Theoretical study on the reaction of the Δ ground state of ZrO with CS2 in the gas phase |
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Authors: | Dong-Bao Hu Xiao-Mei Yang Li-Feng Yao Ling-Xia Zhang Shu-Ye Ma Shi-Wen Yu Tao-Hong Li Xiao-Guang Xie |
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Institution: | aDepartment of Chemistry, Yunnan University, Kunming 650091, China;bYunnan University of Traditional Chinese Medicine, Kunming 650091, China;cFaculty of Chemistry, Southwest Forestry University, Kunming 650224, China;dKey Laboratory of Medicinal Chemistry for Natural Resource (Yunnan University), Ministry of Education, Kunming 650091, China |
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Abstract: | The mechanisms for the three products ZrS+, and ZrOS+ of the title reaction have been studied by using B3LYP/6-311+G* and CCSD(T)/SDD+6-311+G* methods. It is found that both ZrS+ and formations involve the same O/S exchange process via a four-center transition state TS12 to form an intermediate IM2. Exception of that IM2 can dissociate into the ZrS+ product, a favorable intramolecular rearrangement mechanism associated with the formation has been identified, which explains why ZrS+ was excluded as a precusor for the formation and why the lower efficiency of the ZrS+ formation was observed in experiment. For the formation of ZrOS+, two parallel channels (path A and B) yielding their corresponding product isomer have been identified. Path B involving an insertion–elimination mechanism with a calculated barrier underestimated by ca. 25.0 kJ/mol should be attributed to the threshold of 114.8 ± 12.5 kJ/mol assigned in the experiment. But path A should make some contributions to the formation of ZrOS+ at elevated energy. |
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Keywords: | Zirconium oxide cation CS2 Reaction mechanism B3LYP CCSD(T) |
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