Energy and Biocides Storage Compounds: Synthesis and Characterization of Energetic Bridged Bis(triiodoazoles).

PubMed

He, Chunlin; Zhao, Gang; Hooper, Joseph P; Shreeve, Jean'ne M

2017-11-06

Energetic bridged triiodopyrazoles and triiodoimidazoles were designed and synthsized by reacting potassium triiodopyrazolate or triiodoimidazolate with corresponding dichloro compounds. All compounds were fully characterized by 1 H and 13 C NMR spectroscopy, IR spectroscopy, and elemental analyses. The structure of compound 1 was further confirmed by single-crystal X-ray diffraction. All of the compounds exhibit good thermal stability with decomposition temperatures between 199 and 270 °C and high densities ranging from 2.804 to 3.358 g/cm 3 . The detonation performances and the detonation products were calculated by CHEETAH 7. Compound 3 (D v = 4765 m s -1 ; P = 17.9 GPa) and compound 7 (D v = 4841 m s -1 ; P = 18.5 GPa) show comparable detonation pressure to TNT, and high iodine content makes them promising as energy and biocides storage compounds.

A density functional theory study on the thermodynamic and dynamic properties of anthraquinone analogue cathode materials for rechargeable lithium ion batteries.

PubMed

Yang, Shu-Jing; Qin, Xiao-Ya; He, Rongxing; Shen, Wei; Li, Ming; Zhao, Liu-Bin

2017-05-21

Organic redox compounds have become the emerging electrode materials for rechargeable lithium ion batteries. The high electrochemical performance provides organic electrode materials with great opportunities to be applied in electric energy storage devices. Among the different types of organic materials, conjugated carbonyl compounds are the most promising type at present, because only they can simultaneously achieve, high energy density, high cycling stability, and high power density. In this research, a series of heteroatom substituted anthraquinone (AQ) derivatives were designed theoretically so that the high theoretical capacity of AQ remained. The discharge and charge mechanism as well as the thermodynamic and dynamic properties of AQ and its derivatives were investigated using first-principles density functional theory. Using heteroatom substitution, both the thermodynamic and dynamic properties of AQ as cathode materials could be largely improved. Among these conjugated carboxyl compounds, BDOZD and BDIOZD with a simultaneously high theoretical capacity and high working potential exhibit the largest energy density of about 780 W h kg -1 , which is 41% larger than that of AQ. The PQD with the smallest value of λ gives the largest charge transfer rate constant, which is about four times as large as the prototype molecule, AQ. The most interesting finding is that the lithium ion transfer plays a very important role in influencing both the discharge potential and electrochemical charge transfer rate. The present study illustrates that theoretical calculations provide a highly effective way to discover potential materials for use with rechargeable lithium ion batteries.

Relationship between electronic properties and drug activity of seven quinoxaline compounds: A DFT study

NASA Astrophysics Data System (ADS)

Behzadi, Hadi; Roonasi, Payman; Assle taghipour, Khatoon; van der Spoel, David; Manzetti, Sergio

2015-07-01

The quantum chemical calculations at the DFT/B3LYP level of theory were carried out on seven quinoxaline compounds, which have been synthesized as anti-Mycobacterium tuberculosis agents. Three conformers were optimized for each compound and the lowest energy structure was found and used in further calculations. The electronic properties including EHOMO, ELUMO and related parameters as well as electron density around oxygen and nitrogen atoms were calculated for each compound. The relationship between the calculated electronic parameters and biological activity of the studied compounds were investigated. Six similar quinoxaline derivatives with possible more drug activity were suggested based on the calculated electronic descriptors. A mechanism was proposed and discussed based on the calculated electronic parameters and bond dissociation energies.

Hybrid system for rechargeable magnesium battery with high energy density

PubMed Central

Chang, Zheng; Yang, Yaqiong; Wang, Xiaowei; Li, Minxia; Fu, Zhengwen; Wu, Yuping; Holze, Rudolf

2015-01-01

One of the main challenges of electrical energy storage (EES) is the development of environmentally friendly battery systems with high safety and high energy density. Rechargeable Mg batteries have been long considered as one highly promising system due to the use of low cost and dendrite-free magnesium metal. The bottleneck for traditional Mg batteries is to achieve high energy density since their output voltage is below 2.0 V. Here, we report a magnesium battery using Mg in Grignard reagent-based electrolyte as the negative electrode, a lithium intercalation compound in aqueous solution as the positive electrode, and a solid electrolyte as a separator. Its average discharge voltage is 2.1 V with stable discharge platform and good cycling life. The calculated energy density based on the two electrodes is high. These findings open another door to rechargeable magnesium batteries. PMID:26173624

Adsorption studies of volatile organic compounds on germanene nanotube emitted from banana fruit for quality assessment - A density functional application.

PubMed

Srimathi, U; Nagarajan, V; Chandiramouli, R

2018-06-01

We report the density functional application of adsorption behavior of volatile organic compounds (VOCs) emitted from the different ripening stages of banana fruit on germanene nanotube (GNT). Initially, the geometric structural stability of GNT is ascertained and the tunable electronic properties lead to the application of GNT as a base material in order to know the adsorption features of VOCs. We further explored the adsorption behavior of VOCs on to GNT through charge transfer, adsorption energy and band gap variation. The energy band structure and density of states (DOS) spectrum shows a noteworthy variation upon adsorption of different VOCs on to the GNT. Also, the electron density variation is noticed upon adsorption of VOCs emitted from the banana on to the GNT base material. Besides, the difference in the energy band gap of GNT upon emission of VOCs from banana leads to the use of GNT as a chemiresistor to assess fruit freshness with adsorption studies. Moreover, we suggest the use of GNT to discriminate the fruit freshness of banana through the adsorption process of VOCs on to GNT. Copyright © 2018 Elsevier Inc. All rights reserved.

Photon mass attenuation coefficients, effective atomic numbers and electron densities of some thermoluminescent dosimetric compounds

NASA Astrophysics Data System (ADS)

Gowda, Shivalinge; Krishnaveni, S.; Yashoda, T.; Umesh, T. K.; Gowda, Ramakrishna

2004-09-01

Photon mass attenuation coefficients of some thermoluminescent dosimetric (TLD) compounds, such as LiF, CaCO_3, CaSO_4, CaSO_4\\cdot2H_2O, SrSO_4, CdSO_4, BaSO_4, C_4H_6BaO_4 and 3CdSO_4\\cdot8H_2O were determined at 279.2, 320.07, 514.0, 661.6, 1115.5, 1173.2 and 1332.5 keV in a well-collimated narrow beam good geometry set-up using a high resolution, hyper pure germanium detector. The attenuation coefficient data were then used to compute the effective atomic number and the electron density of TLD compounds. The interpolation of total attenuation cross-sections of photons of energy E in elements of atomic number Z was performed using the logarithmic regression analysis of the data measured by the authors and reported earlier. The best-fit coefficients so obtained in the photon energy range of 279.2 to 320.07 keV, 514.0 to 661.6 keV and 1115.5 to 1332.5 keV by a piece-wise interpolation method were then used to find the effective atomic number and electron density of the compounds. These values are found to be in agreement with other available published values.

Synthesis, XRD crystal structure, spectroscopic characterization (FT-IR, 1H and 13C NMR), DFT studies, chemical reactivity and bond dissociation energy studies using molecular dynamics simulations and evaluation of antimicrobial and antioxidant activities of a novel chalcone derivative, (E)-1-(4-bromophenyl)-3-(4-iodophenyl)prop-2-en-1-one

NASA Astrophysics Data System (ADS)

Zainuri, D. Alwani; Arshad, Suhana; Khalib, N. Che; Razak, I. Abdul; Pillai, Renjith Raveendran; Sulaiman, S. Fariza; Hashim, N. Shafiqah; Ooi, K. Leong; Armaković, Stevan; Armaković, Sanja J.; Panicker, C. Yohannan; Van Alsenoy, C.

2017-01-01

In the present study, the title compound named as (E)-1-(4-bromophenyl)-3-(4-iodophenyl)prop-2-en-1-one was synthesized and structurally characterized by single-crystal X-ray diffraction. The compound crystallizes in the monoclinic system with P21/c space group with the unit cell parameters of a = 16.147 (2) Å, b = 14.270 (2) Å, c = 5.9058 (9) Å, β = 92.577 (3)° and Z = 4. The molecular geometry obtained from X-Ray structure determination was optimized by Density Functional Theory (DFT) using B3LYP/6-31G+(d, p)/Lanl2dz(f) method in the ground state. The IR spectrum was recorded and interpreted in details with the aid of Density Functional Theory (DFT) calculations and Potential Energy Distribution (PED) analysis. In order to investigate local reactivity properties of the title molecule, we have conducted DFT calculations of average local ionization energy surface and Fukui functions which were mapped to the electron density surface. In order to predict the open air stability and possible degradation properties, within DFT approach, we have also calculated bond dissociation energies. 1H and 13C NMR spectra were recorded and chemical shifts were calculated theoretically and compared with the experimental values. In addition, in vitro antimicrobial results show that the title compound has great potential of antibacterial activity against Staphylococcus aureus, Staphylococcus epidermidis and Micrococcus luteus bacteria and antifungal activity against Candida albicans in comparison to some reported chalcone derivatives. Antioxidant studies revealed the highest metal chelating activity of this compound.

Phonon and thermodynamical properties of CuSc: A DFT study

NASA Astrophysics Data System (ADS)

Jain, Ekta; Pagare, Gitanjali; Dubey, Shubha; Sanyal, S. P.

2018-05-01

A detailed systematic theoretical investigation of phonon and thermodynamical behavior of CuSc intermetallic compound has been carried out by uing first-principles density functional theory in B2-type (CsCl) crystal structure. Phonon dispersion curve and phonon density of states (PhDOS) are studied which confirm the stability of CuSc intermetallic compound in B2 phase. It is found that PhDOS at high frequencies mostly composed of Sc states. We have also presented some temperature dependent properties such as entropy, free energy, heat capacity, internal energy and thermal displacement, which are computed under PHONON code. The various features of these quantities are discussed in detail. From these results we demonstrate that the particular intermetallic have better ductility and larger thermal expansion.

Magnetized Target Fusion Driven by Plasma Liners

NASA Technical Reports Server (NTRS)

Thio, Y. C. Francis; Kirkpatrick, Ronald C.; Knapp, Charles E.; Rodgers, Stephen L. (Technical Monitor)

2002-01-01

Magnetized target fusion is an emerging, relatively unexplored approach to fusion for electrical power and propulsion application. The physical principles of the concept are founded upon both inertial confinement fusion (ICF) and magnetic confinement fusion (MCF). It attempts to combine the favorable attributes of both these orthogonal approaches to fusion, but at the same time, avoiding the extreme technical challenges of both by exploiting a fusion regime intermediate between them. It uses a material liner to compress, heat and contain the fusion reacting plasma (the target plasma) mentally. By doing so, the fusion burn could be made to occur at plasma densities as high as six orders of magnitude higher than conventional MCF such as tokamak, thus leading to an approximately three orders of magnitude reduction in the plasma energy required for ignition. It also uses a transient magnetic field, compressed to extremely high intensity (100's T to 1000T) in the target plasma, to slow down the heat transport to the liner and to increase the energy deposition of charged-particle fusion products. This has several compounding beneficial effects. It leads to longer energy confinement time compared with conventional ICF without magnetized target, and thus permits the use of much lower plasma density to produce reasonable burn-up fraction. The compounding effects of lower plasma density and the magneto-insulation of the target lead to greatly reduced compressional heating power on the target. The increased energy deposition rate of charged-particle fusion products also helps to lower the energy threshold required for ignition and increasing the burn-up fraction. The reduction in ignition energy and the compressional power compound to lead to reduced system size, mass and R&D cost. It is a fusion approach that has an affordable R&D pathway, and appears attractive for propulsion application in the nearer term.

Theoretical Studies on Structures and Relative Stability for Polynitrohexaazaadamantanes

NASA Astrophysics Data System (ADS)

Xu, Xiao-juan; Xiao, He-ming; Wang, Gui-xiang; Ju, Xue-hai

2006-10-01

The density function theory at the B3LYP/6-31G* level was employed to study the structures, including the total energies (EZPE), the geometries, the oxygen balances (OB100), the dipole moments, of polynitro-hexaazaadamantanes (PNHAAs) and the potential candidates of high energy density compounds (HEDCs). The structural parameters of PNHAAs, such as the the maximum N—NO2 bond length (LBmax), the least N—N Mulliken population (BN—N), the least negative charge on the nitro group (QNO2) and OB100, were studied to predict their relative stability or sensitivity (the easiness for initiating a detonation, high sensitivity means low stability). It was found that the same conclusion was drawn from the four parameters. With the number of nitro groups increasing, the stabilities of these compounds decrease. OB100 failed in identifying the isomers, but the EZPE energy and the dipole moment were considered to give more reliable results for the isomers.

Revealing Extremely Low Energy Amplitude Modes in the Charge-Density-Wave Compound LaAgSb_{2}.

PubMed

Chen, R Y; Zhang, S J; Zhang, M Y; Dong, T; Wang, N L

2017-03-10

Using infrared spectroscopy and ultrafast pump probe measurement, we have studied the two charge-density-wave (CDW) instabilities in the layered compound LaAgSb_{2}. The development of CDW energy gaps was clearly observed by optical spectroscopy, which removed most of the free carrier spectral weight. More interestingly, our time-resolved measurements revealed two coherent oscillations that softened by approaching the two phase transition temperatures, respectively. We addressed that these two oscillations come from the amplitude modes of CDW collective excitations, the surprisingly low energies (0.12 THz and 0.34 THz for the higher and lower temperature ones, respectively) of which are associated with the extremely small nesting wave vectors. Additionally, the amplitude and relaxation time of photoinduced reflectivity of LaAgSb_{2} single crystals stayed unchanged across the CDW phase transitions, which is quite rare and deserves further investigation.

The Mechanisms of Adhesion of Enteromorpha Clathrata.

DTIC Science & Technology

1982-08-24

showed the importance of adsorbed organic compounds to attachment. Both surface charge density and surface free energy can be influenced through...adsorption of organic 10 compounds . Fletcher (36) further showed that attachment of cells to unsuitable surfaces (those not normally adhered to) may be...attained by these tankers (39,69). Presently, the method to combat algal fouling is the use of surface paints containing toxic compounds . The majority of

Density functional theory calculations for the band gap and formation energy of Pr4-xCaxSi12O3+xN18-x; a highly disordered compound with low symmetry and a large cell size.

PubMed

Hong, Sung Un; Singh, Satendra Pal; Pyo, Myoungho; Park, Woon Bae; Sohn, Kee-Sun

2017-06-28

A novel oxynitride compound, Pr 4-x Ca x Si 12 O 3+x N 18-x , synthesized using a solid-state route has been characterized as a monoclinic structure in the C2 space group using Rietveld refinement on synchrotron powder X-ray diffraction data. The crystal structure of this compound was disordered due to the random distribution of Ca/Pr and N/O ions at various Wyckoff sites. A pragmatic approach for an ab initio calculation based on density function theory (DFT) for this disordered compound has been implemented to calculate an acceptable value of the band gap and formation energy. In general, for the DFT calculation of a disordered compound, a sufficiently large super cell and infinite variety of ensemble configurations is adopted to simulate the random distribution of ions; however, such an approach is time consuming and cost ineffective. Even a single unit cell model gave rise to 43 008 independent configurations as an input model for the DFT calculations. Since it was nearly impossible to calculate the formation energy and the band gap energy for all 43 008 configurations, an elitist non-dominated sorting genetic algorithm (NSGA-II) was employed to find the plausible configurations. In the NSGA-II, all 43 008 configurations were mathematically treated as genomes and the calculated band gap and the formation energy as the objective (fitness) function. Generalized gradient approximation (GGA) was first employed in the preliminary screening using NSGA-II, and thereafter a hybrid functional calculation (HSE06) was executed only for the most plausible GGA-relaxed configurations with lower formation and higher band gap energies. The final band gap energy (3.62 eV) obtained after averaging over the selected configurations, resembles closely the experimental band gap value (4.11 eV).

Electronic, thermoelectric and transport properties of cesium cadmium trifluoride: A DFT study

NASA Astrophysics Data System (ADS)

Abraham, Jisha Annie; Pagare, G.; Sanyal, Sankar P.

2018-04-01

The full potential linearized augmented plane wave method based on density functional theory is employed to investigate the electronic structure of CsCdF3. The electronic properties of this compound have been studied from the band structure plot and density of states. The presence of indirect energy gap reveals its insulating nature. Using constant relaxation time, the electrical conductivity, electronic thermal conductivity, Seebeck coefficient and figure of merit are calculated by using Boltzmann transport theory. We have also studied the temperature dependence of thermoelectric properties of this compound.

Redox Species of Redox Flow Batteries: A Review.

PubMed

Pan, Feng; Wang, Qing

2015-11-18

Due to the capricious nature of renewable energy resources, such as wind and solar, large-scale energy storage devices are increasingly required to make the best use of the renewable power. The redox flow battery is considered suitable for large-scale applications due to its modular design, good scalability and flexible operation. The biggest challenge of the redox flow battery is the low energy density. The redox active species is the most important component in redox flow batteries, and the redox potential and solubility of redox species dictate the system energy density. This review is focused on the recent development of redox species. Different categories of redox species, including simple inorganic ions, metal complexes, metal-free organic compounds, polysulfide/sulfur and lithium storage active materials, are reviewed. The future development of redox species towards higher energy density is also suggested.

Molecular orbital studies (hardness, chemical potential, electronegativity and electrophilicity), vibrational spectroscopic investigation and normal coordinate analysis of 5-{1-hydroxy-2-[(propan-2-yl)amino]ethyl}benzene-1,3-diol

NASA Astrophysics Data System (ADS)

Muthu, S.; Renuga, S.

2014-01-01

FT-IR and FT-Raman spectra of 5-{1-hydroxy-2-[(propan-2-yl) amino] ethyl} benzene-1,3-diol (abbrevi- 54 ated as HPAEBD) were recorded in the region 4000-450 cm-1 and 4000-100 cm-1 respectively. The structure of the molecule was optimized and the structural characteristics were determined by density functional theory (B3LYP) and HF method with 6-31 G(d,p) as basis set. The theoretical wave numbers were scaled and compared with experimental FT-IR and FT-Raman spectra. A detailed interpretation of the vibrational spectra of this compound has been made on the basis of the calculated Potential energy distribution (PED). Stability of the molecule arising from hyperconjugation and charge delocalization is confirmed by the natural bond orbital analysis (NBO). The results show that electron density (ED) in the σ antibonding orbitals and E (2) energies confirm the occurrence of intra molecular charge transfer (ICT) within the molecule. The molecule orbital contributions were studied by using the total (TDOS), sum of α and β electron (αβDOS) density of States. Mulliken population analysis of atomic charges is also calculated. The calculated HOMO and LUMO energy gap shows that charge transfer occurs within the molecule. The electron density-based local reactivity descriptors such as Fukui functions were calculated to explain the chemical selectivity or reactivity site in this compound. On the basis of vibrational analyses, the thermodynamic properties of title compound at different temperatures have been calculated.

A chromatographic estimate of the degree of heterogeneity of RPLC packing materials. 1. Non-endcapped polymeric C30-bonded stationary phase

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

Gritti, Fabrice; Guiochon, Georges A

2006-01-01

A new chromatographic method estimating the degree of heterogeneity of RPLC packing materials is based on the results of systematic measurements of the adsorption data in a wide concentration range for selected probe compounds. These data are acquired by frontal analysis (FA), modeled, and used for the calculation of the adsorption energy distribution (AED). Four compounds were used, two neutral compounds of different molecular sizes (caffeine and phenol) and two ionizable compounds of opposite charges, 2-naphthalene sulfonate, an anion, and propranololium, a cation. This work was done on a C{sub 30}-bonded silica stationary phase (Prontosil-C{sub 30}), using the same aqueousmore » mobile phase (30% methanol, v/v) for all compounds, except that sodium chloride (25 mM) was added to elute the ionizable compounds. All four adsorption isotherms have Langmuirian behavior. The AEDs are tri-modal for phenol, quadri-modal for caffeine. The total saturation capacity of the stationary phase is four-fold lower for caffeine than for phenol, due in part to its larger molecular size. The equilibrium constants on the low-energy sites of types 1 and 2 are eight-fold larger. These two types of sites characterize the heterogeneity of the bonded layer itself. The density of the high-energy sites of types 3 and 4 is higher for caffeine, suggesting that caffeine molecules can be accommodated in some hydrophobic cages into which smaller molecules like phenol cannot. These high-energy types of sites characterize the heterogeneity of the whole stationary phase (silica support included). The ionizable compounds have larger molecules than the neutral ones and, accordingly, a lower relative density of sites of type 2 to sites of type 1. A tri-modal and a quadri-modal energy distributions were observed for the 2-naphthalene sulfonate anion and the propranololium cation, respectively. The fourth types of sites measured and its unusually high equilibrium constant are most probably due to ion-exchange interactions between the non-endcapped ionized silanols and the propranololium ion. No such strong interactions are observed with the anionic compound.« less

Structural, Electronic and Dynamical Properties of Curium Monopnictides: Density Functional Calculations

NASA Astrophysics Data System (ADS)

Roondhe, Basant; Upadhyay, Deepak; Som, Narayan; Pillai, Sharad B.; Shinde, Satyam; Jha, Prafulla K.

2017-03-01

The structural, electronic, dynamical and thermodynamical properties of CmX (X = N, P, As, Sb, and Bi) compounds are studied using first principles calculations within density functional theory. The Perdew-Burke-Ernzerhof spin polarized generalized gradient approximation and Perdew-Wang (PW) spin polarized local density approximation as the exchange correlational functionals are used in these calculations. There is a good agreement between the present and previously reported data. The calculated electronic density of states suggests that the curium monopnictides are metallic in nature, which is consistent with earlier studies. The significant values of magnetic moment suggest their magnetic nature. The phonon dispersion curves and phonon density of states are also calculated, which depict the dynamical stability of these compounds. There is a significant separation between the optical and acoustical phonon branches. The temperature dependence of the thermodynamical functions are also calculated and discussed. Internal energy and vibrational contribution to the Helmholtz free energy increases and decreases, respectively, with temperature. The entropy increases with temperature. The specific heat at constant volume and Debye temperature obey Debye theory. The temperature variation of the considered thermodynamical functions is in line with those of other crystalline solids.

Density-functional theory computer simulations of CZTS0.25Se0.75 alloy phase diagrams

NASA Astrophysics Data System (ADS)

Chagarov, E.; Sardashti, K.; Haight, R.; Mitzi, D. B.; Kummel, A. C.

2016-08-01

Density-functional theory simulations of CZTS, CZTSe, and CZTS0.25Se0.75 photovoltaic compounds have been performed to investigate the stability of the CZTS0.25Se0.75 alloy vs. decomposition into CZTS, CZTSe, and other secondary compounds. The Gibbs energy for vibrational contributions was estimated by calculating phonon spectra and thermodynamic properties at finite temperatures. It was demonstrated that the CZTS0.25Se0.75 alloy is stabilized not by enthalpy of formation but primarily by the mixing contributions to the Gibbs energy. The Gibbs energy gains/losses for several decomposition reactions were calculated as a function of temperature with/without intermixing and vibration contributions to the Gibbs energy. A set of phase diagrams was built in the multidimensional space of chemical potentials at 300 K and 900 K temperatures to demonstrate alloy stability and boundary compounds at various chemical conditions. It demonstrated for CZTS0.25Se0.75 that the chemical potentials for stability differ between typical processing temperature (˜900 K) and operating temperature (300 K). This implies that as cooling progresses, the flux/concentration of S should be increased in MBE growth to maintain the CZTS0.25Se0.75 in a thermodynamically stable state to minimize phase decomposition.

Quantum mechanical and spectroscopic (FT-IR, FT-Raman) study, NBO analysis, HOMO-LUMO, first order hyperpolarizability and molecular docking study of methyl[(3R)-3-(2-methylphenoxy)-3-phenylpropyl]amine by density functional method

NASA Astrophysics Data System (ADS)

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

2018-01-01

Quantum chemical techniques such as density functional theory (DFT) have become a powerful tool in the investigation of the molecular structure and vibrational spectrum and are finding increasing use in application related to biological systems. The Fourier transform infrared (FT-IR) and Fourier transform Raman (FT-Raman) techniques are employed to characterize the title compound. The vibrational frequencies were obtained by DFT/B3LYP calculations with 6-31G(d,p) and 6-311 ++G(d,p) as basis sets. The geometry of the title compound was optimized. The vibrational assignments and the calculation of Potential Energy Distribution (PED) were carried out using the Vibrational Energy Distribution Analysis (VEDA) software. Molecular electrostatic potential was calculated for the title compound to predict the reactive sites for electrophilic and nucleophilic attack. In addition, the first-order hyperpolarizability, HOMO and LUMO energies, Fukui function and NBO were computed. The thermodynamic properties of the title compound were calculated at different temperatures, revealing the correlations between heat capacity (C), entropy (S) and enthalpy changes (H) with temperatures. Molecular docking studies were also conducted as part of this study. The paper further explains the experimental results which are in line with the theoretical calculations and provide optimistic evidence through molecular docking that the title compound can act as a good antidepressant. It also provides sufficient justification for the title compound to be selected as a good candidate for further studies related to NLO properties.

Studies on effective atomic numbers, electron densities from mass attenuation coefficients near the K edge in some samarium compounds.

PubMed

Akman, F; Durak, R; Turhan, M F; Kaçal, M R

2015-07-01

The effective atomic numbers and electron densities of some samarium compounds were determined using the experimental total mass attenuation coefficient values near the K edge in the X-ray energy range from 36.847 up to 57.142 keV. The measurements, in the region from 36.847 to 57.142 keV, were done in a transmission geometry utilizing the Kα2, Kα1, Kβ1 and Kβ2 X-rays from different secondary source targets excited by the 59.54 keV gamma-photons from an Am-241 annular source. This paper presents the first measurement of the effective atomic numbers and electron densities for some samarium compounds near the K edge. The results of the study showed that the measured values were in good agreement with the theoretically calculated ones. Copyright © 2015 Elsevier Ltd. All rights reserved.

DFT Insights into the Competitive Adsorption of Sulfur- and Nitrogen-Containing Compounds and Hydrocarbons on Co-Promoted Molybdenum Sulfide Catalysts

DOE PAGES

Rangarajan, Srinivas; Mavrikakis, Manos

2016-04-07

The adsorption of 20 nitrogen-/sulfur-containing and hydrocarbon compounds on the sulfur edge of cobalt-promoted molybdenum sulfide (CoMoS) catalyst was studied using density functional theory, accounting for van der Waals interactions, to elicit comparative structure–property trends across different classes of molecules relevant to hydrotreating. Unhindered organosulfur compounds preferentially adsorb on a “CUS-like” site formed by the dimerization of two neighboring sulfur atoms on the edge to create a vacancy. Nitrogen-containing compounds and 4,6-dimethyldibenzothiophene, however, prefer the brim sites. Binding energy trends indicate that nitrogen-containing compounds will inhibit hydrodesulfurization on the brim sites and, relatively weakly, on the CUS-like sites. Edge vacanciesmore » are,thus, likely to be essential for hydrodesulfurization of unhindered organosulfur compounds. Furthermore, van der Waals forces contribute significantly to the binding energy of compounds (up to 1.0 eV for large compounds such as alkyl-substituted acridines) on CoMoS.« less

Electron affinities and ionization energies of Cu and Ag delafossite compounds: A hybrid functional study

NASA Astrophysics Data System (ADS)

Miao, Mao-Sheng; Yarbro, Sam; Barton, Phillip T.; Seshadri, Ram

2014-01-01

Using density functional theory with a hybrid functional, we calculate the ionization energies and electron affinities of a series of delafossite compounds (AMO2: A =Cu, Ag; M =B, Al, Ga, In, Sc). The alignments of the valence band maximum and the conduction band minimum, which directly relate to the ionization energies and electron affinities, were obtained by calculations of supercell slab models constructed in a nonpolar orientation. Our calculations reveal that the ionization energy decreases with an increasing atomic number of group-III elements, and thus suggest an improved p-type doping propensity for heavier compounds. For keeping both a low ionization energy and a band gap of sufficient size, CuScO2 is superior to the Cu-based group-III delafossites. By analyzing the electronic structures, we demonstrate that the compositional trend of the ionization energies and electron affinities is the result of a combined effect of d-band broadening due to Cu(Ag)-Cu(Ag) coupling and a repositioning of the d-band center.

Density of states, optical and thermoelectric properties of perovskite vanadium fluorides Na3VF6

NASA Astrophysics Data System (ADS)

Reshak, A. H.; Azam, Sikander

2014-05-01

The electronic structure, charge density and Fermi surface of Na3VF6 compound have been examined with the support of density functional theory (DFT). Using the full potential linear augmented plane wave method, we employed the local density approximation (LDA), generalized gradient approximation (GGA) and Engel-Vosko GGA (EVGGA) to treat the exchange correlation potential to solve Kohn-Sham equations. The calculation show that Na3VF6 compound has metallic nature and the Fermi energy (EF) is assessed by overlapping of V-d state. The calculated density of states at the EF are about 18.655, 51.932 and 13.235 states/eV, and the bare linear low-temperature electronic specific heat coefficient (γ) is found to be 3.236 mJ/mol-K2, 9.008 mJ/mol-K2 and 2.295 mJ/mol-K2 for LDA, GGA and EVGGA, respectively. The Fermi surface is composed of two sheets. The chemical bonding of Na3VF6 compound is analyzed through the electronic charge density in the (1 1 0) crystallographic plane. The optical constants and thermal properties were also calculated and discussed.

Total-energy Assisted Tight-binding Method Based on Local Density Approximation of Density Functional Theory

NASA Astrophysics Data System (ADS)

Fujiwara, Takeo; Nishino, Shinya; Yamamoto, Susumu; Suzuki, Takashi; Ikeda, Minoru; Ohtani, Yasuaki

2018-06-01

A novel tight-binding method is developed, based on the extended Hückel approximation and charge self-consistency, with referring the band structure and the total energy of the local density approximation of the density functional theory. The parameters are so adjusted by computer that the result reproduces the band structure and the total energy, and the algorithm for determining parameters is established. The set of determined parameters is applicable to a variety of crystalline compounds and change of lattice constants, and, in other words, it is transferable. Examples are demonstrated for Si crystals of several crystalline structures varying lattice constants. Since the set of parameters is transferable, the present tight-binding method may be applicable also to molecular dynamics simulations of large-scale systems and long-time dynamical processes.

Electronic structure of the alkyne-bridged dicobalt hexacarbonyl complex Co(2) micro-C(2)H(2) (CO)(6): evidence for singlet diradical character and implications for metal-metal bonding.

PubMed

Platts, James A; Evans, Gareth J S; Coogan, Michael P; Overgaard, Jacob

2007-08-06

A series of ab initio calculations are presented on the alkyne-bridged dicobalt hexacarbonyl cluster Co2 micro-C2H2 (CO)6, indicating that this compound has substantial multireference character, which we interpret as evidence of singlet diradical behavior. As a result, standard theoretical methods such as restricted Hartree-Fock (RHF) or Kohn-Sham (RKS) density functional theory cannot properly describe this compound. We have therefore used complete active space (CAS) methods to explore the bonding in and spectroscopic properties of Co2 micro-C2H2 (CO)6. CAS methods identify significant population of a Co-Co antibonding orbital, along with Co-pi* back-bonding, and a relatively large singlet-triplet energy splitting. Analysis of the electron density and related quantities, such as energy densities and atomic overlaps, indicates a small but significant amount of covalent bonding between cobalt centers.

Theoretical studies of the nitrogen containing compounds adsorption behavior on Na(I)Y and rare earth exchanged RE(III)Y zeolites.

PubMed

Geng, Wei; Zhang, Haitao; Zhao, Xuefei; Zan, Wenyan; Gao, Xionghou; Yao, Xiaojun

2015-01-01

In this work, the adsorption behavior of nitrogen containing compounds including NH3, pyridine, quinoline, and carbazole on Na(I)Y and rare earth exchanged La(III)Y, Pr(III)Y, Nd(III)Y zeolites was investigated by density functional theory (DFT) calculations. The calculation results demonstrate that rare earth exchanged zeolites have stronger adsorption ability for nitrogen containing compounds than Na(I)Y. Rare earth exchanged zeolites exhibit strongest interaction with quinoline while weakest with carbazole. Nd(III)Y zeolites are found to have strongest adsorption to all the studied nitrogen containing compounds. The analysis of the electronic total charge density and electron orbital overlaps show that nitrogen containing compounds interact with zeolites by π-electrons of the compounds and the exchanged metal atom. Mulliken charge population analysis also proves that adsorption energies are strongly dependent on the charge transfer between the nitrogen containing molecules and exchanged metal atom in the zeolites.

Computational investigation of half-Heusler compounds for spintronics applications

NASA Astrophysics Data System (ADS)

Ma, Jianhua; Hegde, Vinay I.; Munira, Kamaram; Xie, Yunkun; Keshavarz, Sahar; Mildebrath, David T.; Wolverton, C.; Ghosh, Avik W.; Butler, W. H.

2017-01-01

We present first-principles density functional calculations of the electronic structure, magnetism, and structural stability of 378 XYZ half-Heusler compounds (with X = Cr, Mn, Fe, Co, Ni, Ru, Rh; Y = Ti, V, Cr, Mn, Fe, Ni; Z = Al, Ga, In, Si, Ge, Sn, P, As, Sb). We find that a "Slater-Pauling gap" in the density of states (i.e., a gap or pseudogap after nine states in the three atom primitive cell) in at least one spin channel is a common feature in half-Heusler compounds. We find that the presence of such a gap at the Fermi energy in one or both spin channels contributes significantly to the stability of a half-Heusler compound. We calculate the formation energy of each compound and systematically investigate its stability against all other phases in the open quantum materials database (OQMD). We represent the thermodynamic phase stability of each compound as its distance from the convex hull of stable phases in the respective chemical space and show that the hull distance of a compound is a good measure of the likelihood of its experimental synthesis. We find low formation energies and mostly correspondingly low hull distances for compounds with X = Co, Rh, or Ni, Y = Ti or V, and Z = P, As, Sb, or Si. We identify 26 18-electron semiconductors, 45 half-metals, and 34 near half-metals with negative formation energy that follow the Slater-Pauling rule of three electrons per atom. Our calculations predict several new, as-yet unknown, thermodynamically stable phases, which merit further experimental exploration—RuVAs, CoVGe, FeVAs in the half-Heusler structure, and NiScAs, RuVP, RhTiP in the orthorhombic MgSrSi-type structure. Further, two interesting zero-moment half-metals, CrMnAs and MnCrAs, are calculated to have negative formation energy. In addition, our calculations predict a number of hitherto unreported semiconducting (e.g., CoVSn and RhVGe), half-metallic (e.g., RhVSb), and near half-metallic (e.g., CoFeSb and CoVP) half-Heusler compounds to lie close to the respective convex hull of stable phases, and thus may be experimentally realized under suitable synthesis conditions, resulting in potential candidates for various semiconducting and spintronics applications.

Structural, thermodynamic, and electronic properties of Laves-phase NbMn2 from first principles, x-ray diffraction, and calorimetric experiments

NASA Astrophysics Data System (ADS)

Yan, X.; Chen, Xing-Qiu; Michor, H.; Wolf, W.; Witusiewicz, V. T.; Bauer, E.; Podloucky, R.; Rogl, P.

2018-03-01

By combining theoretical density functional theory (DFT) and experimental studies, structural and magnetic phase stabilities and electronic structural, elastic, and vibrational properties of the Laves-phase compound NbMn2 have been investigated for the C14, C15, and C36 crystal structures. At low temperatures C14 is the ground-state structure, with ferromagnetic and antiferromagnetic orderings being degenerate in energy. The degenerate spin configurations result in a rather large electronic density of states at Fermi energy for all magnetic cases, even for the spin-polarized DFT calculations. Based on the DFT-derived phonon dispersions and densities of states, temperature-dependent free energies were derived for the ferromagnetic and antiferromagnetic C14 phase, demonstrating that the spin-configuration degeneracy possibly exists up to finite temperatures. The heat of formation Δ298H0=-45.05 ±3.64 kJ (molf .u .NbMn2) -1 was extracted from drop isoperibolic calorimetry in a Ni bath. The DFT-derived enthalpy of formation of NbMn2 is in good agreement with the calorimetric measurements. Second-order elastic constants for NbMn2 as well as for related compounds were calculated.

Quantum chemical calculations of glycine glutaric acid

NASA Astrophysics Data System (ADS)

Arioǧlu, ćaǧla; Tamer, Ömer; Avci, Davut; Atalay, Yusuf

2017-02-01

Density functional theory (DFT) calculations of glycine glutaric acid were performed by using B3LYP levels with 6-311++G(d,p) basis set. The theoretical structural parameters such as bond lengths and bond angles are in a good agreement with the experimental values of the title compound. HOMO and LUMO energies were calculated, and the obtained energy gap shows that charge transfer occurs in the title compound. Vibrational frequencies were calculated and compare with experimental ones. 3D molecular surfaces of the title compound were simulated using the same level and basis set. Finally, the 13C and 1H NMR chemical shift values were calculated by the application of the gauge independent atomic orbital (GIAO) method.

Molecular orbital studies (hardness, chemical potential, electronegativity and electrophilicity), vibrational spectroscopic investigation and normal coordinate analysis of 5-{1-hydroxy-2-[(propan-2-yl)amino]ethyl}benzene-1,3-diol.

PubMed

Muthu, S; Renuga, S

2014-01-24

FT-IR and FT-Raman spectra of 5-{1-hydroxy-2-[(propan-2-yl) amino] ethyl} benzene-1,3-diol (abbrevi- 54 ated as HPAEBD) were recorded in the region 4000-450 cm(-1) and 4000-100 cm(-1) respectively. The structure of the molecule was optimized and the structural characteristics were determined by density functional theory (B3LYP) and HF method with 6-31 G(d,p) as basis set. The theoretical wave numbers were scaled and compared with experimental FT-IR and FT-Raman spectra. A detailed interpretation of the vibrational spectra of this compound has been made on the basis of the calculated Potential energy distribution (PED). Stability of the molecule arising from hyperconjugation and charge delocalization is confirmed by the natural bond orbital analysis (NBO). The results show that electron density (ED) in the σ antibonding orbitals and E (2) energies confirm the occurrence of intra molecular charge transfer (ICT) within the molecule. The molecule orbital contributions were studied by using the total (TDOS), sum of α and β electron (αβDOS) density of States. Mulliken population analysis of atomic charges is also calculated. The calculated HOMO and LUMO energy gap shows that charge transfer occurs within the molecule. The electron density-based local reactivity descriptors such as Fukui functions were calculated to explain the chemical selectivity or reactivity site in this compound. On the basis of vibrational analyses, the thermodynamic properties of title compound at different temperatures have been calculated. Copyright © 2013 Elsevier B.V. All rights reserved.

Structural, electronic, elastic, thermoelectric and thermodynamic properties of the NbMSb half heusler (M=Fe, Ru, Os) compounds with first principle calculations

NASA Astrophysics Data System (ADS)

Abid, O. Miloud; Menouer, S.; Yakoubi, A.; Khachai, H.; Omran, S. Bin; Murtaza, G.; Prakash, Deo; Khenata, R.; Verma, K. D.

2016-05-01

The structural, electronic, elastic, thermoelectric and thermodynamic properties of NbMSb (M = Fe, Ru, Os) half heusler compounds are reported. The full-potential linearized augmented plane wave (FP-LAPW) plus local orbital (lo) method, based on the density functional theory (DFT) was employed for the present study. The equilibrium lattice parameter results are in good compliance with the available experimental measurements. The electronic band structure and Boltzmann transport calculations indicated a narrow indirect energy band gap for the compound having electronic structure favorable for thermoelectric performance as well as with substantial thermopowers at temperature ranges from 300 K to 800 K. Furthermore, good potential for thermoelectric performance (thermopower S ≥ 500 μeV) was found at higher temperature. In addition, the analysis of the charge density, partial and total densities of states (DOS) of three compounds demonstrate their semiconducting, ionic and covalent characters. Conversely, the calculated values of the Poisson's ratio and the B/G ratio indicate their ductile makeup. The thermal properties of the compounds were calculated by quasi-harmonic Debye model as implemented in the GIBBS code.

Metal-free aqueous redox capacitor via proton rocking-chair system in an organic-based couple

PubMed Central

Tomai, Takaaki; Mitani, Satoshi; Komatsu, Daiki; Kawaguchi, Yuji; Honma, Itaru

2014-01-01

Safe and inexpensive energy storage devices with long cycle lifetimes and high power and energy densities are mandatory for the development of electrical power grids that connect with renewable energy sources. In this study, we demonstrated metal-free aqueous redox capacitors using couples comprising low-molecular-weight organic compounds. In addition to the electric double layer formation, proton insertion/extraction reactions between a couple consisting of inexpensive quinones/hydroquinones contributed to the energy storage. This energy storage mechanism, in which protons are shuttled back and forth between two electrodes upon charge and discharge, can be regarded as a proton rocking-chair system. The fabricated capacitor showed a large capacity (>20 Wh/kg), even in the applied potential range between 0–1 V, and high power capability (>5 A/g). The support of the organic compounds in nanoporous carbon facilitated the efficient use of the organic compounds with a lifetime of thousands of cycles. PMID:24395117

Metal-free aqueous redox capacitor via proton rocking-chair system in an organic-based couple.

PubMed

Tomai, Takaaki; Mitani, Satoshi; Komatsu, Daiki; Kawaguchi, Yuji; Honma, Itaru

2014-01-07

Safe and inexpensive energy storage devices with long cycle lifetimes and high power and energy densities are mandatory for the development of electrical power grids that connect with renewable energy sources. In this study, we demonstrated metal-free aqueous redox capacitors using couples comprising low-molecular-weight organic compounds. In addition to the electric double layer formation, proton insertion/extraction reactions between a couple consisting of inexpensive quinones/hydroquinones contributed to the energy storage. This energy storage mechanism, in which protons are shuttled back and forth between two electrodes upon charge and discharge, can be regarded as a proton rocking-chair system. The fabricated capacitor showed a large capacity (>20 Wh/kg), even in the applied potential range between 0-1 V, and high power capability (>5 A/g). The support of the organic compounds in nanoporous carbon facilitated the efficient use of the organic compounds with a lifetime of thousands of cycles.

Metal-free aqueous redox capacitor via proton rocking-chair system in an organic-based couple

NASA Astrophysics Data System (ADS)

Tomai, Takaaki; Mitani, Satoshi; Komatsu, Daiki; Kawaguchi, Yuji; Honma, Itaru

2014-01-01

Safe and inexpensive energy storage devices with long cycle lifetimes and high power and energy densities are mandatory for the development of electrical power grids that connect with renewable energy sources. In this study, we demonstrated metal-free aqueous redox capacitors using couples comprising low-molecular-weight organic compounds. In addition to the electric double layer formation, proton insertion/extraction reactions between a couple consisting of inexpensive quinones/hydroquinones contributed to the energy storage. This energy storage mechanism, in which protons are shuttled back and forth between two electrodes upon charge and discharge, can be regarded as a proton rocking-chair system. The fabricated capacitor showed a large capacity (>20 Wh/kg), even in the applied potential range between 0-1 V, and high power capability (>5 A/g). The support of the organic compounds in nanoporous carbon facilitated the efficient use of the organic compounds with a lifetime of thousands of cycles.

Crystal structure, detonation performance, and thermal stability of a new polynitro cage compound: 2, 4, 6, 8, 10, 12, 13, 14, 15-nonanitro-2, 4, 6, 8, 10, 12, 13, 14, 15-nonaazaheptacyclo [5.5.1.1(3, 11).1 (5, 9)] pentadecane.

PubMed

Zhang, Jian-ying; Du, Hong-chen; Wang, Fang; Gong, Xue-dong; Ying, San-jiu

2012-06-01

A new polynitro cage compound 2, 4, 6, 8, 10, 12, 13, 14, 15-nonanitro-2, 4, 6, 8, 10, 12, 13, 14, 15-nonaazaheptcyclo [5.5.1.1(3,11).1(5,9)] pentadecane (NNNAHP) was designed in the present work. Its molecular structure was optimized at the B3LYP/6-31 G(d,p) level of density functional theory (DFT) and crystal structure was predicted using the Compass and Dreiding force fields and refined by DFT GGA-RPBE method. The obtained crystal structure of NNNAHP belongs to the P-1 space group and the lattice parameters are a = 9.99 Å, b = 10.78 Å, c = 9.99 Å, α = 90.01°, β = 120.01°, γ = 90.00°, and Z = 2, respectively. Based on the optimized crystal structure, the band gap, density of state, thermodynamic properties, infrared spectrum, strain energy, detonation characteristics, and thermal stability were predicted. Calculation results show that NNNAHP has detonation properties close to those of CL-20 and is a high energy density compound with moderate stability.

Evolution of the orbitals Dy-4f in the DyB2 compound using the LDA, PBE approximations, and the PBE0 hybrid functional

NASA Astrophysics Data System (ADS)

Rasero Causil, Diego; Ortega López, César; Espitia Rico, Miguel

2018-04-01

Computational calculations of total energy based on density functional theory were used to investigate the structural, electronic, and magnetic properties of the DyB2 compounds in the hexagonal structure. The calculations were carried out by means of the full-potential linearized augmented plane wave (FP-LAPW) method, employing the computational Wien2k package. The local density approximation (LDA) and the generalized gradient approximation (GGA) were used for the electron-electron interactions. Additionally, we used the functional hybrid PBE0 for a better description the electronic and magnetic properties, because the DyB2 compound is a strongly-correlated system. We found that the calculated lattice constant agrees well with the values reported theoretically and experimentally. The density of states (DOS) calculation shows that the compound exhibits a metallic behavior and has magnetic properties, with a total magnetic moment of 5.47 μ0/cell determined mainly by the 4f states of the rare earth elements. The functional PBE0 shows a strong localization of the Dy-4f orbitals.

A conceptual DFT study of the molecular properties of glycating carbonyl compounds.

PubMed

Frau, Juan; Glossman-Mitnik, Daniel

2017-01-01

Several glycating carbonyl compounds have been studied by resorting to the latest Minnesota family of density functional with the objective of determinating their molecular properties. In particular, the chemical reactivity descriptors that arise from conceptual density functional theory and chemical reactivity theory have been calculated through a [Formula: see text]SCF protocol. The validity of the KID (Koopmans' in DFT) procedure has been checked by comparing the reactivity descriptors obtained from the values of the HOMO and LUMO with those calculated through vertical energy values. The reactivity sites have been determined by means of the calculation of the Fukui function indices, the condensed dual descriptor [Formula: see text] and the electrophilic and nucleophilic Parr functions. The glycating power of the studied compounds have been compared with the same property for simple carbohydrates.Graphical abstractSeveral glycating carbonyl compounds have been studied by resorting to the latest Minnesota family of density functional with the objective of determinating their molecular properties, the chemical reactivity descriptors and the validity of the KID (Koopmans' in DFT) procedure.

Quantum mechanical and spectroscopic (FT-IR, FT-Raman) study, NBO analysis, HOMO-LUMO, first order hyperpolarizability and molecular docking study of methyl[(3R)-3-(2-methylphenoxy)-3-phenylpropyl]amine by density functional method.

PubMed

Kuruvilla, Tintu K; Prasana, Johanan Christian; Muthu, S; George, Jacob; Mathew, Sheril Ann

2018-01-05

Quantum chemical techniques such as density functional theory (DFT) have become a powerful tool in the investigation of the molecular structure and vibrational spectrum and are finding increasing use in application related to biological systems. The Fourier transform infrared (FT-IR) and Fourier transform Raman (FT-Raman) techniques are employed to characterize the title compound. The vibrational frequencies were obtained by DFT/B3LYP calculations with 6-31G(d,p) and 6-311++G(d,p) as basis sets. The geometry of the title compound was optimized. The vibrational assignments and the calculation of Potential Energy Distribution (PED) were carried out using the Vibrational Energy Distribution Analysis (VEDA) software. Molecular electrostatic potential was calculated for the title compound to predict the reactive sites for electrophilic and nucleophilic attack. In addition, the first-order hyperpolarizability, HOMO and LUMO energies, Fukui function and NBO were computed. The thermodynamic properties of the title compound were calculated at different temperatures, revealing the correlations between heat capacity (C), entropy (S) and enthalpy changes (H) with temperatures. Molecular docking studies were also conducted as part of this study. The paper further explains the experimental results which are in line with the theoretical calculations and provide optimistic evidence through molecular docking that the title compound can act as a good antidepressant. It also provides sufficient justification for the title compound to be selected as a good candidate for further studies related to NLO properties. Copyright © 2017. Published by Elsevier B.V.

Exploring the Photovoltaic Properties of Metal Bipyridine Complexes (Metal = Fe, Zn, Cr, and Ru) by Density Functional Theory

NASA Astrophysics Data System (ADS)

Irfan, Ahmad; Abbas, Ghulam

2018-03-01

The synthesis and characterisation of mononuclear Fe complexes were carried out by using bipyridine (Compound 1) at ambient conditions. Additionally, three more derivatives were designed by substituting the central Fe metal with Zn, Cr, and Ru (Compound 2, Compound 3, and Compound 4), respectively. The ground state geometry calculations were carried out by using density functional theory (DFT) at B3LYP/6-31G** (LANL2DZ) level of theory. We shed light on the frontier molecular orbitals, electronic properties, photovoltaic parameters, and structure-property relationship. The open-circuit voltage is a promising parameter that considerably affects the photovoltaic performance; thus, we have estimated its value by considering the complexes as donors whereas TiO2 and/or Si were used as acceptors. The solar cell performance behaviour was also studied by shedding light on the band alignment and energy level offset.

Theoretical studies on the crystal structure, thermodynamic properties, detonation performance and thermal stability of cage-tetranitrotetraazabicyclooctane as a novel high energy density compound.

PubMed

Zhao, Guo-zheng; Lu, Ming

2013-01-01

The B3LYP/6-31G (d) method of density functional theory (DFT) was used to study molecular geometry, electronic structure, infrared spectrum (IR) and thermodynamic properties. The heat of formation (HOF) and calculated density were estimated to evaluate the detonation properties using Kamlet-Jacobs equations. Thermal stability of 3,5,7,10,12,14,15,16-octanitro- 3,5,7,10,12,14,15,16-octaaza-heptacyclo[7.5.1.1(2,8).0(1,11).0(2,6).0(4,13).0(6,11)]hexadecane (cage-tetranitrotetraazabicyclooctane) was investigated by calculating the bond dissociation energy (BDE) at unrestricted B3LYP/6-31G (d) level. The calculated results show that the N-NO2 bond is a trigger bond during thermolysis initiation process. The crystal structure obtained by molecular mechanics (MM) methods belongs to Pna2(1) space group, with cell parameters a=12.840 Å, b=9.129 Å, c=14.346 Å, Z=6 and ρ=2.292 g·cm(-3). Both the detonation velocity of 9.96 km·s(-1) and the detonation pressure of 47.47 GPa are better than those of CL-20. According to the quantitative standard of energetics and stability, as a high energy density compound (HEDC), cage-tetranitrotetraazabicyclooctane essentially satisfies this requirement.

Aqueous lithium air batteries

DOEpatents

Visco, Steven J.; Nimon, Yevgeniy S.; De Jonghe, Lutgard C.; Petrov, Alexei; Goncharenko, Nikolay

2017-05-23

Aqueous Li/Air secondary battery cells are configurable to achieve high energy density and prolonged cycle life. The cells include a protected a lithium metal or alloy anode and an aqueous catholyte in a cathode compartment. The aqueous catholyte comprises an evaporative-loss resistant and/or polyprotic active compound or active agent that partakes in the discharge reaction and effectuates cathode capacity for discharge in the acidic region. This leads to improved performance including one or more of increased specific energy, improved stability on open circuit, and prolonged cycle life, as well as various methods, including a method of operating an aqueous Li/Air cell to simultaneously achieve improved energy density and prolonged cycle life.

Magneto-structural correlations in a family of Fe(II)Re(IV)(CN)2 single-chain magnets: density functional theory and ab initio calculations.

PubMed

Zhang, Yi-Quan; Luo, Cheng-Lin; Wu, Xin-Bao; Wang, Bing-Wu; Gao, Song

2014-04-07

Until now, the expressions of the anisotropic energy barriers Δξ and ΔA, using the uniaxial magnetic anisotropy D, the intrachain coupling strength J, and the high-spin ground state S for single-chain magnets (SCMs) in the intermediate region between the Ising and the Heisenberg limits, were unknown. To explore this relationship, we used density functional theory and ab initio methods to obtain expressions of Δξ and ΔA in terms of D, J, and S of six R4Fe(II)-Re(IV)Cl4(CN)2 (R = diethylformamide (1), dibutylformamide (2), dimethylformamide (3), dimethylbutyramide (4), dimethylpropionamide (5), and diethylacetamide (6)) SCMs in the intermediate region. The ΔA value for compounds 1-3 was very similar to the magnetic anisotropic energy of a single Fe(II), while the value of Δξ was predicted using the exchange interaction of Fe(II) with the neighboring Re(IV), which could be expressed as 2JSReSFe. Similar to compounds 1-3, the anisotropy energy barrier ΔA of compounds 4 and 5 was also equal to (Di - Ei)SFe(2), but the correlation energy Δξ was closely equal to 2JSReSFe(cos 98.4 - cos 180) due to the reversal of the spins on the opposite Fe(II). For compound 6, one unit cell of Re(IV)Fe(II) was regarded as a domain wall since it had two different Re(IV)-Fe(II) couplings. Thus, the Δξ of compound 6 was expressed as 4J″SRe1Fe1SRe2Fe2, where J″ was the coupling constant of the neighboring unit cells of Re1Fe1 and Re2Fe2, and ΔA was equal to the anisotropic energy barrier of one domain wall given by DRe1Fe1(S(2)Re1Fe1 - 1/4).

Density-functional theory computer simulations of CZTS{sub 0.25}Se{sub 0.75} alloy phase diagrams

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

Chagarov, E.; Sardashti, K.; Kummel, A. C.

2016-08-14

Density-functional theory simulations of CZTS, CZTSe, and CZTS{sub 0.25}Se{sub 0.75} photovoltaic compounds have been performed to investigate the stability of the CZTS{sub 0.25}Se{sub 0.75} alloy vs. decomposition into CZTS, CZTSe, and other secondary compounds. The Gibbs energy for vibrational contributions was estimated by calculating phonon spectra and thermodynamic properties at finite temperatures. It was demonstrated that the CZTS{sub 0.25}Se{sub 0.75} alloy is stabilized not by enthalpy of formation but primarily by the mixing contributions to the Gibbs energy. The Gibbs energy gains/losses for several decomposition reactions were calculated as a function of temperature with/without intermixing and vibration contributions to themore » Gibbs energy. A set of phase diagrams was built in the multidimensional space of chemical potentials at 300 K and 900 K temperatures to demonstrate alloy stability and boundary compounds at various chemical conditions. It demonstrated for CZTS{sub 0.25}Se{sub 0.75} that the chemical potentials for stability differ between typical processing temperature (∼900 K) and operating temperature (300 K). This implies that as cooling progresses, the flux/concentration of S should be increased in MBE growth to maintain the CZTS{sub 0.25}Se{sub 0.75} in a thermodynamically stable state to minimize phase decomposition.« less

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.

Ab initio prediction of half-metallic properties for the ferromagnetic Heusler alloys Co2MSi (M=Ti,V,Cr)

NASA Astrophysics Data System (ADS)

Chen, Xing-Qiu; Podloucky, R.; Rogl, P.

2006-12-01

By means of density functional calculations, the magnetic and electronic properties and phase stabilities of the Heusler compounds Co2MSi (with M =Ti,V,Cr,Mn,Fe,Co,Ni) were investigated. Based on the calculated results, we predict the ferromagnetic phases of the compounds Co2TiSi, Co2VSi, and Co2CrSi to be half metals. Of particular interest is Co2CrSi because of its high density of majority-spin states at Fermi energy in combination with a reasonably high estimated Curie temperature of 747K. The compounds Co2TiSi and Co2VSi are thermodynamically stable, whereas Co2CrSi is of a metastable phase which might be stabilized by suitable experimental techniques.

Spectrophotometric, voltammetric and cytotoxicity studies of 2-hydroxy-5-methoxyacetophenone thiosemicarbazone and its N(4)-substituted derivatives: A combined experimental-computational study

NASA Astrophysics Data System (ADS)

Akgemci, Emine Guler; Saf, Ahmet Ozgur; Tasdemir, Halil Ugur; Türkkan, Ercan; Bingol, Haluk; Turan, Suna Ozbas; Akkiprik, Mustafa

2015-02-01

In this study, 2-hydroxy-5-methoxyacetophenone thiosemicarbazone (HMAT) and its novel N(4) substituted derivatives were synthesized and characterized by different techniques. The optical band gap of the compounds and the energy of HOMO were experimentally examined by UV-vis spectra and cyclic voltammetry measurements, respectively. Furthermore, the conformational spaces of the compounds were scanned with molecular mechanics method. The geometry optimization, HOMO and LUMO energies, the energy gap of the HOMO-LUMO, dipole moment of the compounds were theoretically calculated by the density functional theory B3LYP/6-311++G(d,p) level. The minimal electronic excitation energy and maximum wavelength calculations of the compounds were also performed by TD-DFT//B3LYP/6-311++G(d,p) level of theory. Theoretically calculated values were compared with the related experimental values. The combined results exhibit that all compounds have good electron-donor properties which affect anti-proliferative activity. The cytotoxic effects of the compounds were also evaluated against HeLa (cervical carcinoma), MCF-7 (breast carcinoma) and PC-3 (prostatic carcinoma) cell lines using the standard MTT assay. All tested compounds showed antiproliferative effect having IC50 values in different range. In comparison with that of HMAT, it was obtained that while ethyl group on 4(N)-substituted position decreased in potent anti-proliferative effect, the phenyl group on the position increased in anti-proliferative effect for the tested cancer cell line. Considering the molecular energy parameters, the cytotoxicity activities of the compounds were discussed.

Combined spectroscopic, DFT, TD-DFT and MD study of newly synthesized thiourea derivative

NASA Astrophysics Data System (ADS)

Menon, Vidya V.; Sheena Mary, Y.; Shyma Mary, Y.; Panicker, C. Yohannan; Bielenica, Anna; Armaković, Stevan; Armaković, Sanja J.; Van Alsenoy, Christian

2018-03-01

A novel thiourea derivative, 1-(3-bromophenyl)-3-[3-(trifluoromethyl)phenyl]thiourea (ANF-22) is synthesized and characterized by FTIR, FT-Raman and NMR spectroscopy experimentally and theoretically. A detailed conformational analysis of the title molecule has been conducted in order to locate the lowest energy geometry, which was further subjected to the detailed investigation of spectroscopic, reactive, degradation and docking studies by density functional theory (DFT) calculations and molecular dynamics (MD) simulations. Time dependent DFT (TD-DFT) calculations have been used also in order to simulate UV spectra and investigate charge transfer within molecule. Natural bond orbital analysis has been performed analyzing the charge delocalization and using HOMO and LUMO energies the electronic properties are analyzed. Molecular electrostatic potential map is used for the quantitative measurement of active sites in the molecule. In order to determine the locations possibly prone to electrophilic attacks we have calculated average local ionization energies and mapped them to the electron density surface. Further insight into the local reactivity properties have been obtained by calculation of Fukui functions, also mapped to the electron density surface. Possible degradation properties by the autoxidation mechanism have been assessed by calculations of bond dissociation energies for hydrogen abstraction. Atoms of title molecule with significant interactions with water molecules have been determined by calculations of radial distribution functions. The title compound can be a lead compound for developing new analgesic drug.

DFT-BASED AB INITIO STUDY OF THE ELECTRONIC AND OPTICAL PROPERTIES OF CESIUM BASED FLUORO-PEROVSKITE CsMF3 (M = Ca AND Sr)

NASA Astrophysics Data System (ADS)

Harmel, M.; Khachai, H.; Ameri, M.; Khenata, R.; Baki, N.; Haddou, A.; Abbar, B.; UǦUR, Ş.; Omran, S. Bin; Soyalp, F.

2012-12-01

Density functional theory (DFT) is performed to study the structural, electronic and optical properties of cubic fluoroperovskite AMF3 (A = Cs; M = Ca and Sr) compounds. The calculations are based on the total-energy calculations within the full-potential linearized augmented plane wave (FP-LAPW) method. The exchange-correlation potential is treated by local density approximation (LDA) and generalized gradient approximation (GGA). The structural properties, including lattice constants, bulk modulus and their pressure derivatives are in very good agreement with the available experimental and theoretical data. The calculations of the electronic band structure, density of states and charge density reveal that compounds are both ionic insulators. The optical properties (namely: the real and the imaginary parts of the dielectric function ɛ(ω), the refractive index n(ω) and the extinction coefficient k(ω)) were calculated for radiation up to 40.0 eV.

Crystal structures, spectroscopic and theoretical study of novel Schiff bases of 2-(methylthiomethyl)anilines.

PubMed

Olalekan, Temitope E; Adejoro, Isaiah A; VanBrecht, Bernardus; Watkins, Gareth M

2015-03-15

New Schiff bases derived from p-methoxysalicylaldehyde and 2-(methylthiomethyl)anilines (substituted with methyl, methoxy, nitro) were synthesized and characterized by elemental analyses, FT-IR, NMR, electronic spectra and quantum chemical calculations. X-ray crystallography of two compounds showed the solid structures are stabilized by intramolecular and intermolecular H-bonds. The effect of OH⋯N interaction between the phenolic hydrogen and imine nitrogen on the proton and carbon NMR shifts, and the role of CH⋯O and CH⋯S contacts are discussed. The bond lengths and angles, (1)H and (13)C NMR data, E(LUMO-HOMO), dipole moments and polarizability of the compounds were predicted by density functional theory, DFT (B3LYP/6-31G∗∗) method. The experimental geometric parameters and the NMR shifts were compared with the calculated values, which gave good correlations. The electronic effects of aryl ring substituents (methyl, methoxy and nitro) on the properties of the resulting compounds, such as the color, NMR shifts, electronic spectra and the calculated energy band gaps, dipole moments and polarizability are discussed. Increase in electron density shifted the phenolic proton resonance to lower fields. The methoxy-substituted compound has a small dipole moment and subsequent large polarizability value. Highest polarity was indicated by the nitro compound which also showed high polarizability due to its larger size. The energy gaps obtained from E(LUMO-HOMO) calculations suggest these compounds may have applications as organic semiconducting materials. Copyright © 2014 Elsevier B.V. All rights reserved.

From grand-canonical density functional theory towards rational compound design

NASA Astrophysics Data System (ADS)

von Lilienfeld, Anatole

2008-03-01

The fundamental challenge of rational compound design, ie the reverse engineering of chemical compounds with predefined specific properties, originates in the high-dimensional combinatorial nature of chemical space. Chemical space is the hyper-space of a given set of molecular observables that is spanned by the grand-canonical variables (particle densities of electrons and nuclei) which define chemical composition. A brief but rigorous description of chemical space within the molecular grand-canonical ensemble multi-component density functional theory framework will be given [1]. Numerical results will be presented for intermolecular energies as a continuous function of alchemical variations within a neutral and isoelectronic 10 proton system, including CH4, NH3, H2O, and HF, interacting with formic acid [2]. Furthermore, engineering the Fermi level through alchemical generation of boron-nitrogen doped mutants of benzene shall be discussed [3].[1] von Lilienfeld and Tuckerman JCP 125 154104 (2006)[2] von Lilienfeld and Tuckerman JCTC 3 1083 (2007)[3] Marcon et al. JCP 127 064305 (2007)

Investigation of metal-dithiolate fold angle effects: implications for molybdenum and tungsten enzymes.

PubMed

Joshi, Hemant K; Cooney, J Jon A; Inscore, Frank E; Gruhn, Nadine E; Lichtenberger, Dennis L; Enemark, John H

2003-04-01

Gas-phase photoelectron spectroscopy and density functional theory have been used to investigate the interactions between the sulfur pi-orbitals of arene dithiolates and high-valent transition metals as minimum molecular models of the active site features of pyranopterin MoW enzymes. The compounds (Tp*)MoO(bdt) (compound 1), Cp(2)Mo(bdt) (compound 2), and Cp(2)Ti(bdt) (compound 3) [where Tp* is hydrotris(3,5-dimethyl-1-pyrazolyl)borate, bdt is 1,2-benzenedithiolate, and Cp is eta(5)- cyclopentadienyl] provide access to three different electronic configurations of the metal, formally d(1), d(2), and d(0), respectively. The gas-phase photoelectron spectra show that ionizations from occupied metal and sulfur based valence orbitals are more clearly observed in compounds 2 and 3 than in compound 1. The observed ionization energies and characters compare very well with those calculated by density functional theory. A "dithiolate-folding-effect" involving an interaction of the metal in-plane and sulfur-pi orbitals is proposed to be a factor in the electron transfer reactions that regenerate the active sites of molybdenum and tungsten enzymes.

Designing lead-free antiferroelectrics for energy storage

PubMed Central

Xu, Bin; Íñiguez, Jorge; Bellaiche, L.

2017-01-01

Dielectric capacitors, although presenting faster charging/discharging rates and better stability compared with supercapacitors or batteries, are limited in applications due to their low energy density. Antiferroelectric (AFE) compounds, however, show great promise due to their atypical polarization-versus-electric field curves. Here we report our first-principles-based theoretical predictions that Bi1−xRxFeO3 systems (R being a lanthanide, Nd in this work) can potentially allow high energy densities (100–150 J cm−3) and efficiencies (80–88%) for electric fields that may be within the range of feasibility upon experimental advances (2–3 MV cm−1). In addition, a simple model is derived to describe the energy density and efficiency of a general AFE material, providing a framework to assess the effect on the storage properties of variations in doping, electric field magnitude and direction, epitaxial strain, temperature and so on, which can facilitate future search of AFE materials for energy storage. PMID:28555655

Approaching an experimental electron density model of the biologically active trans -epoxysuccinyl amide group-Substituent effects vs. crystal packing

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

Shi, Ming W.; Stewart, Scott G.; Sobolev, Alexandre N.

The trans-epoxysuccinyl amide group as a biologically active moiety in cysteine protease inhibitors such as loxistatin acid E64c has been used as a benchmark system for theoretical studies of environmental effects on the electron density of small active ingredients in relation to their biological activity. Here, the synthesis and the electronic properties of the smallest possible active site model compound are reported to close the gap between the unknown experimental electron density of trans-epoxysuccinyl amides and the well-known function of related drugs. Intramolecular substituent effects are separated from intermolecular crystal packing effects on the electron density, which allows us tomore » predict the conditions under which an experimental electron density investigation on trans-epoxysuccinyl amides will be possible. In this context, the special importance of the carboxylic acid function in the model compound for both crystal packing and biological activity is revealed through the novel tool of model energy analysis.« less

Pink-beam focusing with a one-dimensional compound refractive lens

DOE PAGES

Dufresne, Eric M.; Dunford, Robert W.; Kanter, Elliot P.; ...

2016-07-28

The performance of a cooled Be compound refractive lens (CRL) has been tested at the Advanced Photon Source (APS) to enable vertical focusing of the pink beam and permit the X-ray beam to spatially overlap with an 80 µm-high low-density plasma that simulates astrophysical environments. Focusing the fundamental harmonics of an insertion device white beam increases the APS power density; here, a power density as high as 500 W mm –2 was calculated. A CRL is chromatic so it does not efficiently focus X-rays whose energies are above the fundamental. Only the fundamental of the undulator focuses at the experiment.more » A two-chopper system reduces the power density on the imaging system and lens by four orders of magnitude, enabling imaging of the focal plane without any X-ray filter. As a result, a method to measure such high power density as well as the performance of the lens in focusing the pink beam is reported.« less

Comparative theoretical studies of differently bridged nitramino-substituted ditetrazole 2-N-oxides with high detonation performance and an oxygen balance of around zero.

PubMed

Wu, Qiong; Kou, Bo; Hang, Zusheng; Zhu, Weihua

2017-06-01

In this work, six (A-F) nitramino (-NHNO 2 )-substituted ditetrazole 2-N-oxides with different bridging groups (-CH 2 -, -CH 2 -CH 2 -, -NH-, -N=N-, and -NH-NH-) were designed. The six compounds were based on the parent compound tetrazole 2-N-oxide, which possesses a high oxygen balance and high density. The structure, heat of formation, density, detonation properties (detonation velocity D and detonation pressure P), and the sensitivity of each compound was investigated systematically via density functional theory, by studying the electrostatic potential, and using molecular mechanics. The results showed that compounds A-F all have outstanding energetic properties (D: 9.1-10.0 km/s; P: 38.0-46.7 GPa) and acceptable sensitivities (h 50 : 28-37 cm). The bridging group present was found to greatly affect the detonation performance of each ditetrazole 2-N-oxide, and the compound with the -NH-NH- bridging group yielded the best results. Indeed, this compound (F) was calculated to have comparable sensitivity to the famous and widely used high explosive 1,3,5,7-tetranitro-1,3,5,7-tetrazocane (HMX), but with values of D and P that were about 8.7% and 19.4% higher than those for HMX, respectively. The present study shows that tetrazole 2-N-oxide is a useful parent compound which could potentially be used in the design of new and improved high-energy compounds to replace existing energetic compounds such as HMX.

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.

On the mechanism of influence of explosive compounds: Destruction process on sensitivity of these compounds to mechanic impacts

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

Filin, V.P.; Loboyko, B.G.; Averin, A.N.

1996-05-01

The results of investigations into sensitivity of the HMX-based explosive compound samples to mechanic stimuli are shown in the presented report. As a result of experimental studies it was illustrated, that explosives deformation and destruction processes under mechanical stimuli are accompanied by occurrence of different electric phenomena. The hypothesis on possible influence of electric phenomena occurring under deformation and destruction on the mechanism of formation of zones with high density of energy is discussed in the report. {copyright} {ital 1996 American Institute of Physics.}

Prediction and characterization of an Mg-Al intermetallic compound with potentially improved ductility via orbital-free and Kohn-Sham density functional theory

NASA Astrophysics Data System (ADS)

Zhuang, Houlong L.; Chen, Mohan; Carter, Emily A.

