Coupled-cluster treatment of molecular strong-field ionization

Ionization rates and Stark shifts of H${}_2$, CO, O${}_2$, H${}_2$O, and CH${}_4$ in static electric fields have been computed with coupled-cluster methods in a basis set of atom-centered Gaussian functions with complex-scaled exponent. Consideration of electron correlation is found to be of great importance even for a qualitatively correct description of the dependence of ionization rates and Stark shifts on the strength and orientation of the external field. The analysis of the second moments of the molecular charge distribution suggests a simple criterion for distinguishing tunnel and barrier suppression ionization in polyatomic molecules.