NH₂(A²A′)的从头算全局势能面及伦纳-泰勒A²A′-X²A″体系的振动光谱

An ab initio global potential-energy surface for NH2(A(2)A') and vibrational spectrum of the Renner-Teller A(2)A'-X(2)A" system.

作者信息

Zhou Shulan, Li Zheng, Xie Daiqian, Lin Shi Ying, Guo Hua

机构信息

Department of Chemistry and Chemical Biology, University of New Mexico, Albuquerque, New Mexico 87131, USA.

出版信息

J Chem Phys. 2009 May 14;130(18):184307. doi: 10.1063/1.3125511.

DOI:10.1063/1.3125511

PMID:19449921

Abstract

A global potential-energy surface for the first excited electronic state of NH(2)(A(2)A(')) has been constructed by three-dimensional cubic spline interpolation of more than 20,000 ab initio points, which were calculated at the multireference configuration-interaction level with the Davidson correction using the augmented correlation-consistent polarized valence quadruple-zeta basis set. The (J=0) vibrational energy levels for the ground (X(2)A(")) and excited (A(2)A(')) electronic states of NH(2) were calculated on our potential-energy surfaces with the diagonal Renner-Teller terms. The results show a good agreement with the experimental vibrational frequencies of NH(2) and its isotopomers.

摘要

通过对20000多个从头算点进行三维三次样条插值，构建了NH₂（A²A′）第一激发电子态的全局势能面，这些点是在多参考组态相互作用水平下，使用增强的相关一致极化价四重zeta基组并采用戴维森校正计算得到的。利用对角的伦纳 - 泰勒项，在我们构建的势能面上计算了NH₂基态（X²A″）和激发态（A²A′）的（J = 0）振动能级。结果表明，计算结果与NH₂及其同位素变体的实验振动频率吻合良好。