A hybrid variational-perturbational nuclear motion algorithm

A hybrid variational-perturbational nuclear motion algorithm based on the perturbative treatment of the Coriolis coupling terms of the Eckart-Watson kinetic energy operator following a variational treatment of the rest of the operator is described. The algorithm has been implemented in the quantum chemical code DEWE. Performance of the hybrid treatment is assessed by comparing selected numerically exact variational vibration-only and rovibrational energy levels of the C2H4, C2D4, and CH4 molecules with their perturbatively corrected counterparts. For many of the rotational-vibrational states examined, numerical tests reveal excellent agreement between the variational and even the first-order perturbative energy levels, whilst the perturbative approach is able to reduce the computational cost of the matrix-vector product evaluations, needed by the iterative Lanczos eigensolver, by almost an order of magnitude.