Multidimensional Hamiltonian for tunneling with position-dependent mass

Abstract

A multidimensional Hamiltonian for tunneling is formulated, based on the mode with imaginary frequency of the transition state as a reaction coordinate. To prepare it for diagonalization, it is transformed into a lower-dimension Hamiltonian by incorporating modes that move faster than the tunneling into a coordinate-dependent kinetic energy operator, for which a Hermitian form is chosen and tested for stability of the eigenvalues. After transformation to a three-dimensional form, which includes two normal modes strongly coupled to the tunneling mode, this Hamiltonian is diagonalized in terms of a basis set of harmonic oscillator functions centered at the transition state. This involves a sparse matrix which is easily partially diagonalized to yield tunneling splittings for the zero-point level and the two fundamental levels of the coupled modes. The method is tested on the well-known benchmark molecule malonaldehyde and a deuterium isotopomer, for which these splittings have been measured. Satisfactory agreement with experiment results is obtained