Nonadiabatic molecular dynamics simulations of the photofragmentation and geminate recombination dynamics in size-selected I2−⋅(CO2)n cluster ions

Abstract

Erratum: "On nonadiabatic molecular dynamics simulations of the photofragmentation and geminate recombination dynamics in size-selected I 2 − Ar n cluster ions" [J.Nonadiabatic molecular dynamics simulations of the photofragmentation and geminate recombination dynamics in size-selected I 2 − Ar n cluster ionsIn this paper we investigate the photodissociation, geminate recombination and relaxation dynamics in size-selected I 2 Ϫ •(CO 2 ) n cluster ions using an electronically nonadiabatic molecular dynamics method and a model Hamiltonian gained from diatomics-in-ionic systems ͑DIIS͒. These theoretical studies make contact with recent time resolved pump-probe and photoelectron detachment experiments. Our studies reveal a rich excited state dynamics in which various competing electronic relaxation channels as well as vibrational relaxation influence the recovery of signal in these experiments.

Simulation of UV photodissociation of I2−(CO2)n: Spin-orbit quenching via solvent mediated electron transfer

“…[41][42][43][44][45][46] Nonadiabatic molecular dynamics simulations computed with these Hamiltonians have successfully reproduced the results of both time-independent and time-dependent experiments. The results of these simulations demonstrate that physical pictures based on the isolated molecule potential curves can be highly misleading.…”

“…1͒; however, both simulations 43,46 and experiment 11 show that in a cluster of CO 2 molecules this channel is closed and that dissociation only occurs via nonadiabatic transitions to the lower A and X states.…”

“…In this respect, the short-time dynamics on the B state following UV excitation resemble those observed on the AЈ state following visible excitation. 45,46 Once on the aЈ state, however, the system may hop to the AЈ or a state at the points of intersection with the aЈ curve, arrow 3. This charge transfer differs from transitions seen in our 790 nm simulations, in that it occurs only from highly asymmetric solvent configurations.…”

“…Clusters in the size range nϭ6 -13, on which we focus this discussion, contain approximately half a solvation shell of CO 2 molecules, which group together about one end of I 2 Ϫ , producing an asymmetric solvent environment. 27,37,43,46 At tϭ0, the solute is promoted to the repulsive B state. The excess charge flows rapidly to the less solvated iodine atom, and the solvent responds to this change in the solute polarization on a time scale of a few hundred femtoseconds.…”

Femtosecond stimulated emission pumping:

“…I tion. Experiments by Lineberger et al [5][6][7][8][9], Barbara 2 has become a model system for ultrafast studies of et al [2][3][4], and our group [10][11][12] have probed vibrational energy transfer in a variety of polar these aspects of the dynamics, while molecular solvents [2][3][4] and size-selected clusters [5][6][7][8][9][10][11][12], due dynamics simulations have been performed by Parson et al [13][14][15][16] and Coker et al [17,18]. One problem in interpreting the experiments is that by the known a priori.…”