Huang, Xinchuan; Taylor, Peter R; Lee, Timothy J
2011-05-19
High levels of theory have been used to compute quartic force fields (QFFs) for the cyclic and linear forms of the C(3)H(3)(+) molecular cation, referred to as c-C(3)H(3)(+) and l-C(3)H(3)(+). Specifically, the singles and doubles coupled-cluster method that includes a perturbational estimate of connected triple excitations, CCSD(T), has been used in conjunction with extrapolation to the one-particle basis set limit, and corrections for scalar relativity and core correlation have been included. The QFFs have been used to compute highly accurate fundamental vibrational frequencies and other spectroscopic constants by use of both vibrational second-order perturbation theory and variational methods to solve the nuclear Schrödinger equation. Agreement between our best computed fundamental vibrational frequencies and recent infrared photodissociation experiments is reasonable for most bands, but there are a few exceptions. Possible sources for the discrepancies are discussed. We determine the energy difference between the cyclic and linear forms of C(3)H(3)(+), obtaining 27.9 kcal/mol at 0 K, which should be the most reliable available. It is expected that the fundamental vibrational frequencies and spectroscopic constants presented here for c-C(3)H(3)(+) and l-C(3)H(3)(+) are the most reliable available for the free gas-phase species, and it is hoped that these will be useful in the assignment of future high-resolution laboratory experiments or astronomical observations. PMID:21510653
NASA Technical Reports Server (NTRS)
Huang, Xinchuan; Taylor, Peter R.; Lee, Timothy J.
2011-01-01
High levels of theory have been used to compute quartic force fields (QFFs) for the cyclic and linear forms of the C H + molecular cation, referred to as c-C H + and I-C H +. Specifically the 33 3333 singles and doubles coupled-cluster method that includes a perturbational estimate of connected triple excitations, CCSD(T), has been used in conjunction with extrapolation to the one-particle basis set limit and corrections for scalar relativity and core correlation have been included. The QFFs have been used to compute highly accurate fundamental vibrational frequencies and other spectroscopic constants using both vibrational 2nd-order perturbation theory and variational methods to solve the nuclear Schroedinger equation. Agreement between our best computed fundamental vibrational frequencies and recent infrared photodissociation experiments is reasonable for most bands, but there are a few exceptions. Possible sources for the discrepancies are discussed. We determine the energy difference between the cyclic and linear forms of C H +, 33 obtaining 27.9 kcal/mol at 0 K, which should be the most reliable available. It is expected that the fundamental vibrational frequencies and spectroscopic constants presented here for c-C H + 33 and I-C H + are the most reliable available for the free gas-phase species and it is hoped that 33 these will be useful in the assignment of future high-resolution laboratory experiments or astronomical observations.
NASA Technical Reports Server (NTRS)
Lee, Timothy J.; Dateo, Christopher E.; Schwenke, David W.; Chaban, Galina M.
2005-01-01
Accurate quartic force fields have been determined for the CCH- and NH2- molecular anions using the singles and doubles coupled-cluster method that includes a perturbational estimate of the effects of connected triple excitations, CCSD(T). Very large one-particle basis sets have been used including diffuse functions and up through g-type functions. Correlation of the nitrogen and carbon core electrons has been included, as well as other "small" effects, such as the diagonal Born-Oppenheimer correction, and basis set extrapolation, and corrections for higher-order correlation effects and scalar relativistic effects. Fundamental vibrational frequencies have been computed using standard second-order perturbation theory as well as variational methods. Comparison with the available experimental data is presented and discussed. The implications of our research for the astronomical observation of molecular anions will be discussed.
Accurate lineshape spectroscopy and the Boltzmann constant
Truong, G.-W.; Anstie, J. D.; May, E. F.; Stace, T. M.; Luiten, A. N.
2015-01-01
Spectroscopy has an illustrious history delivering serendipitous discoveries and providing a stringent testbed for new physical predictions, including applications from trace materials detection, to understanding the atmospheres of stars and planets, and even constraining cosmological models. Reaching fundamental-noise limits permits optimal extraction of spectroscopic information from an absorption measurement. Here, we demonstrate a quantum-limited spectrometer that delivers high-precision measurements of the absorption lineshape. These measurements yield a very accurate measurement of the excited-state (6P1/2) hyperfine splitting in Cs, and reveals a breakdown in the well-known Voigt spectral profile. We develop a theoretical model that accounts for this breakdown, explaining the observations to within the shot-noise limit. Our model enables us to infer the thermal velocity dispersion of the Cs vapour with an uncertainty of 35 p.p.m. within an hour. This allows us to determine a value for Boltzmann's constant with a precision of 6 p.p.m., and an uncertainty of 71 p.p.m. PMID:26465085
Accurate lineshape spectroscopy and the Boltzmann constant.
Truong, G-W; Anstie, J D; May, E F; Stace, T M; Luiten, A N
2015-01-01
Spectroscopy has an illustrious history delivering serendipitous discoveries and providing a stringent testbed for new physical predictions, including applications from trace materials detection, to understanding the atmospheres of stars and planets, and even constraining cosmological models. Reaching fundamental-noise limits permits optimal extraction of spectroscopic information from an absorption measurement. Here, we demonstrate a quantum-limited spectrometer that delivers high-precision measurements of the absorption lineshape. These measurements yield a very accurate measurement of the excited-state (6P1/2) hyperfine splitting in Cs, and reveals a breakdown in the well-known Voigt spectral profile. We develop a theoretical model that accounts for this breakdown, explaining the observations to within the shot-noise limit. Our model enables us to infer the thermal velocity dispersion of the Cs vapour with an uncertainty of 35 p.p.m. within an hour. This allows us to determine a value for Boltzmann's constant with a precision of 6 p.p.m., and an uncertainty of 71 p.p.m. PMID:26465085
Huang, Xinchuan; Valeev, Edward F; Lee, Timothy J
2010-12-28
One-particle basis set extrapolation is compared with one of the new R12 methods for computing highly accurate quartic force fields (QFFs) and spectroscopic data, including molecular structures, rotational constants, and vibrational frequencies for the H(2)O, N(2)H(+), NO(2)(+), and C(2)H(2) molecules. In general, agreement between the spectroscopic data computed from the best R12 and basis set extrapolation methods is very good with the exception of a few parameters for N(2)H(+) where it is concluded that basis set extrapolation is still preferred. The differences for H(2)O and NO(2)(+) are small and it is concluded that the QFFs from both approaches are more or less equivalent in accuracy. For C(2)H(2), however, a known one-particle basis set deficiency for C-C multiple bonds significantly degrades the quality of results obtained from basis set extrapolation and in this case the R12 approach is clearly preferred over one-particle basis set extrapolation. The R12 approach used in the present study was modified in order to obtain high precision electronic energies, which are needed when computing a QFF. We also investigated including core-correlation explicitly in the R12 calculations, but conclude that current approaches are lacking. Hence core-correlation is computed as a correction using conventional methods. Considering the results for all four molecules, it is concluded that R12 methods will soon replace basis set extrapolation approaches for high accuracy electronic structure applications such as computing QFFs and spectroscopic data for comparison to high-resolution laboratory or astronomical observations, provided one uses a robust R12 method as we have done here. The specific R12 method used in the present study, CCSD(T)(R12), incorporated a reformulation of one intermediate matrix in order to attain machine precision in the electronic energies. Final QFFs for N(2)H(+) and NO(2)(+) were computed, including basis set extrapolation, core-correlation, scalar
Huang Xinchuan; Fortenberry, Ryan C.; Lee, Timothy J.
2013-05-10
Very recently, molecular rotational transitions observed in the photon-dominated region of the Horsehead nebula have been attributed to l-C{sub 3}H{sup +}. In an effort to corroborate this finding, we employed state-of-the-art and proven high-accuracy quantum chemical techniques to compute spectroscopic constants for this cation and its isotopologues. Even though the B rotational constant from the fit of the observed spectrum and our computations agree to within 20 MHz, a typical level of accuracy, the D rotational constant differs by more than 40%, while the H rotational constant differs by three orders of magnitude. With the likely errors in the rotational transition energies resulting from this difference in D on the order of 1 MHz for the lowest observed transition (J = 4 {yields} 3) and growing as J increases, the assignment of the observed rotational lines from the Horsehead nebula to l-C{sub 3}H{sup +} is questionable.
NASA Astrophysics Data System (ADS)
Huang, Xinchuan; Fortenberry, Ryan C.; Lee, Timothy J.
2013-05-01
Very recently, molecular rotational transitions observed in the photon-dominated region of the Horsehead nebula have been attributed to l-C3H+. In an effort to corroborate this finding, we employed state-of-the-art and proven high-accuracy quantum chemical techniques to compute spectroscopic constants for this cation and its isotopologues. Even though the B rotational constant from the fit of the observed spectrum and our computations agree to within 20 MHz, a typical level of accuracy, the D rotational constant differs by more than 40%, while the H rotational constant differs by three orders of magnitude. With the likely errors in the rotational transition energies resulting from this difference in D on the order of 1 MHz for the lowest observed transition (J = 4 → 3) and growing as J increases, the assignment of the observed rotational lines from the Horsehead nebula to l-C3H+ is questionable.
NASA Technical Reports Server (NTRS)
Huang, Xinchuan; Fortenberry, Ryan Clifton; Lee, Timothy J.
2013-01-01
Very recently, molecular rotational transitions observed in the photon-dominated region of the Horsehead nebula have been attributed to l-C3H+. In an effort to corroborate this finding, we employed state-of-the art and proven high-accuracy quantum chemical techniques to compute spectroscopic constants for this cation and its isotopologues. Even though the B rotational constant from the fit of the observed spectrum and our computations agree to within 20 MHz, a typical level of accuracy, the D rotational constant differs by more than 40%, while the H rotational constant differs by three orders of magnitude. With the likely errors in the rotational transition energies resulting from this difference in D on the order of 1 MHz for the lowest observed transition (J = 4 yields 3) and growing as J increases, the assignment of the observed rotational lines from the Horsehead nebula to l-C3H+ is questionable.
On determining dose rate constants spectroscopically
Rodriguez, M.; Rogers, D. W. O.
2013-01-15
Purpose: To investigate several aspects of the Chen and Nath spectroscopic method of determining the dose rate constants of {sup 125}I and {sup 103}Pd seeds [Z. Chen and R. Nath, Phys. Med. Biol. 55, 6089-6104 (2010)] including the accuracy of using a line or dual-point source approximation as done in their method, and the accuracy of ignoring the effects of the scattered photons in the spectra. Additionally, the authors investigate the accuracy of the literature's many different spectra for bare, i.e., unencapsulated {sup 125}I and {sup 103}Pd sources. Methods: Spectra generated by 14 {sup 125}I and 6 {sup 103}Pd seeds were calculated in vacuo at 10 cm from the source in a 2.7 Multiplication-Sign 2.7 Multiplication-Sign 0.05 cm{sup 3} voxel using the EGSnrc BrachyDose Monte Carlo code. Calculated spectra used the initial photon spectra recommended by AAPM's TG-43U1 and NCRP (National Council of Radiation Protection and Measurements) Report 58 for the {sup 125}I seeds, or TG-43U1 and NNDC(2000) (National Nuclear Data Center, 2000) for {sup 103}Pd seeds. The emitted spectra were treated as coming from a line or dual-point source in a Monte Carlo simulation to calculate the dose rate constant. The TG-43U1 definition of the dose rate constant was used. These calculations were performed using the full spectrum including scattered photons or using only the main peaks in the spectrum as done experimentally. Statistical uncertainties on the air kerma/history and the dose rate/history were Less-Than-Or-Slanted-Equal-To 0.2%. The dose rate constants were also calculated using Monte Carlo simulations of the full seed model. Results: The ratio of the intensity of the 31 keV line relative to that of the main peak in {sup 125}I spectra is, on average, 6.8% higher when calculated with the NCRP Report 58 initial spectrum vs that calculated with TG-43U1 initial spectrum. The {sup 103}Pd spectra exhibit an average 6.2% decrease in the 22.9 keV line relative to the main peak when
Isomerism of Cyanomethanimine: Accurate Structural, Energetic, and Spectroscopic Characterization.
Puzzarini, Cristina
2015-11-25
The structures, relative stabilities, and rotational and vibrational parameters of the Z-C-, E-C-, and N-cyanomethanimine isomers have been evaluated using state-of-the-art quantum-chemical approaches. Equilibrium geometries have been calculated by means of a composite scheme based on coupled-cluster calculations that accounts for the extrapolation to the complete basis set limit and core-correlation effects. The latter approach is proved to provide molecular structures with an accuracy of 0.001-0.002 Å and 0.05-0.1° for bond lengths and angles, respectively. Systematically extrapolated ab initio energies, accounting for electron correlation through coupled-cluster theory, including up to single, double, triple, and quadruple excitations, and corrected for core-electron correlation and anharmonic zero-point vibrational energy, have been used to accurately determine relative energies and the Z-E isomerization barrier with an accuracy of about 1 kJ/mol. Vibrational and rotational spectroscopic parameters have been investigated by means of hybrid schemes that allow us to obtain rotational constants accurate to about a few megahertz and vibrational frequencies with a mean absolute error of ∼1%. Where available, for all properties considered, a very good agreement with experimental data has been observed. PMID:26529434
Spectroscopic Constants of the Known Electronic States of Lead Monofluoride
McRaven, C.P.; Sivakumar, P.; Shafer-Ray, N.E.; Hall, G.E.; Sears, T.J.
2010-08-01
Based on measurements made by mass-resolved 1 + 1{prime} + 1{double_prime} resonance-enhanced multiphoton ionization spectroscopy, we have determined new molecular constants describing the rotational and fine structure levels of the B, D, E, and F states of the most abundant isotopic variant {sup 208}Pb{sup 19}F, and we summarize the spectroscopic constants for all the know electronic states of the radical. Many spectroscopic constants for the isotopologues {sup 206}Pb{sup 19}F and {sup 207}Pb{sup 19}F have also been determined. The symmetry of the D-state is found to be {sup 2}{pi}{sub 1/2}, and the F-state is found to be an {Omega} = 3/2 state.
History and progress on accurate measurements of the Planck constant
NASA Astrophysics Data System (ADS)
Steiner, Richard
2013-01-01
The measurement of the Planck constant, h, is entering a new phase. The CODATA 2010 recommended value is 6.626 069 57 × 10-34 J s, but it has been a long road, and the trip is not over yet. Since its discovery as a fundamental physical constant to explain various effects in quantum theory, h has become especially important in defining standards for electrical measurements and soon, for mass determination. Measuring h in the International System of Units (SI) started as experimental attempts merely to prove its existence. Many decades passed while newer experiments measured physical effects that were the influence of h combined with other physical constants: elementary charge, e, and the Avogadro constant, NA. As experimental techniques improved, the precision of the value of h expanded. When the Josephson and quantum Hall theories led to new electronic devices, and a hundred year old experiment, the absolute ampere, was altered into a watt balance, h not only became vital in definitions for the volt and ohm units, but suddenly it could be measured directly and even more accurately. Finally, as measurement uncertainties now approach a few parts in 108 from the watt balance experiments and Avogadro determinations, its importance has been linked to a proposed redefinition of a kilogram unit of mass. The path to higher accuracy in measuring the value of h was not always an example of continuous progress. Since new measurements periodically led to changes in its accepted value and the corresponding SI units, it is helpful to see why there were bumps in the road and where the different branch lines of research joined in the effort. Recalling the bumps along this road will hopefully avoid their repetition in the upcoming SI redefinition debates. This paper begins with a brief history of the methods to measure a combination of fundamental constants, thus indirectly obtaining the Planck constant. The historical path is followed in the section describing how the improved
History and progress on accurate measurements of the Planck constant.
Steiner, Richard
2013-01-01
The measurement of the Planck constant, h, is entering a new phase. The CODATA 2010 recommended value is 6.626 069 57 × 10(-34) J s, but it has been a long road, and the trip is not over yet. Since its discovery as a fundamental physical constant to explain various effects in quantum theory, h has become especially important in defining standards for electrical measurements and soon, for mass determination. Measuring h in the International System of Units (SI) started as experimental attempts merely to prove its existence. Many decades passed while newer experiments measured physical effects that were the influence of h combined with other physical constants: elementary charge, e, and the Avogadro constant, N(A). As experimental techniques improved, the precision of the value of h expanded. When the Josephson and quantum Hall theories led to new electronic devices, and a hundred year old experiment, the absolute ampere, was altered into a watt balance, h not only became vital in definitions for the volt and ohm units, but suddenly it could be measured directly and even more accurately. Finally, as measurement uncertainties now approach a few parts in 10(8) from the watt balance experiments and Avogadro determinations, its importance has been linked to a proposed redefinition of a kilogram unit of mass. The path to higher accuracy in measuring the value of h was not always an example of continuous progress. Since new measurements periodically led to changes in its accepted value and the corresponding SI units, it is helpful to see why there were bumps in the road and where the different branch lines of research joined in the effort. Recalling the bumps along this road will hopefully avoid their repetition in the upcoming SI redefinition debates. This paper begins with a brief history of the methods to measure a combination of fundamental constants, thus indirectly obtaining the Planck constant. The historical path is followed in the section describing how the
A spectroscopic transfer standard for accurate atmospheric CO measurements
NASA Astrophysics Data System (ADS)
Nwaboh, Javis A.; Li, Gang; Serdyukov, Anton; Werhahn, Olav; Ebert, Volker
2016-04-01
Atmospheric carbon monoxide (CO) is a precursor of essential climate variables and has an indirect effect for enhancing global warming. Accurate and reliable measurements of atmospheric CO concentration are becoming indispensable. WMO-GAW reports states a compatibility goal of ±2 ppb for atmospheric CO concentration measurements. Therefore, the EMRP-HIGHGAS (European metrology research program - high-impact greenhouse gases) project aims at developing spectroscopic transfer standards for CO concentration measurements to meet this goal. A spectroscopic transfer standard would provide results that are directly traceable to the SI, can be very useful for calibration of devices operating in the field, and could complement classical gas standards in the field where calibration gas mixtures in bottles often are not accurate, available or stable enough [1][2]. Here, we present our new direct tunable diode laser absorption spectroscopy (dTDLAS) sensor capable of performing absolute ("calibration free") CO concentration measurements, and being operated as a spectroscopic transfer standard. To achieve the compatibility goal stated by WMO for CO concentration measurements and ensure the traceability of the final concentration results, traceable spectral line data especially line intensities with appropriate uncertainties are needed. Therefore, we utilize our new high-resolution Fourier-transform infrared (FTIR) spectroscopy CO line data for the 2-0 band, with significantly reduced uncertainties, for the dTDLAS data evaluation. Further, we demonstrate the capability of our sensor for atmospheric CO measurements, discuss uncertainty calculation following the guide to the expression of uncertainty in measurement (GUM) principles and show that CO concentrations derived using the sensor, based on the TILSAM (traceable infrared laser spectroscopic amount fraction measurement) method, are in excellent agreement with gravimetric values. Acknowledgement Parts of this work have been
Spectroscopically Accurate Line Lists for Application in Sulphur Chemistry
NASA Astrophysics Data System (ADS)
Underwood, D. S.; Azzam, A. A. A.; Yurchenko, S. N.; Tennyson, J.
2013-09-01
Monitoring sulphur chemistry is thought to be of great importance for exoplanets. Doing this requires detailed knowledge of the spectroscopic properties of sulphur containing molecules such as hydrogen sulphide (H2S) [1], sulphur dioxide (SO2), and sulphur trioxide (SO3). Each of these molecules can be found in terrestrial environments, produced in volcano emissions on Earth, and analysis of their spectroscopic data can prove useful to the characterisation of exoplanets, as well as the study of planets in our own solar system, with both having a possible presence on Venus. A complete, high temperature list of line positions and intensities for H32 2 S is presented. The DVR3D program suite is used to calculate the bound ro-vibration energy levels, wavefunctions, and dipole transition intensities using Radau coordinates. The calculations are based on a newly determined, spectroscopically refined potential energy surface (PES) and a new, high accuracy, ab initio dipole moment surface (DMS). Tests show that the PES enables us to calculate the line positions accurately and the DMS gives satisfactory results for line intensities. Comparisons with experiment as well as with previous theoretical spectra will be presented. The results of this study will form an important addition to the databases which are considered as sources of information for space applications; especially, in analysing the spectra of extrasolar planets, and remote sensing studies for Venus and Earth, as well as laboratory investigations and pollution studies. An ab initio line list for SO3 was previously computed using the variational nuclear motion program TROVE [2], and was suitable for modelling room temperature SO3 spectra. The calculations considered transitions in the region of 0-4000 cm-1 with rotational states up to J = 85, and includes 174,674,257 transitions. A list of 10,878 experimental transitions had relative intensities placed on an absolute scale, and were provided in a form suitable
NASA Astrophysics Data System (ADS)
Tu, Zhe-Yan; Wang, Wen-Liang; Li, Ren-Zhong; Xia, Cai-Juan; Li, Lian-Bi
2016-07-01
The CCSD(T) approach based on two-component relativistic effective core potential with spin-orbit interaction just included in coupled cluster iteration is adopted to study the spectroscopic constants of ground states of Kr2, Xe2 and Rn2 dimers. The spectroscopic constants have significant basis set dependence. Extrapolation to the complete basis set limit provides the most accurate values. The spin-orbit interaction hardly affects the spectroscopic constants of Kr2 and Xe2. However, the equilibrium bond length is shortened about 0.013 Å and the dissociation energy is augmented about 18 cm-1 by the spin-orbit interaction for Rn2 in the complete basis set limit.
Spectroscopic constants and potential energy curves of tungsten carbide
Balasubramanian, K.
2000-05-01
Spectroscopic constants (R{sub e},{omega}{sub e},T{sub e},{mu}{sub e}) and potential energy curves for 40 low-lying electronic states of the diatomic tungsten carbide (WC) were obtained using the complete active space multiconfiguration self-consistent field followed by the multireference singles+doubles configuration interaction and full first- and second-order configuration interaction calculations that included up to 6.4 mil configurations. Spin-orbit effects were included through the enhanced relativistic configuration interaction method described here for 28 electronic states of WC lying below {approx}20 000 cm-1. The spin-orbit splitting of the ground state of WC was found to be very large (4394 cm-1). The ground and excited electronic states of the W atom were also computed and were found to be in good agreement with the experimental data. The nature of bonding was analyzed through the composition of orbitals, leading configurations, Mulliken populations, and dipole moments. The dissociation energy of WC was computed including spin-orbit and electron correlation effects. The recent photoelectron spectra of WC{sup -} were assigned on the basis of our computed results. (c) 2000 American Institute of Physics.
NASA Technical Reports Server (NTRS)
Fortenberry, Ryan C.; Crawford, T. Daniel; Lee, Timothy J.
2012-01-01
The A 1B1 <-1A0 excitation into the dipole-bound state of the cyanomethyl anion (CH2CN??) has been hypothesized as the carrier for one di use interstellar band. However, this particular molecular system has not been detected in the interstellar medium even though the related cyanomethyl radical and the isoelectronic ketenimine molecule have been found. In this study we are employing the use of proven quartic force elds and second-order vibrational perturbation theory to compute accurate spectroscopic constants and fundamental vibrational frequencies for X 1A0 CH2CN?? in order to assist in laboratory studies and astronomical observations. Keywords: Astrochemistry, ISM: molecular anions, Quartic force elds, Rotational constants, Vibrational frequencies
Spectroscopically Accurate Calculations of the Rovibrational Energies of Diatomic Hydrogen
NASA Astrophysics Data System (ADS)
Perry, Jason
2005-05-01
The Born-Oppenheimer approximation has been used to calculate the rotational and vibrational states of diatomic hydrogen. Because it is an approximation, our group now wants to use a Born-Oppenheimer potential to calculate the electronic energy that has been corrected to match closely with spectroscopic results. We are using a code that has corrections for adiabatic, relativistic, radiative, and non-adiabatic effects. The rovibrational energies have now been calculated for both bound and quasi-bound states. We also want to compute quadrupole transition probabilities for diatomic hydrogen. These calculations aspire to investigate diatomic hydrogen in astrophysical environments.
NASA Astrophysics Data System (ADS)
Hochlaf, M.; Puzzarini, C.; Senent, M. L.
2015-07-01
We present multi-component computations for rotational constants, vibrational and torsional levels of medium-sized molecules. Through the treatment of two organic sulphur molecules, ethyl mercaptan and dimethyl sulphide, which are relevant for atmospheric and astrophysical media, we point out the outstanding capabilities of explicitly correlated coupled clusters (CCSD(T)-F12) method in conjunction with the cc-pVTZ-F12 basis set for the accurate predictions of such quantities. Indeed, we show that the CCSD(T)-F12/cc-pVTZ-F12 equilibrium rotational constants are in good agreement with those obtained by means of a composite scheme based on CCSD(T) calculations that accounts for the extrapolation to the complete basis set (CBS) limit and core-correlation effects [CCSD(T)/CBS+CV], thus leading to values of ground-state rotational constants rather close to the corresponding experimental data. For vibrational and torsional levels, our analysis reveals that the anharmonic frequencies derived from CCSD(T)-F12/cc-pVTZ-F12 harmonic frequencies and anharmonic corrections (Δν = ω - ν) at the CCSD/cc-pVTZ level closely agree with experimental results. The pattern of the torsional transitions and the shape of the potential energy surfaces along the torsional modes are also well reproduced using the CCSD(T)-F12/cc-pVTZ-F12 energies. Interestingly, this good accuracy is accompanied with a strong reduction of the computational costs. This makes the procedures proposed here as schemes of choice for effective and accurate prediction of spectroscopic properties of organic compounds. Finally, popular density functional approaches are compared with the coupled cluster (CC) methodologies in torsional studies. The long-range CAM-B3LYP functional of Handy and co-workers is recommended for large systems.
Bellili, A; Linguerri, R; Hochlaf, M; Puzzarini, C
2015-11-14
In an effort to provide an accurate structural and spectroscopic characterization of acetyl cyanide, its two enolic isomers and the corresponding cationic species, state-of-the-art computational methods, and approaches have been employed. The coupled-cluster theory including single and double excitations together with a perturbative treatment of triples has been used as starting point in composite schemes accounting for extrapolation to the complete basis-set limit as well as core-valence correlation effects to determine highly accurate molecular structures, fundamental vibrational frequencies, and rotational parameters. The available experimental data for acetyl cyanide allowed us to assess the reliability of our computations: structural, energetic, and spectroscopic properties have been obtained with an overall accuracy of about, or better than, 0.001 Å, 2 kcal/mol, 1-10 MHz, and 11 cm(-1) for bond distances, adiabatic ionization potentials, rotational constants, and fundamental vibrational frequencies, respectively. We are therefore confident that the highly accurate spectroscopic data provided herein can be useful for guiding future experimental investigations and/or astronomical observations. PMID:26567669
The trans-HOCO radical: Quartic force fields, vibrational frequencies, and spectroscopic constants
NASA Astrophysics Data System (ADS)
Fortenberry, Ryan C.; Huang, Xinchuan; Francisco, Joseph S.; Crawford, T. Daniel; Lee, Timothy J.
2011-10-01
In the search for a full mechanism creating CO2 from OH + CO, it has been suggested that creation of the hydroxyformyl or HOCO radical may be a necessary step. This reaction and its transient intermediate may also be responsible for the regeneration of CO2 in such high quantities in the atmosphere of Mars. Past spectroscopic observations of this radical have been limited and a full gas phase set of the fundamental vibrational frequencies of the HOCO radical has not been reported. Using established, highly accurate quantum chemical coupled cluster techniques and quartic force fields, we are able to compute all six fundamental vibrational frequencies and other spectroscopic constants for trans-HOCO in the gas phase. These methods have yielded rotational constants that are within 0.01 cm-1 for A0 and 10-4 cm-1 for B0 and C0 compared with experiment as well as fundamental vibrational frequencies within 4 cm-1 of the known gas phase experimental ν1 and ν2 modes. Such results lead us to conclude that our prediction of the other four fundamental modes of trans-HOCO are also quite reliable for comparison to future experimental observation, though the discrepancy for the torsional mode may be larger since it is fairly anharmonic. With the upcoming European Space Agency/NASA ExoMars Trace Gas Orbiter, these data may help to establish whether HOCO is present in the Martian sky and what role it may play in the retention of a CO2-rich atmosphere. Furthermore, these data may also help to clear up questions built around the fundamental chemical process of how exactly the OH + CO reaction progresses.
The ab initio potential energy surface and spectroscopic constants of HOCl
NASA Astrophysics Data System (ADS)
Koput, Jacek; Peterson, Kirk A.
1998-02-01
The potential energy surface of hypochlorous acid, HOCl, has been determined from large-scale ab initio calculations using the coupled-cluster method CCSD(T), with basis sets of quadruple- and quintuple-zeta quality. The effect of core-electron correlation on the calculated structural parameters has been investigated. The vibrational-rotational energy levels of the three isotopic species of HOCl have then been calculated using the variational method and have been further characterized by the spectroscopic constants determined using the perturbational approach. The spectroscopic constants determined, are found to be in excellent agreement with experimental data.
Huang, Xinchuan; Fortenberry, Ryan C; Lee, Timothy J
2013-08-28
The interstellar presence of protonated nitrous oxide has been suspected for some time. Using established high-accuracy quantum chemical techniques, spectroscopic constants and fundamental vibrational frequencies are provided for the lower energy O-protonated isomer of this cation and its deuterated isotopologue. The vibrationally-averaged B0 and C0 rotational constants are within 6 MHz of their experimental values and the D(J) quartic distortion constants agree with experiment to within 3%. The known gas phase O-H stretch of NNOH(+) is 3330.91 cm(-1), and the vibrational configuration interaction computed result is 3330.9 cm(-1). Other spectroscopic constants are also provided, as are the rest of the fundamental vibrational frequencies for NNOH(+) and its deuterated isotopologue. This high-accuracy data should serve to better inform future observational or experimental studies of the rovibrational bands of protonated nitrous oxide in the interstellar medium and the laboratory. PMID:24007003
NASA Technical Reports Server (NTRS)
Huang, Xinchuan; Fortenberry, Ryan C.; Lee, Timothy J.
2013-01-01
The interstellar presence of protonated nitrous oxide has been suspected for some time. Using established high-accuracy quantum chemical techniques, spectroscopic constants and fundamental vibrational frequencies are provided for the lower energy O-protonated isomer of this cation and its deuterated isotopologue. The vibrationally-averaged B0 and C0 rotational constants are within 6 MHz of their experimental values and the D(subJ) quartic distortion constants agree with experiment to within 3%. The known gas phase O-H stretch of NNOH(+) is 3330.91 cm(exp-1), and the vibrational configuration interaction computed result is 3330.9 cm(exp-1). Other spectroscopic constants are also provided, as are the rest of the fundamental vibrational frequencies for NNOH(+) and its deuterated isotopologue. This high-accuracy data should serve to better inform future observational or experimental studies of the rovibrational bands of protonated nitrous oxide in the ISM and the laboratory.
Puzzarini, Cristina; Ali, Ashraf; Biczysko, Malgorzata; Barone, Vincenzo
2014-09-10
An accurate spectroscopic characterization of protonated oxirane has been carried out by means of state-of-the-art computational methods and approaches. The calculated spectroscopic parameters from our recent computational investigation of oxirane together with the corresponding experimental data available were used to assess the accuracy of our predicted rotational and IR spectra of protonated oxirane. We found an accuracy of about 10 cm{sup –1} for vibrational transitions (fundamentals as well as overtones and combination bands) and, in relative terms, of 0.1% for rotational transitions. We are therefore confident that the spectroscopic data provided herein are a valuable support for the detection of protonated oxirane not only in Titan's atmosphere but also in the interstellar medium.
Puzzarini, Cristina; Ali, Ashraf; Biczysko, Malgorzata; Barone, Vincenzo
2015-01-01
An accurate spectroscopic characterization of protonated oxirane has been carried out by means of state-of-the-art computational methods and approaches. The calculated spectroscopic parameters from our recent computational investigation of oxirane together with the corresponding experimental data available were used to assess the accuracy of our predicted rotational and IR spectra of protonated oxirane. We found an accuracy of about 10 cm−1 for vibrational transitions (fundamentals as well as overtones and combination bands) and, in relative terms, of 0.1% for rotational transitions. We are therefore confident that the spectroscopic data provided herein are a valuable support for the detection of protonated oxirane not only in Titan’s atmosphere but also in the interstellar medium. PMID:26543241
Quick and accurate estimation of the elastic constants using the minimum image method
NASA Astrophysics Data System (ADS)
Tretiakov, Konstantin V.; Wojciechowski, Krzysztof W.
2015-04-01
A method for determining the elastic properties using the minimum image method (MIM) is proposed and tested on a model system of particles interacting by the Lennard-Jones (LJ) potential. The elastic constants of the LJ system are determined in the thermodynamic limit, N → ∞, using the Monte Carlo (MC) method in the NVT and NPT ensembles. The simulation results show that when determining the elastic constants, the contribution of long-range interactions cannot be ignored, because that would lead to erroneous results. In addition, the simulations have revealed that the inclusion of further interactions of each particle with all its minimum image neighbors even in case of small systems leads to results which are very close to the values of elastic constants in the thermodynamic limit. This enables one for a quick and accurate estimation of the elastic constants using very small samples.
Li, Rui; Ye, Hongfei; Zhang, Weisheng; Ma, Guojun; Su, Yewang
2015-01-01
Spring constant calibration of the atomic force microscope (AFM) cantilever is of fundamental importance for quantifying the force between the AFM cantilever tip and the sample. The calibration within the framework of thin plate theory undoubtedly has a higher accuracy and broader scope than that within the well-established beam theory. However, thin plate theory-based accurate analytic determination of the constant has been perceived as an extremely difficult issue. In this paper, we implement the thin plate theory-based analytic modeling for the static behavior of rectangular AFM cantilevers, which reveals that the three-dimensional effect and Poisson effect play important roles in accurate determination of the spring constants. A quantitative scaling law is found that the normalized spring constant depends only on the Poisson’s ratio, normalized dimension and normalized load coordinate. Both the literature and our refined finite element model validate the present results. The developed model is expected to serve as the benchmark for accurate calibration of rectangular AFM cantilevers. PMID:26510769
Li, Rui; Ye, Hongfei; Zhang, Weisheng; Ma, Guojun; Su, Yewang
2015-01-01
Spring constant calibration of the atomic force microscope (AFM) cantilever is of fundamental importance for quantifying the force between the AFM cantilever tip and the sample. The calibration within the framework of thin plate theory undoubtedly has a higher accuracy and broader scope than that within the well-established beam theory. However, thin plate theory-based accurate analytic determination of the constant has been perceived as an extremely difficult issue. In this paper, we implement the thin plate theory-based analytic modeling for the static behavior of rectangular AFM cantilevers, which reveals that the three-dimensional effect and Poisson effect play important roles in accurate determination of the spring constants. A quantitative scaling law is found that the normalized spring constant depends only on the Poisson's ratio, normalized dimension and normalized load coordinate. Both the literature and our refined finite element model validate the present results. The developed model is expected to serve as the benchmark for accurate calibration of rectangular AFM cantilevers. PMID:26510769
NASA Astrophysics Data System (ADS)
Li, Rui; Ye, Hongfei; Zhang, Weisheng; Ma, Guojun; Su, Yewang
2015-10-01
Spring constant calibration of the atomic force microscope (AFM) cantilever is of fundamental importance for quantifying the force between the AFM cantilever tip and the sample. The calibration within the framework of thin plate theory undoubtedly has a higher accuracy and broader scope than that within the well-established beam theory. However, thin plate theory-based accurate analytic determination of the constant has been perceived as an extremely difficult issue. In this paper, we implement the thin plate theory-based analytic modeling for the static behavior of rectangular AFM cantilevers, which reveals that the three-dimensional effect and Poisson effect play important roles in accurate determination of the spring constants. A quantitative scaling law is found that the normalized spring constant depends only on the Poisson’s ratio, normalized dimension and normalized load coordinate. Both the literature and our refined finite element model validate the present results. The developed model is expected to serve as the benchmark for accurate calibration of rectangular AFM cantilevers.
