期刊
JOURNAL OF CHEMICAL PHYSICS
卷 130, 期 17, 页码 -出版社
AMER INST PHYSICS
DOI: 10.1063/1.3120607
关键词
configuration interactions; coupled cluster calculations; curve fitting; dissociation energies; Jahn-Teller effect; least squares approximations; organic compounds; potential energy surfaces
资金
- US Department of Energy, Office of Science [DE-FG02-07ER54914, DE-AC02-05CH11231]
- Office of Naval Research [N00014-05-1-0460, N00014-05-1-0235]
The potential energy landscape and two permutationally invariant, full-dimensional ab initio-based potential energy surfaces (PESs) for the doublet vinyl radical, C2H3, are described. The first of the two surfaces, denoted as PES/S, describes the equivalent CH2CH global minimum and the saddle point separating them, planar and nonplanar H-atom migration saddle points, a methylcarbyne local minimum that is due to a Jahn-Teller conical intersection, and the saddle point connecting it with the global minimum. The second PES, denoted PES/D, contains all stationary points of PES/S and in addition describes dissociation to C2H2+H fragments, including the saddle point to dissociation along a least-energy path. The surfaces are least-squares fits to electronic energies obtained with use of the spin-restricted coupled cluster singles and doubles with perturbative treatment of triples method and augmented correlation consistent polarized valence triple zeta basis sets, using permutationally invariant polynomials in Morse variables and a many-body expansion. PES/S is a fit to roughly 34 000 and PES/D to roughly 50 000 electronic structure energies. PES/S is used in full-dimensional, vibrational configuration interaction calculations of the vinyl zero-point energy and fundamental vibrational energies, which are compared to recent experiments.
作者
我是这篇论文的作者
点击您的名字以认领此论文并将其添加到您的个人资料中。
推荐
暂无数据