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Non-adiabatic direct quantum dynamics using force fields: Toward solvation

Quantum dynamics simulations are becoming a powerful tool for understanding photo-excited molecules. Their poor scaling, however, means that it is hard to study molecules with more than a few atoms accurately, and a major challenge at the moment is the inclusion of the molecular environment. Here, we present a proof of principle for a way to break the two bottlenecks preventing large but accurate simulations. First, the problem of providing the potential energy surfaces for a general system is addressed by parameterizing a standard force field to reproduce the potential surfaces of the molecule’s excited-states, including the all-important vibronic coupling. While not shown here, this would trivially enable the use of an explicit solvent. Second, to help the scaling of the nuclear dynamics propagation, a hierarchy of approximations is introduced to the variational multi-configurational Gaussian method that retains the variational quantum wavepacket description of the key quantum degrees of freedom and uses classical trajectories for the remaining in a quantum mechanics/molecular mechanics like approach. The method is referred to as force field quantum dynamics (FF-QD), and a two-state ππ*/nπ* model of uracil, excited to its lowest bright ππ* state, is used as a test case.
- Goethe University Frankfurt Germany
- National Research Council Italy
- University College London United Kingdom
- Institute of Biostructure and Bioimaging Italy
- University of Salamanca Spain
quantum chemistry, Quantum dynamics simulations, standard force field, potential surfaces, vibronic coupling, potential energy surfaces, dynamics, Química, Degrees of freedom (mechanics), potential energy
quantum chemistry, Quantum dynamics simulations, standard force field, potential surfaces, vibronic coupling, potential energy surfaces, dynamics, Química, Degrees of freedom (mechanics), potential energy
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