Charge-transfer excited states: Seeking a balanced and efficient wave function ansatz in variational Monte Carlo

TL;DR

This paper introduces a new wave function ansatz for efficiently modeling charge-transfer excited states in quantum Monte Carlo, enabling improved orbital optimization beyond traditional methods with minimal computational overhead.

Contribution

The authors develop a simple, efficient wave function ansatz that enhances orbital optimization for excited states in real-space quantum Monte Carlo methods, requiring only two Slater determinants.

Findings

Successfully applied to stretched LiF molecule

Effective for excited states of formaldehyde

Demonstrated on ethylene-tetrafluoroethylene molecule

Abstract

We present a simple and efficient wave function ansatz for the treatment of excited charge-transfer states in real-space quantum Monte Carlo methods. Using the recently-introduced variation-after-response method [J. Chem. Phys. 145, 081103 (2016)], this ansatz allows a crucial orbital optimization step to be performed beyond a configuration interaction singles expansion, while only requiring calculation of two Slater determinant objects. We demonstrate this ansatz for the illustrative example of the stretched LiF molecule, for a range of excited states of formaldehyde, and finally for the more challenging ethylene-tetrafluoroethylene molecule.