NASA Astrophysics Data System (ADS)
Horie, Masahiro; Postava, Kamil; Yamaguchi, Tomuo; Akashika, Kumiko; Hayashi, Hideki; Kitamura, Fujikazu
2003-05-01
The dielectric function spectra of low dielectric constants (low-k) materials have been determined using spectroscopic ellipsometry, normal incidence spectroscopic reflectometry, and Fourier transform infrared transmission spectrometry over a wide spectral range from 0.03 to 5.4 eV (230nm to 40.5um wavelength region). The electric and ionic contributions to the overall static dielectric constants were determined for representative materials used in the semiconductor industry for interlayer dielectrics: (1) FLARE - organic spin-on polymer, (2) HOSP - spin-on hybrid organic-siloxane polymer from the Honeywell Electric Materials Company, and (3) SiLK- organic dielectric resin from the Dow Chemical Company. The main contributions to the static dielectric constant of the low-k materials studied were found to be the electric and ionic absorption.
NASA Astrophysics Data System (ADS)
Gates, Richard S.; Osborn, William A.; Shaw, Gordon A.
2015-06-01
Calibration of the flexural spring constant for atomic force microscope (AFM) colloid probe cantilevers provides significant challenges. The presence of a large attached spherical added mass complicates many of the more common calibration techniques such as reference cantilever, Sader, and added mass. Even the most promising option, AFM thermal calibration, can encounter difficulties during the optical lever sensitivity measurement due to strong adhesion and friction between the sphere and a surface. This may cause buckling of the end of the cantilever and hysteresis in the approach-retract curves resulting in increased uncertainty in the calibration. Most recently, a laser Doppler vibrometry thermal method has been used to accurately calibrate the normal spring constant of a wide variety of tipped and tipless commercial cantilevers. This paper describes a variant of the technique, scanning laser Doppler vibrometry, optimized for colloid probe cantilevers and capable of spring constant calibration uncertainties near ±1%.
NASA Technical Reports Server (NTRS)
Lee, Timothy J.; Dateo, Christopher E.
2005-01-01
The singles and doubles coupled-cluster method that includes a perturbational estimate of connected triple excitations, denoted CCSD(T), has been used, in conjunction with approximate integral techniques, to compute highly accurate rovibrational spectroscopic constants of cyclopropenylidene, C3H2. The approximate integral technique was proposed in 1994 by Rendell and Lee in order to avoid disk storage and input/output bottlenecks, and today it will also significantly aid in the development of algorithms for distributed memory, massively parallel computer architectures. It is shown in this study that use of approximate integrals does not impact the accuracy of CCSD(T) calculations. In addition, the most accurate spectroscopic data yet for C3H2 is presented based on a CCSD(T)/cc-pVQZ quartic force field that is modified to include the effects of core-valence electron correlation. Cyclopropenylidene is of great astronomical and astrobiological interest because it is the smallest aromatic ringed compound to be positively identified in the interstellar medium, and is thus involved in the prebiotic processing of carbon and hydrogen. The singles and doubles coupled-cluster method that includes a perturbational estimate of
Accurate measurements of the dielectric constant of seawater at L band
NASA Astrophysics Data System (ADS)
Lang, Roger; Zhou, Yiwen; Utku, Cuneyt; Le Vine, David
2016-01-01
This paper describes measurements of the dielectric constant of seawater at a frequency of 1.413 GHz, the center of the protected band (i.e., passive use only) used in the measurement of sea surface salinity from space. The objective of the measurements is to accurately determine the complex dielectric constant of seawater as a function of salinity and temperature. A resonant cylindrical microwave cavity in transmission mode has been employed to make the measurements. The measurements are made using standard seawater at salinities of 30, 33, 35, and 38 practical salinity units over a range of temperatures from 0°C to 35°C in 5°C intervals. Repeated measurements have been made at each temperature and salinity. Mean values and standard deviations are then computed. The total error budget indicates that the real and imaginary parts of the dielectric constant have a combined standard uncertainty of about 0.3 over the range of salinities and temperatures considered. The measurements are compared with the dielectric constants obtained from the model functions of Klein and Swift and those of Meissner and Wentz. The biggest differences occur at low and high temperatures.
Accurate Measurements of the Dielectric Constant of Seawater at L Band
NASA Technical Reports Server (NTRS)
Lang, Roger; Zhou, Yiwen; Utku, Cuneyt; Le Vine, David
2016-01-01
This paper describes measurements of the dielectric constant of seawater at a frequency of 1.413 GHz, the center of the protected band (i.e., passive use only) used in the measurement of sea surface salinity from space. The objective of the measurements is to accurately determine the complex dielectric constant of seawater as a function of salinity and temperature. A resonant cylindrical microwave cavity in transmission mode has been employed to make the measurements. The measurements are made using standard seawater at salinities of 30, 33, 35, and 38 practical salinity units over a range of temperatures from 0 degree C to 35 degree C in 5 degree C intervals. Repeated measurements have been made at each temperature and salinity. Mean values and standard deviations are then computed. The total error budget indicates that the real and imaginary parts of the dielectric constant have a combined standard uncertainty of about 0.3 over the range of salinities and temperatures considered. The measurements are compared with the dielectric constants obtained from the model functions of Klein and Swift and those of Meissner and Wentz. The biggest differences occur at low and high temperatures.
Fortenberry, Ryan C.; Lee, Timothy J.; Crawford, T. Daniel E-mail: Timothy.J.Lee@nasa.gov
2013-01-10
The A {sup 1}B{sub 1} Leftwards-Open-Headed-Arrow X-tilde{sup 1}A' excitation into the dipole-bound state of the cyanomethyl anion (CH{sub 2}CN{sup -}) has been hypothesized as the carrier for one diffuse interstellar band. However, this particular molecular system has not been detected in the interstellar medium even though the related cyanomethyl radical and the isoelectronic ketenimine molecule have been found. In this study, we are employing the use of proven quartic force fields and second-order vibrational perturbation theory to compute accurate spectroscopic constants and fundamental vibrational frequencies for X-tilde{sup 1} A' CH{sub 2}CN{sup -} in order to assist in laboratory studies and astronomical observations.
Accurate Measurements of the Dielectric Constant of Seawater at L Band
NASA Technical Reports Server (NTRS)
Lang, Roger H.; Utku, Cuneyt; Tarkocin, Yalcin; LeVine, David M.
2010-01-01
This report describes measurements of the dielectric constant of seawater at a frequency of 1.413 GHz that is at the center of the L-Sand radiometric protected frequency spectrum. Aquarius will be sensing the sea surface salinity from space in this band. The objective of the project is to refine the model function for the dielectric constant as a function of salinity and temperature so that remote sensing measurements can be made with the accuracy needed to meet the measurement goals (0.2 psu) of the Aquarius mission. The measurements were made, using a microwave cavity operated in the transmission configuration. The cavity's temperature was accurately regulated to 0.02 C by immersing it in a temperature controlled bath of distilled water and ethanol glycol. Seawater had been purchased from Ocean Scientific International Limited (OS1L) at salinities of 30, 35 and 38 psu. Measurements of these seawater samples were then made over a range of temperatures, from l0 C to 35 C in 5 C intervals. Repeated measurements were made at each temperature and salinity, Mean values and standard deviations were then computed. Total error budgets indicated that the real and imaginary parts of the dielectric constant had a relative accuracy of about l%.
Inostroza, Natalia; Fortenberry, Ryan C.; Lee, Timothy J.; Huang, Xinchuan
2013-12-01
Through established, highly accurate ab initio quartic force fields, a complete set of fundamental vibrational frequencies, rotational constants, and rovibrational coupling and centrifugal distortion constants have been determined for both the cyclic 1 {sup 1} A' and bent 2 {sup 1} A' DCCN, H{sup 13}CCN, HC{sup 13}CN, and HCC{sup 15}N isotopologues of HCCN. Spectroscopic constants are computed for all isotopologues using second-order vibrational perturbation theory (VPT2), and the fundamental vibrational frequencies are computed with VPT2 and vibrational configuration interaction (VCI) theory. Agreement between VPT2 and VCI results is quite good, with the fundamental vibrational frequencies of the bent isomer isotopologues in accord to within a 0.1-3.2 cm{sup –1} range. Similar accuracies are present for the cyclic isomer isotopologues. The data generated here serve as a reference for astronomical observations of these closed-shell, highly dipolar molecules using new, high-resolution telescopes and as reference for laboratory studies where isotopic labeling may lead to elucidation of the formation mechanism for the known interstellar molecule: X {sup 3} A' HCCN.
NASA Technical Reports Server (NTRS)
Inostroza, Natalia; Fortenberry, Ryan C.; Huang, Xinchuan; Lee, Timothy J.
2013-01-01
Through established, highly-accurate ab initio quartic force fields (QFFs), a complete set of fundamental vibrational frequencies, rotational constants, and rovibrational coupling and centrifugal distortion constants have been determined for both the cyclic 1(sup 1) 1A' and bent 2(sup 1)A' DCCN, H(C13)CCN, HC(C-13)N, and HCC(N-15) isotopologues of HCCN. Spectroscopic constants are computed for all isotopologues using second-order vibrational perturbation theory (VPT2), and the fundamental vibrational frequencies are computed with VPT2 and vibrational configuration interaction (VCI) theory. Agreement between VPT2 and VCI results is quite good with the fundamental vibrational frequencies of the bent isomer isotopologues in accord to within a 0.1 to 3.2 / cm range. Similar accuracies are present for the cyclic isomer isotopologues. The data generated here serve as a reference for astronomical observations of these closed-shell, highly-dipolar molecules using new, high-resolution telescopes and as reference for laboratory studies where isotopic labeling may lead to elucidation of the formation mechanism for the known interstellar molecule: X 3A0 HCCN.
Puzzarini, Cristina; Biczysko, Malgorzata; Bloino, Julien; Barone, Vincenzo
2014-04-20
In an effort to provide an accurate spectroscopic characterization of oxirane, state-of-the-art computational methods and approaches have been employed to determine highly accurate fundamental vibrational frequencies and rotational parameters. Available experimental data were used to assess the reliability of our computations, and an accuracy on average of 10 cm{sup –1} for fundamental transitions as well as overtones and combination bands has been pointed out. Moving to rotational spectroscopy, relative discrepancies of 0.1%, 2%-3%, and 3%-4% were observed for rotational, quartic, and sextic centrifugal-distortion constants, respectively. We are therefore confident that the highly accurate spectroscopic data provided herein can be useful for identification of oxirane in Titan's atmosphere and the assignment of unidentified infrared bands. Since oxirane was already observed in the interstellar medium and some astronomical objects are characterized by very high D/H ratios, we also considered the accurate determination of the spectroscopic parameters for the mono-deuterated species, oxirane-d1. For the latter, an empirical scaling procedure allowed us to improve our computed data and to provide predictions for rotational transitions with a relative accuracy of about 0.02% (i.e., an uncertainty of about 40 MHz for a transition lying at 200 GHz).
Puzzarini, Cristina; Biczysko, Malgorzata; Bloino, Julien; Barone, Vincenzo
2015-01-01
In an effort to provide an accurate spectroscopic characterization of oxirane, state-of-the-art computational methods and approaches have been employed to determine highly accurate fundamental vibrational frequencies and rotational parameters. Available experimental data were used to assess the reliability of our computations, and an accuracy on average of 10 cm−1 for fundamental transitions as well as overtones and combination bands has been pointed out. Moving to rotational spectroscopy, relative discrepancies of 0.1%, 2%–3%, and 3%–4% were observed for rotational, quartic, and sextic centrifugal-distortion constants, respectively. We are therefore confident that the highly accurate spectroscopic data provided herein can be useful for identification of oxirane in Titan’s atmosphere and the assignment of unidentified infrared bands. Since oxirane was already observed in the interstellar medium and some astronomical objects are characterized by very high D/H ratios, we also considered the accurate determination of the spectroscopic parameters for the mono-deuterated species, oxirane-d1. For the latter, an empirical scaling procedure allowed us to improve our computed data and to provide predictions for rotational transitions with a relative accuracy of about 0.02% (i.e., an uncertainty of about 40 MHz for a transition lying at 200 GHz). PMID:26543240
Spectroscopic Method for Fast and Accurate Group A Streptococcus Bacteria Detection.
Schiff, Dillon; Aviv, Hagit; Rosenbaum, Efraim; Tischler, Yaakov R
2016-02-16
Rapid and accurate detection of pathogens is paramount to human health. Spectroscopic techniques have been shown to be viable methods for detecting various pathogens. Enhanced methods of Raman spectroscopy can discriminate unique bacterial signatures; however, many of these require precise conditions and do not have in vivo replicability. Common biological detection methods such as rapid antigen detection tests have high specificity but do not have high sensitivity. Here we developed a new method of bacteria detection that is both highly specific and highly sensitive by combining the specificity of antibody staining and the sensitivity of spectroscopic characterization. Bacteria samples, treated with a fluorescent antibody complex specific to Streptococcus pyogenes, were volumetrically normalized according to their Raman bacterial signal intensity and characterized for fluorescence, eliciting a positive result for samples containing Streptococcus pyogenes and a negative result for those without. The normalized fluorescence intensity of the Streptococcus pyogenes gave a signal that is up to 16.4 times higher than that of other bacteria samples for bacteria stained in solution and up to 12.7 times higher in solid state. This method can be very easily replicated for other bacteria species using suitable antibody-dye complexes. In addition, this method shows viability for in vivo detection as it requires minute amounts of bacteria, low laser excitation power, and short integration times in order to achieve high signal. PMID:26752013
Spectroscopic Constants of the X1Σ+ and 13Π states of AlO+
NASA Astrophysics Data System (ADS)
Sghaier, Onsi; Linguerri, Roberto; Mogren, Muneerah Mogren Al; Francisco, Joseph S.; Hochlaf, Majdi
2016-08-01
Using both standard and explicitly correlated ab initio methods in conjunction with several atomic basis sets, the ground state of AlO(X2Σ+) and the two lowest electronic states of AlO+ (1Σ+ and 3Π) are investigated. Potential energy curves for these species are mapped, which are incorporated later to solve the nuclear motion problem. Benchmark computations on AlO(X2Σ+) are used to determine the reliability of the theoretical methods and basis sets used for an accurate description of aluminum oxide compounds. The electronic ground state of AlO+ is X1Σ+, followed by the low-lying 13Π state. For both cationic electronic states, a set of spectroscopic parameters are recommended that may help in the identification of this ion in laboratory and astrophysical media. An accurate estimation of the adiabatic ionization energy of AlO, AIE = 9.70 eV, is also reported.
NASA Astrophysics Data System (ADS)
Sow, P. L. T.; Merji, S.; Tokunaga, S. K.; Lemarchand, C.; Triki, M.; Borde, C.; Chardonnet, C.; Darquie, B.; Daussy, C.
2013-06-01
Accurate molecular spectroscopy in the mid-infrared region allows precision measurements of fundamental constants. For instance, measuring the linewidth of an isolated Doppler-broadened absorption line of ammonia around 10 μm enables a determination of the Boltzmann constant k_{{B}}. We report on our latest measurements. The main systematic effects, including the temperature control, will be discussed and an error budget will be presented in which the global uncertainty on systematic effects is at the level of a few ppm. This is valid provided that data is recorded under the optimized experimental conditions determined by the studies of systematic effects and provided that spectra are fitted to the speed-dependent Voigt profile, identified as the most suitable lineshape for our measurements. A determination of k_{{B}} by Doppler spectroscopy with a combined uncertainty of a few ppm is within reach. This is comparable to the best current uncertainty obtained using acoustic methods and would make a significant contribution to any new value of k_{{B}} determined by the CODATA. Furthermore, having multiple independent measurements at these accuracies opens the possibility of defining the Kelvin by fixing k_{{B}}, an exciting prospect considering the upcoming redefinition of the International System of Units (SI). C. Lemarchand, M. Triki, B. Darquié, C. J. Bordé, C. Chardonnet and C. Daussy, New J. Phys. 13, 073028 (2011). M. Triki, C. Lemarchand, B. Darquié, P. L. T. Sow, V. Roncin, C. Chardonnet, and C. Daussy, Phys. Rev. A 85, 062510 (2012).
Malin, Martha J.; Bartol, Laura J.; DeWerd, Larry A. E-mail: ladewerd@wisc.edu
2015-05-15
Purpose: To investigate why dose-rate constants for {sup 125}I and {sup 103}Pd seeds computed using the spectroscopic technique, Λ{sub spec}, differ from those computed with standard Monte Carlo (MC) techniques. A potential cause of these discrepancies is the spectroscopic technique’s use of approximations of the true fluence distribution leaving the source, φ{sub full}. In particular, the fluence distribution used in the spectroscopic technique, φ{sub spec}, approximates the spatial, angular, and energy distributions of φ{sub full}. This work quantified the extent to which each of these approximations affects the accuracy of Λ{sub spec}. Additionally, this study investigated how the simplified water-only model used in the spectroscopic technique impacts the accuracy of Λ{sub spec}. Methods: Dose-rate constants as described in the AAPM TG-43U1 report, Λ{sub full}, were computed with MC simulations using the full source geometry for each of 14 different {sup 125}I and 6 different {sup 103}Pd source models. In addition, the spectrum emitted along the perpendicular bisector of each source was simulated in vacuum using the full source model and used to compute Λ{sub spec}. Λ{sub spec} was compared to Λ{sub full} to verify the discrepancy reported by Rodriguez and Rogers. Using MC simulations, a phase space of the fluence leaving the encapsulation of each full source model was created. The spatial and angular distributions of φ{sub full} were extracted from the phase spaces and were qualitatively compared to those used by φ{sub spec}. Additionally, each phase space was modified to reflect one of the approximated distributions (spatial, angular, or energy) used by φ{sub spec}. The dose-rate constant resulting from using approximated distribution i, Λ{sub approx,i}, was computed using the modified phase space and compared to Λ{sub full}. For each source, this process was repeated for each approximation in order to determine which approximations used in
NASA Astrophysics Data System (ADS)
Andronesi, Ovidiu C.; Ramadan, Saadallah; Ratai, Eva-Maria; Jennings, Dominique; Mountford, Carolyn E.; Sorensen, A. Gregory
2010-04-01
The purpose of this work was to design and implement constant adiabaticity gradient modulated pulses that have improved slice profiles and reduced artifacts for spectroscopic imaging on 3 T clinical scanners equipped with standard hardware. The newly proposed pulses were designed using the gradient offset independent adiabaticity (GOIA, Tannus and Garwood [13]) method using WURST modulation for RF and gradient waveforms. The GOIA-WURST pulses were compared with GOIA-HS n (GOIA based on nth-order hyperbolic secant) and FOCI (frequency offset corrected inversion) pulses of the same bandwidth and duration. Numerical simulations and experimental measurements in phantoms and healthy volunteers are presented. GOIA-WURST pulses provide improved slice profile that have less slice smearing for off-resonance frequencies compared to GOIA-HS n pulses. The peak RF amplitude of GOIA-WURST is much lower (40% less) than FOCI but slightly higher (14.9% more) to GOIA-HS n. The quality of spectra as shown by the analysis of lineshapes, eddy currents artifacts, subcutaneous lipid contamination and SNR is improved for GOIA-WURST. GOIA-WURST pulse tested in this work shows that reliable spectroscopic imaging could be obtained in routine clinical setup and might facilitate the use of clinical spectroscopy.
Gampp, H; Maeder, M; Meyer, C J; Zuberbühler, A D
1985-02-01
Multiwavelength spectrophotometric and spectroscopic data in general contain considerably more information about complexation equilibria than potentiometric data do. With the construction of a fully automatic titration set-up built into a high-precision spectrophotometer, the problems related to the wider use of this method have shifted from the quality of the primary data to the complexity of their numerical treatment. Matrix algebra is used to show how these problems can be overcome. An algorithm is described for calculation of stability constants and absorption spectra, together with the associated standard errors, at a reasonable expense of computer time. Problems in finding the minimum in a multidimensional parameter space are reduced by elimination of the molar absorptivities from the algorithm for the iterative refinement. Numerical safety and speed of calculation are improved by use of analytical instead of numerical derivatives. The number of data to be fitted is decreased by principal-component analysis. PMID:18963802
Muhamadali, Howbeer; Subaihi, Abdu; Mohammadtaheri, Mahsa; Xu, Yun; Ellis, David I; Ramanathan, Rajesh; Bansal, Vipul; Goodacre, Royston
2016-08-15
Despite the fact that various microorganisms (e.g., bacteria, fungi, viruses, etc.) have been linked with infectious diseases, their crucial role towards sustaining life on Earth is undeniable. The huge biodiversity, combined with the wide range of biochemical capabilities of these organisms, have always been the driving force behind their large number of current, and, as of yet, undiscovered future applications. The presence of such diversity could be said to expedite the need for the development of rapid, accurate and sensitive techniques which allow for the detection, differentiation, identification and classification of such organisms. In this study, we employed Fourier transform infrared (FT-IR), Raman, and surface enhanced Raman scattering (SERS) spectroscopies, as molecular whole-organism fingerprinting techniques, combined with multivariate statistical analysis approaches for the classification of a range of industrial, environmental or clinically relevant bacteria (P. aeruginosa, P. putida, E. coli, E. faecium, S. lividans, B. subtilis, B. cereus) and yeast (S. cerevisiae). Principal components-discriminant function analysis (PC-DFA) scores plots of the spectral data collected from all three techniques allowed for the clear differentiation of all the samples down to sub-species level. The partial least squares-discriminant analysis (PLS-DA) models generated using the SERS spectral data displayed lower accuracy (74.9%) when compared to those obtained from conventional Raman (97.8%) and FT-IR (96.2%) analyses. In addition, whilst background fluorescence was detected in Raman spectra for S. cerevisiae, this fluorescence was quenched when applying SERS to the same species, and conversely SERS appeared to introduce strong fluorescence when analysing P. putida. It is also worth noting that FT-IR analysis provided spectral data of high quality and reproducibility for the whole sample set, suggesting its applicability to a wider range of samples, and perhaps the
A theoretical benchmark study of the spectroscopic constants of the very heavy rare gas dimers.
Shee, Avijit; Knecht, Stefan; Saue, Trond
2015-04-28
Spectroscopic constants for the homonuclear dimers of the very heavy rare gases radon (Rn) and eka-radon (Uuo) are reported. A computational protocol using the eXact 2-Component molecular-mean field Hamiltonian has been established based on extensive calculations of the xenon dimer. We find that reliable results require CCSD(T) calculations at the extrapolated basis set limit. In this limit counterpoise corrected results are closer to experimentally derived values than uncorrected ones. Furthermore, in an attempt to reduce the computational cost while retaining very high accuracy, we studied the performance of range-separated density functional theory. Although we observe a somewhat more favorable basis set convergence and reduced importance of connected triples by range-separated methods compared to pure wave function theory, in practice we have to employ the same computational protocol for obtaining converged results. At the Dirac-Coulomb level we find an almost fourfold increase of binding energy when going from the radon to the eka-radon dimer, but the inclusion of spin-other orbit interaction reduces the dissociation energy of the heaviest dimer by about 40%. PMID:25825068
Spectroscopic ellipsometry of anisotropic materials: application to the optical constants of HgI2.
En Naciri, A; Johann, L; Kleim, R; Sieskind, M; Amann, M
1999-02-01
A variable angle-of-incidence spectroscopic fixed-polarizer, rotating-polarizer, fixed-analyzer ellipsometer (PRPSE) across a spectral range from 300 to 800 nm is used to determine the optical properties of anisotropic uniaxial tetragonal red mercuric iodide (HgI(2)). For the first time, to our knowledge, the bulk crystal HgI(2) surface measured by ellipsometry was not subjected to potassium iodide cutting or etching. Measurements were made at an air-HgI(2) interface with the optic axis parallel to the sample surface. To determine the optical constants, we varied both the angle of incidence and the azimuth of the optic axis with the plane of incidence. The detailed formulas needed for reliable procedures for analyzing the data are presented. The ordinary and extraordinary complex indices of refraction, (n(o)--ik(o)) and (n(e)--ik(e)), respectively, are determined. Good agreement between PRPSE and the prism technique for the refractive index is observed. The surface aging effects of the ellipsometric parameters of HgI(2), during 30 h of exposure to air, were detected by PRPSE. PMID:18305658
NASA Astrophysics Data System (ADS)
Takada, Syozo; Hata, Nobuhiro; Seino, Yutaka; Fujii, Nobutoshi; Kikkawa, Takamaro
2005-06-01
Porous-silica low-dielectric-constant (low-k) films were prepared using a sol-gel method based on the self-assembly of surfactant templates. No change in the refractive index at 633 nm nor in the infrared-absorption intensities of C-H and O-H stretching vibrations at around 2900 and 3400cm-1 of porous-silica low-k films were observed after annealing at each temperature from 523 to 723 K. On the other hand, the Young's elastic modulus and hardness increased with the increase of annealing temperature. The structure in the complex dielectric function of porous-silica low-k films observed in between 1000 and 1400cm-1 is assigned as the asymmetric stretching vibration mode of the Si-O-Si bond. By applying the effective-medium theory by Bruggeman to the experimental results from infrared spectroscopic ellipsometry, we analyzed the skeletal silica structures. The peak positions of transverse (ωTO) and longitudinal (ωLO) vibration modes for Si-O-Si network in the silica skeleton of porous-silica films changed from 1061 to 1068cm-1 and from 1219 to 1232cm-1, respectively, with the annealing temperature. It is shown that the ωLO2/ωTO2 of skeletal silica correlates with Young's elastic modulus of porous-silica low-k films.
Accurate calculations of the high-pressure elastic constants based on the first-principles
NASA Astrophysics Data System (ADS)
Wang, Chen-Ju; Gu, Jian-Bing; Kuang, Xiao-Yu; Yang, Xiang-Dong
2015-08-01
The energy term corresponding to the first order of the strain in Taylor series expansion of the energy with respect to strain is always ignored when high-pressure elastic constants are calculated. Whether the modus operandi would affect the results of the high-pressure elastic constants is still unsolved. To clarify this query, we calculate the high-pressure elastic constants of tantalum and rhenium when the energy term mentioned above is considered and neglected, respectively. Results show that the neglect of the energy term corresponding to the first order of the strain indeed would influence the veracity of the high-pressure elastic constants, and this influence becomes larger with pressure increasing. Therefore, the energy term corresponding to the first-order of the strain should be considered when the high-pressure elastic constants are calculated. Project supported by the National Natural Science Foundation of China (Grant No. 11274235), the Young Scientist Fund of the National Natural Science Foundation of China (Grant No. 11104190), and the Doctoral Education Fund of Education Ministry of China (Grant Nos. 20100181110086 and 20110181120112).
Song, Yunpeng; Wu, Sen; Xu, Linyan; Fu, Xing
2015-01-01
Measurement of force on a micro- or nano-Newton scale is important when exploring the mechanical properties of materials in the biophysics and nanomechanical fields. The atomic force microscope (AFM) is widely used in microforce measurement. The cantilever probe works as an AFM force sensor, and the spring constant of the cantilever is of great significance to the accuracy of the measurement results. This paper presents a normal spring constant calibration method with the combined use of an electromagnetic balance and a homemade AFM head. When the cantilever presses the balance, its deflection is detected through an optical lever integrated in the AFM head. Meanwhile, the corresponding bending force is recorded by the balance. Then the spring constant can be simply calculated using Hooke’s law. During the calibration, a feedback loop is applied to control the deflection of the cantilever. Errors that may affect the stability of the cantilever could be compensated rapidly. Five types of commercial cantilevers with different shapes, stiffness, and operating modes were chosen to evaluate the performance of our system. Based on the uncertainty analysis, the expanded relative standard uncertainties of the normal spring constant of most measured cantilevers are believed to be better than 2%. PMID:25763650
Theoretical spectroscopic constants for the low-lying states of the oxides and sulfides of Mo and Tc
NASA Technical Reports Server (NTRS)
Langhoff, Stephen R.; Bauschlicher, Charles W., Jr.; Pettersson, Lars G. M.; Siegbahn, Per E. M.
1989-01-01
Spectroscopic results were determined for the ground and low-lying states of the oxides and sulfides of Mo and Tc, using the single-reference-based modified coupled pair functional method of Ahlrichs et al. (1985) and Chong et al. (1986) and the multireference-based state-averaged CASSCF/MRCI method. Spectroscopic constants, dipole moments, Mulliken populations, and radiative lifetimes were calculated for selected low-lying states of these molecular systems. The spectroscopy of the MoS and TcS molecules was found to be quite analogous to the corresponding oxides.
NASA Astrophysics Data System (ADS)
Kisiel, Z.; Desyatnyk, O.; Pszczółkowski, L.; Charnley, S. B.; Ehrenfreund, P.
2003-01-01
Rotational spectra of quinoline and of isoquinoline have been observed in the centimeter- and millimeter-wave regions. The spectra were assigned on the basis of bands formed by high- J transitions, which were measured up to J″⩽128 and ν⩽234 GHz. Complementary measurements were also made on low- J, centimeter-wave spectra observed in supersonic expansion and with fully resolved nuclear quadrupole hyperfine structure. Accurate rotational, centrifugal distortion and hyperfine splitting constants for the ground states of both molecules are reported. The electric dipole moments for the two molecules were also determined from Stark effect measurements and are μa=0.14355(19), μb=2.0146(17), μtot=2.0197(17) D for quinoline, and μa=2.3602(21), μb=0.9051(14), μtot=2.5278(20) D for isoquinoline. The experimental observables were found to be rather accurately predicted by MP2/6-31G** ab initio calculations, and corresponding molecular geometries are also reported.
Recent Results on the Accurate Measurements of the Dielectric Constant of Seawater at 1.413GHZ
NASA Technical Reports Server (NTRS)
Lang, R.H.; Tarkocin, Y.; Utku, C.; Le Vine, D.M.
2008-01-01
Measurements of the complex. dielectric constant of seawater at 30.00 psu, 35.00 psu and 38.27 psu over the temperature range from 5 C to 3 5 at 1.413 GHz are given and compared with the Klein-Swift results. A resonant cavity technique is used. The calibration constant used in the cavity perturbation formulas is determined experimentally using methanol and ethanediol (ethylene glycol) as reference liquids. Analysis of the data shows that the measurements are accurate to better than 1.0% in almost all cases studied.
Highly accurate analytical energy of a two-dimensional exciton in a constant magnetic field
NASA Astrophysics Data System (ADS)
Hoang, Ngoc-Tram D.; Nguyen, Duy-Anh P.; Hoang, Van-Hung; Le, Van-Hoang
2016-08-01
Explicit expressions are given for analytically describing the dependence of the energy of a two-dimensional exciton on magnetic field intensity. These expressions are highly accurate with the precision of up to three decimal places for the whole range of the magnetic field intensity. The results are shown for the ground state and some excited states; moreover, we have all formulae to obtain similar expressions of any excited state. Analysis of numerical results shows that the precision of three decimal places is maintained for the excited states with the principal quantum number of up to n=100.
Dunning, T.H. , Jr.; Peterson, K.A.
1998-03-01
The convergence of Mo/ller{endash}Plesset perturbation expansions (MP2{endash}MP4/MP5) for the spectroscopic constants of a selected set of diatomic molecules (BH, CH, HF, N{sub 2}, CO, and F{sub 2}) has been investigated. It was found that the second-order perturbation contributions to the spectroscopic constants are strongly dependent on basis set, more so for HF and CO than for BH. The MP5 contributions for HF were essentially zero for the cc-pVDZ basis set, but increased significantly with basis set illustrating the difficulty of using small basis sets as benchmarks for correlated calculations. The convergence behavior of the {ital exact} Mo/ller{endash}Plesset perturbation expansions were investigated using estimates of the {ital complete basis set limits} obtained using large correlation consistent basis sets. For BH and CH, the perturbation expansions of the spectroscopic constants converge monotonically toward the experimental values, while for HF, N{sub 2}, CO, and F{sub 2}, the expansions oscillate about the experimental values. The perturbation expansions are, in general, only slowly converging and, for HF, N{sub 2}, CO, and F{sub 2}, appear to be far from convergence at MP4. In fact, for HF, N{sub 2}, and CO, the errors in the calculated spectroscopic constants for the MP4 method are {ital larger} than those for the MP2 method (the only exception is D{sub e}). The current study, combined with other recent studies, raises serious doubts about the use of Mo/ller{endash}Plesset perturbation theory to describe electron correlation effects in atomic and molecular calculations. {copyright} {ital 1998 American Institute of Physics.}
NASA Astrophysics Data System (ADS)
Teale, Andrew M.; Lutnæs, Ola B.; Helgaker, Trygve; Tozer, David J.; Gauss, Jürgen
2013-01-01
Accurate sets of benchmark nuclear-magnetic-resonance shielding constants and spin-rotation constants are calculated using coupled-cluster singles-doubles (CCSD) theory and coupled-cluster singles-doubles-perturbative-triples [CCSD(T)] theory, in a variety of basis sets consisting of (rotational) London atomic orbitals. The accuracy of the calculated coupled-cluster constants is established by a careful comparison with experimental data, taking into account zero-point vibrational corrections. Coupled-cluster basis-set convergence is analyzed and extrapolation techniques are employed to estimate basis-set-limit quantities, thereby establishing an accurate benchmark data set. Together with the set provided for rotational g-tensors and magnetizabilities in our previous work [O. B. Lutnæs, A. M. Teale, T. Helgaker, D. J. Tozer, K. Ruud, and J. Gauss, J. Chem. Phys. 131, 144104 (2009)], 10.1063/1.3242081, it provides a substantial source of consistently calculated high-accuracy data on second-order magnetic response properties. The utility of this benchmark data set is demonstrated by examining a wide variety of Kohn-Sham exchange-correlation functionals for the calculation of these properties. None of the existing approximate functionals provide an accuracy competitive with that provided by CCSD or CCSD(T) theory. The need for a careful consideration of vibrational effects is clearly illustrated. Finally, the pure coupled-cluster results are compared with the results of Kohn-Sham calculations constrained to give the same electronic density. Routes to future improvements are discussed in light of this comparison.
