Equilibrium Structure and Spectroscopic Constants of Difluorovinylidene: An ab Initio Study

Breidung, Jürgen; Thiel, Walter

doi:10.1006/jmsp.2000.8244

Cited by 17 publications

(7 citation statements)

References 47 publications

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“…For a given basis, BCCD(T) yields CC equilibrium distances and CC harmonic stretching wavenumbers that are smaller than those from MP2 (by 1.0-1.1 pm and 30-35 cm −1 , respectively). Compared with experiment (25), the equilibrium internuclear distance in C 2 is overestimated by 0.35 pm at the BCCD(T)/VQZ + aug(C) level which is mainly due to the neglect of innershell correlation contributions to r e (CC) (26). At the same level, the harmonic stretching wavenumber ω e in C 2 is-of course somewhat fortuitously-in virtually perfect agreement with the experimental value (see Table 3).…”

Section: Resultssupporting

confidence: 64%

Ab Initio Study of the Charge-Transfer Complex of Xenon and Dicarbon

Breidung

Thiel

2002

Journal of Molecular Spectroscopy

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Section: Resultssupporting

confidence: 64%

Ab Initio Study of the Charge-Transfer Complex of Xenon and Dicarbon

Breidung

Thiel

2002

Journal of Molecular Spectroscopy

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“…The optimized geometrical parameters, computed relative electronic energies and vibrational frequencies of the various states of CF 2 studied and its anion are summarized in Tables 1 and 2, together with theoretical9, 11, 24–29 and experimental5, 6, 8, 9, 12, 23, 30–32 values available in the literature. (It should be noted that only relatively recent and reliable values are included in Tables 1 and 2 for comparison.…”

Section: Resultsmentioning

confidence: 99%

The Singlet–Triplet Separation in CF₂: State‐of‐the‐Art Ab Initio Calculations and Franck–Condon Simulations Including Anharmonicity

et al. 2005

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Geometrical parameters, vibrational frequencies and relative electronic energies of the X2B1 state of CF2- and the X1A1 and ã3B1 states of CF2 have been calculated. Core-electron effects on the computed minimum-energy geometries and relative electronic energies have been investigated, and relativistic contributions to the computed relative electronic energies calculated. Potential energy functions of the X2B1 state of CF2- and the X1A1 and ã3B1 states of CF2 have been determined, and anharmonic vibrational wavefunctions of these states calculated variationally. Franck-Condon factors including anharmonicity and Duschinsky rotation have been computed and used to simulate the ã-X emission spectrum of CF2 determined by S. Koda [Chem. Phys. Lett. 1978, 55, 353] and the 364 nm laser photodetachment spectrum of CF2- obtained by R. L. Schwartz et al. [J. Phys. Chem. A 1999, 103, 8213]. Comparison between theory and experiment shows that the theoretical approach benchmarked in the present study is able to give highly reliable positions for the CF2(X1A1) + e <-- CF2-(X2B1) and CF2(ã3B1) + e <-- CF2-(X2B1) bands in the photoelectron spectrum of CF2- and a reliable singlet-triplet gap for CF2. It is therefore concluded that the same theoretical approach should give reliable simulated CCl2(X1A1) + e <-- CCl2-(X2B1) and CCl2(ã3B1) + e <-- CCl2-(X2B1) bands in the photodetachment spectrum of CCl2- and a reliable singlet-triplet gap for CCl2.

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“…The highest level of calculation on the X 1 A 1 state of CF 2 is the RCCSD͑T͒/aug-cc-pCVQZ ͑all electrons correlated͒ level from Ref. 9. However, vibrational frequencies are not available at this level.…”

Section: Discussionmentioning

confidence: 99%

Simulation of Ã 1B1→X̃ 1A1 CF2 single vibronic level emissions: Including anharmonic and Duschinsky effects

Chau

Dyke

Lee

et al. 2001

The Journal of Chemical Physics

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CASSCF/MRCI/aug-cc-pVQZ͑no g͒ and RCCSD͑T͒/aug-cc-pVQZ potential energy functions were reported for the Ã 1 B 1 and X 1 A 1 states of CF 2 , respectively. Vibrational wave functions of the symmetric stretching and bending modes of the two states of CF 2 were obtained in variational calculations, employing Watson's Hamiltonian for a nonlinear molecule and anharmonic vibrational wave functions expressed as linear combinations of harmonic basis functions. Franck-Condon factors ͑FCFs͒ were computed for Ã 1 B 1 →X 1 A 1 CF 2 single vibronic level ͑SVL͒ emissions and the SVL emission spectra were simulated with the computed FCFs. When compared with the observed spectra, the simulated spectra obtained in the present investigation, which include allowance for anharmonicity and the Duschinsky effect, were found to be significantly superior to those reported previously, based on the harmonic oscillator model. Using the iterative Franck-Condon analysis procedure, with the geometry of the X 1 A 1 state fixed at the recently determined experimental equilibrium geometry, the geometry of the Ã 1 B 1 state of CF 2 , which gave the best match between simulated and observed spectra, was found to be r e (CF͒ϭ1.317 Å and e (FCF)ϭ121.25°.

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Equilibrium Structure and Spectroscopic Constants of Difluorovinylidene: An ab Initio Study

Cited by 17 publications

References 47 publications

Ab Initio Study of the Charge-Transfer Complex of Xenon and Dicarbon

Ab Initio Study of the Charge-Transfer Complex of Xenon and Dicarbon

The Singlet–Triplet Separation in CF₂: State‐of‐the‐Art Ab Initio Calculations and Franck–Condon Simulations Including Anharmonicity

Simulation of Ã 1B1→X̃ 1A1 CF2 single vibronic level emissions: Including anharmonic and Duschinsky effects

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Equilibrium Structure and Spectroscopic Constants of Difluorovinylidene: An ab Initio Study

Cited by 17 publications

References 47 publications

Ab Initio Study of the Charge-Transfer Complex of Xenon and Dicarbon

Ab Initio Study of the Charge-Transfer Complex of Xenon and Dicarbon

The Singlet–Triplet Separation in CF2: State‐of‐the‐Art Ab Initio Calculations and Franck–Condon Simulations Including Anharmonicity

Simulation of Ã 1B1→X̃ 1A1 CF2 single vibronic level emissions: Including anharmonic and Duschinsky effects

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The Singlet–Triplet Separation in CF₂: State‐of‐the‐Art Ab Initio Calculations and Franck–Condon Simulations Including Anharmonicity