Abstract
We present an account of our recent effort to improve simulation of the photodissociation of small heteroaromatic molecules using the Ab Initio Multiple Cloning (AIMC) algorithm. The ultimate goal is to create a quantitative and converged technique for fully quantum simulations which treats both electrons and nuclei on a fully quantum level. We calculate and analyse the total kinetic energy release (TKER) spectra and Velocity Map Images (VMI), and compare the results directly with experimental measurements. In this work, we perform new extensive calculations using an improved AIMC algorithm that now takes into account the tunnelling of hydrogen atoms. This can play an extremely important role in photodissociation dynamics.
Highlights
Quantum non-adiabatic molecular dynamics is a powerful tool for understanding the details of the mechanisms of important photo-induced processes, such as the photodissociation of pyrrole and other heteroaromatic molecules
We introduced the ab initio multiple cloning (AIMC)10 method, where trajectory-guided Gaussian basis functions (TBF) are moving along Ehrenfest trajectories, as in the multicon gurational Ehrenfest (MCE)8,9 approach, with bifurcation of the wave-functions taken into account via basis function cloning
We present a new implementation of the Ab Initio Multiple Cloning (AIMC) approach that is improved to take into account the tunnelling of hydrogen atoms by identifying possible tunnelling points and placing additional TBFs of the other side of the barrier
Summary
While leading to the growth of the number of trajectories, the use of cloning helps to adopt the basis set to quantum dynamics signi cantly better than in the classical MCE approach. We present a new implementation of the AIMC approach that is improved to take into account the tunnelling of hydrogen atoms by identifying possible tunnelling points and placing additional TBFs of the other side of the barrier. We use this new implementation to simulate the dynamics of the photodissociation of pyrrole, a process where tunnelling can play a very important role.
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