFT method. The thermodynamic properties of both the zwitterionic and neutral form of GP at different temperatures have been calculated.
Study of conformational stability, structural, electronic and charge transfer properties of cladrin using vibrational spectroscopy and DFT calculations.

PubMed

Singh, Swapnil; Singh, Harshita; Srivastava, Anubha; Tandon, Poonam; Sinha, Kirti; Bharti, Purnima; Kumar, Sudhir; Kumar, Padam; Maurya, Rakesh

2014-11-11

In the present work, a detailed conformational study of cladrin (3-(3,4-dimethoxy phenyl)-7-hydroxychromen-4-one) has been done by using spectroscopic techniques (FT-IR/FT-Raman/UV-Vis/NMR) and quantum chemical calculations. The optimized geometry, wavenumber and intensity of the vibrational bands of the cladrin in ground state were calculated by density functional theory (DFT) employing 6-311++G(d,p) basis sets. The study has been focused on the two most stable conformers that are selected after the full geometry optimization of the molecule. A detailed assignment of the FT-IR and FT-Raman spectra has been done for both the conformers along with potential energy distribution for each vibrational mode. The observed and scaled wavenumber of most of the bands has been found to be in good agreement. The UV-Vis spectrum has been recorded and compared with calculated spectrum. In addition, 1H and 13C nuclear magnetic resonance spectra have been also recorded and compared with the calculated data that shows the inter or intramolecular hydrogen bonding. The electronic properties such as HOMO-LUMO energies were calculated by using time-dependent density functional theory. Molecular electrostatic potential has been plotted to elucidate the reactive part of the molecule. Natural bond orbital analysis was performed to investigate the molecular stability. Non linear optical property of the molecule have been studied by calculating the electric dipole moment (μ) and the first hyperpolarizability (β) that results in the nonlinearity of the molecule. Copyright © 2014 Elsevier B.V. All rights reserved.

FT-IR, FT-Raman, UV spectra and DFT calculations on monomeric and dimeric structure of 2-amino-5-bromobenzoic acid.

PubMed

Karabacak, Mehmet; Cinar, Mehmet

2012-02-01

In this work, the molecular conformation, vibrational and electronic transition analysis of 2-amino-5-bromobenzoic acid (2A5BrBA) were presented for the ground state using experimental techniques (FT-IR, FT-Raman and UV) and density functional theory (DFT) employing B3LYP exchange correlation with the 6-311++G(d,p) basis set. FT-IR and FT-Raman spectra were recorded in the regions of 400-4000 cm(-1) and 50-4000 cm(-1), respectively. There are four conformers, C1, C2, C3 and C4 for this molecule. The geometrical parameters, energies and wavenumbers have been obtained for all four conformers. The computational results diagnose the most stable conformer of 2A5BrBA as the C1 form. The complete assignments of fundamental vibrations were performed on the basis of the total energy distribution (TED) of the vibrational modes, calculated with scaled quantum mechanics (SQM) method. Raman activities calculated by DFT method have been converted to the corresponding Raman intensities using Raman scattering theory. The UV spectra of investigated compound were recorded in the region of 200-400 nm for ethanol and water solutions. The electronic properties were evaluated with help of time-dependent DFT (TD-DFT) theoretically and results were compared with experimental observations. The thermodynamic properties of the studied compound at different temperatures were calculated, revealing the correlations between standard heat capacity, standard entropy, standard enthalpy changes and temperatures. The observed and the calculated geometric parameters, vibrational wavenumbers and electronic transitions were compared with observed data and found to be in good agreement. Copyright © 2011 Elsevier B.V. All rights reserved.
Vibrational studies on (E)-1-((pyridine-2-yl)methylene)semicarbazide using experimental and theoretical method

NASA Astrophysics Data System (ADS)

Subashchandrabose, S.; Ramesh Babu, N.; Saleem, H.; Syed Ali Padusha, M.

2015-08-01

The (E)-1-((pyridine-2-yl)methylene)semicarbazide (PMSC) was synthesized. The experimental and theoretical study on molecular structure and vibrational spectra were carried out. The FT-IR (400-4000 cm-1), FT-Raman (50-3500 cm-1) and UV-Vis (200-500 nm) spectra of PMSC were recorded. The geometric structure, conformational analysis, vibrational wavenumbers of PMSC in the ground state have been calculated using B3LYP method of 6-311++G(d,p) basis set. The complete vibrational assignments were made on the basis of TED, calculated by SQM method. The Non-linear optical activity was measured by means of first order hyperpolarizability calculation and π-electrons of conjugative bond in the molecule. The intra-molecular charge transfer, mode hyperconjugative interaction and molecular stabilization energies were calculated. The band gap energies between occupied and unoccupied molecular orbitals were analyzed; it proposes lesser band gap with more reactivity. To understand the electronic properties of this molecule the Mulliken charges were also calculated.
Molecular structure and vibrational spectra of three substituted 4-thioflavones by density functional theory and ab initio Hartree-Fock calculations

NASA Astrophysics Data System (ADS)

Li, Xiao-Hong; Liu, Xiang-Ru; Zhang, Xian-Zhou

2011-01-01

The vibrational frequencies of three substituted 4-thioflavones in the ground state have been calculated using the Hartree-Fock and density functional method (B3LYP) with 6-31G* and 6-31+G** basis sets. The structural analysis shows that there exists H-bonding in the selected compounds and the hydrogen bond lengths increase with the augment of the conjugate parameters of the substituent group on the benzene ring. A complete vibrational assignment aided by the theoretical harmonic wavenumber analysis was proposed. The theoretical spectrograms for FT-IR spectra of the title compounds have been constructed. In addition, it is noted that the selected compounds show significant activity against Shigella flexniri. Several electronic properties and thermodynamic parameters were also calculated.
Molecular structure, vibrational spectroscopic, first order hyperpolarizability and HOMO-LUMO studies of 7-amino-8-oxo-3-vinyl-5-thia-1-azabicyclo[4.2.0]oct-2-ene-2-carboxylic acid

NASA Astrophysics Data System (ADS)

Ramalingam, M.; Sethuraman, V.; Sundaraganesan, N.

2011-02-01

The FT-IR and FT-Raman spectra of 7-amino-8-oxo-3-vinyl-5-thia-1-azabicyclo[4.2.0]oct-2-ene-2-carboxylic acid (7AVCA) were recorded in the region 4000-400 cm -1 and 3500-10 cm -1, respectively. Quantum chemical calculations of energies, geometrical structure and vibrational wavenumbers were carried out by ab initio HF and density functional theoretical methods invoking 6-311G(d,p) basis set. The differences between the observed and scaled wavenumber values of most of the fundamentals are very small. The electric dipole moment ( μ) and the first order hyperpolarizability ( β0) values have been computed quantum mechanically. The calculated results show that 7AVCA may have microscopic nonlinear optical (NLO) behavior with non-zero values. A detailed interpretation of the FT-IR and FT-Raman spectra of 7AVCA is reported. The theoretical IR and Raman spectra of 7AVCA have also been constructed. The calculated HOMO and LUMO energies show that the charge transfer occurs within the molecule.
Experimental and theoretical spectroscopic studies of anticancer drug rosmarinic acid using HF and density functional theory.

PubMed

Mariappan, G; Sundaraganesan, N; Manoharan, S

2012-11-01

In this work, we reported a combined experimental and theoretical study on molecular structure, vibrational spectra and NBO analysis of anticancer drug of rosmarinic acid. The optimized molecular structure, atomic charges, vibrational frequencies, natural bond orbital analysis and ultraviolet-visible spectral interpretation of rosmarinic acid have been studied by performing HF and DFT/B3LYP/6-31G(d,p) level of theory. The FT-IR (solid and solution phase), FT-Raman (solid phase) spectra were recorded in the region 4000-400 and 3500-50 cm(-1), respectively. The UV-Visible absorption spectra of the compound that dissolved in ethanol were recorded in the range of 200-800 nm. The scaled wavenumbers are compared with the experimental values. The difference between the observed and scaled wavenumber values of most of the fundamentals is very small. The formation of hydrogen bond was investigated in terms of the charge density by the NBO calculations. Based on the UV spectra and TD-DFT calculations, the electronic structure and the assignments of the absorption bands were carried out. Besides, molecular electrostatic potential (MEP), frontier molecular orbitals (FMO) analysis were investigated using theoretical calculations. Copyright © 2012 Elsevier B.V. All rights reserved.
Molecular structure, vibrational spectroscopic, first order hyperpolarizability and HOMO-LUMO studies of 7-amino-8-oxo-3-vinyl-5-thia-1-azabicyclo[4.2.0]oct-2-ene-2-carboxylic acid.

PubMed

Ramalingam, M; Sethuraman, V; Sundaraganesan, N

2011-02-01

The FT-IR and FT-Raman spectra of 7-amino-8-oxo-3-vinyl-5-thia-1-azabicyclo[4.2.0]oct-2-ene-2-carboxylic acid (7AVCA) were recorded in the region 4000-400 cm(-1) and 3500-10 cm(-1), respectively. Quantum chemical calculations of energies, geometrical structure and vibrational wavenumbers were carried out by ab initio HF and density functional theoretical methods invoking 6-311G(d,p) basis set. The differences between the observed and scaled wavenumber values of most of the fundamentals are very small. The electric dipole moment (μ) and the first order hyperpolarizability (β0) values have been computed quantum mechanically. The calculated results show that 7AVCA may have microscopic nonlinear optical (NLO) behavior with non-zero values. A detailed interpretation of the FT-IR and FT-Raman spectra of 7AVCA is reported. The theoretical IR and Raman spectra of 7AVCA have also been constructed. The calculated HOMO and LUMO energies show that the charge transfer occurs within the molecule. Copyright Â© 2010 Elsevier B.V. All rights reserved.
Raman bandshape analysis on CH and CSC stretching modes of dimethyl sulfoxide in liquid binary mixture: comparative study with quantum-chemical calculations.

PubMed

Upadhyay, Ganesh; Gomti Devi, Th

2014-12-10

The interacting nature of dimethyl sulfoxide (DMSO) in binary mixtures has been carried out on CH and CSC stretching modes of vibration using chloroform (CLF), chloroform-d (CLFd), acetonitrile (ACN) and acetonitrile-d3 (ACNd) solvents. Peak frequencies of both the stretching modes show blue shift with the increase in solvent concentration. Variation of Raman bandwidth with the solvent concentration was discussed using different mechanisms. Ab initio calculation for geometry optimization and vibrational wavenumber calculation have been performed on monomer and dimer structures of DMSO to explain the experimentally observed Raman spectra. Theoretically calculated values are found in good agreement with the experimental results. Vibrational and reorientational relaxation times have been studied corresponding to solvent concentrations to elucidate the interacting mechanisms of binary mixtures. Copyright © 2014 Elsevier B.V. All rights reserved.
Analysis of molecular structure, spectroscopic properties (FT-IR, micro-Raman and UV-vis) and quantum chemical calculations of free and ligand 2-thiopheneglyoxylic acid in metal halides (Cd, Co, Cu, Ni and Zn).

PubMed

Gökce, Halil; Bahçeli, Semiha

2013-12-01

In this study, molecular geometries, experimental vibrational wavenumbers, electronic properties and quantum chemical calculations of 2-thiopheneglyoxylic acid molecule, (C6H4O3S), and its metal halides (Cd, Co, Cu, Ni and Zn) which are used as pharmacologic agents have been investigated experimentally by FT-IR, micro-Raman and UV-visible spectroscopies and elemental analysis. Meanwhile the vibrational calculations were verified by DFT/B3LYP method with 6-311++G(d,p) and LANL2DZ basis sets in the ground state, for free TPGA molecule and its metal halide complexes, respectively, for the first time. The calculated fundamental vibrational frequencies for the title compounds are in a good agreement with the experimental data. Copyright © 2013 Elsevier B.V. All rights reserved.
Experimental and theoretical IR and Raman spectra of picolinic, nicotinic and isonicotinic acids

NASA Astrophysics Data System (ADS)

Koczoń, P.; Dobrowolski, J. Cz.; Lewandowski, W.; Mazurek, A. P.

2003-07-01

The experimental and theoretical (B3PW91/6-311++G**) vibrational (IR and Raman) spectra of picolinic, nicotinic and isonicotinic acids (pyridine-2-, -3-, and -4-carboxylic acid, respectively) were studied. Three stable calculated structures were found for picolinic acid: the structure with intramolecular hydrogen COOH⋯N bond, and the two without hydrogen bond. For the nicotinic acid two stable theoretical structures differ in orientation of the COOH group with respect to the nitrogen atom, whereas for the isonicotinic acid only one form was stable. The theoretical vibrational spectra of the three acids were interpreted by means of potential energy distributions (PEDs) using VEDA 3 program. Next, selected experimental bands were assigned based on the scaled theoretical wavenumbers. Finally, the wavenumbers and intensities for the three isomeric acids were compared and discussed in terms of location of the carboxylic group.
Natural bond orbital analysis, electronic structure and vibrational spectral analysis of N-(4-hydroxyl phenyl) acetamide: A density functional theory

NASA Astrophysics Data System (ADS)

Govindasamy, P.; Gunasekaran, S.; Ramkumaar, G. R.

2014-09-01

The Fourier transform infrared (FT-IR) and FT-Raman spectra of N-(4-hydroxy phenyl) acetamide (N4HPA) of painkiller agent were recorded in the region 4000-450 cm-1 and 4000-50 cm-1 respectively. Density functional theory (DFT) has been used to calculate the optimized geometrical parameter, atomic charges, and vibrational wavenumbers and intensity of the vibrational bands. The computed vibrational wave numbers were compared with the FT-IR and FT-Raman experimental data. The computational calculations at DFT/B3LYP level with 6-31G(d,p), 6-31++G(d,p), 6-311G(d,p) and 6-311++G(d,p) basis sets. The complete vibrational assignments were performed on the basis of the potential energy distribution (PED) of the vibrational modes calculated using Vibrational energy distribution analysis (VEDA 4) program. The oscillator’s strength calculated by TD-DFT and N4HPA is approach complement with the experimental findings. The NMR chemical shifts 13C and 1H were recorded and calculated using the gauge independent atomic orbital (GIAO) method. The molecular electrostatic potential (MESP) and electron density surfaces of the molecule were constructed. The Natural charges and intermolecular contacts have been interpreted using Natural Bond orbital (NBO) analysis the HOMO-LUMO energy gap has been calculated. The thermodynamic properties like entropy, heat capacity and zero vibrational energy have been calculated.
Natural bond orbital analysis, electronic structure and vibrational spectral analysis of N-(4-hydroxyl phenyl) acetamide: a density functional theory.

PubMed

Govindasamy, P; Gunasekaran, S; Ramkumaar, G R

2014-09-15

The Fourier transform infrared (FT-IR) and FT-Raman spectra of N-(4-hydroxy phenyl) acetamide (N4HPA) of painkiller agent were recorded in the region 4000-450 cm(-1) and 4000-50 cm(-1) respectively. Density functional theory (DFT) has been used to calculate the optimized geometrical parameter, atomic charges, and vibrational wavenumbers and intensity of the vibrational bands. The computed vibrational wave numbers were compared with the FT-IR and FT-Raman experimental data. The computational calculations at DFT/B3LYP level with 6-31G(d,p), 6-31++G(d,p), 6-311G(d,p) and 6-311++G(d,p) basis sets. The complete vibrational assignments were performed on the basis of the potential energy distribution (PED) of the vibrational modes calculated using Vibrational energy distribution analysis (VEDA 4) program. The oscillator's strength calculated by TD-DFT and N4HPA is approach complement with the experimental findings. The NMR chemical shifts 13C and 1H were recorded and calculated using the gauge independent atomic orbital (GIAO) method. The molecular electrostatic potential (MESP) and electron density surfaces of the molecule were constructed. The Natural charges and intermolecular contacts have been interpreted using Natural Bond orbital (NBO) analysis the HOMO-LUMO energy gap has been calculated. The thermodynamic properties like entropy, heat capacity and zero vibrational energy have been calculated. Copyright © 2014 Elsevier B.V. All rights reserved.
Structural, vibrational and theoretical studies of anilinium trichloroacetate: New hydrogen bonded molecular crystal with nonlinear optical properties

NASA Astrophysics Data System (ADS)

Tanak, H.; Pawlus, K.; Marchewka, M. K.; Pietraszko, A.

2014-01-01

In this work, we report a combined experimental and theoretical study on molecular structure, vibrational spectra and NBO analysis of the potential nonlinear optical (NLO) material anilinium trichloroacetate. The FT-IR and FT-Raman spectra of the compound have been recorded together between 4000-80 cm-1 and 3600-80 cm-1 regions, respectively. The compound crystallizes in the noncentrosymmetric space group of monoclinic system. The optimized molecular structure, vibrational wavenumbers, IR intensities and Raman activities have been calculated by using density functional method (B3LYP) with 6-311++G(d,p) as higher basis set. The obtained vibrational wavenumbers and optimized geometric parameters were seen to be in good agreement with the experimental data. DSC measurements on powder samples do not indicate clearly on the occurrence of phase transitions in the temperature 113-293 K. The Kurtz and Perry powder reflection technique appeared to be very effective in studies of second-order nonlinear optical properties of the molecule. The non-linear optical properties are also addressed theoretically. The predicted NLO properties of the title compound are much greater than ones of urea. In addition, DFT calculations of the title compound, molecular electrostatic potential, frontier orbitals and thermodynamic properties were also performed at 6-311++G(d,p) level of theory. For title crystal the SHG efficiency was estimated by Kurtz-Perry method to be deff = 0.70 deff (KDP).
Structural, vibrational and theoretical studies of anilinium trichloroacetate: new hydrogen bonded molecular crystal with nonlinear optical properties.

PubMed

Tanak, H; Pawlus, K; Marchewka, M K; Pietraszko, A

2014-01-24

In this work, we report a combined experimental and theoretical study on molecular structure, vibrational spectra and NBO analysis of the potential nonlinear optical (NLO) material anilinium trichloroacetate. The FT-IR and FT-Raman spectra of the compound have been recorded together between 4000-80 cm(-1) and 3600-80 cm(-1) regions, respectively. The compound crystallizes in the noncentrosymmetric space group of monoclinic system. The optimized molecular structure, vibrational wavenumbers, IR intensities and Raman activities have been calculated by using density functional method (B3LYP) with 6-311++G(d,p) as higher basis set. The obtained vibrational wavenumbers and optimized geometric parameters were seen to be in good agreement with the experimental data. DSC measurements on powder samples do not indicate clearly on the occurrence of phase transitions in the temperature 113-293 K. The Kurtz and Perry powder reflection technique appeared to be very effective in studies of second-order nonlinear optical properties of the molecule. The non-linear optical properties are also addressed theoretically. The predicted NLO properties of the title compound are much greater than ones of urea. In addition, DFT calculations of the title compound, molecular electrostatic potential, frontier orbitals and thermodynamic properties were also performed at 6-311++G(d,p) level of theory. For title crystal the SHG efficiency was estimated by Kurtz-Perry method to be d(eff)=0.70 d(eff) (KDP). Copyright © 2013 Elsevier B.V. All rights reserved.
4-Methyl-1H-Indazole-5-Boronic acid: Crystal structure, vibrational spectra and DFT simulations

NASA Astrophysics Data System (ADS)

Dikmen, Gökhan

2017-12-01

Molecular structure, conformer forms, geometric parameters and vibrational assignments and properties of 4-Methyl-1H-Indazole-5-Boronic Acid (4M1HI5BA) were theoretically and experimentally studied using Raman, FT-IR, XRD spectroscopic methods and quantum chemical calculations. Raman and FT-IR spectra were examined range from 4000 to 400 cm-1. Moreover, single crystals of 4M1HI5BA were prepared in order to use in XRD experiments. Vibrational assignments were carried out using total energy distribution (TED) values. Furthermore, HOMO and LUMO were calculated for 4M1HI5BA. Four different conformations of 4M1HI5BA were calculated in only gas phase. The theoretical and experimental results show that in order to predict vibrational wavenumbers B3LYP/6-311++G(d,p) may provide acceptable results and the most stable conformer of 4M1HI5BA is predicted to be envelope conformer.
Natural bond orbital analysis, electronic structure, non-linear properties and vibrational spectral analysis of L-histidinium bromide monohydrate: a density functional theory.

PubMed

Sajan, D; Joseph, Lynnette; Vijayan, N; Karabacak, M

2011-10-15

The spectroscopic properties of the crystallized nonlinear optical molecule L-histidinium bromide monohydrate (abbreviated as L-HBr-mh) have been recorded and analyzed by FT-IR, FT-Raman and UV techniques. The equilibrium geometry, vibrational wavenumbers and the first order hyperpolarizability of the crystal were calculated with the help of density functional theory computations. The optimized geometric bond lengths and bond angles obtained by using DFT (B3LYP/6-311++G(d,p)) show good agreement with the experimental data. The complete assignments of fundamental vibrations were performed on the basis of the total energy distribution (TED) of the vibrational modes, calculated with scaled quantum mechanics (SQM) method. The natural bond orbital (NBO) analysis confirms the occurrence of strong intra and intermolecular N-H⋯O hydrogen bonding. Copyright © 2011 Elsevier B.V. All rights reserved.
FT-IR, micro-Raman and UV-vis spectroscopic and quantum chemical investigations of free 2,2'-dithiodipyridine and its metal (Co, Cu and Zn) halide complexes.

PubMed

Gökce, Halil; Bahçeli, Semiha

2013-10-01

In this study the elemental analysis results, molecular geometries, vibrational and electronic absorption spectra of free 2,2'-dithiodipyridine(C10H8N2S2), (or DTDP) (with synonym, 2,2'-dipyridyl disulfide) and M(C10H8N2S2)Cl2 (M=Co, Cu and Zn) complexes have been reported. Vibrational wavenumbers of free DTDP and its metal halide complexes have been calculated by using DFT/B3LYP calculation method with 6-31++G(d,p) and Lanl2DZ basis sets, respectively, in the ground state, for the first time. The calculated fundamental vibrational frequencies are in a good agreement with experimental data. The HOMO, LUMO and MEP analyses of all compounds are performed by DFT method. Copyright © 2013. Published by Elsevier B.V.
DFT, FT-IR, FT-Raman and NMR studies of 4-(substituted phenylazo)-3,5-diacetamido-1H-pyrazoles

NASA Astrophysics Data System (ADS)

Kınalı, Selin; Demirci, Serkan; Çalışır, Zühre; Kurt, Mustafa; Ataç, Ahmet

2011-05-01

We present a detailed analysis of the structural and vibrational spectra of some novel azo dyes. 2-(Substituted phenylazo)malononitriles were synthesized by the coupling reaction of the diazonium salts, which were prepared with the use of various aniline derivatives with malononitrile, and then 4-(substituted phenylazo)-3,5-diamino-1H-pyrazole azo dyes were obtained via the ring closure of the azo compounds with hydrazine monohydrate. The experimental and theoretical vibrational spectra of azo dyes were studied. The structural and spectroscopic analysis of the molecules were carried out by using Becke's three-parameters hybrid functional (B3LYP) and density functional harmonic calculations. The 1H nuclear magnetic resonance (NMR) chemical shifts of the azo dye molecules were calculated using the gauge-invariant-atomic orbital (GIAO) method. The calculated vibrational wavenumbers and chemical shifts were compared with the experimental data of the molecules.
Three-dimensional spectroscopy of vibrational energy in liquids: nitromethane and acetonitrile.

PubMed

Sun, Yuxiao; Pein, Brandt C; Dlott, Dana D

2013-12-12

We introduce a novel type of three-dimensional (3D) spectroscopy to study vibrational energy transfer, where an IR pulse tunable through the CH-stretching and CD-stretching regions was used to create parent vibrational excitations in liquids and a visible probe pulse was used to generate both Stokes and anti-Stokes Raman spectra as a function of delay time. The Raman spectra determine how much vibrational excitation was present in each probed state. The three dimensions are the wavenumber of the pumped state, the wavenumber of the probed state, and the time interval. The technique was used to study nitromethane (NM) and acetonitrile (ACN) and their deuterated analogues at ambient temperature. The 3D spectra were quite complicated. Three types of artifacts due to nonlinear light scattering were observed. Along the diagonal were two fundamental CH-stretch (or CD-stretch) transitions and several weaker combination bands or overtone transitions. Because Raman spectroscopy allows us to simultaneously probe a wide wavenumber region, for every diagonal peak, there were ∼10 off-diagonal peaks. The cross-peaks at shorter delay times reveal the nature of the initial excitation by showing which lower-wavenumber excitations were produced along with the pumped CH-stretch or CD-stretch. The longer-time spectra characterized vibrational energy relaxation processes, and showed how daughter vibrations were generated by different parent excitations.
Fourier transform infrared spectroscopic study of gamma irradiated SiO2 nanoparticles

NASA Astrophysics Data System (ADS)

Huseynov, Elchin; Garibov, Adil; Mehdiyeva, Ravan; Huseynova, Efsane

2018-03-01

In the present work, nano SiO2 particles are investigated before and after gamma irradiation (25, 50, 75, 100 and 200 kGy) using Fourier transform infrared (FTIR) spectroscopy method for the wavenumber between 400-4000 cm-1. It is found that as a result of spectroscopic analysis, five new peaks have appeared after gamma radiation. Two of new obtained peaks (which are located at 687 cm-1 and 2357 cm-1 of wavenumber) were formed as a result of gamma radiation interaction with Si-O bonds. Another three new peaks (peaks appropriate to 941, 2052 and 2357 cm-1 values of wavenumber) appear as a result of interaction of water with nano SiO2 particles after gamma irradiation. It has been defined as asymmetrical bending vibration, symmetrical bending vibration, symmetrical stretching vibration and asymmetrical stretching vibration of Si-O bonds appropriate to peaks.
FT-IR, FT-Raman, NMR spectra, density functional computations of the vibrational assignments (for monomer and dimer) and molecular geometry of anticancer drug 7-amino-2-methylchromone

NASA Astrophysics Data System (ADS)

Mariappan, G.; Sundaraganesan, N.

2014-04-01

Vibrational assignments for the 7-amino-2-methylchromone (abbreviated as 7A2MC) molecule using a combination of experimental vibrational spectroscopic measurements and ab initio computational methods are reported. The optimized geometry, intermolecular hydrogen bonding, first order hyperpolarizability and harmonic vibrational wavenumbers of 7A2MC have been investigated with the help of B3LYP density functional theory method. The calculated molecular geometry parameters, the theoretically computed vibrational frequencies for monomer and dimer and relative peak intensities were compared with experimental data. DFT calculations using the B3LYP method and 6-31 + G(d,p) basis set were found to yield results that are very comparable to experimental IR and Raman spectra. Detailed vibrational assignments were performed with DFT calculations and the potential energy distribution (PED) obtained from the Vibrational Energy Distribution Analysis (VEDA) program. Natural Bond Orbital (NBO) study revealed the characteristics of the electronic delocalization of the molecular structure. 13C and 1H NMR spectra have been recorded and 13C and 1H nuclear magnetic resonance chemical shifts of the molecule have been calculated using the gauge independent atomic orbital (GIAO) method. Furthermore, All the possible calculated values are analyzed using correlation coefficients linear fitting equation and are shown strong correlation with the experimental data.

Infrared spectrum, NBO, HOMO-LUMO, MEP and molecular docking studies (2E)-3-(3-nitrophenyl)-1-[4-piperidin-1-yl]prop-2-en-1-one.

PubMed

Panicker, C Yohannan; Varghese, Hema Tresa; Nayak, Prakash S; Narayana, B; Sarojini, B K; Fun, H K; War, Javeed Ahamad; Srivastava, S K; Van Alsenoy, C

2015-09-05

FT-IR spectrum of (2E)-3-(3-nitrophenyl)-1-[4-piperidin-1-yl]prop-2-en-1-one was recorded and analyzed. The vibrational wavenumbers were computed using HF and DFT quantum chemical calculations. The data obtained from wavenumber calculations are used to assign IR bands. Potential energy distribution was done using GAR2PED software. The geometrical parameters of the title compound are in agreement with the XRD results. NBO analysis, HOMO-LUMO, first and second hyperpolarizability and molecular electrostatic potential results are also reported. The possible electrophile attacking sites of the title molecule is identified using MEP surface plot study. Molecular docking results predicted the anti-leishmanic activity for the compound. Copyright © 2015. Published by Elsevier B.V.
A vibrational spectroscopic study of hydrated Fe(3+) hydroxyl-sulfates; polymorphic minerals butlerite and parabutlerite.

PubMed

Cejka, Jiří; Sejkora, Jiří; Plášil, Jakub; Bahfenne, Silmarilly; Palmer, Sara J; Frost, Ray L

2011-09-01

Raman and infrared spectra of two polymorphous minerals with the chemical formula Fe3+(SO4)(OH)·2H2O, monoclinic butlerite and orthorhombic parabutlerite, are studied and the spectra assigned. Observed bands are attributed to the (SO4)2- stretching and bending vibrations, hydrogen bonded water molecules, stretching and bending vibrations of hydroxyl ions, water librational modes, Fe-O and Fe-OH stretching vibrations, Fe-OH bending vibrations and lattice vibrations. The O-H⋯O hydrogen bond lengths in the structures of both minerals are calculated from the wavenumbers of the stretching vibrations. One symmetrically distinct (SO4)2- unit in the structure of butlerite and two symmetrically distinct (SO4)2- units in the structure of parabutlerite are inferred from the Raman and infrared spectra. This conclusion agrees with the published crystal structures of both mineral phases. Copyright © 2011 Elsevier B.V. All rights reserved.
Predicting vibratory stresses from aero-acoustic loads

NASA Astrophysics Data System (ADS)

Shaw, Matthew D.

Sonic fatigue has been a concern of jet aircraft engineers for many years. As engines become more powerful, structures become more lightly damped and complex, and materials become lighter, stiffer, and more complicated, the need to understand and predict structural response to aeroacoustic loads becomes more important. Despite decades of research, vibration in panels caused by random pressure loads, such as those found in a supersonic jet, is still difficult to predict. The work in this research improves on current prediction methods in several ways, in particular for the structural response due to wall pressures induced by supersonic turbulent flows. First, solutions are calculated using time-domain input pressure loads that include shock cells and their interaction with turbulent flow. The solutions include both mean (static) and oscillatory components. Second, the time series of stresses are required for many fatigue assessment counting algorithms. To do this, a method is developed to compute time-dependent solutions in the frequency domain. The method is first applied to a single-degree-of-freedom system. The equations of motion are derived and solved in both the frequency domain and the time domain. The pressure input is a random (broadband) signal representative of jet flow. The method is then applied to a simply-supported beam vibrating in flexure using a line of pressure inputs computed with computational fluid dynamics (CFD). A modal summation approach is used to compute structural response. The coupling between the pressure field and the structure, through the joint acceptance, is reviewed and discussed for its application to more complicated structures. Results from the new method and from a direct time domain method are compared for method verification. Because the match is good and the new frequency domain method is faster computationally, it is chosen for use in a more complicated structure. The vibration of a two-dimensional panel loaded by jet nozzle discharge flow is addressed. The surface pressures calculated at Pratt and Whitney using viscous and compressible CFD are analyzed and compared to surface pressure measurements made at the United Technologies Research Center (UTRC). A structural finite element model is constructed to represent a flexible panel also used in the UTRC setup. The mode shapes, resonance frequencies, modal loss factors, and surface pressures are input into the solution method. Displacement time series and power spectral densities are computed and compared to measurement and show good agreement. The concept of joint acceptance is further addressed for two-dimensional plates excited by supersonic jet flow. Static and alternating stresses in the panel are also computed, and the most highly stressed modes are identified. The surface pressures are further analyzed in the wavenumber domain for insight into the physics of sonic fatigue. Most of the energy in the wall pressure wavenumber-frequency spectrum at subsonic speeds is in turbulent structures near the convective wavenumber. In supersonic flow, however, the shock region dominates the spectrum at low frequencies, but convective behavior is still dominant at higher frequencies. When the forcing function wavenumber energy overlaps the modal wavenumbers, the acceptance of energy by the structure from the flow field is greatest. The wavenumber analysis suggests a means of designing structures to minimize overlap of excitation and structural wavenumber peaks to minimize vibration and sonic fatigue.
Primidone--an antiepileptic drug--characterisation by quantum chemical and spectroscopic (FTIR, FT-Raman, 1H, 13C NMR and UV-Visible) investigations.

PubMed

Arjunan, V; Santhanam, R; Subramanian, S; Mohan, S

2013-05-15

The solid phase FTIR and FT-Raman spectra of primidone were recorded in the regions 4000-400 cm(-1) and 4000-100 cm(-1), respectively. The vibrational spectra were analysed and the observed fundamentals were assigned and analysed. The experimental wavenumbers were compared with the theoretical scaled vibrational wavenumbers determined by DFT methods. The Raman intensities were also determined with B3LYP/6-31G(d,p) method. The total electron density and molecular electrostatic potential surface of the molecule were constructed by using B3LYP/6-311++G(d,p) method to display electrostatic potential (electron+nuclei) distribution. The HOMO and LUMO energies were measured. Natural bond orbital analysis of primidone has been performed to indicate the presence of intramolecular charge transfer. The (1)H and (13)C NMR spectra were recorded and the chemical shifts of the molecule were calculated. Copyright © 2013 Elsevier B.V. All rights reserved.
Theoretical study of the changes in the vibrational characteristics arising from the hydrogen bonding between Vitamin C ( L-ascorbic acid) and H 2O

NASA Astrophysics Data System (ADS)

Dimitrova, Yordanka

2006-02-01

The vibrational characteristics (vibrational frequencies, infrared intensities and Raman activities) for the hydrogen-bonded system of Vitamin C ( L-ascorbic acid) with five water molecules have been predicted using ab initio SCF/6-31G(d, p) calculations and DFT (BLYP) calculations with 6-31G(d, p) and 6-31++G(d, p) basis sets. The changes in the vibrational characteristics from free monomers to a complex have been calculated. The ab initio and BLYP calculations show that the complexation between Vitamin C and five water molecules leads to large red shifts of the stretching vibrations for the monomer bonds involved in the hydrogen bonding and very strong increase in their IR intensity. The predicted frequency shifts for the stretching vibrations from Vitamin C taking part in the hydrogen bonding are up to -508 cm -1. The magnitude of the wavenumber shifts is indicative of relatively strong OH···H hydrogen-bonded interactions. In the same time the IR intensity and Raman activity of these vibrations increase upon complexation. The IR intensity increases dramatically (up to 12 times) and Raman activity increases up to three times. The ab initio and BLYP calculations show, that the symmetric OH vibrations of water molecules are more sensitive to the complexation. The hydrogen bonding leads to very large red shifts of these vibrations and very strong increase in their IR intensity. The asymmetric OH stretching vibrations of water, free from hydrogen bonding are less sensitive to the complexation than the hydrogen-bonded symmetric O sbnd H stretching vibrations. The increases of the IR intensities for these vibrations are lower and red shifts are negligible.
Monomeric and dimeric structures, electronic properties and vibrational spectra of azelaic acid by HF and B3LYP methods

NASA Astrophysics Data System (ADS)

Kumar, Amarendra; Narayan, Vijay; Prasad, Onkar; Sinha, Leena

2012-08-01

Quantum chemical calculations of energies, dipole moment, polarizability, hyperpolarizability and vibrational wavenumbers of Azelaic acid (AZA) were carried out by using ab initio HF and B3LYP methods with 6-311++G(d,p) basis set. Hydrogen-bonded dimer of AZA, optimized by counterpoise correction, has also been studied by HF and B3LYP at the 6-311++G(d,p) level and the effects of molecular association through Osbnd H⋯O hydrogen bonding have been discussed. A complete vibrational analysis of AZA has been performed and assignments are made on the basis of potential energy distribution. The comparisons and assignments of the vibrational frequencies indicate that the experimental spectra also correspond acceptably with those of theoretically simulated spectra except the hydrogen-bonded coupled infrared vibrations.
Quantum chemical study of a derivative of 3-substituted dithiocarbamic flavanone

NASA Astrophysics Data System (ADS)

Gosav, Steluta; Paduraru, Nicoleta; Maftei, Dan; Birsa, Mihail Lucian; Praisler, Mirela

2017-02-01

The aim of this work is to characterize a quite novel 3-dithiocarbamic flavonoid by vibrational spectroscopy in conjunction with Density Functional Theory (DFT) calculations. Quantum mechanics calculations of energies, geometries and vibrational wavenumbers in the ground state were carried out by using hybrid functional B3LYP with 6-311G(d,p) as basis set. The results indicate a remarkable agreement between the calculated molecular geometries, as well as vibrational frequencies, and the corresponding experimental data. In addition, a complete assignment of all the absorption bands present in the vibrational spectrum has been performed. In order to assess its chemical potential, quantum molecular descriptors characterizing the interactions between the 3-dithiocarbamic flavonoid and its biological receptors have been computed. The frontier molecular orbitals and the HOMO-LUMO energy gap have been used in order to explain the way in which the new molecule can interact with other species and to characterize its molecular chemical stability/reactivity. The molecular electrostatic potential (MEP) map, computed in order to identify the sites of the studied flavonoid that are most likely to interact with electrophilic and nucleophilic species, is discussed.
Molecular conformational analysis, vibrational spectra, NBO analysis and first hyperpolarizability of (2E)-3-phenylprop-2-enoic anhydride based on density functional theory calculations.

PubMed

Sheena Mary, Y; Raju, K; Panicker, C Yohannan; Al-Saadi, Abdulaziz A; Thiemann, Thies; Van Alsenoy, Christian

2014-07-15

The conformational behavior and structural stability of (2E)-3-phenylprop-2-enoic anhydride were investigated by using density functional theory. Seventeen possible stable conformations of the title compound were determined and verified with their calculated vibrational frequencies being all positive. The optimized molecular structure, vibrational wavenumbers, corresponding vibrational assignments of (2E)-3-phenylprop-2-enoic anhydride have been investigated experimentally and theoretically using Gaussian09 software package. Potential energy distribution of normal modes vibrations was done using GAR2PED program. The HOMO and LUMO analysis are used to determine the charge transfer within the molecule. The stability of the molecule arising from hyper-conjugative interaction and charge delocalization has been analyzed using NBO analysis. The calculated first hyperpolarizability of the title compound is 12×10(-30) esu and is 92.31 times that of the standard NLO material urea and the title compound is an attractive object for future studies of nonlinear optical properties. MEP was performed by the DFT method and the predicted infrared intensities and Raman activities have also been reported. Copyright © 2014 Elsevier B.V. All rights reserved.
Vibrational spectroscopic study and NBO analysis on tranexamic acid using DFT method

NASA Astrophysics Data System (ADS)

Muthu, S.; Prabhakaran, A.

2014-08-01

In this work, we reported the vibrational spectra of tranexamic acid (TA) by experimental and quantum chemical calculation. The solid phase FT-Raman and FT-IR spectra of the title compound were recorded in the region 4000 cm-1 to 100 cm-1 and 4000 cm-1 to 400 cm-1 respectively. The molecular geometry, harmonic vibrational frequencies and bonding features of TA in the ground state have been calculated by using density functional theory (DFT) B3LYP method with standard 6-31G(d,p) basis set. The scaled theoretical wavenumber showed very good agreement with the experimental values. The vibrational assignments were performed on the basis of the potential energy distribution (PED) of the vibrational modes. Stability of the molecule, arising from hyperconjugative interactions and charge delocalization, has been analyzed using Natural Bond Orbital (NBO) analysis. The results show that ED in the σ* and π* antibonding orbitals and second order delocalization energies E(2) confirm the occurrence of intramolecular charge transfer (ICT) within the molecule. The electrostatic potential mapped onto an isodensity surface has been obtained. The calculated HOMO and LUMO energies show that charge transfer occurs within the molecule. The thermodynamic properties (heat capacity, entropy, and enthalpy) of the title compound at different temperatures were calculated in gas phase.
Nonplanar property study of antifungal agent tolnaftate-spectroscopic approach

NASA Astrophysics Data System (ADS)

Arul Dhas, D.; Hubert Joe, I.; Roy, S. D. D.; Balachandran, S.

2011-09-01

Vibrational analysis of the thionocarbamate fungicide tolnaftate which is antidermatophytic, antitrichophytic and antimycotic agent, primarily inhibits the ergosterol biosynthesis in the fungus, was carried out using NIR FT-Raman and FTIR spectroscopic techniques. The equilibrium geometry, various bonding features, harmonic vibrational wavenumbers and torsional potential energy surface (PES) scan studies have been computed using density functional theory method. The detailed interpretation of the vibrational spectra has been carried out with the aid of VEDA.4 program. Vibrational spectra, natural bonding orbital (NBO) analysis and optimized molecular structure show the clear evidence for electronic interaction of thionocarbamate group with aromatic ring. Predicted electronic absorption spectrum from TD-DFT calculation has been compared with the UV-vis spectrum. The Mulliken population analysis on atomic charges and the HOMO-LUMO energy were also calculated. Vibrational analysis reveals that the simultaneous IR and Raman activation of the C-C stretching mode in the phenyl and naphthalene ring provide evidence for the charge transfer interaction between the donor and acceptor groups and is responsible for its bioactivity as a fungicide.
Explicitly correlated coupled cluster calculations for propadienylidene (H(2)CCC).

PubMed

Botschwina, Peter; Oswald, Rainer

2010-09-16

Propadienylidene (H(2)CCC), a reactive carbene of interest to combustion processes and astrochemistry, has been studied by explicitly correlated coupled cluster theory at the CCSD(T)-F12x (x = a, b) level. Vibrational configuration interaction (VCI) has been employed to calculate accurate wavenumbers for the fundamental vibrations of H(2)CCC, D(2)CCC, and HDCCC. The symmetric CH stretching vibration of H(2)CCC is predicted to occur at ν(1) = 2984 cm(-1). Absorptions observed by argon matrix infrared spectroscopy at 3049.5 and 3059.6 cm(-1) are reassigned to the combination tone ν(2) + ν(4), which interacts with ν(1) and is predicted to have a higher intensity than the latter. Furthermore, IR bands detected at 865.4 and 868.8 cm(-1) are assigned to ν(6)(HDCCC), and those observed at 904.0 and 909.8 cm(-1) are assigned to the out-of-plane bending vibration ν(8)(HDCCC). An accurate value of 79.8 +/- 0.2 kJ mol(-1) is recommended for the zero-point vibrational energy of H(2)CCC.
The vibrational spectrum and lattice dynamics of polycrystalline ammonium hydrosulfide. [Jupiter atmosphere implications

NASA Technical Reports Server (NTRS)

Bragin, J.; Diem, M.; Guthals, D.; Chang, S.

1977-01-01

The infrared spectra of alkali metal and ammonium hydrosulfides have been recorded from wavenumbers of 200 to 4000 at liquid nitrogen temperatures, and the Raman spectra of these substances have been recorded from wavenumbers of 0 to 4000 over the temperature range 83-390 K. No evidence of a second solid phase was obtained. Internal and external fundamentals were assigned, in detail, based on selection rules, isotopic frequency shifts, and analogy with structurally similar salts. Barriers to anion and cation reorientation of 3.8 and 1.9 kcal/mole, respectively, have been calculated from librational assignments. The implications of the infrared spectrum of ammonium hydrosulfide for the possible spectroscopic detection of this substance in the atmosphere of the planet Jupiter are discussed.
Neutron scattering, solid state NMR and quantum chemistry studies of 11-keto-progesterone

NASA Astrophysics Data System (ADS)

Szyczewski, A.; Hołderna-Natkaniec, K.; Natkaniec, I.

2004-07-01

The molecule geometry, frequency and intensity of the IINS and IR vibrational bands of 11-ketoprogesterone have been obtained by the HF, PM3 and density functional theory (DFT) with the B3LYP functionals and 6-31G(d,p) basis set. The optimised bond lengths and bond angles of the steroid skeleton are in good agreement with the X-ray data. The IR and IINS spectra of ketoprogesterone, computed at the DFT level, well reproduce the vibrational wavenumbers and intensities to an accuracy allowing reliable vibrational assignments. The molecular dynamic study by 1H NMR has confirmed the sequence of onset of reorientations of subsequent methyl groups indicated by the results of quantum chemistry calculations and INS spectra.
On the molecular structure, vibrational spectra, HOMO-LUMO, molecular electrostatic potential, UV-Vis, first order hyperpolarizability, and thermodynamic investigations of 3-(4-chlorophenyl)-1-(1yridine-3-yl) prop-2-en-1-one by quantum chemistry calculations

NASA Astrophysics Data System (ADS)

Rahmani, Rachida; Boukabcha, Nourdine; Chouaih, Abdelkader; Hamzaoui, Fodil; Goumri-Said, Souraya

2018-03-01

A recent experimental study has allowed synthesis of a new organic nonlinear optical material 3-(4-chlorophenyl)-1-(pyridin-3-yl)prop-2-en-1-one(CPP) with a high second harmonic generation efficiency. We apply density functional theory (DFT, GGA and B3LYP) and Hartree-Fock (HF) methods to calculate the vibrational wavenumbers. They are assigned with by using the potential energy distribution method. The calculated first hyperpolarizability of the title compound is comparable with the reported values of similar derivatives and 25 times that of the standard NLO material urea. The HOMO-LUMO calculations lead to consider GGA-PBE as the best functional to determine the electronic band gap of CPP molecule. We complete this study with assignment of the vibrational modes and perform a comparison with the experimental results. The analysis of MEP map shows that the most reactive site of the CPP molecule is the site containing the oxygen atom. Furthermore, because of the enhancement of molecular vibration within the CPP molecule, the thermodynamic parameters are increasing with the increase of temperature. The FTIR, Raman and NMR spectra are calculated using DFT approach and corroborate the experimental available data.
Vibrational study and Natural Bond Orbital analysis of serotonin in monomer and dimer states by density functional theory

NASA Astrophysics Data System (ADS)

Borah, Mukunda Madhab; Devi, Th. Gomti

2018-06-01

The vibrational spectral analysis of Serotonin and its dimer were carried out using the Fourier Transform Infrared (FTIR) and Raman techniques. The equilibrium geometrical parameters, harmonic vibrational wavenumbers, Frontier orbitals, Mulliken atomic charges, Natural Bond orbitals, first order hyperpolarizability and some optimized energy parameters were computed by density functional theory with 6-31G(d,p) basis set. The detailed analysis of the vibrational spectra have been carried out by computing Potential Energy Distribution (PED, %) with the help of Vibrational Energy Distribution Analysis (VEDA) program. The second order delocalization energies E(2) confirms the occurrence of intramolecular Charge Transfer (ICT) within the molecule. The computed wavenumbers of Serotonin monomer and dimer were found in good agreement with the experimental Raman and IR values.
Molecular structure, vibrational spectra, AIM, HOMO-LUMO, NBO, UV, first order hyperpolarizability, analysis of 3-thiophenecarboxylic acid monomer and dimer by Hartree-Fock and density functional theory

NASA Astrophysics Data System (ADS)

Issaoui, Noureddine; Ghalla, Houcine; Muthu, S.; Flakus, H. T.; Oujia, Brahim

2015-02-01

In this work, the molecular structure, harmonic vibrational frequencies, UV, NBO and AIM of 3-thiophenecarboxilic acid (abbreviated as 3-TCA) monomer and dimer has been investigated. The FT-IR and FT-Raman spectra were recorded. The ground-state molecular geometry and vibrational frequencies have been calculated by using the Hartree-Fock (HF) and density functional theory (DFT)/B3LYP methods and 6-311++G(d,p) as a basis set. The fundamental vibrations were assigned on the basis of the total energy distribution (TED) of the vibrational modes, calculated with VEDA program. Comparison of the observed fundamental vibrational frequencies of 3-TCA with calculated results by HF and DFT methods indicates that B3LYP is better to HF method for molecular vibrational problems. The difference between the observed and scaled wavenumber values is very small. The theoretically predicted FT-IR and FT-Raman spectra of the title compound have been constructed. A study on the Mulliken atomic charges, the electronic properties were performed by time-dependent DFT (TD-DFT) approach, frontier molecular orbitals (HOMO-LUMO), molecular electrostatic potential (MEP) and thermodynamic properties have been performed. The electric dipole moment (μ) and the first hyperpolarizability (β) values of the investigated molecule have been also computed.
Molecular structure, vibrational spectra, AIM, HOMO-LUMO, NBO, UV, first order hyperpolarizability, analysis of 3-thiophenecarboxylic acid monomer and dimer by Hartree-Fock and density functional theory.

PubMed

Issaoui, Noureddine; Ghalla, Houcine; Muthu, S; Flakus, H T; Oujia, Brahim

2015-02-05

In this work, the molecular structure, harmonic vibrational frequencies, UV, NBO and AIM of 3-thiophenecarboxilic acid (abbreviated as 3-TCA) monomer and dimer has been investigated. The FT-IR and FT-Raman spectra were recorded. The ground-state molecular geometry and vibrational frequencies have been calculated by using the Hartree-Fock (HF) and density functional theory (DFT)/B3LYP methods and 6-311++G(d,p) as a basis set. The fundamental vibrations were assigned on the basis of the total energy distribution (TED) of the vibrational modes, calculated with VEDA program. Comparison of the observed fundamental vibrational frequencies of 3-TCA with calculated results by HF and DFT methods indicates that B3LYP is better to HF method for molecular vibrational problems. The difference between the observed and scaled wavenumber values is very small. The theoretically predicted FT-IR and FT-Raman spectra of the title compound have been constructed. A study on the Mulliken atomic charges, the electronic properties were performed by time-dependent DFT (TD-DFT) approach, frontier molecular orbitals (HOMO-LUMO), molecular electrostatic potential (MEP) and thermodynamic properties have been performed. The electric dipole moment (μ) and the first hyperpolarizability (β) values of the investigated molecule have been also computed. Copyright © 2014 Elsevier B.V. All rights reserved.
Spectroscopic and quantum chemical studies on bromopyrazone.

PubMed

Gökce, Halil; Bahçeli, Semiha

2014-12-10

In this study, the FT-IR, micro-Raman and UV-vis. spectra of bromopyrazone molecule, C10H8BrN3O, (with synonym,1-phenyl-4-amino-5-bromopyridazon-(6) or 5-amino-4-bromo-2-phenyl-3(2H)-pyridazinone) were recorded experimentally. The molecular structure, vibrational wavenumbers, electronic transition absorption wavelengths in ethanol solvent, HOMOs and LUMOs analyses, molecular electrostatic potential (MEP), natural bond orbitals (NBO), nonlinear optical (NLO) properties and atomic charges of bromopyrazone molecule have been calculated by using DFT/B3LYP method with 6-311++G(d,p) basis set in ground state. The obtained results show that the calculated vibrational frequencies and UV-vis. values are in a good agreement with experimental data. Copyright © 2014 Elsevier B.V. All rights reserved.
Vibrational and structural study of onopordopicrin based on the FTIR spectrum and DFT calculations.

PubMed

Chain, Fernando E; Romano, Elida; Leyton, Patricio; Paipa, Carolina; Catalán, César A N; Fortuna, Mario; Brandán, Silvia Antonia

2015-01-01

In the present work, the structural and vibrational properties of the sesquiterpene lactone onopordopicrin (OP) were studied by using infrared spectroscopy and density functional theory (DFT) calculations together with the 6-31G(∗) basis set. The harmonic vibrational wavenumbers for the optimized geometry were calculated at the same level of theory. The complete assignment of the observed bands in the infrared spectrum was performed by combining the DFT calculations with Pulay's scaled quantum mechanical force field (SQMFF) methodology. The comparison between the theoretical and experimental infrared spectrum demonstrated good agreement. Then, the results were used to predict the Raman spectrum. Additionally, the structural properties of OP, such as atomic charges, bond orders, molecular electrostatic potentials, characteristics of electronic delocalization and topological properties of the electronic charge density were evaluated by natural bond orbital (NBO), atoms in molecules (AIM) and frontier orbitals studies. The calculated energy band gap and the chemical potential (μ), electronegativity (χ), global hardness (η), global softness (S) and global electrophilicity index (ω) descriptors predicted for OP low reactivity, higher stability and lower electrophilicity index as compared with the sesquiterpene lactone cnicin containing similar rings. Copyright © 2015 Elsevier B.V. All rights reserved.
Synthesis and spectroscopical study of rhodanine derivative using DFT approaches

NASA Astrophysics Data System (ADS)

Anbarasan, R.; Dhandapani, A.; Manivarman, S.; Subashchandrabose, S.; Saleem, H.

2015-07-01

The optimized molecular structure, vibrational frequencies, corresponding vibrational assignments of (E)-5-benzylidene-2-thioxothiazolidine-4-one (E5BTTO) have been investigated experimentally and theoretically based on Density Functional Theory (DFT) approach. The FT-Raman and FT-IR spectra of E5BTTO were recorded in solid phase. Theoretical calculations were performed at the DFT level using the Gaussian 03 program. The experimental bands were assigned and characterized on the basis of the scaled theoretical wavenumber by their Total Energy Distribution (TED). The results of the calculation were applied to simulate infrared and raman spectra of the title compound which showed good agreement with the observed spectra. The calculated HOMO and LUMO energies show that charge transfer occur within the molecule. Stability arising from hyperconjugative interactions leading to its NLO activity and charge delocalization were analyzed using Natural Bond Orbital (NBO) analysis.

Structural and vibrational analyses of new potential anticancer drug 2-(phenylmethyl)-2-azaspiro[5.11]heptadecane-1,3,7-trione

NASA Astrophysics Data System (ADS)

Vitnik, Željko J.; Popović-Đorđević, Jelena B.; Vitnik, Vesna D.

2017-06-01

The establishment of the most stable structures of 2-(phenylmethyl)-2-azaspiro[5.11]heptadecane-1,3,7-trione, potential anticancer and antimicrobial drug has been investigated in this work. A detailed interpretation of experimental and calculated IR, UV and NMR spectra were reported. The equilibrium geometry, harmonic vibrational frequencies and electronic properties have been investigated with Density Functional Theory using B3LYP/6-311++G(d,p) method. The scaled theoretical wavenumber showed very good agreement with the experimental values. The charge transfer in the molecule was confirmed with NBO analysis. Ultraviolet-visible spectrum was calculated using TD-DFT method and compared with experimental spectrum. The calculated energy and oscillator strength well reproduce the experimental data. The molecular electrostatic potential surface map portrays potential binding sites of the title molecule.
Spectral analysis, vibrational assignments, NBO analysis, NMR, UV-Vis, hyperpolarizability analysis of 2-aminofluorene by density functional theory.

PubMed

Jone Pradeepa, S; Sundaraganesan, N

2014-05-05

In this present investigation, the collective experimental and theoretical study on molecular structure, vibrational analysis and NBO analysis has been reported for 2-aminofluorene. FT-IR spectrum was recorded in the range 4000-400 cm(-1). FT-Raman spectrum was recorded in the range 4000-50 cm(-1). The molecular geometry, vibrational spectra, and natural bond orbital analysis (NBO) were calculated for 2-aminofluorene using Density Functional Theory (DFT) based on B3LYP/6-31G(d,p) model chemistry. (13)C and (1)H NMR chemical shifts of 2-aminofluorene were calculated using GIAO method. The computed vibrational and NMR spectra were compared with the experimental results. The total energy distribution (TED) was derived to deepen the understanding of different modes of vibrations contributed by respective wavenumber. The experimental UV-Vis spectra was recorded in the region of 400-200 nm and correlated with simulated spectra by suitably solvated B3LYP/6-31G(d,p) model. The HOMO-LUMO energies were measured with time dependent DFT approach. The nonlinearity of the title compound was confirmed by hyperpolarizabilty examination. Using theoretical calculation Molecular Electrostatic Potential (MEP) was investigated. Copyright © 2014 Elsevier B.V. All rights reserved.
Structural characterization, solvent effects on nuclear magnetic shielding tensors, experimental and theoretical DFT studies on the vibrational and NMR spectra of 3-(acrylamido)phenylboronic acid

NASA Astrophysics Data System (ADS)

Alver, Özgür; Kaya, Mehmet Fatih; Dikmen, Gökhan

2015-12-01

Structural elucidation of 3-(acrylamido)phenylboronic acid (C9H10BNO3) was carried out with 1H, 13C and HETCOR NMR techniques. Solvent effects on nuclear magnetic shielding tensors were examined with deuterated dimethyl sulfoxide, acetone, methanol and water solvents. The correct order of appearance of carbon and hydrogen atoms on NMR scale from highest magnetic field region to the lowest one were investigated using different types of theoretical levels and the details of the levels were presented in this study. Stable structural conformers and vibrational band analysis of the title molecule (C9H10BNO3) were studied both experimental and theoretical viewpoints using FT-IR, Raman spectroscopic methods and density functional theory (DFT). FT-IR and Raman spectra were obtained in the region of 4000-400 cm-1, and 3700-10 cm-1, respectively. Becke-3-Lee-Yang-Parr (B3LYP) hybrid density functional theory method with 6-31++G(d, p) basis set was included in the search for optimized structures and vibrational wavenumbers. Experimental and theoretical results show that after application of a suitable scaling factor density functional B3LYP method resulted in acceptable results for predicting vibrational wavenumbers except OH and NH stretching modes which is most likely arising from increasing unharmonicity in the high wave number region and possible intra and inter molecular interaction at OH edges those of which are not fully taken into consideration in theoretical processes. To make a more quantitative vibrational assignments, potential energy distribution (PED) values were calculated using VEDA 4 (Vibrational Energy Distribution Analysis) program.
Computational investigation of CO adsorbed on Aux, Agx and (AuAg)x nanoclusters (x = 1 - 5, 147) and monometallic Au and Ag low-energy surfaces*

NASA Astrophysics Data System (ADS)

Gould, Anna L.; Catlow, C. Richard A.; Logsdail, Andrew J.

2018-02-01

Density functional theory calculations have been performed to investigate the use of CO as a probe molecule for the determination of the structure and composition of Au, Ag and AuAg nanoparticles. For very small nanoclusters (x = 1 - 5), the CO vibrational frequencies can be directly correlated to CO adsorption strength, whereas larger 147-atom nanoparticles show a strong energetic preference for CO adsorption at a vertex position but the highest wavenumbers are for the bridge positions. We also studied CO adsorption on Au and Ag (100) and (111) surfaces, for a 1 monolayer coverage, which proves to be energetically favourable on atop only and bridge positions for Au (100) and atop for Ag (100); vibrational frequencies of the CO molecules red-shift to lower wavenumbers as a result of increased metal coordination. We conclude that CO vibrational frequencies cannot be solely relied upon in order to obtain accurate compositional analysis, but we do propose that elemental rearrangement in the core@shell nanoclusters, from Ag@Au (or Au@Ag) to an alloy, would result in a shift in the CO vibrational frequencies that indicate changes in the surface composition. Contribution to the Topical Issue "Shaping Nanocatalysts", edited by Francesca Baletto, Roy L. Johnston, Jochen Blumberger and Alex Shluger.Supplementary material in the form of one pdf file available from the Journal web page at http://https://doi.org/10.1140/epjb/e2017-80280-7
Synthesis, spectroscopic characterization and quantum chemical computational studies of (S)-N-benzyl-1-phenyl-5-(pyridin-2-yl)-pent-4-yn-2-amine

NASA Astrophysics Data System (ADS)

Kose, Etem; Atac, Ahmet; Karabacak, Mehmet; Karaca, Caglar; Eskici, Mustafa; Karanfil, Abdullah

2012-11-01

The synthesis and characterization of a novel compound (S)-N-benzyl-1-phenyl-5-(pyridin-2-yl)-pent-4-yn-2-amine (abbreviated as BPPPYA) was presented in this study. The spectroscopic properties of the compound were investigated by FT-IR, NMR and UV spectroscopy experimentally and theoretically. The molecular geometry and vibrational frequencies of the BPPPYA in the ground state were calculated by using density functional theory (DFT) B3LYP method invoking 6-311++G(d,p) basis set. The geometry of the BPPPYA was fully optimized, vibrational spectra were calculated and fundamental vibrations were assigned on the basis of the total energy distribution (TED) of the vibrational modes, calculated with scaled quantum mechanics (SQM) method and PQS program. The results of the energy and oscillator strength calculated by time-dependent density functional theory (TD-DFT) and CIS approach complement with the experimental findings. Total and partial density of state (TDOS and PDOS) and also overlap population density of state (COOP or OPDOS) diagrams analysis were presented. The theoretical NMR chemical shifts (1H and 13C) complement with experimentally measured ones. The dipole moment, linear polarizability and first hyperpolarizability values were also computed. The linear polarizabilities and first hyper polarizabilities of the studied molecule indicate that the compound is a good candidate of nonlinear optical materials. The calculated vibrational wavenumbers, absorption wavelengths and chemical shifts showed the best agreement with the experimental results.
A complete vibrational study on a potential environmental toxicant agent, the 3,3',4,4'-tetrachloroazobenzene combining the FTIR, FTRaman, UV-Visible and NMR spectroscopies with DFT calculations.

PubMed

Castillo, María V; Pergomet, Jorgelina L; Carnavale, Gustavo A; Davies, Lilian; Zinczuk, Juan; Brandán, Silvia A

2015-01-05

In this study 3,3',4,4'-tetrachloroazobenzene (TCAB) was prepared and then characterized by infrared, Raman, multidimensional nuclear magnetic resonance (NMR) and ultraviolet-visible spectroscopies. The density functional theory (DFT) together with the 6-31G(*) and 6-311++G(**) basis sets were used to study the structures and vibrational properties of the two cis and trans isomers of TCAB. The harmonic vibrational wavenumbers for the optimized geometries were calculated at the same theory levels. A complete assignment of all the observed bands in the vibrational spectra of TCAB was performed combining the DFT calculations with the scaled quantum mechanical force field (SQMFF) methodology. The molecular electrostatic potentials, atomic charges, bond orders and frontier orbitals for the two isomers of TCAB were compared and analyzed. The comparison of the theoretical ultraviolet-visible spectrum with the corresponding experimental demonstrates a good concordance while the calculated (1)H and (13)C chemicals shifts are in good conformity with the corresponding experimental NMR spectra of TCAB in solution. The npp(*) transitions for both forms were studied by natural bond orbital (NBO) while the topological properties were calculated by employing Bader's Atoms in the Molecules (AIM) theory. This study shows that the cis and trans isomers exhibit different structural and vibrational properties and absorption bands. Copyright © 2014. Published by Elsevier B.V.
DFT, FT-IR, FT-Raman and vibrational studies of 3-methoxyphenyl boronic acid

NASA Astrophysics Data System (ADS)

Patil, N. R.; Hiremath, Sudhir M.; Hiremath, C. S.

2018-05-01

The aim of this work is to study the possible stable, geometrical molecular structure, experimental and theoretical FT-IR and FT-Raman spectroscopic methods of 3-Methoxyphenyl boronic acid (3MPBA). FT-IR and FT-Raman spectra were recorded in the region of 4000-400 cm-1 and 40000-50 cm-1 respectively. The optimized geometric structure and vibrational wavenumbers of the title compound were searched by B3LYP hybrid density functional theory method with 6-311++G (d, p) basis set. The Selectedexperimentalbandswereassignedandcharacterizedonthebasisofthescaledtheoreticalwavenumbersby their potential energy distribution (PED) of the vibrational modes obtained from VEDA 4 program. Finally, the predicted calculation results were applied to simulated FT-IR and FT-Raman spectra of the title compound, which show agreement with the observed spectra. Whereas, it is observed that, the theoretical frequencies are more than the experimental one for O-H stretching vibration modes of the title molecule.
Study of the solvent effects on the molecular structure and Cdbnd O stretching vibrations of flurbiprofen

NASA Astrophysics Data System (ADS)

Tekin, Nalan; Pir, Hacer; Sagdinc, Seda

2012-12-01

The effects of 15 solvents on the C=O stretching vibrational frequency of flurbiprofen (FBF) were determined to investigate solvent-solute interactions. Solvent effects on the geometry and C=O stretching vibrational frequency, ν(C=O), of FBF were studied theoretically at the DFT/B3LYP and HF level in combination with the polarizable continuum model and experimentally using attenuated total reflection infrared spectroscopy (ATR-IR). The calculated C=O stretching frequencies in the liquid phase are in agreement with experimental values. Moreover, the wavenumbers of ν(C=O) of FBF in different solvents have been obtained and correlated with the Kirkwood-Bauer-Magat equation (KBM), the solvent acceptor numbers (ANs), and the linear solvation energy relationships (LSERs). The solvent-induced stretching vibrational frequency shifts displayed a better correlation with the LSERs than with the ANs and KBM.
Molecular conformational analysis, vibrational spectra, NBO analysis and first hyperpolarizability of (2E)-3-(3-chlorophenyl)prop-2-enoic anhydride based on density functional theory calculations.

PubMed

Mary, Y Sheena; Raju, K; Panicker, C Yohannan; Al-Saadi, Abdulaziz A; Thiemann, Thies

2014-10-15

The conformational behavior and structural stability of (2E)-3-(3-chlorophenyl)prop-2-enoic anhydride were investigated by using density functional theory. The optimized molecular structure, vibrational wavenumbers, corresponding vibrational assignments of (2E)-3-(3-chlorophenyl)prop-2-enoic anhydride have been investigated experimentally and theoretically. The HOMO and LUMO analysis are used to determine the charge transfer within the molecule. The stability of the molecule arising from hyperconjugative interaction and charge delocalization has been analyzed using NBO analysis. The calculated first hyperpolarizability of the title compound is 15.8×10(-30)esu, and is 121.54 times that of the standard NLO material urea and the title compound is an attractive object for future studies of nonlinear optical properties. MEP was performed by the DFT method and the predicted infrared intensities and Raman activities have also been reported. Copyright © 2014 Elsevier B.V. All rights reserved.
Theoretical and vibrational spectroscopic approach to keto-enol tautomerism in methyl-2-(4-methoxybenzoyl)-3-(4-methoxyphenyl)-3-oxopropanoylcarbamate

NASA Astrophysics Data System (ADS)

Arı, Hatice; Özpozan, Talat; Büyükmumcu, Zeki; Kabacalı, Yiğit; Saçmaci, Mustafa

2016-10-01

A carbamate compound having tricarbonyl groups, methyl-2-(4-methoxybenzoyl)-3-(4-methoxyphenyl)-3-oxopropanoylcarbamate (BPOC) was investigated from theoretical and vibrational spectroscopic point of view employing quantum chemical methods. Hybrid Density Functionals (B3LYP, X3LYP and B3PW91) with 6-311 G(d,p) basis set were used for the calculations. Rotational barrier and conformational analyses were performed to find the most stable conformers of keto and enol forms of the molecule. Three transition states for keto-enol tautomerism in gas phase were determined. The results of the calculations show that enol-1 form of BPOC is more stable than keto and enol-2 forms. Hydrogen bonding investigation including Natural bond orbital analysis (NBO) for all the tautomeric structures was employed to compare intra-molecular interactions. The energies of HOMO and LUMO molecular orbitals for all tautomeric forms of BPOC were predicted. Normal Coordinate Analysis (NCA) was carried out for the enol-1 to assign vibrational bands of IR and Raman spectra. The scaling factors were calculated as 0.9721, 0.9697 and 0.9685 for B3LYP, X3LYP and B3PW91 methods, respectively. The correlation graphs of experimental versus calculated vibrational wavenumbers were plotted and X3LYP method gave better frequency agreement than the others.
Characterization of Meldrum's acid derivative 5-(5-Ethyl-1,3,4-thiadiazol-2-ylamino)methylene-2,2-dimethyl-1,3-dioxane-4,6-dione by Raman and FT-IR spectroscopy and DFT calculations

NASA Astrophysics Data System (ADS)

de Toledo, T. A.; da Silva, L. E.; Teixeira, A. M. R.; Freire, P. T. C.; Pizani, P. S.

2015-07-01

In this study, the structural and vibrational properties of Meldrum's acid derivative 5-(5-Ethyl-1,3,4-thiadiazol-2-ylamino)methylene-2,2-dimethyl-1,3-dioxane-4,6-dione, C11H13N3O4S were studied combining experimental techniques such as Raman and FT-IR spectroscopy and density functional theory (DFT) calculations. The Raman and FT-IR spectra were recorded at room conditions in the regions from 80 to 3400 cm-1 and 400 to 4000 cm-1, respectively. Vibrational wavenumbers were predicted using DFT calculations with the hybrid functional B3LYP and basis set 6-31G(d,p). A comparison between experimental and theoretical data is provided for the Raman and FT-IR spectra. The descriptions of the normal modes were carried by means of potential energy distribution (PED).
Infrared spectra and other properties predictions of 5-amino-3-methyl-4-isoxazolecarbohydrazide with electric field simulation using CPC model

NASA Astrophysics Data System (ADS)

Regiec, Andrzej; Wojciechowski, Piotr; Pietraszko, Adam; Mączyński, Marcin

2018-06-01

Here, the Conductor-like Polarizable Continuum Model (CPCM) was used as a less demanding substitute of Periodic Boundary Conditions (PBC) method to attempt to reliably simulate infrared spectra and some structural parameters of solid compound - 5-amino-3-methyl-4-isoxazolecarbohydrazide (HIX). The measured relative electric permittivity of HIX was used as a simplified equivalent of electric intensity generating by other molecules of 5-amino-3-methyl-4-isoxazolecarbohydrazide in crystal structure. The application of CPCM has resulted in better conformity of calculated molecular parameters with experimentally found. Theoretical geometry was compared with data obtained with X-ray crystallography. Comparison of harmonic approximation with anharmonic one, based on the six selected characteristic vibrations, shows that non-scaled harmonic wavenumbers, calculated with CPCM, well correspond to experimental spectra. Additionally, the results point out that anharmonic approximation appeared to be strong sensitive for input geometry and calculation parameters used, so the results are sometimes unreliable, especially for low wavenumbers. Also, the new feasible ways of the synthesis of the titled compound is presented, one of which is particularly easy and highly efficient.
Synthesis, X-ray crystallography characterization, vibrational spectroscopic, molecular electrostatic potential maps, thermodynamic properties studies of N,N'-di(p-thiazole)formamidine.

PubMed

Rofouei, M K; Fereyduni, E; Sohrabi, N; Shamsipur, M; Attar Gharamaleki, J; Sundaraganesan, N

2011-01-01

In this work, we will report a combined experimental and theoretical study on molecular and vibrational structure of N,N'-di(p-thiazole)formamidine (DpTF). DpTF has been synthesized and characterized by elemental analysis, FT-IR, FT-Raman, 1H NMR, 13C NMR spectroscopy and X-ray single crystal diffraction. The FT-IR and FT-Raman spectra of DpTF were recorded in the solid phase. The optimized geometry was calculated by HF and B3LYP methods using 6-31G(d) basis set. The FT-IR and FT-Raman spectra of DpTF was calculated at the HF/B3LYP/6-31G(d) level and were interpreted in terms of potential energy distribution (PED) analysis. The scaled theoretical wavenumber showed very good agreement with the experimental values. A detailed interpretation of the infrared and Raman spectra of DpTF was reported. On the basis of vibrational analyses, the thermodynamic properties of the title compound at different temperatures have been calculated, revealing the correlations between Cp,m°, Sm°, Hm° and temperatures. Furthermore, molecular electrostatic potential maps (MESP) and total dipole moment properties of the compound have been calculated. Copyright © 2010 Elsevier B.V. All rights reserved.
Spectroscopic characteristic (FT-IR, FT-Raman, UV, 1H and 13C NMR), theoretical calculations and biological activity of alkali metal homovanillates

NASA Astrophysics Data System (ADS)

Samsonowicz, M.; Kowczyk-Sadowy, M.; Piekut, J.; Regulska, E.; Lewandowski, W.

2016-04-01

The structural and vibrational properties of lithium, sodium, potassium, rubidium and cesium homovanillates were investigated in this paper. Supplementary molecular spectroscopic methods such as: FT-IR, FT-Raman in the solid phase, UV and NMR were applied. The geometrical parameters and energies were obtained from density functional theory (DFT) B3LYP method with 6-311++G** basis set calculations. The geometry of the molecule was fully optimized, vibrational spectra were calculated and fundamental vibrations were assigned. Geometric and magnetic aromaticity indices, atomic charges, dipole moments, HOMO and LUMO energies were also calculated. The microbial activity of investigated compounds was tested against Bacillus subtilis (BS), Pseudomonas aeruginosa (PA), Escherichia coli (EC), Staphylococcus aureus (SA) and Candida albicans (CA). The relationship between the molecular structure of tested compounds and their antimicrobial activity was studied. The principal component analysis (PCA) was applied in order to attempt to distinguish the biological activities of these compounds according to selected band wavenumbers. Obtained data show that the FT-IR spectra can be a rapid and reliable analytical tool and a good source of information for the quantitative analysis of the relationship between the molecular structure of the compound and its biological activity.
Binding effects of Mn²⁺ and Zn²⁺ ions on the vibrational properties of guanine-cytosine base pairs in the Watson-Crick and Hoogsteen configurations.

PubMed

Morari, Cristian; Bogdan, Diana; Muntean, Cristina M

2012-11-01

The binding effects of Mn²⁺ and Zn²⁺ ions on the vibrational properties of guanine-cytosine base pairs have been performed using density functional theory investigations. The calculations were carried out on Watson-Crick and Hoogsteen configurations of the base pairs. We have found, that in Watson-Crick configuration, the metal is coordinated to N7 atom of guanine while, in the case of Hoogsteen configuration, the coordination is at N3 atom of guanine. We have pointed out the vibrational bands that can be used to detect the presence of metallic ions in the Watson-Crick and Hoogsteen structures. Our results show that the vibrational amplitudes of metallic atoms are strong for wavenumbers lower than 600 cm⁻¹. Also, we predict that the distinction between Watson-Crick and Hoogsteen configurations can be seen around 85, 170 and 310 cm⁻¹.
Temperature effect on the vibrational dynamics of cyclodextrin inclusion complexes: investigation by FTIR-ATR spectroscopy and numerical simulation.

PubMed

Crupi, Vincenza; Majolino, Domenico; Venuti, Valentina; Guella, Graziano; Mancini, Ines; Rossi, Barbara; Verrocchio, Paolo; Viliani, Gabriele; Stancanelli, Rosanna

2010-07-01

The vibrational dynamics of solid inclusion complexes of the nonsteroidal anti-inflammatory drug Ibuprofen (IBP) with beta-cyclodextrin (beta-CD) and methyl-beta-cyclodextrin (Me-beta-CD) has been investigated by using attenuated total reflection-Fourier transform infrared FTIR-ATR spectroscopy, in order to monitor the changes induced, as a consequence of complexation, on the vibrational spectrum of IBP, in the wavenumber range 600-4000 cm(-1). Quantum chemical calculations were performed on monomeric and dimeric structures of IBP, derived from symmetric hydrogen bonding of the two carboxylic groups, in order to unambiguously assign some characteristic IR bands in the IBP spectrum. The evolution in temperature from 250 to 340 K of the C horizontal lineO stretching vibration, described by a best-fit procedure, allowed us to extract the thermodynamic parameter DeltaH associated to the binding of IBP with betaCDs in the solid phase. By comparing these results, Me-beta-CD has been shown to be the most effective carrier for IBP.
Largely reduced grid densities in a vibrational self-consistent field treatment do not significantly impact the resultingwavenumbers.

