Theoretical study on the reaction of NbS^+(~3∑^-,~1Γ) with CO  

作　　者：Shi Wen Yu TaoHong Li Xiao Mei Yang Li Qing Yin Li Feng Yao Xiao Guang Xie 

机构地区：[1]Department of Chemistry, Yunnan University, Kunming 650091, China [2]Department of Chemistry, Qujing Normal University, Qujing 650011, China [3]Faculty of Chemistry, Southwest Forestry University, Kunming 650224, China [4]Yunnan University of Traditional Chinese Medicine, Kunming 650091, China

出　　处：《Chinese Chemical Letters》2009年第6期755-758,共4页中国化学快报（英文版）

基　　金：supported by the National Natural Science Foundation of China(No.20563005);the Key Laboratory of Forest Resources Conservation and Use in the Southwest Mountains of China(Southwest Forestry University);the General Program of the Applied Basic Research of Science and Technology Department of Yunnan Province

摘　　要：Two possible reactions of NbS＋ （3∑^-, 1Г） with CO in the gas phase have been studied by using B3LYP and CCSD（T） methods： the O/S exchange reaction （NbS^＋ ＋ CO → NbO^＋ ＋ CS） and the S-transfer reaction （NbS＋ ＋ CO → Nb^＋ ＋ COS）. The two reactions have a one-step mechanism. The barriers of the O/S exchange reaction on the triplet and singlet surfaces are 51.2 and 52.4 kcal/mol, respectively, and the barriers of the S-transfer reaction are 58.3 and 78.0 kcal/mol, respectively. The results indicate that the Stransfer and the O/S exchange reaction of the 3∑^- ground state of NbS＋ are competing, but, for the S-transfer reaction, the 1F exited state is more reactive. The differences between the reactions of NbS＋ （3∑^_, 1Г） and VS＋ （3∑^_, 1Г） are discussed.Two possible reactions of NbS＋ （3∑^-, 1Г） with CO in the gas phase have been studied by using B3LYP and CCSD（T） methods： the O/S exchange reaction （NbS^＋ ＋ CO → NbO^＋ ＋ CS） and the S-transfer reaction （NbS＋ ＋ CO → Nb^＋ ＋ COS）. The two reactions have a one-step mechanism. The barriers of the O/S exchange reaction on the triplet and singlet surfaces are 51.2 and 52.4 kcal/mol, respectively, and the barriers of the S-transfer reaction are 58.3 and 78.0 kcal/mol, respectively. The results indicate that the Stransfer and the O/S exchange reaction of the 3∑^- ground state of NbS＋ are competing, but, for the S-transfer reaction, the 1F exited state is more reactive. The differences between the reactions of NbS＋ （3∑^_, 1Г） and VS＋ （3∑^_, 1Г） are discussed.

关 键 词：Niobium sulfide cation CO REACTION CCSD（T） 

分 类 号：O613.71[理学—无机化学] C829.23[理学—化学]