High-dimensional ab initio potential energy surfaces for reaction dynamics calculations

被引：268

作者：

Bowman, Joel M. ^{[1
]}

Czako, Gabor ^{[1
]}

Fu, Bina

机构：

[1] Emory Univ, Dept Chem, Atlanta, GA 30322 USA

来源：

PHYSICAL CHEMISTRY CHEMICAL PHYSICS | 2011年 / 13卷 / 18期

基金：

美国国家科学基金会;

关键词：

HYDROGEN ABSTRACTION REACTION; TRANSITION-STATE THEORY; QUANTUM SCATTERING CALCULATIONS; BENDING MODE EXCITATIONS; REDUCED DIMENSIONALITY; PHOTODISSOCIATION DYNAMICS; CONICAL INTERSECTIONS; COMPARING REACTIONS; OH(A (2)SIGMA(+)); POLYNOMIAL BASIS;

D O I：

10.1039/c0cp02722g

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：

There has been great progress in the development of potential energy surfaces (PESs) for reaction dynamics that are fits to ab initio energies. The fitting techniques described here explicitly represent the invariance of the PES with respect to all permutations of like atoms. A review of a subset of dynamics calculations using such PESs (currently 16 such PESs exist) is then given. Bimolecular reactions of current interest to the community, namely, H + CH4 and F + CH4, are focused on. Unimolecular reactions are then reviewed, with a focus on the photodissociation dynamics of H2CO and CH3CHO, where so-called "roaming'' pathways have been discovered. The challenges for electronically non-adiabatic reactions, and associated PESs, are presented with a focus on the OH* + H-2 reaction. Finally, some thoughts on future directions and challenges are given.

引用

页码：8094 / 8111

页数：18

共 163 条

[31] Evidence for Vinylidene Production in the Photodissociation of the Allyl Radical [J].