Systematic Microsolvation Approach with a Cluster-Continuum Scheme and Conformational Sampling

TL;DR

This paper introduces a systematic quantum chemical microsolvation approach combining conformational sampling with a cluster-continuum scheme, improving the accuracy of solvation modeling in liquid-phase chemistry.

Contribution

It presents an automated algorithm for microsolvation that incorporates conformational sampling and solvent shell rearrangements, advancing the systematic treatment of solvation effects.

Findings

Algorithm reliably monitors solvent effects through observable spread and averages.

Enhanced accuracy in quantum chemical solvation modeling.

Demonstrates the importance of conformational sampling in microsolvation.

Abstract

Solvation is a notoriously difficult and nagging problem for the rigorous theoretical description of chemistry in the liquid phase. Successes and failures of various approaches ranging from implicit solvation modeling through dielectric continuum embedding and microsolvated quantum chemical modeling to explicit molecular dynamics highlight this situation. Here, we focus on quantum chemical microsolvation and discuss an explicit conformational sampling ansatz to make this approach systematic. For this purpose, we introduce an algorithm for the rolling and automated microsolvation of solutes. Our protocol takes conformational sampling and rearrangements in the solvent shell into account. Its reliability is assessed by monitoring the evolution of the spread and average of the observables of interest.