Unimolecular reactions on formaldehyde S0PES

被引：24

作者：

Bauerfeldt, GF ^{[1
]}

de Albuquerque, LMM ^{[1
]}

Arbilla, G ^{[1
]}

da Silva, EC ^{[1
]}

机构：

[1] Univ Fed Rio de Janeiro, Inst Quim, Dept Fisicoquim, Ctr Tecnol, BR-21949900 Rio De Janeiro, Brazil

来源：

JOURNAL OF MOLECULAR STRUCTURE-THEOCHEM | 2002年 / 580卷

关键词：

H2CO; unimolecular reactions; direct dynamics; variational RRKM rate coefficients;

D O I：

10.1016/S0166-1280(01)00609-1

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：

The competitive unimolecular reactions of formaldehyde., H2CO --> H-2 + CO; H2CO --> trans-HCOH and H2CO --> H + HCO, were comparatively studied under the direct dynamics formalism, using Density functional and ab initio levels of theory. In addition, the geometric isomerization trans-HCOH --> cis-HCOH was evaluated. Calculated reaction path properties were used in the determination of Rice-Ramsperger-Kassel-Marcus microcanonical rate coefficients. The reaction dynamics was evaluated for each individual process based on the nuclear displacements in the reaction path and normal coordinate analysis. Our results found are in very good agreement with experimental barrier heights and quantum yields trends. (C) 2002 Elsevier Science B.V. All rights reserved.

引用

页码：147 / 160

页数：14

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