The von Neumann basis in non-Cartesian coordinates: application to floppy triatomic molecules

Asaf Shimshovitz; Zlatko Bačić; David J Tannor

doi:10.1063/1.4902553

The von Neumann basis in non-Cartesian coordinates: application to floppy triatomic molecules

J Chem Phys. 2014 Dec 21;141(23):234106. doi: 10.1063/1.4902553.

Authors

Asaf Shimshovitz¹, Zlatko Bačić², David J Tannor¹

Affiliations

¹ Department of Chemical Physics, Weizmann Institute of Science, Rehovot 76100, Israel.
² Department of Chemistry, New York University, New York, New York 10003, USA.

PMID: 25527918
DOI: 10.1063/1.4902553

Abstract

We extend the periodic von Neumann basis to non-Cartesian coordinates. The bound states of two isomerizing triatomic molecules, LiCN/LiNC and HCN/HNC, are calculated using the vibrational Hamiltonian in Jacobi coordinates. The phase space localization of the basis functions leads to a flexible and accurate representation of the Hamiltonian. This results in significant savings compared to a basis localized just in coordinate space. The favorable scaling of the method with dimensionality makes it promising for applications to larger systems.