Beyond pairwise additivity in London dispersion interactions
Article first published online: 19 FEB 2014
Copyright © 2014 Wiley Periodicals, Inc.
International Journal of Quantum Chemistry
Special Issue: VIIIth Congress of the International Society for Theoretical Chemical Physics
Volume 114, Issue 18, pages 1157–1161, September 15, 2014
How to Cite
How to cite this article: Int. J. Quantum Chem. 2014, 114, 1157–1161. DOI: 10.1002/qua.24635.
- Issue published online: 4 AUG 2014
- Article first published online: 19 FEB 2014
- Manuscript Accepted: 29 JAN 2014
- Manuscript Revised: 25 JAN 2014
- Manuscript Received: 2 DEC 2013
- Australian Research Council. Grant Number: DP1096240
- London dispersion forces;
- DFT + D;
- direct random-phase approximation;
- nonpairwise interactions;
- van der Waal's forces;
The simplest way to predict London dispersion energies involving complex multiatom objects is to add separate contributions from each pair of atoms. Semiempirical, and even certain less empirical, ways to do this can be very efficient computationally and have recently been developed to a high level of sophistication, with considerable success. There are, however, effects that are not captured in this way, including surprising dependences of the dispersion energy on the number N of atoms and on separation D. Higher level quantum chemical, perturbative, and random-phase approximation (RPA)-like theories can capture these beyond pairwise effects, but at a high computational cost. Very recent simplified RPA-like approaches based on localized oscillators account for the unusual N dependence in a computationally efficient way. To proceed further, the present work proposes three physically distinct categories of nonpairwise effects (types A, B, and C) against which the performance of existing and future theories can be assessed. © 2014 Wiley Periodicals, Inc.