Application of the weak-field asymptotic theory to tunneling ionization ofH2O

Abstract

The weak-field asymptotic theory of tunneling ionization in a static electric field is applied to ${\mathrm{H}}_{2}\mathrm{O}$. The orientation dependence of the ionization rate is studied. The use of polarization-consistent basis sets with up to heptuble-zeta accuracy and variationally optimized exponents improves the asymptotic form of the wave function and allows for an accurate extraction of the structure factor defining the ionization rate. The results are presented based on Hartree-Fock wave functions and density functional theory. The density functional theory reproduces closely the experimental vertical ionization potential. We find that the rate peaks at an angle of ${81}^{\ensuremath{\circ}}$ between the field and molecular principal inertial axis through the O atom. The predictions for the orientation dependence of the rate are compared to available theoretical results.