PubMed

Lutz, Oliver M D; Rode, Bernd M; Bonn, Günther K; Huck, Christian W

2014-12-17

Especially for larger molecules relevant to life sciences, vibrational self-consistent field (VSCF) calculations can become unmanageably demanding even when only first and second order potential coupling terms are considered. This paper investigates to what extent the grid density of the VSCF's underlying potential energy surface can be reduced without sacrificing accuracy of the resulting wavenumbers. Including single-mode and pair contributions, a reduction to eight points per mode did not introduce a significant deviation but improved the computational efficiency by a factor of four. A mean unsigned deviation of 1.3% from the experiment could be maintained for the fifteen molecules under investigation and the approach was found to be applicable to rigid, semi-rigid and soft vibrational problems likewise. Deprotonated phosphoserine, stabilized by two intramolecular hydrogen bonds, was investigated as an exemplary application.
Conformational analysis, spectroscopic study (FT-IR, FT-Raman, UV, 1H and 13C NMR), molecular orbital energy and NLO properties of 5-iodosalicylic acid

NASA Astrophysics Data System (ADS)

Karaca, Caglar; Atac, Ahmet; Karabacak, Mehmet

2015-02-01

In this study, 5-iodosalicylic acid (5-ISA, C7H5IO3) is structurally characterized by FT-IR, FT-Raman, NMR and UV spectroscopies. There are eight conformers, Cn, n = 1-8 for this molecule therefore the molecular geometry for these eight conformers in the ground state are calculated by using the ab-initio density functional theory (DFT) B3LYP method approach with the aug-cc-pVDZ-PP basis set for iodine and the aug-cc-pVDZ basis set for the other elements. The computational results identified that the most stable conformer of 5-ISA is the C1 form. The vibrational spectra are calculated DFT method invoking the same basis sets and fundamental vibrations are assigned on the basis of the total energy distribution (TED) of the vibrational modes, calculated with scaled quantum mechanics (SQM) method with PQS program. Total density of state (TDOS) and partial density of state (PDOS) and also overlap population density of state (COOP or OPDOS) diagrams analysis for C1 conformer were calculated using the same method. The energy and oscillator strength are calculated by time-dependent density functional theory (TD-DFT) results complement with the experimental findings. Besides, charge transfer occurring in the molecule between HOMO and LUMO energies, frontier energy gap, molecular electrostatic potential (MEP) are calculated and presented. The NMR chemical shifts (1H and 13C) spectra are recorded and calculated using the gauge independent atomic orbital (GIAO) method. Mulliken atomic charges of the title molecule are also calculated, interpreted and compared with salicylic acid. The optimized bond lengths, bond angles and calculated NMR and UV, vibrational wavenumbers showed the best agreement with the experimental results.
FT-IR and FT-Raman spectra, molecular structure and first-order molecular hyperpolarizabilities of a potential antihistaminic drug, cyproheptadine HCl

NASA Astrophysics Data System (ADS)

Sagdinc, Seda G.; Erdas, Dilek; Gunduz, Ilknur; Sahinturk, Ayse Erbay

2015-01-01

Cyproheptadine hydrochloride (CYP HCl) {4-(5H-dibenzo[a,d]-cyclohepten-5-ylidene)-1-methylpiperidine hydrochloride} is a first-generation antihistamine with additional anticholinergic, antiserotonergic, and local-anesthetic properties. The geometry optimization, Mulliken atomic charges and wavenumber and intensity of the vibrational bands of all of the possible modes of CYP HCl have been calculated using ab initio Hartree-Fock (HF) and density functional theory (DFT) employing the B3LYP functional with the 6-311G(d,p) basis set. We have compared the calculated IR and Raman wavenumbers with experimental data. Quantum-chemical calculations of the geometrical structure, energies, and molecular electrostatic potential and NBO analysis of CYP HCl have been performed using the B3LYP/6-311G(d,p) method. The electric dipole moment (μ), static polarizability (α) and the first hyperpolarizability (β) values of the title compound have been computed using HF and DFT methods. The study reveals that the antihistaminic pharmacological property of CYP HCl has a large β value and, hence, may in general have potential applications in the development of non-linear optical materials. The experimental and calculated results for CYP HCl have also been compared with those for mianserin HCl.
Experimental (FT-IR, FT-Raman, 1H, 13C NMR) and theoretical study of alkali metal 2-aminobenzoates

NASA Astrophysics Data System (ADS)

Samsonowicz, M.; Świsłocka, R.; Regulska, E.; Lewandowski, W.

2008-09-01

The influence of lithium, sodium, potassium, rubidium and cesium on the electronic system of the 2-aminobenzoic acid was studied by the methods of molecular spectroscopy. The vibrational (FT-IR, FT-Raman) and NMR ( 1H and 13C) spectra for 2-aminobenzoic acid and its alkali metal salts were recorded. The assignment of vibrational spectra was done on the basis of literature data, theoretical calculations and our previous experience. Characteristic shifts of bands and changes in intensities of bands along the metal series were observed. The changes of chemical shifts of protons ( 1H NMR) and carbons ( 13C NMR) in the series of studied alkali metal 2-aminobenzoates were observed too. Optimized geometrical structures of studied compounds were calculated by B3LYP method using 6-311++G ∗∗ basis set. Geometric aromaticity indices, dipole moments and energies were also calculated. The theoretical wavenumbers and intensities of IR and Raman spectra were obtained. The calculated parameters were compared to experimental characteristic of studied compounds.

Application of comparative vibrational spectroscopic and mechanistic studies in analysis of fisetin structure

NASA Astrophysics Data System (ADS)

Dimitrić Marković, Jasmina M.; Marković, Zoran S.; Milenković, Dejan; Jeremić, Svetlana

2011-12-01

This paper addresses experimental and theoretical research in fisetin (2-(3,4-dihydroxyphenyl)-3,7-dihydroxychromen-4-one) structure by means of experimental IR and Raman spectroscopies and mechanistic calculations. Density Functional Theory calculations, with M05-2X functional and the 6-311+G (2df, p) basis set implemented in the Gaussian 09 package, are performed with the aim to support molecular structure, vibrational bands' positions and their intensities. Potential energy distribution (PED) values and the description of the largest vibrational contributions to the normal modes are calculated. The most intense bands appear in the 1650-1500 cm -1 wavenumber region. This region involves a combination of the C dbnd O, C2 dbnd C3 and C-C stretching vibrational modes. Most of the bands in the 1500-1000 cm -1 range involve C-C stretching, O-C stretching and in-plane C-C-H, C-O-H, C-C-O and C-C-C bending vibrations of the rings. The region below 1000 cm -1 is characteristic to the combination of in plane C-C-C-H, H-C-C-H, C-C-C-C, C-C-O-C and out of plane O-C-C-C, C-C-O-C, C-C-C-C torsional modes. The Raman spectra of baicalein and quercetin were used for qualitative comparison with fisetin spectrum and verification of band assignments. The applied detailed vibrational spectral analysis and the assignments of the bands, proposed on the basis of fundamentals, reproduced the experimental results with high degree of accuracy.
Application of comparative vibrational spectroscopic and mechanistic studies in analysis of fisetin structure.

PubMed

Dimitrić Marković, Jasmina M; Marković, Zoran S; Milenković, Dejan; Jeremić, Svetlana

2011-12-01

This paper addresses experimental and theoretical research in fisetin (2-(3,4-dihydroxyphenyl)-3,7-dihydroxychromen-4-one) structure by means of experimental IR and Raman spectroscopies and mechanistic calculations. Density Functional Theory calculations, with M05-2X functional and the 6-311+G (2df, p) basis set implemented in the Gaussian 09 package, are performed with the aim to support molecular structure, vibrational bands' positions and their intensities. Potential energy distribution (PED) values and the description of the largest vibrational contributions to the normal modes are calculated. The most intense bands appear in the 1650-1500 cm(-1) wavenumber region. This region involves a combination of the CO, C2C3 and C-C stretching vibrational modes. Most of the bands in the 1500-1000 cm(-1) range involve C-C stretching, O-C stretching and in-plane C-C-H, C-O-H, C-C-O and C-C-C bending vibrations of the rings. The region below 1000 cm(-1) is characteristic to the combination of in plane C-C-C-H, H-C-C-H, C-C-C-C, C-C-O-C and out of plane O-C-C-C, C-C-O-C, C-C-C-C torsional modes. The Raman spectra of baicalein and quercetin were used for qualitative comparison with fisetin spectrum and verification of band assignments. The applied detailed vibrational spectral analysis and the assignments of the bands, proposed on the basis of fundamentals, reproduced the experimental results with high degree of accuracy. Copyright © 2011 Elsevier B.V. All rights reserved.
A study of vibrational spectra and investigations of charge transfer and chemical bonding features of 2-chloro benzimidazole based on DFT computations

NASA Astrophysics Data System (ADS)

Muthunatesan, S.; Ragavendran, V.

2015-01-01

Benzimidazoles are bicyclic heteroatomic molecules. Polycyclic heteroatomic molecules have extensive coupling of different modes leading to strong coupling of force constants associated with the various chemical bonds of the molecules. To carry out a detailed vibrational spectroscopic analysis of such a bicyclic heteroatomic molecule, FT-IR and FT-Raman spectra of 2-chloro benzimidazole (CBZ) have been recorded in the condensed phase. Density Functional Theory calculations in the B3LYP/6-31G* level have been carried out to determine the optimized geometry and vibrational frequencies. In order to obtain a close agreement between theoretical and observed frequencies and hence to perform a reliable assignment, the theoretical DFT force field was transformed from Cartesian to local symmetry co-ordinates and then scaled empirically using SQM methodology. The SQM treatment resulted in a RMS deviation of 9.4 cm-1. For visual comparison, the observed and calculated spectra are presented on a common wavenumber scale. From the NBO analysis, the electron density (ED) charge transfers in the σ* and π* antibonding orbitals and second order delocalization energies E(2) confirms the occurrence of intramolecular charge transfer (ICT) within the molecule. The calculated Homo and Lumo energies show that charge transfer occurs within the molecule. The results obtained from the vibrational, NBO and HOMO-LUMO analyses have been properly tabulated.
Molecular structure, spectroscopic studies and first-order molecular hyperpolarizabilities of ferulic acid by density functional study

NASA Astrophysics Data System (ADS)

Sebastian, S.; Sundaraganesan, N.; Manoharan, S.

2009-10-01

Quantum chemical calculations of energies, geometrical structure and vibrational wavenumbers of ferulic acid (FA) (4-hydroxy-3-methoxycinnamic acid) were carried out by using density functional (DFT/B3LYP/BLYP) method with 6-31G(d,p) as basis set. The optimized geometrical parameters obtained by DFT calculations are in good agreement with single crystal XRD data. The vibrational spectral data obtained from solid phase FT-IR and FT-Raman spectra are assigned based on the results of the theoretical calculations. The observed spectra are found to be in good agreement with calculated values. The electric dipole moment ( μ) and the first hyperpolarizability ( β) values of the investigated molecule have been computed using ab initio quantum mechanical calculations. The calculation results also show that the FA molecule might have microscopic nonlinear optical (NLO) behavior with non-zero values. A detailed interpretation of the infrared and Raman spectra of FA was also reported. The energy and oscillator strength calculated by time-dependent density functional theory (TD-DFT) results complements with the experimental findings. The calculated HOMO and LUMO energies shows that charge transfer occur within the molecule. The theoretical FT-IR and FT-Raman spectra for the title molecule have been constructed.
Fourth-Order Vibrational Transition State Theory and Chemical Kinetics

NASA Astrophysics Data System (ADS)

Stanton, John F.; Matthews, Devin A.; Gong, Justin Z.

2015-06-01

Second-order vibrational perturbation theory (VPT2) is an enormously successful and well-established theory for treating anharmonic effects on the vibrational levels of semi-rigid molecules. Partially as a consequence of the fact that the theory is exact for the Morse potential (which provides an appropriate qualitative model for stretching anharmonicity), VPT2 calculations for such systems with appropriate ab initio potential functions tend to give fundamental and overtone levels that fall within a handful of wavenumbers of experimentally measured positions. As a consequence, the next non-vanishing level of perturbation theory -- VPT4 -- offers only slight improvements over VPT2 and is not practical for most calculations since it requires information about force constants up through sextic. However, VPT4 (as well as VPT2) can be used for other applications such as the next vibrational correction to rotational constants (the ``gammas'') and other spectroscopic parameters. In addition, the marriage of VPT with the semi-classical transition state theory of Miller (SCTST) has recently proven to be a powerful and accurate treatment for chemical kinetics. In this talk, VPT4-based SCTST tunneling probabilities and cumulative reaction probabilities are give for the first time for selected low-dimensional model systems. The prospects for VPT4, both practical and intrinsic, will also be discussed.
Density functional theoretical analysis with experimental, invitro bioactivity and molecular docking investigations on the pesticide Albendazole

NASA Astrophysics Data System (ADS)

Divya, P.; Bena Jothy, V.

2018-03-01

Optimized structural parameters of Albendazole and corresponding vibrational assignments have been studied using infrared and Raman spectroscopy combined with quantum-chemical calculations. Results of these spectroscopic studies have been successfully compared against obtained experimental data. Difference between experimental and calculated CH3 group wavenumbers was blue-shifted by 58 cm-1 and 43 cm-1, respectively due to electronic effects. In NBO analysis the increase in energies and the shortening of Csbnd N and Cdbnd O bonds gives clear evidence that the resonance of the benzimidazole ring is increased by the groups. Best binding score of Albendazole was obtained with protein 4NQ6 (-5.58 kcal/mol).
Molecular structure, vibrational spectra, NBO analysis, first hyperpolarizability, and HOMO-LUMO studies of 2-amino-4-hydroxypyrimidine by density functional method

NASA Astrophysics Data System (ADS)

Jeyavijayan, S.

2015-04-01

This study is a comparative analysis of FTIR and FT-Raman spectra of 2-amino-4-hydroxypyrimidine. The total energies of different conformations have been obtained from DFT (B3LYP) method with 6-31+G(d,p) and 6-311++G(d,p) basis sets. The barrier of planarity between the most stable and planar form is also predicted. The molecular structure, vibrational wavenumbers, infrared intensities, Raman scattering activities were calculated for the molecule using the B3LYP density functional theory (DFT) method. The computed values of frequencies are scaled using multiple scaling factors to yield good coherence with the observed values. Reliable vibrational assignments were made on the basis of total energy distribution (TED) along with scaled quantum mechanical (SQM) method. The stability of the molecule arising from hyperconjugative interactions, charge delocalization has been analyzed using natural bond orbital (NBO) analysis. Non-linear properties such as electric dipole moment (μ), polarizability (α), and hyperpolarizability (β) values of the investigated molecule have been computed using B3LYP quantum chemical calculation. The calculated HOMO and LUMO energies show that charge transfer occurs within the molecule. Besides, molecular electrostatic potential (MEP), Mulliken's charges analysis, and several thermodynamic properties were performed by the DFT method.
Vibrational spectra, optical properties, NBO and HOMO-LUMO analysis of L-Phenylalanine L-Phenylalaninium Perchlorate: DFT calculations

NASA Astrophysics Data System (ADS)

Elleuch, Nabil; Ben Ahmed, Ali; Feki, Habib; Abid, Younes; Minot, Christian

2014-03-01

In this work, we report a combined experimental and theoretical study of a nonlinear optical material, L-Phenylalanine L-Phenylalaninium Perchlorate. Single crystals of the title compound have been grown by slow evaporation of an aqueous solution at room temperature. Theoretical calculations were preceded by redetermination of the crystal X-ray structure. The compound crystallizes in the non-centro symmetric space group P212121 of the orthorhombic system. The FT-IR and Raman spectra of the crystal were recorded and analyzed. The density functional theory (DFT) computations have been performed at B3LYP/6-31G(d) level to derive equilibrium geometry, vibrational wavenumbers, intensity and NLO properties. All observed vibrational bands have been discussed and assigned to normal mode or to combinations on the basis of our DFT calculations as a primary source of attribution and also by comparison with the previous results for similar compounds. Natural bond orbital analysis was carried out to demonstrate the various inter-and intramolecular interaction that are responsible of the stabilization of the compound. The lowering of highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) energy gap appears to be the cause of its enhanced charge transfer interaction leading to high NLO activity.
DFT approach to (benzylthio)acetic acid: Conformational search, molecular (monomer and dimer) structure, vibrational spectroscopy and some electronic properties

NASA Astrophysics Data System (ADS)

Sienkiewicz-Gromiuk, Justyna

2018-01-01

The DFT studies were carried out with the B3LYP method utilizing the 6-31G and 6-311++G(d,p) basis sets depending on whether the aim of calculations was to gain the geometry at equilibrium, or to calculate the optimized molecular structure of (benzylthio)acetic acid (Hbta) in the forms of monomer and dimer. The minimum conformational energy search was followed by the potential energy surface (PES) scan of all rotary bonds existing in the acid molecule. The optimized geometrical monomeric and dimeric structures of the title compound were compared with the experimental structural data in the solid state. The detailed vibrational interpretation of experimental infrared and Raman bands was performed on the basis of theoretically simulated ESFF-scaled wavenumbers calculated for the monomer and dimer structures of Hbta. The electronic characteristics of Hbta is also presented in terms of Mulliken atomic charges, frontier molecular orbitals and global reactivity descriptors. Additionally, the MEP and ESP surfaces were computed to predict coordination sites for potential metal complex formation.
Synthesis, spectroscopic (FT-IR, FT-Raman, NMR, UV-Visible), NLO, NBO, HOMO-LUMO, Fukui function and molecular docking study of (E)-1-(5-bromo-2-hydroxybenzylidene)semicarbazide

NASA Astrophysics Data System (ADS)

Raja, M.; Raj Muhamed, R.; Muthu, S.; Suresh, M.

2017-08-01

The title compound, (E)-1-(5-bromo-2-hydroxybenzylidene)semicarbazide (15BHS) was synthesized and characterized by FT-IR, FT-Raman, UV, 1HNMR and 13CNMR spectral analysis. The optimized molecular geometry, the vibrational wavenumbers, the infrared intensities and the Raman scattering activities were calculated by using density functional theory(DFT) B3LYP method with 6-311++G(d,p) basis set. The detailed interpretation of the vibrational spectra has been carried out by VEDA program. The calculated HOMO and LUMO energies show that charge transfer within the molecule. Stability of the molecule arising from hyperconjugative interactions, charge delocalization have been analyzed using natural bond orbital analysis (NBO). The first order hyperpolarizability, Molecular electrostatic potential (MEP) and Fukui functions were also performed. To study the biological activity of the investigation molecule, molecular docking was done to identify the hydrogen bond lengths and binding energy with different antifungal proteins. The thermodynamic properties (heat capacity, entropy, and enthalpy) of the 15BHS at different temperatures have been calculated.
Vibrational spectra, DFT quantum chemical calculations and conformational analysis of P-iodoanisole.

PubMed

Arivazhagan, M; Anitha Rexalin, D; Geethapriya, J

2013-09-01

The solid phase FT-IR and FT-Raman spectra of P-iodoanisole (P-IA) have been recorded in the regions 400-4000 and 50-4000 cm(-1), respectively. The spectra were interpreted in terms of fundamentals modes, combination and overtone bands. The structure of the molecule was optimized and the structural characteristics were determined by ab initio (HF) and density functional theory (B3LYP) methods with LanL2DZ as basis set. The potential energy surface scan for the selected dihedral angle of P-IA has been performed to identify stable conformer. The optimized structure parameters and vibrational wavenumbers of stable conformer have been predicted by density functional B3LYP method with LanL2DZ (with effective core potential representations of electrons near the nuclei for post-third row atoms) basis set. The nucleophilic and electrophilic sites obtained from the molecular electrostatic potential (MEP) surface were calculated. The temperature dependence of thermodynamic properties has been analyzed. Several thermodynamic parameters have been calculated using B3LYP with LanL2DZ basis set. Copyright © 2013 Elsevier B.V. All rights reserved.
Spectroscopic (FT-IR, FT-Raman, UV and NMR) investigation and NLO, HOMO-LUMO, NBO analysis of organic 2,4,5-trichloroaniline.

PubMed

Govindarajan, M; Karabacak, M; Periandy, S; Tanuja, D

2012-11-01

In this work, the experimental and theoretical study on the molecular structure and vibrational spectra of 2,4,5-trichloroaniline (C(6)H(4)NCl(3), abbreviated as 2,4,5-TClA) were studied. The FT-IR and FT-Raman spectra were recorded. The molecular geometry and vibrational frequencies in the ground state were calculated by using the Hartree-Fock (HF) and density functional theory (DFT) methods (B3LYP) with 6-311++G(d,p) basis set. Comparison of the observed fundamental vibrational frequencies of 2,4,5-TClA with calculated results by HF and DFT indicates that B3LYP is superior to HF method for molecular vibrational problems. The difference between the observed and scaled wavenumber values of most of the fundamentals is very small. The theoretically predicted FT-IR and FT-Raman spectra of the title molecule have been constructed. A study on the electronic properties, such as HOMO and LUMO energies, were performed by time-dependent DFT (TD-DFT) approach. Besides, molecular electrostatic potential (MEP) and thermodynamic properties were performed. The electric dipole moment (μ) and the first hyperpolarizability (β) values of the investigated molecule were computed using ab initio quantum mechanical calculations. The calculated results also show that the 2,4,5-TClA molecule may have microscopic nonlinear optical (NLO) behavior with non-zero values. Mulliken atomic charges of 2,4,5-TClA was calculated and compared with aniline and chlorobenzene molecules. The (13)C nuclear magnetic resonance (NMR) chemical shifts of the molecule were calculated by the gauge independent atomic orbital (GIAO) method and compared with experimental results. Copyright © 2012 Elsevier B.V. All rights reserved.
VizieR Online Data Catalog: CH4 and hot methane continuum hybrid line list (Yurchenko+, 2017)

NASA Astrophysics Data System (ADS)

Yurchenko, S. N.; Amundsen, D. S.; Tennyson, J.; Waldmann, I. P.

2017-07-01

The states file ch4_e50.dat contains a list of rovibrational states. Each state is labelled with: nine normal mode vibrational quantum numbers and the vibrational symmetry; three rotational quantum numbers including the total angular momentum J and rotational symmetry; the total symmetry quantum number Gamma and the running number in the same (J,Gamma) block. In addition there are nine local mode vibrational numbers and the largest coefficient used to assign the state in question. Each rovibrational state has a unique number, which is the number of the row in which it appears in the file. This number is the means by which the state is related to the second part of the data system, the transitions files. The total degeneracy is also given to facilitate the intensity calculations. Because of their size, the transitions are listed in 120 separate files, each containing all the transitions in a 100cm-1 frequency range. These transition files t_*.dat contain the strong methane lines lines consisting of three columns: the reference number in the energy file of the upper state, that of the lower state, the Einstein A coefficient of the transition and the transition wavenumber. These entries are ordered by increasing frequency. The name of the file includes the lowest frequency in the range; thus the t-00500.dat file contains all the transitions in the frequency range 500-600cm-1. 19 histograms xYYYYK.dat files contain CH4_ super-lines representing the continuum computed at the temperature T=YYYYK using R=1000000 (7090081 super-lines each) covering the wavenumber range from 10 to 12000cm-1. The energy file, the transitions files and the histograms files are bzipped, and need to be extracted before use. The pressure broadening parameters used in the calculations are listed in broad.dat. A programme ExoCross to generate synthetic spectra from these line lists can be obtained at www.exomol.com. (4 data files).
Synthesis, molecular structure, FT-IR and XRD investigations of 2-(4-chlorophenyl)-2-oxoethyl 2-chlorobenzoate: a comparative DFT study.

PubMed

Chidan Kumar, C S; Fun, Hoong Kun; Tursun, Mahir; Ooi, Chin Wei; Chandraju, Siddegowda; Quah, Ching Kheng; Parlak, Cemal

2014-04-24

2-(4-Chlorophenyl)-2-oxoethyl 2-chlorobenzoate has been synthesized, its structural and vibrational properties have been reported using FT-IR and single-crystal X-ray diffraction (XRD) studies. The conformational analysis, optimized geometric parameters, normal mode frequencies and corresponding vibrational assignments of the synthesized compound (C15H10Cl2O3) have been examined by means of Becke-3-Lee-Yang-Parr (B3LYP) density functional theory (DFT) method together with 6-31++G(d,p) basis set. Furthermore, reliable conformational investigation and vibrational assignments have been made by the potential energy surface (PES) and potential energy distribution (PED) analyses, respectively. Calculations are performed with two possible conformations. The title compound crystallizes in orthorhombic space group Pbca with the unit cell dimensions a=12.312(5) Å, b=8.103(3) Å, c=27.565(11) Å, V=2750.0(19) Å(3). B3LYP method provides satisfactory evidence for the prediction of vibrational wavenumbers and structural parameters. Copyright © 2014 Elsevier B.V. All rights reserved.
Vibrational modes of 2,6-, 2,7-, and 2,3-diisopropylnaphthalene. A DFT study

NASA Astrophysics Data System (ADS)

Jamróz, Michał H.; Dobrowolski, Jan Cz.; Brzozowski, Robert

2006-04-01

The IR and Raman spectra of three diisopropylnaphthalene (DIPN) isomers, 2,6-; 2,7-, and 2,3-DIPN, were calculated at the B3PW91/6-311G* level and were interpreted in terms of potential energy distribution (PED) analysis. Two types of internal coordinates were constructed to increase clarity of the PED interpretation: one expressing movements in which at least one H-atom participated and the other in which only the C-atoms were active (60 and 42 coordinates, respectively). The internal coordinates were optimized repeatedly for few hundred times to maximize the PED contributions. The similarities and differences between the vibrational spectra of the three molecules studied were pointed out. The IR and Raman bands useful for detection of the unknown 2,3-DIPN isomer were proposed. Comparison of the experimental vibrational spectra of the 2,6-DIPN isomer with the B3PW91/6-311G* theoretical wavenumbers shows very good agreement: usually the two wave numbers are within 10 cm -1 interval. Such an agreement allows for almost undoubtful assignment of the vibrational spectra.
Conformational stability, vibrational spectra, molecular structure, NBO and HOMO-LUMO analysis of 5-nitro-2-furaldehyde oxime based on DFT calculations.

PubMed

Arivazhagan, M; Jeyavijayan, S; Geethapriya, J

2013-03-01

The FTIR and FT-Raman spectra of 5-nitro-2-furaldehyde oxime (NFAO) have been recorded in the regions 4000-400 cm(-1) and 3500-50 cm(-1), respectively. The total energies of different conformations have been obtained from DFT (B3LYP) with 6-311++G(d,p) basis set calculations. The computational results identify the most stable conformer of NFAO as the C1 form. Utilizing the observed FTIR and FT-Raman data, a complete vibrational assignment and analysis of the fundamental modes of the compound were carried out. The optimum molecular geometry, harmonic vibrational frequencies, infrared intensities and Raman scattering activities, were calculated by density functional theory (DFT/B3LYP) method with 6-31+G(d,p) and 6-311++G(d,p) basis sets. The difference between the observed and scaled wavenumber values of most of the fundamentals is very small. A detailed interpretation of the infrared and Raman spectra of NFAO is also reported based on total energy distribution (TED). Stability of the molecule arising from hyperconjugative interactions, charge delocalization have been analyzed using natural bond orbital (NBO) analysis. Besides, molecular electrostatic potential (MEP), HOMO and LUMO analysis, and several thermodynamic properties were performed by the DFT method. Mulliken's net charges have been calculated and compared with the natural atomic charges. Ultraviolet-visible spectrum of the title molecule has also been calculated using TD-DFT method. Copyright © 2012 Elsevier B.V. All rights reserved.
Vibrational spectra and natural bond orbital analysis of organic crystal L-prolinium picrate

NASA Astrophysics Data System (ADS)

Edwin, Bismi; Amalanathan, M.; Hubert Joe, I.

2012-10-01

Vibrational spectral analysis and quantum chemical computations based on density functional theory (DFT) have been performed on the organic crystal L-prolinium picrate (LPP). The equilibrium geometry, various bonding features and harmonic vibrational wavenumbers of LPP have been investigated using B3LYP method. The calculated molecular geometry has been compared with the experimental data. The detailed interpretation of the vibrational spectra has been carried out with the aid of VEDA 4 program. The various intramolecular interactions confirming the biological activity of the compound have been exposed by natural bond orbital analysis. The distribution of Mulliken atomic charges and bending of natural hybrid orbitals associated with hydrogen bonding also reflects the presence of intramolecular hydrogen bonding thereby enhancing bioactivity. The analysis of the electron density of HOMO and LUMO gives an idea of the delocalization and low value of energy gap indicates electron transport in the molecule and thereby bioactivity. Vibrational analysis reveals the presence of strong O-H⋯O and N-H⋯O interaction between L-prolinium and picrate ions providing evidence for the charge transfer interaction between the donor and acceptor groups and is responsible for its bioactivity.
Vibrational dynamics of acetate in D2O studied by infrared pump-probe spectroscopy.

PubMed

Banno, Motohiro; Ohta, Kaoru; Tominaga, Keisuke

2012-05-14

Solute-solvent interactions between acetate and D(2)O were investigated by vibrational spectroscopic methods. The vibrational dynamics of the COO asymmetric stretching mode in D(2)O was observed by time-resolved infrared (IR) pump-probe spectroscopy. The pump-probe signal contained both decay and oscillatory components. The time dependence of the decay component could be explained by a double exponential function with time constants of 200 fs and 2.6 ps, which are the same for both the COO asymmetric and symmetric stretching modes. The Fourier spectrum of the oscillatory component contained a band around 80 cm(-1), which suggests that the COO asymmetric stretching mode couples to a low-frequency vibrational mode with a wavenumber of 80 cm(-1). Based on quantum chemistry calculations, we propose that a bridged complex comprising an acetate ion and one D(2)O molecule, in which the two oxygen atoms in the acetate anion form hydrogen bonds with the two deuterium atoms in D(2)O, is the most stable structure. The 80 cm(-1) low-frequency mode was assigned to the asymmetric stretching vibration of the hydrogen bond in the bridged complex. This journal is © the Owner Societies 2012
Electronic torsional sound in linear atomic chains: Chemical energy transport at 1000 km/s

NASA Astrophysics Data System (ADS)

Kurnosov, Arkady A.; Rubtsov, Igor V.; Maksymov, Andrii O.; Burin, Alexander L.

2016-07-01

We investigate entirely electronic torsional vibrational modes in linear cumulene chains. The carbon nuclei of a cumulene are positioned along the primary axis so that they can participate only in the transverse and longitudinal motions. However, the interatomic electronic clouds behave as a torsion spring with remarkable torsional stiffness. The collective dynamics of these clouds can be described in terms of electronic vibrational quanta, which we name torsitons. It is shown that the group velocity of the wavepacket of torsitons is much higher than the typical speed of sound, because of the small mass of participating electrons compared to the atomic mass. For the same reason, the maximum energy of the torsitons in cumulenes is as high as a few electronvolts, while the minimum possible energy is evaluated as a few hundred wavenumbers and this minimum is associated with asymmetry of zero point atomic vibrations. Theory predictions are consistent with the time-dependent density functional theory calculations. Molecular systems for experimental evaluation of the predictions are proposed.
T-dependence of the vibrational dynamics of IBP/diME-β-CD in solid state: A FT-IR spectral and quantum chemical study

NASA Astrophysics Data System (ADS)

Crupi, V.; Guella, G.; Majolino, D.; Mancini, I.; Rossi, B.; Stancanelli, R.; Venuti, V.; Verrocchio, P.; Viliani, G.

2010-05-01

Solid inclusion complex of the non-steroidal anti-inflammatory drug Ibuprofen (IBP, (2-[4-(2-methylpropyl)phenyl]-propanoic acid) with (2,6-dimethyl)-β-cyclodextrin (diME-β-CD) has been investigated by Fourier transform infrared spectroscopy in attenuated total reflectance geometry (FTIR-ATR spectroscopy) and numerical simulation. The complexation-induced changes in the FTIR-ATR spectrum of IBP have been interpreted by comparison with the theoretical vibrational wavenumbers and IR intensities of dimeric structures of IBP, derived from symmetric hydrogen bonding of the two carboxylic groups, computed by using Density Functional Theory (DFT) calculations. From temperature-dependent studies, the enthalpy change ΔH associated with the binding of IBP with diME-β-CD for 1:1 stoichiometry, in solid phase, has been estimated.

Modulational instabilities in acetanilide taking into account both the N H and the C=O vibrational self-trappings

NASA Astrophysics Data System (ADS)

Simo, Elie

2007-02-01

A model of crystalline acetanilide, ACN accounting for the C=O and N-H vibrational self-trappings is presented. We develop a fully discrete version of ACN. We show that ACN can be described by a set of two coupled discrete nonlinear Schrödinger (DNLS) equations. Modulational instabilities (MI) are studied both theoretically and numerically. Dispersion laws for the wavenumbers and frequencies of the linear modulation waves are determined. We also derived the criterion for the existence of MI. Numerical simulations are carried out for a variety of selected wave amplitudes in the unstable zone. It is shown that instabilities grow as the wavenumbers and amplitudes of the modulated waves increase. MI grow faster in the N-H mode than in the C=O mode. Temporal evolution of the density probabilities of the vibrational excitons are obtained by the numerical integration of the coupled DNLS equations governing the ACN molecule. These investigations confirm the generation of localized modes by the phenomenon of MI and the predominance of the N-H vibrational mode in the MI process of the ACN.
New measurements and analysis of the far-infrared spectrum of CH2DOH in the lowest torsional vibrational state (e0)

NASA Astrophysics Data System (ADS)

Mukhopadhyay, Indra

2016-05-01

In this work the far infrared (FIR) absorption spectrum has been measured for the asymmetrically mono deuterated Methanol (CH2DOH) species in the wavenumber range of 15-1200 cm-1 better accuracy and signal/noise ratio than known before. Assignments have been made for b-type transitions in the lowest lying torsional vibrational state trans-(e0) for a wide range of rotational angular momentum. The assignments have been rigorously confirmed by the residual loop defect methods. The rR-branch wavenumbers are analyzed by the usual state dependent expansion parameters and the Q-Branch origins. These origins have been used to calculate the torsional and torsional-rotation interaction contributions. These findings are in good agreement with predicted from the Hamiltonian model described in recent publications. A large number of assignments have also been made in the millimeter wave spectrum recorded earlier and thereby evaluated the asymmetry splitting parameters for 4 different axial rotational angular momentum quantum numbers. The analysis and interpretation of the spectra are reported. New assignments for about 260 transitions are included the text and a catalog of about 1500 transitions belonging to the e0 species is prepared (Appendix 1) and is made available through the open server in "Research Gate" and will be freely available to others.
Conformational stability, r(0) structural parameters, vibrational assignments and ab initio calculations of ethyldichlorophosphine.

PubMed

Darkhalil, Ikhlas D; Paquet, Charles; Waqas, Mohammad; Gounev, Todor K; Durig, James R

2015-02-05

Variable temperature (-60 to -100 °C) studies of ethyldichlorophosphine, CH3CH2PCl2, of the infrared spectra (4000-400 cm(-1)) dissolved in liquid xenon have been carried out. From these data, the two conformers have been identified and the enthalpy difference has been determined between the more stable trans conformer and the less stable gauche form to be 88±9 cm(-1) (1.04±0.11 kJ/mol). The percentage of abundance of the gauche conformer is estimated to be 57% at ambient temperature. The conformational stabilities have been predicted from ab initio calculations by utilizing many different basis sets up to aug-cc-pVTZ for both MP2(full) and density functional theory calculations by the B3LYP method. Vibrational assignments have been provided for both conformers which have been predicted by MP2(full)/6-31G(d) ab initio calculations to predict harmonic force fields, wavenumbers of the fundamentals, infrared intensities, Raman activities and depolarization ratios for both conformers. Estimated r0 structural parameters have been obtained from adjusted MP2(full)/6-311+G(d,p) calculations. The results are discussed and compared to the corresponding properties of some related molecules. Copyright © 2014 Elsevier B.V. All rights reserved.
Vibrational spectra, optical properties, NBO and HOMO-LUMO analysis of L-Phenylalanine L-Phenylalaninium Perchlorate: DFT calculations.

PubMed

Elleuch, Nabil; Ben Ahmed, Ali; Feki, Habib; Abid, Younes; Minot, Christian

2014-01-01

In this work, we report a combined experimental and theoretical study of a nonlinear optical material, L-Phenylalanine L-Phenylalaninium Perchlorate. Single crystals of the title compound have been grown by slow evaporation of an aqueous solution at room temperature. Theoretical calculations were preceded by redetermination of the crystal X-ray structure. The compound crystallizes in the non-centro symmetric space group P2(1)2(1)2(1) of the orthorhombic system. The FT-IR and Raman spectra of the crystal were recorded and analyzed. The density functional theory (DFT) computations have been performed at B3LYP/6-31G(d) level to derive equilibrium geometry, vibrational wavenumbers, intensity and NLO properties. All observed vibrational bands have been discussed and assigned to normal mode or to combinations on the basis of our DFT calculations as a primary source of attribution and also by comparison with the previous results for similar compounds. Natural bond orbital analysis was carried out to demonstrate the various inter-and intramolecular interaction that are responsible of the stabilization of the compound. The lowering of highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) energy gap appears to be the cause of its enhanced charge transfer interaction leading to high NLO activity. Copyright © 2013 Elsevier B.V. All rights reserved.
The study on molecular structure and microbiological activity of alkali metal 3-hydroxyphenylycetates

NASA Astrophysics Data System (ADS)

Samsonowicz, M.; Regulska, E.; Kowczyk-Sadowy, M.; Butarewicz, A.; Lewandowski, W.

2017-10-01

The biological activity of chemical compounds depends on their molecular structure. In this paper molecular structure of 3-hydroxyphenylacetates in comparison to 3-hydroxyphenylacetic acid was studied. FT-IR, FT-Raman and NMR spectroscopy and density functional theory (DFT) calculations was used. The B3LYP/6-311++G(d,p) hybrid functional method was used to calculate optimized geometrical structures of studied compounds. The Mulliken, APT, MK, ChelpG and NBO atomic charges as well as dipole moment and energy values were calculated. Theoretical chemical shifts in NMR spectra and the wavenumbers and intensities of the bands in vibrational spectra were analyzed. Calculated parameters were compared to experimental characteristic of studied compounds. Microbiological analysis of studied compounds was performed relative to: Bacillus subtilis, Pseudomonas aeruginosa, Escherichia coli and Klebsiella oxytoca. The relationship between spectroscopic and structure parameters of studied compounds in regard to their activity was analyzed.
Investigation of hydrogen bonding and self-association in neat HCONH 2 and the binary mixture (HCONH 2+CH 3OH) by concentration dependent Raman study and ab initio calculations

NASA Astrophysics Data System (ADS)

Ojha, Animesh K.; Srivastava, Sunil K.; Koster, J.; Shukla, M. K.; Leszczynski, J.; Asthana, B. P.; Kiefer, W.

2004-02-01

Raman spectra of neat formamide (HCONH 2) and its binary mixture (HCONH 2+CH 3OH) with hydrogen donor solvent, methanol (CH 3OH) were investigated using a sensitive scanning multichannel detection scheme, which is simultaneously more precise also, especially when the observed Raman line profile has multiple component bands. The spectra in the two regions, namely 1200-1500 and 1500-1800 cm -1 were recorded with varying mole fractions of the reference molecule, HCONH 2, from 0.1 to 0.9. The spectra in the region 1200-1500 cm -1 show a broad band at ˜1312 cm -1, which shows a peculiar concentration dependence, and a relatively sharp peak at ˜1392 cm -1, whose peak position is not influenced by concentration. The spectra in the region 1500-1800 cm -1 also show two peaks, one at ˜1593 cm -1 and the other one at ˜1668 cm -1 which are assigned to NH 2 bending and ν(CO) stretching vibrations, respectively. Both these Raman bands show an appreciable upshift of ˜15-20 cm -1 and the one at ˜1668 cm -1 has also a distinct asymmetry towards higher wavenumber. The optimized geometries and vibrational wavenumbers of various normal modes for neat formamide as well as its hydrogen-bonded complexes were also calculated using ab initio theory at the MP2 level. The results have been used to understand and explain the concentration dependent changes in the spectral features in terms of hydrogen bonding and self-association.
Structural-acoustic coupling in aircraft fuselage structures

NASA Technical Reports Server (NTRS)

Mathur, Gopal P.; Simpson, Myles A.

1992-01-01

Results of analytical and experimental investigations of structural-acoustic coupling phenomenon in an aircraft fuselage are described. The structural and acoustic cavity modes of DC-9 fuselage were determined using a finite element approach to vibration analysis. Predicted structural and acoustic dispersion curves were used to determine possible occurrences of structural-acoustic coupling for the fuselage. An aft section of DC-9 aircraft fuselage, housed in an anechoic chamber, was used for experimental investigations. The test fuselage was excited by a shaker and vibration response and interior sound field were measured using accelerometer and microphone arrays. The wavenumber-frequency structural and cavity response maps were generated from the measured data. Analysis and interpretation of the spatial plots and wavenumber maps provided the required information on modal characteristics, fuselage response and structural-acoustic coupling.
Newly synthesized dihydroquinazoline derivative from the aspect of combined spectroscopic and computational study

NASA Astrophysics Data System (ADS)

El-Azab, Adel S.; Mary, Y. Sheena; Mary, Y. Shyma; Panicker, C. Yohannan; Abdel-Aziz, Alaa A.-M.; El-Sherbeny, Magda A.; Armaković, Stevan; Armaković, Sanja J.; Van Alsenoy, Christian

2017-04-01

In this work, spectroscopic characterization of 2-(2-(4-oxo-3-phenethyl-3,4-dihydroquinazolin-2-ylthio)ethyl)isoindoline-1,3-dione have been obtained with experimentally and theoretically. Complete assignments of fundamental vibrations were performed on the basis of the potential energy distribution of the vibrational modes and good agreement between the experimental and scaled wavenumbers has been achieved. Frontier molecular orbitals have been used as indicators of stability and reactivity. Intramolecular interactions have been investigated by NBO analysis. The dipole moment, linear polarizability and first and second order hyperpolarizability values were also computed. In order to determine molecule sites prone to electrophilic attacks DFT calculations of average local ionization energy (ALIE) and Fukui functions have been performed as well. Intra-molecular non-covalent interactions have been determined and analyzed by the analysis of charge density. Stability of title molecule have also been investigated from the aspect of autoxidation, by calculations of bond dissociation energies (BDE), and hydrolysis, by calculations of radial distribution functions after molecular dynamics (MD) simulations. In order to assess the biological potential of the title compound a molecular docking study towards breast cancer type 2 complex has been performed.
Structural characterization of tellurite glasses doped with transition metal oxides using Raman spectra and ab initio calculations.

PubMed

Mohamed, Tarek A; Shaltout, I; Al Yahyaei, K M

2006-05-01

Systems of iron tellurite glasses were prepared by melt quenching with compositions of [85%TeO2+5%Fe2O3+10%TMO], where transition metal oxides (TMO) are TiO2, V2O5, MnO, CoO, NiO and CuO. Furthermore, the main structural units of these samples have been characterized by means of Raman spectra (150-1200 cm(-1)) as well as wavenumber predictions by means of Gaussian 98 ab initio calculations for the proposed site symmetries of TeO4(4-) triagonal bipyramid (C2v) and Te2O7(6-) bridged tetrahedra (Cs and C1). Aided by normal coordinate analysis, calculated vibrational frequencies, Raman scattering activities, force constants in internal coordinates and potential energy distributions (PEDs), revised vibrational assignments for the fundamental modes have been proposed. The main structural features are correlated to the dominant units of triagonal bipyramid (tbp) or bridged tetrahedral (TeO3+1 binds to TeO3 through TeOTe bridge; corner sharing). Moreover, the Raman spectra of the investigated tellurites reflect a structural change from tbp (coordination number is four) to triagonal pyramidal (coordination number is three).
Structural confirmation and spectroscopic study of a biomolecule: Norepinephrine.

PubMed

Yadav, T; Mukherjee, V

2018-05-21

The present work deals with the conformational and vibrational spectroscopic study of an important bio-molecule named norepinephrine in gas phase. The FTIR and FTRaman spectrum of norepinephrine in amorphous form were recorded in wavenumber range 4000-400 cm -1 and 4000-50 cm -1 respectively. We have investigated twenty-seven stable conformational structures of norepinephrine molecule. All the calculations have been done using Density Functional Theory with exchange functional B3LYP incorporated with the 6-31++G(d, p) basis set. The effect of hydrochloride on different bond lengths, bond angles and dihedral angles in the most stable conformer has also been studied. The total potential energy distribution for both the most stable conformer and the most stable conformer in hydrochloride was performed with the help Normal coordinate analysis method. Most of the calculated vibrational frequencies are in good agreement with the experimental frequencies. The natural bond orbital analysis was also performed to ensure the stability of electronic structures of norepinephrine. To know chemical reactivity of norepinephrine molecule we have calculated the energy gap between HOMO and LUMO orbitals and it has found above 5 eV in all the conformers. Copyright © 2018 Elsevier B.V. All rights reserved.
FTIR, FT-Raman, FT-NMR and quantum chemical investigations of 3-acetylcoumarin

NASA Astrophysics Data System (ADS)

Arjunan, V.; Sakiladevi, S.; Marchewka, M. K.; Mohan, S.

2013-05-01

3-Acetylcoumarin (3AC) was synthesised by a Knoevenagel reaction. Conformational analysis using the B3LYP method was also carried out to determine the most stable conformation of the compound. FTIR and FT-Raman spectra of 3AC have been recorded in the range 4000-400 and 4000-100 cm-1, respectively. 1H and 13C NMR spectra have also been recorded. The complete vibrational assignment and analysis of the fundamental modes of the compound were carried out using the experimental FTIR and FT-Raman data and quantum mechanical studies. The experimental vibrational frequencies were compared with the wavenumbers obtained theoretically from the DFT-B3LYP/B3PW91 gradient calculations employing the standard 6-31G**, high level 6-311++G** and cc-pVTZ basis sets for optimised geometry of the compound. The frontier molecular orbital energies of the compound are determined by DFT method.
Modeling the IR spectra of aqueous metal carboxylate complexes: correlation between bonding geometry and stretching mode wavenumber shifts.

PubMed

Sutton, Catherine C R; da Silva, Gabriel; Franks, George V

2015-04-27

A widely used principle is that shifts in the wavenumber of carboxylate stretching modes upon bonding with a metal center can be used to infer if the geometry of the bonding is monodentate or bidentate. We have tested this principle with ab initio modeling for aqueous metal carboxylate complexes and have shown that it does indeed hold. Modeling of the bonding of acetate and formate in aqueous solution to a range of cations was used to predict the infrared spectra of the metal-carboxylate complexes, and the wavenumbers of the symmetric and antisymmetric vibrational modes are reported. Furthermore, we have shown that these shifts in wavenumber occur primarily due to how bonding with the metal changes the carboxylate C-O bond lengths and O-C-O angle. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
ExoMol line lists - XXII. The rotation-vibration spectrum of silane up to 1200 K

NASA Astrophysics Data System (ADS)

Owens, A.; Yachmenev, A.; Thiel, W.; Tennyson, J.; Yurchenko, S. N.

2017-11-01

A variationally computed 28SiH4 rotation-vibration line list applicable for temperatures up to T = 1200 K is presented. The line list, called OY2T, considers transitions with rotational excitation up to J = 42 in the wavenumber range 0-5000 cm-1 (wavelengths λ > 2 μm). Just under 62.7 billion transitions have been calculated between 6.1 million energy levels. Rovibrational calculations have utilized a new `spectroscopic' potential energy surface determined by empirical refinement to 1452 experimentally derived energy levels up to J = 6, and a previously reported ab initio dipole moment surface. The temperature-dependent partition function of silane, the OY2T line list format, and the temperature dependence of the OY2T line list are discussed. Comparisons with the PNNL spectral library and other experimental sources indicate that the OY2T line list is robust and able to accurately reproduce weaker intensity features. The full line list is available from the ExoMol data base and the CDS data base.
Molecular structure, vibrational spectra, NBO analysis and molecular packing prediction of 3-nitroacetanilide by ab initio HF and density functional theory.

PubMed

Li, Xiao-Hong; Li, Tong-Wei; Ju, Wei-Wei; Yong, Yong-Liang; Zhang, Xian-Zhou

2014-01-24

Quantum chemical calculations of geometries and vibrational wavenumbers of 3-nitroacetanilide (C8H8N2O3) in the ground state were carried out by using ab initio HF and density functional theory (DFT/B3LYP) methods with 6-31+G(*) basis set. The -311++G(**) basis set is also used for B3LYP level. The scaled harmonic vibrational frequencies have been compared with experimental FT-IR spectra. Theoretical vibrational spectra of the title compound were interpreted by means of potential energies distributions (PEDs) using MOLVIB program. The theoretical spectrograms for IR spectra of the title compound have been constructed. The shortening of C-H bond length and the elongation of N-H bond length suggest the existence of weak C-H⋯O and N-H⋯O hydrogen bonds, which is confirmed by the natural bond orbital analysis. In addition, the crystal structure obtained by molecular mechanics belongs to the P2(1) space group, with lattice parameters Z=4, a=14.9989 Å, b=4.0367 Å, c=12.9913 Å, ρ=0.998 g cm(-3). Copyright © 2013 Elsevier B.V. All rights reserved.
Molecular structure, vibrational spectra, NBO analysis and molecular packing prediction of 3-nitroacetanilide by ab initio HF and density functional theory

NASA Astrophysics Data System (ADS)

Li, Xiao-Hong; Li, Tong-Wei; Ju, Wei-Wei; Yong, Yong-Liang; Zhang, Xian-Zhou

2014-01-01

Quantum chemical calculations of geometries and vibrational wavenumbers of 3-nitroacetanilide (C8H8N2O3) in the ground state were carried out by using ab initio HF and density functional theory (DFT/B3LYP) methods with 6-31+G* basis set. The -311++G** basis set is also used for B3LYP level. The scaled harmonic vibrational frequencies have been compared with experimental FT-IR spectra. Theoretical vibrational spectra of the title compound were interpreted by means of potential energies distributions (PEDs) using MOLVIB program. The theoretical spectrograms for IR spectra of the title compound have been constructed. The shortening of Csbnd H bond length and the elongation of Nsbnd H bond length suggest the existence of weak Csbnd H⋯O and Nsbnd H⋯O hydrogen bonds, which is confirmed by the natural bond orbital analysis. In addition, the crystal structure obtained by molecular mechanics belongs to the P21 space group, with lattice parameters Z = 4, a = 14.9989 Å, b = 4.0367 Å, c = 12.9913 Å, ρ = 0.998 g cm-3.
Spectroscopic and molecular docking studies on N,N-di-tert-butoxycarbonyl (Boc)-2-amino pyridine: A potential bioactive agent for lung cancer treatment

NASA Astrophysics Data System (ADS)

Mohamed Asath, R.; Premkumar, R.; Mathavan, T.; Milton Franklin Benial, A.

2017-09-01

Potential energy surface scan was performed and the most stable molecular structure of the N,N-di-tert-butoxycarbonyl (Boc)-2-amino pyridine (DBAP) molecule was predicted. The most stable molecular structure of the molecule was optimized using B3LYP method with cc-pVTZ basis set. Anticancer activity of the DBAP molecule was evaluated by molecular docking analysis. The structural parameters and vibrational wavenumbers were calculated for the optimized molecular structure. The experimental and theoretical wavenumbers were assigned and compared. Ultraviolet-Visible spectrum was simulated and validated experimentally. The molecular electrostatic potential surface was simulated and Fukui function calculations were also carried out to investigate the reactive nature of the DBAP molecule. The natural bond orbital analysis was also performed to probe the intramolecular interactions and confirm the bioactivity of the DBAP molecule. The molecular docking analysis reveals the better inhibitory nature of the DBAP molecule against the epidermal growth factor receptor (EGFR) protein which causes lung cancer. Hence, the present study unveils the structural and bioactive nature of the title molecule. The DBAP molecule was identified as a potential inhibitor against the lung cancer which may be useful in further development of drug designing in the treatment of lung cancer.
A comparative study of the infrared and Raman spectra of aniline and o-, m-, p-phenylenediamine isomers.

PubMed

Badawi, Hassan M; Förner, Wolfgang; Ali, Shaikh A

2013-08-01

The structural stabilities of o-, m- and p-phenylenediamine (PDA) isomers were investigated by DFT-B3LYP and ab initio MP2 calculations with the 6-311G(**) basis set. From the calculations the three isomers were predicted to exist predominantly in an anti (transoid) structure. In the o-isomer, the syn (cisoid) form is calculated to turn to the anti (transoid) form with the two HNCC torsional angles of about 44 and 10° and the NH2 inversion barrier of 3-4 kcal/mol. The CCNH torsional angles in the m-PDA and p-PDA isomers were calculated to be about 25-26° as compared to 20° in aniline. A comparison of the Raman spectra of the three PDA-s with those of aniline shows the high sensitivity of the ring breathing mode to the nature of substituents in the aniline ring. The vibrational wavenumbers were computed at the DFT-B3LYP for aniline and the o-, m- and p-PDA isomers for the purpose of comparison. Complete vibrational assignments were made on the basis of normal coordinate analyses and potential energy distributions for aniline and the o-, m- and p-PDA molecules. Copyright © 2013 Elsevier B.V. All rights reserved.
Very high resolution far infrared synchrotron radiation spectrum of methanol-D1 (CH2DOH) in the first three torsional-vibrational modes

NASA Astrophysics Data System (ADS)

Mukhopadhyay, Indra; Billinghurst, B. E.

2016-11-01

In our effort to systematically study the far infrared (FIR) spectra of asymmetrically mono deuterated methanol (CH2DOH) and thereby obtain the transition wavenumbers with better and better accuracy (Mukhopadhyay, 2016a,b), the complete Fourier transform (FT) spectra from FIR to infrared (IR) vibrational bands (in the range 50-1190 cm-1) have been re-recorded using the Synchrotron Radiation Source at the Canadian Light Sources in Saskatchewan, Canada. The resolution of the spectrum is unprecedented, reaching beyond the Doppler limited resolution as low as about 0.0008 cm-1 with a signal to noise (S/N) ratio is many fold better than that can be obtained by commercially available FT spectrometer using thermal sources (e.g., Globar). Spectra were also recorded beyond 1190 cm-1 to about 5000 cm-1 at a somewhat lower resolution of 0.002-0.004 cm-1. In this report the analysis of the b-type and c-type torsional - rotational spectra in the ground vibrational state corresponding to gauche- (e1/o1) to gauche- (e1/o1) and gauche- (e1/o1) to trans- (e0) states in the ground vibrational state are reported and an atlas of the wavenumber for about 2500 FIR assigned absorption lines has been prepared. The transitions within a given sub-band are analyzed using state dependent expansion parameters and the Q-branch origins. The data from previous results (Mukhopadhyay, 2016a,b) along with the present work allowed a global analysis yielding a complete set of molecular parameters. The state dependent molecular parameters reproduce the experimental wavenumbers within experimental uncertainty. In addition, the sensitivity of the spectrum allowed observation of forbidden transitions previously unobserved and helped reassignment of rotational angular momentum quantum numbers of some ΔK = ±1, Q-branch transitions in highly excited states recently reported in the literature. To our knowledge the wavenumbers reported in the present work are the most accurate so far reported in the literature and represent the highest resolution spectra for this molecular species.
Global Analysis of Broadband Rotation and Vibration-Rotation Spectra of Sulfur Dicyanide

NASA Astrophysics Data System (ADS)

Kisiel, Zbigniew; Winnewissser, Manfred; Winnewisser, Brenda P.; De Lucia, Frank C.; Tokaryk, Dennis W.; Billinghurst, Brant E.

2013-06-01

The successful analysis of the quantum monodromy induced features in the rotational spectrum of the NCNCS molecule prompted a quest for similar behaviour in its vibration-rotation spectrum and several high-resolution FT-IR spectra were recorded on the IFS125HR interferometer at the Canadian Light Source. The sulfur dicyanide, S(CN)_2, molecule is a precursor to NCNCS and the analysis of its spectrum proved to be a prerequisite to a search for the elusive NCNCS transitions. The CLS spectra provided the opportunity to augment the previous extensive analysis of the FASSST rotational spectrum of S(CN)_2 with vibration-rotation data, in particular from the ν_4 fundamental at 121 cm^{-1} and its related hot-band series. A global fit of the two data sets allowed retaining the detailed analysis of the previously reported perturbations in the 3ν_4 triad and 4ν_4 tetrad of states, while allowing for determination of precise energies of all low-lying vibrational states of S(CN)_2. In this way we have determined wavenumbers for five lowest fundamentals of this experimentally difficult molecule and obtained an extensive set of benchmark data for calibration of anharmonic force field calculations of such quantities as the vibration-rotation changes in rotational constants, and anharmonicity coefficients. Comparisons with results of several such calculations are presented. B.P.Winnewisser, et al., Phys. Chem. Chem. Phys. {12}, 8158 (2010). M.Winnewisser et al., 67^th OSU Symposium on Molecular Spectroscopy, The Ohio State University, Ohio 2012, TF-01. Z.Kisiel et al., J. Mol. Spectrosc. {246}, 39 (2007).
DFT calculations and experimental FT-IR, FT-Raman, NMR, UV-Vis spectral studies of 3-fluorophenylboronic acid

NASA Astrophysics Data System (ADS)

Karabacak, M.; Kose, E.; Sas, E. B.; Kurt, M.; Asiri, A. M.; Atac, A.

2015-02-01

The spectroscopic (FT-IR, FT-Raman, 1H and 13C NMR, UV-Vis), structural, electronic and thermodynamical properties of 3-fluorophenylboronic acid (C6H4FB(OH)2), 3FPBA) were submitted by using both experimental techniques and theoretical methods (quantum chemical calculations) in this work. The experimental infrared and Raman spectra were obtained in the region 4000-400 cm-1 and 3500-10 cm-1, respectively. The equilibrium geometry and vibrational spectra were calculated by using DFT (B3LYP) with 6-311++G(d,p) basis set. The vibrational wavenumbers were also corrected with scale factor to take better results for the calculated data. The total energy distributions (TED) of the vibrational modes were performed for the assignments of the title molecule by using scaled quantum mechanics (SQM) method. The NMR chemical shifts (1H and 13C) were recorded in DMSO solution. The 1H and 13C NMR spectra were computed by using the gauge-invariant atomic orbital (GIAO) method, showing a good agreement with the experimental ones. The last one UV-Vis absorption spectra were analyzed in two solvents (ethanol and water), saved in the range of 200-400 nm. In addition these, HOMO and LUMO energies, the excitation energies, density of states (DOS) diagrams, thermodynamical properties and molecular electrostatic potential surface (MEPs) were presented. Nonlinear optical (NLO) properties and thermodynamic features were performed. The experimental results are combined with the theoretical calculations using DFT calculations to fortification of the paper. At the end of this work, the results were proved our paper had been indispensable for the literature backing.

DFT calculations and experimental FT-IR, FT-Raman, NMR, UV-Vis spectral studies of 3-fluorophenylboronic acid.

PubMed

Karabacak, M; Kose, E; Sas, E B; Kurt, M; Asiri, A M; Atac, A

2015-02-05

The spectroscopic (FT-IR, FT-Raman, (1)H and (13)C NMR, UV-Vis), structural, electronic and thermodynamical properties of 3-fluorophenylboronic acid (C6H4FB(OH)2), 3FPBA) were submitted by using both experimental techniques and theoretical methods (quantum chemical calculations) in this work. The experimental infrared and Raman spectra were obtained in the region 4000-400 cm(-1) and 3500-10 cm(-1), respectively. The equilibrium geometry and vibrational spectra were calculated by using DFT (B3LYP) with 6-311++G(d,p) basis set. The vibrational wavenumbers were also corrected with scale factor to take better results for the calculated data. The total energy distributions (TED) of the vibrational modes were performed for the assignments of the title molecule by using scaled quantum mechanics (SQM) method. The NMR chemical shifts ((1)H and (13)C) were recorded in DMSO solution. The (1)H and (13)C NMR spectra were computed by using the gauge-invariant atomic orbital (GIAO) method, showing a good agreement with the experimental ones. The last one UV-Vis absorption spectra were analyzed in two solvents (ethanol and water), saved in the range of 200-400 nm. In addition these, HOMO and LUMO energies, the excitation energies, density of states (DOS) diagrams, thermodynamical properties and molecular electrostatic potential surface (MEPs) were presented. Nonlinear optical (NLO) properties and thermodynamic features were performed. The experimental results are combined with the theoretical calculations using DFT calculations to fortification of the paper. At the end of this work, the results were proved our paper had been indispensable for the literature backing. Copyright © 2014 Elsevier B.V. All rights reserved.
Vibrational, NMR spectrum and orbital analysis of 3,3',5,5'-tetrabromobisphenol A: a combined experimental and computational study.

PubMed

Qiu, Shanshan; Wei, Jin; Pan, Feng; Liu, Jingping; Zhang, Aiqian

2013-03-15

In the present work, the experimental and theoretical studies on the structure, vibrations, NMR and HOMO-LUMO analysis of 3,3',5,5'-tetrabromobisphenol A (TBBPA) are presented. The FT-IR (400-4000 cm(-1)) and FT-Raman (100-4000 cm(-1)) spectra of TBBPA were recorded. The molecular geometry, vibrational frequencies were calculated by using density functional theory (DFT) method with the 6-31G(d) basis set. The optimized geometric properties, scaled vibrational wavenumbers, IR intensities, Raman activities show good agreement with the experimental data. The assigned vibrational modes of the IR and Raman spectra were compared with the corresponding properties of the polybrominated diphenyl ethers (PBDEs). Comparative analysis indicated that the red shift of C-Br vibration could probably be ascribed to the further electronic density equalization due to the p-π conjugation between O atom and the benzene. The natural bonding orbital (NBO) analysis demonstrated that the intermolecular hyperconjugative interactions are mainly formed by the orbital overlap between σ (O-H), σ(*) (C-C), π (C-C), π(*) (C-C) bond orbitals. Compared to the higher E((2)) value (33.65-34.82 kcal/mol) originated from LP(2)O to π(*) (C-C), the one (E((2)): 8.23-9.73 kcal/mol) from LP(3)Br and π(*) (C-C) contributes to the preferential tendency of C-Br breakage to the C-O breakage in the transformation. The calculated NMR results obtained on the 6-31G(d) level proves good agreement with the experimental data (r(2)=0.999). Analysis of isosurface of the related orbital shows that all the main excitation exhibit π-π(*) character localized on the benzene rings. Copyright © 2012 Elsevier B.V. All rights reserved.
Electronic torsional sound in linear atomic chains: Chemical energy transport at 1000 km/s

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kurnosov, Arkady A.; Rubtsov, Igor V.; Maksymov, Andrii O.

2016-07-21

We investigate entirely electronic torsional vibrational modes in linear cumulene chains. The carbon nuclei of a cumulene are positioned along the primary axis so that they can participate only in the transverse and longitudinal motions. However, the interatomic electronic clouds behave as a torsion spring with remarkable torsional stiffness. The collective dynamics of these clouds can be described in terms of electronic vibrational quanta, which we name torsitons. It is shown that the group velocity of the wavepacket of torsitons is much higher than the typical speed of sound, because of the small mass of participating electrons compared to themore » atomic mass. For the same reason, the maximum energy of the torsitons in cumulenes is as high as a few electronvolts, while the minimum possible energy is evaluated as a few hundred wavenumbers and this minimum is associated with asymmetry of zero point atomic vibrations. Theory predictions are consistent with the time-dependent density functional theory calculations. Molecular systems for experimental evaluation of the predictions are proposed.« less
Infrared optical constants, dielectric constants, molar polarizabilities, transition moments, dipole moment derivatives and Raman spectrum of liquid cyclohexane

NASA Astrophysics Data System (ADS)

Keefe, C. Dale; Pickup, Janet E.

2009-06-01

Previous studies have been done in this laboratory focusing on the optical properties of several liquid aromatic and aliphatic hydrocarbons in the infrared. The current study reports the infrared and absorption Raman spectra of liquid cyclohexane. Infrared spectra were recorded at 25 °C over a wavenumber range of 7400-490 cm -1. Infrared measurements were taken using transmission cells with pathlengths ranging from 3 to 5000 μm. Raman spectra were recorded between 3700 and 100 cm -1 at 25 °C using a 180° reflection geometry. Ab initio calculations of the vibrational wavenumbers at the B3LYP/6311G level of theory were performed and used to help assign the observed IR and Raman spectra. Extensive assignments of the fundamentals and binary combinations observed in the infrared imaginary molar polarizability spectrum are reported. The imaginary molar polarizability spectrum was curve fitted to separate the intensity from the various transitions and used to determine the transition moments and magnitudes of the derivatives of the dipole moment with respect to the normal coordinates for the fundamentals.
Photothermal microfluidic cantilever deflection spectroscopy reflecting clustering mechanism of ethanol water mixtures

NASA Astrophysics Data System (ADS)

Ghoraishi, Maryam; Hawk, John; Thundat, Thomas

Aqueous mixture of alcohol is a typical prototype for biomolecules, micelle formation, and structural stability of proteins. Therefore, Short chain alcohols such as EtOH have been used as a simple model for understanding of more complex aqueous biomolecules. Here we study vibrational energy peaks of EtOH water binary mixtures using micromechanical calorimetric spectroscopy using bimaterial microfluidic cantilevers (BMC). The IR spectra of EtOH-water are experimentally collected employing a BMC as concentration of EtOH changes from 20-100 wt%. As concentration of EtOH varies in the mixture, considerable shifts in the wavenumber at IR absorption peak maxima are reported. The experimentally measured shifts in the wavenumber at IR absorption peak maxima are related to changes in dipole moment (μ) of EtOH at different concentration. The relationship between IR absorption wavenumber for both anti and gauche conformers of EtOH, and inverse dipole moment, 1/ μ, of EtOH at different concentrations follows a power law dependence. Our technique offers a platform to investigate dipole effect on molecular vibrations of mixtures in confined picoliter volumes, previously unexplored with other analytical techniques due to limitations of volume under study.
Wavenumber selection based analysis in Raman spectroscopy improves skin cancer diagnostic specificity at high sensitivity levels (Conference Presentation)

NASA Astrophysics Data System (ADS)

Zhao, Jianhua; Zeng, Haishan; Kalia, Sunil; Lui, Harvey

2017-02-01

Background: Raman spectroscopy is a non-invasive optical technique which can measure molecular vibrational modes within tissue. A large-scale clinical study (n = 518) has demonstrated that real-time Raman spectroscopy could distinguish malignant from benign skin lesions with good diagnostic accuracy; this was validated by a follow-up independent study (n = 127). Objective: Most of the previous diagnostic algorithms have typically been based on analyzing the full band of the Raman spectra, either in the fingerprint or high wavenumber regions. Our objective in this presentation is to explore wavenumber selection based analysis in Raman spectroscopy for skin cancer diagnosis. Methods: A wavenumber selection algorithm was implemented using variably-sized wavenumber windows, which were determined by the correlation coefficient between wavenumbers. Wavenumber windows were chosen based on accumulated frequency from leave-one-out cross-validated stepwise regression or least and shrinkage selection operator (LASSO). The diagnostic algorithms were then generated from the selected wavenumber windows using multivariate statistical analyses, including principal component and general discriminant analysis (PC-GDA) and partial least squares (PLS). A total cohort of 645 confirmed lesions from 573 patients encompassing skin cancers, precancers and benign skin lesions were included. Lesion measurements were divided into training cohort (n = 518) and testing cohort (n = 127) according to the measurement time. Result: The area under the receiver operating characteristic curve (ROC) improved from 0.861-0.891 to 0.891-0.911 and the diagnostic specificity for sensitivity levels of 0.99-0.90 increased respectively from 0.17-0.65 to 0.20-0.75 by selecting specific wavenumber windows for analysis. Conclusion: Wavenumber selection based analysis in Raman spectroscopy improves skin cancer diagnostic specificity at high sensitivity levels.
Structural and vibrational spectroscopic studies on charge transfer and ionic hydrogen bonding interactions of melaminium benzoate dihydrate

NASA Astrophysics Data System (ADS)

Kanagathara, N.; Marchewka, M. K.; Drozd, M.; Gunasekaran, S.; Rajakumar, P. R.; Anbalagan, G.

2015-06-01

Single crystals of melaminium benzoate dihydrate (MBDH) have been grown from aqueous solution by the slow solvent evaporation method at room temperature. Crystalline nature of the grown crystal has been confirmed by X-ray powder diffraction studies. The optimized geometry, frequency and intensity of the vibrational bands of MBDH were obtained by the Hartree-Fock and density functional theory using B3LYP/cam-B3LYP with 6-311++G(d,p) basis set. The harmonic vibrational frequencies were calculated and the scaled values have been compared with the experimental FT-IR and FT-Raman spectral values. The obtained vibrational wavenumbers and optimized geometric parameters are found to be in good agreement with the experimental data. UV-Visible spectrum was recorded in the region 200-400 nm and the electronic properties, HOMO-LUMO energies and other related electronic parameters are calculated. The isotropic chemical shifts computed by 1H and 13C NMR analysis also show good agreement with experimental observation. Natural bond orbital (NBO) analysis has been performed on MBDH compound to analyze the stability of the molecule arising from hyperconjugative interactions and charge delocalization. Molecular electrostatic potential surface (MEP) has also been performed by DFT/cam-B3LYP method with 6-311++G(d,p) basis set. Differential scanning calorimetric measurements performed on the powder sample indicate the phase transition point approximately at 368 and 358 K for heating and cooling, respectively.
Structural and vibrational spectroscopic studies on charge transfer and ionic hydrogen bonding interactions of melaminium benzoate dihydrate.

PubMed

Kanagathara, N; Marchewka, M K; Drozd, M; Gunasekaran, S; Rajakumar, P R; Anbalagan, G

2015-06-15

Single crystals of melaminium benzoate dihydrate (MBDH) have been grown from aqueous solution by the slow solvent evaporation method at room temperature. Crystalline nature of the grown crystal has been confirmed by X-ray powder diffraction studies. The optimized geometry, frequency and intensity of the vibrational bands of MBDH were obtained by the Hartree-Fock and density functional theory using B3LYP/cam-B3LYP with 6-311++G(d,p) basis set. The harmonic vibrational frequencies were calculated and the scaled values have been compared with the experimental FT-IR and FT-Raman spectral values. The obtained vibrational wavenumbers and optimized geometric parameters are found to be in good agreement with the experimental data. UV-Visible spectrum was recorded in the region 200-400 nm and the electronic properties, HOMO-LUMO energies and other related electronic parameters are calculated. The isotropic chemical shifts computed by (1)H and (13)C NMR analysis also show good agreement with experimental observation. Natural bond orbital (NBO) analysis has been performed on MBDH compound to analyze the stability of the molecule arising from hyperconjugative interactions and charge delocalization. Molecular electrostatic potential surface (MEP) has also been performed by DFT/cam-B3LYP method with 6-311++G(d,p) basis set. Differential scanning calorimetric measurements performed on the powder sample indicate the phase transition point approximately at 368 and 358K for heating and cooling, respectively. Copyright © 2015 Elsevier B.V. All rights reserved.
Vibrational and electronic investigations, NLO, FMO analysis on a hetarylazoindole disperse dye by density functional theory

NASA Astrophysics Data System (ADS)

Çatıkkaş, Berna; Aktan, Ebru; Yalçın, Ergin

2016-08-01

This work deals with the optimized molecular structure, vibrational spectra, nonlinear optic (NLO) and frontier molecule orbital (FMO) properties of 1-Methyl-2-phenyl-3-(1,3,4-thiadiazol-2-yldiazenyl)-1H-indole (MPI) by quantum chemical calculations. The Fourier transform infrared (FT-MIR and FT-FIR) and Raman spectra of 1-Methyl-2-phenyl-3-(1,3,4-thiadiazol-2-yldiazenyl)-1H-indole (MPI) were recorded in the region (4000-400 cm-1 and 400-30 cm-1) and (3200-92 cm-1), respectively. The analysis and complete vibrational assignments of the fundamental modes of the MPI molecule were carried out by using the observed FT-IR and FT-Raman data and calculated Total Energy Distribution (TED) according to Scaled Quantum Mechanics procedure. The calculated geometrical parameters of the MPI molecule are in agreement with the obtained values from XRD studies. On the other hand, the difference between the scaled and observed wavenumber values of the most of the fundamentals are very small. 1H NMR and 13C NMR chemical shift values, and energy gap between LUMO-HOMO and molecular electrostatic potential (MEP) were investigated by using density functional theory (B3LYP) methods. UV/Visible spectra and λ maximum absorption values, the oscillator strengths in the chloroform, methanol and DMSO solvation in combination with different basis sets were calculated by using the time-dependent density functional theory (TD-DFT). Additionally, the predicted nonlinear optical (NLO) properties of the MPI are quite greater than that of urea at the B3LYP/6-31++G(d,p) level.
Theoretical and experimental vibrational spectroscopy study on rotational isomer of 4-phenylbutylamine

NASA Astrophysics Data System (ADS)

Ünal, A.; Okur, M.

2017-02-01

The possible four stable rotational isomers of 4-phenylbutylamine (4PBA) molecule were experimentally and theoretically studied by vibrational spectroscopy. The FT-IR (4000-400 cm-1) and Raman (3700-60 cm-1) spectra of 4PBA were recorded at room temperature in liquid phase. The complete vibrational wavenumbers and corresponding vibrational assignments of 4PBA molecule were discussed assisted with B3LYP/6-311++G(d,p) level of theory along with scaled quantum mechanics force field (SQM-FF) method. Results from experimental and theoretical data the most stable form of 4PBA molecule was obtained.
[Comparative studies on the characteristics of the Fourier-transform infrared spectra between sturgeon and shark chondroitin sulfates].

PubMed

Zheng, Jiang; Guan, Rui-Zhang; Huang, Shi-Yu

2008-01-01

The characteristics of the Fourier-transform infrared spectra of sturgeon and shark chondroitin sulfates (CHSs) were comparatively studied. The results show that sturgeon CHS exhibits special vibrations at the wavenumbers of 1 376, 1 344, 1 310, 1 157, 883 and 856 cm(-1). Further analysis shows that shark CHS contains 6-sulfated-CHS, while sturgeon CHS contains 4, 6-disulfated CHS, indicating that sturgeon CHS could have higher biological activities in decreasing the toxicity of medicine and in killing cancer cells. In general, the two kinds of CHSs have similar infrared spectra and groups of acylamino, carboxyl, sulfate, and saccharide ring. But the N-H variable-angle vibration of acylamino group of sturgeon CHS occurs at the higher wavenumber, and the vibration intensity of carboxyl group at 1 415 cm(-1) is also stronger than that of shark CHS. Chemical analysis shows that sturgeon CHS has a higher content of glucuronic acid, suggesting that it probably could be a better kind of medical materials for the bone mineralization.
Vortex-induced vibrations of a flexible cylinder at large inclination angle

PubMed Central

Bourguet, Rémi; Triantafyllou, Michael S.

2015-01-01

The free vibrations of a flexible circular cylinder inclined at 80° within a uniform current are investigated by means of direct numerical simulation, at Reynolds number 500 based on the body diameter and inflow velocity. In spite of the large inclination angle, the cylinder exhibits regular in-line and cross-flow vibrations excited by the flow through the lock-in mechanism, i.e. synchronization of body motion and vortex formation. A profound reconfiguration of the wake is observed compared with the stationary body case. The vortex-induced vibrations are found to occur under parallel, but also oblique vortex shedding where the spanwise wavenumbers of the wake and structural response coincide. The shedding angle and frequency increase with the spanwise wavenumber. The cylinder vibrations and fluid forces present a persistent spanwise asymmetry which relates to the asymmetry of the local current relative to the body axis, owing to its in-line bending. In particular, the asymmetrical trend of flow–body energy transfer results in a monotonic orientation of the structural waves. Clockwise and counter-clockwise figure eight orbits of the body alternate along the span, but the latter are found to be more favourable to structure excitation. Additional simulations at normal incidence highlight a dramatic deviation from the independence principle, which states that the system behaviour is essentially driven by the normal component of the inflow velocity. PMID:25512586
Vibrational Properties of Bulk Boric Acid 2A and 3T Polymorphs and Their Two-Dimensional Layers: Measurements and Density Functional Theory Calculations.

