ViBra: Configuration Interaction for Anharmonic Vibrational Spectroscopy and Quantum-Sampled Configuration Spaces

Abstract

Quantum-centric workflows are a promising route to improving the accuracy of property predictions in computational chemistry and materials science. By integrating quantum sampling algorithms with classical solvers, electronic structure calculations have recently demonstrated their potential even on noisy intermediate-scale quantum devices. In principle, the method of Vibrational Configuration Interaction (VCI) is suitable for integration with quantum sampling algorithms as well. However, demonstrations of computational workflows for quantum-centric, vibrational property predictions are still lacking. Here, we introduce a methodology for performing anharmonic vibrational structure calculations that can be deployed in a hybrid, quantum-classical mode. Starting from a quartic force field, the approach combines a Vibrational Self-Consistent Field (VSCF) with VCI in either Full, Selected (S-VCI), or Symmetry-Adapted (SA-VCI) mode. In S-VCI, an Epstein-Nesbet perturbative screening significantly reduces the configuration space while retaining high predictive accuracy. A state-list input enables the integration of externally generated vibrational configurations as a seed space. As a proof-of-concept, we demonstrate a hybrid, quantum-classical computational workflow, in which a quantum sampling algorithm provides the seed. Our vibrational wave function analysis package ViBra, equipped with a graphical interface, is available at https://github.com/raphafe96/ViBra.