Computing solvated excited states using fragment-effective-field coupled-cluster perturbation theory with application to the electronic spectra of nucleobases in water

TL;DR

This paper introduces a scalable, coupled-cluster fragment method for accurately computing excited states and spectra of solvated molecules, validated through extensive benchmarking on organic molecules and molecular crystals.

Contribution

It presents a systematic, scalable coupled-cluster fragment method (MCPT) for excited states, with applications to solvation energies and crystal polymorphs, advancing electronic structure calculations for large systems.

Findings

Accurate solvation free energies for small organic molecules.

Insights into crystal lattice polymorph energies and the role of many-body effects.

Validation of the method against experimental and high-level ab initio data.

Abstract

Molecular fragment or embedding methods are powerful techniques for overcoming scalability limitations in electronic structure theory by dividing large molecular systems into individual units that are small enough to be treated using standard techniques. Our group has developed a linear-scaling coupled-cluster based fragment effective field method, molecular cluster perturbation theory (MCPT), that provides a systematically improvable description of the electronic wavefunction and is scalable to thousands of atoms using the Aces4 massively parallel software package. We will present a systematic computational benchmarking study of small organic molecule solvation free energies obtained from MCPT using various perturbation corrections using experimental and large-scale ab initio reference values. We will also present recent work on the relative crystal lattice polymorph energies of several molecular crystals where the roles of many-body dispersion and intermol ecular electron exchange will be investigated. The molecular solvent and crystal systems presented here are carefully chosen so as to provide a robust test set for the fragment electronic structure community.