Ab initio calculations of the thermolysis reaction of β-hydroxyalkynes in the gas phase

被引：7
|
作者：
Quijano, J
Sánchez, C
David, J
Rincón, E
León, LA
Notario, R
Abboud, JLM
机构：
[1] Univ Nacl Colombia, Dept Quim, Lab Fisicoquim Organ, Sede Medellin, Medellin, Colombia
[2] Escuela Ingn Antioquia, Envigado, Colombia
[3] CSIC, Inst Quim Fis Rocasolano, E-28006 Madrid, Spain
来源：
JOURNAL OF MOLECULAR STRUCTURE-THEOCHEM | 2001年 / 572卷
关键词：
transition state structures; ab initio computational methods; thermolysis reactions; beta-hydroxy acetylenes; reaction mechanisms;
D O I：
10.1016/S0166-1280(01)00577-2
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：
Thermolysis of three beta -hydroxyacetylenes were studied with the second-order Moller-Plesset perturbation theory using a split valence polarization 6-31G(d) basis set. The obtained optimized geometries, atomic charge distributions and energy values are in agreement with the experimental measurements. The rate coefficients, calculated theoretically over the temperature range of 500-700 K, are given by the Arrhenius equation: for the primary, log k(1) (s(-1)) = 12.5-175.6 kJ mol(-1) (2.303RT)(-1); for the secondary, log k(2) (s(-1)) = 11.7-171.0 kJ mol(-1) (2.303RT)(-1); and for the tertiary, log k(3) (s(-1)) = 12.5-172.7 kJ mol(-1) (2.303RT)(-1). The values of log A, from 11.7 to 12.5 (DeltaS(not equal) < 0), indicate that these decompositions are concerted processes with a six-membered cyclic transition state. (C) 2001 Elsevier Science BN. All rights reserved.
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收藏
页码：135 / 139
页数：5
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