A practical and efficient diabatization that combines Lorentz and Laplace functions to approximate nonadiabatic coupling terms

A fixed relation of alpha x beta = 1.397 between the alpha- and beta-parameters of a Lorentz function and a Laplace function that approximates nonadiabatic coupling terms and maximizes the overlap area between the two functions was found. The mixing angle corresponding to the geometric average between the potential couplings calculated using the individual path-integral of the two functions was then used in the construction of diabatic states and the coupling of the states. Employing the new method, the actual computation of nonadiabatic coupling terms at just a few geometries before and after the guessed conical intersection is enough, and the remaining steps are straightforward and almost automatic. The new method was tested for the one-dimensional LiF system and the two-dimensional space of the collinear case of NH3Cl, and promising results were achieved. (C) 2015 AIP Publishing LLC.