Hydrogen migration in the phenylethen-2-yl radical

被引：49

作者：

Moriarty, NW

Brown, NJ

Frenklach, M ^{[1
]}

机构：

[1] Univ Calif Berkeley, Dept Mech Engn, Berkeley, CA 94720 USA

[2] Univ Calif Berkeley, Lawrence Berkeley Lab, Energy & Environm Technol Div, Berkeley, CA 94720 USA

来源：

JOURNAL OF PHYSICAL CHEMISTRY A | 1999年 / 103卷 / 35期

关键词：

D O I：

10.1021/jp991481f

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 migration of hydrogen in the phenylethen-2-yl radical is investigated by determining optimal geometries and barrier and reaction energies using several quantum mechanical methods. Rate coefficients and equilibrium constants are obtained using the calculated data and RRKM theory. Theoretical methods compared include PM3, MP2, B3-LYP, CASPT2, and G2MP2. The applicability of these methods and comparisons with two others, G2M and CBS-RAD proposed to improve treatment of radicals, are discussed. The results obtained at the most reliable level of theory produce reaction rates sufficiently fast for these reactions to play a role in high-temperature aromatic chemistry.

引用

页码：7127 / 7135

页数：9

共 42 条

[1] THE CR-2 POTENTIAL-ENERGY CURVE STUDIED WITH MULTICONFIGURATIONAL 2ND-ORDER PERTURBATION-THEORY [J].