On the electron wavepacket dynamics of photoionizing states

Abstract

To study electron wavepacket dynamics of photoionizing states in polyatomic molecules, we discuss two crucial issues to be overcome in the theory of molecular electronic wavepacket dynamics in an intense laser field (Takatsuka and Yonehara 2011 Phys. Chem. Chem. Phys. 13 4987). One is about the description of the ionization process from electronically excited states composed of many multiply excited configuration-state functions. The other is how to reconstruct the electronic states remaining in the molecular site while electrons are flowing out of the molecular bounds. These are both critical to extend the realm of the theories of electron dynamics based on the so-called expansion (algebraic) method in terms of basis functions. To calculate the photoionization amplitude and thereby to estimate the time-dependent amount of electron loss from a molecule, we extract the electron flux (probability current density) from the electron wavepackets without use of scattering theory. This is justified by the success of the recent works by Bandrauk’s group for attosecond photoionization dynamics from the hydrogen molecule ion, who performed numerical integration of the relevant Schrödinger equation (Yuan et al 2013 J. Chem. Phys. 138 134316). A key feature in the present study, on the other hand, is to calculate the electron flux in terms of complex-valued NOs, which arise from the complex electronic wavepackets. Through the change of these NOs, we reconstruct the involved electronic configurations during the flow of electrons out of molecular regions. These repopulated electronic wavefunctions are (non-adiabatically) evolved in time under laser fields.