New ideas for using contracted basis functions with a Lanczos eigensolver for computing vibrational spectra of molecules with four or more atoms

摘要

We propose new methods for using contracted basis functions in conjunction with the Lanczos algorithm to calcualte vibrational (or rovibrational) spectra. As basis functions we use products of eignefunctions of reduced-dimension Hamiltonians obtained by freezing coordinates at equilibrium. The basis functions represent the desired wave functions well, yet are simple enough that matrix-vector products may be evaluated efficiently. The methods we suggest obviate the need to transform from the contracted to an original product basis each time a matrix-vector product is evaluated. For HOOH the most efficient of the methods we present is about an order of magnitude faster than a product basis Lanczos calculation.