The spectroscopic constants and anharmonic force field of AgSH: An ab initio study.
Zhao, Yanliang; Wang, Meishan; Yang, Chuanlu; Ma, Xiaoguang; Zhu, Ziliang
2016-07-01
The equilibrium structure, spectroscopy constants, and anharmonic force field of silver hydrosulfide (AgSH) have been calculated at B3P86, B3PW91 and MP2 methods employing two basis sets, TZP and QZP, respectively. The calculated geometries, ground state rotational constants, harmonic vibrational wave numbers, and quartic and sextic centrifugal distortion constants are compared with the available experimental and theoretical data. The equilibrium rotational constants, fundamental frequencies, anharmonic constants, and vibration-rotation interaction constants, Coriolis coupling constants, cubic and quartic force constants are predicted. The calculated results show that the MP2/TZP results are in good agreement with experiment observation and are also an advisable choice to study the anharmonic force field of AgSH. PMID:27085293
The spectroscopic constants and anharmonic force field of AgSH: An ab initio study
NASA Astrophysics Data System (ADS)
Zhao, Yanliang; Wang, Meishan; Yang, Chuanlu; Ma, Xiaoguang; Zhu, Ziliang
2016-07-01
The equilibrium structure, spectroscopy constants, and anharmonic force field of silver hydrosulfide (AgSH) have been calculated at B3P86, B3PW91 and MP2 methods employing two basis sets, TZP and QZP, respectively. The calculated geometries, ground state rotational constants, harmonic vibrational wave numbers, and quartic and sextic centrifugal distortion constants are compared with the available experimental and theoretical data. The equilibrium rotational constants, fundamental frequencies, anharmonic constants, and vibration-rotation interaction constants, Coriolis coupling constants, cubic and quartic force constants are predicted. The calculated results show that the MP2/TZP results are in good agreement with experiment observation and are also an advisable choice to study the anharmonic force field of AgSH.
NASA Astrophysics Data System (ADS)
Wang, Xinxin; Shi, Deheng; Sun, Jinfeng; Zhu, Zunlue
2016-08-01
The potential energy curves were calculated for the 21 states (X2Π, A2Π, 32Π, 42Π, 52Π, 12Σ+, 22Σ+, 32Σ+, 12Σ-, 22Σ-, 32Σ-, 12Δ, 22Δ, 32Δ, 12Φ, 14Σ+, a4Σ-, 24Σ-, 14Π, 24Π and 14Δ), which originated from the two lowest dissociation channels of ClO radical. The calculations were done for internuclear separations approximately from 0.08 to 1.10 nm using the CASSCF method, which was followed by the icMRCI approach with the aug-cc-pV5Z basis set. Of these 21 states, the 14Π, 24Π, 32Δ, 42Π, 52Π, 12Φ, 32Σ+, 14Δ and 24Σ- states are repulsive. The 12Δ, 12Σ-, 14Σ+, 22Σ-, 12Σ+, 22Σ+, 22Δ and 32Σ- states are very weakly bound. Only the A2Π state has one barrier. The avoided crossing exists between the A2Π and the 32Π state. However, the avoided crossing does not generate any double wells. Core- valence correlation correction was accounted for at the level of an aug-cc-pCVQZ basis set. Scalar relativistic correction was included by the third-order Douglas-Kroll Hamiltonian approximation at the level of an aug-cc-pVQZ basis set. All the potential energy curves were extrapolated to the complete basis set limit. The spectroscopic parameters were determined. The 12Σ-, 22Σ-, 32Σ- and 14Σ+ states may be very difficult to be detected in an experiment, since each of these Λ-S states has only one or two vibrational states. The Franck-Condon factors and radiative lifetimes were calculated for several low vibrational levels of the A2Π - X2Π, 32Π - a4Σ-, 22Δ - a4Σ- and 32Σ- - 12Σ- transitions. The spin-orbit coupling effect on the spectroscopic parameters of the X2Π, A2Π, 32Π, a4Σ- and 22Σ+ states were discussed. The spectroscopic properties reported here can be expected to be reliably predicted ones.
Puzzarini, C.; Senent, M. L.; Domínguez-Gómez, R.; Carvajal, M.; Hochlaf, M.; Al-Mogren, M. Mogren E-mail: senent@iem.cfmac.csic.es E-mail: miguel.carvajal@dfa.uhu.es E-mail: mmogren@ksu.edu.sa
2014-11-20
Using state-of-the-art computational methodologies, we predict a set of reliable rotational and torsional parameters for ethyl mercaptan and dimethyl sulfide monosubstituted isotopologues. This includes rotational, quartic, and sextic centrifugal-distortion constants, torsional levels, and torsional splittings. The accuracy of the present data was assessed from a comparison to the available experimental data. Generally, our computed parameters should help in the characterization and the identification of these organo-sulfur molecules in laboratory settings and in the interstellar medium.
Wang, Xinxin; Shi, Deheng; Sun, Jinfeng; Zhu, Zunlue
2016-08-01
The potential energy curves were calculated for the 21 states (X(2)Π, A(2)Π, 3(2)Π, 4(2)Π, 5(2)Π, 1(2)Σ(+), 2(2)Σ(+), 3(2)Σ(+), 1(2)Σ(-), 2(2)Σ(-), 3(2)Σ(-), 1(2)Δ, 2(2)Δ, 3(2)Δ, 1(2)Φ, 1(4)Σ(+), a(4)Σ(-), 2(4)Σ(-), 1(4)Π, 2(4)Π and 1(4)Δ), which originated from the two lowest dissociation channels of ClO radical. The calculations were done for internuclear separations approximately from 0.08 to 1.10nm using the CASSCF method, which was followed by the icMRCI approach with the aug-cc-pV5Z basis set. Of these 21 states, the 1(4)Π, 2(4)Π, 3(2)Δ, 4(2)Π, 5(2)Π, 1(2)Φ, 3(2)Σ(+), 1(4)Δ and 2(4)Σ(-) states are repulsive. The 1(2)Δ, 1(2)Σ(-), 1(4)Σ(+), 2(2)Σ(-), 1(2)Σ(+), 2(2)Σ(+), 2(2)Δ and 3(2)Σ(-) states are very weakly bound. Only the A(2)Π state has one barrier. The avoided crossing exists between the A(2)Π and the 3(2)Π state. However, the avoided crossing does not generate any double wells. Core- valence correlation correction was accounted for at the level of an aug-cc-pCVQZ basis set. Scalar relativistic correction was included by the third-order Douglas-Kroll Hamiltonian approximation at the level of an aug-cc-pVQZ basis set. All the potential energy curves were extrapolated to the complete basis set limit. The spectroscopic parameters were determined. The 1(2)Σ(-), 2(2)Σ(-), 3(2)Σ(-) and 1(4)Σ(+) states may be very difficult to be detected in an experiment, since each of these Λ-S states has only one or two vibrational states. The Franck-Condon factors and radiative lifetimes were calculated for several low vibrational levels of the A(2)Π - X(2)Π, 3(2)Π - a(4)Σ(-), 2(2)Δ - a(4)Σ(-) and 3(2)Σ(-) - 1(2)Σ(-) transitions. The spin-orbit coupling effect on the spectroscopic parameters of the X(2)Π, A(2)Π, 3(2)Π, a(4)Σ(-) and 2(2)Σ(+) states were discussed. The spectroscopic properties reported here can be expected to be reliably predicted ones. PMID:27111157
Han, Huixian; Li, Anyang; Guo, Hua
2014-12-28
A new full-dimensional global potential energy surface (PES) for the acetylene-vinylidene isomerization on the ground (S{sub 0}) electronic state has been constructed by fitting ∼37 000 high-level ab initio points using the permutation invariant polynomial-neural network method with a root mean square error of 9.54 cm{sup −1}. The geometries and harmonic vibrational frequencies of acetylene, vinylidene, and all other stationary points (two distinct transition states and one secondary minimum in between) have been determined on this PES. Furthermore, acetylene vibrational energy levels have been calculated using the Lanczos algorithm with an exact (J = 0) Hamiltonian. The vibrational energies up to 12 700 cm{sup −1} above the zero-point energy are in excellent agreement with the experimentally derived effective Hamiltonians, suggesting that the PES is approaching spectroscopic accuracy. In addition, analyses of the wavefunctions confirm the experimentally observed emergence of the local bending and counter-rotational modes in the highly excited bending vibrational states. The reproduction of the experimentally derived effective Hamiltonians for highly excited bending states signals the coming of age for the ab initio based PES, which can now be trusted for studying the isomerization reaction.
Construction of Spectroscopically Accurate IR Linelists for NH3 and CO2
NASA Astrophysics Data System (ADS)
Huang, X.; Schwenke, D. W.; Lee, T. J.
2011-05-01
The strategy of using the best theory together with high-resolution experi-ment was applied to NH3 and CO2: that is, refine a highly accurate ab initio PES with the most reliable HITRAN or pure experimental data. With 0.01 - 0.02 cm-1 accuracy, our calculations are clearly far beyond simply reproducing experimental data, but are also capable of revealing many deficiencies in the cur- rent experimental analysis of the various isotopologues, as well as provide reliable predictions with similar accuracy.
NASA Astrophysics Data System (ADS)
Kassinopoulos, Michalis; Pitris, Costas
2016-03-01
The modulations appearing on the backscattering spectrum originating from a scatterer are related to its diameter as described by Mie theory for spherical particles. Many metrics for Spectroscopic Optical Coherence Tomography (SOCT) take advantage of this observation in order to enhance the contrast of Optical Coherence Tomography (OCT) images. However, none of these metrics has achieved high accuracy when calculating the scatterer size. In this work, Mie theory was used to further investigate the relationship between the degree of modulation in the spectrum and the scatterer size. From this study, a new spectroscopic metric, the bandwidth of the Correlation of the Derivative (COD) was developed which is more robust and accurate, compared to previously reported techniques, in the estimation of scatterer size. The self-normalizing nature of the derivative and the robustness of the first minimum of the correlation as a measure of its width, offer significant advantages over other spectral analysis approaches especially for scatterer sizes above 3 μm. The feasibility of this technique was demonstrated using phantom samples containing 6, 10 and 16 μm diameter microspheres as well as images of normal and cancerous human colon. The results are very promising, suggesting that the proposed metric could be implemented in OCT spectral analysis for measuring nuclear size distribution in biological tissues. A technique providing such information would be of great clinical significance since it would allow the detection of nuclear enlargement at the earliest stages of precancerous development.
Gampp, H; Maeder, M; Meyer, C J; Zuberbühler, A D
1985-04-01
A new program (SPECFIT), written in HP BASIC or FORTRAN 77, for the calculation of stability constants from spectroscopic data, is presented. Stability constants have been successfully calculated from multiwavelength spectrophotometric and EPR data, but the program can be equally well applied to the numerical treatment of other spectroscopic measurements. The special features included in SPECFIT to improve convergence, increase numerical reliability, and minimize memory as well as computing time requirements, include (i) elimination of the linear parameters (i.e., molar absorptivities), (ii) the use of analytical instead of numerical derivatives and (iii) factor analysis. Calculation of stability constants from spectroscopic data is then as straightforward as from potentiometric titration curves and gives results of analogous reproducibility. The spectroscopic method has proved, however, to be superior in discrimination between chemical models. PMID:18963840
NASA Astrophysics Data System (ADS)
Pérez-Jordá, José M.; San-Fabián, Emilio; Moscardó, Federico
1992-04-01
The Kohn-Sham energy with exact exchange [using the exact Hartree-Fock (HF) exchange but an approximate correlation-energy functional] may be computed very accurately by adding the correlation obtained from the HF density to the total HF energy. Three density functionals are used: local spin density (LSD), LSD with self-interaction correction, and LSD with generalized gradient correction. This scheme has been extended (Lie-Clementi, Colle-Salvetti, and Moscardo-San-Fabian) to be used with general-valence-bond (GVB) energies and wave functions, so that the extra correlation included in the GVB energy is not counted again. The effect of all these approximate correlations on HF or GVB spectroscopic constants (Re,ωe, and De) is studied. Approximate relations showing how correlation affects them are derived, and may be summarized as follows: (1) the effect on Re and ωe depends only on the correlation derivative at Re, and (2) the effect on De depends mainly on the correlation difference between quasidissociated and equilibrium geometries. A consequence is that all the correlation corrections tested here give larger ωe and De and shorter Re than the uncorrected HF or GVB values. This trend is correct for De for both HF and GVB. For Re and ωe, it is correct in most cases for GVB, but it often fails for the HF cases. A comparison is made with Kohn-Sham calculations with both exchange and correlation approximated. As a final conclusion, it is found that, within the present scheme, a qualitatively correct HF or GVB potential-energy curve, together with a correlation-energy approximation with correct dissociation behavior, is crucial for obtaining good estimates of spectroscopic constants.
Den, Takuya S.; Frey, Hans-Martin; Leutwyler, Samuel
2014-11-21
The gas-phase rotational motion of hexafluorobenzene has been measured in real time using femtosecond (fs) time-resolved rotational Raman coherence spectroscopy (RR-RCS) at T = 100 and 295 K. This four-wave mixing method allows to probe the rotation of non-polar gas-phase molecules with fs time resolution over times up to ∼5 ns. The ground state rotational constant of hexafluorobenzene is determined as B{sub 0} = 1029.740(28) MHz (2σ uncertainty) from RR-RCS transients measured in a pulsed seeded supersonic jet, where essentially only the v = 0 state is populated. Using this B{sub 0} value, RR-RCS measurements in a room temperature gas cell give the rotational constants B{sub v} of the five lowest-lying thermally populated vibrationally excited states ν{sub 7/8}, ν{sub 9}, ν{sub 11/12}, ν{sub 13}, and ν{sub 14/15}. Their B{sub v} constants differ from B{sub 0} by between −1.02 MHz and +2.23 MHz. Combining the B{sub 0} with the results of all-electron coupled-cluster CCSD(T) calculations of Demaison et al. [Mol. Phys. 111, 1539 (2013)] and of our own allow to determine the C-C and C-F semi-experimental equilibrium bond lengths r{sub e}(C-C) = 1.3866(3) Å and r{sub e}(C-F) = 1.3244(4) Å. These agree with the CCSD(T)/wCVQZ r{sub e} bond lengths calculated by Demaison et al. within ±0.0005 Å. We also calculate the semi-experimental thermally averaged bond lengths r{sub g}(C-C)=1.3907(3) Å and r{sub g}(C-F)=1.3250(4) Å. These are at least ten times more accurate than two sets of experimental gas-phase electron diffraction r{sub g} bond lengths measured in the 1960s.
Tripura Sundari, S. Ramaseshan, R.; Jose, Feby; Dash, S.; Tyagi, A. K.
2014-01-21
The temperature dependence of optical constants of titanium nitride thin film is investigated using Spectroscopic Ellipsometry (SE) between 1.4 and 5 eV in the temperature range of 300 K to 650 K in steps of 50 K. The real and imaginary parts of the dielectric functions ε{sub 1}(E) and ε{sub 2}(E) marginally increase with increase in temperature. A Drude Lorentz dielectric analysis based on free electron and oscillator model are carried out to describe the temperature behavior. With increase in temperature, the unscreened plasma frequency and broadening marginally decreased and increased, respectively. The parameters of the Lorentz oscillator model also showed that the relaxation time decreased with temperature while the oscillator energies increased. This study shows that owing to the marginal change in the refractive index with temperature, titanium nitride can be employed for surface plasmon sensor applications even in environments where rise in temperature is imminent.
Huang Xinchuan; Lee, Timothy J. E-mail: Timothy.J.Lee@nasa.gov
2011-07-20
Recently, we reported ab initio quartic force fields (QFFs) for the cyclic and linear forms of the C{sub 3}H{sub 3}{sup +} molecular cation, referred to as c-C{sub 3}H{sub 3}{sup +} and l-C{sub 3}H{sub 3}{sup +}. These were computed using high levels of theory. Specifically the singles and doubles coupled-cluster method that includes a perturbational estimate of connected triple excitations, CCSD(T), was used in conjunction with extrapolation to the one-particle basis set limit, and corrections for scalar relativity and core correlation were included. In the present study, we use these QFFs to compute highly accurate fundamental vibrational frequencies and other spectroscopic constants for the c-{sup 13}CC{sub 2}H{sub 3}{sup +}, c-C{sub 3}H{sub 2}D{sup +}, c-{sup 13}CC{sub 2}H{sub 2}D{sup +} isotoplogues of c-C{sub 3}H{sub 3}{sup +}, and the H{sub 2}CCCD{sup +}, HDCCCH{sup +}, H{sub 2}{sup 13}CCCH{sup +}, H{sub 2}C{sup 13}CCH{sup +}, and H{sub 2}CC{sup 13}CH{sup +} isotopologues of l-C{sub 3}H{sub 3}{sup +}. Improvements in ab intitio methods have now made it possible to identify small molecules in an astronomical observation without the aid of high-resolution experimental data. We also report dipole moment values and show that the above-mentioned cyclic isotopologues have values of 0.094, 0.225, and 0.312 D, respectively, while the l-C{sub 3}H{sub 3}{sup +} isotopologues have values that range between 0.325 and 0.811 D. Thus, it is hoped that the highly accurate spectroscopic constants and data provided herein for the {sup 13}C and deuterium isotopologues of the cyclic and linear forms of C{sub 3}H{sub 3}{sup +} will enable their identification in astronomical observations from the Herschel Space Observatory, the Stratospheric Observatory for Infrared Astronomy, the Atacama Large Millimeter Array, and in the future, the James Webb Space Telescope.
NASA Technical Reports Server (NTRS)
Fortenberry, Ryan C.; Huang, Xinchuan; Crawford, T. Daniel; Lee, Timothy J.
2013-01-01
It has been shown that rotational lines observed in the Horsehead nebula photon-dominated-region (PDR) are probably not caused by l-C3H+, as was originally suggested. In the search for viable alternative candidate carriers, quartic force fields are employed here to provide highly accurate rotational constants, as well as fundamental vibrational frequencies, for another candidate carrier: 1 (sup 1)A' C3H(-). The ab initio computed spectroscopic constants provided in this work are, compared to those necessary to define the observed lines, as accurate as the computed spectroscopic constants for many of the known interstellar anions. Additionally, the computed D-eff for C3H(-) is three times closer to the D deduced from the observed Horsehead nebula lines relative to l-C3H(+). As a result, 1 (sup 1)A' C3H(-). is a more viable candidate for these observed rotational transitions and would be the seventh confirmed interstellar anion detected within the past decade and the first C(sub n)H(-) molecular anion with an odd n.
NASA Astrophysics Data System (ADS)
Nečas, D.; Ohlídal, I.; Franta, D.; Ohlídal, M.; Vodák, J.
2016-01-01
A rough non-uniform ZnSe thin film on a GaAs substrate is optically characterised using imaging spectroscopic reflectometry (ISR) in the visible, UV and near IR region, applied as a standalone technique. A global-local data processing algorithm is used to fit spectra from all pixels together and simultaneously determine maps of the local film thickness, roughness and overlayer thickness as well as spectral dependencies of film optical constants determined for the sample as a whole. The roughness of the film upper boundary is modelled using scalar diffraction theory (SDT), for which an improved calculation method is developed to process the large quantities of experimental data produced by ISR efficiently. This method avoids expensive operations by expressing the series obtained from SDT using a double recurrence relation and it is shown that it essentially eliminates the necessity for any speed-precision trade-offs in the SDT calculations. Comparison of characterisation results with the literature and other techniques shows the ability of multi-pixel processing to improve the stability and reliability of least-squares data fitting and demonstrates that standalone ISR, coupled with suitable data processing methods, is viable as a characterisation technique, even for thin films that are relatively far from ideal and require complex modelling.
NASA Astrophysics Data System (ADS)
Wang, Jie-Min; Feng, Heng-Qiang; Sun, Jin-Feng; Shi, De-Heng
2012-02-01
The potential energy curves (PECs) of three low-lying electronic states (X1Σg+, w3Δu, and W1Δu) of P2 molecule are investigated using the full valence complete active space self-consistent field (CASSCF) method followed by the highly accurate valence internally contracted multireference configuration interaction (MRCI) approach in conjunction with the correlation-consistent basis set in the valence range. The PECs of the electronic states involved are modified by the Davidson correction and extrapolated to the complete basis set (CBS) limit. With these PECs, the spectroscopic parameters of the three electronic states are determined and compared in detail with the experimental data. The comparison shows that excellent agreement exists between the present results and the available experimental data. The complete vibrational states are computed for the w3Δu and W1Δu electronic states when the rotational quantum number J equals zero and the vibrational level G(υ), the inertial rotation constant Bυ, and the centrifugal distortion constant Dυ of the first 30 vibrational states are reported, which accord well with the experimental data. The present results show that the two-point extrapolation scheme can obviously improve the quality of spectroscopic parameters and molecular constants.
NASA Astrophysics Data System (ADS)
Orkin, V. L.; Khamaganov, V. G.; Martynova, L. E.; Kurylo, M. J.
2013-12-01
Reactions with hydroxyl radicals and photolysis are the main processes dictating the compound residence time in the atmosphere for a majority of trace gases. In case of very short lived compounds their reaction with OH dictates both the atmospheric lifetime and active halogen release. Therefore, the accuracy of OH kinetic data is of primary importance for the purpose of comprehensive atmospheric modeling of compound's impact on the atmosphere, such as in ozone depletion (ODP) and climate change (GWP). The currently recommended uncertainties of OH reaction rate constants (NASA/JPL Publications and IUPAC Publications) exceed 10% at room temperature for the majority of compounds to be larger at lower temperatures of atmospheric interest. Thus, uncertainties in the photochemical properties of potential and current atmospheric trace gases obtained under controlled laboratory conditions may constitute a major source of uncertainty in estimating the compound's environmental impact. We will present the higher accuracy results of OH reaction rate constant determinations between 220 K and 370 K. A statistical analysis of the data will be discussed. The high precision of kinetic measurements performed at low temperatures allows reliable determination of temperature dependences of the rate constants. This is especially important because we found that many OH reactions exhibit the curvature of the Arrhenius plots. A detailed inventory of sources of instrumental uncertainties related to our experiment proves a total uncertainty of the OH reaction rate constant to be as small as ~2-3%. The estimation of the atmospheric lifetime of a compound based on its OH reaction rate constant will be discussed.
Fortenberry, Ryan C.; Lee, Timothy J.; Huang, Xinchuan; Crawford, T. Daniel
2013-07-20
It has been shown that rotational lines observed in the Horsehead nebula photodissociation region (PDR) are probably not caused by l-C{sub 3}H{sup +}, as was originally suggested. In the search for viable alternative candidate carriers, quartic force fields are employed here to provide highly accurate rotational constants, as well as fundamental vibrational frequencies, for another candidate carrier: 1 {sup 1} A' C{sub 3}H{sup -}. The ab initio computed spectroscopic constants provided in this work are, compared to those necessary to define the observed lines, as accurate as the computed spectroscopic constants for many of the known interstellar anions. Additionally, the computed D{sub eff} for C{sub 3}H{sup -} is three times closer to the D deduced from the observed Horsehead nebula lines relative to l-C{sub 3}H{sup +}. As a result, 1 {sup 1} A' C{sub 3}H{sup -} is a more viable candidate for these observed rotational transitions. It has been previously proposed that at least C{sub 6}H{sup -} may be present in the Horsehead nebular PDR formed by way of radiative attachment through its dipole-bound excited state. C{sub 3}H{sup -} could form in a similar way through its dipole-bound state, but its valence excited state increases the number of relaxation pathways possible to reach the ground electronic state. In turn, the rate of formation for C{sub 3}H{sup -} could be greater than the rate of its destruction. C{sub 3}H{sup -} would be the seventh confirmed interstellar anion detected within the past decade and the first C{sub n}H{sup -} molecular anion with an odd n.
NASA Astrophysics Data System (ADS)
Fortenberry, Ryan C.; Huang, Xinchuan; Crawford, T. Daniel; Lee, Timothy J.
2013-07-01
It has been shown that rotational lines observed in the Horsehead nebula photodissociation region (PDR) are probably not caused by l-C3H+, as was originally suggested. In the search for viable alternative candidate carriers, quartic force fields are employed here to provide highly accurate rotational constants, as well as fundamental vibrational frequencies, for another candidate carrier: 1 1 A' C3H-. The ab initio computed spectroscopic constants provided in this work are, compared to those necessary to define the observed lines, as accurate as the computed spectroscopic constants for many of the known interstellar anions. Additionally, the computed D eff for C3H- is three times closer to the D deduced from the observed Horsehead nebula lines relative to l-C3H+. As a result, 1 1 A' C3H- is a more viable candidate for these observed rotational transitions. It has been previously proposed that at least C6H- may be present in the Horsehead nebular PDR formed by way of radiative attachment through its dipole-bound excited state. C3H- could form in a similar way through its dipole-bound state, but its valence excited state increases the number of relaxation pathways possible to reach the ground electronic state. In turn, the rate of formation for C3H- could be greater than the rate of its destruction. C3H- would be the seventh confirmed interstellar anion detected within the past decade and the first C n H- molecular anion with an odd n.
Kim, Yong-Hyun; Kim, Ki-Hyun
2016-01-01
A novel technique is developed to determine the Henry's law constants (HLCs) of seven volatile fatty acids (VFAs) with significantly high solubility using a combined application of thermal desorber/gas chromatography/mass spectrometry (TD/GC/MS). In light of the strong sorptive properties of these semi-volatile organic compounds (SVOCs), their HLCs were determined by properly evaluating the fraction lost on the surface of the materials used to induce equilibrium (vial, gas-tight syringe, and sorption tube). To this end, a total of nine repeated experiments were conducted in a closed (static) system at three different gas/liquid volume ratios. The best estimates for HLCs (M/atm) were thus 7,200 (propionic acid), 4,700 (i-butyric acid), 4,400 (n-butyric acid), 2,700 (i-valeric acid), 2,400 (n-valeric acid), 1,000 (hexanoic acid), and 1,500 (heptanoic acid). The differences in the HLC values between this study and previous studies, if assessed in terms of the percent difference, ranged from 9.2% (n-valeric acid) to 55.7% (i-valeric acid). We overcame the main cause of errors encountered in previous studies by performing the proper correction of the sorptive losses of the SVOCs that inevitably took place, particularly on the walls of the equilibration systems (mainly the headspace vial and/or the glass tight syringe). PMID:26577086
ERIC Educational Resources Information Center
Ford, T. A.
1979-01-01
In one option for this project, the rotation-vibration infrared spectra of a number of gaseous diatomic molecules were recorded, from which the fundamental vibrational wavenumber, the force constant, the rotation-vibration interaction constant, the equilibrium rotational constant, and the equilibrium internuclear distance were determined.…
Alias, Mohd Sharizal; Dursun, Ibrahim; Saidaminov, Makhsud I; Diallo, Elhadj Marwane; Mishra, Pawan; Ng, Tien Khee; Bakr, Osman M; Ooi, Boon S
2016-07-25
The lack of optical constants information for hybrid perovskite of CH_{3}NH_{3}PbBr_{3} in thin films form can delay the progress of efficient LED or laser demonstration. Here, we report on the optical constants (complex refractive index and dielectric function) of CH_{3}NH_{3}PbBr_{3} perovskite thin films using spectroscopic ellipsometry. Due to the existence of voids, the refractive index of the thin films is around 8% less than the single crystals counterpart. The energy bandgap is around 2.309 eV as obtained from photoluminescence and spectrophotometry spectra, and calculated from the SE analysis. The precise measurement of optical constants will be useful in designing optical devices using CH_{3}NH_{3}PbBr_{3} thin films. PMID:27464113
NASA Astrophysics Data System (ADS)
Yang, Tao; Coker, James; Furneaux, John; Shafer-Ray, Neil
2012-06-01
Lead mono-fluoride (PbF) is ideally suited to carry out a search for an e-EDM: PbF has relatively large molecular dipole moment (making it easy to polarize), a strong effective internal field (making it sensitive to an e-EDM), ground-state sensitivity to the e-EDM (allowing for long coherence time), a small magnetic moment (making it less sensitive to stray magnetic fields) and convenient optical spectroscopy. Here we use a sensitive multi-photon ionization technique (pseudo-continuous-REMPI) to carry out A<-X1 spectroscopic measurements. New dipole moments and spectroscopic constants for the A state are presented. With these new data we have isolated an e-EDM sensitive Stark transition at a magic electric field that both polarizes the molecule and allows for sharp transitions that are immune to variations in electric field.
NASA Technical Reports Server (NTRS)
Fortenberry, Ryan C.; Crawford, T. Daniel; Lee, Timothy J.
2014-01-01
The spectroscopic constants and vibrational frequencies for the 1(sup 3)A' states of HNC, DNC, HOC+, and DOC+ are computed and discussed in this work. The reliable CcCR quartic force field based on high-level coupled cluster ab initio quantum chemical computations is exclusively utilized to provide the anharmonic potential. Then, second order vibrational perturbation theory and vibrational configuration interaction methods are employed to treat the nuclear Schroedinger equation. Second-order perturbation theory is also employed to provide spectroscopic data for all molecules examined. The relationship between these molecules and the corresponding 1(sup 3)A' HCN and HCO+ isomers is further developed here. These data are applicable to laboratory studies involving formation of HNC and HOC+ as well as astronomical observations of chemically active astrophysical environments.
Bakker, Chris J G; de Leeuw, Hendrik; van de Maat, Gerrit H; van Gorp, Jetse S; Bouwman, Job G; Seevinck, Peter R
2013-01-01
Lack of spatial accuracy is a recognized problem in magnetic resonance imaging (MRI) which severely detracts from its value as a stand-alone modality for applications that put high demands on geometric fidelity, such as radiotherapy treatment planning and stereotactic neurosurgery. In this paper, we illustrate the potential and discuss the limitations of spectroscopic imaging as a tool for generating purely phase-encoded MR images and parameter maps that preserve the geometry of an object and allow localization of object features in world coordinates. Experiments were done on a clinical system with standard facilities for imaging and spectroscopy. Images were acquired with a regular spin echo sequence and a corresponding spectroscopic imaging sequence. In the latter, successive samples of the acquired echo were used for the reconstruction of a series of evenly spaced images in the time and frequency domain. Experiments were done with a spatial linearity phantom and a series of test objects representing a wide range of susceptibility- and chemical-shift-induced off-resonance conditions. In contrast to regular spin echo imaging, spectroscopic imaging was shown to be immune to off-resonance effects, such as those caused by field inhomogeneity, susceptibility, chemical shift, f(0) offset and field drift, and to yield geometrically accurate images and parameter maps that allowed object structures to be localized in world coordinates. From these illustrative examples and a discussion of the limitations of purely phase-encoded imaging techniques, it is concluded that spectroscopic imaging offers a fundamental solution to the geometric deficiencies of MRI which may evolve toward a practical solution when full advantage will be taken of current developments with regard to scan time reduction. This perspective is backed up by a demonstration of the significant scan time reduction that may be achieved by the use of compressed sensing for a simple phantom. PMID:22898694
NASA Astrophysics Data System (ADS)
Wang, Xinxin; Shi, Deheng; Sun, Jinfeng; Zhu, Zunlue
2015-02-01
The spectroscopic properties are in detail studied for the 11Σ-, 21Σ-, b1Σ+, c1Π, 21Π, 31Π, a1Δ, 21Δ, X3Σ-, C3Σ-, 33Σ-, 13Σ+, A3Π, B3Π, 33Π, 13Δ, 23Δ, 15Σ- and 15Π states, which are yielded from the first two dissociation limits, P(4Su) + Cl(2Pu) and P(2Du) + Cl(2Pu), of the PCl radical. Of the nineteen states, the 33Σ-, 13Σ+, 13Δ, 23Δ and 15Π states are the repulsive ones. The 21Σ-, 21Δ and 15Σ- states and the second well of A3Π state are very weakly-bound ones. The A3Π and B3Π states, the B3Π and 33Π states, and the 21Π and 31Π states have the avoided crossings. The A3Π state is found to possess the double well. The potential energy curves (PECs) are calculated with the CASSCF method followed by the internally contracted MRCI approach with Davidson correction together with the Dunning's correlation-consistent basis sets, aug-cc-pV6Z. To improve the quality of PECs, core-valence correlation and scalar relativistic correction calculations are included simultaneously. The PECs are extrapolated to the complete basis set limit. The vibrational properties are evaluated for several weakly-bound states. The spectroscopic parameters are determined, and compared with those available in the literature. The Franck-Condon factors and radiative lifetimes of the transitions from the A3Π, B3Π and 33Π states to the X3Σ- state and from the c1Π, 21Π and 31Π states to the a1Δ state are calculated for several low vibrational states. And some necessary discussion is performed. Analyses demonstrate that the spectroscopic properties of PCl radical reported in this paper can be expected to be reliably predicted ones.
Boschen, Jeffery S.; Theis, Daniel; Ruedenberg, Klaus; Windus, Theresa L.
2013-12-07
The diatomic carbon molecule has a complex electronic structure with a large number of low-lying electronic excited states. In this work, the potential energy curves (PECs) of the four lowest lying singlet states (X-1 Sigma(+)(g), A(1)Pi(u), B-1 Delta(g), and B'(1)Sigma(+)(g)) were obtained by high-level ab initio calculations. Valence electron correlation was accounted for by the correlation energy extrapolation by intrinsic scaling (CEEIS) method. Additional corrections to the PECs included core-valence correlation and relativistic effects. Spin-orbit corrections were found to be insignificant. The impact of using dynamically weighted reference wave functions in conjunction with CEEIS was examined and found to give indistinguishable results from the even weighted method. The PECs showed multiple curve crossings due to the B-1 Delta(g) state as well as an avoided crossing between the two (1)Sigma(+)(g) states. Vibrational energy levels were computed for each of the four electronic states, as well as rotational constants and spectroscopic parameters. Comparison between the theoretical and experimental results showed excellent agreement overall. Equilibrium bond distances are reproduced to within 0.05 %. The dissociation energies of the states agree with experiment to within similar to 0.5 kcal/mol, achieving "chemical accuracy." Vibrational energy levels show average deviations of similar to 20 cm(-1) or less. The B-1 Delta(g) state shows the best agreement with a mean absolute deviation of 2.41 cm(-1). Calculated rotational constants exhibit very good agreement with experiment, as do the spectroscopic constants.
NASA Astrophysics Data System (ADS)
Haidu, Francisc; Fronk, Michael; Gordan, Ovidiu D.; Scarlat, Camelia; Salvan, Georgeta; Zahn, Dietrich R. T.
2011-11-01
Cuprous oxide is a highly interesting material for the emerging field of transparent oxide electronics. In this work the energy dispersion of the dielectric function of Cu2O bulk material is revised by spectroscopic ellipsometry measurements in an extended spectral range from 0.73 to 10 eV. For the first time, the magneto-optical Kerr effect was measured in the spectral range from 1.7 to 5.5 eV and the magneto-optical Voigt constant of Cu2O was obtained by numerical calculations from the magneto-optical Kerr effect spectra and the dielectric function.
NASA Astrophysics Data System (ADS)
Tao, W.; McGoverin, C.; Lydiard, S.; Song, Y.; Cheng, M.; Swift, S.; Singhal, N.; Vanholsbeeck, F.
