从头算价键理论的研究进展

(厦门大学化学化工学院,固体表面物理化学国家重点实验室,福建省理论与计算化学重点实验室,福建 厦门 361005)

价键理论; 矩阵元计算; 计算程序; 从头算; 化学键理论

Progress in ab initio valence bond theory
WU Wei*,ZHENG Peikun

(State Key Laboratory of Physical Chemistry of Solid Surfaces,Fujian Provincial Key Laboratory of Theoretical and Computational Chemistry,College of Chemistry and Chemical Engineering,Xiamen University,Xiamen,361005,China)

DOI: 10.6043/j.issn.0438-0479.202009044

备注

作为现代化学键理论之一,价键理论为分子电子结构性质和化学反应机理提供了直观的化学图像理解.虽然当前分子轨道理论占据着量子电子结构研究的主导地位,但是随着计算机运算能力的迅速提升以及量子理论计算算法的日益完善,从头算价键理论重新引起了人们的重视.本文简要回顾了40年来从头算价键理论方法所取得的突破,着重阐述厦门大学化学键理论研究团队在这一领域取得的研究进展.首先介绍早期从头算价键理论方法的发展历史; 然后讨论从头算价键理论中的计算方法,包括最基本的价键自洽场方法,在此基础上考虑动态电子相关的价键计算方法,以及溶液环境下的计算方法; 最后简要介绍价键理论中的矩阵元计算方法以及国际上具有重要影响的从头算价键程序,并展望未来发展方向.
As one of the modern chemical bond theories,valence bond(VB)theory provides an intuitive chemical picture for understanding electronic structure properties of molecules and chemical reaction mechanisms.Although molecular orbital theory dominates the quantum electronic structure computation,with rapid improvement in the computing power of computers and the increasing algorithm perfection for quantum theoretical computation,the VB theory based ab initio quantum chemistry calculation attracts chemists' attention again.This article briefly reviews the breakthrough in ab initio VB theory over the past four decades, and highlights recent progress made by our group.Firstly,we introduce the early history of VB theory.Subsequently,the computational methods at ab initio level in VB theory are discussed,which include VB self-consistent field method,VB method sincorporating dynamic electron correlation,as well as the methods for systems in solutions.Finally,the algorithms for matrix elements calculation in VB theory and some well-known ab initio VB programs are also briefly discussed, and the review ends with an outlook.