Photodissociation Dynamics of ClCN at Different Wavelengths

Abstract

The photodissociation dynamics of small molecules in the gas and condensed phase is an important source of information for better characterizing intermolecular interactions. Herein, classical molecular dynamics simulations with provisions to follow reactive processes between different electronic states are used to probe the wavelength dependence of product state distributions after laser excitation of ClCN. It is found that the maximum of the rotational excitation distribution P(j) of the CN product shifts to lower j-values with increasing wavelength and the width of the distribution narrows. Both observations are in accord with earlier experiments and provide improvements over previous theoretical treatments of the process with the same interaction potentials. For the reaction in a water droplet, strong quenching of rotational excitation is found.

Competitive reaction pathways in vibrationally induced photodissociation of H2SO4

“…Related work on Cl-CN following a more simplistic approach than the one pursued in the present work showed that a direct link between experiment and atomistic simulations can be established. 61,62 Contrary to previous simulations for water elimination in H 2 SO 4 which were more qualitative in nature, 30,32 the present work employs a refined and physically more meaningful PES which allows us to follow both H-transfer and water elimination within the same framework. This is necessary because the two processes have similar barrier heights and can compete with each other.…”

Atomistic simulations of reactive processes in the gas- and condensed-phase

“…Recent examples include photodissociation dynamics of ICN [103,104] and ClCN [100] in explicit solvent. Recent examples include photodissociation dynamics of ICN [103,104] and ClCN [100] in explicit solvent.…”

“…Extending ARMD to electronic transitions allowed to more realistically model this process [100]. Using the original PESs [96,101], several thousand trajectories were statistically analysed and found good agreement between computed and experimentally observed P(j) was found.…”

CO-dynamics in the active site of cytochrome c oxidase

“…More appropriate treatments of such processes have been recently discussed in the context of photodissociation of small molecules together with final state analysis. 61 After applying the photodissociating pulse, the system is switched back -after time delays ranging from 20 to 200 fs -to the ground state surface in order to follow the reactive dynamics. For this the bond between Fe and CO was removed and replaced by Eq.…”