2015-07-01
Accurate in situ monitoring of bacterial transport is important for increased understanding and improvement of bioremediation processes where microorganisms convert toxic compounds to more benign compounds. Bioremediation methods have become the preferred mechanism for the rehabilitation of hard to reach contaminated environments. In this study, we have used fluorescence spectroscopy to monitor the movement of fluorescently labelled bacteria (Rhodococcus erythropolis and Pseudomonas putida) within a bench-top column filled with a porous medium. In situ fluorescence measurements made using a fibre optic based instrument (`optrode') were compared to ex situ measurements made using a plate reader. In situ monitoring using this fibre optic based instrument is a promising alternative to ex situ measurements as the initial flow of bacteria is reliably observed. However, a greater understanding of the effect of the porous medium on fluorescence measurements is required to develop an accurate calibration for bacterial concentration based in situ measurements.
NASA Astrophysics Data System (ADS)
Orkin, V. L.; Khamaganov, V. G.; Martynova, L. E.; Kurylo, M. J.
2012-12-01
The emissions of halogenated (Cl, Br containing) organics of both natural and anthropogenic origin contribute to the balance of and changes in the stratospheric ozone concentration. The associated chemical cycles are initiated by the photochemical decomposition of the portion of source gases that reaches the stratosphere. Reactions with hydroxyl radicals and photolysis are the main processes dictating the compound lifetime in the troposphere and release of active halogen in the stratosphere for a majority of halogen source gases. Therefore, the accuracy of photochemical data is of primary importance for the purpose of comprehensive atmospheric modeling and for simplified kinetic estimations of global impacts on the atmosphere, such as in ozone depletion (i.e., the Ozone Depletion Potential, ODP) and climate change (i.e., the Global Warming Potential, GWP). The sources of critically evaluated photochemical data for atmospheric modeling, NASA/JPL Publications and IUPAC Publications, recommend uncertainties within 10%-60% for the majority of OH reaction rate constants with only a few cases where uncertainties lie at the low end of this range. These uncertainties can be somewhat conservative because evaluations are based on the data from various laboratories obtained during the last few decades. Nevertheless, even the authors of the original experimental works rarely estimate the total combined uncertainties of the published OH reaction rate constants to be less than ca. 10%. Thus, uncertainties in the photochemical properties of potential and current atmospheric trace gases obtained under controlled laboratory conditions still may constitute a major source of uncertainty in estimating the compound's environmental impact. One of the purposes of the presentation is to illustrate the potential for obtaining accurate laboratory measurements of the OH reaction rate constant over the temperature range of atmospheric interest. A detailed inventory of accountable sources of
Barone, Vincenzo; Biczysko, Malgorzata; Bloino, Julien; Cimino, Paola; Penocchio, Emanuele; Puzzarini, Cristina
2015-09-01
The structures and relative stabilities as well as the rotational and vibrational spectra of the three low-energy conformers of pyruvic acid (PA) have been characterized using a state-of-the-art quantum-mechanical approach designed for flexible molecules. By making use of the available experimental rotational constants for several isotopologues of the most stable PA conformer, Tc-PA, the semiexperimental equilibrium structure has been derived. The latter provides a reference for the pure theoretical determination of the equilibrium geometries for all conformers, thus confirming for these structures an accuracy of 0.001 Å and 0.1 deg for bond lengths and angles, respectively. Highly accurate relative energies of all conformers (Tc-, Tt-, and Ct-PA) and of the transition states connecting them are provided along with the thermodynamic properties at low and high temperatures, thus leading to conformational enthalpies accurate to 1 kJ mol(-1). Concerning microwave spectroscopy, rotational constants accurate to about 20 MHz are provided for the Tt- and Ct-PA conformers, together with the computed centrifugal-distortion constants and dipole moments required to simulate their rotational spectra. For Ct-PA, vibrational frequencies in the mid-infrared region accurate to 10 cm(-1) are reported along with theoretical estimates for the transitions in the near-infrared range, and the corresponding infrared spectrum including fundamental transitions, overtones, and combination bands has been simulated. In addition to the new data described above, theoretical results for the Tc- and Tt-PA conformers are compared with all available experimental data to further confirm the accuracy of the hybrid coupled-cluster/density functional theory (CC/DFT) protocol applied in the present study. Finally, we discuss in detail the accuracy of computational models fully based on double-hybrid DFT functionals (mainly at the B2PLYP/aug-cc-pVTZ level) that avoid the use of very expensive CC
Fundamental spectroscopic studies of carbenes and hydrocarbon radicals
Gottlieb, C.A.; Thaddeus, P.
1993-12-01
Highly reactive carbenes and carbon-chain radicals are studied at millimeter wavelengths by observing their rotational spectra. The purpose is to provide definitive spectroscopic identification, accurate spectroscopic constants in the lowest vibrational states, and reliable structures of the key intermediates in reactions leading to aromatic hydrocarbons and soot particles in combustion.
Fortenberry, Ryan C.; Francisco, Joseph S.
2015-08-28
The SNO and OSN radical isomers are likely to be of significance in atmospheric and astrochemistry, but very little is known about their gas phase spectroscopic properties. State-of-the-art ab initio composite quartic force fields are employed to analyze the rovibrational features for both systems. Comparison to condensed-phase experimental data for SNO has shown that the 1566.4 cm{sup −1} ν{sub 1} N–O stretch is indeed exceptionally bright and likely located in this vicinity for subsequent gas phase experimental analysis. The OSN ν{sub 1} at 1209.4 cm{sup −1} is better described as the antisymmetric stretch in this molecule and is also quite bright. The full vibrational, rotational, and rovibrational data are provided for SNO and OSN and their single {sup 15}N, {sup 18}O, and {sup 34}S isotopic substitutions in order to give a more complete picture as to the chemical physics of these molecules.
Shi, Deheng; Li, Peiling; Sun, Jinfeng; Zhu, Zunlue
2014-01-01
The potential energy curves (PECs) of 28 Ω states generated from 9 Λ-S states (X(2)Π, 1(4)Π, 1(6)Π, 1(2)Σ(+), 1(4)Σ(+), 1(6)Σ(+), 1(4)Σ(-), 2(4)Π and 1(4)Δ) are studied for the first time using an ab initio quantum chemical method. All the 9 Λ-S states correlate to the first two dissociation limits, N((4)Su)+Se((3)Pg) and N((4)Su)+Se((3)Dg), of NSe radical. Of these Λ-S states, the 1(6)Σ(+), 1(4)Σ(+), 1(6)Π, 2(4)Π and 1(4)Δ are found to be rather weakly bound states. The 1(2)Σ(+) is found to be unstable and has double wells. And the 1(6)Σ(+), 1(4)Σ(+), 1(4)Π and 1(6)Π are found to be the inverted ones with the SO coupling included. The PEC calculations are made by the complete active space self-consistent field method, which is followed by the internally contracted multireference configuration interaction approach with the Davidson modification. The spin-orbit coupling is accounted for by the state interaction approach with the Breit-Pauli Hamiltonian. The convergence of the present calculations is discussed with respect to the basis set and the level of theory. Core-valence correlation corrections are included with a cc-pCVTZ basis set. Scalar relativistic corrections are calculated by the third-order Douglas-Kroll Hamiltonian approximation at the level of a cc-pV5Z basis set. All the PECs are extrapolated to the complete basis set limit. The variation with internuclear separation of spin-orbit coupling constants is discussed in brief for some Λ-S states with one shallow well on each PEC. The spectroscopic parameters of 9 Λ-S and 28 Ω states are determined by fitting the first ten vibrational levels whenever available, which are calculated by solving the rovibrational Schrödinger equation with Numerov's method. The splitting energy in the X(2)Π Λ-S state is determined to be about 864.92 cm(-1), which agrees favorably with the measurements of 891.80 cm(-1). Moreover, other spectroscopic parameters of Λ-S and Ω states involved here are
Optical constants of concentrated aqueous ammonium sulfate.
NASA Technical Reports Server (NTRS)
Remsberg, E. E.
1973-01-01
Using experimental data obtained from applying spectroscopy to a 39-wt-% aqueous ammonium sulfate solution, it is shown that, even though specific aerosol optical constants appear quite accurate, spectral variations may exist as functions of material composition or concentration or both. Prudent users of optical constant data must then include liberal data error estimates when performing calculations or in interpreting spectroscopic surveys of collected aerosol material.
NASA Astrophysics Data System (ADS)
Othman, Maslina T.
My research will address issues at the back-end-of-line in microelectronics fabrication, specifically the need for Low-k extendibility. The International Roadmap for Semiconductors (2005) suggested that interconnect insulation must be replaced with a material having an ultra-low dielectric constant (k) of < 2.0 and can withstand rigorous current process integration for the 65 nm technology. Creating porosity in the films produces k-values as low (1.0) air. In this research, supercritical CO2 (SCCO2) process is utilized to create pores, remove water, repair plasma-damaged sample and seal pores. These multi-step processing does not only produce low-k film but also create device reliability. Spectroscopy ellipsometric (SE) analysis is used to evaluate the performance of each process on porous film. In SE analysis, Cauchy, Bruggeman Effective Medium Approximation and graded models are used to model the processed samples. The depth profile SE analysis demonstrates the individual process performance based on its changes of refractive index (n) throughout the film thickness. SE also provide important film properties like thickness, porosity etc. In addition to SE, Fourier Transform Infra-red (FT-IR), Scanning Electron Microscopy (SEM) and electrical characterizations are used. Results show that SCCO2/co-solvents can extract porogens and remove water effectively at a significantly shorter time (≤1 hr) and at a low temperature (≤160°C) without thickness shrinkage in contrast with thermal annealing which uses 450°C and 5 hours without significantly shrinkage. SCCO2/TMCS removes water and terminates silanol group with methyl group, and hence preventing water re-adsorption which increases k. The dense layer on the sample surface that formed through the vapor treatment/HMDS helps to seal pores and prevent metal diffusion. This research also shows that patterning samples prior to porogen/water removal can minimize plasma damages on porous sample.
Vargas, M.; Rubio, E. J.; Gutierrez, A.; Ramana, C. V.
2014-04-07
Titanium (Ti) doped tungsten oxide (WO{sub 3}) thin films were grown by co-sputter deposition of W and Ti metal targets. The sputtering powers to the W and Ti were kept constant at 100 W and 50 W, respectively, while varying the growth temperature (T{sub s}) in the range of 25–400 °C. The structural quality of Ti-doped WO{sub 3} films is dependent on T{sub s}. Ti-doped WO{sub 3} films grown at T{sub s} < 400 °C were amorphous. A temperature of 400 °C is critical to promote the structural order and formation of monoclinic, nanocrystalline films. The optical constants and their dispersion profiles determined from spectroscopic ellipsometry indicate that there is no significant inter-diffusion at the film-substrate interface for W-Ti oxide film growth of ∼40 nm. The index refraction (n) at λ = 550 nm varies in the range of 2.15–2.40 with a gradual increase in T{sub s}. Lorentz-Lorenz analysis (n{sub (λ)} = 550 nm) of the data indicates the gradual improvement in the packing density coupled with structural transformation accounts for the observed optical quality of the Ti-doped WO{sub 3} films as a function of T{sub s}. A correlation between the growth conditions and optical constants is discussed.
NASA Astrophysics Data System (ADS)
Shi, De-Heng; Liu, Qionglan; Yu, Wei; Sun, Jinfeng; Zhu, Zunlue
2014-05-01
The potential energy curves (PECs) of 23 Ω states generated from the 12 electronic states (X1 Σ +, 21 Σ +, 11 Σ -, 11 Π, 21 Π, 11 Δ, 13 Σ +, 23 Σ +, 13 Σ -, a3 Π, 23 Π and 13 Δ) are studied for the first time. All the states correlate to the first dissociation channel of the SiBr+ cation. Of these electronic states, the 23 Σ + is the repulsive one without the spin-orbit coupling, whereas it becomes the bound one with the spin-orbit coupling added. On the one hand, without the spin-orbit coupling, the 11 Π, 21 Π and 23 Π are the rather weakly bound states, and only the 11 Π state possesses the double well; on the other hand, with the spin-orbit coupling included, the a3 Π and 11 Π states possess the double well, and the 13 Σ + and 13 Σ - are the inverted states. The PECs are calculated by the CASSCF method, which is followed by the internally contracted MRCI approach with the Davidson modification. Scalar relativistic correction is calculated by the third-order Douglas-Kroll Hamiltonian approximation with a cc-pVTZ-DK basis set. Core-valence correlation correction is included with a cc-pCVTZ basis set. The spin-orbit coupling is accounted for by the state interaction method with the Breit-Pauli Hamiltonian using the all-electron aug-cc-pCVTZ basis set. All the PECs are extrapolated to the complete basis set limit. The variation with internuclear separation of the spin-orbit coupling constant is discussed in brief. The spectroscopic parameters are evaluated for the 11 bound electronic states and the 23 bound Ω states, and are compared with available measurements. Excellent agreement has been found between the present results and the experimental data. It demonstrates that the spectroscopic parameters reported here can be expected to be reliably predicted ones. The Franck-Condon factors and radiative lifetimes of the transitions from the a3 Π 0 + and a3 Π 1 states to the X1 Σ + 0+ state are calculated for several low vibrational levels, and
Shi, Deheng; Li, Wentao; Sun, Jinfeng; Zhu, Zunlue
2012-02-15
The potential energy curves (PECs) of the X(1)Σ(+), a(3)Σ(+), A(1)Π and C(1)Σ(-) electronic states of the SiO molecule are studied using an ab initio quantum chemical method. The calculations have been made employing the complete active space self-consistent field (CASSCF) method, which is followed by the valence internally contracted multireference configuration interaction (MRCI) approach in combination with several correlation-consistent basis sets. The effect on the PECs by the core-valence correlation and relativistic corrections is included. The way to consider the relativistic correction is to use the third-order Douglas-Kroll Hamiltonian approximation. The core-valence correlation correction is carried out with the cc-pCVQZ basis set, and the relativistic correction is performed at the level of the cc-pVQZ basis set. To obtain more reliable results, the PECs determined by the MRCI calculations are also corrected for size-extensivity errors by means of the Davidson modification (MRCI+Q). The PECs of these electronic states are extrapolated to the complete basis set limit by the total-energy extrapolation scheme. Employing these PECs, the spectroscopic parameters are calculated and compared with those reported in the literature. With these PECs determined by the MRCI+Q/CV+DK+56 calculations, by solving the radial Schrödinger equation of nuclear motion, 110 vibrational states for the X(1)Σ(+), 69 for the a(3)Σ(+), 54 for the A(1)Π and 67 for the C(1)Σ(-) electronic state are predicted when the rotational quantum number J equals zero. The vibrational manifolds of the first 20 vibrational states are reported and compared with the available RKR data for each electronic state. On the whole, as expected, the most accurate spectroscopic parameters and molecular constants of the SiO molecule are obtained by the MRCI+Q/CV+DK+56 calculations. And the present molecular constants of the a(3)Σ(+), C(1)Σ(-) and A(1)Π electronic states determined by the MRCI
Marszałek, I; Krężel, A; Goch, W; Zhukov, I; Paczkowska, I; Bal, W
2016-08-01
2-[2-[2-[2-[bis(carboxylatomethyl)amino]-5-methoxyphenoxy]ethoxy]-4-(2,7-difluoro-3-oxido-6-oxo-4a,9a-dihydroxanthen-9-yl)anilino]acetate (FluoZin-3) is used very broadly in life sciences as intra- and extracellular Zn(II) sensor selective for Zn(II) over Co(II), Ca(II) and Mg(II) ions at their physiological concentrations. It has been used for determination of relative and absolute levels of exchangeable Zn(II) in cells and extracellular fluids. Despite its popularity, the knowledge of its acid/base and Zn(II) coordination abilities and of its spectroscopic properties remained very limited. Also the published conditional dissociation constant ((C)Kd) values at pH7.4 are slightly discrepant, (15nM or 8.9nM). In this work we determined the (C)Kd for Zn(II) complexation by FluoZin-3 at pH7.4 with nitrilotriacetic acid (NTA) as competitor using two independent methods: fluorimetry and UV-Vis spectroscopy. For the first time, we investigated FluoZin-3 alone and complexed with Zn(II) in the wide range of pH, determining the total of eight pKa values from fluorescence spectra and from various regions of UV-Vis spectra. The validated values of (C)Kd (9.1±0.4nM; -log (C)Kd=8.04) and of the absolute (pH-independent) stability constant log βZnL (8.16±0.05) were provided by fluorescence spectroscopy experiments performed at 1μM concentrations. Our experiments demonstrated that both of aminocarboxylate moieties of FluoZin-3 bind the Zn(II) ion synergistically. PMID:27216451
NASA Astrophysics Data System (ADS)
Inostroza Pino, N.; Cardenas, C.; Fuentealba, P.
2014-10-01
Reaction channels and spectroscopic properties of a series of silicon-carbon-bearing isomers of SiC3H+ and SiC3H, which are suitable species for astrophysical detection in carbon-rich sources, are calculated with correlated ab initio CCSD(T) and density functional theory methods. We present four isomers of SiC3H+ for which the electronic ground states have closed-shell configurations. For SiC3H, we considered the same structures in order to present a complete study. The global minimum among the SiC3H+ isomers corresponds to the rhomboidal structure with a transannular bond in a 1A1 electronic state (rb3-SiC3H+ C2v X1A1). The next minima correspond to a second rhomboid 1A1 isomer and a linear isomer (X1Σ+) with relative energies 0.86 and 0.93 eV, respectively at the CCSD(T)/cc-pvTZ level of theory. The most stable mono-hydrogenated silicon carbon isomer is linear, followed by two rhomboidal isomers, rb2-SiC3H and rb3-SiC3H (0.23 and 0.31 eV). For each structure, a set of spectroscopic parameters including their equilibrium structures, rotational constants, harmonic frequencies and dipole moment is presented. Furthermore, we discuss plausible formation pathways of SiC3H+ isomers which are classified as charge-exchange, ion-neutral and dissociative recombination reactions. These results show one favourable pathway to produce rb3-SiC3H+ from rb-SiC3-3s. The formation energy of the cation's isomers coming from neutral isomers as linear l1-SiC3H, rb3-SiC3H and rb2-SiC3H plus H+ as reactants (charge-exchange reaction) are 203.8 kcal mol-1 (8.84eV), 175.4 kcal mol-1 (7.60 eV) and 195.2 kcal mol-1 (8.46 eV), which provides us with evidence of the endergonic character of these reactions. As a consequence, it does not seem to be feasible to produce a cation from neutral reactant plus H+ by a charge-exchange reaction that was proposed by UMIST.
NASA Astrophysics Data System (ADS)
Moore, Keith; McLaughlin, Brendan M.; Lane, Ian C.
2016-04-01
BaH (and its isotopomers) is an attractive molecular candidate for laser cooling to ultracold temperatures and a potential precursor for the production of ultracold gases of hydrogen and deuterium. The theoretical challenge is to simulate the laser cooling cycle as reliably as possible and this paper addresses the generation of a highly accurate ab initio 2Σ+ potential for such studies. The performance of various basis sets within the multi-reference configuration-interaction (MRCI) approximation with the Davidson correction is tested and taken to the Complete Basis Set (CBS) limit. It is shown that the calculated molecular constants using a 46 electron effective core-potential and even-tempered augmented polarized core-valence basis sets (aug-pCVnZ-PP, n = 4 and 5) but only including three active electrons in the MRCI calculation are in excellent agreement with the available experimental values. The predicted dissociation energy De for the X2Σ+ state (extrapolated to the CBS limit) is 16 895.12 cm-1 (2.094 eV), which agrees within 0.1% of a revised experimental value of <16 910.6 cm-1, while the calculated re is within 0.03 pm of the experimental result.
NASA Astrophysics Data System (ADS)
Panetta, R. J.; Hsiao, G.
2011-12-01
Trace levels of organic contaminants such as short alcohols and terpenoids have been shown to cause spectral interference in water isotope analysis by spectroscopic techniques. The result is degraded precision and accuracy in both δD and δ18O for samples such as beverages, plant extracts or slightly contaminated waters. An initial approach offered by manufacturers is post-processing software that analyzes spectral features to identify and flag contaminated samples. However, it is impossible for this software to accurately reconstruct the water isotope signature, thus it is primarily a metric for data quality. Here, we describe a novel in-line pyrolysis system (Micro-Pyrolysis Technology, MPT) placed just prior to the inlet of a cavity ring-down spectroscopy (CRDS) analyzer that effectively removes interfering organic molecules without altering the isotope values of the water. Following injection of the water sample, N2 carrier gas passes the sample through a micro-pyrolysis tube heated with multiple high temperature elements in an oxygen-free environment. The temperature is maintained above the thermal decomposition threshold of most organic compounds (≤ 900 oC), but well below that of water (~2000 oC). The main products of the pyrolysis reaction are non-interfering species such as elemental carbon and H2 gas. To test the efficacy and applicability of the system, waters of known isotopic composition were spiked with varying amounts of common interfering alcohols (methanol, ethanol, propanol, hexanol, trans-2-hexenol, cis-3-hexanol up to 5 % v/v) and common soluble plant terpenoids (carveol, linalool, geraniol, prenol). Spiked samples with no treatment to remove the organics show strong interfering absorption peaks that adversely affect the δD and δ18O values. However, with the MPT in place, all interfering absorption peaks are removed and the water absorption spectrum is fully restored. As a consequence, the δD and δ18O values also return to their original
NASA Astrophysics Data System (ADS)
Pamukchieva, V.; Szekeres, A.; Arsova, D.
2011-02-01
The effects of illumination and post-illumination thermal annealing on the optical properties of chalcogenide thin (~150 nm) films were studied by spectroscopic ellipsometry. The films were thermally evaporated from Ge30.8As5.7S63.5 and Ge32As5S63 glasses. They were exposed to illumination with an HBO 500 lamp and to subsequent thermal annealing at a temperature of 350 °C. Ellipsometric measurements in the spectral range 300-820 nm were carried out after each technological step. From the ellipsometric data analysis the optical constants (n, k, ɛ), optical band gap energy Eog and film thickness have been determined, while the oscillator energies E0 and Ed have been estimated applying the single-oscillator approximation theory. In the ɛ2 spectra three peaks, denoted by E1, E2 and E3, have appeared, which are attributed to interband transitions. By illumination, the values of the complex refractive index (\\tilde n = n - {\\rm{i}}k), dielectric function (\\skew3\\tilde \\varepsilon = \\varepsilon _1 - {\\rm{i}}\\varepsilon _{\\rm{2}} ) and dispersion energy Ed decrease, whereas the band gap energy (Eog) and the oscillator energy (E0) values increase. All these are accompanied by a ~12-13% enhancement of film thickness. Thermal annealing leads to a further increase of the energetic parameters values, but causes a ~14-15% decrease of film thickness in comparison to that of illuminated films. The E1 and E2 peaks diminish on illumination and post-illumination annealing, whereas the magnitude of the E3 peak decreases on illumination and increases by annealing, approaching its initial value for the as-deposited state.
Accurate decay-constant ratios fB*/fB and fBs*/fBs from Borel QCD sum rules
NASA Astrophysics Data System (ADS)
Lucha, Wolfgang; Melikhov, Dmitri; Simula, Silvano
2015-06-01
We present our analysis of the decay constants of the beauty vector mesons B* and Bs* within the framework of dispersive sum rules for the two-point correlator of vector currents in QCD. While the decay constants of the vector mesons fB* and fBs* —similar to the decay constants of the pseudoscalar mesons fB and fBs—individuallyhave large uncertainties induced by theory parameters not known with a satisfactory precision, these uncertainties almost entirely cancel out in the ratios of vector over pseudoscalar decay constants. These ratios, thus, may be predicted with very high accuracy due to the good control over the systematic uncertainties of the decay constants gained upon application of our hadron-parameter extraction algorithm. Our final results read fB*/fB=0.944 ±0.01 1OPE±0.01 8syst and fBs*/fB s=0.947 ±0.02 3OPE±0.02 0syst . Thus, both fB*/fB and fBs*/fBs are less than unity at 2.5 σ and 2 σ level, respectively.
Deridder, Sander; Desmet, Gert
2012-02-01
Using computational fluid dynamics (CFD), the effective B-term diffusion constant γ(eff) has been calculated for four different random sphere packings with different particle size distributions and packing geometries. Both fully porous and porous-shell sphere packings are considered. The obtained γ(eff)-values have subsequently been used to determine the value of the three-point geometrical constant (ζ₂) appearing in the 2nd-order accurate effective medium theory expression for γ(eff). It was found that, whereas the 1st-order accurate effective medium theory expression is accurate to within 5% over most part of the retention factor range, the 2nd-order accurate expression is accurate to within 1% when calculated with the best-fit ζ₂-value. Depending on the exact microscopic geometry, the best-fit ζ₂-values typically lie in the range of 0.20-0.30, holding over the entire range of intra-particle diffusion coefficients typically encountered for small molecules (0.1 ≤ D(pz)/D(m) ≤ 0.5). These values are in agreement with the ζ₂-value proposed by Thovert et al. for the random packing they considered. PMID:22236565
NASA Astrophysics Data System (ADS)
Desforges, Jean; Deschamps, Clément; Gauvin, Serge
2015-08-01
The determination of the complex refractive index of thin films usually requires the highest accuracy. In this paper, we report on a new and accurate method based on a spectral rectifying process of a single transmittance curve. The agreements with simulated and real experimental data show the helpfulness of the method. The case of materials having arbitrary absorption bands at midpoint in spectral range, such as pigments in guest-host polymers, is also encompassed by this method.
Calibration method for spectroscopic systems
Sandison, David R.
1998-01-01
Calibration spots of optically-characterized material placed in the field of view of a spectroscopic system allow calibration of the spectroscopic system. Response from the calibration spots is measured and used to calibrate for varying spectroscopic system operating parameters. The accurate calibration achieved allows quantitative spectroscopic analysis of responses taken at different times, different excitation conditions, and of different targets.
Calibration method for spectroscopic systems
Sandison, D.R.
1998-11-17
Calibration spots of optically-characterized material placed in the field of view of a spectroscopic system allow calibration of the spectroscopic system. Response from the calibration spots is measured and used to calibrate for varying spectroscopic system operating parameters. The accurate calibration achieved allows quantitative spectroscopic analysis of responses taken at different times, different excitation conditions, and of different targets. 3 figs.
NASA Astrophysics Data System (ADS)
Shi, Deheng; Liu, Qionglan; Wang, Shuai; Sun, Jinfeng; Zhu, Zunlue
2015-01-01
The potential energy curves (PECs) of 59 Ω states generated from the 17 Λ-S states (X1Σ+, a3Σ+, 15Σ+, b3Δ, c3Π, 15Π, 25Σ+, 23Δ, 23Π, 33Σ+, A1Π, 23Σ+, 35Σ+, 17Σ+, 15Δ, 25Δ, and 25Π) of AsP molecule are studied for the first time for internuclear separations from about 0.10 to 1.10 nm. All the Λ-S states are contributed to the first three dissociation channels of AsP molecule except for the A1Π. The 23Σ+, 35Σ+, 17Σ+, 15Δ, 25Δ, and 25Π are found to be the repulsive states. The a3Σ+, 15Π, b3Δ, 17Σ+, 15Δ, 25Δ, and 25Π are found to be the inverted states. Each of the 33Σ+, c3Π, 23Π, 15Π, and 15Σ+ states has one potential barrier. The PECs are calculated by the CASSCF method, which is followed by the internally contracted MRCI approach with Davidson correction. Core-valence correlation and scalar relativistic corrections are included. The convergent behavior of present calculations is discussed with respect to the basis set and level of theory. The spin-orbit coupling effect is accounted for. All these PECs are extrapolated to the complete basis set limit. The spectroscopic parameters are evaluated for the bound states involved, and are compared with available measurements. Excellent agreement has been found between the present results and the measurements. It shows that the spectroscopic parameters reported in this paper can be expected to be reliably predicted ones. The conclusion is gained that the effect of spin-orbit coupling on the spectroscopic parameters is not obvious for all the Λ-S bound states except for few ones such as 15Σ+ and c3Π.
Zhu, Zunlue; Yu, Wei; Wang, Shuai; Sun, Jinfeng; Shi, Deheng
2014-10-15
The spectroscopic properties of 23 Ω states generated from the 13 Λ-S states of BO radical are studied for the first time for internuclear separations from about 0.07 to 1.0nm. Of the 13 Λ-S states, each of the F(2)Π, 1(2)Φ and 1(2)Δ states is found to possess the double well. Each of the 1(4)Π, C(2)Π, 1(2)Σ(-) and 2(2)Σ(-) states possesses one well with one barrier. The A(2)Π, 1(4)Π and F(2)Π are the inverted states with the spin-orbit coupling effect taken into account. All the states possess the deep well except for the 1(2)Φ. The potential energy curves (PECs) are calculated by the complete active space self-consistent field method, which is followed by the internally contracted multireference configuration interaction approach with the Davidson correction. Core-valence correlation and scalar relativistic corrections are included into the calculations. The PECs are extrapolated to the complete basis set limit. The spin-orbit coupling effect is accounted for by the state interaction approach with the Breit-Pauli Hamiltonian. The spectroscopic parameters are evaluated, and compared with the available measurements and other theoretical results. The Franck-Condon factors and radiative lifetimes of the transitions from the B(2)Σ(+), C(2)Π, D(2)Σ(+), 1(2)Σ(-) and 1(4)Π Λ-S states to the ground state are calculated for several low vibrational levels, and some necessary discussion is made. Analyses show that the spectroscopic parameters reported in this paper can be expected to be reliably predicted ones. PMID:24820321
NASA Astrophysics Data System (ADS)
Yu, Bingwu; van Ingen, Hugo; Freedberg, Darón I.
2013-03-01
Strong 1H-1H coupling can significantly reduce the accuracy of 1JCH measured from frequency differences in coupled HSQC spectra. Although accurate 1JCH values can be extracted from spectral simulation, it would be more convenient if the same accurate 1JCH values can be obtained experimentally. Furthermore, simulations reach their limit for residual dipolar coupling (RDC) measurement, as many significant, but immeasurable RDCs are introduced into the spin system when a molecule is weakly aligned, thus it is impossible to have a model spin system that truly represents the real spin system. Here we report a new J modulated method, constant-time INEPT CT-HSQC (CTi-CT-HSQC), to accurately measure one-bond scalar coupling constant and RDCs without strong coupling interference. In this method, changing the spacing between the two 180° pulses during a constant time INEPT period selectively modulates heteronuclear coupling in quantitative J fashion. Since the INEPT delays for measuring one-bond carbon-proton spectra are short compared to 3JHH, evolution due to (strong) 1H-1H coupling is marginal. The resulting curve shape is practically independent of 1H-1H coupling and only correlated to the heteronuclear coupling evolution. Consequently, an accurate 1JCH can be measured even in the presence of strong coupling. We tested this method on N-acetyl-glucosamine and mannose whose apparent isotropic 1JCH values are significantly affected by strong coupling with other methods. Agreement to within 0.5 Hz or better is found between 1JCH measured by this method and previously published simulation data. We further examined the strong coupling effects on RDC measurements and observed an error up to 100% for one bond RDCs using coupled HSQC in carbohydrates. We demonstrate that RDCs can be obtained with higher accuracy by CTi-CT-HSQC, which compensates the limitation of simulation method.
NASA Astrophysics Data System (ADS)
Shi, Deheng; Song, Ziyue; Niu, Xianghong; Sun, Jinfeng; Zhu, Zunlue
2016-01-01
The PECs are calculated for the 27 Λ-S states and their corresponding 73 Ω states of AsS radical. Of these Λ-S states, only the 22Δ and 54Π states are replulsive. The 12Σ+, 22Σ+, 42Π, 34Δ, 34Σ+, and 44Π states possess double wells. The 32Σ+ state possesses three wells. The A2Π, 32Π, 12Φ, 24Π, 34Π, 24Δ, 34Δ, 16Σ+, and 16Π states are inverted with the SO coupling effect included. The 14Σ+, 24Σ+, 24Σ-, 24Δ, 14Φ, 16Σ+, and 16Π states, the second wells of 12Σ+, 34Σ+, 42Π, 44Π, and 34Δ states, and the third well of 32Σ+ state are very weakly-bound states. The PECs are extrapolated to the CBS limit. The effect of SO coupling on the PECs is discussed. The spectroscopic parameters are evaluated, and compared with available measurements and other theoretical ones. The vibrational properties of several weakly-bound states are determined. The spectroscopic properties reported here can be expected to be reliably predicted ones.
Shi, Deheng; Liu, Qionglan; Wang, Shuai; Sun, Jinfeng; Zhu, Zunlue
2015-01-25
The potential energy curves (PECs) of 59 Ω states generated from the 17 Λ-S states (X(1)Σ(+), a(3)Σ(+), 1(5)Σ(+), b(3)Δ, c(3)Π, 1(5)Π, 2(5)Σ(+), 2(3)Δ, 2(3)Π, 3(3)Σ(+), A(1)Π, 2(3)Σ(+), 3(5)Σ(+), 1(7)Σ(+), 1(5)Δ, 2(5)Δ, and 2(5)Π) of AsP molecule are studied for the first time for internuclear separations from about 0.10 to 1.10nm. All the Λ-S states are contributed to the first three dissociation channels of AsP molecule except for the A(1)Π. The 2(3)Σ(+), 3(5)Σ(+), 1(7)Σ(+), 1(5)Δ, 2(5)Δ, and 2(5)Π are found to be the repulsive states. The a(3)Σ(+), 1(5)Π, b(3)Δ, 1(7)Σ(+), 1(5)Δ, 2(5)Δ, and 2(5)Π are found to be the inverted states. Each of the 3(3)Σ(+), c(3)Π, 2(3)Π, 1(5)Π, and 1(5)Σ(+) states has one potential barrier. The PECs are calculated by the CASSCF method, which is followed by the internally contracted MRCI approach with Davidson correction. Core-valence correlation and scalar relativistic corrections are included. The convergent behavior of present calculations is discussed with respect to the basis set and level of theory. The spin-orbit coupling effect is accounted for. All these PECs are extrapolated to the complete basis set limit. The spectroscopic parameters are evaluated for the bound states involved, and are compared with available measurements. Excellent agreement has been found between the present results and the measurements. It shows that the spectroscopic parameters reported in this paper can be expected to be reliably predicted ones. The conclusion is gained that the effect of spin-orbit coupling on the spectroscopic parameters is not obvious for all the Λ-S bound states except for few ones such as 1(5)Σ(+) and c(3)Π. PMID:25145917
Shi, Deheng; Liu, Qionglan; Sun, Jinfeng; Zhu, Zunlue
2014-03-25
The potential energy curves (PECs) of 28 Ω states generated from the 12 states (X(4)Σ(-), 1(2)Π, 1(2)Σ(-), 1(2)Δ, 1(2)Σ(+), 2(2)Π, A(4)Π, B(4)Σ(-), 3(2)Π, 1(6)Σ(-), 2(2)Σ(-) and 1(6)Π) of the BN(+) cation are studied for the first time for internuclear separations from about 0.1 to 1.0 nm using an ab initio quantum chemical method. All the Λ-S states correlate to the first four dissociation channels. The 1(6)Σ(-), 3(2)Π and A(4)Π states are found to be the inverted ones. The 1(2)Σ(+), 2(2)Π, 3(2)Π and 2(2)Σ(-) states are found to possess the double well. The PECs are calculated by the complete active space self-consistent field method, which is followed by the internally contracted multireference configuration interaction approach with the Davidson correction. Core-valence correlation correction is included by a cc-pCV5Z basis set. Scalar relativistic correction is calculated by the third-order Douglas-Kroll Hamiltonian approximation at the level of a cc-pV5Z basis set. The convergent behavior of present calculations is discussed with respect to the basis set and level of theory. The spin-orbit coupling is accounted for by the state interaction approach with the Breit-Pauli Hamiltonian using the all-electron cc-pCV5Z basis set. All the PECs are extrapolated to the complete basis set limit. The spectroscopic parameters are obtained, and the vibrational properties of 1(2)Σ(+), 2(2)Π, 3(2)Π and 2(2)Σ(-) states are evaluated. Analyses demonstrate that the spectroscopic parameters reported here can be expected to be reliably predicted ones. The conclusion is gained that the effect of spin-orbit coupling on the spectroscopic parameters are not obvious almost for all the Λ-S states involved in the present paper. PMID:24334021
NASA Astrophysics Data System (ADS)
Diniz, Leonardo G.; Kirnosov, Nikita; Alijah, Alexander; Mohallem, José R.; Adamowicz, Ludwik
2016-04-01
A very accurate dipole moment curve (DMC) for the ground X1Σ+ electronic state of the 7LiH molecule is reported. It is calculated with the use of all-particle explicitly correlated Gaussian functions with shifted centers. The DMC - the most accurate to our knowledge - and the corresponding highly accurate potential energy curve are used to calculate the transition energies, the transition dipole moments, and the Einstein coefficients for the rovibrational transitions with ΔJ = - 1 and Δv ⩽ 5 . The importance of the non-adiabatic effects in determining these properties is evaluated using the model of a vibrational R-dependent effective reduced mass in the rovibrational calculations introduced earlier (Diniz et al., 2015). The results of the present calculations are used to assess the quality of the two complete linelists of 7LiH available in the literature.
