Prediction Challenge: Simulating Rydberg Photoexcited Cyclobutanone with Surface Hopping Dynamics based on Different Electronic Structure Methods

This research examines the nonadiabatic dynamics of cyclobutanone after excitation into the n-3s Rydberg S2 state. It stems from our contribution to the Special Topic of the Journal of Chemical Physics to test the predictive capability of computational chemistry against unseen experimental data. Decoherence-corrected fewest-switches surface hopping (DC-FSSH) was used to simulate nonadiabatic dynamics with full and approximated nonadiabatic couplings. Several simulation sets were computed with different electronic structure methods, including a multiconfigurational wavefunction (MCSCF) specially built to describe dissociative channels, multireference semiempirical approach, time-dependent density functional theory, algebraic diagrammatic construction, and coupled cluster. MCSCF dynamics predicts a slow deactivation of the S2 state (10 ps), followed by an ultrafast population transfer from S1 to S0 (<100 fs). CO elimination (C3 channel) dominates C2H4 formation (C2 channel). These findings radically differ from the other methods, which predicted S2 lifetimes 10 to 250 times shorter and C2 channel predominance. These results suggest that routine electronic structure methods may hold low predictive power for the outcome of nonadiabatic dynamics.Comment: The main manuscript contains 28 pages with 8 figures. The supplementary material contains 14 pages with 12 figures. In total, the merged pdf document has 42 pages with 20 figure

Trajectory integration with potential energy discontinuities

Many approximate methods of quantum chemistry yield potential energy surfaces with discontinuities. While clearly unphysical, such features often fall within the typical error bounds of the method, and cannot be easily eliminated. The integration of nuclear trajectories when the potential energy is locally discontinuous is obviously problematic. We propose a method to smooth out the discontinuities that are detected along a trajectory, based on the definition of a continuous function that fits locally the computed potential, and is used to integrate the trajectory across the discontinuity. With this correction, the energy conservation error can be reduced by about one order of magnitude, and a considerable improvement is obtained in the energy distribution among the internal coordinates