基于片段的量子化学方法能否用于中等尺寸的水簇?
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- 英文论文题名：Are fragment-based quantum chemistry methods applicable to medium-sized water clusters?
- 论文作者：袁丹丹 ; 沈笑凌 ; 李伟 ; 黎书华
- 英文论文作者：Dandan Yuan ; Xiaoling Shen ; Wei Li ; Shuhua Li ; School of Chemistry and Chemical Engineering ; Key Laboratory of Mesoscopic Chemistry of Ministry of Education ; Institute of Theoretical and Computational Chemistry ; Nanjing University
- 年：2016
- 作者机构：南京大学;
- 论文关键词：基于片段的量子化学方法 ; 水簇 ; 基态能量
- 会议召开时间：2016-07-01
- 会议录名称：中国化学会第30届学术年会摘要集-第十八分会：电子结构理论方法的发展与应用
- 语种：中文
- 分类号：O641.121
- 学会代码：ZGHY
- 会议名称：中国化学会第30届学术年会-第十八分会 ; 电子结构理论方法的发展与应用
- 会议地点：中国辽宁大连
- 主办单位：中国化学会
- 学会名称：中国化学会
- 页数：1
- 文件大小：220k
- 原文格式：D
- 会议级别：全国
摘要
基于片段的量子化学方法可归为两类,一类基于多体展开(many-body expansion),另一类基于容斥原理(inclusion-exclusion principle)。为了比较这两类方法的性能,我们选定推广的基于能量的分块方法(GEBF)和多体展开方法(EE-MB)作为这两类方法的代表并系统地研究了它们用于水簇(H_2O)_n(n=10,20,30)的性能。我们发现在一系列计算水平下,GEBF方法能准确的计算三类水簇的基态能量;然而当使用含有弥散函数的基组时EE-MB方法不能正确计算(H_2O)_(20)和(H_2O)_(30)的基态能量,这是因为在计算子体系时没有考虑其它原子的基组叠加效应(BSSE)带来的误差;我们还通过计算证明BSSE不影响GEBF方法的精度。总的来说,GEBF方法适用于任何基组下的水簇体系的计算。
Fragment-based quantum chemistry methods are either based on the many-body expansion or the inclusion-exclusion principle.To compare the applicability of these two categories of methods, we have systematically evaluated the performance of the generalized energy based fragmentation(GEBF) method and the electrostatically embedded many-body(EE-MB) method for medium-sized water clusters(H_2O)_n(n=10, 20, 30).Our calculations demonstrate that the GEBF method provides uniformly accurate ground-state energies for 10 low-energy isomers of three water clusters under study at a series of theory levels, while the EE-MB method shows a poor convergence for(H_2O)_(20) and(H_2O)_(30) when the basis set contains diffuse functions.Our analysis shows that the neglect of the basis set superposition error for each subsystem has little effect on the accuracy of the GEBF method, but leads to much less accurate results for the EE-MB method.The GEBF method is demonstrated to be applicable for electronic structure calculations of water clusters at any basis set.
Fragment-based quantum chemistry methods are either based on the many-body expansion or the inclusion-exclusion principle.To compare the applicability of these two categories of methods, we have systematically evaluated the performance of the generalized energy based fragmentation(GEBF) method and the electrostatically embedded many-body(EE-MB) method for medium-sized water clusters(H_2O)_n(n=10, 20, 30).Our calculations demonstrate that the GEBF method provides uniformly accurate ground-state energies for 10 low-energy isomers of three water clusters under study at a series of theory levels, while the EE-MB method shows a poor convergence for(H_2O)_(20) and(H_2O)_(30) when the basis set contains diffuse functions.Our analysis shows that the neglect of the basis set superposition error for each subsystem has little effect on the accuracy of the GEBF method, but leads to much less accurate results for the EE-MB method.The GEBF method is demonstrated to be applicable for electronic structure calculations of water clusters at any basis set.
引文
[1]S.Li,W.Li,J.Ma,Acc.Chem.Res.2014,47:2712.
[2]W.Li,S.Li,Y.Jiang,J.Phys.Chem.A 2007,111:2193.
[3]E.E.Dahlke,D.G.Truhlar,J.Chem.Theory Comput.2007,3:46.
[2]W.Li,S.Li,Y.Jiang,J.Phys.Chem.A 2007,111:2193.
[3]E.E.Dahlke,D.G.Truhlar,J.Chem.Theory Comput.2007,3:46.