Multiscale non-adiabatic dynamics with radiative decay, case study on the post-ionization fragmentation of rare-gas tetramers

Abstract

In this supplementary material, we recollect, for reader's convenience, the general scheme of suggested multiscale model (Sec. 1), and basic informations about approaches used for pilot study: a detailed description of the interaction model (Sec. 2) and dynamical methods used for the dark dynamics step (Sec. 3) reported previously in two preceding studies [1,2]. In addition, a detailed description of the treatment of radiative processes is also given (Sec. 4).

Non-adiabatic dynamics combining Ehrenfest, decoherence, and multiscale approaches applied to ionic rare-gas clusters photodissociation, post-ionization fragmentation, and collisions

“…Starting from a pioneering "on-the-fly" method [14,16,22,23,24] and challenged by interesting experimental results, we have improved our hybrid dynamical approach (quantum treatment of electrons and classical description of nuclei) [32] in two directions consisting in: a) the inclusion of periodic decoherence [19] to face sequential fragmentation and fix the fractionary charge problem, and b) a multiscale approach [20] to include long-time evolution involving radiative and non-radiative processes. These developments allowed us to treat complex non-adiabatic dynamics occurring in photodissociation, postionization fragmentation, and collisions of ionic rare-gas clusters.…”

“…Mainly for this reason, an approximate extension of the direct non-adiabatic dynamics calculations, which overcomes this limitation, has been recently proposed for radiative transitions [20] as well as for both radiative and non-radiative transitions considered [21]. This approximate methodology consists in extending the short-time non-adiabatic dynamics calculations by a kinetic rate theory treatment.…”

“…A general scheme of this multiscale method can be typically split into two phases and several partial steps [20,21]:…”

“…Note also that alternative names like hemiquantal method [14,16,22,23,24,25,26,27] and semiclassical method [19,28,29,20,30,21,31] were also used in our previous studies.…”

“…Further on, clusters remaining in excited electronic states for extremely long lifetimes faced the theoretical treatment to another computational limitation. As an approximate solution, we proposed a multiscale treatment [20,21] including radiative and non-radiative transitions.…”