2017-10-01

Magnesium-aluminum (Mg-Al) intermetallic compounds that form as precipitates can significantly influence the mechanical properties of Mg-Al alloys. A computational evaluation of known and unknown Mg-Al intermetallic compounds could help design new Mg-Al alloy microstructures with optimal properties. Here, we employ the cluster-expansion method with energies efficiently calculated with orbital-free density functional theory (OFDFT) and predict a new, metastable intermetallic compound Mg3Al with a D019 hexagonal structure that is slightly more stable than an alternative L12 cubic structure. We apply Kohn-Sham DFT (KSDFT) to accurately evaluate various metastability criteria for D019 and L12 Mg3Al, including Born’s criterion and phonon dispersion. We show that both Mg3Al crystalline phases satisfy the metastability criteria and hence should be at least metastable. We further compare ductility metrics for D019 and L12 Mg3Al to that of hexagonal-close-packed Mg by computing Pugh’s ratio and generalized stacking fault energies. The ductility is predicted to follow the order: D019 Mg3Al > L12 Mg3Al > Mg, based on the highest Pugh’s ratio and the lowest unstable stacking and twinning fault energies of D019 Mg3Al compared to that of Mg. We also predict a very low antiphase boundary energy for Mg3Al and therefore expect D019 Mg3Al to be beneficial for improving the ductility of Mg-rich Mg-Al alloys. A computational design of Mg-Al alloy microstructures may become possible by combining the strengths of both OFDFT and KSDFT, i.e., the efficiency of the former and the accuracy of the latter, as demonstrated here.

Test of level density models from reactions of Li6 on Fe58 and Li7 on Fe57

NASA Astrophysics Data System (ADS)

Oginni, B. M.; Grimes, S. M.; Voinov, A. V.; Adekola, A. S.; Brune, C. R.; Carter, D. E.; Heinen, Z.; Jacobs, D.; Massey, T. N.; O'Donnell, J. E.; Schiller, A.

2009-09-01

The reactions of Li6 on Fe58 and Li7 on Fe57 have been studied at 15 MeV beam energy. These two reactions produce the same compound nucleus, Cu64. The charged particle spectra were measured at backward angles. The data obtained have been compared with Hauser-Feshbach model calculations. The level density parameters of Ni63 and Co60 have been obtained from the particle evaporation spectra. We also find contributions from the break up of the lithium projectiles to the low energy region of the α spectra.

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.

Comparative studies of structural, thermal, optical, and electrochemical properties of azines with different end groups with their azomethine analogues toward application in (opto)electronics.

PubMed

Sek, Danuta; Siwy, Mariola; Bijak, Katarzyna; Grucela-Zajac, Marzena; Malecki, Grzegorz; Smolarek, Karolina; Bujak, Lukasz; Mackowski, Sebastian; Schab-Balcerzak, Ewa

2013-10-10

Two series of azines and their azomethine analogues were prepared via condensation reaction of benzaldehyde, 2-hydroxybenzaldehyde, 4-pyridinecarboxaldehyde, 2-thiophenecarboxaldehyde, and 4-(diphenylamino)benzaldehyde with hydrazine monohydrate and 1,4-phenylenediamine, respectively. The structures of given compounds were characterized by FTIR, (1)H NMR, and (13)C NMR spectroscopy as well as elemental analysis. Optical, electrochemical, and thermal properties of all compounds were investigated by means of differential scanning calorimetry (DSC), UV-vis spectroscopy, stationary and time-resolved photoluminescence spectroscopy, and cycling voltammetry (CV). Additionally, the electronic properties, that is, orbital energies and resulting energy gap were calculated theoretically by density functional theory (DFT). Influence of chemical structure of the compounds on their properties was analyzed.

Structural, vibrational and thermodynamic properties of Mg2 FeH6 complex hydride

NASA Astrophysics Data System (ADS)

Zhou, H. L.; Yu, Y.; Zhang, H. F.; Gao, T.

2011-02-01

Mg2FeH6, which has one of the highest hydrogen storage capacities among Mg based 3d-transitional metal hydrides, is considered as an attractive material for hydrogen storage. Within density-functional perturbation theory (DFPT), we have investigated the structural, vibrational and thermodynamic properties of Mg2FeH6. The band structure calculation shows that this compound is a semiconductor with a direct X-X energy gap of 1.96 eV. The calculated phonon frequencies for the Raman-active and the infrared-active modes are assigned. The phonon dispersion curves together with the corresponding phonon density of states and longitudinal-transverse optical (LO-TO) splitting are also calculated. Findings are also presented for the temperature-dependent behaviors of some thermodynamic properties such as free energy, internal energy, entropy and heat capacity within the quasi-harmonic approximation based on the calculated phonon density of states.

Experimental signature of collective enhancement in nuclear level density

NASA Astrophysics Data System (ADS)

Pandit, Deepak; Bhattacharya, Srijit; Mondal, Debasish; Roy, Pratap; Banerjee, K.; Mukhopadhyay, S.; Pal, Surajit; De, A.; Dey, Balaram; Banerjee, S. R.

2018-04-01

We present a probable experimental signature of collective enhancement in the nuclear level density (NLD) by measuring the neutron and the giant dipole resonance (GDR) γ rays emitted from the rare-earth 169Tm compound nucleus populated at 26.1 MeV excitation energy. An enhanced yield is observed in both neutron and γ -ray spectra corresponding to the same excitation energy in the daughter nuclei. The enhancement could only be reproduced by including a collective enhancement factor in the Fermi gas model of NLD to explain the neutron and GDR spectra simultaneously. The experimental results show that the relative enhancement factor is of the order of 10 and the fadeout occurs at ˜14 MeV excitation energy, much before the commonly accepted transition from deformed to spherical shape. We also explain how the collective enhancement contribution changes the inverse level density parameter k from 8 to 9.5 MeV observed recently in several deformed nuclei.

Ionic conduction in sodium azide under high pressure: Experimental and theoretical approaches

NASA Astrophysics Data System (ADS)

Wang, Qinglin; Ma, Yanzhang; Sang, Dandan; Wang, Xiaoli; Liu, Cailong; Hu, Haiquan; Wang, Wenjun; Zhang, Bingyuan; Fan, Quli; Han, Yonghao; Gao, Chunxiao

2018-04-01

Alkali metal azides can be used as starting materials for the synthesis of polymeric nitrogen, a potential material of high energy density. In this letter, we report the ionic transport behavior in sodium azide under high pressure by in situ impedance spectroscopy and density functional theory calculations. The ionic transportation consists of ion transfer and Warburg diffusion processes. The ionic migration channels and barrier energy were given for the high-pressure phases. The enhanced ionic conductivity of the γ phase with pressure is because of the formation of space charge regions in the grain boundaries. This ionic conduction and grain boundary effect in NaN3 under pressures could shed light on the better understanding of the conduction mechanism of alkali azides and open up an area of research for polymeric nitrogen in these compounds and other high-energy-density polynitrides.

Sol-gel Technology and Advanced Electrochemical Energy Storage Materials

NASA Technical Reports Server (NTRS)

Chu, Chung-tse; Zheng, Haixing

1996-01-01

Advanced materials play an important role in the development of electrochemical energy devices such as batteries, fuel cells, and electrochemical capacitors. The sol-gel process is a versatile solution for use in the fabrication of ceramic materials with tailored stoichiometry, microstructure, and properties. This processing technique is particularly useful in producing porous materials with high surface area and low density, two of the most desirable characteristics for electrode materials. In addition,the porous surface of gels can be modified chemically to create tailored surface properties, and inorganic/organic micro-composites can be prepared for improved material performance device fabrication. Applications of several sol-gel derived electrode materials in different energy storage devices are illustrated in this paper. V2O5 gels are shown to be a promising cathode material for solid state lithium batteries. Carbon aerogels, amorphous RuO2 gels and sol-gel derived hafnium compounds have been studied as electrode materials for high energy density and high power density electrochemical capacitors.

Synthesis and first-principle calculations of the structural and electronic properties of Ge-substituted type-VIII Ba8Ga16Sn30 clathrate

NASA Astrophysics Data System (ADS)

Shen, Lanxian; Li, Decong; Liu, Hongxia; Liu, Zuming; Deng, Shukang

2016-12-01

In this study, the structural and electronic structural properties of Ba8Ga16Sn30-xGex (0≤x≤30) are determined by the first-principle method on the basis of density functional theory. Consistent with experimental findings, calculated results reveal that Ge atoms preferentially occupy the 2a and 24g sites in these compounds. As the content of Ge in Ge-substituted clathrate is increased, the lattice parameter is decreased, and the structural stability is enhanced. The bandgaps of the compound at 1≤x≤10 are smaller than those of Ba8Ga16Sn30. By contrast, the bandgaps of the compound at x>10 are larger than those of Ba8Ga16Sn30. The substitution of Ge for Sn affects p-type conductivity but not n-type conductivity. As Ge content increases, the whole conduction band moves to the direction of high energy, and the density of states of valence-band top decreases. The calculated potential energy versus displacement of Ba indicates that the vibration energy of this atom increases as cage size decreases. Because Ge substitution also affects clathrate structural symmetry, the distance of Ba atom deviation from the center of the cage initially increases and subsequently decreases as the Ge content increases.

Novel Phenoxazinones as potent agonist of PPAR-α: design, synthesis, molecular docking and in vivo studies.

PubMed

Ugwu, David I; Okoro, Uchechukwu C; Mishra, Narendra K; Okafor, Sunday N

2018-05-22

The use of statin, a 3-hydroxy-3-methylglutaryl coenzyme A reductase inhibitor for the treatment of dyslipidemia has been associated with dose limiting hepatoxicity, mytotoxicity and tolerability due to myalgias thereby necessitating the synthesis of new drug candidates for the treatment of lipid disorder. The reaction of appropriate benzenesulphonamide with substituted phenoxazinone in the presence of phenylboronic acid gave the targeted compounds. The molecular docking study were carried out using autodock tool against peroxisome proliferator activated receptor alpha. The in vivo lipid profile were assayed using conventional methods. The kidney and liver function test were carried out to assess the effect of the derivatives on the organs. The LD 50 of the most active derivatives were determined using mice. The targeted compounds were successfully synthesized in excellent yields and characterized using spectroscopic techniques. The results of the molecular docking experiment showed that they were good stimulant of peroxisome proliferator activated receptor alpha. Compound 9f showed activity at Ki of 2.8 nM and binding energy of 12.6 kcal/mol. All the compounds tested reduced triglyceride, total cholesterol, low density lipoprotein cholesterol and very low density lipoprotein cholesterol level in the mice model. Some of the reported compounds also increased high density lipoprotein cholesterol level in the mice. The compounds did not have appreciable effect on the kidney and liver of the mice used. The LD 50 showed that the novel compounds have improved toxicity profile. The synthesis of fifteen new derivatives of carboxamides bearing phenoxazinone and sulphonamide were successful. The compounds possessed comparable activity to gemfibrozil. The reported compounds had better toxicity profile than gemfibrozil and could serve as a replacement for the statins and fibrate class of lipid agents.

Synthesis, crystal structure analysis, spectral investigations, DFT computations and molecular dynamics and docking study of 4-benzyl-5-oxomorpholine-3-carbamide, a potential bioactive agent

NASA Astrophysics Data System (ADS)

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

2017-04-01

4-benzyl-5-oxomorpholine-3-carbamide has been synthesized; single crystals were grown by slow evaporation solution growth technique at room temperature and characterized by single crystal X-ray diffraction, FT-IR, FT-Raman and 1H-NMR. The compound crystallizes in the monoclinic space group P21/n. The molecular geometry of the compound was optimized by using Density Functional Theory (DFT/B3LYP) method with 6-311++G(d,p) basis set in the ground state and geometric parameters are in agreement with the X-ray analysis results of the structure. The experimental vibrational spectra were compared with the calculated spectra and each vibrational wave number was assigned on the basis of potential energy distribution (PED). The electronic and charge transfer properties have been explained on the basis of highest occupied molecular orbital's (HOMOs) and lowest unoccupied molecular orbital's (LUMOs). Besides molecular electrostatic potential (MEP), frontier molecular orbital's (FMOs), some global reactivity descriptors, thermodynamic properties, non-linear optical (NLO) behavior and Mullikan charge analysis of the title compound were computed with the same method in gas phase, theoretically. Potential reactive sites of the title compound have been identified by average local ionization energy and Fukui functions, both mapped to the electron density surface. Bond dissociation energies for all single acyclic bonds have been calculated in order to investigate autoxidation and degradation properties of the title compound. Atoms with pronounced interactions with water molecules have been detected by calculations of radial distribution functions after molecular dynamics simulations. The experimental results are compared with the theoretical calculations using DFT methods for the fortification of the paper. Further the docking studies revealed that the title compound as a docked ligand forms a stable complex with pyrrole inhibitor with a binding affinity value of -7.5 kcal/mol. This suggests that the title compound might exhibit inhibitory activity against pyrrole inhibitor. To confirm the potential practical applicability of the title compound antimicrobial activity was tested against gram negative and gram positive bacteria.

Investigation of metal–dithiolate fold angle effects: Implications for molybdenum and tungsten enzymes

PubMed Central

Joshi, Hemant K.; Cooney, J. Jon A.; Inscore, Frank E.; Gruhn, Nadine E.; Lichtenberger, Dennis L.; Enemark, John H.

2003-01-01

Gas-phase photoelectron spectroscopy and density functional theory have been used to investigate the interactions between the sulfur π-orbitals of arene dithiolates and high-valent transition metals as minimum molecular models of the active site features of pyranopterin Mo/W enzymes. The compounds (Tp*)MoO(bdt) (compound 1), Cp2Mo(bdt) (compound 2), and Cp2Ti(bdt) (compound 3) [where Tp* is hydrotris(3,5-dimethyl-1-pyrazolyl)borate, bdt is 1,2-benzenedithiolate, and Cp is η5- cyclopentadienyl] provide access to three different electronic configurations of the metal, formally d1, d2, and d0, respectively. The gas-phase photoelectron spectra show that ionizations from occupied metal and sulfur based valence orbitals are more clearly observed in compounds 2 and 3 than in compound 1. The observed ionization energies and characters compare very well with those calculated by density functional theory. A “dithiolate-folding-effect” involving an interaction of the metal in-plane and sulfur-π orbitals is proposed to be a factor in the electron transfer reactions that regenerate the active sites of molybdenum and tungsten enzymes. PMID:12655066

New hybrid lead iodides: From one-dimensional chain to two-dimensional layered perovskite structure

NASA Astrophysics Data System (ADS)

Xiong, Kecai; Liu, Wei; Teat, Simon J.; An, Litao; Wang, Hao; Emge, Thomas J.; Li, Jing

2015-10-01

Two new hybrid lead halides (H2BDA)[PbI4] (1) (H2BDA=1,4-butanediammonium dication) and (HNPEIM)[PbI3] (2) (HNPEIM=N-​phenyl-ethanimidamidine cation) have been synthesized and structurally characterized. X-ray diffraction analyses reveal that compound 1 features a two-dimensional corner-sharing perovskite layer whereas compound 2 contains one-dimensional edge-sharing double chains. The N-​phenyl-ethanimidamidine cation within compound 2 was generated in-situ under solvothermal conditions. The optical absorption spectra collected at room temperature suggest that both compounds are semiconductors having direct band gaps, with estimated values of 2.64 and 2.73 eV for 1 and 2, respectively. Results from the density functional theory (DFT) calculations are consistent with the experimental data. Density of states (DOS) analysis reveals that in both compounds 1 and 2, the energy states in the valence band maximum region are iodine 5p atomic orbitals with a small contribution from lead 6s, while in the region of conduction band minimum, the major contributions are from the inorganic (Pb 6p atomic orbitals) and organic components (C and N 2p atomic orbitals) in compound 1 and 2, respectively.

Computational discovery of stable M2A X phases

NASA Astrophysics Data System (ADS)

Ashton, Michael; Hennig, Richard G.; Broderick, Scott R.; Rajan, Krishna; Sinnott, Susan B.

2016-08-01

The family of layered Mn +1A Xn compounds provides a large class of materials with applications ranging from magnets to high-temperature coatings to nuclear cladding. In this work, we employ a density-functional-theory-based discovery approach to identify a large number of thermodynamically stable Mn +1A Xn compounds, where n =1 , M =Sc, Ti, V, Cr, Zr, Nb, Mo, Hf, Ta; A =Al, Si, P, S, Ga, Ge, As, Cd, In, Sn, Tl, Pb; and X =C, N. We calculate the formation energy for 216 pure M2A X compounds and 10 314 solid solutions, (MM') 2(A A') (X X') , relative to their competing phases. We find that the 49 experimentally known M2A X phases exhibit formation energies of less than 30 meV/atom. Among the 10 530 compositions considered, 3140 exhibit formation energies below 30 meV/atom, most of which have yet to be experimentally synthesized. A significant subset of 301 compositions exhibits strong exothermic stability in excess of 100 meV/atom, indicating favorable synthesis conditions. We identify empirical design rules for stable M2A X compounds. Among the metastable M2A X compounds are two Cr-based compounds with ferromagnetic ordering and expected Curie temperatures around 75 K. These results can serve as a map for the experimental design and synthesis of different M2A X compounds.

Level density and mechanism of deuteron-induced reactions on Fe 54 , 56 , 58

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

Ramirez, A. P. D.; Voinov, A. V.; Grimes, S. M.

Here, deuteron elastic cross sections, as well as neutron, proton, and α-particle emission spectra, from d+ 54,56,58Fe reactions have been measured with deuteron beam energies of 5, 7, and 9 MeV. Optical model parameters have been tested against our experimental data. The fraction of total reaction cross section responsible for the formation of compound nuclei has been deduced from the angular distributions. The degree of discrepancy between calculated and experimental compound cross sections was found to increase with increasing neutron number. The nuclear level densities of the residual nuclei 55Co, 57Co, 55Fe, 57Fe, 52Mn, and 54Mn have been deduced frommore » the compound double differential cross sections. The Gilbert-Cameron model with Iljinov parameter systematics [A. S. Iljinov and M. V. Mebel, Nucl. Phys. A 543, 517 (1992)] was found to have a good agreement with our results.« less

Level density and mechanism of deuteron-induced reactions on Fe 54 , 56 , 58

DOE PAGES

Ramirez, A. P. D.; Voinov, A. V.; Grimes, S. M.; ...

2015-07-06

Here, deuteron elastic cross sections, as well as neutron, proton, and α-particle emission spectra, from d+ 54,56,58Fe reactions have been measured with deuteron beam energies of 5, 7, and 9 MeV. Optical model parameters have been tested against our experimental data. The fraction of total reaction cross section responsible for the formation of compound nuclei has been deduced from the angular distributions. The degree of discrepancy between calculated and experimental compound cross sections was found to increase with increasing neutron number. The nuclear level densities of the residual nuclei 55Co, 57Co, 55Fe, 57Fe, 52Mn, and 54Mn have been deduced frommore » the compound double differential cross sections. The Gilbert-Cameron model with Iljinov parameter systematics [A. S. Iljinov and M. V. Mebel, Nucl. Phys. A 543, 517 (1992)] was found to have a good agreement with our results.« less

Level Densities of Residual Nuclei from particle evaporation of 64Cu

NASA Astrophysics Data System (ADS)

Oginni, B. M.; Grimes, S. M.; Voinov, A. V.; Adekola, A. S.; Brune, C. R.; Carter, D.; Heinen, Z.; Jacobs, D.; Massey, T. N.; O'Donnell, J.

2009-07-01

The reactions of 6Li on 58Fe and 7Li on 57Fe have been studied at beam energy 15 MeV. These two reactions produce the same compound nucleus, 64Cu. The neutron, proton, and alpha spectra were measured at backward angles. The data obtained have been compared with Hauser Fesh-bach model calculations. The level density parameters of the residual nuclei have been obtained from the particle evaporation spectra.

Fast‐Rate Capable Electrode Material with Higher Energy Density than LiFePO4: 4.2V LiVPO4F Synthesized by Scalable Single‐Step Solid‐State Reaction

PubMed Central

Kim, Minkyung; Lee, Seongsu

2015-01-01

Use of compounds that contain fluorine (F) as electrode materials in lithium ion batteries has been considered, but synthesizing single‐phase samples of these compounds is a difficult task. Here, it is demonstrated that a simple scalable single‐step solid‐state process with additional fluorine source can obtain highly pure LiVPO4F. The resulting material with submicron particles achieves very high rate capability ≈100 mAh g−1 at 60 C‐rate (1‐min discharge) and even at 200 C‐rate (18 s discharge). It retains superior capacity, ≈120 mAh g−1 at 10 C charge/10 C discharge rate (6‐min) for 500 cycles with >95% retention efficiency. Furthermore, LiVPO4F shows low polarization even at high rates leading to higher operating potential >3.45 V (≈3.6 V at 60 C‐rate), so it achieves high energy density. It is demonstrated for the first time that highly pure LiVPO4F can achieve high power capability comparable to LiFePO4 and much higher energy density (≈521 Wh g−1 at 20 C‐rate) than LiFePO4 even without nanostructured particles. LiVPO4F can be a real substitute of LiFePO4. PMID:27774395

Fast-Rate Capable Electrode Material with Higher Energy Density than LiFePO4: 4.2V LiVPO4F Synthesized by Scalable Single-Step Solid-State Reaction.

PubMed

Kim, Minkyung; Lee, Seongsu; Kang, Byoungwoo

2016-03-01

Use of compounds that contain fluorine (F) as electrode materials in lithium ion batteries has been considered, but synthesizing single-phase samples of these compounds is a difficult task. Here, it is demonstrated that a simple scalable single-step solid-state process with additional fluorine source can obtain highly pure LiVPO 4 F. The resulting material with submicron particles achieves very high rate capability ≈100 mAh g -1 at 60 C-rate (1-min discharge) and even at 200 C-rate (18 s discharge). It retains superior capacity, ≈120 mAh g -1 at 10 C charge/10 C discharge rate (6-min) for 500 cycles with >95% retention efficiency. Furthermore, LiVPO 4 F shows low polarization even at high rates leading to higher operating potential >3.45 V (≈3.6 V at 60 C-rate), so it achieves high energy density. It is demonstrated for the first time that highly pure LiVPO 4 F can achieve high power capability comparable to LiFePO 4 and much higher energy density (≈521 Wh g -1 at 20 C-rate) than LiFePO 4 even without nanostructured particles. LiVPO 4 F can be a real substitute of LiFePO 4.

Theoretical investigation of thermoelectric and elastic properties of intermetallic compounds ScTM (TM = Cu, Ag, Au and Pd)

NASA Astrophysics Data System (ADS)

Iqbal, R.; Bilal, M.; Jalali-Asadabadi, S.; Rahnamaye Aliabad, H. A.; Ahmad, Iftikhar

2018-01-01

In this paper, we explore the structural, electronic, thermoelectric and elastic properties of intermetallic compounds ScTM (TM = Cu, Ag, Au and Pd) using density functional theory. The produced results show high values of Seebeck coefficients and electrical conductivity for these materials. High power factor for these materials at room-temperature shows that these materials may be beneficial for low-temperature thermoelectric devices and alternative energy sources. Furthermore, elastic properties of these compounds are also calculated, which are used to evaluate their mechanical properties. The Cauchy’s pressure and B/G ratio figure out that these compounds are ductile in nature. The calculated results also predict that these compounds are stable against deforming force.

Vibrational spectra, NLO analysis, and HOMO-LUMO studies of 2-chloro-6-fluorobenzoic acid and 3,4-dichlorobenzoic acid by density functional method

NASA Astrophysics Data System (ADS)

Senthil kumar, J.; Arivazhagan, M.; Thangaraju, P.

2015-08-01

The FTIR and FT-Raman spectra of 2-chloro-6-fluorobenzoic acid and 3,4-dichlorobenzoic acid have been recorded in the region 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 fundamental modes of the compounds were carried out. The optimized molecular geometries, vibrational frequencies, thermodynamic properties and atomic charge of the compounds were calculated by using density functional theory (B3LYP) method with 6-311+G and 6-311++G basis sets. The difference between the observed and scaled wave number values of most of fundamentals is very small. Unambiguous vibration assignment of all the fundamentals is made up the total energy distribution (TED). The calculated HOMO and LUMO energies show that charge transfer occurs within the molecules. Besides, molecular electro static potential (MESP), Mulliken's charge analysis, first order hyper polarizability and several thermodynamic properties were performed by the DFT method.

Guaiacol hydrodeoxygenation mechanism on Pt(111): insights from density functional theory and linear free energy relations.

PubMed

Lee, Kyungtae; Gu, Geun Ho; Mullen, Charles A; Boateng, Akwasi A; Vlachos, Dionisios G

2015-01-01

Density functional theory is used to study the adsorption of guaiacol and its initial hydrodeoxygenation (HDO) reactions on Pt(111). Previous Brønsted-Evans-Polanyi (BEP) correlations for small open-chain molecules are inadequate in estimating the reaction barriers of phenolic compounds except for the side group (methoxy) carbon-dehydrogenation. New BEP relations are established using a select group of phenolic compounds. These relations are applied to construct a potential-energy surface of guaiacol-HDO to catechol. Analysis shows that catechol is mainly produced via dehydrogenation of the methoxy functional group followed by the CHx (x<3) removal of the functional group and hydrogenation of the ring carbon, in contrast to a hypothesis of a direct demethylation path. Dehydroxylation and demethoxylation are slow, implying that phenol is likely produced from catechol but not through its direct dehydroxylation followed by aromatic carbon-ring hydrogenation. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Synthesis, crystal structure analysis, molecular docking studies and density functional theory predictions of the local reactive properties and degradation properties of a novel halochalcone

NASA Astrophysics Data System (ADS)

Arshad, Suhana; Pillai, Renjith Raveendran; Zainuri, Dian Alwani; Khalib, Nuridayanti Che; Razak, Ibrahim Abdul; Armaković, Stevan; Armaković, Sanja J.

2017-09-01

In the present study, single crystals of E)-3-(3,5-dichlorophenyl)-1-(4-fluorophenyl)prop-2-en-1-one, were prepared and structurally characterized by single crystal X-ray diffraction analysis. The molecular structure crystallized in monoclinic crystal system with P21/c space group. Sensitivity of the title molecule towards electrophilic attacks has been examined by calculations of average localized ionization energies (ALIE) and their mapping to electron density surface. Further determination of atoms that could be important reactive centres has been performed by calculations of Fukui functions. Sensitivity of title molecule towards autoxidation and hydrolysis mechanisms has been assessed by calculations of bond dissociation energies and radial distribution functions (RDF), respectively. Also, in order to explore possible binding mode of the title compound towards Dihydrofolate reductase enzyme, we have utilized in silico molecular docking to explore possible binding modes of the title compound with the DHFR enzyme.

Study, selection, and preparation of solid cationic conductors. [characteristics of solid electrolytes for rechargeable high energy and high power density batteries

NASA Technical Reports Server (NTRS)

Roth, W. L.; Muller, O.

1974-01-01

Crystal chemical principles and transport theory have been used to predict structures and specific compounds which might find application as solid electrolytes in rechargeable high energy and high power density batteries operating at temperatures less than 200 C. Structures with 1-, 2-, and 3-dimensional channels were synthesized and screened by nuclear magnetic resonance, dielectric loss, and conductivity. There is significant conductivity at room temperature in some of the materials but none attain a level that is comparable to beta-alumina. Microwave and fast pulse methods were developed to measure conductivity in powders and in small crystals.

Fast Computation of Solvation Free Energies with Molecular Density Functional Theory: Thermodynamic-Ensemble Partial Molar Volume Corrections.

PubMed

Sergiievskyi, Volodymyr P; Jeanmairet, Guillaume; Levesque, Maximilien; Borgis, Daniel

2014-06-05

Molecular density functional theory (MDFT) offers an efficient implicit-solvent method to estimate molecule solvation free-energies, whereas conserving a fully molecular representation of the solvent. Even within a second-order approximation for the free-energy functional, the so-called homogeneous reference fluid approximation, we show that the hydration free-energies computed for a data set of 500 organic compounds are of similar quality as those obtained from molecular dynamics free-energy perturbation simulations, with a computer cost reduced by 2-3 orders of magnitude. This requires to introduce the proper partial volume correction to transform the results from the grand canonical to the isobaric-isotherm ensemble that is pertinent to experiments. We show that this correction can be extended to 3D-RISM calculations, giving a sound theoretical justification to empirical partial molar volume corrections that have been proposed recently.

Excitations and magnetization density distribution in the dilute ferromagnetic semiconductor Yb 14 MnSb 11

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

Stone, M. B.; Garlea, V. O.; Gillon, B.

2017-01-23

One rare example of a Kondo lattice compound with ferromagnetic dominated RKKY interactions is Ybmore » $$_{14}$$MnSb$$_{11}$$. As a ferromagnetic semiconductor with $$T_c \\approx 53$$~K, it is also a potential compound for exploration of spintronic devices. This material is furthermore one of the most efficient high temperature thermoelectrics. We describe measurements which answer remaining questions regarding the energy scales of the exchange interactions, the valence and the magnetization density distribution in this system. We also find that the system consists of RKKY exchange coupled Mn$$^{2+}$$ sites with nearest and next nearest exchange interactions dominating the magnetic spectrum with no significant magnetization density localized on other atomic sites. The extended spread of a negative magnetization around each of the Mn ions supports a Kondo screening cloud scenario for Yb$$_{14}$$MnSb$$_{11}$$.« less

Effects of ultrasound energy density on the non-thermal pasteurization of chocolate milk beverage.

PubMed

Monteiro, Sara H M C; Silva, Eric Keven; Alvarenga, Verônica O; Moraes, Jeremias; Freitas, Mônica Q; Silva, Márcia C; Raices, Renata S L; Sant'Ana, Anderson S; Meireles, M Angela A; Cruz, Adriano G

2018-04-01

This study presents the emerging high-intensity ultrasound (HIUS) processing as a non-thermal alternative to high-temperature short-time pasteurization (HTST). Chocolate milk beverage (CMB) was subjected to different ultrasound energy densities (0.3-3.0 kJ/cm 3 ), as compared to HTST pasteurization (72 °C/15 s) aimed to verify the effect of the HIUS processing on the microbiological and physicochemical characteristics of the beverage. The application of HIUS at an energy density of 3.0 kJ/cm 3 was able to reduce 3.56 ± 0.02 logarithmic cycles in the total aerobic counts. In addition, the ultrasound energy density affected the physical properties of the beverage as the size distribution of fat globule and rheological behavior, as well as the chemical properties such as antioxidant activity, ACE inhibitory activity, fatty acid profile, and volatile profile. In general, the different energetic densities used as a non-thermal method of pasteurization of CMB were more effective when compared to the conventional pasteurization by HTST, since they improved the microbiological and physicochemical quality, besides preserving the bioactive compounds and the nutritional quality of the product. Copyright © 2017 Elsevier B.V. All rights reserved.

Hybrid energy storage systems utilizing redox active organic compounds

DOEpatents

Wang, Wei; Xu, Wu; Li, Liyu; Yang, Zhenguo

2015-09-08

Redox flow batteries (RFB) have attracted considerable interest due to their ability to store large amounts of power and energy. Non-aqueous energy storage systems that utilize at least some aspects of RFB systems are attractive because they can offer an expansion of the operating potential window, which can improve on the system energy and power densities. One example of such systems has a separator separating first and second electrodes. The first electrode includes a first current collector and volume containing a first active material. The second electrode includes a second current collector and volume containing a second active material. During operation, the first source provides a flow of first active material to the first volume. The first active material includes a redox active organic compound dissolved in a non-aqueous, liquid electrolyte and the second active material includes a redox active metal.

Antiproton powered propulsion with magnetically confined plasma engines

NASA Technical Reports Server (NTRS)

Lapointe, Michael R.

1989-01-01

Matter-antimatter annihilation releases more energy per unit mass than any other method of energy production, making it an attractive energy source for spacecraft propulsion. In the magnetically confined plasma engine, antiproton beams are injected axially into a pulsed magnetic mirror system, where they annihilate with an initially neutral hydrogen gas. The resulting charged annihilation products transfer energy to the hydrogen propellant, which is then exhausted through one end of the pulsed mirror system to provide thrust. The calculated energy transfer efficiencies for a low number density (10(14)/cu cm) hydrogen propellant are insufficient to warrant operating the engine in this mode. Efficiencies are improved using moderate propellant number densities (10(16)/cu cm), but the energy transferred to the plasma in a realistic magnetic mirror system is generally limited to less than 2 percent of the initial proton-antiproton annihilation energy. The energy transfer efficiencies are highest for high number density (10(18)/cu cm) propellants, but plasma temperatures are reduced by excessive radiation losses. Low to moderate thrust over a wide range of specific impulse can be generated with moderate propellant number densities, while higher thrust but lower specific impulse may be generated using high propellant number densities. Significant mass will be required to shield the superconducting magnet coils from the high energy gamma radiation emitted by neutral pion decay. The mass of such a radiation shield may dominate the total engine mass, and could severely diminish the performance of antiproton powered engines which utilize magnetic confinement. The problem is compounded in the antiproton powered plasma engine, where lower energy plasma bremsstrahlung radiation may cause shield surface ablation and degradation.

Study, selection, and preparation of solid cationic conductors

NASA Technical Reports Server (NTRS)

Roth, W. L.; Mitoff, S. P.; King, R. N.

1972-01-01

Crystal chemical principles and transport theory were used to predict structures and specific compounds which might find application as solid electrolytes in rechargeable high energy and high power density batteries operating at temperatures less than 200 C. More than twenty compounds were synthesized or obtained and screened by nuclear magnetic resonance and conductivity. Many were densified by sintering or hot pressing. Encouraging results were obtained for nine of these materials but none have yet been good ionic conductors at low temperature.

Single Crystal Growth, Resistivity, and Electronic Structure of the Weyl Semimetals NbP and TaP

DOE PAGES

Sapkota, Deepak; Mukherjee, Rupam; Mandrus, David

2016-12-06

We have successfully synthesized niobium monophosphide and tantalum monophosphide crystals by a chemical vapor transport technique. We report resistivity vs. temperature of both materials in the temperature range from 2 K to 300 K. We have also performed electronic structure calculations and present the band structure and density of states of these two compounds. The calculations show that both compounds are semimetals, as their conduction and valence bands overlap near the Fermi energy.

DIPPR Project 871 For 1995 - Thermodynamic Properties and Ideal-Gas Enthalpies of Formation for Methyl Benzoate, Ethyl Benzoate, (R)-(+)-Limonene, Tert-Amyl Methyl Ether, Trans-Crotonaldehyde, and

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

Steele, W.V.

2002-07-01

Ideal-gas enthalpies of formation of methyl benzoate, ethyl benzoate, (R)-(+)-limonene, tert-amyl methyl ether, trans-crotonaldehyde, and diethylene glycol are reported. The standard energy of combustion and hence standard enthalpy of formation of each compound in the liquid phase has been measured using an oxygen rotating-bomb calorimeter without rotation. Vapor pressures were measured to a pressure limit of 270 kPa or the lower decomposition point for each of the six compounds using a twin ebulliometric apparatus. Liquid-phase densities along the saturation line were measured for each compound over a range of temperature (ambient to a maximum of 548 K). A differential scanningmore » calorimeter was used to measure two-phase (liquid + vapor) heat capacities for each compound in the temperature region ambient to the critical temperature or lower decomposition point. For methyl benzoate and tert-amyl methyl ether, critical temperatures and critical densities were determined from the DSC results and corresponding critical pressures derived from the fitting procedures. Fitting procedures were used to derive critical temperatures, critical pressures, and critical densities for each of the remaining compounds. The results of the measurements were combined to derive a series of thermophysical properties including critical temperature, critical density, critical pressure, acentric factor, enthalpies of vaporization (restricted to within {+-}50 K of the temperature region of the experimentally determined vapor pressures), and heat capacities along the saturation line. Wagner-type vapor-pressure equations were derived for each compound. All measured and derived values were compared with those obtained in a search of the literature. Recommended critical parameters are listed for each of the compounds studied. Group-additivity parameters, useful in the application of the Benson gas-phase group-contribution correlations, were derived.« less

Optoelectronic and transport properties of LiBZ (B = Al, In, Ga and Z = Si, Ge, Sn) semiconductors

NASA Astrophysics Data System (ADS)

Shah, Syed Hatim; Khan, Shah Haider; Laref, A.; Murtaza, G.

2018-02-01

Half-Heusler compounds LiBZ (B = Al, In, Ga and Z = Si, Ge, Sn) are comprehensively investigated using state of the art full potential linearized augmented plane wave (FP-LAPW) method. Stable geometry of the compounds obtained through energy minimization procedure. Lattice constant increased while bulk modulus decreased in replacing the ions of size increasing from top to bottom of the periodic table. Band structure calculations show LiInGe and LiInSn as direct bandgap while LiAlSi, LiInGe and LiGaSn indirect bandgap semiconductors. Density of states demonstrates mixed s, p, d states of cations and anions in the valence and conduction bands. These compounds have mixed ionic and covalent bonding. Compounds show dominant optical response in the visible and low frequency ultraviolet energy region. The transport properties of the compounds are described in terms of Seebeck coefficient, electrical and thermal conductivities. The calculated figure of merit of LiAlSi is in good agreement with the recent experimental results.

GW-BSE approach on S1 vertical transition energy of large charge transfer compounds: A performance assessment.

PubMed

Ziaei, Vafa; Bredow, Thomas

2016-11-07

In this work, we apply many-body perturbation theory (MBPT) on large critical charge transfer (CT) complexes to assess its performance on the S 1 excitation energy. Since the S 1 energy of CT compounds is heavily dependent on the Hartree-Fock (HF) exchange fraction in the reference density functional, MBPT opens a new way for reliable prediction of CT S 1 energy without explicit knowledge of suitable amount of HF-exchange, in contrary to the time-dependent density functional theory (TD-DFT), where depending on various functionals, large errors can arise. Thus, simply by starting from a (semi-)local reference functional and performing update of Kohn-Sham (KS) energies in the Green's function G while keeping dynamical screened interaction (W(ω)) frozen to the mean-field level, we obtain impressingly highly accurate S 1 energy at slightly higher computational cost in comparison to TD-DFT. However, this energy-only updating mechanism in G fails to work if the initial guess contains a fraction or 100% HF-exchange, and hence considerably inaccurate S 1 energy is predicted. Furthermore, eigenvalue updating both in G and W(ω) overshoots the S 1 energy due to enhanced underscreening of W(ω), independent of the (hybrid-)DFT starting orbitals. A full energy-update on top of HF orbitals even further overestimates the S 1 energy. An additional update of KS wave functions within the Quasi-Particle Self-Consistent GW (QSGW) deteriorates results, in stark contrast to the good results obtained from QSGW for periodic systems. For the sake of transferability, we further present data of small critical non-charge transfer systems, confirming the outcomes of the CT-systems.

Novel LLM series high density energy materials: Synthesis, characterization, and thermal stability

NASA Astrophysics Data System (ADS)

Pagoria, Philip; Zhang, Maoxi; Tsyshevskiy, Roman; Kuklja, Maija

Novel high density energy materials must satisfy specific requirements, such as an increased performance, reliably high stability to external stimuli, cost-efficiency and ease of synthesis, be environmentally benign, and be safe for handling and transportation. During the last decade, the attention of researchers has drifted from widely used nitroester-, nitramine-, and nitroaromatic-based explosives to nitrogen-rich heterocyclic compounds. Good thermal stability, the low melting point, high density, and moderate sensitivity make heterocycle materials attractive candidates for use as oxidizers in rocket propellants and fuels, secondary explosives, and possibly as melt-castable ingredients of high explosive formulations. In this report, the synthesis, characterization, and results of quantum-chemical DFT study of thermal stability of LLM-191, LLM-192 and LLM-200 high density energy materials are presented. Work performed under the auspices of the DOE by the LLNL (Contract DE-AC52-07NA27344). This research is supported in part by ONR (Grant N00014-12-1-0529) and NSF. We used NSF XSEDE (Grant DMR-130077) and DOE NERSC (Contract DE-AC02-05CH11231) resources.

Synthesis, characterization, crystal structure and theoretical study of a compound with benzodiazole ring: antimicrobial activity and DNA binding.

PubMed

Latha, P; Kodisundaram, P; Sundararajan, M L; Jeyakumar, T

2014-08-14

2-(Thiophen-2-yl)-1-((thiophen-2-yl)methyl)-1H-1,3-benzodiazole (HL) is synthesized and characterized by elemental analysis, UV-Vis, FT-IR, (1)H, (13)C NMR, mass spectra, scanning electron microscope (SEM) and single crystal X-ray diffraction. The crystal structure is stabilized by intermolecular CH⋯N and CH⋯π interactions. The molecular structure is also optimized at the B3LYP/6-31G level using density functional theory (DFT). The structural parameters from the theory are nearer to those of crystal, the calculated total energy of coordination is -1522.814a.u. The energy of HOMO-LUMO and the energy gap are -0.20718, -0.04314, 0.16404a.u, respectively. All data obtained from the spectral studies support the structural properties of the compound HL. The benzimidazole ring is essentially planar. The in vitro biological screening effects of the synthesized compound is tested against four bacterial and four fungal strains by well diffusion method. Antioxidant property and DNA binding behaviour of the compound has been investigated using spectrophotometric method. Copyright © 2014 Elsevier B.V. All rights reserved.

A comparative study between para-aminophenyl and ortho-aminophenyl benzothiazoles using NMR and DFT calculations.

PubMed

Pierens, G K; Venkatachalam, T K; Reutens, D

2014-08-01

Ortho-substituted and para-substituted aminophenyl benzothiazoles were synthesised and characterised using NMR spectroscopy. A comparison of the proton chemical shift values reveals significant differences in the observed chemical shift values for the NH protons indicating the presence of a hydrogen bond in all ortho-substituted compounds as compared to the para compounds. The presence of intramolecular hydrogen bond in the ortho amino substituted aminophenyl benzothiazole forces the molecule to be planar which may be an additional advantage in developing these compounds as Alzheimer's imaging agent because the binding to amyloid fibrils prefers planar compounds. The splitting pattern of the methylene proton next to the amino group also showed significant coupling to the amino proton consistent with the notion of the existence of slow exchange and hydrogen bond in the ortho-substituted compounds. This is further verified by density functional theory calculations which yielded a near planar low energy conformer for all the o-aminophenyl benzothiazoles and displayed a hydrogen bond from the amine proton to the nitrogen of the thiazole ring. A detailed analysis of the (1)H, (13)C and (15)N NMR chemical shifts and density functional theory calculated structures of the compounds are described. Copyright © 2014 John Wiley & Sons, Ltd.

FP-LAPW based investigation of structural, electronic and mechanical properties of CePb{sub 3} intermetallic compound

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

Pagare, Gitanjali, E-mail: gita-pagare@yahoo.co.in; Jain, Ekta, E-mail: jainekta05@gmail.com; Abraham, Jisha Annie, E-mail: disisjisha@yahoo.com

A theoretical study of structural, electronic, elastic and mechanical properties of CePb{sub 3} intermetallic compound has been investigated systematically using first principles density functional theory. The calculations are carried out within the three different forms of generalized gradient approximation (GGA) and LSDA for the exchange correlation potential. The ground state properties such as lattice parameter (a{sub 0}), bulk modulus (B) and its pressure derivative (B′) are calculated and obtained lattice parameter of this compound shows well agreement with the experimental results. We have calculated three independent second order elastic constants (C{sub 11}, C{sub 12} and C{sub 44}), which has notmore » been calculated and measured yet. From energy dispersion curves, it is found that the studied compound is metallic in nature. Ductility of this compound is analyzed using Pugh’s criteria and Cauchy's pressure (C{sub 11}-C{sub 12}). The mechanical properties such as Young's modulus, shear modulus, anisotropic ratio, Poison's ratio have been calculated for the first time using the Voigt–Reuss–Hill (VRH) averaging scheme. The average sound velocities (v{sub m}), density (ρ) and Debye temperature (θ{sub D}) of this compound are also estimated from the elastic constants.« less

Efficient electricity production and simultaneously wastewater treatment via a high-performance photocatalytic fuel cell.

PubMed

Liu, Yanbiao; Li, Jinhua; Zhou, Baoxue; Li, Xuejin; Chen, Hongchong; Chen, Quanpeng; Wang, Zhongsheng; Li, Lei; Wang, Jiulin; Cai, Weimin

2011-07-01

A great quantity of wastewater were discharged into water body, causing serious environmental pollution. Meanwhile, the organic compounds in wastewater are important sources of energy. In this work, a high-performance short TiO(2) nanotube array (STNA) electrode was applied as photoanode material in a novel photocatalytic fuel cell (PFC) system for electricity production and simultaneously wastewater treatment. The results of current work demonstrate that various model compounds as well as real wastewater samples can be used as substrates for the PFC system. As a representative of model compounds, the acetic acid solution produces the highest cell performance with short-circuit current density 1.42 mA cm(-2), open-circuit voltage 1.48 V and maximum power density output 0.67 mW cm(-2). The STNA photoanode reveals obviously enhanced cell performance compared with TiO(2) nanoparticulate film electrode or other long nanotubes electrode. Moreover, the photoanode material, electrolyte concentration, pH of the initial solution, and cathode material were found to be important factors influencing the system performance of PFC. Therefore, the proposed fuel cell system provides a novel way of energy conversion and effective disposal mode of organics and serves well as a promising technology for wastewater treatment. Copyright © 2011 Elsevier Ltd. All rights reserved.

The role of charge transfer in the energy level alignment at the pentacene/C60 interface.

PubMed

Beltrán, J; Flores, F; Ortega, J

2014-03-07

Understanding the mechanism of energy level alignment at organic-organic interfaces is a crucial line of research to optimize applications in organic electronics. We address this problem for the C60-pentacene interface by performing local-orbital Density Functional Theory (DFT) calculations, including the effect of the charging energies on the energy gap of both organic materials. The results are analyzed within the induced density of interface states (IDIS) model. We find that the induced interface potential is in the range of 0.06-0.10 eV, in good agreement with the experimental evidence, and that such potential is mainly induced by the small, but non-negligible, charge transfer between the two compounds and the multipolar contribution associated with pentacene. We also suggest that an appropriate external intercompound potential could create an insulator-metal transition at the interface.

Perovskite- and Heusler based materials for thermoelectric converters

NASA Astrophysics Data System (ADS)

Weidenkaff, Anke

2015-03-01

The broad application of thermoelectric converters in future energy technologies requires the development of active, stable, low cost and sustainable materials. Semiconductors based on perovskite and heusler structures show substantial potential for thermoelectric energy conversion processes. Their good performance can be explained based on their suitable band structure, adjusted charge carrier density, mass and mobility, limited phonon transport, electron filtering possibilities, strongly correlated electronic systems, etc. These properties are widely tuneable by following theoretical concepts and a deep composition-structure-property understanding to change the composition, structure and size of the crystallites in innovative scalable synthesis procedures. Improved thermoelectric materials are developed, synthesised and tested in diverse high temperature applications to improve the efficiency and energy density of the thermoelectric conversion process. The lecture will provide a summary on the field of advanced perovskite-type ceramics and Heusler compounds gaining importance for a large number of future energy technologies.

Low-energy ion irradiation in HiPIMS to enable anatase TiO2 selective growth

NASA Astrophysics Data System (ADS)

Cemin, Felipe; Tsukamoto, Makoto; Keraudy, Julien; Antunes, Vinícius Gabriel; Helmersson, Ulf; Alvarez, Fernando; Minea, Tiberiu; Lundin, Daniel

2018-06-01

High power impulse magnetron sputtering (HiPIMS) has already demonstrated great potential for synthesizing the high-energy crystalline phase of titanium dioxide (rutile TiO2) due to large quantities of highly energetic ions present in the discharge. In this work, it is shown that the metastable anatase phase can also be obtained by HiPIMS. The required deposition conditions have been identified by systematically studying the phase formation, microstructure and chemical composition as a function of mode of target operation as well as of substrate temperature, working pressure, and peak current density. It is found that films deposited in the metal and transition modes are predominantly amorphous and contain substoichiometric TiO x compounds, while in compound mode they are well-crystallized and present only O2‑ ions bound to Ti4+, i.e. pure TiO2. Anatase TiO2 films are obtained for working pressures between 1 and 2 Pa, a peak current density of ~1 A cm‑2 and deposition temperatures lower than 300 °C. Rutile is favored at lower pressures (<1 Pa) and higher peak current densities (>2 A cm‑2), while amorphous films are obtained at higher pressures (5 Pa). Microstructural characterization of selected films is also presented.

Ab Initio Study of Electronic Structure, Elastic and Transport Properties of Fluoroperovskite LiBeF3

NASA Astrophysics Data System (ADS)

Benmhidi, H.; Rached, H.; Rached, D.; Benkabou, M.

2017-04-01

The aim of this work is to investigate the electronic, mechanical, and transport properties of the fluoroperovskite compound LiBeF3 by first-principles calculations using the full-potential linear muffin-tin orbital method based on density functional theory within the local density approximation. The independent elastic constants and related mechanical properties including the bulk modulus ( B), shear modulus ( G), Young's modulus ( E), and Poisson's ratio ( ν) have been studied, yielding the elastic moduli, shear wave velocities, and Debye temperature. According to the electronic properties, this compound is an indirect-bandgap material, in good agreement with available theoretical data. The electron effective mass, hole effective mass, and energy bandgaps with their volume and pressure dependence are investigated for the first time.

Negative-pressure polymorphs made by heterostructural alloying

PubMed Central

Perkins, John D.

2018-01-01

The ability of a material to adopt multiple structures, known as polymorphism, is a fascinating natural phenomenon. Various polymorphs with unusual properties are routinely synthesized by compression under positive pressure. However, changing a material’s structure by applying tension under negative pressure is much more difficult. We show how negative-pressure polymorphs can be synthesized by mixing materials with different crystal structures—a general approach that should be applicable to many materials. Theoretical calculations suggest that it costs less energy to mix low-density structures than high-density structures, due to less competition for space between the atoms. Proof-of-concept experiments confirm that mixing two different high-density forms of MnSe and MnTe stabilizes a Mn(Se,Te) alloy with a low-density wurtzite structure. This Mn(Se,Te) negative-pressure polymorph has 2× to 4× lower electron effective mass compared to MnSe and MnTe parent compounds and has a piezoelectric response that none of the parent compounds have. This example shows how heterostructural alloying can lead to negative-pressure polymorphs with useful properties—materials that are otherwise nearly impossible to make. PMID:29725620

Synthesis, spectroscopic and structural characterization of 5-benzoyl-4-phenyl-2-methylthio-1H-pyrimidine with theoretical calculations using density functional theory.

PubMed

Inkaya, Ersin; Dinçer, Muharrem; Sahan, Emine; Yıldırım, Ismail

2013-10-01

In this paper, we will report a combined experimental and theoretical investigation of the molecular structure and spectroscopic parameters (FT-IR, (1)H NMR, (13)C NMR) of 5-benzoyl-4-phenyl-2-methylthio-1H-pyrimidine. The compound crystallizes in the triclinic space group P-1 with Z=2. The molecular geometry was also optimized using density functional theory (DFT/B3LYP) method with the 6-311G(d,p) and 6-311++G(d,p) basis sets in ground state and compared with the experimental data. All the assignments of the theoretical frequencies were performed by potential energy distributions using VEDA 4 program. 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 (ESP). Also, non-linear optical properties of the title compound were performed at B3LYP/6-311++G(d,p) level. The theoretical results showed an excellent agreement with the experimental values. Copyright © 2013 Elsevier B.V. All rights reserved.

Synthesis, spectroscopic and structural characterization of 5-benzoyl-4-phenyl-2-methylthio-1H-pyrimidine with theoretical calculations using density functional theory

NASA Astrophysics Data System (ADS)

İnkaya, Ersin; Dinçer, Muharrem; Şahan, Emine; Yıldırım, İsmail

2013-10-01

In this paper, we will report a combined experimental and theoretical investigation of the molecular structure and spectroscopic parameters (FT-IR, 1H NMR, 13C NMR) of 5-benzoyl-4-phenyl-2-methylthio-1H-pyrimidine. The compound crystallizes in the triclinic space group P-1 with Z = 2. The molecular geometry was also optimized using density functional theory (DFT/B3LYP) method with the 6-311G(d,p) and 6-311++G(d,p) basis sets in ground state and compared with the experimental data. All the assignments of the theoretical frequencies were performed by potential energy distributions using VEDA 4 program. 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 (ESP). Also, non-linear optical properties of the title compound were performed at B3LYP/6-311++G(d,p) level. The theoretical results showed an excellent agreement with the experimental values.

Negative-pressure polymorphs made by heterostructural alloying.

PubMed

Siol, Sebastian; Holder, Aaron; Steffes, James; Schelhas, Laura T; Stone, Kevin H; Garten, Lauren; Perkins, John D; Parilla, Philip A; Toney, Michael F; Huey, Bryan D; Tumas, William; Lany, Stephan; Zakutayev, Andriy

2018-04-01

The ability of a material to adopt multiple structures, known as polymorphism, is a fascinating natural phenomenon. Various polymorphs with unusual properties are routinely synthesized by compression under positive pressure. However, changing a material's structure by applying tension under negative pressure is much more difficult. We show how negative-pressure polymorphs can be synthesized by mixing materials with different crystal structures-a general approach that should be applicable to many materials. Theoretical calculations suggest that it costs less energy to mix low-density structures than high-density structures, due to less competition for space between the atoms. Proof-of-concept experiments confirm that mixing two different high-density forms of MnSe and MnTe stabilizes a Mn(Se,Te) alloy with a low-density wurtzite structure. This Mn(Se,Te) negative-pressure polymorph has 2× to 4× lower electron effective mass compared to MnSe and MnTe parent compounds and has a piezoelectric response that none of the parent compounds have. This example shows how heterostructural alloying can lead to negative-pressure polymorphs with useful properties-materials that are otherwise nearly impossible to make.

Systematic analysis of hot Yb* isotopes using the energy density formalism

NASA Astrophysics Data System (ADS)

Jain, Deepika; Sharma, Manoj K.; Rajni; Kumar, Raj; Gupta, Raj K.

2014-10-01

A systematic study of the spin-orbit density interaction potential is carried out, with spherical as well as deformed choices of nuclei, for a variety of near-symmetric and asymmetric colliding nuclei leading to various isotopes of the compound nucleus Yb*, using the semiclassical extended Thomas-Fermi formulation (ETF) of the Skyrme energy density formalism (SEDF). We observe that the spin-orbit density interaction barrier height ( and barrier position ( increase systematically with the increase in number of neutrons in both the projectile and target, for spherical systems. On allowing deformation effects with optimum orientations, the barrier-height increases by a large order of magnitude, as compared to the spherical case, in going from 156Yb* to 172Yb* nuclear systems formed via near-symmetric Ni+Mo or asymmetric O+Sm colliding nuclei, except that for the oblate-shaped nuclei, the is the highest and shifts towards a smaller (compact) interaction radius. The temperature does not change the behavior of spin-orbit density dependent ( and independent ( interaction potentials, except for some minor changes in the magnitude. The orientation degree of freedom also plays an important role in modifying the barrier characteristics and hence produces a large effect on the fusion cross section. The fusion excitation function of the compound nuclei 160, 164Yb* formed in different incoming channels, show clearly that the new forces GSkI and KDE0v1 respond better than the old SIII force. Among the first two, KDE0v1 seems to perform better. The fusion cross-sections are also predicted for a few other isotopes of Yb*.

A comparative DFT study on the antioxidant activity of apigenin and scutellarein flavonoid compounds

NASA Astrophysics Data System (ADS)

Sadasivam, K.; Kumaresan, R.

2011-03-01

The potent antioxidant activity of flavonoids relevant to their ability to scavenge reactive oxygen species is the most important function of flavonoids. Density functional theory calculations were explored to investigate the antioxidant activity of flavonoid compounds such as apigenin and scutellarein. The biological characteristics are dependent on electronic parameters, describing the charge distribution on the rings of the flavonoid molecules. The computation of structural and various molecular descriptors such as polarizability, dipole moment, energy gap, homolytic O-H bond dissociation enthalpies (BDEs), ionization potential (IP), electron affinity, hardness, softness, electronegativity, electrophilic index and density plot of molecular orbital for neutral as well as radical species were carried out and studied. The B3LYP/6-311G(d,p) basis set was adopted for all the computations. This computation reveals that scutellarein exhibits higher degree of antioxidant activity than apigenin. Their dipole moment and polarizability analysis show that both the compounds are polar in nature and have the capacity to polarize other atoms.

Analysis of the structural, electronic and optic properties of Ni doped MgSiP{sub 2} semiconductor chalcopyrite compound

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

Kocak, Belgin, E-mail: koakbelgin@gmail.com; Ciftci, Yasemin Oztekin, E-mail: yasemin@gazi.edu.tr

2016-03-25

The structural, electronic band structure and optic properties of the Ni doped MgSiP{sub 2} chalcopyrite compound have been performed by using first-principles method in the density functional theory (DFT) as implemented in Vienna Ab-initio Simulation Package (VASP). The generalized gradient approximation (GGA) in the scheme of Perdew, Burke and Ernzerhof (PBE) is used for the exchange and correlation functional. The present lattice constant (a) follows generally the Vegard’s law. The electronic band structure, total and partial density of states (DOS and PDOS) are calculated. We present data for the frequency dependence of imaginary and real parts of dielectric functions ofmore » Ni doped MgSiP{sub 2}. For further investigation of the optical properties the reflectivity, refractive index, extinction coefficient and electron energy loss function are also predicted. Our obtained results indicate that the lattice constants, electronic band structure and optical properties of this compound are dependent on the substitution concentration of Ni.« less

Estimating the densities of benzene-derived explosives using atomic volumes.

PubMed

Ghule, Vikas D; Nirwan, Ayushi; Devi, Alka

2018-02-09

The application of average atomic volumes to predict the crystal densities of benzene-derived energetic compounds of general formula C a H b N c O d is presented, along with the reliability of this method. The densities of 119 neutral nitrobenzenes, energetic salts, and cocrystals with diverse compositions were estimated and compared with experimental data. Of the 74 nitrobenzenes for which direct comparisons could be made, the % error in the estimated density was within 0-3% for 54 compounds, 3-5% for 12 compounds, and 5-8% for the remaining 8 compounds. Among 45 energetic salts and cocrystals, the % error in the estimated density was within 0-3% for 25 compounds, 3-5% for 13 compounds, and 5-7.4% for 7 compounds. The absolute error surpassed 0.05 g/cm 3 for 27 of the 119 compounds (22%). The largest errors occurred for compounds containing fused rings and for compounds with three -NH 2 or -OH groups. Overall, the present approach for estimating the densities of benzene-derived explosives with different functional groups was found to be reliable. Graphical abstract Application and reliability of average atom volume in the crystal density prediction of energetic compounds containing benzene ring.

Computational assessment of organic photovoltaic candidate compounds

NASA Astrophysics Data System (ADS)

Borunda, Mario; Dai, Shuo; Olivares-Amaya, Roberto; Amador-Bedolla, Carlos; Aspuru-Guzik, Alan

2015-03-01

Organic photovoltaic (OPV) cells are emerging as a possible renewable alternative to petroleum based resources and are needed to meet our growing demand for energy. Although not as efficient as silicon based cells, OPV cells have as an advantage that their manufacturing cost is potentially lower. The Harvard Clean Energy Project, using a cheminformatic approach of pattern recognition and machine learning strategies, has ranked a molecular library of more than 2.6 million candidate compounds based on their performance as possible OPV materials. Here, we present a ranking of the top 1000 molecules for use as photovoltaic materials based on their optical absorption properties obtained via time-dependent density functional theory. This computational search has revealed the molecular motifs shared by the set of most promising molecules.

O-desmethylquinine as a cyclooxygenase-2 (COX-2) inhibitors using AutoDock Vina

NASA Astrophysics Data System (ADS)

Damayanti, Sophi; Mahardhika, Andhika Bintang; Ibrahim, Slamet; Chong, Wei Lim; Lee, Vannajan Sanghiran; Tjahjono, Daryono Hadi

2014-10-01

Computational approach was employed to evaluate the biological activity of novel cyclooxygenase-2 COX-2 inhibitor, O-desmethylquinine, in comparison to quinine as common inhibitor which can also be used an agent of antipyretic, antimalaria, analgesic and antiinflamation. The molecular models of the compound were constructed and optimized with the density function theory with at the B3LYP/6-31G (d,p) level using Gaussian 09 program. Molecular docking studies of the compounds were done to obtain the COX-2 complex structures and their binding energies were analyzed using the AutoDock Vina. The results of docking of the two ligands were comparable and cannot be differentiated from the energy scoring function with AutoDock Vina.

Inelastic Neutron Scattering Studies of the Spin and Lattice Dynamics inIron Arsenide Compounds

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

Christianson, Andrew D; Osborn, R.; Rosenkranz, Stephen

2009-01-01

Although neutrons do not couple directly to the superconducting order parameter, they have nevertheless played an important role in advancing our understanding of the pairing mechanism and the symmetry of the superconducting energy gap in the iron arsenide compounds. Measurements of the spin and lattice dynamics have been performed on non-superconducting 'parent' compounds based on the LaFeAsO ('1111') and BaFe{sub 2}As{sub 2} ('122') crystal structures, and on electron and hole-doped superconducting compounds, using both polycrystalline and single crystal samples. Neutron measurements of the phonon density-of-state, subsequently supported by single crystal inelastic X-ray scattering, are in good agreement with ab initiomore » calculations, provided the magnetism of the iron atoms is taken into account. However, when combined with estimates of the electron-phonon coupling, the predicted superconducting transition temperatures are less than 1 K, making a conventional phononic mechanism for superconductivity highly unlikely. Measurements of the spin dynamics within the spin density wave phase of the parent compounds show evidence of strongly dispersive spin waves with exchange interactions consistent with the observed magnetic order and a large anisotropy gap. Antiferromagnetic fluctuations persist in the normal phase of the superconducting compounds, but they are more diffuse. Below T{sub c}, there is evidence in three '122' compounds that these fluctuations condense into a resonant spin excitation at the antiferromagnetic wavevector with an energy that scales with T{sub c}. Such resonances have been observed in the high-T{sub c} copper oxides and a number of heavy fermion superconductors, where they are considered to be evidence of d-wave symmetry. In the iron arsenides, they also provide evidence of unconventional superconductivity, but a comparison with ARPES and other measurements, which indicate that the gaps are isotropic, suggests that the symmetry is more likely to be extended-s{sub {+-}} wave in character.« less

Inelastic neutron scattering studies of the spin and lattice dynamics in iron arsenide compounds.

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

Osborn, R.; Rosenkranz, S.; Goremychkin, E. A.

2009-03-20

Although neutrons do not couple directly to the superconducting order parameter, they have nevertheless played an important role in advancing our understanding of the pairing mechanism and the symmetry of the superconducting energy gap in the iron arsenide compounds. Measurements of the spin and lattice dynamics have been performed on non-superconducting 'parent' compounds based on the LaFeAsO ('1111') and BaFe{sub 2}As{sub 2} ('122') crystal structures, and on electron and hole-doped superconducting compounds, using both polycrystalline and single crystal samples. Neutron measurements of the phonon density-of-state, subsequently supported by single crystal inelastic X-ray scattering, are in good agreement with ab initiomore » calculations, provided the magnetism of the iron atoms is taken into account. However, when combined with estimates of the electron-phonon coupling, the predicted superconducting transition temperatures are less than 1 K, making a conventional phononic mechanism for superconductivity highly unlikely. Measurements of the spin dynamics within the spin density wave phase of the parent compounds show evidence of strongly dispersive spin waves with exchange interactions consistent with the observed magnetic order and a large anisotropy gap. Antiferromagnetic fluctuations persist in the normal phase of the superconducting compounds, but they are more diffuse. Below T{sub c}, there is evidence in three '122' compounds that these fluctuations condense into a resonant spin excitation at the antiferromagnetic wavevector with an energy that scales with T{sub c}. Such resonances have been observed in the high-T{sub c} copper oxides and a number of heavy fermion superconductors, where they are considered to be evidence of d-wave symmetry. In the iron arsenides, they also provide evidence of unconventional superconductivity, but a comparison with ARPES and other measurements, which indicate that the gaps are isotropic, suggests that the symmetry is more likely to be extended-s{sub {+-}} wave in character.« less

Control of malodorous hydrogen sulfide compounds using microbial fuel cell.

PubMed

Eaktasang, Numfon; Min, Hyeong-Sik; Kang, Christina; Kim, Han S

2013-10-01

In this study, a microbial fuel cell (MFC) was used to control malodorous hydrogen sulfide compounds generated from domestic wastewaters. The electricity production demonstrated a distinct pattern of a two-step increase during 170 h of system run: the first maximum current density was 118.6 ± 7.2 mA m⁻² followed by a rebound of current density increase, reaching the second maximum of 176.8 ± 9.4 mA m⁻². The behaviors of the redox potential and the sulfate level in the anode compartment indicated that the microbial production of hydrogen sulfide compounds was suppressed in the first stage, and the hydrogen sulfide compounds generated from the system were removed effectively as a result of their electrochemical oxidation, which contributed to the additional electricity production in the second stage. This was also directly supported by sulfur deposits formed on the anode surface, which was confirmed by analyses on those solids using a scanning electron microscope equipped with energy dispersive X-ray spectroscopy as well as an elemental analyzer. To this end, the overall reduction efficiencies for HS⁻ and H₂S(g) were as high as 67.5 and 96.4 %, respectively. The correlations among current density, redox potential, and sulfate level supported the idea that the electricity signal generated in the MFC can be utilized as a potential indicator of malodor control for the domestic wastewater system.

Infrared, Raman and density functional characterization and structural study of 2-Nitro-2-phenyl-propane-1,3-diol

NASA Astrophysics Data System (ADS)

Kaya, Mehmet Fatih; Bağlayan, Özge; Kaya, Esma Güneş; Alver, Özgür

2017-12-01

Nitro compound and nitro derivatives are industrially important to produce rubber and agricultural chemicals. In this study, one of the promising derivatives of nitro compound 2-Nitro-2-phenyl-propane-1,3-diol (2NPP) is examined in detail. FT-Infrared and dispersive Raman spectra of 2NPP (C9H11NO4) were respectively recorded in 4000-10 cm-1 and 4000-100 cm-1. The bond distances and angles, conformational distributions, vibrational frequencies and the assignment of each mode, some thermodynamic parameters and reactivity descriptors: total energy, hardness, chemical potential, electrophilicity index, electronegativity, frontier orbitals energy gap of 2NPP were investigated by using DFT/B3LYP method with 6-31++G (d,p) basis set. In order to locate the global minimum on the potential energy surface of 2NPP, a beforehand conformational examinations were carried out using Spartan 10 along with semi-emprical PM6 method. The results of conformational analyses showed that there are five possible conformations having energies under 2 kcal/mol. Comparison of the theoretical and experimental results clearly indicates that density functional hybrid B3LYP/6-31++G (d,p) level of theory can be used to predict vibrational frequencies and structural parameters of 2NPP. Further, C1 geometry is considered to be the global minimum conformation of 2NPP.

FT-IR, FT-Raman, UV, NMR spectra and molecular structure investigation of (E)-2-(3-chloropyrazin-2-yl)-1-(3-ethyl-2, 6-diphenyl piperidin-4-ylidene) hydrazine: A combined experimental and theoretical study

NASA Astrophysics Data System (ADS)

Therasa Alphonsa, A.; Loganathan, C.; Athavan Alias Anand, S.; Kabilan, S.

2015-11-01

This work presents the characterization of (E)-2-(3-chloropyrazin-2-yl)-1-(3-ethyl-2, 6-diphenyl piperidin-4-ylidene) hydrazine (HDE) by quantum chemical calculations and spectral techniques. The structure was investigated by FT-IR, FT-Raman, UV-vis and NMR techniques. The geometrical parameters and energies have been obtained from Density functional theory (DFT) B3LYP (6-31G (d, p)) basis set calculations. The geometry of the molecule was fully optimized, vibrational spectra were calculated and fundamental vibrations were assigned on the basis of total energy distribution (TED) of the vibrational modes, calculated with scaled quantum mechanics (SQM) method. 1H and 13C NMR chemical shifts of the molecule were calculated using Gauge-independent atomic orbital method (GIAO). The electronic properties such as excitation energies, wavelength, HOMO, LUMO energies performed by Time dependent density functional theory (TD-DFT) results complements with the experimental findings. NBO analysis has been performed for analyzing charge delocalization throughout the molecule. The calculation results were applied to simulate spectra of the title compound, which show excellent agreement with observed spectra. To provide information about the interactions between human cytochrome protein and the novel compound theoretically, docking studies were carried out using Schrödinger software.

Coordinated regulation of nitrogen supply mode and initial cell density for energy storage compounds production with economized nitrogen utilization in a marine microalga Isochrysis zhangjiangensis.

PubMed

Chi, Lei; Yao, Changhong; Cao, Xupeng; Xue, Song

2016-01-01

Lipids and carbohydrates are main energy storage compounds (ESC) of microalgae under stressed conditions and they are potential feedstock for biofuel production. Yet, the sustainable and commercially successful production of ESC in microalgae needs to consider nitrogen utilization efficiency. Here the impact of different initial cell densities (ICDs) on ESC accumulation in Isochrysis zhangjiangensis under two nitrogen supply modes (an initially equal concentration of nitrogen per-cell in the medium (N1) and an equal total concentration of nitrogen in the culture system (N2)) were investigated. The results demonstrated that the highest ESC yield (1.36gL(-1)) at N1, which included a maximal nitrogen supply in the cultivation system, and the highest ESC content (66.5%) and ESC productivity per mass of nitrogen (3.28gg(-1) (N) day(-1)) at N2, were all obtained under a high ICD of 8.0×10(6)cellsmL(-1). Therefore I. zhangjiangensis qualifies for ESC-enriched biomass production with economized nitrogen utilization. Copyright © 2015 Elsevier Ltd. All rights reserved.

Sulfur/lithium-insertion compound composite cathodes for Li-S batteries

NASA Astrophysics Data System (ADS)

Su, Yu-Sheng; Manthiram, Arumugam

2014-12-01

A part of carbon additives in sulfur cathodes is replaced by lithium-insertion compounds as they can contribute extra capacity and increase the overall energy density. Accordingly, VO2(B) and TiS2 were incorporated into sulfur cathodes as they can work within the same voltage window as that of sulfur. However, VO2(B) was found to be incompatible with the glyme-based electrolytes that are usually used in Li-S cells, but TiS2 performs well while coupled with sulfur. The S/C/TiS2 composite cathode delivers 252 mAh g-1 more than that of pristine sulfur cathode (1334 mAh g-1 vs. 1082 mAh g-1). The increased capacity is not only due to the contribution by TiS2 itself but also due to a better active-material dispersion and utilization. Serving as active reaction sites during cycling, TiS2 suppresses agglomeration of sulfur and facilitates better ionic/electronic transport within the cathode structure. This composite cathode design provides another direction for Li-S batteries to improve the overall energy density.

First principle study of electronic nanoscale structure of In x Ga1- x P with variable size, shape and alloying percentage

NASA Astrophysics Data System (ADS)

Hussein, M. T.; Kasim, T.; Abdulsattar, M. A.