PubMed

Bezerra da Silva, M; Santos, R C R; Freire, P T C; Caetano, E W S; Freire, V N

2018-02-08

Boric acid (H 3 BO 3 ) is being used effectively nowadays in traps/baits for the management of Aedes aegypti L. and Aedes albopictus Skuse species of mosquitoes, which are the main spreading vectors worldwide for diseases such as malaria, dengue, and zika. Previously, we published results on the structural, electronic, and optical properties of its molecular triclinic H 3 BO 3 -2A and trigonal H 3 BO 3 -3T polymorphs within the framework of density functional theory (DFT). Because of the renewed importance of these materials, the focus of this work is on the vibrational properties of the bulk boric acid 2A and 3T polymorphs. We measured the infrared and Raman spectra of the former, which was accompanied and interpreted through state-of-the-art DFT calculations, supplemented by computations regarding the H 3 BO 3 molecule and two-dimensional layers based on the bulk structures. We identify/assign their normal modes and find vibrational signatures for each polymorph as well as in- and out-of-plane motions and molecular vibrations, unveiling a nice agreement between the DFT level of theory employed and our improved spectroscopic measurements in the wavenumber ranges of 400-2000 cm -1 (infrared) and 0-1500 cm -1 (Raman). We show that a dispersion-corrected DFT functional within the generalized gradient approximation (GGA) can be very accurate in describing the vibrational properties of the boric acid polymorphs. Besides, several issues left open/not clearly resolved in previously published works on the vibrational mode assignments of the bulk and 2D sheets of boric acid are explained satisfactorily. Finally, phonon dispersions and associated densities of states were also evaluated for each polymorph along with their temperature-dependent DFT-calculated entropy, enthalpy, free energy, heat capacity, and Debye temperature. In particular, our DFT calculations suggest a possible way to differentiate the 2A and 3T boric acid polymorphs through Raman spectroscopy and heat capacity measurements.
FT-IR, UV-vis, 1H and 13C NMR spectra and the equilibrium structure of organic dye molecule disperse red 1 acrylate: a combined experimental and theoretical analysis.

PubMed

Cinar, Mehmet; Coruh, Ali; Karabacak, Mehmet

2011-12-01

This study reports the characterization of disperse red 1 acrylate compound by spectral techniques and quantum chemical calculations. The spectroscopic properties were analyzed by FT-IR, UV-vis, (1)H NMR and (13)C NMR techniques. FT-IR spectrum in solid state was recorded in the region 4000-400 cm(-1). The UV-vis absorption spectrum of the compound that dissolved in methanol was recorded in the range of 200-800 nm. The (1)H and (13)C NMR spectra were recorded in CDCl(3) solution. The structural and spectroscopic data of the molecule in the ground state were calculated using density functional theory (DFT) employing B3LYP exchange correlation and the 6-311++G(d,p) basis set. The vibrational wavenumbers were calculated and scaled values were compared with experimental FT-IR spectrum. A satisfactory consistency between the experimental and theoretical spectra was obtained and it shows that the hybrid DFT method is very useful in predicting accurate vibrational structure, especially for high-frequency region. The complete assignments were performed on the basis of the experimental results and total energy distribution (TED) of the vibrational modes, calculated with scaled quantum mechanics (SQM) method. Isotropic chemical shifts were calculated using the gauge-invariant atomic orbital (GIAO) method. A study on the electronic properties were performed by timedependent DFT (TD-DFT) and CIS(D) approach. To investigate non linear optical properties, the electric dipole moment μ, polarizability α, anisotropy of polarizability Δα and molecular first hyperpolarizability β were computed. The linear polarizabilities and first hyperpolarizabilities of the studied molecule indicate that the compound can be a good candidate of nonlinear optical materials. Copyright © 2011 Elsevier B.V. All rights reserved.
Quantum mechanical, spectroscopic study (FT-IR and FT - Raman), NBO analysis, HOMO-LUMO, first order hyperpolarizability and docking studies of a non-steroidal anti-inflammatory compound

NASA Astrophysics Data System (ADS)

Sakthivel, S.; Alagesan, T.; Muthu, S.; Abraham, Christina Susan; Geetha, E.

2018-03-01

Experimental and theoretical studies on the optimized geometrical structure, electronic and vibrational characteristics of (+)-(S)-2-(6-methoxynaphthalen-2-yl) propanoic acid are presented employing B3LYP/6-311++G (d,p) basis set. Simulated FT-IR and FT-Raman spectra were in concurrence with the observed spectra attained in a spectral range of FT-IR (4000 - 400 cm-1) and FT-Raman (4000 - 100 cm-1). Quantum chemical calculations and the comprehensive vibrational assignments of wavenumbers of the optimized geometry using Potential Energy Distribution (PED) were calculated with scaled quantum mechanics. The infrared intensities and Raman intensities of (+)-(S)-2-(6-methoxynaphthalen-2-yl) propanoic acid were reported. Frontier molecular orbital analysis and reactivity parameters were calculated. Molecular Electrostatic Potential (MEP), Natural Bond Orbital (NBO) analysis, Non Linear Optical (NLO) behavior and thermodynamic properties were studied. In addition, the Mulliken charge distribution and Fukui function were analyzed. Molecular docking was used to dock in the title molecule into the active site of the protein 5L9B which belongs to the class of proteins exhibiting the property as a HIF1A (Hypoxia-inducible factor 1-alpha) expression inhibitor and the minimum binding energy was detected to be -6.2 kcal/mol.
A Theoretical Study on N'-[(Z)-(4-Methylphenyl)Methylidene]-4-Nitrobenzohydrazide (NMPMN)

NASA Astrophysics Data System (ADS)

Okur, Muhammet; Albayrak, Nazmiye; Tamer, Ömer; Avcı, Davut; Atalay, Yusuf

2018-05-01

Quantum mechanical calculations of ground state energy, vibration wavenumbers, and electronic absorption wavelengths of N'-[(Z)-(4-methylphenyl)methylidene]-4-nitrobenzohydrazide with C15H13N3O3 empirical formula was performed by using Gaussian 09 program. Becke's three-parameter exchange functional in conjunction with the Lee-Yang-Parr correlation functional and Heyd-Scuseria-Ernzerhof functional levels of density functional theory (DFT) with the 6-311++G(d,p) basis set were used in the performing of above mentioned calculations. The highest occupied and lowest unoccupied molecular orbital (HOMO and LUMO) energies have been also calculated at the same levels. Stability of the molecule arising from hyperconjugative interactions and charge delocalization has been analyzed using natural bond orbital (NBO) analysis. Nonlinear optical (NLO) behavior of the title molecule has been examined by the determining of electric dipole moment (μ), polarizability (α), and static first-order hyperpolarizability (β). Finally, molecular electrostatic potential (MEP) surface as well as Mulliken and NBO atomic charges were calculated by using Gaussian 09 program.
On the calculation of the complex wavenumber of plane waves in rigid-walled low-Mach-number turbulent pipe flows

NASA Astrophysics Data System (ADS)

Weng, Chenyang; Boij, Susann; Hanifi, Ardeshir

2015-10-01

A numerical method for calculating the wavenumbers of axisymmetric plane waves in rigid-walled low-Mach-number turbulent flows is proposed, which is based on solving the linearized Navier-Stokes equations with an eddy-viscosity model. In addition, theoretical models for the wavenumbers are reviewed, and the main effects (the viscothermal effects, the mean flow convection and refraction effects, the turbulent absorption, and the moderate compressibility effects) which may influence the sound propagation are discussed. Compared to the theoretical models, the proposed numerical method has the advantage of potentially including more effects in the computed wavenumbers. The numerical results of the wavenumbers are compared with the reviewed theoretical models, as well as experimental data from the literature. It shows that the proposed numerical method can give satisfactory prediction of both the real part (phase shift) and the imaginary part (attenuation) of the measured wavenumbers, especially when the refraction effects or the turbulent absorption effects become important.
Nonplanar tertiary amides in rigid chiral tricyclic dilactams. Peptide group distortions and vibrational optical activity.

PubMed

Pazderková, Markéta; Profant, Václav; Hodačová, Jana; Sebestík, Jaroslav; Pazderka, Tomáš; Novotná, Pavlína; Urbanová, Marie; Safařík, Martin; Buděšínský, Miloš; Tichý, Miloš; Bednárová, Lucie; Baumruk, Vladimír; Maloň, Petr

2013-08-22

We investigate amide nonplanarity in vibrational optical activity (VOA) spectra of tricyclic spirodilactams 5,8-diazatricyclo[6,3,0,0(1,5)]undecan-4,9-dione (I) and its 6,6',7,7'-tetradeuterio derivative (II). These rigid molecules constrain amide groups to nonplanar geometries with twisted pyramidal arrangements of bonds to amide nitrogen atoms. We have collected a full range vibrational circular dichroism (VCD) and Raman optical activity (ROA) spectra including signals of C-H and C-D stretching vibrations. We report normal-mode analysis and a comparison of calculated to experimental VCD and ROA. The data provide band-to-band assignment and offer a possibility to evaluate roles of constrained nonplanar tertiary amide groups and rigid chiral skeletons. Nonplanarity shows as single-signed VCD and ROA amide I signals, prevailing the couplets expected to arise from the amide-amide interaction. Amide-amide coupling dominates amide II (mainly C'-N stretching, modified in tertiary amides by the absence of a N-H bond) transitions (strong couplet in VCD, no significant ROA) probably due to the close proximity of amide nitrogen atoms. At lower wavenumbers, ROA spectra exhibit another likely manifestation of amide nonplanarity, showing signals of amide V (δ(oop)(N-C) at ~570 cm(-1)) and amide VI (δ(oop)(C'═O) at ~700 cm(-1) and ~650 cm(-1)) vibrations.
ExoMol line lists - XXIX. The rotation-vibration spectrum of methyl chloride up to 1200 K

NASA Astrophysics Data System (ADS)

Owens, A.; Yachmenev, A.; Thiel, W.; Fateev, A.; Tennyson, J.; Yurchenko, S. N.

2018-06-01

Comprehensive rotation-vibration line lists are presented for the two main isotopologues of methyl chloride, 12CH335Cl and 12CH337Cl. The line lists, OYT-35 and OYT-37, are suitable for temperatures up to T = 1200 K and consider transitions with rotational excitation up to J = 85 in the wavenumber range 0-6400 cm-1 (wavelengths λ > 1.56 μm). Over 166 billion transitions between 10.2 million energy levels have been calculated variationally for each line list using a new empirically refined potential energy surface, determined by refining to 739 experimentally derived energy levels up to J = 5, and an established ab initio dipole moment surface. The OYT line lists show excellent agreement with newly measured high-temperature infrared absorption cross-sections, reproducing both strong and weak intensity features across the spectrum. The line lists are available from the ExoMol database and the CDS database.
FTIR, FT-Raman, FT-NMR and quantum chemical investigations of 3-acetylcoumarin.

PubMed

Arjunan, V; Sakiladevi, S; Marchewka, M K; Mohan, S

2013-05-15

3-Acetylcoumarin (3AC) was synthesised by a Knoevenagel reaction. Conformational analysis using the B3LYP method was also carried out to determine the most stable conformation of the compound. FTIR and FT-Raman spectra of 3AC have been recorded in the range 4000-400 and 4000-100 cm(-1), respectively. (1)H and (13)C NMR spectra have also been recorded. The complete vibrational assignment and analysis of the fundamental modes of the compound were carried out using the experimental FTIR and FT-Raman data and quantum mechanical studies. The experimental vibrational frequencies were compared with the wavenumbers obtained theoretically from the DFT-B3LYP/B3PW91 gradient calculations employing the standard 6-31G(**), high level 6-311++G(**) and cc-pVTZ basis sets for optimised geometry of the compound. The frontier molecular orbital energies of the compound are determined by DFT method. Copyright © 2013 Elsevier B.V. All rights reserved.

A FINITE-DIFFERENCE, DISCRETE-WAVENUMBER METHOD FOR CALCULATING RADAR TRACES

EPA Science Inventory

A hybrid of the finite-difference method and the discrete-wavenumber method is developed to calculate radar traces. The method is based on a three-dimensional model defined in the Cartesian coordinate system; the electromagnetic properties of the model are symmetric with respect ...
Detection of OH stretching mode of CH3OH chemisorbed on Ni3+ and Ni4+ by infrared photodissociation spectroscopy.

PubMed

Hirabayashi, Shinichi; Okawa, Ryuji; Ichihashi, Masahiko; Kondow, Tamotsu; Kawazoe, Yoshiyuki

2007-08-09

Structures of nickel cluster ions adsorbed with methanol, Ni3+ (CH3OH)m (m = 1-3) and Ni4+ (CH3OH)m (m = 1-4) were investigated by using infrared photodissociation (IR-PD) spectroscopy based on a tandem-type mass spectrometer, where they were produced by passing Ni3,4+ through methanol vapor under a multiple collision condition. The IR-PD spectra were measured in the wavenumber region between 3100 and 3900 cm-1. In each IR-PD spectrum, a single peak was observed at a wavenumber lower by approximately 40 cm-1 than that of the OH stretching vibration of a free methanol molecule and was assigned to the OH stretching vibrations of the methanol molecules in Ni3,4+ (CH3OH)m. The photodissociation was analyzed by assuming that Ni3,4+ (CH3OH)m dissociate unimolecularly after the photon energy absorbed by them is statistically distributed among the accessible modes of Ni3,4+ (CH3OH)m. In comparison with the calculations performed by the density functional theory, it is concluded that (1) the oxygen atom of each methanol molecule is bound to one of the nickel atoms in Ni3,4+ (defined as molecular chemisorption), (2) the methanol molecules in Ni3,4+ (CH3OH)m do not form any hydrogen bonds, and (3) the cross section for demethanation [CH4 detachment from Nin+ (CH3OH)] is related to the electron density distribution inside the methanol molecule.
Structures and vibrational spectra of pinacol.. 1. Infrared and matrix infrared spectra of monomeric pinacol. Ab initio calculations on conformers and vibrational frequencies

NASA Astrophysics Data System (ADS)

Dahlqvist, Martti; Hotokka, Matti; Räsänen, Markku

1998-04-01

The infrared spectra of monomeric pinacol molecules (2,3-dimethyl-2,3-butanediol; (CH 3) 2C(OH)C(OH)(CH 3) 2) have been recorded in the gas phase and dilute nonpolar solutions, and in an argon matrix. The vibrational data are consistent with the intramolecularly hydrogen-bonded G-type (gauche with respect to the central C-C bond) conformers and there is no evidence for the T-type (trans with respect to the central C-C bond) conformers, which have been observed in the condensed phases. This was confirmed by studying the infrared region 835-815 cm -1, which was found to be the most indicative to show spectral changes within the type of the conformers. In this region the band of the T-type conformers (assigned to the hybridized asymmetric vibration of the central CC and CO stretching modes) disappears when going from the condensed phases to phases, where pinacol molecules are monomeric. Ab initio HF/6-311G** (MP2/6-311G**) calculations support the experimental findings; the calculated relative energies for the tGg', gGg', g'Gg', tTt, and gTg' conformers are 0.0 (0.0), 3.4 (3.4), 5.1 (5.9), 7.9 (11.3), and 12.0 (14.0) kJ mol -1, respectively. Consequently, only the G-type conformers are sufficiently populated to give rise to observable spectral lines. Both experimental findings and theoretical calculations demonstrated that the bands in the argon matrix spectrum of pinacol are due to the most stable tGg' conformer. Although the ab initio calculations predict that also the gGg' and g'Gg' conformers are present in the gas phase and in dilute nonpolar solutions their existence could not be confirmed experimentally. Hence, we conclude that the conformation sensitive bands may coincide in the spectra. The HF/6-311G** ab initio calculations for vibrational frequencies of pinacol are consistent with this conclusion, suggesting only small differences between the wavenumbers of the G-type conformers. Pinacol does not show infrared-induced photorotamerization in the low-temperature argon matrix. This is due to the high energy barrier to internal rotation around the central C-C bond as demonstrated by ab initio calculations. Assignments of the vibrational bands were made with the aid of computer animations of the ab initio calculated harmonic vibrations, common group frequencies, and analogy conclusions from related compounds. The deuterium derivatives [(CD 3) 2C(OH)C(OH)(CD 3) 2 and (CH 3) 2C(OD)C(OD)(CH 3) 2] of pinacol were also utilized even though their spectra were recorded only in the condensed phases.
A FINITE-DIFFERENCE, DISCRETE-WAVENUMBER METHOD FOR CALCULATING RADAR TRACES

EPA Science Inventory

A hybrid of the finite-difference method and the discrete-wavenumber method is developed to calculate radar traces. The method is based on a three-dimensional model defined in the Cartesian coordinate system; the electromag-netic properties of the model are symmetric with respect...
Structural, vibrational and thermal studies of a new nonlinear optical crystal tetrapropylammonium dihydrogenmonoarsenate bis arsenic acid.

PubMed

Dhouib, Ikram; Feki, Habib; Guionneau, Philippe; Mhiri, Tahar; Elaoud, Zakaria

2014-10-15

Single crystals of tetrapropylammonium dihydrogenmonoarsenate bis arsenic acid [CH3CH2CH2]4N (H2AsO4) (H3AsO4)2, a potential new nonlinear optical (NLO) material of interest were prepared by the slow evaporation technique and characterized by means of single-crystal X-ray diffraction, thermal analysis, FT-IR and Raman spectroscopy. The title compound belongs to the monoclinic space group Ia with the following unit cell dimensions: a=8.116(2) Ǻ, b=33.673(4) Ǻ, c=8.689(2) Ǻ, β=95.34(2)°. The structure consists of infinite parallel two-dimensional planes built of mutually [H2AsO4(-)] and [H3AsO4] tetrahedra connected by strong O-H⋯O hydrogen bonding giving birth to trimmers. The planes of inorganic groups are alternated with those of the organic cations. The geometry, first hyperpolarizability and harmonic vibrational wavenumbers were calculated by means of density functional theory DFT with the B3LYP/6-31G(d) level of theory. Good consistency was found between the calculated results and the experimental structure, IR, and Raman spectra. The detailed interpretation of the vibrational modes was carried out building on the proposed DFT calculations as primary source of assignment and by comparison with the spectroscopic studies of similar compounds. The first hyperpolarizability βtot of the title compound is about 14.6 times more than that of the reference crystal KDP, which may explain the importance of the compound under study. Copyright © 2014 Elsevier B.V. All rights reserved.
Conformational stability, spectroscopic (FT-IR, FT-Raman and UV-Vis) analysis, NLO, NBO, FMO and Fukui function analysis of 4-hexylacetophenone by density functional theory.

PubMed

Saravanan, S; Balachandran, V

2015-03-05

The experimental and theoretical study on the structures and vibrations of 4-hexylacetophenone (abbreviated as 4HAP) are presented. The FT-IR and FT-Raman spectra of the title compound have been recorded in the region 4000-400cm(-1) and 3500-100cm(-1) respectively. The molecular structures, vibrational wavenumbers, infrared intensities and Raman activities were calculated using DFT (B3LYP and LSDA) method with 6-311++G(d,p) basis set. The most stable conformer of 4HAP is identified from the computational results. The assignments of the vibrational spectra have been carried out with the aid of normal coordinate analysis (NCA) following the scaled quantum mechanical force field methodology (SQMEF). The linear polarizability (α) and the first hyperpolarizability (βtot) values of the investigated molecule have been computed using B3LYP and LSDA with 6-311++G(d,p) basis set. Stability of the molecule arising from hyper conjugative interaction and charge transfer delocalization has been analyzed using natural bond orbital (NBO) analysis. The molecule orbital contributions are studied by density of energy states (DOSs). UV-Vis spectrum and effects of solvents have been discussed effects of solvents have been discussed and the electronic properties such as HOMO and LUMO energies were determined by time-dependent TD-DFT approach. Fukui function and Mulliken analysis on atomic charges of the title compound have been calculated. Finally, electrophilic and nucleophilic descriptors of the title molecule have been calculated. Copyright © 2014 Elsevier B.V. All rights reserved.
Molecular docking and structural analysis of non-opioid analgesic drug acemetacin with halogen substitution: A DFT approach

NASA Astrophysics Data System (ADS)

Leenaraj, D. R.; Manimaran, D.; Joe, I. Hubert

2016-11-01

Acemetacin is a non-opioid analgesic which belongs to the class, the non-steroidal anti-inflammatory drug. The bioactive conformer was identified through potential energy surface scan studies. Spectral features of acemetacin have been probed by the techniques of Fourier transform infrared, Raman and Nuclear magnetic resonance combined with density functional theory calculations at the B3LYP level with 6-311 + G(d,p) basis set. The detailed interpretation of vibrational spectral assignments has been carried out on the basis of potential energy distribution method. Geometrical parameters reveal that the carbonyl substitution in between chlorophenyl and indole ring leads to a significant loss of planarity. The red-shifted Cdbnd O stretching wavenumber describe the conjugation between N and O atoms. The shifted Csbnd H stretching wavenumbers of Osbnd CH3 and Osbnd CH2 groups depict the back-donation and induction effects. The substitution of halogen atoms on the title molecule influences the charge distribution and the geometrical parameters. Drug activity and binding affinity of halogen substitution in title molecule with target protein were undertaken by molecular docking study. This study enlightens the effects of bioefficiency due to the halogen substitution in the molecule.
Experimental and theoretical infrared spectra of famotidine and its interaction with ofloxacin

NASA Astrophysics Data System (ADS)

Sagdinc, Seda; Bayarı, Sevgi

2005-06-01

We present FTIR spectrum of B polymorphic forms of famotidine (fam) that is a powerful histamine H2-receptor antagonist used in the treatment of peptic ulcer. Molecular mechanics and semi empirical AM1, PM3, MNDO and MINDO3 methods have been used to study the molecular geometry, and the harmonic vibrational spectra with the purpose to assist the experimental assignments of famotidine. The calculated geometric parameters have been compared to the corresponding X-ray structure of famotidine and it is found that AM1 structure in agreement with the crystal data. We are also investigated the interaction of famotidine with ofloxacin which is a synthetic antimicrobial agent. The changes observed in the some bands (wavenumber, shape) of interacted compound indicated that there is a weak interaction between two molecules. PM3 calculations are also carried out to determine the possible molecular structure of the interacted compound.
First principle study of a potential bioactive molecule with tetrahydroisoquinoline, carbothiomide and adamantane scaffolds

NASA Astrophysics Data System (ADS)

Al-Shehri, Mona M.; Al-Majed, Abdul-Rahman A.; Aljohar, Haya I.; El-Emam, Ali A.; Pathak, Shilendra K.; Sachan, Alok K.; Prasad, Onkar; Sinha, Leena

2017-09-01

The FT-Raman and FT-IR spectra of N-(adamantan-1-yl)-1,2,3,4-tetrahydroisoquinoline-2-carbothioamide were recorded and investigated. The DFT/M06-2X/6-311++G(d,p) method was used to compute the vibrational wavenumbers. The effect of solvents (water, carbon tetrachloride and chloroform) on the dipole moment and polarizability has been evaluated. UV-Vis spectrum of the title compound was recorded and compared with the theoretical spectrum calculated by TD-DFT approach. To investigate the movement of electrons within the system when excited, the difference of the excited and ground state densities has also been plotted. The molecular docking studies reveals that the investigated compound may exhibit HIV-1 Protease inhibitory activity.
Infrared, Raman and NMR spectra, conformational stability, normal coordinate analysis and B3LYP calculations of 5-Amino-3-methyl-1-phenyl-1H-pyrazole-4-carbaldehyde

NASA Astrophysics Data System (ADS)

Bahgat, Khaled; EL-Emary, Talaat

2013-02-01

FT Raman and IR spectra of the crystallized biologically active molecule, 5-Amino-3-methyl-1-phenyl-1H-pyrazole-4-carbaldehyde (5-APHC, C11H11N3O) have been recorded and analyzed. The equilibrium geometry, bonding features and harmonic vibrational frequencies of 5-APHC have been investigated with the help of B3LYP density functional theory (DFT) method with 6-31G(d) and 6-311+G(d,p) as basis set. The calculated molecular geometry has been compared with the experimental data. The assignments of the vibrational spectra have been carried out with the help of normal coordinate analysis (NCA) following the scaled quantum mechanical force field (SQM) technique. The optimized geometry shows the co-planarity of the aldehyde group with pyrazole ring. Potential energy surface (PES) scan studies has also been carried out by ab initio calculations with B3LYP/6-311+G(d,p) basis set. The red shifting of NH2 stretching wavenumber indicates the formation of N-H⋯O hydrogen bonding. 1H and 13C NMR spectra were recorded and 1H and 13C nuclear magnetic resonance chemical shifts of the molecule were calculated using the gauge independent atomic orbital (GIAO) method. UV-Vis spectrum of the compound was recorded in the region 200-400 nm and the electronic properties HOMO and LUMO energies were calculated by time-dependent TD-DFT approach. Mulliken charges of the 5-APHC molecule was also calculated and interpreted.
Vibrational tug-of-war: The pKA dependence of the broad vibrational features of strongly hydrogen-bonded carboxylic acids

NASA Astrophysics Data System (ADS)

Van Hoozen, Brian L.; Petersen, Poul B.

2018-04-01

Medium and strong hydrogen bonds give rise to broad vibrational features frequently spanning several hundred wavenumbers and oftentimes exhibiting unusual substructures. These broad vibrational features can be modeled from first principles, in a reduced dimensional calculation, that adiabatically separates low-frequency modes, which modulate the hydrogen bond length, from high-frequency OH stretch and bend modes that contribute to the vibrational structure. Previously this method was used to investigate the origin of an unusual vibrational feature frequently found in the spectra of dimers between carboxylic acids and nitrogen-containing aromatic bases that spans over 900 cm-1 and contains two broad peaks. It was found that the width of this feature largely originates from low-frequency modes modulating the hydrogen bond length and that the structure results from Fermi resonance interactions. In this report, we examine how these features change with the relative acid and base strength of the components as reflected by their aqueous pKA values. Dimers with large pKA differences are found to have features that can extend to frequencies below 1000 cm-1. The relationships between mean OH/NH frequency, aqueous pKA, and O-N distance are examined in order to obtain a more rigorous understanding of the origin and shape of the vibrational features. The mean OH/NH frequencies are found to correlate well with O-N distances. The lowest OH stretch frequencies are found in dimer geometries with O-N distances between 2.5 and 2.6 Å. At larger O-N distances, the hydrogen bonding interaction is not as strong, resulting in higher OH stretch frequencies. When the O-N distance is smaller than 2.5 Å, the limited space between the O and N determines the OH stretch frequency, which gives rise to frequencies that decrease with O-N distances. These two effects place a lower limit on the OH stretch frequency which is calculated to be near 700 cm-1. Understanding how the vibrational features of strongly hydrogen-bonded structures depend on the relative pKA and other structural parameters will guide studies of biological structures and analysis of proton transfer studies using photoacids.
Molecular structure, spectroscopic (FTIR, FT-Raman, 13C and 1H NMR, UV), polarizability and first-order hyperpolarizability, HOMO-LUMO analysis of 2,4-difluoroacetophenone

NASA Astrophysics Data System (ADS)

Jeyavijayan, S.

2015-02-01

The FTIR and FT-Raman spectra of 2,4-difluoroacetophenone (DFAP) have been recorded in the regions 4000-400 cm-1 and 3500-50 cm-1, respectively. Utilizing the observed FTIR and FT-Raman data, a complete vibrational assignment and analysis of the fundamental modes of the compound were carried out. The optimum molecular geometry, harmonic vibrational frequencies, infrared intensities and Raman scattering activities, were calculated by density functional theory (DFT/B3LYP) method with 6-31+G(d,p) and 6-311++G(d,p) basis sets. The difference between the observed and scaled wavenumber values of most of the fundamentals is very small. A detailed interpretation of the infrared and Raman spectra of DFAP is also reported based on total energy distribution (TED). Stability of the molecule arising from hyperconjugative interactions, charge delocalization have been analyzed using natural bond orbital (NBO) analysis. The MEP map shows the negative potential sites are on oxygen atom as well as the positive potential sites are around the hydrogen atoms. The UV-Vis spectral analysis of DFAP has also been done which confirms the charge transfer of DFAP. The chemical shifts of H atoms and C atoms were calculated using NMR analysis. Furthermore, the polarizability, the first hyperpolarizability and total dipole moment of the molecule have been calculated.
Low temperature investigations of dynamic properties in l-leucine - chloranilic acid complex.

PubMed

Hetmańczyk, J; Nowicka-Scheibe, J; Maurin, J K; Pawlukojć, A

2018-07-05

Inelastic neutron scattering (INS) and infra-red (IR) spectroscopy methods were used for determination of dynamic structure of l-leucine - chloranilic acid complex. A theoretical dynamic pattern calculated by the density functional theory (DFT) method for periodic boundary conditions accompanied the experimental ones. Normal modes in the vibrational spectra were defined and described. The characteristic presence of the Hadži's trio enriched by numerous submaxima is observed in the wavenumber range 3200-800 cm -1 . Bands assigned to CH 3 torsion vibrations in the leucine cation were observed at 231 cm -1 and 258 cm -1 in the INS spectrum. Temperature-dependent far-infrared spectra in the temperature range 9 K-290 K were obtained. Vibrational bands were analyzed as a function of temperature. Activation energies for reorientational motion of CH 3 and CH 2 groups were determined by means of the band shape analysis performed for torsional and twisting vibrations of these groups. The estimated energy is equal to E a  = 2.7 ± 0.2 kJ/mol and E a  = 2.17 ± 0.12 kJ/mol for CH 3 and CH 2 groups, respectively. A phase transition at about 130 K in the l-leucine - chloranilic acid complex was observed. Copyright © 2018 Elsevier B.V. All rights reserved.
Synthesis, spectroscopic (FT-IR, FT-Raman, NMR, UV-Visible), Fukui function, antimicrobial and molecular docking study of (E)-1-(3-bromobenzylidene)semicarbazide by DFT method

NASA Astrophysics Data System (ADS)

Raja, M.; Raj Muhamed, R.; Muthu, S.; Suresh, M.; Muthu, K.

2017-02-01

The title compound, (E)-1-(3-bromobenzylidene)semicarbazide (3BSC) was synthesized and characterized by FT-IR, FT-Raman, UV, 1HNMR and 13CNMR spectral analysis. The optimized molecular geometry, the vibrational wavenumbers, the infrared intensities and the Raman scattering activities were calculated by using density functional theory (DFT) B3LYP method with 6-311++G(d,p) basis set. The calculated HOMO and LUMO energies show that charge transfer within the molecule. Stability of the molecule arising from hyperconjugative interactions, charge delocalization have been analyzed using natural bond orbital analysis (NBO). The hyperpolarizability calculation reveals the present material has a reasonably good propensity for nonlinear optical activity. Molecular electrostatic potential (MEP) and Fukui functions were also performed. The thermodynamic properties (heat capacity, entropy, and enthalpy) of the 3BSC at different temperatures have been calculated. The biological applications of 3BSC have been screened for its antimicrobial activity and found to exhibit antifungal and antibacterial effects. In addition, the Molecular docking was also performed for the different receptors.
Effect of Methyl Substitution on the N-H···O Interaction in Complexes of Pyrrole with Water, Methanol, and Dimethyl Ether: Matrix Isolation Infrared Spectroscopy and ab Initio Computational Studies.

PubMed

Sarkar, Shubhra; Ramanathan, N; Sundararajan, K

2018-03-08

Hydrogen-bonded interactions of pyrrole with water and methanol have been studied using matrix isolation infrared spectroscopy and compared with the calculation performed on dimethyl ether. Computations carried out at MP2/aug-cc-pVDZ level of theory yielded two minima for the pyrrole-water and pyrrole-methanol complexes. The global and local minima correspond to the N-H···O and O-H···π complexes, respectively, where the N-H group of pyrrole interacts with oxygen of water/methanol and O-H of water and methanol interacts with the π cloud of pyrrole. Computations performed on the pyrrole-dimethyl ether gave only N-H···O type complex. From the experimental vibrational wavenumber shifts in the N-H stretching and N-H bending modes of pyrrole, as well as in the O-H stretching modes of water and methanol, the 1:1 N-H···O complexes were discerned. The strength of the N-H···O hydrogen bond and the corresponding shift in the N-H stretching vibrational wavenumbers increases in the order pyrrole-water < pyrrole-methanol < pyrrole-dimethyl ether, where a proton is successively replaced by a methyl group. Apart from the 1:1 complexes, higher clusters of 2:1 and 1:2 pyrrole-water and pyrrole-methanol complexes were also generated in N 2 matrix. Atoms in molecules and natural bond orbital analyses were carried out at the MP2/aug-cc-pVDZ level to understand the nature of interaction in the 1:1 pyrrole-water, pyrrole-methanol and pyrrole-dimethyl ether complexes.
Spectroscopic investigations and molecular docking study of 3-(1H-imidazol-1-yl)-1-phenylpropan-1-one, a potential precursor to bioactive agents

NASA Astrophysics Data System (ADS)

Al-Alshaikh, Monirah A.; Mary Y, Sheena; Panicker, C. Yohannan; Attia, Mohamed I.; El-Emam, Ali A.; Alsenoy, C. Van

2016-04-01

The optimized molecular structure, vibrational wavenumbers, corresponding vibrational assignments of 3-(1H-imidazol-1-yl)-1-phenylpropan-1-one have been investigated theoretically and experimentally. The calculated geometrical parameters of the title compound are in agreement with the reported XRD data. The HOMO and LUMO analysis is used to determine the charge transfer within the molecule. The stability of the molecule arising from hyper-conjugative interaction and charge delocalization has been analyzed using NBO analysis. Molecular electrostatic potential was performed by the DFT method and from the MEP plot, it is evident that the negative charge covers the carbonyl group and the nitrogen atom N3 of the imidazole ring and the positive region is over the remaining portions of the molecule. The first and second hyperpolarizabilities are calculated and the first hyperpolarizability of the title compound is 16.99 times that of standard NLO material urea and the title compound and its derivatives are good object for further studies in nonlinear optics. The docked ligand title compound forms a stable complex with plasmodium falciparum and gives a binding affinity value of -5.5 kcal/mol and the preliminary results suggest that the compound might exhibit antimalarial activity against plasmodium falciparum.
Combine experimental and theoretical investigation on an alkaloid-Dimethylisoborreverine

NASA Astrophysics Data System (ADS)

Singh, Swapnil; Singh, Harshita; Karthick, T.; Agarwal, Parag; Erande, Rohan D.; Dethe, Dattatraya H.; Tandon, Poonam

2016-01-01

A combined experimental (FT-IR, 1H and 13C NMR) and theoretical approach is used to study the structure and properties of antimalarial drug dimethylisoborreverine (DMIB). Conformational analysis, has been performed by plotting one dimensional potential energy curve that was computed using density functional theory (DFT) with B3LYP/6-31G method and predicted conformer A1 as the most stable conformer. After full geometry optimization, harmonic wavenumbers were computed for conformer A1 at the DFT/B3LYP/6-311++G(d,P) level. A complete vibrational assignment of all the vibrational modes have been performed on the bases of the potential energy distribution (PED) and theoretical results were found to be in good agreement with the observed data. To predict the solvent effect, the UV-Vis spectra were calculated in different solvents by polarizable continuum model using TD-DFT method. Molecular docking studies were performed to test the biological activity of the sample using SWISSDOCK web server and Hex 8.0.0 software. The molecular electrostatic potential (MESP) was plotted to identify the reactive sites of the molecule. Natural bond orbital (NBO) analysis was performed to get a deep insight of intramolecular charge transfer. Thermodynamical parameters were calculated to predict the direction of chemical reaction.
Investigation of antimicrobial activities, DNA interaction, structural and spectroscopic properties of 2-chloro-6-(trifluoromethyl)pyridine

NASA Astrophysics Data System (ADS)

Evecen, Meryem; Kara, Mehmet; Idil, Onder; Tanak, Hasan

2017-06-01

2-Chloro-6-(trifluoromethyl)pyridine has been characterized by FT-IR, 1H and 13C NMR experiment. FT-IR spectra of the molecule has been recorded in the 4000-400 cm-1 region. The molecular structural parameters and vibrational frequencies were computed using the HF and DFT (B3LYP, B3PW91) methods with the 6-31+G(d,p) and 6-311++G(d,p) basis sets. 1H and 13C NMR Gauge Including Atomic Orbital (GIAO) chemical shifts of the compound were calculated using the density functional method (B3LYP) with the 6-311++G(d,p) basis set. The vibrational wavenumbers and chemical shifts were compared with the experimental data of the compound. Using the TD-DFT methodology, electronic absorption spectra of the compound have been computed. Besides, solvent effects on the excitation energies and chemical shifts were carried out using the integral equation formalism of the polarisable continuum model (IEF-PCM). DFT calculations of the compound, Mulliken's charges, molecular electrostatic potential (MEP), natural bond orbital (NBO) and thermodynamic properties were also obtained theoretically. In addition, the antimicrobial activities were tested by using minimal inhibitory concentration method (MIC) and also the effect of the molecule on pBR322 plasmid DNA was monitored byagarose gel electrophoresis experiments.
Electronic absorption, vibrational spectra, nonlinear optical properties, NBO analysis and thermodynamic properties of N-(4-nitro-2-phenoxyphenyl) methanesulfonamide molecule by ab initio HF and density functional methods.

PubMed

Rajamani, T; Muthu, S; Karabacak, M

2013-05-01

In this work, the vibrational spectral analysis was carried out by using FT-Raman and FT-IR spectroscopy in the range 4000-100 cm(-1) and 4000-400 cm(-1), respectively, for N-(4-nitro-2-phenoxyphenyl) methanesulfonamide molecule. Theoretical calculations were performed by ab initio RHF and density functional theory (DFT) method using 6-31G(d,p) and 6-311G(d,p) basis sets. The complete vibrational assignments of wavenumbers were made on the basis of potential energy distribution (PED). The results of the calculations were applied to simulated spectra of the title compound, which show excellent agreement with observed spectra. The frontier orbital energy gap and dipole moment illustrates the high reactivity of the title molecule. The first order hyperpolarizability (β0) and related properties (μ, α and Δα) of the molecule were also calculated. Stability of the molecule arising from hyperconjugative interactions and charge delocalization were analyzed using natural bond orbital (NBO) analysis. The results show that electron density (ED) in the σ(*) and π(*) anti-bonding orbitals and second order delocalization energies (E2) confirm the occurrence of intramolecular charge transfer (ICT) within the molecule. UV-vis spectrum of the compound was recorded in the region 200-500 nm in ethanol and electronic properties such as excitation energies, oscillator strength and wavelength were calculated by TD-DFT/B3LYP, CIS and TD-HF methods using 6-31G(d,p) basis set. Molecular electrostatic potential (MEP) and HOMO-LUMO energy levels are also constructed. The thermodynamic properties of the title compound were calculated at different temperatures and the results reveals the heat capacity (C), and entropy (S) increases with rise in temperature. Copyright © 2013 Elsevier B.V. All rights reserved.
Antimicrobial activity, structural evaluation and vibrational (FT-IR and FT-Raman) study of pyrrole containing vinyl derivatives

NASA Astrophysics Data System (ADS)

Singh, R. N.; Rawat, Poonam; Sahu, Sangeeta; Kumar, Yashvinder

2016-02-01

In this paper we present structural and vibrational study of three vinylpyrrole derivatives: 2-Cyano-3-(1H-pyrrol-2-yl)-acrylamide (CPA), 1-(1H-Pyrrol-2-yl)-Pent-1-en-3-one (PP) and 1-(1H-Pyrrol-2-yl)-but-1-en-3-one (PB), using ab initio, DFT and experimental approaches. The quantum chemical calculation have been performed on B3LYP method and 6-311 + G(d,p) basis set. The experimental FT-IR and Raman wavenumbers were compared with the respective theoretical values obtained from DFT calculations and found to agree well. The experimental FT-IR and Raman study clearly indicate that the compound exist as dimer in solid state. The binding energies of (CPA), (PP) and (PB) dimers are found to be 20.95, 18.75 and 19.18 kcal/mol, respectively. The vibrational analysis shows red shifts in vN-H and vCdbnd O stretching as result of dimer formation. Stability of the molecule arising from hyperconjugative interactions and charge delocalization has been analyzed using NBO analysis. Topological and energetic parameters reveal the nature of interactions in dimer. The local electronic descriptors analyses were used to predict the reactive sites in the molecule. Calculated first static hyperpolarizability of CPA, PP and PB is found to be 10.41 × 10- 30, 18.93 × 10- 30, 18.29 × 10- 30 esu, respectively, shows that investigated molecules will have non-linear optical response and might be used as non-linear optical (NLO) material. These vinylpyrrole compounds (CPA), (PP) and (PB) showed antifungal and antibacterial activity against Aspergillus niger and gram-positive bacteria Bacillus subtili.

Electronic structure investigation of neutral titanium oxide molecules TixOy

NASA Astrophysics Data System (ADS)

Jeong, K. S.; Chang, Ch; Sedlmayr, E.; Sülzle, D.

2000-09-01

Electronic and structural properties of energetically low-lying isomers of isolated TixOy (x = 1-6, y = 1-12) molecular systems have been investigated by density functional theoretical methods. A variety of stationary points are thoroughly characterized. We report total cluster energies, equilibrium geometries and harmonic vibrational wavenumbers.
Spectroscopic and DFT studies of flurbiprofen as dimer and its Cu(II) and Hg(II) complexes

NASA Astrophysics Data System (ADS)

Sagdinc, Seda; Pir, Hacer

2009-07-01

The vibrational study in the solid state of flurbiprofen and its Cu(II) and Hg(II) complexes was performed by IR and Raman spectroscopy. The changes observed between the IR and Raman spectra of the ligand and of the complexes allowed us to establish the coordination mode of the metal in both complexes. The comparative vibrational analysis of the free ligand and its complexes gave evidence that flurbiprofen binds metal (II) through the carboxylate oxygen. The fully optimized equilibrium structure of flurbiprofen and its metal complexes was obtained by density functional B3LYP method by using LanL2DZ and 6-31 G(d,p) basis sets. The harmonic vibrational frequencies, infrared intensities and Raman scattering activities of flurbiprofen were calculated by density functional B3LYP methods by using 6-31G(d,p) basis set. The scaled theoretical wavenumbers showed very good agreement with the experimental values. The electronic properties of the free molecule and its complexes were also performed at B3LYP/6-31G(d,p) level of theory. Detailed interpretations of the infrared and Raman spectra of flurbiprofen are reported. The UV-vis spectra of flurbiprofen and its metal complexes were also investigated in organic solvents.
Effects of the synthesis temperature on the crystalline structure and the magnetic properties of cobalt ferrite nanoparticles prepared via coprecipitation

NASA Astrophysics Data System (ADS)

Hutamaningtyas, Evangelin; Utari; Suharyana; Purnama, Budi; Wijayanta, Agung Tri

2016-08-01

The effects of the synthesis temperature on the crystalline structure and the magnetic properties of cobalt ferrite (CoFe2O4) nanoparticles prepared via coprecipitation are discussed. The synthesis was conducted at temperatures of 75 °C, 85 °C and 95 °C. Fourier transform infrared spectroscopy characterization related to a stretching vibration at a wavenumber of 590 cm-1 indicated the formation of a CoFe2O4 metal oxide. In addition, powder X ray diffraction (XRD) characterization proved that the metal oxide was CoFe2O4. Crystallite sizes calculated using the Scherer formula at the strongest peak of the XRD spectra of the samples synthesized at 75 °C, 85 °C and 95 °C were 32 nm, 43 nm and 50.4 nm, respectively. Finally, the results of the vibrating sample magnetometer characterization showed that the saturation magnetization decreased with increasing synthesis temperature, which is related to the dominant preference of Co2+ over Fe3+ cations at the octahedral sites.
Vibronic Coupling Analysis of the Ligand-Centered Phosphorescence of Gas-Phase Gd(III) and Lu(III) 9-Oxophenalen-1-one Complexes.

PubMed

Chmela, Jiří; Greisch, Jean-François; Harding, Michael E; Klopper, Wim; Kappes, Manfred M; Schooss, Detlef

2018-03-08

The gas-phase laser-induced photoluminescence of cationic mononuclear gadolinium and lutetium complexes involving two 9-oxophenalen-1-one ligands is reported. Performing measurements at a temperature of 83 K enables us to resolve vibronic transitions. Via comparison to Franck-Condon computations, the main vibrational contributions to the ligand-centered phosphorescence are determined to involve rocking, wagging, and stretching of the 9-oxophenalen-1-one-lanthanoid coordination in the low-energy range, intraligand bending, and stretching in the medium- to high-energy range, rocking of the carbonyl and methine groups, and C-H stretching beyond. Whereas Franck-Condon calculations based on density-functional harmonic frequency computations reproduce the main features of the vibrationally resolved emission spectra, the absolute transition energies as determined by density functional theory are off by several thousand wavenumbers. This discrepancy is found to remain at higher computational levels. The relative energy of the Gd(III) and Lu(III) emission bands is only reproduced at the coupled-cluster singles and doubles level and beyond.
Acid-base properties, FT-IR, FT-Raman spectroscopy and computational study of 1-(pyrid-4-yl)piperazine.

PubMed

Mary, Y Sheena; Panicker, C Yohannan; Varghese, Hema Tresa; Van Alsenoy, Christian; Procházková, Markéta; Sevčík, Richard; Pazdera, Pavel

2014-01-01

We report the vibrational spectral analysis was carried out using FT-IR and FT-Raman spectroscopy for 1-(pyrid-4-yl)piperazine (PyPi). Single crystals of PyPi suitable for X-ray structural analysis were obtained. The acid-base properties are also reported. PyPi supported on a weak acid cation-exchanger in the single protonated form and this system can be used efficiently as the solid supported analogue of 4-N,N-dimethyl-aminopyridine. The complete vibrational assignments of wavenumbers were made on the basis of potential energy distribution. The HOMO and LUMO analysis is used to determine the charge transfer within the molecule and with the molecular electrostatic potential map was applied for the reactivity assessment of PyPi molecule toward proton, electrophiles and nucleopholes as well. The stability of the molecule arising from hyper-conjugative interaction and charge delocalization has been analyzed using NBO analysis. The calculated first hyperpolarizability of PyPi is 17.46 times that of urea. Copyright © 2013 Elsevier B.V. All rights reserved.
Felix Spectroscopy of Likely Astronomical Molecular Ions: HC_3O^+, C_2H_3CNH^+, and C_2H_5CNH^+

NASA Astrophysics Data System (ADS)

Thorwirth, Sven; Asvany, Oskar; Brünken, Sandra; Jusko, Pavol; Schlemmer, Stephan; Martin-Drumel, Marie-Aline; McCarthy, Michael C.

2017-06-01

Infrared signatures of three molecular ions of relevance to the interstellar medium and planetary atmospheres have been detected at the Free Electron Laser for Infrared eXperiments, FELIX, at Radboud University (Nijmegen, The Netherlands) in combination with the 4K FELion 22-pole ion trap facility. Mid-infrared vibrational modes of protonated tricarbon monoxide, HC_3O^+, protonated vinyl cyanide, C_2H_3CNH^+, and protonated ethyl cyanide, C_2H_5CNH^+, were detected using resonant photodissociation of the respective Ne-complexes by monitoring the depletion of their cluster mass signal as a function of wavenumber. The infrared fingerprints compare very favorably with results from high-level quantum-chemical calculations performed at the CCSD(T) level of theory.
Spectroscopic investigation, hirshfeld surface analysis and molecular docking studies on anti-viral drug entecavir

NASA Astrophysics Data System (ADS)

Fathima Rizwana, B.; Prasana, Johanan Christian; Abraham, Christina Susan; Muthu, S.

2018-07-01

Entecavir, a new deoxyguanine nucleoside analogue, is a selective inhibitor of the replication of the hepatitis B virus. In the present study, Quantum mechanical approach was carried out on the title compound to study the vibrational spectrum, the stability of the compound, the intermolecular and intramolecular interactions by using Density Functional Theory (DFT) with B3LYP 6-311++G(d,p) basis set. The B3LYP/DFT method was chosen because diverse studies have shown that the results obtained with it are in good agreement with those determined by other costly computational methods. The computational methods were aided by the experimental spectroscopic techniques, namely FTIR and FT Raman spectroscopies. The optimized molecular geometry, vibrational wavenumbers, infrared intensities and Raman scattering activities were calculated. The calculated HOMO and LUMO energies were found to be -6.397 eV and -1.504 eV which indicate the charge transfer within the molecule. The maximum absorption wavelength and the band gap energy of the title compound were obtained from the UV absorption spectrum computed theoretically. Natural Bond Orbital analysis has been carried out to explain the charge transfer (or) delocalization of charge due to the intra molecular interactions. The molecule orbital contributions are studied by using the total (TDOS), partial (PDOS), and overlap population (OPDOS) density of states. Molecular electrostatic potential (MEP), First order hyperpolarizability, Hirshfield surface analysis and Fukui functions calculation were also performed. From the calculations the first order hyperpolarizability was found to be 2.3854 × 10-30 esu. The thermodynamic properties (heat capacity, entropy, and enthalpy) of the title compound at different temperatures have been calculated. Molecular docking studies were made on the title compound to study the hydrogen bond interactions and the minimum binding energy was calculated.
The molecular structure of the phosphate mineral chalcosiderite - A vibrational spectroscopic study

NASA Astrophysics Data System (ADS)

Frost, Ray L.; Xi, Yunfei; Scholz, Ricardo; Ribeiro, Carlos Augusto de Brito

2013-07-01

The mineral chalcosiderite with formula CuFe6(PO4)4(OH)8ṡ4H2O has been studied by Raman spectroscopy and by infrared spectroscopy. A comparison of the chalcosiderite spectra is made with the spectra of turquoise. The spectra of the mineral samples are very similar in the 1200-900 cm-1 region but strong differences are observed in the 900-100 cm-1 region. The effect of substitution of Fe for Al in chalcosiderite shifts the bands to lower wavenumbers. Factor group analysis (FGA) implies four OH stretching vibrations for both the water and hydroxyl units. Two bands ascribed to water are observed at 3276 and 3072 cm-1. Three hydroxyl stretching vibrations are observed. Calculations using a Libowitzky type formula show that the hydrogen bond distances of the water molecules are 2.745 and 2.812 Å which are considerably shorter than the values for the hydroxyl units 2.896, 2.917 and 2.978 Å. Two phosphate stretching vibrations at 1042 and 1062 cm-1 in line with the two independent phosphate units in the structure of chalcosiderite. Three bands are observed at 1102, 1159 and 1194 cm-1 assigned to the phosphate antisymmetric stretching vibrations. FGA predicts six bands but only three are observed due to accidental degeneracy. Both the ν2 and ν4 bending regions are complex. Four Raman bands observed at 536, 580, 598 and 636 cm-1 are assigned to the ν4 bending modes. Raman bands at 415, 420, 475 and 484 cm-1are assigned to the phosphate ν2 bending modes. Vibrational spectroscopy enables aspects of the molecular structure of chalcosiderite to be assessed.
Vibrational spectroscopic (FT-IR, FT-Raman) and quantum mechanical study of 4-(2-chlorophenyl)-2-ethyl-9-methyl-6H-thieno[3,2-f] [1,2,4]triazolo[4,3-a][1,4] diazepine

NASA Astrophysics Data System (ADS)

Kuruvilla, Tintu K.; Prasana, Johanan Christian; Muthu, S.; George, Jacob

2018-04-01

The spectroscopic properties of 4-(2-chlorophenyl)-2-ethyl-9-methyl-6H-thieno [3,2-f] [1,2,4] triazolo [4,3-a] [1,4] diazepine were investigated in the present study using FT-IR and FT-Raman techniques. The results obtained were compared with quantum mechanical methods, as it serves as an important tool in interpreting and predicting vibrational spectra. The optimized molecular geometry, the vibrational wavenumbers, the infrared intensities and Raman scattering were calculated using density functional theory B3LYP method with 6-311++g (d,p) basis set. All the experimental results were in line with the theoretical data. The molecular electrostatic potential (MEP) and HOMO LUMO energies of the title compound were accounted. The results indicated that the title compound has a lower softness value (0.27) and high electrophilicity index (4.98) hence describing its biological activity. Further, natural bond orbital was also analyzed as part of the work. Fukui functions were calculated in order to explain the chemical selectivity or the reactivity site in 4-(2-chlorophenyl)-2-ethyl-9-methyl-6H-thieno [3,2-f] [1,2,4] triazolo [4,3-a] [1,4] diazepine. The thermodynamic properties of the title compound were closely examined at different temperatures. It revealed the correlations between heat capacity (C), entropy (S) and enthalpy changes (H) with temperatures. The paper further explains that the title compound can act as good antidepressant through molecular docking studies.
Experimental IR and Raman spectra and quantum chemical studies of molecular structures, conformers and vibrational characteristics of L-ascorbic acid and its anion and cation

NASA Astrophysics Data System (ADS)

Yadav, R. A.; Rani, P.; Kumar, M.; Singh, R.; Singh, Priyanka; Singh, N. P.

2011-12-01

IR and spectra of the L-ascorbic acid ( L-AA) also known as vitamin C have been recorded in the region 4000-50 cm -1. In order to make vibrational assignments of the observed IR and Raman bands computations were carried out by employing the RHF and DFT methods to calculate the molecular geometries and harmonic vibrational frequencies along with other related parameters for the neutral L-AA and its singly charged anionic ( L-AA -) and cationic ( L-AA +) species. Significant changes have been found for different characteristics of a number of vibrational modes. The four ν(O-H) modes of the L-AA molecule are found in the order ν(O 9-H 10) > ν(O 19-H 20) > ν(O 7-H 8) > ν(O 14-H 15) which could be due to complexity of hydrogen bonding in the lactone ring and the side chain. The C dbnd O stretching wavenumber ( ν46) decreases by 151 cm -1 in going from the neutral to the anionic species whereas it increases by 151 cm -1 in going from the anionic to the cationic species. The anionic radicals have less kinetic stabilities and high chemical reactivity as compared to the neutral molecule. It is found that the cationic radical of L-AA is kinetically least stable and chemically most reactive as compared to its neutral and anionic species.
Molecular structure, vibrational spectra and DFT computational studies of melaminium N-acetylglycinate dihydrate

NASA Astrophysics Data System (ADS)

Tanak, H.; Pawlus, K.; Marchewka, M. K.

2016-10-01

Melaminium N-acetylglycinate dihydrate, an organic material has been synthesized and characterized by X-ray diffraction, FT-IR, and FT-Raman spectroscopies for the protiated and deuteriated crystals. The title complex crystallizes in the triclinic system, and the space group is P-1 with a = 5.642(1) Å, b = 7.773(2) Å, c = 15.775(3) Å, α = 77.28(1)°, β = 84.00(1)°, γ = 73.43(1)° and Z = 2. The molecular geometry, vibrational frequencies and intensity of the vibrational bands have been interpreted with the aid of structure optimization based on density functional method (B3LYP) with the 6-311++G(d,p) basis set. The obtained vibrational wavenumbers and optimized geometric parameters were seen to be in good agreement with the experimental data. The intermolecular hydrogen bonding interactions of the title compound have been investigated using the natural bonding orbital analysis. It reveals that the O-H···O, N-H···N and N-H···O intermolecular interactions significantly influence crystal packing of this molecule. The non-linear optical properties are also addressed theoretically. The predicted NLO properties of the title compound are much greater than ones of urea. In addition, DFT calculations of the title compound, molecular electrostatic potential, thermodynamic properties, frontier orbitals and chemical reactivity descriptors were also performed at 6-311++G(d,p) level of theory.
The dynamic Casimir effect within a vibrating metal photonic crystal

NASA Astrophysics Data System (ADS)

Ueta, Tsuyoshi

2014-09-01

The lattice-vibrating metal photonic crystal is exactly a system of dynamical Casimir effect connected in series, and so we can expect that a dynamical Casimir effect is enhanced by the photonic band effect. In the present study, when an electromagnetic field between metal plates is in the ground state in a one-dimensional metal photonic crystal, the radiation of electromagnetic wave in excited states has been investigated by artificially introducing lattice vibration to the photonic crystal. In this case as well as a dynamical Casimir effect, it has been shown that the harmonics of a ground state are generated just by vibrating a photonic crystal even without an incident wave. The dependencies of the radiating power on the number of layers and on the wavenumber of the lattice vibration are remarkable. It has been found that the radiation amplitude on lower excited states is not necessarily large and radiation on specific excited levels is large.
Vibrational tug-of-war: The pKA dependence of the broad vibrational features of strongly hydrogen-bonded carboxylic acids.

PubMed

Van Hoozen, Brian L; Petersen, Poul B

2018-04-07

Medium and strong hydrogen bonds give rise to broad vibrational features frequently spanning several hundred wavenumbers and oftentimes exhibiting unusual substructures. These broad vibrational features can be modeled from first principles, in a reduced dimensional calculation, that adiabatically separates low-frequency modes, which modulate the hydrogen bond length, from high-frequency OH stretch and bend modes that contribute to the vibrational structure. Previously this method was used to investigate the origin of an unusual vibrational feature frequently found in the spectra of dimers between carboxylic acids and nitrogen-containing aromatic bases that spans over 900 cm -1 and contains two broad peaks. It was found that the width of this feature largely originates from low-frequency modes modulating the hydrogen bond length and that the structure results from Fermi resonance interactions. In this report, we examine how these features change with the relative acid and base strength of the components as reflected by their aqueous pK A values. Dimers with large pK A differences are found to have features that can extend to frequencies below 1000 cm -1 . The relationships between mean OH/NH frequency, aqueous pK A , and O-N distance are examined in order to obtain a more rigorous understanding of the origin and shape of the vibrational features. The mean OH/NH frequencies are found to correlate well with O-N distances. The lowest OH stretch frequencies are found in dimer geometries with O-N distances between 2.5 and 2.6 Å. At larger O-N distances, the hydrogen bonding interaction is not as strong, resulting in higher OH stretch frequencies. When the O-N distance is smaller than 2.5 Å, the limited space between the O and N determines the OH stretch frequency, which gives rise to frequencies that decrease with O-N distances. These two effects place a lower limit on the OH stretch frequency which is calculated to be near 700 cm -1 . Understanding how the vibrational features of strongly hydrogen-bonded structures depend on the relative pK A and other structural parameters will guide studies of biological structures and analysis of proton transfer studies using photoacids.
The spatial variability of coastal surface water temperature during upwelling. [in Lake Superior

NASA Technical Reports Server (NTRS)

Scarpace, F. L.; Green, T., III

1979-01-01

Thermal scanner imagery acquired during a field experiment designed to study an upwelling event in Lake Superior is investigated. Temperature data were measured by the thermal scanner, with a spatial resolution of 7 m. These data were correlated with temperatures measured from boats. One- and two-dimensional Fourier transforms of the data were calculated and temperature variances as a function of wavenumber were plotted. A k-to-the-minus-three dependence of the temperature variance on wavenumber was found in the wavenumber range of 1-25/km. At wavenumbers greater than 25/km, a k-to-the-minus-five-thirds dependence was found.
Intramolecular Vibrational Energy Redistribution (ivr) in Selected S_{1} Levels above 1000 cm^{-1} in Para-Fluorotoluene

NASA Astrophysics Data System (ADS)

Whalley, Laura E.; Gardner, Adrian M.; Tuttle, William Duncan; Davies, Julia A.; Reid, Katharine L.; Wright, Timothy G.

2017-06-01

With increasing vibrational wavenumber, the density of states of a molecule is expected to rise dramatically, especially so when low wavenumber torsions (internal rotations) are present, as in the case of para-fluorotoluene (pFT). This in turn is expected to lead to more opportunities for coupling between vibrational modes, which is the driving force for intramolecular vibrational energy redistribution (IVR). Previous studies at higher energies have focussed on the two close lying vibrational levels at 1200 cm^{-1} in the S_{1} electronic state of pFT which were assigned to two zero-order bright states (ZOBSs), whose characters predominantly involve C-CH_{3} and C-F stretching modes. A surprising result of these studies was that the photoelectron spectra showed evidence that IVR is more extensive following excitation of the C-F mode than it is following excitation of the C-CH_{3} mode, despite these levels being separated by only 35 cm^{-1}. This observation provides evidence that the IVR dynamics are mode-specific, which in turn may be a consequence of the IVR route being dependent on couplings to nearby states that are only available to the C-F mode. In this work, in order to further investigate this behaviour, we have employed resonance-enhanced multiphoton ionisation (REMPI) spectroscopy and zero-kinetic-energy (ZEKE) spectroscopy to probe S_{1} levels above 1000 cm^{-1} in pFT. Such ZEKE spectra have been recorded via a number of S_{1} intermediate levels allowing the character and coupling between vibrations to be unravelled; the consequence of this coupling will be discussed with a view to understanding any IVR dynamics seen. C. J. Hammond, V. L. Ayles, D. E. Bergeron, K. L. Reid and T. G. Wright, J. Chem. Phys., 125, 124308 (2006) J. A. Davies, A. M. Green, A. M. Gardner, C. D. Withers, T. G. Wright and K. L. Reid, Phys. Chem. Chem. Phys., 16, 430 (2014)
Adsorption of 6-mercaptopurine and 6-mercaptopurine riboside on silver colloid: a pH dependent surface enhanced Raman spectroscopy and density functional theory study. Part I. 6-Mercaptopurine

NASA Astrophysics Data System (ADS)

Szeghalmi, A. V.; Leopold, L.; Pînzaru, S.; Chis, V.; Silaghi-Dumitrescu, I.; Schmitt, M.; Popp, J.; Kiefer, W.

2005-02-01

Surface enhanced Raman spectroscopy (SERS) on silver colloid has been applied to characterize the interaction of 6-mercaptopurine (6MP), an active drug used in chemotherapy of acute lymphoblastic leukemia, with a model biological substrate at therapeutical concentrations and as function of the pH value. The adsorption active sites and molecular orientation on the metal surface have been determined on the basis of SERS 'surface selection rules' subsequent to a detailed vibrational analysis of the 6MP tautomeric forms. Therefore, DFT calculations (vibrational wavenumbers, Raman scattering activities, partial atomic charges) of the optimized tautomers and potential energy distribution calculations have been performed. Around neutral pH value reorientation of the molecule has been observed. Under basic conditions the 6MP molecule is probably adsorbed on the silver colloid through the N1 atom of the purine ring and possibly the S atom, and adopts a tilted orientation to the surface. A reduction in the number of adsorbed molecules under basic conditions is proposed, since the SERS spectrum recorded at 10-6 M concentration at neutral pH value resembles the SERS spectra obtained under basic conditions at 10-5 M concentration. At acidic pH values a stronger interaction through the N9 and N3 atoms is suggested with an end-on orientation.
Torsional, Vibrational and Vibration-Torsional Levels in the S_{1} and Ground Cationic D_{0}^{+} States of Para-Fluorotoluene

NASA Astrophysics Data System (ADS)

Gardner, Adrian M.; Tuttle, William Duncan; Whalley, Laura E.; Claydon, Andrew; Carter, Joseph H.; Wright, Timothy G.

2017-06-01

The S_{1} electronic state and ground state of the cation of para-fluorotoluene (pFT) have been investigated using resonance-enhanced multiphoton ionization (REMPI) spectroscopy and zero-kinetic-energy (ZEKE) spectroscopy. Here we focus on the low wavenumber region where a number of "pure" torsional, fundamental vibrational and vibration-torsional levels are expected; assignments of observed transitions are discussed, which are compared to results of published work on toluene (methylbenzene) from the Lawrance group. The similarity in the activity observed in the excitation spectrum of the two molecules is striking. A. M. Gardner, W. D. Tuttle, L. Whalley, A. Claydon, J. H. Carter and T. G. Wright, J. Chem. Phys., 145, 124307 (2016). J. R. Gascooke, E. A. Virgo, and W. D. Lawrance J. Chem. Phys., 143, 044313 (2015).
Vibrational Fingerprints of Low-Lying Pt(n)P(2n) (n = 1-5) Cluster Structures from Global Optimization Based on Density Functional Theory Potential Energy Surfaces.

PubMed

Jedidi, Abdesslem; Li, Rui; Fornasiero, Paolo; Cavallo, Luigi; Carbonniere, Philippe

2015-12-03

Vibrational fingerprints of small Pt(n)P(2n) (n = 1-5) clusters were computed from their low-lying structures located from a global exploration of their DFT potential energy surfaces with the GSAM code. Five DFT methods were assessed from the CCSD(T) wavenumbers of PtP2 species and CCSD relative energies of Pt2P4 structures. The eight first Pt(n)P(2n) isomers found are reported. The vibrational computations reveal (i) the absence of clear signatures made by overtone or combination bands due to very weak mechanical and electrical anharmonicities and (ii) some significant and recurrent vibrational fingerprints in correlation with the different PP bonding situations in the Pt(n)P(2n) structures.
Vibrational analysis of α-cyanohydroxycinnamic acid

NASA Astrophysics Data System (ADS)

Mojica, Elmer-Rico E.; Vedad, Jayson; Desamero, Ruel Z. B.

2015-08-01

In the present study, a comparative Raman vibrational analysis of alpha-cyano-4-hydroxycinnamic acid (4CHCA) and its derivative, alpha-cyano-3-hydroxycinnamic acid (3CHCA), was performed. The Raman spectra of the 4CHCA and 3CHCA in solid form were obtained and analyzed to determine differences between the two structurally similar derivatives. For comparison, the CHCA derivatives cyanocinnamic acid (CCA) and coumaric acid (CA) were also studied. The plausible vibrational assignments were made and matched with those obtained theoretically using density functional theory (DFT) based method employing a 6-31 g basis set. The computational wavenumbers obtained were in good agreement with the observed experimental results. This was the first reported Raman study of CCA, 3CHCA and 4CHCA.
Conformational analysis, spectroscopic, structure-activity relations and quantum chemical simulation studies of 4-(trifluoromethyl)benzylamine

NASA Astrophysics Data System (ADS)

Arjunan, V.; Devi, L.; Mohan, S.

2018-05-01

The FT-IR and FT-Raman spectra of 4-trifluoromethylbenzylamine (TFMBA) have been recorded in the range 4000-450 and 4000-100 cm-1 respectively. The conformational analysis of the compound has been carried out to attain stable geometry of the compound. The complete vibrational assignment and analysis of the fundamental modes of the compound are carried out using the experimental FTIR and FT-Raman data and quantum chemical studies. The experimental vibrational frequencies are compared with the wavenumbers obtained theoretically from the B3LYP gradient calculations employing the standard high level 6-311++G** and cc-pVTZ basis sets for the optimised geometry of the compound. The structural parameters, thermodynamic properties and vibrational frequencies of the normal modes obtained from the B3LYP methods are in good agreement with the experimental data. The 1H (400 MHz; CDCl3) and 13C (100 MHz; CDCl3) nuclear magnetic resonance (NMR) spectra were also recorded. The electronic properties, highest occupied molecular orbital and lowest unoccupied molecular orbital energies are measured by DFT approach. The charges of the atoms by natural bond orbital (NBO) analysis are determined by B3LYP/cc-pVTZ method. The structure-chemical reactivity relations of the compound are determined through chemical potential, global hardness, global softness, electronegativity, electrophilicity and local reactivity descriptors by conceptual DFT methods.

Impact imaging of aircraft composite structure based on a model-independent spatial-wavenumber filter.

PubMed

Qiu, Lei; Liu, Bin; Yuan, Shenfang; Su, Zhongqing

2016-01-01

The spatial-wavenumber filtering technique is an effective approach to distinguish the propagating direction and wave mode of Lamb wave in spatial-wavenumber domain. Therefore, it has been gradually studied for damage evaluation in recent years. But for on-line impact monitoring in practical application, the main problem is how to realize the spatial-wavenumber filtering of impact signal when the wavenumber of high spatial resolution cannot be measured or the accurate wavenumber curve cannot be modeled. In this paper, a new model-independent spatial-wavenumber filter based impact imaging method is proposed. In this method, a 2D cross-shaped array constructed by two linear piezoelectric (PZT) sensor arrays is used to acquire impact signal on-line. The continuous complex Shannon wavelet transform is adopted to extract the frequency narrowband signals from the frequency wideband impact response signals of the PZT sensors. A model-independent spatial-wavenumber filter is designed based on the spatial-wavenumber filtering technique. Based on the designed filter, a wavenumber searching and best match mechanism is proposed to implement the spatial-wavenumber filtering of the frequency narrowband signals without modeling, which can be used to obtain a wavenumber-time image of the impact relative to a linear PZT sensor array. By using the two wavenumber-time images of the 2D cross-shaped array, the impact direction can be estimated without blind angle. The impact distance relative to the 2D cross-shaped array can be calculated by using the difference of time-of-flight between the frequency narrowband signals of two different central frequencies and the corresponding group velocities. The validations performed on a carbon fiber composite laminate plate and an aircraft composite oil tank show a good impact localization accuracy of the model-independent spatial-wavenumber filter based impact imaging method. Copyright © 2015 Elsevier B.V. All rights reserved.
Experimental investigation of the influence of internal frames on the vibroacoustic behavior of a stiffened cylindrical shell using wavenumber analysis

NASA Astrophysics Data System (ADS)

Meyer, V.; Maxit, L.; Renou, Y.; Audoly, C.

2017-09-01

The understanding of the influence of non-axisymmetric internal frames on the vibroacoustic behavior of a stiffened cylindrical shell is of high interest for the naval or aeronautic industries. Several numerical studies have shown that the non-axisymmetric internal frame can increase the radiation efficiency significantly in the case of a mechanical point force. However, less attention has been paid to the experimental verification of this statement. That is why this paper proposes to compare the radiation efficiency estimated experimentally for a stiffened cylindrical shell with and without internal frames. The experimental process is based on scanning laser vibrometer measurements of the vibrations on the surface of the shell. A transform of the vibratory field in the wavenumber domain is then performed. It allows estimating the far-field radiated pressure with the stationary phase theorem. An increase of the radiation efficiency is observed in the low frequencies. Analysis of the velocity field in the physical and wavenumber spaces allows highlighting the coupling of the circumferential orders at the origin of the increase in the radiation efficiency.
Specific coupling between the 13-keto carbonyl and chlorin skeletal vibrational modes of synthetic 13 1- 18O-(un)labelled metallochlorophyll derivatives

NASA Astrophysics Data System (ADS)

Morishita, Hidetada; Tamiaki, Hitoshi

2009-03-01

Metal complexes of methyl 13 1- 18O-labelled pyropheophorbide- a1-M- 18O (M = Zn, Cu and Ni) were prepared by metallation of the 18O-labelled free base ( 1- 18O) and 18O-labelling of unlabelled nickel complex ( 1-Ni). The FT-IR spectra of 1-Zn and 1-Zn- 18O in CH 2Cl 2 showed that the 13-keto carbonyl stretching vibration mode moved to about a 30-cm -1 lower wavenumber by 18O-labelling of the 13 1-oxo moiety. In 1-Cu- 18O and 1-Ni- 18O, the 13-C dbnd 18O stretching modes were close to the highest-energy wavenumber mode of chlorin skeletal C-C/C-N vibrations at around 1650 cm -1 and they were coupled in CH 2Cl 2 to give two split IR bands (Fermi resonance). A similar coupling was observed in the resonance Raman scattering of 1-Ni- 18O in the solid state. The hydrogen-bonded 13-C dbnd 16O vibration mode of 1-Ni similarly coupled with the skeletal C-C/C-N mode in CCl 4 containing 1% (v/v) 1,1,1,3,3,3-hexafluoro-2-propanol, while such a coupling was not observed in a neat CCl 4 solution of 1-Ni possessing the 13-C dbnd 16O free from any interaction. The skeletal C-C/C-N band selectively coupled with the 13-C dbnd O, not with the 3-C dbnd O, when the difference in their peak maxima was less than 20 cm -1.
Anomalous torsional tripling in the ν9 and ν10 CH3-deformation modes of ethane 12CH313CH3

NASA Astrophysics Data System (ADS)

Lattanzi, F.; di Lauro, C.

2017-12-01

We have investigated the anomalous torsional behavior in the coupled ν9 and ν10 vibrational fundamentals of 12CH313CH3, both states exhibiting a splitting into three components, instead of two, only in those rotational levels which are very close to resonance. We conclude that the intrinsic additional splitting, which occurs in the E-torsional components, for these two vibrational states is too small to be detected in the high resolution infrared spectrum, but it is substantively enhanced by their coupling. It is shown that this effect requires the simultaneous action of torsion independent operators, such as Fermi-type and z-Coriolis, not allowed in the more symmetric isotopologue 12CH312CH3, and torsion dependent operators, such as torsional-Coriolis, connecting the two vibrational states. Our conclusions lead to a simple model for the coupling of ν9 and ν10, with effective Fermi-type matrix elements W for the A-torsional components, and W ± w for the two pairs of E-torsional components. This causes the additional splitting in the E-pairs. This model is consistent with the mechanism causing the Coriolis-dependent decrease of the A-E torsional splitting in degenerate vibrational states. Exploratory calculations were performed making use of results from a normal mode analysis, showing that the effects predictable by the proposed model are of the correct order of magnitude compared to the observed features, with coupling parameter values reasonably consistent with those determined by the least squares fit of the observed transition wavenumbers.
Towards the new heterocycle based molecule: Synthesis, characterization and reactivity study

NASA Astrophysics Data System (ADS)

Murthy, P. Krishna; Sheena Mary, Y.; Suneetha, V.; Panicker, C. Yohannan; Armaković, Stevan; Armaković, Sanja J.; Giri, L.; Suchetan, P. A.; Van Alsenoy, C.

2017-06-01

4-Chloro-2-(3-fluorophenyl)-2,3-dihydro-1H-pyrrolo[3,4-c]pyridin-1-one (CFPDPPO) have been synthesized by hydride transfer from Et3SiH to carbenium ions(reduction reaction), which is formed by reaction between 4-chloro-2-(3-fluorophenyl)-3-hydroxy-2,3-dihydro-1H-pyrrolo[3,4-c]pyridin-1-one with TFA, the single crystals were grown in acetonitrile by slow evaporation technique at room temperature and characterized by single crystal X-ray diffraction, FT-IR, FT-Raman, 1H NMR, 13C NMR and ESI-MS. The experimental vibrational spectra were compared with the calculated spectra and each vibrational wavenumber was assigned on the basis of potential energy distribution (PED). Gauge-including atomic orbital 1H NMR and 13C NMR chemical shifts calculations were carried out and compared with experimental data. The HOMO and LUMO analysis is used to determine the charge transfer within the molecule. The stability of the molecule arising from hyper-conjugative interactions and charge delocalization has been analysed using NBO analysis. First hyperpolarizability is calculated in order to find its role in non-linear optics. Besides molecular electrostatic potential (MEP), global reactivity descriptors, thermodynamic properties, and Mullikan charge analysis of the title compound were computed with the same method in gas phase, theoretically. Further, employing combination of DFT calculations and molecular dynamics (MD) simulations, we have investigated in detail reactive properties of the title molecule. Investigation of local reactive properties encompassed calculations of average local ionization energies (ALIE) and Fukui functions. Stability in water has been investigated by calculations of radial distribution functions (RDF), while sensitivity towards the mechanism of autoxidation has been investigated by calculations of bond dissociation energies (BDE). The docked ligand forms a stable complex with human alpha9 nicotinic acetylcholine receptor antagonist and can be a lead compound for developing new anti-cancerous drug.
Infrared absorption spectra of partially deuterated methoxy radicals CH2DO and CHD2O isolated in solid para-hydrogen.

