Doppler-limited dye laser excitation spectroscopy of DCF

Kakimoto, Masanori; Saito, Shuji; Hirota, Eizi

doi:10.1016/0022-2852(81)90138-7

Cited by 54 publications

(39 citation statements)

References 13 publications

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“…In CHF, CHCl, and CF 2 , on the other hand, the C-X bonds in the singlets are calculated to be too long by 0·03, 0·05, and 0·03 Å, respectively, at the DFT level. There do not appear to be any ambiguities in the experiments; moreover, Rodriquez and Hopkinson 30 found predicted bond lengths at the MP2/6-311 + + G** level to be in very good agreement with the experimental results for CHF, 92 CHCl 93 and CF 2 .…”

Section: Structuresmentioning

confidence: 59%

Density functional calculations of the influence of substitution on singlet–triplet gaps in carbenes and vinylidenes

Worthington¹,

Cramer²

1997

J. Phys. Org. Chem.

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Density functional theory calculations of multiplet splittings are presented that agree closely with experimental measurements for six carbenes and six vinylidenes. The calculations are further analyzed to gauge the relative importance of different factors influencing the stabilities of the different spin and electronic states. In the carbene series, with halogen substituents, orbital rehybridization effects and charge redistribution effects are large. The magnitude of -conjugation (back-bonding) is calculated to be only moderately larger (6-8 kcal mol ؊ 1 ) for singlets than for triplets based on natural bond orbital-derived conjugation energies. In the vinylidene series, substituion effects are primarily associated with through-space and through-bond inductive stabilization effects, especially hyperconjugation; -conjugation effects are found to be small

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Section: Structuresmentioning

confidence: 59%

Density functional calculations of the influence of substitution on singlet–triplet gaps in carbenes and vinylidenes

Worthington¹,

Cramer²

1997

J. Phys. Org. Chem.

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“…Building upon previous work of Hirota and colleagues, 24,26,27 our recent polarization QBS studies of HCF identified local singlet-triplet perturbations in the Ã 1 AЉ state, and analysis of these spectra in concert with density functional theory ͑DFT͒ calculations provided the first information on the hyperfine coupling constants of ã 3 AЉ and the magnitude of the spin-orbit matrix elements ͑ϳ0.5 cm −1 ͒. 52 To date such perturbations have not been observed in X 1 AЈ, as the vibrational structure has been probed only up to ϳ4200 cm −1 above the vibrationless level, and predicted values for ⌬E ST range from 4617 to 5537 cm −1 , [17][18][19][20]22,[30][31][32][34][35][36][37][39][40][41][42][43]45 consistent with an experimental value of 5210± 140 cm −1 derived from photoelectron spectra of HCF − .…”

Section: Introductionmentioning

confidence: 87%

“…33,38 In this article, we report new results concerning dispersed fluorescence spectroscopy of the X 1 AЈ state of both HCF and DCF. By exciting single vibronic levels in the progressions 2 0 n , 2 0 n 3 0 1 , and 1 0 1 2 0 n , which were identified in previous studies, 14,23,24,44,46,48,49 Franck-Condon access was provided to the majority of ground-state levels, allowing a comprehensive view of the vibrational level structure up to ϳ10 000 cm −1 .…”

Section: Introductionmentioning

confidence: 99%

Dispersed fluorescence spectroscopy of jet-cooled HCF and DCF: Vibrational structure of the X̃A′1 state

Fan

Mukarakate

Deselnicu

et al. 2005

The Journal of Chemical Physics

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We recorded dispersed fluorescence (DF) spectra following excitation of the pure bending levels 2(0) (n) and the combination states 1(0) (1)2(0) (n) and 2(0) (n)3(0) (1) in the A 1A"<--X 1A' system of HCF and DCF. Spectra were measured with a 0.3 m spectrograph equipped with a gated intensified charge coupled device (CCD) detector and obtained under jet-cooled conditions using a pulsed discharge source. The DF spectra reveal rich detail concerning the vibrational structure of the X state up to 10 000 cm(-1). For HCF, resonances among the nearly degenerate levels 1(1)2n, 2n+13(1), and 2n+2 produce a polyadlike structure in the spectrum, and the usual effective spectroscopic Hamiltonian (Dunham expansion) poorly reproduces the experimental term energies. In contrast, this Hamiltonian works well for the term energies of DCF. Density functional calculations of the ground state vibrational frequencies were performed; the results are in excellent agreement with the experimentally derived vibrational parameters. The search for perturbations involving the low-lying a 3A" state is described.

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“…The small Caa factor may be ascribed to a small hyperfine parameter a, as suggested by the a hyperfine constant being smaller in SiF than in CF (see Table Ill). nj n~ Suzuki et al [87] have also investigated the AIA"(OOO)-XIA'(O00) band of DCF and have determined the molecular structure for both the ~ and ~ ground vibrational states, as listed in Table X. While the C-F distance remains more or r b ru less the same upon A÷X excitation, the C-H distance decreases by 0.075 A and the HCF angle increases by 19.7 °.…”

Section: B the Hcf And Hcci Moleculesmentioning

confidence: 99%