2013-11-01

In present work, we investigate electronic properties of alloying percentage of In x Ga1- x P compound with different sizes of superlattice large unit cell (LUC) method with 8, 16, 54, and 64 nanocrystals core atoms. The size and type of alloying compound are varied so that it can be tuned to a required application. To determine properties of indium gallium phosphide nanocrystals density functional theory at the generalized-gradient approximation level coupled with LUC method is used to simulate electronic structure of zinc blende indium gallium phosphide nanocrystals that have dimensions around 2-2.8 nm. The calculated properties include lattice constant, energy gap, valence band width, cohesive energy, density of states (DOS) etc. Results show that laws that are applied at microscale alloying percentage are no more applicable at the present nanoscale. Results also show that size, shape and quantum effects are strong. Many properties fluctuate at nanoscale while others converge to definite values. DOS summarizes many of the above quantities.

Investigation of attractive and repulsive interactions associated with ketones in supercritical CO2, based on Raman spectroscopy and theoretical calculations.

PubMed

Kajiya, Daisuke; Saitow, Ken-ichi

2013-08-07

Carbonyl compounds are solutes that are highly soluble in supercritical CO2 (scCO2). Their solubility governs the efficiency of chemical reactions, and is significantly increased by changing a chromophore. To effectively use scCO2 as solvent, it is crucial to understand the high solubility of carbonyl compounds, the solvation structure, and the solute-solvent intermolecular interactions. We report Raman spectroscopic data, for three prototypical ketones dissolved in scCO2, and four theoretical analyses. The vibrational Raman spectra of the C=O stretching modes of ketones (acetone, acetophenone, and benzophenone) were measured in scCO2 along the reduced temperature Tr = T∕Tc = 1.02 isotherm as a function of the reduced density ρr = ρ∕ρc in the range 0.05-1.5. The peak frequencies of the C=O stretching modes shifted toward lower energies as the fluid density increased. The density dependence was analyzed by using perturbed hard-sphere theory, and the shift was decomposed into attractive and repulsive energy components. The attractive energy between the ketones and CO2 was up to nine times higher than the repulsive energy, and its magnitude increased in the following order: acetone < acetophenone < benzophenone. The Mulliken charges of the three solutes and CO2 molecules obtained by using quantum chemistry calculations described the order of the magnitude of the attractive energy and optimized the relative configuration between each solute and CO2. According to theoretical calculations for the dispersion energy, the dipole-induced-dipole interaction energy, and the frequency shift due to their interactions, the experimentally determined attractive energy differences in the three solutes were attributed to the dispersion energies that depended on a chromophore attached to the carbonyl groups. It was found that the major intermolecular interaction with the attractive shift varied from dipole-induced dipole to dispersion depending on the chromophore in the ketones in scCO2. As the common conclusion for the Raman spectral measurements and the four theoretical calculations, solute polarizability, modified by the chromophore, was at the core of the solute-solvent interactions of the ketones in scCO2.

Ternary alloy material prediction using genetic algorithm and cluster expansion

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

Chen, Chong

2015-12-01

This thesis summarizes our study on the crystal structures prediction of Fe-V-Si system using genetic algorithm and cluster expansion. Our goal is to explore and look for new stable compounds. We started from the current ten known experimental phases, and calculated formation energies of those compounds using density functional theory (DFT) package, namely, VASP. The convex hull was generated based on the DFT calculations of the experimental known phases. Then we did random search on some metal rich (Fe and V) compositions and found that the lowest energy structures were body centered cube (bcc) underlying lattice, under which we didmore » our computational systematic searches using genetic algorithm and cluster expansion. Among hundreds of the searched compositions, thirteen were selected and DFT formation energies were obtained by VASP. The stability checking of those thirteen compounds was done in reference to the experimental convex hull. We found that the composition, 24-8-16, i.e., Fe 3VSi 2 is a new stable phase and it can be very inspiring to the future experiments.« less

Experimental and modeling studies of ultrasound-assisted release of phenolics from oak chips into model wine.

PubMed

Tao, Yang; Zhang, Zhihang; Sun, Da-Wen

2014-09-01

The enhancement of release of oak-related compounds from oak chips during wine aging with oak chips may interest the winemaking industry. In this study, the 25-kHz ultrasound waves were used to intensify the mass transfer of phenolics from oak chips into a model wine. The influences of acoustic energy density (6.3-25.8 W/L) and temperature (15-25 °C) on the release kinetics of total phenolics were investigated systematically. The results exhibited that the total phenolic yield released was not affected by acoustic energy density significantly whereas it increased with the increase of temperature during sonication. Furthermore, to describe the mechanism of mass transfer of phenolics in model wine under ultrasonic field, the release kinetics of total phenolics was simulated by both a second-order kinetic model and a diffusion model. The modeling results revealed that the equilibrium concentration of total phenolics in model wine, the initial release rate and effective diffusivity of total phenolics generally increased with acoustic energy density and temperature. In addition, temperature had a negative effect on the second-order release rate constant whereas acoustic energy density had an opposite effect. Copyright © 2014 Elsevier B.V. All rights reserved.

Can Baird's and Clar's Rules Combined Explain Triplet State Energies of Polycyclic Conjugated Hydrocarbons with Fused 4nπ- and (4n + 2)π-Rings?

PubMed

Ayub, Rabia; Bakouri, Ouissam El; Jorner, Kjell; Solà, Miquel; Ottosson, Henrik

2017-06-16

Compounds that can be labeled as "aromatic chameleons" are π-conjugated compounds that are able to adjust their π-electron distributions so as to comply with the different rules of aromaticity in different electronic states. We used quantum chemical calculations to explore how the fusion of benzene rings onto aromatic chameleonic units represented by biphenylene, dibenzocyclooctatetraene, and dibenzo[a,e]pentalene modifies the first triplet excited states (T 1 ) of the compounds. Decreases in T 1 energies are observed when going from isomers with linear connectivity of the fused benzene rings to those with cis- or trans-bent connectivities. The T 1 energies decreased down to those of the parent (isolated) 4nπ-electron units. Simultaneously, we observe an increased influence of triplet state aromaticity of the central 4n ring as given by Baird's rule and evidenced by geometric, magnetic, and electron density based aromaticity indices (HOMA, NICS-XY, ACID, and FLU). Because of an influence of triplet state aromaticity in the central 4nπ-electron units, the most stabilized compounds retain the triplet excitation in Baird π-quartets or octets, enabling the outer benzene rings to adapt closed-shell singlet Clar π-sextet character. Interestingly, the T 1 energies go down as the total number of aromatic cycles within a molecule in the T 1 state increases.

Probing vibrational activities, electronic properties, molecular docking and Hirshfeld surfaces analysis of 4-chlorophenyl ({[(1E)-3-(1H-imidazol-1-yl)-1-phenylpropylidene]amino}oxy)methanone: A promising anti-Candida agent

NASA Astrophysics Data System (ADS)

Jayasheela, K.; Al-Wahaibi, Lamya H.; Periandy, S.; Hassan, Hanan M.; Sebastian, S.; Xavier, S.; Daniel, Joseph C.; El-Emam, Ali A.; Attia, Mohamed I.

2018-05-01

The promising anti-Candida agent, 4-chlorophenyl ({[1E-3(1H-imidazole-1-yl)-1-phenylpropylidene}oxy)methanone (4-CPIPM) was comprehensively characterized by FT-IR, FT-Raman, UV, as well as 1H and 13C spectroscopic techniques. The theoretical calculations in the current study utilized Gaussian 09 W software with DFT approach of the B3LYP/6-311++G(d,p) method. The experimental X-ray diffraction data of the 4-CPIPM molecule were compared with the optimized structure and showed well agreement. Intermolecular electronic interactions and their stabilization energies have been analyzed by natural bond orbital method. Potential energy distribution confirmed the normal fundamental mode of vibration with the aid of MOLVIB software. The chemical shift values of the 1H and 13C spectra of the title compound were computed using gauge independent atomic orbital and the results were compared with the experimental values. The time-dependent density function theory method was used to predict the electronic, absorption wavelength and frontier molecular orbital energies. The HOMO-LUMO plots proved the charge transfer in the molecular system of the title compound through conjugated paths. The molecular electrostatic potential analysis provided the electrophilic and nucleophilic reactive sites in the title molecule which have been analyzed using Hirshfeld surface and two dimensions fingerprint plots. Non covalent interactions were also studied using reduced density gradient analysis and color filled electron density diagram. Molecular docking studies of the ligand-protein interactions along with their binding energies were carried out aiming to explain the potent anti-Candida activity of the title molecule.

Computational screening of oxetane monomers for novel hydroxy terminated polyethers.

PubMed

Sarangapani, Radhakrishnan; Ghule, Vikas D; Sikder, Arun K

2014-06-01

Energetic hydroxy terminated polyether prepolymers find paramount importance in search of energetic binders for propellant applications. In the present study, density functional theory (DFT) has been employed to screen the various novel energetic oxetane derivatives, which usually construct the backbone for these energetic polymers. Molecular structures were investigated at the B3LYP/6-31G* level, and isodesmic reactions were designed for calculating the gas phase heats of formation. The condensed phase heats of formation for designed compounds were calculated by the Politzer approach using heats of sublimation. Among the designed oxetane derivatives, T4 and T5 possess condensed phase heat of formation above 210 kJ mol(-1). The crystal packing density of the designed oxetane derivatives varied from 1.2 to 1.6 g/cm(3). The detonation velocities and pressures were evaluated using the Kamlet-Jacobs equations, utilizing the predicted densities and HOFCond. It was found that most of the designed oxetane derivatives have detonation performance comparable to the monomers of benchmark energetic polymers viz., NIMMO, AMMO, and BAMO. The strain energy (SE) for the oxetane derivatives were calculated using homodesmotic reactions, while intramolecular group interactions were predicted through the disproportionation energies. The concept of chemical hardness is used to analyze the susceptibility of designed compounds to reactivity and chemical transformations. The heats of formation, density, and predicted performance imply that the designed molecules are expected to be candidates for polymer synthesis and potential molecules for energetic binders.

A comparative study on the experimentally derived electron densities of three protease inhibitor model compounds.

PubMed

Grabowsky, Simon; Pfeuffer, Thomas; Morgenroth, Wolfgang; Paulmann, Carsten; Schirmeister, Tanja; Luger, Peter

2008-07-07

In order to contribute to a rational design of optimised protease inhibitors which can covalently block the nucleophilic amino acids of the proteases' active sites, we have chosen three model compounds (aziridine , oxirane and acceptor-substituted olefin ) for the examination of their electron-density distribution. Therefore, high-resolution low temperature (9, 27 and 100 K) X-ray diffraction experiments on single-crystals were carried out with synchrotron and conventional X-radiation. It could be shown by the analysis of the electron density using mainly Bader's Theory of Atoms in Molecules, Volkov's EPMM method for interaction energies, electrostatic potentials and Gatti's Source Function that aziridine is most suitable for drug design in this field. A regioselective nucleophilic attack at carbon atom C1 could be predicted and even hints about the reaction's stereoselectivity could be obtained. Moreover, the comparison between two data sets of aziridine (conventional X-ray source vs. synchrotron radiation) gave an estimate concerning the reproducibility of the quantitative results.

Ionic Graphitization of Ultrathin Films of Ionic Compounds.

PubMed

Kvashnin, A G; Pashkin, E Y; Yakobson, B I; Sorokin, P B

2016-07-21

On the basis of ab initio density functional calculations, we performed a comprehensive investigation of the general graphitization tendency in rocksalt-type structures. In this paper, we determine the critical slab thickness for a range of ionic cubic crystal systems, below which a spontaneous conversion from a cubic to a layered graphitic-like structure occurs. This conversion is driven by surface energy reduction. Using only fundamental parameters of the compounds such as the Allen electronegativity and ionic radius of the metal atom, we also develop an analytical relation to estimate the critical number of layers.

Backbone N xH compounds at high pressures

DOE PAGES

Goncharov, Alexander F.; Holtgrewe, Nicholas; Qian, Guangrui; ...

2015-06-05

Optical and synchrotron x-ray diffraction diamond anvil cell experiments have been combined with first principles theoretical structure predictions to investigate mixtures of N 2 and H 2 up to 55 GPa. Our experiments show the formation of structurally complex van der Waals compounds above 10 GPa. However, we found that these N xH (0.52, H 2, and NH 3 above approximately 40 GPa. Lastly, our results suggest new pathways for synthesis of environmentally benign high energy-density materials. These materials could also exist as alternative planetary ices.

Spinel compounds as multivalent battery cathodes: A systematic evaluation based on ab initio calculations

DOE PAGES

Liu, Miao; Rong, Ziqin; Malik, Rahul; ...

2014-12-16

In this study, batteries that shuttle multivalent ions such as Mg 2+ and Ca 2+ ions are promising candidates for achieving higher energy density than available with current Li-ion technology. Finding electrode materials that reversibly store and release these multivalent cations is considered a major challenge for enabling such multivalent battery technology. In this paper, we use recent advances in high-throughput first-principles calculations to systematically evaluate the performance of compounds with the spinel structure as multivalent intercalation cathode materials, spanning a matrix of five different intercalating ions and seven transition metal redox active cations. We estimate the insertion voltage, capacity,more » thermodynamic stability of charged and discharged states, as well as the intercalating ion mobility and use these properties to evaluate promising directions. Our calculations indicate that the Mn 2O 4 spinel phase based on Mg and Ca are feasible cathode materials. In general, we find that multivalent cathodes exhibit lower voltages compared to Li cathodes; the voltages of Ca spinels are ~0.2 V higher than those of Mg compounds (versus their corresponding metals), and the voltages of Mg compounds are ~1.4 V higher than Zn compounds; consequently, Ca and Mg spinels exhibit the highest energy densities amongst all the multivalent cation species. The activation barrier for the Al³⁺ ion migration in the Mn₂O₄ spinel is very high (~1400 meV for Al 3+ in the dilute limit); thus, the use of an Al based Mn spinel intercalation cathode is unlikely. Amongst the choice of transition metals, Mn-based spinel structures rank highest when balancing all the considered properties.« less

Chemically Integrated Inorganic-Graphene Two-Dimensional Hybrid Materials for Flexible Energy Storage Devices.

PubMed

Peng, Lele; Zhu, Yue; Li, Hongsen; Yu, Guihua

2016-12-01

State-of-the-art energy storage devices are capable of delivering reasonably high energy density (lithium ion batteries) or high power density (supercapacitors). There is an increasing need for these power sources with not only superior electrochemical performance, but also exceptional flexibility. Graphene has come on to the scene and advancements are being made in integration of various electrochemically active compounds onto graphene or its derivatives so as to utilize their flexibility. Many innovative synthesis techniques have led to novel graphene-based hybrid two-dimensional nanostructures. Here, the chemically integrated inorganic-graphene hybrid two-dimensional materials and their applications for energy storage devices are examined. First, the synthesis and characterization of different kinds of inorganic-graphene hybrid nanostructures are summarized, and then the most relevant applications of inorganic-graphene hybrid materials in flexible energy storage devices are reviewed. The general design rules of using graphene-based hybrid 2D materials for energy storage devices and their current limitations and future potential to advance energy storage technologies are also discussed. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Bioenergy from Coastal bermudagrass receiving subsurface drip irrigation with advance-treated swine wastewater.

PubMed

Cantrell, Keri B; Stone, Kenneth C; Hunt, Patrick G; Ro, Kyoung S; Vanotti, Matias B; Burns, Joseph C

2009-07-01

Coastal bermudagrass (Cynodon dactylon L.) may be a potentially important source of bio-based energy in the southern US due to its vast acreage. It is often produced as part of a waste management plan with varying nutrient composition and energy characteristics on fields irrigated with livestock wastewater. The objective of this study was to determine the effect of subsurface drip irrigation with treated swine wastewater on both the quantity and quality of bermudagrass bioenergy. The treated wastewater was recycled from an advanced treatment system and used for irrigation of bermudagrass in two crop seasons. The experiment had nine water and drip line spacing treatments arrayed in a randomized complete block-design with four replicates. The bermudagrass was analyzed for calorific and mineral contents. Bermudagrass energy yields for 2004 and 2005 ranged from 127.4 to 251.4MJ ha(-1). Compared to irrigation with commercial nitrogen fertilizer, the least biomass energy density was associated with bermudagrass receiving treated swine wastewater. Yet, in 2004 the wastewater irrigated bermudagrass had greater hay yields leading to greater energy yield per ha. This decrease in energy density of wastewater irrigated bermudagrass was associated with increased concentrations of K, Ca, and Na. After thermal conversion, these compounds are known to remain in the ash portion thereby decreasing the energy density. Nonetheless, the loss of energy density using treated effluent via SDI may be offset by the positive influence of these three elements for their catalytic properties in downstream thermal conversion processes such as promoting a lesser char yield and greater combustible gas formation.

High-energy green supercapacitor driven by ionic liquid electrolytes as an ultra-high stable next-generation energy storage device

NASA Astrophysics Data System (ADS)

Thangavel, Ranjith; Kannan, Aravindaraj G.; Ponraj, Rubha; Thangavel, Vigneysh; Kim, Dong-Won; Lee, Yun-Sung

2018-04-01

Development of supercapacitors with high energy density and long cycle life using sustainable materials for next-generation applications is of paramount importance. The ongoing challenge is to elevate the energy density of supercapacitors on par with batteries, while upholding the power and cyclability. In addition, attaining such superior performance with green and sustainable bio-mass derived compounds is very crucial to address the rising environmental concerns. Herein, we demonstrate the use of watermelon rind, a bio-waste from watermelons, towards high energy, and ultra-stable high temperature green supercapacitors with a high-voltage ionic liquid electrolyte. Supercapacitors assembled with ultra-high surface area, hierarchically porous carbon exhibits a remarkable performance both at room temperature and at high temperature (60 °C) with maximum energy densities of ∼174 Wh kg-1 (25 °C), and 177 Wh kg-1 (60 °C) - based on active mass of both electrodes. Furthermore, an ultra-high specific power of ∼20 kW kg-1 along with an ultra-stable cycling performance with 90% retention over 150,000 cycles has been achieved even at 60 °C, outperforming supercapacitors assembled with other carbon based materials. These results demonstrate the potential to develop high-performing, green energy storage devices using eco-friendly materials for next generation electric vehicles and other advanced energy storage systems.

Random-Phase Approximation Methods

NASA Astrophysics Data System (ADS)

Chen, Guo P.; Voora, Vamsee K.; Agee, Matthew M.; Balasubramani, Sree Ganesh; Furche, Filipp

2017-05-01

Random-phase approximation (RPA) methods are rapidly emerging as cost-effective validation tools for semilocal density functional computations. We present the theoretical background of RPA in an intuitive rather than formal fashion, focusing on the physical picture of screening and simple diagrammatic analysis. A new decomposition of the RPA correlation energy into plasmonic modes leads to an appealing visualization of electron correlation in terms of charge density fluctuations. Recent developments in the areas of beyond-RPA methods, RPA correlation potentials, and efficient algorithms for RPA energy and property calculations are reviewed. The ability of RPA to approximately capture static correlation in molecules is quantified by an analysis of RPA natural occupation numbers. We illustrate the use of RPA methods in applications to small-gap systems such as open-shell d- and f-element compounds, radicals, and weakly bound complexes, where semilocal density functional results exhibit strong functional dependence.

Collisional, radiative and total electron interaction in compound semiconductor detectors and solid state nuclear track detectors: effective atomic number and electron density.

PubMed

Kurudirek, Murat; Kurudirek, Sinem V

2015-05-01

Effective atomic numbers, Zeff and electron densities, Ne are widely used for characterization of interaction processes in radiation related studies. A variety of detectors are employed to detect different types of radiations i.e. photons and charged particles. In the present work, some compound semiconductor detectors (CSCD) and solid state nuclear track detectors (SSNTD) were investigated with respect to the partial as well as total electron interactions. Zeff and Ne of the given detectors were calculated for collisional, radiative and total electron interactions in the kinetic energy region 10keV-1GeV. Maximum values of Zeff and Ne were observed at higher kinetic energies of electrons. Significant variations in Zeff and Ne up to ≈20-25% were noticed for the detectors, GaN, ZnO, Amber and CR-39 for total electron interaction. Moreover, the obtained Zeff and Ne for electrons were compared to those obtained for photons in the entire energy region. Significant variations in Zeff were also noted not only for photons (up to ≈40% for GaN) but also between photons and electrons (up to ≈60% for CR-39) especially at lower energies. Except for the lower energies, Zeff and Ne keep more or less constant values for the given materials. The energy regions where Zeff and Ne keep constant clearly show the availability of using these parameters for characterization of the materials with respect to the radiation interaction processes. Copyright © 2015 Elsevier Ltd. All rights reserved.

Synthesis, theoretical studies and molecular docking of a novel chlorinated tetracyclic: (Z/E)-3-(1,8-dichloro-9,10-dihydro-9,10-ethanoanthracen-11-yl)acrylaldehyde

NASA Astrophysics Data System (ADS)

Sultan, Mujeeb A.; Almansour, Abdulrahman I.; Pillai, Renjith Raveendran; Kumar, Raju Suresh; Arumugam, Natarajan; Armaković, Stevan; Armaković, Sanja J.; Soliman, Saied M.

2017-12-01

(Z/E)-3-(1,8-Dichloro-9,10-dihydro-9,10-ethanoanthracen-11-yl)acrylaldehyde 2 has been investigated experimentally and theoretically. The Wittig reaction of 1,8-dichloro-9,10-dihydro-9,10-ethanoanthracene-11-carbaldehyde 1 and (triphenylphosphoranylidene) acetaldehyde in toluene under reflux conditions resulted in compound 2. Spectroscopic characterization of compound 2 was performed by the Fourier-transform infrared spectroscopy, nuclear magnetic resonance, and high-resolution mass spectroscopy techniques. Density functional theory (DFT) calculations were conducted to study various global and local reactive properties. The spectra were also obtained by DFT calculations and corresponding comparisons were performed to validate the level of theory. Using DFT calculations, reactivity has been studied based on frontier molecular orbitals, charge distribution, average local ionization energies, Fukui functions, and bond dissociation energies for hydrogen abstraction. Molecular dynamics simulations have been used to investigate the influence of water as a solvent for compound 2. Finally, compound 2 was docked into the central and allosteric binding sites of the serotonin transporter enzyme and was found to be a good candidate as an antidepressant-like compound.

First-Principles Study of the Li-Mg-N-H System: Compound Structures and Hydrogen Storage Properties

NASA Astrophysics Data System (ADS)

Michel, Kyle; Ozolins, Vidvuds

2009-03-01

The Li-Mg-N-H system is studied with the addition of the Li4Mg(NH)3, MgNH, and Li4NH compounds using first-principles density-functional theory (DFT) calculations. A structure for the mixed imide Li4Mg(NH)3 is proposed, belonging to the Imm2 space group. A new structure for Li2Mg(NH)2 is given that has Pca21 symmetry; this compound has been previously reported as having Iba2 symmetry. The stability of the Li4Mg-imide is studied with respect to its decomposition reactions. The static, zero-point (ZPE), and vibrational energies of all relevant compounds belonging to this system are reported along with their predicted lowest-energy structures. Dehydrogenation reactions are presented that involve these phases and which are found to be spontaneously occurring within 400 K of room temperature. It is predicted that mixing LiH, LiNH2, and Li2Mg(NH)2 at 505 K will form Li4Mg(NH)3 with the release of 2.04 wt. % H2.

Electronic Structure of GdCuGe Intermetallic Compound

NASA Astrophysics Data System (ADS)

Lukoyanov, A. V.; Knyazev, Yu. V.; Kuz'min, Yu. I.

2018-04-01

The electronic structure of GdCuGe intermetallic compound has been studied. Spin-polarized energy spectrum calculations have been performed by the band method with allowance for strong electron correlations in the 4 f-shell of gadolinium ions. Antiferromagnetic ordering of GdCuGe at low temperatures has been obtained in a theoretical calculation, with the value of the effective magnetic moment of gadolinium ions reproduced in fair agreement with experimental data. The electronic density of states has been analyzed. An optical conductivity spectrum has been calculated for GdCuGe; it reveals specific features that are analogous to the ones discovered previously in the GdCuSi compound with a similar hexagonal structure.

Conformations and charge distributions of diazocyclopropanes

NASA Astrophysics Data System (ADS)

Borges, Itamar, Jr.

Three diazo-substituted cyclopropane compounds, which have been suggested as new potential high energy compounds, were studied employing the B3LYP-DFT/6-31G(d,p) method. Geometries were optimized. Distributed multipole analysis, computed from the B3LYP-DFT/6-31G(d,p) density matrix, was used to describe the details of the molecular charge distribution of the three molecules. It was verified that electron withdrawing from the C ring atoms and charge build-up on the N atoms bonded to the ring increased with the number of diazo groups. These effects were related to increased sensitivity to impact and easiness of C bond N bond breaking in the three compounds.

Li intercalation in graphite: A van der Waals density-functional study

NASA Astrophysics Data System (ADS)

Hazrati, E.; de Wijs, G. A.; Brocks, G.

2014-10-01

Modeling layered intercalation compounds from first principles poses a problem, as many of their properties are determined by a subtle balance between van der Waals interactions and chemical or Madelung terms, and a good description of van der Waals interactions is often lacking. Using van der Waals density functionals we study the structures, phonons and energetics of the archetype layered intercalation compound Li-graphite. Intercalation of Li in graphite leads to stable systems with calculated intercalation energies of -0.2 to -0.3 eV/Li atom, (referred to bulk graphite and Li metal). The fully loaded stage 1 and stage 2 compounds LiC6 and Li1 /2C6 are stable, corresponding to two-dimensional √{3 }×√{3 } lattices of Li atoms intercalated between two graphene planes. Stage N >2 structures are unstable compared to dilute stage 2 compounds with the same concentration. At elevated temperatures dilute stage 2 compounds easily become disordered, but the structure of Li3 /16C6 is relatively stable, corresponding to a √{7 }×√{7 } in-plane packing of Li atoms. First-principles calculations, along with a Bethe-Peierls model of finite temperature effects, allow for a microscopic description of the observed voltage profiles.

Modeling of oxygen incorporation in Th, ThC, and ThN by density functional theory calculations

NASA Astrophysics Data System (ADS)

Pérez Daroca, D.; Llois, A. M.; Mosca, H. O.

2017-12-01

Oxygen incorporation in nuclear fuel materials is an important issue deserving investigation due to its influence on thermophysical and structural properties. Even if there has been a renewed interest in thorium and thorium compounds in the last years, there is still not much research done on this topic. In this work, we study, by means of density functional theory calculations, the incorporation of oxygen in Th, ThC, and ThN. We analyze the electronic structure finding a characteristic peak to be attributed to oxygen incorporation. We also calculate incorporation and solution energies and obtain migration energies of oxygen through different paths finding that migration through vacancy sites is more energetically favorable than through interstitial ones.

High Density Hydrogen Storage System Demonstration Using NaAlH4 Based Complex Compound Hydrides

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

Daniel A. Mosher; Xia Tang; Ronald J. Brown

2007-07-27

This final report describes the motivations, activities and results of the hydrogen storage independent project "High Density Hydrogen Storage System Demonstration Using NaAlH4 Based Complex Compound Hydrides" performed by the United Technologies Research Center under the Department of Energy Hydrogen Program, contract # DE-FC36-02AL67610. The objectives of the project were to identify and address the key systems technologies associated with applying complex hydride materials, particularly ones which differ from those for conventional metal hydride based storage. This involved the design, fabrication and testing of two prototype systems based on the hydrogen storage material NaAlH4. Safety testing, catalysis studies, heat exchangermore » optimization, reaction kinetics modeling, thermochemical finite element analysis, powder densification development and material neutralization were elements included in the effort.« less

Self-interaction-corrected local-spin-density calculations for rare earth materials

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

Svane, A.; Temmerman, W.M.; Szotek, Z.

2000-04-20

The ab initio self-interaction-corrected (SIC) local-spin-density (LSD) approximation is discussed with emphasis on the ability to describe localized f-electron states in rare earth solids. Two methods for minimizing the SIC-LSD total energy functional are discussed, one using a unified Hamiltonian for all electron states, thus having the advantages of Bloch's theorem, the other one employing an iterative scheme in real space. Results for cerium and cerium compounds as well as other rare earths are presented. For the cerium compounds the onset of f-electron delocalization can be accurately described, including the intricate isostructural phase transitions in elemental cerium and CeP. Inmore » Pr and Sm the equilibrium lattice constant and zero temperature equation of state is greatly improved in comparison with the LSD results.« less

First-principles calculations of the structural, elastic and thermodynamic properties of mackinawite (FeS) and pyrite (FeS2)

NASA Astrophysics Data System (ADS)

Wen, Xiangli; Liang, Yuxuan; Bai, Pengpeng; Luo, Bingwei; Fang, Teng; Yue, Luo; An, Teng; Song, Weiyu; Zheng, Shuqi

2017-11-01

The thermodynamic properties of Fe-S compounds with different crystal structure are very different. In this study, the structural, elastic and thermodynamic properties of mackinawite (FeS) and pyrite (FeS2) were investigated by first-principles calculations. Examination of the electronic density of states shows that mackinawite (FeS) is metallic and that pyrite (FeS2) is a semiconductor with a band gap of Eg = 1.02 eV. Using the stress-strain method, the elastic properties including the bulk modulus and shear modulus were derived from the elastic Cij data. Density functional perturbation theory (DFPT) calculations within the quasi-harmonic approximation (QHA) were used to calculate the thermodynamic properties, and the two Fe-S compounds are found to be dynamically stable. The isothermal bulk modulus, thermal expansion coefficient, heat capacities, Gibbs free energy and entropy of the Fe-S compounds are obtained by first-principles phonon calculations. Furthermore, the temperature of the mackinawite (FeS) ⟶ pyrite (FeS2) phase transition at 0 GPa was predicted. Based on the calculation results, the model for prediction of Fe-S compounds in the Fe-H2S-H2O system was improved.

Two-dimensional materials from high-throughput computational exfoliation of experimentally known compounds.

PubMed

Mounet, Nicolas; Gibertini, Marco; Schwaller, Philippe; Campi, Davide; Merkys, Andrius; Marrazzo, Antimo; Sohier, Thibault; Castelli, Ivano Eligio; Cepellotti, Andrea; Pizzi, Giovanni; Marzari, Nicola

2018-03-01

Two-dimensional (2D) materials have emerged as promising candidates for next-generation electronic and optoelectronic applications. Yet, only a few dozen 2D materials have been successfully synthesized or exfoliated. Here, we search for 2D materials that can be easily exfoliated from their parent compounds. Starting from 108,423 unique, experimentally known 3D compounds, we identify a subset of 5,619 compounds that appear layered according to robust geometric and bonding criteria. High-throughput calculations using van der Waals density functional theory, validated against experimental structural data and calculated random phase approximation binding energies, further allowed the identification of 1,825 compounds that are either easily or potentially exfoliable. In particular, the subset of 1,036 easily exfoliable cases provides novel structural prototypes and simple ternary compounds as well as a large portfolio of materials to search from for optimal properties. For a subset of 258 compounds, we explore vibrational, electronic, magnetic and topological properties, identifying 56 ferromagnetic and antiferromagnetic systems, including half-metals and half-semiconductors.

Two-dimensional materials from high-throughput computational exfoliation of experimentally known compounds

NASA Astrophysics Data System (ADS)

Mounet, Nicolas; Gibertini, Marco; Schwaller, Philippe; Campi, Davide; Merkys, Andrius; Marrazzo, Antimo; Sohier, Thibault; Castelli, Ivano Eligio; Cepellotti, Andrea; Pizzi, Giovanni; Marzari, Nicola

2018-02-01

Two-dimensional (2D) materials have emerged as promising candidates for next-generation electronic and optoelectronic applications. Yet, only a few dozen 2D materials have been successfully synthesized or exfoliated. Here, we search for 2D materials that can be easily exfoliated from their parent compounds. Starting from 108,423 unique, experimentally known 3D compounds, we identify a subset of 5,619 compounds that appear layered according to robust geometric and bonding criteria. High-throughput calculations using van der Waals density functional theory, validated against experimental structural data and calculated random phase approximation binding energies, further allowed the identification of 1,825 compounds that are either easily or potentially exfoliable. In particular, the subset of 1,036 easily exfoliable cases provides novel structural prototypes and simple ternary compounds as well as a large portfolio of materials to search from for optimal properties. For a subset of 258 compounds, we explore vibrational, electronic, magnetic and topological properties, identifying 56 ferromagnetic and antiferromagnetic systems, including half-metals and half-semiconductors.

Synthesis, spectroscopic investigations (FT-IR, NMR, UV-Vis, and TD-DFT), and molecular docking of (E)-1-(benzo[d][1, 3]dioxol-6-yl)-3-(6-methoxynaphthalen-2-yl)prop-2-en-1-one

NASA Astrophysics Data System (ADS)

Therasa Alphonsa, A.; Loganathan, C.; Athavan Alias Anand, S.; Kabilan, S.

2017-02-01

The compound (E)-1-(benzo [d] [1, 3] dioxol-6-yl)-3-(6-methoxy naphthalen-2-yl) prop-2-en-1-one (AKN) was synthesized and characterized by FT-IR, NMR, and UV-Vis spectrometer. The optimized molecular geometry, bond lengths, bond angles, atomic charges, harmonic vibrational wave numbers and intensities of vibrational bonds of the title compound have been investigated by Time dependent- Density Functional Theory (TD-DFT) using a standard B3LYP method with 6-31 G (d, p) basis set available in the Gaussian 09W package. 1H and 13C NMR chemical shifts of the molecule were calculated using Gauge-independent atomic orbital method (GIAO). Experimental excitation energies of the molecules were matched with the theoretically calculated energies. The atomic charge distributions of the various atoms present in the AKN were obtained by Mulliken charge population analysis. The Molecular Electrostatic Potential (MEP) analysis reveals the sites for electrophilic attack and nucleophilic reactions in the molecule. The difference between the observed and scaled frequencies was small. The HOMO to LUMO transition implies an electron density transfer. The intramolecular contacts have been interpreted using Natural Bond Orbital (NBO) analysis. The calculation results were applied to simulate spectra of the title compound, which show excellent agreement with observed spectra. To provide information about the interactions between human cytochrome protein and the novel compound theoretically, docking studies were carried out using Schrödinger software.

Radiological properties of plastics and TLD materials its application in radiation dosimetry

NASA Astrophysics Data System (ADS)

Jabaseelan Samuel, E. James; Srinivasan, K.; Poopathi, V.

2017-05-01

In the current study, we evaluated the tissue equivalency of nine different commonly used thermoluminescence compounds and six plastic materials over the photon energy range of 15 KeV to 20 MeV. Our result confirmed that the ratio of number of electrons per gram, electron density of the entire TLD compounds and plastic materials to ICRU-44 soft tissue was lesser than unity, except in the case of polypropylene plastics. The effective atomic number ratio of all the plastic materials was also <1 excluding Poly-vinyl-chloride, and for TLD lithium borate material, it was <1 others which showed the deviation with respect to photon energy. Mass attenuation coefficient (µ/ϼ), mass absorption coefficient (µen/ρ) was calculated and the results are discussed in this paper.

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.

Energy decomposition analysis of single bonds within Kohn-Sham density functional theory.

PubMed

Levine, Daniel S; Head-Gordon, Martin

2017-11-28

An energy decomposition analysis (EDA) for single chemical bonds is presented within the framework of Kohn-Sham density functional theory based on spin projection equations that are exact within wave function theory. Chemical bond energies can then be understood in terms of stabilization caused by spin-coupling augmented by dispersion, polarization, and charge transfer in competition with destabilizing Pauli repulsions. The EDA reveals distinguishing features of chemical bonds ranging across nonpolar, polar, ionic, and charge-shift bonds. The effect of electron correlation is assessed by comparison with Hartree-Fock results. Substituent effects are illustrated by comparing the C-C bond in ethane against that in bis(diamantane), and dispersion stabilization in the latter is quantified. Finally, three metal-metal bonds in experimentally characterized compounds are examined: a [Formula: see text]-[Formula: see text] dimer, the [Formula: see text]-[Formula: see text] bond in dizincocene, and the Mn-Mn bond in dimanganese decacarbonyl.

Theoretical Investigation of Half-Metallic Oxides XFeO3 (X = Sr, Ba) via Modified Becke-Johnson Potential Scheme

NASA Astrophysics Data System (ADS)

Maqsood, Saba; Rashid, Muhammad; Din, Fasih Ud; Saddique, M. Bilal; Laref, A.

2018-03-01

The cubic XFeO3 (X = Sr, Ba) perovskite oxides are studied for their thermodynamic stability in the ferromagnetic phase by using density functional theory calculations. We also explore the elastic properties of these compounds in terms of elastic constants C ij, bulk modulus B, shear modulus G, anisotropy factor A, Poisson's ratio ν and the B/ G ratio. The electronic properties are examined to elucidate the magnetic order, and the thermoelectric properties of XFeO3 (X = Sr, Ba) materials are also presented. The modified Becke-Johnson local density approximation scheme has been used to compute the electronic band structure and density of states, which show that these materials are half-metallic ferromagnetic. We study the magnetic properties by computing the crystal field energy (ΔCF), John-Teller energy (ΔJT) and the exchange splitting energies Δx( d) and Δx( pd). Our results indicate that strong hybridization causes a decrease in the magnetic moment of Fe, which then produces permanent magnetic moments in the nonmagnetic sites.

Remote Substituent Effects on the Structures and Stabilities of P═E π-Stabilized Diphosphatetrylenes (R2P)2E (E = Ge, Sn).

PubMed

Izod, Keith; Evans, Peter; Waddell, Paul G; Probert, Michael R

2016-10-17

A rare P-E π interaction between the lone pair of a planar P center and the vacant p orbital at the Ge or Sn center provides efficient stabilization for P-substituted tetrylenes (R 2 P) 2 E (E = Ge, Sn) and enables isolation of the first example of a compound with a crystallographically authenticated P═Sn bond. Subtle changes in the electronic properties of the bulky aryl substituents in these compounds change the preference for planar versus pyramidal P centers in the solid state; however, variable-temperature NMR spectroscopy indicates that in solution these species are subject to a dynamic equilibrium, which interconverts the planar and pyramidal P centers. Consistent with this, density functional theory studies suggest that there is only a small energy difference between the planar and pyramidal forms of these compounds and reveal a small singlet-triplet energy separation, suggesting potentially interesting reactivities.

Modeling Organochlorine Compounds and the σ-Hole Effect Using a Polarizable Multipole Force Field

PubMed Central

2015-01-01

The charge distribution of halogen atoms on organochlorine compounds can be highly anisotropic and even display a so-called σ-hole, which leads to strong halogen bonds with electron donors. In this paper, we have systematically investigated a series of chloromethanes with one to four chloro substituents using a polarizable multipole-based molecular mechanics model. The atomic multipoles accurately reproduced the ab initio electrostatic potential around chloromethanes, including CCl4, which has a prominent σ-hole on the Cl atom. The van der Waals parameters for Cl were fitted to the experimental density and heat of vaporization. The calculated hydration free energy, solvent reaction fields, and interaction energies of several homo- and heterodimer of chloromethanes are in good agreement with experimental and ab initio data. This study suggests that sophisticated electrostatic models, such as polarizable atomic multipoles, are needed for accurate description of electrostatics in organochlorine compounds and halogen bonds, although further improvement is necessary for better transferability. PMID:24484473

A theoretical study on 2-amino-5-nitroprydinium trifluoroaceta

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

Arioğlu, Çağla, E-mail: caglaarioglu@gmail.com; Tamer, Ömer, E-mail: omertamer@sakarya.edu.tr; Başoğlu, Adil, E-mail: abasoglu@sakarya.edu.tr

The geometry optimization of 2-amino-5-nitroprydinium trifluoroacetate molecule was carried out by using Becke’s three-parameter exchange functional in conjunction with the Lee-Yang-Parr correlation functional (B3LYP) level of density functional theory (DFT) and 6-311++G(d,p) basis set at GAUSSIAN 09 program. The vibration spectrum of the title compound was simulated to predict the presence of functional groups and their vibrational modes. The highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) energies were calculated at the same level, and the obtained small energy gap shows that charge transfer occurs in the title compound. The molecular dipole moment, polarizability and hyperpolarizability parametersmore » were determined to evaluate nonlinear optical efficiency of the title compound. Finally, the {sup 13}C and {sup 1}H Nuclear Magnetic Resonance (NMR) chemical shift values were calculated by the application of the gauge independent atomic orbital (GIAO) method. All of the calculations were carried out by using GAUSSIAN 09 program.« less

Electronic and total energy properties of ternary and quaternary semiconductor compounds, alloys, and superlattices: Theoretical study of Cu/graphite bonding

NASA Technical Reports Server (NTRS)

Lambrecht, Walter R. L.

1992-01-01

The goals of the research were to provide a fundamental science basis for why the bonding of Cu to graphite is weak, to critically evaluate the previous analysis of the wetting studies with particular regard to the values used for the surface energies of Cu and graphite, and to make recommendations for future experiments or other studies which could advance the understanding and solution of this technological problem. First principles electronic structure calculations were used to study the problem. These are based on density functional theory in the local density approximation and the use of the linear muffin-tin orbital band structure method. Calculations were performed for graphite monolayers, single crystal graphite with the hexagonal AB stacking, bulk Cu, Cu(111) surface, and Cu/graphite superlattices. The study is limited to the basal plane of graphite because this is the graphite plane exposed to Cu and graphite surface energies and combined with the measured contact angles to evaluate the experimental adhesion energy.

Negative-pressure polymorphs made by heterostructural alloying

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

Siol, Sebastian; Holder, Aaron; Steffes, James

The ability of a material to adopt multiple structures, known as polymorphism, is a fascinating natural phenomenon. Various polymorphs with unusual properties are routinely synthesized by compression under positive pressure. However, changing a material's structure by applying tension under negative pressure is much more difficult. We show how negative-pressure polymorphs can be synthesized by mixing materials with different crystal structures - a general approach that should be applicable to many materials. Theoretical calculations suggest that it costs less energy to mix low-density structures than high-density structures, due to less competition for space between the atoms. Proof-of-concept experiments confirm that mixingmore » two different high-density forms of MnSe and MnTe stabilizes a Mn(Se,Te) alloy with a low-density wurtzite structure. This Mn(Se,Te) negative-pressure polymorph has 2x to 4x lower electron effective mass compared to MnSe and MnTe parent compounds and has a piezoelectric response that none of the parent compounds have. Lastly, this example shows how heterostructural alloying can lead to negative-pressure polymorphs with useful properties - materials that are otherwise nearly impossible to make.« less

Negative-pressure polymorphs made by heterostructural alloying

DOE PAGES

Siol, Sebastian; Holder, Aaron; Steffes, James; ...

2018-04-20

The ability of a material to adopt multiple structures, known as polymorphism, is a fascinating natural phenomenon. Various polymorphs with unusual properties are routinely synthesized by compression under positive pressure. However, changing a material's structure by applying tension under negative pressure is much more difficult. We show how negative-pressure polymorphs can be synthesized by mixing materials with different crystal structures - a general approach that should be applicable to many materials. Theoretical calculations suggest that it costs less energy to mix low-density structures than high-density structures, due to less competition for space between the atoms. Proof-of-concept experiments confirm that mixingmore » two different high-density forms of MnSe and MnTe stabilizes a Mn(Se,Te) alloy with a low-density wurtzite structure. This Mn(Se,Te) negative-pressure polymorph has 2x to 4x lower electron effective mass compared to MnSe and MnTe parent compounds and has a piezoelectric response that none of the parent compounds have. Lastly, this example shows how heterostructural alloying can lead to negative-pressure polymorphs with useful properties - materials that are otherwise nearly impossible to make.« less

Studies on mass attenuation coefficient, effective atomic number and electron density of some thermoluminescent dosimetric compounds

NASA Astrophysics Data System (ADS)

Önder, P.; Turşucu, A.; Demir, D.; Gürol, A.

2012-12-01

Mass attenuation coefficient, μm , effective atomic number, Zeff, and effective electron density, Nel, were determined experimentally and theoretically for some thermoluminescent dosimetric (TLD) compounds such as MgSO4, CdSO4, Al2O3, Mg2SiO4, ZnSO4, CaSO4, CaF2, NaSO4, Na4P2O7, Ca5F(PO4)3, SiO2, CaCO3 and BaSO4 at 8.04, 8.91, 13.37, 14.97, 17.44, 19.63, 22.10, 24.90, 30.82, 32.06, 35.40, 36.39, 37.26, 43.74, 44.48, 50.38, 51.70, 53.16, 80.99, 276.40, 302.85, 356.01, 383.85 and 661.66 keV photon energies by using an HPGe detector with a resolution of 182 eV at 5.9 keV. The theoretical mass attenuation coefficients were estimated using mixture rule. The calculated values were compared with the experimental values for all compounds. Good agreement has been observed between experimental and theoretical values within experimental uncertainties.

A novel process-based model of microbial growth: self-inhibition in Saccharomyces cerevisiae aerobic fed-batch cultures.

PubMed

Mazzoleni, Stefano; Landi, Carmine; Cartenì, Fabrizio; de Alteriis, Elisabetta; Giannino, Francesco; Paciello, Lucia; Parascandola, Palma

2015-07-30

Microbial population dynamics in bioreactors depend on both nutrients availability and changes in the growth environment. Research is still ongoing on the optimization of bioreactor yields focusing on the increase of the maximum achievable cell density. A new process-based model is proposed to describe the aerobic growth of Saccharomyces cerevisiae cultured on glucose as carbon and energy source. The model considers the main metabolic routes of glucose assimilation (fermentation to ethanol and respiration) and the occurrence of inhibition due to the accumulation of both ethanol and other self-produced toxic compounds in the medium. Model simulations reproduced data from classic and new experiments of yeast growth in batch and fed-batch cultures. Model and experimental results showed that the growth decline observed in prolonged fed-batch cultures had to be ascribed to self-produced inhibitory compounds other than ethanol. The presented results clarify the dynamics of microbial growth under different feeding conditions and highlight the relevance of the negative feedback by self-produced inhibitory compounds on the maximum cell densities achieved in a bioreactor.

Self-assembling process of Oxalamide compounds and their nucleation efficiency in bio-degradable Poly(hydroxyalkanoate)s

NASA Astrophysics Data System (ADS)

Ma, Piming; Deshmukh, Yogesh S.; Wilsens, Carolus H. R. M.; Ryan Hansen, Michael; Graf, Robert; Rastogi, Sanjay

2015-08-01

One of the key requirements in semi-crystalline polyesters, synthetic or bio-based, is the control on crystallization rate and crystallinity. One of the limiting factors in the commercialization of the bio-based polyesters, for example polyhydroxyalkanoates synthesized by bacteria for energy storage purposes, is the slow crystallization rate. In this study, we show that by tailoring the molecular structure of oxalamide compounds, it is possible to dissolve these compounds in molten poly(hydroxybutyrate) (PHB), having a hydroxyvalerate co-monomer content of less than 2 mol%. Upon cooling the polymer melt, the homogeneously dispersed oxalamide compound crystallizes just below the melting temperature of the polymer. The phase-separated compound reduces the nucleation barrier of the polymer, thus enhancing the crystallization rate, nucleation density and crystallinity. The findings reported in this study provide a generic route for the molecular design of oxalamide-based compounds that can be used for enhancing nucleation efficiency of semi-crystalline bio-based polyesters.

O3-type Na(Mn₀.₂₅Fe₀.₂₅Co₀.₂₅Ni₀.₂₅)O₂: a quaternary layered cathode compound for rechargeable Na ion batteries

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

Li, Xi; Zhou, Yong-Ning; Wu, Di

2014-12-01

We report a new layered Na(Mn₀.₂₅Fe₀.₂₅Co₀.₂₅Ni₀.₂₅)O₂ compound with O3 oxygen stacking. It delivers 180 mAh/g initial discharge capacity and 578 Wh/kg specific energy density with good cycling capability at high cutoff voltage. In situ X-ray diffraction (XRD) shows a reversible structure evolution of O3-P3-O3'-O3'' upon Na de-intercalation. The excellent capacity and cycling performance at high cutoff voltage make it an important model system for studying the general issue of capacity fading in layered Na cathode compounds.

Some issues for blast from a structural reactive material solid

NASA Astrophysics Data System (ADS)

Zhang, F.

2018-07-01

Structural reactive material (SRM) is consolidated from a mixture of micro- or nanometric reactive metals and metal compounds to the mixture theoretical maximum density. An SRM can thus possess a higher energy density, relying on various exothermic reactions, and higher mechanical strength and heat resistance than that of conventional CHNO explosives. Progress in SRM solid studies is reviewed specifically as an energy source for air blast through the reaction of fine SRM fragments under explosive loading. This includes a baseline SRM solid explosion characterization, material properties of an SRM solid, and its dynamic fine fragmentation mechanisms and fragment reaction mechanisms. The overview is portrayed mainly from the author's own experimental studies combined with theoretical and numerical explanation. These advances have laid down some fundamentals for the next stage of developments.

A quantitative relationship for the shock sensitivities of energetic compounds based on X-NO(2) (X=C, N, O) bond dissociation energy.

PubMed

Li, Jinshan

2010-08-15

The ZPE-corrected X-NO(2) (X=C, N, O) bond dissociation energies (BDEs(ZPE)) of 11 energetic nitrocompounds of different types have been calculated employing density functional theory methods. Computed results show that using the 6-31G** basis set the UB3LYP calculated BDE(ZPE) is less than the UB3P86. For these typical energetic nitrocompounds the shock-initiated pressure (P(98)) is strongly related to the BDE(ZPE) indeed, and a polynomial correlation of ln(P(98)) with the BDE(ZPE) has been established successfully at different density functional theory levels, which provides a method to address the shock sensitivity problem. Copyright 2010 Elsevier B.V. All rights reserved.

Some issues for blast from a structural reactive material solid

NASA Astrophysics Data System (ADS)

Zhang, F.

2018-03-01

Structural reactive material (SRM) is consolidated from a mixture of micro- or nanometric reactive metals and metal compounds to the mixture theoretical maximum density. An SRM can thus possess a higher energy density, relying on various exothermic reactions, and higher mechanical strength and heat resistance than that of conventional CHNO explosives. Progress in SRM solid studies is reviewed specifically as an energy source for air blast through the reaction of fine SRM fragments under explosive loading. This includes a baseline SRM solid explosion characterization, material properties of an SRM solid, and its dynamic fine fragmentation mechanisms and fragment reaction mechanisms. The overview is portrayed mainly from the author's own experimental studies combined with theoretical and numerical explanation. These advances have laid down some fundamentals for the next stage of developments.

Density functional theory calculations of magnetocrystalline anisotropy energies for (Fe(1-x)Co(x))(2)B.

PubMed

Däne, Markus; Kim, Soo Kyung; Surh, Michael P; Åberg, Daniel; Benedict, Lorin X

2015-07-08

We present and discuss density functional theory calculations of magnetic properties of the family of ferromagnetic compounds, (Fe(1-x)Co(x))(2)B, focusing specifically on the magnetocrystalline anisotropy energy (MAE). Using periodic supercells of various sizes (up to 96 atoms), it is shown that the general qualitative features of the composition dependence of the MAE is in agreement with experimental findings, while our predicted magnitudes are larger than those of experiment. We find that the use of small supercells (6 and 12-atom) favors larger MAE values relative to a statistical sample of configurations constructed with 96-atom supercells. The effect of lattice relaxations is shown to be small. Calculations of the Curie temperature for this alloy are also presented.

System and process for production of magnesium metal and magnesium hydride from magnesium-containing salts and brines

DOEpatents

McGrail, Peter B.; Nune, Satish K.; Motkuri, Radha K.; Glezakou, Vassiliki-Alexandra; Koech, Phillip K.; Adint, Tyler T.; Fifield, Leonard S.; Fernandez, Carlos A.; Liu, Jian

2016-11-22

A system and process are disclosed for production of consolidated magnesium metal products and alloys with selected densities from magnesium-containing salts and feedstocks. The system and process employ a dialkyl magnesium compound that decomposes to produce the Mg metal product. Energy requirements and production costs are lower than for conventional processing.

Theoretical and experimental study of fenofibrate and simvastatin

NASA Astrophysics Data System (ADS)

Nicolás Vázquez, Inés; Rodríguez-Núñez, Jesús Rubén; Peña-Caballero, Vicente; Ruvalcaba, Rene Miranda; Aceves-Hernandez, Juan Manuel

2017-12-01

Fenofibrate, an oral fibrate lipid lowering agent, and simvastatin, which reduces plasma levels of low-density lipoprotein cholesterol, are active pharmaceutical ingredients (APIs), currently in the market. We characterized these APIs by thermal analysis and conducted X-ray powder diffraction techniques. Studies should be carried out in the formulation stage before the final composition of a polypill may be established. Thus, it was found in thermochemical studies that both compounds present no chemical interactions in an equimolar mixture of solid samples at room temperature. Theoretical studies were employed to determine possible interactions between fenofibrate and simvastatin. A very weak intramolecular hydrogen bond is formed between the hydroxyl group (O5H5) of the simvastatin with chlorine and carbonyl group (C11O4, C1O2) of the fenofibrate molecule. These weak energy hydrogen bonds have no effect on the chemical stability of the compounds studied. The results were obtained using Density Functional Theory methods; particularly the BPE1BPE and B3LYP functional and 6-31++G** basis set. The values of energy show good approximation when are compared with similar calculations previously reported. Infrared spectra of monomers and dimers were obtained via theoretical calculations.

Stability and ionic mobility in argyrodite-related lithium-ion solid electrolytes.

PubMed

Chen, Hao Min; Maohua, Chen; Adams, Stefan

2015-07-07

In the search for fast lithium-ion conducting solids for the development of safe rechargeable all-solid-state batteries with high energy density, thiophosphates and related compounds have been demonstrated to be particularly promising both because of their record ionic conductivities and their typically low charge transfer resistances. In this work we explore a wide range of known and predicted thiophosphates with a particular focus on the cubic argyrodite phase with a robust three-dimensional network of ion migration pathways. Structural and hydrolysis stability are calculated employing density functional method in combination with a generally applicable method of predicting the relevant critical reaction. The activation energy for ion migration in these argyrodites is then calculated using the empirical bond valence pathway method developed in our group, while bandgaps of selected argyrodites are calculated as a basis for assessing the electrochemical window. Findings for the lithium compounds are also compared to those of previously known copper argyrodites and hypothetical sodium argyrodites. Therefrom, guidelines for experimental work are derived to yield phases with the optimum balance between chemical stability and ionic conductivity in the search for practical lithium and sodium solid electrolyte materials.

Quantum many-body intermetallics: Phase stability of Fe3Al and small-gap formation in Fe2VAl

NASA Astrophysics Data System (ADS)

Kristanovski, Oleg; Richter, Raphael; Krivenko, Igor; Lichtenstein, Alexander I.; Lechermann, Frank

2017-01-01

Various intermetallic compounds harbor subtle electronic correlation effects. To elucidate this fact for the Fe-Al system, we perform a realistic many-body investigation based on a combination of density functional theory with dynamical mean-field theory in a charge self-consistent manner. A better characterization and understanding of the phase stability of bcc-based D 03-Fe3Al through an improved description of the correlated charge density and the magnetic energy is achieved. Upon replacement of one Fe sublattice with V, the Heusler compound Fe2VAl is realized, known to display bad-metal behavior and increased specific heat. Here we document a charge-gap opening at low temperatures in line with previous experimental work. The gap structure does not match conventional band theory and is reminiscent of (pseudo)gap characteristics in correlated oxides.

Electronic and optical properties of Praseodymium trifluoride

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

Saini, Sapan Mohan, E-mail: smsaini.phy@nitrr.ac.in

2014-10-24

We report the role of f- states on electronic and optical properties of Praseodymium trifluoride (PrF{sub 3}) compound. Full potential linearized augmented plane wave (FPLAPW) method with the inclusion of spin orbit coupling has been used. We employed the local spin density approximation (LSDA) and Coulomb-corrected local spin density approximation (LSDA+U). LSDA+U is known for treating the highly correlated 4f electrons properly. Our theoretical investigation shows that LSDA+U approximation reproduce the correct insulating ground state of PrF{sub 3}. On the other hand there is no significant difference of reflectivity calculated by LSDA and LSDA+U. We find that the reflectivity formore » PrF{sub 3} compound stays low till around 7 eV which is consistent with their large energy gaps. Our calculated reflectivity compares well with the experimental data. The results are analyzed in the light of transitions involved.« less

Band structure modification of the thermoelectric Heusler-phase TiFe2Sn via Mn substitution.

PubMed

Zou, Tianhua; Jia, Tiantian; Xie, Wenjie; Zhang, Yongsheng; Widenmeyer, Marc; Xiao, Xingxing; Weidenkaff, Anke

2017-07-19

Doping (or substitution)-induced modification of the electronic structure to increase the electronic density of states (eDOS) near the Fermi level is considered as an effective strategy to enhance the Seebeck coefficient, and may consequently boost the thermoelectric performance. Through density-functional theory calculations of Mn-substituted TiFe 2-x Mn x Sn compounds, we demonstrate that the d-states of the substituted Mn atoms induce a strong resonant level near the Fermi energy. Our experimental results are in good agreement with the calculations. They show that Mn substitution results in a large increase of the Seebeck coefficient, arising from an enhanced eDOS in Heusler compounds. The results prove that a proper substitution position and element selection can increase the eDOS, leading to a higher Seebeck coefficient and thermoelectric performance of ecofriendly materials.

Preparation, crystal structure, vibrational spectral and density functional studies of bis (4-nitrophenol)-2,4,6-triamino-1,3,5-triazine monohydrate

NASA Astrophysics Data System (ADS)

Kanagathara, N.; Marchewka, M. K.; Drozd, M.; Renganathan, N. G.; Gunasekaran, S.; Anbalagan, G.

2013-10-01

An organic-organic salt, bis (4-nitrophenol) 2,4,6-triamino 1,3,5-triazine monohydrate (BNPM) has been prepared by slow evaporation technique at room temperature. Single crystal X-ray diffraction analysis reveals that the compound crystallizes in triclinic system with centrosymmetric space group P-1. IR and Raman spectra of BNPM have been recorded and analyzed. The study has been extended to confocal Raman spectral analysis. Band assignments have been made for the melamine and p-nitrophenol molecules. Vibrational spectra have also been discussed on the basis of quantum chemical density functional theory calculations using Firefly (PC GAMESS) Version 7.1 G. Vibrational frequencies are calculated and scaled values are compared with the experimental one. The Mulliken charges, HOMO-LUMO orbital energies are calculated and analyzed. The chemical structure of the compound was established by 1H NMR and 13C NMR spectra.

Measurement of the mass attenuation coefficients and electron densities for BiPbSrCaCuO superconductor at different energies

NASA Astrophysics Data System (ADS)

Çevik, U.; Baltaş, H.

2007-03-01

The mass attenuation coefficients for Bi, Pb, Sr, Ca, Cu metals, Bi2O3, PbO, SrCO3, CaO, CuO compounds and solid-state forms of Bi1.7Pb0.3Sr2Ca2Cu3O10 superconductor were determined at 57.5, 65.2, 77.1, 87.3, 94.6, 122 and 136 keV energies. The samples were irradiated using a 57Co point source emitted 122 and 136 keV γ-ray energies. The X-ray energies were obtained using secondary targets such as Ta, Bi2O3 and (CH3COO)2UO22H2O. The γ- and X-rays were counted by a Si(Li) detector with a resolution of 0.16 keV at 5.9 keV. The effect of absorption edges on electron density, effective atomic numbers and their variation with photon energy in composite superconductor samples was discussed. Obtained values were compared with theoretical values.

Towards lead-free perovskite photovoltaics and optoelectronics by ab-initio simulations.

PubMed

Roknuzzaman, Md; Ostrikov, Kostya Ken; Wang, Hongxia; Du, Aijun; Tesfamichael, Tuquabo

2017-10-25

Lead (Pb) free non-toxic perovskite solar cells have become more important in the commercialization of the photovoltaic devices. In this study the structural, electronic, optical and mechanical properties of Pb-free inorganic metal halide cubic perovskites CsBX 3 (B = Sn, Ge; X = I, Br, Cl) for perovskite solar cells are simulated using first-principles Density Functional Theory (DFT). These compounds are semiconductors with direct band gap energy and mechanically stable. Results suggest that the materials have high absorption coefficient, low reflectivity and high optical conductivity with potential application in solar cells and other optoelectronic energy devices. On the basis of the optical properties, one can expect that the Germanium (Ge) would be a better replacement of Pb as Ge containing compounds have higher optical absorption and optical conductivity than that of Pb containing compounds. A combinational analysis of the electronic, optical and mechanical properties of the compounds suggests that CsGeI 3 based perovskite is the best Pb-free inorganic metal halide semiconductor for the solar cell application. However, the compound with solid solution of CsGe(I 0.7 Br 0.3 ) 3 is found to be mechanically more ductile than CsGeI 3 . This study will also guide to obtain Pb-free organic perovskites for optoelectronic devices.

Adsorption of TNT, DNAN, NTO, FOX7, and NQ onto cellulose, chitin, and cellulose triacetate. Insights from Density Functional Theory calculations

NASA Astrophysics Data System (ADS)

Todde, Guido; Jha, Sanjiv K.; Subramanian, Gopinath; Shukla, Manoj K.

2018-02-01

Insensitive munitions (IM) compounds such as DNAN (2,4-dinitroanisole), NTO (3-nitro-1,2,4-triazol-5-one), NQ (nitroguanidine), and FOX7 (1,1-diamino-2,2-dinitroethene) reduce the risk of accidental explosions due to shock and high temperature exposure. These compounds are being used as replacements for sensitive munition compounds such as TNT (2,4,6-trinitromethylbenzene) and RDX (1,3,5-hexahydro-1,3,5-trinitro-1,3,5-triazine). NTO and NQ in IM compounds are more soluble than TNT or RDX, hence they can easily spread in the environment and get dissolved if exposed to precipitation. DNAN solubility is comparable to TNT solubility. Cellulosic biomass, due to its abundance in the environment and its chemical structure, has a high probability of adsorbing these IM compounds, and thus, it is important to investigate the interactions between cellulose and cellulose like biopolymers (e.g. cellulose triacetate and chitin) with IM compounds. Using Density Functional Theory methods, we have studied the adsorption of TNT, DNAN, NTO, NQ, and FOX7 onto cellulose Iα and Iβ, chitin, and cellulose triacetate I (CTA I). Solvent effects on the adsorption were also investigated. Our results show that all contaminants are more strongly adsorbed onto chitin and cellulose Iα than onto CTA I and cellulose Iβ. Dispersion forces were found to be the predominant contribution to the adsorption energies of all contaminants.

Studies on Electronic Structure and Magnetic Properties of an Organic Magnet with Metallic Mn2+ and Cu2+ Ions

NASA Astrophysics Data System (ADS)

Yao, Jian-Guo; Peng, Guang-Xiong

2004-11-01

The electronic structure and the magnetic properties of the non-pure organic ferromagnetic compound MnCu(pbaOH)(H2O)3 with pbaOH = 2-hydroxy-1, 3-propylenebis (oxamato) are studied by using the density-functional theory with local-spin-density approximation. The density of states, total energy, and the spin magnetic moment are calculated. The calculations reveal that the compound MnCu(pbaOH)(H20)3 has a stable metal-ferromagnetic ground state, and the spin magnetic moment per molecule is 2.208 μB, and the spin magnetic moment is mainly from Mn ion and Cu ion. An antiferromagnetic order is expected and the antiferromagnetic exchange interaction of d-electrons of Cu and Mn passes through the antiferromagnetic interaction between the adjacent C, O, and N atoms along the path linking the atoms Cu and Mn. The project supported by National Natural Science Foundation of China under Grant No. 10375074 and Hubei Automotive Industries Institute Foundation under Grant No. QY2002-16

First-principles study of Al2Sm intermetallic compound on structural, mechanical properties and electronic structure

NASA Astrophysics Data System (ADS)

Lin, Jingwu; Wang, Lei; Hu, Zhi; Li, Xiao; Yan, Hong

2017-02-01

The structural, thermodynamic, mechanical and electronic properties of cubic Al2Sm intermetallic compound are investigated by the first-principles method on the basis of density functional theory. In light of the strong on-site Coulomb repulsion between the highly localized 4f electrons of Sm atoms, the local spin density approximation approach paired with additional Hubbard terms is employed to achieve appropriate results. Moreover, to examine the reliability of this study, the experimental value of lattice parameter is procured from the analysis of the TEM image and diffraction pattern of Al2Sm phase in the AZ31 alloy to verify the authenticity of the results originated from the computational method. The value of cohesive energy reveals Al2Sm to be a stable in absolute zero Kelvin. According to the stability criteria, the subject of this work is mechanically stable. Afterward, elastic moduli are deduced by performing Voigt-Reuss-Hill approximation. Furthermore, elastic anisotropy and anisotropy of sound velocity are discussed. Finally, the calculation of electronic density of states is implemented to explore the underlying mechanism of structural stability.

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.

An integrated theoretical and experimental investigation of insensitive munition compounds adsorption on cellulose, cellulose triacetate, chitin and chitosan surfaces.

PubMed

Gurtowski, Luke A; Griggs, Chris S; Gude, Veera G; Shukla, Manoj K

2018-02-01

This manuscript reports results of combined computational chemistry and batch adsorption investigation of insensitive munition compounds, 2,4-dinitroanisole (DNAN), triaminotrinitrobenzene (TATB), 1,1-diamino-2,2-dinitroethene (FOX-7) and nitroguanidine (NQ), and traditional munition compound 2,4,6-trinitrotoluene (TNT) on the surfaces of cellulose, cellulose triacetate, chitin and chitosan biopolymers. Cellulose, cellulose triacetate, chitin and chitosan were modeled as trimeric form of the linear chain of 4 C 1 chair conformation of β-d-glucopyranos, its triacetate form, β-N-acetylglucosamine and D-glucosamine, respectively, in the 1➔4 linkage. Geometries were optimized at the M062X functional level of the density functional theory (DFT) using the 6-31G(d,p) basis set in the gas phase and in the bulk water solution using the conductor-like polarizable continuum model (CPCM) approach. The nature of potential energy surfaces of the optimized geometries were ascertained through the harmonic vibrational frequency analysis. The basis set superposition error (BSSE) corrected interaction energies were obtained using the 6-311G(d,p) basis set at the same theoretical level. The computed BSSE in the gas phase was used to correct interaction energy in the bulk water solution. Computed and experimental results regarding the ability of considered surfaces in adsorbing the insensitive munitions compounds are discussed. Copyright © 2017. Published by Elsevier B.V.

Theoretical modeling of low-energy electronic absorption bands in reduced cobaloximes

DOE PAGES

Bhattacharjee, Anirban; Chavarot-Kerlidou, Murielle; Dempsey, Jillian L.; ...

2014-08-11

Here, we report that the reduced Co(I) states of cobaloximes are powerful nucleophiles that play an important role in the hydrogen-evolving catalytic activity of these species. In this work we have analyzed the low energy electronic absorption bands of two cobaloxime systems experimentally and using a variety of density functional theory and molecular orbital ab initio quantum chemical approaches. Overall we find a reasonable qualitative understanding of the electronic excitation spectra of these compounds but show that obtaining quantitative results remains a challenging task.

Dangling bond energetics in carbon nitride and phosphorus carbide thin films with fullerene-like and amorphous structure

NASA Astrophysics Data System (ADS)

Gueorguiev, G. K.; Broitman, E.; Furlan, A.; Stafström, S.; Hultman, L.

2009-11-01

The energy cost for dangling bond formation in Fullerene-like Carbon Nitride (FL-CN x) and Phosphorus carbide (FL-CP x) as well as their amorphous counterparts: a-CN x, a-CP x, and a-C has been calculated within the framework of Density Functional Theory and compared with surface water adsorption measurements. The highest energy cost is found in the FL-CN x (about 1.37 eV) followed by FL-CP x compounds (0.62-1.04 eV).

Kinetic modeling of ultrasound-assisted extraction of phenolic compounds from grape marc: influence of acoustic energy density and temperature.

PubMed

Tao, Yang; Zhang, Zhihang; Sun, Da-Wen

2014-07-01

The effects of acoustic energy density (6.8-47.4 W/L) and temperature (20-50 °C) on the extraction yields of total phenolics and tartaric esters during ultrasound-assisted extraction from grape marc were investigated in this study. The ultrasound treatment was performed in a 25-kHz ultrasound bath system and the 50% aqueous ethanol was used as the solvent. The initial extraction rate and final extraction yield increased with the increase of acoustic energy density and temperature. The two site kinetic model was used to simulate the kinetics of extraction process and the diffusion model based on the Fick's second law was employed to determine the effective diffusion coefficient of phenolics in grape marc. Both models gave satisfactory quality of data fit. The diffusion process was divided into one fast stage and one slow stage and the diffusion coefficients in both stages were calculated. Within the current experimental range, the diffusion coefficients of total phenolics and tartaric esters for both diffusion stages increased with acoustic energy density. Meanwhile, the rise of temperature also resulted in the increase of diffusion coefficients of phenolics except the diffusion coefficient of total phenolics in the fast stage, the value of which being the highest at 40 °C. Moreover, an empirical equation was suggested to correlate the effective diffusion coefficient of phenolics in grape marc with acoustic energy density and temperature. In addition, the performance comparison of ultrasound-assisted extraction and convention methods demonstrates that ultrasound is an effective and promising technology to extract bioactive substances from grape marc. Copyright © 2014 Elsevier B.V. All rights reserved.

Experimental evidence for importance of Hund's exchange interaction for incoherence of charge carriers in iron-based superconductors

NASA Astrophysics Data System (ADS)

Fink, J.; Rienks, E. D. L.; Thirupathaiah, S.; Nayak, J.; van Roekeghem, A.; Biermann, S.; Wolf, T.; Adelmann, P.; Jeevan, H. S.; Gegenwart, P.; Wurmehl, S.; Felser, C.; Büchner, B.

2017-04-01

Angle-resolved photoemission spectroscopy is used to study the scattering rates of charge carriers from the hole pockets near Γ in the iron-based high-Tc hole-doped superconductors KxBa1 -xFe2As2 , x =0.4 , and KxEu1 -xFe2As2 , x =0.55 , and the electron-doped compound Ba (Fe1-xCox) 2As2 , x =0.075 . The scattering rate for any given band is found to depend linearly on the energy, indicating a non-Fermi-liquid regime. The scattering rates in the hole-doped compound are considerably higher than those in the electron-doped compounds. In the hole-doped systems the scattering rate of the charge carriers of the inner hole pocket is about three times higher than the binding energy, indicating that the spectral weight is heavily incoherent. The strength of the scattering rates and the difference between electron- and hole-doped compounds signals the importance of Hund's exchange coupling for correlation effects in these iron-based high-Tc superconductors. The experimental results are in qualitative agreement with theoretical calculations in the framework of combined density functional dynamical mean-field theory.

