Zeno and Anti-Zeno Effects in Nonadiabatic Molecular Dynamics.

Decoherence plays an important role in nonadiabatic (NA) molecular dynamics (MD) simulations because it provides a physical mechanism for trajectory hopping and can alter transition rates by orders of magnitude. Generally, decoherence effects slow quantum transitions, as exemplified by the quantum Zeno effect: in the limit of infinitely fast decoherence, the transitions stop. If the measurements are not sufficiently frequent, an opposite quantum anti-Zeno effect occurs, in which the transitions are accelerated with faster decoherence. Using two common NA-MD approaches, fewest switches surface hopping and decoherence-induced surface hopping, combined with analytic examination, we demonstrate that including decoherence into NA-MD slows down NA transitions; however, many realistic systems operate in the anti-Zeno regime. Therefore, it is important that NA-MD methods describe both Zeno and anti-Zeno effects. Numerical simulations of charge trapping and relaxation in graphitic carbon nitride suggest that time-dependent NA Hamiltonians encountered in realistic systems produce robust results with respect to errors in the decoherence time, a favorable feature for NA-MD simulations.