NASA Astrophysics Data System (ADS)
Wang, Xinxin; Shi, Deheng; Zhou, Dan; Zhu, Zunlue; Sun, Jinfeng
2015-11-01
The potential energy curves of 10 Λ-S states of BS+ yielded from the first four dissociation limits are calculated by the internally contracted multireference configuration interaction approach with the Davidson correction. The core-valence correlation and scalar relativistic corrections are included. Basis on the calculated potential energy curves, the spectroscopic parameters are evaluated. All the PECs are extrapolated to the complete basis set limit. The spin-orbit coupling are taken into account by the state interaction method with the Breit-Pauli Hamiltonian. Finally, the transition dipole moments, Franck-Condon Factors and radiative lifetimes of transitions from the 23Π0-, 23Π0+, 23Σ0- and 23Σ1- states to ground state 13Π2 are predicted for future experiment.
Shi, Deheng; Song, Ziyue; Niu, Xianghong; Sun, Jinfeng; Zhu, Zunlue
2016-01-15
The PECs are calculated for the 27 Λ-S states and their corresponding 73 Ω states of AsS radical. Of these Λ-S states, only the 2(2)Δ and 5(4)Π states are replulsive. The 1(2)Σ(+), 2(2)Σ(+), 4(2)Π, 3(4)Δ, 3(4)Σ(+), and 4(4)Π states possess double wells. The 3(2)Σ(+) state possesses three wells. The A(2)Π, 3(2)Π, 1(2)Φ, 2(4)Π, 3(4)Π, 2(4)Δ, 3(4)Δ, 1(6)Σ(+), and 1(6)Π states are inverted with the SO coupling effect included. The 1(4)Σ(+), 2(4)Σ(+), 2(4)Σ(-), 2(4)Δ, 1(4)Φ, 1(6)Σ(+), and 1(6)Π states, the second wells of 1(2)Σ(+), 3(4)Σ(+), 4(2)Π, 4(4)Π, and 3(4)Δ states, and the third well of 3(2)Σ(+) state are very weakly-bound states. The PECs are extrapolated to the CBS limit. The effect of SO coupling on the PECs is discussed. The spectroscopic parameters are evaluated, and compared with available measurements and other theoretical ones. The vibrational properties of several weakly-bound states are determined. The spectroscopic properties reported here can be expected to be reliably predicted ones. PMID:26282321
Liu, Hui; Shi, Deheng; Sun, Jinfeng; Zhu, Zunlue; Shulin, Zhang
2014-04-24
The potential energy curves (PECs) of 54 spin-orbit states generated from the 22 electronic states of O2 molecule are investigated for the first time for internuclear separations from about 0.1 to 1.0nm. Of the 22 electronic states, the X(3)Σg(-), A(')(3)Δu, A(3)Σu(+), B(3)Σu(-), C(3)Πg, a(1)Δg, b(1)Σg(+), c(1)Σu(-), d(1)Πg, f(1)Σu(+), 1(5)Πg, 1(3)Πu, 2(3)Σg(-), 1(5)Σu(-), 2(1)Σu(-) and 2(1)Δg are found to be bound, whereas the 1(5)Σg(+), 2(5)Σg(+), 1(1)Πu, 1(5)Δg, 1(5)Πu and 2(1)Πu are found to be repulsive ones. The B(3)Σu(-) and d(1)Πg states possess the double well. And the 1(3)Πu, C(3)Πg, A'(3)Δu, 1(5)Δg and 2(5)Σg(+) states are the inverted ones when the spin-orbit coupling is included. The PEC calculations are done by the complete active space self-consistent field (CASSCF) method, which is followed by the internally contracted multireference configuration interaction (icMRCI) approach with the Davidson correction. Core-valence correlation and scalar relativistic corrections are taken into account. The convergence of present calculations is evaluated with respect to the basis set and level of theory. The vibrational properties are discussed for the 1(5)Πg, 1(3)Πu, d(1)Πg and 1(5)Σu(-) states and for the second well of the B(3)Σu(-) state. The spin-orbit coupling effect is accounted for by the state interaction method with the Breit-Pauli Hamiltonian. The PECs of all the electronic states and spin-orbit states are extrapolated to the complete basis set limit. The spectroscopic parameters are obtained, and compared with available experimental and other theoretical results. Analyses demonstrate that the spectroscopic parameters reported here can be expected to be reliably predicted ones. The conclusion is obtained that the effect of spin-orbit coupling on the spectroscopic parameters are small almost for all the electronic states involved in this paper except for the 1(5)Σu(-), 1(5)Πg and 1(3)Πu. PMID:24486866
Vidot, Kévin; Achir, Nawel; Mertz, Christian; Sinela, André; Rawat, Nadirah; Prades, Alexia; Dangles, Olivier; Fulcrand, Hélène; Dornier, Manuel
2016-05-25
Delphinidin-3-O-sambubioside and cyanidin-3-O-sambubioside are the main anthocyanins of Hibiscus sabdariffa calyces, traditionally used to make a bright red beverage by decoction in water. At natural pH, these anthocyanins are mainly in their flavylium form (red) in equilibrium with the quinonoid base (purple) and the hemiketal (colorless). For the first time, their acidity and hydration equilibrium constants were obtained from a pH-jump method followed by UV-vis spectroscopy as a function of temperature from 4 to 37 °C. Equilibrium constant determination was also performed by multivariate curve resolution (MCR). Acidity and hydration constants of cyanidin-3-O-sambubioside at 25 °C were 4.12 × 10(-5) and 7.74 × 10(-4), respectively, and were significantly higher for delphinidin-3-O-sambubioside (4.95 × 10(-5) and 1.21 × 10(-3), respectively). MCR enabled the obtaining of concentration and spectrum of each form but led to overestimated values for the equilibrium constants. However, both methods showed that formations of the quinonoid base and hemiketal were endothermic reactions. Equilibrium constants of anthocyanins in the hibiscus extract showed comparable values as for the isolated anthocyanins. PMID:27124576
Vijayarangamuthu, K.; Singh, Chaman; Rath, Shyama; Kabiraj, D.
2011-09-15
Sub-stoichiometric GeO{sub x} films were fabricated by electron-beam evaporation method. The films were irradiated with 100 MeV Ag{sup 7+} ions at fluences between 1 x 10{sup 12} and 1 x 10{sup 14} ions-cm{sup -2}. Spectroscopic ellipsometric measurements were performed in air at room temperature. The values of the layer thickness and refractive index were extracted from ellipsometry using a multilayer analysis and the Tauc Lorentz model. The refractive index (at 633 nm) of the as-deposited GeO{sub x} film was estimated to be 1.860 and decreased to 1.823 for films irradiated at an ion fluence of 1 x 10{sup 14} ions-cm{sup -2}. The thickness of the films also decreased after irradiation and is due to a sputtering induced by the ion beam. The change in the refractive index with ion fluence is attributed to a stoichiometric change and structural transformation represented by GeO{sub x}{yields} Ge + GeO{sub y} (y > x) occurring due to a thermal spike induced by ion irradiation. Swift heavy ions thus provide a scope for modulating the refractive index of GeO{sub x} films. The thickness and stoichiometric changes are supported by Rutherford backscattering measurements.
Kim, Yong-Hyun; Kim, Ki-Hyun
2014-05-16
Accurate values for the Henry's law constants are essential to describe the environmental dynamics of a solute, but substantial errors are recognized in many reported data due to practical difficulties in measuring solubility and/or vapor pressure. Despite such awareness, validation of experimental approaches has scarcely been made. An experimental approach based on thermal desorption-gas chromatography-mass spectrometery (TD-GC-MS) method was developed to concurrently allow the accurate determination of target compounds from the headspace and aqueous samples in closed equilibrated system. The analysis of six aromatics and eight non-aromatic oxygenates was then carried out in a static headspace mode. An estimation of the potential bias and mass balance (i.e., sum of mass measured individually from gas and liquid phases vs. the mass initially added to the system) demonstrates compound-specific phase dependency so that the best results are obtained by aqueous (less soluble aromatics) and headspace analysis (more soluble non-aromatics). Accordingly, we were able to point to the possible sources of biases in previous studies and provide the best estimates for the Henry's constants (Matm(-1)): benzene (0.17), toluene (0.15), p-xylene (0.13), m-xylene (0.13), o-xylene (0.19), styrene (0.27); propionaldehyde (9.26), butyraldehyde (6.19), isovaleraldehyde (2.14), n-valeraldehyde (3.98), methyl ethyl ketone (10.5), methyl isobutyl ketone (3.93), n-butyl acetate (2.41), and isobutyl alcohol (22.2). PMID:24704185
NASA Astrophysics Data System (ADS)
Davila, Y. A.; Sancho, M. I.; Almandoz, M. C.; Blanco, S. E.
2012-09-01
Stoichiometry and apparent stability constant (KC) of the complex formed between Al(III) and 3-hydroxyflavone were determined in methanol and water-methanol mixtures (% water w/w: 3.11; 6.15; 10.4; 15.2; 19.9 and 25.3) by UV-vis spectroscopy at 25.0 °C and constant ionic strength (0.05 M, sodium chloride). Stoichiometry of the complex (1:2, metal:ligand) is not modified with an increase in water percentage in the analyzed interval. The value of KC in methanol is greater than in the binary solutions. The effects of changing solvent composition on KC data were explained by linear solvation free energy relationships using the solvatochromic parameter of Kamlet and Taft (α, β and π*). Multiple linear regression analysis indicates that the hydrogen bond donating ability (α) of the solvent and non-specific interactions (π*) play an important role in the degree of occurrence of the reaction. The effect of temperature on KC was also analyzed by assessing standard entropy and enthalpy variations of the reaction in methanol. Finally, the structure of the complex was investigated using FTIR spectroscopy and DFT calculations. The ligand exhibits small structural changes upon complexation, localized on the chelating site. The calculated vibrational frequencies of the complex were successfully compared against the experimental values.
Yang, X X; Li, J W; Zhou, Z F; Wang, Y; Yang, L W; Zheng, W T; Sun, Chang Q
2012-01-21
From the perspective of bond relaxation and bond vibration, we have formulated the Raman phonon relaxation of graphene, under the stimuli of the number-of-layers, the uni-axial strain, the pressure, and the temperature, in terms of the response of the length and strength of the representative bond of the entire specimen to the applied stimuli. Theoretical unification of the measurements clarifies that: (i) the opposite trends of the Raman shifts, which are due to the number-of-layers reduction, of the G-peak shift and arises from the vibration of a pair of atoms, while the D- and the 2D-peak shifts involve the z-neighbor of a specific atom; (ii) the tensile strain-induced phonon softening and phonon-band splitting arise from the asymmetric response of the C(3v) bond geometry to the C(2v) uni-axial bond elongation; (iii) the thermal softening of the phonons originates from bond expansion and weakening; and (iv) the pressure stiffening of the phonons results from bond compression and work hardening. Reproduction of the measurements has led to quantitative information about the referential frequencies from which the Raman frequencies shift as well as the length, energy, force constant, Debye temperature, compressibility and elastic modulus of the C-C bond in graphene, which is of instrumental importance in the understanding of the unusual behavior of graphene. PMID:22105904
The cosmological constant problem
Dolgov, A.D.
1989-05-01
A review of the cosmological term problem is presented. Baby universe model and the compensating field model are discussed. The importance of more accurate data on the Hubble constant and the Universe age is stressed. 18 refs.
NASA Astrophysics Data System (ADS)
Jalbout, Abraham F.; Li, Xin-Hua; Abou-Rachid, Hakima
The molecular spectroscopic constants for the chalcogenide complexes MX (M dbond Ge, Sn, Pb; X dbond O, S, Se, Te, Po) and their corresponding MX- anions are presented with the LSDA/SDD, B1LYP/SDD, and B3LYP/SDD methods. Although many methods were attempted, only the most promising results are reported. We show that the best results are obtained by LSDA/SDD calculations, and thus this method is emphasized as an illustrative example of our methodology. The potential energy curves and physical property characterizations for X1 ?+ state of LuH and LuF are presented with a variety of density functional theory (DFT) methods. Comparisons with wave function-based treatments (HF, MP2, CCSD, QCISD) are made in addition to experimental correlations. We show that the best results are obtained by the B3LYP/SDD method for LuH, and the MPW1PW91/SDD method for LuF.
Comment on: "Universal relation between spectroscopic constants"
NASA Astrophysics Data System (ADS)
Chandra, Suresh
2004-05-01
Kaur and Mahajan [1] have claimed to derive a universal relation [ ln G = 1.91578 (pm 0.09727) + 0.97111 (pm 0.03809) ln Delta ] between the Sutherland parameter Delta (= omega_e r_e^2/2D_e) and the dimensionless parameter G(= 8 omega_e x_e/B_e) for the ground as well as excited electronic states of diatomic molecules. Validity of this relation is checked and we find that the relation is not correct. Next, we checked the validity of the relation De = 2.2r_e for the alkali group diatomic molecules. This relation is also found not to be correct.
Accurate ab initio Quartic Force Fields of Cyclic and Bent HC2N Isomers
NASA Technical Reports Server (NTRS)
Inostroza, Natalia; Huang, Xinchuan; Lee, Timothy J.
2012-01-01
Highly correlated ab initio quartic force field (QFFs) are used to calculate the equilibrium structures and predict the spectroscopic parameters of three HC2N isomers. Specifically, the ground state quasilinear triplet and the lowest cyclic and bent singlet isomers are included in the present study. Extensive treatment of correlation effects were included using the singles and doubles coupled-cluster method that includes a perturbational estimate of the effects of connected triple excitations, denoted CCSD(T). Dunning s correlation-consistent basis sets cc-pVXZ, X=3,4,5, were used, and a three-point formula for extrapolation to the one-particle basis set limit was used. Core-correlation and scalar relativistic corrections were also included to yield highly accurate QFFs. The QFFs were used together with second-order perturbation theory (with proper treatment of Fermi resonances) and variational methods to solve the nuclear Schr dinger equation. The quasilinear nature of the triplet isomer is problematic, and it is concluded that a QFF is not adequate to describe properly all of the fundamental vibrational frequencies and spectroscopic constants (though some constants not dependent on the bending motion are well reproduced by perturbation theory). On the other hand, this procedure (a QFF together with either perturbation theory or variational methods) leads to highly accurate fundamental vibrational frequencies and spectroscopic constants for the cyclic and bent singlet isomers of HC2N. All three isomers possess significant dipole moments, 3.05D, 3.06D, and 1.71D, for the quasilinear triplet, the cyclic singlet, and the bent singlet isomers, respectively. It is concluded that the spectroscopic constants determined for the cyclic and bent singlet isomers are the most accurate available, and it is hoped that these will be useful in the interpretation of high-resolution astronomical observations or laboratory experiments.
A priori predictions of the rotational constants for protonated formaldehyde and protonated methanol
NASA Technical Reports Server (NTRS)
Defrees, D. J.; Mclean, A. D.
1986-01-01
Protonated formaldehyde and protonated methanol are candidate interstellar molecules and models for classes of protonated oxygen compounds. Ab initio molecular orbital theory has been used to compute rotational constants to guide spectroscopic searches both in the laboratory and in space. The ab initio results are empirically correct to account for systematic deficiencies in the theory and zero-point vibrational effects; they are expected to be accurate to about + or - 2 percent. For H2COH(+) the resultant constants are (in GHz) A = 194.3, B = 34.28, and C = 29.14; for H3COH2(+) A = 103.7, B = 21.18, and C = 20.30.
NASA Astrophysics Data System (ADS)
Batten, A.; Murdin, P.
2000-11-01
Historically, spectroscopic binary stars were binary systems whose nature was discovered by the changing DOPPLER EFFECT or shift of the spectral lines of one or both of the component stars. The observed Doppler shift is a combination of that produced by the constant RADIAL VELOCITY (i.e. line-of-sight velocity) of the center of mass of the whole system, and the variable shift resulting from the o...
Accurate quantum chemical calculations
NASA Technical Reports Server (NTRS)
Bauschlicher, Charles W., Jr.; Langhoff, Stephen R.; Taylor, Peter R.
1989-01-01
An important goal of quantum chemical calculations is to provide an understanding of chemical bonding and molecular electronic structure. A second goal, the prediction of energy differences to chemical accuracy, has been much harder to attain. First, the computational resources required to achieve such accuracy are very large, and second, it is not straightforward to demonstrate that an apparently accurate result, in terms of agreement with experiment, does not result from a cancellation of errors. Recent advances in electronic structure methodology, coupled with the power of vector supercomputers, have made it possible to solve a number of electronic structure problems exactly using the full configuration interaction (FCI) method within a subspace of the complete Hilbert space. These exact results can be used to benchmark approximate techniques that are applicable to a wider range of chemical and physical problems. The methodology of many-electron quantum chemistry is reviewed. Methods are considered in detail for performing FCI calculations. The application of FCI methods to several three-electron problems in molecular physics are discussed. A number of benchmark applications of FCI wave functions are described. Atomic basis sets and the development of improved methods for handling very large basis sets are discussed: these are then applied to a number of chemical and spectroscopic problems; to transition metals; and to problems involving potential energy surfaces. Although the experiences described give considerable grounds for optimism about the general ability to perform accurate calculations, there are several problems that have proved less tractable, at least with current computer resources, and these and possible solutions are discussed.
NASA Astrophysics Data System (ADS)
1995-08-01
about the distances to galaxies and thereby about the expansion rate of the Universe. A simple way to determine the distance to a remote galaxy is by measuring its redshift, calculate its velocity from the redshift and divide this by the Hubble constant, H0. For instance, the measured redshift of the parent galaxy of SN 1995K (0.478) yields a velocity of 116,000 km/sec, somewhat more than one-third of the speed of light (300,000 km/sec). From the universal expansion rate, described by the Hubble constant (H0 = 20 km/sec per million lightyears as found by some studies), this velocity would indicate a distance to the supernova and its parent galaxy of about 5,800 million lightyears. The explosion of the supernova would thus have taken place 5,800 million years ago, i.e. about 1,000 million years before the solar system was formed. However, such a simple calculation works only for relatively ``nearby'' objects, perhaps out to some hundred million lightyears. When we look much further into space, we also look far back in time and it is not excluded that the universal expansion rate, i.e. the Hubble constant, may have been different at earlier epochs. This means that unless we know the change of the Hubble constant with time, we cannot determine reliable distances of distant galaxies from their measured redshifts and velocities. At the same time, knowledge about such change or lack of the same will provide unique information about the time elapsed since the Universe began to expand (the ``Big Bang''), that is, the age of the Universe and also its ultimate fate. The Deceleration Parameter q0 Cosmologists are therefore eager to determine not only the current expansion rate (i.e., the Hubble constant, H0) but also its possible change with time (known as the deceleration parameter, q0). Although a highly accurate value of H0 has still not become available, increasing attention is now given to the observational determination of the second parameter, cf. also the Appendix at the
Kushkuley, Boris; Stavrov, Solomon S.
1997-01-01
The quantum chemical calculations, vibronic theory of activation, and London-Pople approach are used to study the dependence of the C-O vibrational frequency, 17O isotropic chemical shift, and nuclear quadrupole coupling constant on the distortion of the porphyrin ring and geometry of the CO coordination, changes in the iron-carbon and iron-imidazole distances, magnitude of the iron displacement out of the porphyrin plane, and presence of the charged groups in the heme environment. It is shown that only the electrostatic interactions can cause the variation of all these parameters experimentally observed in different heme proteins, and the heme distortions could modulate this variation. The correlations between the theoretically calculated parameters are shown to be close to the experimentally observed ones. The study of the effect of the electric field of the distal histidine shows that the presence of the four C-O vibrational bands in the infrared absorption spectra of the carbon monoxide complexes of different myoglobins and hemoglobins can be caused by the different orientations of the different tautomeric forms of the distal histidine. The dependence of the 17O isotropic chemical shift and nuclear quadrupole coupling constant on pH and the distal histidine substitution can be also explained from the same point of view. PMID:9017215
Casa, G.; Castrillo, A.; Galzerano, G.; Wehr, R.; Merlone, A.; Di Serafino, D.; Laporta, P.; Gianfrani, L.
2008-05-23
We report on a new optical implementation of primary gas thermometry based on laser-absorption spectrometry in the near infrared. The method consists in retrieving the Doppler broadening from highly accurate observations of the line shape of the R(12) {nu}{sub 1}+2{nu}{sub 2}{sup 0}+{nu}{sub 3} transition in CO{sub 2} gas at thermodynamic equilibrium. Doppler width measurements as a function of gas temperature, ranging between the triple point of water and the gallium melting point, allowed for a spectroscopic determination of the Boltzmann constant with a relative accuracy of {approx}1.6x10{sup -4}.
Connecting Fundamental Constants
Di Mario, D.
2008-05-29
A model for a black hole electron is built from three basic constants only: h, c and G. The result is a description of the electron with its mass and charge. The nature of this black hole seems to fit the properties of the Planck particle and new relationships among basic constants are possible. The time dilation factor in a black hole associated with a variable gravitational field would appear to us as a charge; on the other hand the Planck time is acting as a time gap drastically limiting what we are able to measure and its dimension will appear in some quantities. This is why the Planck time is numerically very close to the gravitational/electric force ratio in an electron: its difference, disregarding a {pi}{radical}(2) factor, is only 0.2%. This is not a coincidence, it is always the same particle and the small difference is between a rotating and a non-rotating particle. The determination of its rotational speed yields accurate numbers for many quantities, including the fine structure constant and the electron magnetic moment.
Tully, R B
1993-06-01
Five methods of estimating distances have demonstrated internal reproducibility at the level of 5-20% rms accuracy. The best of these are the cepheid (and RR Lyrae), planetary nebulae, and surface-brightness fluctuation techniques. Luminosity-line width and Dn-sigma methods are less accurate for an individual case but can be applied to large numbers of galaxies. The agreement is excellent between these five procedures. It is determined that Hubble constant H0 = 90 +/- 10 km.s-1.Mpc-1 [1 parsec (pc) = 3.09 x 10(16) m]. It is difficult to reconcile this value with the preferred world model even in the low-density case. The standard model with Omega = 1 may be excluded unless there is something totally misunderstood about the foundation of the distance scale or the ages of stars. PMID:11607391
Tully, R B
1993-01-01
Five methods of estimating distances have demonstrated internal reproducibility at the level of 5-20% rms accuracy. The best of these are the cepheid (and RR Lyrae), planetary nebulae, and surface-brightness fluctuation techniques. Luminosity-line width and Dn-sigma methods are less accurate for an individual case but can be applied to large numbers of galaxies. The agreement is excellent between these five procedures. It is determined that Hubble constant H0 = 90 +/- 10 km.s-1.Mpc-1 [1 parsec (pc) = 3.09 x 10(16) m]. It is difficult to reconcile this value with the preferred world model even in the low-density case. The standard model with Omega = 1 may be excluded unless there is something totally misunderstood about the foundation of the distance scale or the ages of stars. PMID:11607391
NASA Technical Reports Server (NTRS)
Parkinson, W. H.; Yoshino, K.; Freeman, D. E.
1988-01-01
Progress is given on work on: cross section measurements in the transmission window regions of the Schumann-Runge bands of oxygen; the determinations of predissociation linewidths; the theoretical calculation of band oscillator strengths of the Schumann-Runge absorption bands of O-16O-18; the determination of molecular spectroscopic constants; and the combined Herzberg continuum cross sections. The experimental investigations relevant to the cross section measurements, predissociation linewidths, and molecular spectroscopic constants are effected at high resolution with a 6.65 m scanning spectrometer which is, by virtue of its small instrumental width (FWHM = 0.0013 nm), suitable for cross section measurements of molecular bands with discrete rotational structure. Such measurements are needed for accurate calculations of the stratospheric production of atomic oxygen and heavy ozone formed following the photo-predissociation of O-16O-18 by solar radiation penetrating between the absorption lines of O-16(sub 2).
Infrared Spectra and Optical Constants of Astronomical Ices: II. Ethane and Ethylene
NASA Technical Reports Server (NTRS)
Hudson, Reggie L.; Gerakines, Perry A.; Moore, M. H.
2014-01-01
Infrared spectroscopic observations have established the presence of hydrocarbon ices on Pluto and other TNOs, but the abundances of such molecules cannot be deduced without accurate optical constants (n, k) and reference spectra. In this paper we present our recent measurements of near- and mid-infrared optical constants for ethane (C2H6) and ethylene (C2H4) in multiple ice phases and at multiple temperatures. As in our recent work on acetylene (C2H2), we also report new measurements of the index of refraction of each ice at 670 nm. Comparisons are made to earlier work where possible, and electronic versions of our new results are made available.
Infrared spectra and optical constants of astronomical ices: II. Ethane and ethylene
NASA Astrophysics Data System (ADS)
Hudson, R. L.; Gerakines, P. A.; Moore, M. H.
2014-11-01
Infrared spectroscopic observations have established the presence of hydrocarbon ices on Pluto and other TNOs, but the abundances of such molecules cannot be deduced without accurate optical constants (n, k) and reference spectra. In this paper we present our recent measurements of near- and mid-infrared optical constants for ethane (C2H6) and ethylene (C2H4) in multiple ice phases and at multiple temperatures. As in our recent work on acetylene (C2H2), we also report new measurements of the index of refraction of each ice at 670 nm. Comparisons are made to earlier work where possible, and electronic versions of our new results are made available.
A procedure for computing accurate ab initio quartic force fields: Application to HO2+ and H2O
NASA Astrophysics Data System (ADS)
Huang, Xinchuan; Lee, Timothy J.
2008-07-01
A procedure for the calculation of molecular quartic force fields (QFFs) is proposed and investigated. The goal is to generate highly accurate ab initio QFFs that include many of the so-called ``small'' effects that are necessary to achieve high accuracy. The small effects investigated in the present study include correlation of the core electrons (core correlation), extrapolation to the one-particle basis set limit, correction for scalar relativistic contributions, correction for higher-order correlation effects, and inclusion of diffuse functions in the one-particle basis set. The procedure is flexible enough to allow for some effects to be computed directly, while others may be added as corrections. A single grid of points is used and is centered about an initial reference geometry that is designed to be as close as possible to the final ab initio equilibrium structure (with all effects included). It is shown that the least-squares fit of the QFF is not compromised by the added corrections, and the balance between elimination of contamination from higher-order force constants while retaining energy differences large enough to yield meaningful quartic force constants is essentially unchanged from the standard procedures we have used for many years. The initial QFF determined from the least-squares fit is transformed to the exact minimum in order to eliminate gradient terms and allow for the use of second-order perturbation theory for evaluation of spectroscopic constants. It is shown that this step has essentially no effect on the quality of the QFF largely because the initial reference structure is, by design, very close to the final ab initio equilibrium structure. The procedure is used to compute an accurate, purely ab initio QFF for the H2O molecule, which is used as a benchmark test case. The procedure is then applied to the ground and first excited electronic states of the HO2+ molecular cation. Fundamental vibrational frequencies and spectroscopic
Relation between spectroscopic constants with limited Dunham coefficients
NASA Astrophysics Data System (ADS)
Chandra, Suresh
2005-12-01
Statement of Kaur and Mahajan [1] about the definition of Delta used by Chandra [2] is not correct. Even if we take Delta = mu omega_e^2 r_e^2/2 D_e, the relation between Delta and G(=8 omega_e x_e/B_e) is obtained as Delta = 4.21452856 G, provided the vibrational energy of a diatomic molecule is expressed in terms of limited Dunham coefficients, Y_{10}, Y_{20}, Y_{01} and Y_{11}. This relation is still different from that of Kaur and Mahajan [3].
Monitoring spectroscopic binaries in anticipation of Gaia
NASA Astrophysics Data System (ADS)
Pourbaix, Dimitri; Halbwachs, Jean-Louis; Arenou, Frederic
2015-08-01
For several already known spectroscopic binaries, it is anticipated that Gaia will provide an exquisite astrometric orbit of the photocenter. In case of double-lined spectroscopic binaries, the orbital inclination supplied by Gaia will lead to the mass of both components.. For those masses to be useful, an accuracy of 2-3% is required. This can only be achieved if the spectroscopic orbit is very accurate too. A long term monitoring of good spectroscopic candidates in on going on Sophie at the Observatory of Haute Provence and on Hermes on the Mercator telescope in La Palma. For some of these systems, we have already derived a definitive SB2 orbital solution while, for others, the secondary remains unreachable. We present these new solutions in conjunction with the possible impact on the Hipparcos astrometric solution.
Accurate rest-frequencies of ketenimine (CH2CNH) at submillimetre wavelength
NASA Astrophysics Data System (ADS)
Degli Esposti, C.; Dore, L.; Bizzocchi, L.
2014-05-01
Context. Imine compounds are thought to have a role in the interstellar formation of complex organic species, including pre-biotic molecules. Ketenimine (CH2CNH) is one of the four imines discovered in space. It was identified in Sgr B2(N-LMH) through the detection of three rotational lines in absorption. Aims: We present an extensive laboratory study of the ground-state rotational spectrum of CH2CNH at submillimetre wavelengths, aimed at obtaining accurate rest-frequencies for radio-astronomical searches. Methods: The investigation was carried out using a source-modulation microwave spectrometer equipped with a cell that is coupled to a pyrolysis apparatus working at 1000°. The spectrum was recorded in the frequency range 80-620 GHz with the detection of 150 transitions. Results: The newly measured transition frequencies were analysed with previously available microwave and far-infrared data, yielding accurate rotational constants of CH2CNH, the complete sets of quartic and sextic centrifugal distortion constants, and three octic constants. Several transitions exhibit a hyperfine structure due to the quadrupole and spin-rotation couplings of the 14N nucleus, which were accounted for in the analysis. Conclusions: The determined spectroscopic constants allowed for the computation of a list of highly accurate rest-frequencies for astrophysical purposes in the submillimetre and THz region with 1σ uncertainties that are lower than 0.1 km s-1 in radial equivalent velocity. Full Tables 1 and 3 are only available at the CDS via anonymous ftp to http://cdsarc.u-strasbg.fr (ftp://130.79.128.5) or via http://cdsarc.u-strasbg.fr/viz-bin/qcat?J/A+A/565/A66
NASA Astrophysics Data System (ADS)
Elliott, Ben M.; Sung, Keeyoon; Miller, Charles E.
2015-06-01
In this report, we extend our Fourier transform infrared (FT-IR) spectroscopy measurements of CO2 in the ν3 region (2200-2450 cm-1, 65-75 THz) to the 18O-, and 13C-substituted isotopologues, using the JPL Bruker IFS-125HR Fourier Transform Spectrometer (JPL-FTS). High quality (S/N ∼ 2000) spectra were obtained separately for each of the 18O-, and 13C-isotopically enriched samples. The absolute wavenumber accuracies were better than 3 × 10-6 cm-1 (∼100 kHz) for strong, isolated transitions, calibrated against the highest accuracy reported CO and 16O12C16O (626) frequency measurements. The JPL-FTS performance and calibration procedure is shown to be reliable and consistent, achievable through vigorous maintenance of the optical alignment and regular monitoring of its instrumental line shape function. Effective spectroscopic constant fits of the 00011 ← 00001 fundamental bands for 16O12C18O (628), 18O12C18O (828), and 16O13C16O (636) were obtained with RMS residuals of 2.9 × 10-6 cm-1, 2.8 × 10-6 cm-1, and 2.9 × 10-6 cm-1, respectively. The observed bands encompassed 79 lines over the Jmax range of P67/R67, 47 lines over P70/R62, and 60 lines over P70/R70 for 628, 828, and 636, respectively. These results complement our recent work on the 17O-enriched isotopologues (Elliott et al., 2014), providing additional high-quality frequency measurements for atmospheric remote sensing applications.
Infrared Spectra and Optical Constants of Acetylene and Ethane Ices
NASA Astrophysics Data System (ADS)
Moore, Marla H.; Ferrante, R. F.; Hudson, R. L.; Moore, W. J.
2012-10-01
Hydrocarbon-containing ices have characteristic absorption bands in both the mid- and near-infrared spectral regions, yet accurate optical constants are not available for most of these molecules. Ices with a hydrocarbon component have been identified on several TNOs (1) and the presence of volatiles, such as hydrocarbons, is inferred for intermediate or large TNOs based on sublimation models (2, 3). In our laboratory we recently have undertaken low-temperature spectroscopic studies of C2 hydrocarbons. We report IR spectra for acetylene (C2H2) and ethane (C2H6) ice in both the amorphous and crystalline phases at multiple temperatures. We include measurements of the refractive index at 670 nm for both the amorphous and crystalline phases of each ice. The optical constants, the real (n) and imaginary (k) components of the complex index of refraction, were determined from 7000 - 400 cm-1 (1.4 - 25 microns) at multiple temperatures using a Kramers-Kronig analysis. A goal of the present work is to provide a data base of optical constants of C2 molecules similar to that of Hudgins et al. (4) and Moore et al. (5). These values, as well as our calculated individual band strengths, will have great practical importance for the ongoing analysis of TNO spectra. (1) Brown, M.E. et al., Astron J., 133, 284, 2007. (2) Delsanti, A. et al., A&A, 52, A40, 2010. (3) Schaller, E. L. & Brown, M. E., ApJ, 659, L61, 2007. (4) Hudgins, D. M. et al., ApJS, 86, 713, 1993. (5) Moore, M. H. et al., ApJS, 191, 96, 2010. This work is supported by NASA’s Planetary Atmospheres, Outer Planets, and Cassini Data Analysis programs, and The Goddard Center for Astrobiology.