Structural inheritance and difference between Ti 2AlC, Ti 3AlC 2  and Ti 5Al 2C 3 under pressure from first principles

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

Gao, Qing -He; Du, An; Yang, Ze -Jin

The structural inheritance and difference between Ti 2AlC, Ti 3AlC 2 and Ti 5Al 2C 3 under pressure from first principles are studied. The results indicate that the lattice parameter a are almost the same within Ti 2AlC, Ti 3AlC 2 and Ti 5Al 2C 3, and the value of c in Ti 5Al 2C 3 is the sum of Ti 2AlC and Ti 3AlC 2 which is revealed by the covalently bonded chain in the electron density difference: Al–Ti–C–Ti–Al for Ti 2AlC, Al–Ti 2–C–Ti 1–C–Ti 2–Al for Ti 3AlC 2 and Al–Ti 3–C 2–Ti 3–Al–Ti 2–C 1–Ti 1–C 1–Timore » 2–Al for Ti 5Al 2C 3. The calculated axial compressibilities, volumetric shrinkage, elastic constant c 11, c 33/c 11 ratio, bulk modulus, shear modulus, and Young’s modulus of Ti 5Al 2C 3 are within the range of the end members (Ti 2AlC and Ti 3AlC 2) in a wide pressure range of 0–100 GPa. Only Ti 2AlC is isotropic crystal at about 50 GPa within the Ti–Al–C compounds. All of the Ti 3 d density of states curves of the three compounds move from lower energy to higher energy level with pressure increasing. The similarities of respective bond length, bond overlap population (Ti–C, Ti–Al and Ti–Ti), atom Mulliken charges under pressure as well as the electron density difference for the three compounds are discovered. Among the Ti–Al–C ternary compounds, Ti–Ti bond behaves least compressibility, whereas the Ti–Al bond is softer than that of Ti–C bonds, which can also been confirmed by the density of states and electron density difference. Bond overlap populations of Ti–Ti, Ti–C and Ti–Al indicate that the ionicity interaction becomes more and more stronger in the three structures as the pressure increasing. Lastly, Mulliken charges of Ti 1, Ti 2, Ti 3, C and Al are 0.65, 0.42, 0.39, –0.73, –0.04 at 0 GPa, respectively, which are consistent with the Pauling scale.« less

Structural inheritance and difference between Ti 2AlC, Ti 3AlC 2  and Ti 5Al 2C 3 under pressure from first principles

DOE PAGES

Gao, Qing -He; Du, An; Yang, Ze -Jin

2017-02-08

The structural inheritance and difference between Ti 2AlC, Ti 3AlC 2 and Ti 5Al 2C 3 under pressure from first principles are studied. The results indicate that the lattice parameter a are almost the same within Ti 2AlC, Ti 3AlC 2 and Ti 5Al 2C 3, and the value of c in Ti 5Al 2C 3 is the sum of Ti 2AlC and Ti 3AlC 2 which is revealed by the covalently bonded chain in the electron density difference: Al–Ti–C–Ti–Al for Ti 2AlC, Al–Ti 2–C–Ti 1–C–Ti 2–Al for Ti 3AlC 2 and Al–Ti 3–C 2–Ti 3–Al–Ti 2–C 1–Ti 1–C 1–Timore » 2–Al for Ti 5Al 2C 3. The calculated axial compressibilities, volumetric shrinkage, elastic constant c 11, c 33/c 11 ratio, bulk modulus, shear modulus, and Young’s modulus of Ti 5Al 2C 3 are within the range of the end members (Ti 2AlC and Ti 3AlC 2) in a wide pressure range of 0–100 GPa. Only Ti 2AlC is isotropic crystal at about 50 GPa within the Ti–Al–C compounds. All of the Ti 3 d density of states curves of the three compounds move from lower energy to higher energy level with pressure increasing. The similarities of respective bond length, bond overlap population (Ti–C, Ti–Al and Ti–Ti), atom Mulliken charges under pressure as well as the electron density difference for the three compounds are discovered. Among the Ti–Al–C ternary compounds, Ti–Ti bond behaves least compressibility, whereas the Ti–Al bond is softer than that of Ti–C bonds, which can also been confirmed by the density of states and electron density difference. Bond overlap populations of Ti–Ti, Ti–C and Ti–Al indicate that the ionicity interaction becomes more and more stronger in the three structures as the pressure increasing. Lastly, Mulliken charges of Ti 1, Ti 2, Ti 3, C and Al are 0.65, 0.42, 0.39, –0.73, –0.04 at 0 GPa, respectively, which are consistent with the Pauling scale.« less

Electronic and magnetic properties of TiO2 (co)-doped with (V, Mn)

NASA Astrophysics Data System (ADS)

Rami, R.; Rkhioui, N.; Ahl Laamara, R.; Drissi, L. B.

2017-12-01

The effect of dopage and co-dopage with vanadium and manganese on the structural, the electronic and the magnetic properties of TiO2 is studied using ab initio calculations. The calculations are based on the Korringa-Kohn-Rostoker method combined with the coherent potential approach, employing the local density approximation (LDA). The density of states are plotted in the energy diagram for different concentrations of dopants. The magnetic moments and half-metallic character of the doped compounds are investigated and the mechanism of exchange interaction is determined. In addition, the Curie temperature is given for different concentrations.

Structural and electronic properties of GaAs and GaP semiconductors

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

Rani, Anita; Kumar, Ranjan

2015-05-15

The Structural and Electronic properties of Zinc Blende phase of GaAs and GaP compounds are studied using self consistent SIESTA-code, pseudopotentials and Density Functional Theory (DFT) in Local Density Approximation (LDA). The Lattice Constant, Equillibrium Volume, Cohesive Energy per pair, Compressibility and Band Gap are calculated. The band gaps calcultated with DFT using LDA is smaller than the experimental values. The P-V data fitted to third order Birch Murnaghan equation of state provide the Bulk Modulus and its pressure derivatives. Our Structural and Electronic properties estimations are in agreement with available experimental and theoretical data.

Coordinatively Unsaturated Metal-Organic Frameworks M3(btc)2 (M = Cr, Fe, Co, Ni, Cu, and Zn) Catalyzing the Oxidation of CO by N2O: Insight from DFT Calculations.

PubMed

Ketrat, Sombat; Maihom, Thana; Wannakao, Sippakorn; Probst, Michael; Nokbin, Somkiat; Limtrakul, Jumras

2017-11-20

The oxidation of CO by N 2 O over metal-organic framework (MOF) M 3 (btc) 2 (M = Fe, Cr, Co, Ni, Cu, and Zn) catalysts that contain coordinatively unsaturated sites has been investigated by means of density functional theory calculations. The reaction proceeds in two steps. First, the N-O bond of N 2 O is broken to form a metal oxo intermediate. Second, a CO molecule reacts with the oxygen atom of the metal oxo site, forming one C-O bond of CO 2 . The first step is a rate-determining step for both Cu 3 (btc) 2 and Fe 3 (btc) 2 , where it requires the highest activation energy (67.3 and 19.6 kcal/mol, respectively). The lower value for the iron compound compared to the copper one can be explained by the larger amount of electron density transferred from the catalytic site to the antibonding of N 2 O molecules. This, in turn, is due to the smaller gap between the highest occupied molecular orbital (HOMO) of the MOF and the lowest unoccupied molecular orbital (LUMO)  of N 2 O for Fe 3 (btc) 2 compared to Cu 3 (btc) 2 . The results indicate the important role of charge transfer for the N-O bond breaking in N 2 O. We computationally screened other MOF M 3 (btc) 2 (M = Cr, Fe, Co, Ni, Cu, and Zn) compounds in this respect and show some relationships between the activation energy and orbital properties like HOMO energies and the spin densities of the metals at the active sites of the MOFs.

Quantitative structure activity relationships of some pyridine derivatives as corrosion inhibitors of steel in acidic medium.

PubMed

El Ashry, El Sayed H; El Nemr, Ahmed; Ragab, Safaa

2012-03-01

Quantum chemical calculations using the density functional theory (B3LYP/6-31G DFT) and semi-empirical AM1 methods were performed on ten pyridine derivatives used as corrosion inhibitors for mild steel in acidic medium to determine the relationship between molecular structure and their inhibition efficiencies. Quantum chemical parameters such as total negative charge (TNC) on the molecule, energy of highest occupied molecular orbital (E (HOMO)), energy of lowest unoccupied molecular orbital (E (LUMO)) and dipole moment (μ) as well as linear solvation energy terms, molecular volume (Vi) and dipolar-polarization (π) were correlated to corrosion inhibition efficiency of ten pyridine derivatives. A possible correlation between corrosion inhibition efficiencies and structural properties was searched to reduce the number of compounds to be selected for testing from a library of compounds. It was found that theoretical data support the experimental results. The results were used to predict the corrosion inhibition of 24 related pyridine derivatives.

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.

Clean hydrogen generation through the electrocatalytic oxidation of ethanol in a Proton Exchange Membrane Electrolysis Cell (PEMEC): Effect of the nature and structure of the catalytic anode

NASA Astrophysics Data System (ADS)

Lamy, Claude; Jaubert, Thomas; Baranton, Stève; Coutanceau, Christophe

2014-01-01

The electrocatalytic oxidation of ethanol was investigated in a Proton Exchange Membrane Electrolysis Cell (PEMEC) working at low temperature (20°C) on several Pt-based catalysts (Pt/C, PtSn/C, PtSnRu/C) in order to produce very clean hydrogen by electrolysis of a biomass compound. The electrocatalytic activity was determined by cyclic voltammetry and the rate of hydrogen evolution was measured for each catalyst at different current densities. The cell voltages UEtOH were recorded as a function of time for each current density. At 100 mA cm-2, i.e. 0.5 A with the 5 cm2 surface area PEMEC used, the cell voltage did not exceed 0.9 V for an evolution rate of about 220 cm3 of hydrogen per hour and the electrical energy consumed was less than 2.3 kWh (Nm3)-1, i.e. less than one half of the energy needed for water electrolysis (4.7 kWh (Nm3)-1 at UH2O = 2 V). This result is valid for the decomposition of any organic compound, particularly those originated from biomass resource, provided that their electro-oxidation rate is sufficient (>100 mA cm-2) at a relatively low cell voltage (Ucell < 1 V) which necessitates the development of efficient electrocatalysts for the electrochemical decomposition of this compound.

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.

Hydrodynamic electronic fluid instability in GaAs MESFETs at terahertz frequencies

NASA Astrophysics Data System (ADS)

Li, Kang; Hao, Yue; Jin, Xiaoqi; Lu, Wu

2018-01-01

III-V compound semiconductor field effect transistors (FETs) are potential candidates as solid state THz emitters and detectors due to plasma wave instability in these devices. Using a 2D hydrodynamic model, here we present the numerical studies of electron fluid instability in a FET structure. The model is implemented in a GaAs MESFET structure with a gate length of 0.2 µm as a testbed by taking into account the non-equilibrium transport and multi-valley non-parabolicity energy bands. The results show that the electronic density instability in the channel can produce stable periodic oscillations at THz frequencies. Along with stable oscillations, negative differential resistance in output characteristics is observed. The THz emission energy density increases monotonically with the drain bias. The emission frequency of electron density oscillations can be tuned by both gate and drain biases. The results suggest that III-V FETs can be a kind of versatile THz devices with good tunability on both radiative power and emission frequency.

Method of filtering a target compound from a first solvent that is above its critical density

DOEpatents

Phelps, Max R [Richland, WA; Yonker, Clement R [Kennewick, WA; Fulton, John L [Richland, WA; Bowman, Lawrence E [Richland, WA

2001-07-24

The present invention is a method of separating a first compound having a macromolecular structure from a mixture. The first solvent is a fluid that is a gas at standard temperature and pressure and is at a density greater than a critical density of the fluid. A macromolecular structure containing a first compound is dissolved therein as a mixture. The mixture is contacted onto a selective barrier and the first solvent passed through the selective barrier thereby retaining the first compound, followed by recovering the first compound. By using a fluid that is a gas at standard temperature and pressure at a density greater than its critical density, separation without depressurization is fast and efficient.

Tuning of electronic band gaps and optoelectronic properties of binary strontium chalcogenides by means of doping of magnesium atom(s)- a first principles based theoretical initiative with mBJ, B3LYP and WC-GGA functionals

NASA Astrophysics Data System (ADS)

Debnath, Bimal; Sarkar, Utpal; Debbarma, Manish; Bhattacharjee, Rahul; Chattopadhyaya, Surya

2018-02-01

First principle based theoretical initiative is taken to tune the optoelectronic properties of binary strontium chalcogenide semiconductors by doping magnesium atom(s) into their rock-salt unit cells at specific concentrations x = 0.0, 0.25, 0.50, 0.75 and 1.0 and such tuning is established by studying structural, electronic and optical properties of designed binary compounds and ternary alloys employing WC-GGA, B3LYP and mBJ exchange-correlation functionals. Band structure of each compound is constructed and respective band gaps under all the potential schemes are measured. The band gap bowing and its microscopic origin are calculated using quadratic fit and Zunger's approach, respectively. The atomic and orbital origins of electronic states in the band structure of any compound are explored from its density of states. The nature of chemical bonds between the constituent atoms in each compound is explored from the valence electron density contour plots. Optical properties of any specimen are explored from the computed spectra of its dielectric function, refractive index, extinction coefficient, normal incidence reflectivity, optical conductivity optical absorption and energy loss function. Several calculated results are compared with available experimental and earlier theoretical data.

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

Dufresne, Eric M.; Dunford, Robert W.; Kanter, Elliot P.

The performance of a cooled Be compound refractive lens (CRL) has been tested at the Advanced Photon Source (APS) to enable vertical focusing of the pink beam and permit the X-ray beam to spatially overlap with an 80 µm-high low-density plasma that simulates astrophysical environments. Focusing the fundamental harmonics of an insertion device white beam increases the APS power density; here, a power density as high as 500 W mm –2 was calculated. A CRL is chromatic so it does not efficiently focus X-rays whose energies are above the fundamental. Only the fundamental of the undulator focuses at the experiment.more » A two-chopper system reduces the power density on the imaging system and lens by four orders of magnitude, enabling imaging of the focal plane without any X-ray filter. As a result, a method to measure such high power density as well as the performance of the lens in focusing the pink beam is reported.« less

A method to estimate statistical errors of properties derived from charge-density modelling

PubMed Central

Lecomte, Claude

2018-01-01

Estimating uncertainties of property values derived from a charge-density model is not straightforward. A methodology, based on calculation of sample standard deviations (SSD) of properties using randomly deviating charge-density models, is proposed with the MoPro software. The parameter shifts applied in the deviating models are generated in order to respect the variance–covariance matrix issued from the least-squares refinement. This ‘SSD methodology’ procedure can be applied to estimate uncertainties of any property related to a charge-density model obtained by least-squares fitting. This includes topological properties such as critical point coordinates, electron density, Laplacian and ellipticity at critical points and charges integrated over atomic basins. Errors on electrostatic potentials and interaction energies are also available now through this procedure. The method is exemplified with the charge density of compound (E)-5-phenylpent-1-enylboronic acid, refined at 0.45 Å resolution. The procedure is implemented in the freely available MoPro program dedicated to charge-density refinement and modelling. PMID:29724964

Application of Molecular Dynamics Simulations in Molecular Property Prediction I: Density and Heat of Vaporization

PubMed Central

Wang, Junmei; Tingjun, Hou

2011-01-01

Molecular mechanical force field (FF) methods are useful in studying condensed phase properties. They are complementary to experiment and can often go beyond experiment in atomic details. Even a FF is specific for studying structures, dynamics and functions of biomolecules, it is still important for the FF to accurately reproduce the experimental liquid properties of small molecules that represent the chemical moieties of biomolecules. Otherwise, the force field may not describe the structures and energies of macromolecules in aqueous solutions properly. In this work, we have carried out a systematic study to evaluate the General AMBER Force Field (GAFF) in studying densities and heats of vaporization for a large set of organic molecules that covers the most common chemical functional groups. The latest techniques, such as the particle mesh Ewald (PME) for calculating electrostatic energies, and Langevin dynamics for scaling temperatures, have been applied in the molecular dynamics (MD) simulations. For density, the average percent error (APE) of 71 organic compounds is 4.43% when compared to the experimental values. More encouragingly, the APE drops to 3.43% after the exclusion of two outliers and four other compounds for which the experimental densities have been measured with pressures higher than 1.0 atm. For heat of vaporization, several protocols have been investigated and the best one, P4/ntt0, achieves an average unsigned error (AUE) and a root-mean-square error (RMSE) of 0.93 and 1.20 kcal/mol, respectively. How to reduce the prediction errors through proper van der Waals (vdW) parameterization has been discussed. An encouraging finding in vdW parameterization is that both densities and heats of vaporization approach their “ideal” values in a synchronous fashion when vdW parameters are tuned. The following hydration free energy calculation using thermodynamic integration further justifies the vdW refinement. We conclude that simple vdW parameterization can significantly reduce the prediction errors. We believe that GAFF can greatly improve its performance in predicting liquid properties of organic molecules after a systematic vdW parameterization, which will be reported in a separate paper. PMID:21857814

Silicon clathrates for lithium ion batteries: A perspective

NASA Astrophysics Data System (ADS)

Warrier, Pramod; Koh, Carolyn A.

2016-12-01

Development of novel energy storage techniques is essential for the development of sustainable energy resources. Li-ion batteries have the highest rated energy density among rechargeable batteries and have attracted a lot of attention for energy storage in the last 15-20 years. However, significant advancements are required in anode materials before Li-ion batteries become viable for a wide variety of applications, including in renewable energy storage, grid storage, and electric vehicles. While graphite is the current standard anode material in commercial Li-ion batteries, it is Si that exhibits the highest specific energy density among all materials considered for this purpose. Si, however, suffers from significant volume expansion/contraction and the formation of a thick solid-electrolyte interface layer. To resolve these issues, Si clathrates are being considered for anode materials. Clathrates are inclusion compounds and contain cages in which Li could be captured. While Si clathrates offer promising advantages due to their caged structure which enables negligible volume change upon Li insertion, there remains scientific challenges and knowledge gaps to be overcome before these materials can be utilized for Li-ion battery applications, i.e., understanding lithiation/de-lithiation mechanisms, optimizing guest concentrations, as well as safe and economic synthesis routes.

Theoretical, spectroscopic and antioxidant activity studies on (E)-2-[(2-fluorophenylimino)methyl]-4-hydroxyphenol and (E)-2-[(3-fluorophenylimino)methyl]-4-hydroxyphenol compounds

NASA Astrophysics Data System (ADS)

Alaşalvar, Can; Güder, Aytaç; Gökçe, Halil; Albayrak Kaştaş, Çiğdem; Çatak Çelik, Raziye

2017-04-01

We studied synthesis and characterization of the title compounds by using X-ray crystallographic technique, FT-IR spectroscopy, UV-Vis spectroscopy and Density functional method. Optimized geometry, vibrational frequencies and UV-Vis parameters of the title compounds in the ground state have been calculated by using B3LYP with the 6-311G+ (d,p) basis set. HOMO - LUMO energy gap, Non-linear optical properties are performed at B3LYP/6-311G+(d,p) level. For determination of antioxidant properties of the title compounds (CMPD1 and CMPD2) have been investigated by using different methods, i.e. ferric reducing antioxidant power (FRAP), hydrogen peroxide scavenging (HPSA), free radical scavenging (FRSA) and ferrous ion chelating activities (FICA). In comparison with standard antioxidants (BHA, BHT, and α-tocopherol), CPMD1 and CMPD2 have influential FRAP, HPSA, FRSA and FICA.

Radical scavenging behavior of eriodictyol and fustin flavonoid compounds - A DFT study

NASA Astrophysics Data System (ADS)

Sadasivam, K.; Praveena, R.; Anbakzhakan, K.

2018-05-01

The density functional theory (DFT) protocol together with B3LYP/6-311G(d,p) level of theory has been utilized to explore and compare the structural features and molecular characteristics of two naturally occurring flavonoid compounds eriodictyol and fustin. The -OH bond dissociation energy (BDE) for all the radical species have been computed and interpreted in accordance with the radical scavenging activity. The ionization potential (IP) value of fustin flavonoid compound was found to be within the range of synthetic food additives. The polar nature and their capacity to polarise other atoms are established through the dipole moment analysis. Additionally, various parameters that are relevant to chemical potential such as electron affinity, hardness, softness, electro negativity and electrophilic index were calculated and analysed in the light of quercetin flavonoid compound in view of their antioxidant activity. The antioxidant capability of fustin is found to be superior to eriodictyol flavonoid.

Theoretical simulations of the structural stabilities, elastic, thermodynamic and electronic properties of Pt3Sc and Pt3Y compounds

NASA Astrophysics Data System (ADS)

Boulechfar, R.; Khenioui, Y.; Drablia, S.; Meradji, H.; Abu-Jafar, M.; Omran, S. Bin; Khenata, R.; Ghemid, S.

2018-05-01

Ab-initio calculations based on density functional theory have been performed to study the structural, electronic, thermodynamic and mechanical properties of intermetallic compounds Pt3Sc and Pt3Y using the full-potential linearized augmented plane wave(FP-LAPW) method. The total energy calculations performed for L12, D022 and D024 structures confirm the experimental phase stability. Using the generalized gradient approximation (GGA), the values of enthalpies formation are -1.23 eV/atom and -1.18 eV/atom for Pt3Sc and Pt3Y, respectively. The densities of states (DOS) spectra show the existence of a pseudo-gap at the Fermi level for both compounds which indicate the strong spd hybridization and directing covalent bonding. Furthermore, the density of states at the Fermi level N(EF), the electronic specific heat coefficient (γele) and the number of bonding electrons per atom are predicted in addition to the elastic constants (C11, C12 and C44). The shear modulus (GH), Young's modulus (E), Poisson's ratio (ν), anisotropy factor (A), ratio of B/GH and Cauchy pressure (C12-C44) are also estimated. These parameters show that the Pt3Sc and Pt3Y are ductile compounds. The thermodynamic properties were calculated using the quasi-harmonic Debye model to account for their lattice vibrations. In addition, the influence of the temperature and pressure was analyzed on the heat capacities (Cp and Cv), thermal expansion coefficient (α), Debye temperature (θD) and Grüneisen parameter (γ).

Skyrme forces and decay of the Rf266*104 nucleus synthesized via different incoming channels

NASA Astrophysics Data System (ADS)

Niyti, Deep, Aman; Kharab, Rajesh; Chopra, Sahila; Gupta, Raj K.

2017-03-01

The excitation functions for the production of 262Rf, 261Rf, and 260Rf isotopes via 4 n -, 5 n -, and 6 n -decay channels from the *266Rf compound nucleus are studied within the dynamical cluster-decay model (DCM), including deformations β2 i and so-called hot-optimum orientations θi which support symmetric fission, in agreement with experiments. The data are available for 18O+248Cm and 22Ne+244Pu reactions, respectively, at the energy ranges of Elab=88.2 to 101.3 and 109.0 to 124.8 MeV. For the nuclear interaction potentials, we use the Skyrme energy density functional (SEDF) based on semiclassical extended Thomas Fermi (ETF) approach, which means an extension of the earlier study of excitation functions of *266Rf formed in 18O+248Cm reaction, based on the DCM using the pocket formula for nuclear proximity potential, showing interaction dependence. The Skyrme forces used here are the old SIII and SIV and new GSkI and KDE0(v1) given for both normal and isospin-rich nuclei, with densities added in frozen density approximation. Interestingly, the DCM gives an excellent fit to the measured data on fusion evaporation residue (ER) for both the incoming channels (18O+248Cm and 22Ne+244Pu ) at the energy range Elab=88.2 to 124.8 MeV, independent of the entrance channel and Skyrme force used. The possible fusion-fission (ff) and quasifission (qf) mass regions of fragments on DCM are also predicted. The DCM with Skyrme forces is further used to look for all the possible target-projectile (t-p) combinations forming the cold compound nucleus (CN) *266Rf at the CN excitation energy of Elab for hot compact configurations. The fusion evaporation residue cross sections, for the proposed new reactions in synthesizing the CN *266Rf, are also estimated for the future experiments, and role of mass asymmetry of nuclei is indicated.

FP-LAPW investigation of Al3(Sc1‑xTix) alloys properties in L12 and D022 structures

NASA Astrophysics Data System (ADS)

Khenioui, Youcef; Boulechfar, Rahima; Maazi, Noureddine; Ghemid, Sebti

2018-06-01

The ab-initio calculations based on the density functional theory (DFT) have been performed to study the structural, mechanical, electronic, thermal and thermodynamic properties of Al3Sc and Al3Ti binary compounds and their ternary mixture Al3(Sc1‑xTix) in L12 and D022 structures. The total energy calculations show that the L12 structure is the more stable one. The Al3Sc0.25Ti0.75 undergoes a martensitic transformation and the formation enthalpies and the lattice parameters decrease with increasing concentration x. The elastic constants are determined and the results show that all compounds are mechanically stable and the cubic cells are more easily deformed by shearing than by unidirectional compression. The elastic modulus indicates that the addition of Ti atoms to Al3Sc improves its ductility. The densities of states (DOSs) calculations show the strong spd hybridization which leads to the formation of a pseudo-gap near the Fermi level in ternary alloys. The densities of states at the Fermi level N(EF) confirm the phase stability. The quasi-harmonic Debye model is used to predict the thermal properties such as heat capacity, Debye temperature, Grüneisen parameter and thermal expansion coefficient of the considered alloys. The determination of Gibbs free mixing energy at different concentrations has been used to calculate the T-x diagram.

The Chemistry of MoS2 and Related Compounds and Their Applications in Electrocatalysis and Photoelectrochemistry

NASA Astrophysics Data System (ADS)

Ding, Qi

The increasing energy demand in our society has stimulated intensive research in the development of sustainable and renewable energy sources to lessen our strong dependence on fossil fuels. Hydrogen is a clean, storable, and high-energy density energy carrier, and is a promising sustainable solution to achieve an environmentally friendly fuel economy. Electrochemical and solar-driven photoelectrochemical water splitting is regarded as one of the most promising approaches to utilize renewable energy to product hydrogen fuel, yet Pt remains the best electrocatalyst for hydrogen evolution reaction (HER), the high cost of which ultimately limit the scalability of such technologies. Layered transition metal dichalcogenides (TMDCs) is a family of compounds that has attracted widespread attention due to their broad range of applications in electronics, optoelectronics, sensing, energy storage, and catalysis. My research has primarily focused on understanding the chemistry of MoS2 and related compounds, and developing rational approaches to enable these materials for efficient electrocatalytic and photoelectrochemical (PEC) hydrogen evolution. We demonstrated highly efficient and robust photocathodes based on heterostructures of chemically exfoliated metallic 1T-MoS2 and planar p-type Si for PEC-HER. Photocurrents up to 17.6 mA/cm2 at 0 V vs reversible hydrogen electrode (RHE) were achieved under simulated 1 sun irradiation, and excellent stability was demonstrated over long-term operation. Building upon the 1T-MoS2 groundwork, amorphous ternary compounds MoQxCly (Q = S, Se) were then developed as excellent catalysts for HER. The preparation of MoQxCly requires much lower temperature and easier fabrication, yet the PEC performance of MoSxCly-based photocathode is even better than 1T-MoS2-based photocathode. Moreover, when MoSxCly is incorporated with n+pp+ Si micropyramids (MPs), we demonstrate the highest current density ever reported for Si-based photocathodes. Furthermore, to fully harness the potentials of MoS2 and utilize it for a broader range of applications, we demonstrate covalent functionalization on the basal plane of 2H-MoS2 via thiol conjugation, despite the general belief that the basal plane is too inert for functionalization. We correlate the degree of functionalization to the amount of sulfur vacancies on MoS2 basal plane, and successfully demonstrated the preparation of MoS2-PbSe quantum dot heterostructures using a bi-functional dithiol linker molecule.

Lignin-derived oak phenolics: a theoretical examination of additional potential health benefits of red wine.

PubMed

Setzer, William N

2011-08-01

Lignin-derived phenolic compounds can be extracted from oak barrels during the aging of red wine, and it is hypothesized that these compounds may contribute to the health benefits of red wine by their antioxidant, radical-scavenging, or chemopreventive activities. Density functional calculations (B3LYP/6-311++G) support the radical-scavenging abilities of the oak phenolics. Sinapaldehyde, syringaldehyde, syringol, and syringylacetone all have bond dissociation energies that are lower than resveratrol and comparable to the flavonoid catechin. Molecular docking studies of the oak phenolics with known resveratrol protein targets also show that these compounds dock favorably to the protein targets. Thus, lignin-derived oak phenolics, although found in small concentrations, may contribute to the beneficial antioxidant, chemopreventive, and cardioprotective effects of red wine.

On the Preferred Active Sites of Promoted MoS 2 for Hydrodesulfurization with Minimal Organonitrogen Inhibition

DOE PAGES

Rangarajan, Srinivas; Mavrikakis, Manos

2016-12-14

Hydrodesulfurization is a process to produce ultralow-sulfur diesel fuel. Although promoted molybdenum sulfide (MoS 2) catalysts have been used industrially for several decades, the active site requirements for selective hydrodesulfurization of organosulfur compounds with minimal inhibition by organonitrogen constituents of a real gasoil feed has not been resolved. By using molecular binding energy descriptors derived from plane wave density functional theory calculations for comparative adsorption of organosulfur and organonitrogen compounds, we analyzed more than 20 potential sites on unpromoted and Ni- and Co-promoted MoS 2. We also found that hydrogen sulfide and ammonia are simple descriptors of adsorption of stericallymore » unhindered organosulfur and organonitrogen compounds such as dibenzothiophene and acridine, respectively. Further, organonitrogen compounds in gasoil bind more strongly than organosulfur compounds on all sites except on sites with exposed metal atoms on the corner and sulfur edges of promoted MoS 2. Consequently, these sites are proposed as required for maximum-hydrodesulfurization minimum-inhibition catalysis.« less

Hydrogen storage in lithium hydride: A theoretical approach

NASA Astrophysics Data System (ADS)

Banger, Suman; Nayak, Vikas; Verma, U. P.

2018-04-01

First principles calculations have been carried out to analyze structural stability of lithium hydride (LiH) in NaCl phase using the full potential linearized augmented plane wave (FP-LAPW) method within the framework of density functional theory (DFT). Calculations have been extended to physiosorbed H-atom compounds LiH·H2, LiH·3H2 and LiH·4H2. The obtained results are discussed in the paper. The results for LiH are in excellent agreement with earlier reported data. The obtained direct energy band gap of LiH is 3.0 eV which is in excellent agreement with earlier reported theoretical band gap. The electronic band structure plots of the hydrogen adsorbed compounds show metallic behavior. The elastic constants, anisotropy factor, shear modulus, Young's modulus, Poisson's ratio and cohesive energies of all the compounds are calculated. Calculation of the optical spectra such as the real and imaginary parts of dielectric function, optical reflectivity, absorption coefficient, optical conductivity, refractive index, extinction coefficient and electron energy loss are performed for the energy range 0-15 eV. The obtained results for LiH·H2, LiH·3H2 and LiH·4H2, are reported for the first time. This study has been made in search of materials for hydrogen storage. It is concluded that LiH is a promising material for hydrogen storage.

Ab initio and kinetic Monte Carlo study of lithium diffusion in LiSi, Li12Si7, Li13Si5 and Li15Si4

NASA Astrophysics Data System (ADS)

Moon, Janghyuk; Lee, Byeongchan; Cho, Maenghyo; Cho, Kyeongjae

2016-10-01

The kinetics of lithium atoms in various Li-Si binary compounds are investigated using density functional theory calculations and kinetic Monte Carlo calculations. The values of the Li migration energy barriers are identified by NEB calculations with vacancy-mediated, interstitial and exchange migration mechanisms in crystalline LiSi, Li12Si7, Li13Si4, and Li15Si4. A comparison of these NEB results shows that the vacancy-mediated Li migration is identified as the dominant diffusion mechanisms in Li-Si compounds. The diffusion coefficients of Li in Li-Si compounds at room temperature are determined by KMC simulation. From the KMC results, the recalculated migration energy barriers in LiSi, Li12Si7, Li13Si4, and Li15Si4 correspond to 0.306, 0.301, 0.367 and 0.320 eV, respectively. Compared to the Li migration energy barrier of 0.6 eV in crystalline Si, the drastic reduction in the Li migration energy barriers in the lithiated silicon indicates that the initial lithiation of the Si anode is the rate-limiting step. Furthermore, it is also found that Si migration is possible in Li-rich configurations. On the basis of these findings, the underlying mechanisms of kinetics on the atomic scale details are elucidated.

Graphite fiber intercalation: Basic properties of copper chloride intercalated fibers

NASA Technical Reports Server (NTRS)

Jaworske, D. A.; Miller, J. D.

1986-01-01

In situ resistance measurements were used to follow the intercalation of copper chloride in pitch-based fibers. Subsequent single fiber resistivity measurements reveal a large range of resistivities, from 13 to 160 micro-ohms cm. Additional density measurements reveal a bimodal distribution of mass densities. The dense fibers have lower resistivities and correspond to the stage III compound identified by X-ray diffraction. Neither resistivity nor density correlate with diameter. Both energy dispersive spectroscopy and mass density data suggest that excess chlorine resides in the intercalated fiber, resulting in a stoichiometry of C4.9n CuCl2.5 (where n is the stage number) for the denser fibers. Finally, thermogravimetric analysis shows a 33 percent loss in mass upon heating to 700C. This loss in mass is attributed to loss of both chlorine and carbon.

Thermodynamic assessment of the U–Y–O system

DOE PAGES

Brese, R. G.; McMurray, J. W.; Shin, D.; ...

2015-02-03

We developed a CALPHAD assessment of the U-Y-O system. To represent the YO2 compound in the compound energy formalism (CEF) for U 1-yY yO 2± x, the lattice stability was calculated using density functional theory (DFT) while a partially ionic liquid sub-lattice model is used to describe the liquid phase. Moreover, a Gibbs function for the stoichiometric rhombohedral UY 6O 12 phase is proposed. Models representing the phases in the U-O and Y-O systems taken from the literature along with the phases that appear in the U-Y-O ternary are combined to form a unified assessment.

Stability and spatial arrangement of the 2,4-dichlorophenoxyacetic acid and β-cyclodextrin inclusion compound: A theoretical study

NASA Astrophysics Data System (ADS)

Pereira, Robson A.; Anconi, Cleber P. A.; Nascimento, Clebio S.; De Almeida, Wagner B.; Dos Santos, Hélio F.

2015-07-01

The present letter reports results from a comprehensive theoretical analysis of the inclusion process involving 2,4-dichlorophenoxyacetic acid (2,4-D) and β-cyclodextrin (β-CD) for which the experimental data of formation is available. Spatial arrangement and stabilization energies were evaluated in gas phase and aqueous solution through density functional theory (DFT) and through the use of SMD implicit solvation approach. The discussed methodology was applied to predict the stability and identify the most favorable form (deprotonated or neutral) as well as the most probable spatial arrangement of the studied inclusion compound.

Quantitative analysis of intermolecular interactions in orthorhombic rubrene

DOE PAGES

Hathwar, Venkatesha R.; Sist, Mattia; Jørgensen, Mads R. V.; ...

2015-08-14

Rubrene is one of the most studied organic semiconductors to date due to its high charge carrier mobility which makes it a potentially applicable compound in modern electronic devices. Previous electronic device characterizations and first principles theoretical calculations assigned the semiconducting properties of rubrene to the presence of a large overlap of the extended π-conjugated core between molecules. We present here the electron density distribution in rubrene at 20 K and at 100 K obtained using a combination of high-resolution X-ray and neutron diffraction data. The topology of the electron density and energies of intermolecular interactions are studied quantitatively. Specifically,more » the presence of C π...C πinteractions between neighbouring tetracene backbones of the rubrene molecules is experimentally confirmed from a topological analysis of the electron density, Non-Covalent Interaction (NCI) analysis and the calculated interaction energy of molecular dimers. A significant contribution to the lattice energy of the crystal is provided by H—H interactions. The electron density features of H—H bonding, and the interaction energy of molecular dimers connected by H—H interaction clearly demonstrate an importance of these weak interactions in the stabilization of the crystal structure. Finally, the quantitative nature of the intermolecular interactions is virtually unchanged between 20 K and 100 K suggesting that any changes in carrier transport at these low temperatures would have a different origin. The obtained experimental results are further supported by theoretical calculations.« less

Investigations of mechanical, electronic, and magnetic properties of non-magnetic MgTe and ferro-magnetic Mg0.75 TM 0.25Te (TM = Fe, Co, Ni): An ab-initio calculation

NASA Astrophysics Data System (ADS)

Q, Mahmood; S, M. Alay-e.-Abbas; I, Mahmood; Mahmood, Asif; N, A. Noor

2016-04-01

The mechanical, electronic and magnetic properties of non-magnetic MgTe and ferro-magnetic (FM) Mg0.75 TM 0.25Te (TM = Fe, Co, Ni) in the zinc-blende phase are studied by ab-initio calculations for the first time. We use the generalized gradient approximation functional for computing the structural stability, and mechanical properties, while the modified Becke and Johnson local (spin) density approximation (mBJLDA) is utilized for determining the electronic and magnetic properties. By comparing the energies of non-magnetic and FM calculations, we find that the compounds are stable in the FM phase, which is confirmed by their structural stabilities in terms of enthalpy of formation. Detailed descriptions of elastic properties of Mg0.75 TM 0.25Te alloys in the FM phase are also presented. For electronic properties, the spin-polarized electronic band structures and density of states are computed, showing that these compounds are direct bandgap materials with strong hybridizations of TM 3d states and Te p states. Further, the ferromagnetism is discussed in terms of the Zener free electron model, RKKY model and double exchange model. The charge density contours in the (110) plane are calculated to study bonding properties. The spin exchange splitting and crystal field splitting energies are also calculated. The distribution of electron spin density is employed in computing the magnetic moments appearing at the magnetic sites (Fe, Co, Ni), as well as at the non-magnetic sites (Mg, Te). It is found that the p-d hybridization causes not only magnetic moments on the magnetic sites but also induces negligibly small magnetic moments at the non-magnetic sites.

Molecular design of new nitramine explosives: 1,3,5,7-tetranitro-8-(nitromethyl)-4-imidazolino[4,5-b]4-imidazolino-[4,5-e] pyridine and its N-oxide.

PubMed

Liu, Hui; Du, Hongchen; Wang, Guixiang; Liu, Yan; Gong, Xuedong

2012-04-01

Two new nitramine compounds containing pyridine, 1,3,5,7-tetranitro-8-(nitromethyl) -4-imidazolino[4,5-b]4-imidazolino-[4,5-e]pyridine and its N-oxide 1,3,5,7-tetranitro-8- (nitromethyl)-4-imidazolino[4,5-b]4-imidazolino-[4,5-e]pyridine-4-ol were proposed. Density functional theory (DFT) has been employed to study the molecular geometries, electronic structures, infrared spectra, and thermodynamic properties at the B3LYP/6-31G* level. Their detonation performances evaluated using the Kamlet-Jacobs equations with the calculated densities and heats of formation are superior to those of HMX. The predicted densities of them were ca. 2 g cm(-3), detonation velocities were over 9 km s(-1), and detonation pressures were about 40 GPa, showing that they may be potential candidates of high energy density materials (HEDMs). The natural bond orbital analysis indicated that N-NO(2) bond is the trigger bond during thermolysis process. The stability of the title compounds is slightly lower than that of 2,4,6,8,10,12-hexanitro-2,4,6,8,10,12- hexaazaisowurtzitane (CL-20). The results of this study may provide basic information for the molecular design of new HEDMs.

Effects of an electric field on interaction of aromatic systems.

PubMed

Youn, Il Seung; Cho, Woo Jong; Kim, Kwang S

2016-04-30

The effect of uniform external electric field on the interactions between small aromatic compounds and an argon atom is investigated using post-HF (MP2, SCS-MP2, and CCSD(T)) and density functional (PBE0-D3, PBE0-TS, and vdW-DF2) methods. The electric field effect is quantified by the difference of interaction energy calculated in the presence and absence of the electric field. All the post-HF methods describe electric field effects accurately although the interaction energy itself is overestimated by MP2. The electric field effect is explained by classical electrostatic models, where the permanent dipole moment from mutual polarization mainly determines its sign. The size of π-conjugated system does not have significant effect on the electric field dependence. We found out that PBE0-based methods give reasonable interaction energies and electric field response in every case, while vdW-DF2 sometimes shows spurious artifact owing to its sensitivity toward the real space electron density. © 2015 Wiley Periodicals, Inc.

Density functional perturbational orbital theory of spin polarization in electronic systems. II. Transition metal dimer complexes.

PubMed

Seo, Dong-Kyun

2007-11-14

We present a theoretical scheme for a semiquantitative analysis of electronic structures of magnetic transition metal dimer complexes within spin density functional theory (DFT). Based on the spin polarization perturbational orbital theory [D.-K. Seo, J. Chem. Phys. 125, 154105 (2006)], explicit spin-dependent expressions of the spin orbital energies and coefficients are derived, which allows to understand how spin orbitals form and change their energies and shapes when two magnetic sites are coupled either ferromagnetically or antiferromagnetically. Upon employment of the concept of magnetic orbitals in the active-electron approximation, a general mathematical formula is obtained for the magnetic coupling constant J from the analytical expression for the electronic energy difference between low-spin broken-symmetry and high-spin states. The origin of the potential exchange and kinetic exchange terms based on the one-electron picture is also elucidated. In addition, we provide a general account of the DFT analysis of the magnetic exchange interactions in compounds for which the active-electron approximation is not appropriate.

New 1,3,4-thiadiazole compounds including pyrazine moiety: Synthesis, structural properties and antimicrobial features

NASA Astrophysics Data System (ADS)

Gür, Mahmut; Şener, Nesrin; Muğlu, Halit; Çavuş, M. Serdar; Özkan, Osman Emre; Kandemirli, Fatma; Şener, İzzet

2017-07-01

In the study, some new 1,3,4-thiadiazole compounds were synthesized and we have reported identification of the structures by using UV-Vis, FT-IR, 1H NMR, 13C NMR and Mass spectroscopic methods. Antimicrobial activities of the compounds against three microorganisms, namely, Candida albicans ATCC 26555, Staphylococcus aureus ATCC 9144, and Escherichia coli ATCC 25922 were investigated by using disk diffusion method. These thiadiazoles exhibited an antimicrobial activity against Staphylococcus aureus and Candida albicans. The experimental data was supported by the quantum chemical calculations. Density functional theory (DFT) calculations were carried out to obtain the ground state optimized geometries of the molecules using the B3LYP, M06 and PBE1PBE methods with 3-21 g, 4-31 g, 6-311++g(2d,2p), cc-pvtz and cc-pvqz basis sets in the different combinations. Frontier molecular orbitals (FMOs) energies, band gap energies and some chemical reactivity parameters were calculated by using the aforementioned methods and basis sets, and the results were also compared with the experimental UV-Vis data.

Structures of cycloserine and 2-oxazolidinone probed by X-ray photoelectron spectroscopy: theory and experiment.

PubMed

Ahmed, Marawan; Wang, Feng; Acres, Robert G; Prince, Kevin C

2014-05-22

The electronic structures and properties of 2-oxazolidinone and the related compound cycloserine (CS) have been investigated using theoretical calculations and core and valence photoelectron spectroscopy. Isomerization of the central oxazolidine heterocycle and the addition of an amino group yield cycloserine. Theory correctly predicts the C, N, and O 1s core spectra, and additionally, we report theoretical natural bond orbital (NBO) charges. The valence ionization energies are also in agreement with theory and previous measurements. Although the lowest binding energy part of the spectra of the two compounds shows superficial similarities, further analysis of the charge densities of the frontier orbitals indicates substantial reorganization of the wave functions as a result of isomerization. The highest occupied molecular orbital (HOMO) of CS shows leading carbonyl π character with contributions from other heavy (non-H) atoms in the molecule, while the HOMO of 2-oxazolidinone (OX2) has leading nitrogen, carbon, and oxygen pπ characters. The present study further theoretically predicts bond resonance effects of the compounds, evidence for which is provided by our experimental measurements and published crystallographic data.

Sodium titanate nanotubes as negative electrode materials for sodium-ion capacitors.

PubMed

Yin, Jiao; Qi, Li; Wang, Hongyu

2012-05-01

The lithium-based energy storage technology is currently being considered for electric automotive industry and even electric grid storage. However, the hungry demand for vast energy sources in the modern society will conflict with the shortage of lithium resources on the earth. The first alternative choice may be sodium-related materials. Herein, we propose an electric energy storage system (sodium-ion capacitor) based on porous carbon and sodium titanate nanotubes (Na-TNT, Na(+)-insertion compounds) as positive and negative electrode materials, respectively, in conjunction with Na(+)-containing non-aqueous electrolytes. As a low-voltage (0.1-2 V) sodium insertion nanomaterial, Na-TNT was synthesized via a simple hydrothermal reaction. Compared with bulk sodium titanate, the predominance of Na-TNT is the excellent rate performance, which exactly caters to the need for electrochemical capacitors. The sodium-ion capacitors exhibited desirable energy density and power density (34 Wh kg(-1), 889 W kg(-1)). Furthermore, the sodium-ion capacitors had long cycling life (1000 cycles) and high coulombic efficiency (≈ 98 % after the second cycle). More importantly, the conception of sodium-ion capacitor has been put forward.

Constructing the electricity-carbohydrate-hydrogen cycle for a sustainability revolution.

PubMed

Zhang, Y-H Percival; Huang, Wei-Dong

2012-06-01

In this opinion, we suggest the electricity-carbohydrate-hydrogen (ECHo) cycle which bridges primary energies and secondary energies. Carbohydrates are sources of food, feed, liquid biofuels, and renewable materials and are a high-density hydrogen carrier and electricity storage compounds (e.g. >3000 Wh/kg). One element of this ECHo cycle can be converted to another reversibly and efficiently depending on resource availability, needs and costs. This cycle not only supplements current and future primary energy utilization systems for facilitating electricity and hydrogen storage and enhancing secondary energy conversion efficiencies, but also addresses such sustainability challenges as transportation fuel production, CO(2) utilization, fresh water conservation, and maintenance of a small closed ecosystem in emergency situations. Copyright © 2012 Elsevier Ltd. All rights reserved.

Predicting hydration free energies of amphetamine-type stimulants with a customized molecular model

NASA Astrophysics Data System (ADS)

Li, Jipeng; Fu, Jia; Huang, Xing; Lu, Diannan; Wu, Jianzhong

2016-09-01

Amphetamine-type stimulants (ATS) are a group of incitation and psychedelic drugs affecting the central nervous system. Physicochemical data for these compounds are essential for understanding the stimulating mechanism, for assessing their environmental impacts, and for developing new drug detection methods. However, experimental data are scarce due to tight regulation of such illicit drugs, yet conventional methods to estimate their properties are often unreliable. Here we introduce a tailor-made multiscale procedure for predicting the hydration free energies and the solvation structures of ATS molecules by a combination of first principles calculations and the classical density functional theory. We demonstrate that the multiscale procedure performs well for a training set with similar molecular characteristics and yields good agreement with a testing set not used in the training. The theoretical predictions serve as a benchmark for the missing experimental data and, importantly, provide microscopic insights into manipulating the hydrophobicity of ATS compounds by chemical modifications.

Thermodynamic assessment of the U–La–O system

DOE PAGES

McMurray, J. W.; Shin, D.; Besmann, T. M.

2014-10-03

The CALPHAD methodology was used to develop a thermodynamic assessment of the U-La-O system. The solid solution and liquid phases are described with the compound energy formalism and the partially ionic two-sublattice liquid model respectively. A density functional theory (DFT) calculation for the lattice stability of the fictive lanthanum oxide fluorite structure compound is used to determine the Gibbs energies for the La containing end-members in the CEF model for U 1-yLa yO 2+x. Experimental thermodynamic and phase equilibria data were then used in optimizations to develop representations of the phases in the system that can be extended to includemore » other actinide and fission products to develop multi-component models. The models that comprise this assessment very well reproduce experimentally determined oxygen potentials and the observed phase relations for the U-La-O system.« less

Identification and in silico prediction of metabolites of the model compound, tebufenozide by human CYP3A4 and CYP2C19.

PubMed

Shirotani, Naoki; Togawa, Moe; Ikushiro, Shinichi; Sakaki, Toshiyuki; Harada, Toshiyuki; Miyagawa, Hisashi; Matsui, Masayoshi; Nagahori, Hirohisa; Mikata, Kazuki; Nishioka, Kazuhiko; Hirai, Nobuhiro; Akamatsu, Miki

2015-10-15

The metabolites of tebufenozide, a model compound, formed by the yeast-expressed human CYP3A4 and CYP2C19 were identified to clarify the substrate recognition mechanism of the human cytochrome P450 (CYP) isozymes. We then determined whether tebufenozide metabolites may be predicted in silico. Hydrogen abstraction energies were calculated with the density functional theory method B3LYP/6-31G(∗). A docking simulation was performed using FRED software. Several alkyl sites of tebufenozide were hydroxylated by CYP3A4 whereas only one site was modified by CYP2C19. The accessibility of each site of tebufenozide to the reaction center of CYP enzymes and the susceptibility of each hydrogen atom for metabolism by CYP enzymes were evaluated by a docking simulation and hydrogen abstraction energy estimation, respectively. Copyright © 2015 Elsevier Ltd. All rights reserved.

Densities, Viscosities and Derived Thermophysical Properties of Water-Saturated Imidazolium-Based Ionic Liquids.

PubMed

Martins, Mónia A R; Neves, Catarina M S S; Kurnia, Kiki A; Carvalho, Pedro J; Rocha, Marisa A A; Santos, Luís M N B F; Pinho, Simão P; Freire, Mara G

2016-01-15

In order to evaluate the impact of the alkyl side chain length and symmetry of the cation on the thermophysical properties of water-saturated ionic liquids (ILs), densities and viscosities as a function of temperature were measured at atmospheric pressure and in the (298.15 to 363.15) K temperature range, for systems containing two series of bis(trifluoromethylsulfonyl)imide-based compounds: the symmetric [C n C n im][NTf 2 ] (with n = 1-8 and 10) and asymmetric [C n C 1 im][NTf 2 ] (with n = 2-5, 7, 9 and 11) ILs. For water-saturated ILs, the density decreases with the increase of the alkyl side chain length while the viscosity increases with the size of the aliphatic tails. The saturation water solubility in each IL was further estimated with a reasonable agreement based on the densities of water-saturated ILs, further confirming that for the ILs investigated the volumetric mixing properties of ILs and water follow a near ideal behaviour. The water-saturated symmetric ILs generally present lower densities and viscosities than their asymmetric counterparts. From the experimental data, the isobaric thermal expansion coefficient and energy barrier were also estimated. A close correlation between the difference in the energy barrier values between the water-saturated and pure ILs and the water content in each IL was found, supporting that the decrease in the viscosity of ILs in presence of water is directly related with the decrease of the energy barrier.

Synthesis of a new class of carbon-bonded anionic sigma complexes with 1,3-dimethyl-2,6-dioxo-5-(2,4,6-trinitrophenyl)-1,2,3,6-tetrahydropyrimidin-4-olate moiety as insensitive high energy density materials -- implications from impact sensitivity and thermal testings.

PubMed

Kulandaiya, Rajamani; Doraisamyraja, Kalaivani

2015-01-01

Poly nitro aromatic compounds are high energy density materials. Carbon-bonded anionic sigma complexes derived from them have remarkable thermal stability. At present there is a strong requirement for thermally stable insensitive high energy density materials (IHEDMs) in the energetic field which necessitates the present investigation. Three new carbon-bonded anionic sigma complexes were synthesized from 2-chloro-1,3,5-trinitrobenzene, 1,3-dimethylpyrimidine-2,4,6(1H,3H,5H)-trione (1,3-dimethylbarbituric acid) and bases such as triethanolamine, pyridine and N,N-diethylaniline, characterized by UV-VIS, IR, (1)H NMR, (13)C NMR and elemental analysis data. Their molecular structures were further ascertained through single crystal X-ray diffraction studies. TGA/DTA testings were undertaken at four different heating rates (5, 10, 20 and 40 K/min) and energy of activation was determined employing Ozawa and Kissinger plots. The reported carbon-bonded anionic sigma complexes were prepared through single pot synthesis in good yield with high purity. These complexes are molecular salts comprise of cation and anion moieties. Because of the salt-like nature, they are highly stable upto 300°C and decompose in two stages on further heating. They are stable towards impact of 2 kg mass hammer upto height limit (160 cm) of the instrument. The delocalization of the negative charge and various hydrogen bonds noticed in their crystals are the added factors of their thermal stability. The new insensitive high energy density materials of the present findings may receive attention in the field of energetics in future. Graphical AbstractA new class of carbon-bonded anionic sigma complexes as insensitive high energy density materials.

Alchemical and structural distribution based representation for universal quantum machine learning

NASA Astrophysics Data System (ADS)

Faber, Felix A.; Christensen, Anders S.; Huang, Bing; von Lilienfeld, O. Anatole

2018-06-01

We introduce a representation of any atom in any chemical environment for the automatized generation of universal kernel ridge regression-based quantum machine learning (QML) models of electronic properties, trained throughout chemical compound space. The representation is based on Gaussian distribution functions, scaled by power laws and explicitly accounting for structural as well as elemental degrees of freedom. The elemental components help us to lower the QML model's learning curve, and, through interpolation across the periodic table, even enable "alchemical extrapolation" to covalent bonding between elements not part of training. This point is demonstrated for the prediction of covalent binding in single, double, and triple bonds among main-group elements as well as for atomization energies in organic molecules. We present numerical evidence that resulting QML energy models, after training on a few thousand random training instances, reach chemical accuracy for out-of-sample compounds. Compound datasets studied include thousands of structurally and compositionally diverse organic molecules, non-covalently bonded protein side-chains, (H2O)40-clusters, and crystalline solids. Learning curves for QML models also indicate competitive predictive power for various other electronic ground state properties of organic molecules, calculated with hybrid density functional theory, including polarizability, heat-capacity, HOMO-LUMO eigenvalues and gap, zero point vibrational energy, dipole moment, and highest vibrational fundamental frequency.

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.

New Linear Partitioning Models Based on Experimental Water: Supercritical CO2 Partitioning Data of Selected Organic Compounds.

PubMed

Burant, Aniela; Thompson, Christopher; Lowry, Gregory V; Karamalidis, Athanasios K

2016-05-17

Partitioning coefficients of organic compounds between water and supercritical CO2 (sc-CO2) are necessary to assess the risk of migration of these chemicals from subsurface CO2 storage sites. Despite the large number of potential organic contaminants, the current data set of published water-sc-CO2 partitioning coefficients is very limited. Here, the partitioning coefficients of thiophene, pyrrole, and anisole were measured in situ over a range of temperatures and pressures using a novel pressurized batch-reactor system with dual spectroscopic detectors: a near-infrared spectrometer for measuring the organic analyte in the CO2 phase and a UV detector for quantifying the analyte in the aqueous phase. Our measured partitioning coefficients followed expected trends based on volatility and aqueous solubility. The partitioning coefficients and literature data were then used to update a published poly parameter linear free-energy relationship and to develop five new linear free-energy relationships for predicting water-sc-CO2 partitioning coefficients. A total of four of the models targeted a single class of organic compounds. Unlike models that utilize Abraham solvation parameters, the new relationships use vapor pressure and aqueous solubility of the organic compound at 25 °C and CO2 density to predict partitioning coefficients over a range of temperature and pressure conditions. The compound class models provide better estimates of partitioning behavior for compounds in that class than does the model built for the entire data set.

New Linear Partitioning Models Based on Experimental Water: Supercritical CO 2 Partitioning Data of Selected Organic Compounds

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

Burant, Aniela; Thompson, Christopher; Lowry, Gregory V.

2016-05-17

Partitioning coefficients of organic compounds between water and supercritical CO2 (sc-CO2) are necessary to assess the risk of migration of these chemicals from subsurface CO2 storage sites. Despite the large number of potential organic contaminants, the current data set of published water-sc-CO2 partitioning coefficients is very limited. Here, the partitioning coefficients of thiophene, pyrrole, and anisole were measured in situ over a range of temperatures and pressures using a novel pressurized batch reactor system with dual spectroscopic detectors: a near infrared spectrometer for measuring the organic analyte in the CO2 phase, and a UV detector for quantifying the analyte inmore » the aqueous phase. Our measured partitioning coefficients followed expected trends based on volatility and aqueous solubility. The partitioning coefficients and literature data were then used to update a published poly-parameter linear free energy relationship and to develop five new linear free energy relationships for predicting water-sc-CO2 partitioning coefficients. Four of the models targeted a single class of organic compounds. Unlike models that utilize Abraham solvation parameters, the new relationships use vapor pressure and aqueous solubility of the organic compound at 25 °C and CO2 density to predict partitioning coefficients over a range of temperature and pressure conditions. The compound class models provide better estimates of partitioning behavior for compounds in that class than the model built for the entire dataset.« less

Density functional theory analysis of the impact of steric interaction on the function of switchable polarity solvents

DOE PAGES

McNally, Joshua S.; Noll, Bruce; Orme, Christopher J.; ...

2015-05-04

Here, a density functional theory (DFT) analysis has been performed to explore the impact of steric interactions on the function of switchable polarity solvents (SPS) and their implications on a quantitative structure-activity relationship (QSAR) model previously proposed for SPS. An x-ray crystal structure of the N,N-dimethylcyclohexylammonium bicarbonate (Hdmcha) salt has been solved as an asymmetric unit containing two cation/anion pairs, with a hydrogen bonding interaction observed between the bicarbonate anions, as well as between the cation and anion in each pair. DFT calculations provide an optimized structure of Hdmcha that closely resembles experimental data and reproduces the cation/anion interaction withmore » the inclusion of a dielectric field. Relaxed potential energy surface (PES) scans have been performed on Hdmcha-based computational model compounds, differing in the size of functional group bonded to the nitrogen center, to assess the steric impact of the group on the relative energy and structural properties of the compound. Results suggest that both the length and amount of branching associated with the substituent impact the energetic limitations on rotation of the group along the N-R bond and NC-R bond, and disrupt the energy minimized position of the hydrogen bonded bicarbonate group. The largest interaction resulted from functional groups that featured five bonds between the ammonium proton and a proton on a functional group with the freedom of rotation to form a pseudo-six membered ring which included both protons.« less

Structural, elastic, electronic, optical and thermoelectric properties of the Zintl-phase Ae3AlAs3 (Ae = Sr, Ba)

NASA Astrophysics Data System (ADS)

Benahmed, A.; Bouhemadou, A.; Alqarni, B.; Guechi, N.; Al-Douri, Y.; Khenata, R.; Bin-Omran, S.

2018-05-01

First-principles calculations were performed to investigate the structural, elastic, electronic, optical and thermoelectric properties of the Zintl-phase Ae3AlAs3 (Ae = Sr, Ba) using two complementary approaches based on density functional theory. The pseudopotential plane-wave method was used to explore the structural and elastic properties whereas the full-potential linearised augmented plane wave approach was used to study the structural, electronic, optical and thermoelectric properties. The calculated structural parameters are in good consistency with the corresponding measured ones. The single-crystal and polycrystalline elastic constants and related properties were examined in details. The electronic properties, including energy band dispersions, density of states and charge-carrier effective masses, were computed using Tran-Blaha modified Becke-Johnson functional for the exchange-correlation potential. It is found that both studied compounds are direct band gap semiconductors. Frequency-dependence of the linear optical functions were predicted for a wide photon energy range up to 15 eV. Charge carrier concentration and temperature dependences of the basic parameters of the thermoelectric properties were explored using the semi-classical Boltzmann transport model. Our calculations unveil that the studied compounds are characterised by a high thermopower for both carriers, especially the p-type conduction is more favourable.

Shifting in optoelectronic properties from pure K2O and Rb2O compounds to their V- and Cr-doped alloys

NASA Astrophysics Data System (ADS)

Monir, Mohammed El Amine; Ullah, Hayat; Baltach, Hadj; Mouchaal, Younes; Merabiha, Omar; Bahnes, Aicha; Rached, Djamel

2018-04-01

First principle calculations within the density functional theory (DFT) have been used in this approach to study the electronic and optical properties of vanadium (V) and chromium (Cr) doped K2O and Rb2O compounds. Based on the structure properties reported in our previous work, the study of electronic and optoelectronic properties of V- and Cr-doped K2O and Rb2O alloys have been vastly investigated. K2O and Rb2O are found to be semiconductors while their V- and Cr-alloys are metallic in nature. The optical functions like complex dielectric constant, complex index of refraction, absorption coefficient, and reflectivity of these alloys are computed and compared with those of pure K2O and Rb2O compounds. It has been shown that due to TM-doping (TM = V and Cr transition metals), many distinguished peaks appeared in the lower energy part (infrared) of the spectrum. The negative value of 𝜀1 (ω) in this energy range confirmed the metallic behavior of these alloys. Furthermore, the frequency-dependent optical conductivity is also predicted in the entire spectrum, where it increases with increasing photon energy for all the studied alloys. The significant results of α (ω) predict that all these compounds are useful in different optoelectronic applications in a wide part of the spectrum (between 13 eV and 27 eV).

Kondo interactions from band reconstruction in YbInCu 4

DOE PAGES

Jarrige, I.; Kotani, A.; Yamaoka, H.; ...

2015-03-27

We combine resonant inelastic X-ray scattering (RIXS) and model calculations in the Kondo lattice compound YbInCu₄, a system characterized by a dramatic increase in Kondo temperature and associated valence fluctuations below a first-order valence transition at T≃42 K. In this study, the bulk-sensitive, element-specific, and valence-projected charge excitation spectra reveal an unusual quasi-gap in the Yb-derived state density which drives an instability of the electronic structure and renormalizes the low-energy effective Hamiltonian at the transition. Our results provide long-sought experimental evidence for a link between temperature-driven changes in the low-energy Kondo scale and the higher-energy electronic structure of this system.

High performance of mixed halide perovskite solar cells: Role of halogen atom and plasmonic nanoparticles on the ideal current density of cell

NASA Astrophysics Data System (ADS)

Mohebpour, Mohammad Ali; Saffari, Mohaddeseh; Soleimani, Hamid Rahimpour; Tagani, Meysam Bagheri

2018-03-01

To be able to increase the efficiency of perovskite solar cells which is one of the most substantial challenges ahead in photovoltaic industry, the structural and optical properties of perovskite CH3NH3PbI3-xBrx for values x = 1-3 have been studied employing density functional theory (DFT). Using the optical constants extracted from DFT calculations, the amount of light reflectance and ideal current density of a simulated single-junction perovskite solar cell have been investigated. The results of DFT calculations indicate that adding halogen bromide to CH3NH3PbI3 compound causes the relocation of energy bands in band structure which its consequence is increasing the bandgap. In addition, the effect of increasing Br in this structure can be seen as a reduction in lattice constant, refractive index, extinction and absorption coefficient. As well, results of the simulation suggest a significant current density enhancement as much as 22% can be achieved by an optimized array of Platinum nanoparticles that is remarkable. This plan is able to be a prelude for accomplishment of solar cells with higher energy conversion efficiency.

Investigation of structural, electronic, elastic and optical properties of Cd1-x-yZnxHgyTe alloys

NASA Astrophysics Data System (ADS)

Tamer, M.

2016-06-01

Structural, optical and electronic properties and elastic constants of Cd1-x-yZnx HgyTe alloys have been studied by employing the commercial code Castep based on density functional theory. The generalized gradient approximation and local density approximation were utilized as exchange correlation. Using elastic constants for compounds, bulk modulus, band gap, Fermi energy and Kramers-Kronig relations, dielectric constants and the refractive index have been found through calculations. Apart from these, X-ray measurements revealed elastic constants and Vegard's law. It is seen that results obtained from theory and experiments are all in agreement.

Electronic properties and structural phase transition in A4 [M4O4] (A=Li, Na, K and Rb; M=Ag and Cu): A first principles study

NASA Astrophysics Data System (ADS)

Umamaheswari, R.; Yogeswari, M.; Kalpana, G.

2013-02-01

Self-consistent scalar relativistic band structure calculations for AMO (A=Li, Na, K and Rb; M=Ag and Cu) compounds have been performed using the tight-binding linear muffin-tin orbital (TB-LMTO) method within the local density approximation (LDA). At ambient conditions, these compounds are found to crystallize in tetragonal KAgO-type structure with two different space group I-4m2 and I4/mmm. Nowadays, hypothetical structures are being considered to look for new functional materials. AMO compounds have stoichiometry similar to eight-electron half-Heusler materials of type I-I-VI which crystallizes in cubic (C1b) MgAgAs-type structure with space group F-43m. For all these compounds, by interchanging the positions of atoms in the hypothetical cubic structure, three phases (α, β and γ) are formed. The energy-volume relation for these compounds in tetragonal KAgO-type structure and cubic α, β and γ phases of related structure have been obtained. Under ambient conditions these compounds are more stable in tetragonal KAgO-type (I4/mmm) structure. The total energies calculated within the atomic sphere approximation (ASA) were used to determine the ground state properties such as equilibrium lattice parameters, c/a ratio, bulk modulus, cohesive energy and are compared with the available experimental results. The results of the electronic band structure calculations at ambient condition show that LiCuO and NaMO are indirect band gap semiconductors whereas KMO and RbMO are direct band gap semiconductors. At high pressure the band gap decreases and the phenomenon of band overlap metallization occur. Also these compounds undergo structural phase transition from tetragonal I-4m2 phase to cubic α-phase and transition pressures were calculated.

Lattice constant changes leading to significant changes of the spin-gapless features and physical nature in a inverse Heusler compound Zr2MnGa

NASA Astrophysics Data System (ADS)

Wang, Xiaotian; Cheng, Zhenxiang; Khenata, Rabah; Wu, Yang; Wang, Liying; Liu, Guodong

2017-12-01

The spin-gapless semiconductors with parabolic energy dispersions [1-3] have been recently proposed as a new class of materials for potential applications in spintronic devices. In this work, according to the Slater-Pauling rule, we report the fully-compensated ferrimagnetic (FCF) behavior and spin-gapless semiconducting (SGS) properties for a new inverse Heusler compound Zr2MnGa by means of the plane-wave pseudo-potential method based on density functional theory. With the help of GGA-PBE, the electronic structures and the magnetism of Zr2MnGa compound at its equilibrium and strained lattice constants are systematically studied. The calculated results show that the Zr2MnGa is a new SGS at its equilibrium lattice constant: there is an energy gap between the conduction and valence bands for both the majority and minority electrons, while there is no gap between the majority electrons in the valence band and the minority electrons in the conduction band. Remarkably, not only a diverse physical nature transition, but also different types of spin-gapless features can be observed with the change of the lattice constants. Our calculated results of Zr2MnGa compound indicate that this material has great application potential in spintronic devices.

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.

Structure and cation ordering in La 2UO 6, Ce 2UO 6, LaUO 4, and CeUO 4 by first principles calculations

DOE PAGES

Casillas-Trujillo, Luis; Xu, H.; McMurray, Jake W.; ...

2016-07-06

In the present work, we have used density functional theory (DFT) and DFT+U to investigate the crystal structure and phase stability of four model compounds in the Ln 2O 3-UO 2-UO 3 ternary oxide system: La2UO 6, Ce 2UO 6, LaUO 4, CeUO 4, due to the highly-correlated nature of the f-electrons in uranium. We have considered both hypothetical ordered compounds and compounds in which the cations randomly occupy atomic sites in a fluorite-like lattice. We determined that ordered compounds are stable and are energetically favored compared to disordered configurations, though the ordering tendencies are weak. To model and analyzemore » the structures of these complex oxides, we have used supercells based on a layered atomic model. In the layer model, the supercell is composed of alternating planes of anions and cations. We have considered two different ordering motifs for the cations, namely single species (isoatomic) cation layers versus mixed species cation layers. Energy differences between various ordered cationic arrangements were found to be small. This may have implications regarding radiation stability, since cationic arrangements should be able to change under irradiation with little cost in energy.« less

Cohesive properties of (Cu,Ni)-(In,Sn) intermetallics: Database, electron-density correlations and interpretation of bonding trends

NASA Astrophysics Data System (ADS)

Ramos, S. B.; González Lemus, N. V.; Cabeza, G. F.; Fernández Guillermet, A.

2016-06-01

This paper presents a systematic and comparative study of the composition and volume dependence of the cohesive properties for a large group of Me-X intermetallic phases (IPs) with Me=Cu,Ni and X=In,Sn, which are of interest in relation with the design of lead-free soldering (LFS) alloys. The work relies upon a database with total-energy versus volume information developed by using projected augmented waves (PAW) calculations. In previous papers by the current authors it was shown that these results account satisfactorily for the direct and indirect experimental data available. In the present work, the database is further expanded to investigate the composition dependence of the volume (V0), and the composition and volume dependence of the bulk modulus (B0) and cohesive energy (Ecoh). On these bases, an analysis is performed of the systematic effects of replacing Cu by Ni in several Me-X phases (Me=Cu,Ni and X=In,Sn) reported as stable and metastable, as well as various hypothetical compounds involved in the thermodynamic modeling of IPs using the Compound-Energy Formalism. Moreover, it is shown that the cohesion-related quantities (B0/V0)½ and (Ecoh½/V0) can be correlated with a parameter expressing the number of valence electrons per unit volume. These findings are compared in detail with related relations involving the Miedema empirical electron density at the boundary of the Wigner-Seitz cell. In view of the co-variation of the cohesive properties, Ecoh is selected as a key property and its composition and structure dependence is examined in terms of a theoretical view of the bonding which involves the hybridization of the d-states of Cu or Ni with the s and p-states of In or Sn, for this class of compounds. In particular, a comparative analysis is performed of the DOS of various representative, iso-structural Me-X compounds. Various effects of relevance to understand the consequences of replacing Cu by Ni in LFS alloys are highlighted and explained microscopically for the first time.

Structural and elastic properties of AIBIIIC 2 VI semiconductors

NASA Astrophysics Data System (ADS)

Kumar, V.; Singh, Bhanu P.

2018-01-01

The plane wave pseudo-potential method within density functional theory has been used to calculate the structural and elastic properties of AIBIIIC 2 VI semiconductors. The electronic band structure, density of states, lattice constants (a and c), internal parameter (u), tetragonal distortion (η), energy gap (Eg), and bond lengths of the A-C (dAC) and B-C (dBC) bonds in AIBIIIC 2 VI semiconductors have been calculated. The values of elastic constants (Cij), bulk modulus (B), shear modulus (G), Young's modulus (Y), Poisson's ratio (υ), Zener anisotropy factor (A), Debye temperature (ϴD) and G/B ratio have also been calculated. The values of all 15 parameters of CuTlS2 and CuTlSe2 compounds, and 8 parameters of 20 compounds of AIBIIIC 2 VI family, except AgInS2 and AgInSe2, have been calculated for the first time. Reasonably good agreement has been obtained between the calculated, reported and available experimental values.

