Theoretical Study on the Gas Phase Reaction of Au^+ with CS_2  

作　　者：李涛洪 余仕问 刘祥义 谢小光 

机构地区：[1]Faculty of Chemistry,Southwest Forestry College [2]Department of Chemistry,Qujing Normal University [3]Department of Chemistry,Yunnan University

出　　处：《Chinese Journal of Structural Chemistry》2010年第9期1347-1352,共6页结构化学（英文）

基　　金：Supported by the General Program of the Applied Basic Research of Science and Technology Department of Yunnan Province (No.2008ZC095);the Scientific Research Fund of Yunnan Provincial Education Department (No.08Y0195);supported by the Key Laboratory of Forest Resources Conservation and Use in the Southwest Mountains of China (Southwest Forestry University)

摘　　要：The reaction of Au＋（1S,3D） with CS2 has been investigated at the B3LYP and CCSD（T） levels of theory.The identified reaction pathways revealed that the experimentally observed products,AuS＋ and AuCS＋,can be produced by the insertion of Au＋ into C-S bond.The calculated energetics shows that the reactions on singlet surface lead to excited-state products,AuS＋（1Σ） ＋ 1CS and AuCS＋（1Σ） ＋ 1S,and have notable energy barriers,whereas the reactions on triplet surface producing the ground state products of AuS＋（3Σ） ＋ 1CS and AuCS＋（1Σ） ＋ 3S are energetically much more favorable.This result suggests that the minor formations of AuS＋ and AuCS＋ observed in the previous experiment under room-temperature condition should result from the reactions of excited-state Au＋（3D） with CS2.Further,the possibility for singlet-triplet surface crossing was also discussed by approximately determining the crossing region.The reaction of Au＋（1S,3D） with CS2 has been investigated at the B3LYP and CCSD（T） levels of theory.The identified reaction pathways revealed that the experimentally observed products,AuS＋ and AuCS＋,can be produced by the insertion of Au＋ into C-S bond.The calculated energetics shows that the reactions on singlet surface lead to excited-state products,AuS＋（1Σ） ＋ 1CS and AuCS＋（1Σ） ＋ 1S,and have notable energy barriers,whereas the reactions on triplet surface producing the ground state products of AuS＋（3Σ） ＋ 1CS and AuCS＋（1Σ） ＋ 3S are energetically much more favorable.This result suggests that the minor formations of AuS＋ and AuCS＋ observed in the previous experiment under room-temperature condition should result from the reactions of excited-state Au＋（3D） with CS2.Further,the possibility for singlet-triplet surface crossing was also discussed by approximately determining the crossing region.

关 键 词：gold cation carbon disulfide INSERTION theoretical study 

分 类 号：O643.1[理学—物理化学]