Approaching the Full Configuration Interaction Low-Energy Spectrum from an Arbitrary Reference Subspace

TL;DR

This paper extends a previous method to optimize low-energy subspaces of Hamiltonians from arbitrary references, enabling efficient calculation of excited states and spectra in quantum chemistry.

Contribution

It introduces an approach to optimize low-energy subspaces from arbitrary references, generalizing previous ground state methods to excited states and spectra.

Findings

Successfully applied to LiF avoided crossing

Accurately described formaldehyde's low-lying spectrum

Demonstrated effectiveness with non-orthogonal reference states

Abstract

In a previous work (arXiv:2010.02027) we showed how the full configuration interaction (FCI) ground state energy can be obtained as a functional of an arbitrary reference wavefunction by means of a gradient descent or quasi-Newton algorithm. Here, we extend this approach and consider the optimization of the low-energy subspace of the Hamiltonian from an arbitrary reference subspace. The energies along the optimization path are obtained in terms of transition matrix elements among the states in the reference subspace. We show an application of the algorithm with a reference subspace constructed from a non-orthogonal configuration interaction (NOCI) formalism to describe the avoided crossing in LiF and the low-lying singlet and triplet spectrum of formaldehyde.