Reduced Basis Set Dependence in Anharmonic Frequency Calculations Involving Localized Coordinates

Localized normal coordinates are known to be effective in speeding up anharmonic frequency calculations by reducing the complexity of the nuclear Hamiltonian and wave function. Displacing atoms in localized coordinates can also cause relatively small changes in the electronic structure, which can be exploited for further computational efficiency improvements during ab initio electronic structure calculations of the potential energy surface by reducing the electronic basis set dependence. Three different schemes for reducing the basis set dependence have been investigated in this work. These include combining localized coordinate schemes with general mixed basis sets, distance based force-field reductions, and using coordinate specific basis sets. The importance of accurately describing electronic interactions is found to diminish both for multicoordinate terms involving the displacement of remote atoms and when describing the interactions between more remote atoms within specific coordinates.