Signatures of van der Waals binding: a coupling-constant scaling analysis

TL;DR

This paper introduces a coupling-constant scaling analysis for van der Waals density functionals, enabling the calculation of kinetic-correlation energy and providing detailed spatial insights into vdW binding in various systems.

Contribution

It presents a novel coupling-constant scaling method to analyze and compute the kinetic-correlation energy specific to vdW interactions within density functional theory.

Findings

Kinetic-correlation energy significantly influences vdW interactions.

Spatial variation in nonlocal-correlation energy highlights vdW binding regions.

Nonlocal-correlation binding is concentrated in electron density pockets between fragments.

Abstract

The van der Waals (vdW) density functional (vdW-DF) method [ROPP 78, 066501 (2015)] describes dispersion or vdW binding by tracking the effects of an electrodynamic coupling among pairs of electrons and their associated exchange-correlation holes. This is done in a nonlocal-correlation energy term $E_c^{nl}$, which permits density functional theory calculation in the Kohn-Sham scheme. However, to map the nature of vdW forces in the fully interacting materials system, it is necessary to compensate for associated kinetic-correlation energy effects. Here we present a coupling-constant scaling analysis that also permits us to compute the kinetic-correlation energy $T_c^{nl}$ that is specific to the vdW-DF account of nonlocal correlations. We thus provide a spatially-resolved analysis of the total nonlocal-correlation binding, including vdW forces, in both covalently and non-covalently bonded systems. We find that kinetic-correlation energy effects play a significant role in the account of vdW or dispersion interactions among molecules. We also find that the signatures that we reveal in our full-interaction mapping are typically given by the spatial variation in the $E_c^{nl}$ binding contributions, at least in a qualitative discussion. Furthermore, our full mapping shows that the total nonlocal-correlation binding is concentrated to pockets in the sparse electron distribution located between the material fragments.