High performance, high density hydrocarbon fuels

NASA Technical Reports Server (NTRS)

Frankenfeld, J. W.; Hastings, T. W.; Lieberman, M.; Taylor, W. F.

1978-01-01

The fuels were selected from 77 original candidates on the basis of estimated merit index and cost effectiveness. The ten candidates consisted of 3 pure compounds, 4 chemical plant streams and 3 refinery streams. Critical physical and chemical properties of the candidate fuels were measured including heat of combustion, density, and viscosity as a function of temperature, freezing points, vapor pressure, boiling point, thermal stability. The best all around candidate was found to be a chemical plant olefin stream rich in dicyclopentadiene. This material has a high merit index and is available at low cost. Possible problem areas were identified as low temperature flow properties and thermal stability. An economic analysis was carried out to determine the production costs of top candidates. The chemical plant and refinery streams were all less than 44 cent/kg while the pure compounds were greater than 44 cent/kg. A literature survey was conducted on the state of the art of advanced hydrocarbon fuel technology as applied to high energy propellents. Several areas for additional research were identified.

Alkyl ammonium cation stabilized biocidal polyiodides with adaptable high density and low pressure.

PubMed

He, Chunlin; Parrish, Damon A; Shreeve, Jean'ne M

2014-05-26

The effective application of biocidal species requires building the active moiety into a molecular back bone that can be delivered and decomposed on demand under conditions of low pressure and prolonged high-temperature detonation. The goal is to destroy storage facilities and their contents while utilizing the biocidal products arising from the released energy to destroy any remaining harmful airborne agents. Decomposition of carefully selected iodine-rich compounds can produce large amounts of the very active biocides, hydroiodic acid (HI) and iodine (I2). Polyiodide anions, namely, I3(-), I5(-), which are excellent sources of such biocides, can be stabilized through interactions with large, symmetric cations, such as alkyl ammonium salts. We have designed and synthesized suitable compounds of adaptable high density up to 3.33 g cm(-3) that are low-pressure polyiodides with various alkyl ammonium cations, deliverable iodine contents of which range between 58.0-90.9%. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

The excited-state intramolecular proton transfer in Nsbnd H-type dye molecules with a seven-membered-ring intramolecular hydrogen bond: A theoretical insight

NASA Astrophysics Data System (ADS)

Yuan, Huijuan; Feng, Songyan; Wen, Keke; Guo, Xugeng; Zhang, Jinglai

2018-02-01

Excited-state intramolecular proton transfer (ESIPT) reactions of a series of N(R)sbnd H ⋯ N-type seven-membered-ring hydrogen-bonding compounds were explored by employing density functional theory/time-dependent density functional theory calculations with the PBE0 functional. Our results indicate that the absorption and emission spectra predicted theoretically match very well the experimental findings. Additionally, as the electron-withdrawing strength of R increases, the intramolecular H-bond of the Nsbnd S1 form gradually enhances, and the forward energy barrier along the ESIPT reaction gradually decreases. For compound 4, its ESIPT reaction is found to be a barrierless process due to the involvement of a strong electron-withdrawing COCF3 group. It is therefore a reasonable presumption that the ESIPT efficiency of these N(R)sbnd H ⋯ N-type seven-membered-ring H-bonding systems can be improved when a strong electron-withdrawing group in R is introduced.

First-principles calculations of phonons and Raman and infrared spectra in Cd-IV-N2 compounds

NASA Astrophysics Data System (ADS)

Lyu, Sai; Lambrecht, Walter R. L.

2018-05-01

A first-principles study of the phonons at the zone center in Cd-IV-N2 compounds is presented with IV = Si, Ge, Sn. The calculations are performed for the most likely Pbn21 crystal structure, after showing that it is indeed lower in total energy compared to the closely related Pmc21 structure. The normal mode frequencies are calculated using density functional perturbation theory and symmetry labeled. The longitudinal optical-transverse optical splittings are determined using the Born effective charges which are also reported. These are used to simulate polarized Raman spectra for different scattering configurations as well as the infrared absorption and reflection spectra. The mode frequencies are found to decrease from Si to Ge to Sn as group-IV cation. The spectra show a wide variety of number of prominent peaks and relative intensities in spite of the great similarities of these three materials. Phonon densities of states and their analysis in atom by atom contributions are also reported.

Spectroscopic and density functional theory studies of trans-3-(trans-4-imidazolyl)acrylic acid.

PubMed

Arjunan, V; Remya, P; Sathish, U; Rani, T; Mohan, S

2014-08-14

The structural parameters, thermodynamic properties and vibrational frequencies of the optimised geometry of trans-3-(trans-4-imidazolyl)acrylic acid have been determined from B3LYP methods with 6-311++G(**) and cc-pVTZ basis sets. The effects of substituents (acrylyl group) on the imidazole vibrational frequencies are analysed. The vibrational frequencies of the fundamental modes of trans-3-(trans-4-imidazolyl)acrylic acid have been precisely assigned and analysed and the theoretical results are compared with the experimental vibrations. (1)H and (13)C NMR isotropic chemical shifts are calculated and the assignments made are compared with the experimental values. The energies of important MO's of the compound are also determined from DFT method. The total electron density and electrostatic potential of the compound are determined by natural bond orbital analysis. Various reactivity and selectivity descriptors such as chemical hardness, chemical potential, softness, electrophilicity, nucleophilicity and the appropriate local quantities employing natural population analysis (NPA) are calculated. Copyright © 2014 Elsevier B.V. All rights reserved.

Induced Charge Fluctuations in Semiconductor Detectors with a Cylindrical Geometry

NASA Astrophysics Data System (ADS)

Samedov, Victor V.

2018-01-01

Now, compound semiconductors are very appealing for hard X-ray room-temperature detectors for medical and astrophysical applications. Despite the attractive properties of compound semiconductors, such as high atomic number, high density, wide band gap, low chemical reactivity and long-term stability, poor hole and electron mobility-lifetime products degrade the energy resolution of these detectors. The main objective of the present study is in development of a mathematical model of the process of the charge induction in a cylindrical geometry with accounting for the charge carrier trapping. The formulae for the moments of the distribution function of the induced charge and the formulae for the mean amplitude and the variance of the signal at the output of the semiconductor detector with a cylindrical geometry were derived. It was shown that the power series expansions of the detector amplitude and the variance in terms of the inverse bias voltage allow determining the Fano factor, electron mobility lifetime product, and the nonuniformity level of the trap density of the semiconductor material.

A topological screening heuristic for low-energy, high-index surfaces

NASA Astrophysics Data System (ADS)

Sun, Wenhao; Ceder, Gerbrand

2018-03-01

Robust ab initio investigations of nanoparticle surface properties require a method to identify candidate low-energy surface facets a priori. By assuming that low-energy surfaces are planes with high atomic density, we devise an efficient algorithm to screen for low-energy surface orientations, even if they have high (hkl) miller indices. We successfully predict the observed low-energy, high-index { 10 12 bar } and { 10 1 bar 4 } surfaces of hematite α-Fe2O3, the {311} surfaces of cuprite Cu2O, and the {112} surfaces of anatase TiO2. We further tabulate candidate low-energy surface orientations for nine of the most common binary oxide structures. Screened surfaces are found to be generally applicable across isostructural compounds with varying chemistries, although relative surface energies between facets may vary based on the preferred coordination of the surface atoms.

Theoretical analysis of the electronic properties of the sex pheromone and its analogue derivatives in the female processionary moth Thaumetopoea pytiocampa.

PubMed

Chamorro, Ester R; Sequeira, Alfredo F; Zalazar, M Fernanda; Peruchena, Nélida M

2008-09-15

In the present work, the distribution of the electronic charge density of the natural sex pheromone, the (Z)-13-hexadecen-11-ynyl acetate, in the female processionary moth, Thaumetopoea pytiocampa, and its nine analogue derivatives was studied within the framework of the Density Functional Theory and the Atoms in Molecules (AIM) Theory at B3LYP/6-31G *//B3LYP/6-31++G * * level. Additionally, molecular electrostatic potential (MEP) maps of the previously mentioned compounds were computed and compared. Furthermore, the substitution of hydrogen atoms from the methyl group in the acetate group by electron withdrawing substituents (i.e., halogen atoms) as well as the replacement effect of hydrogen by electron donor substituents (+I effect) as methyl group, were explored. The key feature of the topological distribution of the charge density in analogue compounds, such as the variations of the topological properties encountered in the region formed by neighbouring atoms from the substitution site were presented and discussed. Using topological parameters, such as electronic charge density, Laplacian, kinetic energy density, and potential energy density evaluated at bond critical points (BCP), we provide here a detailed analysis of the nature of the chemical bonding of these molecules. In addition, the atomic properties (population, charge, energy, volume, and dipole moment) were determined on selected atoms. These properties were analyzed at the substitution site (with respect to the natural sex pheromone) and related to the biological activity and to the possible binding site with the pheromone binding protein, (PBP). Moreover, the Laplacian function of the electronic density was used to locate electrophilic regions susceptible to be attacked (by deficient electron atoms or donor hydrogen). Our results indicate that the change in the atomic properties, such as electronic population and atomic volume, are sensitive indicators of the loss of the biological activity in the analogues studied here. The crucial interaction between the acetate group of the natural sex pheromone and the PBP is most likely to be a hydrogen bonding and the substitution of hydrogen atoms by electronegative atoms in the pheromone molecule reduces the hydrogen acceptor capacity. This situation is mirrored by the diminish of the electronic population on carbon and oxygen atoms at the carbonylic group in the halo-acetate group. Additionally, the modified acetate group (with electronegative atoms) shows new charge concentration critical points or regions of concentration of charge density in which an electrophilic attack can also occur. Finally, the use of the topological analysis based in the charge density distribution and its Laplacian function, in conjunction with MEP maps provides valuable information about the steric volume and electronic requirement of the sex pheromone for binding to the PBP.

Electronic and optical properties of RESn{sub 3} (RE=Pr & Nd) intermetallics: A first principles study

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

Pagare, G., E-mail: gita-pagare@yahoo.co.in; Abraham, Jisha A.; Department of Physics, National Defence Academy, Pune-411023

2015-06-24

A theoretical study of structural, electronic and optical properties of RESn{sub 3} (RE = Pr & Nd) intermetallics have been investigated systematically using first principles density functional theory. The calculations are carried out within the PBE-GGA and LSDA for the exchange correlation potential. The ground state properties such as lattice parameter (a{sub 0}), bulk modulus (B) and its pressure derivative (B′) are calculated and the calculated lattice parameters show well agreement with the experimental results. We first time predict elastic constants for these compounds. From energy dispersion curves, it is found that these compounds are metallic in nature. The linearmore » optical response of these compounds are also studied and the higher value of static dielectric constant shows the possibility to use them as good dielectric materials.« less

National Institute for Petroleum and Energy Research quarterly technical report, July 1--September 30, 1992. [Dinitrogen compound 1,10-phenanthroline

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

Not Available

Progress reports are presented for the following two fuel research programs: (1) development of analytical methodology for analysis of heavy crudes; and (2) thermochemistry and thermophysical properties of organic nitrogen and diheteroatom-containing compounds. For the first research program, gasoline range (82--43[degree]) components in liquid products from catalytic cracking whole Wilmington >650[degree]F resid, Wilmington >650[degree]F neutrals, and blends of neutrals plus 650--1000[degree]F acids and bases were determined by gas chromatography/mass spectroscopy. For the second research program, density measurements were completed for thianthrene between 450 K and near 570 K, and for phenoxathiin between 348 K and 548 K. Heat capacity measurementsmore » were begun for the dinitrogen compound 1,10-phenanthroline.« less

Theoretical calculations of high-pressure phases of NiF2: An ab initio constant-pressure study

NASA Astrophysics Data System (ADS)

Kürkçü, Cihan; Merdan, Ziya; Öztürk, Hülya

2016-12-01

We have studied the structural properties of the antiferromagnetic NiF2 tetragonal structure with P42/ mnm symmetry using density functional theory (DFT) under rapid hydrostatic pressure up to 400 GPa. For the exchange correlation energy we used the local density approximation (LDA) of Ceperley and Alder (CA). Two phase transformations are successfully observed through the simulations. The structures of XF2-type compounds crystallize in rutile-type structure. NiF2 undergoes phase transformations from the tetragonal rutile-type structure with space group P42/ mnm to orthorhombic CaCl2-type structure with space group Pnnm and from this orthorhombic phase to monoclinic structure with space group C2/ m at 152 GPa and 360 GPa, respectively. These phase changes are also studied by total energy and enthalpy calculations. According to these calculations, we perdict these phase transformations at about 1.85 and 30 GPa.

Thermokinetic analysis and product characterization of Medium Density Fiberboard pyrolysis.

PubMed

Aslan, Dilan Irmak; Özoğul, Buğçe; Ceylan, Selim; Geyikçi, Feza

2018-06-01

This study investigates the pyrolysis of Medium Density Fiberboard (MDF) as a potential waste management solution. Thermal behaviour of MDF was analysed via TG/DSC. The primary decomposition step occurred between 190 °C and 425 °C. Evolved gaseous products over this step were evaluated by a FTIR spectrometer coupled with TGA. Peaks for phenolic, alcohols and aldehydes were detected at the maximum decomposition temperature. Py-GC/MS analysis revealed phenols, ketones and cyclic compounds as the primary non-condensable pyrolysis products. The kinetics of pyrolysis were investigated by the widely applied Distributed Activation Energy Model, resulting in an average activation energy and pre-exponential factor of 127.40 kJ mol -1 and 8.4E+11. The results of this study suggest that pyrolyzing MDF could potentially provide renewable fuels and prevent environmental problems related with MDF disposal. Copyright © 2018 Elsevier Ltd. All rights reserved.

Effect of structural distortion on the electronic band structure of NaOsO3 studied within density functional theory and a three-orbital model

NASA Astrophysics Data System (ADS)

Mohapatra, Shubhajyoti; Bhandari, Churna; Satpathy, Sashi; Singh, Avinash

2018-04-01

Effects of the structural distortion associated with the OsO6 octahedral rotation and tilting on the electronic band structure and magnetic anisotropy energy for the 5 d3 compound NaOsO3 are investigated using the density functional theory (DFT) and within a three-orbital model. Comparison of the essential features of the DFT band structures with the three-orbital model for both the undistorted and distorted structures provides insight into the orbital and directional asymmetry in the electron hopping terms resulting from the structural distortion. The orbital mixing terms obtained in the transformed hopping Hamiltonian resulting from the octahedral rotations are shown to account for the fine features in the DFT band structure. Staggered magnetization and the magnetic character of states near the Fermi energy indicate weak coupling behavior.

Experimental and density functional theory studies on benzalkonium ibuprofenate, a double active pharmaceutical ingredient.

PubMed

Safna Hussan, K P; Thayyil, M Shahin; Rajan, Vijisha K; Muraleedharan, K

2018-02-01

Molecular aspects of a double active pharmaceutical ingredient in ionic liquid form, benzalkonium ibuprofenate (BaIb), were studied using density functional theory (DFT/B3LYP/6-31+G (d, p)). A detailed discussion on optimized geometry, energy, heat and the enthalpy of BaIb was carried out. The computed vibrational results agree well with the experimental results. The stability and biological activity were compared to the parent drugs on the basis of global descriptive parameters. The electrophilic and nucleophilic sites were pointed out in the MESP structures well evidently. NBO analysis was also done to predict the relative aromaticity, delocalization effects and the contribution towards stabilization energy of the title compound. The information about non-covalent, non-ionic weak interaction between the cation and anion was obtained from the list of Mulliken charges and NBO analysis. Copyright © 2017 Elsevier Ltd. All rights reserved.

Lithium sulfur batteries and electrolytes and sulfur cathodes thereof

DOEpatents

Visco, Steven J.; Goncharenko, Nikolay; Nimon, Vitaliy; Petrov, Alexei; Nimon, Yevgeniy S.; De Jonghe, Lutgard C.; Katz, Bruce D.; Loginova, Valentina

2017-05-23

Lithium sulfur battery cells that use water as an electrolyte solvent provide significant cost reductions. Electrolytes for the battery cells may include water solvent for maintaining electroactive sulfur species in solution during cell discharge and a sufficient amount of a cycle life-enhancing compound that facilitates charging at the cathode. The combination of these two components enhances one or more of the following cell attributes: energy density, power density and cycle life. For instance, in applications where cost per Watt-Hour (Wh) is paramount, such as grid storage and traction applications, the use of an aqueous electrolyte in combination with inexpensive sulfur as the cathode active material can be a key enabler for the utility and automotive industries, for example, providing a cost effective and compact solution for load leveling, electric vehicles and renewable energy storage. Sulfur cathodes, and methods of fabricating lithium sulfur cells, in particular for loading lithium sulfide into the cathode structures, provide further advantages.

Density functional computational studies on the glucose and glycine Maillard reaction: Formation of the Amadori rearrangement products

NASA Astrophysics Data System (ADS)

Jalbout, Abraham F.; Roy, Amlan K.; Shipar, Abul Haider; Ahmed, M. Samsuddin

Theoretical energy changes of various intermediates leading to the formation of the Amadori rearrangement products (ARPs) under different mechanistic assumptions have been calculated, by using open chain glucose (O-Glu)/closed chain glucose (A-Glu and B-Glu) and glycine (Gly) as a model for the Maillard reaction. Density functional theory (DFT) computations have been applied on the proposed mechanisms under different pH conditions. Thus, the possibility of the formation of different compounds and electronic energy changes for different steps in the proposed mechanisms has been evaluated. B-Glu has been found to be more efficient than A-Glu, and A-Glu has been found more efficient than O-Glu in the reaction. The reaction under basic condition is the most favorable for the formation of ARPs. Other reaction pathways have been computed and discussed in this work.0

Inelastic neutron scattering study of phonon density of states in nanostructured Si1 xGex thermoelectrics

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

Dhital, Chetan; Abernathy, Douglas L; Zhu, Gaohua

2012-01-01

Inelastic neutron scattering measurements are utilized to explore relative changes in the generalized phonon density of states of nanocrystalline Si1 xGex thermoelectric materials prepared via ball-milling and hot-pressing techniques. Dynamic signatures of Ge clustering can be inferred from the data by referencing the resulting spectra to a density functional theoretical model assuming homogeneous alloying via the virtual-crystal approximation. Comparisons are also presented between as-milled Si nanopowder and bulk, polycrystalline Si where a preferential low-energy enhancement and lifetime broadening of the phonon density of states appear in the nanopowder. Negligible differences are however observed between the phonon spectra of bulk Simore » andhot-pressed, nanostructured Si samples suggesting that changes to the single-phonon dynamics above 4 meV play only a secondary role in the modified heat conduction of this compound.« less

Investigation of half-metallic ferromagnetism in Heusler compounds Co2VZ (Z = Ga, Ge, As, Se)

NASA Astrophysics Data System (ADS)

Han, Jiajia; Wang, Zhengwei; Xu, Weiwei; Wang, Cuiping; Liu, Xingjun

2017-11-01

The electronic structures and magnetic properties of 3d transition metal-based full Heusler compounds Co2VZ (Z = Ga, Ge, As, Se) are investigated using the projector augmented wave (PAW) pseudopotential method. By considering the strong localization of Co 3d-states and V 3d-states at the Fermi level, these Co2VZ (Z = Ga, Ge, As, Se) compounds were treated in the framework of the generalized gradient approximation (GGA)+U method, and the results from the conventional GGA method are presented for comparison. The results that were obtained from the density of states with the GGA+U and GGA methods show that the Co2VGa compound is a half-metallic ferromagnet. For the Co2VGe and Co2VAs compounds, the GGA+U method predicts that these two compounds are half-metallic ferromagnetic by shifting the Fermi level to a lower value with respect to the gap in the minority states, when compared to the conventional GGA method. The energy gaps are determined to be 0.283 eV and 0.425 eV, respectively. However, these results show that the density of states of the Co2VSe compound has a metallic character, although the 3d states were corrected when using the GGA+U method. We found that the characteristic of half-metallic ferromagnetism is attributed to the interaction between the V 3d-states other than Co 3d-states. The calculated total magnetic moments are 2.046 μB, 3.054 μB and 4.012 μB respectively for the Co2VZ (Z = Ga, Ge, As) compounds with the GGA+U method. The relationship between total spin magnetic moment per formula unit and total number of valence electrons of these Heusler compounds is in agreement with the Slater-Pauling rule.

Elastic, Optoelectronic and Thermoelectric Properties of the Lead-Free Halide Semiconductors Cs2AgBi X 6 ( X = Cl, Br): Ab Initio Investigation

NASA Astrophysics Data System (ADS)

Guechi, N.; Bouhemadou, A.; Bin-Omran, S.; Bourzami, A.; Louail, L.

2018-02-01

We report a detailed investigation of the elastic moduli, electronic band structure, density of states, chemical bonding, electron and hole effective masses, optical response functions and thermoelectric properties of the lead-free halide double perovskites Cs2AgBiCl6 and Cs2AgBiBr6 using the full potential linearized augmented plane wave (FP-LAPW) method with the generalized gradient approximation (GGA-PBEsol) and the Tran-Blaha modified Becke-Johnson (TB-mBJ) potential. Because of the presence of heavy elements in the studied compounds, we include the spin-orbit coupling (SOC) effect. Our calculated structural parameters agree very well with the available experimental and theoretical findings. Single-crystal and polycrystalline elastic constants are predicted using the total-energy versus strain approach. Three-dimensional representations of the crystallographic direction dependence on the shear modulus, Young's modulus and Poisson's ratio demonstrate a noticeable elastic anisotropy. The TB-mBJ potential with SOC yields an indirect band gap of 2.44 (1.93) eV for Cs2AgBiCl6 (Cs2AgBiBr6), in good agreement with the existing experimental data. The chemical bonding features are probed via density of states and valence electron density distribution calculations. Optical response functions were predicted from the calculated band structure. Both of the investigated compounds have a significant absorption coefficient (˜ 25 × 104 {cm}^{ - 1} ) in the visible range of sunlight. The thermoelectric properties of the title compounds were investigated using the FP-LAPW approach in combination with the semi-classical Boltzmann transport theory. The Cs2AgBiCl6 and Cs2AgBiBr6 compounds have a large thermopower S, which makes them potential candidates for thermoelectric applications.

One-atom-layer 4×4 compound in (Tl, Pb)/Si(111) system

NASA Astrophysics Data System (ADS)

Mihalyuk, A. N.; Hsing, C. R.; Wei, C. M.; Gruznev, D. V.; Bondarenko, L. V.; Tupchaya, A. Y.; Zotov, A. V.; Saranin, A. A.

2017-03-01

An ordered 4×4-periodicity 2D compound has been found in the (Tl, Pb)/Si(111) system and its composition, structure and electronic properties have been characterized using low-energy electron diffraction, scanning tunneling microscopy observations and density-functional-theory calculations. The compound has been concluded to contain 9 Tl atoms and 12 Pb atoms per 4×4 unit cell, i.e., 0.56 ML of Tl and 0.75 ML of Pb. Structural model was proposed for the 4×4-(Tl, Pb) compound where building blocks are a hexagonal array of 12 Pb atoms, a triangular array of 6 Tl atoms and a Tl trimer. The proposed structure has a C3 symmetry and occurs in the two equivalent orientations. The electron band structure of the compound contains two metallic spin-split surface-state bands. Bearing in mind the advanced properties of the known √{ 3 } ×√{ 3 } 2D compound in the same (Tl, Pb)/Si(111) system (i.e., combination of giant Rashba effect and superconductivity), the found 4×4-(Tl, Pb) compound is believed to be a promising object for exploration of its superconductive properties.

Effect of van der Waals interactions on the structural and binding properties of GaSe

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

Sarkisov, Sergey Y., E-mail: sarkisov@mail.tsu.ru; Kosobutsky, Alexey V., E-mail: kosobutsky@kemsu.ru; Kemerovo State University, Krasnaya 6, 650043 Kemerovo

The influence of van der Waals interactions on the lattice parameters, band structure, elastic moduli and binding energy of layered GaSe compound has been studied using projector-augmented wave method within density functional theory. We employed the conventional local/semilocal exchange-correlation functionals and recently developed van der Waals functionals which are able to describe dispersion forces. It is found that application of van der Waals density functionals allows to substantially increase the accuracy of calculations of the lattice constants a and c and interlayer distance in GaSe at ambient conditions and under hydrostatic pressure. The pressure dependences of the a-parameter, Ga–Ga, Ga–Semore » bond lengths and Ga–Ga–Se bond angle are characterized by a relatively low curvature, while c(p) has a distinct downward bowing due to nonlinear shrinking of the interlayer spacing. From the calculated binding energy curves we deduce the interlayer binding energy of GaSe, which is found to be in the range 0.172–0.197 eV/layer (14.2–16.2 meV/Å{sup 2}). - Highlights: • Effects of van der Waals interactions are analyzed using advanced density functionals. • Calculations with vdW-corrected functionals closely agree with experiment. • Interlayer binding energy of GaSe is estimated to be 14.2–16.2 meV/Å{sup 2}.« less

Machine learning predictions of molecular properties: Accurate many-body potentials and nonlocality in chemical space

DOE PAGES

Hansen, Katja; Biegler, Franziska; Ramakrishnan, Raghunathan; ...

2015-06-04

Simultaneously accurate and efficient prediction of molecular properties throughout chemical compound space is a critical ingredient toward rational compound design in chemical and pharmaceutical industries. Aiming toward this goal, we develop and apply a systematic hierarchy of efficient empirical methods to estimate atomization and total energies of molecules. These methods range from a simple sum over atoms, to addition of bond energies, to pairwise interatomic force fields, reaching to the more sophisticated machine learning approaches that are capable of describing collective interactions between many atoms or bonds. In the case of equilibrium molecular geometries, even simple pairwise force fields demonstratemore » prediction accuracy comparable to benchmark energies calculated using density functional theory with hybrid exchange-correlation functionals; however, accounting for the collective many-body interactions proves to be essential for approaching the “holy grail” of chemical accuracy of 1 kcal/mol for both equilibrium and out-of-equilibrium geometries. This remarkable accuracy is achieved by a vectorized representation of molecules (so-called Bag of Bonds model) that exhibits strong nonlocality in chemical space. The same representation allows us to predict accurate electronic properties of molecules, such as their polarizability and molecular frontier orbital energies.« less

Machine Learning Predictions of Molecular Properties: Accurate Many-Body Potentials and Nonlocality in Chemical Space

PubMed Central

2015-01-01

Simultaneously accurate and efficient prediction of molecular properties throughout chemical compound space is a critical ingredient toward rational compound design in chemical and pharmaceutical industries. Aiming toward this goal, we develop and apply a systematic hierarchy of efficient empirical methods to estimate atomization and total energies of molecules. These methods range from a simple sum over atoms, to addition of bond energies, to pairwise interatomic force fields, reaching to the more sophisticated machine learning approaches that are capable of describing collective interactions between many atoms or bonds. In the case of equilibrium molecular geometries, even simple pairwise force fields demonstrate prediction accuracy comparable to benchmark energies calculated using density functional theory with hybrid exchange-correlation functionals; however, accounting for the collective many-body interactions proves to be essential for approaching the “holy grail” of chemical accuracy of 1 kcal/mol for both equilibrium and out-of-equilibrium geometries. This remarkable accuracy is achieved by a vectorized representation of molecules (so-called Bag of Bonds model) that exhibits strong nonlocality in chemical space. In addition, the same representation allows us to predict accurate electronic properties of molecules, such as their polarizability and molecular frontier orbital energies. PMID:26113956

FT-IR and Raman vibrational analysis, B3LYP and M06-2X simulations of 4-bromomethyl-6-tert-butyl-2H-chromen-2-one

NASA Astrophysics Data System (ADS)

Sert, Yusuf; Puttaraju, K. B.; Keskinoğlu, Sema; Shivashankar, K.; Ucun, Fatih

2015-01-01

In this study, the experimental and theoretical vibrational frequencies of a newly synthesized bacteriostatic and anti-tumor molecule namely, 4-bromomethyl-6-tert-butyl-2H-chromen-2-one have been investigated. The experimental FT-IR (4000-400 cm-1) and Raman spectra (4000-100 cm-1) of the compound in solid phase have been recorded. The theoretical vibrational frequencies and optimized geometric parameters have been calculated using density functional theory (DFT/B3LYP: Becke, 3-parameter, Lee-Yang-Parr and DFT/M06-2X: highly parametrized, empirical exchange correlation function) with 6-311++G(d, p) basis set by Gaussian 03 software, for the first time. The assignments of the vibrational frequencies have been done by potential energy distribution (PED) analysis using VEDA 4 software. The theoretical optimized geometric parameters and vibrational frequencies have been found to be in good agreement with the corresponding experimental data and results in the literature. In addition, the highest occupied molecular orbital (HOMO) energy, the lowest unoccupied molecular orbital (LUMO) energy and the other related molecular energy values of the compound have been investigated using the same theoretical calculations.

Theoretical insights into effects of molar ratios on stabilities, mechanical properties and detonation performance of CL-20/RDX cocrystal explosives by molecular dynamics simulation

NASA Astrophysics Data System (ADS)

Hang, Gui-yun; Yu, Wen-li; Wang, Tao; Wang, Jin-tao; Li, Zhen

2017-08-01

The CL-20/RDX cocrystal models with different molar ratios were established by substitution method and molecular dynamics (MD) simulation method was applied to investigate the influences of molar ratios on mechanical properties, stabilities and detonation performance of cocrystal explosives. The crystal parameters, structures, binding energies, mechanical properties and some detonation parameters of different cocrystal explosives were got and compared. The results illustrate that the molar ratio has a direct influence on properties of cocrystal explosive and each of the cocrystal model holds different mechanical properties, binding energies and detonation parameters. The mechanical properties of CL-20/RDX cocrystal explosive can be effectively improved and the cocrystal model with molar ratio in 1:1 has the best mechanical properties. Besides, it has the highest binding energy, so the stability and compatibility is the best. The detonation parameters show that the cocrystal explosive has better detonation performance than RDX. In a word, the cocrystal explosive with molar ratio in 1:1 has the best mechanical properties, highest binding energy and excellent energy density and detonation performance, it is quite promising and can satisfy the requirements of high energy density compounds (HEDC). This paper could offer some theoretical instructions and novel insights for the CL-20 cocrystal explosive designing.

Silicon clathrates for lithium ion batteries: A perspective

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

Warrier, Pramod, E-mail: pramod.warrier@gmail.com; Koh, Carolyn A.

2016-12-15

Development of novel energy storage techniques is essential for the development of sustainable energy resources. Li-ion batteries have the highest rated energy density among rechargeable batteries and have attracted a lot of attention for energy storage in the last 15–20 years. However, significant advancements are required in anode materials before Li-ion batteries become viable for a wide variety of applications, including in renewable energy storage, grid storage, and electric vehicles. While graphite is the current standard anode material in commercial Li-ion batteries, it is Si that exhibits the highest specific energy density among all materials considered for this purpose. Si,more » however, suffers from significant volume expansion/contraction and the formation of a thick solid-electrolyte interface layer. To resolve these issues, Si clathrates are being considered for anode materials. Clathrates are inclusion compounds and contain cages in which Li could be captured. While Si clathrates offer promising advantages due to their caged structure which enables negligible volume change upon Li insertion, there remains scientific challenges and knowledge gaps to be overcome before these materials can be utilized for Li-ion battery applications, i.e., understanding lithiation/de-lithiation mechanisms, optimizing guest concentrations, as well as safe and economic synthesis routes.« less

Thermoelectric power factor of La0.9M0.1FeO3 (M = Ca and Ba) system: Structural, band gap and electrical transport evaluations

NASA Astrophysics Data System (ADS)

Karthikeyan, N.; Kumar, R. Ramesh; Jaiganesh, G.; Sivakumar, K.

2018-01-01

The search for thermoelectric materials has been incredibly increased due to the increase in global energy demand. Hence the present work focus on preparation and characterization of thermal transport phenomena of pure and Ba/Ca substituted perovskite LaFeO3 orthoferrite system. The conventional solid state reaction technique is utilized for the preparation of LaFeO3 and La0.9M0.1FeO3 (M = Ca and Ba) compounds. Crystal structure analyses of the prepared samples are analyses using Rietveld refinement process which confirms the orthoferrite crystal structure of all the prepared compounds with induced distortion in position of atoms by the incorporation of substituent atoms. The electronic structure calculations are performed by VASP. As the LaFeO3 compound is a strongly energy correlated system, the Density Functional Theory (DFT) calculations are performed by DFT + U (Hubbard function) method. The computed band gap values are compared with the energy gap values calculated from UV-Vis spectral analysis. Electrical conductivity measurement and Arrhenius behavior for the temperature range of room temperature to 650 K are analyzed and the drift increase in conductivity with respect to temperature is due to the thermally activated mobility of charge carriers. Temperature dependent thermopower analysis is also examined using homemade seebeck coefficient measurement system. The calculation of thermoelectric power factor reveals that the Ba substituted LaFeO3 compound show highest power factor value of 3.73 μW/K2 cm at higher temperature and the superior power factor values observed in the Ba substituted compound determine the material's capability in power generating devices based on thermoelectric effect.

High performance all-solid-state symmetric supercapacitor based on porous carbon made from a metal-organic framework compound

NASA Astrophysics Data System (ADS)

Yu, Feng; Wang, Teng; Wen, Zubiao; Wang, Hongxia

2017-10-01

In this work, we demonstrate the synthesis of porous carbon material with high specific surface area by using metal-organic framework (MOF) as precursor. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) have confirmed that the material was amorphous and consisted of nanoparticles (5-6 nm) and hierarchical distribution of pores. The characterization of the material by N2 adsorption/desorption isotherm measurement have shown that the material had a high specific surface area reaching to 2618.7 m2 g-1 and abundant porosity with pore size less than 10 nm. The investigation of the electrochemical properties of the material has shown the porous carbon electrode possessed excellent rate performance with high specific capacitances of 150.8 F g-1 at a current density of 5 A g-1, and 133.6 F g-1 at a current density of 50 A g-1, respectively. An all-solid-state symmetric supercapacitor assembled using the as-prepared porous carbon as electrodes and Na2SO4/PVA gel as an electrolyte delivered a high power density of 13 516.4 W kg-1 with an energy density of 8.26 Wh kg-1. A high energy density of 17.37 Wh kg-1 was obtained at discharge current density of 1 A g-1. In addition, the device exhibited superior cycling performance with 94.8% retention rate after 10 000 cycles at a current density of 10 A g-1.

Porous Materials for Hydrolytic Dehydrogenation of Ammonia Borane

PubMed Central

Umegaki, Tetsuo; Xu, Qiang; Kojima, Yoshiyuki

2015-01-01

Hydrogen storage is still one of the most significant issues hindering the development of a “hydrogen energy economy”. Ammonia borane is notable for its high hydrogen densities. For the material, one of the main challenges is to release efficiently the maximum amount of the stored hydrogen. Hydrolysis reaction is a promising process by which hydrogen can be easily generated from this compound. High purity hydrogen from this compound can be evolved in the presence of solid acid or metal based catalyst. The reaction performance depends on the morphology and/or structure of these materials. In this review, we survey the research on nanostructured materials, especially porous materials for hydrogen generation from hydrolysis of ammonia borane. PMID:28793453

Electronic structure and magnetism of titanium substituted Cd3P2: An ab-initio study

NASA Astrophysics Data System (ADS)

Jaiganesh, G.; Jaya, S. Mathi

2018-05-01

Using the ab-initio computations that are based on the density functional theory, we have investigated the magnetism and electronic properties of one and two Ti atom substituted Cd3P2 compound. The magnetic stability of the substituted compounds was obtained by analyzing the minimum total energies in nonmagnetic, ferromagnetic and antiferromagnetic phases. Our results indicated the formation of magnetic order in one and two Ti atom substituted Cd3P2 as well as metallic characteristics in these systems. A significant value of the magnetic moment of Ti atom is observed from our calculations. We further find that the neighboring Cd and P atoms too acquire a small magnetic moment.

Tuning the Curie temperature of FeCo compounds by tetragonal distortion

NASA Astrophysics Data System (ADS)

Jakobsson, A.; Şaşıoǧlu, E.; Mavropoulos, Ph.; Ležaić, M.; Sanyal, B.; Bihlmayer, G.; Blügel, S.

2013-09-01

Combining density-functional theory calculations with a classical Monte Carlo method, we show that for B2-type FeCo compounds, tetragonal distortion gives rise to a strong reduction of the Curie temperature TC. The TC monotonically decreases from 1575 K (for c /a=1) to 940 K (for c /a=√2 ). We find that the nearest neighbor Fe-Co exchange interaction is sufficient to explain the c/a behavior of the TC. Combination of high magnetocrystalline anisotropy energy with a moderate TC value suggests tetragonal FeCo grown on the Rh substrate with c /a=1.24 to be a promising material for heat-assisted magnetic recording applications.

Quantum mechanical study of the structure and spectroscopic (FT-IR, FT-Raman, 13C, 1H and UV), first order hyperpolarizabilities, NBO and TD-DFT analysis of the 4-methyl-2-cyanobiphenyl

NASA Astrophysics Data System (ADS)

Sebastian, S.; Sundaraganesan, N.; Karthikeiyan, B.; Srinivasan, V.

2011-02-01

The Fourier transform infrared (FT-IR) and FT-Raman of 4-methyl-2-cyanobiphenyl (4M2CBP) have been recorded and analyzed. The equilibrium geometry, bonding features and harmonic vibrational frequencies have been investigated with the help of density functional theory (DFT) method. 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 methodology (SQMFF). The 1H and 13C nuclear magnetic resonance (NMR) chemical shifts of the molecule were calculated by the Gauge including atomic orbital (GIAO) method. The first order hyperpolarizability ( β0) of this novel molecular system and related properties ( β, α0 and Δ α) of 4M2CBP are calculated using HF/6-311G(d,p) method on the finite-field approach. Stability of the molecule arising from hyperconjugative interactions, charge delocalization have been analyzed using natural bond orbital (NBO) analysis. The results show that charge in electron density (ED) in the σ* and π* antibonding orbitals and second order delocalization energies ( E2) confirms the occurrence of intramolecular charge transfer (ICT) within the molecule. UV-vis spectrum of the compound was recorded and the electronic properties, such as HOMO and LUMO energies, were performed by time-dependent density functional theory (TD-DFT) approach. Finally the calculations results were applied to simulated infrared and Raman spectra of the title compound which show good agreement with observed spectra.

DFT study of the effect of substitution on the molecular structure of copper phthalocyanine

NASA Astrophysics Data System (ADS)

Kaur, Prabhjot; Sachdeva, Ritika; Singh, Sukhwinder; Saini, G. S. S.

2016-05-01

To study the effect of sulfonic acid group as substituent on the molecular structure of an organic compound copper Phthalocyanine, the optimized geometry, mulliken charges, energies and dipole momemts of copper phthalocyanine and copper phthalocyaninetetrasulfonic acid tetra sodium salt have been investigated using density functional theory. Also to predict the change in reactive sites after substitution, molecular electrostatic potential maps for both the molecules have been calculated.

Comparative Ab-Initio Study of Substituted Norbornadiene-Quadricyclane Compounds for Solar Thermal Storage.

PubMed

Kuisma, Mikael J; Lundin, Angelica M; Moth-Poulsen, Kasper; Hyldgaard, Per; Erhart, Paul

2016-02-25

Molecular photoswitches that are capable of storing solar energy, so-called molecular solar thermal storage systems, are interesting candidates for future renewable energy applications. In this context, substituted norbornadiene-quadricyclane systems have received renewed interest due to recent advances in their synthesis. The optical, thermodynamic, and kinetic properties of these systems can vary dramatically depending on the chosen substituents. The molecular design of optimal compounds therefore requires a detailed understanding of the effect of individual substituents as well as their interplay. Here, we model absorption spectra, potential energy storage, and thermal barriers for back-conversion of several substituted systems using both single-reference (density functional theory using PBE, B3LYP, CAM-B3LYP, M06, M06-2x, and M06-L functionals as well as MP2 calculations) and multireference methods (complete active space techniques). Already the diaryl substituted compound displays a strong red-shift compared to the unsubstituted system, which is shown to result from the extension of the conjugated π-system upon substitution. Using specific donor/acceptor groups gives rise to a further albeit relatively smaller red-shift. The calculated storage energy is found to be rather insensitive to the specific substituents, although solvent effects are likely to be important and require further study. The barrier for thermal back-conversion exhibits strong multireference character and as a result is noticeably correlated with the red-shift. Two possible reaction paths for the thermal back-conversion of diaryl substituted quadricyclane are identified and it is shown that among the compounds considered the path via the acceptor side is systematically favored. Finally, the present study establishes the basis for high-throughput screening of norbornadiene-quadricyclane compounds as it provides guidelines for the level of accuracy that can be expected for key properties from several different techniques.

Partition coefficients of methylated DNA bases obtained from free energy calculations with molecular electron density derived atomic charges.

PubMed

Lara, A; Riquelme, M; Vöhringer-Martinez, E

2018-05-11

Partition coefficients serve in various areas as pharmacology and environmental sciences to predict the hydrophobicity of different substances. Recently, they have also been used to address the accuracy of force fields for various organic compounds and specifically the methylated DNA bases. In this study, atomic charges were derived by different partitioning methods (Hirshfeld and Minimal Basis Iterative Stockholder) directly from the electron density obtained by electronic structure calculations in a vacuum, with an implicit solvation model or with explicit solvation taking the dynamics of the solute and the solvent into account. To test the ability of these charges to describe electrostatic interactions in force fields for condensed phases, the original atomic charges of the AMBER99 force field were replaced with the new atomic charges and combined with different solvent models to obtain the hydration and chloroform solvation free energies by molecular dynamics simulations. Chloroform-water partition coefficients derived from the obtained free energies were compared to experimental and previously reported values obtained with the GAFF or the AMBER-99 force field. The results show that good agreement with experimental data is obtained when the polarization of the electron density by the solvent has been taken into account, and when the energy needed to polarize the electron density of the solute has been considered in the transfer free energy. These results were further confirmed by hydration free energies of polar and aromatic amino acid side chain analogs. Comparison of the two partitioning methods, Hirshfeld-I and Minimal Basis Iterative Stockholder (MBIS), revealed some deficiencies in the Hirshfeld-I method related to the unstable isolated anionic nitrogen pro-atom used in the method. Hydration free energies and partitioning coefficients obtained with atomic charges from the MBIS partitioning method accounting for polarization by the implicit solvation model are in good agreement with the experimental values. © 2018 Wiley Periodicals, Inc. © 2018 Wiley Periodicals, Inc.

Predictions of the physicochemical properties of amino acid side chain analogs using molecular simulation.

PubMed

Ahmed, Alauddin; Sandler, Stanley I

2016-03-07

A candidate drug compound is released for clinical trails (in vivo activity) only if its physicochemical properties meet desirable bioavailability and partitioning criteria. Amino acid side chain analogs play vital role in the functionalities of protein and peptides and as such are important in drug discovery. We demonstrate here that the predictions of solvation free energies in water, in 1-octanol, and self-solvation free energies computed using force field-based expanded ensemble molecular dynamics simulation provide good accuracy compared to existing empirical and semi-empirical methods. These solvation free energies are then, as shown here, used for the prediction of a wide range of physicochemical properties important in the assessment of bioavailability and partitioning of compounds. In particular, we consider here the vapor pressure, the solubility in both water and 1-octanol, and the air-water, air-octanol, and octanol-water partition coefficients of amino acid side chain analogs computed from the solvation free energies. The calculated solvation free energies using different force fields are compared against each other and with available experimental data. The protocol here can also be used for a newly designed drug and other molecules where force field parameters and charges are obtained from density functional theory.

Adsorption of alanine with heteroatom substituted fullerene for solar cell application: A DFT study.

PubMed

Dheivamalar, S; Sugi, L; Ravichandran, K; Sriram, S

2018-09-05

C 20 is the most important fullerene cage and alanine is the simplest representation of a backbone unit of the protein. The absorption feasibility of alanine molecule in the Si-doped C 20 and B-doped C 20 fullerenes has been studied based on calculated electronic properties of fullerenes using density functional theory (DFT). In this work, we explore the ability of Si-doped C 20 , B-doped C 20 fullerene to interact with alanine at the DFT-B3LYP/6-31G, RHF level of theory. We find that noticeable structural change takes place in C 20 when one of its carbon is substituted with Si or B. The molecular geometry, electronic properties and vibrational analysis have also been performed on the title compounds. The NMR study reveals the aromaticity of the pure and doped fullerene compounds. Stability of the doped fullerene - alanine compound arises from hyper conjugative interactions. It leads to one of the major property of bioactivity, charge transfer and delocalization of charge and this properties has been analyzed using Natural Bond Orbital (NBO) analysis. The energy gap of the doped fullerene reveals that there is a decrease in the size of energy gap significantly, making them more reactive as compared to C 20 fullerene. Theoretical studies of the electronic spectra by using time - dependent density functional theory (TD-DFT) method were helpful to interpret the observed electronic transition state. We aim to optimize the performance of the solar cells by altering the frontier orbital energy gaps. Considering all studied properties, it may be inferred that the applicability of C 20 fullerene as the non-linear optical (NLO) material and its NLO property would increase on doping fullerene with Si and B atom. Specifically C 19 Si would be better among them. Copyright © 2018. Published by Elsevier B.V.

Design, synthesis, α-glucosidase inhibitory activity, molecular docking and QSAR studies of benzimidazole derivatives

NASA Astrophysics Data System (ADS)

Dinparast, Leila; Valizadeh, Hassan; Bahadori, Mir Babak; Soltani, Somaieh; Asghari, Behvar; Rashidi, Mohammad-Reza

2016-06-01

In this study the green, one-pot, solvent-free and selective synthesis of benzimidazole derivatives is reported. The reactions were catalyzed by ZnO/MgO containing ZnO nanoparticles as a highly effective, non-toxic and environmentally friendly catalyst. The structure of synthesized benzimidazoles was characterized using spectroscopic technics (FT-IR, 1HNMR, 13CNMR). Synthesized compounds were evaluated for their α-glucosidase inhibitory potential. Compounds 3c, 3e, 3l and 4n were potent inhibitors with IC50 values ranging from 60.7 to 168.4 μM. In silico studies were performed to explore the binding modes and interactions between enzyme and synthesized benzimidazoles. Developed linear QSAR model based on density and molecular weight could predict bioactivity of newly synthesized compounds well. Molecular docking studies revealed the availability of some hydrophobic interactions. In addition, the bioactivity of most potent compounds had good correlation with estimated free energy of binding (ΔGbinding) which was calculated according to docked best conformations.

Structural, vibrational, and electronic properties of an uncoordinated pseudoephedrine derivative and its mononuclear and trinuclear copper(II)-coordinated compounds: A combined theoretical and experimental study

NASA Astrophysics Data System (ADS)

Valencia, Israel; Ávila-Torres, Yenny; Barba-Behrens, Norah; Garzón, Ignacio L.

2014-11-01

Multicopper oxidases are fundamental in a variety of biological processes in bacteria, fungi and vertebrates. The catalytic center in these enzymes is formed basically by three copper ions, bridged by oxygen bonds. In order to get insights into the reactivity of these complex systems, biomimetic compounds are usually synthesized. Accordingly, in this work, we studied structural, vibrational, and electronic properties of an uncoordinated pseudoephedrine derivative, as well as its corresponding mononuclear and trinuclear copper(II)-coordinated complexes by means of density functional theory. The calculations are compared with experimental results using measurements of the infrared spectra. It is obtained that the molecular configuration of the pseudoephedrine amino-alcohol derivative is stabilized by hydrogen bonding Osbnd H⋯N and by Csbnd H⋯π interactions that are not present in the mononuclear and trinuclear compounds. The coordination compounds show octahedral and square pyramid geometries, respectively, which are slightly distorted by Jahn-Teller effects. The analysis of their theoretical and experimental IR spectra reveals signals related with hydrogen bonding as well as metal-ligand vibrational modes. Regarding the electronic structure, the density of states was calculated in order to analyze the atomic orbital contributions present in these compounds. This analysis would provide useful insights about the optical behavior, for example, in the visible region of the spectrum of the coordinated compounds. At these energies, the optical absorption would be influenced by the orbital interaction of the Cu2+d orbitals with sp ones of the ligand, reflecting a decrease of the HOMO-LUMO gap of the organic ligand due to the presence of the copper(II) ions.

X-ray photoelectron spectrum and electronic properties of a noncentrosymmetric chalcopyrite compound HgGa(2)S(4): LDA, GGA, and EV-GGA.

PubMed

Reshak, Ali Hussain; Khenata, R; Kityk, I V; Plucinski, K J; Auluck, S

2009-04-30

An all electron full potential linearized augmented plane wave method has been applied for a theoretical study of the band structure, density of states, and electron charge density of a noncentrosymmetric chalcopyrite compound HgGa(2)S(4) using three different approximations for the exchange correlation potential. Our calculations show that the valence band maximum (VBM) and conduction band minimum (CBM) are located at Gamma resulting in a direct energy gap of about 2.0, 2.2, and 2.8 eV for local density approximation (LDA), generalized gradient approximation (GGA), and Engel-Vosko (EVGGA) compared to the experimental value of 2.84 eV. We notice that EVGGA shows excellent agreement with the experimental data. This agreement is attributed to the fact that the Engel-Vosko GGA formalism optimizes the corresponding potential for band structure calculations. We make a detailed comparison of the density of states deduced from the X-ray photoelectron spectra with our calculations. We find that there is a strong covalent bond between the Hg and S atoms and Ga and S atoms. The Hg-Hg, Ga-Ga, and S-S bonds are found to be weaker than the Hg-S and Ga-S bonds showing that a covalent bond exists between Hg and S atoms and Ga and S atoms.

Electronic and optical properties of the LiCdX (X = N, P, As and Sb) filled-tetrahedral compounds with the Tran–Blaha modified Becke–Johnson density functional

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

Bouhemadou, A., E-mail: a_bouhemadou@yahoo.fr; Bin-Omran, S.; Department of Physics, Faculty of Science & Humanitarian Studies, Salman Bin Abdalaziz University, Alkharj 11942

Highlights: • Electronic and optical properties of the LiCdX compounds have been predicted. • Tran–Blaha-modified Becke–Johnson functional significantly improves the band gap. • We predict a direct band gap in all of the considered LiCdX compounds. • Origin of the peaks in the optical spectra is determined. - Abstract: The structural, electronic and optical properties of the LiCdN, LiCdP, LiCdAs and LiCdSb filled-tetrahedral compounds have been explored from first-principles. The calculated structural parameters are consistent with the available experimental results. Since DFT with the common LDA and GGA underestimates the band gap, we use a new developed functional able tomore » accurately describe the electronic structure of semiconductors, namely the Tran–Blaha-modified Becke–Johnson potential. The four investigated compounds demonstrate semiconducting behavior with direct band gap ranging from about 0.32 to 1.65 eV. The charge-carrier effective masses are evaluated at the topmost valence band and at the bottommost conduction band. The evolution of the value and nature of the energy band gap under pressure effect is also investigated. The frequency-dependent complex dielectric function and some macroscopic optical constants are estimated. The microscopic origins of the structures in the optical spectra are determined in terms of the calculated energy band structures.« less

Topological analysis (BCP) of vibrational spectroscopic studies, docking, RDG, DSSC, Fukui functions and chemical reactivity of 2-methylphenylacetic acid

NASA Astrophysics Data System (ADS)

Kavimani, M.; Balachandran, V.; Narayana, B.; Vanasundari, K.; Revathi, B.

2018-02-01

Experimental FT-IR and FT-Raman spectra of 2-methylphenylacetic acid (MPA) were recorded and theoretical values are also analyzed. The non-linear optical (NLO) properties were evaluated by determination of first (5.5053 × 10- 30 e.s.u.) and second hyper-polarizabilities (7.6833 × 10- 36 e.s.u.) of the title compound. The Multiwfn package is used to find the weak non-covalent interaction (Van der Wall interaction) and strong repulsion (steric effect) of the molecule and examined by reduced density gradient. The molecular electrostatic potential (MEP) analysis used to find the most reactive sites for the electrophilic and nucleophilic attack. The chemical activity (electronegativity, hardness, chemical softness and chemical potential) of the title compound was predicted with the help of HOMO-LUMO energy values. The natural bond orbital (NBO) has been analyzed the stability of the molecule arising from the hyper-conjugative interaction. DSSCs were discussed in structural modifications that improve the electron injection efficiency of the title compound (MPA). The Fukui functions are calculated in order to get information associated with the local reactivity properties of the title compound. The binding sites of the two receptors were reported by molecular docking field and active site bond distance is same 1.9 Å. The inhibitor of the title compound forms a stable complex with 1QYV and 2H1K proteins at the binding energies are - 5.38 and - 5.85 (Δ G in kcal/mol).

Investigation of structural, electronic, elastic and optical properties of Cd{sub 1-x-y}Zn{sub x}Hg{sub y}Te alloys

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

Tamer, M., E-mail: mehmet.tamer@zirve.edu.tr

2016-06-15

Structural, optical and electronic properties and elastic constants of Cd1{sub -x-y}Zn{sub x} Hg{sub y}Te alloys have been studied by employing the commercial code Castep based on density functional theory. The generalized gradient approximation and local density approximation were utilized as exchange correlation. Using elastic constants for compounds, bulk modulus, band gap, Fermi energy and Kramers–Kronig relations, dielectric constants and the refractive index have been found through calculations. Apart from these, X-ray measurements revealed elastic constants and Vegard’s law. It is seen that results obtained from theory and experiments are all in agreement.

Symbolic computation of the Hartree-Fock energy from a chiral EFT three-nucleon interaction at N 2LO

NASA Astrophysics Data System (ADS)

Gebremariam, B.; Bogner, S. K.; Duguet, T.

2010-06-01

We present the first of a two-part Mathematica notebook collection that implements a symbolic approach for the application of the density matrix expansion (DME) to the Hartree-Fock (HF) energy from a chiral effective field theory (EFT) three-nucleon interaction at N 2LO. The final output from the notebooks is a Skyrme-like energy density functional that provides a quasi-local approximation to the non-local HF energy. In this paper, we discuss the derivation of the HF energy and its simplification in terms of the scalar/vector-isoscalar/isovector parts of the one-body density matrix. Furthermore, a set of steps is described and illustrated on how to extend the approach to other three-nucleon interactions. Program summaryProgram title: SymbHFNNN Catalogue identifier: AEGC_v1_0 Program summary URL:http://cpc.cs.qub.ac.uk/summaries/AEGC_v1_0.html Program obtainable from: CPC Program Library, Queen's University, Belfast, N. Ireland Licensing provisions: Standard CPC licence, http://cpc.cs.qub.ac.uk/licence/licence.html No. of lines in distributed program, including test data, etc.: 96 666 No. of bytes in distributed program, including test data, etc.: 378 083 Distribution format: tar.gz Programming language: Mathematica 7.1 Computer: Any computer running Mathematica 6.0 and later versions Operating system: Windows Xp, Linux/Unix RAM: 256 Mb Classification: 5, 17.16, 17.22 Nature of problem: The calculation of the HF energy from the chiral EFT three-nucleon interaction at N 2LO involves tremendous spin-isospin algebra. The problem is compounded by the need to eventually obtain a quasi-local approximation to the HF energy, which requires the HF energy to be expressed in terms of scalar/vector-isoscalar/isovector parts of the one-body density matrix. The Mathematica notebooks discussed in this paper solve the latter issue. Solution method: The HF energy from the chiral EFT three-nucleon interaction at N 2LO is cast into a form suitable for an automatic simplification of the spin-isospin traces. Several Mathematica functions and symbolic manipulation techniques are used to obtain the result in terms of the scalar/vector-isoscalar/isovector parts of the one-body density matrix. Running time: Several hours

Electricity Generation in Microbial Fuel Cell (MFC) by Bacterium Isolated from Rice Paddy Field Soil

NASA Astrophysics Data System (ADS)

Fakhirruddin, Fakhriah; Amid, Azura; Salim, Wan Wardatul Amani Wan; Suhaida Azmi, Azlin

2018-03-01

Microbial fuel cell (MFC) is an alternative approach in generating renewable energy by utilising bacteria that will oxidize organic or inorganic substrates, producing electrons yielded as electrical energy. Different species of exoelectrogenic bacteria capable of generating significant amount of electricity in MFC has been identified, using various organic compounds for fuel. Soil sample taken from rice paddy field is proven to contain exoelectrogenic bacteria, thus electricity generation using mixed culture originally found in the soil, and pure culture isolated from the soil is studied. This research will isolate the exoelectrogenic bacterial species in the rice paddy field soil responsible for energy generation. Growth of bacteria isolated from the MFC is observed by measuring the optical density (OD), cell density weight (CDW) and viable cell count. Mixed bacterial species found in paddy field soil generates maximum power of 77.62 μW and 0.70 mA of current. In addition, the research also shows that the pure bacterium in rice paddy field soil can produce maximum power and current at 51.32 μW and 0.28 mA respectively.

Molecular structure and spectroscopic characterization of Carbamazepine with experimental techniques and DFT quantum chemical calculations

NASA Astrophysics Data System (ADS)

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

2015-04-01

A systematic vibrational spectroscopic assignment and analysis of Carbamazepine has been carried out by using FT-IR, FT-Raman and UV spectral data. The vibrational analysis were aided by electronic structure calculations - ab initio (RHF) and hybrid density functional methods (B3LYP) performed with standard basis set 6-31G(d,p). Molecular equilibrium geometries, electronic energies, natural bond order analysis, harmonic vibrational frequencies and IR intensities have been computed. A detailed interpretation of the vibrational spectra of the molecule has been made on the basis of the calculated Potential Energy Distribution (PED) by VEDA program. UV-visible spectrum of the compound was also recorded and the electronic properties, such as HOMO and LUMO energies and λmax were determined by HF/6-311++G(d,p) Time-Dependent method. The thermodynamic functions of the title molecule were also performed using the RHF and DFT methods. The restricted Hartree-Fock and density functional theory-based nuclear magnetic resonance (NMR) calculation procedure was also performed, and it was used for assigning the 13C and 1H NMR chemical shifts of Carbamazepine.

Self-diffusion in MgO--a density functional study.

PubMed

Runevall, Odd; Sandberg, Nils

2011-08-31

Density functional theory calculations have been performed to study self-diffusion in magnesium oxide, a model material for a wide range of ionic compounds. Formation energies and entropies of Schottky defects and divacancies were obtained by means of total energy and phonon calculations in supercell configurations. Transition state theory was used to estimate defect migration rates, with migration energies taken from static calculations, and the corresponding frequency factors estimated from the phonon spectrum. In all static calculations we corrected for image effects using either a multipole expansion or an extrapolation to the low concentration limit. It is shown that both methods give similar results. The results for self-diffusion of Mg and O confirm the previously established picture, namely that in materials of nominal purity, Mg diffuses extrinsically by a single vacancy mechanism, while O diffuses intrinsically by a divacancy mechanism. Quantitatively, the current results are in very good agreement with experiments concerning O diffusion, while for Mg the absolute diffusion rate is generally underestimated by a factor of 5-10. The reason for this discrepancy is discussed.

Electronic structures of Plutonium compounds with the NaCl-type monochalcogenides structure

NASA Astrophysics Data System (ADS)

Maehira, Takahiro; Tatetsu, Yasutomi

2012-12-01

We calculate the energy band structure and the Fermi surface of PuS, PuSe and PuTe by using a self-consistent relativistic linear augmented-plane-wave method with the exchange and correlation potential in a local density approximation. It is found in common that the energy bands in the vicinity of the Fermi level are mainly due to the hybridization between Pu 5/ and monochalcogenide p electrons. The obtained main Fermi surfaces are composed of two hole sheets and one electron sheet, all of which are constructed from the band having the Pu 5/ state and the monochalcogenide p state.

Voltage clustering in redox-active ligand complexes: mitigating electronic communication through choice of metal ion

DOE PAGES

Zarkesh, Ryan A.; Ichimura, Andrew S.; Monson, Todd C.; ...

2016-02-01

We used the redox-active bis(imino)acenapthene (BIAN) ligand to synthesize homoleptic aluminum, chromium, and gallium complexes of the general formula (BIAN) 3M. The resulting compounds were characterized using X-ray crystallography, NMR, EPR, magnetic susceptibility and cyclic voltammetry measurements and modeled using both DFT and ab initio wavefunction calculations to compare the orbital contributions of main group elements and transition metals in ligand-based redox events. Ultimately, complexes of this type have the potential to improve the energy density and electrolyte stability of grid-scale energy storage technologies, such as redox flow batteries, through thermodynamically-clustered redox events.

DFT calculations, spectroscopy and antioxidant activity studies on (E)-2-nitro-4-[(phenylimino)methyl]phenol

NASA Astrophysics Data System (ADS)

Temel, Ersin; Alaşalvar, Can; Gökçe, Halil; Güder, Aytaç; Albayrak, Çiğdem; Alpaslan, Yelda Bingöl; Alpaslan, Gökhan; Dilek, Nefise

2015-02-01

We have reported synthesis and characterization of (E)-2-nitro-4-[(phenylimino)methyl]phenol by using X-ray crystallographic method, FT-IR and UV-vis spectroscopies and density functional theory (DFT). Optimized geometry and vibrational frequencies of the title compound in the ground state have been computed by using B3LYP with the 6-311G+(d,p) basis set. HOMO-LUMO energy gap, Non-linear optical properties and NBO analysis of the compound are performed at B3LYP/6-311G+(d,p) level. Additionally, as remarkable properties, antioxidant activity of the title compound (CMPD) has been determined by using different antioxidant test methods i.e. ferric reducing antioxidant power (FRAP), hydrogen peroxide scavenging (HPSA), free radical scavenging (FRSA) and ferrous ion chelating activities (FICA). When compared with standards (BHA, BHT, and α-tocopherol), we have concluded that CPMD has effective FRAP, HPSA, FRSA and FICA.

RADIATION DOSIMETER

DOEpatents

Balkwell, W.R. Jr.; Adams, G.D. Jr.

1960-05-10

An improvement was made in the determination of amounts of ionizing radiation, particularly low-energy beta particles of less than 1000 rad total dose by means of fluid-phase dosimeter employing a stabilized-- sensitized ferrous-ferric colorimetric system in a sulphuric acid medium. The improvement in the dosimeter consists of adding to the ferrous-ferric system in concentrations of 10/sub -2/ to 10/sup -4/M an organic compound having one or more carboxylic or equivalent groups, such compounds being capable of chelating or complexing the iron ions in the solution. Suitable sensitizing and stabilizing agents are benzoic, phthalic, salicylic, malonic, lactic, maleic, oxalic, citric, succinic, phenolic tartaric, acetic, and adipic acid, as well as other compounds which are added to the solution alone or in certain combinations. As in conventional fluid-phase dosimeters, the absorbed dosage is correlated with a corresponding change in optical density at particular wavelengths of the solution.

Defect structures in ordered intermetallics; grain boundaries and surfaces in FeAl, NiAl, CoAl and TiAl

NASA Astrophysics Data System (ADS)

Mutasa, Batsirai Manyara

Ordered intermetallics based on transition metal aluminides have been proposed as structural materials for advanced aerospace applications. The development of these materials, which have the advantages of low density and high operating temperatures, have been focused on the aluminides of titanium, nickel and iron. Though these materials exhibit attractive properties at elevated temperatures, their utilization is limited due to their propensity for low temperature fracture and susceptibility to decreased ductility due to environmental effects. A major embrittlement mechanism at ambient temperatures in these aluminides has been by the loss of cohesive strength at the interfaces (intergranular failure). This study focuses on this mechanism of failure, by undertaking a systematic study of the energies and structures of specific grain boundaries in some of these compounds. The relaxed atomistic grain boundary structures in B2 aluminides, FeAl, NiAl and CoAl and L10 gamma-TiAl were investigated using molecular statics and embedded atom potentials in order to explore general trends for a series of B2 compounds as well as TiAl. The potentials used correctly predict the proper mechanism of compositional disorder of these compounds. Using these potentials, point defects, free surface energies and various grain boundary structures of similar energies in three B2 compounds, FeAl, NiAl and CoAl were studied. These B2 alloys exhibited increasing anti-phase boundary energies respectively. The misorientations chosen for detailed study correspond to the Sigma5(310) and Sigma5(210) boundaries. These boundaries were investigated with consideration given to possible variations in the local chemical composition. The effects of both boundary stoichiometry and bulk stoichiometry on grain boundary energetics were also considered. Defect energies were calculated for boundaries contained in both stoichiometric and off-stoichiometric bulk. The surface energies for these aluminides were also calculated so that trends concerning the cohesive energy of the boundaries could be studied. The implications of stoichiometry, the multiplicity of the boundary structures and possible transformations between them for grain boundary brittleness are also discussed.

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

Kuechler, Erich R.; Department of Chemistry, University of Minnesota, Minneapolis, Minnesota 55455-0431; Giese, Timothy J.

To better represent the solvation effects observed along reaction pathways, and of ionic species in general, a charge-dependent variable-radii smooth conductor-like screening model (VR-SCOSMO) is developed. This model is implemented and parameterized with a third order density-functional tight binding quantum model, DFTB3/3OB-OPhyd, a quantum method which was developed for organic and biological compounds, utilizing a specific parameterization for phosphate hydrolysis reactions. Unlike most other applications with the DFTB3/3OB model, an auxiliary set of atomic multipoles is constructed from the underlying DFTB3 density matrix which is used to interact the solute with the solvent response surface. The resulting method is variational,more » produces smooth energies, and has analytic gradients. As a baseline, a conventional SCOSMO model with fixed radii is also parameterized. The SCOSMO and VR-SCOSMO models shown have comparable accuracy in reproducing neutral-molecule absolute solvation free energies; however, the VR-SCOSMO model is shown to reduce the mean unsigned errors (MUEs) of ionic compounds by half (about 2-3 kcal/mol). The VR-SCOSMO model presents similar accuracy as a charge-dependent Poisson-Boltzmann model introduced by Hou et al. [J. Chem. Theory Comput. 6, 2303 (2010)]. VR-SCOSMO is then used to examine the hydrolysis of trimethylphosphate and seven other phosphoryl transesterification reactions with different leaving groups. Two-dimensional energy landscapes are constructed for these reactions and calculated barriers are compared to those obtained from ab initio polarizable continuum calculations and experiment. Results of the VR-SCOSMO model are in good agreement in both cases, capturing the rate-limiting reaction barrier and the nature of the transition state.« less

DFT Predictions of Electronic, Transport, and Bulk Properties of Cubic Antifluorite A2B Compounds (A = Li, Na, B = O,S,Se)

NASA Astrophysics Data System (ADS)

Malozovsky, Yuriy; Franklin, Lashounda; Bagayoko, Diola

We present results from ab-initio,self-consistent calculations of electronic, transport, and bulk properties of cubic antifluorite (anti-CaF2) compounds A2B (A = Li, Na, B = O, S, Se). Our computations employed the local density approximation (LDA) potential of Ceperley and Alder and the linear combination of atomic orbital (LCAO) formalism. The implementation of the LCAO formalism followed the Bagayoko, Zhao, and Williams method, as enhanced by Ekuma and Franklin (BZW-EF). Consequently, our calculations search for and attained the ground states of the systems under study, as required by DFT; our results therefore possess the full, physical content of DFT. We discuss band structures, band gaps, and related properties of these materials, including calculated, total and partial densities of states (DOS and PDOS), effective masses of charge carriers, equilibrium lattice constants, and the bulk moduli of cubic antifluorite compounds A2B (A = Li, Na, B = O, S, Se). Our results are predictions in some cases, due to the lack of experimental data. Work funded in part by the US Department of Energy (DOE), National Nuclear Security Administration (NNSA) (Award No.DE-NA0002630), the National Science Foundation (NSF) (Award No, 1503226), LaSPACE, and LONI-SUBR.

Theoretical studies on 2-diazo-4,6-dinitrophenol derivatives aimed at finding superior propellants.

PubMed

Liu, Yan; Wang, Lianjun; Wang, Guixiang; Du, Hongchen; Gong, Xuedong

2012-04-01

In an attempt to find superior propellants, 2-diazo-4,6-dinitrophenol (DDNP) and its -NO(2), -NH(2), -CN, -NC, -ONO(2), and -NF(2) derivatives were studied at the B3LYP/6-311++G level of density functional theory (DFT). Sensitivity was evaluated using bond dissociation enthalpies (BDEs) and molecular surface electrostatic potentials. The C-NO(2) bond appears to be the trigger bond during the thermolysis process for these compounds, except for the -ONO(2) and -NF(2) derivatives. Electrostatic potential results show that electron-withdrawing substituents make the charge imbalance more anomalous, which may change the strength of the bond, especially the weakest trigger bond. Most of the DDNP derivatives have the impact sensitivities that are higher than that of DDNP, making them favorable for use as solid propellants in micro-rockets. The theoretical densities (ρ), heats of formation (HOFs), detonation energies (Q), detonation pressures (P), and detonation velocities (D) of the compounds were estimated. The effects of various substituent groups on ρ, HOF, Q, D, and P were investigated. Some derivatives exhibit perfect detonation properties. The calculated relative specific impulses (I (r,sp)) of all compounds except for -NH(2) derivatives were higher than that of DDNP, and also meet the requirements of propellants.

The structural diversity of ABS{sub 3} compounds with d{sup 0} electronic configuration for the B-cation

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

Brehm, John A., E-mail: brehmj@sas.upenn.edu; Bennett, Joseph W.; Schoenberg, Michael Rutenberg

2014-06-14

We use first-principles density functional theory within the local density approximation to ascertain the ground state structure of real and theoretical compounds with the formula ABS{sub 3} (A = K, Rb, Cs, Ca, Sr, Ba, Tl, Sn, Pb, and Bi; and B = Sc, Y, Ti, Zr, V, and Nb) under the constraint that B must have a d{sup 0} electronic configuration. Our findings indicate that none of these AB combinations prefer a perovskite ground state with corner-sharing BS{sub 6} octahedra, but that they prefer phases with either edge- or face-sharing motifs. Further, a simple two-dimensional structure field map createdmore » from A and B ionic radii provides a neat demarcation between combinations preferring face-sharing versus edge-sharing phases for most of these combinations. We then show that by modifying the common Goldschmidt tolerance factor with a multiplicative term based on the electronegativity difference between A and S, the demarcation between predicted edge-sharing and face-sharing ground state phases is enhanced. We also demonstrate that, by calculating the free energy contribution of phonons, some of these compounds may assume multiple phases as synthesis temperatures are altered, or as ambient temperatures rise or fall.« less

Adsorption properties of polar/apolar inducers at a charged interface and their relevance to leukemia cell differentiation.