PubMed

Haupa, Karolina A; Johnson, Britta A; Sibert, Edwin L; Lee, Yuan-Pern

2017-10-21

The investigation of partially deuterated methoxy radicals is important because the symmetry lowering from C 3v to C s provides new insights into the couplings between rovibronic states via Jahn-Teller and spin-orbit interactions. The vibrational spectrum of the partially deuterated methoxy radical CH 2 DO in a matrix of p-H 2 has been recorded. This species was prepared by irradiating a p-H 2 matrix containing deuterated d 1 -nitritomethane (CH 2 DONO) at 3.3 K with laser light at 355 nm. The identification of the radical is based on the photochemical behavior of the precursor and comparison of observed vibrational wavenumbers and infrared (IR) intensities with those predicted from a refined quartic, curvilinear, internal coordinate force field calculated with the coupled-cluster singles and doubles with perturbative triples/cc-pVTZ method. CH 2 DO reacts with H 2 with a rate coefficient (3.5 ± 1.0) × 10 -3 s -1 . Predominantly c-CHDOH and a negligibly small amount of t-CHDOH were produced. This stereoselectivity results from the reaction H + C s -CH 2 DOH, which was demonstrated by an additional experiment on irradiation of a CH 2 DOH/Cl 2 /p-H 2 matrix with ultraviolet and IR light to induce the H + CH 2 DOH reaction; only c-CHDOH was observed from this experiment. Even though the energies of transition states and products for the formation of c-CHDOH and t-CHDOH differ by only ∼10 cm -1 , the selective formation of c-CHDOH can be explained by tunneling of the hydrogen atom via an optimal tunneling path. Similarly, the vibronic spectrum for the partially deuterated specie d 2 -methoxy radical (CHD 2 O) was obtained upon irradiation of d 2 -nitritomethane (CHD 2 ONO) at 355 nm. Lines associated with the fundamental vibrational modes were observed and assigned; line positions agree with theoretically predicted vibrational wavenumbers. CHD 2 O reacts with H 2 with a rate coefficient (6.0 ± 1.4) × 10 -3 s -1 ; CD 2 OH was produced as a major product because the barrier for the formation of CHDOH from H + CHD 2 OH is greater by ∼400 cm -1 . Rate coefficients of the decays of CH 3 O, CH 2 DO, CHD 2 O, and CD 3 O and their corresponding potential energy surfaces are compared.
Infrared absorption spectra of partially deuterated methoxy radicals CH2DO and CHD2O isolated in solid para-hydrogen

NASA Astrophysics Data System (ADS)

Haupa, Karolina A.; Johnson, Britta A.; Sibert, Edwin L.; Lee, Yuan-Pern

2017-10-01

The investigation of partially deuterated methoxy radicals is important because the symmetry lowering from C3v to Cs provides new insights into the couplings between rovibronic states via Jahn-Teller and spin-orbit interactions. The vibrational spectrum of the partially deuterated methoxy radical CH2DO in a matrix of p-H2 has been recorded. This species was prepared by irradiating a p-H2 matrix containing deuterated d1-nitritomethane (CH2DONO) at 3.3 K with laser light at 355 nm. The identification of the radical is based on the photochemical behavior of the precursor and comparison of observed vibrational wavenumbers and infrared (IR) intensities with those predicted from a refined quartic, curvilinear, internal coordinate force field calculated with the coupled-cluster singles and doubles with perturbative triples/cc-pVTZ method. CH2DO reacts with H2 with a rate coefficient (3.5 ± 1.0) × 10-3 s-1. Predominantly c-CHDOH and a negligibly small amount of t-CHDOH were produced. This stereoselectivity results from the reaction H + Cs-CH2DOH, which was demonstrated by an additional experiment on irradiation of a CH2DOH/Cl2/p-H2 matrix with ultraviolet and IR light to induce the H + CH2DOH reaction; only c-CHDOH was observed from this experiment. Even though the energies of transition states and products for the formation of c-CHDOH and t-CHDOH differ by only ˜10 cm-1, the selective formation of c-CHDOH can be explained by tunneling of the hydrogen atom via an optimal tunneling path. Similarly, the vibronic spectrum for the partially deuterated specie d2-methoxy radical (CHD2O) was obtained upon irradiation of d2-nitritomethane (CHD2ONO) at 355 nm. Lines associated with the fundamental vibrational modes were observed and assigned; line positions agree with theoretically predicted vibrational wavenumbers. CHD2O reacts with H2 with a rate coefficient (6.0 ± 1.4) × 10-3 s-1; CD2OH was produced as a major product because the barrier for the formation of CHDOH from H + CHD2OH is greater by ˜400 cm-1. Rate coefficients of the decays of CH3O, CH2DO, CHD2O, and CD3O and their corresponding potential energy surfaces are compared.
Synthesis, Hirshfeld surface analysis, laser damage threshold, third-order nonlinear optical property and DFT computation studies of Dichlorobis(DL-valine)zinc(II): A spectroscopic approach

NASA Astrophysics Data System (ADS)

Chitrambalam, S.; Manimaran, D.; Hubert Joe, I.; Rastogi, V. K.; Ul Hassan, Israr

2018-01-01

The organometallic crystal of Dichlorobis(DL-valine)zinc(II) was grown by solution growth method. The computed structural geometry, vibrational wavenumbers and UV-visible spectra were compared with experimental results. Hirshfeld surface map was used to locate electron density and the fingerprint plots percentages are responsible for the stabilization of intermolecular interactions in molecular crystal. The second-order hyperpolarizability value of the molecule was also calculated at density functional theory method. The surface resistance and third-order nonlinear optical property of the crystal were studied by laser induced surface damage threshold and Z-scan techniques, respectively using Nd:YAG laser with wavelength 532 nm. The open aperture result exhibits the reverse saturation absorption, which indicate that this material has potential candidate for optical limiting and optoelectronic applications.
Structural properties and FTIR-Raman spectra of the anti-hypertensive clonidine hydrochloride agent and their dimeric species

NASA Astrophysics Data System (ADS)

Romano, Elida; Davies, Lilian; Brandán, Silvia Antonia

2017-04-01

The structural and vibrational properties of the α-adrenergic agonist clonidine hydrochloride agent and their anionic and dimeric species were studied combining the experimental FT-IR and Raman spectra in solid phase with ab-initio calculations based on the density functional theory (DFT). All the calculations were performed by using the hybrid B3LYP with the 6-31G* and 6-311++G** basis sets. The structural properties for those species were studied employing the Natural Bond Orbital (NBO), Atoms in Molecules theory (AIM) and frontier orbitals calculations. The complete assignments of the FTIR and Raman spectra were performed combining the DFT calculations with the Pulay's Scaled Quantum Mechanics Force Field (SQMFF) methodology. Very good concordances between the theoretical and experimental spectra were found. In addition, the force constants for those three species were computed and compared with the values reported for similar antihypertensive agents. The ionic nature of the H→Cl bond and the high value of the LP(1)N4 → LP*(1)H18 charge transfer could explain the high reactivity of clonidine hydrochloride in relation to other antihypertensive agent and the strong shifthing of the band assigned to the Nsbnd H stretching mode linked to the Hsbnd Cl bond toward lower wavenumbers.
Inelastic neutron scattering, Raman, vibrational analysis with anharmonic corrections, and scaled quantum mechanical force field for polycrystalline L-alanine

NASA Astrophysics Data System (ADS)

Williams, Robert W.; Schlücker, Sebastian; Hudson, Bruce S.

2008-01-01

A scaled quantum mechanical harmonic force field (SQMFF) corrected for anharmonicity is obtained for the 23 K L-alanine crystal structure using van der Waals corrected periodic boundary condition density functional theory (DFT) calculations with the PBE functional. Scale factors are obtained with comparisons to inelastic neutron scattering (INS), Raman, and FT-IR spectra of polycrystalline L-alanine at 15-23 K. Calculated frequencies for all 153 normal modes differ from observed frequencies with a standard deviation of 6 wavenumbers. Non-bonded external k = 0 lattice modes are included, but assignments to these modes are presently ambiguous. The extension of SQMFF methodology to lattice modes is new, as are the procedures used here for providing corrections for anharmonicity and van der Waals interactions in DFT calculations on crystals. First principles Born-Oppenheimer molecular dynamics (BOMD) calculations are performed on the L-alanine crystal structure at a series of classical temperatures ranging from 23 K to 600 K. Corrections for zero-point energy (ZPE) are estimated by finding the classical temperature that reproduces the mean square displacements (MSDs) measured from the diffraction data at 23 K. External k = 0 lattice motions are weakly coupled to bonded internal modes.
Sample presentation, sources of error and future perspectives on the application of vibrational spectroscopy in the wine industry.

PubMed

Cozzolino, Daniel

2015-03-30

Vibrational spectroscopy encompasses a number of techniques and methods including ultra-violet, visible, Fourier transform infrared or mid infrared, near infrared and Raman spectroscopy. The use and application of spectroscopy generates spectra containing hundreds of variables (absorbances at each wavenumbers or wavelengths), resulting in the production of large data sets representing the chemical and biochemical wine fingerprint. Multivariate data analysis techniques are then required to handle the large amount of data generated in order to interpret the spectra in a meaningful way in order to develop a specific application. This paper focuses on the developments of sample presentation and main sources of error when vibrational spectroscopy methods are applied in wine analysis. Recent and novel applications will be discussed as examples of these developments. © 2014 Society of Chemical Industry.
Overtone spectroscopy of N2H+ molecular ions—application of cavity ring-down spectroscopy

NASA Astrophysics Data System (ADS)

Kálosi, Á.; Dohnal, P.; Shapko, D.; Roučka, Š.; Plašil, R.; Johnsen, R.; Glosík, J.

2017-10-01

A stationary afterglow apparatus in conjunction with a laser absorption cavity ring-down spectrometer has been employed to observe absorption lines in the P- and R-branches of the (200) <-- (000) and (2110) <-- (0110) vibrational bands of the N2H+ molecular ion as a part of an ongoing study of the electron-ion recombination of N2H+ in afterglow plasmas. The probed absorption lines lie in the near-infrared spectral region around 1580 nm. The observed transition wavenumbers were fitted to experimental accuracy and improved molecular constants for the (200) vibrational state were obtained. The employed experimental technique enables probing of the translational, rotational and vibrational temperature of the studied ions as well as the determination of the number densities of different quantum states of the ion in discharge and afterglow plasma.
A 2.5D finite element and boundary element model for the ground vibration from trains in tunnels and validation using measurement data

NASA Astrophysics Data System (ADS)

Jin, Qiyun; Thompson, David J.; Lurcock, Daniel E. J.; Toward, Martin G. R.; Ntotsios, Evangelos

2018-05-01

A numerical model is presented for the ground-borne vibration produced by trains running in tunnels. The model makes use of the assumption that the geometry and material properties are invariant in the axial direction. It is based on the so-called two-and-a-half dimensional (2.5D) coupled Finite Element and Boundary Element methodology, in which a two-dimensional cross-section is discretised into finite elements and boundary elements and the third dimension is represented by a Fourier transform over wavenumbers. The model is applied to a particular case of a metro line built with a cast-iron tunnel lining. An equivalent continuous model of the tunnel is developed to allow it to be readily implemented in the 2.5D framework. The tunnel structure and the track are modelled using solid and beam finite elements while the ground is modelled using boundary elements. The 2.5D track-tunnel-ground model is coupled with a train consisting of several vehicles, which are represented by multi-body models. The response caused by the passage of a train is calculated as the sum of the dynamic component, excited by the combined rail and wheel roughness, and the quasi-static component, induced by the constant moving axle loads. Field measurements have been carried out to provide experimental validation of the model. These include measurements of the vibration of the rail, the tunnel invert and the tunnel wall. In addition, simultaneous measurements were made on the ground surface above the tunnel. Rail roughness and track characterisation measurements were also made. The prediction results are compared with measured vibration obtained during train passages, with good agreement.
Generation of interior cavity noise due to window vibration excited by turbulent flows past a generic side-view mirror

NASA Astrophysics Data System (ADS)

Yao, Hua-Dong; Davidson, Lars

2018-03-01

We investigate the interior noise caused by turbulent flows past a generic side-view mirror. A rectangular glass window is placed downstream of the mirror. The window vibration is excited by the surface pressure fluctuations and emits the interior noise in a cuboid cavity. The turbulent flows are simulated using a compressible large eddy simulation method. The window vibration and interior noise are predicted with a finite element method. The wavenumber-frequency spectra of the surface pressure fluctuations are analyzed. The spectra are identified with some new features that cannot be explained by the Chase model for turbulent boundary layers. The spectra contain a minor hydrodynamic domain in addition to the hydrodynamic domain caused by the main convection of the turbulent boundary layer. The minor domain results from the local convection of the recirculating flow. These domains are formed in bent elliptic shapes. The spanwise expansion of the wake is found causing the bending. Based on the wavenumber-frequency relationships in the spectra, the surface pressure fluctuations are decomposed into hydrodynamic and acoustic components. The acoustic component is more efficient in the generation of the interior noise than the hydrodynamic component. However, the hydrodynamic component is still dominant at low frequencies below approximately 250 Hz since it has low transmission losses near the hydrodynamic critical frequency of the window. The structural modes of the window determine the low-frequency interior tonal noise. The combination of the mode shapes of the window and cavity greatly affects the magnitude distribution of the interior noise.
Quantum mechanical study and spectroscopic (FT-IR, FT-Raman, UV-Visible) study, potential energy surface scan, Fukui function analysis and HOMO-LUMO analysis of 3-tert-butyl-4-methoxyphenol by DFT methods.

PubMed

Saravanan, S; Balachandran, V

2014-09-15

This study represents an integral approach towards understanding the electronic and structural aspects of 3-tert-butyl-4-methoxyphenol (TBMP). Fourier-transform Infrared (FT-IR) and Fourier-transform Raman (FT-Raman) spectra of TBMP was recorded in the region 4000-400 cm(-1) and 3500-100 cm(-1), respectively. The molecular structures, vibrational wavenumbers, infrared intensities and Raman activities were calculated using DFT (B3LYP and LSDA) methods using 6-311++G (d,p) basis set. The most stable conformer of TBMP was identified from the computational results. The assignments of vibrational spectra have been carried out with the help of normal co-ordinate analysis (NCA) following the scaled quantum mechanical force field (SQMFF) methodology. The first order hyperpolarizability (β0) and related properties (β, α0 and Δα) of TBMP have been discussed. The stability and charge delocalization of the molecule was studied by Natural Bond Orbital (NBO) analysis. UV-Visible spectrum and effects of solvents have been discussed and the electronic properties such as HOMO and LUMO energies were determined by time-dependent TD-DFT approach with B3LYP/6-311++G (d,p) level of theory. The molecule orbital contributions are studied by density of energy states (DOSs). The reactivity sites are identified by mapping the electron density into electrostatic potential surface (MEP). Mulliken analysis of atomic charges is also calculated. The thermodynamic properties at different temperatures were calculated, revealing the correlations between standard heat capacities, standard entropy and standard enthalpy changes with temperatures. Global hardness, global softness, global electrophilicity and ionization potential of the title compound are determined. Copyright © 2014 Elsevier B.V. All rights reserved.
Synthesis, spectroscopic characterization, theoretical study and anti-hepatic cancer activity study of 4-(1E,3Z,6E)-3-hydroxy-7-(4-hydroxy-3-methoxyphenyl)-5-oxohepta-1,3,6-trien-1-yl)-2-methoxyphenyl 4-nitrobenzoate, a novel curcumin congener

NASA Astrophysics Data System (ADS)

Srivastava, Sangeeta; Gupta, Preeti; Singh, Ranvijay Pratap; Jafri, Asif; Arshad, M.; Banerjee, Monisha

2017-08-01

In the present work 4-(1E,3Z,6E)-3-hydroxy-7-(4-hydroxy-3-methoxyphenyl)-5-oxohepta-1,3,6-trien-1-yl)-2-methoxyphenyl 4-nitrobenzoate (2), a novel curcumin ester was synthesized. The molecular structure and spectroscopic analysis were performed using experimental techniques like FT-IR, 1H,13C NMR, mass and UV-visible as well as theoretical calculations. The theoretical calculations were done by DFT level of theory using B3LYP/6-31G (d,p) basis set. The vibrational wavenumbers were calculated using DFT method and assigned with the help of potential energy distribution (PED). The electronic properties such as frontier orbitals and band gap energies have been calculated using time dependent density functional theory (TD-DFT). The strength and nature of weak intramolecular interactions have been studied by AIM approach. Global and local reactivity descriptors have been computed to predict reactivity and reactive sites in the molecule. First hyperpolarizability values have been calculated to describe the nonlinear optical (NLO) property of the synthesized compounds. Molecular electrostatic potential (MEP) analysis has also been carried out. The anti-hepatic cancer activity of compound 2 was also carried out.
Synthesis, crystal growth, single crystal X-ray analysis and vibrational spectral studies of (2E)-3-(2-chloro-4-fluorophenyl)-1-(3,4-dimethoxyphenyl)prop-2-en-1-one: A combined DFT study

NASA Astrophysics Data System (ADS)

Chidan Kumar, C. S.; Balachandran, V.; Fun, Hoong-Kun; Chandraju, Siddegowda; Quah, Ching Kheng

2015-11-01

A new chalcone derivative, (2E)-3-(2-chloro-4-fluorophenyl)-1-(3,4-dimethoxyphenyl)prop-2-en-1-one (a) was synthesized and single crystals were grown by slow evaporation technique. The FT-Raman and FT-IR spectra of the sample were recorded in the region 3500-100 cm-1 and 4000-400 cm-1 respectively. The spectra were interpreted with the aid of normal coordinate analysis, following structure optimizations and force field calculations based on B3LYP/6-31G (d) level of theory. Normal coordinate calculations were performed using the DFT force field corrected by a recommended set of scaling factors yielding fairly good agreement between the observed and calculated wavenumbers. The total electron density and molecular electrostatic potential surfaces of the molecule were constructed using B3LYP/6-31G (d) method to display electrostatic potential (electron + nuclei) distribution, molecular shape, size, and dipole moments of the molecule. HOMO and LUMO energies were also calculated. Stability of the molecule arising from hyperconjugative interactions and charge delocalization has been analyzed using natural bond orbital (NBO) analysis. Global and local reactivity descriptors and dipole moment (μ), static polarizability (α), first order hyperpolarizability (β) and optical gap (ΔE) were also calculated to study the NLO property of our title compound.
Vibrational spectroscopic study, charge transfer interaction and nonlinear optical properties of L-asparaginium picrate: a density functional theoretical approach.

PubMed

Elleuch, Nabil; Amamou, Walid; Ben Ahmed, Ali; Abid, Younes; Feki, Habib

2014-07-15

Single crystals of L-asparaginium picrate (LASP) were grown by slow evaporation technique at room temperature and were the subject of an X-ray powder diffraction study to confirm the crystalline nature of the synthesized compound. FT-IR and Raman spectra were recorded and analyzed with the aid of the density functional theory (DFT) calculations in order to make a suitable assignment of the observed bands. The optimum molecular geometry, normal mode wavenumbers, infrared and Raman intensities and the first hyperpolarizability were investigated with the help of B3LYP method using 6-31G(d) basis set. The theoretical FT-IR and Raman spectra of LASP were simulated and compared with the experimental data. A good agreement was shown and a reliable vibrational assignment was made. Natural bond orbital (NBO) analysis was carried out to demonstrate the various inter and intramolecular interactions that are responsible for the stabilization of the title compound leading to high NLO activity. A study on the electronic properties was performed by time-dependent DFT (TD-DFT) approach. The lowering in the HOMO and LUMO energy gap explains the eventual charge transfer interactions that take place within the molecules. Copyright © 2014 Elsevier B.V. All rights reserved.
Multiplex coherent raman spectroscopy detector and method

NASA Technical Reports Server (NTRS)

Joyner, Candace C. (Inventor); Patrick, Sheena T. (Inventor); Chen, Peter (Inventor); Guyer, Dean R. (Inventor)

2004-01-01

A multiplex coherent Raman spectrometer (10) and spectroscopy method rapidly detects and identifies individual components of a chemical mixture separated by a separation technique, such as gas chromatography. The spectrometer (10) and method accurately identify a variety of compounds because they produce the entire gas phase vibrational Raman spectrum of the unknown gas. This is accomplished by tilting a Raman cell (20) to produce a high-intensity, backward-stimulated, coherent Raman beam of 683 nm, which drives a degenerate optical parametric oscillator (28) to produce a broadband beam of 1100-1700 nm covering a range of more than 3000 wavenumber. This broadband beam is combined with a narrowband beam of 532 nm having a bandwidth of 0.003 wavenumbers and focused into a heated windowless cell (38) that receives gases separated by a gas chromatograph (40). The Raman radiation scattered from these gases is filtered and sent to a monochromator (50) with multichannel detection.
Multiplex coherent raman spectroscopy detector and method

DOEpatents

Chen, Peter; Joyner, Candace C.; Patrick, Sheena T.; Guyer, Dean R.

2004-06-08

A multiplex coherent Raman spectrometer (10) and spectroscopy method rapidly detects and identifies individual components of a chemical mixture separated by a separation technique, such as gas chromatography. The spectrometer (10) and method accurately identify a variety of compounds because they produce the entire gas phase vibrational Raman spectrum of the unknown gas. This is accomplished by tilting a Raman cell (20) to produce a high-intensity, backward-stimulated, coherent Raman beam of 683 nm, which drives a degenerate optical parametric oscillator (28) to produce a broadband beam of 1100-1700 nm covering a range of more than 3000 wavenumber. This broadband beam is combined with a narrowband beam of 532 nm having a bandwidth of 0.003 wavenumbers and focused into a heated windowless cell (38) that receives gases separated by a gas chromatograph (40). The Raman radiation scattered from these gases is filtered and sent to a monochromator (50) with multichannel detection.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Costa, R. C. da; Universidade Federal de Campina Grande, Pombal-PB, 58840-000; Toledo, T. A. de

The effects of the atomic substitution of Pb by Ni in the PbTiO{sub 3} ferroelectric perovskite on the vibrational and structural properties was studied using x-ray diffraction and Raman scattering. It was observed that for Ni concentrations between 0.0 and 0.4, there is the formation of a solid solution with reduction of the Raman wavenumber of the E(TO1) soft mode and the tetragonallity factor, which influence directly the temperature of the tetragonal ferroelectric to cubic paraelectric phase transition, the Curie temperature. For concentrations greater than 0.4, it is observed the formation of a PbTiO{sub 3} and NiTiO{sub 3} composite, denouncedmore » by the recovering of the both, tetragonallity factor and the E(TO1) soft mode wavenumber. The values of the Curie temperatures were estimated by the Raman scattering measurements for temperatures ranging from 300 to 950 K.« less
The ground state infrared spectrum of the MnH radical ( 7Σ) from diode laser spectroscopy

NASA Astrophysics Data System (ADS)

Urban, Rolf-Dieter; Jones, Harold

1989-11-01

The infrared spectrum of the manganese hydride radical ( 55MnH) in its ground electronic state ( 7Σ) has been observed using a diode laser spectrometer. The wavenumbers of twelve transitions of the v=1→0 band, five of the v=2→1 band and seven of the v=3→2 band have been measured with a nominal accuracy of ±0.001 cm -1. Coupling between the electronic spin ( S=3) and the overall molecular rotation causes each ro-vibrational transition with N>3 to be split (γ splitting) into seven components each separated by a few hundredths of a wavenumber. In most cases the complete structure was resolved. Correction terms arising from spin-spin coupling had to be included in the analysis. This work has produced the most accurate set of ground-state parameters available for MnH.
Fuselage shell and cavity response measurements on a DC-9 test section

NASA Technical Reports Server (NTRS)

Simpson, M. A.; Mathur, G. P.; Cannon, M. R.; Tran, B. N.; Burge, P. L.

1991-01-01

A series of fuselage shell and cavity response measurements conducted on a DC-9 aircraft test section are described. The objectives of these measurements were to define the shell and cavity model characteristics of the fuselage, understand the structural-acoustic coupling characteristics of the fuselage, and measure the response of the fuselage to different types of acoustic and vibration excitation. The fuselage was excited with several combinations of acoustic and mechanical sources using interior and exterior loudspeakers and shakers, and the response to these inputs was measured with arrays of microphones and accelerometers. The data were analyzed to generate spatial plots of the shell acceleration and cabin acoustic pressure field, and corresponding acceleration and pressure wavenumber maps. Analysis and interpretation of the spatial plots and wavenumber maps provided the required information on modal characteristics, structural-acoustic coupling, and fuselage response.
Anharmonic Resonances among Low-Lying Vibrational Levels of Methyl Iso-Cyanide (H_3CNC)

NASA Astrophysics Data System (ADS)

Pracna, P.; Urban, J.; Urban, V. S.; Varga, J.; Horneman, V.-M.

2010-06-01

Vibrational levels up to 1000 wn of H_3C-N≡C are currently studied in FTIR spectra together with rotational transitions within these levels. This investigation comprises the low-lying excited vibrational levels of the CNC doubly degenerate bending vibration v8=1^± 1 (267.3 wn), v8=20,± 2 (524.6 wn (A), 545.3 wn (E)), and v8=3^± 1,± 3 (792.5 wn (A1+A2), 833.9 wn (E)), respectively, and the next higher fundamental level of the C-N valence vibration v4=1 (945 wn). All these vibrational levels exhibit cubic and quartic anharmonic resonances localized to moderate values of the rotational quantum number K≤10. Therefore the system of rovibrational levels has to be treated as a global polyad in order to describe all the available data quantitatively. The ground state constants have been improved considerably by extending the assignments to higher J/K rotational states both in the purely rotational spectra recorded in the ground vibrational level and in the ground state combination differences generated from the wavenumbers assigned in the fundamental ν_4 band. Similarities and differences with respect to isoelectronic molecules CH_3CN and CH_3CCH are discussed.
Structural and spectroscopic characterization, reactivity study and charge transfer analysis of the newly synthetized 2-(6-hydroxy-1-benzofuran-3-yl) acetic acid

NASA Astrophysics Data System (ADS)

Murthy, P. Krishna; Krishnaswamy, G.; Armaković, Stevan; Armaković, Sanja J.; Suchetan, P. A.; Desai, Nivedita R.; Suneetha, V.; SreenivasaRao, R.; Bhargavi, G.; Aruna Kumar, D. B.

2018-06-01

The title compound 2-(6-hydroxy-1-benzofuran-3-yl) acetic acid (abbreviated as HBFAA) has been synthetized and characterized by FT-IR, FT-Raman and NMR spectroscopic techniques. Solid state crystal structure of HBFAA has been determined by single crystal X-ray diffraction technique. The crystal structure features O-H⋯O and C-H⋯O intermolecular interactions resulting in a two dimensional supramolecular architecture. The presence of various intermolecular interactions is well supported by the Hirshfeld surface analysis. The molecular properties of HBFAA were performed by Density functional theory (DFT) using B3LYP/6-311G++(d,p) method at ground state in gas phase, compile these results with experimental values and shows mutual agreement. The vibrational spectral analysis were carried out using FT-IR and FT-Raman spectroscopic techniques and assignment of each vibrational wavenumber made on the basis of potential energy distribution (PED). And also frontier orbital analysis (FMOs), global reactivity descriptors, non-linear optical properties (NLO) and natural bond orbital analysis (NBO) of HBFAA were computed with same method. Efforts were made in order to understand global and local reactivity properties of title compound by calculations of MEP, ALIE, BDE and Fukui function surfaces in gas phase, together with thermodynamic properties. Molecular dynamics simulation and radial distribution functions were also used in order to understand the influence of water to the stability of title compound. Charge transfer between molecules of HBFAA has been investigated thanks to the combination of MD simulations and DFT calculations.
Synthesis of 4-((1E, 6E)-7-(4-hydroxy-3-methoxyphenyl)-3, 5-dioxohepta-1, 6-dienyl)-2-methoxyphenyl 4-fluorobenzoate, a novel monoester derivative of curcumin, its experimental and theoretical (DFT) studies

NASA Astrophysics Data System (ADS)

Srivastava, Sangeeta; Gupta, Preeti; Amandeep; Singh, Ranvijay Pratap

2016-04-01

Curcumin (1), isolated as a major component from the chloroform extract of Curcuma longa was converted to its ester derivative 4-((1E, 6E)-7-(4-hydroxy-3-methoxyphenyl)-3,5-dioxohepta-1,6-dienyl)-2-methoxyphenyl 4-fluorobenzoate (2). The compound has been characterized with the help of 1H, 13C NMR, UV, IR and mass spectrometry. The molecular geometry of synthesized compound was calculated in ground state by Density functional theory (DFT/B3LYP) using 6-31G (d,p) basis set. 1H and 13C NMR chemical shifts were calculated in ground state by using Gauge-Including Atomic Orbital (GIAO) approach and these values were correlated with experimental observations. The electronic properties such as HOMO and LUMO energies were calculated using time dependent Density Functional Theory (TD-DFT). Stability of the molecule as a result of hyper conjugative interactions and electron delocalization were analysed using Natural bond orbital (NBO) analysis. Intramolecular interactions were analysed by AIM (Atom in molecule) approach. Global reactivity descriptors were calculated to study the reactive site within molecule. The vibrational wavenumbers were calculated using DFT method and assigned with the help of potential energy distribution (PED). First hyperpolarizability values have been calculated to describe the nonlinear optical (NLO) property of the synthesized compounds. Molecular electrostatic potential (MEP) analysis has also been carried out.
Analysis of bubble plume spacing produced by regular breaking waves

NASA Astrophysics Data System (ADS)

Phaksopa, J.; Haller, M. C.

2012-12-01

The breaking wave process in the ocean is a significant mechanism for energy dissipation, splash, and entrainment of air. The relationship between breaking waves and bubble plume characteristics is still a mystery because of the complexity of the breaking wave mechanism. This study takes a unique approach to quantitatively analyze bubble plumes produced by regular breaking waves. Various previous studies have investigated the formation and the characteristics of bubble plumes using either field observations, laboratory experiments, or numerical modeling However, in most observational work the plume characteristics have been studied from the underneath the water surface. In addition, though numerical simulations are able to include much of the important physics, the computational costs are high and bubble plume events are only simulated for short times. Hence, bubble plume evolution and generation throughout the surf zone is not yet computationally feasible. In the present work we take a unique approach to analyzing bubble plumes. These data may be of use for model/data comparisons as numerical simulations become more tractable. The remotely sensed video data from freshwater breaking waves in the OSU Large Wave Flume (Catalan and Haller, 2008) are analyzed. The data set contains six different regular wave conditions and the video intensity data are used to estimate the spacing of plume events (wavenumber spectrum), to calculate the spectral width (i.e. the range of plume spacing), and to relate these with the wave conditions. The video intensity data capture the evolution of the wave passage over a fixed bed arranged in a bar-trough morphology. Bright regions represent the moving path or trajectory coincident with bubble plume of each wave. It also shows the bubble foam were generated and released from wave crest shown in the form of bubble tails with almost regular spacing for each wave. The bubble tails show that most bubbles did not move along with wave. For the estimation of wavenumber spectrum, the density is high at low wavenumber and it decreases toward high wavenumber. The average spectrum bandwidth was estimated and represented as the bubble event spacing for each run. It is found that its magnitude varies with wave conditions range from 8.81 - 11.82 and is related to the waveheight. Additionally, the calculated wavenumbers from power density function vary in the range of 0.80 - 1.58 meters-1. It is found that the bubble wavenumbers are mostly higher than the wavenumbers calculated from the linear wave theory between 0.2L-0.7L. In other words, the bubble plume length does not exceed the progressive wavelength.
Torsional Splitting in the Degenerate Vibrational States of (70)Ge(2)H(6): Rotation-Torsion Analysis of the nu(7) and nu(9) Fundamentals.

PubMed

Lattanzi; di Lauro C; Bürger; Mkadmi

2000-09-01

The rotational and torsional structure of the nu(7) and nu(9) degenerate fundamentals of (70)Ge(2)H(6) has been analyzed under high resolution. The torsional structure of both v(7) = 1 and v(9) = 1 states can be fitted by a simple one-parameter formula. The x,y-Coriolis interaction with the parallel nu(5) fundamental was accounted for in the analysis of nu(7). A strong perturbation of the J structure of the E(3s) torsional component of the KDeltaK = -2 subbranches of nu(9) can be explained by the resonance with an E(3s) excited level of the pure torsional manifold. The perturber is centered at 361.58 cm(-1), very close to the value estimated with a barrier height of 285 cm(-1). This confirms that the fundamental torsional wavenumber is close to 103 cm(-1), in good agreement with the "ab initio" prediction. The torsional splittings of all the infrared active degenerate fundamentals, nu(7), nu(8), and nu(9), follow the trend predicted by theory, and have been fitted by exploratory calculations accounting only for the torsional Coriolis-coupling mechanism of all degenerate vibrational fundamentals in several torsional states. This confirms that torsional Coriolis coupling is the dominant mechanism responsible for the decrease of the torsional splitting in the degenerate vibrational states. A higher value of the barrier had to be used for the nu(9) mode. Copyright 2000 Academic Press.
DFT simulation, quantum chemical electronic structure, spectroscopic and structure-activity investigations of 2-benzothiazole acetonitrile.

PubMed

Arjunan, V; Thillai Govindaraja, S; Jose, Sujin P; Mohan, S

2014-07-15

The Fourier transform infrared and FT-Raman spectra of 2-benzothiazole acetonitrile (BTAN) have been recorded in the range 4000-450 and 4000-100 cm(-1) respectively. The conformational analysis of the compound has been carried out to obtain the stable geometry of the compound. The complete vibrational assignment and analysis of the fundamental modes of the compound are carried out using the experimental FTIR and FT-Raman data and quantum chemical studies. The experimental vibrational frequencies are compared with the wavenumbers derived theoretically by B3LYP gradient calculations employing the standard 6-31G(**), high level 6-311++G(**) and cc-pVTZ basis sets. The structural parameters, thermodynamic properties and vibrational frequencies of the normal modes obtained from the B3LYP methods are in good agreement with the experimental data. The (1)H (400 MHz; CDCl3) and (13)C (100 MHz;CDCl3) nuclear magnetic resonance (NMR) spectra are also recorded. The electronic properties, the energies of the highest occupied and lowest unoccupied molecular orbitals are measured by DFT approach. The kinetic stability of the molecule has been determined from the frontier molecular orbital energy gap. The charges of the atoms and the structure-chemical reactivity relations of the compound are determined by its chemical potential, global hardness, global softness, electronegativity, electrophilicity and local reactivity descriptors by conceptual DFT methods. The non-linear optical properties of the compound have been discussed by measuring the polarisability and hyperpolarisability tensors. Copyright © 2014 Elsevier B.V. All rights reserved.
Hydrogen bonding in hydrates with one acetic acid molecule.

PubMed

Pu, Liang; Sun, Yueming; Zhang, Zhibing

2010-10-14

Hydrogen bonding (H-bond) interaction significantly influences the separation of acetic acid (HAc) from the HAc/H(2)O mixtures, especially the dilute solution, in distillation processes. It has been examined from the HAc mono-, di-, tri-, and tetrahydrates by analyzing the structures, binding energies, and infrared vibrational frequencies from quantum chemical calculations. For the first coordinate shell the 6-membered head-on ring is surely the most favorable structure because it has (1) the most favorable H-bonding parameters, (2) almost the largest binding energy per H-bond, (3) the biggest wavenumber shifts, and (4) the highest ring distribution (the AIMD simulations). Moreover, the comparison of the calculations with the experiments (the X-ray scattering data and IR frequencies) suggests that the possible structures in dilute aqueous solution are those involving two or more coordinate shells. The H-bonding in these water-surrounded HAc hydrates are the origin of the low-efficiency problem of isolating HAc from the dilute HAc/H(2)O mixtures. It is apparently a tougher work to break the H-bonds among HAc and the surrounded H(2)O molecules with respect to the case of more concentrated solutions, where the dominant structures are HAc or H(2)O aggregates.
Linear stiff string vibrations in musical acoustics: Assessment and comparison of models.

PubMed

Ducceschi, Michele; Bilbao, Stefan

2016-10-01

Strings are amongst the most common elements found in musical instruments and an appropriate physical description of string dynamics is essential to modelling, analysis, and simulation. For linear vibration in a single polarisation, the most common model is based on the Euler-Bernoulli beam equation under tension. In spite of its simple form, such a model gives unbounded phase and group velocities at large wavenumbers, and such behaviour may be interpreted as unphysical. The Timoshenko model has, therefore, been employed in more recent works to overcome such shortcoming. This paper presents a third model based on the shear beam equations. The three models are here assessed and compared with regard to the perceptual considerations in musical acoustics.
Infrared spectrometric study of acid-degradable glasses.

PubMed

De Maeyer, E A P; Verbeeck, R M H; Vercruysse, C W J

2002-08-01

The composition of glasses used in glass-ionomer cements affects their leaching behavior and hence the properties of the cement. The aim of this study was to correlate the composition and leaching behavior of these glasses with their infrared absorption characteristics. The wavenumber of the absorption band of the Si-O asymmetric stretching vibration shifts to a higher value with decreasing content of mono- and bivalent cations in the glass. This effect can be ascribed to the influence of these extraneous ions on the glass network order and connectivity. Preferential leaching of these ions induces an increase of asymmetric stretching vibration and a general modification of the band profile. The results can be correlated with the x-ray diffraction characteristics of the glass.
Environment-dependent conformation investigation of 3-amino-1,2,4-triazole (3-AT): Raman Spectroscopy and density functional theory

NASA Astrophysics Data System (ADS)

Meng, Shuang; Zhao, Yanying; Xue, Jiadan; Zheng, Xuming

2018-02-01

In the paper, diverse tautomers of 3-amino-1,2,4-triazole (3AT) in solid and polar solvent have been explored by FT-IR, FT-Raman and 488 nm Raman experiments combing with quantum chemical theoretical calculation using PCM solvent model and normal mode analysis. The vibrational spectra prefer the 3-amino-1,2,4-2H-triazole (2H-3AT) dimer in solid, while in a polar solvent 3AT is apt to the 3-amino-1,2,4-2H-triazole (2H-3AT) monomer. The significant wavenumber difference and Raman intensity patterns in solid and different solvents are induced by hydrogen bond perturbation along > NH ⋯ N ≤ hydrogen bonds on five-membered N-heterocyclic ring. The ground state proton transfer reaction mechanism along the five-membered N-heterocyclic ring is supported by intermolecular hydrogen bonding between 3AT and protonic solvent molecules.
A highly accurate ab initio potential energy surface for methane.

PubMed

Owens, Alec; Yurchenko, Sergei N; Yachmenev, Andrey; Tennyson, Jonathan; Thiel, Walter

2016-09-14

A new nine-dimensional potential energy surface (PES) for methane has been generated using state-of-the-art ab initio theory. The PES is based on explicitly correlated coupled cluster calculations with extrapolation to the complete basis set limit and incorporates a range of higher-level additive energy corrections. These include core-valence electron correlation, higher-order coupled cluster terms beyond perturbative triples, scalar relativistic effects, and the diagonal Born-Oppenheimer correction. Sub-wavenumber accuracy is achieved for the majority of experimentally known vibrational energy levels with the four fundamentals of (12)CH4 reproduced with a root-mean-square error of 0.70 cm(-1). The computed ab initio equilibrium C-H bond length is in excellent agreement with previous values despite pure rotational energies displaying minor systematic errors as J (rotational excitation) increases. It is shown that these errors can be significantly reduced by adjusting the equilibrium geometry. The PES represents the most accurate ab initio surface to date and will serve as a good starting point for empirical refinement.
Structural and DC electrical resistivity, magnetic properties of Co0.5M0.5Fe2O4 (M= Ni, Zn, and Mg) ferrite nanoparticles

NASA Astrophysics Data System (ADS)

Ramakrishna, A.; Murali, N.; Mammo, Tulu Wegayehu; Samatha, K.; Veeraiah, V.

2018-04-01

Inverse spinel structured nanoparticles of cobalt ferrite partially substituted by divalent cations of Ni, Zn, and Mg have been synthesized through sol-gel auto combustion route. Structural parameters are studied by powder X-ray diffraction at the diffraction angle range of 10-80°; and FT-IR spectroscopy in the wavenumber range of 1600-400 cm-1. Lattice parameters were calculated from the (hkl) values of the diffraction planes and interplanar spacing and found to be in the range of 8.3659-8.4197 Å. The surface morphology and crystalline nature are studied using scanning electron microscopy and also using HRTEM. The magnetic properties are analyzed through vibrating sample magnetometer. High saturation magnetization of 90.12 emu/g has been achieved from Co-Zn sample whereas high coercive force of 883.45 Oe is achieved in Co-Ni sample. A two-probe DC resistivity was measured in temperature ranges of 300-450 K.
Full-field inspection of three-dimensional structures using steady-state acoustic wavenumber spectroscopy

NASA Astrophysics Data System (ADS)

Koskelo, Elise Anne C.; Flynn, Eric B.

2017-02-01

Inspection of and around joints, beams, and other three-dimensional structures is integral to practical nondestructive evaluation of large structures. Non-contact, scanning laser ultrasound techniques offer an automated means of physically accessing these regions. However, to realize the benefits of laser-scanning techniques, simultaneous inspection of multiple surfaces at different orientations to the scanner must not significantly degrade the signal level nor diminish the ability to distinguish defects from healthy geometric features. In this study, we evaluated the implementation of acoustic wavenumber spectroscopy for inspecting metal joints and crossbeams from interior angles. With this technique, we used a single-tone, steady-state, ultrasonic excitation to excite the joints via a single transducer attached to one surface. We then measured the full-field velocity responses using a scanning Laser Doppler vibrometer and produced maps of local wavenumber estimates. With the high signal level associated with steady-state excitation, scans could be performed at surface orientations of up to 45 degrees. We applied camera perspective projection transformations to remove the distortion in the scans due to a known projection angle, leading to a significant improvement in the local estimates of wavenumber. Projection leads to asymmetrical distortion in the wavenumber in one direction, making it possible to estimate view angle even when neither it nor the nominal wavenumber is known. Since plate thinning produces a purely symmetric increase in wavenumber, it also possible to independently estimate the degree of hidden corrosion. With a two-surface joint, using the wavenumber estimate maps, we were able to automatically calculate the orthographic projection component of each angled surface in the scan area.
Analysis of Distribution of Polyvinyl Alcohol Hydrogel Nanocrystalline by using SAXS Synchrotron

NASA Astrophysics Data System (ADS)

Sunaryono; Taufiq, A.; Mufti, N.; Hidayat, N.; Rugmai, S.; Soontaranon, S.; Putra, E. G. R.; Darminto

2017-05-01

Polyvinyl alcohol (PVA) hydrogel has been successfully synthesized through freezing-thawing (F-T) process by using time-variation. This work is aimed to investigate the distribution of nanocrystalline from the hydrogel. Fourier Transform Infrared (FTIR) Spectroscopy, Differential Thermal Analysis/Thermogravimetric (DTA/TG), and Synchrotron Small-Angle X-ray Scattering (SAXS) were used as the instruments in characterizing the PVA hydrogel, respectively to observe the frequency of absorption, thermal degradation, and structural dimensions. The functional groups which represent the PVA polymer chains were verified on the wavenumber of 1450-1480 cm-1 and 850-870 cm-1 which is in accordance with the stretching of -CH2 vibration mode. The absorption band of PVA polymer chains was also found on the wavenumber of 1090-1150 cm-1 which is in accordance with the stretching of carboxyl vibration mode (CO), and this wavenumber gave a contribution towards the crystallinity of PVA polymer. Furthermore, the PVA polymer only interacted with the distilled water in the sample of PVA hydrogel without experiencing any chemical interactions between the PVA polymer and other substances. Meanwhile, the graphic of PVA hydrogel thermal degradation shows three thermal decompositions which are indicated by three areas in which there was sample weight loss. The second decomposition with sample weight loss was equivalent to 61.62%-73.04% occurred at the temperature of 282-376 °C which became the highest sample weight loss due to polymer chain degradation. Teubner-Strey and Beaucage models were used to analyze the characterization of structural dimension and distribution of PVA Hydrogel nanocrystalline with SAXS Synchrotron. With a high compatibility between the model data and the experiment, the average structural dimension of PVA hydrogel nanocrystalline is the equivalent of 3.96 nm, with an inter-crystalline average distance of 16.9 nm. These results indicate that PVA hydrogel is very potential to be applied as a primary material for human implants.
CH stretching vibration of N-methylformamide as a sensitive probe of its complexation: infrared matrix isolation and computational study.

PubMed

Sałdyka, M; Mielke, Z; Mierzwicki, K; Coussan, S; Roubin, P

2011-08-21

The complexes between trans-N-methylformamide (t-NMF) and Ar, N(2), CO, H(2)O have been studied by infrared matrix isolation spectroscopy and/or ab initio calculations. The infrared spectra of NMF/Ne, NMF/Ar and NMF/N(2)(CO,H(2)O)/Ar matrices have been measured and the effect of the complexation on the perturbation of t-NMF frequencies was analyzed. The geometries of the complexes formed between t-NMF and Ar, N(2), CO and H(2)O were optimized in two steps at the MP2/6-311++G(2d,2p) level of theory. The four structures, found for every system at this level, were reoptimized on the CP-corrected potential energy surface; both normal and CP corrected harmonic frequencies and intensities were calculated. For every optimized structure the interaction energy was partitioned according to the SAPT scheme and the topological distribution of the charge density (AIM theory) was performed. The analysis of the experimental and theoretical results indicates that the t-NMF-N(2) and CO complexes present in the matrices are stabilized by very weak N-H···N and N-H···C hydrogen bonds in which the N-H group of t-NMF serves as a proton donor. In turn, the t-NMF-H(2)O complex present in the matrix is stabilized by O-H···O(C) hydrogen bonding in which the carbonyl group of t-NMF acts as a proton acceptor. Both, the theoretical and experimental results indicate that involvement of the NH group of t-NMF in formation of very weak hydrogen bonds with the N(2) or CO molecules leads to a clearly noticeable red shift of the CH stretching wavenumber whereas engagement of the CO group as a proton acceptor triggers a blue shift of this wavenumber.
One pot synthesis of Curcumin-NSAIDs prodrug, spectroscopic characterization, conformational analysis, chemical reactivity, intramolecular interactions and first order hyperpolarizability by DFT method

NASA Astrophysics Data System (ADS)

Srivastava, Sangeeta; Gupta, Preeti; Sethi, Arun; Singh, Ranvijay Pratap

2016-08-01

A novel Curcumin-NSAIDs prodrug 4-((1E, 3Z, 6E)-3-hydroxy-(4-hydroxy-3-methoxyphenyl)-5-oxohepta-1,3,3-trienyl)-2-methoxyphenyl-2-(4-isobutylphenyl) propanoate (2) derivative was synthesized by Steglich esterification in high yield and characterized with the help of 1H, 13C NMR, 1H-1H COSY, UV, FT-IR spectroscopy and mass spectrometry. The molecular geometry of synthesized compound was calculated in ground state by Density functional theory (DFT/B3LYP) using two different basis set 6-31G (d, p) and 6-311G (d, p). Conformational analysis of 2 was carried out to determine the most stable conformation. Stability of the molecule as a result of hyperconjugative interactions and electron delocalization were analysed using Natural bond orbital (NBO) analysis. Intramolecular interactions were analysed by AIM (Atom in molecule) approach. Global and local reactivity descriptors were calculated to study the reactive site within molecule. The electronic properties such as HOMO and LUMO energies were calculated using time dependent Density Functional Theory (TD-DFT). The vibrational wavenumbers were calculated using DFT method and assigned with the help of potential energy distribution (PED). First hyperpolarizability value has been calculated to describe the nonlinear optical (NLO) property of the synthesized compound. Molecular electrostatic potential (MEP) for synthesized compounds have also been determined to check their electrophilic or nucleophilic reactivity.
CH3Cl, CH2Cl2, CHCl3, and CCl4: Infrared spectra, radiative efficiencies, and global warming potentials

NASA Astrophysics Data System (ADS)

Wallington, Timothy J.; Pivesso, Bruno Pasquini; Lira, Alane Moura; Anderson, James E.; Nielsen, Claus Jørgen; Andersen, Niels Højmark; Hodnebrog, Øivind

2016-05-01

Infrared spectra for the title compounds were measured experimentally in 700 Torr of air at 295 K and systematically modeled in B3LYP, M06-2X and MP2 calculations employing various basis sets. Calibrated infrared spectra over the wavenumber range 600-3500 cm-1 are reported and combined with literature data to provide spectra for use in experimental studies and radiative transfer calculations. Integrated absorption cross sections are (units of cm-1 molecule-1): CH3Cl, 660-780 cm-1, (3.89±0.19)×10-18; CH2Cl2, 650-800 cm-1, (2.16±0.11)×10-17; CHCl3, 720-810 cm-1, (4.08±0.20)×10-17; and CCl4, 730-825 cm-1, (6.30±0.31)×10-17. CH3Cl, CH2Cl2, CHCl3, and CCl4 have radiative efficiencies of 0.004, 0.028, 0.070, and 0.174 W m-2 ppb-1 and global warming potentials (100 year horizon) of 5, 8, 15, and 1775, respectively. Quantum chemistry calculations generally predict larger band intensities than the experimental values. The best agreement with experiments is obtained in MP2(Full) calculations employing basis sets of at least triple-zeta quality augmented by diffuse functions. The B3LYP functional is found ill-suited for calculating vibrational frequencies and infrared intensities of halocarbons.

DFT investigation of the vibrational properties of GC Watson-Crick and Hoogsteen base pairs in the presence of Mg²⁺, Ca²⁺, and Cu²⁺ ions.

PubMed

Morari, Cristian; Muntean, Cristina M; Tripon, Carmen; Buimaga-Iarinca, Luiza; Calborean, Adrian

2014-04-01

The binding effects of Mg²⁺, Ca²⁺, and Cu²⁺ ions on the vibrational properties of guanine-cytosine base pairs have been performed using density functional theory investigations. Both Watson-Crick and Hoogsteen configurations of the base pairs were investigated. In Watson-Crick configuration, the metal was coordinated at N7 atom of guanine, while in the case of Hoogsteen configuration, the coordination is at N3 atom of guanine. We have pointed out the geometric properties of the metal-GC base pairs structure, as well as the vibrational bands that can be used to detect the presence of metallic ions in the Watson-Crick and Hoogsteen GC structures. For the geometric models used by us, the vibrational amplitudes of metallic atoms were stronger for wavenumbers lower than 500 cm⁻¹. This suggests that in the experimental studies on DNA the presence of the three metallic atoms (Mg, Ca, and Cu) can be explicitly detected at low frequencies.
Vibrational normal modes of diazo-dimedone: A comparative study by Fourier infrared/Raman spectroscopies and conformational analysis by MM/QM

NASA Astrophysics Data System (ADS)

Téllez Soto, C. A.; Ramos, J. M.; Rianelli, R. S.; de Souza, M. C. B. V.; Ferreira, V. F.

2007-07-01

The 2-diazo-5,5-dimethyl-cyclohexane-1,3-dione ( 3) was synthesized and the FT-IR/Raman spectra were measured with the purpose of obtain a full assignment of the vibrational modes. Singular aspects concerning the -C dbnd N dbnd N oscillator are discussed in view of two strong bands observed in the region of 2300-2100 cm -1 in both, Infrared and Raman spectra. The density functional theory (DFT) was used to obtain the geometrical structure and for assisting in the vibrational assignment joint to the traditional normal coordinate analysis (NCA). The observed wavenumbers at 2145 (IR), 2144(R) are assigned as the coupled ν(N dbnd N) + ν(C dbnd N) vibrational mode with higher participation of the N dbnd N stretching. A 2188 cm -1 (IR) and at 2186 cm -1 (R) can be assigned as a overtone of one of ν(CC) normal mode or to a combination band of the fundamentals δ(CCH) found at 1169 cm -1 and the δ (CC dbnd N) found at 1017 cm -1 enhanced by Fermi resonance.
Consistent assignment of the vibrations of symmetric and asymmetric para-disubstituted benzene molecules

NASA Astrophysics Data System (ADS)

Andrejeva, Anna; Gardner, Adrian M.; Tuttle, William D.; Wright, Timothy G.

2016-03-01

We give a description of the phenyl-ring-localized vibrational modes of the ground states of the para-disubstituted benzene molecules including both symmetric and asymmetric cases. In line with others, we quickly conclude that the use of Wilson mode labels is misleading and ambiguous; we conclude the same regarding the related ones of Varsányi. Instead we label the modes consistently based upon the Mulliken (Herzberg) method for the modes of para-difluorobenzene (pDFB). Since we wish the labelling scheme to cover both symmetrically- and asymmetrically-substituted molecules, we apply the Mulliken labelling under C2v symmetry. By studying the variation of the vibrational wavenumbers with mass of the substituent, we are able to identify the corresponding modes across a wide range of molecules and hence provide consistent assignments. Particularly interesting are pairs of vibrations that evolve from in- and out-of-phase motions in pDFB to more localized modes in asymmetric molecules. We consider the para isomers of the following: the symmetric dihalobenzenes, xylene, hydroquinone, the asymmetric dihalobenzenes, halotoluenes, halophenols and cresol.
Vibrational spectroscopic (FT-IR and FT-Raman) studies, HOMO-LUMO, NBO analysis and MEP of 6-methyl-1-({[(2E)-2-methyl-3-phenyl-prop-2-en-1-yl]oxy}methyl)-1,2,3,4-tetra-hydroquinazoline-2,4-dione, a potential chemotherapeutic agent, using density functional methods.

PubMed

Sebastian, Sr S H Roseline; Al-Tamimi, Abdul-Malek S; El-Brollosy, Nasser R; El-Emam, Ali A; Yohannan Panicker, C; Van Alsenoy, Christian

2015-01-05

6-Methyl-1-({[(2E)-2-methyl-3-phenyl-prop-2-en-1-yl]oxy}methyl)-1,2,3,4-tetra-hydro quinazoline-2,4-dione was prepared via treatment of silylated 6-methylquinazoline-2,4-dione with bis-[(E)-2-methyl-3-phenylallyloxy]methane. FT-IR and FT-Raman spectra were recorded and analyzed. The vibrational wavenumbers were computed using DFT methods and are assigned with the help of potential energy distribution method. The first hyperpolarizability, infrared intensities and Raman activities also reported. The geometrical parameters of the title compound obtained from XRD studies are in agreement with the calculated (B3LYP) values. The stability of the molecule arising from hyper-conjugative interaction and charge delocalization has been analyzed using NBO analysis. The HOMO and LUMO analysis are used to determine the charge transfer within the molecule. MEP was performed by the B3LYP method and from the MEP it is evident that the negative charge covers the CO group and the positive region is over the phenyl ring and NH group. Copyright © 2014 Elsevier B.V. All rights reserved.
High-Resolution Infrared Studies of Perdeutero-Spiropentane, C 5D 8

DOE Office of Scientific and Technical Information (OSTI.GOV)

Erickson, Blake A.; Ju, X.; Nibler, Joseph W.

Perdeutero-spiropentane (C 5D 8) has been synthesized and infrared and Raman spectra are reported for the first time. Wavenumber assignments are made for most of the fundamental vibrational modes. Gas phase infrared spectra were recorded at a resolution (0.002 cm -1) sufficient to resolve individual rovibrational lines and show evidence of strong Coriolis and/or Fermi resonance interactions for most bands. However a detailed rovibrational analysis of the fundamental v 15 (b 2) parallel band proved possible and a fit of more than 1600 lines yielded a band origin of 1053.84465(10) cm -1 and ground state constants (in units of cmmore » -1): B 0 = 0.1120700(9), D J = 1.51(3) x10 -8, D JK = 3.42(15) x10 -8. We note that the B 0 value is significantly less than a value of Ba = 0.1140 cm-1 calculated using structural parameters from an earlier electron diffraction (ED) study, whereas one expects B a to be lower than B 0 because of thermal averaging over higher vibrational levels. A similar discrepancy was noted in an earlier study of C 5H 8 [1]. The structural and spectroscopic results are in good accord with values computed at the anharmonic level using the B3LYP density functional method with a cc-pVTZ basis set.« less
Density functional theory investigation of the geometric and electronic structures of [UO2(H2O)m(OH)n](2 - n) (n + m = 5).

PubMed

Ingram, Kieran I M; Häller, L Jonas L; Kaltsoyannis, Nikolas

2006-05-28

Gradient corrected density functional theory has been used to calculate the geometric and electronic structures of the family of molecules [UO2(H2O)m(OH)n](2 - n) (n + m = 5). Comparisons are made with previous experimental and theoretical structural and spectroscopic data. r(U-O(yl)) is found to lengthen as water molecules are replaced by hydroxides in the equatorial plane, and the nu(sym) and nu(asym) uranyl vibrational wavenumbers decrease correspondingly. GGA functionals (BP86, PW91 and PBE) are generally found to perform better for the cationic complexes than for the anions. The inclusion of solvent effects using continuum models leads to spurious low frequency imaginary vibrational modes and overall poorer agreement with experimental data for nu(sym) and nu(asym). Analysis of the molecular orbital structure is performed in order to trace the origin of the lengthening and weakening of the U-O(yl) bond as waters are replaced by hydroxides. No evidence is found to support previous suggestions of a competition for U 6d atomic orbitals in U-O(yl) and U-O(hydroxide)pi bonding. Rather, the lengthening and weakening of U-O(yl) is attributed to reduced ionic bonding generated in part by the sigma-donating ability of the hydroxide ligands.
Vibrational spectroscopic characterization of the phosphate mineral ludlamite (Fe,Mn,Mg)₃(PO₄)₂⋅4H₂O - a mineral found in lithium bearing pegmatites.

PubMed

Frost, Ray L; Xi, Yunfei; Scholz, Ricardo; Belotti, Fernanda M

2013-02-15

The objective of this work is to analyze ludlamite (Fe,Mn,Mg)(3)(PO(4))(2)⋅4H(2)O from Boa Vista mine, Galiléia, Brazil and to assess the molecular structure of the mineral. The phosphate mineral ludlamite has been characterized by EMP-WDS, Raman and infrared spectroscopic measurements. The mineral is shown to be a ferrous phosphate with some minor substitution of Mg and Mn. Raman bands at 917 and 950 cm(-1) are assigned to the symmetric stretching mode of HOPO(3)(2-) and PO(4)(3-) units. Raman bands at 548, 564, 599 and 634 cm(-1) are assigned to the ν(4)PO(4)(3-) bending modes. Raman bands at 2605, 2730, 2896 and 3190 cm(-1) and infrared bands at 2623, 2838, 3136 and 3185 cm(-1) are attributed to water stretching vibrations. By using a Libowitzky empirical function, hydrogen bond distances are calculated from the OH stretching wavenumbers. Strong hydrogen bonds in the structure of ludlamite are observed as determined by their hydrogen bond distances. The application of infrared and Raman spectroscopy to the study of ludlamite enables the molecular structure of the pegmatite mineral ludlamite to be assessed. Copyright © 2012 Elsevier B.V. All rights reserved.
The solvent dependent shift of the amide I band of a fully solvated peptide in methanol/water mixtures as a local probe for the solvent composition in the peptide/solvent interface

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gnanakaran, S

2008-01-01

We determine the shift and line-shape of the amide I band of a model AK-peptide from molecular dynamics (MD) simulations of the peptide dissolved in methanol/water mixtures with varying composition. The IR-spectra are determined from a transition dipole coupling exciton model. A simplified empirical model Hamiltonian is employed, taking both the effect of hydrogen bonding, as well as intramolecular vibrational coupling into account. We consider a single isolated AK-peptide in a mostly helical conformation, while the solvent is represented by 2600 methanol or water molecules, simulated for a pressure of 1 bar and a temperature of 300 K. Over themore » course of the simulations minor reversible conformational changes at the termini are observed, which are found to only slightly affect the calculated spectral properties. Over the entire composition range, varying from pure water to the pure methanol solvent, a monotonous blue-shift of the IR amide I band of about 8 wavenumbers is observed. The shift is found to be caused by two counter-compensating effects: An intramolecular red-shift of about 1.2 wavenumbers, due to stronger intramolecular hydrogen-bonding in a methanol-rich environment. Dominating, however, is the intermolecular solvent-dependent blue-shift of about 10 wavenumbers, being attributed to the less effective hydrogen bond donor capabilities of methanol compared to water. The importance of solvent-contribution to the IR-shift, as well as the significantly different hydrogen formation capabilities of water and methanol make the amide I band sensitive to composition changes in the local environment close the peptide/solvent interface. This allows, in principle, an experimental determination of the composition of the solvent in close proximity to the peptide surface. For the AK-peptide case they observe at low methanol concentrations a significantly enhanced methanol concentration at the peptide/solvent-interface, supposedly promoted by the partially hydrophobic character of the AK-peptide's solvent accessible surface.« less
Raman spectroscopic study of DL valine under pressure up to 20 GPa

NASA Astrophysics Data System (ADS)

Rêgo, F. S. C.; Lima, J. A.; Freire, P. T. C.; Melo, F. E. A.; Mendes Filho, J.; Polian, A.

2016-04-01

DL-valine crystal was studied by Raman spectroscopy under hydrostatic pressure using a diamond anvil cell from ambient pressure up to 19.4 GPa in the spectral range from 40 to 3300 cm-1. Modifications in the spectra furnished evidence of the occurrence of two structural phase transitions undergone by this racemic amino acid crystal. The classification of the vibrational modes, the behavior of their wavenumber as a function of the pressure and the reversibility of the phase transitions are discussed.
Vibrational structure and antimicrobial activity of selected isonicotinates, potassium picolinate and nicotinate

NASA Astrophysics Data System (ADS)

Koczoń, P.; Piekut, J.; Borawska, M.; Lewandowski, W.

2003-06-01

The lithium, sodium, potassium, rubidium and caesium isonicotinates, potassium picolinate and nicotinate (microbiological data) as well as sodium benzoate (as a referee for microbiological tests) were under study. The selected experimental bands occurring in the FT-IR and FT-Raman spectra of studied alkaline metal isonicotinates and potassium picolinate were assigned. The change of wavenumber of those bands was observed along the metal series and along the change of position of nitrogen in the aromatic ring. The linear combination of wavenumber of assigned bands (the principal component analysis) was performed to estimate the change in the electronic properties of the molecule along the metal series. The antimicrobial activity of studied complexes against yeasts Hansenula anomala, Saccharomyces cerevisiae, and bacteria Escherichia coli and Bacillus subtilis was measured after 24 and 48 h of incubation. The attempt was made, to find out if there is any correlation between the first principal component and the degree of growth inhibition exhibited by studied complexes in relation to studied microorganisms.
Distributed friction damping of travelling wave vibration in rods.

PubMed

Tangpong, Xiangqing W; Wickert, Jonathan A; Akay, Adnan

2008-03-13

A ring damper can be affixed to a rotating base structure such as a gear, an automotive brake rotor or a gas turbine's labyrinth air seal. Depending on the frequency range, wavenumber and level of preload, vibration of the base structure can be effectively and passively attenuated by friction that develops along the interface between it and the damper. The assembly is modelled as two rods that couple in longitudinal vibration through spatially distributed hysteretic friction, with each rod having periodic boundary conditions in a manner analogous to an unwrapped ring and disc. As is representative of rotating machinery applications, the system is driven by a travelling wave disturbance, and for that form of excitation, the base structure's and the damper's responses are determined without the need for computationally intensive simulation. The damper's performance can be optimized with respect to normal preload, and its effectiveness is insensitive to variations in preload or the excitation's magnitude when its natural frequency is substantially lower than the base structure's in the absence of contact.
ExoMol molecular line lists - XXVI: spectra of SH and NS

NASA Astrophysics Data System (ADS)

Yurchenko, Sergei N.; Bond, Wesley; Gorman, Maire N.; Lodi, Lorenzo; McKemmish, Laura K.; Nunn, William; Shah, Rohan; Tennyson, Jonathan

2018-04-01

Line lists for the sulphur-containing molecules SH (the mercapto radical) and NS are computed as part of the ExoMol project. These line lists consider transitions within the X 2Π ground state for 32SH, 33SH, 34SH and 32SD, and 14N32S, 14N33S, 14N34S, 14N36S and 15N32S. Ab initio potential energy (PEC) and spin-orbit coupling (SOC) curves are computed and then improved by fitting to experimentally observed transitions. Fully ab initio dipole moment curves (DMCs) computed at high level of theory are used to produce the final line lists. For SH, our fit gives a root-mean-square (rms) error of 0.03 cm-1 between the observed (vmax = 4, Jmax = 34.5) and calculated transitions wavenumbers; this is extrapolated such that all X 2Π rotational-vibrational-electronic (rovibronic) bound states are considered. For 32SH the resulting line list contains about 81 000 transitions and 2 300 rovibronic states, considering levels up to vmax = 14 and Jmax = 60.5. For NS the refinement used a combination of experimentally determined frequencies and energy levels and led to an rms fitting error of 0.002 cm-1. Each NS calculated line list includes around 2.8 million transitions and 31 000 rovibronic states with a vibrational range up to v = 53 and rotational range to J = 235.5, which covers up to 23 000 cm-1. Both line lists should be complete for temperatures up to 5000 K. Example spectra simulated using this line list are shown and comparisons made to the existing data in the CDMS database. The line lists are available from the CDS (http://cdsarc.u-strasbg.fr) and ExoMol (www.exomol.com) data bases.
The IUPAC Database of Rotational-Vibrational Energy Levels and Transitions of Water Isotopologues from Experiment and Theory

NASA Astrophysics Data System (ADS)

Császár, Attila G.; Furtenbacher, T.; Tennyson, Jonathan; Bernath, Peter F.; Brown, Linda R.; Campargue, Alain; Daumont, Ludovic; Gamache, Robert R.; Hodges, Joseph T.; Naumenko, Olga V.; Polyansky, Oleg L.; Rothman, Laurence S.; Vandaele, Ann Carine; Zobov, Nikolai F.

2014-06-01

The results of an IUPAC Task Group formed in 2004 on "A Database of Water Transitions from Experiment and Theory" (Project No. 2004-035-1-100) are presented. Energy levels and recommended labels involving exact and approximate quantum numbers for the main isotopologues of water in the gas phase, H216O, H218O, H217O, HD16O, HD18O, HD17O, D216O, D218O, and D217O, are determined from measured transition wavenumbers. The transition wavenumbers and energy levels are validated using the MARVEL (measured active rotational-vibrational energy levels) approach and first-principles nuclear motion computations. The extensive data, e.g., more than 200,000 transitions have been handled for H216O, including lines and levels that are required for analysis and synthesis of spectra, thermochemical applications, the construction of theoretical models, and the removal of spectral contamination by ubiquitous water lines. These datasets can also be used to assess where measurements are lacking for each isotopologue and to provide accurate frequencies for many yet-to-be measured transitions. The lack of high-quality frequency calibration standards in the near infrared is identified as an issue that has hindered the determination of high-accuracy energy levels at higher frequencies. The generation of spectra using the MARVEL energy levels combined with transition intensities computed using high accuracy ab initio dipole moment surfaces are discussed.
Raman spectroscopic analysis of oral squamous cell carcinoma and oral dysplasia in the high-wavenumber region

NASA Astrophysics Data System (ADS)

Carvalho, Luis Felipe C. S.; Bonnier, Franck; O'Callaghan, Kate; O'Sullivan, Jeff; Flint, Stephen; Neto, Lazaro P. M.; Soto, Cláudio A. T.; dos Santos, Laurita; Martin, Airton A.; Byrne, Hugh J.; Lyng, Fiona M.

2015-06-01

Raman spectroscopy can provide a molecular-level signature of the biochemical composition and structure of cells with excellent spatial resolution and could be useful to monitor changes in composition for early stage and non-invasive cancer diagnosis, both ex-vivo and in vivo. In particular, the fingerprint spectral region (400-1,800 cm-1) has been shown to be very promising for optical biopsy purposes. However, limitations to discrimination of dysplastic and inflammatory processes based on the fingerprint region still persist. In addition, the Raman spectral signal of dysplastic cells is one important source of misdiagnosis of normal versus pathological tissues. The high wavenumber region (2,800-3,600 cm-1) provides more specific information based on N-H, O-H and C-H vibrations and can be used to identify the subtle changes which could be important for discrimination of samples. In this study, we demonstrate the potential of the highwavenumber spectral region by collecting Raman spectra of nucleoli, nucleus and cytoplasm from oral epithelial cancer (SCC-4) and dysplastic (DOK) cell lines and from normal oral epithelial primary cells, in vitro, which were then analyzed by area under the curve as a method to discriminate the spectra. In this region, we will show the discriminatory potential of the CH vibrational modes of nucleic acids, proteins and lipids. This technique demonstrated more efficient discrimination than the fingerprint region when we compared the cell cultures.
Optical diagnosis of actinic cheilitis by infrared spectroscopy.

PubMed

das Chagas E Silva de Carvalho, Luis Felipe; Pereira, Thiago Martini; Magrini, Taciana Depra; Cavalcante, Ana Sueli Rodrigues; da Silva Martinho, Herculano; Almeida, Janete Dias

2016-12-01

Actinic cheilitis (AC) is considered a potentially malignant disorder of the lip. Biomolecular markers study is important to understand malignant transformation into squamous cell carcinoma. Fourier transform infra red (FT-IR) spectroscopy was used to analyze AC in this study. The aim of the study was to evaluate if FT-IR spectral regions of nucleic acids and collagen can help in early diagnosis of malignant transformation. Tissues biopsies of 14 patients diagnosed with AC and 14 normal tissues were obtained. FT-IR spectra were measured at five different points resulting in 70 spectra of each. Analysis of Principal components analysis (PCA) and linear discrimination analysis (LDA) model were also used. In order to verify the statistical difference in the spectra, Mann-Whitney U test was performed in each variable (wavenumber) with p-value <0.05. After the Mann-Whitney U test the vibrational modes of CO (Collagen 1), PO2 (Nucleic Acids) and CO asymmetric (Triglycerides/Lipids) were observed as a possible spectral biomarker. These bands were chosen because they represent the vibrational modes related to collagen and DNA, which are supposed to be changed in AC samples. Based on the PCA-LDA results, the predictive model corresponding to the area under the curve was 0.91 for the fingerprint region and 0.83 for the high wavenumber region, showing the greater accuracy of the test. FT-IR changes in collagen and nucleic acids could be used as molecular biomarkers for malignant transformation. Copyright Â© 2016 Elsevier B.V. All rights reserved.
Vibrational characterization of pheomelanin and trichochrome F by Raman spectroscopy

NASA Astrophysics Data System (ADS)

Galván, Ismael; Jorge, Alberto; Solano, Francisco; Wakamatsu, Kazumasa

2013-06-01

We characterize for the first time the vibrational state of natural pheomelanin using Raman spectroscopy and model pigment synthesized from 5-S-cysteinyldopa. The shape of the Raman spectrum was very different from that of eumelanin. Four Raman bands were visible in the 500-2000 cm-1 wavenumber region about 500, 1150, 1490 and 2000 cm-1, which we assigned to the out-of-plane deformation and the stretching vibration of the phenyl rings, to the stretching vibration of C-N bonds or the stretching and wagging vibration of CH2, and to overtone or combination bands. Interestingly, we also show that the Raman spectrum of synthetic trichochrome F, a pigment that may be produced along with pheomelanin during pheomelanogenesis, is different from that of pheomelanin and similar to the spectrum of eumelanin. We could detect Raman signal of both eumelanin and pheomelanin in feathers and hairs where both pigments simultaneously occur without the need of isolating the pigment. This indicates that Raman spectroscopy represents a non-invasive method to detect pheomelanin and distinguish it from other pigments. This may be especially relevant to detect pheomelanin in animal skin including humans, where it has been associated with animal appearance and classification, human phototypes, prevention of skin diseases and cancer risk.
Wavenumber Imaging For Damage Detection and Measurement

NASA Technical Reports Server (NTRS)

Rogge, Matthew D.; Johnson, Pat H.

2011-01-01

This paper presents a method for analyzing ultrasonic wavefield data using the Continuous Wavelet Transform (CWT) applied in the spatial domain. Unlike data obtained by sparse arrays of transducers, full wavefield data contains information local to the structure and can be used to obtain more detailed measurements of damage type, location, size, etc. By calculating the CWT of the wavefield in the spatial domain, the wavenumber spectrum is determined for the inspected locations. Because wavenumber is affected by the local geometry and material properties of the structure through which Lamb waves propagate, the wavenumber spectrum can be analyzed to assess the location, severity, and size of damage. The technique is first applied to experimental wavefield data obtained using a laser Doppler vibrometer and automated positioning stage. The out-of-plane velocity along the length of a composite stringer was measured to detect the presence of delaminations within the composite overwrap. Next, simulated corrosion is detected and measured within an aluminum plate using the two dimensional CWT. The experimental results show the usefulness of the technique for vehicle structure inspection applications.
Facile synthesis of corticosteroids prodrugs from isolated hydrocortisone acetate and their quantum chemical calculations

NASA Astrophysics Data System (ADS)

Sethi, Arun; Singh, Ranvijay Pratap; Prakash, Rohit; Amandeep

2017-02-01

In the present research paper corticosteroids prodrugs of hydrocortisone acetate (1) have been synthesized, which was isolated from the flowers of Allamanda Violacea. The hydrocortisone acetate (1) was hydrolyzed to hydrocortisone (2) which was subsequently converted to prednisolone (3). Both the hydrocortisone (1) and prednisolone (2) underwent Steglich esterification with naproxen and Ibuprofen yielding compounds 11, 17 dihydroxy-21-(2-(6-methoxynaphthalene-2yl) propionoxy)-pregn-4-ene-3, 20-dione (4), 11, 17-dihydroxy-21-(2-(4-isobutylphenyl) propionoxy)-pregn-4-ene-3, 20-dione (5), 21-(2-(6-methoxynaphthalene-2-yl) propionoxy) 11,17-di-hydroxy-3,20-diketo-pregn-1,4-diene (6) and 11,17-di-hydroxy-3,20-diketo-pregn-1,4-diene-21-yl-2-(4-isobutylphenyl) propanoate (7). The synthesized compounds have been characterized with the help of spectroscopic techniques like 1H, 13C NMR, FT-IR spectroscopy and mass spectrometry. Density functional theory (DFT) with B3LYP functional and 6-31G (d, p) basis set has been used for the Quantum chemical calculations. The electronic properties such as frontier orbitals and band gap energies were calculated by TD-DFT approach. Intramolecular interactions have been identified by AIM (Atoms in Molecule) approach and vibrational wavenumbers have been calculated using DFT method. The reactivity and reactive site within the synthesized prodrugs have been examined with the help of reactivity descriptors. Dipole moment, polarizability and first static hyperpolarizability have been calculated to get a better insight of the properties of synthesized prodrugs. The molecular electrostatic potential (MEP) surface analysis has also been carried out.
Vibrational spectral signatures of crystalline cellulose using high resolution broadband sum frequency generation vibrational spectroscopy (HR-BB-SFG-VS)

DOE PAGES

Zhang, Libing; Lu, Zhou; Velarde, Luis; ...

