Structure factors for tunneling ionization rates of molecules: General grid-based methodology and convergence studies.

Abstract

We present a general methodology for evaluating structure factors defining the orientation dependence of tunneling ionization rates of molecules, which is a key process in strong-field physics. The method is implemented at the Hartree-Fock level of electronic structure theory and is based on an integral-equation approach to the weak-field asymptotic theory of tunneling ionization, which expresses the structure factor in terms of an integral involving the ionizing orbital and a known analytical function. The evaluation of the required integrals is done by three-dimensional quadrature which allows calculations using conventional quantum chemistry software packages. This extends the applications of the weak-field asymptotic theory to polyatomic molecules of almost arbitrary size. The method is tested by comparison with previous results and illustrated by calculating structure factors for the two degenerate highest occupied molecular orbitals (HOMOs) of benzene and for the HOMO and HOMO-1 of naphthalene.