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Theoretical study of the mechanism for spin‐forbidden quenching process O( 1 D) + CO 2 ( 1 Σ + g ) → O( 3 P) + CO 2 ( 1 Σ + g )
Author(s) -
Yang Guanghui,
Yao Li,
Zhang Xin,
Meng Qingtian,
Han KeLi
Publication year - 2005
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/qua.20672
Subject(s) - singlet state , atomic physics , ab initio , chemistry , spin (aerodynamics) , quenching (fluorescence) , potential energy surface , spin–orbit interaction , coupling (piping) , ab initio quantum chemistry methods , physics , molecule , excited state , fluorescence , materials science , condensed matter physics , quantum mechanics , thermodynamics , organic chemistry , metallurgy
The mechanism of the spin‐forbidden quenching process O( 1 D) + CO 2 ( 1 Σ + g ) → O( 3 P) + CO 2 ( 1 Σ + g ) was investigated by ab initio quantum chemistry methods. The calculations showed the singlet potential surface [O( 1 D)+CO 2 ] is attractive where a strongly bound intermediate complex CO 3 is formed in the potential basin without a transition state, whereas the complex CO 3 that is formed on the triplet surface [O( 3 P)+CO 3 ] must overcome a barrier. The complex channel was documented by searching minimum energy intersection points in the region of the bound complex CO 3 and calculating spin‐orbit coupling at the point. A direct channel was proposed by a study of cross point of singlet and triplet PESs with different collision angles and calculations of spin‐orbit coupling at those cross points in a nonbound region of the [O( 1 D)+CO 3 ] system. The mechanism of the energy transfer is discussed on the basis of the theoretical results. © 2005 Wiley Periodicals, Inc. Int J Quantum Chem, 2005