Topologically correct quantum nonadiabatic formalism for on-the-fly dynamics

Abstract: On-the-fly quantum nonadiabatic dynamics for large systems greatly benefits from the adiabatic representation readily available from the electronic structure programs. However, frequently occurring in this representation conical intersections introduce non-trivial geometric or Berry phases which require a special treatment for adequate modelling of the nuclear dynamics. We analyze two approaches for nonadiabatic dynamics using the time-dependent variational principle and the adiabatic representation. The first approach employs adiabatic electronic functions with global parametric dependence on the nuclear coordinates. The second approach uses adiabatic electronic functions obtained only at the centres of moving localized nuclear basis functions (e.g. frozen-width Gaussians). Unless a gauge transformation is used to enforce single-valued boundary conditions, the first approach fails to capture the geometric phase. In contrast, the second approach accounts for the geometric phase naturally because of the absence of the global nuclear coordinate dependence in the electronic functions.