A scheme to interpolate potential energy surfaces and derivative coupling vectors without performing a global diabatization

摘要

Simulation of non-adiabatic molecular dynamics requires the description of multiple electronic state potential energy surfaces and their couplings. Ab initio molecular dynamics approaches provide an attractive avenue to accomplish this, but at great computational expense. Interpolation approaches provide a possible route to achieve flexible descriptions of the potential energy surfaces and their couplings at reduced expense. A previously developed approach based on modified Shepard interpolation required global diabatization, which can be problematic. Here, we extensively revise this previous approach, avoiding the need for global diabatization. The resulting interpolated potentials provide only adiabatic energies, gradients, and derivative couplings. This new interpolation approach has been integrated with the ab initio multiple spawning method and it has been rigorously validated against direct dynamics. It is shown that, at least for small molecules, constructing an interpolated PES can be more efficient than performing direct dynamics as measured by the total number of ab initio calculations that are required for a given accuracy.