Tailoring CIPSI Expansions for QMC Calculations of Electronic Excitations: The Case Study of Thiophene

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 and 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, a similar estimated distance 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 that are accurate to better than 0.01 angstrom. Therefore, while the full treatment at the CIPSI level of this system is 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.

Automated summary

The perturbatively selected configuration interaction scheme (CIPSI) is effective in constructing determinantal expansions for quantum Monte Carlo simulations with Jastrow-Slater wave functions, providing accurate excitation energies. By elaborating on the CIPSI selection criterion for excited states with the same symmetry as the ground state, expansions can be generated for challenging systems like thiophene with high-quality excitation energies. Additionally, using CIPSI expansions with relatively few well-chosen determinants allows for accurate determination of excited-state structural parameters in QMC simulations.