对分子氯最低23个态的势能面进行的全相对论计算。

Fully relativistic calculations on the potential energy surfaces of the lowest 23 states of molecular chlorine.

作者信息

de Macedo Luiz Guilherme M, de Jong Wibe A

机构信息

Laboratório de Simulação Computacional, Departamento de Quimica, Universidade Estadual Paulista (UNESP), Bauru, São Paulo 17033-360, Brazil.

出版信息

J Chem Phys. 2008 Jan 28;128(4):041101. doi: 10.1063/1.2827457.

DOI:10.1063/1.2827457

PMID:18247920

Abstract

The electronic structure and spectroscopic properties (R(e), omega(e), omega(e)x(e), beta(e), and T(e)) of the ground state and the 22 lowest excited states of chlorine molecule were studied within a four-component relativistic framework using the MOLFDIR program package. The potential energy curves of all possible 23 covalent states were calculated using relativistic complete open shell configuration interaction approach. In addition, four component multireference configuration interaction with single and double excitation calculations were performed in order to infer the effects due to dynamical correlation in vertical excitations. The calculated properties are in good agreement with the available experimental data.

摘要

使用MOLFDIR程序包，在四分量相对论框架内研究了氯分子基态和22个最低激发态的电子结构和光谱性质（R(e)、ω(e)、ω(e)x(e)、β(e)和T(e)）。使用相对论完全开壳层组态相互作用方法计算了所有可能的23个共价态的势能曲线。此外，进行了包含单激发和双激发的四分量多参考组态相互作用计算，以推断垂直激发中动态关联的影响。计算得到的性质与现有的实验数据吻合良好。