摘要
基准集是训练和评价量子化学计算方法的重要工具,稀有气体二聚体作为典型的弱色散体系,目前为止仍没有一个真正意义的完备基准集,而近年来Head Gordon研究组构建的RG10(Rare gas, 10代表共有10个体系)基准集仍沿用了Tang-Toennies经验势。本文首先以最近所发表的NgD×15(Noble gas dimer)基准集为基础,在CCSD(T)/aug-cc-pV5Z-{6s6p6d3f2g1h}-CP计算水平下继续对15种异核稀有气体二聚体的势能曲线进行了计算;并且增加了量子化学方法难以计算的近核区相互作用势的计算,同时扩充了NgD×15中的数据,从而构建了RG21基准集。以此为标准,利用非线性拟合算法对全部稀有气体二聚体势能曲线进行了Murrell—Sorbie势能函数拟合;同时以RG21为标准与RG10以及拟合结果进行了比较;经数据分析,本文的拟合计算精度非常高,进一步证明了Tang-Toennies经验势在近核区的不可靠性。
Benchmark set is an important tool for training and evaluating the computational methods of quantum chemistry.However,rare gas dimers(RGD)as an typical weak dispersion system,there is still no a complete benchmark set in the true sense.So,when the RG10(Rare gas,10 represents 10 systems in total)benchmark set was recently published by the Head Gordon research group,the Tang-Toennies empirical potential was still used for the standard database.In this work,first based on the NgD×15(Noble gas dimer)benchmark set published recently,continue to calculate the potential energy curves of 15 heteronuclear noble gas dimers in the CCSD(T)/aug-c-pV5Z-{6s6p6d3f2g1h}calculation level.Moreover,the calculation of the interaction potential in the near-nuclear region which is difficult to calculate by quantum chemical methods is added and NgD×15 benchmark set is expanded.Thus,the RG21 benchmark set was constructed.Taking this as a standard,the Murrell-Sorbie potential energy function was fitted to all the potential energy curves of rare gas dimers using the nonlinear fitting algorithm.At the same time,RG21 benchmark set are taken as the standard for comparing with the existing data of RG10 benchmark set and fitting results.After data ananlysis,the fitting calculation accuracy is very high in this paper,and this result further proves that the Tang-Toennies empirical potential is unreliable in the near-nuclear region.
作者
王裕平
魏孝珍
WANG Yu-ping;WEI Xiao-zhen(The Key Laboratory of Drug Molecular Design,Guizhou Vocational Institute of Technology,Qiannan 558000,Chian)
出处
《化学研究与应用》
CAS
北大核心
2023年第4期785-792,共8页
Chemical Research and Application
基金
贵州应用技术职业学院教科研资助项目(GZYYXY2022007)
贵州省黔南重点科技平台建设资助项目(黔南科发[2022]6号)
国家自然科学基金资助项目(21767005)。
作者简介
联系人:王裕平(1990-),男,讲师,主要从事量子化学以及非共价相互作用研究。E-mail:yupingchem@sina.com。
