New dispersed fluorescence spectra of HCBr and DCBr

Chang, Wei Zhong; Hsu, Hui Ju; Chang, Ben

doi:10.1016/j.cplett.2005.07.059

Cited by 25 publications

(4 citation statements)

References 20 publications

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“…With the development of high-resolution laser spectroscopy, researchers have obtained information regarding the structures and vibrational frequencies of the X 1 A′, A 1 A′′, a 3 A′′ states as well as the singlet–triplet gap of CHBr. 28–31 Theoretically, potential energy curves (PECs), equilibrium geometries, and the vibrational frequencies of the lowest three states of the CHBr molecule have been studied using different quantitative methods. 32–36…”

Section: Introductionmentioning

confidence: 99%

“…With the development of highresolution laser spectroscopy, researchers have obtained information regarding the structures and vibrational frequencies of the X 1 A 0 , A 1 A 00 , a 3 A 00 states as well as the singlet-triplet gap of CHBr. [28][29][30][31] Theoretically, potential energy curves (PECs), equilibrium geometries, and the vibrational frequencies of the lowest three states of the CHBr molecule have been studied using different quantitative methods. [32][33][34][35][36] Compared to the three lowest-energy electronic states, there is still insufficient information regarding the spectrum and dynamics of the highly excited states of CHBr.…”

Section: Introductionmentioning

confidence: 99%

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An ab initio study 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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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

An ab initio study 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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“…Coupling of the triplet to the singlet groundX 1 A ′ state is important, as the states cross close to the minimum of each surface. This interaction was found to play a major role in the perturbation of vibrational levels of the interacting states, 5,6,[12][13][14][15][16][17][18][19][20][21] which has been examined in detail using laser-induced fluorescence (LIF), single vibronic level emission (SVLE) spectroscopy, [22][23][24][25][26][27][28][29][30][31][32] and stimulated emission pumping (SEP) spectroscopy. 33,34 While on one hand these studies have been remarkably successful in providing estimates for the singlet-triplet gaps, which have been compared with the predictions of ab initio and Density Functional Theory (DFT) calculations, 18, and revealed perturbations of the singlet level structure by SO-coupling, which have been analyzed in some detail, on the other hand, a global analysis of the SO-coupling in these systems has not been performed.…”

Section: Introductionmentioning

confidence: 99%

Towards a global model of spin-orbit coupling in the halocarbenes

Nyambo

Karshenas

Reid

et al. 2015

The Journal of Chemical Physics

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We report a global analysis of spin-orbit coupling in the mono-halocarbenes, CH(D)X, where X = Cl, Br, and I. These are model systems for examining carbene singlet-triplet energy gaps and spin-orbit coupling. Over the past decade, rich data sets collected using single vibronic level emission spectroscopy and stimulated emission pumping spectroscopy have yielded much information on the ground vibrational level structure and clearly demonstrated the presence of perturbations involving the low-lying triplet state. To model these interactions globally, we compare two approaches. First, we employ a diabatic treatment of the spin-orbit coupling, where the coupling matrix elements are written in terms of a purely electronic spin-orbit matrix element which is independent of nuclear coordinates, and an integral representing the overlap of the singlet and triplet vibrational wavefunctions. In this way, the structures, harmonic frequencies, and normal mode displacements from ab initio calculations were used to calculate the vibrational overlaps of the singlet and triplet state levels, including the full effects of Duschinsky mixing. These calculations have allowed many new assignments to be made, particularly for CHI, and provided spin-orbit coupling parameters and values for the singlet-triplet gaps. In a second approach, we have computed and fit full geometry dependent spin-orbit coupling surfaces and used them to compute matrix elements without the product form approximation. Those matrix elements were used in similar fits varying the anharmonic constants and singlet-triplet gap to reproduce the experimental levels. The derived spin-orbit parameters for carbenes CHX (X = Cl, Br, and I) show an excellent linear correlation with the atomic spin-orbit constant of the corresponding halogen, indicating that the spin-orbit coupling in the carbenes is consistently around 14% of the atomic value.

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“…Finally the cleavage of the C-Br bond occurs, and Br draws the H atom at the same time, generating P 2 (CO 2 + HBr). The processes are denoted as the route (5).…”

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confidence: 99%

Theoretical Study of the 1CHBr + 3O2 Reaction

Shi

Zhan

Liu

et al. 2011

AMR

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The mechanism of the reaction of the monobromocarbene (1CHBr) with3O2was studied theoretically at the B3LYP/6-311++G(d,p) level on the singlet potential energy surface (PES). All structures of the stationary points (reactants, intermediates, transition states and products) were optimized and their energies were obtained. Three product channels, P1(HCO + BrO), P2(CO2+ HBr) and P3(CO + HOBr), are found. P2(CO2+ HBr) is the most favorable one both kinetically and thermodynamically.

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New dispersed fluorescence spectra of HCBr and DCBr

Cited by 25 publications

References 20 publications

An ab initio study on the electronic excited states and photodissociation mechanism of bromocarbene molecule

An ab initio study on the electronic excited states and photodissociation mechanism of bromocarbene molecule

Towards a global model of spin-orbit coupling in the halocarbenes

Theoretical Study of the <sup>1</sup>CHBr + <sup>3</sup>O<sub>2</sub> Reaction

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