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亮点文章
基于MP2+ΔCCSD(T)方法检验DFT范德华力方法PBE+D3和SCAN+rVV10的准确性
第一作者 | 陈劼
通讯作者 | 孙宜阳
研究亮点
本文设计了三种典型的分子间相互作用力体系,采用MP2+ΔCCSD(T)方法得到了这三种体系的势能曲线(包括转动和拉伸),以此为基准检验目前被广泛使用的密度泛函理论(DFT)中的范德华力方法PBE+D3和SCAN+rVV10的准确性。
研究背景
常见的分子间相互作用力包括伦敦色散力、氢键以及π键堆积等。量子化学方法,如MP2和CCSD(T)等,虽然可以很好地描述这些相互作用,但是计算量过大限制了这些方法的使用,尤其对于晶体材料。密度泛函理论相较于量子化学方法明显省时,但是密度泛函理论中传统的交换关联势不能很好地描述这些分子间相互作用力。针对这个问题,许多方法被提出以求弥补密度泛函理论的这一不足。其中,PBE+D3和SCAN+rVV10是近些年来最常用的两种密度泛函理论框架下的计算分子间相互作用力的方法。
研究方法及结果
本文运用甘氨酸分子(Gly)和尿嘧啶分子(U)设计了三种不同的分子间相互作用力体系,即伦敦色散力、氢键和π键堆积体系,并且对这三种体系的分子间相互作用能分别与分子间距离和相互转动角度的关系进行计算,一共得到六条势能曲线。以在完备基组极限下的MP2+ΔCCSD(T)方法计算得到的势能曲线作为基准,来检验PBE+D3和SCAN+rVV10方法的计算准确性。计算结果显示,在相对距离小于平衡距离的情况下,两种方法的结果均与基准曲线相差较大;但是总体而言,两种方法的平均误差都小于1 kcal/mol,即达到了所谓的“化学精度”。另外,SCAN+rVV10方法可以再现基准曲线中的一些细节,意味着SCAN+rVV10能够更好地描述一些精细的势能曲面结构。
研究意义或前景
本工作根据分子间相互作用力的种类不同,详细比较了现在最为常用的两种DFT范德华力方法:PBE+D3和SCAN+rVV10,为今后含有分子间相互作用力体系的DFT计算应该选取怎样的方法提供了一定的指导。另外,本文也指出了这两种方法的不足之处,为如何进一步改进DFT框架下计算范德华力的方法提供了新的建议。
文章来源
Chin. Phys. B, 2020, 29 (1): 013102
原文概览
Benchmarking PBE+D3 and SCAN+rVV10 methods using potential energy surfaces generated with MP2+ ΔCCSD(T) calculation
Jie Chen(陈劼)1,2, Weiyu Xie(谢炜宇)3, Kaihang Li(李开航)1,
Shengbai Zhang(张绳百)4, Yi-Yang Sun(孙宜阳)2
1 Department of Physics, Xiamen University, Xiamen 361005, China;
2 State Key Laboratory of High Performance Ceramics and Superfine Microstructure, Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai 201899, China;
3 Institute of Chemical Materials, China Academy of Engineering Physics, Mianyang 621999, China;
4 Department of Physics, Applied Physics, and Astronomy, Rensselaer Polytechnic Institute, Troy, New York 12180, USA
Keywords: van der Waals force, meta-GGA, density functional theory, CCSD(T)
We develop a benchmark system for van der Waals interactions obtained with MP2+ΔCCSD(T) method at complete basis set limit. With this benchmark, we examine the widely used PBE+D3 method and recently developed SCAN+rVV10 method for density functional theory calculations. Our benchmark is based on two molecules:glycine (or Gly, an amino acid) and uracil (or U, an RNA base). We consider six dimer configurations of the two monomers and their potential energy surfaces as a function of relative distance and rotation angle. The Gly-Gly, Gly-U, and U-U pairs represent London dispersion, hydrogen bonding, and π-π stacking interactions, respectively. Our results show that both PBE+D3 and SCAN+rVV10 methods can yield accuracy better than 1 kcal/mol, except for the cases when the distance between the two monomers is significantly smaller than the equilibrium distance. In such a case, neither of these methods can yield uniformly accurate results for all the configurations. In addition, it is found that the SCAN and SCAN+rVV10 methods can reproduce some subtle features in a rotational potential energy curve, while the PBE, PBE+D3, and the local density approximation fail.
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