NASA Astrophysics Data System (ADS)
Townley-Smith, Keeley; Nave, Gillian; Imperial College London
2016-01-01
There is an on-going project in the Atomic Spectroscopy Group at NIST to obtain comprehensive spectral data for all of the singly ionized iron group elements and acquire more accurate energy levels, wavelengths and hyperfine structure (HFS) constants. The heavy abundance of the iron group elements and their contributions to a wide range of stellar spectra makes them of interest for astrophysical observations.Existing spectroscopic data for Mn are insufficient to model spectra obtained from HgMn stars such as HD 175640. Since manganese has an odd number of nucleons, its spectral lines generally exhibit HFS, a relativistic effect due to interaction between the magnetic moment of the nucleus and the orbiting electrons. If proper treatment of line broadening effects such as HFS is not taken, there is a poor fit of the lines in stellar spectra, leading to an overestimate of the abundance of Mn. The abnormally high abundance of manganese in HgMn stars means both weak and strong transitions are important. Weak lines may not be observed in the laboratory, but HFS constants for them can be derived from stronger transitions that combine with the two levels involved in the weak transition.Holt et al. (1999) measured HFS constants for 56 energy levels using laser spectroscopy. We have analyzed Fourier Transform spectra of a high current Mn/Ni hollow cathode lamp to obtain magnetic dipole A constants levels of Mn II. The A constants of Holt et al. (1999, MNRAS 306, 1007) for the z5P, z7P2, a5P and z5F levels were the starting point for our analysis, from which we derived A constants for 71 energy levels, including 51 previously unstudied levels. Our A constant for the a7S3 ground level differs by 5x10-4 cm-1 from that of Blackwell-Whitehead et al. (2005, ApJS 157, 402) and has a factor of 6 lower uncertainty.
Accurate rotational rest-frequencies of CH2NH at submillimetre wavelengths
NASA Astrophysics Data System (ADS)
Dore, L.; Bizzocchi, L.; Degli Esposti, C.
2012-08-01
Context. Methanimine (CH2NH) has been detected in different astronomical sources, both galactic (as in several "hot cores", the circumstellar enevolope IRC+10216, and the L183 pre-stellar core) and extragalactic, and is considered a pre-biotic interstellar molecule. Its ground-state rotational spectrum has been studied in the laboratory up to 172 GHz, well below the spectral ranges covered by Herschel/HIFI and the ALMA bands 9 and 10. Aims: In this laboratory study, we extend into the submillimetre-wave region the detection of the rotational spectrum of CH2NH in its vibrational ground state. Methods: The investigation was carried out using a source-modulation microwave spectrometer equipped with a cell coupled to a pyrolysis apparatus working at 1150 °C. The spectrum was recorded in the frequency range 329-629 GHz, with the detection of 58 transitions. Results: The newly measured transition frequencies, along with those available from previous microwave studies, allow us to determine fairly accurate rotational constants of CH2NH and the complete sets of quartic and sextic centrifugal distortion constants, in addition to two octic constants. Several transitions have an hyperfine structure due to the 14N nucleus, which was accounted for in the analysis. Conclusions: The determined spectroscopic constants make it possible to build a list of very accurate rest-frequencies for astrophysical purposes in the THz region with 1σ uncertainties lower than 0.01 km s-1 in radial equivalent velocity. Table 1 is only available at the CDS via anonymous ftp to cdsarc.u-strasbg.fr (130.79.128.5) or via http://cdsarc.u-strasbg.fr/viz-bin/qcat?J/A+A/544/A19
NASA Technical Reports Server (NTRS)
Bailey, David H.; Borwein, Jonathan M.; Crandall, Richard E.; Craw, James M. (Technical Monitor)
1995-01-01
We prove known identities for the Khinchin constant and develop new identities for the more general Hoelder mean limits of continued fractions. Any of these constants can be developed as a rapidly converging series involving values of the Riemann zeta function and rational coefficients. Such identities allow for efficient numerical evaluation of the relevant constants. We present free-parameter, optimizable versions of the identities, and report numerical results.
Solar constant secular changes
NASA Technical Reports Server (NTRS)
Schatten, Kenneth H.; Orosz, Jerome A.
1990-01-01
A recent model for solar constant secular changes is used to calculate a 'proxy' solar constant for: (1) the past four centuries, based upon the sunspot record, (2) the past nine centuries, based upon C-14 observations and their relation to solar activity, and (3) the next decade, based upon a dynamo theory model for the solar cycle. The proxy solar constant data is tabulated as it may be useful for climate modelers studying global climate changes.
ERIC Educational Resources Information Center
Rom, Mark Carl
2011-01-01
Grades matter. College grading systems, however, are often ad hoc and prone to mistakes. This essay focuses on one factor that contributes to high-quality grading systems: grading accuracy (or "efficiency"). I proceed in several steps. First, I discuss the elements of "efficient" (i.e., accurate) grading. Next, I present analytical results…
Fundamental Physical Constants
National Institute of Standards and Technology Data Gateway
SRD 121 CODATA Fundamental Physical Constants (Web, free access) This site, developed in the Physics Laboratory at NIST, addresses three topics: fundamental physical constants, the International System of Units (SI), which is the modern metric system, and expressing the uncertainty of measurement results.
Accurate monotone cubic interpolation
NASA Technical Reports Server (NTRS)
Huynh, Hung T.
1991-01-01
Monotone piecewise cubic interpolants are simple and effective. They are generally third-order accurate, except near strict local extrema where accuracy degenerates to second-order due to the monotonicity constraint. Algorithms for piecewise cubic interpolants, which preserve monotonicity as well as uniform third and fourth-order accuracy are presented. The gain of accuracy is obtained by relaxing the monotonicity constraint in a geometric framework in which the median function plays a crucial role.
Accurate Finite Difference Algorithms
NASA Technical Reports Server (NTRS)
Goodrich, John W.
1996-01-01
Two families of finite difference algorithms for computational aeroacoustics are presented and compared. All of the algorithms are single step explicit methods, they have the same order of accuracy in both space and time, with examples up to eleventh order, and they have multidimensional extensions. One of the algorithm families has spectral like high resolution. Propagation with high order and high resolution algorithms can produce accurate results after O(10(exp 6)) periods of propagation with eight grid points per wavelength.
Space Shuttle astrodynamical constants
NASA Technical Reports Server (NTRS)
Cockrell, B. F.; Williamson, B.
1978-01-01
Basic space shuttle astrodynamic constants are reported for use in mission planning and construction of ground and onboard software input loads. The data included here are provided to facilitate the use of consistent numerical values throughout the project.
NASA Astrophysics Data System (ADS)
Senent, M. L.; Dumouchel, F.; Lique, F.
2012-02-01
Modelling molecular abundances in the interstellar medium requires accurate molecular data. In this work, structural and spectroscopic properties of a series of metal cyanides/isocyanide species containing Na, Mg, Al and Si are calculated and compared using highly correlated ab initio calculations. The metal substitution effect on molecular properties is discussed. Isomerization pathways and transitions states are detailed. NaCN shows three isomeric structures, one T shaped and two linear forms, whereas the remaining compounds display two linear minimum energy geometries. For the first time, NaCN secondary minima are described. Second-order perturbation theory spectroscopic parameters are determined from an anharmonic RCCSD(T)/aug-cc-pV5Z force field. Very accurate rotational constants are calculated using a complete basis set and taking into account vibrational effects and the structure variation with core electron correlation. For l-SiCN and l-SiNC, spin-orbit parameters are also provided. Present theoretical results are compared with available experimental data attaining a good agreement.
Constant potential pulse polarography
Christie, J.H.; Jackson, L.L.; Osteryoung, R.A.
1976-01-01
The new technique of constant potential pulse polarography, In which all pulses are to be the same potential, is presented theoretically and evaluated experimentally. The response obtained is in the form of a faradaic current wave superimposed on a constant capacitative component. Results obtained with a computer-controlled system exhibit a capillary response current similar to that observed In normal pulse polarography. Calibration curves for Pb obtained using a modified commercial pulse polarographic instrument are in good accord with theoretical predictions.
Absolute radiometry and the solar constant
NASA Technical Reports Server (NTRS)
Willson, R. C.
1974-01-01
A series of active cavity radiometers (ACRs) are described which have been developed as standard detectors for the accurate measurement of irradiance in absolute units. It is noted that the ACR is an electrical substitution calorimeter, is designed for automatic remote operation in any environment, and can make irradiance measurements in the range from low-level IR fluxes up to 30 solar constants with small absolute uncertainty. The instrument operates in a differential mode by chopping the radiant flux to be measured at a slow rate, and irradiance is determined from two electrical power measurements together with the instrumental constant. Results are reported for measurements of the solar constant with two types of ACRs. The more accurate measurement yielded a value of 136.6 plus or minus 0.7 mW/sq cm (1.958 plus or minus 0.010 cal/sq cm per min).
Spectroscopic Sensitivity Workout: First-order modes
NASA Astrophysics Data System (ADS)
Brown, Thomas
2001-07-01
This program is the basic sensitivity measurement for all supported MAMA and CCD first-order spectroscopic modes. It is run once in Cycle 10. Sensitivity measurements are done for all supported tilts of the gratings, at a S/N suitable to any particular setting, in order to get all measurements done in a reasonable number of orbits but still get a very accurate sensitivity measurement. Data for the newly available "pseudo-apertures" near CCD row 900 are also taken.
NASA Astrophysics Data System (ADS)
Itano, Wayne M.; Ramsey, Norman F.
1993-07-01
The paper discusses current methods for accurate measurements of time by conventional atomic clocks, with particular attention given to the principles of operation of atomic-beam frequency standards, atomic hydrogen masers, and atomic fountain and to the potential use of strings of trapped mercury ions as a time device more stable than conventional atomic clocks. The areas of application of the ultraprecise and ultrastable time-measuring devices that tax the capacity of modern atomic clocks include radio astronomy and tests of relativity. The paper also discusses practical applications of ultraprecise clocks, such as navigation of space vehicles and pinpointing the exact position of ships and other objects on earth using the GPS.
Spectroscopic Studies of Abell Clusters
NASA Astrophysics Data System (ADS)
Way, Michael Joseph
The objectives of this work are to use spectroscopic techniques to accurately categorize galaxies as either HII region star forming galaxies or as Active Galactic Nuclei powered via a black hole, and to use radial velocities and projected positions of galaxies in clusters to obtain the total cluster mass and its distribution. The masses and distributions compare well to X-ray mass measurements. The commonly used Dressler, A., Thompson, I. & Shectman, S. 1985, ApJ, 288, 481 technique for discriminating between Active Galactic Nuclei and HII region galaxies uses the measurement of the equivalent width of the emission lines (OII) 3727 A, H/beta, and (OIII) 5007 A. High quality spectra from 42 galaxies were taken and it is shown that their method is not capable of distinguishing between Active Galactic Nuclei and HII region galaxies. The emission line flux from H/beta, (OIII) 5007 A, (OI) 6300 A, Hα, (NII) 6583 A, and (SII) 6716+6731 A in combination with the method of Veilleux, S. & Osterbrock, D. E. 1987, ApJS, 63, 295 must be used to accurately distinguish between Active Galactic Nuclei and HII region galaxies. Galaxy radial velocities from spectroscopic data and their projected 2-D positions in clusters are used to obtain robust estimates of the total mass and mass distribution in two clusters. The total mass is calculated using the Virial theorem after removing substructure. The mass distribution is estimated via several robust statistical tests for 1-D, 2-D and 3-D structure. It is shown that the derived mass estimates agree well with those found independently from hot X-ray gas emission in clusters.
Dielectric Constant of Suspensions
NASA Astrophysics Data System (ADS)
Mendelson, Kenneth S.; Ackmann, James J.
1997-03-01
We have used a finite element method to calculate the dielectric constant of a cubic array of spheres. Extensive calculations support preliminary conclusions reported previously (K. Mendelson and J. Ackmann, Bull. Am. Phys. Soc. 41), 657 (1996).. At frequencies below 100 kHz the real part of the dielectric constant (ɛ') shows oscillations as a function of the volume fraction of suspension. These oscillations disappear at low conductivities of the suspending fluid. Measurements of the dielectric constant (J. Ackmann, et al., Ann. Biomed. Eng. 24), 58 (1996). (H. Fricke and H. Curtis, J. Phys. Chem. 41), 729 (1937). are not sufficiently sensitive to show oscillations but appear to be consistent with the theoretical results.
Peselnick, L.; Robie, R.A.
1962-01-01
The recent measurements of the elastic constants of calcite by Reddy and Subrahmanyam (1960) disagree with the values obtained independently by Voigt (1910) and Bhimasenachar (1945). The present authors, using an ultrasonic pulse technique at 3 Mc and 25??C, determined the elastic constants of calcite using the exact equations governing the wave velocities in the single crystal. The results are C11=13.7, C33=8.11, C44=3.50, C12=4.82, C13=5.68, and C14=-2.00, in units of 1011 dyncm2. Independent checks of several of the elastic constants were made employing other directions and polarizations of the wave velocities. With the exception of C13, these values substantially agree with the data of Voigt and Bhimasenachar. ?? 1962 The American Institute of Physics.
New Quasar Studies Keep Fundamental Physical Constant Constant
NASA Astrophysics Data System (ADS)
2004-03-01
fundamental constant at play here, alpha. However, the observed distribution of the elements is consistent with calculations assuming that the value of alpha at that time was precisely the same as the value today. Over the 2 billion years, the change of alpha has therefore to be smaller than about 2 parts per 100 millions. If present at all, this is a rather small change indeed. But what about changes much earlier in the history of the Universe? To measure this we must find means to probe still further into the past. And this is where astronomy can help. Because, even though astronomers can't generally do experiments, the Universe itself is a huge atomic physics laboratory. By studying very remote objects, astronomers can look back over a long time span. In this way it becomes possible to test the values of the physical constants when the Universe had only 25% of is present age, that is, about 10,000 million years ago. Very far beacons To do so, astronomers rely on spectroscopy - the measurement of the properties of light emitted or absorbed by matter. When the light from a flame is observed through a prism, a rainbow is visible. When sprinkling salt on the flame, distinct yellow lines are superimposed on the usual colours of the rainbow, so-called emission lines. Putting a gas cell between the flame and the prism, one sees however dark lines onto the rainbow: these are absorption lines. The wavelength of these emission and absorption lines is directly related to the energy levels of the atoms in the salt or in the gas. Spectroscopy thus allows us to study atomic structure. The fine structure of atoms can be observed spectroscopically as the splitting of certain energy levels in those atoms. So if alpha were to change over time, the emission and absorption spectra of these atoms would change as well. One way to look for any changes in the value of alpha over the history of the Universe is therefore to measure the spectra of distant quasars, and compare the wavelengths of
Energy Science and Technology Software Center (ESTSC)
2005-06-20
This application (XrayOpticsConstants) is a tool for displaying X-ray and Optical properties for a given material, x-ray photon energy, and in the case of a gas, pressure. The display includes fields such as the photo-electric absorption attenuation length, density, material composition, index of refraction, and emission properties (for scintillator materials).
Impact of long-range wavelength-scale distortion on fine-structure constant measurements.
NASA Astrophysics Data System (ADS)
Dumont, Vincent; Webb, John Kelvin
2015-08-01
New ideas in unification theories suggest space-time variations of dimensionless physical constants may exist and that they might be within reach of current instrumental precision available from the world's best observatories. State-of-the-art observations already hint at such an effect. If confirmed, fundamental revisions in standard physics would be required.Accurate calibrations are of course crucial in searches for space-time variations of dimensionless physical constants using spectroscopic observations from the world's best observatories. Several recent studies reveal wavelength distortions in optical echelle spectrographs. These are not yet understood and they have not yet been measured using the actual science data used to derive constraints on space-time variation of alpha (critical since they appear to vary with time). In this work we study the impact of such distortions on measurements of the fine structure constant, alpha, observed at high redshift using high-resolution quasar spectroscopy.We have carried out extensive high-performance computing calculations that quantify the effect accurately for the first time, using the same quasar spectra used to measure alpha at high redshift. The spectra we use were obtained using the Keck telescope in Hawaii and the European Southern Observatory's VLT.We explain the detailed methodologies required, using instrumental configuration information from each wavelength setting used in forming a final summed spectrum. Our results show that whilst long-range wavelength-scale distortions do exist, and hence contribute an additional systematic error, these systematics (measured directly from the science exposures themselves) are small and unlikely to explain the spatial variations alpha of reported recently.
Olive, Keith A.; Peloso, Marco; Uzan, Jean-Philippe
2011-02-15
We consider the signatures of a domain wall produced in the spontaneous symmetry breaking involving a dilatonlike scalar field coupled to electromagnetism. Domains on either side of the wall exhibit slight differences in their respective values of the fine-structure constant, {alpha}. If such a wall is present within our Hubble volume, absorption spectra at large redshifts may or may not provide a variation in {alpha} relative to the terrestrial value, depending on our relative position with respect to the wall. This wall could resolve the contradiction between claims of a variation of {alpha} based on Keck/Hires data and of the constancy of {alpha} based on Very Large Telescope data. We derive the properties of the wall and the parameters of the underlying microscopic model required to reproduce the possible spatial variation of {alpha}. We discuss the constraints on the existence of the low-energy domain wall and describe its observational implications concerning the variation of the fundamental constants.
Renormalization of Newton's constant
NASA Astrophysics Data System (ADS)
Falls, Kevin
2015-12-01
The problem of obtaining a gauge independent beta function for Newton's constant is addressed. By a specific parametrization of metric fluctuations a gauge independent functional integral is constructed for the semiclassical theory around an arbitrary Einstein space. The effective action then has the property that only physical polarizations of the graviton contribute, while all other modes cancel with the functional measure. We are then able to compute a gauge independent beta function for Newton's constant in d dimensions to one-loop order. No Landau pole is present provided Ng<18 , where Ng=d (d -3 )/2 is the number of polarizations of the graviton. While adding a large number of matter fields can change this picture, the absence of a pole persists for the particle content of the standard model in four spacetime dimensions.
Varying constants quantum cosmology
Leszczyńska, Katarzyna; Balcerzak, Adam; Dabrowski, Mariusz P. E-mail: abalcerz@wmf.univ.szczecin.pl
2015-02-01
We discuss minisuperspace models within the framework of varying physical constants theories including Λ-term. In particular, we consider the varying speed of light (VSL) theory and varying gravitational constant theory (VG) using the specific ansätze for the variability of constants: c(a) = c{sub 0} a{sup n} and G(a)=G{sub 0} a{sup q}. We find that most of the varying c and G minisuperspace potentials are of the tunneling type which allows to use WKB approximation of quantum mechanics. Using this method we show that the probability of tunneling of the universe ''from nothing'' (a=0) to a Friedmann geometry with the scale factor a{sub t} is large for growing c models and is strongly suppressed for diminishing c models. As for G varying, the probability of tunneling is large for G diminishing, while it is small for G increasing. In general, both varying c and G change the probability of tunneling in comparison to the standard matter content (cosmological term, dust, radiation) universe models.
NASA Astrophysics Data System (ADS)
Jackson, Neal
2015-09-01
I review the current state of determinations of the Hubble constant, which gives the length scale of the Universe by relating the expansion velocity of objects to their distance. There are two broad categories of measurements. The first uses individual astrophysical objects which have some property that allows their intrinsic luminosity or size to be determined, or allows the determination of their distance by geometric means. The second category comprises the use of all-sky cosmic microwave background, or correlations between large samples of galaxies, to determine information about the geometry of the Universe and hence the Hubble constant, typically in a combination with other cosmological parameters. Many, but not all, object-based measurements give H_0 values of around 72-74 km s^-1 Mpc^-1, with typical errors of 2-3 km s^-1 Mpc^-1. This is in mild discrepancy with CMB-based measurements, in particular those from the Planck satellite, which give values of 67-68 km s^-1 Mpc^-1 and typical errors of 1-2 km s^-1 Mpc^-1. The size of the remaining systematics indicate that accuracy rather than precision is the remaining problem in a good determination of the Hubble constant. Whether a discrepancy exists, and whether new physics is needed to resolve it, depends on details of the systematics of the object-based methods, and also on the assumptions about other cosmological parameters and which datasets are combined in the case of the all-sky methods.
NASA Astrophysics Data System (ADS)
Bittner, Dror M.; Walker, Nicholas R.; Legon, Anthony C.
2016-02-01
A two force-constant model is proposed for complexes of the type B⋯MX, in which B is a simple Lewis base of at least C2v symmetry and MX is any diatomic molecule lying along a Cn axis (n ≥ 2) of B. The model assumes a rigid subunit B and that force constants beyond quadratic are negligible. It leads to expressions that allow, in principle, the determination of three quadratic force constants F11, F12, and F22 associated with the r(B⋯M) = r2 and r(M-X) = r1 internal coordinates from the equilibrium centrifugal distortion constants DJ e or ΔJ e , the equilibrium principal axis coordinates a1 and a2, and equilibrium principal moments of inertia. The model can be applied generally to complexes containing different types of intermolecular bond. For example, the intermolecular bond of B⋯MX can be a hydrogen bond if MX is a hydrogen halide, a halogen-bond if MX is a dihalogen molecule, or a stronger, coinage-metal bond if MX is a coinage metal halide. The equations were tested for BrCN, for which accurate equilibrium spectroscopic constants and a complete force field are available. In practice, equilibrium values of DJ e or ΔJ e for B⋯MX are not available and zero-point quantities must be used instead. The effect of doing so has been tested for BrCN. The zero-point centrifugal distortion constants DJ 0 or ΔJ 0 for all B⋯MX investigated so far are of insufficient accuracy to allow F11 and F22 to be determined simultaneously, even under the assumption F12 = 0 which is shown to be reasonable for BrCN. The calculation of F22 at a series of fixed values of F11 reveals, however, that in cases for which F11 is sufficiently larger than F22, a good approximation to F22 is obtained. Plots of F22 versus F11 have been provided for Kr⋯CuCl, Xe⋯CuCl, OC⋯CuCl, and C2H2⋯AgCl as examples. Even in cases where F22 ˜ F11 (e.g., OC⋯CuCl), such plots will yield either F22 or F11 if the other becomes available.
Bittner, Dror M; Walker, Nicholas R; Legon, Anthony C
2016-02-21
A two force-constant model is proposed for complexes of the type B⋯MX, in which B is a simple Lewis base of at least C2v symmetry and MX is any diatomic molecule lying along a Cn axis (n ≥ 2) of B. The model assumes a rigid subunit B and that force constants beyond quadratic are negligible. It leads to expressions that allow, in principle, the determination of three quadratic force constants F11, F12, and F22 associated with the r(B⋯M) = r2 and r(M-X) = r1 internal coordinates from the equilibrium centrifugal distortion constants DJ (e) or ΔJ (e), the equilibrium principal axis coordinates a1 and a2, and equilibrium principal moments of inertia. The model can be applied generally to complexes containing different types of intermolecular bond. For example, the intermolecular bond of B⋯MX can be a hydrogen bond if MX is a hydrogen halide, a halogen-bond if MX is a dihalogen molecule, or a stronger, coinage-metal bond if MX is a coinage metal halide. The equations were tested for BrCN, for which accurate equilibrium spectroscopic constants and a complete force field are available. In practice, equilibrium values of DJ (e) or ΔJ (e) for B⋯MX are not available and zero-point quantities must be used instead. The effect of doing so has been tested for BrCN. The zero-point centrifugal distortion constants DJ (0) or ΔJ (0) for all B⋯MX investigated so far are of insufficient accuracy to allow F11 and F22 to be determined simultaneously, even under the assumption F12 = 0 which is shown to be reasonable for BrCN. The calculation of F22 at a series of fixed values of F11 reveals, however, that in cases for which F11 is sufficiently larger than F22, a good approximation to F22 is obtained. Plots of F22 versus F11 have been provided for Kr⋯CuCl, Xe⋯CuCl, OC⋯CuCl, and C2H2⋯AgCl as examples. Even in cases where F22 ∼ F11 (e.g., OC⋯CuCl), such plots will yield either F22 or F11 if the other becomes available. PMID:26896987
Spectroscopic ellipsometry study of novel nanostructured transparent conducting oxide structures
NASA Astrophysics Data System (ADS)
Khosroabadi, Akram A.; Norwood, R. A.
2013-02-01
Spectroscopic ellipsometry has been used to find the optical constants, including refractive index, extinction coefficient, thickness and volume fraction of nanostructured transparent conducting oxides including indium tin oxide (ITO) and indium zinc oxide (IZO). We observed sharp features in the ellipsometry data, with the spectral peaks and positions depending on the nanostructure dimensions and material. A superposition of Lorentzian oscillators and the effective medium approximation has been applied to determine the volume ratio of voids and nanopillars, thereby providing the effective optical constants.
Effective optical constants of anisotropic materials
NASA Technical Reports Server (NTRS)
Aronson, J. R.; Emslie, A. G.
1980-01-01
The applicability of a technique for determining the optical constants of soil or aerosol components on the basis of measurements of the reflectance or transmittance of inhomogeneous samples of component material is investigated. Optical constants for a sample of very pure quartzite were obtained by a specular reflection technique and line parameters were calculated by classical dispersion theory. Predictions of the reflectance of powdered quartz were then derived from optical constants measured for the anisotropic quartz and for pure quartz crystals, and compared with experimental measurements. The calculated spectra are found to resemble each other moderately well in shape, however the reflectance level calculated from the psuedo-optical constants (quartzite) is consistently below that calculated from quartz values. The spectrum calculated from the quartz optical constants is also shown to represent the experimental nonrestrahlen features more accurately. It is thus concluded that although optical constants derived from inhomogeneous materials may represent the spectral features of a powdered sample qualitatively a quantitative fit to observed data is not likely.
RNA structure and scalar coupling constants
Tinoco, I. Jr.; Cai, Z.; Hines, J.V.; Landry, S.M.; SantaLucia, J. Jr.; Shen, L.X.; Varani, G.
1994-12-01
Signs and magnitudes of scalar coupling constants-spin-spin splittings-comprise a very large amount of data that can be used to establish the conformations of RNA molecules. Proton-proton and proton-phosphorus splittings have been used the most, but the availability of {sup 13}C-and {sup 15}N-labeled molecules allow many more coupling constants to be used for determining conformation. We will systematically consider the torsion angles that characterize a nucleotide unit and the coupling constants that depend on the values of these torsion angles. Karplus-type equations have been established relating many three-bond coupling constants to torsion angles. However, one- and two-bond coupling constants can also depend on conformation. Serianni and coworkers measured carbon-proton coupling constants in ribonucleosides and have calculated their values as a function of conformation. The signs of two-bond coupling can be very useful because it is easier to measure a sign than an accurate magnitude.
NASA Astrophysics Data System (ADS)
Lee, Timothy J.; Huang, Xinchuan; Fortenberry, Ryan C.; Schwenke, David W.
2013-06-01
Theoretical chemists have been computing vibrational and rovibrational spectra of small molecules for more than 40 years, but over the last decade the interest in this application has grown significantly. The increased interest in computing accurate rotational and rovibrational spectra for small molecules could not come at a better time, as NASA and ESA have begun to acquire a mountain of high-resolution spectra from the Herschel mission, and soon will from the SOFIA and JWST missions. In addition, the ground-based telescope, ALMA, has begun to acquire high-resolution spectra in the same time frame. Hence the need for highly accurate line lists for many small molecules, including their minor isotopologues, will only continue to increase. I will present the latest developments from our group on using the "Best Theory + High-Resolution Experimental Data" strategy to compute highly accurate rotational and rovibrational spectra for small molecules, including NH3, CO2, and SO2. I will also present the latest work from our group in producing purely ab initio line lists and spectroscopic constants for small molecules thought to exist in various astrophysical environments, but for which there is either limited or no high-resolution experimental data available. These more limited line lists include purely rotational transitions as well as rovibrational transitions for bands up through a few combination/overtones.
Spectroscopic infrared ellipsometry
NASA Astrophysics Data System (ADS)
Roseler, A.
1992-03-01
The spectroscopic infrared ellipsometry (SIRE) by means of the combination of a photometric ellipsometer with a Fourier transform spectrometer is used to measure optical properties in the infrared. From the observed four Stokes parameters, the spectrum of the degree of polarization after the reflection at the sample is calculated and discussed.
NASA Technical Reports Server (NTRS)
Madzsar, George C. (Inventor)
1993-01-01
The elemental composition of a material exposed to hot gases and subjected to wear is determined. Atoms of an elemental species not appearing in this material are implanted in a surface at a depth based on the maximum allowable wear. The exhaust gases are spectroscopically monitored to determine the exposure of these atoms when the maximum allowable wear is reached.
New model accurately predicts reformate composition
Ancheyta-Juarez, J.; Aguilar-Rodriguez, E. )
1994-01-31
Although naphtha reforming is a well-known process, the evolution of catalyst formulation, as well as new trends in gasoline specifications, have led to rapid evolution of the process, including: reactor design, regeneration mode, and operating conditions. Mathematical modeling of the reforming process is an increasingly important tool. It is fundamental to the proper design of new reactors and revamp of existing ones. Modeling can be used to optimize operating conditions, analyze the effects of process variables, and enhance unit performance. Instituto Mexicano del Petroleo has developed a model of the catalytic reforming process that accurately predicts reformate composition at the higher-severity conditions at which new reformers are being designed. The new AA model is more accurate than previous proposals because it takes into account the effects of temperature and pressure on the rate constants of each chemical reaction.
Accurate colorimetric feedback for RGB LED clusters
NASA Astrophysics Data System (ADS)
Man, Kwong; Ashdown, Ian
2006-08-01
We present an empirical model of LED emission spectra that is applicable to both InGaN and AlInGaP high-flux LEDs, and which accurately predicts their relative spectral power distributions over a wide range of LED junction temperatures. We further demonstrate with laboratory measurements that changes in LED spectral power distribution with temperature can be accurately predicted with first- or second-order equations. This provides the basis for a real-time colorimetric feedback system for RGB LED clusters that can maintain the chromaticity of white light at constant intensity to within +/-0.003 Δuv over a range of 45 degrees Celsius, and to within 0.01 Δuv when dimmed over an intensity range of 10:1.
Beiu, V.
1997-04-01
In this paper the authors discuss several complexity aspects pertaining to neural networks, commonly known as the curse of dimensionality. The focus will be on: (1) size complexity and depth-size tradeoffs; (2) complexity of learning; and (3) precision and limited interconnectivity. Results have been obtained for each of these problems when dealt with separately, but few things are known as to the links among them. They start by presenting known results and try to establish connections between them. These show that they are facing very difficult problems--exponential growth in either space (i.e. precision and size) and/or time (i.e., learning and depth)--when resorting to neural networks for solving general problems. The paper will present a solution for lowering some constants, by playing on the depth-size tradeoff.
Unitaxial constant velocity microactuator
McIntyre, Timothy J.
1994-01-01
A uniaxial drive system or microactuator capable of operating in an ultra-high vacuum environment. The mechanism includes a flexible coupling having a bore therethrough, and two clamp/pusher assemblies mounted in axial ends of the coupling. The clamp/pusher assemblies are energized by voltage-operated piezoelectrics therewithin to operatively engage the shaft and coupling causing the shaft to move along its rotational axis through the bore. The microactuator is capable of repeatably positioning to sub-manometer accuracy while affording a scan range in excess of 5 centimeters. Moreover, the microactuator generates smooth, constant velocity motion profiles while producing a drive thrust of greater than 10 pounds. The system is remotely controlled and piezoelectrically driven, hence minimal thermal loading, vibrational excitation, or outgassing is introduced to the operating environment.
NASA Technical Reports Server (NTRS)
Stevens, F W
1924-01-01
This report describes a new optical method of unusual simplicity and of good accuracy suitable to study the kinetics of gaseous reactions. The device is the complement of the spherical bomb of constant volume, and extends the applicability of the relationship, pv=rt for gaseous equilibrium conditions, to the use of both factors p and v. The method substitutes for the mechanical complications of a manometer placed at some distance from the seat of reaction the possibility of allowing the radiant effects of reaction to record themselves directly upon a sensitive film. It is possible the device may be of use in the study of the photoelectric effects of radiation. The method makes possible a greater precision in the measurement of normal flame velocities than was previously possible. An approximate analysis shows that the increase of pressure and density ahead of the flame is negligible until the velocity of the flame approaches that of sound.
Infrared spectrum and potential constants of silicon tetrafluoridea)
NASA Astrophysics Data System (ADS)
McDowell, Robin S.; Reisfeld, Martin J.; Patterson, Chris W.; Krohn, Burton J.; Vasquez, Mariena C.; Laguna, Glenn A.
1982-11-01
Doppler-limited tunable diode laser spectra of ν4 of 28SiF4 have been analyzed and the spectroscopic constants determined. In contrast to most earlier low-resolution studies, the Coriolis constant ζ4, when combined with ζ3 as obtained from previous laser spectroscopy, yields a zeta sum that is within 5% of the expected harmonic value of 1/2. The band origins of 12 overtones and combinations have been obtained from Fourier-transform spectra (0.04 cm-1 resolution), resulting in estimates of the anharmonicity constants and harmonic frequencies. From the Coriolis constants and the isotope shifts in ν3 we have redetermined the general quadratic force field of SiF4.
Spectroscopic Low Coherence Interferometry
NASA Astrophysics Data System (ADS)
Bosschaart, Nienke; van Leeuwen, T. G.; Aalders, Maurice C.; Hermann, Boris; Drexler, Wolfgang; Faber, Dirk J.
Low-coherence interferometry (LCI) allows high-resolution volumetric imaging of tissue morphology and provides localized optical properties that can be related to the physiological status of tissue. This chapter discusses the combination of spatial and spectroscopic information by means of spectroscopic OCT (sOCT) and low-coherence spectroscopy (LCS). We describe the theory behind these modalities for the assessment of spatially resolved optical absorption and (back)scattering coefficient spectra. These spectra can be used for the highly localized quantification of chromophore concentrations and assessment of tissue organization on (sub)cellular scales. This leads to a wealth of potential clinical applications, ranging from neonatology for the determination of billibrubin concentrations, to oncology for the optical assessment of the aggressiveness of a cancerous lesion.
