Reduced-gradient analysis of van der Waals complexes

被引:12
作者
Jenkins, T. [1 ,2 ]
Berland, K. [3 ]
Thonhauser, T. [1 ,2 ]
机构
[1] Wake Forest Univ, Dept Phys, Winston Salem, NC 27109 USA
[2] Wake Forest Univ, Ctr Funct Mat, Winston Salem, NC 27109 USA
[3] Norwegian Univ Life Sci, Fac Sci & Technol, As, Norway
来源
ELECTRONIC STRUCTURE | 2021年 / 3卷 / 03期
基金
美国国家科学基金会;
关键词
van der Waals interactions; density functional theory; vdW-DF; exchange interaction energy; DENSITY-FUNCTIONAL THEORY; EXCHANGE-ENERGY; APPROXIMATION; ACCURATE;
D O I
10.1088/2516-1075/ac25d7
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
Different methods to describe dispersion interactions within density functional theory have been developed, which is essential to describe binding in van der Waals complexes. However, several key aspects of such complexes-including binding energies, lattice constants, and binding distances-also depend on the exchange description that is paired with the description of dispersion interactions. This is particularly true for the vdW-DF family of van der Waals density functionals, which has a clear division between truly non-local correlations and semi-local generalized-gradient exchange. Here, we present a systematic analysis of the reduced-gradient values that determine the semi-local exchange for different classes of van der Waals complexes. In particular, we analyze molecular dimers, layered structures, surface adsorption, and molecular crystals. We find that reduced-gradient values of less than similar to 1 to similar to 1.5-depending on the system-contribute attractively to the exchange binding, while reduced gradients above those values are repulsive. We find that the attractive contributions can be attributed to low-density regions between the constituents with disk-like iso-surfaces. We further identify a mechanism wherein the surface area of these disks decreases through merging with other iso-surfaces and switches the gradient-correction to exchange from attractive to repulsive. This analysis allows us to explain some of the differences in performance of vdW-DF variants and initiates a discussion of desirable features of the exchange enhancement factor. While our analysis is focused on vdW-DF, it also casts light on van der Waals binding in a broader context and can be used to understand why methods perform differently for different classes of van der Waals systems.
引用
收藏
页数:15
相关论文
共 50 条
[41]   Van der Waals coefficients of atoms and molecules from a simple approximation for the polarizability [J].
Nguyen, Huy-Viet ;
de Gironcoli, Stefano .
PHYSICAL REVIEW B, 2009, 79 (11)
[42]   Benchmarking several van der Waals dispersion approaches for the description of intermolecular interactions [J].
Claudot, Julien ;
Kim, Won June ;
Dixit, Anant ;
Kim, Hyungjun ;
Gould, Tim ;
Rocca, Dario ;
Lebegue, Sebastien .
JOURNAL OF CHEMICAL PHYSICS, 2018, 148 (06)
[43]   Many-body van der Waals interactions in molecules and condensed matter [J].
DiStasio, Robert A., Jr. ;
Gobre, Vivekanand V. ;
Tkatchenko, Alexandre .
JOURNAL OF PHYSICS-CONDENSED MATTER, 2014, 26 (21)
[44]   Study of van der Waals bonding and interactions in metal organic framework materials [J].
Zuluaga, Sebastian ;
Canepa, Pieremanuele ;
Tan, Kui ;
Chabal, Yves J. ;
Thonhauser, Timo .
JOURNAL OF PHYSICS-CONDENSED MATTER, 2014, 26 (13)
[45]   Faraday cage screening reveals intrinsic aspects of the van der Waals attraction [J].
Li, Musen ;
Reimers, Jeffrey R. ;
Dobson, John F. ;
Gould, Tim .
PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA, 2018, 115 (44) :E10295-E10302
[46]   Light-induced magnetic phase transition in van der Waals antiferromagnets [J].
Chen, Jiabin ;
Li, Yang ;
Yu, Hongyu ;
Yang, Yali ;
Jin, Heng ;
Huang, Bing ;
Xiang, Hongjun .
SCIENCE CHINA-PHYSICS MECHANICS & ASTRONOMY, 2023, 66 (07)
[47]   noloco: An efficient implementation of van der Waals density functionals based on a Monte-Carlo integration technique [J].
Nabok, Dmitrii ;
Puschnig, Peter ;
Ambrosch-Draxl, Claudia .
COMPUTER PHYSICS COMMUNICATIONS, 2011, 182 (08) :1657-1662
[48]   Glass-Box Molekulardynamische Simulationen zur Vermittlung der van der Waals-WechselwirkungGlass-box molecular dynamics simulation for teaching the van der Waals interaction [J].
Kraska, Thomas .
CHEMKON, 2023, 30 (08) :341-348
[49]   Direct Growth of van der Waals Tin Diiodide Monolayers [J].
Yuan, Qian-Qian ;
Zheng, Fawei ;
Shi, Zhi-Qiang ;
Li, Qi-Yuan ;
Lv, Yang-Yang ;
Chen, Yanbin ;
Zhang, Ping ;
Li, Shao-Chun .
ADVANCED SCIENCE, 2021, 8 (20)
[50]   The study of performance of DFT functional for van der Waals interactions [J].
Kolandaivel, P. ;
Maheswari, D. Uma ;
Senthilkumar, L. .
COMPUTATIONAL AND THEORETICAL CHEMISTRY, 2013, 1004 :56-60