Tailoring CIPSI expansions for QMC calculations of electronic excitations: the case study of thiophene

TL;DR

This paper demonstrates that tailored CIPSI expansions can efficiently produce accurate excitation energies and structural parameters for complex molecules like thiophene within quantum Monte Carlo simulations, using relatively small determinant sets.

Contribution

It introduces a CIPSI selection criterion for excited states of the same symmetry, enabling effective QMC calculations of challenging multireference systems.

Findings

Excitation energies within 0.05 eV of theoretical estimates.

Bond lengths accurate to better than 0.01 Å.

Few thousand determinants suffice for high-quality results.

Abstract

The perturbatively selected configuration interaction scheme (CIPSI) is particularly effective in constructing determinantal expansions for quantum Monte Carlo (QMC) simulations with Jastrow-Slater wave functions: fast and smooth convergence of ground-state properties, as well as balanced descriptions of ground- and excited-states of different symmetries have been reported. In particular, accurate excitation energies have been obtained by the pivotal requirement of using CIPSI expansions with similar second-order perturbation corrections for each state, that is, similar estimated errors with respect to the full configuration interaction limit. Here we elaborate on the CIPSI selection criterion for excited states of the same symmetry as the ground state, generating expansions from a common orbital set. Using these expansions in QMC as determinantal components of Jastrow-Slater wave functions, we compute the lowest, bright excited state of thiophene, which is challenging due to its significant multireference character. The resulting vertical excitation energies are within 0.05~eV of the best theoretical estimates, already with expansions of only a few thousand determinants. Furthermore, we relax the ground- and excited-state structures following the corresponding root in variational Monte Carlo and obtain bond lengths which are accurate to better than 0.01~\AA. Therefore, while the full treatment at the CIPSI level of this system would be quite demanding, in QMC we can compute high-quality excitation energies and excited-state structural parameters building on affordable CIPSI expansions with relatively few, well chosen determinants.