稀有气体二聚体基准集NgD×15构建及其对DFT方法的评价  

Construction of benchmark set NgD×15 for rare gas dimers and its application to evaluation of DFT methods

作　　者：王裕平 魏孝珍 王一波[1] WANG Yu-Ping;WEI Xiao-Zhen;WANG Yi-Bo(Key Laboratory of High Performance Computational Chemistry, Department of Chemistry, Guizhou University, Guiyang 550025, China)

机构地区：[1]贵州大学化学系贵州省高性能计算化学重点实验室,贵阳550025

出　　处：《原子与分子物理学报》2020年第3期343-348,共6页Journal of Atomic and Molecular Physics

基　　金：国家自然科学基金(21767005);贵州省科技计划项目(黔科合平台人才[2017]5788号)。

摘　　要：基准集是训练和评价量子化学计算方法的重要工具,稀有气体二聚体Ng2作为重要的弱色散体系,目前为止仍没有一个较为完整、精确的基准集,最近Head Gordon研究组发表MGCD84数据库时,其RG10基准集仍沿用了Tang-Toennies经验势.本文首先以He2为例,证明了在CCSD(T)水平,使用中点键函数{6s6p6d3f2g1h}的aug-cc-pV5Z基组收敛性;并在CCSD(T)/aug-cc-pV5Z-{6s6p6d3f2g1h}水平下,经BSSE均衡校正后,获得了He2至Rn2全部同核稀有气体二聚体的15点相互作用势,构建了NgD×15基准集.并以此为标准,重新评价了目前常用的DFT的非局域和色散校正方法.总体上,非局域校正的精度较D3色散校正高,ωB97X-V及ωB97X-rV两种方法是该体系最优性价比的DFT-NL方法.Benchmark set is an important tool for training and evaluating the computational methods of quantum chemistry.However,Noble-gas dimers(NgDs)as an important weak dispersion system,there is still no integrated and accurate benchmark set.So,when the main-group-chemistry database MGCD84 database was recently published by the Head-Gordon research group,the Tang-Toennies empirical potential was still used of the potential energy curves of He2 to Kr2 for the RG10 benchmark set in the database.In this work,the He2 dimer is first utilized as an example to verified the convergence of the aug-cc-pV5Z basis set plus mid-point bond function of{6s6p6d3f2g1h}at the coupled-cluster theory singles,doubles,and perturbative triples,CCSD(T)level.Furthermore,the 15-point interaction potentials for NgDs from He2 to Rn2 were obtained with the CCSD(T)/aug-cc-pV5Z-{6s6p6d3f2g1h}methods to build NgD×15 benchmark set,where basis-set superposition errors BSSE has been corrected using the counterpoise procedure.Finally,the NgD×15 benchmark set has been used as the criterion to re-evaluate the non-local(NL)and dispersion(D3)correction methods of the density functional theory(DFT).In general,the accuracy of the non-local correction is higher than that of the DFT-D3 dispersion correction,and density functionalsωB97X-V andωB97X-rV are the most optimal DFT-NL functionals with cost-effective performance for Noble-gas dimers.

关 键 词：稀有气体二聚体 NgD×15基准集 CCSD(T) DFT 键函数 

分 类 号：O641[理学—物理化学]