2015-03-03

Both the C–H and O–H region spectra of crystalline cellulose were studied using the sub-wavenumber high-resolution broadband sum frequency generation vibrational spectroscopy (HR-BB-SFG-VS) for the first time. The resolution of HR-BB-SFG-VS is about 10-times better than conventional scanning SFG-VS and has the capability of measuring the intrinsic spectral lineshape and revealing many more spectral details. With HR-BB-SFG-VS, we found that in cellulose samples from different sources, including Avicel and cellulose crystals isolated from algae Valonia (Iα) and tunicates (Iβ), the spectral signatures in the O–H region were unique for the two allomorphs, i.e. Iα and Iβ, while the spectral signaturesmore » in the C–H regions varied in all samples examined. Even though the origin of the different spectral signatures of the crystalline cellulose in the O–H and C–H vibrational frequency regions are yet to be correlated to the structure of cellulose, these results lead to new spectroscopic methods and opportunities to classify and to understand the basic crystalline structures, as well as variations in polymorphism of the crystalline cellulose.« less
Vibrational spectral signatures of crystalline cellulose using high resolution broadband sum frequency generation vibrational spectroscopy (HR-BB-SFG-VS)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhang, Libing; Lu, Zhou; Velarde, Luis

Both the C–H and O–H region spectra of crystalline cellulose were studied using the sub-wavenumber high-resolution broadband sum frequency generation vibrational spectroscopy (HR-BB-SFG-VS) for the first time. The resolution of HR-BB-SFG-VS is about 10-times better than conventional scanning SFG-VS and has the capability of measuring the intrinsic spectral lineshape and revealing many more spectral details. With HR-BB-SFG-VS, we found that in cellulose samples from different sources, including Avicel and cellulose crystals isolated from algae Valonia (Iα) and tunicates (Iβ), the spectral signatures in the O–H region were unique for the two allomorphs, i.e. Iα and Iβ, while the spectral signaturesmore » in the C–H regions varied in all samples examined. Even though the origin of the different spectral signatures of the crystalline cellulose in the O–H and C–H vibrational frequency regions are yet to be correlated to the structure of cellulose, these results lead to new spectroscopic methods and opportunities to classify and to understand the basic crystalline structures, as well as variations in polymorphism of the crystalline cellulose.« less

Many Molecular Properties from One Kernel in Chemical Space

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ramakrishnan, Raghunathan; von Lilienfeld, O. Anatole

We introduce property-independent kernels for machine learning modeling of arbitrarily many molecular properties. The kernels encode molecular structures for training sets of varying size, as well as similarity measures sufficiently diffuse in chemical space to sample over all training molecules. Corresponding molecular reference properties provided, they enable the instantaneous generation of ML models which can systematically be improved through the addition of more data. This idea is exemplified for single kernel based modeling of internal energy, enthalpy, free energy, heat capacity, polarizability, electronic spread, zero-point vibrational energy, energies of frontier orbitals, HOMOLUMO gap, and the highest fundamental vibrational wavenumber. Modelsmore » of these properties are trained and tested using 112 kilo organic molecules of similar size. Resulting models are discussed as well as the kernels’ use for generating and using other property models.« less
Excitation of Continuous and Discrete Modes in Incompressible Boundary Layers

NASA Technical Reports Server (NTRS)

Ashpis, David E.; Reshotko, Eli

1998-01-01

This report documents the full details of the condensed journal article by Ashpis & Reshotko (JFM, 1990) entitled "The Vibrating Ribbon Problem Revisited." A revised formal solution of the vibrating ribbon problem of hydrodynamic stability is presented. The initial formulation of Gaster (JFM, 1965) is modified by application of the Briggs method and a careful treatment of the complex double Fourier transform inversions. Expressions are obtained in a natural way for the discrete spectrum as well as for the four branches of the continuous spectra. These correspond to discrete and branch-cut singularities in the complex wave-number plane. The solutions from the continuous spectra decay both upstream and downstream of the ribbon, with the decay in the upstream direction being much more rapid than that in the downstream direction. Comments and clarification of related prior work are made.
A statistical formulation of one-dimensional electron fluid turbulence

NASA Technical Reports Server (NTRS)

Fyfe, D.; Montgomery, D.

1977-01-01

A one-dimensional electron fluid model is investigated using the mathematical methods of modern fluid turbulence theory. Non-dissipative equilibrium canonical distributions are determined in a phase space whose co-ordinates are the real and imaginary parts of the Fourier coefficients for the field variables. Spectral densities are calculated, yielding a wavenumber electric field energy spectrum proportional to k to the negative second power for large wavenumbers. The equations of motion are numerically integrated and the resulting spectra are found to compare well with the theoretical predictions.
Origin of the Hadži ABC structure: An ab initio study

DOE Office of Scientific and Technical Information (OSTI.GOV)

Van Hoozen, Brian L.; Petersen, Poul B.

2015-11-14

Medium and strong hydrogen bonds are well known to give rise to broad features in the vibrational spectrum often spanning several hundred wavenumbers. In some cases, these features can span over 1000 cm{sup −1} and even contain multiple broad peaks. One class of strongly hydrogen-bonded dimers that includes many different phosphinic, phosphoric, sulfinic, and selenic acid homodimers exhibits a three-peaked structure over 1500 cm{sup −1} broad. This unusual feature is often referred to as the Hadži ABC structure. The origin of this feature has been debated since its discovery in the 1950s. Only a couple of theoretical studies have attemptedmore » to interpret the origin of this feature; however, no previous study has been able to reproduce this feature from first principles. Here, we present the first ab initio calculation of the Hadži ABC structure. Using a reduced dimensionality calculation that includes four vibrational modes, we are able to reproduce the three-peak structure and much of the broadness of the feature. Our results indicate that Fermi resonances of the in-plane bend, out-of-plane bend, and combination of these bends play significant roles in explaining this feature. Much of the broadness of the feature and the ability of the OH stretch mode to couple with many overtone bending modes are captured by including an adiabatically separated dimer stretch mode in the model. This mode modulates the distance between the monomer units and accordingly the strength of the hydrogen-bonds causing the OH stretch frequency to shift from 2000 to 3000 cm{sup −1}. Using this model, we were also able to reproduce the vibrational spectrum of the deuterated isotopologue which consists of a single 500 cm{sup −1} broad feature. Whereas previous empirical studies have asserted that Fermi resonances contribute very little to this feature, our study indicates that while not appearing as a separate peak, a Fermi resonance of the in-plane bend contributes substantially to the feature.« less
Antimycobacterial, antimicrobial activity, experimental (FT-IR, FT-Raman, NMR, UV-Vis, DSC) and DFT (transition state, chemical reactivity, NBO, NLO) studies on pyrrole-isonicotinyl hydrazine

NASA Astrophysics Data System (ADS)

Rawat, Poonam; Singh, R. N.; Ranjan, Alok; Ahmad, Sartaj; Saxena, Rajat

2017-05-01

As part of a study of pyrrole hydrazone, we have investigated quantum chemical calculations, molecular geometry, relative energy, vibrational properties and antimycobacterial/antimicrobial activity of pyrrole-2-carboxaldehyde isonicotinyl hydrazone (PCINH), by applying the density functional theory (DFT) and Hartree Fock (HF). Good reproduction of experimental values is obtained and with small percentage error in majority of the cases in comparison to theoretical result (DFT). The experimental FT-IR and Raman wavenumbers were compared with the respective theoretical values obtained from DFT calculations and found to agree well. In crystal structure studies the hydrated PCINH (syn-syn conformer) shows different conformation than from anhydrous form (syn-anti conformer). The rotational barrier between syn-syn and syn-anti conformers of PCINH is 12.7 kcal/mol in the gas phase. In this work, use of FT-IR, FT-Raman, 1H NMR, 13C NMR and UV-Vis spectroscopies has been made for full characterization of PCINH. A detailed interpretation of the vibrational spectrum was carried out with the aid of normal coordinate analysis using single scaling factor. Our results support the hydrogen bonding pattern proposed by reported crystalline structure. The calculated nature of electronic transitions within molecule found to be π → π*. The electronic descriptors study indicates that PCINH can be used as robust synthon for synthesis of new heterocyclic compounds. The first static hyperpolarizability (β0) of PCINH is calculated as 33.89 × 10- 30 esu, (gas phase); 68.79 × 10- 30 (CHCl3), esu; 76.76 × 10- 30 esu (CH2Cl2), 85.16 × 10- 30 esu (DMSO). The solvent induced effects on the first static hyperpolarizability were studied and found to increase as dielectric constants of the solvents increases. Investigated molecule shows better NLO value than Para nitroaniline (PNA). The compound PCINH shows good antifungal and antibacterial activity against Aspergillus niger and gram-positive bacteria Bacillus subtilis, respectively. The compound also shows good antituberculosis activity against Mycobacterium tuberculosis H37Rv using the microplate alamar blue assay (MABA).
Sensing of fluid viscoelasticity from piezoelectric actuation of cantilever flexural vibration

DOE Office of Scientific and Technical Information (OSTI.GOV)

Park, Jeongwon; Jeong, Seongbin; Kim, Seung Joon

2015-01-15

An experimental method is proposed to measure the rheological properties of fluids. The effects of fluids on the vibration actuated by piezoelectric patches were analyzed and used in measuring viscoelastic properties. Fluid-structure interactions induced changes in the beam vibration properties and frequency-dependent variations of the complex wavenumber of the beam structure were used in monitoring these changes. To account for the effects of fluid-structure interaction, fluids were modelled as a simple viscoelastic support at one end of the beam. The measured properties were the fluid’s dynamic shear modulus and loss tangent. Using the proposed method, the rheological properties of variousmore » non-Newtonian fluids were measured. The frequency range for which reliable viscoelasticity results could be obtained was 10–400 Hz. Viscosity standard fluids were tested to verify the accuracy of the proposed method, and the results agreed well with the manufacturer’s reported values. The simple proposed laboratory setup for measurements was flexible so that the frequency ranges of data acquisition were adjustable by changing the beam’s mechanical properties.« less
Ab initio molecular orbital studies of the vibrational spectra of the van der Waals complexes of boron trifluoride with the noble gases.

PubMed

Ford, Thomas A

2005-05-01

The molecular structures, interaction energies, charge transfer properties and vibrational spectra of the van der Waals complexes formed between boron trifluoride and the noble gases neon, argon, krypton and xenon have been computed using second and fourth order Møller-Plesset perturbation theory and the Los Alamos National Laboratory LANL2DZ basis set. The complexes are all symmetric tops, with the noble gas atom acting as a sigma electron donor along the C3 axis of the BF3 molecule. The interaction energies are all vanishingly small, and the amount of charge transferred in each case is of the order of 0.01e. The directions of the wavenumber shifts of the symmetric bending (nu2) and antisymmetric stretching (nu3) modes of the BF3 fragment confirm those determined experimentally, and the shifts are shown to correlate well with the polarizability of the noble gas atom and the inverse sixth power of the intermonomer separation. The nu2 mode is substantially more sensitive to complexation than the nu3 vibration.
Reconstruction of transient vibration and sound radiation of an impacted plate using time domain plane wave superposition method

NASA Astrophysics Data System (ADS)

Geng, Lin; Zhang, Xiao-Zheng; Bi, Chuan-Xing

2015-05-01

Time domain plane wave superposition method is extended to reconstruct the transient pressure field radiated by an impacted plate and the normal acceleration of the plate. In the extended method, the pressure measured on the hologram plane is expressed as a superposition of time convolutions between the time-wavenumber normal acceleration spectrum on a virtual source plane and the time domain propagation kernel relating the pressure on the hologram plane to the normal acceleration spectrum on the virtual source plane. By performing an inverse operation, the normal acceleration spectrum on the virtual source plane can be obtained by an iterative solving process, and then taken as the input to reconstruct the whole pressure field and the normal acceleration of the plate. An experiment of a clamped rectangular steel plate impacted by a steel ball is presented. The experimental results demonstrate that the extended method is effective in visualizing the transient vibration and sound radiation of an impacted plate in both time and space domains, thus providing the important information for overall understanding the vibration and sound radiation of the plate.
Raman spectra of oriented and non-oriented Cu hydroxy-phosphate minerals: libethenite, cornetite, pseudomalachite, reichenbachite and ludjibaite.

PubMed

Kharbish, Sherif; Andráš, Peter; Luptáková, Jarmila; Milovská, Stanislava

2014-09-15

Oriented cornetite [Cu3PO4(OH)3], libethenite [Cu2PO4(OH)] and pseudomalachite [Cu5(PO4)2(OH)4] and non-oriented reichenbachite [Cu5(PO4)2(OH)4] and ludjibaite [Cu5(PO4)2(OH)4] minerals from Ľubietová and Špania Dolina dump fields, Banská Bystrica, Slovakia were examined by polarized Raman spectroscopy. The examined minerals display the characteristic vibrational modes of PO4 and OH groups and further lattice modes. The PO4 stretching and bending vibrations of the investigated minerals occur between 1150 and 900 cm(-1) and between 700 and 350 cm(-1), respectively. On the other hand, the hydroxyl group stretching and bending modes appear above 3350 cm(-1) and between 900 and 700 cm(-1), respectively. The lattice vibrations occur below 350 cm(-1). The different bond distances of the PO4 groups readily explain the shift of the bands to higher or lower wavenumbers among the studied Cu hydroxy-phosphate minerals. Copyright © 2014. Published by Elsevier B.V.
Intraseasonal and Interannual Variability of the Quasi-Two Day Wave in the Northern Hemisphere Summer Mesosphere

NASA Technical Reports Server (NTRS)

McCormack, J. P.; Coy, L.; Singer, W.

2013-01-01

This study uses global synoptic meteorological fields from a high-altitude data assimilation system to investigate the spatial and temporal characteristics of the quasi-2 day wave (Q2DW) and migrating diurnal tide during the Northern Hemisphere summers of 2007, 2008, and 2009. By applying a 2-dimensional fast Fourier transform to meridional wind and temperature fields, we are able to identify Q2DW source regions and to diagnose propagation of Q2DW activity into the upper mesosphere and lower thermosphere. We find that Q2DW is comprised primarily of westward propagating zonal wavenumber 3 and wavenumber 4 components that originate from within baroclinically unstable regions along the equatorward flank of the summer midlatitude easterly jet. Amplitude variations of wavenumbers 3 and 4 tend to be anti-correlated throughout the summer, with wavenumber 3 maximizing in July and wavenumber 4 maximizing in late June and early August. Monthly mean Q2DW amplitudes between 30 50N latitude are largest when diurnal tidal amplitudes are smallest and vice versa. However, there is no evidence of any rapid amplification of the Q2DW via nonlinear interaction with the diurnal tide. Instead, variations of Q2DW amplitudes during July are closely linked to variations in the strength and location of the easterly jet core from one summer to the next, with a stronger jet producing larger Q2DW amplitudes. Linear instability model calculations based on the assimilated wind fields find fast growing zonal wavenumber 3 and 4 modes with periods near 2 days in the vicinity of the easterly jet.
Analysis of railway track vibration

NASA Astrophysics Data System (ADS)

Ono, K.; Yamada, M.

1989-04-01

Analytical formulae are developed for estimating the amplitudes of the vibrations generated in railway tracks by wheels and rail discontinuities or by unevennesses on their surfaces. Rails are assumed to be supported elastically on concrete sleepers by resilient rail-pads inserted between them. The elasticities and the masses of track materials and those of the roadbed are also taken into consideration. It is shown that after an impulse is applied to the track, not only is a vibration with a comparatively low natural frequency generated, but also traveling waves with higher frequencies, and the latter propagate lengthwise along the track or downwards into the roadbed. With the assumption that the power spectral density of the unevennesses on the rail surface is in proportion to the third power of the wavelength, or to (wavenumber) -3, the amplitudes of the vibrations in railway tracks supported by rail-pads and roadbeds with various magnitudes of elastic constants are analyzed and the values for each one-third octave band are estimated. The velocity of the vibration takes on a maximum value for the band with a center frequency of 63 Hz, which corresponds to the resonant frequency of the system composed of the wheel and the track. As the frequency increases beyond this value, the velocity of the vibration takes on a second maximum value at a frequency of about 1000 Hz. These estimates are compared with the data obtained from field measurements and reasonably good correlations are found between them.
Synchrotron Radiation and the Far-Infrared and Mid-Infrared Spectra of Ncncs

NASA Astrophysics Data System (ADS)

Winnewisser, Manfred; Winnewisser, Brenda P.; De Lucia, Frank C.; Tokaryk, Dennis; Ross, Stephen Cary; Billinghurst, Brant E.

2014-06-01

The large-amplitude in-plane bending vibration of NCNCS at 85 wn has a potential energy function which includes a barrier to linearity with a height of about 285 wn. The topology of the surface of the space defined by this two-dimensional potential function exhibits non-trivial monodromy. Therefore an energy/momentum map for a quantum system with its motion determined by such a potential takes the form of a lattice which contains a defect associated with the top of the barrier. In NCNCS, the wavenumber values of the fundamental vibrational excitation and the barrier height mean that easily accessible energy levels allow us to observe 3 bending vibrational levels below and 3 above the barrier, yet still below all of the other vibrational levels, allowing the study of all the levels in the neighborhood of the defect. In three measuring campaigns at the Canadian Light Source in May of the years 2011, 2012, and 2013 we have now obtained 8 of the 9 fundamental vibrational band systems of NCNCS in high resolution, in particular that of the large-amplitude bend in the FIR. So far only a-type spectra have been assigned. Thus we have now determined the Δvb = 1, and ΔKa = 0 vibrational intervals (using bent molecule notation) but do not yet have experimental values for either rotational ΔKa = +/- 1 intervals nor ro-vibrational Δvb = 1, ΔKa = +/- 1 intervals. In May of 2014 we will have our last measuring campaign and hope to observe the more elusive b-type transitions.
A comparison of the far-infrared and low-frequency Raman spectra of glass-forming liquids

NASA Astrophysics Data System (ADS)

Perova, T. S.; Vij, J. K.; Christensen, D. H.; Nielsen, O. F.

1999-04-01

Far-infrared and low-frequency Raman spectra in the wavenumber range from 15 to 500 cm -1 were recorded for glycerol, triacetin (glycerol triacetate) and o-terphenyl at temperatures from 253 to 355 K. The far-infrared spectra of glycerol appear complex compared with the spectra of triacetin owing to the presence of hydrogen bonding in glycerol. The experimental results obtained for o-terphenyl are in good agreement with normal mode analyses carried out for crystalline o-terphenyl (A. Criado, F.J. Bermejo, A. de Andres, Mol. Phys. 82 (1994) 787). The far-infrared results are compared with the low-frequency Raman spectra of these three glass-forming liquids. The difference in temperature dependences found from these spectra is explained on the basis of different temperature contributions of the relaxational and vibrational processes to the low-frequency vibrational spectra.
XRD, SEM and infrared study into the intercalation of sodium hexadecyl sulfate (SHS) into hydrocalumite.

PubMed

Zhang, Ping; Wang, Tianqi; Zhang, Longlong; Wu, Daishe; Frost, Ray L

2015-12-05

Hydrocalumite (CaAl-LDH-Cl) interacted with a natural anionic surfactant, sodium hexadecyl sulfate (SHS), was performed using an intercalation method. To understand the intercalation behavior and characterize the resulting products, powder X-ray diffraction (XRD), scan electron microscopy (SEM) and mid-infrared (MIR) spectroscopy combined with near-infrared (NIR) spectroscopy technique were used. The XRD analysis indicated that SHS was intercalated into CaAl-LDH-Cl successfully, resulting in an expansion of the interlayer (from 0.78 nm to 2.74 nm). The bands of C-H stretching vibrations of SHS were observed in the near-infrared spectra, which indicated that the resulting products were indeed CaAl-LDH-SHS. In addition, the bands of water stretching vibrations and OH groups shifted to higher wavenumbers when SHS was intercalated into CaAl-LDH-Cl interlayer space. Copyright © 2015 Elsevier B.V. All rights reserved.
The Renormalization-Group Method in the Problem on Calculation of the Spectral Energy Density of Fluid Turbulence

NASA Astrophysics Data System (ADS)

Teodorovich, E. V.

2018-03-01

In order to find the shape of energy spectrum within the framework of the model of stationary homogeneous isotropic turbulence, the renormalization-group equations, which reflect the Markovian nature of the mechanism of energy transfer along the wavenumber spectrum, are used in addition to the dimensional considerations and the energy balance equation. For the spectrum, the formula depends on three parameters, namely, the wavenumber, which determines the upper boundary of the range of the turbulent energy production, the spectral flux through this boundary, and the fluid kinematic viscosity.
Enhancement of the dynamic Casimir effect within a metal photonic crystal

NASA Astrophysics Data System (ADS)

Ueta, Tsuyoshi

2013-05-01

If the counterposed metal plates are vibrated, when the gap between the plates becomes narrow, the energy of stationary states between the plates increases, and when it spreads, the energy decreases. Light with the energy for this energy difference arises. This is called dynamical Casimir effect. The author has so far investigated the interaction between lattice vibration and light in a one-dimensional metal photonic crystal whose stacked components are artificially vibrated by using actuators. A simple model was numerically analyzed, and the following novel phenomena were found out. The lattice vibration generates the light of frequency which added the integral multiple of the vibration frequency to that of the incident wave and also amplifies the incident wave resonantly. On a resonance, the amplification factor increases very rapidly with the number of layers. Resonance frequencies change with the phases of lattice vibration. The amplification phenomenon was analytically discussed for low frequency of the lattice vibration and is confirmed by numerical works. The lattice-vibrating metal photonic crystal is a system of dynamical Casimir effect connected in series, and so we can expect that a dynamical Casimir effect is enhanced by the photonic band effect. In the present study, when an electromagnetic field between metal plates is in the ground state in a one-dimensional metal photonic crystal, the radiation of electromagnetic wave in excited states has been investigated by artificially introducing lattice vibration to the photonic crystal. In this case as well as a dynamical Casimir effect, it has been shown that the harmonics of a ground state are generated just by vibrating a photonic crystal even without an incident wave. The dependencies of the radiating power on the number of layers and on the wavenumber of the lattice vibration are remarkable. It has found that the radiation amplitude on lower excited states is not necessarily large and radiation on specific excited levels is large.
Towards an automated and efficient calculation of resonating vibrational states based on state-averaged multiconfigurational approaches

NASA Astrophysics Data System (ADS)

Meier, Patrick; Oschetzki, Dominik; Pfeiffer, Florian; Rauhut, Guntram

2015-12-01

Resonating vibrational states cannot consistently be described by single-reference vibrational self-consistent field methods but request the use of multiconfigurational approaches. Strategies are presented to accelerate vibrational multiconfiguration self-consistent field theory and subsequent multireference configuration interaction calculations in order to allow for routine calculations at this enhanced level of theory. State-averaged vibrational complete active space self-consistent field calculations using mode-specific and state-tailored active spaces were found to be very fast and superior to state-specific calculations or calculations with a uniform active space. Benchmark calculations are presented for trans-diazene and bromoform, which show strong resonances in their vibrational spectra.
Towards an automated and efficient calculation of resonating vibrational states based on state-averaged multiconfigurational approaches

DOE Office of Scientific and Technical Information (OSTI.GOV)

Meier, Patrick; Oschetzki, Dominik; Pfeiffer, Florian

Resonating vibrational states cannot consistently be described by single-reference vibrational self-consistent field methods but request the use of multiconfigurational approaches. Strategies are presented to accelerate vibrational multiconfiguration self-consistent field theory and subsequent multireference configuration interaction calculations in order to allow for routine calculations at this enhanced level of theory. State-averaged vibrational complete active space self-consistent field calculations using mode-specific and state-tailored active spaces were found to be very fast and superior to state-specific calculations or calculations with a uniform active space. Benchmark calculations are presented for trans-diazene and bromoform, which show strong resonances in their vibrational spectra.
Progress in the Rotational Analysis of the Ground and Low-Lying Vibrationally Excited States of Malonaldehyde

NASA Astrophysics Data System (ADS)

Goudreau, E. S.; Tokaryk, Dennis W.; Ross, Stephen Cary; Billinghurst, Brant E.

2016-06-01

Despite being an important prototype molecule for intramolecular proton tunnelling, the far-IR spectrum of the internally hydrogen-bonded species malonaldehyde (C_3O_2H_4) is not yet well understood. In the talk I gave at the ISMS meeting in 2015 I discussed the high-resolution spectra we obtained at the Canadian Light Source synchrotron in Saskatoon, Saskatchewan. These spectra include a number of fundamental vibrational bands in the 100-2000 cm-1 region. In our efforts to analyze these bands we have noticed that our ground state combination differences show a large drift (up to an order of magnitude larger than our experimental error) away from those calculated using constants established by Baba et al., particularly in regions of high J (above 30) and low Ka (below 5). An examination of the previous microwave and far-IR studies reveals that this region of J-Ka space was not represented in the lines that Baba et al. used to generate the values for their fitting parameters. By including our own measurements in the fitting, we were able to improve the characterization of the ground state so that it is now consistent with all of the existing data. This characterization now covers a much larger range of J-Ka space and has enabled us to make significant progress in analyzing our far-IR synchrotron spectra. These include an excited vibrational state at 241 cm-1 as well as several states split by the tunnelling effect at higher wavenumber. T. Baba, T. Tanaka, I. Morino, K. M. T. Yamada, K. Tanaka. Detection of the tunneling-rotation transitions of malonaldehyde in the submillimeter-wave region. J. Chem. Phys., 110. 4131-4133 (1999) P. Turner, S. L. Baughcum, S. L. Coy, Z. Smith. Microwave Spectroscopic Study of Malonaldehyde. 4. Vibration-Rotation Interaction in Parent Species. J. Am. Chem. Soc., 106. 2265-2267 (1984) D. W. Firth, K. Beyer, M. A. Dvorak, S. W. Reeve, A. Grushow, K. R. Leopold. Tunable far-infrared spectroscopy of malonaldehyde. J. Chem. Phys., 94. 1812-1819 (1991)
The influence of ionic strength on carbonate-based spectroscopic barometry for aqueous fluids: an in-situ Raman study on Na2CO3-NaCl solutions

PubMed Central

Wu, Jia; Wang, Shixia; Zheng, Haifei

2016-01-01

The Raman wavenumber of the symmetric stretching vibration of carbonate ion (ν1-CO32−) was measured in three aqueous solutions containing 2.0 mol·L−1 Na2CO3 and 0.20, 0.42, or 0.92 mol·L−1 NaCl, respectively, from 122 to 1538 MPa at 22 °C using a moissanite anvil cell. The ν1 Raman signal linearly shifted to higher wavenumbers with increasing pressure. Most importantly, the slope of ν1-CO32− Raman frequency shift (∂ν1/∂P)I was independent of NaCl concentration. Moreover, elevated ionic strength was found to shift the apparent outline of the carbonate peak toward low wavenumbers, possibly by increasing the proportion of the contact ion pair NaCO3−. Further investigations revealed no cross-interaction between the pressure effect and the ionic strength effect on the Raman spectra, possibly because the distribution of different ion-pair species in the carbonate equilibrium was largely pressure-independent. These results suggested that the ionic strength should be incorporated as an additional constraint for measuring the internal pressure of various solution-based systems. Combining the ν1-CO32− Raman frequency slope with the pressure herein with the values for the temperature or the ionic strength dependencies determined from previous studies, we developed an empirical equation that can be used to estimate the pressure of carbonate-bearing aqueous solutions. PMID:27982064

Study on the structure, vibrational analysis and molecular docking of fluorophenyl derivatives using FT-IR and density functional theory computations

NASA Astrophysics Data System (ADS)

Al-Tamimi, Abdul-Malek S.; Mary, Y. Sheena; Hassan, Hanan M.; Resmi, K. S.; El-Emam, Ali A.; Narayana, B.; Sarojini, B. K.

2018-07-01

The density functional calculations were performed at the B3LYP/6-311++G (5D, 7F) level to find the geometrical parameters, vibrational wavenumbers and various molecular properties of three fluorophenyl derivatives, methyl 4,4″-difluoro-5‧-methoxy-1,1':3‧,1″-terphenyl-4‧-carboxylate (MDFMTPC), 2,2'-(disulfanediyl)bis[4,6-(4-fluorophenyl)pyrimidine] (DFFPPY) and (6Z)-3,5‧-bis(4-fluorophenyl)-6-(1-hydroxyethylidene)cyclohex-2-en-1-one (FPHYCY). The phenyl ring Csbnd C, Cdbnd O and Csbnd H stretching modes produces VCD spectrum and these modes are efficient configuration markers. Using natural bond orbital analysis the stability of the molecules due to hyper-conjugative interactions were discussed. From the HOMO and LUMO energies, the chemical descriptors are compared for the title compounds. The first hyperpolarizabilities of MDFMTPC, DFFPPY and FPHYCY are respectively, 41.08, 69.27 and 38.38 times that of urea. Molar refractivity values are increasing in the order, FPHYCY > MDFMTPC > DFFPPY and this is responsible for the binding nature of the molecular assembly and can be used for the cure of different diseases. PASS analysis of the title compounds predicts chlordecone reductase inhibitor activity for MDFMTPC, thioredoxin inhibitor activity for DFFPPY and testosterone 17beta-dehydrogenase (NADP+) inhibitor activity for FPHYCY. Docking studies reveal that MDFMTPC, DFFPPY and FPHYCY can be lead compounds for developing new anti-cancerous, anti-tumor, prostate cancer drugs. Using Hirshfeld surface and 2D-finger print plots, the type and nature of intermolecular interactions were reported.
Spectroscopic, quantum chemical studies, Fukui functions, in vitro antiviral activity and molecular docking of 5-chloro-N-(3-nitrophenyl)pyrazine-2-carboxamide

NASA Astrophysics Data System (ADS)

Sebastian, S. H. Rosline; Al-Alshaikh, Monirah A.; El-Emam, Ali A.; Panicker, C. Yohannan; Zitko, Jan; Dolezal, Martin; VanAlsenoy, C.

2016-09-01

The molecular structural parameters and vibrational frequencies of 5-chloro-N-(3-nitrophenyl)pyrazine-2-carboxamide have been obtained using density functional theory technique in the B3LYP approximation and CC-pVDZ (5D, 7F) basis set. Detailed vibrational assignments of observed FT-IR and FT-Raman bands have been proposed on the basis of potential energy distribution and most of the modes have wavenumbers in the expected range. In the present case, the NH stretching mode is a doublet in the IR spectrum with a difference of 138 cm-1 and is red shifted by 76 cm-1 from the computed value, which indicates the weakening of NH bond resulting in proton transfer to the neighboring oxygen atom. The molecular electrostatic potential has been mapped for predicting sites and relative reactivities towards electrophilic and nucleophilic attack. The hyperpolarizability values are calculated in order to find its role in nonlinear optics. From the molecular docking study, amino acids Asn161, His162 forms H-bond with pyrazine ring and Trp184, Gln19 shows H-bond with Cdbnd O group and the docked ligand, title compound forms a stable complex with cathepsin K and the results suggest that the compound might exhibit inhibitory activity against cathepsin K. Moderate in vitro antiviral activity with EC50 at tens of μM was detected against feline herpes virus, coxsackie virus B4, and influenza A/H1N1 and A/H3N2.
Single crystal, vibrational and computational studies of Theophylline (a bronchodilator drug) and its chloride salt

NASA Astrophysics Data System (ADS)

Mary Novena, L.; Suresh Kumar, S.; Athimoolam, S.; Saminathan, K.; Sridhar, B.

2017-04-01

The crystal structure of Theophylline (TH) and Theophyillinium chloride monohydrate (THC) and its complete molecular structure analysis on theoretical and experimental methods is reported here. The hydrogen bonding studies were carried out as a special note of the present work. The electron density analyses of the compounds were also analyzed in view of the intermolecular interactions. Moreover, it is an ever first quantum chemical report of this drug (TH) and its chloride salt. In TH crystal, the water molecule connects the Theophylline molecules through Osbnd H⋯N hydrogen bond forming discrete D22(7) motif and dimeric ring R22(10) motif through Nsbnd H⋯O hydrogen bond. In THC, the two classical (Nsbnd H⋯O, Nsbnd H⋯Cl) and one non-classical (Csbnd H⋯O) hydrogen bonds produce two pentameric chain C55 (16) and C55(17) motifs. These two chain motifs are interconnected by Osbnd H⋯O hydrogen bond and cross linked by Nsbnd H⋯Cl and Osbnd H⋯Cl hydrogen bonds to produce octametric ring R88(27) and R88(28) motifs. The solubility test is carried out to enhance the drug solubility and the therapeutic effectiveness of the drug. Experimentally obtained vibrational wavenumbers are compared with the spectra obtained theoretically for both the compound. The strong intensity bands and the shifting of bands due to intermolecular hydrogen bonds are also investigated. The Mulliken atomic charges, HOMO-LUMO and thermodynamic properties are calculated using Density Functional Theory (DFT) and Hartree-Fock Theory (HF) using 6-311++G(d,p) basis set.
ExoMol molecular line lists - XXVI: spectra of SH and NS

NASA Astrophysics Data System (ADS)

Yurchenko, Sergei N.; Bond, Wesley; Gorman, Maire N.; Lodi, Lorenzo; McKemmish, Laura K.; Nunn, William; Shah, Rohan; Tennyson, Jonathan

2018-07-01

Line lists for the sulphur-containing molecules SH (the mercapto radical) and NS are computed as part of the ExoMol project. These line lists consider transitions within the X2Π ground state for 32SH, 33SH, 34SH,36SH and, 32SD, and 14N32S, 14N33S, 14N34S, 14N36S, and 15N32S. Ab initio potential energy (PEC) and spin-orbit coupling (SOC) curves are computed and then improved by fitting to experimentally observed transitions. Fully ab initio dipole moment curves (DMCs) computed at high level of theory are used to produce the final line lists. For SH, our fit gives a root-mean-square (rms) error of 0.03 cm-1 between the observed (vmax = 4, Jmax = 34.5) and calculated transitions wavenumbers; this is extrapolated such that all X2Π rotational-vibrational-electronic (rovibronic) bound states are considered. For 32SH the resulting line list contains about 81 000 transitions and 2300 rovibronic states, considering levels up to vmax = 14 and Jmax = 60.5. For NS the refinement used a combination of experimentally determined frequencies and energy levels and led to an rms-fitting error of 0.002 cm-1. Each NS-calculated line list includes around 2.8 million transitions and 31 000 rovibronic states with a vibrational range up to v = 53 and rotational range up to J = 235.5, which covers up to 23 000 cm-1. Both line lists should be complete for temperatures up to 5000 K. Example spectra simulated using this line list are shown and comparisons made to the existing data in the CDMS data base. The line lists are available from the CDS (http://cdsarc.u-strasbg.fr) and ExoMol (www.exomol.com) data bases.
Free and forced vibrations of a tyre using a wave/finite element approach

NASA Astrophysics Data System (ADS)

Waki, Y.; Mace, B. R.; Brennan, M. J.

2009-06-01

Free and forced vibrations of a tyre are predicted using a wave/finite element (WFE) approach. A short circumferential segment of the tyre is modelled using conventional finite element (FE) methods, a periodicity condition applied and the mass and stiffness matrices post-processed to yield wave properties. Since conventional FE methods are used, commercial FE packages and existing element libraries can be utilised. An eigenvalue problem is formulated in terms of the transfer matrix of the segment. Zhong's method is used to improve numerical conditioning. The eigenvalues and eigenvectors give the wavenumbers and wave mode shapes, which in turn define transformations between the physical and wave domains. A method is described by which the frequency dependent material properties of the rubber components of the tyre can be included without the need to remesh the structure. Expressions for the forced response are developed which are numerically well-conditioned. Numerical results for a smooth tyre are presented. Dispersion curves for real, imaginary and complex wavenumbers are shown. The propagating waves are associated with various forms of motion of the tread supported by the stiffness of the side wall. Various dispersion phenomena are observed, including curve veering, non-zero cut-off and waves for which the phase velocity and the group velocity have opposite signs. Results for the forced response are compared with experimental measurements and good agreement is seen. The forced response is numerically determined for both finite area and point excitations. It is seen that the size of area of the excitation is particularly important at high frequencies. When the size of the excitation area is small enough compared to the tread thickness, the response at high frequencies becomes stiffness-like (reactive) and the effect of shear stiffness becomes important.
Influence of methyl and propyl groups on the vibrational spectra of two imidazolium ionic liquids and their non-ionic precursors

NASA Astrophysics Data System (ADS)

Haddad, Boumediene; Mokhtar, Drai; Goussem, Mimanne; Belarbi, El-habib; Villemin, Didier; Bresson, Serge; Rahmouni, Mustapha; Dhumal, Nilesh R.; Kim, Hyung J.; Kiefer, Johannes

2017-04-01

Imidazolium-based ionic liquids (ILs) are usually synthesized using non-ionic imidazole compounds as precursors. While the ILs have been extensively studied in the past, the precursors was not paid much attention to. The structural analysis of the precursors, however, may offer an opportunity to better understand the behavior of the ionic compounds of interest. In this paper, a comparative study of two ionic liquids and their imidazole precursors is presented. The precursors 1-methylimidazole [1-MIM] and 1,2-dimethylimidazole [1,2-DMIM] are compared in order to explain the influences of the methyl group at the C(2) position (methylation). Since the imidazole compounds are non-ionic, the spectroscopic properties of [1-MIM] and [1,2-DMIM] are not affected by cation-anion interactions. In addition, the products obtained by alkylation using propyl iodide leading to the corresponding IL compounds 1-methyl-3-propylimidazolium iodide [1-MPrIM+][I-] and 1,2-dimethyl-3-propylimidazolium iodide [1,2-DMPrIM+][I-] were studied. For this purpose, vibrational spectroscopy in terms of FT-Raman and FTIR in the wavenumber range from [45 to 3500 cm-1] and from [600 to 4000 cm-1], respectively, was performed. Moreover, to aid the spectral assignment, density functional theory (DFT) calculations were carried out. The aim was to investigate the vibrational structure, to understand the effects of the propyl group at the N(3) and of the methyl group at the C(2) position, and to analyze the resulting cation-anion interactions. The data indicate that the iodide ion predominantly interacts with the C(2)sbnd H group via hydrogen bonding. Upon methylation, the C(4/5)sbnd H moiety becomes the main interaction site. However, an interaction takes place only with one of the two hydrogen atoms resulting in a split of the initially degenerate CH stretching modes.
Unified treatment and measurement of the spectral resolution and temporal effects in frequency-resolved sum-frequency generation vibrational spectroscopy (SFG-VS).

PubMed

Velarde, Luis; Wang, Hong-Fei

2013-12-14

The lack of understanding of the temporal effects and the restricted ability to control experimental conditions in order to obtain intrinsic spectral lineshapes in surface sum-frequency generation vibrational spectroscopy (SFG-VS) have limited its applications in surface and interfacial studies. The emergence of high-resolution broadband sum-frequency generation vibrational spectroscopy (HR-BB-SFG-VS) with sub-wavenumber resolution [Velarde et al., J. Chem. Phys., 2011, 135, 241102] offers new opportunities for obtaining and understanding the spectral lineshapes and temporal effects in SFG-VS. Particularly, the high accuracy of the HR-BB-SFG-VS experimental lineshape provides detailed information on the complex coherent vibrational dynamics through direct spectral measurements. Here we present a unified formalism for the theoretical and experimental routes for obtaining an accurate lineshape of the SFG response. Then, we present a detailed analysis of a cholesterol monolayer at the air/water interface with higher and lower resolution SFG spectra along with their temporal response. With higher spectral resolution and accurate vibrational spectral lineshapes, it is shown that the parameters of the experimental SFG spectra can be used both to understand and to quantitatively reproduce the temporal effects in lower resolution SFG measurements. This perspective provides not only a unified picture but also a novel experimental approach to measuring and understanding the frequency-domain and time-domain SFG response of a complex molecular interface.
Conductivity and transport studies of plasticized chitosan-based proton conducting biopolymer electrolytes

NASA Astrophysics Data System (ADS)

Shukur, M. F.; Yusof, Y. M.; Zawawi, S. M. M.; Illias, H. A.; Kadir, M. F. Z.

2013-11-01

This paper focuses on the conductivity and transport properties of chitosan-based solid biopolymer electrolytes containing ammonium thiocyanate (NH4SCN). The sample containing 40 wt% NH4SCN exhibited the highest conductivity value of (1.81 ± 0.50) × 10-4 S cm-1 at room temperature. Conductivity has increased to (1.51 ± 0.12) × 10-3 S cm-1 with the addition of 25 wt% glycerol. The temperature dependence of conductivity for both salted and plasticized systems obeyed the Arrhenius rule. The activation energy (Ea) was calculated for both systems and it is found that the sample with 40 wt% NH4SCN in the salted system obtained an Ea value of 0.148 eV and that for the sample containing 25 wt% glycerol in the plasticized system is 0.139 eV. From the Fourier transform infrared studies, carboxamide and amine bands shifted to lower wavenumbers, indicating that chitosan has interacted with NH4SCN salt. Changes in the C-O stretching vibration band intensity are observed at 1067 cm-1 with the addition of glycerol. The Rice and Roth model was used to explain the transport properties of the salted and plasticized systems.
Slow Photoelectron Spectroscopy and State-Selected Unimolecular Decomposition of Ionized DNA Bases Analogues

NASA Astrophysics Data System (ADS)

Mahjoub, Ahmed; Hochlaf, Majdi; Poisson, Lionel; Garcia, Gustavo A.; Nahon, Laurent

2013-06-01

We studied the single-photon ionization of gas-phase 2-Piperidone (DNA basis analogue) and of its dimer using vacuum-ultraviolet (VUV) synchrotron radiation coupled to a velocity map imaging electron/ion coincidence spectrometer The slow photoelectron spectrum (SPES) of the monomer is dominated by the vibrational transitions to the ground state. These spectra are assigned with the help of theoretical calculations dealing with the equilibrium geometries, electronic-state patterns and evolutions, harmonic and anharmonic wavenumbers. After its formation, dimer is subject of intramolecular isomerization, H transfer and then unimolecular fragmentation processes. The near threshold photofragmentation pattern of the cationic 2-Piperidone cation and its dimer has been recorded. The experimental method yields the fragment intensity as a function of the internal energy deposited into the parent cation. In parallel, ab initio studies on ionic and neutral fragmentation products have been performed with the aim of determining the isomers of the ionic products observed experimentally as well as of their neutral counterparts. L. Nahon, N. De Oliveria,J. F. Gil,B. Pilette,O. Marcouillé, B. La garde and F. Polack Journal of Synchrotron Radiation {19}(4), 508-520; 2012
Bias in the effective field theory of large scale structures

DOE PAGES

Senatore, Leonardo

2015-11-05

We study how to describe collapsed objects, such as galaxies, in the context of the Effective Field Theory of Large Scale Structures. The overdensity of galaxies at a given location and time is determined by the initial tidal tensor, velocity gradients and spatial derivatives of the regions of dark matter that, during the evolution of the universe, ended up at that given location. Similarly to what was recently done for dark matter, we show how this Lagrangian space description can be recovered by upgrading simpler Eulerian calculations. We describe the Eulerian theory. We show that it is perturbatively local inmore » space, but non-local in time, and we explain the observational consequences of this fact. We give an argument for why to a certain degree of accuracy the theory can be considered as quasi time-local and explain what the operator structure is in this case. Furthermore, we describe renormalization of the bias coefficients so that, after this and after upgrading the Eulerian calculation to a Lagrangian one, the perturbative series for galaxies correlation functions results in a manifestly convergent expansion in powers of k/k NL and k/k M, where k is the wavenumber of interest, k NL is the wavenumber associated to the non-linear scale, and k M is the comoving wavenumber enclosing the mass of a galaxy.« less
FT-IR and FT-Raman characterization and investigation of reactive properties of N-(3-iodo-4-methylphenyl)pyrazine-2-carboxamide by molecular dynamics simulations and DFT calculations

NASA Astrophysics Data System (ADS)

Ranjith, P. K.; Al-Abdullah, Ebtehal S.; Al-Omary, Fatmah A. M.; El-Emam, Ali A.; Anto, P. L.; Sheena, Mary Y.; Armaković, Stevan; Armaković, Sanja J.; Zitko, Jan; Dolezal, Martin; Van Alsenoy, C.

2017-05-01

The FT-IR and FT-Raman spectra of N-(3-iodo-4-methylphenyl)pyrazine-2-carboxamide were recorded and the experimentally observed wavenumbers are compared with the theoretically obtained wavenumbers. The redshift of the Nsbnd H stretching mode in the IR spectrum from the computed value indicated the weakening of the Nsbnd H bond. The ring breathing modes of the phenyl ring and pyrazine ring are assigned at 819 and 952 cm-1 theoretically. Using natural bond orbital analysis, the stability of the molecule arising from hyperconjugative interaction and charge delocalization has been analyzed. The most reactive sites in the molecule were identified by molecular electrostatic potential map. The calculations of the average local ionization energy (ALIE) were used for visualization and determination of molecule sites possibly prone to electrophilic attacks. Further information on possible reactive centers of title molecule has been obtained by calculations of Fukui functions. Vulnerability of title molecule towards autoxidation mechanism was investigated by calculations of bond dissociation energies (BDE), while vulnerability towards hydrolysis was investigated by calculations of radial distribution functions (RDF) as obtained after molecular dynamics (MD) simulations. Molecular docking studies suggest that the compound might exhibit inhibitory activity against mGluRs.
Fourier Transform Spectroscopy of Doubly Ionized Iron Group Elements for Astrophysical Applications

NASA Astrophysics Data System (ADS)

Smillie, D. G.; Pickering, J. C.; Smith, P. L.

2005-05-01

Exciting new astrophysical spectra provided by both space-based (such as STIS, Hubble) and ground-based spectrographs (such as HIRES, Keck-1 telescope) are unable to be fully interpreted due to deficiencies in the database of laboratory measured atomic data such as transition wavelengths and oscillator strengths. The transition elements, particularly the Iron (3d) group, are extremely important for stellar astrophysics providing much of the observed stellar opacity, and the doubly ionized species dominate the spectra of hot (B-type) stars [1]. Transition wavelengths with uncertainties of ˜1:107 and oscillator strengths with uncertainties of ˜10% are required to fully interpret the astrophysical spectra. At Imperial College, we use a Penning discharge lamp with our unique Fourier transform spectrometer (FTS) [1] capable of measurements from the visible to the VUV (down to 135nm) at high resolution (typical wavenumber uncertainty ˜1:108). These measurements are supplemented by IR FTS spectra and grating spectra (beyond the 135nm limit) taken at the National Institute of Standards and Technology (NIST), USA. The spectra are analyzed to provide intensity and wavenumber calibrated linelists. This allows term analysis (calculating energy levels from the measured transition line wavelengths) and branching ratios (which can be combined with level lifetimes to produce oscillator strengths) to be determined. FTS measurements of Fe III in the UV and IR have been completed at Imperial and NIST and grating measurements are planned at NIST to complete the Fe III work. Similarly, Co III and Cr III measurements are currently ongoing at both Imperial and NIST. After completion of the analysis, the data will be disseminated to atomic databases (such as the NIST Atomic Spectra Database and the Vienna Atomic Line Database). This work is supported in part by NASA Grant NAG5-12668, PPARC and the Royal Society of the UK. [1] J. C. Pickering, Vibrational Spectroscopy, 29, 27-43 (2002)
A new potential energy surface for vibration-vibration coupling in HF-HF collisions. Formulation and quantal scattering calculations

NASA Astrophysics Data System (ADS)

Schwenke, David W.; Truhlar, Donald G.

1988-04-01

We present new ab initio calculations of the HF-HF interaction potential for the case where both molecules are simultaneously displaced from their equilibrium internuclear distance. These and previous ab initio calculations are then fit to a new analytic representation which is designed to be efficient to evaluate and to provide an especially faithful account of the forces along the vibrational coordinates. We use the new potential for two sets of quantal scattering calculations for collisions in three dimensions with total angular momentum zero. First we test that the angular harmonic representation of the anisotropy is adequate by comparing quantal rigid rotator calculations to those carried out for potentials involving higher angular harmonics and for which the expansion in angular harmonics is systematically increased to convergence. Then we carry out large-scale quantal calculations of vibration-vibration energy transfer including the coupling of both sets of vibrational and rotational coordinates. These calculations indicate that significant rotational energy transfer accompanies the vibration-to-vibration energy transfer process.
Temperature dependence of the Raman spectrum of UO2

NASA Astrophysics Data System (ADS)

Elorrieta, J. M.; Bonales, L. J.; Baonza, V. G.; Cobos, J.

2018-05-01

The position of the main spectral features (located at ∼445, ∼575, ∼625, ∼925 and ∼1145 cm-1) in the Raman spectrum of UO2 has been examined from room temperature up to 600 °C. The wavenumber shifts measured for the observed bands have allowed us to obtain the temperature dependence (dω/dT) of the different vibrational modes. Our measurements corroborate the assignment of the band observed at ∼1145 cm-1 to the 2LO overtone. In addition, the temperature dependence of the bandwidths of the T2g and 2LO modes has been analysed.
IR Spectroscopy of Ethylene Glycol Solutions of Dimethylsulfoxide

NASA Astrophysics Data System (ADS)

Kononova, E. G.; Rodnikova, M. N.; Solonina, I. A.; Sirotkin, D. A.

2018-07-01

Features of ethylene glycol (EG) solutions of dimethylsulfoxide (DMSO) with low and moderate concentrations (from 2 to 50 mol % of DMSO) are studied by IR spectroscopy on a Bruker Tensor 37 FT-IR spectrometer in the wavenumber range of 400 to 4000 cm-1. The main monitored bands are the S=O stretching vibration band of DMSO (1057 cm-1) and the C-O (1086 and 1041 cm-1) and O-H (3350 cm-1) stretching vibration bands of EG. The obtained data show complex DMSO · 2EG to be present in all solutions with the studied concentrations due to formation of H-bonds between the S=O group of DMSO and the OH group of EG. In the concentration range of 6 to 25 mol % DMSO, the OH stretching vibration of EG is found to be broadened (by up to 70 cm-1), suggesting the strengthening of hydrogen bonds in the spatial network of the system due to the solvophobic effect of DMSO molecules and the formation of DMSO · 2EG. Starting from 25 mol % DMSO, narrowing of the OH stretching vibration is noted, and the bands of free DMSO appear along with the DMSO · 2EG complex, suggesting microseparation in the investigated system. At 50 mol % DMSO, the amounts of free and bound species in the system became comparable.
Novel Molecular Spectroscopic Multimethod Approach for Monitoring Water Absorption/Desorption Kinetics of CAD/CAM Poly(Methyl Methacrylate) Prosthodontics.

PubMed

Wiedemair, Verena; Mayr, Sophia; Wimmer, Daniel S; Köck, Eva Maria; Penner, Simon; Kerstan, Andreas; Steinmassl, Patricia-Anca; Dumfahrt, Herbert; Huck, Christian W

2017-07-01

Water absorbed to poly(methyl methacrylate) (PMMA)-based CAD/CAM (computer-assisted design/computer-assisted manufacturing) prosthodontics can alter their properties including hardness and stability. In the present contribution, water absorption and desorption kinetics under defined experimental conditions were monitored employing several supplementary and advanced Fourier transform infrared (FT-IR) spectroscopic techniques in combination with multivariate analysis (MVA). In this synergistic vibrational spectroscopic multimethod approach, first a novel near-infrared (NIR) diffuse fiber optic probe reflection spectroscopic method was established for time-resolved analysis of water uptake within seven days under controlled conditions. Near-infrared water absorbance spectra in a wavenumber range between 5288-5100 cm -1 (combination band) and 5424-5352 cm -1 (second overtone) were used establishing corresponding calibration and validation models to quantify the amount of water in the milligram range. Therefore, 14 well-defined samples exposed to prior optimized experimental conditions were taken into consideration. The average daily water uptake conducting reference analysis was calculated as 22 mg/day for one week. Additionally, in this study for the first time NIR two-dimensional correlation spectroscopy (2D-COS) was conducted to monitor and interpret the spectral dynamics of water absorption on the prosthodontics in a wavenumber range of 5100-5300 cm -1 . For sensitive time-resolved recording of water desorption, a recently developed high-temperature, high-pressure FT-IR reaction cell with water-free ultra-dry in situ and operando operation was applied. The reaction cell, as well as the sample holder, was fully made of quartz glass, with no hot metal or ceramic parts in the vicinity of the high temperature zone. Applying a temperature gradient in the range of 25-150 ℃, mid-infrared (MIR) 2D-COS was successfully conducted to get insights into the dynamic behavior of O-H (1400-1800 cm -1 ) absorption bands with increasing temperature over time and the release of CO 2 (2450 cm -1 ) from the polymers. In addition, an ATR FT-IR imaging setup was optimized in order to investigate the surface homogeneity of the PMMA-based resins with a spatial resolution to 2 µm. From this vibrational spectroscopic multimethod approach and the collection of several analytical data, conclusions were drawn as to which degree the surface structure and/or its porosity have an impact onto the amount of water absorption.
Vibrational and electronic spectroscopic studies of melatonin

NASA Astrophysics Data System (ADS)

Singh, Gurpreet; Abbas, J. M.; Dogra, Sukh Dev; Sachdeva, Ritika; Rai, Bimal; Tripathi, S. K.; Prakash, Satya; Sathe, Vasant; Saini, G. S. S.

2014-01-01

We report the infrared absorption and Raman spectra of melatonin recorded with 488 and 632.8 nm excitations in 3600-2700 and 1700-70 cm-1 regions. Further, we optimized molecular structure of the three conformers of melatonin within density functional theory calculations. Vibrational frequencies of all three conformers have also been calculated. Observed vibrational bands have been assigned to different vibrational motions of the molecules on the basis of potential energy distribution calculations and calculated vibrational frequencies. Observed band positions match well with the calculated values after scaling except Nsbnd H stretching mode frequencies. It is found that the observed and calculated frequencies mismatch of Nsbnd H stretching is due to intermolecular interactions between melatonin molecules.
Stress-induced crystal transition of poly(butylene succinate) studied by terahertz and low-frequency Raman spectroscopy and quantum chemical calculation

NASA Astrophysics Data System (ADS)

Tatsuoka, Seika; Sato, Harumi

2018-05-01

We measured terahertz (THz) and low-frequency Raman spectra of Poly (butylene succinate) (PBS) which shows the crystal transition from α to β by stretching. For the assignment of the absorption peaks in the low-frequency region, we performed quantum chemical calculations with Cartesian-coordinate tensor transfer (CCT) method. Four major peaks appeared in the THz spectra of PBS at around 58, 76, 90, and 100 cm-1, and in the low-frequency Raman spectra a peak was observed at 88 cm-1. The THz peak at 100 cm-1 and the Raman peak at 88 cm-1 show a shift to a lower wavenumber region with increasing temperature. The quantum chemical calculation of β crystal form reveals the new peak appears above 100 cm-1. It was found that two kinds of peaks overlapped at around 100 cm-1 in the THz spectra of PBS. One of them can be assigned to a weak hydrogen bond between the C=O and CH2 groups in the intermolecular chains, which is perpendicular to the molecular chain of the α crystal form. Another one showed a parallel polarization which can be assigned to the intramolecular interaction between O (ether) and H-C groups in the β crystal form. The position of the peak at around 100 cm-1 in the perpendicular polarization changed to a lower wavenumber region with stretching, because of the weakening of the intermolecular hydrogen bonding by increasing the interatomic distances. On the other hand, that of the parallel polarization shifts to a higher wavenumber region because of the shortening of the interatomic distance from α to β crystal form (the strength of the intramolecular hydrogen bonding became stronger) by stretching.
Consistent assignment of the vibrations of symmetric and asymmetric meta-disubstituted benzenes

NASA Astrophysics Data System (ADS)

Kemp, David J.; Tuttle, William D.; Jones, Florence M. S.; Gardner, Adrian M.; Andrejeva, Anna; Wakefield, Jonathan C. A.; Wright, Timothy G.

2018-04-01

The assignment of vibrational structure in spectra gives valuable insights into geometric and electronic structure changes upon electronic excitation or ionization; particularly when such information is available for families of molecules. We give a description of the phenyl-ring-localized vibrational modes of the ground (S0) electronic states of sets of meta-disubstituted benzene molecules including both symmetrically- and asymmetrically-substituted cases. As in our earlier work on monosubstituted benzenes (Gardner and Wright, 2011), para-disubstituted benzenes (Andrejeva et al., 2016), and ortho-disubstituted benzenes (Tuttle et al., 2018), we conclude that the use of the commonly-used Wilson or Varsányi mode labels, which are based on the vibrational motions of benzene itself, is misleading and ambiguous. Instead, we label the phenyl-ring-localized modes consistently based upon the Mulliken (Herzberg) method for the modes of meta-difluorobenzene (mDFB) under Cs symmetry, since we wish the labelling scheme to cover both symmetrically- and asymmetrically-substituted molecules. By studying the vibrational wavenumbers obtained from the same force-field while varying the mass of the substituent, we are able to follow the evolving modes across a wide range of molecules and hence provide consistent assignments. We assign the vibrations of the following sets of molecules: the symmetric meta-dihalobenzenes, meta-xylene and resorcinol (meta-dihydroxybenzene); and the asymmetric meta-dihalobenzenes, meta-halotoluenes, meta-halophenols and meta-cresol. In the symmetrically-substituted species, we find two pairs of in-phase and out-of-phase carbon-substituent stretches, and this motion persists in asymmetrically-substituted molecules for heavier substituents; however, when at least one of the substituents is light, then we find that these evolve into localized carbon-substituent stretches.
Experimental validation of a numerical model for subway induced vibrations

NASA Astrophysics Data System (ADS)

Gupta, S.; Degrande, G.; Lombaert, G.

2009-04-01

This paper presents the experimental validation of a coupled periodic finite element-boundary element model for the prediction of subway induced vibrations. The model fully accounts for the dynamic interaction between the train, the track, the tunnel and the soil. The periodicity or invariance of the tunnel and the soil in the longitudinal direction is exploited using the Floquet transformation, which allows for an efficient formulation in the frequency-wavenumber domain. A general analytical formulation is used to compute the response of three-dimensional invariant or periodic media that are excited by moving loads. The numerical model is validated by means of several experiments that have been performed at a site in Regent's Park on the Bakerloo line of London Underground. Vibration measurements have been performed on the axle boxes of the train, on the rail, the tunnel invert and the tunnel wall, and in the free field, both at the surface and at a depth of 15 m. Prior to these vibration measurements, the dynamic soil characteristics and the track characteristics have been determined. The Bakerloo line tunnel of London Underground has been modelled using the coupled periodic finite element-boundary element approach and free field vibrations due to the passage of a train at different speeds have been predicted and compared to the measurements. The correspondence between the predicted and measured response in the tunnel is reasonably good, although some differences are observed in the free field. The discrepancies are explained on the basis of various uncertainties involved in the problem. The variation in the response with train speed is similar for the measurements as well as the predictions. This study demonstrates the applicability of the coupled periodic finite element-boundary element model to make realistic predictions of the vibrations from underground railways.

Wavenumber-domain separation of rail contribution to pass-by noise

NASA Astrophysics Data System (ADS)

Zea, Elias; Manzari, Luca; Squicciarini, Giacomo; Feng, Leping; Thompson, David; Arteaga, Ines Lopez

2017-11-01

In order to counteract the problem of railway noise and its environmental impact, passing trains in Europe must be tested in accordance to a noise legislation that demands the quantification of the noise generated by the vehicle alone. However, for frequencies between about 500 Hz and 1600 Hz, it has been found that a significant part of the measured noise is generated by the rail, which behaves like a distributed source and radiates plane waves as a result of the contact with the train's wheels. Thus the need arises for separating the rail contribution to the pass-by noise in that particular frequency range. To this end, the present paper introduces a wavenumber-domain filtering technique, referred to as wave signature extraction, which requires a line microphone array parallel to the rail, and two accelerometers on the rail in the vertical and lateral direction. The novel contributions of this research are: (i) the introduction and application of wavenumber (or plane-wave) filters to pass-by data measured with a microphone array located in the near-field of the rail, and (ii) the design of such filters without prior information of the structural properties of the rail. The latter is achieved by recording the array pressure, as well as the rail vibrations with the accelerometers, before and after the train pass-by. The performance of the proposed method is investigated with a set of pass-by measurements performed in Germany. The results seem to be promising when compared to reference data from TWINS, and the largest discrepancies occur above 1600 Hz and are attributed to plane waves radiated by the rail that so far have not been accounted for in the design of the filters.
Calculation of Vibrational and Electronic Excited-State Absorption Spectra of Arsenic-Water Complexes Using Density Functional Theory

DTIC Science & Technology

2016-06-03

Naval Research Laboratory Washington, DC 20375-5320 NRL/MR/6390--16-9681 Calculation of Vibrational and Electronic Excited-State Absorption Spectra...NUMBER OF PAGES 17. LIMITATION OF ABSTRACT Calculation of Vibrational and Electronic Excited-State Absorption Spectra of Arsenic-Water Complexes Using...Unclassified Unlimited Unclassified Unlimited 59 Samuel G. Lambrakos (202) 767-2601 Calculations are presented of vibrational and electronic excited-state
Variational study on the vibrational level structure and vibrational level mixing of highly vibrationally excited S₀ D₂CO.

PubMed

Rashev, Svetoslav; Moule, David C; Rashev, Vladimir

2012-11-01

We perform converged high precision variational calculations to determine the frequencies of a large number of vibrational levels in S(0) D(2)CO, extending from low to very high excess vibrational energies. For the calculations we use our specific vibrational method (recently employed for studies on H(2)CO), consisting of a combination of a search/selection algorithm and a Lanczos iteration procedure. Using the same method we perform large scale converged calculations on the vibrational level spectral structure and fragmentation at selected highly excited overtone states, up to excess vibrational energies of ∼17,000 cm(-1), in order to study the characteristics of intramolecular vibrational redistribution (IVR), vibrational level density and mode selectivity. Copyright © 2012 Elsevier B.V. All rights reserved.
Wavenumber-frequency Spectra of Pressure Fluctuations Measured via Fast Response Pressure Sensitive Paint

NASA Technical Reports Server (NTRS)

Panda, J.; Roozeboom, N. H.; Ross, J. C.

2016-01-01

The recent advancement in fast-response Pressure-Sensitive Paint (PSP) allows time-resolved measurements of unsteady pressure fluctuations from a dense grid of spatial points on a wind tunnel model. This capability allows for direct calculations of the wavenumber-frequency (k-?) spectrum of pressure fluctuations. Such data, useful for the vibro-acoustics analysis of aerospace vehicles, are difficult to obtain otherwise. For the present work, time histories of pressure fluctuations on a flat plate subjected to vortex shedding from a rectangular bluff-body were measured using PSP. The light intensity levels in the photographic images were then converted to instantaneous pressure histories by applying calibration constants, which were calculated from a few dynamic pressure sensors placed at selective points on the plate. Fourier transform of the time-histories from a large number of spatial points provided k-? spectra for pressure fluctuations. The data provides first glimpse into the possibility of creating detailed forcing functions for vibro-acoustics analysis of aerospace vehicles, albeit for a limited frequency range.
Synthesis of wavelet envelope in 2-D random media having power-law spectra: comparison with FD simulations

NASA Astrophysics Data System (ADS)

Sato, Haruo; Fehler, Michael C.

2016-10-01

The envelope broadening and the peak delay of the S-wavelet of a small earthquake with increasing travel distance are results of scattering by random velocity inhomogeneities in the earth medium. As a simple mathematical model, Sato proposed a new stochastic synthesis of the scalar wavelet envelope in 3-D von Kármán type random media when the centre wavenumber of the wavelet is in the power-law spectral range of the random velocity fluctuation. The essential idea is to split the random medium spectrum into two components using the centre wavenumber as a reference: the long-scale (low-wavenumber spectral) component produces the peak delay and the envelope broadening by multiple scattering around the forward direction; the short-scale (high-wavenumber spectral) component attenuates wave amplitude by wide angle scattering. The former is calculated by the Markov approximation based on the parabolic approximation and the latter is calculated by the Born approximation. Here, we extend the theory for the envelope synthesis of a wavelet in 2-D random media, which makes it easy to compare with finite difference (FD) simulation results. The synthetic wavelet envelope is analytically written by using the random medium parameters in the angular frequency domain. For the case that the power spectral density function of the random velocity fluctuation has a steep roll-off at large wavenumbers, the envelope broadening is small and frequency independent, and scattering attenuation is weak. For the case of a small roll-off, however, the envelope broadening is large and increases with frequency, and the scattering attenuation is strong and increases with frequency. As a preliminary study, we compare synthetic wavelet envelopes with the average of FD simulation wavelet envelopes in 50 synthesized random media, which are characterized by the RMS fractional velocity fluctuation ε = 0.05, correlation scale a = 5 km and the background wave velocity V0 = 4 km s-1. We use the radiation of a 2 Hz Ricker wavelet from a point source. For all the cases of von Kármán order κ = 0.1, 0.5 and 1, we find the synthetic wavelet envelopes are a good match to the characteristics of FD simulation wavelet envelopes in a time window starting from the onset through the maximum peak to the time when the amplitude decreases to half the peak amplitude.
[Spectrum characterization and fine structure of copper phthalocyanine-doped TiO2 microcavities].

PubMed

Liu, Cheng-lin; Zhang, Xin-yi; Zhong, Ju-hua; Zhu, Yi-hua; He, Bo; Wei, Shi-qiang

2007-10-01

Copper phthalocyanine-doped TiO2 microcavities were fabricated by chemistry method. Their spectrum characterization was studied by Fourier transform infrared (FTIR) and Raman spectroscopy, and their fine structure was analyzed by X-ray absorption fine structure (XAFS). The results show that there is interaction of copper phthalocyanine (CuPc) and TiO2 microcavities after TiO2 microcavities was doped with CuPc. For example, there is absorption at 900.76 cm(-1) in FTIR spectra, and the "red shift" of both OH vibration at 3392.75 cm(-1) and CH vibration at 2848.83 cm(-1). There exist definite peak shifts and intensity changes in infrared absorption in the C-C or C-N vibration in the planar phthalocyanine ring, the winding vibration of C-H inside and C-N outside plane of benzene ring. In Raman spectrum, there are 403.4, 592.1 and 679.1 cm(-1) characterized peaks of TiO2 in CuPc-doped TiO2 microcavities, but their wave-numbers show shifts to anatase TiO2. The vibration peaks at 1586.8 and 1525.6 cm(-1) show that there exists the composite material of CuPc and TiO2. These changes are related to the plane tropism of the molecule structure of copper phthalocyanine. XAFS showed tetrahedron TiO4 structure of Ti in TiO2 microcavities doped with copper phthalocyanine, and the changes of inner "medial distances" and the surface structure of TiO2 microcavities.
Antimicrobial activities, DNA interactions, spectroscopic (FT-IR and UV-Vis) characterizations, and DFT calculations for pyridine-2-carboxylic acid and its derivates

NASA Astrophysics Data System (ADS)

Tamer, Ömer; Tamer, Sevil Arabacı; İdil, Önder; Avcı, Davut; Vural, Hatice; Atalay, Yusuf

2018-01-01

In this paper, pyridine- 2- carboxylic acid, also known as picolinic acid (pic), and its two derivate, 4- methoxy-pyridine- 2- carboxylic acid (4-Mpic) and 4- chloro-pyridine- 2- carboxylic acid (4-Clpic) have been characterized by FT-IR and UV-Vis spectroscopy techniques as well as DFT calculations. B3LYP level of Density Functional Theory (DFT) method was used to obtain ground state geometries, vibration wavenumbers, first order hyperpolarizabilities and molecular electrostatic potential (MEP) surfaces for pic, 4Clpic and 4Mpic. The electronic absorption wavelengths and HOMO-LUMO energies were investigated by time dependent B3LYP (TD-B3LYP) level with the conductor-like polarizable continuum model (CPCM). The effects of Cl atom and OCH3 group on HOMO-LUMO energy gaps and first order hyperpolarizability parameters of pic, 4Clpic and 4Mpic molecules were examined. All molecules were screened for their antibacterial activities against Gram-positive and Gram-negative bacteria and for their antifungal activities against yeast strains by using minimal inhibitory concentration method (MIC). All compounds (pic, 4Mpic and 4Clpic) have been found to be very active against to the Gram (+) and Gram (-) bacteria. The DNA interactions of pic, 4Clpic and 4Mpic were analyzed by molecular docking simulations, and the interaction of the 4Mpic molecule with DNA is found to be higher than 4Clpic and pic.
Infrared Spectrum of N-Oxidohydroxylamine [ONH(OH)] Produced in Reaction H + Hono in Solid Para-Hydrogen

NASA Astrophysics Data System (ADS)

Haupa, Karolina Anna; Lee, Yuan-Pern

2017-06-01

Hydrogenation reactions in the N/O chemical network are important for an understanding of the mechanism of formation of organic molecules in dark interstellar clouds, but many reactions remain unknown. We present the results of the reaction H + HONO in solid {para}-hydrogen ({p}-H_{2}) at 3.3 K investigated with infrared spectra. Two methods that produced hydrogen atoms were the irradiation of HONO molecules in {p}-H_{2} at 365 nm to produce OH radicals that reacted readily with nearby H_{2} to produce mobile H atoms, and irradiation of Cl_{2} molecules (co-deposited with HONO) in {p}-H_{2} at 405 nm to produce Cl atoms that reacted readily with nearby H_{2} to produce mobile H atoms. In both experiments, we assigned IR lines at 3549.6 (νb{1}), 1465.0 (νb{3}), 1372.2 (νb{4}), 895.6/898.5 (νb{6}), and 630.9 (νb{7}) \\wn to N-oxidohydroxylamine [ONH(OH)], the primary product of HONO hydrogenation. The assignments were derived according to the consideration of possible reactions and comparison of observed vibrational wavenumbers and their IR intensities with values predicted with the B3LYP/aug-cc-pVTZ method of quantum-chemical calculations. The agreement between observed and calculated D/H- and ^{15}N/^{14}N-isotopic ratios further supports these assignments. The role of this reaction in the N/O chemical network in dark interstellar clouds is discussed.
Critical effects of alkyl chain length on fibril structures in benzene-trans(RR)- or (SS)-N,N'-alkanoyl-1,2-diaminocyclohexane gels.

PubMed

Sato, Hisako; Nakae, Takahiro; Morimoto, Kazuya; Tamura, Kenji

2012-02-28

Vibrational circular dichroism (VCD) spectra were recorded on benzene-d(6) gels formed by chiral low molecular mass gelators (LMGs), trans(RR)- or trans(SS)-N,N'-alkanoyl-1,2-diaminocyclohexane (denoted by RR-C(n) or SS-C(n), respectively; n = the number of carbon atoms in an introduced alkanoyl group). Attention was focused on the effects of alkyl chain length on the structures of the gels. When n was changed from 6 to 12, the signs of the coupled peaks around 1550 cm(-1) in the VCD spectra, which were assigned to the symmetric and asymmetric C=O stretching vibrations from the higher to lower wavenumber, respectively, critically depended on the alkyl chain length. In the case of RR-C(n), for example, the signs of the couplet were plus and minus for n = 8, 9, 10 and 12, while the signs of the same couplet were reversed for n = 6 and 7. The conformations of LMGs in fibrils were determined by comparing the observed IR and VCD spectra with those calculated for a monomeric molecule. The observed reversal of signs in the C=O couplet was rationalized in terms of the different modes of hydrogen bonding. In the case of C(8), C(9), C(10) and C(12), gelator molecules were stacked with their cyclohexyl rings in parallel, forming double anti-parallel chains of intermolecular hydrogen bonds using two pairs of >NH and >C=O groups. In case of C(6) and C(7), gelator molecules were stacked through a single chain of intermolecular hydrogen bonds using a pair of >NH and >C=O groups. The remaining pair of >NH and >C=O groups formed an intramolecular hydrogen bond.
Fourier Transform Ultraviolet Spectroscopy of the A Pi-2(3/2) Direct Current X Pi-2(3/2) Transition of BrO

NASA Technical Reports Server (NTRS)

Wilmouth, David M.; Hanisco, Thomas F.; Donahue, Neil M.; Anderson, James G.

1999-01-01

The first spectra of the A (2)Pi(sub 3/2) from X (2)Pi(sub 3/2) electronic transition of BrO using Fourier transform ultraviolet spectroscopy are obtained. Broadband vibrational spectra acquired at 298 +/- 2 K and 228 +/- 5 K, as well as high-resolution rotational spectra of the A from X 7,0 and 12,0 vibrational bands are presented. Wavenumber positions for the spectra are obtained with high accuracy, and cross section assignments are made, incorporating the existing literature. With 35 cm(exp -1) (0.40 nm) resolution the absolute cross section at the peak of the 7,0 band is determined to be (1.58 +/- 0.12) x 10(exp -17) sq cm/molecule at 298 +/- 2 K and (1.97 +/- 0.15) x 10(exp -17) sq cm/molecule at 228 +/- 5 K. BrO dissociation energies are determined with a graphical Birge-Sponer technique, using Le Roy-Bernstein theory to place an upper limit on the extrapolation. From the ground-state dissociation energy, D(sub o)" = 231.0 +/- 1.7 kJ/mol, the heat of formation of BrO(g) is calculated, del(sub f)H(0 K) = 133.7 +/- 1.7 kJ/mol and del(sub f)H(298.15 K) = 126.2 +/- 1.7 kJ/mol. Cross sections for the high-resolution 7,0 and 12,0 rotational peaks are the first to be reported. The band structures are modeled, and improved band origins, rotational constants, centrifugal distortion constants, and linewidths are determined. In particular, J-dependent linewidths and lifetimes are observed for the both the 7,0 and 12,0 bands.
Standard deviation of vertical two-point longitudinal velocity differences in the atmospheric boundary layer.

NASA Technical Reports Server (NTRS)

Fichtl, G. H.

1971-01-01

Statistical estimates of wind shear in the planetary boundary layer are important in the design of V/STOL aircraft, and for the design of the Space Shuttle. The data analyzed in this study consist of eleven sets of longitudinal turbulent velocity fluctuation time histories digitized at 0.2 sec intervals with approximately 18,000 data points per time history. The longitudinal velocity fluctuations were calculated with horizontal wind and direction data collected at the 18-, 30-, 60-, 90-, 120-, and 150-m levels. The data obtained confirm the result that Eulerian time spectra transformed to wave-number spectra with Taylor's frozen eddy hypothesis possess inertial-like behavior at wave-numbers well out of the inertial subrange.
On magnetothermal instability in cluster cooling flows

NASA Technical Reports Server (NTRS)

Balbus, Steven A.

1991-01-01

Lagrangian techniques appropriate to a local calculation are used to show that a weak ordered magnetic field can result in a generic condensational mode in cluster cooling flows. However, thermal instability appears possible only if the conductivity is well below its Spitzer value, for all nonradial wavenumbers. Wavenumbers not subject to conductive damping are subject to buoyant oscillations. It is shown that when instability is present, lateral magnetic confinement of high thermal pressure regions in the plasma by radial magnetic field lines is responsible in at least equal measure with radially directed magnetic tension for the suppression of oscillations and the reappearance of local condensational modes. The general importance of even very modest magnetic fields for destabilizing thermal time scale perturbations is emphasized.
Investigations on structural, vibrational, morphological and optical properties of CdS and CdS/Co films by ultrasonic spray pyrolysis

NASA Astrophysics Data System (ADS)

Aksay, S.; Polat, M.; Özer, T.; Köse, S.; Gürbüz, G.

2011-09-01

CdS and CdS/Co films have been deposited on glass substrates by an ultrasonic spray pyrolysis method. The effects of Co incorporation on the structural, optical, morphological, elemental and vibrational properties of these films were investigated. XRD analysis confirmed the hexagonal wurtzite structure of all films and had no impurity phase. While CdS film has (0 0 2) as the preferred orientation, CdS/Co films have (1 1 0) as the preferred orientation. The direct optical band gap was found to decrease from 2.42 to 2.39 eV by Co incorporation. The decrease of the direct energy gaps by increasing Co contents is mainly due to the sp-d exchange interaction between the localized d-electrons of Co2+ ions and band electrons of CdS. After the optical investigations, it was seen that the transmittance of CdS films decreased by Co content. The Raman measurements revealed two peaks corresponding to the 1LO and 2LO modes of hexagonal CdS. The vibrational modes of Cd-S were obtained in the wavenumber range (590-715 cm-1) using Fourier transform infrared spectroscopy (FTIR). The elemental analysis of the film was done by energy dispersive X-ray spectrometry.
Vibrational multiconfiguration self-consistent field theory: implementation and test calculations.

