Basis pruning in rovibrational configuration interaction (RVCI) calculations

Abstract

The variational calculation of rovibrational spectra without model Hamiltonians remains challenging, with the size and composition of the vibrational basis constituting a major bottleneck. Preceding vibrational configuration interaction (VCI) calculations reduce this basis, but leave the question of which vibrational state functions to include. In close analogy to configuration-selective VCI theory, we propose a basis-pruning algorithm in which candidate vibrational states are represented by inexpensive approximate wavefunctions and selected according to their impact on rovibrational energies in a spectral window of interest. For formaldehyde, comparisons with widely used polyad schemes controlling the vibrational basis are provided. Calculations on thioketene benchmark the accuracy and efficiency of the pruning approach for different threshold values.