Vibrationally correlated calculations in polyspherical coordinates: Taylor expansion-based kinetic energy operators

F Bader; D Lauvergnat; O Christiansen

doi:10.1063/5.0171912

Vibrationally correlated calculations in polyspherical coordinates: Taylor expansion-based kinetic energy operators

J Chem Phys. 2023 Dec 7;159(21):214107. doi: 10.1063/5.0171912.

Authors

F Bader¹, D Lauvergnat², O Christiansen¹

Affiliations

¹ Department of Chemistry, Aarhus University, DK-8000 Aarhus C, Denmark.
² Université Paris-Saclay, CNRS, Institut de Chimie Physique UMR8000, Orsay 91405, France.

PMID: 38047511
DOI: 10.1063/5.0171912

Abstract

The efficiency of quantum chemical simulations of nuclear motion can in many cases greatly benefit from the application of curvilinear coordinate systems. This is rooted in the fact that a set of smartly selected curvilinear coordinates may represent the motion naturally well, thus decreasing the couplings between motions in these coordinates. In this study, we assess the validity of different Taylor expansion-based approximations of kinetic energy operators in a (curvilinear) polyspherical parametrization. To this end, we investigate the accuracy as well as the numerical performance of the approximations in time-independent vibrational coupled cluster and full vibrational interaction calculations for several test cases ranging from tri- to penta-atomic molecules. We find that several of the proposed schemes reproduce the vibrational ground state and excitation energies to a decent accuracy, justifying their application in future investigations. Furthermore, due to the restricted mode coupling and their inherent sum-of-products form, the new approximations open up the possibility of treating large molecular systems with efficient vibrational coupled cluster schemes in general coordinates.