PubMed

Heislbetz, Sandra; Rauhut, Guntram

2010-03-28

A state-specific vibrational multiconfiguration self-consistent field (VMCSCF) approach based on a multimode expansion of the potential energy surface is presented for the accurate calculation of anharmonic vibrational spectra. As a special case of this general approach vibrational complete active space self-consistent field calculations will be discussed. The latter method shows better convergence than the general VMCSCF approach and must be considered the preferred choice within the multiconfigurational framework. Benchmark calculations are provided for a small set of test molecules.
Amide I vibrational circular dichroism of dipeptide: Conformation dependence and fragment analysis

NASA Astrophysics Data System (ADS)

Choi, Jun-Ho; Cho, Minhaeng

2004-03-01

The amide I vibrational circular dichroic response of alanine dipeptide analog (ADA) was theoretically investigated and the density functional theory calculation and fragment analysis results are presented. A variety of vibrational spectroscopic properties, local and normal mode frequencies, coupling constant, dipole, and rotational strengths, are calculated by varying two dihedral angles determining the three-dimensional ADA conformation. Considering two monopeptide fragments separately, we show that the amide I vibrational circular dichroism of the ADA can be quantitatively predicted. For several representative conformations of the model ADA, vibrational circular dichroism spectra are calculated by using both the density functional theory calculation and fragment analysis methods.
Vibrational energy transport in acetylbenzonitrile described by an ab initio-based quantum tier model

NASA Astrophysics Data System (ADS)

Fujisaki, Hiroshi; Yagi, Kiyoshi; Kikuchi, Hiroto; Takami, Toshiya; Stock, Gerhard

2017-01-01

Performing comprehensive quantum-chemical calculations, a vibrational Hamiltonian of acetylbenzonitrile is constructed, on the basis of which a quantum-mechanical "tier model" is developed that describes the vibrational dynamics following excitation of the CN stretch mode. Taking into account 36 vibrational modes and cubic and quartic anharmonic couplings between up to three different modes, the tier model calculations are shown to qualitatively reproduce the main findings of the experiments of Rubtsov and coworkers (2011), including the energy relaxation of the initially excited CN mode and the structure-dependent vibrational transport. Moreover, the calculations suggest that the experimentally measured cross-peak among the CN and CO modes does not correspond to direct excitation of the CO normal mode but rather reflects excited low-frequency vibrations that anharmonically couple to the CO mode. Complementary quasiclassical trajectory calculations are found to be in good overall agreement with the quantum calculations.
Crack Detection with Lamb Wave Wavenumber Analysis

NASA Technical Reports Server (NTRS)

Tian, Zhenhua; Leckey, Cara; Rogge, Matt; Yu, Lingyu

2013-01-01

In this work, we present our study of Lamb wave crack detection using wavenumber analysis. The aim is to demonstrate the application of wavenumber analysis to 3D Lamb wave data to enable damage detection. The 3D wavefields (including vx, vy and vz components) in time-space domain contain a wealth of information regarding the propagating waves in a damaged plate. For crack detection, three wavenumber analysis techniques are used: (i) two dimensional Fourier transform (2D-FT) which can transform the time-space wavefield into frequency-wavenumber representation while losing the spatial information; (ii) short space 2D-FT which can obtain the frequency-wavenumber spectra at various spatial locations, resulting in a space-frequency-wavenumber representation; (iii) local wavenumber analysis which can provide the distribution of the effective wavenumbers at different locations. All of these concepts are demonstrated through a numerical simulation example of an aluminum plate with a crack. The 3D elastodynamic finite integration technique (EFIT) was used to obtain the 3D wavefields, of which the vz (out-of-plane) wave component is compared with the experimental measurement obtained from a scanning laser Doppler vibrometer (SLDV) for verification purposes. The experimental and simulated results are found to be in close agreement. The application of wavenumber analysis on 3D EFIT simulation data shows the effectiveness of the analysis for crack detection. Keywords: : Lamb wave, crack detection, wavenumber analysis, EFIT modeling
FTIR, FT-RAMAN, NMR, spectra, normal co-ordinate analysis, NBO, NLO and DFT calculation of N,N-diethyl-4-methylpiperazine-1-carboxamide molecule

NASA Astrophysics Data System (ADS)

Muthu, S.; Elamurugu Porchelvi, E.

2013-11-01

The Fourier Transform Infrared (FT-IR) and FT-Raman of N,N-diethyl-4-methylpiperazine-1-carboxamide (NND4MC) have been recorded and analyzed. The structure of the compound was optimized and the structural characteristics were determined by density functional theory (DFT) using B3LYP method with 6-31G(d,p) and 6-311G(d,p) basis sets. The difference between the observed and scaled wavenumber values of most of the fundamentals is very small. The theoretically predicted FT-IR and FT-Raman spectra of the title molecule have been constructed. The detailed interpretation of the vibrational spectra has been carried out with aid of normal coordinate analysis (NCA) following the scaled quantum mechanical force field methodology. Stability of the molecule arising from hyperconjugative interactions and charge delocalization has been analyzed using natural bond orbital (NBO) analysis. The results show that electron density (ED) in the σ* and π* antibonding orbitals and second order delocalization energies (E2) confirm the occurrence of intramolecular charge transfer (ICT) within the molecule. The electronic dipole moment (μD) and the first hyperpolarizability (βtot) values of the investigated molecule were computed using Density Functional Theory (DFT/B3LYP) with 6-31G(d,p) and 6-311G(d,p) basis sets. The calculated results also show that the NND4MC molecule may have microscopy nonlinear optical (NLO) behavior with non zero values. Mulliken atomic charges of NND4MC were calculated. The 13C nuclear magnetic resonance (NMR) chemical shifts of the molecule were calculated by the gauge independent atomic orbital (GIAO) method and compared with experimental results. The UV-Vis spectrum of the compound was recorded. The theoretical electronic absorption spectra have been calculated by using CIS, TD-DFT methods. A study on the electronic properties, such as HOMO and LUMO energies, molecular electrostatic potential (MEP) were also performed.
High Resolution Infrared Studies of the v2, v4 Bands of 34S16O3, Including Both Intensity and Wavenumber Perturbations

DOE Office of Scientific and Technical Information (OSTI.GOV)

Barber, Jeffrey B.; Masiello, Tony; Chrysostom, Engelene

2003-06-15

The infrared spectrum of the v2, v4 bending mode region of 34S-substituted sulfur trioxide, 34S16O3, has been recorded at a resolution of 0.0025 cm-1. The v2 and v4 levels are coupled by a Coriolis interaction, yielding significant spectral shifts that have been successfully analyzed to obtain rovibrational constants for the ground state and both fundamentals. Comparisons are made with 32S16O3 parameters and the Bo rotational constant is found to be 0.348 556 04(28) cm-1, only very slightly larger than the corresponding value of 0.348 543 33(5) cm-1 for 32S16O3. Coriolis and l-type resonance interactions between the v2 and v4 levelsmore » produce frequency shifts and strong intensity perturbations in the spectra that are considered for both 34S16O3 and 32S16O3. The resulting analysis yields an average value of+0.62(8) for the dipole derivative ratio (?x/?Q4x) (?z/?Q2) and a positive sign for the product of this ratio with the?y2,4 Coriolis constant, for which experiment gives+0.5940(15) . Ab initio calculations indicate that the signs of?x/?Q4x and?z/?Q2 are both positive and hence?y2,4 is also positive, in agreement with earlier calculations. These signs indicate that the effective charge movement in the xz plane has the same sense of rotation as Q2, Q4x atom motion in this plane that produces a py vibrational angular momentum component, correlated motion that is confirmed by ab initio calculations.« less
Inclusion complexes of cypermethrin and permethrin with monochlorotriazinyl-beta-cyclodextrin: A combined spectroscopy, TG/DSC and DFT study

NASA Astrophysics Data System (ADS)

Yao, Qi; You, Bin; Zhou, Shuli; Chen, Meng; Wang, Yujiao; Li, Wei

2014-01-01

The suitable size hydrophobic cavity and monochlorotriazinyl group as a reactive anchor make MCT-β-CD to be widely used in fabric finishing. In this paper, the inclusion complexes of monochlorotriazinyl-beta-cyclodextrin (MCT-β-CD) with cypermethrin (CYPERM) and permethrin (PERM) are synthesized and analyzed by TG/DSC, FT-IR and Raman spectroscopy. TG/DSC reveals that the decomposed temperatures of inclusion complexes are lower by 25-30 °C than that of physical mixtures. DFT calculations in conjunction with FT-IR and Raman spectral analyses are used to study the structures of MCT-β-CD and their inclusion complexes. Four isomers of trisubstituted MCT-β-CD are designed and DFT calculations reveal that 1,3,5-trisubstituted MCT-β-CD has the lowest energy and can be considered as main component of MCT-β-CD. The ground-state geometries, vibrational wavenumbers, IR and Raman intensities of MCT-β-CD and their inclusion complexes were calculated at B3LYP/6-31G (d) level of theory. Upon examining the optimized geometry of inclusion complex, we find that the CYPERM and PERM are inserted into the toroid of MCT-β-CD from the larger opening. The band at 1646 cm-1 in IR and at 1668 cm-1 in Raman spectrum reveals that monochloroazinyl group of MCT-β-CD exists in ketone form but not in anion form. The noticeable IR and Raman shift of phenyl reveals that these two benzene rings of CYPERM and PERM stays inside the cavity of MCT-β-CD and has weak interaction with MCT-β-CD. This spectroscopy conclusion is consistent with theoretical predicted structure.

Crack Imaging and Quantification in Aluminum Plates with Guided Wave Wavenumber Analysis Methods

NASA Technical Reports Server (NTRS)

Yu, Lingyu; Tian, Zhenhua; Leckey, Cara A. C.

2015-01-01

Guided wavefield analysis methods for detection and quantification of crack damage in an aluminum plate are presented in this paper. New wavenumber components created by abrupt wave changes at the structural discontinuity are identified in the frequency-wavenumber spectra. It is shown that the new wavenumbers can be used to detect and characterize the crack dimensions. Two imaging based approaches, filter reconstructed imaging and spatial wavenumber imaging, are used to demonstrate how the cracks can be evaluated with wavenumber analysis. The filter reconstructed imaging is shown to be a rapid method to map the plate and any existing damage, but with less precision in estimating crack dimensions; while the spatial wavenumber imaging provides an intensity image of spatial wavenumber values with enhanced resolution of crack dimensions. These techniques are applied to simulated wavefield data, and the simulation based studies show that spatial wavenumber imaging method is able to distinguish cracks of different severities. Laboratory experimental validation is performed for a single crack case to confirm the methods' capabilities for imaging cracks in plates.
Investigation of damping and radiation using full plane wave decomposition in ducts

NASA Astrophysics Data System (ADS)

Allam, Sabry; Åbom, Mats

2006-05-01

A general plane wave decomposition procedure that determines both the wave amplitudes (or the reflection coefficient) and the wavenumbers is proposed for in-duct measurements. To improve the quality of the procedure, overdetermination and a nonlinear least-squares procedure is used. The procedure has been tested using a six microphone array, and used for accurate measurements of the radiation from an open unflanged pipe with flow. The experimental results for the reflection coefficient magnitude and the end correction have been compared with the theory of Munt. The agreement is very good if the maximum speed rather than the average is used to compare measurements and theory. This result is the first complete experimental validation of the theory of Munt [Acoustic transmission properties of a jet pipe with subsonic jet flow, I: the cold jet reflection coefficient, Journal of Sound and Vibration 142(3) (1990) 413-436]. The damping of the plane wave (the imaginary part of the wavenumber) could also be obtained from the experimental data. It is found that the damping increases strongly, compared with the damping for a quiescent fluid, when the acoustic boundary layer becomes thicker than the viscous sublayer. This finding is in agreement with a few earlier measurements and is also in agreement with a theoretical model proposed by Howe [The damping of sound by wall turbulent sheer layers, Journal of Acoustic Society of America 98(3) (1995) 1723-1730]. The results reported here are the first experimental verifications of Howe's model. It is found that the model works well typically up to a normalized acoustic boundary layer thickness δA+ of 30-40. For values of a δA+ less than 10, corresponding to higher frequencies or lower flow speeds, the model proposed by Dokumaci [A note on transmission of sound in a wide pipe with mean flow and viscothermal attenuation, Journal of Sound and Vibration 208(4) (1997) 653-655] is also in good agreement with the experimental data.
Spectral study of wintertime kinetic energy of the Northern Hemisphere in the troposphere

NASA Technical Reports Server (NTRS)

Lee, H. N.; Zhao, Z.; Kao, S. K.

1983-01-01

Characteristics of the kinetic energy of wind fields at various pressure levels were analyzed, and significant wavenumbers in the wavenumber-frequency domain were identified. The nonlinear interaction terms of the kinetic energy equation were examined, and the distribution of the kinetic energy at the 850 mb, 500 mb, and 200 mb levels was calculated. A 5 deg latitude-longitude square grid was used, with NMC data for the 1975-1976 winter in the 20-60 deg N at 500 mb and 20-85 deg N for the 200 mb and 850 mb levels. The kinetic energy distribution was determined to be geography-dependent, with wavenumbers 6-9 westerly waves in the midfrequency range contributing significantly to kinetic energy maxima over the North Pacific and the east coast of North America. The contribution of the nonlinear interactions of these waves, which correspond to the longitudinal convergence of the kinetic energy flux, was found to be larger than the meridional convergence of the kinetic energy flux, and to occur mainly between 30-50 deg N. The nonlinear interactions were a negative contribution over the North Pacific at the 200 mb level.
Excitation of high wavenumber fluctuations by externally-imposed helical fields in edge pedestal plasmas

NASA Astrophysics Data System (ADS)

Singh, R.; Kim, J.-H.; Jhang, Hogun; Das, S.

2018-03-01

Two-step mode coupling analyses for nonlinear excitation of the ballooning mode (BM) in pedestal plasma by external helical magnetic field perturbation [Resonant Magnetic Perturbations (RMP)] are presented. This technique allows calculating the effect of higher harmonic sidebands generated by interaction of long scale RMP pump and BM. It is shown that RMP field perturbations can modify the BM growth rate and frequency through nonlinear Reynolds stress and magnetic stress. In particular, it is shown that both stresses can efficiently excite high wavenumber BM fluctuations which, in turn, can enhance the transport in the pedestal. Another notable feature of this analysis is the existence of short scale (high- k y ) nonlinear instability at Alfven time scale near the ideal BM threshold boundary.
Martian tidal pressure and wind fields obtained from the Mariner 9 infrared spectroscopy experiment

NASA Technical Reports Server (NTRS)

Pirraglia, J. A.; Conrath, B. J.

1973-01-01

Using temperature fields derived from the Mariner 9 infrared spectroscopy experiment, the Martian atmospheric tidal pressure and wind fields are calculated. Temperature as a function of local time, latitude, and atmospheric pressure level is obtained by secular and longitudinal averaging of the data. The resulting temperature field is approximated by a spherical harmonic expansion, retaining one symmetric and one asymmetric term for wavenumber zero and wavenumber one. Vertical averaging of the linearized momentum and continuity equations results in an inhomogeneous tidal equation for surface pressure fluctuations with the driving function related to the temperature field through the geopotential function and the hydrostatic equation. Solutions of the tidal equation show a diurnal fractional pressure amplitude approximately equal to one half of the vertically averaged diurnal fractional temperature amplitude.
Martian tidal pressure and wind fields obtained from the Mariner 9 infrared spectroscopy experiment

NASA Technical Reports Server (NTRS)

Pirraglia, J. A.; Conrath, B. J.

1974-01-01

Using temperature fields derived from the Mariner 9 infrared spectroscopy experiment, the Martian atmospheric tidal pressure and wind fields are calculated. Temperature as a function of local time, latitude, and atmospheric pressure level is obtained by secular and longitudinal averaging of the data. The resulting temperature field is approximated by a spherical harmonic expansion, retaining one symmetric and one asymmetric term each for wavenumber zero and wavenumber one. Vertical averaging of the linearized momentum and continuity equations results in an inhomogeneous tidal equation for surface pressure fluctuations with the driving function related to the temperature field through the geopotential function and the hydrostatic equation. Solutions of the tidal equation show a diurnal fractional pressure amplitude approximately equal to one-half the vertically averaged diurnal fractional temperature amplitude.
Software to compute elastostatic Green's functions for sources in 3D homogeneous elastic layers above a (visco)elastic halfspace

NASA Astrophysics Data System (ADS)

Bradley, A. M.; Segall, P.

2012-12-01

We describe software, in development, to calculate elastostatic displacement Green's functions and their derivatives for point and polygonal dislocations in three-dimensional homogeneous elastic layers above an elastic or a viscoelastic halfspace. The steps to calculate a Green's function for a point source at depth zs are as follows. 1. A grid in wavenumber space is chosen. 2. A six-element complex rotated stress-displacement vector x is obtained at each grid point by solving a two-point boundary value problem (2P-BVP). If the halfspace is viscoelastic, the solution is inverse Laplace transformed. 3. For each receiver, x is propagated to the receiver depth zr (often zr = 0) and then, 4, inverse Fourier transformed, with the Fourier component corresponding to the receiver's horizontal position. 5. The six elements are linearly combined into displacements and their derivatives. The dominant work is in step 2. The grid is chosen to represent the wavenumber-space solution with as few points as possible. First, the wavenumber space is transformed to increase sampling density near 0 wavenumber. Second, a tensor-product grid of Chebyshev points of the first kind is constructed in each quadrant of the transformed wavenumber space. Moment-tensor-dependent symmetries further reduce work. The numerical solution of the 2P-BVP problem in step 2 involves solving a linear equation A x = b. Half of the elements of x are of geophysical interest; the subset depends on whether zr ≤ zs. Denote these \\hat x. As wavenumber k increases, \\hat x can become inaccurate in finite precision arithmetic for two reasons: 1. The condition number of A becomes too large. 2. The norm-wise relative error (NWRE) in \\hat x is large even though it is small in x. To address this problem, a number of researchers have used determinants to obtain x. This may be the best approach for 6-dimensional or smaller 2P-BVP, where the combinatorial increase in work is still moderate. But there is an alternative. Let \\bar A be the matrix after scaling its columns to unit infinity norm and \\bar x the scaled x. If \\bar A is well conditioned, as it often is in (visco)elastostatic problems, then using determinants is unnecessary. Multiply each side of A x = b by a propagator matrix to the computation depth zcd prior to storing the matrix in finite precision. zcd is determined by the rule that zr and zcd must be on opposite sides of zs. Let the resulting matrix be A(zcd). Three facts imply that this rule controls the NWRE in \\hat x: 1. Diagonally scaling a matrix changes the accuracy of an element of the solution by about one ULP (unit in the last place). 2. If the NWRE of \\bar x is small, then the largest elements are accurate. 3. zcd controls the magnitude of elements in \\bar x. In step 4, to avoid numerically Fourier transforming the (nearly) non-square-integrable functions that arise when the receiver and source depths are (nearly) the same, a function is divided into an analytical part and a numerical part that goes quickly to 0 as k -> ∞ . Our poster will describe these calculations, present a preliminary interface to a C-language package in development, and show some physical results.
Structure of selected basic zinc/copper (II) phosphate minerals based upon near-infrared spectroscopy--implications for hydrogen bonding.

PubMed

Frost, Ray L; Reddy, B Jagannadha; Palmer, Sara J; Keeffe, Eloise C

2011-03-01

The NIR spectra of reichenbachite, scholzite and parascholzite have been studied at 298 K. The spectra of the minerals are different, in line with composition and crystal structural variations. Cation substitution effects are significant in their electronic spectra and three distinctly different electronic transition bands are observed in the near-infrared spectra at high wavenumbers in the 12,000-7600 cm(-1) spectral region. Reichenbachite electronic spectrum is characterised by Cu(II) transition bands at 9755 and 7520 cm(-1). A broad spectral feature observed for ferrous ion in the 12,000-9000 cm(-1) region both in scholzite and parascholzite. Some what similarities in the vibrational spectra of the three phosphate minerals are observed particularly in the OH stretching region. The observation of strong band at 5090 cm(-1) indicates strong hydrogen bonding in the structure of the dimorphs, scholzite and parascholzite. The three phosphates exhibit overlapping bands in the 4800-4000 cm(-1) region resulting from the combinations of vibrational modes of (PO(4))(3-) units. Copyright © 2010 Elsevier B.V. All rights reserved.
DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhang, Libing; Lu, Zhou; Velarde Ruiz Esparza, Luis A.

Here we reported the first sub-wavenumber high-resolution broadband sum frequency generation vibrational spectroscopy (HR-BB-SFG-VS) study on both the C-H and O-H region spectra of crystalline cellulose. HR-BB-SFG-VS has about 10 times better resolution than the conventional scanning SFG-VS and is known to be able to measure the intrinsic spectral lineshape and to resolve much more spectral details. With HR-BB-SFG-VS, we found that in cellulose from different sources, including Avicel and cellulose crystals isolated from algae Valonia (Iα) and tunicates (Iβ), the spectral signatures in the OH regions were unique for different allomorphs, i.e. Iα and Iβ, while the spectral signaturesmore » in the C-H regions varied in all samples examined. Even though the origin of the different behaviors of the crystalline cellulose in the O-H and C-H vibrational frequency regions is yet to be correlated to the structure of cellulose, these results provided new spectroscopic methods and opportunities to classify and understand the basic crystalline structure, as well as variations, in polymorphism of the crystalline cellulose structure.« less
COMBIC, Combined Obscuration Model for Battlefield Induced Contaminants: Volume 1-Technical Documentation and Users Guide

DTIC Science & Technology

2000-08-01

12345678901234567890123456789012345678901234567890123456789012345678901234567890 WAVL WAVE1 WAVE2 MULDV Name Units Typically Description WAVE1 µm 1.06 Wavelength used for...the calculation. Alternatively, one can specify either frequency or wavenumber by using a FREQ or WVNUM record instead of WAVL. If WAVE2 is not...specified, WAVE1 is the single wave- length used; if WAVE2 is specified, the modules will attempt to do their calculation for a range of wavelengths. There
Design of a k-space spectrometer for ultra-broad waveband spectral domain optical coherence tomography.

PubMed

Lan, Gongpu; Li, Guoqiang

2017-03-07

Nonlinear sampling of the interferograms in wavenumber (k) space degrades the depth-dependent signal sensitivity in conventional spectral domain optical coherence tomography (SD-OCT). Here we report a linear-in-wavenumber (k-space) spectrometer for an ultra-broad bandwidth (760 nm-920 nm) SD-OCT, whereby a combination of a grating and a prism serves as the dispersion group. Quantitative ray tracing is applied to optimize the linearity and minimize the optical path differences for the dispersed wavenumbers. Zemax simulation is used to fit the point spread functions to the rectangular shape of the pixels of the line-scan camera and to improve the pixel sampling rates. An experimental SD-OCT is built to test and compare the performance of the k-space spectrometer with that of a conventional one. Design results demonstrate that this k-space spectrometer can reduce the nonlinearity error in k-space from 14.86% to 0.47% (by approximately 30 times) compared to the conventional spectrometer. The 95% confidence interval for RMS diameters is 5.48 ± 1.76 μm-significantly smaller than both the pixel size (14 μm × 28 μm) and the Airy disc (25.82 μm in diameter, calculated at the wavenumber of 7.548 μm -1 ). Test results demonstrate that the fall-off curve from the k-space spectrometer exhibits much less decay (maximum as -5.20 dB) than the conventional spectrometer (maximum as -16.84 dB) over the whole imaging depth (2.2 mm).
Design of a k-space spectrometer for ultra-broad waveband spectral domain optical coherence tomography

NASA Astrophysics Data System (ADS)

Lan, Gongpu; Li, Guoqiang

2017-03-01

Nonlinear sampling of the interferograms in wavenumber (k) space degrades the depth-dependent signal sensitivity in conventional spectral domain optical coherence tomography (SD-OCT). Here we report a linear-in-wavenumber (k-space) spectrometer for an ultra-broad bandwidth (760 nm-920 nm) SD-OCT, whereby a combination of a grating and a prism serves as the dispersion group. Quantitative ray tracing is applied to optimize the linearity and minimize the optical path differences for the dispersed wavenumbers. Zemax simulation is used to fit the point spread functions to the rectangular shape of the pixels of the line-scan camera and to improve the pixel sampling rates. An experimental SD-OCT is built to test and compare the performance of the k-space spectrometer with that of a conventional one. Design results demonstrate that this k-space spectrometer can reduce the nonlinearity error in k-space from 14.86% to 0.47% (by approximately 30 times) compared to the conventional spectrometer. The 95% confidence interval for RMS diameters is 5.48 ± 1.76 μm—significantly smaller than both the pixel size (14 μm × 28 μm) and the Airy disc (25.82 μm in diameter, calculated at the wavenumber of 7.548 μm-1). Test results demonstrate that the fall-off curve from the k-space spectrometer exhibits much less decay (maximum as -5.20 dB) than the conventional spectrometer (maximum as -16.84 dB) over the whole imaging depth (2.2 mm).
A global ab initio potential for HCN/HNC, exact vibrational energies, and comparison to experiment

NASA Technical Reports Server (NTRS)

Bentley, Joseph A.; Bowman, Joel M.; Gazdy, Bela; Lee, Timothy J.; Dateo, Christopher E.

1992-01-01

An ab initio (i.e., from first principles) calculation of vibrational energies of HCN and HNC is reported. The vibrational calculations were done with a new potential derived from a fit to 1124 ab initio electronic energies which were calculated using the highly accurate CCSD(T) coupled-cluster method in conjunction with a large atomic natural orbital basis set. The properties of this potential are presented, and the vibrational calculations are compared to experiment for 54 vibrational transitions, 39 of which are for zero total angular momentum, J = 0, and 15 of which are for J = 1. The level of agreement with experiment is unprecedented for a triatomic with two nonhydrogen atoms, and demonstrates the capability of the latest computational methods to give reliable predictions on a strongly bound triatomic molecule at very high levels of vibrational excitation.
DFT calculation and vibrational spectroscopic studies of 2-(tert-butoxycarbonyl (Boc) -amino)-5-bromopyridine

NASA Astrophysics Data System (ADS)

Premkumar, S.; Jawahar, A.; Mathavan, T.; Kumara Dhas, M.; Sathe, V. G.; Milton Franklin Benial, A.

2014-08-01

The molecular structure of 2-(tert-butoxycarbonyl (Boc) -amino)-5-bromopyridine (BABP) was optimized by the DFT/B3LYP method with 6-311G (d,p), 6-311++G (d,p) and cc-pVTZ basis sets using the Gaussian 09 program. The most stable optimized structure of the molecule was predicted by the DFT/B3LYP method with cc-pVTZ basis set. The vibrational frequencies, Mulliken atomic charge distribution, frontier molecular orbitals and thermodynamical parameters were calculated. These calculations were done at the ground state energy level of BABP without applying any constraint on the potential energy surface. The vibrational spectra were experimentally recorded using Fourier Transform-Infrared (FT-IR) and micro-Raman spectrometer. The computed vibrational frequencies were scaled by scale factors to yield a good agreement with observed experimental vibrational frequencies. The complete theoretically calculated and experimentally observed vibrational frequencies were assigned on the basis of Potential Energy Distribution (PED) calculation using the VEDA 4.0 program. The vibrational modes assignments were performed by using the animation option of GaussView 05 graphical interface for Gaussian program. The Mulliken atomic charge distribution was calculated for BABP molecule. The molecular reactivity and stability of BABP were also studied by frontier molecular orbitals (FMOs) analysis.
Spectra-structure correlations of saturated and unsaturated medium-chain fatty acids. Near-infrared and anharmonic DFT study of hexanoic acid and sorbic acid

NASA Astrophysics Data System (ADS)

Grabska, Justyna; Beć, Krzysztof B.; Ishigaki, Mika; Wójcik, Marek J.; Ozaki, Yukihiro

2017-10-01

Quantum chemical reproduction of entire NIR spectra is a new trend, enabled by contemporary advances in the anharmonic approaches. At the same time, recent increase of the importance of NIR spectroscopy of biological samples raises high demand for gaining deeper understanding of NIR spectra of biomolecules, i.e. fatty acids. In this work we investigate saturated and unsaturated medium-chain fatty acids, hexanoic acid and sorbic acid, in the near-infrared region. By employing fully anharmonic density functional theory (DFT) calculations we reproduce the experimental NIR spectra of these systems, including the highly specific spectral features corresponding to the dimerization of fatty acids. Broad range of concentration levels from 5 · 10- 4 M in CCl4 to pure samples are investigated. The major role of cyclic dimers can be evidenced for the vast majority of these samples. A highly specific NIR feature of fatty acids, the elevation of spectral baseline around 6500-4000 cm- 1, is being explained by the contributions of combination bands resulting from the vibrations of hydrogen-bonded OH groups in the cyclic dimers. Based on the high agreement between the calculated and experimental NIR spectra, a detailed NIR band assignments are proposed for hexanoic acid and sorbic acid. Subsequently, the correlations between the structure and NIR spectra are elucidated, emphasizing the regions in which clear and universal traces of specific bands corresponding to saturated and unsaturated alkyl chains can be established, thus demonstrating the wavenumber regions highly valuable for structural identifications.
Spectra-structure correlations of saturated and unsaturated medium-chain fatty acids. Near-infrared and anharmonic DFT study of hexanoic acid and sorbic acid.

PubMed

Grabska, Justyna; Beć, Krzysztof B; Ishigaki, Mika; Wójcik, Marek J; Ozaki, Yukihiro

2017-10-05

Quantum chemical reproduction of entire NIR spectra is a new trend, enabled by contemporary advances in the anharmonic approaches. At the same time, recent increase of the importance of NIR spectroscopy of biological samples raises high demand for gaining deeper understanding of NIR spectra of biomolecules, i.e. fatty acids. In this work we investigate saturated and unsaturated medium-chain fatty acids, hexanoic acid and sorbic acid, in the near-infrared region. By employing fully anharmonic density functional theory (DFT) calculations we reproduce the experimental NIR spectra of these systems, including the highly specific spectral features corresponding to the dimerization of fatty acids. Broad range of concentration levels from 5·10 -4 M in CCl 4 to pure samples are investigated. The major role of cyclic dimers can be evidenced for the vast majority of these samples. A highly specific NIR feature of fatty acids, the elevation of spectral baseline around 6500-4000cm -1 , is being explained by the contributions of combination bands resulting from the vibrations of hydrogen-bonded OH groups in the cyclic dimers. Based on the high agreement between the calculated and experimental NIR spectra, a detailed NIR band assignments are proposed for hexanoic acid and sorbic acid. Subsequently, the correlations between the structure and NIR spectra are elucidated, emphasizing the regions in which clear and universal traces of specific bands corresponding to saturated and unsaturated alkyl chains can be established, thus demonstrating the wavenumber regions highly valuable for structural identifications. Copyright © 2017 Elsevier B.V. All rights reserved.
First-principles investigation of hydrous post-perovskite

DOE PAGES

Townsend, Joshua P.; Tsuchiya, Jun; Bina, Craig R.; ...

2015-04-11

A stable, hydrogen-defect structure of post-perovskite (hy-ppv, Mg 1–xSiH 2xO 3) has been determined by first-principles calculations of the vibrational and elastic properties up to 150 GPa. Among three potential hy-ppv structures analyzed, one was found to be stable at pressures relevant to the lower-mantle D" region. Hydrogen has a pronounced effect on the elastic properties of post-perovskite due to magnesium defects associated with hydration, including a reduction of the zero-pressure bulk (K 0) and shear (G 0) moduli by 5% and 8%, respectively, for a structure containing ~1 wt.% H 2O. However, with increasing pressure the moduli of hy-ppvmore » increase significantly relative to ppv, resulting in a structure that is only 1% slower in bulk compressional velocity and 2.5% slower in shear-wave velocity than ppv at 120 GPa. In contrast, the reduction of certain anisotropic elastic constants (C ij) in hy-ppv increases with pressure (notably, C 55, C 66, and C 23), indicating that hydration generally increases elastic anisotropy in hy-ppv at D" pressures. Calculated infrared absorption spectra show two O–H stretching bands at ~3500 cm –1 that shift with pressure to lower wavenumber by about 2 cm –1/GPa. At 120 GPa the hydrogen bonds in hy-ppv are still asymmetric. Furthermore, the stability of a hy-ppv structure containing 1–2 wt.% H 2O at D" pressures implies that post-perovskite may be a host for recycled or primordial hydrogen near the Earth’s core-mantle boundary.« less
The assessment of human skin biomatrixes using raman spectroscopy method

NASA Astrophysics Data System (ADS)

Timchenko, E. V.; Timchenko, P. E.; Volova, L. T.; Dolgushkin, D. A.; Shalkovskaya, P. Y.; Pershutkina, S. V.; Nefedova, I. F.

2017-01-01

There are presented the results of the analysis of the implants made of human skin by Raman scattering method. The main spectral distinctions of bioimplants by using various methods for their manufacture are shown at wavenumbers 1062 cm-1, 1645 cm-1, 1260 cm-1, 850 cm-1, 863 cm-1, corresponding to components that are important for the quality of implant: glycosaminoglycans, amide type I, amide type III, asymmetrical association C-O-S of vibration of glycosaminoglycans GAGs, tyrosine and a C-C stretching of proline ring, ribose. Has been carried out two-dimensional analysis of optical coefficients providing an opportunity to control the quality of cutaneous implants in the process of manufacturing it, and detailed analysis of Raman scattering spectroscopy.
Diagnostics and control of wavenumber stability and purity of tunable diode lasers relevant to their use as local oscillators in heterodyne systems

NASA Technical Reports Server (NTRS)

Poultney, S.; Chen, D.; Steinberg, G.; Wu, F.; Pires, A.; Miller, M. D.; Mcnally, M.

1980-01-01

Initial operation of the tunable diode lasers (TDL) showed that it was not possible to adjust the wavenumber to one selected a priori in the TDL tuning range. During operation, the operating point would change by 0.1/cm over the longer term with even larger changes occurring during some thermal cycles. Most changes during thermal cycling required using lower temperatures and higher currents to reach the former wavenumber (when it could be reached). In many cases, an operating point could be selected by changing TDL current and temperature to give both the desired wavenumber and most of the power in a single mode. The selection procedure had to be used after each thermal cycling. Wavenumber nonlinearities of about 10% over a 0.5 cm tuning range were observed. Diagnostics of the single mode selected by a grating monochromator showed wavenumber fine structure under certain operating conditions. The characteristics due to the TDL environment included short term wavenumber stability, the instrument lineshape function, and intermediate term wavenumber stability.
The wavenumber algorithm for full-matrix imaging using an ultrasonic array.

PubMed

Hunter, Alan J; Drinkwater, Bruce W; Wilcox, Paul D

2008-11-01

Ultrasonic imaging using full-matrix capture, e.g., via the total focusing method (TFM), has been shown to increase angular inspection coverage and improve sensitivity to small defects in nondestructive evaluation. In this paper, we develop a Fourier-domain approach to full-matrix imaging based on the wavenumber algorithm used in synthetic aperture radar and sonar. The extension to the wavenumber algorithm for full-matrix data is described and the performance of the new algorithm compared with the TFM, which we use as a representative benchmark for the time-domain algorithms. The wavenumber algorithm provides a mathematically rigorous solution to the inverse problem for the assumed forward wave propagation model, whereas the TFM employs heuristic delay-and-sum beamforming. Consequently, the wavenumber algorithm has an improved point-spread function and provides better imagery. However, the major advantage of the wavenumber algorithm is its superior computational performance. For large arrays and images, the wavenumber algorithm is several orders of magnitude faster than the TFM. On the other hand, the key advantage of the TFM is its flexibility. The wavenumber algorithm requires a regularly sampled linear array, while the TFM can handle arbitrary imaging geometries. The TFM and the wavenumber algorithm are compared using simulated and experimental data.

Wavenumber selection method to determine the concentration of cocaine and adulterants in cocaine samples.

PubMed

Kahmann, A; Anzanello, M J; Fogliatto, F S; Marcelo, M C A; Ferrão, M F; Ortiz, R S; Mariotti, K C

2018-04-15

Street cocaine is typically altered with several compounds that increase its harmful health-related side effects, most notably depression, convulsions, and severe damages to the cardiovascular system, lungs, and brain. Thus, determining the concentration of cocaine and adulterants in seized drug samples is important from both health and forensic perspectives. Although FTIR has been widely used to identify the fingerprint and concentration of chemical compounds, spectroscopy datasets are usually comprised of thousands of highly correlated wavenumbers which, when used as predictors in regression models, tend to undermine the predictive performance of multivariate techniques. In this paper, we propose an FTIR wavenumber selection method aimed at identifying FTIR spectra intervals that best predict the concentration of cocaine and adulterants (e.g. caffeine, phenacetin, levamisole, and lidocaine) in cocaine samples. For that matter, the Mutual Information measure is integrated into a Quadratic Programming problem with the objective of minimizing the probability of retaining redundant wavenumbers, while maximizing the relationship between retained wavenumbers and compounds' concentrations. Optimization outputs guide the order of inclusion of wavenumbers in a predictive model, using a forward-based wavenumber selection method. After the inclusion of each wavenumber, parameters of three alternative regression models are estimated, and each model's prediction error is assessed through the Mean Average Error (MAE) measure; the recommended subset of retained wavenumbers is the one that minimizes the prediction error with maximum parsimony. Using our propositions in a dataset of 115 cocaine samples we obtained a best prediction model with average MAE of 0.0502 while retaining only 2.29% of the original wavenumbers, increasing the predictive precision by 0.0359 when compared to a model using the complete set of wavenumbers as predictors. Copyright © 2018 Elsevier B.V. All rights reserved.
Consistent assignment of the vibrations of symmetric and asymmetric ortho-disubstituted benzenes

NASA Astrophysics Data System (ADS)

Tuttle, William D.; Gardner, Adrian M.; Andrejeva, Anna; Kemp, David J.; Wakefield, Jonathan C. A.; Wright, Timothy G.

2018-02-01

The form of molecular vibrations, and changes in these, give valuable insights into geometric and electronic structure upon electronic excitation or ionization, and within families of molecules. Here, we give a description of the phenyl-ring-localized vibrational modes of the ground (S0) electronic states of a wide range of ortho-disubstituted benzene molecules including both symmetrically- and asymmetrically-substituted cases. We conclude that the use of the commonly-used Wilson or Varsányi mode labels, which are based on the vibrational motions of benzene itself, is misleading and ambiguous. In addition, we also find the use of the Mi labels for monosubstituted benzenes [A.M. Gardner, T.G. Wright. J. Chem. Phys. 135 (2011) 114305], or the recently-suggested labels for para-disubstituted benzenes [A. Andrejeva, A.M. Gardner, W.D. Tuttle, T.G. Wright, J. Molec. Spectrosc. 321, 28 (2016)] are not appropriate. Instead, we label the modes consistently based upon the Mulliken (Herzberg) method for the modes of ortho-difluorobenzene (pDFB) under Cs symmetry, since we wish the labelling scheme to cover both symmetrically- and asymmetrically-substituted molecules. By studying the vibrational wavenumbers from the same force field while varying the mass of the substituent, we are able to identify the corresponding modes across a wide range of molecules and hence provide consistent assignments. We assign the vibrations of the following sets of molecules: the symmetric o-dihalobenzenes, o-xylene and catechol (o-dihydroxybenzene); and the asymmetric o-dihalobenzenes, o-halotoluenes, o-halophenols and o-cresol. In the symmetrically-substituted species, we find a pair of in-phase and out-of-phase carbon-substituent stretches, and this motion persists in asymmetrically-substituted molecules for heavier substituents. When at least one of the substituents is light, then we find that these evolve into localized carbon-substituent stretches.
Non-Born-Oppenheimer calculations of the pure vibrational spectrum of HeH+.

PubMed

Pavanello, Michele; Bubin, Sergiy; Molski, Marcin; Adamowicz, Ludwik

2005-09-08

Very accurate calculations of the pure vibrational spectrum of the HeH(+) ion are reported. The method used does not assume the Born-Oppenheimer approximation, and the motion of both the electrons and the nuclei are treated on equal footing. In such an approach the vibrational motion cannot be decoupled from the motion of electrons, and thus the pure vibrational states are calculated as the states of the system with zero total angular momentum. The wave functions of the states are expanded in terms of explicitly correlated Gaussian basis functions multipled by even powers of the internuclear distance. The calculations yielded twelve bound states and corresponding eleven transition energies. Those are compared with the pure vibrational transition energies extracted from the experimental rovibrational spectrum.
Conformational and Structural Studies of Isopropylamine from Temperature Dependent Raman Spectra of Xenon Solutions and {AB INITIO} Calculations

NASA Astrophysics Data System (ADS)

Klaassen, Joshua J.; Darkhalil, Ikhlas D.; Durig, James R.

2012-06-01

The Raman and infrared spectra (4000 to 50 cm-1) of the gas, liquid or solution, and solid have been recorded of isopropylamine, (CH3)2CHNH2. Variable temperature (-50 to -100oC) studies of the Raman spectra (3500 to 100 cm-1) dissolved in liquid xenon have been carried out. From these data, both the {trans} and {gauche} conformers have been identified and their relative stability obtained. The enthalpy difference has been determined from 20 band pairs at 6 temperatures to be 113 +/- 11 cm-1 (1.35 +/- 0.13 kJ mol-1) with the {trans} conformer the more stable form. The percentage of the {gauche} conformer is estimated to be 54 +/- 1 percent at ambient temperature. The conformational stabilities have been predicted from {ab initio} calculations utilizing several different basis sets up to aug-cc-pVTZ from both MP2(full) and density functional theory calculations by the B3LYP method. By utilizing previously reported microwave rotational constants along with {ab initio} MP2(full)/6-311+G(d,p) predicted structural values, adjusted r0 parameters have been obtained for the {trans} conformer. The determined heavy atom and NH2 distances in angstroms are C-C = 1.530(3), C-N = 1.465(3), N-H = 1.019(3) and angles in degrees NCC = 108.9(5), CCC = 111.0(5), HNC = 110.3(5). The structural parameters for the {gauche} conformer were estimated by using the same adjustment differences to the {gauche} form as those obtained for the corresponding {trans} parameters. Vibrational assignments have been provided for the observed bands for both conformers which are supported by MP2(full)/6-31G(d) {ab initio} calculations to predict harmonic force constants, wavenumbers, infrared intensities, Raman activities and depolarization ratios for both conformers. The results are discussed and compared to the corresponding properties of some related molecules.
A Comparison of Molecular Vibrational Theory to Huckel Molecular Orbital Theory.

ERIC Educational Resources Information Center

Keeports, David

1986-01-01

Compares the similar mathematical problems of molecular vibrational calculations (at any intermediate level of sophistication) and molecular orbital calculations (at the Huckel level). Discusses how the generalizations of Huckel treatment of molecular orbitals apply to vibrational theory. (TW)
Theoretical analysis of the sound absorption characteristics of periodically stiffened micro-perforated plates

NASA Astrophysics Data System (ADS)

Zhou, Hai-An; Wang, Xiao-Ming; Mei, Yu-Lin

2014-10-01

The vibro-acoustic responses and sound absorption characteristics of two kinds of periodically stiffened micro-perforated plates are analyzed theoretically. The connected periodical structures of the stiffened plates can be ribs or block-like structures. Based on fundamental acoustic formulas of the micro-perforated plate of Maa and Takahashi, semi-analytical models of the vibrating stiffened plates are developed in this paper. Approaches like the space harmonicmethod, Fourier transforms and finite elementmethod (FEM) are adopted to investigate both kinds of the stiffened plates. In the present work, the vibro-acoustic responses of micro-perforated stiffened plates in the wavenumber space are expressed as functions of plate displacement amplitudes. After approximate numerical solutions of the amplitudes, the vibration equations and sound absorption coefficients of the two kinds of stiffened plates in the physical space are then derived by employing the Fourier inverse transform. In numerical examples, the effects of some physical parameters, such as the perforation ratio, incident angles and periodical distances etc., on the sound absorption performance are examined. The proposed approaches are also validated by comparing the present results with solutions of Takahashi and previous studies of stiffened plates. Numerical results indicate that the flexural vibration of the plate has a significant effect on the sound absorption coefficient in the water but has little influence in the air.
[Laser Raman spectrum analysis of carbendazim pesticide].

PubMed

Wang, Xiao-bin; Wu, Rui-mei; Liu, Mu-hua; Zhang, Lu-ling; Lin, Lei; Yan, Lin-yuan

2014-06-01

Raman signal of solid and liquid carbendazim pesticide was collected by laser Raman spectrometer. The acquired Raman spectrum signal of solid carbendazim was preprocessed by wavelet analysis method, and the optimal combination of wavelet denoising parameter was selected through mixed orthogonal test. The results showed that the best effect was got with signal to noise ratio (SNR) being 62.483 when db2 wavelet function was used, decomposition level was 2, the threshold option scheme was 'rigisure' and reset mode was 'sln'. According to the vibration mode of different functional groups, the de-noised Raman bands could be divided into 3 areas: 1 400-2 000, 700-1 400 and 200-700 cm(-1). And the de-noised Raman bands were assigned with and analyzed. The characteristic vibrational modes were gained in different ranges of wavenumbers. Strong Raman signals were observed in the Raman spectrum at 619, 725, 964, 1 022, 1 265, 1 274 and 1 478 cm(-1), respectively. These characteristic vibrational modes are characteristic Raman peaks of solid carbendazim pesticide. Find characteristic Raman peaks at 629, 727, 1 001, 1 219, 1 258 and 1 365 cm(-1) in Raman spectrum signal of liquid carbendazim. These characteristic peaks were basically tallies with the solid carbendazim. The results can provide basis for the rapid screening of pesticide residue in food and agricultural products based on Raman spectrum.
Ring Laser Gyro Resonator Design

DTIC Science & Technology

1994-06-20

vibration environment could cause errors in measured RLG rotation rates due to vibration (tilt) of the resonator mirrors . Vibration-induced mirror tilt...the RLG resonator design theoretically and calculated pertinent parameters such as the beam diameter at the aperture, cavity mirror alignment...sensitivities, and power loss due to aperture occlusion. The mirror vibration levels required to significantly affect the laser power were then calculated for
Dependence of calculated postshock thermodynamic variables on vibrational equilibrium and input uncertainty

DOE Office of Scientific and Technical Information (OSTI.GOV)

Campbell, Matthew Frederick; Owen, Kyle G.; Davidson, David F.

The purpose of this article is to explore the dependence of calculated postshock thermodynamic properties in shock tube experiments upon the vibrational state of the test gas and upon the uncertainties inherent to calculation inputs. This paper first offers a comparison between state variables calculated according to a Rankine–Hugoniot–equation-based algorithm, known as FROSH, and those derived from shock tube experiments on vibrationally nonequilibrated gases. It is shown that incorrect vibrational relaxation assumptions could lead to errors in temperature as large as 8% for 25% oxygen/argon mixtures at 3500 K. Following this demonstration, this article employs the algorithm to show themore » importance of correct vibrational equilibration assumptions, noting, for instance, that errors in temperature of up to about 2% at 3500 K may be generated for 10% nitrogen/argon mixtures if vibrational relaxation is not treated properly. Lastly, this article presents an extensive uncertainty analysis, showing that postshock temperatures can be calculated with root-of-sum-of-square errors of better than ±1% given sufficiently accurate experimentally measured input parameters.« less
Dependence of calculated postshock thermodynamic variables on vibrational equilibrium and input uncertainty

DOE PAGES

Campbell, Matthew Frederick; Owen, Kyle G.; Davidson, David F.; ...

2017-01-30

The purpose of this article is to explore the dependence of calculated postshock thermodynamic properties in shock tube experiments upon the vibrational state of the test gas and upon the uncertainties inherent to calculation inputs. This paper first offers a comparison between state variables calculated according to a Rankine–Hugoniot–equation-based algorithm, known as FROSH, and those derived from shock tube experiments on vibrationally nonequilibrated gases. It is shown that incorrect vibrational relaxation assumptions could lead to errors in temperature as large as 8% for 25% oxygen/argon mixtures at 3500 K. Following this demonstration, this article employs the algorithm to show themore » importance of correct vibrational equilibration assumptions, noting, for instance, that errors in temperature of up to about 2% at 3500 K may be generated for 10% nitrogen/argon mixtures if vibrational relaxation is not treated properly. Lastly, this article presents an extensive uncertainty analysis, showing that postshock temperatures can be calculated with root-of-sum-of-square errors of better than ±1% given sufficiently accurate experimentally measured input parameters.« less
On Ultrafast Time-Domain TeraHertz Spectroscopy in the Condensed Phase: Linear Spectroscopic Measurements of Hydrogen-Bond Dynamics of Astrochemical Ice Analogs and Nonlinear TeraHertz Kerr Effect Measurements of Vibrational Quantum Beats

NASA Astrophysics Data System (ADS)

Allodi, Marco A.

Much of the chemistry that affects life on planet Earth occurs in the condensed phase. The TeraHertz (THz) or far-infrared (far-IR) region of the electromagnetic spectrum (from 0.1 THz to 10 THz) has been shown to provide unique possibilities in the study of condensed-phase processes. The goal of this work is to expand the possibilities available in the THz region and undertake new investigations of fundamental interest to chemistry. Since we are fundamentally interested in condensed-phase processes, this thesis focuses on two areas where THz spectroscopy can provide new understanding: astrochemistry and solvation science. To advance these fields, we had to develop new instrumentation that would enable the experiments necessary to answer new questions in either astrochemistry or solvation science. We first developed a new experimental setup capable of studying astrochemical ice analogs in both the TeraHertz (THz), or far-Infrared (far-IR), region (0.3 - 7.5 THz; 10 - 250 wavenumbers) and the mid-IR (400 - 4000 wavenumbers). The importance of astrochemical ices lies in their key role in the formation of complex organic molecules, such as amino acids and sugars in space. Thus, the instruments are capable of performing variety of spectroscopic studies that can provide especially relevant laboratory data to support astronomical observations from telescopes such as the Herschel Space Telescope, the Stratospheric Observatory for Infrared Astronomy (SOFIA), and the Atacama Large Millimeter Array (ALMA). The experimental apparatus uses a THz time-domain spectrometer, with a 1750/875 nm plasma source and a GaP detector crystal, to cover the bandwidth mentioned above with 10 GHz (0.3 wavenumber) resolution. Using the above instrumentation, experimental spectra of astrochemical ice analogs of water and carbon dioxide in pure, mixed, and layered ices were collected at different temperatures under high-vacuum conditions with the goal of investigating the structure of the ice. We tentatively observe a new feature in both amorphous solid water and crystalline water at 33 wavenumbers (1 THz). In addition, our studies of mixed and layered ices show how it is possible to identify the location of carbon dioxide as it segregates within the ice by observing its effect on the THz spectrum of water ice. The THz spectra of mixed and layered ices are further analyzed by fitting their spectra features to those of pure amorphous solid water and crystalline water ice to quantify the effects of temperature changes on structure. From the results of this work, it appears that THz spectroscopy is potentially well suited to study thermal transformations within the ice. To advance the study of liquids with THz spectroscopy, we developed a new ultrafast nonlinear THz spectroscopic technique: heterodyne-detected, ultrafast THz Kerr effect (TKE) spectroscopy. We implemented a heterodyne-detection scheme into a TKE spectrometer that uses a stilbazoium-based THz emitter, 4-N,N-dimethylamino-4-N-methyl-stilbazolium 2,4,6-trimethylbenzenesulfonate (DSTMS), and high numerical aperture optics which generates THz electric field in excess of 300 kV/cm, in the sample. This allows us to report the first measurement of quantum beats at terahertz (THz) frequencies that result from vibrational coherences initiated by the nonlinear, dipolar interaction of a broadband, high-energy, (sub)picosecond THz pulse with the sample. Our instrument improves on both the frequency coverage, and sensitivity previously reported; it also ensures a backgroundless measurement of the THz Kerr effect in pure liquids. For liquid diiodomethane, we observe a quantum beat at 3.66 THz (122 wavenumbers), in exact agreement with the fundamental transition frequency of the lowest energy vibration of the molecule. This result provides new insight into dipolar vs. Raman selection rules at terahertz frequencies. To conclude we discuss future directions for the nonlinear THz spectroscopy in the Blake lab. We report the first results from an experiment using a plasma-based THz source for nonlinear spectroscopy that has the potential to enable nonlinear THz spectra with a sub-100 fs temporal resolution, and how the optics involved in the plasma mechanism can enable THz pulse shaping. Finally, we discuss how a single-shot THz detection scheme could improve the acquisition of THz data and how such a scheme could be implemented in the Blake lab. The instruments developed herein will hopefully remain a part of the group's core competencies and serve as building blocks for the next generation of THz instrumentation that pushes the frontiers of both chemistry and the scientific enterprise as a whole.
The ideal Kolmogorov inertial range and constant

NASA Technical Reports Server (NTRS)

Zhou, YE

1993-01-01

The energy transfer statistics measured in numerically simulated flows are found to be nearly self-similar for wavenumbers in the inertial range. Using the measured self-similar form, an 'ideal' energy transfer function and the corresponding energy flux rate were deduced. From this flux rate, the Kolmogorov constant was calculated to be 1.5, in excellent agreement with experiments.
DFT calculation and vibrational spectroscopic studies of 2-(tert-butoxycarbonyl (Boc) -amino)-5-bromopyridine.

PubMed

Premkumar, S; Jawahar, A; Mathavan, T; Kumara Dhas, M; Sathe, V G; Milton Franklin Benial, A

2014-08-14

The molecular structure of 2-(tert-butoxycarbonyl (Boc) -amino)-5-bromopyridine (BABP) was optimized by the DFT/B3LYP method with 6-311G (d,p), 6-311++G (d,p) and cc-pVTZ basis sets using the Gaussian 09 program. The most stable optimized structure of the molecule was predicted by the DFT/B3LYP method with cc-pVTZ basis set. The vibrational frequencies, Mulliken atomic charge distribution, frontier molecular orbitals and thermodynamical parameters were calculated. These calculations were done at the ground state energy level of BABP without applying any constraint on the potential energy surface. The vibrational spectra were experimentally recorded using Fourier Transform-Infrared (FT-IR) and micro-Raman spectrometer. The computed vibrational frequencies were scaled by scale factors to yield a good agreement with observed experimental vibrational frequencies. The complete theoretically calculated and experimentally observed vibrational frequencies were assigned on the basis of Potential Energy Distribution (PED) calculation using the VEDA 4.0 program. The vibrational modes assignments were performed by using the animation option of GaussView 05 graphical interface for Gaussian program. The Mulliken atomic charge distribution was calculated for BABP molecule. The molecular reactivity and stability of BABP were also studied by frontier molecular orbitals (FMOs) analysis. Copyright © 2014 Elsevier B.V. All rights reserved.
A new Morse-oscillator based Hamiltonian for H 3+: Calculation of line strengths

NASA Astrophysics Data System (ADS)

Jensen, Per; Špirko, V.

1986-07-01

In two recent publications [V. Špirko, P. Jensen, P. R. Bunker, and A. Čejchan, J. Mol. Spectrosc.112, 183-202 (1985); P. Jensen, V. Špirko, and P. R. Bunker, J. Mol. Spectrosc.115, 269-293 (1986)], we have described the development of Morse oscillator adapted rotation-vibration Hamiltonians for equilateral triangular X3 and Y2X molecules, and we have used these Hamiltonians to calculate the rotation-vibration energies for H 3+ and its X3+ and Y2X+ isotopes from ab initio potential energy functions. The present paper presents a method for calculating rotation-vibration line strengths of H 3+ and its isotopes using an ab initio dipole moment function [G. D. Carney and R. N. Porter, J. Chem. Phys.60, 4251-4264 (1974)] together with the energies and wave-functions obtained by diagonalization of the Morse oscillator adapted Hamiltonians. We use this method for calculating the vibrational transition moments involving the lowest vibrational states of H 3+, D 3+, H 2D +, and D 2H +. Further, we calculate the line strengths of the low- J transitions in the rotational spectra of H 3+ in the vibrational ground state and in the ν1 and ν2 states. We hope that the calculations presented will facilitate the search for further rotation-vibration transitions of H 3+ and its isotopes.
Time, Temperature, and Cationic Dependence of Alkali Activation of Slag: Insights from Fourier Transform Infrared Spectroscopy and Spectral Deconvolution.

PubMed

Dakhane, Akash; Madavarapu, Sateesh Babu; Marzke, Robert; Neithalath, Narayanan

2017-08-01

The use of waste/by-product materials, such as slag or fly ash, activated using alkaline agents to create binding materials for construction applications (in lieu of portland cement) is on the rise. The influence of activation parameters (SiO 2 to Na 2 O ratio or M s of the activator, Na 2 O to slag ratio or n, cation type K + or Na + ) on the process and extent of alkali activation of slag under ambient and elevated temperature curing, evaluated through spectroscopic techniques, is reported in this paper. Fourier transform infrared spectroscopy along with a Fourier self-deconvolution method is used. The major spectral band of interest lies in the wavenumber range of ∼950 cm -1 , corresponding to the antisymmetric stretching vibration of Si-O-T (T = Si or Al) bonds. The variation in the spectra with time from 6 h to 28 days is attributed to the incorporation of Al in the gel structure and the enhancement in degree of polymerization of the gel. 29 Si nuclear magnetic resonance spectroscopy is used to quantify the Al incorporation with time, which is found to be higher when Na silicate is used as the activator. The Si-O-T bond wavenumbers are also generally lower for the Na silicate activated systems.
FT-IR spectroscopy characterization of schwannoma: a case study

NASA Astrophysics Data System (ADS)

Ferreira, Isabelle; Neto, Lazaro P. M.; das Chagas, Maurilio José; Carvalho, Luís. Felipe C. S.; dos Santos, Laurita; Ribas, Marcelo; Loddi, Vinicius; Martin, Airton A.

2016-03-01

Schwannoma are rare benign neural neoplasia. The clinical diagnosis could be improved if novel optical techniques are performed. Among these techniques, FT-IR is one of the currently techniques which has been applied for samples discrimination using biochemical information with minimum sample preparation. In this work, we report a case of a schwannoma in the cervical region. A histological examination described a benign process. An immunohistochemically examination demonstrated positivity to anti-S100 protein antibody, indicating a diagnosis of schwannoma. The aim of this analysis was to characterize FT-IR spectrum of the neoplastic and normal tissue in the fingerprint (1000-1800 cm-1) and high wavenumber region (2800-3600 cm-1). The IR spectra were collect from tumor tissue and normal nerve samples by a FT-IR spectrophotometer (Spotlight Perkin Elmer 400, USA) with 64 scans, and resolution of 4 cm-1. A total of twenty spectra were recorded (10 from schwannoma and 10 from nerve). Multivariate Analysis was used to classify the data. Through average and standard deviation analysis we observed that the main spectral change occurs at ≍1600 cm-1 (amide I) and ≍1400 cm-1 (amide III) in the fingerprint region, and in CH2/CH3 protein-lipids and OH-water vibrations for the high wavenumber region. In conclusion, FT-IR could be used as a technique for schwannoma analysis helping to establish specific diagnostic.
THE SUN’S PHOTOSPHERIC CONVECTION SPECTRUM

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hathaway, David H.; Teil, Thibaud; Kitiashvili, Irina

2015-10-01

Spectra of the cellular photospheric flows are determined from full-disk Doppler velocity observations acquired by the Helioseismic and Magnetic Imager (HMI) instrument on the Solar Dynamics Observatory spacecraft. Three different analysis methods are used to separately determine spectral coefficients representing the poloidal flows, the toroidal flows, and the radial flows. The amplitudes of these spectral coefficients are constrained by simulated data analyzed with the same procedures as the HMI data. We find that the total velocity spectrum rises smoothly to a peak at a wavenumber of about 120 (wavelength of about 35 Mm), which is typical of supergranules. The spectrummore » levels off out to wavenumbers of about 400, and then rises again to a peak at a wavenumber of about 3500 (wavelength of about 1200 km), which is typical of granules. The velocity spectrum is dominated by the poloidal flow component (horizontal flows with divergence but no curl) at wavenumbers above 30. The toroidal flow component (horizontal flows with curl but no divergence) dominates at wavenumbers less than 30. The radial flow velocity is only about 3% of the total flow velocity at the lowest wavenumbers, but increases in strength to become about 50% at wavenumbers near 4000. The spectrum compares well with the spectrum of giant cell flows at the lowest wavenumbers and with the spectrum of granulation from a 3D radiative-hydrodynamic simulation at the highest wavenumbers.« less
Smagorinsky-type diffusion in a high-resolution GCM

NASA Astrophysics Data System (ADS)

Schaefer-Rolffs, Urs; Becker, Erich

2013-04-01

The parametrization of the (horizontal) momentum diffusion is a paramount component of a Global Circulation Model (GCM). Aside from friction in the boundary layer, a relevant fraction of kinetic energy is dissipated in the free atmosphere, and it is known that a linear harmonic turbulence model is not sufficient to obtain a reasonable simulation of the kinetic energy spectrum. Therefore, often empirical hyper-diffusion schemes are employed, regardless of disadvantages like the violation of energy conservation and the second law of thermodynamics. At IAP we have developed an improved parametrization of the horizontal diffusion that is based on Smagorinsky's nonlinear and energy conservation formulation. This approach is extended by the dynamic Smagorinsky model (DSM) of M. Germano. In this new scheme, the mixing length is no longer a prescribed parameter but calculated dynamically from the resolved flow such as to preserve scale invariance for the horizontal energy cascade. The so-called Germano identity is solved by a tensor norm ansatz which yields a positive definite frictional heating. We present results from an investigation using the DSM as a parametrization of horizontal diffusion in a high-resolution version of the Kühlungborn Mechanistic general Circulation Model (KMCM) with spectral truncation at horizontal wavenumber 330. The DSM calculates the Smagorinsky parameter cS independent from the resolution scale. We find that this method yields an energy spectrum that exhibits a pronounced transition from a synoptic -3 to a mesoscale -5-3 slope at wavenumbers around 50. At the highest wavenumber end, a behaviour similar to that often obtained by tuning the hyper-diffusion is achieved self-consistently. This result is very sensitive to the explicit choice of the test filter in the DSM.
Structural sensitivity of Csbnd H vibrational band in methyl benzoate

NASA Astrophysics Data System (ADS)

Roy, Susmita; Maiti, Kiran Sankar

2018-05-01

The Csbnd H vibrational bands of methyl benzoate are studied to understand its coupling pattern with other vibrational bands of the biological molecule. This will facilitate to understand the biological structure and dynamics in spectroscopic as well as in microscopic study. Due to the congested spectroscopic pattern, near degeneracy, and strong anharmonicity of the Csbnd H stretch vibrations, assignment of the Csbnd H vibrational frequencies are often misleading. Anharmonic vibrational frequency calculation with multidimensional potential energy surface interprets the Csbnd H vibrational spectra more accurately. In this article we have presented the importance of multidimensional potential energy surface in anharmonic vibrational frequency calculation and discuss the unexpected red shift of asymmetric Csbnd H stretch vibration of methyl group. The Csbnd D stretch vibrational band which is splitted to double peaks due to the Fermi resonance is also discussed here.
Non-axisymmetric annular curtain stability

NASA Astrophysics Data System (ADS)

Ahmed, Zahir U.; Khayat, Roger E.; Maissa, Philippe; Mathis, Christian

2013-08-01

A stability analysis of non-axisymmetric annular curtain is carried out for an axially moving viscous jet subject in surrounding viscous gas media. The effect of inertia, surface tension, gas-to-liquid density ratio, inner-to-outer radius ratio, and gas-to-liquid viscosity ratio on the stability of the jet is studied. In general, the axisymmetric disturbance is found to be the dominant mode. However, for small wavenumber, the non-axisymmetric mode is the most unstable mode and the one likely observed in reality. Inertia and the viscosity ratio for non-axisymmetric disturbances show a similar stability influence as observed for axisymmetric disturbances. The maximum growth rate in non-axisymmetric flow, interestingly, appears at very small wavenumber for all inertia levels. The dominant wavenumber increases (decreases) with inertia for non-axisymmetric (axisymmetric) flow. Gas-to-liquid density ratio, curvature effect, and surface tension, however, exhibit an opposite influence on growth rate compared to axisymmetric disturbances. Surface tension tends to stabilize the flow with reductions of the unstable wavenumber range and the maximum growth rate as well as the dominant wavenumber. The dominant wavenumber remains independent of viscosity ratio indicating the viscosity ratio increases the breakup length of the sheet with very little influence on the size of the drops. The range of unstable wavenumbers is affected only by curvature in axisymmetric flow, whereas all the stability parameters control the range of unstable wavenumbers in non-axisymmetric flow. Inertia and gas density increase the unstable wavenumber range, whereas the radius ratio, surface tension, and the viscosity ratio decrease the unstable wavenumber range. Neutral curves are plotted to separate the stable and unstable domains. Critical radius ratio decreases linearly and nonlinearly with the wavenumber for axisymmetric and non-axisymmetric disturbances, respectively. At smaller Weber numbers, a wider unstable domain is predicted for non-axisymmetric modes. For both axisymmetric and non-axisymmetric modes, the disturbance frequency is found to be the same and equal to the negative of axial wavenumber. Finally, comparison between theory and existing experiment leads to good qualitative agreement. A more accurate comparison is not possible given the difference in flow conditions.

Synthesis, characterization, and DFT studies of a new chiral ionic liquid from (S)-1-phenylethylamine

NASA Astrophysics Data System (ADS)

Cui, Shuya; Wang, Tao; Hu, Xiaoli

2014-12-01

A new chiral ionic liquid was synthesized from (S)-1-phenylethylamine and it was studied by IR, Raman, polarimetry, NMR and X-ray crystal diffraction. Its vibrational spectral bands are precisely ascribed to the studied structure with the aid of DFT theoretical calculations. The optimized geometries and calculated vibrational frequencies are evaluated via comparison with experimental values. The vibrational spectral data obtained from IR and Raman spectra are assigned based on the results of the theoretical calculations by the DFT-B3LYP method at 6-311G(d,p) level. The computed vibrational frequencies were scaled by scale factors to yield a good agreement with observed experimental vibrational frequencies. The vibrational modes assignments were performed by using the animation option of GaussView5.0 graphical interface for Gaussian program.
Design of a k-space spectrometer for ultra-broad waveband spectral domain optical coherence tomography

PubMed Central

Lan, Gongpu; Li, Guoqiang

2017-01-01

Nonlinear sampling of the interferograms in wavenumber (k) space degrades the depth-dependent signal sensitivity in conventional spectral domain optical coherence tomography (SD-OCT). Here we report a linear-in-wavenumber (k-space) spectrometer for an ultra-broad bandwidth (760 nm–920 nm) SD-OCT, whereby a combination of a grating and a prism serves as the dispersion group. Quantitative ray tracing is applied to optimize the linearity and minimize the optical path differences for the dispersed wavenumbers. Zemax simulation is used to fit the point spread functions to the rectangular shape of the pixels of the line-scan camera and to improve the pixel sampling rates. An experimental SD-OCT is built to test and compare the performance of the k-space spectrometer with that of a conventional one. Design results demonstrate that this k-space spectrometer can reduce the nonlinearity error in k-space from 14.86% to 0.47% (by approximately 30 times) compared to the conventional spectrometer. The 95% confidence interval for RMS diameters is 5.48 ± 1.76 μm—significantly smaller than both the pixel size (14 μm × 28 μm) and the Airy disc (25.82 μm in diameter, calculated at the wavenumber of 7.548 μm−1). Test results demonstrate that the fall-off curve from the k-space spectrometer exhibits much less decay (maximum as −5.20 dB) than the conventional spectrometer (maximum as –16.84 dB) over the whole imaging depth (2.2 mm). PMID:28266502
Short wind waves on the ocean: Wavenumber-frequency spectra

NASA Astrophysics Data System (ADS)

Plant, William J.

2015-03-01

Dominant surface waves on the ocean exhibit a dispersion relation that confines their energy to a curve in a wavenumber-frequency spectrum. Short wind waves on the ocean, on the other hand, are advected by these dominant waves so that they do not exhibit a well-defined dispersion relation over many realizations of the surface. Here we show that the short-wave analog to the dispersion relation is a distributed spectrum in the wavenumber-frequency plane that collapses to the standard dispersion relation in the absence of long waves. We compute probability distributions of short-wave wavenumber given a (frequency, direction) pair and of short-wave frequency given a (wavenumber, direction) pair. These two probability distributions must yield a single spectrum of surface displacements as a function of wavenumber and frequency, F(k,f). We show that the folded, azimuthally averaged version of this spectrum has a "butterfly" pattern in the wavenumber-frequency plane if significant long waves are present. Integration of this spectrum over frequency yields the well-known k-3 wavenumber spectrum. When integrated over wavenumber, the spectrum yields an f-4 form that agrees with measurement. We also show that a cut through the unfolded F(k,f) at constant k produces the well-known form of moderate-incidence-angle Doppler spectra for electromagnetic scattering from the sea. This development points out the dependence of the short-wave spectrum on the amplitude of the long waves.
A Deep Analysis of Center Displacement in An Idealized Tropical Cyclone with Low-wavenumber Asymmetries

NASA Astrophysics Data System (ADS)

Zhao, C.; Song, J.; Leng, H.

2017-12-01

The Tropical Cyclone(TC) center-finding technique plays an important role when diagnostic analyses of TC structure are performed, especially when dealing with low-wavenumber asymmetries. Previous works have already established that structure of TCs can vary greatly depending on the displacement induced by center-finding techniques. As it is difficult to define a true TC center in the real world, this work seeks to explore how low-wavenumber azimuthal Fourier analyses can vary with center displacement using idealized, parametric TC-like vortices with different perturbation structures. It is shown that the errors is sensitive to the location and radial structure of the adding perturbation. In the case of adding azimuthal wavenumber 1 and 3 asymmetries, the increasing radial shear of initial asymmetries will enhance the corresponding spectral energy around radius of maximum wind(RMW) significantly, and they also have a great effect on spectral energy of wavenumber 2. On the contrary, the wavenumber 2 cases show a reduction from 1RMW to outer radius when shear is increasing and has little effect on spectral energy of wavenumber 1 or 2. Pervious findings indicated that the aliasing is dependent on the placement of center relative to the location of the asymmetries, which is also valid in these shearing situations. Moreover, it is found that this aliasing caused by phase displacement is less sensitive with the radial shear in wavenumber 2 and 3 cases, while it shows an significant amplification and deformation when wavenumber 1 asymmetry is added.
Contributions of poroelastic-wave potentials to seismoelectromagnetic wavefields and validity of the quasi-static calculation: a view from a borehole model

NASA Astrophysics Data System (ADS)

Guan, Wei; Shi, Peng; Hu, Hengshan

2018-01-01

In this study, we theoretically analyse the contributions of the four poroelastic-wave potentials to seismoelectromagnetic (SEM) wavefields, verify the validity of the quasi-static calculation of the electric field and provide a method to calculate the magnetic field by using the curl-free electric field. Calculations show that both the fast and slow P waves and the SH and SV waves have non-negligible contributions to the SEM fields. The S waves have indirect contribution to the electric field through the EM conversion from the magnetic field, although the direct contribution due to streaming current is negligible if EM wavenumbers are much smaller than those of the S waves. The P waves have indirect contribution to the magnetic field through EM conversion from the electric field, although the direct contribution is absent. The quasi-static calculation of the electric field is practicable since it is normally satisfied in reality that the EM wavenumbers are much smaller than those of poroelastic waves. While the direct contribution of the S waves and the higher-order EM conversions are ignored, the first-order EM conversion from the S-wave-induced magnetic field is reserved through the continuity of the electric-current density. To calculate the magnetic field on this basis, we separate the quasi-static electric field into a rotational and an irrotational part. The magnetic-field solutions are derived through Hertz vectors in which the coefficients of the magnetic Hertz vector are determined from the magnetic-field continuities and those of the electric Hertz vector originate from the irrotational part of the quasi-static electric field.
Calculation of the vibration-rotational transition intensities of water molecules trapped in an argon matrix: stretching O-H vibrations spectral region

NASA Astrophysics Data System (ADS)

Pitsevich, George; Shalamberidze, Elena; Malevich, Alex; Sablinskas, Valdas; Balevicius, Vytautas; Pettersson, Lars G. M.

2017-10-01

The frequencies and intensities of vibration-rotational transitions of water molecules in an argon matrix were calculated for temperatures of 6 and 30 K. The rigid asymmetric top approximation was used with available literature values of the effective rotational constants in the ground and excited vibrational states. The calculations were carried out by taking into account the existence of a non-equilibrium population distribution between the rotational levels of ortho- and para-water isomers. It was assumed that the temperature relaxation of the population of rotational levels is independent of the ortho- and para-isomers. Comparison of the results of the theoretical calculations with experimental literature data shows good agreement for the majority of the rotational structure lines for symmetric and antisymmetric stretching vibrations both in the frequency values and in the values of the relative intensities.
Molecular structure, vibrational spectra and DFT molecular orbital calculations (TD-DFT and NMR) of the antiproliferative drug Methotrexate

NASA Astrophysics Data System (ADS)

Ayyappan, S.; Sundaraganesan, N.; Aroulmoji, V.; Murano, E.; Sebastian, S.

2010-09-01

The FT-IR and FT-Raman spectral studies of the Methotrexate (MTX) were carried out. The equilibrium geometry, various bonding features and harmonic vibrational frequencies of MTX have been investigated with the help of B3LYP density functional theory (DFT) using 6-31G(d) as basis set. Detailed analysis of the vibrational spectra has been made with the aid of theoretically predicted vibrational frequencies. The vibrational analysis confirms the differently acting ring modes, steric repulsion, conjugation and back-donation. The energy and oscillator strength calculated by Time-Dependent Density Functional Theory (TD-DFT) results complement with the experimental findings. The calculated HOMO and LUMO energies show that charge transfer occur within the molecule. Good correlations between the experimental 1H and 13C NMR chemical shifts in DMSO solution and calculated GIAO shielding tensors were found.
Impact Induced Delamination Detection and Quantification With Guided Wavefield Analysis

NASA Technical Reports Server (NTRS)

Tian, Zhenhua; Leckey, Cara A. C.; Yu, Lingyu; Seebo, Jeffrey P.

2015-01-01

This paper studies impact induced delamination detection and quantification by using guided wavefield data and spatial wavenumber imaging. The complex geometry impact-like delamination is created through a quasi-static indentation on a CFRP plate. To detect and quantify the impact delamination in the CFRP plate, PZT-SLDV sensing and spatial wavenumber imaging are performed. In the PZT-SLDV sensing, the guided waves are generated from the PZT, and the high spatial resolution guided wavefields are measured by the SLDV. The guided wavefield data acquired from the PZT-SLDV sensing represent guided wave propagation in the composite laminate and include guided wave interaction with the delamination damage. The measured guided wavefields are analyzed through the spatial wavenumber imaging method, which generates an image containing the dominant local wavenumber at each spatial location. The spatial wavenumber imaging result for the simple single layer Teflon insert delamination provided quantitative information on delamination damage size and location. The location of delamination damage is indicated by the area with larger wavenumbers in the spatial wavenumber image. The impact-like delamination results only partially agreed with the damage size and shape. The results also demonstrated the dependence on excitation frequency. Future work will further investigate the accuracy of the wavenumber imaging method for real composite damage and the dependence on frequency of excitation.
First-principles studies of PETN molecular crystal vibrational frequencies under high pressure

NASA Astrophysics Data System (ADS)

Perger, Warren; Zhao, Jijun

2005-07-01

The vibrational frequencies of the PETN molecular crystal were calculated using the first-principles CRYSTAL03 program which employs an all-electron LCAO approach and calculates analytic first derivatives of the total energy with respect to atomic displacements. Numerical second derivatives were used to enable calculation of the vibrational frequencies at ambient pressure and under various states of compression. Three different density functionals, B3LYP, PW91, and X3LYP were used to examine the effect of the exchange-correlation functional on the vibrational frequencies. The pressure-induced shift of the vibrational frequencies will be presented and compared with experiment. The average deviation with experimental results is shown to be on the order of 2-3%, depending on the functional used.
Wavenumber selection in Benard convection

DOE Office of Scientific and Technical Information (OSTI.GOV)

Catton, I.

