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An ab Initio Investigationof Fluorobromo Carbene.

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Bibliographic Details
Title:	An ab Initio Investigationof Fluorobromo Carbene.
Authors:	Sun, Erping¹, Li, Rui¹, Sun, Qixiang¹, Wei, Changli¹, Xu, Haifeng¹, Yan, Bing¹
Source:	Journal of Physical Chemistry A. Oct2012, Vol. 116 Issue 42, p10435-10440. 6p.
Subjects:	Carbenes, Halogenation, Molecular structure, Perturbation theory, Potential energy surfaces, Basis sets (Quantum mechanics)
Abstract:	Fluorobromo carbene, an important halogenated carbenein the stratosphericozone depletion, has long been received considerable interest. However,the energy, structure, and dynamics of even the lowest excited stateshave not been well understood. In this paper, we performed a detailab 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 theground X1A′ state and the first excited singletA1A″ state. The potential energy surface (PES) ofthe A1A″ state along C–Br bond distance wascarefully examined at CASPT2/cc-pV5Z level, by optimizing C–Fbond and F–C–Br angle at every C–Br bond lengthin contrast to fix them at the equilibrium values. On the basis ofthe PES, a reliable barrier height of the A1A″ statewas obtained from CASPT2 and MRCI+Q calculations with different basissets, considering the scalar relativistic effect, spin–orbitcoupling, and core–valence correlation. Finally, we carriedout the first theoretical study on higher excited state with energyup to 7 eV. The present calculated results were compared with previousexperimental and theoretical results where available. Our resultswill add some understanding and shed more light on the structure anddynamics of electronic states of CFBr radical. [ABSTRACT FROM AUTHOR]
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Database:	Engineering Source

Description
Abstract:	Fluorobromo carbene, an important halogenated carbenein the stratosphericozone depletion, has long been received considerable interest. However,the energy, structure, and dynamics of even the lowest excited stateshave not been well understood. In this paper, we performed a detailab 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 theground X1A′ state and the first excited singletA1A″ state. The potential energy surface (PES) ofthe A1A″ state along C–Br bond distance wascarefully examined at CASPT2/cc-pV5Z level, by optimizing C–Fbond and F–C–Br angle at every C–Br bond lengthin contrast to fix them at the equilibrium values. On the basis ofthe PES, a reliable barrier height of the A1A″ statewas obtained from CASPT2 and MRCI+Q calculations with different basissets, considering the scalar relativistic effect, spin–orbitcoupling, and core–valence correlation. Finally, we carriedout the first theoretical study on higher excited state with energyup to 7 eV. The present calculated results were compared with previousexperimental and theoretical results where available. Our resultswill add some understanding and shed more light on the structure anddynamics of electronic states of CFBr radical. [ABSTRACT FROM AUTHOR]
ISSN:	10895639
DOI:	10.1021/jp307921p