Title: Direct Mapping Hidden Excited State Interaction Patterns from ab initio Dynamics and Its Implications on Force Field Development,
Abstract: The excited states of polyatomic systems are rather complex, and often
exhibit meta-stable dynamical behaviors. Static analysis of reaction pathway
often fails to sufficiently characterize excited state motions due to their
highly non-equilibrium nature. Here, we proposed a time series guided
clustering algorithm to generate most relevant meta-stable patterns directly
from ab initio dynamic trajectories. Based on the knowledge of these
meta-stable patterns, we suggested an interpolation scheme with only a concrete
and finite set of known patterns to accurately predict the ground and excited
state properties of the entire dynamics trajectories. As illustrated with the
example of sinapic acids, the estimation error for both ground and excited
state is very close, which indicates one could predict the ground and excited
state molecular properties with similar accuracy. These results may provide us
some insights to construct an excited state force field with compatible energy
terms as traditional ones.