When the energy levels of two weakly coupled excited states cross the characteristics of the corresponding exited state wave functions tend to exhibit discontinuous changes in their spatial properties. In simulations of adiabatic dynamics this unphysical behavior is known as the trivial crossing problem. A common approach for avoiding the trivial crossing problem is to enforce state changes (i.e., surface hops) that restore wavefunction continuity. In this talk I highlight that an unintended consequence of this approach is that it introduces a discontinuity in the nodal symmetry of the wavefunction. I present a method for preventing this change in symmetry and illustrate the method in simulations of excitons on long chain conjugated polymers.

Avoiding trivial states in adiabatic dynamics can lead to unphysical changes in wave function symmetry

2019 Spring National Meeting

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