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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 55 records · Page 3
All sourcesNASA NTRSDOE OSTI
NASA NTRS1982

Rotational and vibrational spectra of ethynol from quantum-mechanical calculations

It is noted that ethynol (HCCOH), despite the theoretical prediction of its stability to tautomerization to ketene, has thus far not been observed. It is shown here that the identification of this unknown molecule, both in space and in the laboratory, can be aided by an ab initio calculation of spectroscopic parameters. At the HF/3-21G level, harmonic vibrational frequencies are computed by way of analytic second differentiation of the Hartee-Fock (HF) energy with respect to the nuclear coordinates. After applying an empirical scale factor, the resultant frequencies are (per cm) 473, 517, 773, 841, 1003, 1217, 2206, 3285, and 3418. The computed dipole moment at the CISD/DZ+P level is 1.79 D. At the CISD+Q/DZ+P level, the molecule's rotational constants are determined. After scaling by empirical correction factors, they are used in deriving the 4(04) - 3(03) frequency of 76.81 + or - 0.3 GHz with a triplet splitting of 0.30 + or - 0.01 GHz. The triplet splitting involves 4(14) - 3(13) and 4(13) - 3(12) relative to the 4(04) - 3(03) transition as the central line.

Defrees, D. J.↗
NASA NTRS1975

Vibrational spectra and structure of biphosphine and biphosphine-d4

Infrared and Raman spectra have been obtained for biphosphine and biphosphine-d4 in both solid and vapor phases. From the spectral data, it is concluded that only one conformer exists in both solid and fluid phases and that this is the gauche conformer. A normal-coordinate analysis has also been performed, in which the 24 vibrational frequencies of the two isotopes have been fitted by 10 force constants to an overall average error of 1.0%. The PED indicates that there is practically no mixing of the normal modes in the P2H4 molecule but the P-P stretch and the PD2 wagging modes are extensively mixed for the P2D4 molecule.

Odom, J. D.↗
NASA NTRS1992

An extensive ab initio study of the structures, vibrational spectra, quadratic force fields, and relative energetics of three isomers of Cl2O2

Quantum mechanical computational methods are employed for an ab initio investigation of: (1) the molecular properties of the lowest isomers of the ClO dimer; and (2) predicted molecular and thermochemical properties. Techniques employed include electron correlation and particularly singles and doubles coupled-cluster (CCSD) theory with or without perturbational estimates of the effects of connected triple excitations. The isomers ClOClO and ClClO2 are found to have higher energies than the ClOOCl isomer, and the theoretical vibrational frequencies of the isomers are well correlated with experimental data. Experimental values of the heat of formation for the isomers are also compared with calculations based on an isodesmic reaction with Cl2O, H2O, and HOOH.

Lee, Timothy J.↗
DOE OSTI2021

Thermodynamic properties of ε -Fe with thermal electronic excitation effects on vibrational spectra

The thermodynamic properties of hexagonal-close-packed iron (ε–Fe) are essential for investigating the internal structure and dynamic properties of planetary cores. Despite their importance to planetary sciences, experimental investigations of ε–Fe at relevant conditions are still challenging. Therefore, ab initio calculations are crucial to elucidating the thermodynamic properties of this system. Here, we use a free energy calculation scheme based on the phonon gas model compatible with temperature-dependent phonon frequencies. We investigate the effects of electronic thermal excitations, which introduces a temperature dependence on phonon frequencies, and the implication for the thermodynamic properties of ε–Fe at extreme pressure (P) and temperature (T) conditions. We disregard phonon-phonon interactions, i.e., anharmonicity and their effect on phonon frequencies. Nevertheless, the current scheme is also applicable to T -dependent anharmonic frequencies. We conclude that the impact of thermal electronic excitations on vibrational properties is not significant up to ~4000 K at 200 GPa but should not be ignored at higher temperatures or pressures. However, the static free energy F st must always include the effect of thermal excitation fully in a continuum of T. Furthermore, our results for isentropic equations of state show good agreement with data from recent ramp compression experiments up to 1400 GPa conducted at the National Ignition Facility.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