PubMed

Carlà, M; Cuomo, M; Arcangeli, A; Olivotto, M

1995-06-01

The interfacial adsorption properties of polar/apolar inducers of cell differentiation (PAIs) were studied on a mercury electrode. This study, on a clean and reproducible charged surface, unraveled the purely physical interactions among these compounds and the surface, apart from the complexity of the biological membrane. The interfacial behavior of two classical inducers, hexamethylenebisacetamide (HMBA) and dimethylsulfoxide, was compared with that of a typical apolar aliphatic compound, 1-octanol, that has a similar hydrophobic moiety as HMBA but a much smaller dipolar moment. Both HMBA and Octanol adsorb flat in contact with the surface because of hydrophobic forces, with a very similar free energy of adsorption. However, the ratio of polar to apolar moieties in PAIs turned out to be crucial to drive the adsorption maximum toward physiological values of surface charge density, where octanol is desorbed. The electrostatic effects in the interfacial region reflected the adsorption properties: the changes in the potential drop across the interfacial region as a function of the surface charge density, in the physiological range, were opposite in PAIs as compared with apolar aliphatic compounds, as exemplified by octanol. This peculiar electrostatic effect of PAIs has far-reaching relevance for the design of inducers with an adequate therapeutic index to be used in clinical trials.

Understanding the magnetoelastic behavior of pure and Co substituted GdNi

NASA Astrophysics Data System (ADS)

Paudyal, Durga; Mudryk, Y.; Pecharsky, V. K.; Gschneidner, K. A., Jr.

Total-energy calculations employing local spin density approximation including Hubbard U (onsite electron correlation) parameter and temperature and magnetic field dependent x-ray diffraction experiments show large anisotropic shifts in lattice parameters and a giant linear magnetostriction without a structural transformation and a negligible volume magnetostriction in GdNi. In agreement with the magnetization and heat-capacity experiments, the total-energy and band splitting results confirm that the anisotropic shape changes in GdNi are associated with the second-order ferromagnetic to paramagnetic transformation. When the band splitting due to the ferromagnetic ordering of the 4 fmoments increases, the concomitant anisotropic changes in the lattice minimize the total free energy of the crystal indicating an unusual interplay between magnetism and crystal structure. The positive formation energy at 0K and the nature of the density of states at the Fermi level confirm an unstable equiatomic Gd compound when Ni is fully substituted by Co. However, the enhanced effective exchange interactions with small Co substitutions increase the Curie temperature without losing the chemical stability. The Ames Laboratory is operated for the US DOE by Iowa State. This work was supported by the DOE, Office of Basic Energy Sciences, Materials Sciences Division under Contract No. DE-AC02-07CH11358.

First principles study on structural, electronic and optical properties of Ga1-xBxP ternary alloys (x = 0, 0.25, 0.5, 0.75 and 1)

NASA Astrophysics Data System (ADS)

Hoat, D. M.; Rivas Silva, J. F.; Méndez Blas, A.

2018-07-01

The structural, electronic and optical properties of GaP, BP binary compounds and their ternary alloys Ga1-xBxP (x = 0.25, 0.5 and 0.75) have been studied by full-potential linearized augmented plane wave (FP-LAPW) method within the framework of density functional theory (DFT) as implemented in WIEN2k package. Local density approximation (LDA) and generalized gradient approximation (GGA) as proposed by Perdew-Burke-Ernzerhof (PBE), Wu-Cohen (WC) and PBE for solid (PBESol) were used for treatment of exchange-correlation effect in calculations. Additionally, the Tran-Blaha modified Becke-Johnson (mBJ) potential was also employed for electronic and optical calculations due to that it gives very accurate band gap of solids. As B concentration increases, the lattice constant reduces and the energy band gap firstly decreases for small composition x and then it shows increasing trend until pure BP. Our results show that the indirect-direct band gap transition can be reached from x = 0.33. The linear optical properties, such as reflectivity, absorption coefficient, refractive index and optical conductivity of binary compounds and ternary alloys were derived from their calculated complex dielectric function in wide energy range up to 30 eV, and the alloying effect on these properties was also analyzed in detail.

Quantum chemical calculation (electronic and topologic) and experimental (FT-IR, FT-Raman and UV) analysis of isonicotinic acid N-oxide

NASA Astrophysics Data System (ADS)

Karaca, Caglar; Atac, Ahmet; Karabacak, Mehmet

2015-04-01

In this work, the molecular conformation, vibrational and electronic analysis of isonicotinic acid N-oxide (iso-NANO) were presented in 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. The geometry optimization and energies associated possible two conformers (Rot-I and Rot-II) were computed. The 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 obtained structures were analyzed with the Atoms in Molecules (AIMs) methodology. The computational results diagnose the most stable conformer of iso-NANO as the Rot-I form. Total density of state (TDOS) and partial density of state (PDOS) and also overlap population density of state (OPDOS) diagrams analysis for the most stable conformer (Rot-I) were calculated using the same method. Thermodynamic properties (heat capacity, entropy and enthalpy) of the title compound at different temperatures were calculated. As a result, the optimized geometry and calculated spectroscopic data show a good agreement with the experimental results.

Synthesis, spectral characterization and density functional theory exploration of 1-(quinolin-3-yl)piperidin-2-ol

NASA Astrophysics Data System (ADS)

Suresh, M.; Syed Ali Padusha, M.; Bharanidharan, S.; Saleem, H.; Dhandapani, A.; Manivarman, S.

2015-06-01

The experimental and theoretical vibrational frequencies of a newly synthesized compound, namely 1-(quinolin-3-yl)piperidin-2-ol (QPPO) are analyzed. The experimental FT-IR (4000-400 cm-1) and FT-Raman (4000-100 cm-1) of the molecule in solid phase have been recorded. The optimized molecular structure, vibrational assignments of QPPO have been investigated experimentally and theoretically using Gaussian03W software package. The stability of the molecule arising from hyper-conjugative interaction and charge delocalization has been analyzed using NBO analysis. The first order hyperpolarizability (β0) is calculated to find its character in non-linear optics. Gauge including atomic orbital (GIAO) method is used to calculate 1H NMR chemical shift calculations were carried out and compared with experimental data. The electronic properties like UV-Visible spectral analysis and HOMO-LUMO energies were reported. The energy gap shows that the charge transfer occurs within the molecule. Thermodynamic parameters of the title compound were calculated at various temperatures.

The thermodynamic scale of inorganic crystalline metastability

PubMed Central

Sun, Wenhao; Dacek, Stephen T.; Ong, Shyue Ping; Hautier, Geoffroy; Jain, Anubhav; Richards, William D.; Gamst, Anthony C.; Persson, Kristin A.; Ceder, Gerbrand

2016-01-01

The space of metastable materials offers promising new design opportunities for next-generation technological materials, such as complex oxides, semiconductors, pharmaceuticals, steels, and beyond. Although metastable phases are ubiquitous in both nature and technology, only a heuristic understanding of their underlying thermodynamics exists. We report a large-scale data-mining study of the Materials Project, a high-throughput database of density functional theory–calculated energetics of Inorganic Crystal Structure Database structures, to explicitly quantify the thermodynamic scale of metastability for 29,902 observed inorganic crystalline phases. We reveal the influence of chemistry and composition on the accessible thermodynamic range of crystalline metastability for polymorphic and phase-separating compounds, yielding new physical insights that can guide the design of novel metastable materials. We further assert that not all low-energy metastable compounds can necessarily be synthesized, and propose a principle of ‘remnant metastability’—that observable metastable crystalline phases are generally remnants of thermodynamic conditions where they were once the lowest free-energy phase. PMID:28138514

Compound Nucleus Reactions in LENR, Analogy to Uranium Fission

NASA Astrophysics Data System (ADS)

Hora, Heinrich; Miley, George; Philberth, Karl

2008-03-01

The discovery of nuclear fission by Hahn and Strassmann was based on a very rare microanalytical result that could not initially indicate the very complicated details of this most important process. A similarity is discussed for the low energy nuclear reactions (LENRs) with analogies to the yield structure found in measurements of uranium fission. The LENR product distribution measured earlier in a reproducible way in experiments with thin film electrodes and a high density deuteron concentration in palladium has several striking similarities with the uranium fission fragment yield curve.ootnotetextG.H. Miley and J.A. Patterson, J. New Energy 1, 11 (1996); G.H. Miley et al, Proc ICCF6, p. 629 (1997).This comparison is specifically focussed to the Maruhn-Greiner local maximum of the distribution within the large-scale minimum when the fission nuclei are excited. Implications for uranium fission are discussed in comparison with LENR relative to the identification of fission a hypothetical compound nuclear reaction via a element ^306X126 with double magic numbers.

A new look into the quantum chemical and spectroscopic investigations of 5-chloro-1-methyl-4-nitroimidazole.

PubMed

Arjunan, V; Raj, Arushma; Anitha, R; Mohan, S

2014-05-05

Optimised geometrical structural parameters, harmonic vibrational frequencies, natural bonding orbital analysis and frontier molecular orbitals are determined by B3LYP and B3PW91 methods. The exact geometry of 5-chloro-1-methyl-4-nitroimidazole is determined through conformational analysis. The experimentally observed infrared and Raman bands have been assigned and analysed. The (13)C and (1)H NMR chemical shifts of the compound are investigated. The total electron density and molecular electrostatic potentials are determined. The electrostatic potential (electron+nuclei) distribution, molecular shape, size and dipole moments of the molecule have been displayed. The energies of the frontier molecular orbitals and LUMO-HOMO energy gap are measured. The possible electronic transitions of the molecule are studied by TD-DFT method along with the UV-Visible spectrum. The structure-activity relationship of the compound is also investigated by conceptual DFT methods. Copyright © 2014 Elsevier B.V. All rights reserved.

All-solid-state deep ultraviolet laser for single-photon ionization mass spectrometry.

PubMed

Yuan, Chengqian; Liu, Xianhu; Zeng, Chenghui; Zhang, Hanyu; Jia, Meiye; Wu, Yishi; Luo, Zhixun; Fu, Hongbing; Yao, Jiannian

2016-02-01

We report here the development of a reflectron time-of-flight mass spectrometer utilizing single-photon ionization based on an all-solid-state deep ultraviolet (DUV) laser system. The DUV laser was achieved from the second harmonic generation using a novel nonlinear optical crystal KBe2BO3F2 under the condition of high-purity N2 purging. The unique property of this laser system (177.3-nm wavelength, 15.5-ps pulse duration, and small pulse energy at ∼15 μJ) bears a transient low power density but a high single-photon energy up to 7 eV, allowing for ionization of chemicals, especially organic compounds free of fragmentation. Taking this advantage, we have designed both pulsed nanospray and thermal evaporation sources to form supersonic expansion molecular beams for DUV single-photon ionization mass spectrometry (DUV-SPI-MS). Several aromatic amine compounds have been tested revealing the fragmentation-free performance of the DUV-SPI-MS instrument, enabling applications to identify chemicals from an unknown mixture.

Predicting the equilibrium solubility of solid polycyclic aromatic hydrocarbons and dibenzothiophene using a combination of MOSCED plus molecular simulation or electronic structure calculations

NASA Astrophysics Data System (ADS)

Phifer, Jeremy R.; Cox, Courtney E.; da Silva, Larissa Ferreira; Nogueira, Gabriel Gonçalves; Barbosa, Ana Karolyne Pereira; Ley, Ryan T.; Bozada, Samantha M.; O'Loughlin, Elizabeth J.; Paluch, Andrew S.

2017-06-01

Methods to predict the equilibrium solubility of non-electrolyte solids are important for the design of novel separation processes. Here we demonstrate how conventional molecular simulation free energy calculations or electronic structure calculations in a continuum solvent, here SMD or SM8, can be used to predict parameters for the MOdified Separation of Cohesive Energy Density (MOSCED) method. The method is applied to the solutes naphthalene, anthracene, phenanthrene, pyrene and dibenzothiophene, compounds of interested to the petroleum industry and for environmental remediation. Adopting the melting point temperature and enthalpy of fusion of these compounds from experiment, we are able to predict equilibrium solubilities. Comparing to a total of 422 non-aqueous and 193 aqueous experimental solubilities, we find the proposed method is able to well correlate the data. The use of MOSCED is additionally advantageous as it is a solubility parameter-based method useful for intuitive solvent selection and formulation.

Investigation of ionic transport in sodium scandium phosphate (NSP) and related compounds

NASA Astrophysics Data System (ADS)

Bhat, Kaustubh; Blügel, Stefan; Lustfeld, Hans

Sodium ionic conductors offer significant advantages for application in large scale energy storage systems. In this study, we investigate the different pathways available for sodium ion conduction in NSP and calculate energy barriers for ionic transport using Density Functional Theory (DFT) and the Nudged Elastic Band Method. We identify the structural parameters that reduce the energy barrier, by calculating the influence of positive and negative external pressure on the energy barrier. Lattice strain can be introduced by cation or anion substitution within the NASICON structure. We substitute the scandium atom with other trivalent atoms such as aluminium and yttrium, and calculate the resulting energy barriers. Sodium thiophosphate (Na3PS4) has previously shown about two orders of magnitude higher ionic conductivity than sodium phosphate (Na3PO4). We investigate the effect of substituting oxygen with sulphur in NSP. We acknowledge discussions with our experimental colleagues F. Tietz and M. Guin toward this work

Preparation, crystal structure and thermal decomposition kinetics of 1-(2,4-dinitrophenyl)azo-1-nitrocyclohexane

NASA Astrophysics Data System (ADS)

Yang, Desuo; Ma, Haixia; Hu, Rongzu; Song, Jirong; Zhao, Fengqi

2005-11-01

A new three-nitro-group compound of 1-(2,4-dinitrophenyl)azo-1-nitrocyclohexane was prepared by the reaction of cyclohexanone-2,4-dinitrophenylhydrazine with nitric oxide at ambient temperature. The single crystal structure has been determined by a four-circle X-ray diffractometer. The compound is monoclinic with space group P2(1)/ c and unit-cell parameters a=11.300(2) Å, b=12.993(2) Å, c=10.155(1) Å, β=98.33(1) o, F(000)=672, the unit-cell volume V=1475.2(5) Å 3, the molecule number in one unit-cell Z=4, the absorption coefficient μ=1.19 cm -1, the calculated density Dc=1.456 g cm -3. The exothermic decomposition reaction kinetics of the compound has been studied by DSC. The kinetic model function in differential form, apparent activation energy and pre-exponential constant of this reaction are (3/4)(1-α)[-ln(1-α)] 1/4, 123.88 kJ mol -1 and 10 11.49 s -1, respectively. The critical temperature of thermal explosion of the title compound is 161.15 oC and the entropy of activation (ΔS), enthalpy of activation (ΔH), and free energy of activation (ΔG) are -34.16 J mol -1 K -1, 115.7, and 130.48 kJ mol -1, respectively.

FT-IR, FT-Raman and NMR characterization of 2-isopropyl-5-methylcyclohexyl quinoline-2-carboxylate and investigation of its reactive and optoelectronic properties by molecular dynamics simulations and DFT calculations

NASA Astrophysics Data System (ADS)

Menon, Vidya V.; Fazal, Edakot; Mary, Y. Sheena; Panicker, C. Yohannan; Armaković, Stevan; Armaković, Sanja J.; Nagarajan, Subban; Van Alsenoy, C.

2017-01-01

The FT-IR and FT-Raman spectra of the synthesized compound, 2-isopropyl-5-methylcyclohexyl quinoline-2-carboxylate is recorded and analyzed. Optimized molecular structure, wave numbers, corresponding assignments regarding 2-isopropyl-5-methylcyclohexyl quinoline-2-carboxylate has become screened tentatively as well as hypothetically using Gaussian09 program package. Natural bonding orbital assessment has been completed with a reason to clarify charge transfer or conjugative interaction, the intra-molecular re-hybridization and delocalization of electron density within the molecule. The NMR spectral assessment had been made choosing structure property relationship by chemical shifts along with the magnetic shielding effects regarding the title compound. The first and second hyperpolarizabilities were calculated. The calculated first order hyperpolarizability is commensurate with the documented worth of very similar derivatives and could be an interesting object for more experiments on nonlinear optics. Local reactivity properties have been investigated using average local ionization energies and Fukui functions. Investigation of optoelectronic properties encompassed calculations of reorganization energies and hopping rates of charge carriers within the framework of Marcus semi-empiric approach. The docked ligand title compound forms a stable complex with CDK inhibitors and gives a binding affinity value of -9.7 kcal/mol and molecular docking results suggest that the compound might exhibit inhibitory activity against CDK inhibitors.

High-throughput density functional calculations to optimize properties and interfacial chemistry of piezoelectric materials

NASA Astrophysics Data System (ADS)

Barr, Jordan A.; Lin, Fang-Yin; Ashton, Michael; Hennig, Richard G.; Sinnott, Susan B.

2018-02-01

High-throughput density functional theory calculations are conducted to search through 1572 A B O3 compounds to find a potential replacement material for lead zirconate titanate (PZT) that exhibits the same excellent piezoelectric properties as PZT and lacks both its use of the toxic element lead (Pb) and the formation of secondary alloy phases with platinum (Pt) electrodes. The first screening criterion employed a search through the Materials Project database to find A -B combinations that do not form ternary compounds with Pt. The second screening criterion aimed to eliminate potential candidates through first-principles calculations of their electronic structure, in which compounds with a band gap of 0.25 eV or higher were retained. Third, thermodynamic stability calculations were used to compare the candidates in a Pt environment to compounds already calculated to be stable within the Materials Project. Formation energies below or equal to 100 meV/atom were considered to be thermodynamically stable. The fourth screening criterion employed lattice misfit to identify those candidate perovskites that have low misfit with the Pt electrode and high misfit of potential secondary phases that can be formed when Pt alloys with the different A and B components. To aid in the final analysis, dynamic stability calculations were used to determine those perovskites that have dynamic instabilities that favor the ferroelectric distortion. Analysis of the data finds three perovskites warranting further investigation: CsNb O3 , RbNb O3 , and CsTa O3 .

An aqueous, polymer-based redox-flow battery using non-corrosive, safe, and low-cost materials.

PubMed

Janoschka, Tobias; Martin, Norbert; Martin, Udo; Friebe, Christian; Morgenstern, Sabine; Hiller, Hannes; Hager, Martin D; Schubert, Ulrich S

2015-11-05

For renewable energy sources such as solar, wind, and hydroelectric to be effectively used in the grid of the future, flexible and scalable energy-storage solutions are necessary to mitigate output fluctuations. Redox-flow batteries (RFBs) were first built in the 1940s and are considered a promising large-scale energy-storage technology. A limited number of redox-active materials--mainly metal salts, corrosive halogens, and low-molar-mass organic compounds--have been investigated as active materials, and only a few membrane materials, such as Nafion, have been considered for RFBs. However, for systems that are intended for both domestic and large-scale use, safety and cost must be taken into account as well as energy density and capacity, particularly regarding long-term access to metal resources, which places limits on the lithium-ion-based and vanadium-based RFB development. Here we describe an affordable, safe, and scalable battery system, which uses organic polymers as the charge-storage material in combination with inexpensive dialysis membranes, which separate the anode and the cathode by the retention of the non-metallic, active (macro-molecular) species, and an aqueous sodium chloride solution as the electrolyte. This water- and polymer-based RFB has an energy density of 10 watt hours per litre, current densities of up to 100 milliamperes per square centimetre, and stable long-term cycling capability. The polymer-based RFB we present uses an environmentally benign sodium chloride solution and cheap, commercially available filter membranes instead of highly corrosive acid electrolytes and expensive membrane materials.

An aqueous, polymer-based redox-flow battery using non-corrosive, safe, and low-cost materials

NASA Astrophysics Data System (ADS)

Janoschka, Tobias; Martin, Norbert; Martin, Udo; Friebe, Christian; Morgenstern, Sabine; Hiller, Hannes; Hager, Martin D.; Schubert, Ulrich S.

2015-11-01

For renewable energy sources such as solar, wind, and hydroelectric to be effectively used in the grid of the future, flexible and scalable energy-storage solutions are necessary to mitigate output fluctuations. Redox-flow batteries (RFBs) were first built in the 1940s and are considered a promising large-scale energy-storage technology. A limited number of redox-active materials--mainly metal salts, corrosive halogens, and low-molar-mass organic compounds--have been investigated as active materials, and only a few membrane materials, such as Nafion, have been considered for RFBs. However, for systems that are intended for both domestic and large-scale use, safety and cost must be taken into account as well as energy density and capacity, particularly regarding long-term access to metal resources, which places limits on the lithium-ion-based and vanadium-based RFB development. Here we describe an affordable, safe, and scalable battery system, which uses organic polymers as the charge-storage material in combination with inexpensive dialysis membranes, which separate the anode and the cathode by the retention of the non-metallic, active (macro-molecular) species, and an aqueous sodium chloride solution as the electrolyte. This water- and polymer-based RFB has an energy density of 10 watt hours per litre, current densities of up to 100 milliamperes per square centimetre, and stable long-term cycling capability. The polymer-based RFB we present uses an environmentally benign sodium chloride solution and cheap, commercially available filter membranes instead of highly corrosive acid electrolytes and expensive membrane materials.

High energy density redox flow device

DOEpatents

Chiang, Yet -Ming; Carter, W. Craig; Duduta, Mihai; Limthongkul, Pimpa

2015-10-06

Redox flow devices are described including a positive electrode current collector, a negative electrode current collector, and an ion-permeable membrane separating said positive and negative current collectors, positioned and arranged to define a positive electroactive zone and a negative electroactive zone; wherein at least one of said positive and negative electroactive zone comprises a flowable semi-solid composition comprising ion storage compound particles capable of taking up or releasing said ions during operation of the cell, and wherein the ion storage compound particles have a polydisperse size distribution in which the finest particles present in at least 5 vol % of the total volume, is at least a factor of 5 smaller than the largest particles present in at least 5 vol % of the total volume.

High energy density redox flow device

DOEpatents

Chiang, Yet-Ming; Carter, William Craig; Duduta, Mihai; Limthongkul, Pimpa

2014-05-13

Redox flow devices are described including a positive electrode current collector, a negative electrode current collector, and an ion-permeable membrane separating said positive and negative current collectors, positioned and arranged to define a positive electroactive zone and a negative electroactive zone; wherein at least one of said positive and negative electroactive zone comprises a flowable semi-solid composition comprising ion storage compound particles capable of taking up or releasing said ions during operation of the cell, and wherein the ion storage compound particles have a polydisperse size distribution in which the finest particles present in at least 5 vol % of the total volume, is at least a factor of 5 smaller than the largest particles present in at least 5 vol % of the total volume.

The role of dissolved cations in coffee extraction.

PubMed

Hendon, Christopher H; Colonna-Dashwood, Lesley; Colonna-Dashwood, Maxwell

2014-05-28

The flavorsome compounds in coffee beans exist in the form of aprotic charge neutral species, as well as a collection of acids and conjugate salts. The dissolution and extraction of these organic molecules is a process dependent on the dissolved mineral content of the water. It is known that different rates and compositions of coffee extraction are achieved through the control of the water "impurities", Na(+), Mg(2+), and Ca(2+), which coordinate to nucleophilic motifs in coffee. Using density functional theory, we quantify the thermodynamic binding energies of five familiar coffee-contained acids, caffeine, and a representative flavor component, eugenol. From this, we provide insight into the mechanism and ideal mineral composition of water for extraction of flavorsome compounds in coffee.

(Tl, Sb) and (Tl, Bi) binary surface reconstructions on Ge(111) substrate

NASA Astrophysics Data System (ADS)

Gruznev, D. V.; Bondarenko, L. V.; Tupchaya, A. Y.; Yakovlev, A. A.; Mihalyuk, A. N.; Zotov, A. V.; Saranin, A. A.

2018-03-01

2D compounds made of Group-III and Group-V elements on the surface of silicon and germanium attract considerable attention due to prospects of creating III-V binary monolayers, which are predicted to hold advanced physical properties. In the present work, we have investigated two such systems, (Tl, Sb)/Ge(111) and (Tl, Bi)/Ge(111) using scanning tunneling microscopy, low energy electron diffraction observations and density-functional-theory calculations. In addition to the previously reported surface structures of 2D (Tl, Sb) and (Tl, Bi) compounds on Si(111), we found new ones, namely, √{ 7} × √{ 7} and 3 × 3. Formation processes and plausible models of their atomic arrangements are discussed.

Optical properties of novel environmentally benign biologically active ferrocenyl substituted chromophores: A detailed insight via experimental and theoretical approach

NASA Astrophysics Data System (ADS)

Khan, Salman A.; Asiri, Abdullah M.; Al-Ghamdi, Najat Saeed M.; Zayed, Mohie E. M.; Sharma, Kamlesh; Parveen, Humaira

2017-07-01

Series of ferrocenyl substituted chromophores were synthesized via a reaction of acetyl ferrocene and a variety of aldehyde under microwave irradiation. The structure of synthesized compounds were established by spectroscopic (FT-IR, 1H NMR, 13C NMR, ESI-MS) and elemental analysis. UV-Vis and fluorescence spectroscopy measurements provided that all compounds have good absorbent and fluorescent properties. Fluorescence polarity studies demonstrated that these compounds were sensitive to the polarity of the microenvironment provided by different solvents. In addition, spectroscopic and physicochemical parameters, including singlet absorption, extinction coefficient, Stokes shift, oscillator strength and dipole moment, were investigated in order to explore the analytical potential of the synthesized compounds. The anti-bacterial activity of these compounds were first studied in vitro by the disk diffusion assay against two Gram-positive and two Gram-negative bacteria. The minimum inhibitory concentration was then determined with the reference of standard drug chloramphenicol. The results displayed that compound 3 was better inhibitors for both types of the bacteria (Gram-positive and Gram-negative) than chloramphenicol. Based on the density functional theory; total energy, the atomic orbital contribution to frontier orbitals: LUMO and HOMO, of all synthesized compounds were calculated to support the antibacterial activities.

Theory versus experiment for a family of single-layer compounds with a similar atomic arrangement: (Tl,X )/Si(111 )√{3 }×√{3 }(X =Pb,Sn,Bi,Sb,Te,Se)

NASA Astrophysics Data System (ADS)

Matetskiy, A. V.; Kibirev, I. A.; Mihalyuk, A. N.; Eremeev, S. V.; Gruznev, D. V.; Bondarenko, L. V.; Tupchaya, A. Y.; Zotov, A. V.; Saranin, A. A.

2017-08-01

Two-dimensional compounds made of one monolayer of Tl and one-third monolayer of Pb, Bi, Te, or Se (but not of Sn or Sb) on Si(111) have been found to have a similar atomic arrangement which can be visualized as a √{3 }×√{3 } -periodic honeycomb network of chained Tl trimers with atoms of the second adsorbate occupying the centers of the honeycomb units. Structural and electronic properties of the compounds have been examined in detail theoretically using density functional theory (DFT) calculations and experimentally using low-energy electron diffraction (LEED), scanning tunneling microscopy (STM), and angle-resolved photoelectron spectroscopy (ARPES) observations. It has been found that though structural parameters of the compounds are very similar for all species, the only common feature of their band structure is a considerable spin-splitting of the surface-state bands, while other basic electronic properties vary greatly with a change of species. The Tl-Pb compound is strongly metallic with two metallic surface-state bands; the Tl-Bi compound is also metallic but with a single metallic band; the Tl-Te and Tl-Se compounds appear to be insulators.

Gas-phase behaviour of Ru(II) cyclopentadienyl-derived complexes with N-coordinated ligands by electrospray ionization mass spectrometry: fragmentation pathways and energetics.

PubMed

Madeira, Paulo J Amorim; Morais, Tânia S; Silva, Tiago J L; Florindo, Pedro; Garcia, M Helena

2012-08-15

The gas-phase behaviour of six Ru(II) cyclopentadienyl-derived complexes with N-coordinated ligands, compounds with antitumor activities against several cancer lines, was studied. This was performed with the intent of establishing fragmentation pathways and to determine the Ru-L(N) and Ru-L(P) ligand bond dissociation energies. Such knowledge can be an important tool for the postulation of the mechanisms of action of these anticancer drugs. Two types of instruments equipped with electrospray ionisation were used (ion trap and a Fourier transform ion cyclotron resonance (FTICR) mass spectrometer). The dissociation energies were determined using energy-variable collision-induced dissociation measurements in the ion trap. The FTICR instrument was used to perform MS(n) experiments on one of the compounds and to obtain accurate mass measurements. Theoretical calculations were performed at the density functional theory (DFT) level using two different functionals (B3LYP and M06L) to estimate the dissociation energies of the complexes under study. The influence of the L(N) on the bond dissociation energy (D) of RuCp compounds with different nitrogen ligands was studied. The lability order of L(N) was: imidazole<1-butylimidazole<5-phenyl-1H-tetrazole<1-benzylimidazole. Both the functionals used gave the following ligand lability order: imidazole<1-benzylimidazole<5-phenyl-1H-tetrazole<1-butylimidazole. It is clear that there is an inversion between 1-benzylimidazole and 1-butylimidazole for the experimental and theoretical lability orders. The M06L functional afforded values of D closer to the experimental values. The type of phosphane (L(P) ) influenced the dissociation energies, with values of D being higher for Ru-L(N) with 1-butylimidazole when the phosphane was 1,2-bis(diphenylphosphino)ethane. The Ru-L(P) bond dissociation energy for triphenylphosphane was independent of the type of complex. The D values of Ru-L(N) and Ru-L(P) were determined for all six compounds and compared with the values calculated by the DFT method. For the imidazole-derived ligands the energy trend was rationalized in terms of the increasing extension of the σ-donation/π-backdonation effect. The bond dissociation energy of Ru-PPh(3) was independent of the fragmentations. Copyright © 2012 John Wiley & Sons, Ltd.

In Silico Prediction of Cytochrome P450-Mediated Biotransformations of Xenobiotics: A Case Study of Epoxidation.

PubMed

Zhang, Jing; Ji, Li; Liu, Weiping

2015-08-17

Predicting the biotransformation of xenobiotics is important in toxicology; however, as more compounds are synthesized than can be investigated experimentally, powerful computational methods are urgently needed to prescreen potentially useful candidates. Cytochrome P450 enzymes (P450s) are the major enzymes involved in xenobiotic metabolism, and many substances are bioactivated by P450s to form active compounds. An example is the conversion of olefinic substrates to epoxides, which are intermediates in the metabolic activation of many known or suspected carcinogens. We have calculated the activation energies for epoxidation by the active species of P450 enzymes (an iron-oxo porphyrin cation radical oxidant, compound I) for a diverse set of 36 olefinic substrates with state-of-the-art density functional theory (DFT) methods. Activation energies can be estimated by the computationally less demanding method of calculating the ionization potentials of the substrates, which provides a useful and simple predictive model based on the reaction mechanism; however, the preclassification of these diverse substrates into weakly polar and strongly polar groups is a prerequisite for the construction of specific predictive models with good predictability for P450 epoxidation. This approach has been supported by both internal and external validations. Furthermore, the relation between the activation energies for the regioselective epoxidation and hydroxylation reactions of P450s and experimental data has been investigated. The results show that the computational method used in this work, single-point energy calculations with the B3LYP functional including zero-point energy and solvation and dispersion corrections based on B3LYP-optimized geometries, performs well in reproducing the experimental trends of the epoxidation and hydroxylation reactions.

Half-metallic ferromagnetism in {Ti}2 {IrZ} (Z = B, Al, Ga, and In) Heusler alloys: A density functional study

NASA Astrophysics Data System (ADS)

Sadeghi, K. H.; Ahmadian, F.

2018-02-01

The first-principle density functional theory (DFT) calculations were employed to investigate the electronic structures, magnetic properties and half-metallicity of {Ti}2 {IrZ} (Z = B, Al, Ga, and In) Heusler alloys with {AlCu}2 {Mn}- and {CuHg}2 {Ti}-type structures within local density approximation and generalised gradient approximation for the exchange correlation potential. It was found that {CuHg}2 {Ti}-type structure in ferromagnetic state was energetically more favourable than {AlCu}2 {Mn}-type structure in all compounds except {Ti}2 {IrB} which was stable in {AlCu}2 {Mn}-type structure in non-magnetic state. {Ti}2 {IrZ} (Z = B, Al, Ga, and In) alloys in {CuHg}2 {Ti}-type structure were half-metallic ferromagnets at their equilibrium lattice constants. Half-metallic band gaps were respectively equal to 0.87, 0.79, 0.75, and 0.73 eV for {Ti}2 {IrB}, {Ti}2 {IrAl}, {Ti}2 {IrGa}, and {Ti}2 {IrIn}. The origin of half-metallicity was discussed for {Ti}2 {IrGa} using the energy band structure. The total magnetic moments of {Ti}2 {IrZ} (Z = B, Al, Ga, and In) compounds in {CuHg}2 {Ti}-type structure were obtained as 2μ B per formula unit, which were in agreement with Slater-Pauling rule (M_{tot} =Z_{tot}-18). All the four compounds were half-metals in a wide range of lattice constants indicating that they may be suitable and promising materials for future spintronic applications.

Density Estimation for New Solid and Liquid Explosives

DTIC Science & Technology

1977-02-17

The group additivity approach was shown to be applicable to density estimation. The densities of approximately 180 explosives and related compounds... of very diverse compositions were estimated, and almost all the estimates were quite reasonable. Of the 168 compounds for which direct comparisons...could be made (see Table 6), 36.9% of the estimated densities were within 1% of the measured densities, 33.3% were within 1-2%, 11.9% were within 2-3

Quantum mechanical study of the structure and spectroscopic (FT-IR, FT-Raman, 13C, 1H and UV), first order hyperpolarizabilities, NBO and TD-DFT analysis of the 4-methyl-2-cyanobiphenyl.

PubMed

Sebastian, S; Sundaraganesan, N; Karthikeiyan, B; Srinivasan, V

2011-02-01

The Fourier transform infrared (FT-IR) and FT-Raman of 4-methyl-2-cyanobiphenyl (4M2CBP) have been recorded and analyzed. The equilibrium geometry, bonding features and harmonic vibrational frequencies have been investigated with the help of density functional theory (DFT) method. 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 methodology (SQMFF). The 1H and 13C nuclear magnetic resonance (NMR) chemical shifts of the molecule were calculated by the Gauge including atomic orbital (GIAO) method. The first order hyperpolarizability (β0) of this novel molecular system and related properties (β, α0 and Δα) of 4M2CBP are calculated using HF/6-311G(d,p) method on the finite-field approach. Stability of the molecule arising from hyperconjugative interactions, charge delocalization have been analyzed using natural bond orbital (NBO) analysis. The results show that charge in electron density (ED) in the σ* and π* antibonding orbitals and second order delocalization energies (E2) confirms the occurrence of intramolecular charge transfer (ICT) within the molecule. UV-vis spectrum of the compound was recorded and the electronic properties, such as HOMO and LUMO energies, were performed by time-dependent density functional theory (TD-DFT) approach. Finally the calculations results were applied to simulated infrared and Raman spectra of the title compound which show good agreement with observed spectra. Copyright © 2010 Elsevier B.V. All rights reserved.

The effects of radiation damage and annealing on the microstructure of a natural zircon observed by TDPAC

NASA Astrophysics Data System (ADS)

Lacentre, P.; Caracoche, M. C.

1994-06-01

The hyperfine interaction of a natural brazilian zircon sand was determined at zirconium sites between room temperature and 1393K by means of the time-differential perturbed-angular-correlations technique. Complementary measurements of x-ray diffraction, differential thermal analysis and density were also performed. It was found that the starting compound was an intermediate zircon of 4.62 g/cm3 density consisting of a mixture of slightly disordered and highly defectuous materials in a ratio quite different from that determined for non brazilian zircons self irradiated by the same α-dose. Heating the sample resulted in the gradual recovery of the periodic crystalline structure in a two-stage process characterized by activation energies of 3.88 and 4.68 eV. An additional zirconium compound, for which an interpretation is proposed, was observed to be present in a low and nearly constant proportion up to 1393K, temperature at which it evidenced a reduction. A final measurement at RT revealed that this last change, as well as the second annealing stage, were of reversible nature.

Azo compounds as a family of organic electrode materials for alkali-ion batteries.

PubMed

Luo, Chao; Borodin, Oleg; Ji, Xiao; Hou, Singyuk; Gaskell, Karen J; Fan, Xiulin; Chen, Ji; Deng, Tao; Wang, Ruixing; Jiang, Jianjun; Wang, Chunsheng

2018-02-27

Organic compounds are desirable for sustainable Li-ion batteries (LIBs), but the poor cycle stability and low power density limit their large-scale application. Here we report a family of organic compounds containing azo group (N=N) for reversible lithiation/delithiation. Azobenzene-4,4'-dicarboxylic acid lithium salt (ADALS) with an azo group in the center of the conjugated structure is used as a model azo compound to investigate the electrochemical behaviors and reaction mechanism of azo compounds. In LIBs, ADALS can provide a capacity of 190 mAh g -1 at 0.5 C (corresponding to current density of 95 mA g -1 ) and still retain 90%, 71%, and 56% of the capacity when the current density is increased to 2 C, 10 C, and 20 C, respectively. Moreover, ADALS retains 89% of initial capacity after 5,000 cycles at 20 C with a slow capacity decay rate of 0.0023% per cycle, representing one of the best performances in all organic compounds. Superior electrochemical behavior of ADALS is also observed in Na-ion batteries, demonstrating that azo compounds are universal electrode materials for alkali-ion batteries. The highly reversible redox chemistry of azo compounds to alkali ions was confirmed by density-functional theory (DFT) calculations. It provides opportunities for developing sustainable batteries.

Molecular docking, spectroscopic studies and quantum calculations on nootropic drug.

PubMed

Uma Maheswari, J; Muthu, S; Sundius, Tom

2014-04-05

A systematic vibrational spectroscopic assignment and analysis of piracetam [(2-oxo-1-pyrrolidineacetamide)] have been carried out using FT-IR and FT-Raman spectral data. The vibrational analysis was aided by an electronic structure calculation based on the hybrid density functional method B3LYP using a 6-311G++(d,p) basis set. Molecular equilibrium geometries, electronic energies, IR and Raman intensities, and harmonic vibrational frequencies have been computed. The assignments are based on the experimental IR and Raman spectra, and a complete assignment of the observed spectra has been proposed. The UV-visible spectrum of the compound was recorded and the electronic properties, such as HOMO and LUMO energies and the maximum absorption wavelengths λmax were determined by the time-dependent DFT (TD-DFT) method. The geometrical parameters, vibrational frequencies and absorption wavelengths were compared with the experimental data. The complete vibrational assignments are performed on the basis of the potential energy distributions (PED) of the vibrational modes in terms of natural internal coordinates. The simulated FT-IR, FT-Raman, and UV spectra of the title compound have been constructed. Molecular docking studies have been carried out in the active site of piracetam by using Argus Lab. In addition, the potential energy surface, HOMO and LUMO energies, first-order hyperpolarizability and the molecular electrostatic potential have been computed. Copyright © 2014 Elsevier B.V. All rights reserved.

Basic Studies Relative to the Syntheses of Unsymmetrical Dimethylhydrazine and Monomethylhydrazine by Chloramination

DTIC Science & Technology

1979-12-07

8217 changed to faint yellow. After the chloramination, the reaction mixture was allowed to stand at room temperature to allow volatile gases to ’escape. The...energy rocketI and space shuttle fuels. These compounds have large heats of combustion , relatively :,igh densities and high specific impulses. Until...a solution of KOH in n-butanol was carried out in the presence of NH3 at room temperature . The major products were 1,1-dimethylhydrazine, the

Polycyclic High Energy Oxidizers.

DTIC Science & Technology

1983-04-01

D -A128 309 P0 YCYCC HIGH ENER G OXIDIZERS(U) MORTON THIOKOL INC 1/r BRIGHAMCIT UT WASATCH DIV J C HINSHAW APR 83 I N00014-8N C 0204 JNCLASS4FIED /1/9...instability. 1. D . A. Cichra, J. Holden, and C. Dickenson Estimation of "Normal" Densities of hplosive Compounds from Empirical Atomic Volumes, Naval...Surface Weapons Center Report, ISWC TR-79-273, February 19,1980. 3 2. Estimated heats of formation are calculated using a method developed by A. D

Exploring the effect of oxygen-containing functional groups on the water-holding capacity of lignite.

PubMed

Liu, Jie; Jiang, Xiangang; Cao, Yu; Zhang, Chen; Zhao, Guangyao; Zhao, Maoshuang; Feng, Li

2018-05-07

Graphene oxide with different degrees of oxidation was prepared and selected as a model compound of lignite to study quantitatively, using both experiment and theoretical calculation methods, the effect on water-holding capacity of oxygen-containing functional groups. The experimental results showed that graphite can be oxidized, and forms epoxy groups most easily, followed by hydroxyl and carboxyl groups. The prepared graphene oxide forms a membrane-state as a single layer structure, with an irregular surface. The water-holding capacity of lignite increased with the content of oxygen-containing functional groups. The influence on the configuration of water molecule clusters and binding energy of water molecules of different oxygen-containing functional groups was calculated by density functional theory. The calculation results indicated that the configuration of water molecule clusters was totally changed by oxygen-containing functional groups. The order of binding energy produced by oxygen-containing functional groups and water molecules was as follows: carboxyl > edge phenol hydroxyl >epoxy group. Finally, it can be concluded that the potential to form more hydrogen bonds is the key factor influencing the interaction energy between model compounds and water molecules.

Energy Donor Effect on the Sensing Performance for a Series of FRET-Based Two-Photon Fluorescent Hg2+ Probes

PubMed Central

Zhang, Yujin; Hu, Wei

2017-01-01

Nonlinear optical properties of a series of newly-synthesized molecular fluorescent probes for Hg2+ containing the same acceptor (rhodamine group) are analyzed by using time-dependent density functional theory in combination with analytical response theory. Special emphasis is placed on evolution of the probes’ optical properties in the absence and presence of Hg2+. These compounds show drastic changes in their photoabsorption and photoemission properties when they react with Hg2+, indicating that they are excellent candidates for ratiometric and colorimetric fluorescent chemosensors. Most importantly, the energy donor moiety is found to play a dominant role in sensing performance of these probes. Two-photon absorption cross sections of the compounds are increased with the presence of Hg2+, which theoretically suggests the possibility of the probes to be two-photon fluorescent Hg2+ sensors. Moreover, analysis of molecular orbitals is presented to explore responsive mechanism of the probes, where the fluorescence resonant energy transfer process is theoretically demonstrated. Our results elucidate the available experimental measurements. This work provides guidance for designing efficient two-photon fluorescent probes that are geared towards biological and chemical applications. PMID:28772466

Energy Donor Effect on the Sensing Performance for a Series of FRET-Based Two-Photon Fluorescent Hg2+ Probes.

PubMed

Zhang, Yujin; Hu, Wei

2017-01-25

Nonlinear optical properties of a series of newly-synthesized molecular fluorescent probes for Hg 2+ containing the same acceptor (rhodamine group) are analyzed by using time-dependent density functional theory in combination with analytical response theory. Special emphasis is placed on evolution of the probes' optical properties in the absence and presence of Hg 2+ . These compounds show drastic changes in their photoabsorption and photoemission properties when they react with Hg 2+ , indicating that they are excellent candidates for ratiometric and colorimetric fluorescent chemosensors. Most importantly, the energy donor moiety is found to play a dominant role in sensing performance of these probes. Two-photon absorption cross sections of the compounds are increased with the presence of Hg 2+ , which theoretically suggests the possibility of the probes to be two-photon fluorescent Hg 2+ sensors. Moreover, analysis of molecular orbitals is presented to explore responsive mechanism of the probes, where the fluorescence resonant energy transfer process is theoretically demonstrated. Our results elucidate the available experimental measurements. This work provides guidance for designing efficient two-photon fluorescent probes that are geared towards biological and chemical applications.

Recent Progress in Graphite Intercalation Compounds for Rechargeable Metal (Li, Na, K, Al)-Ion Batteries.

PubMed

Xu, Jiantie; Dou, Yuhai; Wei, Zengxi; Ma, Jianmin; Deng, Yonghong; Li, Yutao; Liu, Huakun; Dou, Shixue

2017-10-01

Lithium-ion batteries (LIBs) with higher energy density are very necessary to meet the increasing demand for devices with better performance. With the commercial success of lithiated graphite, other graphite intercalation compounds (GICs) have also been intensively reported, not only for LIBs, but also for other metal (Na, K, Al) ion batteries. In this Progress Report, we briefly review the application of GICs as anodes and cathodes in metal (Li, Na, K, Al) ion batteries. After a brief introduction on the development history of GICs, the electrochemistry of cationic GICs and anionic GICs is summarized. We further briefly summarize the use of cationic GICs and anionic GICs in alkali ion batteries and the use of anionic GICs in aluminium-ion batteries. Finally, we reach some conclusions on the drawbacks, major progress, emerging challenges, and some perspectives on the development of GICs for metal (Li, Na, K, Al) ion batteries. Further development of GICs for metal (Li, Na, K, Al) ion batteries is not only a strong supplement to the commercialized success of lithiated-graphite for LIBs, but also an effective strategy to develop diverse high-energy batteries for stationary energy storage in the future.

Synthesis, XRD crystal structure, spectroscopic characterization, local reactive properties using DFT and molecular dynamics simulations and molecular docking study of (E)-1-(4-bromophenyl)-3-(4-(trifluoromethoxy)phenyl)prop-2-en-1-one

NASA Astrophysics Data System (ADS)

Arshad, Suhana; Raveendran Pillai, Renjith; Zainuri, Dian Alwani; Khalib, Nuridayanti Che; Razak, Ibrahim Abdul; Armaković, Stevan; Armaković, Sanja J.; Renjith, Rishikesh; Panicker, C. Yohannan; Van Alsenoy, C.

2017-06-01

In the present study, the title compound named as (E)-1-(4-bromophenyl)-3-(4-(trifluoromethoxy)phenyl)prop-2-en-1-one was synthesized and structurally characterized by single-crystal X-ray diffraction. The FT-IR spectrum was recorded and interpreted in details with the aid of Density Functional Theory (DFT) calculations and Potential Energy Distribution (PED) analysis. Average local ionization energies (ALIE) and Fukui functions have been used as quantum-molecular descriptors to locate the molecule sites that could be of importance from the aspect of reactivity. Degradation properties have been assessed by calculations of bond dissociation energies (BDE) for hydrogen abstraction and the rest of the single acyclic bonds, while molecular dynamics (MD) simulations were used in order to calculate radial distribution functions and determine the atoms with significant interactions with water. In order to understand how the title molecule inhibits and hence increases the catalytic efficiency of MOA-B enzyme, molecular docking study was performed to fit the title compound into the binding site of MOA-B enzyme.

Ligand-Sensitive But Not Ligand-Diagnostic: Evaluating Cr Valence-to-Core X-ray Emission Spectroscopy as a Probe of Inner-Sphere Coordination

PubMed Central

2015-01-01

This paper explores the strengths and limitations of valence-to-core X-ray emission spectroscopy (V2C XES) as a probe of coordination environments. A library was assembled from spectra obtained for 12 diverse Cr complexes and used to calibrate density functional theory (DFT) calculations of V2C XES band energies. A functional dependence study was undertaken to benchmark predictive accuracy. All 7 functionals tested reproduce experimental V2C XES energies with an accuracy of 0.5 eV. Experimentally calibrated, DFT calculated V2C XES spectra of 90 Cr compounds were used to produce a quantitative spectrochemical series showing the V2C XES band energy ranges for ligands comprising 18 distinct classes. Substantial overlaps are detected in these ranges, which complicates the use of V2C XES to identify ligands in the coordination spheres of unknown Cr compounds. The ligand-dependent origins of V2C intensity are explored for a homologous series of [CrIII(NH3)5X]2+ (X = F, Cl, Br, and I) to rationalize the variable intensity contributions of these ligand classes. PMID:25496512

Recent Progress in Graphite Intercalation Compounds for Rechargeable Metal (Li, Na, K, Al)‐Ion Batteries

PubMed Central

Xu, Jiantie; Dou, Yuhai; Wei, Zengxi; Li, Yutao; Liu, Huakun; Dou, Shixue

2017-01-01

Abstract Lithium‐ion batteries (LIBs) with higher energy density are very necessary to meet the increasing demand for devices with better performance. With the commercial success of lithiated graphite, other graphite intercalation compounds (GICs) have also been intensively reported, not only for LIBs, but also for other metal (Na, K, Al) ion batteries. In this Progress Report, we briefly review the application of GICs as anodes and cathodes in metal (Li, Na, K, Al) ion batteries. After a brief introduction on the development history of GICs, the electrochemistry of cationic GICs and anionic GICs is summarized. We further briefly summarize the use of cationic GICs and anionic GICs in alkali ion batteries and the use of anionic GICs in aluminium‐ion batteries. Finally, we reach some conclusions on the drawbacks, major progress, emerging challenges, and some perspectives on the development of GICs for metal (Li, Na, K, Al) ion batteries. Further development of GICs for metal (Li, Na, K, Al) ion batteries is not only a strong supplement to the commercialized success of lithiated‐graphite for LIBs, but also an effective strategy to develop diverse high‐energy batteries for stationary energy storage in the future. PMID:29051856

LED photochemotherapy against Staphylococcus aureus: an in vitro study

NASA Astrophysics Data System (ADS)

de Oliveira, Susana C. P. S.; Monteiro, Juliana S. C.; Pires-Santos, Gustavo M.; Sampaio, Fernando José Pires; Soares, Luiz Guilherme P.; Soares, Amanda P.; Pinheiro, Antônio L. B.

2018-02-01

Bacterial resistance to antibiotics is reality and need for alternative treatments is urgent. The aim of this work was to evaluate, in vitro, the effect of LED photochemotherapy on Staphylococcus aureus (ATCC 23529) using 25 μg / mL of phenothiazine compound combined with LED light (λ632 +/- 2ηm) using 12 J/cm2 energy density. The experiments were carried out in triplicate and the samples were divided into groups: Control, Irradiated (treated only with light), Photosensitizer (treated only in the presence of the dye), LED-Photochemotherapy (treatment with light associated with dye). Counts of the colony forming units and the data obtained were statistically analyzed (ANOVA, Tukey's test, p<0.05). The present study demonstrated that the efficacy of LED-Photochemotherapy as the use of 25 μg/mL x 12 J/cm2 caused 91.57 % of inhibition of bacterial growth. It is concluded that using energy density of 12 J/cm2 associated to 25 μg/mL caused high in vitro inhibition of S. aureus.

Tunneling interstitial impurity in iron-chalcogenide-based superconductors

NASA Astrophysics Data System (ADS)

Huang, Huaixiang; Zhang, Degang; Gao, Yi; Ren, Wei; Ting, C. S.

2016-02-01

A pronounced local in-gap zero-energy bound state (ZBS) has been observed by recent scanning tunneling microscopy experiments on the interstitial Fe impurity (IFI) and its nearest-neighboring sites in an FeTe0.5Se0.5 superconducting (SC) compound. By introducing an impurity mechanism, the so-called tunneling impurity, and based on the Bogoliubov-de Gennes equations, we investigate the low-lying energy states of the IFI and the underlying Fe plane. The calculations are performed in the presence as well as in the absence of a magnetic field. We find the IFI-induced ZBS does not shift or split in a magnetic field as long as the tunneling parameter between the IFI and the Fe plane is sufficiently small and the Fe plane is deep in the SC state. Our results are in good agreement with experiments. We also show that in the underdoped cases, modulation of the spin density wave or charge density wave will suppress the intensity of the ZBS on the Fe plane in a vortex state.

Quantum mechanical, spectroscopic studies (FT-IR, FT-Raman, NMR, UV) and normal coordinates analysis on 3-([2-(diaminomethyleneamino) thiazol-4-yl] methylthio)-N'-sulfamoylpropanimidamide

NASA Astrophysics Data System (ADS)

Muthu, S.; Uma Maheswari, J.; Sundius, Tom

2013-05-01

Famotidine (3-([2-(diaminomethyleneamino) thiazol-4-yl] methylthio)-N'-sulfamoylpropanimidamide) is a histamine H2-receptor antagonist that inhibits stomach acid production, and it is commonly used in the treatment of peptic ulcer disease (PUD) and gastroesophageal reflux disease (GERD/GORD). Quantum chemical calculations of the equilibrium geometry of famotidine in the ground state were carried out using density functional theory (DFT/B3LYP) with the 6-311G(d,p) basis set. In addition, harmonic vibrational frequencies, infrared intensities and Raman activities were calculated at the same level of theory. A detailed interpretation of the infrared and Raman spectrum of the drug is also reported. Theoretical simulations of the FT-IR, and FT-Raman spectra of the title compound have been calculated. Good correlations between the experimental 1H and 13C NMR chemical shifts and calculated GIAO shielding tensors were found. The results of the energy and oscillator strength calculations by time-dependent density functional theory (TD-DFT) supplement 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 dipole moment, linear polarizability and first order hyperpolarizability values were also computed. The linear polarizability and first order hyperpolarizabilities of the studied molecule indicate that the compound is a good candidate for nonlinear optical materials.

Ab initio simulation of changes in geometry, electronic structure, and Gibbs free energy caused by dehydration of hydrotalcites containing Cl⁻ and CO₃²⁻ counteranions.

PubMed

Costa, Deyse G; Rocha, Alexandre B; Souza, Wladmir F; Chiaro, Sandra Shirley X; Leitão, Alexandre A

2011-04-07

This ab initio study was performed to better understand the correlation between intercalated water molecules and layered double hydroxides (LDH), as well as the changes that occur by the dehydration process of Zn-Al hydrotalcite-like compounds containing Cl⁻ and CO₃²⁻ counterions. We have verified that the strong interaction among intercalated water molecules, cointercalated anions, and OH groups from hydroxyl layers is reflected in the thermal stability of these compounds. The Zn(2/3)Al(1/3)(OH)₂Cl(1/3)·2/3H₂O hydrotalcite loses all the intercalated water molecules around 125 °C, while the Zn(2/3)Al(1/3)(OH)₂(CO₃)(1/6)·4/6H₂O compound dehydrates at about 175 °C. These values are in good agreement with experimental data. The interlayer interactions were discussed on the basis of electron density difference analyses. Our calculation shows that the electron density in the interlayer region decreases during the dehydration process, inducing the migration of the Cl⁻ anion and the displacement of the hydroxyl layer from adjacent layers. Changes in these compound structures occur to recover part of the hydrogen bonds broken due to the removal of water molecules. It was observed that the chloride ion had initially a lower Löwdin charge (Cl(-0.43)), which has increased its absolute value (Cl(-0.58)) after the water molecules removal, while the charges on carbonate ions remain invariant, leading to the conclusion that the Cl⁻ anion can be more influenced by the amount of water molecules in the interlayer space than the CO₃²⁻ anion in hydrotalcite-like compounds.

Effect of broken axial symmetry on the electric dipole strength and the collective enhancement of level densities in heavy nuclei

NASA Astrophysics Data System (ADS)

Grosse, E.; Junghans, A. R.; Wilson, J. N.

2017-11-01

The basic parameters for calculations of radiative neutron capture, photon strength functions and nuclear level densities near the neutron separation energy are determined based on experimental data without an ad hoc assumption about axial symmetry—at variance to previous analysis. Surprisingly few global fit parameters are needed in addition to information on nuclear deformation, taken from Hartree Fock Bogolyubov calculations with the Gogny force, and the generator coordinator method assures properly defined angular momentum. For a large number of nuclei the GDR shapes and the photon strength are described by the sum of three Lorentzians, extrapolated to low energies and normalised in accordance to the dipole sum rule. Level densities are influenced strongly by the significant collective enhancement based on the breaking of shape symmetry. The replacement of axial symmetry by the less stringent requirement of invariance against rotation by 180° leads to a novel prediction for radiative neutron capture. It compares well to recent compilations of average radiative widths and Maxwellian average cross sections for neutron capture by even target nuclei. An extension to higher spin promises a reliable prediction for various compound nuclear reactions also outside the valley of stability. Such predictions are of high importance for future nuclear energy systems and waste transmutation as well as for the understanding of the cosmic synthesis of heavy elements.

Comparative thermodynamic properties, vibrational spectral studies, NBO and HOMO-LUMO analyses of 3-chloro-2,4,5,6-tetrafluoropyridine and 4-bromo-2,3,5,6-tetrafluoropyridine based on density functional theory.

PubMed

Selvarani, C; Balachandran, V; Vishwanathan, K

2014-11-11

Quantum mechanical calculations of energies, geometries and vibrational wave numbers of 3-chloro-2,4,5,6-tetrafluoropyridine and 4-bromo-2,3,5,6-tetrafluoropyridine have been performed by DFT level of theory using B3LYP/6-31+G(d) and B3LYP/6-311++G(d,p) as basis sets. The optimized geometrical parameters obtained by B3LYP method show good agreement with experimental data. The difference between the observed and scaled wave number values of most of the fundamentals is very small. A detailed interpretation of the FT-IR and FT-Raman spectra of 3-chloro-2,4,5,6-tetrafluoropyridine and 4-bromo-2,3,5,6-tetrafluoropyridine were also reported. Molecular stability and bond strength were investigated by applying the natural bond orbital analysis (NBO). The calculated HOMO and LUMO energies show that charge transfer occurs in the molecules. 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 (ESP). Thermodynamic properties (heat capacity, entropy and enthalpy and Gibb's free energy) of the title compounds at different temperatures were calculated. Copyright © 2014 Elsevier B.V. All rights reserved.

Ab initio calculations of the magnetic properties of TM (Ti, V)-doped zinc-blende ZnO

NASA Astrophysics Data System (ADS)

Goumrhar, F.; Bahmad, L.; Mounkachi, O.; Benyoussef, A.

2018-01-01

In order to promote suitable material to be used in spintronics devices, this study purposes to evaluate the magnetic properties of the titanium and vanadium-doped zinc-blende ZnO from first-principles. The calculations of these properties are based on the Korringa-Kohn-Rostoker (KKR) method combined with the coherent potential approximation (CPA), using the local density approximation (LDA). We have calculated and discussed the density of states (DOSs) in the energy phase diagrams for different concentration values, of the dopants. We have also investigated the magnetic and half-metallic properties of this doped compound. Additionally, we showed the mechanism of the exchange coupling interaction. Finally, we estimated and studied the Curie temperature for different concentrations.

Magnetic properties of vanadium doped CdTe: Ab initio calculations

NASA Astrophysics Data System (ADS)

Goumrhar, F.; Bahmad, L.; Mounkachi, O.; Benyoussef, A.

2017-04-01

In this paper, we are applying the ab initio calculations to study the magnetic properties of vanadium doped CdTe. This study is based on the Korringa-Kohn-Rostoker method (KKR) combined with the coherent potential approximation (CPA), within the local density approximation (LDA). This method is called KKR-CPA-LDA. We have calculated and plotted the density of states (DOS) in the energy diagram for different concentrations of dopants. We have also investigated the magnetic and half-metallic properties of this compound and shown the mechanism of exchange interaction. Moreover, we have estimated the Curie temperature Tc for different concentrations. Finally, we have shown how the crystal field and the exchange splittings vary as a function of the concentrations.

Bioconcentration kinetics of hydrophobic chemicals in different densities of Chlorella pyrenoidosa

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

Sijm, D.T.H.M.; Broersen, K.W.; Roode, D.F. de

1998-09-01

Algal density-dependent bioconcentration factors and rate constants were determined for a series of hydrophobic compounds in Chlorella pyrenoidosa. The apparent uptake rate constants of the hydrophobic compounds in algae varied between 200 and 710,000 L/kg/d, slightly increased with hydrophobicity within an experiment, were relatively constant for each algal density, and fitted fairly within existing allometric relationships. The bioavailability of the hydrophobic test compounds was significantly reduced by sorption by algal exudates. The sorption coefficients of the hydrophobic compounds to the algal exudates were between 80 and 1,200 L/kg, and were for most algal densities in the same order of magnitudemore » as the apparent bioconcentration factors to the algae, that is, between 80 and 60,200 L/kg. In typical field situations, however, no significant reduction in bioavailability due to exudates is expected. The apparent elimination rate constants of the hydrophobic compounds were high and fairly constant for each algal density and varied between 2 and 190/d. Because the apparent elimination rate constants were higher than the growth rate constant, and were independent of hydrophobicity, the authors speculated that other factors dominate excretion, such as exudate excretion-enhanced elimination. Bioconcentration factors increased less than proportional with hydrophobicity, i.e., the octanol-water partition coefficient [K{sub ow}]. The role of algal composition in bioconcentration is evaluated. Bioconcentrations (kinetics) of hydrophobic compounds that are determined at high algal densities should be applied with caution to field situations.« less

Electronic structure and optical properties of metal doped tetraphenylporphyrins

NASA Astrophysics Data System (ADS)

Shah, Esha V.; Roy, Debesh R.

2018-05-01

A density functional scrutiny on the structure, electronic and optical properties of metal doped tetraphenylporphyrins MTPP (M=Fe, Co, Ni) is performed. The structural stability of the molecules is evaluated based on the electronic parameters like HOMO-LUMO gap (HLG), chemical hardness (η) and binding energy of the central metal atom to the molecular frame etc. The computed UltraViolet-Visible (UV-Vis) optical absorption spectra for all the compounds are also compared. The molecular structures reported are the lowest energy configurations. The entire calculations are carried out with a widely reliable functional, viz. B3LYP with a popular basis set which includes a scaler relativistic effect, viz. LANL2DZ.

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

Zhang, Yuxuan; Bilheux, Jean -Christophe

ImagingReso is an open-source Python library that simulates the neutron resonance signal for neutron imaging measurements. By defining the sample information such as density, thickness in the neutron path, and isotopic ratios of the elemental composition of the material, this package plots the expected resonance peaks for a selected neutron energy range. Various sample types such as layers of single elements (Ag, Co, etc. in solid form), chemical compounds (UO 3, Gd 2O 3, etc.), or even multiple layers of both types can be plotted with this package. As a result, major plotting features include display of the transmission/attenuation inmore » wavelength, energy, and time scale, and show/hide elemental and isotopic contributions in the total resonance signal.« less

First-principles estimates of free energy barriers for Mg desolvation and intercalation at electrolyte/electrode interfaces

NASA Astrophysics Data System (ADS)

Wan, Liwen; Prendergast, David

2014-03-01

There is a growing interest in developing multivalent ion batteries that could, in principle, double or triple the energy density compared to the monovalent Li-ion batteries. However, the strong electrostatic interaction caused by the extra charge also makes it very challenging to find appropriate intercalation compounds that allow for relatively fast and reversible ion transport. An established working multivalent battery is comprised of Mg(AlCl2BuEt)2 salts in THF solution as the electrolyte, and Mg metal and Mo6S8 Chevrel phase as the anode and cathode, respectively. Currently, we lack a clear understanding of the mechanism for Mg desolvation and intercalation at the interface between the electrolyte and Chevrel phase surfaces, which is critical in designing new advanced battery systems with improved ion diffusion rate. Here, we present a theoretical investigation of the dynamics and kinetics of the Mg desolvation/intercalation process. The surface properties of Mo6S8 are studied for the first time using density functional theory (DFT) and its interaction with the electrolyte is simulated via an ab initio molecular dynamics (AIMD) approach. The free energy barrier for Mg diffusing through the interface is then calculated by performing a set of biased AIMD simulations. This work is supported as part of the Joint Center for Energy Storage Research (JCESR), an Energy Innovation Hub funded by the U.S. Department of Energy, Office of Science, Basic Energy Sciences.

Electron attachment to indole and related molecules

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

Modelli, Alberto, E-mail: alberto.modelli@unibo.it; Centro Interdipartimentale di Ricerca in Scienze Ambientali; Jones, Derek, E-mail: d.jones@isof.cnr.it

Gas-phase formation of temporary negative ion states via resonance attachment of low-energy (0–6 eV) electrons into vacant molecular orbitals of indoline (I), indene (II), indole (III), 2-methylen-1,3,3-trimethylindoline (IV), and 2,3,3-trimethyl-indolenine (V) was investigated for the first time by electron transmission spectroscopy (ETS). The description of their empty-level structures was supported by density functional theory and Hartree-Fock calculations, using empirically calibrated linear equations to scale the calculated virtual orbital energies. Dissociative electron attachment spectroscopy (DEAS) was used to measure the fragment anion yields generated through dissociative decay channels of the parent molecular anions of compounds I-V, detected with a mass filtermore » as a function of the incident electron energy in the 0–14 eV energy range. The vertical and adiabatic electron affinities were evaluated at the B3LYP/6-31+G(d) level as the anion/neutral total energy difference. The same theoretical method is also used for evaluation of the thermodynamic energy thresholds for production of the negative fragments observed in the DEA spectra. The loss of a hydrogen atom from the parent molecular anion ([M-H]{sup −}) provides the most intense signal in compounds I-IV. The gas-phase DEAS data can provide support for biochemical reaction mechanisms in vivo involving initial hydrogen abstraction from the nitrogen atom of the indole moiety, present in a variety of biologically important molecules.« less

(2E)-1-(5-Chlorothiophen-2-yl)-3-{4-[(E)-2-phenylethenyl]phenyl}prop-2-en-1-one: Synthesis, XRD, FT-IR, Raman and DFT studies.

PubMed

Parlak, Cemal; Ramasami, Ponnadurai; Kumar, Chandraju Sadolalu Chidan; Tursun, Mahir; Quah, Ching Kheng; Rhyman, Lydia; Bilge, Metin; Fun, Hoong-Kun; Chandraju, Siddegowda

2015-01-01

A novel (2E)-1-(5-chlorothiophen-2-yl)-3-{4-[(E)-2-phenylethenyl]phenyl}prop-2-en-1-one [C21H15ClOS] compound has been synthesized and its structure has been characterized by FT-IR, Raman and single-crystal X-ray diffraction techniques. The conformational isomers, optimized geometric parameters, normal mode frequencies and corresponding vibrational assignments of the compound have been examined by means of HF, MP2, BP86, BLYP, BMK, B3LYP, B3PW91, B3P86 and M06-2X functionals. Reliable vibrational assignments and molecular orbitals have been investigated by the potential energy distribution and natural bonding orbital analyses, respectively. The compound crystallizes in the triclinic space group P-1 with the cis-trans-trans form. There is a good agreement between the experimentally determined structural parameters and vibrational frequencies of the compound and those predicted theoretically using the density functional theory with the BLYP and BP86 functionals. Copyright © 2015 Elsevier B.V. All rights reserved.

Bayesian-Driven First-Principles Calculations for Accelerating Exploration of Fast Ion Conductors for Rechargeable Battery Application.

PubMed

Jalem, Randy; Kanamori, Kenta; Takeuchi, Ichiro; Nakayama, Masanobu; Yamasaki, Hisatsugu; Saito, Toshiya

2018-04-11

Safe and robust batteries are urgently requested today for power sources of electric vehicles. Thus, a growing interest has been noted for fabricating those with solid electrolytes. Materials search by density functional theory (DFT) methods offers great promise for finding new solid electrolytes but the evaluation is known to be computationally expensive, particularly on ion migration property. In this work, we proposed a Bayesian-optimization-driven DFT-based approach to efficiently screen for compounds with low ion migration energies ([Formula: see text]. We demonstrated this on 318 tavorite-type Li- and Na-containing compounds. We found that the scheme only requires ~30% of the total DFT-[Formula: see text] evaluations on the average to recover the optimal compound ~90% of the time. Its recovery performance for desired compounds in the tavorite search space is ~2× more than random search (i.e., for [Formula: see text] < 0.3 eV). Our approach offers a promising way for addressing computational bottlenecks in large-scale material screening for fast ionic conductors.

Theoretical investigation of the interaction between aromatic sulfur compounds and [BMIM](+)[FeCl4](-) ionic liquid in desulfurization: A novel charge transfer mechanism.

PubMed

Li, Hongping; Zhu, Wenshuai; Chang, Yonghui; Jiang, Wei; Zhang, Ming; Yin, Sheng; Xia, Jiexiang; Li, Huaming

2015-06-01

In this work, interaction nature between a group of aromatic sulfur compounds and [BMIM](+)[FeCl4](-) have been investigated by density functional theory (DFT). A coordination structure is found to be critical to the mechanism of extractive desulfurization. Interaction energy and extractive selectivity follow the order: thiophene (TH)

Measurement of the Auger parameter and Wagner plot for uranium compounds

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

Holliday, Kiel S.; Siekhaus, Wigbert; Nelson, Art J.

2013-05-15

In this study, the photoemission from the U 4f{sub 7/2} and 4d{sub 5/2} states and the U N{sub 6}O{sub 45}O{sub 45} and N{sub 67}O{sub 45}V x-ray excited Auger transitions were measured for a range of uranium compounds. The data are presented in Wagner plots and the Auger parameter is calculated to determine the utility of this technique in the analysis of uranium materials. It was demonstrated that the equal core-level shift assumption holds for uranium. It was therefore possible to quantify the relative relaxation energies, and uranium was found to have localized core-hole shielding. The position of compounds within themore » Wagner plot made it possible to infer information on bonding character and local electron density. The relative ionicity of the uranium compounds studied follows the trend UF{sub 4} > UO{sub 3} > U{sub 3}O{sub 8} > U{sub 4}O{sub 9}/U{sub 3}O{sub 7} Almost-Equal-To UO{sub 2} > URu{sub 2}Si{sub 2}.« less

Influence of silicon defects on the adsorption of thiophene-like compounds on polycyclic aromatic hydrocarbons: a theoretical study using thiophene + coronene as the simplest model.

PubMed

Galano, Annia

2007-03-08

Physisorption and chemisorption processes of thiophene on coronene and 2Si-coronene have been studied using density functional theory and MP2 methods. These systems have been chosen as the simplest models to describe the adsorption of thiophene-like compounds on polycyclic aromatic hydrocarbons (PAHs). The calculated data suggest that the presence of silicon atoms in PAHs could favor their interaction with thiophene and similar compounds. Small stabilization energies have been found for several physisorbed complexes. The thiophene chemisorption on coronene seems very unlikely to occur, while that on 2Si-coronene leads to addition products which are very stable, with respect to the isolated reactants. These chemisorption processes were found to be exoergic (DeltaG < 0) in the gas phase and in the nonpolar liquid phase. The results reported in this work suggest that silicon defects on extended polycyclic aromatic hydrocarbons, such as graphite, soot, and large-diameter carbon nanotubes, could make them useful in the removal processes of aromatic sulfur compounds from oil hydrocarbons.

Systematic study of fission barriers of excited superheavy nuclei

NASA Astrophysics Data System (ADS)

Sheikh, J. A.; Nazarewicz, W.; Pei, J. C.