Yaghlane, Saida Ben; Cotton, C. Eric; Francisco, Joseph S. E-mail: hochlaf@univ-mlv.fr; Linguerri, Roberto; Hochlaf, Majdi E-mail: hochlaf@univ-mlv.fr
2013-11-07
Accurate ab initio computations of structural and spectroscopic parameters for the HPS/HSP molecules and corresponding cations and anions have been performed. For the electronic structure computations, standard and explicitly correlated coupled cluster techniques in conjunction with large basis sets have been adopted. In particular, we present equilibrium geometries, rotational constants, harmonic vibrational frequencies, adiabatic ionization energies, electron affinities, and, for the neutral species, singlet-triplet relative energies. Besides, the full-dimensional potential energy surfaces (PESs) for HPS{sup x} and HSP{sup x} (x = −1,0,1) systems have been generated at the standard coupled cluster level with a basis set of augmented quintuple-zeta quality. By applying perturbation theory to the calculated PESs, an extended set of spectroscopic constants, including τ, first-order centrifugal distortion and anharmonic vibrational constants has been obtained. In addition, the potentials have been used in a variational approach to deduce the whole pattern of vibrational levels up to 4000 cm{sup −1} above the minima of the corresponding PESs.
Spectroscopically Unlocking Exoplanet Characteristics
NASA Astrophysics Data System (ADS)
Lewis, Nikole
2016-05-01
Spectroscopy plays a critical role in a number of areas of exoplanet research. The first exoplanets were detected by precisely measuring Doppler shifts in high resolution (R ~ 100,000) stellar spectra, a technique that has become known as the Radial Velocity (RV) method. The RV method provides critical constraints on exoplanet masses, but is currently limited to some degree by robust line shape predictions. Beyond the RV method, spectroscopy plays a critical role in the characterization of exoplanets beyond their mass and radius. The Hubble Space Telescope has spectroscopically observed the atmospheres of exoplanets that transit their host stars as seen from Earth giving us key insights into atmospheric abundances of key atomic and molecular species as well as cloud optical properties. Similar spectroscopic characterization of exoplanet atmospheres will be carried out at higher resolution (R ~ 100-3000) and with broader wavelength coverage with the James Webb Space Telescope. Future missions such as WFIRST that seek to the pave the way toward the detection and characterization of potentially habitable planets will have the capability of directly measuring the spectra of exoplanet atmospheres and potentially surfaces. Our ability to plan for and interpret spectra from exoplanets relies heavily on the fidelity of the spectroscopic databases available and would greatly benefit from further laboratory and theoretical work aimed at optical properties of atomic, molecular, and cloud/haze species in the pressure and temperature regimes relevant to exoplanet atmospheres.
The STIS CCD Spectroscopic Line Spread Functions
NASA Technical Reports Server (NTRS)
Gull, T.; Lindler, D.; Tennant, D.; Bowers, C.; Grady, C.; Hill, R. S.; Malumuth, E.
2002-01-01
We characterize the spectroscopic line spread functions of the spectroscopic CCD modes for high contrast objects. Our long range goal is to develop tools that accurately extract spectroscopic information of faint, point or extended sources in the vicinity of bright, point sources at separations approaching the realizable angular limits of HST with STIS. Diffracted and scattered light due to the HST optics, and scattered light effects within the STIS are addressed. Filter fringing, CCD fringing, window reflections, and scattering within the detector and other effects are noted. We have obtained spectra of several reference stars, used for flux calibration or for coronagraphic standards, that have spectral distributions ranging from very red to very blue. Spectra of each star were recorded with the star in the aperture and with the star blocked by either the F1 or F2 fiducial. Plots of the detected starlight along the spatial axis of the aperture are provided for four stars. With the star in the aperture, the line spread function is quite noticeable. Placing the star behind one of the fiducials cuts the scattered light and the diffracted light, is detectable even out to 1OOOOA. When the star is placed behind either fiducial, the scattered and diffracted light components, at three arcseconds displacement from the star, are below lop6 the peak of the star at wavelengths below 6000A; at the same angular distance, scattered light does contaminate the background longward of 6000A up to a level of 10(exp -5).
Planck Constant Determination from Power Equivalence
NASA Astrophysics Data System (ADS)
Newell, David B.
2000-04-01
Equating mechanical to electrical power links the kilogram, the meter, and the second to the practical realizations of the ohm and the volt derived from the quantum Hall and the Josephson effects, yielding an SI determination of the Planck constant. The NIST watt balance uses this power equivalence principle, and in 1998 measured the Planck constant with a combined relative standard uncertainty of 8.7 x 10-8, the most accurate determination to date. The next generation of the NIST watt balance is now being assembled. Modification to the experimental facilities have been made to reduce the uncertainty components from vibrations and electromagnetic interference. A vacuum chamber has been installed to reduce the uncertainty components associated with performing the experiment in air. Most of the apparatus is in place and diagnostic testing of the balance should begin this year. Once a combined relative standard uncertainty of one part in 10-8 has been reached, the power equivalence principle can be used to monitor the possible drift in the artifact mass standard, the kilogram, and provide an accurate alternative definition of mass in terms of fundamental constants. *Electricity Division, Electronics and Electrical Engineering Laboratory, Technology Administration, U.S. Department of Commerce. Contribution of the National Institute of Standards and Technology, not subject to copyright in the U.S.
NNLOPS accurate associated HW production
NASA Astrophysics Data System (ADS)
Astill, William; Bizon, Wojciech; Re, Emanuele; Zanderighi, Giulia
2016-06-01
We present a next-to-next-to-leading order accurate description of associated HW production consistently matched to a parton shower. The method is based on reweighting events obtained with the HW plus one jet NLO accurate calculation implemented in POWHEG, extended with the MiNLO procedure, to reproduce NNLO accurate Born distributions. Since the Born kinematics is more complex than the cases treated before, we use a parametrization of the Collins-Soper angles to reduce the number of variables required for the reweighting. We present phenomenological results at 13 TeV, with cuts suggested by the Higgs Cross section Working Group.
NASA Astrophysics Data System (ADS)
1995-08-01
International Astronomer Team Witnesses Very Ancient Stellar Explosion A few months ago, a violent stellar explosion -- a supernova -- was discovered in an extremely distant galaxy by an international team of astronomers [1]. This is the very promising first result of a recently initiated, dedicated search for such objects. Subsequent spectral observations have shown this to be the most distant supernova ever observed. Although it is very faint, it has been possible to classify it as a supernova of Type Ia, a kind that is particularly well suited for cosmological distance determinations. A Very Efficient Supernova Search Programme The present discovery was made during the team's first observations with the 4-metre telescope at the Cerro Tololo Inter-American Observatory in Chile. This telescope is equipped with a wide-field camera at its prime focus that enables the simultaneous recording of the images of even very faint objects in a 15-arcminute field. Hundreds of distant galaxies are located in a field of this size and this observational method is therefore very well suited for a search of faint and transient supernovae in such galaxies. With a carefully planned observing sequence, it is possible to image up to 55 sky fields per night. A comparison with earlier exposures makes it possible to detect suddenly appearing supernovae as faint points of light near the galaxy in which the exploding star is located (the parent galaxy). A crucial feature of the new programme is the possibility to perform follow-up spectroscopic observations, whenever a new supernova is discovered. For this, the team has obtained access to several other large telescopes, including the ESO 3.5-metre New Technology Telescope (NTT), the 3.9-metre Anglo-Australian Telescope (AAT) and the Multi-Mirror Telescope (MMT) in Arizona, U.S.A.. The Spectrum of the Supernova The present supernova was first detected at Tololo on March 30, 1995. It was given the official designation SN 1995K, and its
The mass ratio in spectroscopic binaries
NASA Astrophysics Data System (ADS)
Ducati, J. R.; Penteado, E. M.; Turcati, R.
2003-08-01
The process of formation of binary and multiple stars is not yet fully understood. Possibilities range from simultaneous processes of condensation from the primeval nebula, to isolated star formation and eventual capture to form a double system. Models exist that predict success probabilities for each theoretical process, and comparison with observational data is crucial. Spectroscopic binaries are specially suited to be used as observational data, since several biases that can arise from general catalogues of binary stars can be avoided, including dominance of systems with large separations between components. A very important parameter in these studies is the mass ratio, the quocient of the masses of primary and secundary members. The histogram of mass ratios provides crucial information to models of binary formation, linked to condensation processes and evolutionaty rates.In this case, spectroscopic binaries can be chosen as the observational sample, provided that the spectrum of the primary is from a non-evolved, main-sequence star,whose mass can be derived reliably from its spectral type. Defining an adequate limiting magnitude (6.5), one avoids bias from eclipsing systems with high inclinations, since nearly all systems up to 6.5 mag were detected. In this paper, a critical review is presented of the existing methods for deriving the distribution of the mass ratios from spectroscopic binary orbital data. After showing the incorrectness of some results published in the litterature, the available data (Batten's 8th Catalogue, 1989) is discussed. Simulations for several distributions of mass ratios (constant, quadratic, etc) are performed. It is shown that the existing data permits only to assert that the spectroscopic binaries with small mass ratios (q < 0.4) are more frequent that those with large mass ratios (q = 0.9 to 1.0).
Are your Spectroscopic Data Being Used?
NASA Astrophysics Data System (ADS)
Gordon, Iouli E.; Rothman, Laurence S.; Wilzewski, Jonas
2014-06-01
Spectroscopy is an established and indispensable tool in science, industry, agriculture, medicine, surveillance, etc.. The potential user of spectral data, which is not available in HITRAN or other databases, searches the spectroscopy publications. After finding the desired publication, the user very often encounters the following problems: 1) They cannot find the data described in the paper. There can be many reasons for this: nothing is provided in the paper itself or supplementary material; the authors are not responding to any requests; the web links provided in the paper have long been broken; etc. 2) The data is presented in a reduced form, for instance through the fitted spectroscopic constants. While this is a long-standing practice among spectroscopists, there are numerous serious problems with this practice, such as users getting different energy and intensity values because of different representations of the solution to the Hamiltonian, or even just despairing of trying to generate usable line lists from the published constants. Properly providing the data benefits not only users but also the authors of the spectroscopic research. We will show that this increases citations to the spectroscopy papers and visibility of the research groups. We will also address the quite common issue when researchers obtain the data, but do not feel that they have time, interest or resources to write an article describing it. There are modern tools that would allow one to make these data available to potential users and still get credit for it. However, this is a worst case scenario recommendation, i.e., publishing the data in a peer-reviewed journal is still the preferred way. L. S. Rothman, I. E. Gordon, et al. "The HITRAN 2012 molecular spectroscopic database," JQSRT 113, 4-50 (2013).
How to accurately bypass damage
Broyde, Suse; Patel, Dinshaw J.
2016-01-01
Ultraviolet radiation can cause cancer through DNA damage — specifically, by linking adjacent thymine bases. Crystal structures show how the enzyme DNA polymerase η accurately bypasses such lesions, offering protection. PMID:20577203
Accurate band gaps of semiconductors and insulators from Quantum Monte Carlo calculations
NASA Astrophysics Data System (ADS)
Nazarov, Roman; Hood, Randolph; Morales, Miguel
2015-03-01
Ab initio calculations are useful tools in developing materials with targeted band gaps for semiconductor industry. Unfortunately, the main workhorse of ab initio calculations - density functional theory (DFT) in local density approximation (LDA) or generalized gradient approximation (GGA) underestimates band gaps. Several approaches have been proposed starting from empirical corrections to more elaborate exchange-correlation functionals to deal with this problem. But none of these work well for the entire range of semiconductors and insulators. Deficiencies of DFT as a mean field method can be overcome using many-body techniques. Quantum Monte Carlo (QMC) methods can obtain a nearly exact numerical solutions of both total energies and spectral properties. Diffusion Monte Carlo (DMC), the most widely used QMC method, has been shown to provide gold standard results for different material properties, including spectroscopic constants of dimers and clusters, equation of state for solids, accurate descriptions of defects in metals and insulators. To test DMC's accuracy in a wider range of semiconductors and insulators we have computed band gaps of several semiconductors and insulators. We show that DMC can provide superior agreement with experiment compared with more traditional DFT approaches including high level exchange-correlation functionals (e.g. HSE).
Accurate Evaluation of Quantum Integrals
NASA Technical Reports Server (NTRS)
Galant, David C.; Goorvitch, D.
1994-01-01
Combining an appropriate finite difference method with Richardson's extrapolation results in a simple, highly accurate numerical method for solving a Schr\\"{o}dinger's equation. Important results are that error estimates are provided, and that one can extrapolate expectation values rather than the wavefunctions to obtain highly accurate expectation values. We discuss the eigenvalues, the error growth in repeated Richardson's extrapolation, and show that the expectation values calculated on a crude mesh can be extrapolated to obtain expectation values of high accuracy.
Fast and Accurate Exhaled Breath Ammonia Measurement
Solga, Steven F.; Mudalel, Matthew L.; Spacek, Lisa A.; Risby, Terence H.
2014-01-01
This exhaled breath ammonia method uses a fast and highly sensitive spectroscopic method known as quartz enhanced photoacoustic spectroscopy (QEPAS) that uses a quantum cascade based laser. The monitor is coupled to a sampler that measures mouth pressure and carbon dioxide. The system is temperature controlled and specifically designed to address the reactivity of this compound. The sampler provides immediate feedback to the subject and the technician on the quality of the breath effort. Together with the quick response time of the monitor, this system is capable of accurately measuring exhaled breath ammonia representative of deep lung systemic levels. Because the system is easy to use and produces real time results, it has enabled experiments to identify factors that influence measurements. For example, mouth rinse and oral pH reproducibly and significantly affect results and therefore must be controlled. Temperature and mode of breathing are other examples. As our understanding of these factors evolves, error is reduced, and clinical studies become more meaningful. This system is very reliable and individual measurements are inexpensive. The sampler is relatively inexpensive and quite portable, but the monitor is neither. This limits options for some clinical studies and provides rational for future innovations. PMID:24962141
Spectroscopic survey of LAMOST
NASA Astrophysics Data System (ADS)
Zhao, Yongheng
2014-07-01
LAMOST is a special reflecting Schmidt telescope. LAMOST breaks through the bottleneck of the large scale spectroscopic survey observation with both large aperture (effective aperture of 3.6 - 4.9m) and wide field of view (5 degrees). It is an innovative active reflecting Schmidt configuration achieved by changing mirror surface continuously to achieve a series different reflecting Schmidt system in different moments. By using the parallel controllable fiber positioning technique, the focal surface of 1.75 meters in diameter accommodates 4000 optical fibers. Also, LAMOST has 16 spectrographs with 32 CCD cameras. LAMOST is the telescope of the highest spectrum acquiring rate. As a national large scientific project, LAMOST project was proposed formally in 1996. The construction was started in 2001 and completed in 2008. After commission period, LAMOST pilot survey was started in October 2011 and spectroscopic survey began in September 2012. From October 2011 to June 2013, LAMOST has obtained more than 2 million spectra of celestial objects. There are 1.7 million spectra of stars, in which the stellar parameters (effective temperature, surface gravity, metalicitiy and radial velocity) of more than 1 million stars was obtained. In the first period of spectroscopic survey of LAMOST, 5 million of stellar spectra will be obtained and will make substantial contribution to the study of the stellar astrophysics and the structure of the Galaxy, such as the spheroid substructure of the Galaxy, the galactic gravitational potential and the distribution of the dark matter in the Galaxy, the extremely metal poor stars and hypervelocity stars, the 3D extinction in the Galaxy, the structure of thin and thick disks of the Galaxy, and so on.
Damping constant estimation in magnetoresistive readers
Stankiewicz, Andrzej Hernandez, Stephanie
2015-05-07
The damping constant is a key design parameter in magnetic reader design. Its value can be derived from bulk or sheet film ferromagnetic resonance (FMR) line width. However, dynamics of nanodevices is usually defined by presence of non-uniform modes. It triggers new damping mechanisms and produces stronger damping than expected from traditional FMR. This work proposes a device-level technique for damping evaluation, based on time-domain analysis of thermally excited stochastic oscillations. The signal is collected using a high bandwidth oscilloscope, by direct probing of a biased reader. Recorded waveforms may contain different noise signals, but free layer FMR is usually a dominating one. The autocorrelation function is a reflection of the damped oscillation curve, averaging out stochastic contributions. The damped oscillator formula is fitted to autocorrelation data, producing resonance frequency and damping constant values. Restricting lag range allows for mitigation of the impact of other phenomena (e.g., reader instability) on the damping constant. For a micromagnetically modeled reader, the technique proves to be much more accurate than the stochastic FMR line width approach. Application to actual reader waveforms yields a damping constant of ∼0.03.
Damping constant estimation in magnetoresistive readers
NASA Astrophysics Data System (ADS)
Stankiewicz, Andrzej; Hernandez, Stephanie
2015-05-01
The damping constant is a key design parameter in magnetic reader design. Its value can be derived from bulk or sheet film ferromagnetic resonance (FMR) line width. However, dynamics of nanodevices is usually defined by presence of non-uniform modes. It triggers new damping mechanisms and produces stronger damping than expected from traditional FMR. This work proposes a device-level technique for damping evaluation, based on time-domain analysis of thermally excited stochastic oscillations. The signal is collected using a high bandwidth oscilloscope, by direct probing of a biased reader. Recorded waveforms may contain different noise signals, but free layer FMR is usually a dominating one. The autocorrelation function is a reflection of the damped oscillation curve, averaging out stochastic contributions. The damped oscillator formula is fitted to autocorrelation data, producing resonance frequency and damping constant values. Restricting lag range allows for mitigation of the impact of other phenomena (e.g., reader instability) on the damping constant. For a micromagnetically modeled reader, the technique proves to be much more accurate than the stochastic FMR line width approach. Application to actual reader waveforms yields a damping constant of ˜0.03.
Accurate spring constant calibration for very stiff atomic force microscopy cantilevers
Grutzik, Scott J.; Zehnder, Alan T.; Gates, Richard S.; Gerbig, Yvonne B.; Smith, Douglas T.; Cook, Robert F.
2013-11-15
There are many atomic force microscopy (AFM) applications that rely on quantifying the force between the AFM cantilever tip and the sample. The AFM does not explicitly measure force, however, so in such cases knowledge of the cantilever stiffness is required. In most cases, the forces of interest are very small, thus compliant cantilevers are used. A number of methods have been developed that are well suited to measuring low stiffness values. However, in some cases a cantilever with much greater stiffness is required. Thus, a direct, traceable method for calibrating very stiff (approximately 200 N/m) cantilevers is presented here. The method uses an instrumented and calibrated nanoindenter to determine the stiffness of a reference cantilever. This reference cantilever is then used to measure the stiffness of a number of AFM test cantilevers. This method is shown to have much smaller uncertainty than previously proposed methods. An example application to fracture testing of nanoscale silicon beam specimens is included.
Lippert, Ross A; Predescu, Cristian; Ierardi, Douglas J; Mackenzie, Kenneth M; Eastwood, Michael P; Dror, Ron O; Shaw, David E
2013-10-28
In molecular dynamics simulations, control over temperature and pressure is typically achieved by augmenting the original system with additional dynamical variables to create a thermostat and a barostat, respectively. These variables generally evolve on timescales much longer than those of particle motion, but typical integrator implementations update the additional variables along with the particle positions and momenta at each time step. We present a framework that replaces the traditional integration procedure with separate barostat, thermostat, and Newtonian particle motion updates, allowing thermostat and barostat updates to be applied infrequently. Such infrequent updates provide a particularly substantial performance advantage for simulations parallelized across many computer processors, because thermostat and barostat updates typically require communication among all processors. Infrequent updates can also improve accuracy by alleviating certain sources of error associated with limited-precision arithmetic. In addition, separating the barostat, thermostat, and particle motion update steps reduces certain truncation errors, bringing the time-average pressure closer to its target value. Finally, this framework, which we have implemented on both general-purpose and special-purpose hardware, reduces software complexity and improves software modularity. PMID:24182003
Accurate, conformation-dependent predictions of solvent effects on protein ionization constants
Barth, P.; Alber, T.; Harbury, P. B.
2007-01-01
Predicting how aqueous solvent modulates the conformational transitions and influences the pKa values that regulate the biological functions of biomolecules remains an unsolved challenge. To address this problem, we developed FDPB_MF, a rotamer repacking method that exhaustively samples side chain conformational space and rigorously calculates multibody protein–solvent interactions. FDPB_MF predicts the effects on pKa values of various solvent exposures, large ionic strength variations, strong energetic couplings, structural reorganizations and sequence mutations. The method achieves high accuracy, with root mean square deviations within 0.3 pH unit of the experimental values measured for turkey ovomucoid third domain, hen lysozyme, Bacillus circulans xylanase, and human and Escherichia coli thioredoxins. FDPB_MF provides a faithful, quantitative assessment of electrostatic interactions in biological macromolecules. PMID:17360348
Grant Hill, J; Mitrushchenkov, Alexander; Yousaf, Kazim E; Peterson, Kirk A
2011-10-14
Explicitly correlated CCSD(T)-F12b calculations have been carried out with systematic sequences of correlation consistent basis sets to determine accurate near-equilibrium potential energy surfaces for the X(2)Π and a(4)Σ(-) electronic states of the CCN radical. After including contributions due to core correlation, scalar relativity, and higher order electron correlation effects, the latter utilizing large-scale multireference configuration interaction calculations, the resulting surfaces were employed in variational calculations of the ro-vibronic spectra. These calculations also included the use of accurate spin-orbit and dipole moment matrix elements. The resulting ro-vibronic transition energies, including the Renner-Teller sub-bands involving the bending mode, agree with the available experimental data to within 3 cm(-1) in all cases. Full sets of spectroscopic constants are reported using the usual second-order perturbation theory expressions. Integrated absorption intensities are given for a number of selected vibronic band origins. A computational procedure similar to that used in the determination of the potential energy functions was also utilized to predict the formation enthalpy of CCN, ΔH(f)(0K) = 161.7 ± 0.5 kcal/mol. PMID:22010720
Spectroscopic survey of LAMOST
NASA Astrophysics Data System (ADS)
Zhao, Yongheng
2015-08-01
LAMOST is a special reflecting Schmidt telescope. LAMOST breaks through the bottleneck of the large scale spectroscopic survey observation with both large aperture (effective aperture of 3.6 - 4.9m) and wide field of view (5 degrees). It is an innovative active reflecting Schmidt configuration achieved by changing mirror surface continuously to achieve a series different reflecting Schmidt system in different moments. By using the parallel controllable fiber positioning technique, the focal surface of 1.75 meters in diameter accommodates 4000 optical fibers. Also, LAMOST has 16 spectrographs with 32 CCD cameras. LAMOST is the telescope of the highest spectrum acquiring rate.In the spectroscopic survey of LAMOST from October 2011 to June 2014, LAMOST has obtained more than 4.13 million spectra of celestial objects. There are 3.27 million spectra of stars, in which the stellar parameters of 2.16 million stars were obtained.In the five-year regular survey upto 2017, LAMOST will obtaine 5 million stellar spectra, which would make substantial contribution to the study of the stellar astrophysics and the structure of the Galaxy, such as the spheroid substructure of the Galaxy, the galactic gravitational potential and the distribution of the dark matter in the Galaxy, the extremely metal poor stars and hypervelocity stars, the 3D extinction in the Galaxy, the structure of thin and thick disks of the Galaxy, and so on.
New Quasar Studies Keep Fundamental Physical Constant Constant
NASA Astrophysics Data System (ADS)
2004-03-01
Very Large Telescope sets stringent limit on possible variation of the fine-structure constant over cosmological time Summary Detecting or constraining the possible time variations of fundamental physical constants is an important step toward a complete understanding of basic physics and hence the world in which we live. A step in which astrophysics proves most useful. Previous astronomical measurements of the fine structure constant - the dimensionless number that determines the strength of interactions between charged particles and electromagnetic fields - suggested that this particular constant is increasing very slightly with time. If confirmed, this would have very profound implications for our understanding of fundamental physics. New studies, conducted using the UVES spectrograph on Kueyen, one of the 8.2-m telescopes of ESO's Very Large Telescope array at Paranal (Chile), secured new data with unprecedented quality. These data, combined with a very careful analysis, have provided the strongest astronomical constraints to date on the possible variation of the fine structure constant. They show that, contrary to previous claims, no evidence exist for assuming a time variation of this fundamental constant. PR Photo 07/04: Relative Changes with Redshift of the Fine Structure Constant (VLT/UVES) A fine constant To explain the Universe and to represent it mathematically, scientists rely on so-called fundamental constants or fixed numbers. The fundamental laws of physics, as we presently understand them, depend on about 25 such constants. Well-known examples are the gravitational constant, which defines the strength of the force acting between two bodies, such as the Earth and the Moon, and the speed of light. One of these constants is the so-called "fine structure constant", alpha = 1/137.03599958, a combination of electrical charge of the electron, the Planck constant and the speed of light. The fine structure constant describes how electromagnetic forces hold
NASA Astrophysics Data System (ADS)
Wilmouth, D. M.; Klobas, J. E.; Anderson, J. G.
2015-12-01
Thirty years have now passed since the discovery of the Antarctic ozone hole, and despite comprehensive international agreements being in place to phase out CFCs and halons, polar ozone losses generally remain severe. The relevant halogen compounds have very long atmospheric lifetimes, which ensures that seasonal polar ozone depletion will likely continue for decades to come. Changes in the climate system can further impact stratospheric ozone abundance through changes in the temperature and water vapor structure of the atmosphere and through the potential initiation of solar radiation management efforts. In many ways, the rate at which climate is changing must now be considered fast relative to the slow removal of halogens from the atmosphere. Photochemical models of Earth's atmosphere play a critical role in understanding and projecting ozone levels, but in order for these models to be accurate, they must be built on a foundation of accurate laboratory data. ClOOCl is the centerpiece of the catalytic cycle that accounts for more than 50% of the chlorine-catalyzed ozone loss in the Arctic and Antarctic stratosphere every spring, and so uncertainties in the ultraviolet cross sections of ClOOCl are particularly important. Additionally, the equilibrium constant of the dimerization reaction of ClO merits further study, as there are important discrepancies between in situ measurements and lab-based models, and the JPL-11 recommended equilibrium constant includes high error bars at atmospherically relevant temperatures (~75% at 200 K). Here we analyze available data for the ClOOCl ultraviolet cross sections and equilibrium constant and present new laboratory spectroscopic results.
Molecular structure, spectral constants, and fermi resonances in chlorine nitrate
NASA Astrophysics Data System (ADS)
Petkie, Douglas T.; Butler, Rebecca A. H.; Helminger, Paul; De Lucia, Frank C.
2004-06-01
Chlorine nitrate has two low-lying vibrational modes that lead to a series of Fermi resonances in the 9 υ97 υ7 family of levels that include the 9 2⇔7 1 and 9 3⇔7 19 1 dyads and the 9 4⇔9 27 1⇔7 2 and 9 5⇔9 37 1⇔9 17 2 triads. These states, along with the ground and 9 1 vibrational states, have been previously analyzed with millimeter and submillimeter wave spectroscopy and provide a substantial body of data for the investigation of these resonances and their impact on calculated spectroscopic constants and structural parameters. Due to fitting indeterminacies, these previous analyses did not include the main Fermi resonance interaction term. Consequently, the fitted rotational constants are linear combinations of the unmixed rotational constants of the basis vibrational states. In this paper, we have calculated the contributions of the Fermi resonances to the observed rotational constants in a model that determines the vibrational-rotational constants, the Fermi term and the mixing between interacting vibrational states, the cubic potential constant ( φ997) that connects interacting levels through a Fermi resonance, and the inertial defects. These results agree with predictions from ab initio and harmonic force field calculations and provide further experimental information for the determination of the fundamental molecular properties of chlorine nitrate.
Formulas for determining rotational constants
NASA Astrophysics Data System (ADS)
Guelachvili, G.
This document is part of Subvolume B `Linear Triatomic Molecules', Part 9, of Volume 20 `Molecular Constants mostly from Infrared Spectroscopy' of Landolt-Börnstein Group II `Molecules and Radicals'. Part of the introduction, it states formulas for determining rotational constants, band center, band origin, and quadrupole coupling. Specific comments relate to BHO (HBO) and COS (OCS).
QCD coupling constants and VDM
Erkol, G.; Ozpineci, A.; Zamiralov, V. S.
2012-10-23
QCD sum rules for coupling constants of vector mesons with baryons are constructed. The corresponding QCD sum rules for electric charges and magnetic moments are also derived and with the use of vector-meson-dominance model related to the coupling constants. The VDM role as the criterium of reciprocal validity of the sum rules is considered.
Spatial variations of the fine-structure constant in symmetron models
NASA Astrophysics Data System (ADS)
Silva, Marvin F.; Winther, Hans A.; Mota, David F.; Martins, C. J. A. P.
2014-01-01
We investigate the variation of the fine-structure constant, α, in symmetron models using N-body simulations in which the full spatial distribution of α at different redshifts has been calculated. In particular, we obtain simulated sky maps for this variation, and determine its power spectrum. We find that in high-density regions of space (such as deep inside dark matter halos) the value of α approaches the value measured on Earth. In the low-density outskirts of halos the scalar field value can approach the symmetry breaking value and leads to significantly different values of α. If the scalar-photon coupling strength βγ is of order unity we find that the variation of α inside dark matter halos can be of the same magnitude as the recent claims by Webb et al. of a dipole variation. Importantly, our results also show that with low-redshift symmetry breaking these models exhibit some dependence of α on lookback time (as opposed to a pure spatial dipole) which could in principle be detected by sufficiently accurate spectroscopic measurements, such as those of ALMA and the ELT-HIRES.
NASA Astrophysics Data System (ADS)
Kohlenberg, Elicia M.; Zanca, Jeanne; Brienza, David M.; Levasseur, Michelle A.; Sowa, Michael G.
2005-09-01
Pressure ulcers (sores) can occur when there is constant pressure being applied to tissue for extended periods of time. Immobile people are particularly prone to this problem. Ideally, pressure damage is detected at an early stage, pressure relief is applied and the pressure ulcer is averted. One of the hallmarks of pressure damaged skin is an obliterated blanch response due to compromised microcirculation near the surface of the skin. Visible reflectance spectroscopy can noninvasively probe the blood circulation of the upper layers of skin by measuring the electronic transitions arising from hemoglobin, the primary oxygen carrying protein in blood. A spectroscopic test was developed on a mixed population of 30 subjects to determine if the blanch response could be detected in healthy skin with high sensitivity and specificity regardless of the pigmentation of the skin. Our results suggest that a spectroscopic based blanch response test can accurately detect the blanching of healthy tissue and has the potential to be developed into a screening test for early stage I pressure ulcers.
Extended temperature dependence of elastic constants in cubic crystals.
Telichko, A V; Sorokin, B P
2015-08-01
To extend the theory of the temperature dependence of the elastic constants in cubic crystals beyond the second- and third-order elastic constants, the fourth-order elastic constants, as well as the non-linearity in the thermal expansion temperature dependence, have been taken into account. Theoretical results were represented as temperature functions of the effective elastic constants and compared with experimental data for a number of cubic crystals, such as alkali metal halides, and elements gold and silver. The relations obtained give a more accurate description of the experimental temperature dependences of second-order elastic constants for a number of cubic crystals, including deviations from linear behavior. A good agreement between theoretical estimates and experimental data has been observed. PMID:25819879
NASA Astrophysics Data System (ADS)
Senent, M. L.; Puzzarini, C.; Domínguez-Gómez, R.; Carvajal, M.; Hochlaf, M.
2014-03-01
Highly correlated ab initio methods are used for the spectroscopic characterization of ethyl mercaptan (CH3CH232SH, ETSH) and dimethyl sulfide (CH332SCH3, DMS), considering them on the vibrational ground and excited torsional states. Since both molecules show non-rigid properties, torsional energy barriers and splittings are provided. Equilibrium geometries and the corresponding rotational constants are calculated by means of a composite scheme based on CCSD(T) calculations that accounts for the extrapolation to the complete basis set limit and core-correlation effects. The ground and excited states rotational constants are then determined using vibrational corrections obtained from CCSD/cc-pVTZ force-field calculations, which are also employed to determine anharmonic frequencies for all vibrational modes. CCSD(T) and CCSD force fields are employed to predict quartic and sextic centrifugal-distortion constants, respectively. Equilibrium rotational constants are also calculated using CCSD(T)-F12. The full-dimensional anharmonic analysis does not predict displacements of the lowest torsional excited states due to Fermi resonances with the remaining vibrational modes. Thus, very accurate torsional transitions are calculated by solving variationally two-dimensional Hamiltonians depending on the CH3 and SH torsional coordinates of ethyl mercaptan or on the two methyl groups torsions of dimethyl-sulfide. For this purpose, vibrationally corrected potential energy surfaces are computed at the CCSD(T)/aug-cc-pVTZ level of theory. For ethyl mercaptan, calculations show large differences between the gauche (g) and trans (t) conformer spectral features. Interactions between rotating groups are responsible for the displacements of the g-bands with respect to the t-bands that cannot therefore be described with one-dimensional models. For DMS, the CCSD(T) potential energy surface has been semi-empirically adjusted to reproduce experimental data. New assignments are suggested for
Senent, M L; Puzzarini, C; Domínguez-Gómez, R; Carvajal, M; Hochlaf, M
2014-03-28
Highly correlated ab initio methods are used for the spectroscopic characterization of ethyl mercaptan (CH3CH2 (32)SH, ETSH) and dimethyl sulfide (CH3 (32)SCH3, DMS), considering them on the vibrational ground and excited torsional states. Since both molecules show non-rigid properties, torsional energy barriers and splittings are provided. Equilibrium geometries and the corresponding rotational constants are calculated by means of a composite scheme based on CCSD(T) calculations that accounts for the extrapolation to the complete basis set limit and core-correlation effects. The ground and excited states rotational constants are then determined using vibrational corrections obtained from CCSD/cc-pVTZ force-field calculations, which are also employed to determine anharmonic frequencies for all vibrational modes. CCSD(T) and CCSD force fields are employed to predict quartic and sextic centrifugal-distortion constants, respectively. Equilibrium rotational constants are also calculated using CCSD(T)-F12. The full-dimensional anharmonic analysis does not predict displacements of the lowest torsional excited states due to Fermi resonances with the remaining vibrational modes. Thus, very accurate torsional transitions are calculated by solving variationally two-dimensional Hamiltonians depending on the CH3 and SH torsional coordinates of ethyl mercaptan or on the two methyl groups torsions of dimethyl-sulfide. For this purpose, vibrationally corrected potential energy surfaces are computed at the CCSD(T)/aug-cc-pVTZ level of theory. For ethyl mercaptan, calculations show large differences between the gauche (g) and trans (t) conformer spectral features. Interactions between rotating groups are responsible for the displacements of the g-bands with respect to the t-bands that cannot therefore be described with one-dimensional models. For DMS, the CCSD(T) potential energy surface has been semi-empirically adjusted to reproduce experimental data. New assignments are
Effect of molecular orientation on the elastic constants of polypropylene.
Kumar, S. R.; Renusch, D. P.; Grimsditch, M.; Materials Science Division; Amoco Polymers Research & Development
2000-03-07
The Brillouin spectroscopic measurements of elastic properties of polypropylene films fabricated by different processing techniques are described. We find that the elastic symmetry and the associated elastic constants are dependent on the molecular orientation brought about by the processing conditions used to produce the films. We have shown that Brillouin scattering techniques can successfully be used to track the molecular orientation induced by uniaxial stretching. We find a direct correspondence between the Brillouin measurements and optical birefringence measurements, illustrating that molecular orientation plays a dominant role in determining the mechanical anisotropy in these materials.
