Ab initio calculations of excited states of vinyl bromide

Chang, Jia‐Lin; Tsao, Chih-Wen

doi:10.1016/j.cplett.2006.07.024

Cited by 12 publications

(8 citation statements)

References 31 publications

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“…Ab initio excited-state calculations are available in the literature for VF, 37,80 VC, 38,81,82 and VB. 29,39 While there seems to be agreement in the theoretical assignment of electronic transitions for VF, the cases of VC and VB are still the subject of significant debate. Most studies agree that the p * CC ' p CC transition is a bound-to-bound transition with a large oscillator strength.…”

Section: A Molecular-orbital Characters and Interactions In Vinyl Hal...mentioning

confidence: 99%

“…Electronic-structure calculations were also performed to study the excited states of VF, 37 VC, 34,38 and VB. 39 Besides the quantum-yield measurements of I and HI by Yamashita and coworkers, 6,7 there is only one other gas-phase study of vinyl iodide photodissociation. Cao et al 8 measured an I * : I ratio of 1.33 : 1 at 248 nm in their photofragment translational spectroscopy (PTS) experiment.…”

Section: Introductionmentioning

confidence: 99%

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Ultraviolet photodissociation of vinyl iodide: understanding the halogen dependence of photodissociation mechanisms in vinyl halides

Zou

Strecker

Ramirez-Serrano

et al. 2008

Phys. Chem. Chem. Phys.

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The photodissociation of vinyl iodide has been investigated at several wavelengths between 193 and 266 nm using three techniques: time-resolved Fourier transform emission spectroscopy, multiple pass laser absorption spectroscopy, and velocity-mapped ion imaging. The only dissociation channel observed is C-I bond cleavage to produce C2H3 (nu, N) + I (2P(J)) at all wavelengths investigated. Unlike photodissociation of other vinyl halides (C2H3X, X = F, Cl, Br), in which the HX product channel is significant, no HI elimination is observed. The angular and translational energy distributions of I atoms indicate that atomic products arise solely from dissociation on excited states with negligible contribution from internal conversion to the ground state. We derive an upper limit on the C-I bond strength of D0(C2H3-I) < or = 65 kcal mol(-1). The ground-state potential-energy surface of vinyl iodide is explored by ab initio calculations. We present a model in which the highest occupied molecular orbital in vinyl halides has increasing X(np) non-bonding character with increasing halogen mass. This change leads to reduced torsional force around the C-C bond in the excited state. Because the ground-state energy is highest when the CH2 plane is perpendicular to the CHX plane, a reduced torsional force in the excited state correlates with a lower rate for internal conversion compared to excited-state C-X bond fission. This model explains the gradual change in photodissociation mechanisms of vinyl halides from the dominance of internal conversion in vinyl fluoride to the dominance of excited-state dissociation in vinyl iodide.

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Section: A Molecular-orbital Characters and Interactions In Vinyl Hal...mentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Ultraviolet photodissociation of vinyl iodide: understanding the halogen dependence of photodissociation mechanisms in vinyl halides

Zou

Strecker

Ramirez-Serrano

et al. 2008

Phys. Chem. Chem. Phys.

View full text Add to dashboard Cite

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“…where small off-diagonal matrix elements of J indicate that the Duschinsky effect can be neglected for the PES of SO 2 À . In fact, the PES of SO 2 À simulated in this work was almost, as it should be, identical to that simulated by our FCF model of purely displaced and distorted harmonic oscillators (not shown) [35,36].…”

Section: Photoelectron Spectrum Of Somentioning

confidence: 65%

A general formula of two-dimensional Franck–Condon integral and the photoelectron spectroscopy of sulfur dioxide

Lee

Yang

Kuo

et al. 2009

Journal of Molecular Spectroscopy

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“…In recent years, we have developed some approaches for calculating Franck‐Condon integrals (FCIs) of harmonic oscillators (HOs), which is valuable in interpreting or predicting vibronic spectroscopy and nonradiative processes of molecules. [1–5] The one‐dimensional (1D) FCI of displaced and distorted HO was reported in 2005. [1] The multidimensional FCI of HO up to 4D in which one electronic state was vibrtaionless was presented in 2008.…”

Section: Introductionmentioning

confidence: 99%

An analytical approach for computing Franck‐Condon integrals of harmonic oscillators with arbitrary dimensions

Chang¹,

Huang²,

Chen³

et al. 2012

J Comput Chem

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We have developed an analytical approach for computing Franck-Condon integrals (FCIs) of harmonic oscillators (HOs) with arbitrary dimensions in which the mode-mixing Duschinsky effect is taken into account. A general formula of FCIs of HOs was obtained and was applied to study the photoelectron spectroscopy of vinyl alcohol and ovalene (C(32)H(14)). The equilibrium geometries, harmonic vibrational frequencies and normal modes of vinyl alcohol, ovalene, and their cations were computed at the B3LYP/aug-cc-pVTZ or the B3LYP/6-31G(d) level, from which Franck-Condon factors were calculated and photoelectron spectra were simulated. The adiabatic ionization energies of vinyl alcohol were also computed by extrapolating the CCSD(T) energies to the complete basis set limit with aug-cc-pVXZ (X = D, T, Q, 5). The simulated photoelectron spectra of both vinyl alcohol and ovalene are in agreement with the experiments. The computed adiabatic ionization energies of syn- and anti-vinyl alcohol are in consistent with the experiment within 0.008 eV and 0.014 eV, respectively. We show, for the first time, that the analytical approach of computing FCIs is also efficient and promising for the studies of vibronic spectra of macrosystems.

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Ab initio calculations of excited states of vinyl bromide

Cited by 12 publications

References 31 publications

Ultraviolet photodissociation of vinyl iodide: understanding the halogen dependence of photodissociation mechanisms in vinyl halides

Ultraviolet photodissociation of vinyl iodide: understanding the halogen dependence of photodissociation mechanisms in vinyl halides

A general formula of two-dimensional Franck–Condon integral and the photoelectron spectroscopy of sulfur dioxide

An analytical approach for computing Franck‐Condon integrals of harmonic oscillators with arbitrary dimensions

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