2009-07-01

A systematic study of fission-barrier dependence on excitation energy has been performed using the self-consistent finite-temperature Hartree-Fock + BCS (FT-HF + BCS) formalism with the SkM* Skyrme energy density functional. The calculations have been carried out for even-even superheavy nuclei with Z ranging between 110 and 124. For an accurate description of fission pathways, the effects of triaxial and reflection-asymmetric degrees of freedom have been fully incorporated. Our survey demonstrates that the dependence of isentropic fission barriers on excitation energy changes rapidly with particle number, pointing to the importance of shell effects even at large excitation energies characteristic of compound nuclei. The fastest decrease of fission barriers with excitation energy is predicted for deformed nuclei around N=164 and spherical nuclei around N=184 that are strongly stabilized by ground-state shell effects. For the nuclei Pu240 and Fm256, which exhibit asymmetric spontaneous fission, our calculations predict a transition to symmetric fission at high excitation energies owing to the thermal quenching of static reflection asymmetric deformations.

VR-SCOSMO: A smooth conductor-like screening model with charge-dependent radii for modeling chemical reactions.

PubMed

Kuechler, Erich R; Giese, Timothy J; York, Darrin M

2016-04-28

To better represent the solvation effects observed along reaction pathways, and of ionic species in general, a charge-dependent variable-radii smooth conductor-like screening model (VR-SCOSMO) is developed. This model is implemented and parameterized with a third order density-functional tight binding quantum model, DFTB3/3OB-OPhyd, a quantum method which was developed for organic and biological compounds, utilizing a specific parameterization for phosphate hydrolysis reactions. Unlike most other applications with the DFTB3/3OB model, an auxiliary set of atomic multipoles is constructed from the underlying DFTB3 density matrix which is used to interact the solute with the solvent response surface. The resulting method is variational, produces smooth energies, and has analytic gradients. As a baseline, a conventional SCOSMO model with fixed radii is also parameterized. The SCOSMO and VR-SCOSMO models shown have comparable accuracy in reproducing neutral-molecule absolute solvation free energies; however, the VR-SCOSMO model is shown to reduce the mean unsigned errors (MUEs) of ionic compounds by half (about 2-3 kcal/mol). The VR-SCOSMO model presents similar accuracy as a charge-dependent Poisson-Boltzmann model introduced by Hou et al. [J. Chem. Theory Comput. 6, 2303 (2010)]. VR-SCOSMO is then used to examine the hydrolysis of trimethylphosphate and seven other phosphoryl transesterification reactions with different leaving groups. Two-dimensional energy landscapes are constructed for these reactions and calculated barriers are compared to those obtained from ab initio polarizable continuum calculations and experiment. Results of the VR-SCOSMO model are in good agreement in both cases, capturing the rate-limiting reaction barrier and the nature of the transition state.

Evidence of a multiple boson emission in Sm1-xThxOFeAs

NASA Astrophysics Data System (ADS)

Kuzmichev, S. A.; Kuzmicheva, T. E.; Zhigadlo, N. D.

2017-07-01

We studied a reproducible fine structure observed in dynamic conductance spectra of Andreev arrays in Sm1-x Th x OFeAs superconductors with various thorium concentrations {(x = 0.08\\text{--}0.3)} and critical temperatures Tc = 26\\text{--}50 \\text{K} . This structure is unambiguously caused by a multiple boson emission (of the same energy) during the process of multiple Andreev reflections. The directly determined energy of the bosonic mode reaches \\varepsilon0 = 14.8 +/- 2.2 \\text{meV} for optimal compounds. Within the studied range of T c , this energy as well as the large ΔL and the small ΔS superconducting gaps, nearly scale with critical temperature with the characteristic ratio \\varepsilon_0/k_BTc ≈ 3.2 (and 2Δ_L/k_BTc ≈ 5.3 , respectively) resembling the expected energy ΔL + ΔS of spin resonance and spectral density enhancement in s+/- and s++ states, respectively.

Machine Learning Estimates of Natural Product Conformational Energies

PubMed Central

Rupp, Matthias; Bauer, Matthias R.; Wilcken, Rainer; Lange, Andreas; Reutlinger, Michael; Boeckler, Frank M.; Schneider, Gisbert

2014-01-01

Machine learning has been used for estimation of potential energy surfaces to speed up molecular dynamics simulations of small systems. We demonstrate that this approach is feasible for significantly larger, structurally complex molecules, taking the natural product Archazolid A, a potent inhibitor of vacuolar-type ATPase, from the myxobacterium Archangium gephyra as an example. Our model estimates energies of new conformations by exploiting information from previous calculations via Gaussian process regression. Predictive variance is used to assess whether a conformation is in the interpolation region, allowing a controlled trade-off between prediction accuracy and computational speed-up. For energies of relaxed conformations at the density functional level of theory (implicit solvent, DFT/BLYP-disp3/def2-TZVP), mean absolute errors of less than 1 kcal/mol were achieved. The study demonstrates that predictive machine learning models can be developed for structurally complex, pharmaceutically relevant compounds, potentially enabling considerable speed-ups in simulations of larger molecular structures. PMID:24453952

Extracting electron transfer coupling elements from constrained density functional theory

NASA Astrophysics Data System (ADS)

Wu, Qin; Van Voorhis, Troy

2006-10-01

Constrained density functional theory (DFT) is a useful tool for studying electron transfer (ET) reactions. It can straightforwardly construct the charge-localized diabatic states and give a direct measure of the inner-sphere reorganization energy. In this work, a method is presented for calculating the electronic coupling matrix element (Hab) based on constrained DFT. This method completely avoids the use of ground-state DFT energies because they are known to irrationally predict fractional electron transfer in many cases. Instead it makes use of the constrained DFT energies and the Kohn-Sham wave functions for the diabatic states in a careful way. Test calculations on the Zn2+ and the benzene-Cl atom systems show that the new prescription yields reasonable agreement with the standard generalized Mulliken-Hush method. We then proceed to produce the diabatic and adiabatic potential energy curves along the reaction pathway for intervalence ET in the tetrathiafulvalene-diquinone (Q-TTF-Q) anion. While the unconstrained DFT curve has no reaction barrier and gives Hab≈17kcal /mol, which qualitatively disagrees with experimental results, the Hab calculated from constrained DFT is about 3kcal /mol and the generated ground state has a barrier height of 1.70kcal/mol, successfully predicting (Q-TTF-Q)- to be a class II mixed-valence compound.

Density functional theory study of hydrogen atom abstraction from a series of para-substituted phenols: why is the Hammett σ(p)+ constant able to represent radical reaction rates?

PubMed

Yoshida, Tatsusada; Hirozumi, Koji; Harada, Masataka; Hitaoka, Seiji; Chuman, Hiroshi

2011-06-03

The rate of hydrogen atom abstraction from phenolic compounds by a radical is known to be often linear with the Hammett substitution constant σ(+), defined using the S(N)1 solvolysis rates of substituted cumyl chlorides. Nevertheless, a physicochemical reason for the above "empirical fact" has not been fully revealed. The transition states of complexes between the 2,2-diphenyl-1-picrylhydrazyl radical (dpph·) and a series of para-substituted phenols were determined by DFT (Density Functional Theory) calculations, and then the activation energy as well as the homolytic bond dissociation energy of the O-H bond and charge distribution in the transition state were calculated. The heterolytic bond dissociation energy of the C-Cl bond and charge distribution in the corresponding para-substituted cumyl chlorides were calculated in parallel. Excellent correlations among σ(+), charge distribution, and activation and bond dissociation energies revealed quantitatively that there is a strong similarity between the two reactions, showing that the electron-deficiency of the π-electron system conjugated with a substituent plays a crucial role in determining rates of the two reactions. The results provide a new insight into and physicochemical understanding of σ(+) in the hydrogen abstraction from substituted phenols by a radical.

Preventing droplet deformation during dielectrophoretic centering of a compound emulsion droplet

NASA Astrophysics Data System (ADS)

Randall, Greg; Blue, Brent

2012-11-01

Compound droplets, or droplets-within-droplets, are traditionally key components in applications ranging from drug delivery to the food industry. Presently, millimeter-sized compound droplets are precursors for shell targets in inertial fusion energy work. However, a key constraint in target fabrication is a uniform shell wall thickness, which in turn requires a centered core droplet in the compound droplet precursor. Previously, Bei et al. (2009, 2010) have shown that compound droplets could be centered in a static fluid using an electric field of 0.7 kV/cm at 20 MHz. Randall et al. (2012) developed a process to center the core of a moving compound droplet, though the ~kV/cm field induced small (< 5%) but undesirable droplet stretching. This work shows that by using macromolecular emulsifiers to strengthen the droplet's interfaces, (proteins, tunable peptides, or biotinylated streptavidin) droplet stretching can be greatly inhibited. Proof-of-principle experiments are performed in either a stagnant density-matched aquarium or a vertical channel of buoyancy-driven droplets in a ~kV/cm electric field. A scaling analysis is given from a fluid mechanics and interfacial rheology perspective and we discuss the effective interfacial charge from an emulsifier and its impact on centering. Work funded by General Atomics Internal R&D.

Influence of Donor on the Sensing Performance of a Series of Through-Bond Energy Transfer-Based Two-photon Fluorescent Cu(2+) Probes.

PubMed

Zhang, Yu-Jin; Wang, Xin; Zhou, Yong; Wang, Chuan-Kui

2016-07-01

Optical properties of a series of molecular two-photon fluorescent Cu(2+) probes containing the same acceptor (rhodamine group) are analyzed using time-dependent density functional theory in combination with analytical response theory. Special emphasis is placed on evolution of the probes' optical properties in the presence of Cu(2+) . In this study, the compound with naphthalene as the donor is shown to be excellent ratiometric fluorescent chemosensor, whereas the compound with quinoline derivative as the donor shows off/on-typed colorimetric fluorescent response. For the compound with naphthalimide derivative as the donor, changing the connection between the donor and acceptor can efficiently prevent the fluorescent quenching of the probe both in the absence and presence of Cu(2+) . The donor moiety and the connection between donor and acceptor are thus found to play dominant roles on sensing performance of these probes. Moreover, distributions of molecular orbitals involved in the excitation and emission of the probes are analyzed to explore responsive mechanism of the probes. The through-bond energy transfer process is theoretically demonstrated. Our results are used to elucidate the available experimental measurements. This work is helpful to understand the relationships of structure with optical properties for the studied probes. © 2016 The American Society of Photobiology.

N-(4-Nitrobenzoyl)-N'-(1,5-dimethyl-3-oxo-2-phenyl-1H-3(2H)-pyrazolyl)-thiourea hydrate: Synthesis, spectroscopic characterization, X-ray structure and DFT studies

NASA Astrophysics Data System (ADS)

Arslan, N. Burcu; Kazak, Canan; Aydın, Fatma

2012-04-01

The title molecule (C19H17N5O4S·H2O) was synthesized and characterized by IR-NMR spectroscopy, MS and single-crystal X-ray diffraction. The molecular geometry, vibrational frequencies and gauge-independent atomic orbital (GIAO) 1H and 13C NMR chemical shift values of the compound in the ground state have been calculated by using the density functional theory (DFT) method with 6-31G(d) basis set, and compared with the experimental data. All the assignments of the theoretical frequencies were performed by potential energy distributions using VEDA 4 program. The calculated results show that the optimized geometries can well reproduce the crystal structural parameters, and the theoretical vibrational frequencies and 1H and 13C NMR chemical shift values show good agreement with experimental data. To determine conformational flexibility, the molecular energy profile of the title compound was obtained with respect to the selected torsion angle, which was varied from -180° to +180° in steps of 10°. Besides, molecular electrostatic potential (MEP), frontier molecular orbitals (FMO) analysis and thermodynamic properties of the compound were investigated by theoretical calculations.

Tin phosphide-based anodes for sodium-ion batteries: synthesis via solvothermal transformation of Sn metal and phase-dependent Na storage performance

PubMed Central

Shin, Hyun-Seop; Jung, Kyu-Nam; Jo, Yong Nam; Park, Min-Sik; Kim, Hansung; Lee, Jong-Won

2016-01-01

There is a great deal of current interest in the development of rechargeable sodium (Na)-ion batteries (SIBs) for low-cost, large-scale stationary energy storage systems. For the commercial success of this technology, significant progress should be made in developing robust anode (negative electrode) materials with high capacity and long cycle life. Sn-P compounds are considered promising anode materials that have considerable potential to meet the required performance of SIBs, and they have been typically prepared by high-energy mechanical milling. Here, we report Sn-P-based anodes synthesised through solvothermal transformation of Sn metal and their electrochemical Na storage properties. The temperature and time period used for solvothermal treatment play a crucial role in determining the phase, microstructure, and composition of the Sn-P compound and thus its electrochemical performance. The Sn-P compound prepared under an optimised solvothermal condition shows excellent electrochemical performance as an SIB anode, as evidenced by a high reversible capacity of ~560 mAh g−1 at a current density of 100 mA g−1 and cycling stability for 100 cycles. The solvothermal route provides an effective approach to synthesising Sn-P anodes with controlled phases and compositions, thus tailoring their Na storage behaviour. PMID:27189834

Unsymmetrical and symmetrical azines toward application in organic photovoltaic

NASA Astrophysics Data System (ADS)

Jarczyk-Jedryka, Anna; Bijak, Katarzyna; Sek, Danuta; Siwy, Mariola; Filapek, Michal; Malecki, Grzegorz; Kula, Slawomir; Lewinska, Gabriela; Nowak, Elzbieta M.; Sanetra, Jerzy; Janeczek, Henryk; Smolarek, Karolina; Mackowski, Sebastian; Schab-Balcerzak, Ewa

2015-01-01

The unsymmetrical and symmetrical azines prepared by condensation of benzophenone hydrazone with (di)aldehydes with thiophene rings were reported in this study The structures of obtained compounds were characterized by FTIR, 1H NMR, and 13C NMR spectroscopy as well as elemental analysis. Optical, electrochemical, and thermal properties of azines were investigated. The unsymmetrical azine with bithiophene unit exhibited liquid crystalline properties as was detected by DSC and POM experiments. All compounds are electrochemically active, however, only azines with bithiophene structure undergo reversible reduction process as was found in cyclic and differential pulse voltammetry (CV and DPV) studies. Additionally, the electronic properties, that is, orbital energies and resulting energy gap were calculated theoretically by density functional theory (DFT). The photovoltaic properties of two azines as active layer in organic solar cells at the configuration ITO/PEDOT:PSS/active layer/Al under an illumination of 1.3 mW/cm2 were studied. Active cell layers blends of poly 3-hekxylthiophene (P3HT) or poly 3-butylthiophene (P3OT) with azines were applied. The device comprising P3HT with symmetrical azine containing bithiophene unit showed the highest value of power conversion efficiency (0.82%). To the best of our knowledge, the azines are very seldom considered as potential compounds in active layer in bulk heterojunction (BHJ) solar cells.

Self-consistent method for quantifying indium content from X-ray spectra of thick compound semiconductor specimens in a transmission electron microscope.

PubMed

Walther, T; Wang, X

2016-05-01

Based on Monte Carlo simulations of X-ray generation by fast electrons we calculate curves of effective sensitivity factors for analytical transmission electron microscopy based energy-dispersive X-ray spectroscopy including absorption and fluorescence effects, as a function of Ga K/L ratio for different indium and gallium containing compound semiconductors. For the case of InGaN alloy thin films we show that experimental spectra can thus be quantified without the need to measure specimen thickness or density, yielding self-consistent values for quantification with Ga K and Ga L lines. The effect of uncertainties in the detector efficiency are also shown to be reduced. © 2015 The Authors Journal of Microscopy © 2015 Royal Microscopical Society.

High energy density redox flow device

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

Carter, W. Craig; Chiang, Yet-Ming; Duduta, Mihai

2017-04-04

Redox flow devices are described including a positive electrode current collector, a negative electrode current collector, and an ion-permeable membrane separating said positive and negative current collectors, positioned and arranged to define a positive electroactive zone and a negative electroactive zone; wherein at least one of said positive and negative electroactive zone comprises a flowable semi-solid composition comprising ion storage compound particles capable of taking up or releasing said ions during operation of the cell, and wherein the ion storage compound particles have a polydisperse size distribution in which the finest particles present in at least 5 vol % ofmore » the total volume, is at least a factor of 5 smaller than the largest particles present in at least 5 vol % of the total volume.« less

Zn-VI quasiparticle gaps and optical spectra from many-body calculations.

PubMed

Riefer, A; Weber, N; Mund, J; Yakovlev, D R; Bayer, M; Schindlmayr, Arno; Meier, C; Schmidt, W G

2017-06-01

The electronic band structures of hexagonal ZnO and cubic ZnS, ZnSe, and ZnTe compounds are determined within hybrid-density-functional theory and quasiparticle calculations. It is found that the band-edge energies calculated on the [Formula: see text] (Zn chalcogenides) or GW (ZnO) level of theory agree well with experiment, while fully self-consistent QSGW calculations are required for the correct description of the Zn 3d bands. The quasiparticle band structures are used to calculate the linear response and second-harmonic-generation (SHG) spectra of the Zn-VI compounds. Excitonic effects in the optical absorption are accounted for within the Bethe-Salpeter approach. The calculated spectra are discussed in the context of previous experimental data and present SHG measurements for ZnO.

A computational study of bulk porous two-dimensional polymers related to graphyne.

PubMed

Sánchez-González, A; Dobado, J A; Torneiro, M

2016-08-03

Over the last twelve years there has been an explosion in the area of reticular chemistry with several classes of carbonaceous or carbon-rich reticular compounds coming into the scene and/or suffering an exponential growth in the number of related studies. Examples are MOFs, COFs, graphene and 2D polymers. π-Conjugated reticular compounds in particular are of great interest due to their optoelectronic properties. In this study we use density functional theory methods with periodic boundary conditions to investigate the stacking arrangements of bulk 2D polymer multilayer porous graphyne A, the related carbon allotrope multilayer graphyne B, and the analog bulk 2D polymer C in which the triple bonds of A are substituted by double bonds. The results show that for the three materials the eclipsed stacking arrangements are considerably less stable than staggered and slipped arrangements, with the more stable structures being slipped, staggered and off-centered-staggered arrangements for A, B and C, respectively. To shed light on the π-π interactions responsible for the geometry and relative energies of the different stacking modes we analyze the topology of the electron density using the electron localization function. In addition, simulated patterns for powder X-ray diffraction have been obtained from the optimized systems, which can be used for identification of the bulk 2D reticular compounds in future syntheses.

Systems and methods for solar energy storage, transportation, and conversion utilizing photochemically active organometallic isomeric compounds and solid-state catalysts

DOEpatents

Vollhardt, K. Peter C.; Segalman, Rachel A; Majumdar, Arunava; Meier, Steven

2015-02-10

A system for converting solar energy to chemical energy, and, subsequently, to thermal energy includes a light-harvesting station, a storage station, and a thermal energy release station. The system may include additional stations for converting the released thermal energy to other energy forms, e.g., to electrical energy and mechanical work. At the light-harvesting station, a photochemically active first organometallic compound, e.g., a fulvalenyl diruthenium complex, is exposed to light and is photochemically converted to a second, higher-energy organometallic compound, which is then transported to a storage station. At the storage station, the high-energy organometallic compound is stored for a desired time and/or is transported to a desired location for thermal energy release. At the thermal energy release station, the high-energy organometallic compound is catalytically converted back to the photochemically active organometallic compound by an exothermic process, while the released thermal energy is captured for subsequent use.

Molecular structure and spectroscopic characterization of Carbamazepine with experimental techniques and DFT quantum chemical calculations.

PubMed

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

2015-04-15

A systematic vibrational spectroscopic assignment and analysis of Carbamazepine has been carried out by using FT-IR, FT-Raman and UV spectral data. The vibrational analysis were aided by electronic structure calculations - ab initio (RHF) and hybrid density functional methods (B3LYP) performed with standard basis set 6-31G(d,p). Molecular equilibrium geometries, electronic energies, natural bond order analysis, harmonic vibrational frequencies and IR intensities have been computed. A detailed interpretation of the vibrational spectra of the molecule has been made on the basis of the calculated Potential Energy Distribution (PED) by VEDA program. UV-visible spectrum of the compound was also recorded and the electronic properties, such as HOMO and LUMO energies and λmax were determined by HF/6-311++G(d,p) Time-Dependent method. The thermodynamic functions of the title molecule were also performed using the RHF and DFT methods. The restricted Hartree-Fock and density functional theory-based nuclear magnetic resonance (NMR) calculation procedure was also performed, and it was used for assigning the (13)C and (1)H NMR chemical shifts of Carbamazepine. Copyright © 2015 Elsevier B.V. All rights reserved.

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.

Ignition delays, heats of combustion, and reaction rates of aluminum alkyl derivatives used as ignition and combustion enhancers for supersonic combustion

NASA Technical Reports Server (NTRS)

Ryan, Thomas W., III; Schwab, S. T.; Harlowe, W. W.

1992-01-01

The subject of this paper is the design of supersonic combustors which will be required in order to achieve the needed reaction rates in a reasonable sized combustor. A fuel additive approach, which is the focus of this research, is the use of pyrophorics to shorten the ignition delay time and to increase the energy density of the fuel. Pyrophoric organometallic compounds may also provide an ignition source and flame stabilization mechanism within the combustor, thus permitting use of hydrocarbon fuels in supersonic combustion systems. Triethylaluminum (TEA) and trimethylaluminum (TMA) were suggested for this application due to their high energy density and reactivity. The objective here is to provide comparative data for the ignition quality, the energy content, and the reaction rates of several different adducts of both TEA and TMA. The results of the experiments indicate the aluminum alkyls and their more stable derivatives reduce the ignition delay and total reaction time to JP-10 jet fuel. Furthermore, the temperature dependence of ignition delay and total reaction time of the blends of the adducts are significantly lower than in neat JP-10.

FT-IR and Raman spectra, DFT and SQMFF calculations for geometrical interpretation and vibrational analysis of 3-nitro-p-toluic acid

NASA Astrophysics Data System (ADS)

Nataraj, A.; Balachandran, V.; Karthick, T.

2012-08-01

The Fourier transform infrared (FT-IR) and FT-Raman of 3-nitro-p-toluic acid (NTA) have been recorded and analyzed. The equilibrium geometry, bonding features and harmonic vibrational frequencies have been investigated with the help of ab initio and density functional theory (DFT) methods. 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 methodology (SQMFF). The optimized geometric bond lengths and bond angles obtained by computation show good agreement with experimental data of the relative compound. The computed dimer parameters also show good agreement with experimental data. The first hyperpolarizability (β0) of this noval molecular system and related properties (β, α0, and Δα) of NTA are calculated using B3LYP/6-311++G(d,p) method on the finite-field approach. Stability of the molecule arising from hyperconjugative interactions, charge delocalization have been analyzed using natural bond orbital (NBO) analysis. The results show that charge in electron density (ED) in the σ* and π* antibonding orbital and second order delocalization energies E(2) confirms the occurrence of intramolecular charge transfer (ICT) within the molecule. The calculated HOMO and LUMO energies also show that charge transfer occurs within the molecule. Finally the calculations results were applied to simulated infrared and Raman spectra of the title compound which show good agreement with observed spectra.

Using 1H and 13C NMR chemical shifts to determine cyclic peptide conformations: a combined molecular dynamics and quantum mechanics approach.

PubMed

Nguyen, Q Nhu N; Schwochert, Joshua; Tantillo, Dean J; Lokey, R Scott

2018-05-10

Solving conformations of cyclic peptides can provide insight into structure-activity and structure-property relationships, which can help in the design of compounds with improved bioactivity and/or ADME characteristics. The most common approaches for determining the structures of cyclic peptides are based on NMR-derived distance restraints obtained from NOESY or ROESY cross-peak intensities, and 3J-based dihedral restraints using the Karplus relationship. Unfortunately, these observables are often too weak, sparse, or degenerate to provide unequivocal, high-confidence solution structures, prompting us to investigate an alternative approach that relies only on 1H and 13C chemical shifts as experimental observables. This method, which we call conformational analysis from NMR and density-functional prediction of low-energy ensembles (CANDLE), uses molecular dynamics (MD) simulations to generate conformer families and density functional theory (DFT) calculations to predict their 1H and 13C chemical shifts. Iterative conformer searches and DFT energy calculations on a cyclic peptide-peptoid hybrid yielded Boltzmann ensembles whose predicted chemical shifts matched the experimental values better than any single conformer. For these compounds, CANDLE outperformed the classic NOE- and 3J-coupling-based approach by disambiguating similar β-turn types and also enabled the structural elucidation of the minor conformer. Through the use of chemical shifts, in conjunction with DFT and MD calculations, CANDLE can help illuminate conformational ensembles of cyclic peptides in solution.

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.

Independent and combined effects of eating rate and energy density on energy intake, appetite, and gut hormones.

PubMed

Karl, J Philip; Young, Andrew J; Rood, Jennifer C; Montain, Scott J

2013-03-01

Energy density (ED) and eating rate (ER) influence energy intake; their combined effects on intake and on postprandial pancreatic and gut hormone responses are undetermined. To determine the combined effects of ED and ER manipulation on voluntary food intake, subjective appetite, and postprandial pancreatic and gut hormone responses. Twenty nonobese volunteers each consumed high (1.6 kcal g(-1) ; HED) and low (1.2 kcal g(-1) ; LED) ED breakfasts slowly (20 g min(-1) ; SR) and quickly (80 g min(-1) ; FR) ad libitum to satiation. Appetite, and pancreatic and gut hormone concentrations were measured periodically over 3 h. Ad libitum energy intake during the subsequent lunch was then measured. Main effects of ED and ER on energy intake and a main effect of ER, but not ED, on mass of food consumed were observed, FR and HED being associated with increased intake (P < 0.05). Across all conditions, energy intake was highest during FR-HED (P ≤ 0.01). Area under the curve (AUC) of appetite ratings was not different between meals. Main effects of ED and ER on insulin, peptide-YY, and glucagon-like peptide-1 AUC (P < 0.05) were observed, FR and HED being associated with larger AUC. No effects on active or total ghrelin AUC were documented. Total energy intake over both meals was highest during the FR-HED trial with the greatest difference between FR-HED and SR-LED trials (P ≤ 0.01). Consuming an energy dense meal quickly compounds independent effects of ER and ED on energy intake. Energy compensation at the following meal may not occur despite altered gut hormone responses. Copyright © 2013 The Obesity Society.

Molecular structure, quantum mechanical calculation and radical scavenging activities of (E)-4,6-dibromo-2-[(3,5-dimethylphenylimino)methyl]-3-methoxyphenol and (E)-4,6-dibromo-2-[(2,6-dimethylphenylimino)methyl]-3-methoxyphenol compounds.

PubMed

Alaşalvar, Can; Soylu, Mustafa Serkan; Güder, Aytaç; Albayrak, Çiğdem; Apaydın, Gökhan; Dilek, Nefise

2014-09-15

In this study, (E)-4,6-dibromo-2-[(3,5-dimethylphenylimino)methyl]-3-methoxyphenol and (E)-4,6-dibromo-2-[(2,6-dimethylphenylimino)methyl]-3-methoxyphenol compounds have been synthesized and characterized by using X-ray crystallographic method, FT-IR and Density functional method. The molecular geometry, vibrational frequencies of the title compounds in the ground state have been calculated by using B3LYP with the 6-31G(d,p) basis set. The tautomeric form of the compounds has been demonstrated by using single crystal X-ray method, FT-IR spectrometer and DFT method. In addition, HOMO-LUMO energy gap, molecular electrostatic potential map and NBO analysis of the compounds are performed at B3LYP/6-31G(d,p) level. It may be remarked that the free radical scavenging activities of the title compounds were assessed using DPPH, DMPD+, and ABTS+ assays. The obtained results show that especially compound 2 has effective DPPH (SC50 1.52±0.14 μg/mL), DMPD+ (SC50 1.22±0.21 μg/mL), and ABTS+ (SC50 3.32±0.17 μg/mL) scavenging activities compared with standards (BHA, rutin, and trolox). Copyright © 2014 Elsevier B.V. All rights reserved.

Study of angular momentum variation due to entrance channel effect in heavy ion fusion reactions

NASA Astrophysics Data System (ADS)

Kumar, Ajay

2014-05-01

A systematic investigation of the properties of hot nuclei may be studied by detecting the evaporated particles. These emissions reflect the behavior of the nucleus at various stages of the deexcitation cascade. When the nucleus is formed by the collision of a heavy nucleus with a light particle, the statistical model has done a good job of predicting the distribution of evaporated particles when reasonable choices were made for the level densities and yrast lines. Comparison to more specific measurements could, of course, provide a more severe test of the model and enable one to identify the deviations from the statistical model as the signature of other effects not included in the model. Some papers have claimed that experimental evaporation spectra from heavy-ion fusion reactions at higher excitation energies and angular momenta are no longer consistent with the predictions of the standard statistical model. In order to confirm this prediction we have employed two systems, a mass-symmetric (31P+45Sc) and a mass-asymmetric channel (12C+64Zn), leading to the same compound nucleus 76Kr* at the excitation energy of 75 MeV. Neutron energy spectra of the asymmetric system (12C+64Zn) at different angles are well described by the statistical model predictions using the normal value of the level density parameter a = A/8 MeV-1. However, in the case of the symmetric system (31P+45Sc), the statistical model interpretation of the data requires the change in the value of a = A/10 MeV-1. The delayed evolution of the compound system in case of the symmetric 31P+45Sc system may lead to the formation of a temperature equilibrated dinuclear complex, which may be responsible for the neutron emission at higher temperature, while the protons and alpha particles are evaporated after neutron emission when the system is sufficiently cooled down and the higher g-values do not contribute in the formation of the compound nucleus for the symmetric entrance channel in case of charged particle emission.

Continued development of thallium bromide and related compounds for gamma-ray spectrometers

NASA Astrophysics Data System (ADS)

Kim, H.; Churilov, A.; Ciampi, G.; Cirignano, L.; Higgins, W.; Kim, S.; O'Dougherty, P.; Olschner, F.; Shah, Kanai

2011-02-01

Thallium bromide (TlBr) and related ternary compounds, TlBrI and TlBrCl, have been under development for room temperature gamma-ray spectroscopy due to high density, high Z and wide bandgap of the material. Low melting point and cubic crystal structure of selected compositions of these compounds facilitate crystal growth by melt techniques. Recent advances in material purification, crystal growth, and device processing have led to mobility-lifetime products of electrons in the mid 10 -3 cm 2/V range enabling working detectors of greater than 15 mm thickness to be fabricated. In this paper we report on our recent progress on TlBr detector development and first results from TlBr xCl 1- x devices. Pulse height spectra will be presented from TlBr arrays as thick as 18 mm. Depth corrected spectra will also be presented. For a 5 mm thick TlBr array, energy resolution of less than 1% (FWHM at 662 keV) was obtained after depth correction.

DFT calculations, spectroscopy and antioxidant activity studies on (E)-2-nitro-4-[(phenylimino)methyl]phenol.

PubMed

Temel, Ersin; Alaşalvar, Can; Gökçe, Halil; Güder, Aytaç; Albayrak, Çiğdem; Alpaslan, Yelda Bingöl; Alpaslan, Gökhan; Dilek, Nefise

2015-02-05

We have reported synthesis and characterization of (E)-2-nitro-4-[(phenylimino)methyl]phenol by using X-ray crystallographic method, FT-IR and UV-vis spectroscopies and density functional theory (DFT). Optimized geometry and vibrational frequencies of the title compound in the ground state have been computed by using B3LYP with the 6-311G+(d,p) basis set. HOMO-LUMO energy gap, Non-linear optical properties and NBO analysis of the compound are performed at B3LYP/6-311G+(d,p) level. Additionally, as remarkable properties, antioxidant activity of the title compound (CMPD) has been determined by using different antioxidant test methods i.e. ferric reducing antioxidant power (FRAP), hydrogen peroxide scavenging (HPSA), free radical scavenging (FRSA) and ferrous ion chelating activities (FICA). When compared with standards (BHA, BHT, and α-tocopherol), we have concluded that CPMD has effective FRAP, HPSA, FRSA and FICA. Copyright © 2014 Elsevier B.V. All rights reserved.

Reversible Redox Chemistry of Azo Compounds for Sodium-Ion Batteries

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

Luo, Chao; Xu, Gui-Liang; Ji, Xiao

Sustainable sodium-ion batteries (SSIBs) using renewable organic electrodes are promising alternatives to lithium-ion batteries for the large-scale renewable energy storage. However, the lack of high-performance anode material impedes the development of SSIBs. Herein, we report a new type of organic anode material based on azo group for SSIBs. Azobenzene-4,4'-dicarboxylic acid sodium salt is used as a model to investigate the electrochemical behaviors and reaction mechanism of azo compound. It exhibits a reversible capacity of 170 mAhg -1 at 0.2C. When current density is increased to 20C, the reversible capacities of 98 mAhg -1 can be retained for 2000 cycles, demonstratingmore » excellent cycling stability and high rate capability. The detailed characterizations reveal that azo group acts as an electrochemical active site to reversibly bond with Na +. The reversible redox chemistry between azo compound and Na ions offer opportunities for developing longcycle-life and high-rate SSIBs.« less

Reversible Redox Chemistry of Azo Compounds for Sodium-Ion Batteries

DOE PAGES

Luo, Chao; Xu, Gui-Liang; Ji, Xiao; ...

2018-01-29

Sustainable sodium-ion batteries (SSIBs) using renewable organic electrodes are promising alternatives to lithium-ion batteries for the large-scale renewable energy storage. However, the lack of high-performance anode material impedes the development of SSIBs. Herein, we report a new type of organic anode material based on azo group for SSIBs. Azobenzene-4,4'-dicarboxylic acid sodium salt is used as a model to investigate the electrochemical behaviors and reaction mechanism of azo compound. It exhibits a reversible capacity of 170 mAhg -1 at 0.2C. When current density is increased to 20C, the reversible capacities of 98 mAhg -1 can be retained for 2000 cycles, demonstratingmore » excellent cycling stability and high rate capability. The detailed characterizations reveal that azo group acts as an electrochemical active site to reversibly bond with Na +. The reversible redox chemistry between azo compound and Na ions offer opportunities for developing longcycle-life and high-rate SSIBs.« less

High-throughput search of ternary chalcogenides for p-type transparent electrodes

PubMed Central

Shi, Jingming; Cerqueira, Tiago F. T.; Cui, Wenwen; Nogueira, Fernando; Botti, Silvana; Marques, Miguel A. L.

2017-01-01

Delafossite crystals are fascinating ternary oxides that have demonstrated transparent conductivity and ambipolar doping. Here we use a high-throughput approach based on density functional theory to find delafossite and related layered phases of composition ABX2, where A and B are elements of the periodic table, and X is a chalcogen (O, S, Se, and Te). From the 15 624 compounds studied in the trigonal delafossite prototype structure, 285 are within 50 meV/atom from the convex hull of stability. These compounds are further investigated using global structural prediction methods to obtain their lowest-energy crystal structure. We find 79 systems not present in the materials project database that are thermodynamically stable and crystallize in the delafossite or in closely related structures. These novel phases are then characterized by calculating their band gaps and hole effective masses. This characterization unveils a large diversity of properties, ranging from normal metals, magnetic metals, and some candidate compounds for p-type transparent electrodes. PMID:28266587

Magnetic properties and magnetocrystalline anisotropy of Nd 2Fe 17, Nd 2Fe 17X 3, and related compounds

DOE PAGES

Pandey, Tribhuwan; Parker, David S.

2018-02-26

The electronic and magnetic properties of Nd 2Fe 17 and Nd 2Fe 17X 3 (X = C or N) compounds have been calculated using the first-principles density functional calculations. Among these, the nitrogen and carbon interstitial compounds exhibit all of the required properties such as a saturation moment of 1.6 T, Curie temperature of 700–750 K, however easy magnetic axis lies in the planar direction making them less attractive for permanent magnet applications. The calculated magnetocrystalline anisotropy energy is found to be -2.7 MJ/m 3 for Nd 2Fe 17C 3 and -4.7 MJ/m 3 for Nd 2Fe 17N 3. Finally,more » we further explored the possibility of changing the easy axis direction through La/Ce alloying at Nd site. Although the MAE is found to be smaller in magnitude for all the La/Ce alloys it still maintains planar direction.« less

Compression molded energy storage flywheels

NASA Astrophysics Data System (ADS)

Burdick, P. A.

Materials choices, manufacturing processes, and benefits of flywheels as an effective energy storage device are discussed. Tests at the LL Laboratories have indicated that compressing molding of plies of structural sheet molding compound (SMC) filled with randomly oriented fibers produces a laminated disk with transversely isotropic properties. Good performance has been realized with a carbon/epoxy system, which displays satisfactory stiffness and strength in flywheel applications. A core profile has been selected, consisting of a uniform 1 in cross sectional thickness and a 21 in diam. Test configurations using three different resin paste formulations were compared after being mounted elastomerically on aluminum hubs. Further development was found necessary on accurate balancing and hub bonding. It was concluded that the SMC flywheels display the low-cost, sufficient energy densities, suitable dynamic stability characteristics, and acceptably benign failure modes for automotive applications.

Rapid discovery and functional characterization of terpene synthases from four endophytic xylariaceae

DOE PAGES

Wu, Weihua; Tran, William; Taatjes, Craig A.; ...

2016-02-17

Endophytic fungi are ubiquitous plant endosymbionts that establish complex and poorly understood relationships with their host organisms. Many endophytic fungi are known to produce a wide spectrum of volatile organic compounds (VOCs) with potential energy applications, which have been described as "mycodiesel". Many of these mycodiesel hydrocarbons are terpenes, a chemically diverse class of compounds produced by many plants, fungi, and bacteria. Due to their high energy densities, terpenes, such as pinene and bisabolene, are actively being investigated as potential "drop-in" biofuels for replacing diesel and aviation fuel. In this study, we rapidly discovered and characterized 26 terpene synthases (TPSs)more » derived from four endophytic fungi known to produce mycodiesel hydrocarbons. The TPS genes were expressed in an E. coli strain harboring a heterologous mevalonate pathway designed to enhance terpene production, and their product profiles were determined using Solid Phase Micro-Extraction (SPME) and GC-MS. Lastly, out of the 26 TPS’s profiled, 12 TPS’s were functional, with the majority of them exhibiting both monoterpene and sesquiterpene synthase activity.« less

Rapid discovery and functional characterization of terpene synthases from four endophytic xylariaceae

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

Wu, Weihua; Tran, William; Taatjes, Craig A.

Endophytic fungi are ubiquitous plant endosymbionts that establish complex and poorly understood relationships with their host organisms. Many endophytic fungi are known to produce a wide spectrum of volatile organic compounds (VOCs) with potential energy applications, which have been described as "mycodiesel". Many of these mycodiesel hydrocarbons are terpenes, a chemically diverse class of compounds produced by many plants, fungi, and bacteria. Due to their high energy densities, terpenes, such as pinene and bisabolene, are actively being investigated as potential "drop-in" biofuels for replacing diesel and aviation fuel. In this study, we rapidly discovered and characterized 26 terpene synthases (TPSs)more » derived from four endophytic fungi known to produce mycodiesel hydrocarbons. The TPS genes were expressed in an E. coli strain harboring a heterologous mevalonate pathway designed to enhance terpene production, and their product profiles were determined using Solid Phase Micro-Extraction (SPME) and GC-MS. Lastly, out of the 26 TPS’s profiled, 12 TPS’s were functional, with the majority of them exhibiting both monoterpene and sesquiterpene synthase activity.« less

Characteristics of 2-heptanone decomposition using nanosecond pulsed discharge plasma

NASA Astrophysics Data System (ADS)

Nakase, Yuki; Fukuchi, Yuichi; Wang, Douyan; Namihira, Takao; Akiyama, Hidenori; Kumamoto University Collaboration

2015-09-01

Volatile organic compounds (VOC) evaporate at room temperature. VOCs typically consist of toluene, benzene and ethyl acetate, which are used in cosmetics, dry cleaning products and paints. Exposure to elevated levels of VOCs may cause headaches, dizziness and irritation to the eyes, nose, and throat; they may also cause environmental problems such as air pollution, acid rain and photochemical smog. As such, they require prompt removal. Nanosecond pulsed discharge is a kind of non-thermal plasma consisting of a streamer discharge. Several advantages of nanosecond pulsed discharge plasma have been demonstrated by studies of our research group, including low heat loss, highly energetic electron generation, and the production of highly active radicals. These advantages have shown ns pulsed discharge plasma capable of higher energy efficiency for processes, such as air purification, wastewater treatment and ozone generation. In this research, nanosecond pulsed discharge plasma was employed to treat 2-heptanone, which is a volatile organic compound type and presents several harmful effects. Characteristics of treatment dependent on applied voltage, gas flow rate and input energy density were investigated. Furthermore, byproducts generated by treatment were also investigated.

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.

Insertion compounds and composites made by ball milling for advanced sodium-ion batteries

PubMed Central

Zhang, Biao; Dugas, Romain; Rousse, Gwenaelle; Rozier, Patrick; Abakumov, Artem M.; Tarascon, Jean-Marie

2016-01-01

Sodium-ion batteries have been considered as potential candidates for stationary energy storage because of the low cost and wide availability of Na sources. However, their future commercialization depends critically on control over the solid electrolyte interface formation, as well as the degree of sodiation at the positive electrode. Here we report an easily scalable ball milling approach, which relies on the use of metallic sodium, to prepare a variety of sodium-based alloys, insertion layered oxides and polyanionic compounds having sodium in excess such as the Na4V2(PO4)2F3 phase. The practical benefits of preparing sodium-enriched positive electrodes as reservoirs to compensate for sodium loss during solid electrolyte interphase formation are demonstrated by assembling full C/P′2-Na1[Fe0.5Mn0.5]O2 and C/‘Na3+xV2(PO4)2F3' sodium-ion cells that show substantial increases (>10%) in energy storage density. Our findings may offer electrode design principles for accelerating the development of the sodium-ion technology. PMID:26777573

Adsorption of Emerging Munitions Contaminants on Cellulose Surface: A Combined Theoretical and Experimental Investigation.

PubMed

Shukla, Manoj K; Poda, Aimee

2016-06-01

This manuscript reports results of an integrated theoretical and experimental investigation of adsorption of two emerging contaminants (DNAN and FOX-7) and legacy compound TNT on cellulose surface. Cellulose was modeled as trimeric form of the linear chain of 1 → 4 linked of β-D-glucopyranos in (4)C1 chair conformation. Geometries of modeled cellulose, munitions compounds and their complexes were optimized at the M06-2X functional level of Density Functional Theory using the 6-31G(d,p) basis set in gas phase and in water solution. The effect of water solution was modeled using the CPCM approach. Nature of potential energy surfaces was ascertained through harmonic vibrational frequency analysis. Interaction energies were corrected for basis set superposition error and the 6-311G(d,p) basis set was used. Molecular electrostatic potential mapping was performed to understand the reactivity of the investigated systems. It was predicted that adsorbates will be weakly adsorbed on the cellulose surface in water solution than in the gas phase.

A Membrane‐Free Redox Flow Battery with Two Immiscible Redox Electrolytes

PubMed Central

Navalpotro, Paula; Palma, Jesus; Anderson, Marc

2017-01-01

Abstract Flexible and scalable energy storage solutions are necessary for mitigating fluctuations of renewable energy sources. The main advantage of redox flow batteries is their ability to decouple power and energy. However, they present some limitations including poor performance, short‐lifetimes, and expensive ion‐selective membranes as well as high price, toxicity, and scarcity of vanadium compounds. We report a membrane‐free battery that relies on the immiscibility of redox electrolytes and where vanadium is replaced by organic molecules. We show that the biphasic system formed by one acidic solution and one ionic liquid, both containing quinoyl species, behaves as a reversible battery without any membrane. This proof‐of‐concept of a membrane‐free battery has an open circuit voltage of 1.4 V with a high theoretical energy density of 22.5 Wh L−1, and is able to deliver 90 % of its theoretical capacity while showing excellent long‐term performance (coulombic efficiency of 100 % and energy efficiency of 70 %). PMID:28658538

Effects of alkanolamide addition on crosslink density, mechanical and morphological properties of chloroprene rubber compounds

NASA Astrophysics Data System (ADS)

Surya, I.; Hayeemasae, N.

2018-03-01

The effects of alkanolamide (ALK) addition on crosslink density, mechanical and morphological properties of unfilled polychloroprene rubber (CR) compounds were investigated. The ALK was prepared from Refined Bleached Deodorized Palm Stearin (RBDPS) and diethanolamine and -together with magnesium and zinc oxides-incorporated into the unfilled CR compounds. The ALK loadings were 0.5, 1.0, 1.5 and 2.0 phr. It was found that ALK enhanced crosslink density, tensile modulus, tensile strength and hardness especially up to a 1.5 phr loading. Scanning Electron Microscopy (SEM) proved that the 1.5 phr of ALK exhibited the greatest matrix tearing line and surface roughness, due to the highest degree of crosslink density and mechanical properties.

Vibrational spectroscopy and density functional theory analysis of 3-O-caffeoylquinic acid

NASA Astrophysics Data System (ADS)

Mishra, Soni; Tandon, Poonam; Eravuchira, Pinkie J.; El-Abassy, Rasha M.; Materny, Arnulf

2013-03-01

Density functional theory (DFT) calculations are being performed to investigate the geometric, vibrational, and electronic properties of the chlorogenic acid isomer 3-CQA (1R,3R,4S,5R)-3-{[(2E)-3-(3,4-dihydroxyphenyl)prop-2-enoyl]oxy}-1,4,5-trihydroxycyclohexanecarboxylic acid), a major phenolic compound in coffee. DFT calculations with the 6-311G(d,p) basis set produce very good results. The electrostatic potential mapped onto an isodensity surface has been obtained. A natural bond orbital analysis (NBO) has been performed in order to study intramolecular bonding, interactions among bonds, and delocalization of unpaired electrons. HOMO-LUMO studies give insights into the interaction of the molecule with other species. The calculated HOMO and LUMO energies indicate that a charge transfer occurs within the molecule.

Test of the Brink-Axel Hypothesis for the Pygmy Dipole Resonance

NASA Astrophysics Data System (ADS)

Martin, D.; von Neumann-Cosel, P.; Tamii, A.; Aoi, N.; Bassauer, S.; Bertulani, C. A.; Carter, J.; Donaldson, L.; Fujita, H.; Fujita, Y.; Hashimoto, T.; Hatanaka, K.; Ito, T.; Krugmann, A.; Liu, B.; Maeda, Y.; Miki, K.; Neveling, R.; Pietralla, N.; Poltoratska, I.; Ponomarev, V. Yu.; Richter, A.; Shima, T.; Yamamoto, T.; Zweidinger, M.

2017-11-01

The gamma strength function and level density of 1- states in 96Mo have been extracted from a high-resolution study of the (p → , p→ ' ) reaction at 295 MeV and extreme forward angles. By comparison with compound nucleus γ decay experiments, this allows a test of the generalized Brink-Axel hypothesis in the energy region of the pygmy dipole resonance. The Brink-Axel hypothesis is commonly assumed in astrophysical reaction network calculations and states that the gamma strength function in nuclei is independent of the structure of the initial and final state. The present results validate the Brink-Axel hypothesis for 96Mo and provide independent confirmation of the methods used to separate gamma strength function and level density in γ decay experiments.

Local spin density functional investigations of a manganite with perovskite-type derived structures

NASA Astrophysics Data System (ADS)

Matar, S. F.; Studer, F.; Siberchicot, B.; Subramanian, M. A.; Demazeau, G.; Etourneau, J.

1998-11-01

The electronic and magnetic structures of the perovskite CaMnO3 are self-consistently calculated assuming two crystal structures at the same formula unit volume within the local spin density functional theory and the augmented spherical wave (ASW) method. From the comparisons of energy differences between the different magnetic states the ground state configuration is an insulator with G-type ordering. This result together with the magnitudes of the magnetic moments are in agreement with experiment. The influence of mixing between Mn and O is found spin dependent from the analysis of the crystal orbital overlap population (COOP) which enable to describe the chemical bond. The calculations underline a feature of a half metallic ferromagnet which could be connected with the colossal magnetoresistance (CMR) property of related compounds.

Ab-initio investigations for opto-electronic response of (Cd, Zn)Ga2Te4: Promising solar PV materials

NASA Astrophysics Data System (ADS)

Sahariya, Jagrati; Soni, Amit; Kumar, Pancham

2018-04-01

In this paper, the first principle calculations are performed to analyze the structural, electronic and optical behavior of promising solar materials (Cd,Zn)Ga2Te4. To perform these calculations we have used one of the most accurate Full Potential Linearized Augmented Plane Wave (FP-LAPW) method. The ground state properties of these compounds are confirmed over here after proper examination of energy and charge convergence using Perdew-Burke-Ernzerhof (PBE-sol) exchange correlation potential. The investigations performed such as energy band structure, Density of States (DOS), optical parameters like complex dielectric function and absorption co-efficient are discussed over here to understand the overall response of the chosen system.

Binding matter with antimatter: the covalent positron bond.

PubMed

Charry, Jorge Alfonso; Varella, Marcio T Do N; Reyes, Andrés

2018-05-16

We report sufficient theoretical evidence of the energy stability of the e⁺H₂²⁻ molecule, formed by two H⁻ anions and one positron. Analysis of the electronic and positronic densities of the latter compound undoubtedly points out the formation of a positronic covalent bond between the otherwise repelling hydride anions. The lower limit for the bonding energy of the e⁺H₂²⁻ molecule is 74 kJ/mol (0.77 eV), accounting for the zero-point vibrational correction. The formation of a non electronic covalent bond is fundamentally distinct from positron attachment to stable molecules, as the latter process is characterized by a positron affinity, analogous to the electron affinity. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

ImagingReso: A Tool for Neutron Resonance Imaging

DOE PAGES

Zhang, Yuxuan; Bilheux, Jean -Christophe

2017-11-01

ImagingReso is an open-source Python library that simulates the neutron resonance signal for neutron imaging measurements. By defining the sample information such as density, thickness in the neutron path, and isotopic ratios of the elemental composition of the material, this package plots the expected resonance peaks for a selected neutron energy range. Various sample types such as layers of single elements (Ag, Co, etc. in solid form), chemical compounds (UO 3, Gd 2O 3, etc.), or even multiple layers of both types can be plotted with this package. As a result, major plotting features include display of the transmission/attenuation inmore » wavelength, energy, and time scale, and show/hide elemental and isotopic contributions in the total resonance signal.« less

Point defects in thorium nitride: A first-principles study

NASA Astrophysics Data System (ADS)

Pérez Daroca, D.; Llois, A. M.; Mosca, H. O.

2016-11-01

Thorium and its compounds (carbides and nitrides) are being investigated as possible materials to be used as nuclear fuels for Generation-IV reactors. As a first step in the research of these materials under irradiation, we study the formation energies and stability of point defects in thorium nitride by means of first-principles calculations within the framework of density functional theory. We focus on vacancies, interstitials, Frenkel pairs and Schottky defects. We found that N and Th vacancies have almost the same formation energy and that the most energetically favorable defects of all studied in this work are N interstitials. These kind of results for ThN, to the best authors' knowledge, have not been obtained previously, neither experimentally, nor theoretically.

DFT description of the magnetic properties and electron localization in dinuclear di-mu-oxo-bridged manganese complexes.

PubMed

Barone, Vincenzo; Bencini, Alessandro; Gatteschi, Dante; Totti, Federico

2002-11-04

Density functional theory (DFT) was applied to describe the magnetic and electron-transfer properties of dinuclear systems containing the [MnO2Mn]n+ core, with n=0,1,2,3,4. The calculation of the potential energy surfaces (PESs) of the mixed-valence species (n=1,3) allowed the classification of these systems according to the extent of valence localization as Class II compounds, in the Robin-Day classification scheme. The fundamental frequencies corresponding to the asymmetric breathing vibration were also computed.

Theoretical study of the magnetic behavior of hexanuclear Cu(II) and Ni(II) polysiloxanolato complexes.

PubMed

Ruiz, Eliseo; Cano, Joan; Alvarez, Santiago; Caneschi, Andrea; Gatteschi, Dante

2003-06-04

A theoretical density functional study of the exchange coupling in hexanuclear polysiloxanolato-bridged complexes of Cu(II) and Ni(II) is presented. By calculating the energies of three different spin configurations, we can obtain estimates of the first-, second-, and third-neighbor exchange coupling constants. The study has been carried out for the complete structures of the Cu pristine cluster and of the chloroenclathrated Ni complex as well as for the hypotethical pristine Ni compound and for magnetically dinuclear analogues M(2)Zn(4) (M = Cu, Ni).

Development of Synthesis and Large Scale Production Technology for Ultrahigh Energy and Density Fluoro-Organic Compounds

DTIC Science & Technology

2005-12-01

M-I (H2C=CHSF5). To 3.5 g potassium hydroxide in 4 mL of water was added 10.5 mL of isopropanol in a 50 mL three-necked flask equipped with an...S- 5 2006 Ne Tech New Era Technology, Inc. 3720 NW 4 3rd Street, Suite 105, Gainesville, Florida 32606-6190, USA Final Report TITLE: Development of ...Senior Scientist, NeTech Research Institute (Subcontractor): University of Florida Dr. William R. Dolbier, Jr., P1 - University of Florida, Crow

THERMOCHEMICAL CONVERSION OF FERMENTATION-DERIVED OXYGENATES TO FUELS

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

Ramasamy, Karthikeyan K.; Wang, Yong

2013-06-01

At present ethanol generated from renewable resources through fermentation process is the dominant biofuel. But ethanol suffers from undesirable fuel properties such as low energy density and high water solubility. The production capacity of fermentation derived oxygenates are projected to rise in near future beyond the current needs. The conversion of oxygenates to hydrocarbon compounds that are similar to gasoline, diesel and jet fuel is considered as one of the viable option. In this chapter the thermo catalytic conversion of oxygenates generated through fermentation to fuel range hydrocarbons will be discussed.

Tocopherol transport in the rat erythrocyte

PubMed Central

Silber, R.; Winter, R.; Kayden, H. J.

1969-01-01

The transport of vitamin E (α-tocopherol) has been studied in the rat erythrocyte in vivo and in vitro. Uptake and efflux are independent of energy, but sensitive to temperature. Tocopherol is localized to the cell membrane. Rapid exchange takes place between erythrocytes and serum with an hourly fractional tocopherol efflux of 26%. The vitamin is transferred from the erythrocyte to the low density lipoproteins. These experiments indicate that tocopherol, like cholesterol, is a constituent of the erythrocyte membrane which is in dynamic equilibrium with the corresponding plasma compound. PMID:5824074

The spectroscopic (FTIR, FT-Raman and UV-Vis spectra), DFT and normal coordinate computations of m-nitromethylbenzoate

NASA Astrophysics Data System (ADS)

Gnanasambandan, T.; Gunasekaran, S.; Seshadri, S.

2013-08-01

A combined experimental and theoretical study on molecular structure, vibrational spectra, NBO and UV-spectral analysis of m-nitromethylbenzoate (MNMB) has been reported in the present work. The FT-IR solid phase (4000-400 cm-1) and FT-Raman spectra (3500-100 cm-1) of MNMB was recorded. The molecular geometry, harmonic vibrational frequencies and bonding features of MNMB in the ground-state have been calculated by using the density functional method B3LYP with 6-31G (d,p) and 6-31+G(d,p) basis sets. The assignments of the vibrational spectra have been carried out with the help of normal co-ordinate analysis (NCA) following the Scaled Quantum Mechanical Force Field Methodology (SQMFF). Stability of the molecule arising from hyperconjugative interactions, charge delocalization has been analyzed using natural bond orbital (NBO) analysis. The results show that charge in electron density (ED) in the σ∗ antibonding orbitals and E(2) energies confirms the occurrence of ICT (Intra-molecular Charge Transfer) within the molecule. The UV spectrum was measured in ethyl acetate solution. The energy and oscillator strength calculated by Time-Dependent Density Functional Theory (TD-DFT) result complements the experimental findings. The calculated HOMO and LUMO energies show that charge transfer occurs within the molecule. Finally the calculation results were applied to simulated infrared and Raman spectra of the title compound which show good agreement with observed spectra.

Vibrational spectroscopy investigation using ab initio and density functional theory analysis on the structure of 5-chloro-10-oxa-3-thia-tricyclo[5.2.1.0 1,5]dec-8-ene-3,3-dioxide

NASA Astrophysics Data System (ADS)

Arslan, Hakan; Demircan, Aydın; Göktürk, Ersen

2008-01-01

The IR spectra of 5-chloro-10-oxa-3-thia-tricyclo[5.2.1.0 1,5]dec-8-ene-3,3-dioxide (COTDO) has been recorded in the region 4000-525 cm -1. The optimized molecular geometry, frequency and intensity of the vibrational bands of COTDO in the ground state has been calculated using the Hartree-Fock and density functional using Becke's three-parameter hybrid method with the Lee, Yang, and Parr correlation functional methods with 6-31G(d,p) and 6-311G(d,p) basis sets. The harmonic vibrational frequencies were calculated and the scaled values have been compared with experimental IR spectra. The calculated geometrical parameters and harmonic vibrations are predicted in a very good agreement with the experimental data. The theoretical vibrational spectra of the title compound were interpreted by means of potential energy distributions (PEDs) using VEDA 4 program. With the help of this modern technique we were able to complete the assignment of the vibrational spectra of the title compound.

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.

Four two-dimensional ternary selenides based on group 13 and 14 metals: Syntheses, crystal structures, and electrochemical properties

NASA Astrophysics Data System (ADS)

Wang, Jingrui; Li, Peng; Cai, Ting; Yang, Dan-Dan; Xiong, Wei-Wei

2018-07-01

A series of two-dimensional ternary selenides, [NH4]2[Ga2Sn2Se8] (1), [NH4]2[In2Ge2Se8] (2), [NH4]2[In2Sn2Se8] (3), [NH4]2[Ga2Ge2Se8] (4), have been solvothermally synthesized and characterized by single crystal X-ray diffraction, energy dispersive X-ray (EDX) spectroscopy, solid-state UV-Vis diffuse reflectance spectroscopy, and thermogravimetric analyses. The solid-state optical absorption spectra indicated that these compounds were semiconductors with band gaps of 1.71 eV for 1, 1.95 eV for 2, 1.85 eV for 3, and 1.83 eV for 4. In addition, compound 2 was employed as an anode material for lithium ion battery application, which exhibited a high specific capacity of 479 mA h g-1 over 200 cycles at a current density of 200 mA g-1, and an excellent rate capability of 425.2 mA h g-1 at a current density of 1000 mA g-1. Our results suggest that crystalline chalcogenides could be an alternative anode material for high performance LIBs application.

Soda-based glass fabricated from Thailand quartz sands doped with silver compound

NASA Astrophysics Data System (ADS)

Won-in, Krit; Dararutana, Pisutti

2012-10-01

Yellow colored glass which used for luxury art glass in ancient time was fabricated by the addition of silver compound into the molten glass. It was proved that it was actually silver nanoparticle technology. In this work, the SiO2-(Na2O,K2O)-CaO-B2O3-Al2O3-MgO glass system was prepared in the laboratory scale based on local quartz sands from Trat Province, eastern area of Thailand as the silica raw material. Various concentrations of silver nitrate were added. After the complete conventional melting process, the bubble-free yellow glasses were yielded. Physical and optical properties such as density, refractive index and optical absorption spectra were measured. Scanning electron microscope coupled with energy dispersive spectroscopy was carried out to study their morphology. The refractive indices and densities were increased as the increase of the silver contents. Electron micrographs showed the presence of silver nanoparticle in the glass matrix. UV-VIS spectra were in good agreement with that found from SEM measurements and corresponded with the universally accepted. It was also showed that the more brilliance on the surface of the glass products was obtained after firing with a gas torch.

125Te NMR shielding and optoelectronic spectra in XTe3O8 (X = Ti, Zr, Sn and Hf) compounds: Ab initio calculations

NASA Astrophysics Data System (ADS)

Bashi, M.; Rahnamaye Aliabad, H. A.; Mowlavi, A. A.; Ahmad, Iftikhar

2017-11-01

We have calculated the NMR shielding, structural properties and optoelectronic spectra of XTe3O8 (X = Ti, Zr, Sn and Hf) compounds. The full potential linearized augmented plane wave (FP-LAPW) method and the modified Becke-Johnson (mBJ) are used by density functional theory schemes. The calculated shielding and measured shifts are arranged in a straight line and the tensors of magnetic shielding have a low symmetry and the shielding along the x direction is greater than the y and z directions. Obtained results show that the X ions have the most important influence on the 125Te chemical shift. Calculated chemical shielding components (σii) decrease from Ti to Sn then increases from Sn to Hf so that these behaviors are vice versa for 125Te isotropic chemical shift (δiso). Density of states spectra show that the X-p and d states play key role in the optical and NMR calculations. Optical results illustrate that there is a direct relation between the chemical shielding components for Te atom and the static dielectric function, refractive index and Plasmon energies.

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

Castaño-González, E.-E.; Seña, N.; Mendoza-Estrada, V.

In this paper, we carried out first-principles calculations in order to investigate the structural and electronic properties of the binary compound gallium antimonide (GaSb). This theoretical study was carried out using the Density Functional Theory within the plane-wave pseudopotential method. The effects of exchange and correlation (XC) were treated using the functional Local Density Approximation (LDA), generalized gradient approximation (GGA): Perdew–Burke–Ernzerhof (PBE), Perdew-Burke-Ernzerhof revised for solids (PBEsol), Perdew-Wang91 (PW91), revised Perdew–Burke–Ernzerhof (rPBE), Armiento–Mattson 2005 (AM05) and meta-generalized gradient approximation (meta-GGA): Tao–Perdew–Staroverov–Scuseria (TPSS) and revised Tao–Perdew–Staroverov–Scuseria (RTPSS) and modified Becke-Johnson (MBJ). We calculated the densities of state (DOS) and band structuremore » with different XC potentials identified and compared them with the theoretical and experimental results reported in the literature. It was discovered that functional: LDA, PBEsol, AM05 and RTPSS provide the best results to calculate the lattice parameters (a) and bulk modulus (B{sub 0}); while for the cohesive energy (E{sub coh}), functional: AM05, RTPSS and PW91 are closer to the values obtained experimentally. The MBJ, Rtpss and AM05 values found for the band gap energy is slightly underestimated with those values reported experimentally.« less

Valence structures of aromatic bioactive compounds: a combined theoretical and experimental study.

PubMed

Wickrama Arachchilage, Anoja Pushpamali; Feyer, Vitaliy; Plekan, Oksana; Iakhnenko, Marianna; Prince, Kevin C; Wang, Feng

2012-09-01

Valence electronic structures of three recently isolated aryl bioactive compounds, namely 2-phenylethanol (2PE), p-hydroxyphenylethanol (HPE) and 4-hydroxybenzaldehyde (HBA), are studied using a combined theoretical and experimental method. Density functional theory-based calculations indicate that the side chains cause electron charge redistribution and therefore influence the aromaticity of the benzene derivatives. The simulated IR spectra further reveal features induced by the side chains. Solvent effects on the IR spectra are simulated using the polarizable continuum model, which exhibits enhancement of the O-H stretch vibrations with significant red-shift of 464 cm(-1) in 2PE. A significant spectral peak splitting of 94 cm(-1) between O(4)-H and O(8)-H of HPE is revealed in an aqueous environment. Experimental measurements for valence binding energy spectra for 2PE, HPE and HBA are presented and analyzed using outer-valence Green function calculations. The experimental (predicted) first ionization energies are measured as 9.19 (8.79), 8.47 (8.27) and 8.97 (8.82) eV for 2PE, HPE and HBA, respectively. The frontier orbitals (highest occupied molecular orbitals, HOMOs, and lowest unoccupied molecular orbitals, LUMOs) have similar atomic orbital characters although the HOMO-LUMO energy gaps are quite different.

Investigation of binding features: effects on the interaction between CYP2A6 and inhibitors.

PubMed

Ai, Chunzhi; Li, Yan; Wang, Yonghua; Li, Wei; Dong, Peipei; Ge, Guangbo; Yang, Ling

2010-07-15

A computational investigation has been carried out on CYP2A6 and its naphthalene inhibitors to explore the crucial molecular features contributing to binding specificity. The molecular bioactive orientations were obtained by docking (FlexX) these compounds into the active site of the enzyme. And the density functional theory method was further used to optimize the molecular structures with the subsequent analysis of molecular lipophilic potential (MLP) and molecular electrostatic potential (MEP). The minimal MLPs, minimal MEPs, and the band gap energies (the energy difference between the highest occupied molecular orbital and lowest unoccupied molecular orbital) showed high correlations with the inhibition activities (pIC(50)s), illustrating their significant roles in driving the inhibitor to adopt an appropriate bioactive conformation oriented in the active site of CYP2A6 enzyme. The differences in MLPs, MEPs, and the orbital energies have been identified as key features in determining the binding specificity of this series of compounds to CYP2A6 and the consequent inhibitory effects. In addition, the combinational use of the docking, MLP and MEP analysis is also demonstrated as a good attempt to gain an insight into the interaction between CYP2A6 and its inhibitors. Copyright 2010 Wiley Periodicals, Inc.

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.

The first principle study of Ni{sub 2}ScGa and Ni{sub 2}TiGa

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

Özduran, Mustafa; Turgut, Kemal; Arikan, Nihat

2014-10-06

We computed the electronic structure, elastic moduli, vibrational properties, and Ni{sub 2}TiGa and Ni{sub 2}ScGa alloys in the cubic L2{sub 1} structure. The obtained equilibrium lattice constants of these alloys are in good agreement with available data. In cubic systems, there are three independent elastic constants, namely C{sub 11}, C{sub 12} and C{sub 44}. We calculated elastic constants in L2{sub 1} structure for Ni{sub 2}TiGa and Ni{sub 2}ScGa using the energy-strain method. The electronic band structure, total and partial density of states for these alloys were investigated within density functional theory using the plane-wave pseudopotential method implemented in Quantum-Espresso programmore » package. From band structure, total and projected density of states, we observed metallic characters of these compounds. The electronic calculation indicate that the predominant contributions of the density of states at Fermi level come from the Ni 3d states and Sc 3d states for Ni{sub 2}TiGa, Ni 3d states and Sc 3d states for Ni{sub 2}ScGa. The computed density of states at Fermi energy are 2.22 states/eV Cell for Ni{sub 2}TiGa, 0.76 states/eV Cell for Ni{sub 2}ScGa. The vibrational properties were obtained using a linear response in the framework at the density functional perturbation theory. For the alloys, the results show that the L2{sub 1} phase is unstable since the phonon calculations have imagine modes.« less

Study on Separation of Structural Isomer with Magneto-Archimedes method

NASA Astrophysics Data System (ADS)

Kobayashi, T.; Mori, T.; Akiyama, Y.; Mishima, F.; Nishijima, S.

2017-09-01

Organic compounds are refined by separating their structural isomers, however each separation method has some problems. For example, distillation consumes large energy. In order to solve these problems, new separation method is needed. Considering organic compounds are diamagnetic, we focused on magneto-Archimedes method. With this method, particle mixture dispersed in a paramagnetic medium can be separated in a magnetic field due to the difference of the density and magnetic susceptibility of the particles. In this study, we succeeded in separating isomers of phthalic acid as an example of structural isomer using MnCl2 solution as the paramagnetic medium. In order to use magneto-Archimedes method for separating materials for food or medicine, we proposed harmless medium using oxygen and fluorocarbon instead of MnCl2 aqueous solution. As a result, the possibility of separating every structural isomer was shown.

Dirac cone and pseudogapped density of states in the topological half-Heusler compound YPtBi

NASA Astrophysics Data System (ADS)

Kronenberg, A.; Braun, J.; Minár, J.; Elmers, H.-J.; Kutnyakhov, D.; Zaporozhchenko, A. V.; Wallauer, R.; Chernov, S.; Medjanik, K.; Schönhense, G.; Kläui, M.; Chadov, S.; Ebert, H.; Jourdan, M.

2016-10-01

Topological insulators (TIs) are exciting materials, which exhibit unprecedented properties, such as helical spin-momentum locking, which leads to large torques for magnetic switching and highly efficient spin current detection. Here we explore the compound YPtBi, an example from the class of half-Heusler materials, for which the typical band inversion of topological insulators was predicted. We prepared this material as thin films by conventional cosputtering from elementary targets. By in situ time-of-flight momentum microscopy, a Dirac conelike surface state with a Dirac point ≃300 meV below the Fermi energy was observed, in agreement with electronic structure-photoemission calculations. Only little additional spectral weight due to other states was observed at EF, which corroborates the identification of the topologically protected surface state and is highly relevant for spintronics applications.

National Institute for Petroleum and Energy Research quarterly technical report for April 1--June 30, 1993. Volume 1, Fuels research

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

Not Available

Progress reports are presented for the following fuels researches: Development of analytical methodology for analysis of heave crudes; and thermochemistry and thermophysical properties of organic nitrogen and diheteroatom-containing compounds. Some of the accomplishments are: Topical reports summarizing GC/MS methodology for determination of amines in petroleum and catalytic cracking behavior of compound type in Wilmington 650{degrees} F+ resid were completed; density measurements between 320 K and 550 K were completed for 8-methylquinoline; high-temperature heat-capacities and critical temperature (near 800 K) for 8-methylquinoline were determined; vapor-pressure measurements were completed for 2,6-dimethylpyridine; and a series of enthalpy-of-combustion measurement was completed for 1,10-phenanthroline, phenazine,more » 2-methylquinoline, and 8-methylquinoline.« less

Electronic structure reconstruction across the antiferromagnetic transition in TaFe₁̣₂₃Te₃ spin ladder

DOE PAGES

Xu, Min; Wang, Li -Min; Peng, Rui; ...

2015-02-01

With angle-resolved photoemission spectroscopy, we studied the electronic structure of TaFe₁̣₂₃Te₃, a two-leg spin ladder compound with a novel antiferromagnetic ground state. Quasi-two-dimensional Fermi surface is observed, with sizable inter-ladder hopping. Moreover, instead of observing an energy gap at the Fermi surface in the antiferromagnetic state, we observed the shifts of various bands. Combining these observations with density-functional-theory calculations, we propose that the large scale reconstruction of the electronic structure, caused by the interactions between coexisting itinerant electrons and local moments, is most likely the driving force of the magnetic transition. Thus TaFe₁̣₂₃Te₃ serves as a simpler platform that containsmore » similar ingredients as the parent compounds of iron-based superconductors.« less

First-principles study of the amorphous In3SbTe2 phase change compound

NASA Astrophysics Data System (ADS)

Los, Jan H.; Kühne, Thomas D.; Gabardi, Silvia; Bernasconi, Marco

2013-11-01

Ab initio molecular dynamics simulations based on density functional theory were performed to generate amorphous models of the phase change compound In3SbTe2 by quenching from the melt. In-Sb and In-Te are the most abundant bonds with only a minor fraction of Sb-Te bonds. The bonding geometry in the amorphous phase is, however, strongly dependent on the density in the range 6.448-5.75 g/cm3 that we investigated. While at high density the bonding geometry of In atoms is mostly octahedral-like as in the cubic crystalline phase of the ternary compound In3SbTe2, at low density we observed a sizable fraction of tetrahedral-like geometries similar to those present in the crystalline phase of the two binary compounds InTe and InSb that the ternary system can be thought to be made of. We show that the different ratio between octahedral-like and tetrahedral-like bonding geometries has fingerprints in the optical and vibrational spectra.

