Theoretical Studies on the Mechanism for the Reaction of HNCS with CX (X=H, F, Cl) Radical

Acta Chimica Sinica ›› 2004, Vol. 62 ›› Issue (13): 1191-1196. Previous Articles Next Articles

HNCS与CX(X=H,F,Cl)自由基反应的理论研究

刘朋军^1,2, 赵岷¹, 潘秀梅¹, 苏忠民¹, 王荣顺¹

1. 东北师范大学化学学院功能材料化学研究所, 长春, 130024;
2. 海南师范学院化学系, 海口, 571158

投稿日期:2003-09-04 修回日期:2004-01-31 发布日期:2014-02-17
通讯作者: 王荣顺,E-mail:wangrs@nenu.edu.cn E-mail:wangrs@nenu.edu.cn
基金资助:
教育部"跨世纪优秀人才培养计划"基金(教技函[2001]3)、海南省教育厅科研基金(No.hjkj200312)、东北师范大学年轻教师基金(No.111382)资助项目.

Theoretical Studies on the Mechanism for the Reaction of HNCS with CX (X=H, F, Cl) Radical

LIU Peng-Jun^1,2, ZHAO Min¹, PAN Xiu-Mei¹, SU Zhong-Min¹, WANG Rong-Shun¹

1. Institute of Functional Material Chemistry, Faculty of Chemistry, Northeast Normal University, Changchun 130024;
2. Department of Chemistry, Hainan Normal University, Haikou 571158

Received:2003-09-04 Revised:2004-01-31 Published:2014-02-17

Abstract

DFT-UB3LYP was used to calculate the geometries of reactants, intermediates, transition states and products for HNCS+CX (X=H, F, Cl) reaction on the 6-31+G^* level.The transiton states and intermediates of the reaction were verified by frequency analysis.The relationship among reactants, transition states, intermediates and products was affirmed by IRC (intrinsic reaction coordinate) calculation.The energies along the MEP (minimum energy path) were further refined at the UQCISD(T)/6-311+G^** level.The kinetics of the title reaction was studied by using the "direct dynamics" method of variational transition-state theory.The rate constants of the title reaction were calculated for the range of temperature 250～1500 K.In the calculation, we considered the tunneling correction.The tunneling correction was calculated by using the centrifugal-dominant small curvature semiclassical adiabatic ground-state (CD-SCSAG) method.The results show that the reaction mechanism of the title reactions involves five steps.The reaction pathway is reactants→IMn1→TSn1→IMn2→TSn2→products.These reactions are exothermic.

Key words: isothiocyanic acid(HNCS), CX radical, reaction mechanism, density functional theory(DFT)

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LIU Peng-Jun, ZHAO Min, PAN Xiu-Mei, SU Zhong-Min, WANG Rong-Shun. Theoretical Studies on the Mechanism for the Reaction of HNCS with CX (X=H, F, Cl) Radical[J]. Acta Chimica Sinica, 2004, 62(13): 1191-1196.

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HNCS与CX(X=H,F,Cl)自由基反应的理论研究

Theoretical Studies on the Mechanism for the Reaction of HNCS with CX (X=H, F, Cl) Radical

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