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A density functional theory study on the reactions of Y atom and Y + cation with carbonyl sulfide
Author(s) -
Dai GuoLiang,
Wang ChuanFeng,
Jin YanXian,
Zhong AiGuo
Publication year - 2010
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.22398
Subject(s) - intersystem crossing , chemistry , reaction mechanism , density functional theory , carbonyl sulfide , ground state , excited state , activation energy , atom (system on chip) , computational chemistry , photochemistry , potential energy , catalysis , atomic physics , sulfur , singlet state , physics , organic chemistry , computer science , embedded system
The mechanism of the title reactions have been studied by using the DFT (B3LYP/ECP/6‐311+G*) level of theory. Both ground and excited state potential energy surfaces are discussed. It is found the reaction mechanism is insertion mechanism both along the CS and CO bond activation branches, but the CS bond activation is much more favorable in energy than the CO bond activation. The reaction of Y atom with SCO was shown to occur preferentially on the ground state (doublet) PES throughout the reaction process, and the experimentally observed species, have been explained according to the mechanism revealed in this work. Different from that of Y + SCO system, the reaction between Y + cation and SCO involves potential energy curve‐crossing which dramatically affects reaction mechanism. Due to the intersystem crossing existing in the reaction process of Y + with SCO, the intermediates SY + (η 2 CO) and OY + (η 2 CS) may not form. All our theoretical results not only support the existing conclusions inferred from early experiment, but also complement the pathway and mechanism for this reaction. © 2009 Wiley Periodicals, Inc. Int J Quantum Chem, 2010