Molecular spectra calculations using an optimized quasi-regular Gaussian basis and the collocation method

TL;DR

This paper improves the collocation method for molecular spectra calculations by optimizing Gaussian basis functions using quasi-regular grids, demonstrating enhanced accuracy for formaldehyde vibrational eigenenergies.

Contribution

It introduces an optimized quasi-regular Gaussian basis within the collocation method, improving basis efficiency and accuracy for molecular vibrational spectra calculations.

Findings

QRG-based basis outperforms previous basis choices

Significant reduction in basis size achieved

Accurate eigenenergies for formaldehyde obtained

Abstract

We revisit the collocation method of Manzhos and Carrington (J. Chem. Phys. 145, 224110, 2016) in which a distributed localized (e.g., Gaussian) basis is used to set up a generalized eigenvalue problem to compute the eigenenergies and eigenfunctions of a molecular vibrational Hamiltonian. Although the resulting linear algebra problem involves full matrices, the method provides a number of important advantages. Namely: (i) it is very simple both conceptually and numerically, (ii) it can be formulated using any set of internal molecular coordinates, (iii) it is flexible with respect to the choice of the basis, and (iv) it has the potential to significantly reduce the basis size through optimizing the placement and the shapes of the basis functions. In the present paper we explore the latter aspect of the method using the recently introduced, and here further improved, quasi-regular grids (QRGs). By computing the eigenenergies of the four-atom molecule of formaldehyde, we demonstrate that a QRG-based distributed Gaussian basis is superior to the previously used choices.