Molecular effects in the ionization of N-2, O-2, and F-2 by intense laser fields

In this paper we study the response in time of N-2, O-2, and F-2 to laser pulses having a wavelength of 390 nm. We find single-ionization suppression in O-2 and its absence in F-2, in accordance with experimental results at lambda = 800 nm. Within our framework of time-dependent density functional theory we are able to explain deviations from the predictions of intense-field many-body S-matrix theory (IMST). We confirm the connection of ionization suppression with destructive interference of outgoing electron waves from the ionized electron orbital. However, the prediction of ionization suppression, justified within the IMST approach through the symmetry of the highest occupied molecular orbital (HOMO), is not reliable since it turns out that-e.g., in the case of F-2-the electronic response to the laser pulse is rather complicated and does not lead to dominant depletion of the HOMO. Therefore, the symmetry of the HOMO is not sufficient to predict ionization suppression. However, at least for F-2, the symmetry of the dominantly ionized orbital is consistent with the nonsuppression of ionization.