Abstract
Author(s): Bello, RY; Lucchese, RR; Rescigno, TN; McCurdy, CW | Abstract: We demonstrate a theoretical treatment of dissociative single ionization of the LiH molecule using two-color UV-UV pulse sequences that makes use of a highly correlated description of both the ionization continuum and target molecular ion and neutral states to which it is coupled. The present results emphasize how the details of the ionization process at various internuclear distances combine to form a lens through which such experiments image the dynamics of intermediate electronic states populated by the pump pulse. While ionization yields (dissociative and nondissociative) provide information about the amplitudes and phases that build up the molecular wave packet in the neutral states, molecular frame photoelectron angular distributions exhibit the changing character of those states, i.e., from ionic to covalent. In addition, the time-dependent mean kinetic energy of the wave packet on neutral states is clearly mapped onto the kinetic energy release of the atomic fragments produced by the probe ionization pulse.
Highlights
Time-resolved photoelectron spectroscopy (TRPES) of molecules has long been recognized as a sensitive probe of both nuclear and electronic dynamics, when it can be accomplished experimentally in the molecular frame [1,2,3,4]
OF PUMP AND IONIZING PROBE CALCULATIONS. With this correlated treatment of the bound and continuum electronic states it is instructive to see how the electronic structure and dynamics of the target molecule are revealed in the details of the photoelectron and dissociative kinetic energy release (KER) spectra of the ion produced by the action of the pump pulse
We demonstrated the theoretical tools necessary to treat electron correlation both within the target ion and neutral wave functions and in the ionization continuum at state-ofthe-art levels to predict the physical observables in pump and ionizing probe experiments on small molecules
Summary
Time-resolved photoelectron spectroscopy (TRPES) of molecules has long been recognized as a sensitive probe of both nuclear and electronic dynamics, when it can be accomplished experimentally in the molecular frame [1,2,3,4]. The orientation of the molecule is accomplished experimentally; molecular frame photoelectron angular distributions (MFPADs) can reveal the changes in electronic structure that accompany nuclear motion as the system moves through conical intersections, or in the case of diatomic molecules, avoided crossings [4,9] Experiments of this type pose a particular challenge for theory if it is to address both molecular dynamics and photoionization. There have been several pioneering investigations focusing on the nonadiabatic coupling between bound states of LiH that can be excited by an optical pulse [30,31,32,33,34] Those studies revealed the rich charge transfer dynamics that occur during nuclear vibration and dissociation on excited states of the neutral molecule. IV we summarize our specific findings and the prospects for application of this methodology to a more complete description of such experiments on this molecule and other small molecules that involve different multiple intermediate states and nonadiabatic transitions between them
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