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Theoretical investigations of spin‐orbit coupling and intersystem crossing in reaction carbon dioxide activated by [Re(CO) 2 ] +
Author(s) -
Kang Juanxia,
Wang Yongcheng,
Wu Jingjing,
Zhu Zhiming
Publication year - 2020
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.26109
Subject(s) - intersystem crossing , chemistry , singlet state , atomic physics , triplet state , spin (aerodynamics) , molecular orbital , reaction rate constant , electron , electron transfer , molecular physics , physics , excited state , thermodynamics , molecule , quantum mechanics , kinetics , organic chemistry
In order to further explore the detailed reaction mechanism of carbon dioxide activated by [Re(CO) 2 ] + complex, CCSD(T) methods was performed to determine related potential energy surface (PES). Crossing point is determined by using a partially optimized method. The result shows that larger spin‐orbital coupling (155.37 cm −1 ) and intersystem crossing probabilities in spin‐forbidden region causes the electron to spin flip at the minimum energy crossing point and access to the lower singlet PES. Nonadiabatic rate constant k is estimated to be quite rapid, so transition state ( 1 TS1) is rate‐controlled steps. In addition, the electronic structure of oxygen‐atom transfer process is further analyzed by localized molecular orbital and Mayer bond order. The analysis finds that the form of main bonding orbital is the electron contribution from the p(O) in CO 2 to the empty d(Re) orbital.