Excitations in photoactive molecules from quantum Monte Carlo

TL;DR

This paper evaluates quantum Monte Carlo methods for accurately computing excited states in photoactive molecules, highlighting the importance of wave function optimization and comparing results with other computational approaches.

Contribution

It demonstrates that quantum Monte Carlo can reliably estimate excitation energies when the trial wave function is carefully optimized, offering insights into excited state descriptions.

Findings

Quantum Monte Carlo accurately estimates excitation energies with proper wave function reoptimization.

Time-dependent DFT and quantum Monte Carlo agree generally but differ on isomerization pathways.

Restricted open shell Kohn-Sham method diverges from quantum Monte Carlo in low-symmetry cases.

Abstract

Despite significant advances in electronic structure methods for the treatment of excited states, attaining an accurate description of the photoinduced processes in photoactive biomolecules is proving very difficult. For the prototypical photosensitive molecules, formaldimine, formaldehyde and a minimal protonated Schiff base model of the retinal chromophore, we investigate the performance of various approaches generally considered promising for the computation of excited potential energy surfaces. We show that quantum Monte Carlo can accurately estimate the excitation energies of the studied systems if one constructs carefully the trial wave function, including in most cases the reoptimization of its determinantal part within quantum Monte Carlo. While time-dependent density functional theory and quantum Monte Carlo are generally in reasonable agreement, they yield a qualitatively different description of the isomerization of the Schiff base model. Finally, we find that the restricted open shell Kohn-Sham method is at variance with quantum Monte Carlo in estimating the lowest-singlet excited state potential energy surface for low-symmetry molecular structures.