Issue 15, 2024

Efficient vibrationally correlated calculations using n-mode expansion-based kinetic energy operators

Abstract

Due to its efficiency and flexibility, the n-mode expansion is a frequently used tool for representing molecular potential energy surfaces in quantum chemical simulations. In this work, we investigate the performance of n-mode expansion-based models of kinetic energy operators in general polyspherical coordinate systems. In particular, we assess the operators with respect to accuracy in vibrationally correlated calculations and their effect on potential energy surface construction with the adaptive density guided approach. Our results show that the n-mode expansion-based operator variants are reliable and systematically improvable approximations of the full kinetic energy operator. Moreover, we introduce a workflow to generate the n-mode expanded kinetic energy operators on-the-fly within the adaptive density guided approach. This scheme can be applied in studies of species and coordinate systems, for which an analytical form of the kinetic energy operator is not available.

Graphical abstract: Efficient vibrationally correlated calculations using n-mode expansion-based kinetic energy operators

Supplementary files

Article information

Article type
Paper
Submitted
29 Gen. 2024
Accepted
15 Meur. 2024
First published
28 Meur. 2024

Phys. Chem. Chem. Phys., 2024,26, 11469-11481

Efficient vibrationally correlated calculations using n-mode expansion-based kinetic energy operators

F. Bader, D. Lauvergnat and O. Christiansen, Phys. Chem. Chem. Phys., 2024, 26, 11469 DOI: 10.1039/D4CP00423J

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