1988-11-01

The results of three related studies dealing with wavenumber selection in Rayleigh--Benard convection are reported. The first, an extension of the power integral method, is used to argue for the existence of multi-wavenumbers at all supercritical wavenumbers. Most existing closure schemes are shown to be inadequate. A thermodynamic stability criterion is shown to give reasonable results but requires empirical measurement of one parameter for closure. The third study uses an asymptotic approach based in part on geometric considerations and requires no empiricism to obtain good predictions of the wavenumber. These predictions, however, can only be used for certain planforms ofmore » convection.« less
Short cavity active mode locking fiber laser for optical sensing and imaging

NASA Astrophysics Data System (ADS)

Lee, Hwi Don; Han, Ga Hee; Jeong, Syung Won; Jeong, Myung Yung; Kim, Chang-Seok; Shin, Jun Geun; Lee, Byeong Ha; Eom, Tae Joong

2014-05-01

We demonstrate a highly linear wavenumber- swept active mode locking (AML) fiber laser for optical sensing and imaging without any wavenumber-space resampling process. In this all-electric AML wavenumber-swept mechanism, a conventional wavelength selection filter is eliminated and, instead, the suitable programmed electric modulation signal is directly applied to the gain medium. Various types of wavenumber (or wavelength) tunings can be implemented because of the filter-less cavity configuration. Therefore, we successfully demonstrate a linearly wavenumber-swept AML fiber laser with 26.5 mW of output power to obtain an in-vivo OCT image at the 100 kHz swept rate.
Proton--H/sub 2/ scattering on an ab initio CI potential energy surface. I. Vibrational excitation at 10 eV

DOE Office of Scientific and Technical Information (OSTI.GOV)

Schinke, R.; Dupuis, M.; Lester, W.A. Jr.

1980-04-01

A complete configuration interaction (CI) ground state surface for the H/sub 3//sup +/ system has been calculated using 5S and 3(P/sub x/,P/sub y/,P/sub x/) basis functions at each center. A total of 650 nuclear geometries has been considered which makes the new surface appropriate not only for scattering calculations, but also for the evaluation of the vibrational--rotational spectrum of the H/sub 3//sup +/ molecule. Significant deviations are found from the analytic Giese and Gentry potential used in many previous theoretical studies, especially for large and small nonequilibrium H--H separations which are important for vibrational excitation of the H/sub 2/ molecule.more » Vibrational--rotational excitation cross sections have been calculated in the rotational sudden approximation where the vibrational degree of freedom is treated exactly by solving seven vibrationally coupled radial equations. The use of the new surface leads to increased vibrational excitation compared to previous calculations utilizing the same scattering approximation and to excellent agreement at 10 eV with the angle-dependent measurements of Hermann, Schmidt, and Linder.« less
Modelling of Rail Vehicles and Track for Calculation of Ground-Vibration Transmission Into Buildings

NASA Astrophysics Data System (ADS)

Hunt, H. E. M.

1996-05-01

A methodology for the calculation of vibration transmission from railways into buildings is presented. The method permits existing models of railway vehicles and track to be incorporated and it has application to any model of vibration transmission through the ground. Special attention is paid to the relative phasing between adjacent axle-force inputs to the rail, so that vibration transmission may be calculated as a random process. The vehicle-track model is used in conjunction with a building model of infinite length. The tracking and building are infinite and parallel to each other and forces applied are statistically stationary in space so that vibration levels at any two points along the building are the same. The methodology is two-dimensional for the purpose of application of random process theory, but fully three-dimensional for calculation of vibration transmission from the track and through the ground into the foundations of the building. The computational efficiency of the method will interest engineers faced with the task of reducing vibration levels in buildings. It is possible to assess the relative merits of using rail pads, under-sleeper pads, ballast mats, floating-slab track or base isolation for particular applications.
Synthesis, X-ray diffraction method, spectroscopic characterization (FT-IR, 1H and 13C NMR), antimicrobial activity, Hirshfeld surface analysis and DFT computations of novel sulfonamide derivatives

NASA Astrophysics Data System (ADS)

Demircioğlu, Zeynep; Özdemir, Fethi Ahmet; Dayan, Osman; Şerbetçi, Zafer; Özdemir, Namık

2018-06-01

Synthesized compounds of N-(2-aminophenyl)benzenesulfonamide 1 and (Z)-N-(2-((2-nitrobenzylidene)amino)phenyl)benzenesulfonamide 2 were characterized by antimicrobial activity, FT-IR, 1H and 13C NMR. Two new Schiff base ligands containing aromatic sulfonamide fragment of (Z)-N-(2-((3-nitrobenzylidene)amino)phenyl)benzenesulfonamide 3 and (Z)-N-(2-((4-nitrobenzylidene)amino)phenyl)benzenesulfonamide 4 were synthesized and investigated by spectroscopic techniques including 1H and 13C NMR, FT-IR, single crystal X-ray diffraction, Hirshfeld surface, theoretical method analyses and by antimicrobial activity. The molecular geometry obtained from the X-ray structure determination was optimized Density Functional Theory (DFT/B3LYP) method with the 6-311++G(d,p) basis set in ground state. From the optimized geometry of the molecules of 3 and 4, the geometric parameters, vibrational wavenumbers and chemical shifts were computed. The optimized geometry results, which were well represented the X-ray data, were shown that the chosen of DFT/B3LYP 6-311G++(d,p) was a successful choice. After a successful optimization, frontier molecular orbitals, chemical activity, non-linear optical properties (NLO), molecular electrostatic mep (MEP), Mulliken population method, natural population analysis (NPA) and natural bond orbital analysis (NBO), which cannot be obtained experimentally, were calculated and investigated.
Radiative efficiencies for fluorinated esters: indirect global warming potentials of hydrofluoroethers.

PubMed

Bravo, Iván; Díaz-de-Mera, Yolanda; Aranda, Alfonso; Moreno, Elena; Nutt, David R; Marston, George

2011-10-14

Density Functional Theory (DFT) has been used with an empirically-derived correction for the wavenumbers of vibrational band positions to predict the infrared spectra of several fluorinated esters (FESs). Radiative efficiencies (REs) were then determined using the method of Pinnock et al. and these were used with atmospheric lifetimes from the literature to determine the direct global warming potentials of FESs. FESs, in particular fluoroalkylacetates, alkylfluoroacetates and fluoroalkylformates, are potential greenhouse gases and their likely long atmospheric lifetimes and relatively large REs, compared to their parent HFEs, make them active contributors to global warming. Here, we use the concept of indirect global warming potential (indirect GWP) to assess the contribution to the warming of several commonly used HFEs emitted from the Earth's surface, explicitly taking into account that these HFEs will be converted into the corresponding FESs in the troposphere. The indirect GWP can be calculated using the radiative efficiencies and lifetimes of the HFE and its degradation FES products. We found that the GWPs of those studied HFEs which have the smallest direct GWP can be increased by 100-1600% when taking account of the cumulative effect due to the secondary FESs formed during HFE atmospheric oxidation. This effect may be particularly important for non-segregated HFEs and some segregated HFEs, which may contribute significantly more to global warming than can be concluded from examination of their direct GWPs.
Role of target-substrate distance on the growth of CuInSe{sub 2} thin films by pulsed laser ablation technique

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rawat, Kusum; Dhruvashi; Department of Electronic Science, University of Delhi South Campus, Delhi 110021

2016-05-06

CuInSe{sub 2} thin films have been deposited on corning glass substrates by pulsed laser ablation technique. The chamber pressure and substrate temperature was maintained at 1 × 10{sup −6} torr and 550°C respectively during deposition of the films. The influence of target to substrate (T-S) distance on the structural and optical properties of thin films have been investigated by grazing incidence x-ray diffraction, Raman spectroscopy, scanning electron microscope and UV-Vis-NIR spectroscopy. The study reveals that thin films crystallized in a chalcopyrite structure with highly preferential orientation along (112) plane. Optimum T-S distance has been attained for the growth of thinmore » films with large grain size. An intense Raman peak at 174 cm{sup −1} corresponding to dominant A{sub 1} vibration mode is gradually shifted to smaller wavenumber with the increase in T-S distance. The optical bandgap energy of the films was evaluated and found to vary with the T-S distance. The bandgap tailing was observed to obey the Urbach rule and the Urbach energy was also calculated for the films. Scanning electron micrographs depicts uniform densely packed grains and EDAX studies revealed the elemental composition of CuInSe{sub 2} thin films.« less
Far infrared spectra of solid state aliphatic amino acids in different protonation states

NASA Astrophysics Data System (ADS)

Trivella, Aurélien; Gaillard, Thomas; Stote, Roland H.; Hellwig, Petra

2010-03-01

Far infrared spectra of zwitterionic, cationic, and anionic forms of aliphatic amino acids in solid state have been studied experimentally. Measurements were done on glycine, L-alanine, L-valine, L-leucine, and L-isoleucine powder samples and film samples obtained from dried solutions prepared at pH ranging from 1 to 13. Solid state density functional theory calculations were also performed, and detailed potential energy distributions were obtained from normal mode results. A good correspondence between experimental and simulated spectra was achieved and this allowed us to propose an almost complete band assignment for the far infrared spectra of zwitterionic forms. In the 700-50 cm-1 range, three regions were identified, each corresponding to a characteristic set of normal modes. A first region between 700 and 450 cm-1 mainly contained the carboxylate bending, rocking, and wagging modes as well as the ammonium torsional mode. The 450-250 cm-1 region was representative of backbone and sidechain skeletal bending modes. At last, the low wavenumber zone, below 250 cm-1, was characteristic of carboxylate and skeletal torsional modes and of lattice modes. Assignments are also proposed for glycine cationic and anionic forms, but could not be obtained for all aliphatic amino acids due to the lack of structural data. This work is intended to provide fundamental information for the understanding of peptides vibrational properties.
Infrared absorption spectrum of the simplest deuterated Criegee intermediate CD{sub 2}OO

DOE Office of Scientific and Technical Information (OSTI.GOV)

Huang, Yu-Hsuan; Nishimura, Yoshifumi; Witek, Henryk A., E-mail: hwitek@mail.nctu.edu.tw, E-mail: yplee@mail.nctu.edu.tw

We report a transient infrared (IR) absorption spectrum of the simplest deuterated Criegee intermediate CD{sub 2}OO recorded using a step-scan Fourier-transform spectrometer coupled with a multipass absorption cell. CD{sub 2}OO was produced from photolysis of flowing mixtures of CD{sub 2}I{sub 2}, N{sub 2}, and O{sub 2} (13 or 87 Torr) with laser light at 308 nm. The recorded spectrum shows close structural similarity with the spectrum of CH{sub 2}OO reported previously [Y.-T. Su et al., Science 340, 174 (2013)]. The four bands observed at 852, 1017, 1054, and 1318 cm{sup −1} are assigned to the OO stretching mode, two distinctmore » in-plane OCD bending modes, and the CO stretching mode of CD{sub 2}OO, respectively, according to vibrational wavenumbers, IR intensities, rotational contours, and deuterium-isotopic shifts predicted with extensive quantum-chemical calculations. The CO-stretching mode of CD{sub 2}OO at 1318 cm{sup −1} is blue shifted from the corresponding band of CH{sub 2}OO at 1286 cm{sup −1}; this can be explained by a mechanism based on mode mixing and isotope substitution. A band near 936 cm{sup −1}, observed only at higher pressure (87 Torr), is tentatively assigned to the CD{sub 2} wagging mode of CD{sub 2}IOO.« less
Infrared spectra of ovalene (C32H14) and hydrogenated ovalene (C32H15˙) in solid para-hydrogen.

PubMed

Tsuge, Masashi; Bahou, Mohammed; Wu, Yu-Jong; Allamandola, Louis; Lee, Yuan-Pern

2016-10-19

We report the infrared (IR) spectra of ovalene (C 32 H 14 ) and hydrogenated ovalene (C 32 H 15 ˙) in solid para-hydrogen (p-H 2 ). The hydrogenated ovalene and protonated ovalene were generated from electron bombardment of a mixture of ovalene and p-H 2 during deposition of a matrix at 3.2 K. The features that decreased with time have been previously assigned to 7-C 32 H 15 + , the most stable isomer of protonated ovalene (Astrophys. J., 2016, 825, 96). The spectral features that increased with time are assigned to the most stable isomer of hydrogenated ovalene (7-C 32 H 15 ˙) based on the expected chemistry and on a comparison with the vibrational wavenumbers and IR intensities predicted by the B3PW91/6-311++G(2d,2p) method. The mechanism of formation of 7-C 32 H 15 ˙ is discussed according to the observed changes in intensity and calculated energetics of possible reactions of H + C 32 H 14 and isomerization of C 32 H 15 ˙. The formation of 7-C 32 H 15 ˙ is dominated by the reaction H + C 32 H 14 → 7-C 32 H 15 ˙, implying that, regardless of the presence of a barrier, the hydrogenation of polycyclic aromatic hydrocarbons occurs even at 3.2 K.
The relative importance of fluid and kinetic frequency shifts of an electron plasma wave

NASA Astrophysics Data System (ADS)

Winjum, B. J.; Fahlen, J.; Mori, W. B.

2007-10-01

The total nonlinear frequency shift of a plasma wave including both fluid and kinetic effects is estimated when the phase velocity of the wave is much less than the speed of light. Using a waterbag or fluid model, the nonlinear frequency shift due to harmonic generation is calculated for an arbitrary shift in the wavenumber. In the limit where the wavenumber does not shift, the result is in agreement with previously published work [R. L. Dewar and J. Lindl, Phys. Fluids 15, 820 (1972); T. P. Coffey, Phys. Fluids 14, 1402 (1971)]. This shift is compared to the kinetic shift of Morales and O'Neil [G. J. Morales and T. M. O'Neil, Phys. Rev. Lett. 28, 417 (1972)] for wave amplitudes and values of kλD of interest to Raman backscatter of a laser driver in inertial confinement fusion.

Giant exchange interaction in mixed lanthanides

PubMed Central

Vieru, Veacheslav; Iwahara, Naoya; Ungur, Liviu; Chibotaru, Liviu F.

2016-01-01

Combining strong magnetic anisotropy with strong exchange interaction is a long standing goal in the design of quantum magnets. The lanthanide complexes, while exhibiting a very strong ionic anisotropy, usually display a weak exchange coupling, amounting to only a few wavenumbers. Recently, an isostructural series of mixed (Ln = Gd, Tb, Dy, Ho, Er) have been reported, in which the exchange splitting is estimated to reach hundreds wavenumbers. The microscopic mechanism governing the unusual exchange interaction in these compounds is revealed here by combining detailed modeling with density-functional theory and ab initio calculations. We find it to be basically kinetic and highly complex, involving non-negligible contributions up to seventh power of total angular momentum of each lanthanide site. The performed analysis also elucidates the origin of magnetization blocking in these compounds. Contrary to general expectations the latter is not always favored by strong exchange interaction. PMID:27087470
Vibrational Study of Melatonin and its Radioprotective Activity towards Hydroxyl Radical

NASA Astrophysics Data System (ADS)

Singh, Gurpreet; Kaur, Sarvpreet; Saini, G. S. S.

2011-12-01

Vibrational study of Melatonin (N-acetyl 5-methoxytrypatamin) was done using FTIR and Raman spectroscopy. DFT calculations were employed to the structural analysis of melatonin and to the end products. The theoretical calculations confirmed the different observed vibrational modes. The optimized structure energy calculations of the different end products confirmed the most probable site of the hydroxyl radical attack is the hydrogen attached to nitrogen present in the indole ring.
Real-time vibration measurement by a spatial phase-shifting technique with a tilted holographic interferogram.

PubMed

Nakadate, S; Isshiki, M

1997-01-01

Real-time vibration measurement by a tilted holographic interferogram is presented that utilizes the real-time digital fringe processor of a video signal. Three intensity data sampled at every one-third of the fringe spacing of the tilted fringes are used to calculate the modulation term of the fringe that is a function of a vibration amplitude. A three-dimensional lookup table performs the calculation in a TV repetition rate to give a new fringe profile that contours the vibration amplitude. Vibration modes at the resonant frequencies of a flat speaker were displayed on a monitor as changing the exciting frequency of vibration.
Vibrational excitation and vibrationally resolved electronic excitation cross sections of positron-H2 scattering

NASA Astrophysics Data System (ADS)

Zammit, Mark; Fursa, Dmitry; Savage, Jeremy; Bray, Igor

2016-09-01

Vibrational excitation and vibrationally resolved electronic excitation cross sections of positron-H2 scattering have been calculated using the single-centre molecular convergent close-coupling (CCC) method. The adiabatic-nuclei approximation was utilized to model the above scattering processes and obtain the vibrationally resolved positron-H2 scattering length. As previously demonstrated, the CCC results are converged and accurately account for virtual and physical positronium formation by coupling basis functions with large orbital angular momentum. Here vibrationally resolved integrated and differential cross sections are presented over a wide energy range and compared with previous calculations and available experiments. Los Alamos National Laboratory and Curtin University.
Multi-frequency local wavenumber analysis and ply correlation of delamination damage.

PubMed

Juarez, Peter D; Leckey, Cara A C

2015-09-01

Wavenumber domain analysis through use of scanning laser Doppler vibrometry has been shown to be effective for non-contact inspection of damage in composites. Qualitative and semi-quantitative local wavenumber analysis of realistic delamination damage and quantitative analysis of idealized damage scenarios (Teflon inserts) have been performed previously in the literature. This paper presents a new methodology based on multi-frequency local wavenumber analysis for quantitative assessment of multi-ply delamination damage in carbon fiber reinforced polymer (CFRP) composite specimens. The methodology is presented and applied to a real world damage scenario (impact damage in an aerospace CFRP composite). The methodology yields delamination size and also correlates local wavenumber results from multiple excitation frequencies to theoretical dispersion curves in order to robustly determine the delamination ply depth. Results from the wavenumber based technique are validated against a traditional nondestructive evaluation method. Published by Elsevier B.V.
Synthesis, characterization, and DFT studies of a new chiral ionic liquid from (S)-1-phenylethylamine.

PubMed

Cui, Shuya; Wang, Tao; Hu, Xiaoli

2014-12-10

A new chiral ionic liquid was synthesized from (S)-1-phenylethylamine and it was studied by IR, Raman, polarimetry, NMR and X-ray crystal diffraction. Its vibrational spectral bands are precisely ascribed to the studied structure with the aid of DFT theoretical calculations. The optimized geometries and calculated vibrational frequencies are evaluated via comparison with experimental values. The vibrational spectral data obtained from IR and Raman spectra are assigned based on the results of the theoretical calculations by the DFT-B3LYP method at 6-311G(d,p) level. The computed vibrational frequencies were scaled by scale factors to yield a good agreement with observed experimental vibrational frequencies.The vibrational modes assignments were performed by using the animation option of GaussView5.0 graphical interface for Gaussian program. Copyright © 2014 Elsevier B.V. All rights reserved.
UHB demonstrator interior noise control flight tests and analysis

NASA Astrophysics Data System (ADS)

Simpson, M. A.; Druez, P. M.; Kimbrough, A. J.; Brock, M. P.; Burge, P. L.; Mathur, G. P.; Cannon, M. R.; Tran, B. N.

1989-10-01

The measurement and analysis of MD-UHB (McDonnell Douglas Ultra High Bypass) Demonstrator noise and vibration flight test data are described as they relate to passenger cabin noise. The analyses were done to investigate the interior noise characteristics of advanced turboprop aircraft with aft-mounted engines, and to study the effectiveness of selected noise control treatments in reducing passenger cabin noise. The UHB Demonstrator is an MD-80 test aircraft with the left JT8D engine replaced with a prototype UHB engine. For these tests, the UHB engine was a General Electric Unducted Fan, with either 8x8 or 10x8 counter-rotating propeller configurations. Interior noise level characteristics were studied for several altitudes and speeds, with emphasis on high altitude (35,000 ft), high speed (0.75 Mach) cruise conditions. The effectiveness of several noise control treatments was evaluated based on cabin noise measurements. The important airborne and structureborne transmission paths were identified for both tonal and broadband sources using the results of a sound intensity survey, exterior and interior noise and vibration data, and partial coherence analysis techniques. Estimates of the turbulent boundary layer pressure wavenumber-frequency spectrum were made, based on measured fuselage noise levels.
UHB demonstrator interior noise control flight tests and analysis

NASA Technical Reports Server (NTRS)

Simpson, M. A.; Druez, P. M.; Kimbrough, A. J.; Brock, M. P.; Burge, P. L.; Mathur, G. P.; Cannon, M. R.; Tran, B. N.

1989-01-01

The measurement and analysis of MD-UHB (McDonnell Douglas Ultra High Bypass) Demonstrator noise and vibration flight test data are described as they relate to passenger cabin noise. The analyses were done to investigate the interior noise characteristics of advanced turboprop aircraft with aft-mounted engines, and to study the effectiveness of selected noise control treatments in reducing passenger cabin noise. The UHB Demonstrator is an MD-80 test aircraft with the left JT8D engine replaced with a prototype UHB engine. For these tests, the UHB engine was a General Electric Unducted Fan, with either 8x8 or 10x8 counter-rotating propeller configurations. Interior noise level characteristics were studied for several altitudes and speeds, with emphasis on high altitude (35,000 ft), high speed (0.75 Mach) cruise conditions. The effectiveness of several noise control treatments was evaluated based on cabin noise measurements. The important airborne and structureborne transmission paths were identified for both tonal and broadband sources using the results of a sound intensity survey, exterior and interior noise and vibration data, and partial coherence analysis techniques. Estimates of the turbulent boundary layer pressure wavenumber-frequency spectrum were made, based on measured fuselage noise levels.
Preliminary studies of the effects of psychological stress on circulating lymphocytes analyzed by synchrotron radiation based-Fourier transform infrared microspectroscopy

NASA Astrophysics Data System (ADS)

Vargas-Caraveo, Alejandra; Castillo-Michel, Hiram; Mejia-Carmona, Gloria Erika; Pérez-Ishiwara, David Guillermo; Cotte, Marine; Martínez-Martínez, Alejandro

2014-07-01

Psychological stress is a condition that not only generates behavioral disorders but also disrupts homeostasis and immune activity that can exacerbate or lead to inflammatory diseases. The aim of this work was to study biochemical changes in circulating immune cells from rats under psychological stress by using vibrational spectroscopy. A stress model was used, where exposure to a stressor was repeated for 5 days. Subsequently, circulating lymphocytes were examined for their biomolecular vibrational fingerprints with synchrotron radiation based-Fourier transform infrared microspectroscopy. The results showed an increased absorption at the ester lipid region (1720-1755 cm-1) in lymphocytes from stressed rats, suggesting lipid peroxidation. Statistical significant changes in wavenumber peak position and absorbance in the nucleic acid region were also observed (915-950 cm-1 Z-DNA, 1090-1150 cm-1 symmetric stretching of Psbnd Osbnd C, 1200-1260 cm-1 asymmetric PO2 and 1570-1510 cm-1 methylated nucleotides) which suggest a reduction of transcriptional activity in lymphocytes from stressed rat. These results unravel part of the mechanisms by which psychological stress may affect the immune system leading to systemic consequences.
Vibrational modes in thymine molecule from an ab initio MO calculation

NASA Astrophysics Data System (ADS)

Aida, Misako; Kaneko, Motohisa; Dupuis, Michel; Ueda, Toyotoshi; Ushizawa, Koichi; Ito, Gen; Kumakura, Akiko; Tsuboi, Masamichi

1997-03-01

Ab initio self-consistent field molecular orbital (SCF MO) calculations have been made of the thymine molecule for the equilibrium geometry, harmonic force constants, vibrational frequencies, vibrational modes, infrared intensities, and Raman intensities. The results have been correlated with the observed Raman and infrared spectra of thymine crystalline powder.
A Multi-wavenumber Theory for Eddy Diffusivities: Applications to the DIMES Region

NASA Astrophysics Data System (ADS)

Chen, R.; Gille, S. T.; McClean, J.; Flierl, G.; Griesel, A.

2014-12-01

Climate models are sensitive to the representation of ocean mixing processes. This has motivated recent efforts to collect observations aimed at improving mixing estimates and parameterizations. The US/UK field program Diapycnal and Isopycnal Mixing Experiment in the Southern Ocean (DIMES), begun in 2009, is providing such estimates upstream of and within the Drake Passage. This region is characterized by topography, and strong zonal jets. In previous studies, mixing length theories, based on the assumption that eddies are dominated by a single wavenumber and phase speed, were formulated to represent the estimated mixing patterns in jets. However, in spite of the success of the single wavenumber theory in some other scenarios, it does not effectively predict the vertical structures of observed eddy diffusivities in the DIMES area. Considering that eddy motions encompass a wide range of wavenumbers, which all contribute to mixing, in this study we formulated a multi-wavenumber theory to predict eddy mixing rates. We test our theory for a domain encompassing the entire Southern Ocean. We estimated eddy diffusivities and mixing lengths from one million numerical floats in a global eddying model. These float-based mixing estimates were compared with the predictions from both the single-wavenumber and the multi-wavenumber theories. Our preliminary results in the DIMES area indicate that, compared to the single-wavenumber theory, the multi-wavenumber theory better predicts the vertical mixing structures in the vast areas where the mean flow is weak; however in the intense jet region, both theories have similar predictive skill.
Development of Structure and Characteristics Calculation Method for Γ- shape Rope Vubration Insulator

NASA Astrophysics Data System (ADS)

Ponomarev, Yury K.

2018-01-01

The paper gives an overview of the design of rope vibration insulators with elastic elements of the center line in the form of two rectilinear and one curved section. In the Russian-language scientific literature this type of rope vibration insulators received a stable name "Γ-shaped vibration insulators” by analogy with the shape of the letter “gamma-Γ" of the Greek alphabet and a similar letter of the Cyrillic alphabet. Despite the wide using of vibration insulators designed on this shape, its mathematical calculation model has not yet been developed. In this connection, in this article, for the first time on the basis of the “Method of Forces” and the “Mohr Method”, an analytical technique has been developed for calculating the characteristics of a vibration insulator in the directions of three mutually perpendicular axes. In addition, the article proposes a new structure of a vibration insulator consisting of several tiers of elements of this type, based on a new patented technology for manufacturing quasi-continuous woven rings, proposed by the author of this article in co-authorship with several employees of the Samara National Research University. Simple formulas are obtained for calculating the load characteristics in three mutually perpendicular directions. This makes it possible to calculate the corresponding stiffness and natural frequencies of mechanical vibration protection systems. It is established that the stiffness of the vibration insulator in the direction of the Z axis is greater than the stiffness in the X and Y axis directions, however, if a vibration insulator with equal, or close to equal characteristics, along three axes has to be designed according to the technical specification, this can be done by selecting the parameters included in the equations given in article for load characteristics.
Ab initio study of collective excitations in a disparate mass molten salt.

PubMed

Bryk, Taras; Klevets, Ivan

2012-12-14

Ab initio molecular dynamics simulations and the approach of generalized collective modes are applied for calculations of spectra of longitudinal and transverse collective excitations in molten LiBr. Dispersion and damping of low- and high-frequency branches of collective excitations as well as wave-number dependent relaxing modes were calculated. The main mode contributions to partial, total, and concentration dynamic structure factors were estimated in a wide region of wave numbers. A role of polarization effects is discussed from comparison of mode contributions to concentration dynamic structure factors calculated for molten LiBr from ab initio and classical rigid ion simulations.
Translational vibrations between chains of hydrogen-bonded molecules in solid-state aspirin form I

NASA Astrophysics Data System (ADS)

Takahashi, Masae; Ishikawa, Yoichi

2013-06-01

We perform dispersion-corrected first-principles calculations, and far-infrared (terahertz) spectroscopic experiments at 4 K, to examine translational vibrations between chains of hydrogen-bonded molecules in solid-state aspirin form I. The calculated frequencies and relative intensities reproduce the observed spectrum to accuracy of 11 cm-1 or less. The stronger one of the two peaks assigned to the translational mode includes the stretching vibration of the weak hydrogen bond between the acetyl groups of a neighboring one-dimensional chain. The calculation of aspirin form II performed for comparison gives the stretching vibration of the weak hydrogen bond in one-dimensional chain.
Solvent effect on the vibrational spectra of Carvedilol.

PubMed

Billes, Ferenc; Pataki, Hajnalka; Unsalan, Ozan; Mikosch, Hans; Vajna, Balázs; Marosi, György

2012-09-01

Carvedilol (CRV) is an important medicament for heart arrhythmia. The aim of this work was the interpretation of its vibrational spectra with consideration on the solvent effect. Infrared and Raman spectra were recorded in solid state as well in solution. The experimental spectra were evaluated using DFT quantum chemical calculations computing the optimized structure, atomic net charges, vibrational frequencies and force constants. The same calculations were done for the molecule in DMSO and aqueous solutions applying the PCM method. The calculated force constants were scaled to the experimentally observed solid state frequencies. The characters of the vibrational modes were determined by their potential energy distributions. Solvent effects on the molecular properties were interpreted. Based on these results vibrational spectra were simulated. Copyright © 2012 Elsevier B.V. All rights reserved.
First-Principles Studies of Pentaerythritol Tetranitrate (PETN) Single Crystal Unit Cell Volumes and Vibrational Frequencies under Hydrostatic Pressure

NASA Astrophysics Data System (ADS)

Perger, Warren F.; Zhao, Jijun; Winey, J. M.; Gupta, Y. M.

2006-07-01

The vibrational frequencies of the PETN molecular crystal were calculated using the first-principles CRYSTAL03 program which employs an all-electron LCAO approach and calculates analytic first derivatives of the total energy with respect to atomic displacements. Numerical second derivatives were used to enable calculation of the vibrational frequencies at ambient pressure and under various states of compression. Three different density functionals, B3LYP, PW91, and X3LYP were used to examine the effect of the exchange-correlation functional on the vibrational frequencies. The average deviation with experimental results is shown to be on the order of 2-3%, depending on the functional used. The pressure-induced shift of the vibrational frequencies is presented.
Theoretical study on the vibrational spectra of methoxy- and formyl-dihydroxy- trans-stilbenes and their hydrolytic equilibria

NASA Astrophysics Data System (ADS)

Molnár, Viktor; Billes, Ferenc; Tyihák, Ernő; Mikosch, Hans

2008-02-01

Compounds formed by exchanging one of the resveratrol hydroxy groups to methoxy or formyl groups are biologically important. Quantum chemical DFT calculations were applied for the simulation of some of their properties. Their optimized structures and charge distributions were computed. Based on the calculated vibrational force constants and optimized molecular structure infrared and Raman spectra were calculated. The characteristics of the vibrational modes were determined by normal coordinate analysis. Applying the calculated thermodynamic functions also for resveratrol, methanol, formaldehyde and water, thermodynamic equilibria were calculated for the equilibria between resveratrol and its methyl and formyl substituted derivatives, respectively.
Statistical parameters of random heterogeneity estimated by analysing coda waves based on finite difference method

NASA Astrophysics Data System (ADS)

Emoto, K.; Saito, T.; Shiomi, K.

2017-12-01

Short-period (<1 s) seismograms are strongly affected by small-scale (<10 km) heterogeneities in the lithosphere. In general, short-period seismograms are analysed based on the statistical method by considering the interaction between seismic waves and randomly distributed small-scale heterogeneities. Statistical properties of the random heterogeneities have been estimated by analysing short-period seismograms. However, generally, the small-scale random heterogeneity is not taken into account for the modelling of long-period (>2 s) seismograms. We found that the energy of the coda of long-period seismograms shows a spatially flat distribution. This phenomenon is well known in short-period seismograms and results from the scattering by small-scale heterogeneities. We estimate the statistical parameters that characterize the small-scale random heterogeneity by modelling the spatiotemporal energy distribution of long-period seismograms. We analyse three moderate-size earthquakes that occurred in southwest Japan. We calculate the spatial distribution of the energy density recorded by a dense seismograph network in Japan at the period bands of 8-16 s, 4-8 s and 2-4 s and model them by using 3-D finite difference (FD) simulations. Compared to conventional methods based on statistical theories, we can calculate more realistic synthetics by using the FD simulation. It is not necessary to assume a uniform background velocity, body or surface waves and scattering properties considered in general scattering theories. By taking the ratio of the energy of the coda area to that of the entire area, we can separately estimate the scattering and the intrinsic absorption effects. Our result reveals the spectrum of the random inhomogeneity in a wide wavenumber range including the intensity around the corner wavenumber as P(m) = 8πε2a3/(1 + a2m2)2, where ε = 0.05 and a = 3.1 km, even though past studies analysing higher-frequency records could not detect the corner. Finally, we estimate the intrinsic attenuation by modelling the decay rate of the energy. The method proposed in this study is suitable for quantifying the statistical properties of long-wavelength subsurface random inhomogeneity, which leads the way to characterizing a wider wavenumber range of spectra, including the corner wavenumber.
Decoupling the Role of Particle Inertia and Gravity on Particle Dispersion

NASA Technical Reports Server (NTRS)

Squires, Kyle D.

2002-01-01

Particle dispersion and the influence that particle momentum exchange has on the properties of a turbulent carrier flow in micro-gravity environments challenge present understanding and predictive schemes. The objective of this effort has been to develop and assess high-fidelity simulation tools for predicting particle transport within micro-gravity environments suspended in turbulent flows. The computational technique is based on Direct Numerical Simulation (DNS) of the incompressible Navier-Stokes equations. The particular focus of the present work is on the class of dilute flows in which particle volume fractions and inter-particle collisions are negligible. Particle motion is assumed to be governed by drag with particle relaxation times ranging from the Kolmogorov scale to the Eulerian timescale of the turbulence and particle mass loadings up to one. The velocity field was made statistically stationary by forcing the low wavenumbers of the flow. The calculations were performed using 96(exp 3) collocation points and the Taylor-scale Reynolds number for the stationary flow was 62. The effect of particles on the turbulence was included in the Navier-Stokes equations using the point-force approximation in which 96(exp 3) particles were used in the calculations. DNS results show that particles increasingly dissipate fluid kinetic energy with increased loading, with the reduction in kinetic energy being relatively independent of the particle relaxation time. Viscous dissipation in the fluid decreases with increased loading and is larger for particles with smaller relaxation times. Fluid energy spectra show that there is a non-uniform distortion of the turbulence with a relative increase in small-scale energy. The non-uniform distortion significantly affects the transport of the dissipation rate, with the production and destruction of dissipation exhibiting completely different behaviors. The spectrum of the fluid-particle energy exchange rate shows that the fluid drags particles at low wavenumbers while the converse is true at high wavenumbers for small particles. A spectral analysis shows that the increase of the high wavenumber portion of the fluid energy spectrum can be attributed to transfer of the fluid-particle covariance by the fluid turbulence. This in turn explains the relative increase of small-scale energy caused by small particles observed in the present simulations as well as those of others.
FTIR, FT-RAMAN, NMR, spectra, normal co-ordinate analysis, NBO, NLO and DFT calculation of N,N-diethyl-4-methylpiperazine-1-carboxamide molecule.

PubMed

Muthu, S; Elamurugu Porchelvi, E

2013-11-01

The Fourier Transform Infrared (FT-IR) and FT-Raman of N,N-diethyl-4-methylpiperazine-1-carboxamide (NND4MC) have been recorded and analyzed. The structure of the compound was optimized and the structural characteristics were determined by density functional theory (DFT) using B3LYP method with 6-31G(d,p) and 6-311G(d,p) basis sets. The difference between the observed and scaled wavenumber values of most of the fundamentals is very small. The theoretically predicted FT-IR and FT-Raman spectra of the title molecule have been constructed. The detailed interpretation of the vibrational spectra has been carried out with aid of normal coordinate analysis (NCA) following the scaled quantum mechanical force field methodology. Stability of the molecule arising from hyperconjugative interactions and charge delocalization has been analyzed using natural bond orbital (NBO) analysis. The results show that electron density (ED) in the σ(*) and π(*) antibonding orbitals and second order delocalization energies (E2) confirm the occurrence of intramolecular charge transfer (ICT) within the molecule. The electronic dipole moment (μD) and the first hyperpolarizability (βtot) values of the investigated molecule were computed using Density Functional Theory (DFT/B3LYP) with 6-31G(d,p) and 6-311G(d,p) basis sets. The calculated results also show that the NND4MC molecule may have microscopy nonlinear optical (NLO) behavior with non zero values. Mulliken atomic charges of NND4MC were calculated. The (13)C nuclear magnetic resonance (NMR) chemical shifts of the molecule were calculated by the gauge independent atomic orbital (GIAO) method and compared with experimental results. The UV-Vis spectrum of the compound was recorded. The theoretical electronic absorption spectra have been calculated by using CIS, TD-DFT methods. A study on the electronic properties, such as HOMO and LUMO energies, molecular electrostatic potential (MEP) were also performed. Copyright © 2013 Elsevier B.V. All rights reserved.

Pressure-induced emergence of unusually high-frequency transverse excitations in a liquid alkali metal: Evidence of two types of collective excitations contributing to the transverse dynamics at high pressures

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bryk, Taras; Lviv Polytechnic National University, 12 S. Bandera Street, UA-79013 Lviv; Ruocco, G.

Unlike phonons in crystals, the collective excitations in liquids cannot be treated as propagation of harmonic displacements of atoms around stable local energy minima. The viscoelasticity of liquids, reflected in transition from the adiabatic to elastic high-frequency speed of sound and in absence of the long-wavelength transverse excitations, results in dispersions of longitudinal (L) and transverse (T) collective excitations essentially different from the typical phonon ones. Practically, nothing is known about the effect of high pressure on the dispersion of collective excitations in liquids, which causes strong changes in liquid structure. Here dispersions of L and T collective excitations inmore » liquid Li in the range of pressures up to 186 GPa were studied by ab initio simulations. Two methodologies for dispersion calculations were used: direct estimation from the peak positions of the L/T current spectral functions and simulation-based calculations of wavenumber-dependent collective eigenmodes. It is found that at ambient pressure, the longitudinal and transverse dynamics are well separated, while at high pressures, the transverse current spectral functions, density of vibrational states, and dispersions of collective excitations yield evidence of two types of propagating modes that contribute strongly to transverse dynamics. Emergence of the unusually high-frequency transverse modes gives evidence of the breakdown of a regular viscoelastic theory of transverse dynamics, which is based on coupling of a single transverse propagating mode with shear relaxation. The explanation of the observed high-frequency shift above the viscoelastic value is given by the presence of another branch of collective excitations. With the pressure increasing, coupling between the two types of collective excitations is rationalized within a proposed extended viscoelastic model of transverse dynamics.« less
Molecular structure, vibrational spectral assignments (FT-IR and FT-RAMAN), NMR, NBO, HOMO-LUMO and NLO properties of O-methoxybenzaldehyde based on DFT calculations

NASA Astrophysics Data System (ADS)

Vennila, P.; Govindaraju, M.; Venkatesh, G.; Kamal, C.

2016-05-01

Fourier transform - Infra red (FT-IR) and Fourier transform - Raman (FT-Raman) spectroscopic techniques have been carried out to analyze O-methoxy benzaldehyde (OMB) molecule. The fundamental vibrational frequencies and intensity of vibrational bands were evaluated using density functional theory (DFT). The vibrational analysis of stable isomer of OMB has been carried out by FT-IR and FT-Raman in combination with theoretical method simultaneously. The first-order hyperpolarizability and the anisotropy polarizability invariant were computed by DFT method. The atomic charges, hardness, softness, ionization potential, electronegativity, HOMO-LUMO energies, and electrophilicity index have been calculated. The 13C and 1H Nuclear magnetic resonance (NMR) have also been obtained by GIAO method. Molecular electronic potential (MEP) has been calculated by the DFT calculation method. Electronic excitation energies, oscillator strength and excited states characteristics were computed by the closed-shell singlet calculation method.
Vibrational studies of Thyroxine hormone: Comparative study with quantum chemical calculations

NASA Astrophysics Data System (ADS)

Borah, Mukunda Madhab; Devi, Th. Gomti

2017-11-01

The FTIR and Raman techniques have been used to record spectra of Thyroxine. The stable geometrical parameters and vibrational wave numbers were calculated based on potential energy distribution (PED) using vibrational energy distribution analysis (VEDA) program. The vibrational energies are assigned to monomer, chain dimer and cyclic dimers of this molecule using the basis set B3LYP/LANL2DZ. The computational scaled frequencies are in good agreements with the experimental results. The study is extended to calculate the HOMO-LUMO energy gap, Molecular Electrostatic Potential (MEP) surface, hardness (η), chemical potential (μ), Global electrophilicity index (ω) and different thermo dynamical properties of Thyroxine in different states. The calculated HOMO-LUMO energies show the charge transfer occurs within the molecule. The calculated Natural bond orbital (NBO) analysis confirms the presence of intra-molecular charge transfer as well as the hydrogen bonding interaction.
Numerical Calculation Method for Prediction of Ground-borne Vibration near Subway Tunnel

NASA Astrophysics Data System (ADS)

Tsuno, Kiwamu; Furuta, Masaru; Abe, Kazuhisa

This paper describes the development of prediction method for ground-borne vibration from railway tunnels. Field measurement was carried out both in a subway shield tunnel, in the ground and on the ground surface. The generated vibration in the tunnel was calculated by means of the train/track/tunnel interaction model and was compared with the measurement results. On the other hand, wave propagation in the ground was calculated utilizing the empirical model, which was proposed based on the relationship between frequency and material damping coefficient α in order to predict the attenuation in the ground in consideration of frequency characteristics. Numerical calculation using 2-dimensinal FE analysis was also carried out in this research. The comparison between calculated and measured results shows that the prediction method including the model for train/track/tunnel interaction and that for wave propagation is applicable to the prediction of train-induced vibration propagated from railway tunnel.
A semi-analytical beam model for the vibration of railway tracks

NASA Astrophysics Data System (ADS)

Kostovasilis, D.; Thompson, D. J.; Hussein, M. F. M.

2017-04-01

The high frequency dynamic behaviour of railway tracks, in both vertical and lateral directions, strongly affects the generation of rolling noise as well as other phenomena such as rail corrugation. An improved semi-analytical model of a beam on an elastic foundation is introduced that accounts for the coupling of the vertical and lateral vibration. The model includes the effects of cross-section asymmetry, shear deformation, rotational inertia and restrained warping. Consideration is given to the fact that the loads at the rail head, as well as those exerted by the railpads at the rail foot, may not act through the centroid of the section. The response is evaluated for a harmonic load and the solution is obtained in the wavenumber domain. Results are presented as dispersion curves for free and supported rails and are validated with the aid of a Finite Element (FE) and a waveguide finite element (WFE) model. Closed form expressions are derived for the forced response, and validated against the WFE model. Track mobilities and decay rates are presented to assess the potential implications for rolling noise and the influence of the various sources of vertical-lateral coupling. Comparison is also made with measured data. Overall, the model presented performs very well, especially for the lateral vibration, although it does not contain the high frequency cross-section deformation modes. The most significant effects on the response are shown to be the inclusion of torsion and foundation eccentricity, which mainly affect the lateral response.
Structural, vibrational and luminescence properties of the (1−x)CaWO{sub 4}−xCdWO{sub 4} system

DOE Office of Scientific and Technical Information (OSTI.GOV)

Taoufyq, A.; Laboratoire Matériaux et Environnement LME, Faculté des Sciences, Université Ibn Zohr, BP 8106, Cité Dakhla, Agadir, Maroc; CEA/DEN, Département d’Études des Réacteurs, Laboratoire Dosimétrie Capteurs Instrumentation, CEA Cadarache, 13108, Saint-Paul-lez-Durance

2014-11-15

In the present work, we investigate the structural, microstructural, vibrational and luminescence properties of the system (1−x)CaWO{sub 4}−xCdWO{sub 4} with x ranging between 0 and 1. Polycrystalline samples were elaborated using a coprecipitation technique followed by thermal treatment at 1000 °C. The samples were then characterized using X-ray diffraction, scanning electron microscopy, Raman spectroscopy and luminescence analyses. X-ray diffraction profile analyses using Rietveld method showed that two kinds of solid solutions Ca{sub 1−x}Cd{sub x}WO{sub 4} having scheelite and wolframite structures, with respectively tetragonal and monoclinic crystal cells, were observed, with a biphasic system for compositions x=0.6 and 0.7. The scanningmore » electron microscopy experiments showed a complex evolution of morphologies and crystallite sizes as x increased. The vibration modes of Raman spectra were characteristic of composition-dependent disordered solid solutions with decreasing wavenumbers as x increased. Luminescence experiments were performed under UV-laser light irradiation. The energies of emission bands increased linearly with cadmium composition x. The integrated intensity of luminescence reached a maximum value for the substituted wolframite phase with composition x=0.8. - Graphical abstract: Luminescence on UV excitation (364.5 nm) of (1−x)CaWO{sub 4−x}CdWO{sub 4} system, elaborated from coprecipitation technique at 1000 °C, with 0« less
DOE Office of Scientific and Technical Information (OSTI.GOV)

Zheng, Renhui; Sun, Yuanyuan; Song, Kai

Recent experimental studies have shown that the vibrational dynamics of free OH groups at the water-air interface is significantly different from that in bulk water. In this work, by performing molecular dynamics simulations and mixed quantum/classical calculations, we investigate different vibrational energy transfer pathways of free OH groups at the water-air interface. The calculated intramolecular vibrational energy transfer rate constant and the free OH bond reorientation time scale agree well with the experiment. It is also found that, due to the small intermolecular vibrational couplings, the intermolecular vibrational energy transfer pathway that is very important in bulk water plays amore » much less significant role in the vibrational energy relaxation of the free OH groups at the water-air interface.« less
Enhancement to Non-Contacting Stress Measurement of Blade Vibration Frequency

NASA Technical Reports Server (NTRS)

Platt, Michael; Jagodnik, John

2011-01-01

A system for turbo machinery blade vibration has been developed that combines time-of-arrival sensors for blade vibration amplitude measurement and radar sensors for vibration frequency and mode identification. The enabling technology for this continuous blade monitoring system is the radar sensor, which provides a continuous time series of blade displacement over a portion of a revolution. This allows the data reduction algorithms to directly calculate the blade vibration frequency and to correctly identify the active modes of vibration. The work in this project represents a significant enhancement in the mode identification and stress calculation accuracy in non-contacting stress measurement system (NSMS) technology when compared to time-of-arrival measurements alone.
Temperature dependence of the intensity of the vibration-rotational absorption band ν2 of H2O trapped in an argon matrix

NASA Astrophysics Data System (ADS)

Pitsevich, G.; Doroshenko, I.; Malevich, A..; Shalamberidze, E.; Sapeshko, V.; Pogorelov, V.; Pettersson, L. G. M.

2017-02-01

Using two sets of effective rotational constants for the ground (000) and the excited bending (010) vibrational states the calculation of frequencies and intensities of vibration-rotational transitions for J″ = 0 - 2; and J‧ = 0 - 3; was carried out in frame of the model of a rigid asymmetric top for temperatures from 0 to 40 K. The calculation of the intensities of vibration-rotational absorption bands of H2O in an Ar matrix was carried out both for thermodynamic equilibrium and for the case of non-equilibrium population of para- and ortho-states. For the analysis of possible interaction of vibration-rotational and translational motions of a water molecule in an Ar matrix by 3D Schrödinger equation solving using discrete variable representation (DVR) method, calculations of translational frequencies of H2O in a cage formed after one argon atom deleting were carried out. The results of theoretical calculations were compared to experimental data taken from literature.
A study of vibrating nanotubes with additional adsorbed masses

NASA Astrophysics Data System (ADS)

Adler, Joan; Adler, Omri

2017-11-01

We describe calculations of the electronic density surrounding strained nanotubes. These are then used to estimate the nanotube wall width. This width is an essential parameter for the analysis of the nanotube vibrations. By studying the effect of additional adsorbed molecules on the nanotubes’ vibrations and their frequency changes we can deduce the molecules’ mass. Our calculations show that the strain does not greatly affect the nanotube width, but the vibrations change sufficiently for the mass to be detected.
Effective representation of amide III, II, I, and A modes on local vibrational modes: Analysis of ab initio quantum calculation results.

PubMed

Hahn, Seungsoo

2016-10-28

The Hamiltonian matrix for the first excited vibrational states of a protein can be effectively represented by local vibrational modes constituting amide III, II, I, and A modes to simulate various vibrational spectra. Methods for obtaining the Hamiltonian matrix from ab initio quantum calculation results are discussed, where the methods consist of three steps: selection of local vibrational mode coordinates, calculation of a reduced Hessian matrix, and extraction of the Hamiltonian matrix from the Hessian matrix. We introduce several methods for each step. The methods were assessed based on the density functional theory calculation results of 24 oligopeptides with four different peptide lengths and six different secondary structures. The completeness of a Hamiltonian matrix represented in the reduced local mode space is improved by adopting a specific atom group for each amide mode and reducing the effect of ignored local modes. The calculation results are also compared to previous models using C=O stretching vibration and transition dipole couplings. We found that local electric transition dipole moments of the amide modes are mainly bound on the local peptide planes. Their direction and magnitude are well conserved except amide A modes, which show large variation. Contrary to amide I modes, the vibrational coupling constants of amide III, II, and A modes obtained by analysis of a dipeptide are not transferable to oligopeptides with the same secondary conformation because coupling constants are affected by the surrounding atomic environment.
Bent crystal spectrometer for both frequency and wavenumber resolved x-ray scattering at a seeded free-electron laser.

PubMed

Zastrau, Ulf; Fletcher, Luke B; Förster, Eckhart; Galtier, Eric Ch; Gamboa, Eliseo; Glenzer, Siegfried H; Heimann, Philipp; Marschner, Heike; Nagler, Bob; Schropp, Andreas; Wehrhan, Ortrud; Lee, Hae Ja

2014-09-01

We present a cylindrically curved GaAs x-ray spectrometer with energy resolution ΔE/E = 1.1 × 10(-4) and wave-number resolution of Δk/k = 3 × 10(-3), allowing plasmon scattering at the resolution limits of the Linac Coherent Light Source (LCLS) x-ray free-electron laser. It spans scattering wavenumbers of 3.6 to 5.2/Å in 100 separate bins, with only 0.34% wavenumber blurring. The dispersion of 0.418 eV/13.5 μm agrees with predictions within 1.3%. The reflection homogeneity over the entire wavenumber range was measured and used to normalize the amplitude of scattering spectra. The proposed spectrometer is superior to a mosaic highly annealed pyrolytic graphite spectrometer when the energy resolution needs to be comparable to the LCLS seeded bandwidth of 1 eV and a significant range of wavenumbers must be covered in one exposure.
Broadband ground motion simulation using a paralleled hybrid approach of Frequency Wavenumber and Finite Difference method

NASA Astrophysics Data System (ADS)

Chen, M.; Wei, S.

2016-12-01

The serious damage of Mexico City caused by the 1985 Michoacan earthquake 400 km away indicates that urban areas may be affected by remote earthquakes. To asses earthquake risk of urban areas imposed by distant earthquakes, we developed a hybrid Frequency Wavenumber (FK) and Finite Difference (FD) code implemented with MPI, since the computation of seismic wave propagation from a distant earthquake using a single numerical method (e.g. Finite Difference, Finite Element or Spectral Element) is very expensive. In our approach, we compute the incident wave field (ud) at the boundaries of the excitation box, which surrounding the local structure, using a paralleled FK method (Zhu and Rivera, 2002), and compute the total wave field (u) within the excitation box using a parallelled 2D FD method. We apply perfectly matched layer (PML) absorbing condition to the diffracted wave field (u-ud). Compared to previous Generalized Ray Theory and Finite Difference (Wen and Helmberger, 1998), Frequency Wavenumber and Spectral Element (Tong et al., 2014), and Direct Solution Method and Spectral Element hybrid method (Monteiller et al., 2013), our absorbing boundary condition dramatically suppress the numerical noise. The MPI implementation of our method can greatly speed up the calculation. Besides, our hybrid method also has a potential use in high resolution array imaging similar to Tong et al. (2014).
Simulation of IR and Raman spectra of p-hydroxyanisole and p-nitroanisole based on scaled DFT force fields and their vibrational assignments.

PubMed

Krishnakumar, V; Prabavathi, N

2009-09-15

This work deals with the vibrational spectroscopy of p-hydroxyanisole (PHA) and p-nitroanisole (PNA) by means of quantum chemical calculations. The mid and far FT-IR and FT-Raman spectra were recorded in the condensed state. The fundamental vibrational frequencies and intensity of vibrational bands were evaluated using density functional theory (DFT) with the standard B3LYP/6-31G* method and basis set combination and were scaled using various scale factors which yield a good agreement between observed and calculated frequencies. The vibrational spectra were interpreted with the aid of normal coordinate analysis based on scaled density functional force field. The results of the calculations were applied to simulate infrared and Raman spectra of the title compounds, which showed excellent agreement with the observed spectra.
Accurate ab initio dipole moment surfaces of ozone: First principle intensity predictions for rotationally resolved spectra in a large range of overtone and combination bands.

PubMed

Tyuterev, Vladimir G; Kochanov, Roman V; Tashkun, Sergey A

2017-02-14

Ab initio dipole moment surfaces (DMSs) of the ozone molecule are computed using the MRCI-SD method with AVQZ, AV5Z, and VQZ-F12 basis sets on a dense grid of about 1950 geometrical configurations. The analytical DMS representation used for the fit of ab initio points provides better behavior for large nuclear displacements than that of previous studies. Various DMS models were derived and tested. Vibration-rotation line intensities of 16 O 3 were calculated from these ab initio surfaces by the variational method using two different potential functions determined in our previous works. For the first time, a very good agreement of first principle calculations with the experiment was obtained for the line-by-line intensities in rotationally resolved ozone spectra in a large far- and mid-infrared range. This includes high overtone and combination bands up to ΔV = 6. A particular challenge was a correct description of the B-type bands (even ΔV 3 values) that represented major difficulties for the previous ab initio investigations and for the empirical spectroscopic models. The major patterns of various B-type bands were correctly described without empirically adjusted dipole moment parameters. For the 10 μm range, which is of key importance for the atmospheric ozone retrievals, our ab initio intensity results are within the experimental error margins. The theoretical values for the strongest lines of the ν 3 band lie in general between two successive versions of HITRAN (HIgh-resolution molecular TRANsmission) empirical database that corresponded to most extended available sets of observations. The overall qualitative agreement in a large wavenumber range for rotationally resolved cold and hot ozone bands up to about 6000 cm -1 is achieved here for the first time. These calculations reveal that several weak bands are yet missing from available spectroscopic databases.
Surface-enhanced Raman spectroscopy of genomic DNA from in vitro grown tomato (Lycopersicon esculentum Mill.) cultivars before and after plant cryopreservation.

PubMed

Muntean, Cristina M; Leopold, Nicolae; Tripon, Carmen; Coste, Ana; Halmagyi, Adela

2015-06-05

In this work the surface-enhanced Raman scattering (SERS) spectra of five genomic DNAs from non-cryopreserved control tomato plants (Lycopersicon esculentum Mill. cultivars Siriana, Darsirius, Kristin, Pontica and Capriciu) respectively, have been analyzed in the wavenumber range 400-1800 cm(-1). Structural changes induced in genomic DNAs upon cryopreservation were discussed in detail for four of the above mentioned tomato cultivars. The surface-enhanced Raman vibrational modes for each of these cases, spectroscopic band assignments and structural interpretations of genomic DNAs are reported. We have found, that DNA isolated from Siriana cultivar leaf tissues suffers the weakest structural changes upon cryogenic storage of tomato shoot apices. On the contrary, genomic DNA extracted from Pontica cultivar is the most responsive system to cryopreservation process. Particularly, both C2'-endo-anti and C3'-endo-anti conformations have been detected. As a general observation, the wavenumber range 1511-1652 cm(-1), being due to dA, dG and dT residues seems to be influenced by cryopreservation process. These changes could reflect unstacking of DNA bases. However, not significant structural changes of genomic DNAs from Siriana, Darsirius and Kristin have been found upon cryopreservation process of tomato cultivars. Based on this work, specific plant DNA-ligand interactions or accurate local structure of DNA in the proximity of a metallic surface, might be further investigated using surface-enhanced Raman spectroscopy. Copyright © 2015 Elsevier B.V. All rights reserved.
Surface-enhanced Raman spectroscopy of genomic DNA from in vitro grown tomato (Lycopersicon esculentum Mill.) cultivars before and after plant cryopreservation

NASA Astrophysics Data System (ADS)

Muntean, Cristina M.; Leopold, Nicolae; Tripon, Carmen; Coste, Ana; Halmagyi, Adela

2015-06-01

In this work the surface-enhanced Raman scattering (SERS) spectra of five genomic DNAs from non-cryopreserved control tomato plants (Lycopersicon esculentum Mill. cultivars Siriana, Darsirius, Kristin, Pontica and Capriciu) respectively, have been analyzed in the wavenumber range 400-1800 cm-1. Structural changes induced in genomic DNAs upon cryopreservation were discussed in detail for four of the above mentioned tomato cultivars. The surface-enhanced Raman vibrational modes for each of these cases, spectroscopic band assignments and structural interpretations of genomic DNAs are reported. We have found, that DNA isolated from Siriana cultivar leaf tissues suffers the weakest structural changes upon cryogenic storage of tomato shoot apices. On the contrary, genomic DNA extracted from Pontica cultivar is the most responsive system to cryopreservation process. Particularly, both C2‧-endo-anti and C3'-endo-anti conformations have been detected. As a general observation, the wavenumber range 1511-1652 cm-1, being due to dA, dG and dT residues seems to be influenced by cryopreservation process. These changes could reflect unstacking of DNA bases. However, not significant structural changes of genomic DNAs from Siriana, Darsirius and Kristin have been found upon cryopreservation process of tomato cultivars. Based on this work, specific plant DNA-ligand interactions or accurate local structure of DNA in the proximity of a metallic surface, might be further investigated using surface-enhanced Raman spectroscopy.
The Impact of Complex Forcing on the Viscous Torsional Vibration Damper's Work in the Crankshaft of the Rotating Combustion Engine

NASA Astrophysics Data System (ADS)

Jagiełowicz-Ryznar, C.

2016-12-01

The numerical calculations results of torsional vibration of the multi-cylinder crankshaft in the serial combustion engine (MC), including a viscous damper (VD), at complex forcing, were shown. In fact, in the MC case the crankshaft rotation forcings spectrum is the sum of harmonic forcing whose amplitude can be compared with the amplitude of the 1st harmonic. A significant impact, in the engine operational velocity, on the vibration damping process of MC, may be the amplitude of the 2nd harmonic of a forcing moment. The calculations results of MC vibration, depending on the amplitude of the 2nd harmonic of the forcing moment, for the first form of the torsional vibration, were shown. Higher forms of torsional vibrations have no practical significance. The calculations assume the optimum damping coefficient VD, when the simple harmonic forcing is equal to the base critical velocity of the MC crankshaft.
Structural, vibrational spectroscopic and quantum chemical studies on indole-3-carboxaldehyde

NASA Astrophysics Data System (ADS)

Premkumar, R.; Asath, R. Mohamed; Mathavan, T.; Benial, A. Milton Franklin

2017-05-01

The potential energy surface (PES) scan was performed for indole-3-carboxaldehyde (ICA) and the most stable optimized conformer was predicted using DFT/B3LYP method with 6-31G basis set. The vibrational frequencies of ICA were theoretically calculated by the DFT/B3LYP method with cc-pVTZ basis set using Gaussian 09 program. The vibrational spectra were experimentally recorded by Fourier transform-infrared (FT-IR) and Fourier transform-Raman spectrometer (FT-Raman). The computed vibrational frequencies were scaled by scaling factors to yield a good agreement with observed vibrational frequencies. The theoretically calculated and experimentally observed vibrational frequencies were assigned on the basis of potential energy distribution (PED) calculation using VEDA 4.0 program. The molecular interaction, stability and intramolecular charge transfer of ICA were studied using frontier molecular orbitals (FMOs) analysis and Mulliken atomic charge distribution shows the distribution of the atomic charges. The presence of intramolecular charge transfer was studied using natural bond orbital (NBO) analysis.
Vector Analysis of Ionic Collision on CaCO3 Precipitation Based on Vibration Time History

NASA Astrophysics Data System (ADS)

Mangestiyono, W.; Muryanto, S.; Jamari, J.; Bayuseno, A. P.

2017-05-01

Vibration effects on the piping system can result from the internal factor of fluid or the external factor of the mechanical equipment operation. As the pipe vibrated, the precipitation process of CaCO3 on the inner pipe could be affected. In the previous research, the effect of vibration on CaCO3 precipitation in piping system was clearly verified. This increased the deposition rate and decreased the induction time. However, the mechanism of vibration control in CaCO3 precipitation process as the presence of vibration has not been recognized yet. In the present research, the mechanism of vibration affecting the CaCO3 precipitation was investigated through vector analysis of ionic collision. The ionic vector force was calculated based on the amount of the activation energy and the vibration force was calculated based on the vibration sensor data. The vector resultant of ionic collision based on the vibration time history was analyzed to prove that vibration brings ionic collision randomly to the planar horizontal direction and its collision model was suspected as the cause of the increasing deposition rate.

Ab initio-informed maximum entropy modeling of rovibrational relaxation and state-specific dissociation with application to the O2 + O system

NASA Astrophysics Data System (ADS)

Kulakhmetov, Marat; Gallis, Michael; Alexeenko, Alina

2016-05-01

Quasi-classical trajectory (QCT) calculations are used to study state-specific ro-vibrational energy exchange and dissociation in the O2 + O system. Atom-diatom collisions with energy between 0.1 and 20 eV are calculated with a double many body expansion potential energy surface by Varandas and Pais [Mol. Phys. 65, 843 (1988)]. Inelastic collisions favor mono-quantum vibrational transitions at translational energies above 1.3 eV although multi-quantum transitions are also important. Post-collision vibrational favoring decreases first exponentially and then linearly as Δv increases. Vibrationally elastic collisions (Δv = 0) favor small ΔJ transitions while vibrationally inelastic collisions have equilibrium post-collision rotational distributions. Dissociation exhibits both vibrational and rotational favoring. New vibrational-translational (VT), vibrational-rotational-translational (VRT) energy exchange, and dissociation models are developed based on QCT observations and maximum entropy considerations. Full set of parameters for state-to-state modeling of oxygen is presented. The VT energy exchange model describes 22 000 state-to-state vibrational cross sections using 11 parameters and reproduces vibrational relaxation rates within 30% in the 2500-20 000 K temperature range. The VRT model captures 80 × 106 state-to-state ro-vibrational cross sections using 19 parameters and reproduces vibrational relaxation rates within 60% in the 5000-15 000 K temperature range. The developed dissociation model reproduces state-specific and equilibrium dissociation rates within 25% using just 48 parameters. The maximum entropy framework makes it feasible to upscale ab initio simulation to full nonequilibrium flow calculations.
Improvement of depth resolution in depth-resolved wavenumber-scanning interferometry using wavenumber-domain least-squares algorithm: comparison and experiment.

PubMed

Bai, Yulei; Jia, Quanjie; Zhang, Yun; Huang, Qiquan; Yang, Qiyu; Ye, Shuangli; He, Zhaoshui; Zhou, Yanzhou; Xie, Shengli

2016-05-01

It is important to improve the depth resolution in depth-resolved wavenumber-scanning interferometry (DRWSI) owing to the limited range of wavenumber scanning. In this work, a new nonlinear iterative least-squares algorithm called the wavenumber-domain least-squares algorithm (WLSA) is proposed for evaluating the phase of DRWSI. The simulated and experimental results of the Fourier transform (FT), complex-number least-squares algorithm (CNLSA), eigenvalue-decomposition and least-squares algorithm (EDLSA), and WLSA were compared and analyzed. According to the results, the WLSA is less dependent on the initial values, and the depth resolution δz is approximately changed from δz to δz/6. Thus, the WLSA exhibits a better performance than the FT, CNLSA, and EDLSA.
Analytic calculations of anharmonic infrared and Raman vibrational spectra

PubMed Central

Louant, Orian; Ruud, Kenneth

2016-01-01

Using a recently developed recursive scheme for the calculation of high-order geometric derivatives of frequency-dependent molecular properties [Ringholm et al., J. Comp. Chem., 2014, 35, 622], we present the first analytic calculations of anharmonic infrared (IR) and Raman spectra including anharmonicity both in the vibrational frequencies and in the IR and Raman intensities. In the case of anharmonic corrections to the Raman intensities, this involves the calculation of fifth-order energy derivatives—that is, the third-order geometric derivatives of the frequency-dependent polarizability. The approach is applicable to both Hartree–Fock and Kohn–Sham density functional theory. Using generalized vibrational perturbation theory to second order, we have calculated the anharmonic infrared and Raman spectra of the non- and partially deuterated isotopomers of nitromethane, where the inclusion of anharmonic effects introduces combination and overtone bands that are observed in the experimental spectra. For the major features of the spectra, the inclusion of anharmonicities in the calculation of the vibrational frequencies is more important than anharmonic effects in the calculated infrared and Raman intensities. Using methanimine as a trial system, we demonstrate that the analytic approach avoids errors in the calculated spectra that may arise if numerical differentiation schemes are used. PMID:26784673
Compact Active Vibration Control System for a Flexible Panel

NASA Technical Reports Server (NTRS)

Schiller, Noah H. (Inventor); Cabell, Randolph H. (Inventor); Perey, Daniel F. (Inventor)

2014-01-01

A diamond-shaped actuator for a flexible panel has an inter-digitated electrode (IDE) and a piezoelectric wafer portion positioned therebetween. The IDE and/or the wafer portion are diamond-shaped. Point sensors are positioned with respect to the actuator and measure vibration. The actuator generates and transmits a cancelling force to the panel in response to an output signal from a controller, which is calculated using a signal describing the vibration. A method for controlling vibration in a flexible panel includes connecting a diamond-shaped actuator to the flexible panel, and then connecting a point sensor to each actuator. Vibration is measured via the point sensor. The controller calculates a proportional output voltage signal from the measured vibration, and transmits the output signal to the actuator to substantially cancel the vibration in proximity to each actuator.
Effects of vibration and shock on the performance of gas-bearing space-power Brayton cycle turbomachinery. 2: Sinusoidal and random vibration

NASA Technical Reports Server (NTRS)

Tessarzik, J. M.; Chiang, T.; Badgley, R. H.

1973-01-01

The vibration response of a gas-bearing rotor-support system was analyzed experimentally documented for sinusoidal and random vibration environments. The NASA Brayton Rotating Unit (BRU), 36,000 rpm; 10 KWe turbogenerator; was subjected in the laboratory to sinusoidal and random vibrations to evaluate the capability of the BRU to (1) survive the vibration levels expected to be encountered during periods of nonoperation and (2) operate satisfactorily (that is, without detrimental bearing surface contacts) at the vibration levels expected during normal BRU operation. Response power spectral density was calculated for specified input random excitation, with particular emphasis upon the dynamic motions of the thrust bearing runner and stator. A three-mass model with nonlinear representation of the engine isolator mounts was used to calculate axial rotor-bearing shock response.
DFT simulations and vibrational spectra of 2-amino-2-methyl-1,3-propanediol

NASA Astrophysics Data System (ADS)

Renuga Devi, T. S.; Sharmi kumar, J.; Ramkumaar, G. R.

2014-12-01

The FTIR and FT-Raman spectra of 2-amino-2-methyl-1,3-propanediol were recorded in the regions 4000-400 cm-1 and 4000-50 cm-1 respectively. The structural and spectroscopic data of the molecule in the ground state were calculated using Hartee-Fock and density functional method (B3LYP) with the augmented-correlation consistent-polarized valence double zeta (aug-cc-pVDZ) basis set. The most stable conformer was optimized and the structural and vibrational parameters were determined based on this. The complete assignments were performed on the basis of the Potential Energy Distribution (PED) of the vibrational modes, calculated using Vibrational Energy Distribution Analysis (VEDA) 4 program. With the observed FTIR and FT-Raman data, a complete vibrational assignment and analysis of the fundamental modes of the compound were carried out. Thermodynamic properties and Mulliken charges were calculated using both Hartee-Fock and density functional method using the aug-cc-pVDZ basis set and compared. The calculated HOMO-LUMO energy gap revealed that charge transfer occurs within the molecule. 1H and 13C NMR chemical shifts of the molecule were calculated using Gauge-Independent Atomic Orbital (GIAO) method and were compared with experimental results.
ab initio calculation of the rate of vibrational relaxation and thermal dissociation of hydrogen by helium at high temperatures

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dove, J.E.; Raynor, S.

The master equation for the thermal dissociation of para-H/sub 2/ infinitely dilute in He, was solved for temperatures of 1000 to 10,000/sup 0/K. Transition probabilities, used in the master equation, were obtained, in the case of energy transfer transitions, from distorted wave and quasi-classical trajectory calculations and, for dissociative processes, from trajectory calculations alone. An ab initio potential was used. From the solution, values of the dissociation rate constant, vibrational relaxation times, and incubation times for dissociation and vibrational relaxation were calculated. The sensitivity of the calculated results to variations in the transition probabilities was examined. Vibrational relaxation is mostmore » sensitive to simultaneous transitions in vibration and rotation (VRT processes); pure rotational (RT) transitions also have a substantial effect. Dissociation is most strongly affected by RT processes, but changes in VRT and groups of dissociative transitions also have a significant effect. However complete suppression of all dissociative transitions except those from levels immediately next to the continuum lowers the dissociation rates only by a factor of about 2. The location of the dissociation ''bottleneck'' is discussed. 5 figures, 3 tables.« less
VizieR Online Data Catalog: ExoMol line lists. XXIV. SiH (Yurchenko+, 2018)

NASA Astrophysics Data System (ADS)

Yurchenko, S. N.; Sinden, F.; Lodi, L.; Hill, C.; Gorman, M. N.; Tennyson, J.

2017-11-01

The data for each isotopologue are in two parts. The first, s_*.dat contain lists of rovibronic states. Each state is labelled with the total angular momentum, state degeneracy, life time, Zeeman Lande-g factor, total (+/-) and e/f parities, vibrational quantum number, projection of the electronic, spin and total angular momenta. Each state has a unique number, which is the number of the row in which it appears in the file. This number is the means by which the state is related to the second part of the data system, the transitions files. The transition files t_*.dat contain four columns: the reference number in the energy file of the upper state; that of the lower state; the Einstein A coefficient of the transition; the transition wavenumber. (8 data files).
A computationally efficient software application for calculating vibration from underground railways

NASA Astrophysics Data System (ADS)

Hussein, M. F. M.; Hunt, H. E. M.

2009-08-01

The PiP model is a software application with a user-friendly interface for calculating vibration from underground railways. This paper reports about the software with a focus on its latest version and the plans for future developments. The software calculates the Power Spectral Density of vibration due to a moving train on floating-slab track with track irregularity described by typical values of spectra for tracks with good, average and bad conditions. The latest version accounts for a tunnel embedded in a half space by employing a toolbox developed at K.U. Leuven which calculates Green's functions for a multi-layered half-space.
Properties of Longitudinal Electromagnetic Oscillations in Metals and Their Excitation at Planar and Spherical Surfaces.

PubMed

Datsyuk, Vitaly V; Pavlyniuk, Oleg R

2017-12-01

The common definition of the spatially dispersive permittivity is revised. The response of the degenerate electron gas on an electric field satisfying the vector Helmholtz equation is found with a solution to the Boltzmann equation. The calculated longitudinal dielectric function coincides with that obtained by Klimontovich and Silin in 1952 and Lindhard in 1954. However, it depends on the square of the wavenumber, a parameter of the vector Helmholtz equation, but not the wave vector of a plane electromagnetic wave. This new concept simplifies simulation of the nonlocal effects, for example, with a generalized Lorents-Mie theory, since no Fourier transforms should be made. The Fresnel coefficients are generalized allowing for excitation of the longitudinal electromagnetic waves. To verify the theory, the extinction spectra for silver and gold nanometer-sized spheres are calculated. For these particles, the generalized Lorents-Mie theory gives the blue shift and broadening of the plasmon resonance which are in excellent agreement with experimental data. In addition, the nonlocal theory explains vanishing of the plasmon resonance observed for gold spheres with diameters less than or equal to 2 nm. The calculations using the Klimontovich-Silin-Lindhard and hydrodynamic dielectric functions for silver are found to give close results at photon energies from 3 to 4 eV. We show that the absolute values of the wavenumbers of the longitudinal waves in solids are much higher than those of the transverse waves.
Properties of Longitudinal Electromagnetic Oscillations in Metals and Their Excitation at Planar and Spherical Surfaces

NASA Astrophysics Data System (ADS)

Datsyuk, Vitaly V.; Pavlyniuk, Oleg R.

2017-08-01

The common definition of the spatially dispersive permittivity is revised. The response of the degenerate electron gas on an electric field satisfying the vector Helmholtz equation is found with a solution to the Boltzmann equation. The calculated longitudinal dielectric function coincides with that obtained by Klimontovich and Silin in 1952 and Lindhard in 1954. However, it depends on the square of the wavenumber, a parameter of the vector Helmholtz equation, but not the wave vector of a plane electromagnetic wave. This new concept simplifies simulation of the nonlocal effects, for example, with a generalized Lorents-Mie theory, since no Fourier transforms should be made. The Fresnel coefficients are generalized allowing for excitation of the longitudinal electromagnetic waves. To verify the theory, the extinction spectra for silver and gold nanometer-sized spheres are calculated. For these particles, the generalized Lorents-Mie theory gives the blue shift and broadening of the plasmon resonance which are in excellent agreement with experimental data. In addition, the nonlocal theory explains vanishing of the plasmon resonance observed for gold spheres with diameters less than or equal to 2 nm. The calculations using the Klimontovich-Silin-Lindhard and hydrodynamic dielectric functions for silver are found to give close results at photon energies from 3 to 4 eV. We show that the absolute values of the wavenumbers of the longitudinal waves in solids are much higher than those of the transverse waves.
Production of vibrationally excited N 2 by electron impact

NASA Astrophysics Data System (ADS)

Campbell, L.; Brunger, M. J.; Cartwright, D. C.; Teubner, P. J. O.

2004-08-01

Energy transfer from electrons to neutral gases and ions is one of the dominant electron cooling processes in the ionosphere, and the role of vibrationally excited N 2 in this is particularly significant. We report here the results from a new calculation of electron energy transfer rates ( Q) for vibrational excitation of N 2, as a function of the electron temperature Te. The present study was motivated by the development of a new cross-section compilation for vibrational excitation processes in N 2 which supercedes those used in the earlier calculations of the electron energy transfer rates. We show that the energy dependence and magnitude of these cross sections, particularly in the region of the well-known 2Π g resonance in N 2, significantly affect the calculated values of Q. A detailed comparison between the current and previous calculated electron energy transfer rates is made and coefficients are provided so that these rates for transitions from level 0 to levels 1-10 can be calculated for electron temperatures less than 6000 K.
Summation-by-Parts operators with minimal dispersion error for coarse grid flow calculations

NASA Astrophysics Data System (ADS)

Linders, Viktor; Kupiainen, Marco; Nordström, Jan

2017-07-01

We present a procedure for constructing Summation-by-Parts operators with minimal dispersion error both near and far from numerical interfaces. Examples of such operators are constructed and compared with a higher order non-optimised Summation-by-Parts operator. Experiments show that the optimised operators are superior for wave propagation and turbulent flows involving large wavenumbers, long solution times and large ranges of resolution scales.
Rayleigh and Wood anomalies in the diffraction of light from a perfectly conducting reflection grating

NASA Astrophysics Data System (ADS)

Maradudin, A. A.; Simonsen, I.; Polanco, J.; Fitzgerald, R. M.

