Intermolecular Pauli repulsion: a QMC study of molecules in ground and excited state in free space and in solution

Abstract

In this work we present a method to compute the Pauli repulsion interaction energy between two molecules and for a molecule solvated by a discrete medium. The method of Amovilli and Mennucci, that has been developed within a continuum solvent model approach, is here revised in order to treat the solvation environment with a discrete number of solvent molecules. In our model, one of the two interacting systems, and the solvent in the case of solvation, acts as ‘probe’. A probe has a volume domain defined by the atomic spheres centred on the nuclei of the relevant molecule. The probe measures the fraction of electrons of the solute molecule falling in its domain leading to the evaluation of Pauli repulsion energy. To this end, Quantum Monte Carlo calculations are used to sample the electronic configurations of the solute. The method has been designed to be applied also to excited states. We show results for test systems in the ground state and for the ground and the $n\to {\pi }^{\ast }$ excited states of acetone in a cluster with 14 water molecules.

GRAPHICAL ABSTRACT

Keywords:

• Quantum Monte Carlo
• Pauli repulsion
• solvation
• solvatochromic effect

Disclosure statement

No potential conflict of interest was reported by the author(s).

Additional information

Funding

This work is supported by the University of Pisa under the project PRA_2018_36 Chirality in chemistry: a holistic approach.