大分子和凝聚相体系的快速量子化学计算:普适的基于能量的分块方法的发展和应用  

Fast quantum chemistry calculations for large molecules and condensed-phase systems: The developments and applications of generalized energy-based fragmentation approach

作　　者：廖康 程正 李云志 赵东波 李伟 黎书华 Kang Liao;Zheng Cheng;Yunzhi Li;Dongbo Zhao;Wei Li;Shuhua Li(Institute of Theoretical and Computational Chemistry,Key Laboratory of Mesoscopic Chemistry of Ministry of Education,School of Chemistry and Chemical Engineering,Nanjing University,Nanjing 210023,China)

机构地区：[1]南京大学化学化工学院,介观化学教育部重点实验室,理论与计算化学研究所,南京210023

出　　处：《科学通报》2018年第33期3427-3441,共15页Chinese Science Bulletin

基　　金：国家自然科学基金(21873046,21833002,21473087);中央高校基本科研业务费专项资金(020514380150)资助

摘　　要：大分子和凝聚相体系的量子化学计算是理论化学的挑战之一,为了处理实验研究中越来越复杂的体系,线性标度的量子化学方法发展一直是理论研究的热点.由于简单有效且易于推广,基于能量的分块方法近十几年来得到较快的发展.本文主要介绍本课题组的普适的基于能量的分块量子化学方法的发展和应用,包括大体系的基态能量、结构和性质、局域激发态的计算方法及周期性体系的算法.该方法有望应用于多种类型的大体系(包括团簇、超分子、生物体系、分子晶体和溶液等)的能量、结构、振动光谱、核磁化学位移及电子吸收光谱等性质的计算.It is a challenge in theoretical chemistry to perform the quantum chemistry calculations for large molecules and condensedphase systems due to the high scalings of the conventional quantum chemistry methods. In order to treat more and more complicated systems in experiments, the development of linear scaling quantum chemistry methods is an active area in theoretical studies. There are two categories of these methods. One is the category of first-principle base methods, including linear scaling Hartree-Fock（HF） and density functional theory（DFT） methods and local correlation methods. Another is the category of fragment-based methods, including density matrix based methods and energy-based fragmentation methods. The energy-based fragmentation approach has been developed rapidly in the last decade due to its simplicity, effectiveness, and extendibility. In this article, we review the developments and applications of the generalized energy-based fragmentation（GEBF） approach proposed in our research group. The basic idea of the GEBF approach is that the total ground-state energy of a large system can be linearly combined by the corresponding ground-state energies of various subsystems, each of which is embedded in the background charges on the places of those atoms outside the subsystem. In the GEBF approach, the target system is divided into various medium-sized fragments, each of which（called central fragment） is capped by its neighboring fragments to form a primitive subsystem. Then, the inclusion-exclusion principle is applied to all primitive subsystems to generate the derivative subsystems. The point charges, from natural population analysis, on all atoms are iteratively obtained by extracting the charges on the central fragments in primitive subsystems or combining the charges on all subsystems. Then the energies or energy derivatives of the target system could be combined by the corresponding values of all electrostatically embedded subsystems. The GEBF approach could be applied to the ground-s

关 键 词：量子化学计算 大分子 凝聚相体系 线性标度 基于能量的分块方法 

分 类 号：O641.121[理学—物理化学]