Theoretical study of the reaction of S+ with acetylene

被引：7

作者：

Barrientos, C ^{[1
]}

Redondo, P ^{[1
]}

Largo, A ^{[1
]}

机构：

[1] Univ Valladolid, Fac Ciencias, Dept Quim Fis, E-47005 Valladolid, Spain

来源：

CHEMICAL PHYSICS LETTERS | 1999年 / 306卷 / 3-4期

关键词：

D O I：

10.1016/S0009-2614(99)00428-5

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

A theoretical study of the reaction of S+ with acetylene has been carried out using the G2 procedure and the CCSD(T) method with the cc-pVTZ basis set on B3LYP/cc-pVTZ geometries. Whereas G2 and CCSD(T) methods provide similar results, the B3LYP results differ considerably. The G2(P) procedure (which employs spin-projected MP values for computation of the G2 energy) gives results which are in agreement with the B3LYP ones. Production of SC2H+ is shown to be exothermic at all levels of theory, in agreement with experiment. G1, G2 and CCSD(T) methods predict a small activation barrier for this reaction (about 2-4 kcal mol(-1)) on the quartet surface. Intersystem crossing, leading to the doublet surface, is feasible and the reaction proceeds on this surface without any barrier. Therefore the reaction of S+ ions with acetylene could take place simultaneously by two different mechanisms: direct formation of products on the quartet surface and through the doublet sm face via intersystem crossing. (C) 1999 Elsevier Science B.V. All rights reserved.

引用

页码：168 / 178

页数：11

共 20 条

[1] EVALUATED BIMOLECULAR ION-MOLECULE GAS-PHASE KINETICS OF POSITIVE-IONS FOR USE IN MODELING PLANETARY-ATMOSPHERES, COMETARY COMAE, AND INTERSTELLAR CLOUDS [J].