Spectroscopic Study of the Ã1A" - X~1A' System of CHBr

Shin, Seung-Keun; Park, Seung Min

doi:10.5012/bkcs.2011.32.3.905

Cited by 4 publications

(4 citation statements)

References 25 publications

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“…Due to the numerous interactions between the electronic states, such as Renner–Teller effect, spin–orbit coupling, avoided crossing, or nonadiabatic interaction leading to predissociation, the spectroscopy and photodissociation dynamics of halocarbenes are rather complicated, which stimulate scientists to continuously perform experimental and theoretical studies on these important reactive intermediates. During past several decades, with the advances of high-resolution laser-based spectroscopic techniques along with theoretical methods, a variety of halocarbenes, including monohalogenated carbenes CHF − /CHCl − /CHBr − /CHI, dihalogenated carbenes CCl 2 , − CBr 2 , CFCl, CFBr, − and CFI, and so on, have been widely investigated by using, for example, rotational-resolved laser absorption, laser-induced fluorescence (LIF), optical–optical-double-resonance (OODR), and stimulated emission pumping (SEP) techniques, as well as ab initio calculations. − The structure, spectroscopy, and interactions of the ground state and the lowest singlet/triplet excited states of the halocarbenes have been studied comprehensively. Although sparse studies concerning higher excited states have emerged, for example, photodissociation dynamics of CHF and CDF at the B state, − CCl 2 at 248 nm , and 193 nm, and CHCl, CFCl, and CFBr at 193 nm …”

Section: Introductionmentioning

confidence: 99%

An ab Initio Investigation of Fluorobromo Carbene

Sun

et al. 2012

J. Phys. Chem. A

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Fluorobromo carbene, an important halogenated carbene in the stratospheric ozone depletion, has long been received considerable interest. However, the energy, structure, and dynamics of even the lowest excited states have not been well understood. In this paper, we performed a detail ab initio study on CFBr using complete active space second-order perturbation (CASPT2) and multireference configuration interaction (MRCI) method. We investigated the effect of basis set on the CASPT2 results of the ground X(1)A' state and the first excited singlet A(1)A" state. The potential energy surface (PES) of the A(1)A" state along C-Br bond distance was carefully examined at CASPT2/cc-pV5Z level, by optimizing C-F bond and F-C-Br angle at every C-Br bond length in contrast to fix them at the equilibrium values. On the basis of the PES, a reliable barrier height of the A(1)A" state was obtained from CASPT2 and MRCI+Q calculations with different basis sets, considering the scalar relativistic effect, spin-orbit coupling, and core-valence correlation. Finally, we carried out the first theoretical study on higher excited state with energy up to 7 eV. The present calculated results were compared with previous experimental and theoretical results where available. Our results will add some understanding and shed more light on the structure and dynamics of electronic states of CFBr radical.

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Section: Introductionmentioning

confidence: 99%

An ab Initio Investigation of Fluorobromo Carbene

Sun

et al. 2012

J. Phys. Chem. A

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“…It should be mentioned that 4 1 A′ is a bent state, confirming the prediction of Shin and Park et al that CHBr is initially excited to a nonlinear excited state after absorbing 193 nm photons. 38…”

Section: Resultsmentioning

confidence: 99%

“…Hall et al 37 investigated the visible spectrum of CHBr, indicating the perturbation of parallel sub-bands being attributed to the predicted higher-energy excited state B 1 A′′. Shin and Park et al 38 reported the spectrum of CHBr produced by the pyrolysis of CH 3 Br using fluorescence excitation and emission spectroscopy. The researchers speculated that the CHBr molecule was excited to a nonlinear highly excited state after absorbing a 193 nm-laser photon, but the electronic states involved in the dissociation process and the corresponding photodissociation dynamics remain unclear.…”

Section: Introductionmentioning

confidence: 99%

Anab initiostudy on the electronic excited states and photodissociation mechanism of bromocarbene molecule

Shan

Sun

Gao

et al. 2023

Phys. Chem. Chem. Phys.

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“…Dissociation resulting in a loss of Br is particularly relevant to atmospheric ozone chemistry as the Br atom is much more destructive to ozone than the other halogen atoms − including the Cl atom. Bromine-containing halocarbons especially these bromine-substituted carbenes are the important subject of the experimental and theoretical studies in recent decades. − Herein, we focus on CBr 2 carbene.…”

Section: Introductionmentioning

confidence: 99%

Theoretical Study on the Spectroscopic Properties and Photodissociation Mechanism of Dibromocarbene

Sun,

Shan,

Miao

et al. 2023

J. Phys. Chem. A

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Detailed calculations on the electronic states of dibromocarbene (CBr2) herein are presented. First, the spectroscopic properties of the electronic states including geometry parameters, harmonic vibrational frequencies and transition energies of the lowest electronic states of the neutral radical were calculated in detail using the internally contracted multireference configuration interaction methods including Davidson correction (icMRCI+Q) with correlation consistent basis sets of aug-cc-pVXZ (X = T, Q, 5). Second, as CBr2 including two Br atoms, the Spin–Orbit Coupling (SOC) effect on the spectroscopic parameters and the one-dimensional cuts of the potential energy surface (PESs) of the lowest three states were studied. The barrier to linearity and dissociation of the singlet state were discussed. Third, the one-dimensional cuts along with the vertical transition energy (VTE), the oscillator strength, and so on of the electronic states related to the several lowest dissociation limits of CBr2 were calculated at the icMRCI+Q/aug-cc-pVTZ level. Based on the computed results of the electronic states of the radical, the photodissociation mechanism in the UV region were discussed in detail. The ab initio calculations are compared with the previous theoretical and experimental data and are in good agreement. The present work will provide a comprehensive understanding on the electronic structures and dissociation dynamics for the electronic states of the CBr2 radical.

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Spectroscopic Study of the Ã¹A" - X^~¹A' System of CHBr

Cited by 4 publications

References 25 publications

An ab Initio Investigation of Fluorobromo Carbene

An ab Initio Investigation of Fluorobromo Carbene

Anab initiostudy on the electronic excited states and photodissociation mechanism of bromocarbene molecule

Theoretical Study on the Spectroscopic Properties and Photodissociation Mechanism of Dibromocarbene

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