乙烯基自由基C₂H₃中能级的隧穿分裂和转动常数

Tunneling splitting of energy levels and rotational constants in the vinyl radical C2H3.

作者信息

Mil'nikov Gennady V, Ishida Toshimasa, Nakamura Hiroki

机构信息

Department of Theoretical Studies, Institute for Molecular Science, Myodaiji, Okazaki 444-8585, Japan.

出版信息

J Phys Chem A. 2006 Apr 27;110(16):5430-5. doi: 10.1021/jp055667s.

DOI:10.1021/jp055667s

PMID:16623471

Abstract

The instanton theory newly implemented by two of the authors (G.V.M. and H.N.) is applied to hydrogen tunneling transfer in a vinyl radical. The converged instanton trajectory is found on the CCSD(T)/aug-cc-pVTZ level of an ab initio potential energy surface. The calculated ground-state energy splitting agrees with the recent high-resolution experimental data within 3% of discrepancy. The semiclassical wave function is used to estimate the splitting of the principal rotational constants of the radical.

摘要

两位作者（G.V.M.和H.N.）新实施的瞬子理论被应用于乙烯基自由基中的氢隧穿转移。在从头算势能面的CCSD(T)/aug-cc-pVTZ水平上找到了收敛的瞬子轨迹。计算得到的基态能量分裂与最近的高分辨率实验数据的差异在3%以内。使用半经典波函数来估计自由基主要转动常数的分裂。