Theoretical modeling of postionization fragmentation of rare-gas trimer cations

Abstract

The dynamics of ionic rare-gas trimers (Ar(3) (+), Kr(3) (+), and Xe(3) (+)) produced by a sudden ionization of neutral precursors is investigated theoretically with a hybrid classical-quantum method for solving the equations of motion governed by a Hamiltonian obtained from a previously tested diatomics-in-molecules model. Initial conditions are selected with Monte Carlo sampling. Two possibilities for generating the initial electronic state are considered: diabatic (local) and adiabatic (delocalized). The dynamics generally leads to fragmentation, producing either monomer ions or dimer ions in a relatively short time; however, a large number of long-lived metastable trimer ions are also seen in some cases. We have analyzed the dynamics with respect to the fraction of monomer ions produced, the distribution of the kinetic energy of the products, and the distribution of fragmentation times of the trimers. Initial diabatic ionization is associated with much faster fragmentation than adiabatic ionization. Spin-orbit coupling plays an important role in the fragmentation dynamics.