Theoretical investigations of spin-orbit coupling and intersystem crossing in reaction carbon dioxide activated by [Re(CO)2]+ |
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Authors: | Juanxia Kang Yongcheng Wang Jingjing Wu Zhiming Zhu |
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Institution: | 1. College of Chemistry and Chemical Engineering, Northwest Normal University, Lanzhou, Gansu, China;2. College of Chemical and Biological Engineering, Lanzhou Jiaotong University, Lanzhou, Gansu, China |
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Abstract: | 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 (1TS1) 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 CO2 to the empty d(Re) orbital. |
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Keywords: | CCSD(T) reaction mechanism minimum energy crossing point spin flip spin-orbit coupling |
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