Electronic and optical properties of Cu2XSnS4 (X = Be, Mg, Ca, Mn, Fe, and Ni) and the impact of native defect pairs

NASA Astrophysics Data System (ADS)

Chen, Rongzhen; Persson, Clas

2017-05-01

Reducing or controlling cation disorder in Cu2ZnSnS4 is a major challenge, mainly due to low formation energies of the anti-site pair ( CuZn - + ZnCu +) and the compensated Cu vacancy ( VCu - + ZnCu +). We study the electronic and optical properties of Cu2XSnS4 (CXTS, with X = Be, Mg, Ca, Mn, Fe, and Ni) and the impact of defect pairs, by employing the first-principles method within the density functional theory. The calculations indicate that these compounds can be grown in either the kesterite or stannite tetragonal phase, except Cu2CaSnS4 which seems to be unstable also in its trigonal phase. In the tetragonal phase, all six compounds have rather similar electronic band structures, suitable band-gap energies Eg for photovoltaic applications, as well as good absorption coefficients α(ω). However, the formation of the defect pairs ( C u X + X Cu) and ( V Cu + X Cu) is an issue for these compounds, especially considering the anti-site pair which has formation energy in the order of ˜0.3 eV. The ( C u X + X Cu) pair narrows the energy gap by typically ΔEg ≈ 0.1-0.3 eV, but for Cu2NiSnS4, the complex yields localized in-gap states. Due to the low formation energy of ( C u X + X Cu), we conclude that it is difficult to avoid disordering from the high concentration of anti-site pairs. The defect concentration in Cu2BeSnS4 is however expected to be significantly lower (as much as ˜104 times at typical device operating temperature) compared to the other compounds, which is partly explained by larger relaxation effects in Cu2BeSnS4 as the two anti-site atoms have different sizes. The disadvantage is that the stronger relaxation has a stronger impact on the band-gap narrowing. Therefore, instead of trying to reduce the anti-site pairs, we suggest that one shall try to compensate ( C u X + X Cu) with ( V Cu + X Cu) or other defects in order to stabilize the gap energy.

Characterizing high-energy-density propellants for space propulsion applications

NASA Astrophysics Data System (ADS)

Kokan, Timothy

There exists wide ranging research interest in high-energy-density matter (HEDM) propellants as a potential replacement for existing industry standard fuels for liquid rocket engines. The U.S. Air Force Research Laboratory, the U.S. Army Research Lab, the NASA Marshall Space Flight Center, and the NASA Glenn Research Center each either recently concluded or currently has ongoing programs in the synthesis and development of these potential new propellants. In order to perform conceptual designs using these new propellants, most conceptual rocket engine powerhead design tools (e.g. NPSS, ROCETS, and REDTOP-2) require several thermophysical properties of a given propellant over a wide range of temperature and pressure. These properties include enthalpy, entropy, density, viscosity, and thermal conductivity. Very little thermophysical property data exists for most of these potential new HEDM propellants. Experimental testing of these properties is both expensive and time consuming and is impractical in a conceptual vehicle design environment. A new technique for determining these thermophysical properties of potential new rocket engine propellants is presented. The technique uses a combination of three different computational methods to determine these properties. Quantum mechanics and molecular dynamics are used to model new propellants at a molecular level in order to calculate density, enthalpy, and entropy. Additivity methods are used to calculate the kinematic viscosity and thermal conductivity of new propellants. This new technique is validated via a series of verification experiments of HEDM compounds. Results are provided for two HEDM propellants: quadricyclane and 2-azido-N,N-dimethylethanamine (DMAZ). In each case, the new technique does a better job than the best current computational methods at accurately matching the experimental data of the HEDM compounds of interest. A case study is provided to help quantify the vehicle level impacts of using HEDM propellants. The case study consists of the National Aeronautics and Space Administration's (NASA) Exploration Systems Architecture Study (ESAS) Lunar Surface Access Module (LSAM). The results of this study show that the use of HEDM propellants instead of hypergolic propellants can lower the gross weight of the LSAM and may be an attractive alternative to the current baseline hypergolic propellant choice.

Nonaqueous Hybrid Lithium-Ion and Sodium-Ion Capacitors.

PubMed

Wang, Huanwen; Zhu, Changrong; Chao, Dongliang; Yan, Qingyu; Fan, Hong Jin

2017-12-01

Hybrid metal-ion capacitors (MICs) (M stands for Li or Na) are designed to deliver high energy density, rapid energy delivery, and long lifespan. The devices are composed of a battery anode and a supercapacitor cathode, and thus become a tradeoff between batteries and supercapacitors. In the past two decades, tremendous efforts have been put into the search for suitable electrode materials to overcome the kinetic imbalance between the battery-type anode and the capacitor-type cathode. Recently, some transition-metal compounds have been found to show pseudocapacitive characteristics in a nonaqueous electrolyte, which makes them interesting high-rate candidates for hybrid MIC anodes. Here, the material design strategies in Li-ion and Na-ion capacitors are summarized, with a focus on pseudocapacitive oxide anodes (Nb 2 O 5 , MoO 3 , etc.), which provide a new opportunity to obtain a higher power density of the hybrid devices. The application of Mxene as an anode material of MICs is also discussed. A perspective to the future research of MICs toward practical applications is proposed to close. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

OH-initiated transformation and hydrolysis of aspirin in AOPs system: DFT and experimental studies.

PubMed

He, Lin; Sun, Xiaomin; Zhu, Fanping; Ren, Shaojie; Wang, Shuguang

2017-08-15

Advanced oxidation processes (AOPs) are widely used in wastewater treatment of pharmaceutical and personal care products (PPCPs). In this work, the OH-initiated transformation as well as the hydrolysis of a typical PPCPs, aspirin, was investigated using density functional theory (DFT) calculations and laboratory experiments. For DFT calculations, the frontier electron densities and bond dissociation energies were analyzed. Profiles of the potential energy surface were constructed, and all the possible pathways were discussed. Additionally, rate constants for each pathway were calculated with transition state theory (TST) method. UV/H 2 O 2 experiments of aspirin were performed and degradation intermediates were identified by UPLC-MS-MS analysis. Different findings from previous experimental works were reported that the H-abstraction pathways at methyl position were dominated and OH-addition pathways on benzene ring were also favored. Meantime, hydroxyl ASA was confirmed as the main stable intermediate. Moreover, it was the first time to use DFT method to investigate the hydrolysis mechanisms of organic ester compound. Copyright © 2017 Elsevier B.V. All rights reserved.

Extraction of bioactives from Orthosiphon stamineus using microwave and ultrasound-assisted techniques: Process optimization and scale up.

PubMed

Chan, Chung-Hung; See, Tiam-You; Yusoff, Rozita; Ngoh, Gek-Cheng; Kow, Kien-Woh

2017-04-15

This work demonstrated the optimization and scale up of microwave-assisted extraction (MAE) and ultrasonic-assisted extraction (UAE) of bioactive compounds from Orthosiphon stamineus using energy-based parameters such as absorbed power density and absorbed energy density (APD-AED) and response surface methodology (RSM). The intensive optimum conditions of MAE obtained at 80% EtOH, 50mL/g, APD of 0.35W/mL, AED of 250J/mL can be used to determine the optimum conditions of the scale-dependent parameters i.e. microwave power and treatment time at various extraction scales (100-300mL solvent loading). The yields of the up scaled conditions were consistent with less than 8% discrepancy and they were about 91-98% of the Soxhlet extraction yield. By adapting APD-AED method in the case of UAE, the intensive optimum conditions of the extraction, i.e. 70% EtOH, 30mL/g, APD of 0.22W/mL, AED of 450J/mL are able to achieve similar scale up results. Copyright © 2016 Elsevier Ltd. All rights reserved.

Bonding nature and electron delocalization of An(COT)2, An = Th, Pa, U.

PubMed

Páez-Hernández, Dayán; Murillo-López, Juliana A; Arratia-Pérez, Ramiro

2011-08-18

A systematic study of a series of An(COT)(2) compounds, where An = Th, Pa, U, and COT represents cyclooctatetraene, has been performed using relativistic density functional theory. The ZORA Hamiltonian was applied for the inclusion of relativistic effects, taking into account all of the electrons for the optimization and explicitly including spin-orbit coupling effects. Time-dependent density functional theory (TDDFT) was used to calculate the excitation energies with the GGA SAOP functional, and the electronic transitions were analyzed using double group irreducible representations. The calculated excitation energies are in perfect correlation with the increment of the ring delocalization as it increases along the actinide series. These results are sufficient to ensure that, for these complexes, the increment in delocalization, as indicated by ELF bifurcation and NICS analysis, leads to a shift in the maximum wavelength of absorption in the visible region. Also, delocalization in the COT ring increases along the actinide series, so the systems become more aromatic because of a modulation induced by the actinides. © 2011 American Chemical Society

Competition between the compound and the pre-compound emission processes in α-induced reactions at near astrophysical energy to well above it

NASA Astrophysics Data System (ADS)

Sharma, Manoj Kumar; Sharma, Vijay Raj; Yadav, Abhiskek; Singh, Pushpendra P.; Singh, B. P.; Prasad, R.

2016-04-01

The study of pre-compound emission in α-induced reactions, particularly at the low incident energies, is of considerable interest as the pre-compound emission is more likely to occur at higher energies. With a view to study the competition between the compound and the pre-compound emission processes in α-induced reactions at different energies and with different targets, a systematics for neutron emission channels in targets 51V, 55Mn, 93Nb, 121, 123Sb and 141Pr at energy ranging from astrophysical interest to well above it, has been developed. The off-line γ-ray-spectrometry based activation technique has been adopted to measure the excitation functions. The experimental excitation functions have been analysed within the framework of the compound nucleus mechanism based on the Weisskopf-Ewing model and the pre-compound emission calculations based on the geometry dependent hybrid model. The analysis of the data shows that experimental excitation functions could be reproduced only when the pre-compound emission, simulated theoretically, is taken into account. The strength of pre-compound emission process for each system has been obtained by deducing the pre-compound fraction. Analysis of data indicates that in α-induced reactions, the pre-compound emission process plays an important role, particularly at the low incident energies, where the pure compound nucleus process is likely to dominate.

Extracting electron transfer coupling elements from constrained density functional theory

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

Wu Qin; Van Voorhis, Troy

2006-10-28

Constrained density functional theory (DFT) is a useful tool for studying electron transfer (ET) reactions. It can straightforwardly construct the charge-localized diabatic states and give a direct measure of the inner-sphere reorganization energy. In this work, a method is presented for calculating the electronic coupling matrix element (H{sub ab}) based on constrained DFT. This method completely avoids the use of ground-state DFT energies because they are known to irrationally predict fractional electron transfer in many cases. Instead it makes use of the constrained DFT energies and the Kohn-Sham wave functions for the diabatic states in a careful way. Test calculationsmore » on the Zn{sub 2}{sup +} and the benzene-Cl atom systems show that the new prescription yields reasonable agreement with the standard generalized Mulliken-Hush method. We then proceed to produce the diabatic and adiabatic potential energy curves along the reaction pathway for intervalence ET in the tetrathiafulvalene-diquinone (Q-TTF-Q) anion. While the unconstrained DFT curve has no reaction barrier and gives H{sub ab}{approx_equal}17 kcal/mol, which qualitatively disagrees with experimental results, the H{sub ab} calculated from constrained DFT is about 3 kcal/mol and the generated ground state has a barrier height of 1.70 kcal/mol, successfully predicting (Q-TTF-Q){sup -} to be a class II mixed-valence compound.« less

Density functional theory studies on the nano-scaled composites consisted of graphene and acyl hydrazone molecules

NASA Astrophysics Data System (ADS)

Ren, J. L.; Zhou, L.; Lv, Z. C.; Ding, C. H.; Wu, Y. H.; Bai, H. C.

2016-07-01

Graphene, which is the first obtained single atomic layer 2D materials, has drawn a great of concern in nano biotechnology due to the unique property. On one hand, acyl hydrazone compounds belonging to the Schif bases have aroused considerable attention in medicine, pharmacy, and analytical reagent. However, few understanding about the interaction between graphene and acyl hydrazone molecules is now available. And such investigations are much crucial for the applications of these new nano-scaled composites. The current work revealed theoretical investigations on the nano-scaled composites built by acyl hydrazone molecules loaded on the surface of graphene. The relative energy, electronic property and the interaction between the counterparts of graphene/acyl hydrazone composites are investigated based on the density functional theory calculations. According to the obtained adsorption energy, the formation of the nano-scaled composite from the isolated graphene and acyl hydrazone molecule is exothermic, and thus it is energetically favorable to form these nano composites in viewpoint of total energy change. The frontier molecular orbital for the nano composite is mainly distributed at the graphene part, leading to that the energy levels of the frontier molecular orbital of the nano composites are very close to that of isolated graphene. Moreover, the counterpart interaction for the graphene/acyl hydrazone composites is also explored based on the discussions of orbital hybridization, charge redistribution and Van der Waals interaction.

The effect of ligand substituent on crystal packing: Structural and theoretical studies of two Ga(III) supramolecular compounds

NASA Astrophysics Data System (ADS)

Soleimannejad, Janet; Nazarnia, Esfandiar

2016-07-01

A new Ga(III) supramolecular compound (4,4‧-bipyH2)[Ga(hpydc)2]2·7H2O (2) (where H2hpydc = 4-hydroxy-pyridine-2,6-dicarboxylic acid and 4,4‧-bipy = 4,4‧-bipyridine) was synthesized using the proton transfer reaction. Compound 2 was structurally characterized using single crystal X-ray diffraction, and it was shown that its asymmetric unit consists of two independent anionic Ga(III) complexes, one fully protonated 4,4‧-bipyridine and seven uncoordinated water molecules. In order to understand the effect of pyridine OH substituent on supramolecular interactions and crystal packing, compound 2 was compared with (bipyH2)[Ga(pydc)2]·(H2pydc)·4H2O (1) (where H2pydc = pyridine-2,6-dicarboxylic acid), that does not have an OH group on the pyridine ligand. The Density Functional Theory (DFT) and Natural Bond Orbital (NBO) calculations and also Atoms in Molecules (AIM) analysis were used to analyze the non-covalent interactions in both complexes. The calculation of non-covalent interactions' energy provides a useful means to investigate their effects in the crystal packing.

Copper diffusion in Ti Si N layers formed by inductively coupled plasma implantation

NASA Astrophysics Data System (ADS)

Ee, Y. C.; Chen, Z.; Law, S. B.; Xu, S.; Yakovlev, N. L.; Lai, M. Y.

2006-11-01

Ternary Ti-Si-N refractory barrier films of 15 nm thick was prepared by low frequency, high density, inductively coupled plasma implantation of N into TixSiy substrate. This leads to the formation of Ti-N and Si-N compounds in the ternary film. Diffusion of copper in the barrier layer after annealing treatment at various temperatures was investigated using time-of-flight secondary ion mass spectrometer (ToF-SIMS) depth profiling, X-ray diffractometer (XRD), field emission scanning electron microscopy (FESEM), energy dispersive X-ray (EDX) and sheet resistance measurement. The current study found that barrier failure did not occur until 650 °C annealing for 30 min. The failure occurs by the diffusion of copper into the Ti-Si-N film to form Cu-Ti and Cu-N compounds. FESEM surface morphology and EDX show that copper compounds were formed on the ridge areas of the Ti-Si-N film. The sheet resistance verifies the diffusion of Cu into the Ti-Si-N film; there is a sudden drop in the resistance with Cu compound formation. This finding provides a simple and effective method of monitoring Cu diffusion in TiN-based diffusion barriers.

Electronic Excitations in Solution: The Interplay between State Specific Approaches and a Time-Dependent Density Functional Theory Description.

PubMed

Guido, Ciro A; Jacquemin, Denis; Adamo, Carlo; Mennucci, Benedetta

2015-12-08

We critically analyze the performances of continuum solvation models when coupled to time-dependent density functional theory (TD-DFT) to predict solvent effects on both absorption and emission energies of chromophores in solution. Different polarization schemes of the polarizable continuum model (PCM), such as linear response (LR) and three different state specific (SS) approaches, are considered and compared. We show the necessity of introducing a SS model in cases where large electron density rearrangements are involved in the excitations, such as charge-transfer transitions in both twisted and quadrupolar compounds, and underline the very delicate interplay between the selected polarization method and the chosen exchange-correlation functional. This interplay originates in the different descriptions of the transition and ground/excited state multipolar moments by the different functionals. As a result, the choice of both the DFT functional and the solvent polarization scheme has to be consistent with the nature of the studied electronic excitation.

Ab initio calculation of the deprotonation constants of an atomistically defined nanometer-sized, aluminium hydroxide oligomer

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

Wander, Matthew C. F.; Shuford, Kevin L.; Rustad, James R.

Aluminium possesses significant and diverse chemistry. Numerous compounds have been defined, and the elucidation of their chemistry is of significant geochemical interest. In this paper, a brucite-like, eight-aluminium aqueous cluster is modelled with density functional theory to identify its primary site of deprotonation and the associated pK(a) constant using both explicit (a full first solvent shell) and implicit solvent. Two methods for calculating the pK(a) are compared. We found that a bond density approach is better than a direct energy calculation for ions with large charge and high symmetry. The terminal aluminium atoms have equatorial ligated waters that in solventmore » have one long O-H bond. This site is more reactive than any of the other protons on the particle. Insights into the experimental crystal structure and Bader's Atoms in Molecules density analysis are presented as routes to reduce the computational time required for the identification of protonation sites.« less

Experimental and DFT studies of (E)-2-[2-(2,6-dichlorophenyl)ethenyl]-8-hydroxyquinoline: electronic and vibrational properties.

PubMed

Sun, Wenqi; Yuan, Guozan; Liu, Jingxin; Ma, Li; Liu, Chengbu

2013-04-01

The title molecule (E)-2-[2-(2,6-dichlorophenyl)ethenyl]-8-hydroxyquinoline (DPEQ) was synthesized and characterized by FT-IR, UV-vis, NMR spectroscopy. The molecular geometry, vibrational frequencies and gauge independent atomic orbital (GIAO) 1H and 13C NMR chemical shift values of the compound in the ground state have been calculated by using the density functional theory (DFT) method. All the assignments of the theoretical frequencies were performed by potential energy distributions using VEDA 4 program. The calculated results indicate that the theoretical vibrational frequencies, 1H and 13C NMR chemical shift values show good agreement with experimental data. The electronic properties like UV-vis spectral analysis and HOMO-LUMO analysis of DPEQ have been reported and compared with experimental data. Information about the size, shape, charge density distribution and site of chemical reactivity of the molecule has been obtained by mapping electron density isosurface with molecular electrostatic potential (MEP). Copyright © 2013 Elsevier B.V. All rights reserved.

Experimental and DFT studies of (E)-2-[2-(2,6-dichlorophenyl)ethenyl]-8-hydroxyquinoline: Electronic and vibrational properties

NASA Astrophysics Data System (ADS)

Sun, Wenqi; Yuan, Guozan; Liu, Jingxin; Ma, Li; Liu, Chengbu

2013-04-01

The title molecule (E)-2-[2-(2,6-dichlorophenyl)ethenyl]-8-hydroxyquinoline (DPEQ) was synthesized and characterized by FT-IR, UV-vis, NMR spectroscopy. The molecular geometry, vibrational frequencies and gauge independent atomic orbital (GIAO) 1H and 13C NMR chemical shift values of the compound in the ground state have been calculated by using the density functional theory (DFT) method. All the assignments of the theoretical frequencies were performed by potential energy distributions using VEDA 4 program. The calculated results indicate that the theoretical vibrational frequencies, 1H and 13C NMR chemical shift values show good agreement with experimental data. The electronic properties like UV-vis spectral analysis and HOMO-LUMO analysis of DPEQ have been reported and compared with experimental data. Information about the size, shape, charge density distribution and site of chemical reactivity of the molecule has been obtained by mapping electron density isosurface with molecular electrostatic potential (MEP).

Density Functional Theory (dft) Simulations of Shocked Liquid Xenon

NASA Astrophysics Data System (ADS)

Mattsson, Thomas R.; Magyar, Rudolph J.

2009-12-01

Xenon is not only a technologically important element used in laser technologies and jet propulsion, but it is also one of the most accessible materials in which to study the metal-insulator transition with increasing pressure. Because of its closed shell electronic configuration, xenon is often assumed to be chemically inert, interacting almost entirely through the van der Waals interaction, and at liquid density, is typically modeled well using Leonard-Jones potentials. However, such modeling has a limited range of validity as xenon is known to form compounds under normal conditions and likely exhibits considerably more chemistry at higher densities when hybridization of occupied orbitals becomes significant. We present DFT-MD simulations of shocked liquid xenon with the goal of developing an improved equation of state. The calculated Hugoniot to 2 MPa compares well with available experimental shock data. Sandia is a mul-tiprogram laboratory operated by Sandia Corporation, a Lockheed Martin Company, for the United States Department of Energy's National Nuclear Security Administration under contract DE-AC04-94AL85000.

Density Functional Theory (DFT) Simulations of Shocked Liquid Xenon

NASA Astrophysics Data System (ADS)

Mattsson, Thomas R.; Magyar, Rudolph J.

2009-06-01

Xenon is not only a technologically important element used in laser technologies and jet propulsion, but it is also one of the most accessible materials in which to study the metal-insulator transition with increasing pressure. Because of its closed shell electronic configuration, Xenon is often assumed to be chemically inert, interacting almost entirely through the van der Waals interaction, and at liquid density, is typically modeled well using Leonard-Jones potentials. However, such modeling has a limited range of validity as Xenon is known to form compounds at normal conditions and likely exhibits considerably more chemistry at higher densities when hybridization of occupied orbitals becomes significant. In this talk, we present DFT-MD simulations of shocked liquid Xenon with the goal of developing an improved equation of state. Sandia is a multiprogram laboratory operated by Sandia Corporation, a Lockheed Martin Company, for the United States Department of Energy's National Nuclear Security Administration under contract DE-AC04-94AL85000.

Electrocatalytic upgrading of biomass pyrolysis oils to chemical and fuel

NASA Astrophysics Data System (ADS)

Lam, Chun Ho

The present project's aim is to liquefy biomass through fast pyrolysis and then upgrade the resulting "bio-oil" to renewable fuels and chemicals by intensifying its energy content using electricity. This choice reflects three points: (a) Liquid hydrocarbons are and will long be the most practical fuels and chemical feedstocks because of their energy density (both mass and volume basis), their stability and relative ease of handling, and the well-established infrastructure for their processing, distribution and use; (b) In the U.S., the total carbon content of annually harvestable, non-food biomass is significantly less than that in a year's petroleum usage, so retention of plant-captured carbon is a priority; and (c) Modern technologies for conversion of sunlight into usable energy forms---specifically, electrical power---are already an order of magnitude more efficient than plants are at storing solar energy in chemical form. Biomass fast pyrolysis (BFP) generates flammable gases, char, and "bio-oil", a viscous, corrosive, and highly oxygenated liquid consisting of large amounts of acetic acid and water together with hundreds of other organic compounds. With essentially the same energy density as biomass and a tendency to polymerize, this material cannot practically be stored or transported long distances. It must be upgraded by dehydration, deoxygenation, and hydrogenation to make it both chemically and energetically compatible with modern vehicles and fuels. Thus, this project seeks to develop low cost, general, scalable, robust electrocatalytic methods for reduction of bio-oil into fuels and chemicals.

Halogen atom effect on the photophysical properties of substituted aza-BODIPY derivatives.

PubMed

De Simone, B C; Mazzone, G; Pirillo, J; Russo, N; Sicilia, E

2017-01-18

The influence of halogen atom substitution (Br and I), in different amounts and positions in an aza-BODIPY skeleton, on the photophysical properties of some aza-BODIPY derivatives has been investigated by using density functional theory and its time-dependent extension. The heavy atom effect on excitation energies, singlet-triplet energy gaps and spin-orbit matrix elements has been considered. The maximum absorption within the therapeutic window has been confirmed for all the aza-BODIPY derivatives. The feasible intersystem spin crossing pathways for the population of the lowest triplet state, that will depend on the values of the spin-orbit matrix elements, the energy gap as well as the orbital composition of the involved states have been found to most likely involve the S 1 and T 1 or T 2 states. The outcomes of computations support the potential therapeutic use of these compounds as photosensitizers in photodynamic therapy.

Compositional bowing of band energies and their deformation potentials in strained InGaAs ternary alloys: A first-principles study

NASA Astrophysics Data System (ADS)

Khomyakov, Petr A.; Luisier, Mathieu; Schenk, Andreas

2015-08-01

Using first-principles calculations, we show that the conduction and valence band energies and their deformation potentials exhibit a non-negligible compositional bowing in strained ternary semiconductor alloys such as InGaAs. The electronic structure of these compounds has been calculated within the framework of local density approximation and hybrid functional approach for large cubic supercells and special quasi-random structures, which represent two kinds of model structures for random alloys. We find that the predicted bowing effect for the band energy deformation potentials is rather insensitive to the choice of the functional and alloy structural model. The direction of bowing is determined by In cations that give a stronger contribution to the formation of the InxGa1-xAs valence band states with x ≳ 0.5, compared to Ga cations.

Relations between conspecific density and effects of ultraviolet-b radiation on tadpole size in the striped marsh frog.

PubMed

Mitchell, Toby; Alton, Lesley A; White, Craig R; Franklin, Craig E

2012-12-01

Global increases in ultraviolet-B radiation (UVBR) associated with stratospheric ozone depletion are potentially contributing to the decline of numerous amphibian species around the world. Exposure to UVBR alone reduces survival and induces a range of sublethal effects in embryonic and larval amphibians. When additional environmental stressors are present, UVBR can have compounding negative effects. Thus, examination of the effects of UVBR in the absence of other stressors may substantially underestimate its potential to affect amphibians in natural habitats. We examined the independent and interactive effects of increased UVBR and high conspecific density would have embryonic and larval striped marsh frogs (Limnodynastes peronii). We exposed individuals to a factorial combination of low and high UVBR levels and low, medium, and high densities of striped marsh frog tadpoles. The response variables were time to hatching, hatching success, posthatch survival, burst-swimming performance of tadpoles (maximum instantaneous swim speed following an escape response), and size and morphology of tadpoles. Consistent with results of previous studies, we found that exposure to UVBR alone increased the time to hatching of embryos and reduced the burst-swimming performance and size of tadpoles. Similarly, increasing conspecific density increased the time to hatching of embryos and reduced the size of tadpoles, but had no effect on burst-swimming performance. The negative effect of UVBR on tadpole size was not apparent at high densities of tadpoles. This result suggests that tadpoles living at higher densities may invest relatively less energy in growth and thus have more energy to repair UVBR-induced damage. Lower densities of conspecifics increased the negative effects of UVBR on developing amphibians. Thus, low-density populations, which may include declining populations, may be particularly susceptible to the detrimental effects of increased UVBR and thus may be driven toward extinction faster than might be expected on the basis of results from single-factor studies. ©2012 Society for Conservation Biology.

Crystal structure, spectroscopic studies and quantum mechanical calculations of 2-[((3-iodo-4-methyl)phenylimino)methyl]-5-nitrothiophene.

PubMed

Özdemir Tarı, Gonca; Gümüş, Sümeyye; Ağar, Erbil

2015-04-15

The title compound, 2-[((3-iodo-4-methyl)phenylimino)methyl]-5-nitrothiophene, C12H9O2N2I1S1, was synthesized and characterized by IR, UV-Vis and single-crystal X-ray diffraction technique. The molecular structure was optimized at the B3LYP, B3PW91 and PBEPBE levels of the density functional method (DFT) with the 6-311G+(d,p) basis set. Using the TD-DFT method, the electronic absorption spectra of the title compound was computed in both the gas phase and ethanol solvent. The harmonic vibrational frequencies of the title compound were calculated using the same methods with the 6-311G+(d,p) basis set. The calculated results were compared with the experimental determination results of the compound. The energetic behavior such as the total energy, atomic charges, dipole moment of the title compound in solvent media were examined using the B3LYP, B3PW91 and PBEPBE methods with the 6-311G+(d,p) basis set by applying the Onsager and the polarizable continuum model (PCM). The molecular orbitals (FMOs) analysis, the molecular electrostatic potential map (MEP) and the nonlinear optical properties (NLO) for the title compound were obtained with the same levels of theory. And then thermodynamic properties for the title compound were obtained using the same methods with the 6-311G(d,p) basis set. Copyright © 2015 Elsevier B.V. All rights reserved.

The spectroscopic (FT-IR, FT-Raman, dispersive Raman and NMR) study of ethyl-6-chloronicotinate molecule by combined density functional theory

NASA Astrophysics Data System (ADS)

Karabacak, Mehmet; Calisir, Zuhre; Kurt, Mustafa; Kose, Etem; Atac, Ahmet

2016-01-01

In this study, ethyl-6-chloronicotinate (E-6-ClN) molecule is recorded in the region 4000-400 cm- 1 and 3500-100 cm- 1 (FT-IR, FT-Raman and dispersive Raman, respectively) in the solid phase. 1H and 13C nuclear magnetic resonance (NMR) spectra are recorded in DMSO solution. The structural and spectroscopic data of the molecule are obtained for two possible isomers (S1 and S2) from DFT (B3LYP) with 6-311++G(d,p) basis set calculations. The geometry of the molecule is fully optimized, vibrational spectra are calculated and fundamental vibrations are assigned on the basis of the potential energy distribution (PED) of the vibrational modes. 1H and 13C NMR chemical shifts are calculated by using the gauge-invariant atomic orbital (GIAO) method. The electronic properties, such as excitation energies, oscillator strengths, wavelengths, HOMO and LUMO energies, are performed by time-dependent density functional theory (TD-DFT). Total and partial density of state and overlap population density of state diagrams analysis are presented for E-6-ClN molecule. Furthermore, frontier molecular orbitals (FMO), molecular electrostatic potential, and thermodynamic features are performed. In addition to these, reduced density gradient of the molecule is performed and discussed. As a conclusion, the calculated results are compared with the experimental spectra of the title compound. The results of the calculations are applied to simulate the vibrational spectra of the molecule, which show excellent agreement with the observed ones. The theoretical and tentative results will give us a detailed description of the structural and physicochemical properties of the molecule. Natural bond orbital analysis is done to have more information stability of the molecule arising from charge delocalization, and to reveal the information regarding charge transfer within the molecules.

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.

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.

Development of high energy density electrical double layer capacitors

NASA Astrophysics Data System (ADS)

Devarajan, Thamarai selvi

Electrochemical Double Layer capacitors (EDLCs) have shown themselves as a viable energy storage alternative. EDLCs have high power density, faster charge/discharge, wide operating temperature and long cycle life compared to batteries since it stores charge by physical separation. Despites all their advantages, their low energy density stand as a bottleneck for capacitors. This research aims to increase the energy density of EDLC without compromising the power density. Energy is proportional to the square of cell voltage. Cell voltage is mainly dependent on electrolyte breakdown. Electrolytes also provide ions for charge separation and conduction. Therefore various electrolytes (Solutes and Solvents) which can give high concentration, solubility and decomposition potential were characterized in the first part of the research. In that study, a novel ionic liquid OPBF4 had higher capacitance and comparable voltage window compared to commercial TEABF4 in Acetonitrile. However, the increased polarity of the fixed ring O-atom and the ion-ion interaction in OPBF4 was responsible for lowering its conductivity. Oxygenated ionic compounds with alkyl groups had lower stability due to beta elimination between two electron withdrawing atoms. Volume based thermodynamics and quantum chemical calculations were used to calculate ion size, HOMO/LUMO energies, and free energy changes and establish relationship with capacitance, redox potential and melting points respectively. In addition free energy of fusion was used to predict the melting point. Ion size had correlation with capacitance due to compact double layer formation. Free energy changes did not explain the differences in melting point and predicted dielectric constant was inconsistent with the polarity. This is presumably due to using Van der Waals volume instead of crystal structure volume and insufficient incorporation of polarization term. The HOMO/LUMO energies gave direct relation between oxidation and reduction potential at 1mA/cm 2. A brief study on non-polar co-solvents for EDLC was studied. Among the solvents studied, fluorinated solvents had low melting point and viscosity due to incorporation of asymmetry. However, because of low dielectric constant, TEABF4 is insoluble and had to be mixed with other solvents. The mixed fluorinated solvents had slightly higher voltage window due to decreased donicity of lone pairs of electrons. The second approach to increasing energy density is to increase capacitance. Capacitance is mainly dependent on surface area and porosity of electrodes. Nanostructured materials which can offer multiple charge storage are currently of interest. Hence, novel NiSi nanotubes were studied as electrodes for supercapacitor applications. Silicon material has high capacity and these inert electrodes can enable higher capacitance by controlling the porosity and functional groups in specific electrolytes. The Silicon wafers were made porous by anodization using hydrofluoric acid. In order to improve the conductivity, the porous silicon was doped, then plated with Ni using electroless plating method and annealed to form nickel mono silicide. Gold was deposited on the back side of the electrode to enhance conductivity. Our porous NiSi electrodes gave capacitance of about 1185muF /cm2 in 0.5 M H 2SO4. Further investigation of oxide formation and modification of functional groups will help achieve higher capacitance.

X-ray magnetic circular dichroism in d and f ferromagnetic materials: recent theoretical progress. Part II (Review Article)

NASA Astrophysics Data System (ADS)

Antonov, V. N.; Shpak, A. P.; Yaresko, A. N.

2008-02-01

The present state of theoretical understanding of the x-ray magnetic circular dichroism (XMCD) of 4f and 5f compounds is reviewed. Energy band theory based upon the local spin-density approximation (LSDA) describes the XMCD spectra of transition metal compounds with high accuracy. However, the LSDA does not suffice for lanthanide compounds which have a correlated 4f shell. A satisfactory description of the XMCD spectra could be obtained by using a generalization of the LSDA, in which explicitly f electron Coulomb correlations are taken into account (LSDA +U approach). As examples of this group we consider the compound GdN. We also consider uranium 5f compounds. In those compounds where the 5f electrons are rather delocalized, the LSDA describes the XMCD spectra reasonably well. As an example of this group we consider UFe2. Particular differences occur for uranium compounds in which the 5f electrons are neither delocalized nor localized, but more or less semilocalized. Typical examples are UXAl (X =Co, Rh, and Pt), and UX (X =S, Se, Te). However, the semilocalized 5f's are not inert, but their interaction with conduction electrons plays an important role. We also consider the electronic structure and XMCD spectra of the heavy-fermion compounds UPt3, URu2Si2, UPd2Al3, UNi2Al3, and UBe13, where the degree of the 5f localization is increased in comparison with other uranium compounds. The electronic structure and XMCD spectra of UGe2 which possesses simultaneously ferromagnetism and superconductivity also presented. Recently achieved improvements for describing 5f compounds are discussed.

Density functional calculations on the effect of sulfur substitution for 2'-hydroxypropyl-p-nitrophenyl phosphate: C-O vs. P-O bond cleavage.

PubMed

Xia, Futing; Zhu, Hua

2012-02-01

Density functional theory calculations have been used to investigate the intra-molecular attack of 2'-hydroxypropyl-p-nitrophenyl phosphate (HPpNP) and its analogous compound 2-thiouridyl-p-nitrophenyl phosphate (s-2'pNP). Bulk solvent effect has been tested at the geometry optimization level with the polarized continuum model. It is found that the P-path involving the intra-molecular attack at the phosphorus atom and C-path involving the attack at the beta carbon atom proceed through the S(N)2-type mechanism for HPpNP and s-2'pNP. The calculated results indicate that the P-path with the free energy barrier of about 11 kcal/mol is more accessible than the C-path for the intra-molecular attack of HPpNP, which favors the formation of the five-membered phosphate diester. While for s-2'pNP, the C-path with the free energy barrier of about 21 kcal/mol proceeds more favorably than the P-path. The calculated energy barriers of the favorable pathways for HPpNP and s-2'pNP are both in agreement with the experimental results. Crown Copyright © 2011. Published by Elsevier Inc. All rights reserved.

Density Functional Study on A-Units Based on Thieno[3,4- c]pyrrole-4,6-dione for Organic Solar Cells

NASA Astrophysics Data System (ADS)

Tang, Xiaoqin; Shen, Wei; Fu, Zhiyong; Liu, Xiaorui; Li, Ming

2017-08-01

The use of polymer donor materials has allowed great progress in organic solar cells. To search for potential donor materials, we have designed a series of donor-acceptor (D-A)-type alternating polymers composed of dithieno[3,2- b:2',3'- d]pyrrole (DTP) electron-rich units and thieno[3,4- c]pyrrole-4,6-dione (TPD) electron-deficient units. Their electronic and optical properties have been investigated using density functional theory and Marcus theory. The calculation results demonstrate that introduction of cyclic compounds (furyl, thienyl, and phenyl) into electron-deficient units of the molecules can result in lower highest occupied molecular orbital (HOMO) levels and reorganization energies compared with the experimental molecule ( X 0 ). To investigate the effects of electron-withdrawing units, three electron-withdrawing substituents (-OCH3, -F, and -CN) were introduced into the thienyl. The results indicated that the polymer X 2-3 will show the best performance among the designed polymers, offering low-lying HOMO energy level (-5.47 eV), narrow energy gap (1.97 eV), and high hole mobility (7.45 × 10-2 cm2 V-1 s-1). This work may provide a guideline for the design of efficient D-A polymers for organic solar cells with enhanced performance.

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.

Adiabatic-connection fluctuation-dissipation DFT for the structural properties of solids—The renormalized ALDA and electron gas kernels

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

Patrick, Christopher E., E-mail: chripa@fysik.dtu.dk; Thygesen, Kristian S., E-mail: thygesen@fysik.dtu.dk

2015-09-14

We present calculations of the correlation energies of crystalline solids and isolated systems within the adiabatic-connection fluctuation-dissipation formulation of density-functional theory. We perform a quantitative comparison of a set of model exchange-correlation kernels originally derived for the homogeneous electron gas (HEG), including the recently introduced renormalized adiabatic local-density approximation (rALDA) and also kernels which (a) satisfy known exact limits of the HEG, (b) carry a frequency dependence, or (c) display a 1/k{sup 2} divergence for small wavevectors. After generalizing the kernels to inhomogeneous systems through a reciprocal-space averaging procedure, we calculate the lattice constants and bulk moduli of a testmore » set of 10 solids consisting of tetrahedrally bonded semiconductors (C, Si, SiC), ionic compounds (MgO, LiCl, LiF), and metals (Al, Na, Cu, Pd). We also consider the atomization energy of the H{sub 2} molecule. We compare the results calculated with different kernels to those obtained from the random-phase approximation (RPA) and to experimental measurements. We demonstrate that the model kernels correct the RPA’s tendency to overestimate the magnitude of the correlation energy whilst maintaining a high-accuracy description of structural properties.« less

Ab initio Hartree-Fock and density functional theory investigations on the conformational stability, molecular structure and vibrational spectra of 5-chloro-3-(2-(4-methylpiperazin-1-yl)-2-oxoethyl)benzo[d]thiazol-2(3H)-one drug molecule.

PubMed

Taşal, Erol; Kumalar, Mustafa

2012-09-01

In this work, the experimental and theoretical spectra of 5-chloro-3-(2-(4-methylpiperazin-1-yl)-2-oxoethyl)benzo[d]thiazol-2(3H)-one molecule (abbreviated as 5CMOT) are studied. The molecular geometry and vibrational frequencies are calculated in the ground state of molecule using ab initio Hartree-Fock (HF) and Density Function Theory (DFT) methods with 6-311++G(d,p), 6-31G++(d,p), 6-31G(d,p), 6-31G(d) and 6-31G basis sets. Three staggered stable conformers were observed on the torsional potential energy surfaces. The complete assignments were performed on the basis of the total energy distribution (TED) of the vibrational modes calculated. The comparison of the theoretical and experimental geometries of the title compound indicated that the X-ray parameters fairly well agree with the theoretically obtained values for the most stable conformer. The theoretical results showed an excellent agreement with the experimental values. The calculated HOMO and LUMO energies show that the charge transfer occurs within the molecule. Copyright © 2012 Elsevier B.V. All rights reserved.

Electrochemical and spectroscopic characteristics of p-acryloyloxybenzoyl chloride and p-acryloyloxybenzoic acid and antimicrobial activity of organic compounds

NASA Astrophysics Data System (ADS)

Cakir, I.; Soykan, U.; Cetin, S.; Karaboga, F.; Zalaoglu, Y.; Dogruer, M.; Terzioglu, C.; Yildirim, G.

2014-11-01

The purpose of this multidisciplinary work is to characterize title compounds, p-acryloyloxybenzoyl chloride (ABC) and p-acryloyloxybenzoic acid (ABA) by means of experimental and theoretical evidences. As experimental research, Fourier transformation-infrared spectra (in the region 400-4000 cm-1) and nuclear magnetic resonance (NMR) chemical shifts (with a frequency of 400 MHz) are examined for spectroscopic properties belonging to the new synthesized compounds. Moreover, the compounds are investigated for antimicrobial activity against various microorganisms (Gram-positive and Gram-negative) by means of the visual inhibition zone technique on the agar media. The experimental results observed indicate that ABA exhibits more powerful inhibitors of microorganisms due to the presence of the hydroxyl group leading to higher reactive system, one of the most striking features of the paper. As for the theoretical studies, the optimized molecular structures, vibrational frequencies, corresponding vibrational spectra interpreted with the aid of normal coordinate analysis based on scaled density functional force field, atomic charges, thermodynamic properties at different temperature, 1H NMR chemical shifts by way of density functional theory (DFT) with the standard (B3LYP) methods at 6-311G++(d,p) basis set combination for the first time. According to findings, the 1H NMR chemical shifts and vibrational frequencies are obtained to be in good agreement with the suitable experimental results. Thus, it would be more precise to say that the calculation level chosen is powerful approach for understanding in the identification of the molecules investigated. At the same time, we determine the electrochemical characteristics belonging to the samples via the simulation of translation energy (HOMO-LUMO), molecular electrostatic potential (MEP) and electrostatic potential (ESP) investigations. It is observed that the strong intra-molecular charge transfer (ICT) appears between the donor and acceptor in the both compounds (especially ABA) due to the existence of the strong electronic donating groups and effective π-π* conjugated segments with high electronic donor ability for the electrophilic attack (intermolecular interactions).

Correlation of materials properties with the atomic density concept

NASA Technical Reports Server (NTRS)

1975-01-01

Based on the hypothesis that the number of atoms per unit volume, accurately calculable for any substance of known real density and chemical composition, various characterizing parameters (energy levels of electrons interacting among atoms of the same or different kinds, atomic mass, bond intensity) were chosen for study. A multiple exponential equation was derived to express the relationship. Various properties were examined, and correlated with the various parameters. Some of the properties considered were: (1) heat of atomization, (2) boiling point, (3) melting point, (4) shear elastic modulus of cubic crystals, (5) thermal conductivity, and (6) refractive index for transparent substances. The solid elements and alkali halides were the materials studied. It is concluded that the number of different properties can quantitively be described by a common group of parameters for the solid elements, and a wide variety of compounds.

Current status of environmental, health, and safety issues of lithium ion electric vehicle batteries

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

Vimmerstedt, L.J.; Ring, S.; Hammel, C.J.

The lithium ion system considered in this report uses lithium intercalation compounds as both positive and negative electrodes and has an organic liquid electrolyte. Oxides of nickel, cobalt, and manganese are used in the positive electrode, and carbon is used in the negative electrode. This report presents health and safety issues, environmental issues, and shipping requirements for lithium ion electric vehicle (EV) batteries. A lithium-based electrochemical system can, in theory, achieve higher energy density than systems using other elements. The lithium ion system is less reactive and more reliable than present lithium metal systems and has possible performance advantages overmore » some lithium solid polymer electrolyte batteries. However, the possibility of electrolyte spills could be a disadvantage of a liquid electrolyte system compared to a solid electrolyte. The lithium ion system is a developing technology, so there is some uncertainty regarding which materials will be used in an EV-sized battery. This report reviews the materials presented in the open literature within the context of health and safety issues, considering intrinsic material hazards, mitigation of material hazards, and safety testing. Some possible lithium ion battery materials are toxic, carcinogenic, or could undergo chemical reactions that produce hazardous heat or gases. Toxic materials include lithium compounds, nickel compounds, arsenic compounds, and dimethoxyethane. Carcinogenic materials include nickel compounds, arsenic compounds, and (possibly) cobalt compounds, copper, and polypropylene. Lithiated negative electrode materials could be reactive. However, because information about the exact compounds that will be used in future batteries is proprietary, ongoing research will determine which specific hazards will apply.« less

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

Hamann, Danielle M.; Lygo, Alexander C.; Esters, Marco

Single- and few-layer metal chalcogenide compounds are of significant interest due to structural changes and emergent electronic properties on reducing dimensionality from three to two dimensions. To explore dimensionality effects in SnSe, a series of [(SnSe) 1+δ] mTiSe 2 intergrowth structures with increasing SnSe layer thickness (m = 1-4) were prepared from designed thin-film precursors. In-plane diffraction patterns indicated that significant structural changes occurred in the basal plane of the SnSe constituent as m is increased. Scanning transmission electron microscopy cross-sectional images of the m = 1 compound indicate long-range coherence between layers, whereas the m >/= 2 compounds showmore » extensive rotational disorder between the constituent layers. For m >/= 2, the images of the SnSe constituent contain a variety of stacking sequences of SnSe bilayers. Density functional theory calculations suggest that the formation energy is similar for several different SnSe stacking sequences. The compounds show unexpected transport properties as m is increased, including the first p-type behavior observed in (MSe)m(TiSe 2) n compounds. The resistivity of the m >/- 2 compounds is larger than for m = 1, with m = 2 being the largest. At room temperature, the Hall coefficient is positive for m = 1 and negative for m = 2-4. The Hall coefficient of the m = 2 compound changes sign as temperature is decreased. The room-temperature Seebeck coefficient, however, switches from negative to positive at m = 3. These properties are incompatible with single band transport indicating that the compounds are not simple composites.« less

Energy density of bloaters in the upper Great Lakes

USGS Publications Warehouse

Pothoven, Steven A.; Bunnell, David B.; Madenjian, Charles P.; Gorman, Owen T.; Roseman, Edward F.

2012-01-01

We evaluated the energy density of bloaters Coregonus hoyi as a function of fish size across Lakes Michigan, Huron, and Superior in 2008–2009 and assessed how differences in energy density are related to factors such as biomass density of bloaters and availability of prey. Additional objectives were to compare energy density between sexes and to compare energy densities of bloaters in Lake Michigan between two time periods (1998–2001 and 2008–2009). For the cross-lake comparisons in 2008, energy density increased with fish total length (TL) only in Lake Michigan. Mean energy density adjusted for fish size was 8% higher in bloaters from Lake Superior than in bloaters from Lake Huron. Relative to fish in these two lakes, small (175 mm TL) bloaters had higher energy density. In 2009, energy density increased with bloater size, and mean energy density adjusted for fish size was about 9% higher in Lake Michigan than in Lake Huron (Lake Superior was not sampled during 2009). Energy density of bloaters in Lake Huron was generally the lowest among lakes, reflecting the relatively low densities of opossum shrimp Mysis diluviana and the relatively high biomass of bloaters reported for that lake. Other factors, such as energy content of prey, growing season, or ontogenetic differences in energy use strategies, may also influence cross-lake variation in energy density. Mean energy density adjusted for length was 7% higher for female bloaters than for male bloaters in Lakes Michigan and Huron. In Lake Superior, energy density did not differ between males and females. Finally, energy density of bloaters in Lake Michigan was similar between the periods 2008–2009 and 1998–2001, possibly due to a low population abundance of bloaters, which could offset food availability changes linked to the loss of prey such as the amphipods Diporeia spp.

Synthesis, spectroscopic analyses, chemical reactivity and molecular docking study and anti-tubercular activity of pyrazine and condensed oxadiazole derivatives

NASA Astrophysics Data System (ADS)

Al-Tamimi, Abdul-Malek S.; Mary, Y. Sheena; Miniyar, Pankaj B.; Al-Wahaibi, Lamya H.; El-Emam, Ali A.; Armaković, Stevan; Armaković, Sanja J.

2018-07-01

The FT-IR spectral analysis and theoretical calculations of the wavenumbers of three oxadiazole derivatives, 2-(5-(2-chlorophenyl)-1,3,4-oxadiazol-2-yl)pyrazine (ORTHOPHPZ), 2-(5-(3-chlorophenyl)-1,3,4-oxadiazol-2-yl)pyrazine (METAPHPZ) and 2-(5-(4-chlorophenyl)-1,3,4-oxadiazol-2-yl)pyrazine (PARAPHPZ) were reported in the present work. The theoretically predicted values of polarizability give the nonlinear behaviour of the compounds. The frontier molecular orbital analysis show the chemical stability of the title compounds and the NBO analysis gives the interactions in the molecular systems. Understanding of reactivity of newly synthetiszed oxadiazole derivatives in this study has been achieved thanks to combination of density functional theory (DFT) calculations, molecular dynamics (MD) simulations and molecular docking procedures. New oxadiazole derivatives have also been characterized experimentally through FT-IR and NMR approaches, thanks to which detailed structural properties have been understood. Both global and local reactivity properties have been investigated by calculations of quantum molecular descriptors such as molecular electrostatic potential (MEP), local average ionization energy (ALIE), Fukui functions, bond dissociation energies for hydrogen abstraction (H-BDE), radial distribution functions and binding energies of ligand against selected protein. The first hyperpolarizabilities of ORTHOPHPZ, METAPHPZ and PARAPHPZ are respectively, 84.62, 94.71 and 184.10 times that of urea. The docked ligands form stable complexes with the receptor 1-phosphatidylinositol phosphodiesterase and the results suggest that these compounds can be developed as new anti-cancer drugs. The anti-TB activity of PM series against M. tuberculosis H37RV strain was performed by Middlebrooke 7H-9 method. The compounds, ORTHOPHPZ, METAPHPZ and PARAPHPZ were moderately active between 25 and 50 μg/ml concentration as compared with the standard anti-TB agents and the -log MIC activity was found in the range of 1.011-1.274 as compared with isoniazid (INH) (1.137) and pyrazinamide (PZA) (1.115) standard anti-TB agents.

A study of advanced magnesium-based hydride and development of a metal hydride thermal battery system

NASA Astrophysics Data System (ADS)

Zhou, Chengshang

Metal hydrides are a group of important materials known as energy carriers for renewable energy and thermal energy storage. A concept of thermal battery based on advanced metal hydrides is studied for heating and cooling of cabins in electric vehicles. The system utilizes a pair of thermodynamically matched metal hydrides as energy storage media. The hot hydride that is identified and developed is catalyzed MgH2 due to its high energy density and enhanced kinetics. TiV0.62Mn1.5, TiMn2, and LaNi5 alloys are selected as the matching cold hydride. A systematic experimental survey is carried out in this study to compare a wide range of additives including transitions metals, transition metal oxides, hydrides, intermetallic compounds, and carbon materials, with respect to their effects on dehydrogenation properties of MgH2. The results show that additives such as Ti and V-based metals, hydride, and certain intermetallic compounds have strong catalytic effects. Solid solution alloys of magnesium are exploited as a way to destabilize magnesium hydride thermodynamically. Various elements are alloyed with magnesium to form solid solutions, including indium and aluminum. Thermodynamic properties of the reactions between the magnesium solid solution alloys and hydrogen are investigated, showing that all the solid solution alloys that are investigated in this work have higher equilibrium hydrogen pressures than that of pure magnesium. Cyclic stability of catalyzed MgH2 is characterized and analyzed using a PCT Sievert-type apparatus. Three systems, including MgH2-TiH 2, MgH2-TiMn2, and MgH2-VTiCr, are examined. The hydrogenating and dehydrogenating kinetics at 300°C are stable after 100 cycles. However, the low temperature (25°C to 150°C) hydrogenation kinetics suffer a severe degradation during hydrogen cycling. Further experiments confirm that the low temperature kinetic degradation can be mainly related the extended hydrogenation-dehydrogenation reactions. Proof-of-concept prototypes are built and tested, demonstrating the potential of the system as HVAC for transportation vehicles. The performance of the concept-demonstration-unit show both high heating/cooling power and high energy densities. An extended cycling test shows degradation on the performance of the system. To solve this problem, a metal hydride hydrogen compressor is proposed for aiding the recharge process of the system.

Modeling non-harmonic behavior of materials from experimental inelastic neutron scattering and thermal expansion measurements

NASA Astrophysics Data System (ADS)

Bansal, Dipanshu; Aref, Amjad; Dargush, Gary; Delaire, Olivier

2016-09-01

Based on thermodynamic principles, we derive expressions quantifying the non-harmonic vibrational behavior of materials, which are rigorous yet easily evaluated from experimentally available data for the thermal expansion coefficient and the phonon density of states. These experimentally-derived quantities are valuable to benchmark first-principles theoretical predictions of harmonic and non-harmonic thermal behaviors using perturbation theory, ab initio molecular-dynamics, or Monte-Carlo simulations. We illustrate this analysis by computing the harmonic, dilational, and anharmonic contributions to the entropy, internal energy, and free energy of elemental aluminum and the ordered compound \\text{FeSi} over a wide range of temperature. Results agree well with previous data in the literature and provide an efficient approach to estimate anharmonic effects in materials.

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.

Electronic structure and magnetic anisotropies of antiferromagnetic transition-metal difluorides

NASA Astrophysics Data System (ADS)

Corrêa, Cinthia Antunes; Výborný, Karel

2018-06-01

We compare calculations based on density functional theory (DFT) with available experimental data and analyze the origin of magnetic anisotropies in MnF2, FeF2, CoF2, and NiF2. We confirm that the magnetic anisotropy of MnF2 stems almost completely from the dipolar interaction, while magnetocrystalline anisotropy energy (originating in spin-orbit interaction) plays a dominant role in the other three compounds, and discuss how it depends on the details of band structure. The latter is critically compared to available optical measurements. The case of CoF2, where magnetocrystalline anisotropy energy strongly depends on U (the Hubbard parameter in DFT +U ), is put into contrast with FeF2 where theoretical predictions of magnetic anisotropies are nearly quantitative.

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

Eilert, Andre; Cavalca, Filippo; Roberts, F. Sloan

Copper electrocatalysts derived from an oxide have shown extraordinary electrochemical properties for the carbon dioxide reduction reaction (CO 2RR). Using in situ ambient pressure X-ray photoelectron spectroscopy and quasi in situ electron energy-loss spectroscopy in a transmission electron microscope, we show that there is a substantial amount of residual oxygen in nanostructured, oxide-derived copper electrocatalysts but no residual copper oxide. On the basis of these findings in combination with density functional theory simulations, we propose that residual subsurface oxygen changes the electronic structure of the catalyst and creates sites with higher carbon monoxide binding energy. If such sites are stablemore » under the strongly reducing conditions found in CO 2RR, these findings would explain the high efficiencies of oxide-derived copper in reducing carbon dioxide to multicarbon compounds such as ethylene.« less

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.

Optical study of phase transitions in single-crystalline RuP

NASA Astrophysics Data System (ADS)

Chen, R. Y.; Shi, Y. G.; Zheng, P.; Wang, L.; Dong, T.; Wang, N. L.

2015-03-01

RuP single crystals of MnP-type orthorhombic structure were synthesized by the Sn flux method. Temperature-dependent x-ray diffraction measurements reveal that the compound experiences two structural phase transitions, which are further confirmed by enormous anomalies shown in temperature-dependent resistivity and magnetic susceptibility. Particularly, the resistivity drops monotonically upon temperature cooling below the second transition, indicating that the material shows metallic behavior, in sharp contrast with the insulating ground state of polycrystalline samples. Optical conductivity measurements were also performed in order to unravel the mechanism of these two transitions. The measurement revealed a sudden reconstruction of band structure over a broad energy scale and a significant removal of conducting carriers below the first phase transition, while a charge-density-wave-like energy gap opens below the second phase transition.

Applying an analytical method to study neutron behavior for dosimetry

NASA Astrophysics Data System (ADS)

Shirazi, S. A. Mousavi

2016-12-01

In this investigation, a new dosimetry process is studied by applying an analytical method. This novel process is associated with a human liver tissue. The human liver tissue has compositions including water, glycogen and etc. In this study, organic compound materials of liver are decomposed into their constituent elements based upon mass percentage and density of every element. The absorbed doses are computed by analytical method in all constituent elements of liver tissue. This analytical method is introduced applying mathematical equations based on neutron behavior and neutron collision rules. The results show that the absorbed doses are converged for neutron energy below 15MeV. This method can be applied to study the interaction of neutrons in other tissues and estimating the absorbed dose for a wide range of neutron energy.

Theory and X-ray Absorption Spectroscopy for Aluminum Coordination Complexes – Al K-Edge Studies of Charge and Bonding in (BDI)Al, (BDI)AlR2, and (BDI)AlX2 Complexes.

PubMed

Altman, Alison B; Pemmaraju, C D; Camp, Clément; Arnold, John; Minasian, Stefan G; Prendergast, David; Shuh, David K; Tyliszczak, Tolek

2015-08-19

Polarized aluminum K-edge X-ray absorption near edge structure (XANES) spectroscopy and first-principles calculations were used to probe electronic structure in a series of (BDI)Al, (BDI)AlX2, and (BDI)AlR2 coordination compounds (X = F, Cl, I; R = H, Me; BDI = 2,6-diisopropylphenyl-β-diketiminate). Spectral interpretations were guided by examination of the calculated transition energies and polarization-dependent oscillator strengths, which agreed well with the XANES spectroscopy measurements. Pre-edge features were assigned to transitions associated with the Al 3p orbitals involved in metal-ligand bonding. Qualitative trends in Al 1s core energy and valence orbital occupation were established through a systematic comparison of excited states derived from Al 3p orbitals with similar symmetries in a molecular orbital framework. These trends suggested that the higher transition energies observed for (BDI)AlX2 systems with more electronegative X(1-) ligands could be ascribed to a decrease in electron density around the aluminum atom, which causes an increase in the attractive potential of the Al nucleus and concomitant increase in the binding energy of the Al 1s core orbitals. For (BDI)Al and (BDI)AlH2 the experimental Al K-edge XANES spectra and spectra calculated using the eXcited electron and Core-Hole (XCH) approach had nearly identical energies for transitions to final state orbitals of similar composition and symmetry. These results implied that the charge distributions about the aluminum atoms in (BDI)Al and (BDI)AlH2 are similar relative to the (BDI)AlX2 and (BDI)AlMe2 compounds, despite having different formal oxidation states of +1 and +3, respectively. However, (BDI)Al was unique in that it exhibited a low-energy feature that was attributed to transitions into a low-lying p-orbital of b1 symmetry that is localized on Al and orthogonal to the (BDI)Al plane. The presence of this low-energy unoccupied molecular orbital on electron-rich (BDI)Al distinguishes its valence electronic structure from that of the formally trivalent compounds (BDI)AlX2 and (BDI)AlR2. The work shows that Al K-edge XANES spectroscopy can be used to provide valuable insight into electronic structure and reactivity relationships for main-group coordination compounds.

Enabling iron pyrite (FeS2) and related ternary pyrite compounds for high-performance solar energy applications

NASA Astrophysics Data System (ADS)

Caban Acevedo, Miguel

The success of solar energy technologies depends not only on highly efficient solar-to-electrical energy conversion, charge storage or chemical fuel production, but also on dramatically reduced cost, to meet the future terawatt energy challenges we face. The enormous scale involved in the development of impactful solar energy technologies demand abundant and inexpensive materials, as well as energy-efficient and cost-effective processes. As a result, the investigation of semiconductor, catalyst and electrode materials made of earth-abundant and sustainable elements may prove to be of significant importance for the long-term adaptation of solar energy technologies on a larger scale. Among earth-abundant semiconductors, iron pyrite (cubic FeS2) has been considered the most promising solar energy absorber with the potential to achieve terawatt energy-scale deployment. Despite extensive synthetic progress and device efforts, the solar conversion efficiency of iron pyrite has remained below 3% since the 1990s, primarily due to a low open circuit voltage (V oc). The low photovoltage (Voc) of iron pyrite has puzzled scientists for decades and limited the development of cost-effective solar energy technologies based on this otherwise promising semiconductor. Here I report a comprehensive investigation of the syntheses and properties of iron pyrite materials, which reveals that the Voc of iron pyrite is limited by the ionization of a high density of intrinsic bulk defect states despite high density surface states and strong surface Fermi level pinning. Contrary to popular belief, bulk defects most-likely caused by intrinsic sulfur vacancies in iron pyrite must be controlled in order to enable this earth-abundant semiconductor for cost-effective and sustainable solar energy conversion. Lastly, the investigation of iron pyrite presented here lead to the discovery of ternary pyrite-type cobalt phosphosulfide (CoPS) as a highly-efficient earth-abundant catalyst material for electrochemical and solar energy driven hydrogen production.

Vibrational spectroscopy of metal methanesulfonates: M = Na, Cs, Cu, Ag, Cd

NASA Astrophysics Data System (ADS)

Parker, Stewart F.; Zhong, Lisha

2018-04-01

In this work, we have used a combination of vibrational spectroscopy (infrared, Raman and inelastic neutron scattering) and periodic density functional theory to investigate six metal methanesulfonate compounds that exhibit four different modes of complexation of the methanesulfonate ion: ionic, monodentate, bidentate and pentadentate. We found that the transition energies of the modes associated with the methyl group (C-H stretches and deformations, methyl rock and torsion) are essentially independent of the mode of coordination. The SO3 modes in the Raman spectra also show little variation. In the infrared spectra, there is a clear distinction between ionic (i.e. not coordinated) and coordinated forms of the methanesulfonate ion. This is manifested as a splitting of the asymmetric S-O stretch modes of the SO3 moiety. Unfortunately, no further differentiation between the various modes of coordination: unidentate, bidentate etc … is possible with the compounds examined. While it is likely that such a distinction could be made, this will require a much larger dataset of compounds for which both structural and spectroscopic data are available than that available here.

A comparative study of DFT calculated and experimental UV/Visible spectra for thirty carboline and carbazole based compounds

NASA Astrophysics Data System (ADS)

Zara, Zeenat; Iqbal, Javed; Ayub, Khurshid; Irfan, Muhammad; Mahmood, Athar; Khera, Rasheed Ahmad; Eliasson, Bertil

2017-12-01

A comparative study of UV/Visible spectra of carboline and carbazole derivatives was conducted by employing the Density Functional Theory (DFT) approach. In this study, the geometries of ground and excited states, excitation energy and absorption spectra were estimated by using seven different DFT functional; CAM-B3LYP, B3LYP, MPW1PW91, PBE, B3PW91, WB97XD and HSE06 with 6-31G basis set. Moreover, five different basis sets 3-21G, 6-31G, DGDZVP, DGTZVP and SDD were also investigated with the CAM-B3LYP and WB97XD functional to take out the best combination of functional and basis set. CAM-B3LYP/6-31G and WB97XD/DGDZVP combination were found to have closest agreement with the experimental values of β-carboline derivatives and carbazole derivatives, respectively. This study provided an insight about the electronic characteristics of the selected compounds and provided an effective tool for developing and designing the better UV absorber compounds.

Organic compounds containing methoxy and cyanoacrylic acid: Synthesis, characterization, crystal structures, and theoretical studies

NASA Astrophysics Data System (ADS)

Khalaji, A. D.; Maddahi, E.; Dusek, M.; Fejfarova, K.; Chow, T. J.

2015-12-01

Metal-free organic compounds 24-SC (( E)-2-cyano-3-(2,4-dimethoxyphenyl)acrylic acid) and 34-SC (( E)-2-cyano-3-(3,4-dimethoxyphenyl)acrylic acid), containing methoxy groups as a donor and the acrylic acid as an acceptor were synthesized and characterized by CHN, FT-IR, UV-Vis, 1H-NMR and single crystal X-ray diffraction and used as photosensitizers for the application of dye-sensitized solar cells (DSSC). The sensitizing characteristics of them were evaluated. Both compounds contain the natural molecule, its anionic form and the piperidinium cation and they differ by number of these molecules in the asymmetric unit. To get further insight into the effect of molecular structure on the performance of DSSC, their geometry and energies of HOMO and LUMO were optimized by density functional theory calculation at the B3LYP/6-31G(d) level with Gaussian 03. Overall conversion efficiencies of 0.78 under full sunlight irradiation are obtained for DSSCs based on the new metal-free organic dyes 24-SC and 34-SC.

Vibrational spectrum and assignments of 2-(4-methoxyphenyl)-1 H-benzo[ d]imidazole by ab initio Hartree-Fock and density functional methods

NASA Astrophysics Data System (ADS)

Arslan, Hakan; Algül, Öztekin

2008-06-01

The room temperature attenuated total reflection Fourier transform infrared spectrum of the 2-(4-methoxyphenyl)-1 H-benzo[ d]imidazole has been recorded with diamond/ZnSe prism. The conformational behaviour, structural stability of optimized geometry, frequency and intensity of the vibrational bands of the title compound were investigated by utilizing ab initio calculations with 6-311G** basis set at HF, B3LYP, BLYP, B3PW91 and mPW1PW91 levels. The harmonic vibrational frequencies were calculated and scaled values have been compared with experimental IR spectrum. The observed and the calculated frequencies are found to be in good agreement. The theoretical vibrational spectra of the title compound were interpreted by means of potential energy distributions using VEDA 4 program. Furthermore, the optimal uniform scaling factors calculated for the title compound are 0.9120, 0.9596, 0.9660, 0.9699, and 0.9993 for HF, mPW1PW91, B3PW91, B3LYP and BLYP methods, respectively.

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

Maurya, Arvind; Kulkarni, Ruta; Thamizhavel, Arumugam

Here, we have explored in detail the anisotropic magnetic properties of CeRhAl 4Si 2 and CeIrAl 4Si 2, which undergo two antiferromagnetic transitions, at T N1 = 12.6 and 15.5 K, followed by a second transition at T N2 = 9.4 and 13.8 K, respectively, with the [001]-axis as the relatively easy axis of magnetization. The electrical resistivity at ambient and applied pressure provides evidence of Kondo interaction in both compounds, further supported by a reduced value of the entropy associated with the magnetic ordering. The Sommerfeld coefficient γ is inferred to be 195.6 and 49.4 mJ/(mol K 2) formore » CeRhAl 4Si 2 and CeIrAl 4Si 2, respectively, classifying these materials as moderate heavy-fermion compounds. The crystal electric field energy levels are derived from the peak seen in the Schottky heat capacity. Furthermore, we have also performed electronic structure calculations by using the local spin density approximation + U [LSDA+U] approach, which provide physical insights on the observed magnetic behavior of these two compounds.« less

Reversible Redox Chemistry of Azo Compounds for Sodium-Ion Batteries.

PubMed

Luo, Chao; Xu, Gui-Liang; Ji, Xiao; Hou, Singyuk; Chen, Long; Wang, Fei; Jiang, Jianjun; Chen, Zonghai; Ren, Yang; Amine, Khalil; Wang, Chunsheng

2018-03-05

Sustainable sodium-ion batteries (SSIBs) using renewable organic electrodes are promising alternatives to lithium-ion batteries for the large-scale renewable energy storage. However, the lack of high-performance anode material impedes the development of SSIBs. Herein, we report a new type of organic anode material based on azo group for SSIBs. Azobenzene-4,4'-dicarboxylic acid sodium salt is used as a model to investigate the electrochemical behaviors and reaction mechanism of azo compound. It exhibits a reversible capacity of 170 mAh g -1 at 0.2C. When current density is increased to 20C, the reversible capacities of 98 mAh g -1 can be retained for 2000 cycles, demonstrating excellent cycling stability and high rate capability. The detailed characterizations reveal that azo group acts as an electrochemical active site to reversibly bond with Na + . The reversible redox chemistry between azo compound and Na ions offer opportunities for developing long-cycle-life and high-rate SSIBs. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Surface stability and the selection rules of substrate orientation for optimal growth of epitaxial II-VI semiconductors

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

Yin, Wan-Jian; Department of Physics & Astronomy, and Wright Center for Photovoltaics Innovation and Commercialization, The University of Toledo, Toledo, Ohio 43606; Yang, Ji-Hui

2015-10-05

The surface structures of ionic zinc-blende CdTe (001), (110), (111), and (211) surfaces are systematically studied by first-principles density functional calculations. Based on the surface structures and surface energies, we identify the detrimental twinning appearing in molecular beam epitaxy (MBE) growth of II-VI compounds as the (111) lamellar twin boundaries. To avoid the appearance of twinning in MBE growth, we propose the following selection rules for choosing optimal substrate orientations: (1) the surface should be nonpolar so that there is no large surface reconstructions that could act as a nucleation center and promote the formation of twins; (2) the surfacemore » structure should have low symmetry so that there are no multiple equivalent directions for growth. These straightforward rules, in consistent with experimental observations, provide guidelines for selecting proper substrates for high-quality MBE growth of II-VI compounds.« less

Angle-resolved photoemission observation of Mn-pnictide hybridization and negligible band structure renormalization in BaMn 2 As 2 and BaMn 2 Sb 2

DOE PAGES

Zhang, W. -L.; Richard, P.; van Roekeghem, A.; ...

2016-10-31

We performed an angle-resolved photoemission spectroscopy study of BaMn 2As 2 and BaMn 2Sb 2, which are isostructural to the parent compound BaFe 2As 2 of the 122 family of ferropnictide superconductors. We show the existence of a strongly k z-dependent band gap with a minimum at the Brillouin zone center, in agreement with their semiconducting properties. Despite the half filling of the electronic 3d shell, we show that the band structure in these materials is almost not renormalized from the Kohn-Sham bands of density functional theory. Finally, our photon-energy-dependent study provides evidence for Mn-pnictide hybridization, which may play amore » role in tuning the electronic correlations in these compounds.« less

Role of modified Becke-Johnson potential in computation of electronic and optical properties of mixed crystals CdxZn1-xSe

NASA Astrophysics Data System (ADS)

Talreja, Sonal; Ahuja, B. L.

2015-08-01

Electronic and optical properties of CdxZn1-xSe (x = 0, 0.25, 0.5, 0.75, 1) compounds are investigated using the first-principles full potential linearized augmented plane wave method. In particular, we have used modified version of the exchange potential of Becke and Johnson, so called mBJ potential. We have discussed the energy bands, density of states, and optical properties such as dielectric constants, refractive indices, reflection spectra, extinction coefficients of all the CdxZn1-xSe compounds. Our mBJ potential based data are found to be in excellent agreement with the available experimental data, which unambiguously validates the applicability of orbital independent exchange-correlation potential in mixed semiconductor crystals. The optical properties are discussed in terms of applicability of Cd-Zn-Se system in light-emitting diodes, UV detectors and filters, etc.