USING THE STATIC HEADSPACE METHOD TO DETERMINE HENRY'S LAW CONSTANTS
A new, accurate, and experimentally simple method has been developed to determine dimensionless Henry's law constants using the static headspace method. he method appears applicable to a wide range of volatile and semivolatile organic compounds. he method work well even for methy...
The calculation of elastic constants from displacement fluctuations
NASA Astrophysics Data System (ADS)
Meyers, M. T.; Rickman, J. M.; Delph, T. J.
2005-09-01
We present a methodology for the accurate and efficient extraction of elastic constants in homogeneous solids via the calculation of the atomic displacement correlation function. This approach is validated for cubic solids parametrized by both Lennard-Jones and embedded-atom method potentials. Finally, we also discuss the extension of this method to obtain the elastic properties of inhomogeneous solids.
Spectroscopic Ellipsometry Applications in Advanced Lithography Research
NASA Astrophysics Data System (ADS)
Synowicki, R. A.; Pribil, Greg K.; Hilfiker, James N.; Edwards, Kevin
2005-09-01
Spectroscopic ellipsometry (SE) is an optical metrology technique widely used in the semiconductor industry. For lithography applications SE is routinely used for measurement of film thickness and refractive index of polymer photoresist and antireflective coatings. While this remains a primary use of SE, applications are now expanding into other areas of advanced lithography research. New applications include immersion lithography, phase-shift photomasks, transparent pellicles, 193 and 157 nm lithography, stepper optical coatings, imprint lithography, and even real-time monitoring of etch development rate in liquid ambients. Of recent interest are studies of immersion fluids where knowledge of the fluid refractive index and absorption are critical to their use in immersion lithography. Phase-shift photomasks are also of interest as the thickness and index of the phase-shift and absorber layers must be critically controlled for accurate intensity and phase transmission. Thin transparent pellicles to protect these masks must be also characterized for thickness and refractive index. Infrared ellipsometry is sensitive to chemical composition, film thickness, and how film chemistry changes with processing. Real-time monitoring of polymer film thickness during etching in a liquid developer allows etch rate and endpoint determination with monolayer sensitivity. This work considers these emerging applications to survey the current status of spectroscopic ellipsometry as a characterization technique in advanced lithography applications.
Are your Spectroscopic Data being used?
NASA Astrophysics Data System (ADS)
Gordon, Iouli E.; Rothman, Laurence S.; Wilzewski, Jonas S.
2014-06-01
Spectroscopy is an established and indispensable tool in science, industry, agriculture, medicine, surveillance, etc.. The potential user of spectral data which is not available in HITRAN1 or other databases, searches the spectroscopy publications. After finding the desired publication, the user very often encounters the following problems: 1) They cannot find the data described in the paper. There can be many reasons for this: nothing is provided in the paper itself or supplementary material; the authors are not responding to any requests; the web links provided in the paper have long been broken, etc.. 2) The data is presented in a reduced form, for instance through the fitted spectroscopic constants. While this is a long-standing practice among spectroscopists, there are numerous serious problems with this practice, such as users getting different energy and intensity values because of different representations of the solution to the Hamiltonian, or even just despairing of trying to generate usable line lists from the published constants. Properly providing the data benefits not only users but also the authors of the spectroscopic research. We will show that this increases citations to the spectroscopy papers and visibility of the research groups. We will also address the quite common issue when researchers obtain the data, but do not feel that they have time, interest or resources to write an article describing it. There are modern tools that allow one to make these data available to potential users and still get credit for it. However, this is a worst case scenario recommendation, i.e., publishing the data in a peer-reviewed journal is still the preferred way.
Constant Communities in Complex Networks
NASA Astrophysics Data System (ADS)
Chakraborty, Tanmoy; Srinivasan, Sriram; Ganguly, Niloy; Bhowmick, Sanjukta; Mukherjee, Animesh
2013-05-01
Identifying community structure is a fundamental problem in network analysis. Most community detection algorithms are based on optimizing a combinatorial parameter, for example modularity. This optimization is generally NP-hard, thus merely changing the vertex order can alter their assignments to the community. However, there has been less study on how vertex ordering influences the results of the community detection algorithms. Here we identify and study the properties of invariant groups of vertices (constant communities) whose assignment to communities are, quite remarkably, not affected by vertex ordering. The percentage of constant communities can vary across different applications and based on empirical results we propose metrics to evaluate these communities. Using constant communities as a pre-processing step, one can significantly reduce the variation of the results. Finally, we present a case study on phoneme network and illustrate that constant communities, quite strikingly, form the core functional units of the larger communities.
Spectroscopic classification of supernova candidates
NASA Astrophysics Data System (ADS)
Hodgkin, S. T.; Hall, A.; Fraser, M.; Campbell, H.; Wyrzykowski, L.; Kostrzewa-Rutkowska, Z.; Pietro, N.
2014-09-01
We report the spectroscopic classification of four supernovae at the 2.5m Isaac Newton Telescope on La Palma, using the Intermediate Dispersion Spectrograph and the R300V grating (3500-8000 Ang; ~6 Ang resolution).
Spectroscopic optical coherence elastography
Adie, Steven G.; Liang, Xing; Kennedy, Brendan F.; John, Renu; Sampson, David D.; Boppart, Stephen A.
2010-01-01
We present an optical technique to image the frequency-dependent complex mechanical response of a viscoelastic sample. Three-dimensional hyperspectral data, comprising two-dimensional B-mode images and a third dimension corresponding to vibration frequency, were acquired from samples undergoing external mechanical excitation in the audio-frequency range. We describe the optical coherence tomography (OCT) signal when vibration is applied to a sample and detail the processing and acquisition techniques used to extract the local complex mechanical response from three-dimensional data that, due to a wide range of vibration frequencies, possess a wide range of sample velocities. We demonstrate frequency-dependent contrast of the displacement amplitude and phase of a silicone phantom containing inclusions of higher stiffness. Measurements of an ex vivo tumor margin demonstrate distinct spectra between adipose and tumor regions, and images of displacement amplitude and phase demonstrated spatially-resolved contrast. Contrast was also observed in displacement amplitude and phase images of a rat muscle sample. These results represent the first demonstration of mechanical spectroscopy based on B-mode OCT imaging. Spectroscopic optical coherence elastography (S-OCE) provides a high-resolution imaging capability for the detection of tissue pathologies that are characterized by a frequency-dependent viscoelastic response. PMID:21164898
Spectroscopic optical coherence elastography.
Adie, Steven G; Liang, Xing; Kennedy, Brendan F; John, Renu; Sampson, David D; Boppart, Stephen A
2010-12-01
We present an optical technique to image the frequency-dependent complex mechanical response of a viscoelastic sample. Three-dimensional hyperspectral data, comprising two-dimensional B-mode images and a third dimension corresponding to vibration frequency, were acquired from samples undergoing external mechanical excitation in the audio-frequency range. We describe the optical coherence tomography (OCT) signal when vibration is applied to a sample and detail the processing and acquisition techniques used to extract the local complex mechanical response from three-dimensional data that, due to a wide range of vibration frequencies, possess a wide range of sample velocities. We demonstrate frequency-dependent contrast of the displacement amplitude and phase of a silicone phantom containing inclusions of higher stiffness. Measurements of an ex vivo tumor margin demonstrate distinct spectra between adipose and tumor regions, and images of displacement amplitude and phase demonstrated spatially-resolved contrast. Contrast was also observed in displacement amplitude and phase images of a rat muscle sample. These results represent the first demonstration of mechanical spectroscopy based on B-mode OCT imaging. Spectroscopic optical coherence elastography (S-OCE) provides a high-resolution imaging capability for the detection of tissue pathologies that are characterized by a frequency-dependent viscoelastic response. PMID:21164898
Accurate upwind-monotone (nonoscillatory) methods for conservation laws
NASA Technical Reports Server (NTRS)
Huynh, Hung T.
1992-01-01
The well known MUSCL scheme of Van Leer is constructed using a piecewise linear approximation. The MUSCL scheme is second order accurate at the smooth part of the solution except at extrema where the accuracy degenerates to first order due to the monotonicity constraint. To construct accurate schemes which are free from oscillations, the author introduces the concept of upwind monotonicity. Several classes of schemes, which are upwind monotone and of uniform second or third order accuracy are then presented. Results for advection with constant speed are shown. It is also shown that the new scheme compares favorably with state of the art methods.
Spectroscopic detection of nitrogen concentrations in sagebrush
J. J. MITCHELL; N. F. GLENN; T.T. SANKEY; D. R. DERRYBERRY; R. C. HRUSKA; M. O. Anderson
2012-07-01
The ability to estimate foliar nitrogen (N) in semi-arid landscapes can yield information on nutritional status and improve our limited understanding of controls on canopy photosynthesis. We examined two spectroscopic methods for estimating sagebrush dried leaf and live shrub N content: first derivative reflectance (FDR) and continuum removal. Both methods used partial least squares (PLS) regression to select wavebands most significantly correlated with N concentrations in the samples. Sagebrush dried leaf spectra produced PLS models (R2 = 0.76–0.86) that could predict N concentrations within the dataset more accurately than PLS models generated from live shrub spectra (R2 = 0.41–0.63). Inclusion of wavelengths associated with leaf water in the FDR transformations appeared to improve regression results. Findings are encouraging and warrant further exploration into sagebrush reflectance spectra to characterize N concentrations.
Weaver, Phoebe G; Jagow, Devin M; Portune, Cameron M; Kenney, John W
2016-01-01
The design and operation of a simple liquid nitrogen Dewar/cryostat apparatus based upon a small fused silica optical Dewar, a thermocouple assembly, and a CCD spectrograph are described. The experiments for which this Dewar/cryostat is designed require fast sample loading, fast sample freezing, fast alignment of the sample, accurate and stable sample temperatures, and small size and portability of the Dewar/cryostat cryogenic unit. When coupled with the fast data acquisition rates of the CCD spectrograph, this Dewar/cryostat is capable of supporting cryogenic luminescence spectroscopic measurements on luminescent samples at a series of known, stable temperatures in the 77-300 K range. A temperature-dependent study of the oxygen quenching of luminescence in a rhodium(III) transition metal complex is presented as an example of the type of investigation possible with this Dewar/cryostat. In the context of this apparatus, a stable temperature for cryogenic spectroscopy means a luminescent sample that is thermally equilibrated with either liquid nitrogen or gaseous nitrogen at a known measureable temperature that does not vary (ΔT < 0.1 K) during the short time scale (~1-10 sec) of the spectroscopic measurement by the CCD. The Dewar/cryostat works by taking advantage of the positive thermal gradient dT/dh that develops above liquid nitrogen level in the Dewar where h is the height of the sample above the liquid nitrogen level. The slow evaporation of the liquid nitrogen results in a slow increase in h over several hours and a consequent slow increase in the sample temperature T over this time period. A quickly acquired luminescence spectrum effectively catches the sample at a constant, thermally equilibrated temperature. PMID:27501355
Spectroscopic properties of oxygen vacancies in LaAlO3
NASA Astrophysics Data System (ADS)
Dicks, Oliver A.; Shluger, Alexander L.; Sushko, Peter V.; Littlewood, Peter B.
2016-04-01
Oxygen vacancies in LaAlO3 (LAO) play an important role in the formation of the two-dimensional electron gas observed at the LaAlO3/SrTiO3 interface and affect the performance of MOSFETs using LAO as a gate dielectric. However, their spectroscopic properties are still poorly understood, which hampers their experimental identification. Here we predict the absorption spectra and ESR parameters of oxygen vacancies in LAO using periodic and embedded cluster methods and density functional theory (DFT). The structure, charge distribution, and spectroscopic properties of the neutral (VO0) and charged (VO+ and VO2 +) oxygen vacancies in cubic and rhombohedral LaAlO3 are investigated. The highest intensity optical transitions [calculated using time-dependent DFT (TDDFT)], from the oxygen vacancy states to the conduction-band states have onsets at 3.5 and 4.2 eV for VO0 and 3.6 eV for VO+ in rhombohedral LAO and 3.3 and 4.0 eV for VO0 and 3.4 eV for VO+ in cubic LAO, respectively. Also reported are the isotropic g value (2.004026) and hyperfine coupling constants of VO+, which are compared to the experimental data obtained using electron spin resonance (ESR) spectroscopy, and accurately predict both the position and the width (3 mT) of its ESR signature. These results may further facilitate the experimental identification of oxygen vacancies in LAO and help to establish their role at the LAO/STO interfaces and in nanodevices using LAO.
NASA Astrophysics Data System (ADS)
Moiseev, N. Ya.
2011-04-01
An approach to the construction of high-order accurate monotone difference schemes for solving gasdynamic problems by Godunov's method with antidiffusion is proposed. Godunov's theorem on monotone schemes is used to construct a new antidiffusion flux limiter in high-order accurate difference schemes as applied to linear advection equations with constant coefficients. The efficiency of the approach is demonstrated by solving linear advection equations with constant coefficients and one-dimensional gasdynamic equations.
Effective cosmological constant induced by stochastic fluctuations of Newton's constant
NASA Astrophysics Data System (ADS)
de Cesare, Marco; Lizzi, Fedele; Sakellariadou, Mairi
2016-09-01
We consider implications of the microscopic dynamics of spacetime for the evolution of cosmological models. We argue that quantum geometry effects may lead to stochastic fluctuations of the gravitational constant, which is thus considered as a macroscopic effective dynamical quantity. Consistency with Riemannian geometry entails the presence of a time-dependent dark energy term in the modified field equations, which can be expressed in terms of the dynamical gravitational constant. We suggest that the late-time accelerated expansion of the Universe may be ascribed to quantum fluctuations in the geometry of spacetime rather than the vacuum energy from the matter sector.
Accurate far-infrared rotational frequencies of carbon monoxide
NASA Technical Reports Server (NTRS)
Varberg, Thomas D.; Evenson, Kenneth M.
1992-01-01
This study presents high-resolution measurements of the pure rotational absorption spectrum of CO in its ground state for the range J arcsec - 5-37. A least-squares fit to this data set, augmented by previous microwave measurements of the J arcsec = 0-4 rotational transitions in the literature, determined accurate values for the molecular constants. A table of calculated CO rotational frequencies is provided for the range J arcsec = 0-45.
Optical constants of solid methane
NASA Technical Reports Server (NTRS)
Khare, Bishun N.; Thompson, W. R.; Sagan, C.; Arakawa, E. T.; Bruel, C.; Judish, J. P.; Khanna, R. K.; Pollack, J. B.
1989-01-01
Methane is the most abundant simple organic molecule in the outer solar system bodies. In addition to being a gaseous constituent of the atmospheres of the Jovian planets and Titan, it is present in the solid form as a constituent of icy surfaces such as those of Triton and Pluto, and as cloud condensate in the atmospheres of Titan, Uranus, and Neptune. It is expected in the liquid form as a constituent of the ocean of Titan. Cometary ices also contain solid methane. The optical constants for both solid and liquid phases of CH4 for a wide temperature range are needed for radiative transfer calculations, for studies of reflection from surfaces, and for modeling of emission in the far infrared and microwave regions. The astronomically important visual to near infrared measurements of solid methane optical constants are conspicuously absent from the literature. Preliminary results are presented of the optical constants of solid methane for the 0.4 to 2.6 micron region. K is reported for both the amorphous and the crystalline (annealed) states. Using the previously measured values of the real part of the refractive index, n, of liquid methane at 110 K n is computed for solid methane using the Lorentz-Lorentz relationship. Work is in progress to extend the measurements of optical constants n and k for liquid and solid to both shorter and longer wavelengths, eventually providing a complete optical constants database for condensed CH4.
How fundamental are fundamental constants?
NASA Astrophysics Data System (ADS)
Duff, M. J.
2015-01-01
I argue that the laws of physics should be independent of one's choice of units or measuring apparatus. This is the case if they are framed in terms of dimensionless numbers such as the fine structure constant, ?. For example, the standard model of particle physics has 19 such dimensionless parameters whose values all observers can agree on, irrespective of what clock, rulers or scales? they use to measure them. Dimensional constants, on the other hand, such as ?, c, G, e and k ?, are merely human constructs whose number and values differ from one choice of units to the next. In this sense, only dimensionless constants are 'fundamental'. Similarly, the possible time variation of dimensionless fundamental 'constants' of nature is operationally well defined and a legitimate subject of physical enquiry. By contrast, the time variation of dimensional constants such as ? or ? on which a good many (in my opinion, confusing) papers have been written, is a unit-dependent phenomenon on which different observers might disagree depending on their apparatus. All these confusions disappear if one asks only unit-independent questions. We provide a selection of opposing opinions in the literature and respond accordingly.
Eyink, K. G.; Szmulowicz, F.; Esposito, D.; Grazulis, L.; Hill, M.; Mahalingam, K.; Aronow, A. J.
2014-07-21
We develop a technique for accurately measuring thickness of planar InAs films grown on (001) GaAs by spectroscopic ellipsometry, using bulk optical constants. We observe that the critical point structure for the E{sub 1} and E{sub 1} + Δ{sub 1} transitions extracted from the measured dielectric properties varies with strain in the layer. Transmission electron microscopy confirms the extracted thickness and measures the residual strain based on the dislocation spacing in the film. At small thickness, the E{sub 1} critical point is seen to markedly deviate from the dependence predicted by deformation potential theory and appears to be consistent with additional quantum confinement effects.
Predict amine solution properties accurately
Cheng, S.; Meisen, A.; Chakma, A.
1996-02-01
Improved process design begins with using accurate physical property data. Especially in the preliminary design stage, physical property data such as density viscosity, thermal conductivity and specific heat can affect the overall performance of absorbers, heat exchangers, reboilers and pump. These properties can also influence temperature profiles in heat transfer equipment and thus control or affect the rate of amine breakdown. Aqueous-amine solution physical property data are available in graphical form. However, it is not convenient to use with computer-based calculations. Developed equations allow improved correlations of derived physical property estimates with published data. Expressions are given which can be used to estimate physical properties of methyldiethanolamine (MDEA), monoethanolamine (MEA) and diglycolamine (DGA) solutions.
Accurate thickness measurement of graphene
NASA Astrophysics Data System (ADS)
Shearer, Cameron J.; Slattery, Ashley D.; Stapleton, Andrew J.; Shapter, Joseph G.; Gibson, Christopher T.
2016-03-01
Graphene has emerged as a material with a vast variety of applications. The electronic, optical and mechanical properties of graphene are strongly influenced by the number of layers present in a sample. As a result, the dimensional characterization of graphene films is crucial, especially with the continued development of new synthesis methods and applications. A number of techniques exist to determine the thickness of graphene films including optical contrast, Raman scattering and scanning probe microscopy techniques. Atomic force microscopy (AFM), in particular, is used extensively since it provides three-dimensional images that enable the measurement of the lateral dimensions of graphene films as well as the thickness, and by extension the number of layers present. However, in the literature AFM has proven to be inaccurate with a wide range of measured values for single layer graphene thickness reported (between 0.4 and 1.7 nm). This discrepancy has been attributed to tip-surface interactions, image feedback settings and surface chemistry. In this work, we use standard and carbon nanotube modified AFM probes and a relatively new AFM imaging mode known as PeakForce tapping mode to establish a protocol that will allow users to accurately determine the thickness of graphene films. In particular, the error in measuring the first layer is reduced from 0.1-1.3 nm to 0.1-0.3 nm. Furthermore, in the process we establish that the graphene-substrate adsorbate layer and imaging force, in particular the pressure the tip exerts on the surface, are crucial components in the accurate measurement of graphene using AFM. These findings can be applied to other 2D materials.
Optical constants of solid methane
NASA Technical Reports Server (NTRS)
Khare, Bishun N.; Thompson, W. R.; Sagan, C.; Arakawa, E. T.; Bruel, C.; Judish, J. P.; Khanna, R. K.; Pollack, J. B.
1990-01-01
Methane is the most abundant simple organic molecule in the outer solar system bodies. In addition to being a gaseous constituent of the atmospheres of the Jovian planets and Titan, it is present in the solid form as a constituent of icy surfaces such as those of Triton and Pluto, and as cloud condensate in the atmospheres of Titan, Uranus, and Neptune. It is expected in the liquid form as a constituent of the ocean of Titan. Cometary ices also contain solid methane. The optical constants for both solid and liquid phases of CH4 for a wide temperature range are needed for radiative transfer calculations, for studies of reflection from surfaces, and for modeling of emission in the far infrared and microwave regions. The astronomically important visual to near infrared measurements of solid methane optical constants are conspicuously absent from the literature. Preliminary results are presented on the optical constants of solid methane for the 0.4 to 2.6 micrometer region. Deposition onto a substrate at 10 K produces glassy (semi-amorphous) material. Annealing this material at approximately 33 K for approximately 1 hour results in a crystalline material as seen by sharper, more structured bands and negligible background extinction due to scattering. The constant k is reported for both the amorphous and the crystalline (annealed) states. Typical values (at absorption maxima) are in the .001 to .0001 range. Below lambda = 1.1 micrometers the bands are too weak to be detected by transmission through the films less than or equal to 215 micrometers in thickness, employed in the studies to date. Using previously measured values of the real part of the refractive index, n, of liquid methane at 110 K, n is computed for solid methane using the Lorentz-Lorenz relationship. Work is in progress to extend the measurements of optical constants n and k for liquid and solid to both shorter and longer wavelengths, eventually providing a complete optical constants database for
Accurate Relations Between the Neutron Current Densities and the Neutron Fluxes
Ronen, Yigal
2004-02-15
Accurate relations between neutron current densities and neutron flux are obtained using the integral transport equation. Using these relations and Fick's Law, diffusion constants can be calculated. These diffusion constants are better than those usually used for the cases in which {sigma}{sub a}/{sigma}{sub s} is not small.
Cosmologies with variable gravitational constant
NASA Astrophysics Data System (ADS)
Narlikar, J. V.
1983-03-01
In 1937 Dirac presented an argument, based on the socalled large dimensionless numbers, which led him to the conclusion that the Newtonian gravitational constant G changes with epoch. Towards the end of the last century Ernst Mach had given plausible arguments to link the property of inertia of matter to the large scale structure of the universe. Mach's principle also leads to cosmological models with a variable gravitational constant. Three cosmologies which predict a variable G are discussed in this paper both from theoretical and observational points of view.
Very accurate potential energy curve of the LiH molecule
NASA Astrophysics Data System (ADS)
Tung, Wei-Cheng; Pavanello, Michele; Adamowicz, Ludwik
2011-02-01
We present very accurate calculations of the ground-state potential energy curve (PEC) of the LiH molecule performed with all-electron explicitly correlated Gaussian functions with shifted centers. The PEC is generated with the variational method involving simultaneous optimization of all Gaussians with an approach employing the analytical first derivatives of the energy with respect to the Gaussian nonlinear parameters (i.e., the exponents and the coordinates of the shifts). The LiH internuclear distance is varied between 1.8 and 40 bohrs. The absolute accuracy of the generated PEC is estimated as not exceeding 0.3 cm-1. The adiabatic corrections for the four LiH isotopologues, i.e., 7LiH, 6LiH, 7LiD, and 6LiD, are also calculated and added to the LiH PEC. The aforementioned PECs are then used to calculate the vibrational energies for these systems. The maximum difference between the computed and the experimental vibrational transitions is smaller than 0.9 cm-1. The contribution of the adiabatic correction to the dissociation energy of 7LiH molecule is 10.7 cm-1. The magnitude of this correction shows its importance in calculating the LiH spectroscopic constants. As the estimated contribution of the nonadiabatic and relativistic effects to the ground state dissociation energy is around 0.3 cm-1, their inclusion in the LiH PEC calculation seems to be the next most important contribution to evaluate in order to improve the accuracy achieved in this work.
Very accurate potential energy curve of the LiH molecule.
Tung, Wei-Cheng; Pavanello, Michele; Adamowicz, Ludwik
2011-02-14
We present very accurate calculations of the ground-state potential energy curve (PEC) of the LiH molecule performed with all-electron explicitly correlated Gaussian functions with shifted centers. The PEC is generated with the variational method involving simultaneous optimization of all Gaussians with an approach employing the analytical first derivatives of the energy with respect to the Gaussian nonlinear parameters (i.e., the exponents and the coordinates of the shifts). The LiH internuclear distance is varied between 1.8 and 40 bohrs. The absolute accuracy of the generated PEC is estimated as not exceeding 0.3 cm(-1). The adiabatic corrections for the four LiH isotopologues, i.e., (7)LiH, (6)LiH, (7)LiD, and (6)LiD, are also calculated and added to the LiH PEC. The aforementioned PECs are then used to calculate the vibrational energies for these systems. The maximum difference between the computed and the experimental vibrational transitions is smaller than 0.9 cm(-1). The contribution of the adiabatic correction to the dissociation energy of (7)LiH molecule is 10.7 cm(-1). The magnitude of this correction shows its importance in calculating the LiH spectroscopic constants. As the estimated contribution of the nonadiabatic and relativistic effects to the ground state dissociation energy is around 0.3 cm(-1), their inclusion in the LiH PEC calculation seems to be the next most important contribution to evaluate in order to improve the accuracy achieved in this work. PMID:21322671
Constant-amplitude RC oscillator
NASA Technical Reports Server (NTRS)
Kerwin, W. J.; Westbrook, R. M.
1970-01-01
Sinusoidal oscillator has a frequency determined by resistance-capacitance /RC/ values of two charge control devices and a constant-amplitude voltage independent of frequency and RC values. RC elements provide either voltage-control, resistance-control, or capacitance-control of the frequency.
The 1% concordance Hubble constant
Bennett, C. L.; Larson, D.; Weiland, J. L.; Hinshaw, G.
2014-10-20
The determination of the Hubble constant has been a central goal in observational astrophysics for nearly a hundred years. Extraordinary progress has occurred in recent years on two fronts: the cosmic distance ladder measurements at low redshift and cosmic microwave background (CMB) measurements at high redshift. The CMB is used to predict the current expansion rate through a best-fit cosmological model. Complementary progress has been made with baryon acoustic oscillation (BAO) measurements at relatively low redshifts. While BAO data do not independently determine a Hubble constant, they are important for constraints on possible solutions and checks on cosmic consistency. A precise determination of the Hubble constant is of great value, but it is more important to compare the high and low redshift measurements to test our cosmological model. Significant tension would suggest either uncertainties not accounted for in the experimental estimates or the discovery of new physics beyond the standard model of cosmology. In this paper we examine in detail the tension between the CMB, BAO, and cosmic distance ladder data sets. We find that these measurements are consistent within reasonable statistical expectations and we combine them to determine a best-fit Hubble constant of 69.6 ± 0.7 km s{sup –1} Mpc{sup –1}. This value is based upon WMAP9+SPT+ACT+6dFGS+BOSS/DR11+H {sub 0}/Riess; we explore alternate data combinations in the text. The combined data constrain the Hubble constant to 1%, with no compelling evidence for new physics.
Optical constants of solid methane
Khare, B.N.; Thompson, W.R.; Sagan, C. . Lab. for Planetary Studies); Arakawa, E.T.; Bruel, C.; Judish, J.P. ); Khanna, R.K. . Dept. of Chemistry and Biochemistry); Pollack, J.B. . Ames Research Center)
1989-01-01
Methane is the most abundant simple organic molecule in the outer solar system bodies. In addition to being a gaseous constituent of the atmospheres of the Jovian planets and Titan, it is present in the solid form as a constituent of icy surfaces such as those of Triton and Pluto, and as cloud condensate in the atmospheres of Titan, Uranus, and Neptune. It is expected in the liquid form as a constituent of the ocean of Titan. Cometary ices also contain solid methane. The optical constants for both solid and liquid phases of CH{sub 4} for a wide temperature range are needed for radiative transfer calculations, for studies of reflection from surfaces, and for modeling of emission in the far infrared and microwave regions. The astronomically important visual to near infrared measurements of solid methane optical constants are conspicuously absent from the literature. We present preliminary results of the optical constants of solid methane for the 0.4 {mu}m to 2.6 {mu}m region. We report k for both the amorphous and the crystalline (annealed) states. Using our previously measured values of the real part of the refractive index, n, of liquid methane at 110{degree}K (Bull. Am. Phys. Soc.31, 700 (1986)) we compute n for solid methane using the Lorentz-Lorentz relationship. Work is in progress to extend the measurements of optical constants n and k for liquid and solid to both shorter and longer wavelengths, eventually providing a complete optical constants database for condensed CH{sub 4}. 33 refs., 6 figs., 2 tabs.
Dose rate constant and energy spectrum of interstitial brachytherapy sources.
Chen, Z; Nath, R
2001-01-01
In the past two years, several new manufacturers have begun to market low-energy interstitial brachytherapy seeds containing 125I and 103Pd. Parallel to this development, the National Institute of Standards and Technology (NIST) has implemented a modification to the air-kerma strength (S(K)) standard for 125I seeds and has also established an S(K) standard for 103Pd seeds. These events have generated a considerable number of investigations on the determination of the dose rate constants (inverted V) of interstitial brachytherapy seeds. The aim of this work is to study the general properties underlying the determination of dose rate constant and to develop a simple method for a quick and accurate estimation of dose rate constant. As the dose rate constant of clinical seeds is defined at a fixed reference point, we postulated that dose rate constant may be calculated by treating the seed as an effective point source when the seed's source strength is specified in S(K) and its source characteristics are specified by the photon energy spectrum measured in air at the reference point. Using a semi-analytic approach, an analytic expression for dose rate constant was derived for point sources with known photon energy spectra. This approach enabled a systematic study of dose rate constant as a function of energy. Using the measured energy spectra, the calculated dose rate constant for 125I model 6711 and 6702 seeds and for 192Ir seed agreed with the AAPM recommended values within +/-1%. For the 103Pd model 200 seed, the agreement was 5% with a recently measured value (within the +/-7% experimental uncertainty) and was within 1% with the Monte Carlo simulations. The analytic expression for dose rate constant proposed here can be evaluated using a programmable calculator or a simple spreadsheet and it provides an efficient method for checking the measured dose rate constant for any interstitial brachytherapy seed once the energy spectrum of the seed is known. PMID:11213926
Accurate ab Initio Spin Densities
2012-01-01
We present an approach for the calculation of spin density distributions for molecules that require very large active spaces for a qualitatively correct description of their electronic structure. Our approach is based on the density-matrix renormalization group (DMRG) algorithm to calculate the spin density matrix elements as a basic quantity for the spatially resolved spin density distribution. The spin density matrix elements are directly determined from the second-quantized elementary operators optimized by the DMRG algorithm. As an analytic convergence criterion for the spin density distribution, we employ our recently developed sampling-reconstruction scheme [J. Chem. Phys.2011, 134, 224101] to build an accurate complete-active-space configuration-interaction (CASCI) wave function from the optimized matrix product states. The spin density matrix elements can then also be determined as an expectation value employing the reconstructed wave function expansion. Furthermore, the explicit reconstruction of a CASCI-type wave function provides insight into chemically interesting features of the molecule under study such as the distribution of α and β electrons in terms of Slater determinants, CI coefficients, and natural orbitals. The methodology is applied to an iron nitrosyl complex which we have identified as a challenging system for standard approaches [J. Chem. Theory Comput.2011, 7, 2740]. PMID:22707921
A theoretical study on low-lying electronic states and spectroscopic properties of PH
NASA Astrophysics Data System (ADS)
Gao, Yufeng; Gao, Tao
2014-01-01
The low-lying electronic states (X3∑-, a1Δ, b1Σ+, A3Π, c1Π and 5∑-) of the PH species correlating with the first three dissociation channels have been investigated at the MRCI + Q/aug-cc-PV5Z level of theory. Accurate adiabatic potential energy curves and spectroscopic constants (Te, Re, ωeχe, ωe, Be, De) of these electronic states have been reported. Effect of the spin-orbit coupling on the A3Π and 5∑- states of the PH has been calculated, which lead to the spin-orbit-induced predissociation of the A3Π state. Electronic transition moment, Einstein coefficients and Franck-Condon factors for the A3Π - X3∑- system have been calculated. Dipole moment functions (μe) and radiative lifetime (τv‧) for the A3Π state has also been determined. The radiative lifetime for A3Π - X3∑- transition is computed and compared with the available data.
A Novel Tool for the Spectroscopic Inference of Fundamental Stellar Parameters
NASA Astrophysics Data System (ADS)
Czekala, Ian; Andrews, Sean M.; Latham, David W.; Torres, Guillermo
2014-06-01
We present a novel approach for making accurate and unbiased inferences of fundamental stellar parameters (e.g., effective temperature, surface gravity, metallicity) from spectroscopic observations, with reference to a library of synthetic spectra. The forward-modeling formalism we have developed is generic (easily adaptable to data from any instrument or covering any wavelength range) and modular, in that it can incorporate external prior knowledge or additional data (e.g., broadband photometry) and account for instrumental and non-stellar effects on the spectrum (e.g., parametric treatments of extinction, spots, etc.). An approach that employs adaptive correlated noise is used to account for systematic discrepancies between the observations and the synthetic spectral library, ensuring that issues like uncertainties in atomic or molecular constants do not strongly bias the parameter inferences. In addition to extracting a set of unbiased inferences of the (posterior) probability distributions for basic stellar parameters, our modeling approach also "maps" out problematic spectral regions in the synthetic libraries that could be used as a basis for improving the models. As a demonstration, we present some preliminary results from modeling optical spectra of well-characterized exoplanet host stars and nearby pre-main sequence stars. A basic set of adaptable software that performs this modeling approach will be released publicly.
Extensive and Highly Accurate Line Lists for Hydrogen Halides
NASA Astrophysics Data System (ADS)
Li, G.; Bernath, P. F.; Gordon, I. E.; Rothman, L. S.; Richard, C.; Le Roy, R. J.; Coxon, J. A.; Hajigeorgiou, P.
2011-06-01
New dipole moment functions (DMF) for the ground X 1Σ+ electronic states of the hydrogen halides (HF, HCl, HBr, HI) have been obtained using a direct fit approach that fits the best available and appropriately weighted experimental line intensity data for individual ro-vibrational transitions. Combining the newly developed (taking into account the most recent experiments) empirical potential energy functions and the DMFs, line positions and line intensities of the hydrogen halides and their isotopologues have been calculated numerically using program LEVEL. In addition, new semi-empirical algorithms for assigning line-shape parameters for these species have been developed. Using these improvements, new line lists for hydrogen halides were created to update the HITRAN spectroscopic database. These new lists are more accurate and significantly more extensive than those included in the current version of the database (HITRAN2008). R.J. Le Roy, ``LEVEL 8.0, 2007'', University of Waterloo Chemical Physics Research Report CP-663 (2007); see http://leroy.uwaterloo.ca/programs/. L.S. Rothman, I.E. Gordon, A. Barbe, D.C. Benner, P.F. Bernath, et al., ``The HITRAN 2008 Molecular Spectroscopic Database,'' JQSRT 110, 532-572 (2009).