Solvation Lies Within: Simulating Condensed-Phase Properties from Local Electronic Structures

TL;DR

This paper introduces a new method to simulate solvation effects in condensed phases by analyzing local electronic structures, enabling accurate and efficient predictions of molecular energy shifts in various solvents.

Contribution

It presents a robust protocol based on localized molecular orbitals for sampling solvation effects, improving accuracy and efficiency over previous methods.

Findings

Fast convergence of binding energies with respect to bulk size

Results are invariant to basis set choice

Protocol reflects differences in density functional approximations

Abstract

In transitions between different environmental settings, a molecular system inevitably undergoes a range of detectable changes, and the ability to accurately simulate such responses, e.g., in the form of shifts to molecular energies, remains an important challenge across physical chemistry. Based on an exact decomposition of total energies from Kohn--Sham density functional theory in a basis of spatially localized molecular orbitals, the present work outlines a robust protocol for sampling the effect of solvation within homogeneous condensed phases by focusing on perturbations to local electronic structures only. We report chemically intuitive results for binding energies of water, ethanol, and acetonitrile that all display fast convergence with respect to the bulk size. Results stay largely invariant with respect to the choice of basis set while reflecting differences in density functional approximations, and our protocol thus allows for a physically sound and efficient estimation of general effects related to bulk solvation.