Ab initio and kinetics study of the ground 1A" potential energy surface of the O(1D)+N2O→2NO, N2+O2(a1Δg) reactions

被引：15

作者：

González, M

Sayós, R

Valero, R

机构：

[1] Leiden Univ, Leiden Inst Chem, Gorlaeus Labs, NL-2300 RA Leiden, Netherlands

[2] Univ Barcelona, Dept Quim Fis, E-08028 Barcelona, Spain

[3] Univ Barcelona, Ctr Recerca Quim Teor, E-08028 Barcelona, Spain

来源：

CHEMICAL PHYSICS LETTERS | 2002年 / 355卷 / 1-2期

关键词：

D O I：

10.1016/S0009-2614(02)00195-1

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：

An ab initio CASPT2//CASSCF study of the ground (1)A" potential energy surface (PES) for the title reactions has been carried out, The lowest energy barrier heights correspond to cis-arrangements in both reactive channels. Crossings with the first excited (1)A" PES are located, being complicated by spurious symmetry breaking of the complete active space self-consistent field (CASSCF) wave function, The rate constant values have been calculated employing transition state theory (TST) in the temperature range 500-5000 K, The main contribution to the total rate constant stems from the barrierless ground (1)A' PES, while the (1)A" PES is only relevant at the highest temperatures. (C) 2002 Elsevier Science B.V. All rights reserved.

引用

页码：123 / 132

页数：10

共 34 条

[1] Theoretical investigation of the potential energy surfaces for the O(1D)+N2O reaction [J].