Symmetry-Adapted Ro-vibrational Basis Functions for Variational Nuclear Motion Calculations: TROVE Approach

Journal of Chemical Theory and Computation

5 years ago

Symmetry-Adapted Ro-vibrational Basis Functions for Variational Nuclear Motion Calculations: TROVE Approach

Roman I. Ovsyannikov, Andrey Yachmenev, Sergei N. Yurchenko

We present a general, numerically motivated approach to the construction of symmetry-adapted basis functions for solving ro-vibrational Schrödinger equations. The approach is based on the property of the Hamiltonian operator to commute with the complete set of symmetry operators and, hence, to reflect the symmetry of the system. The symmetry-adapted ro-vibrational basis set is constructed numerically by solving a set of reduced vibrational eigenvalue problems. In order to assign the irreducible representations associated with these eigenfunctions, their symmetry properties are probed on a grid of molecular geometries with the corresponding symmetry operations. The transformation matrices are reconstructed by solving overdetermined systems of linear equations related to the transformation properties of the corresponding wave functions on the grid. Our method is implemented in the variational approach TROVE and has been successfully applied to many problems covering the most important molecular symmetry groups. Several examples are used to illustrate the procedure, which can be easily applied to different types of coordinates, basis sets, and molecular systems.

Publisher URL: http://dx.doi.org/10.1021/acs.jctc.7b00506

DOI: 10.1021/acs.jctc.7b00506