2016-02-01

By means of a modal method we have calculated the angular dependence of the reflectivity and the efficiencies of several other diffracted orders of a perfectly conducting lamellar reflection grating illuminated by p-polarized light. These dependencies display the signatures of Rayleigh and Wood anomalies, usually associated with diffraction from a metallic grating. The Wood anomalies here are caused by the excitation of the surface electromagnetic waves supported by a periodically corrugated perfectly conducting surface, whose dispersion curves in both the nonradiative and radiative regions of the frequency-wavenumber plane are calculated.
A study of the extended-range forecasting problem blocking

NASA Technical Reports Server (NTRS)

Chen, T. C.; Marshall, H. G.; Shukla, J.

1981-01-01

Wavenumber frequency spectral analysis of a 90 day winter (Jan. 15 - April 14) wind field simulated by a climate experiment of the GLAS atmospheric circulation model is made using the space time Fourier analysis which is modified with Tukey's numerical spectral analysis. Computations are also made to examine how the model wave disturbances in the wavenumber frequency domain are maintained by nonlinear interactions. Results are compared with observation. It is found that equatorial easterlies do not show up in this climate experiment at 200 mb. The zonal kinetic energy and momentum transport of stationary waves are too small in the model's Northern Hemisphere. The wavenumber and frequency spectra of the model are generally in good agreement with observation. However, some distinct features of the model's spectra are revealed. The wavenumber spectra of kinetic energy show that the eastward moving waves of low wavenumbers have stronger zonal motion while the eastward moving waves of intermediate wavenumbers have larger meridional motion compared with observation. Furthermore, the eastward moving waves show a band of large spectral value in the medium frequency regime.
Technique to measure wavenumber mismatch between quadratically interacting modes

NASA Astrophysics Data System (ADS)

Hajj, M. R.; Davila, J. B.; Miksad, R. W.; Powers, E. J.

1995-02-01

Nonlinear energy cascade by means of three-wave resonant interactions is a characteristic feature of transitioning and turbulent flows. Resonant wavenumber mismatch between these interacting modes can arise from the dispersive characteristics of the interacting waves and from spectral broadening due to random effects. In this paper, a general technique is presented to estimate the average level of instantaneous wavenumber mismatch, (Delta k) = (k(sub m) - k(sub i) - k(sub j)), between components whose frequencies obey the resonant selection condition, f(sub m) - f(sub i) - f(sub j) = 0. Cross-correlation of the auto-bispectrum is used to quantify the level of mismatch. The concept of bispectrum coupling coherency is introduced to determine the confidence level in the wavenumber mismatch estimates. These techniques are then applied to measure wavenumber mismatch in the transitioning field of a plane wake. The results show that the average of the instantaneous mismatch between the actual interacting modes (k(sub m) - k(sub i) - k(sub j)) is in general not equal to the mismatch between the average wavenumbers of each interacting mode (k(sub m) - (k(sub i)) - (k(sub j)).
Aerodynamic calculations of the Sienna towers buildings complex with respect to human vibrations comfort of their users

NASA Astrophysics Data System (ADS)

Krajewski, Piotr; Flaga, Łukasz; Flaga, Andrzej

2018-01-01

The paper presents aerodynamic calculations of the Sienna Towers high buildings complex in Warsaw using authors mathematical model of the considered issue. Human vibrations comfort criteria were checked according to ISO/6897. Dynamic coefficients used in the calculations were obtained from wind tunnel tests.
Intramolecular hydrogen bonding in N-salicylideneaniline: FT-IR spectrum and quantum chemical calculations

NASA Astrophysics Data System (ADS)

Moosavi-Tekyeh, Zainab; Dastani, Najmeh

2015-12-01

FT-IR and FT-Raman spectra of N-salicylideneaniline (SAn) and its deuterated analogue (D-SAn) are recorded, and the theoretical calculations are performed on their molecular structures and vibrational frequencies. The same calculations are performed for SAn in different solutions using the polarizable conductor continuum model (CPCM) method. Comparisons between the spectra obtained and the corresponding theoretical calculations are used to assign the vibrational frequencies for these compounds. The spectral behavior of SAn upon deuteration is also used to distinguish the positions of OH vibrational frequencies. The hydrogen bond strength of SAn is investigated by applying the atoms-in-molecules (AIM) theory, natural bond orbital (NBO) analysis, and geometry calculations. The harmonic vibrational frequencies of SAn are calculated at B3LYP and X3LYP levels of theory using 6-31G*, 6-311G**, and 6-311++G** basis sets. The AIM results support a medium hydrogen bonding in SAn. The observed νOH/νOD and γOH/γOD for SAn appear at 2940/2122 and 830/589 cm-1, respectively.
Effect of Atmospheric-Pressure Plasma Jet of Neon on 7-Acetoxy-6-(2,3-Dibromopropyl)-4,8-Dimethylcoumarin Molecule

NASA Astrophysics Data System (ADS)

Tanışlı, Murat; Taşal, Erol

2017-06-01

Atmospheric-pressure low-temperature plasma jets and their applications are a topic of great interest in the fields of physics, technology, and medicine. In this study, the used self-made plasma jet is based on a dielectric barrier discharge (DBD) in neon (Ne) with typical processing parameters, such as frequency in the kHz range and voltage in the kV range. The plasma is characterized by optical emission spectroscopy (OES). These types of plasma can be used in various applications such as surface modification, inactivation of microorganisms, and chemical decomposition. This study is concerned with the Fourier transform infrared spectrum (FT-IR) and ultraviolet-visible (UV-vis) absorption spectroscopy of the large 7-acetoxy-6-(2,3-dibromopropyl)-4,8-dimethylcoumarin molecule (abbreviated as 7AC) dissolved in ethanol and methanol solvents and their modification after atmospheric-pressure plasma treatment (APPT) with the DBD. The research is motivated by the significance of this molecule in different fields of application. Also the changes in the structure are recorded. After APPT, the peak corresponding to the carbonyl bond at a wavenumber of 1715 cm-1 disappears in the IR spectrum of the ethanol solution, and when splitting at a wavenumber of 1405 cm-1 is observed, the peak at 1224 cm-1 is found to disappear after plasma is applied. It is seen new peaks at frequencies of 432 and 655 cm-1 are formed. When the same situation is analyzed for the 7AC molecule dissolved in methanol, a new peak is observed at 1634 cm-1. The intensities of the peaks at 3433 and 2075 cm-1 also increase and there is a large change in the wavenumber at 600 cm-1. In the UV spectra, a significant increase in the absorbance of the 7AC molecule dissolved in ethanol is observed after APPT, whereas a small decrease in the absorbance of the 7AC molecule dissolved in methanol is obtained. Owing to the lack of symmetry, many normal bands of vibrations are mixed.
The use of a digital computer for calculation of acoustic fields of complex vibrating structures by the reciprocity principle

NASA Technical Reports Server (NTRS)

Rimskiy-Korsakov, A. V.; Belousov, Y. I.

1973-01-01

A program was compiled for calculating acoustical pressure levels, which might be created by vibrations of complex structures (an assembly of shells and rods), under the influence of a given force, for cases when these fields cannot be measured directly. The acoustical field is determined according to transition frequency and pulse characteristics of the structure in the projection mode. Projection characteristics are equal to the reception characteristics, for vibrating systems in which the reciprocity principle holds true. Characteristics in the receiving mode are calculated on the basis of experimental data on a point pulse space velocity source (input signal) and vibration response of the structure (output signal). The space velocity of a pulse source, set at a point in space r, where it is necessary to calculate the sound field of the structure p(r,t), is determined by measurements of acoustic pressure, created by a point source at a distance R. The vibration response is measured at the point where the forces F and f exciting the system should act.

Computational thermochemistry: Automated generation of scale factors for vibrational frequencies calculated by electronic structure model chemistries

NASA Astrophysics Data System (ADS)

Yu, Haoyu S.; Fiedler, Lucas J.; Alecu, I. M.; Truhlar, Donald G.

2017-01-01

We present a Python program, FREQ, for calculating the optimal scale factors for calculating harmonic vibrational frequencies, fundamental vibrational frequencies, and zero-point vibrational energies from electronic structure calculations. The program utilizes a previously published scale factor optimization model (Alecu et al., 2010) to efficiently obtain all three scale factors from a set of computed vibrational harmonic frequencies. In order to obtain the three scale factors, the user only needs to provide zero-point energies of 15 or 6 selected molecules. If the user has access to the Gaussian 09 or Gaussian 03 program, we provide the option for the user to run the program by entering the keywords for a certain method and basis set in the Gaussian 09 or Gaussian 03 program. Four other Python programs, input.py, input6, pbs.py, and pbs6.py, are also provided for generating Gaussian 09 or Gaussian 03 input and PBS files. The program can also be used with data from any other electronic structure package. A manual of how to use this program is included in the code package.
Molecular geometry and vibrational studies of 3,5-diamino-1,2,4-triazole using quantum chemical calculations and FT-IR and FT-Raman spectroscopies

NASA Astrophysics Data System (ADS)

Guennoun, L.; El jastimi, J.; Guédira, F.; Marakchi, K.; Kabbaj, O. K.; El Hajji, A.; Zaydoun, S.

2011-01-01

The 3,5-diamino-1,2,4-triazole (guanazole) was investigated by vibrational spectroscopy and quantum methods. The solid phase FT-IR and FT-Raman spectra were recorded in the region 4000-400 cm -1 and 3600-50 cm -1 respectively, and the band assignments were supported by deuteration effects. The results of energy calculations have shown that the most stable form is 1H-3,5-diamino-1,2,4-triazole under C 1 symmetry. For this form, the molecular structure, harmonic vibrational wave numbers, infrared intensities and Raman activities were calculated by the ab initio/HF and DFT/B3LYP methods using 6-31G* basis set. The calculated geometrical parameters of the guanazole molecule using B3LYP methodology are in good agreement with the previously reported X-ray data, and the scaled vibrational wave number values are in good agreement with the experimental data. The normal vibrations were characterized in terms of potential energy distribution (PEDs) using VEDA 4 program.
Composite Characterization Using Laser Doppler Vibrometry and Multi-Frequency Wavenumber Analysis

NASA Technical Reports Server (NTRS)

Juarez, Peter; Leckey, Cara

2015-01-01

NASA has recognized the need for better characterization of composite materials to support advances in aeronautics and the next generation of space exploration vehicles. An area of related research is the evaluation of impact induced delaminations. Presented is a non-contact method of measuring the ply depth of impact delamination damage in a composite through use of a Scanning Laser Doppler Vibrometer (SLDV), multi-frequency wavenumber analysis, and a wavenumber-ply correlation algorithm. A single acquisition of a chirp excited lamb wavefield in an impacted composite is post-processed into a numerous single frequency excitation wavefields through a deconvolution process. A spatially windowed wavenumber analysis then extracts local wavenumbers from the wavefield, which are then correlated to theoretical dispersion curves for ply depth determination. SLDV based methods to characterize as-manufactured composite variation using wavefield analysis will also be discussed.
The RAMANITA © method for non-destructive and in situ semi-quantitative chemical analysis of mineral solid-solutions by multidimensional calibration of Raman wavenumber shifts

NASA Astrophysics Data System (ADS)

Smith, David C.

2005-08-01

The "RAMANITA ©" method, for semi-quantitative chemical analysis of mineral solid-solutions by multidimensional calibration of Raman wavenumber shifts and mathematical calculation by simultaneous equations, is published here in detail in English for the first time. It was conceived by the present writer 20 years ago for binary and ternary pyroxene and garnet systems. The mathematical description was set out in 1989, but in an abstract in an obscure French special publication. Detailed "step-by-step" calibration of two garnet ternaries, followed by their linking, by M. Pinet and D.C. Smith in the early 1990s provided a hexary garnet database. Much later, using this garnet database, which forms part of his personal database called RAMANITA ©, the present writer began to develop the method by improving the terminology, automating the calculations, discussing problems and experimenting with different real chemical problems in archaeometry. Although this RAMANITA © method has been very briefly mentioned in two recent books, the necessary full mathematical explanation is given only here. The method will find application in any study which requires obtaining a non-destructive semi-quantitative chemical analysis from mineral solid solutions that cannot be analysed by any destructive analytical method, in particular for archaeological, geological or extraterrestrial research projects, e.g. from gemstones or other crystalline artworks of the cultural heritage (especially by Mobile Raman Microscopy (MRM)) in situ in museums or at archaeological sites, including under water for subaquatic archaeometry; from scientifically precious mineral microinclusions (such as garnet or pyroxene within diamond); from minerals in rocks analysed in situ on planetary bodies by a rover (especially "at distance" by telescopy). Recently some other workers have begun deducing chemical compositions from Raman wavenumber shifts in multivariate chemical space, but the philosophical approach is quite different.
Examining the impact of harmonic correlation on vibrational frequencies calculated in localized coordinates

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hanson-Heine, Magnus W. D., E-mail: magnus.hansonheine@nottingham.ac.uk

Carefully choosing a set of optimized coordinates for performing vibrational frequency calculations can significantly reduce the anharmonic correlation energy from the self-consistent field treatment of molecular vibrations. However, moving away from normal coordinates also introduces an additional source of correlation energy arising from mode-coupling at the harmonic level. The impact of this new component of the vibrational energy is examined for a range of molecules, and a method is proposed for correcting the resulting self-consistent field frequencies by adding the full coupling energy from connected pairs of harmonic and pseudoharmonic modes, termed vibrational self-consistent field (harmonic correlation). This approach ismore » found to lift the vibrational degeneracies arising from coordinate optimization and provides better agreement with experimental and benchmark frequencies than uncorrected vibrational self-consistent field theory without relying on traditional correlated methods.« less
Ab initio-informed maximum entropy modeling of rovibrational relaxation and state-specific dissociation with application to the O{sub 2} + O system

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kulakhmetov, Marat, E-mail: mkulakhm@purdue.edu; Alexeenko, Alina, E-mail: alexeenk@purdue.edu; Gallis, Michael, E-mail: magalli@sandia.gov

Quasi-classical trajectory (QCT) calculations are used to study state-specific ro-vibrational energy exchange and dissociation in the O{sub 2} + O system. Atom-diatom collisions with energy between 0.1 and 20 eV are calculated with a double many body expansion potential energy surface by Varandas and Pais [Mol. Phys. 65, 843 (1988)]. Inelastic collisions favor mono-quantum vibrational transitions at translational energies above 1.3 eV although multi-quantum transitions are also important. Post-collision vibrational favoring decreases first exponentially and then linearly as Δv increases. Vibrationally elastic collisions (Δv = 0) favor small ΔJ transitions while vibrationally inelastic collisions have equilibrium post-collision rotational distributions. Dissociationmore » exhibits both vibrational and rotational favoring. New vibrational-translational (VT), vibrational-rotational-translational (VRT) energy exchange, and dissociation models are developed based on QCT observations and maximum entropy considerations. Full set of parameters for state-to-state modeling of oxygen is presented. The VT energy exchange model describes 22 000 state-to-state vibrational cross sections using 11 parameters and reproduces vibrational relaxation rates within 30% in the 2500–20 000 K temperature range. The VRT model captures 80 × 10{sup 6} state-to-state ro-vibrational cross sections using 19 parameters and reproduces vibrational relaxation rates within 60% in the 5000–15 000 K temperature range. The developed dissociation model reproduces state-specific and equilibrium dissociation rates within 25% using just 48 parameters. The maximum entropy framework makes it feasible to upscale ab initio simulation to full nonequilibrium flow calculations.« less
Dissociative electron attachment and vibrational excitation of CF{sub 3}Cl: Effect of two vibrational modes revisited

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tarana, Michal; JILA, University of Colorado and NIST, Boulder, Colorado 80309-0440; Houfek, Karel

We present a study of dissociative electron attachment and vibrational excitation processes in electron collisions with the CF{sub 3}Cl molecule. The calculations are based on the two-dimensional nuclear dynamics including the C-Cl symmetric stretch coordinate and the CF{sub 3} symmetric deformation (umbrella) coordinate. The complex potential energy surfaces are calculated using the ab initio R-matrix method. The results for dissociative attachment and vibrational excitation of the umbrella mode agree quite well with experiment whereas the cross section for excitation of the C-Cl symmetric stretch vibrations is about a factor-of-three too low in comparison with experimental data.
Scalar decay in two-dimensional chaotic advection and Batchelor-regime turbulence

NASA Astrophysics Data System (ADS)

Fereday, D. R.; Haynes, P. H.

2004-12-01

This paper considers the decay in time of an advected passive scalar in a large-scale flow. The relation between the decay predicted by "Lagrangian stretching theories," which consider evolution of the scalar field within a small fluid element and then average over many such elements, and that observed at large times in numerical simulations, associated with emergence of a "strange eigenmode" is discussed. Qualitative arguments are supported by results from numerical simulations of scalar evolution in two-dimensional spatially periodic, time aperiodic flows, which highlight the differences between the actual behavior and that predicted by the Lagrangian stretching theories. In some cases the decay rate of the scalar variance is different from the theoretical prediction and determined globally and in other cases it apparently matches the theoretical prediction. An updated theory for the wavenumber spectrum of the scalar field and a theory for the probability distribution of the scalar concentration are presented. The wavenumber spectrum and the probability density function both depend on the decay rate of the variance, but can otherwise be calculated from the statistics of the Lagrangian stretching history. In cases where the variance decay rate is not determined by the Lagrangian stretching theory, the wavenumber spectrum for scales that are much smaller than the length scale of the flow but much larger than the diffusive scale is argued to vary as k-1+ρ, where k is wavenumber, and ρ is a positive number which depends on the decay rate of the variance γ2 and on the Lagrangian stretching statistics. The probability density function for the scalar concentration is argued to have algebraic tails, with exponent roughly -3 and with a cutoff that is determined by diffusivity κ and scales roughly as κ-1/2 and these predictions are shown to be in good agreement with numerical simulations.
Guided Wave Delamination Detection and Quantification With Wavefield Data Analysis

NASA Technical Reports Server (NTRS)

Tian, Zhenhua; Campbell Leckey, Cara A.; Seebo, Jeffrey P.; Yu, Lingyu

2014-01-01

Unexpected damage can occur in aerospace composites due to impact events or material stress during off-nominal loading events. In particular, laminated composites are susceptible to delamination damage due to weak transverse tensile and inter-laminar shear strengths. Developments of reliable and quantitative techniques to detect delamination damage in laminated composites are imperative for safe and functional optimally-designed next-generation composite structures. In this paper, we investigate guided wave interactions with delamination damage and develop quantification algorithms by using wavefield data analysis. The trapped guided waves in the delamination region are observed from the wavefield data and further quantitatively interpreted by using different wavenumber analysis methods. The frequency-wavenumber representation of the wavefield shows that new wavenumbers are present and correlate to trapped waves in the damage region. These new wavenumbers are used to detect and quantify the delamination damage through the wavenumber analysis, which can show how the wavenumber changes as a function of wave propagation distance. The location and spatial duration of the new wavenumbers can be identified, providing a useful means not only for detecting the presence of delamination damage but also allowing for estimation of the delamination size. Our method has been applied to detect and quantify real delamination damage with complex geometry (grown using a quasi-static indentation technique). The detection and quantification results show the location, size, and shape of the delamination damage.
Tensor-decomposed vibrational coupled-cluster theory: Enabling large-scale, highly accurate vibrational-structure calculations

NASA Astrophysics Data System (ADS)

Madsen, Niels Kristian; Godtliebsen, Ian H.; Losilla, Sergio A.; Christiansen, Ove

2018-01-01

A new implementation of vibrational coupled-cluster (VCC) theory is presented, where all amplitude tensors are represented in the canonical polyadic (CP) format. The CP-VCC algorithm solves the non-linear VCC equations without ever constructing the amplitudes or error vectors in full dimension but still formally includes the full parameter space of the VCC[n] model in question resulting in the same vibrational energies as the conventional method. In a previous publication, we have described the non-linear-equation solver for CP-VCC calculations. In this work, we discuss the general algorithm for evaluating VCC error vectors in CP format including the rank-reduction methods used during the summation of the many terms in the VCC amplitude equations. Benchmark calculations for studying the computational scaling and memory usage of the CP-VCC algorithm are performed on a set of molecules including thiadiazole and an array of polycyclic aromatic hydrocarbons. The results show that the reduced scaling and memory requirements of the CP-VCC algorithm allows for performing high-order VCC calculations on systems with up to 66 vibrational modes (anthracene), which indeed are not possible using the conventional VCC method. This paves the way for obtaining highly accurate vibrational spectra and properties of larger molecules.
Theoretical and experimental studies on vibrational and nonlinear optic properties of guanidinium 3-nitrobenzoate. Differences and similarity between guanidinium 3-nitrobenzoate and guanidinium 4-nitrobenzoate complexes

NASA Astrophysics Data System (ADS)

Drozd, Marek

2018-03-01

According to literature data two structures of guanidine with nitrobenzoic acids are known. For guanidinium 4-nitrobenzoate the detailed studies of X-ray structure, vibrational and theoretical properties were performed. This compound was classified as second harmonic generator with efficiency of 3.3 times that KDP, standard crystal. On the contrary to mentioned above results for the guanidinium 3-nitrobenzoate the basic X-ray diffraction study was performed, only. On the basis of established crystallographic results, the detailed investigation of geometry and vibrational properties were made on the basis of theoretical calculation. According to this data the equilibrium geometry of investigated molecule was established. On the basis of this calculation the detailed computational studies of vibrational properties were performed. The theoretical IR and Raman frequencies, intensities and PED analysis are presented. Additionally, the NBO charges, HOMO and LUMO shapes and NLO properties of titled crystal were calculated. On the basis of these results the crystal was classified as second order generator in NLO but with bigger efficiency that guanidinium 4-nitorobenzoate compound. The obtained data are compared with experimental crystallographic and vibrational results for real crystal of guanidinium 3-nitrobenzoate. Additionally, the theoretical vibrational spectra are compared with literature calculations of guanidinium 4-nitrobenzoate compound.
Tests of various colorants for application of a Fourier transform infrared imaging system to deciphering obliterated writings

NASA Astrophysics Data System (ADS)

Sugawara, Shigeru

2015-10-01

Obliterated writing is writing that has been obscured by different-colored materials. There are obliterated writings that cannot be detected by conventional methods. A method for deciphering such obliterated writings was developed in this study. Mid-infrared spectroscopic imaging in the wavelength range of 2.5-14 μm was used for deciphering because the infrared spectrum differs among different brands of colorants. Obliterated writings were made by pressing information protection stamps onto characters written by 4 kinds of colorants. The samples were tested for deciphering by the Fourier-transform infrared imaging system. Two peak areas of two specific wavenumber regions of each reflectance spectrum were calculated and the ratio of the two values is displayed as a unique gray scale in the spectroscopic image. As a result, the absorption peak at various wavenumbers could be used to decipher obliterated writings that could not be detected by the conventional methods. Ten different parameters for deciphering obliterated writing were found in this study.
The trispectrum in the Effective Field Theory of Large Scale Structure

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bertolini, Daniele; Schutz, Katelin; Solon, Mikhail P.

2016-06-01

We compute the connected four point correlation function (the trispectrum in Fourier space) of cosmological density perturbations at one-loop order in Standard Perturbation Theory (SPT) and the Effective Field Theory of Large Scale Structure (EFT of LSS). This paper is a companion to our earlier work on the non-Gaussian covariance of the matter power spectrum, which corresponds to a particular wavenumber configuration of the trispectrum. In the present calculation, we highlight and clarify some of the subtle aspects of the EFT framework that arise at third order in perturbation theory for general wavenumber configurations of the trispectrum. We consistently incorporatemore » vorticity and non-locality in time into the EFT counterterms and lay out a complete basis of building blocks for the stress tensor. We show predictions for the one-loop SPT trispectrum and the EFT contributions, focusing on configurations which have particular relevance for using LSS to constrain primordial non-Gaussianity.« less
Determining modes for the 3D Navier-Stokes equations

NASA Astrophysics Data System (ADS)

Cheskidov, Alexey; Dai, Mimi; Kavlie, Landon

2018-07-01

We introduce a determining wavenumber for the forced 3D Navier-Stokes equations (NSE) defined for each individual solution. Even though this wavenumber blows up if the solution blows up, its time average is uniformly bounded for all solutions on the weak global attractor. The bound is compared to Kolmogorov's dissipation wavenumber and the Grashof constant.
On-Line Multi-Damage Scanning Spatial-Wavenumber Filter Based Imaging Method for Aircraft Composite Structure.

PubMed

Ren, Yuanqiang; Qiu, Lei; Yuan, Shenfang; Bao, Qiao

2017-05-11

Structural health monitoring (SHM) of aircraft composite structure is helpful to increase reliability and reduce maintenance costs. Due to the great effectiveness in distinguishing particular guided wave modes and identifying the propagation direction, the spatial-wavenumber filter technique has emerged as an interesting SHM topic. In this paper, a new scanning spatial-wavenumber filter (SSWF) based imaging method for multiple damages is proposed to conduct on-line monitoring of aircraft composite structures. Firstly, an on-line multi-damage SSWF is established, including the fundamental principle of SSWF for multiple damages based on a linear piezoelectric (PZT) sensor array, and a corresponding wavenumber-time imaging mechanism by using the multi-damage scattering signal. Secondly, through combining the on-line multi-damage SSWF and a PZT 2D cross-shaped array, an image-mapping method is proposed to conduct wavenumber synthesis and convert the two wavenumber-time images obtained by the PZT 2D cross-shaped array to an angle-distance image, from which the multiple damages can be directly recognized and located. In the experimental validation, both simulated multi-damage and real multi-damage introduced by repeated impacts are performed on a composite plate structure. The maximum localization error is less than 2 cm, which shows good performance of the multi-damage imaging method. Compared with the existing spatial-wavenumber filter based damage evaluation methods, the proposed method requires no more than the multi-damage scattering signal and can be performed without depending on any wavenumber modeling or measuring. Besides, this method locates multiple damages by imaging instead of the geometric method, which helps to improve the signal-to-noise ratio. Thus, it can be easily applied to on-line multi-damage monitoring of aircraft composite structures.
Can We Infer Ocean Dynamics from Altimeter Wavenumber Spectra?

NASA Technical Reports Server (NTRS)

Richman, James; Shriver, Jay; Arbic, Brian

2012-01-01

The wavenumber spectra of sea surface height (SSH) and kinetic energy (KE) have been used to infer the dynamics of the ocean. When quasi-geostrophic dynamics (QG) or surface quasi-geostrophic (SQG) turbulence dominate and an inertial subrange exists, a steep SSH wavenumber spectrum is expected with k-5 for QG turbulence and a flatter k-11/3 for SQG turbulence. However, inspection of the spectral slopes in the mesoscale band of 70 to 250 km shows that the altimeter wavenumber slopes typically are much flatter than the QG or SQG predictions over most of the ocean. Comparison of the altimeter wavenumber spectra with the spectra estimated from the output of an eddy resolving global ocean circulation model (the Hybrid Coordinate Ocean Model, HYCOM, at 1/25 resolution), which is forced by high frequency winds and includes the astronomical forcing of the sun and the moon, suggests that the flatter slopes of the altimeter may arise from three possible sources, the presence of internal waves, the lack of an inertial subrange in the 70 to 250 km band and noise or submesoscales at small scales. When the wavenumber spectra of SSH and KE are estimated near the internal tide generating regions, the resulting spectra are much flatter than the expectations of QG or SQG theory. If the height and velocity variability are separated into low frequency (periods greater than 2 days) and high frequency (periods less than a day), then a different pattern emerges with a relatively flat wavenumber spectrum at high frequency and a steeper wavenumber spectrum at low frequency. The stationary internal tides can be removed from the altimeter spectrum, which steepens the spectral slopes in the energetic internal wave regions. Away from generating regions where the internal waves
On-Line Multi-Damage Scanning Spatial-Wavenumber Filter Based Imaging Method for Aircraft Composite Structure

PubMed Central

Ren, Yuanqiang; Qiu, Lei; Yuan, Shenfang; Bao, Qiao

2017-01-01

Structural health monitoring (SHM) of aircraft composite structure is helpful to increase reliability and reduce maintenance costs. Due to the great effectiveness in distinguishing particular guided wave modes and identifying the propagation direction, the spatial-wavenumber filter technique has emerged as an interesting SHM topic. In this paper, a new scanning spatial-wavenumber filter (SSWF) based imaging method for multiple damages is proposed to conduct on-line monitoring of aircraft composite structures. Firstly, an on-line multi-damage SSWF is established, including the fundamental principle of SSWF for multiple damages based on a linear piezoelectric (PZT) sensor array, and a corresponding wavenumber-time imaging mechanism by using the multi-damage scattering signal. Secondly, through combining the on-line multi-damage SSWF and a PZT 2D cross-shaped array, an image-mapping method is proposed to conduct wavenumber synthesis and convert the two wavenumber-time images obtained by the PZT 2D cross-shaped array to an angle-distance image, from which the multiple damages can be directly recognized and located. In the experimental validation, both simulated multi-damage and real multi-damage introduced by repeated impacts are performed on a composite plate structure. The maximum localization error is less than 2 cm, which shows good performance of the multi-damage imaging method. Compared with the existing spatial-wavenumber filter based damage evaluation methods, the proposed method requires no more than the multi-damage scattering signal and can be performed without depending on any wavenumber modeling or measuring. Besides, this method locates multiple damages by imaging instead of the geometric method, which helps to improve the signal-to-noise ratio. Thus, it can be easily applied to on-line multi-damage monitoring of aircraft composite structures. PMID:28772879
Anharmonic force field and vibrational dynamics of CH2F2 up to 5000 cm(-1) studied by Fourier transform infrared spectroscopy and state-of-the-art ab initio calculations.

PubMed

Tasinato, Nicola; Regini, Giorgia; Stoppa, Paolo; Pietropolli Charmet, Andrea; Gambi, Alberto

2012-06-07

Difluoromethane (CH(2)F(2), HFC-32) is a molecule used in refrigerant mixtures as a replacement of the more environmentally hazardous, ozone depleting, chlorofluorocarbons. On the other hand, presenting strong vibration-rotation bands in the 9 μm atmospheric window, it is a greenhouse gas which contributes to global warming. In the present work, the vibrational and ro-vibrational properties of CH(2)F(2), providing basic data for its atmospheric modeling, are studied in detail by coupling medium resolution Fourier transform infrared spectroscopy to high-level electronic structure ab initio calculations. Experimentally a full quantum assignment and accurate integrated absorption cross sections are obtained up to 5000 cm(-1). Ab initio calculations are carried out by using CCSD(T) theory and large basis sets of either the correlation consistent or atomic natural orbital hierarchies. By using vibrational perturbation theory to second order a complete set of vibrational and ro-vibrational parameters is derived from the ab initio quartic anharmonic force fields, which well compares with the spectroscopic constants retrieved experimentally. An excellent agreement between theory and experiment is achieved for vibrational energy levels and integrated absorption cross sections: transition frequencies up to four quanta of vibrational excitation are reproduced with a root mean square deviation (RMSD) of 7 cm(-1) while intensities are predicted within few km mol(-1) from the experiment. Basis set performances and core correlation effects are discussed throughout the paper. Particular attention is focused in the understanding of the anharmonic couplings which rule the vibrational dynamics of the |ν(1)>, |2ν(8)>, |2ν(2)> three levels interacting system. The reliability of the potential energy and dipole moment surfaces in reproducing the vibrational eigenvalues and intensities as well as in modeling the vibrational and ro-vibrational mixings over the whole 400-5000 cm(-1) region is also demonstrated by spectacular spectral simulations carried out by using the ro-vibrational Hamiltonian constants, and the relevant coupling terms, obtained from the perturbation treatment of the ab initio anharmonic force field. The present results suggest CH(2)F(2) as a prototype molecule to test ab initio calculations and theoretical models.
Anharmonic force field and vibrational dynamics of CH2F2 up to 5000 cm-1 studied by Fourier transform infrared spectroscopy and state-of-the-art ab initio calculations

NASA Astrophysics Data System (ADS)

Tasinato, Nicola; Regini, Giorgia; Stoppa, Paolo; Charmet, Andrea Pietropolli; Gambi, Alberto

2012-06-01

Difluoromethane (CH2F2, HFC-32) is a molecule used in refrigerant mixtures as a replacement of the more environmentally hazardous, ozone depleting, chlorofluorocarbons. On the other hand, presenting strong vibration-rotation bands in the 9 μm atmospheric window, it is a greenhouse gas which contributes to global warming. In the present work, the vibrational and ro-vibrational properties of CH2F2, providing basic data for its atmospheric modeling, are studied in detail by coupling medium resolution Fourier transform infrared spectroscopy to high-level electronic structure ab initio calculations. Experimentally a full quantum assignment and accurate integrated absorption cross sections are obtained up to 5000 cm-1. Ab initio calculations are carried out by using CCSD(T) theory and large basis sets of either the correlation consistent or atomic natural orbital hierarchies. By using vibrational perturbation theory to second order a complete set of vibrational and ro-vibrational parameters is derived from the ab initio quartic anharmonic force fields, which well compares with the spectroscopic constants retrieved experimentally. An excellent agreement between theory and experiment is achieved for vibrational energy levels and integrated absorption cross sections: transition frequencies up to four quanta of vibrational excitation are reproduced with a root mean square deviation (RMSD) of 7 cm-1 while intensities are predicted within few km mol-1 from the experiment. Basis set performances and core correlation effects are discussed throughout the paper. Particular attention is focused in the understanding of the anharmonic couplings which rule the vibrational dynamics of the |ν1⟩, |2ν8⟩, |2ν2⟩ three levels interacting system. The reliability of the potential energy and dipole moment surfaces in reproducing the vibrational eigenvalues and intensities as well as in modeling the vibrational and ro-vibrational mixings over the whole 400-5000 cm-1 region is also demonstrated by spectacular spectral simulations carried out by using the ro-vibrational Hamiltonian constants, and the relevant coupling terms, obtained from the perturbation treatment of the ab initio anharmonic force field. The present results suggest CH2F2 as a prototype molecule to test ab initio calculations and theoretical models.
Molecular structure, FT-IR, NBO, HOMO and LUMO, MEP and first order hyperpolarizability of (2E)-1-(2,4-Dichlorophenyl)-3-(3,4,5-trimethoxyphenyl)prop-2-en-1-one by HF and density functional methods.

PubMed

Sheena Mary, Y; Yohannan Panicker, C; Anto, P L; Sapnakumari, M; Narayana, B; Sarojini, B K

2015-01-25

(2E)-1-(2,4-Dichlorophenyl)-3-(3,4,5-trimethoxyphenyl)prop-2-en-1-one is synthesized by using 2,4-dichloroacetophenone and 3,4,5-trimethoxybenzaldehyde in ethanol. The structure of the compound was confirmed by IR and single crystal X-ray diffraction studies. FT-IR spectrum of (2E)-1-(2,4-dichloro-phenyl)-3-(3,4,5-trimethoxyphenyl)prop-2-en-1-one was recorded and analyzed. The crystal structure is also described. The vibrational wavenumbers were computed using HF and DFT methods and are assigned with the help of potential energy distribution method. The first hyperpolarizability and infrared intensities are also reported. The geometrical parameters of the title compound obtained from XRD studies are in agreement with the calculated (DFT) values. The stability of the molecule arising from hyper-conjugative interaction and charge delocalization has been analyzed using NBO analysis. The HOMO and LUMO analysis are used to determine the charge transfer within the molecule. MEP was performed by the DFT method. From the MEP map of the title molecule, negative region is mainly localized over the electronegative oxygen atoms, in the carbonyl group and the oxygen atom O4 of the methoxy group and the maximum positive region is localized on the phenyl rings. Copyright © 2014 Elsevier B.V. All rights reserved.

ExoMol line lists XXIV: a new hot line list for silicon monohydride, SiH

NASA Astrophysics Data System (ADS)

Yurchenko, Sergei N.; Sinden, Frances; Lodi, Lorenzo; Hill, Christian; Gorman, Maire N.; Tennyson, Jonathan

2018-02-01

SiH has long been observed in the spectrum of our Sun and other cool stars. Computed line lists for the main isotopologues of silicon monohydride, 28SiH, 29SiH, 30SiH and 28SiD are presented. These line lists consider rotation-vibration transitions within the ground X 2Π electronic state as well as transitions to the low-lying A 2Δ and a 4Σ- states. Ab initio potential energy (PECs) and dipole moment curves along with spin-orbit and electronic angular momentum couplings between them are calculated using the multireference configuration interaction level of theory with the MOLPRO package. The PEC for the ground X 2Π state is refined to available experimental data with a typical accuracy of around 0.01 cm-1 or better. The 28SiH line list includes 11 785 rovibronic states and 1724 841 transitions with associated Einstein-A coefficients for angular momentum J up to 82.5 and covering wavenumbers up to 31 340 cm-1 (λ < 0.319 μm). Spectra are simulated using the new line list and comparisons made with various experimental spectra. These line lists are applicable up to temperatures of 5000 K, making them relevant to astrophysical objects such as exoplanetary atmospheres and cool stars and opening up the possibility of detection in the interstellar medium. These line lists, called SiGHTLY, are available at the ExoMol (www.exomol.com) and CDS data base websites.
Anharmonic calculations of frequencies and intensities of Osbnd H stretching vibrations of (R)-1,3-butanediol conformers in the fundamentals and first overtones by density functional theory

NASA Astrophysics Data System (ADS)

Futami, Yoshisuke; Minamoto, Chihiro; Kudoh, Satoshi

2018-05-01

The frequencies and absorption intensities of the five kinds of conformers of 1,3-butanediol with the same carbon skeleton (GG‧) were calculated by anharmonic calculation for the fundamentals and first overtones of OH stretching vibrations. The four kinds of conformers form intramolecular hydrogen bonds and one conformer did not. Intramolecular hydrogen bond formation shifted the frequency of fundamental and first overtone of H-bonding OH stretching vibration to the lower frequency. The absorption intensities of the fundamentals as well as the vibrational anharmonicities increased upon hydrogen bond formation, while the intensities of first overtones decreased. The differences of conformers were clearly seen in the frequencies of the first overtones of free OH.
Anharmonic frequencies of CX2Y2 (X, Y = O, N, F, H, D) isomers and related systems obtained from vibrational multiconfiguration self-consistent field theory.

PubMed

Pfeiffer, Florian; Rauhut, Guntram

2011-10-13

Accurate anharmonic frequencies are provided for molecules of current research, i.e., diazirines, diazomethane, the corresponding fluorinated and deuterated compounds, their dioxygen analogs, and others. Vibrational-state energies were obtained from state-specific vibrational multiconfiguration self-consistent field theory (VMCSCF) based on multilevel potential energy surfaces (PES) generated from explicitly correlated coupled cluster, CCSD(T)-F12a, and double-hybrid density functional calculations, B2PLYP. To accelerate the vibrational structure calculations, a configuration selection scheme as well as a polynomial representation of the PES have been exploited. Because experimental data are scarce for these systems, many calculated frequencies of this study are predictions and may guide experiments to come.
DFT simulations and vibrational spectra of 2-amino-2-methyl-1,3-propanediol.

PubMed

Renuga Devi, T S; Sharmi kumar, J; Ramkumaar, G R

2014-12-10

The FTIR and FT-Raman spectra of 2-amino-2-methyl-1,3-propanediol were recorded in the regions 4000-400cm(-1) and 4000-50cm(-1) respectively. The structural and spectroscopic data of the molecule in the ground state were calculated using Hartee-Fock and density functional method (B3LYP) with the augmented-correlation consistent-polarized valence double zeta (aug-cc-pVDZ) basis set. The most stable conformer was optimized and the structural and vibrational parameters were determined based on this. The complete assignments were performed on the basis of the Potential Energy Distribution (PED) of the vibrational modes, calculated using Vibrational Energy Distribution Analysis (VEDA) 4 program. With the observed FTIR and FT-Raman data, a complete vibrational assignment and analysis of the fundamental modes of the compound were carried out. Thermodynamic properties and Mulliken charges were calculated using both Hartee-Fock and density functional method using the aug-cc-pVDZ basis set and compared. The calculated HOMO-LUMO energy gap revealed that charge transfer occurs within the molecule. (1)H and (13)C NMR chemical shifts of the molecule were calculated using Gauge-Independent Atomic Orbital (GIAO) method and were compared with experimental results. Copyright © 2014 Elsevier B.V. All rights reserved.
Vibrational cooling of spin-stretched dimer states by He buffer gas: quantum calculations for Li2(a 3Sigma(u)+) at ultralow energies.

PubMed

Bovino, S; Bodo, E; Yurtsever, E; Gianturco, F A

2008-06-14

The interaction between the triplet state of the lithium dimer, (7)Li(2), with (4)He is obtained from accurate ab initio calculations where the vibrational dependence of the potential is newly computed. Vibrational quenching dynamics within a coupled-channel quantum treatment is carried out at ultralow energies, and large differences in efficiency as a function of the initial vibrational state of the targets are found as one compares the triplet results with those of the singlet state of the same target.
Vibrational spectroscopy investigation and density functional theory calculations on (E)-N‧-(4-methoxybenzylidene) benzohydrazide

NASA Astrophysics Data System (ADS)

Saleem, H.; Subashchandrabose, S.; Ramesh Babu, N.; Syed Ali Padusha, M.

2015-05-01

The FT-IR, FT-Raman and UV-Vis spectra of the Schiff base compound (E)-N‧-(4-methoxybenzylidene) benzohydrazide (MBBH) have been recorded and analyzed. The optimized geometrical parameters were calculated. The complete vibrational assignments were performed on the basis of TED of the vibrational modes, calculated with the help of SQM method. NBO analysis has been carried out to explore the hyperconjugative interactions and their second order stabilization energy within the molecule. The molecular orbitals (MO's) and its energy gap were studied. The first order hyperpolarizability (β0) and related properties (β, α0, Δα) of MBBH are also calculated. All theoretical calculations were performed on the basis of B3LYP/6-311++G(d,p) level of theory.
Electromechanical cryocooler

DOEpatents

Neufeld, Kenneth W.

1996-01-01

An electromechanical cryocooler is disclosed for substantially reducing vibrations caused by the cooler. The direction of the force of the vibrations is measured and a counterforce sufficient to substantially reduce this vibration is calculated and generated. The counterforce is 180.degree. out of phase with the direction of the force of the vibrations.
Dynamic cues for whisker-based object localization: An analytical solution to vibration during active whisker touch

PubMed Central

Vaxenburg, Roman; Wyche, Isis; Svoboda, Karel; Efros, Alexander L.

2018-01-01

Vibrations are important cues for tactile perception across species. Whisker-based sensation in mice is a powerful model system for investigating mechanisms of tactile perception. However, the role vibration plays in whisker-based sensation remains unsettled, in part due to difficulties in modeling the vibration of whiskers. Here, we develop an analytical approach to calculate the vibrations of whiskers striking objects. We use this approach to quantify vibration forces during active whisker touch at a range of locations along the whisker. The frequency and amplitude of vibrations evoked by contact are strongly dependent on the position of contact along the whisker. The magnitude of vibrational shear force and bending moment is comparable to quasi-static forces. The fundamental vibration frequencies are in a detectable range for mechanoreceptor properties and below the maximum spike rates of primary sensory afferents. These results suggest two dynamic cues exist that rodents can use for object localization: vibration frequency and comparison of vibrational to quasi-static force magnitude. These complement the use of quasi-static force angle as a distance cue, particularly for touches close to the follicle, where whiskers are stiff and force angles hardly change during touch. Our approach also provides a general solution to calculation of whisker vibrations in other sensing tasks. PMID:29584719
Varying the forcing scale in low Prandtl number dynamos

NASA Astrophysics Data System (ADS)

Brandenburg, A.; Haugen, N. E. L.; Li, Xiang-Yu; Subramanian, K.

2018-06-01

Small-scale dynamos are expected to operate in all astrophysical fluids that are turbulent and electrically conducting, for example the interstellar medium, stellar interiors, and accretion disks, where they may also be affected by or competing with large-scale dynamos. However, the possibility of small-scale dynamos being excited at small and intermediate ratios of viscosity to magnetic diffusivity (the magnetic Prandtl number) has been debated, and the possibility of them depending on the large-scale forcing wavenumber has been raised. Here we show, using four values of the forcing wavenumber, that the small-scale dynamo does not depend on the scale-separation between the size of the simulation domain and the integral scale of the turbulence, i.e., the forcing scale. Moreover, the spectral bottleneck in turbulence, which has been implied as being responsible for raising the excitation conditions of small-scale dynamos, is found to be invariant under changing the forcing wavenumber. However, when forcing at the lowest few wavenumbers, the effective forcing wavenumber that enters in the definition of the magnetic Reynolds number is found to be about twice the minimum wavenumber of the domain. Our work is relevant to future studies of small-scale dynamos, of which several applications are being discussed.
Programmable Calculator Use in Undergraduate Dynamics, Vibrations, and Elementary Structures Courses.

ERIC Educational Resources Information Center

Cutchins, M. A.

1982-01-01

Presents programmable calculator solutions to selected problems, including area moments of inertia and principal values, the 2-D principal stress problem, C.G. and pitch inertia computations, 3-D eigenvalue problems, 3 DOF vibrations, and a complex flutter determinant. (SK)
Electromechanical cryocooler

DOEpatents

Neufeld, K.W.

1996-12-10

An electromechanical cryocooler is disclosed for substantially reducing vibrations caused by the cooler. The direction of the force of the vibrations is measured and a counterforce sufficient to substantially reduce this vibration is calculated and generated. The counterforce is 180{degree} out of phase with the direction of the force of the vibrations. 3 figs.
Ro-vibrational averaging of the isotropic hyperfine coupling constant for the methyl radical

DOE Office of Scientific and Technical Information (OSTI.GOV)

Adam, Ahmad Y.; Jensen, Per, E-mail: jensen@uni-wuppertal.de; Yachmenev, Andrey

2015-12-28

We present the first variational calculation of the isotropic hyperfine coupling constant of the carbon-13 atom in the CH{sub 3} radical for temperatures T = 0, 96, and 300 K. It is based on a newly calculated high level ab initio potential energy surface and hyperfine coupling constant surface of CH{sub 3} in the ground electronic state. The ro-vibrational energy levels, expectation values for the coupling constant, and its temperature dependence were calculated variationally by using the methods implemented in the computer program TROVE. Vibrational energies and vibrational and temperature effects for coupling constant are found to be in verymore » good agreement with the available experimental data. We found, in agreement with previous studies, that the vibrational effects constitute about 44% of the constant’s equilibrium value, originating mainly from the large amplitude out-of-plane bending motion and that the temperature effects play a minor role.« less
Determination of the Oscillator Strengths for the Third and Fourth Vibrational Overtone Transitions in Simple Alcohols

NASA Astrophysics Data System (ADS)

Wallberg, Jens; Kjaergaard, Henrik G.

2017-06-01

Absolute measurements of the weak transitions require sensitive spectroscopic techniques. With our recently constructed pulsed cavity ring down (CRD) spectrometer, we have recorded the third and fourth vibrational overtone of the OH stretching vibration in a series of simple alcohols: methanol (MeOH), ethanol (EtOH), 1-propanol (1-PrOH), 2-propanol (2-PrOH) and tert-butanol (tBuOH). The CRD setup (in a flow cell configuration) is combined with a conventional FTIR spectrometer to determine the partial pressure of the alcohols from the fundamental transitions of the OH-stretching vibration. The oscillator strengths of the overtone transitions are determined from the integrated absorbances of the overtone spectra and the partial pressures. Furthermore, the oscillator strengths were calculated using vibrational local mode theory with energies and dipole moments calculated at CCSD(T)/aug-cc-pVTZ level of theory. We find a good agreement between the observed and calculated oscillator strengths across the series of alcohols.
Vibrationally averaged post Born-Oppenheimer isotopic dipole moment calculations approaching spectroscopic accuracy.

PubMed

Arapiraca, A F C; Jonsson, Dan; Mohallem, J R

2011-12-28

We report an upgrade of the Dalton code to include post Born-Oppenheimer nuclear mass corrections in the calculations of (ro-)vibrational averages of molecular properties. These corrections are necessary to achieve an accuracy of 10(-4) debye in the calculations of isotopic dipole moments. Calculations on the self-consistent field level present this accuracy, while numerical instabilities compromise correlated calculations. Applications to HD, ethane, and ethylene isotopologues are implemented, all of them approaching the experimental values.
From tunneling to contact: Inelastic signals in an atomic gold junction from first principles

NASA Astrophysics Data System (ADS)

Frederiksen, Thomas; Lorente, Nicolás; Paulsson, Magnus; Brandbyge, Mads

2007-06-01

The evolution of electron conductance in the presence of inelastic effects is studied as an atomic gold contact is formed evolving from a low-conductance regime (tunneling) to a high-conductance regime (contact). In order to characterize each regime, we perform density-functional theory (DFT) calculations to study the geometric and electronic structures, together with the strength of the atomic bonds and the associated vibrational frequencies. The conductance is calculated by, first, evaluating the transmission of electrons through the system and, second, by calculating the conductance change due to the excitation of vibrations. As found in previous studies [Paulsson , Phys. Rev. B 72, 201101(R) (2005)], the change in conductance due to inelastic effects permits us to characterize the crossover from tunneling to contact. The most notorious effect is the crossover from an increase in conductance in the tunneling regime to a decrease in conductance in the contact regime when the bias voltage matches a vibrational threshold. Our DFT-based calculations actually show that the effect of vibrational modes in electron conductance is rather complex, in particular, when modes localized in the contact region are permitted to extend into the electrodes. As an example, we find that certain modes can give rise to decreases in conductance when in the tunneling regime, opposite to the above-mentioned result. Whereas details in the inelastic spectrum depend on the size of the vibrational region, we show that the overall change in conductance is quantitatively well approximated by the simplest calculation where only the apex atoms are allowed to vibrate. Our study is completed by the application of a simplified model where the relevant parameters are obtained from the above DFT-based calculations.
Quantum scattering calculations for ro-vibrational de-excitation of CO by hydrogen atoms

DOE Office of Scientific and Technical Information (OSTI.GOV)

Song, Lei; Avoird, Ad van der; Karman, Tijs

2015-05-28

We present quantum-mechanical scattering calculations for ro-vibrational relaxation of carbon monoxide (CO) in collision with hydrogen atoms. Collisional cross sections of CO ro-vibrational transitions from v = 1, j = 0 − 30 to v′ = 0, j′ are calculated using the close coupling method for collision energies between 0.1 and 15 000 cm{sup −1} based on the three-dimensional potential energy surface of Song et al. [J. Phys. Chem. A 117, 7571 (2013)]. Cross sections of transitions from v = 1, j ≥ 3 to v′ = 0, j′ are reported for the first time at this level of theory. Alsomore » calculations by the more approximate coupled states and infinite order sudden (IOS) methods are performed in order to test the applicability of these methods to H–CO ro-vibrational inelastic scattering. Vibrational de-excitation rate coefficients of CO (v = 1) are presented for the temperature range from 100 K to 3000 K and are compared with the available experimental and theoretical data. All of these results and additional rate coefficients reported in a forthcoming paper are important for including the effects of H–CO collisions in astrophysical models.« less
Variational study on the vibrational level structure and IVR behavior of highly vibrationally excited S0 formaldehyde.

PubMed

Rashev, Svetoslav; Moule, David C

2012-02-15

We perform large scale converged variational vibrational calculations on S(0) formaldehyde up to very high excess vibrational energies (E(v)), E(v)∼17,000cm(-1), using our vibrational method, consisting of a specific search/selection/Lanczos iteration procedure. Using the same method we investigate the vibrational level structure and intramolecular vibrational redistribution (IVR) characteristics for various vibrational levels in this energy range in order to assess the onset of IVR. Copyright © 2011 Elsevier B.V. All rights reserved.
Theoretical studies of dissociative recombination

NASA Technical Reports Server (NTRS)

Guberman, S. L.

1985-01-01

The calculation of dissociative recombination rates and cross sections over a wide temperature range by theoretical quantum chemical techniques is described. Model calculations on electron capture by diatomic ions are reported which illustrate the dependence of the rates and cross sections on electron energy, electron temperature, and vibrational temperature for three model crossings of neutral and ionic potential curves. It is shown that cross sections for recombination to the lowest vibrational level of the ion can vary by several orders of magnitude depending upon the position of the neutral and ionic potential curve crossing within the turning points of the v = 1 vibrational level. A new approach for calculating electron capture widths is reported. Ab initio calculations are described for recombination of O2(+) leading to excited O atoms.
Vibrational and thermal properties of β-HMX and TATB from dispersion corrected density functional theory

NASA Astrophysics Data System (ADS)

Landerville, Aaron C.; Oleynik, Ivan I.

2017-01-01

Dispersion Corrected Density Functional Theory (DFT+vdW) calculations are performed to predict vibrational and thermal properties of the bulk energetic materials (EMs) β-octahydrocyclotetramethylene-tetranitramine (β-HMX) and triaminotrinitrobenzene (TATB). DFT+vdW calculations of pressure-dependent crystal structure and the hydrostatic equation of state are followed by frozen-phonon calculations of their respective vibration spectra at each pressure. These are then used under the quasi-harmonic approximation to obtain zero-point and thermal free energy contributions to the pressure, resulting in pressure-volume-temperature (PVT) EOS for each material that are in excellent agreement with experiment. Heat capacities, and coefficients of thermal expansion as functions of temperature are also calculated and compared with experiment.
Effect of hormonal variation on in vivo high wavenumber Raman spectra improves cervical precancer detection

NASA Astrophysics Data System (ADS)

Duraipandian, Shiyamala; Zheng, Wei; Ng, Joseph; Low, Jeffrey J. H.; Ilancheran, A.; Huang, Zhiwei

2012-03-01

Raman spectroscopy is a unique analytical probe for molecular vibration and is capable of providing specific spectroscopic fingerprints of molecular compositions and structures of biological tissues. The aim of this study is to improve the classification accuracy of cervical precancer by characterizing the variations in the normal high wavenumber (HW - 2800-3700cm-1) Raman spectra arising from the menopausal status of the cervix. A rapidacquisition near-infrared (NIR) Raman spectroscopic system was used for in vivo tissue Raman measurements at 785 nm excitation. Individual HW Raman spectrum was measured with a 5s exposure time from both normal and precancer tissue sites of 15 patients recruited. The acquired Raman spectra were stratified based on the menopausal status of the cervix before the data analysis. Significant differences were noticed in Raman intensities of prominent band at 2924 cm-1 (CH3 stretching of proteins) and the broad water Raman band (in the 3100-3700 cm-1 range) with a peak at 3390 cm-1 in normal and dysplasia cervical tissue sites. Multivariate diagnostic decision algorithm based on principal component analysis (PCA) and linear discriminant analysis (LDA) was utilized to successfully differentiate the normal and precancer cervical tissue sites. By considering the variations in the Raman spectra of normal cervix due to the hormonal or menopausal status of women, the diagnostic accuracy was improved from 71 to 91%. By incorporating these variations prior to tissue classification, we can significantly improve the accuracy of cervical precancer detection using HW Raman spectroscopy.

Experimental and Theoretical Vibrational Spectra of Sideridiol Isolated from Sideritis Species

NASA Astrophysics Data System (ADS)

Kilic, Turgut; Sagir, Züleyha Ozer; Carikci, Sema; Azizoğlu, Akın

2017-12-01

Sideridiol ( ent-7α,18β-dihydroxykaur-15-ene) one of the ent-kaurene diterpenoid, is isolated from the genus Sideritis L. belongs to the family of Lamiaceae. The vibrational frequencies of sideridiol in the ground state have been calculated using the Density Functional Theory (DFT) method with the 6-31G( d) and 6 31+G( d, p) basis sets. The calculated vibrational frequencies have been compared with that of obtained experimental IR spectrum.
Vibrational spectroscopy of resveratrol

NASA Astrophysics Data System (ADS)

Billes, Ferenc; Mohammed-Ziegler, Ildikó; Mikosch, Hans; Tyihák, Ernő

2007-11-01

In this article the authors deal with the experimental and theoretical interpretation of the vibrational spectra of trans-resveratrol (3,5,4'-trihydroxy- trans-stilbene) of diverse beneficial biological activity. Infrared and Raman spectra of the compound were recorded; density functional calculations were carried out resulting in the optimized geometry and several properties of the molecule. Based on the calculated force constants, a normal coordinate analysis yielded the character of the vibrational modes and the assignment of the measured spectral bands.
First-principles calculations on anharmonic vibrational frequencies of polyethylene and polyacetylene in the Gamma approximation.

PubMed

Keçeli, Murat; Hirata, So; Yagi, Kiyoshi

2010-07-21

The frequencies of the infrared- and/or Raman-active (k=0) vibrations of polyethylene and polyacetylene are computed by taking account of the anharmonicity in the potential energy surfaces (PESs) and the resulting phonon-phonon couplings explicitly. The electronic part of the calculations is based on Gaussian-basis-set crystalline orbital theory at the Hartree-Fock and second-order Møller-Plesset (MP2) perturbation levels, providing one-, two-, and/or three-dimensional slices of the PES (namely, using the so-called n-mode coupling approximation with n=3), which are in turn expanded in the fourth-order Taylor series with respect to the normal coordinates. The vibrational part uses the vibrational self-consistent field, vibrational MP2, and vibrational truncated configuration-interaction (VCI) methods within the Gamma approximation, which amounts to including only k=0 phonons. It is shown that accounting for both electron correlation and anharmonicity is essential in achieving good agreement (the mean and maximum absolute deviations less than 50 and 90 cm(-1), respectively, for polyethylene and polyacetylene) between computed and observed frequencies. The corresponding values for the calculations including only one of such effects are in excess of 120 and 300 cm(-1), respectively. The VCI calculations also reproduce semiquantitatively the frequency separation and intensity ratio of the Fermi doublet involving the nu(2)(0) fundamental and nu(8)(pi) first overtone in polyethylene.
Theoretical study of the vibrational relaxation of the methyl radical in collisions with helium

NASA Astrophysics Data System (ADS)

Ma, Qianli; Dagdigian, Paul J.; Alexander, Millard H.

2013-03-01

We report a theoretical investigation of the relaxation of the umbrella vibrational mode (the ν2 mode) of the CH3 molecule in its ground tilde{X}^2A_2^' ' } electronic state in collisions with helium. We have calculated a four-dimensional potential energy surface (PES) for the interaction between CH3 with different umbrella displacements and a helium atom, using a restricted open-shell coupled-cluster method with inclusion of all single, double, and (perturbatively) triple excitations [RCCSD(T)]. With this PES we carried out full close-coupling scattering calculations including all CH3 umbrella-rotational levels with v2 ⩽ 3. To our knowledge, this work represents the first fully quantum calculations of ro-vibrational relaxation of a polyatomic. In more detail, we investigate propensities in the calculated ro-vibrational cross sections and the dependence on initial rotational excitation, as well as determining thermal rate constants. Overall, ro-vibrational relaxation is nearly two orders of magnitude less efficient than pure-rotational relaxation, with a noticeable dependence on the initial rotational level. We predict the room temperature v2 = 1 vibrational relaxation rate constant to be 5.4 × 10-12 cm3 molecule-1 s-1, compared to the rate constants for pure-rotational relaxation of the lower rotational levels (˜2.0 × 10-10 cm3 molecule-1 s-1).
Lumley's energy cascade dissipation rate model for boundary-free turbulent shear flows

NASA Technical Reports Server (NTRS)

Duncan, B. S.

1992-01-01

True dissipation occurs mainly at the highest wavenumbers where the eddy sizes are comparatively small. These high wavenumbers receive their energy through the spectral cascade of energy starting with the largest eddies spilling energy into the smaller eddies, passing through each wavenumber until it is dissipated at the microscopic scale. However, a small percentage of the energy does not spill continuously through the cascade but is instantly passed to the higher wavenumbers. Consequently, the smallest eddies receive a certain amount of energy almost immediately. As the spectral energy cascade continues, the highest wavenumber needs a certain time to receive all the energy which has been transferred from the largest eddies. As such, there is a time delay, of the order of tau, between the generation of energy by the largest eddies and the eventual dissipation of this energy. For equilibrium turbulence at high Reynolds numbers, there is a wide range where energy is neither produced by the large eddies nor dissipated by viscosity, but is conserved and passed from wavenumber to higher wavenumbers. The rate at which energy cascades from one wavenumber to another is proportional to the energy contained within that wavenumber. This rate is constant and has been used in the past as a dissipation rate of turbulent kinetic energy. However, this is true only in steady, equilibrium turbulence. Most dissipation models contend that the production of dissipation is proportional to the production of energy and that the destruction of dissipation is proportional to the destruction of energy. In essence, these models state that the change in the dissipation rate is proportional to the change in the kinetic energy. This assumption is obviously incorrect for the case where there is no production of turbulent energy, yet energy continues to cascade from large to small eddies. If the time lag between the onset on the energy cascade to the destruction of energy at the microscale can be modeled, then there will be a better representation of the dissipation process. Development of an energy cascade time scale equation is discussed.
Dissociative recombination of HCl+

NASA Astrophysics Data System (ADS)

Larson, Åsa; Fonseca dos Santos, Samantha; E. Orel, Ann

2017-08-01

The dissociative recombination of HCl+, including both the direct and indirect mechanisms, is studied. For the direct process, the relevant electronic states are calculated ab initio by combining electron scattering calculations to obtain resonance positions and autoionization widths with multi-reference configuration interaction calculations of the ion and Rydberg states. The cross section for the direct dissociation along electronic resonant states is computed by solution of the time-dependent Schrödinger equation. For the indirect process, an upper bound value for the cross section is obtained using a vibrational frame transformation of the elements of the scattering matrix at energies just above the ionization threshold. Vibrational excitations of the ionic core from the ground vibrational state, v = 0 , to the first three excited vibrational states, v = 1 , v = 2 , and v = 3 , are considered. Autoionization is neglected and the effect of the spin-orbit splitting of the ionic potential energy upon the indirect dissociative recombination cross section is considered. The calculated cross sections are compared to measurements.
Dissociative recombination of HCl.

PubMed

Larson, Åsa; Fonseca Dos Santos, Samantha; E Orel, Ann

2017-08-28

The dissociative recombination of HCl + , including both the direct and indirect mechanisms, is studied. For the direct process, the relevant electronic states are calculated ab initio by combining electron scattering calculations to obtain resonance positions and autoionization widths with multi-reference configuration interaction calculations of the ion and Rydberg states. The cross section for the direct dissociation along electronic resonant states is computed by solution of the time-dependent Schrödinger equation. For the indirect process, an upper bound value for the cross section is obtained using a vibrational frame transformation of the elements of the scattering matrix at energies just above the ionization threshold. Vibrational excitations of the ionic core from the ground vibrational state, v = 0, to the first three excited vibrational states, v = 1, v = 2, and v = 3, are considered. Autoionization is neglected and the effect of the spin-orbit splitting of the ionic potential energy upon the indirect dissociative recombination cross section is considered. The calculated cross sections are compared to measurements.
Vibrational spectroscopic and structural investigations on fullerene: A DFT approach

DOE Office of Scientific and Technical Information (OSTI.GOV)

Christy, P. Anto; Premkumar, S.; Asath, R. Mohamed

2016-05-06

The molecular structure of fullerene (C{sub 60}) molecule was optimized by the DFT/B3LYP method with 6-31G and 6-31G(d,p) basis sets using Gaussian 09 program. The vibrational frequencies were calculated for the optimized molecular structure of the molecule. The calculated vibrational frequencies confirm that the molecular structure of the molecule was located at the minimum energy potential energy surface. The calculated vibrational frequencies were assigned on the basis of functional group analysis and also confirmed using the GaussView 05 software. The frontier molecular orbitals analysis was carried out. The FMOs related molecular properties were predicted. The higher ionization potential, higher electronmore » affinity, higher softness, lower band gap energy and lower hardness values were obtained, which confirm that the fullerene molecule has a higher molecular reactivity. The Mulliken atomic charge distribution of the molecule was also calculated. Hence, these results play an important role due to its potential applications as drug delivery devices.« less
Correlation between the structure and the piezoelectric properties of lead-free (K,Na,Li)(Nb,Ta,Sb)O3 ceramics studied by XRD and Raman spectroscopy.

PubMed

Rubio-Marcos, Fernando; Marchet, Pascal; Romero, Juan José; Fernández, Jose F

2011-09-01

This article reviews on the use of Raman spectroscopy for the study of (K,Na,Li)(Nb,Ta,Sb)O(3) lead-free piezoceramics. Currently, this material appears to be one of the most interesting and promising alternatives to the well-known PZT piezoelectric materials. In this work, we prepare piezoceramics with different stoichiometries and study their structural, ferroelectric, and piezoelectric properties. By using both Raman spectroscopy and X-ray diffraction, we establish a direct correlation between the structure and the properties. The results demonstrate that the wavenumber of the A(1g) vibration is proportional to the tetragonality, the remnant polarization, and the piezoelectric coefficients of these materials. Thus, Raman spectroscopy appears as a very useful technique for a fast evaluation of the crystalline structure and the ferroelectric/ piezoelectric properties.
Raman studies of phase transitions in ferroelectric [C2H5NH3]2ZnCl4

NASA Astrophysics Data System (ADS)

Ben Mohamed, C.; Karoui, K.; Bulou, A.; Ben Rhaiem, A.

2017-03-01

The present paper accounted for the synthesis, differential scanning calorimetric and vibrational spectroscopy of [C2H5NH3]2ZnCl4grown at room temperature. Differential scanning calorimetric (DSC) disclosed five phase transitions at T1=231 K, T2=234 K, T3=237 K, T4=247 K and T5=312 K. The temperature dependence of the dielectric constant at different temperatures proved that this compound is ferroelectric below 238 K. Raman spectra as function temperature have been used to characterize these transitions and their nature, which indicates a change of the some peak near the transitions phase. The analysis of the wavenumber and the line width based on the order-disorder model allowed to obtain information relative to the thermal coefficient and the activation energy near the transitions phase.
Phase transitions in heated Sr{sub 2}MgTeO{sub 6} double perovskite oxide probed by X-ray diffraction and Raman spectroscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Manoun, Bouchaib, E-mail: manounb@gmail.com; Tamraoui, Y.; Lazor, P.

2013-12-23

Double-perovskite oxide Sr{sub 2}MgTeO{sub 6} has been synthetized, and its crystal structure was probed by the technique of X-ray diffraction at room temperature. The structure is monoclinic, space group I2/m. Temperature-induced phase transitions in this compound were investigated by Raman spectroscopy up to 550 °C. Two low-wavenumber modes corresponding to external lattice vibrations merge at temperature of around 100 °C, indicating a phase transition from the monoclinic (I2/m) to the tetragonal (I4/m) structure. At 300 °C, changes in the slopes of temperature dependencies of external and O–Te–O bending modes are detected and interpreted as a second phase transition from the tetragonal (I4/m) tomore » the cubic (Fm-3m) structure.« less
Ab initio and DFT studies of the structure and vibrational spectra of anhydrous caffeine

NASA Astrophysics Data System (ADS)

Srivastava, Santosh K.; Singh, Vipin B.

2013-11-01

Vibrational spectra and molecular structure of anhydrous caffeine have been systematically investigated by second order Moller-Plesset (MP2) perturbation theory and density functional theory (DFT) calculations. Vibrational assignments have been made and many previous ambiguous assignments in IR and Raman spectra are amended. The calculated DFT frequencies and intensities at B3LYP/6-311++G(2d,2p) level, were found to be in better agreement with the experimental values. It was found that DFT with B3LYP functional predicts harmonic vibrational wave numbers more close to experimentally observed value when it was performed on MP2 optimized geometry rather than DFT geometry. The calculated TD-DFT vertical excitation electronic energies of the valence excited states of anhydrous caffeine are found to be in consonance to the experimental absorption peaks.
Conformational, vibrational, NMR and DFT studies of N-methylacetanilide.

PubMed

Arjunan, V; Santhanam, R; Rani, T; Rosi, H; Mohan, S

2013-03-01

A detailed conformational, vibrational, NMR and DFT studies of N-methylacetanilide have been carried out. In DFT, B3LYP method have been used with 6-31G(**), 6-311++G(**) and cc-pVTZ basis sets. The vibrational frequencies were calculated resulting in IR and Raman frequencies together with intensities and Raman depolarisation ratios. The dipole moment derivatives were computed analytically. Owing to the complexity of the molecule, the potential energy distributions of the vibrational modes of the compound are also calculated. Isoelectronic molecular electrostatic potential surface (MEP) and electron density surface were examined. (1)H and (13)C NMR isotropic chemical shifts were calculated and the assignments made are compared with the experimental values. The energies of important MO's of the compound were also determined from TD-DFT method. Copyright © 2012 Elsevier B.V. All rights reserved.
DFT analysis on the molecular structure, vibrational and electronic spectra of 2-(cyclohexylamino)ethanesulfonic acid

NASA Astrophysics Data System (ADS)

Renuga Devi, T. S.; Sharmi kumar, J.; Ramkumaar, G. R.

2015-02-01

The FTIR and FT-Raman spectra of 2-(cyclohexylamino)ethanesulfonic acid were recorded in the regions 4000-400 cm-1 and 4000-50 cm-1 respectively. The structural and spectroscopic data of the molecule in the ground state were calculated using Hartee-Fock and Density functional method (B3LYP) with the correlation consistent-polarized valence double zeta (cc-pVDZ) basis set and 6-311++G(d,p) basis set. The most stable conformer was optimized and the structural and vibrational parameters were determined based on this. The complete assignments were performed based on the Potential Energy Distribution (PED) of the vibrational modes, calculated using Vibrational Energy Distribution Analysis (VEDA) 4 program. With the observed FTIR and FT-Raman data, a complete vibrational assignment and analysis of the fundamental modes of the compound were carried out. Thermodynamic properties and Atomic charges were calculated using both Hartee-Fock and density functional method using the cc-pVDZ basis set and compared. The calculated HOMO-LUMO energy gap revealed that charge transfer occurs within the molecule. 1H and 13C NMR chemical shifts of the molecule were calculated using Gauge Including Atomic Orbital (GIAO) method and were compared with experimental results. Stability of the molecule arising from hyperconjugative interactions, charge delocalization have been analyzed using Natural Bond Orbital (NBO) analysis. The first order hyperpolarizability (β) and Molecular Electrostatic Potential (MEP) of the molecule was computed using DFT calculations. The electron density based local reactivity descriptor such as Fukui functions were calculated to explain the chemical reactivity site in the molecule.
Conformational structures of a decapeptide validated by first principles calculations and cold ion spectroscopy.

PubMed

Roy, Tapta Kanchan; Kopysov, Vladimir; Nagornova, Natalia S; Rizzo, Thomas R; Boyarkin, Oleg V; Gerber, R Benny

2015-05-18

Calculated structures of the two most stable conformers of a protonated decapeptide gramicidin S in the gas phase have been validated by comparing the vibrational spectra, calculated from first- principles and measured in a wide spectral range using infrared (IR)-UV double resonance cold ion spectroscopy. All the 522 vibrational modes of each conformer were calculated quantum mechanically and compared with the experiment without any recourse to an empirical scaling. The study demonstrates that first-principles calculations, when accounting for vibrational anharmonicity, can reproduce high-resolution experimental spectra well enough for validating structures of molecules as large as of 200 atoms. The validated accurate structures of the peptide may serve as templates for in silico drug design and absolute calibration of ion mobility measurements. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
Quantum chemical density functional theory studies on the molecular structure and vibrational spectra of mannitol

NASA Astrophysics Data System (ADS)

Moorthi, P. P.; Gunasekaran, S.; Swaminathan, S.; Ramkumaar, G. R.

2015-02-01

A collective experimental and theoretical study was conducted on the molecular structure and vibrational spectra of mannitol. The FT-IR and FT-Raman spectra of mannitol were recorded in the solid phase. The molecular geometry, vibrational frequencies, thermodynamic functions and atomic charges of mannitol in the ground state have been calculated by using the ab initio HF (Hartree-Fock) and density functional methods (B3LYP) invoking cc-pVDZ basis set. The complete vibrational assignments were performed on the basis of Total Energy Distribution (TED) of the vibrational modes. The UV absorption spectra of the title compound dissolved in water. Natural bond orbital analysis has been carried out to explain the charge transfer or delocalization of charge due to the intra-molecular interactions. The 1H and 13C nuclear magnetic resonance (NMR) chemical shifts of the molecule were calculated by GIAO methods. The first order hyperpolarizability (β0) of this novel molecular system and related properties (β, α0 and Δα) of mannitol are calculated using B3LYP/cc-pVDZ and HF/cc-pVDZ methods on the finite-field approach. By using TD-DFT calculation, electronic absorption spectra of the title compound have been predicted and a good agreement with experimental one is established. In addition, the molecular electrostatic potential (MEP) have been investigated using theoretical calculations, the calculated HOMO and LUMO energies shows that the charge transfer within the molecule.
Evaluation of vibration limits and mitigation techniques for urban construction.

DOT National Transportation Integrated Search

2013-10-01

The overriding purpose of this research was to develop a comprehensive framework to address : vibration issues prior to and during construction, including calculation of anticipated ground : vibrations during project design, condition surveys of stru...
General kinetic solution for the Biermann battery with an associated pressure anisotropy generation

NASA Astrophysics Data System (ADS)

Schoeffler, K. M.; Silva, L. O.

2018-01-01

Fully kinetic analytic calculations of an initially Maxwellian distribution with arbitrary density and temperature gradients exhibit the development of temperature anisotropies and magnetic field growth associated with the Biermann battery. The calculation, performed by taking a small order expansion of the ratio of the Debye length to the gradient scale, predicts anisotropies and magnetic fields as a function of space given an arbitrary temperature and density profile. These predictions are shown to qualitatively match the values measured from particle-in-cell simulations, where the development of the Weibel instability occurs at the same location and with a wavenumber aligned with the predicted temperature anisotropy.
Subsonic and Supersonic Jet Noise Calculations Using PSE and DNS

NASA Technical Reports Server (NTRS)

Balakumar, P.; Owis, Farouk

1999-01-01

Noise radiated from a supersonic jet is computed using the Parabolized Stability Equations (PSE) method. The evolution of the instability waves inside the jet is computed using the PSE method and the noise radiated to the far field from these waves is calculated by solving the wave equation using the Fourier transform method. We performed the computations for a cold supersonic jet of Mach number 2.1 which is excited by disturbances with Strouhal numbers St=.2 and .4 and the azimuthal wavenumber m=l. Good agreement in the sound pressure level are observed between the computed and the measured (Troutt and McLaughlin 1980) results.
Sound radiation from randomly vibrating beams of finite circular cross section

NASA Technical Reports Server (NTRS)

Sutterlin, M. W.; Pierce, A. D.

1976-01-01

The radiation of sound from vibrating cylindrical beams is analyzed based on the frequency of the beam vibrations and the physical characteristics of the beam and its surroundings. A statistical analysis of random beam vibrations allows this result to be independent of the boundary conditions at the ends of the beam. The acoustic power radiated by the beam can be determined from a knowledge of the frequency band vibration data without a knowledge of the individual modal vibration amplitudes. A practical example of the usefulness of this technique is provided by the application of the theoretical calculations to the prediction of the octave band acoustic power output of the picking sticks of an automatic textile loom. Calculations are made of the expected octave band sound pressure levels based on measured acceleration data. These theoretical levels are subsequently compared with actual sound pressure level measurements of loom noise.

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