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Determine Which Excited-State Dynamics Method Excels Against Experiment

Determine which excited-state photoinduced dynamics simulation method provides superior predictive accuracy when benchmarked against recent experimental findings, particularly for the Rydberg-excited (n→3s) S2 state of cyclobutanone in gas-phase ultrafast electron diffraction experiments.

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Background

The paper surveys multiple established computational approaches for simulating excited-state nonadiabatic dynamics, noting that despite substantial methodological development, there has been a lack of comprehensive and uniform comparisons to recent experimental data. This gap motivates the Journal of Chemical Physics Prediction Challenge, in which teams predict outcomes for cyclobutanone photoexcited to the n→3s Rydberg S2 state.

Within this paper, decoherence-corrected fewest-switches surface hopping (DC-FSSH) was combined with different electronic structure methods (MCSCF, MRCI/ODM3, TDDFT, ADC(2), CC2), revealing substantial divergence in predicted lifetimes, mechanisms, and photoproducts. The unresolved question is which method, in practice, yields the most reliable predictions when compared to experiment.

References

However, a lack of comprehensive and uniform studies comparing the performance of these methods with recent experimental findings leaves the question of which method excels still unanswered.

— Prediction Challenge: Simulating Rydberg Photoexcited Cyclobutanone with Surface Hopping Dynamics based on Different Electronic Structure Methods (2402.09890 - Mukherjee et al., 15 Feb 2024) in Introduction, page 1