Deciphering the Influence of Ground-State Distributions on the Calculation of Photolysis Observables

Abstract

Nonadiabatic molecular dynamics offers a powerful tool for studying the photochemistry of molecular systems. Key to any nonadiabatic molecular dynamics simulation is the definition of its initial conditions, ideally representing the initial molecular quantum state of the system of interest. In this work, we provide a detailed analysis of how initial conditions may influence the calculation of experimental observables by focusing on the photochemistry of methylhydroperoxide, the simplest and most abundant organic peroxide in our atmosphere. We investigate the outcome of trajectory surface hopping simulations for distinct sets of initial conditions sampled from different approximate quantum distributions, namely harmonic Wigner functions and ab initio molecular dynamics using a quantum thermostat. Calculating photoabsorption cross-sections, quantum yields, and translational kinetic energy maps from the results of these simulations reveals the significant effect of the initial conditions, in particular when low-frequency (~ a few hundred cm-1) normal modes are connected to the photophysics of the molecule. Overall, our results indicate that sampling initial conditions from ab initio molecular dynamics using a quantum thermostat is preferable for flexible molecules with photoactive low-frequency modes. From a photochemical perspective, our nonadiabatic dynamics simulations offer an explanation for a low-energy tail observed at high excitation energy in the translational kinetic energy map of methylhydroperoxide.

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• A Theoretical Perspective on the Photochemistry of Boron-Nitrogen Lewis Adducts