Journal of Physical Chemistry A, Vol.109, No.15, 3476-3484, 2005
N-state adiabatic-to-diabatic transformation angle: Theory and application
In this article is discussed a new diabatization procedure which is expected to be reliable and, also, relatively easy to implement. This procedure takes into account the two main ingredients related to diabatization: (1) The size N of the smallest (relevant) group of states that forms a Hilbert subspace (this fact enforces the dimension of the adiabatic-to-diabatic transformation matrix to be N). (2) The total energy E which determines the number of open states, p, within this group of N states. The main emphasis in this manuscript is on the case that N is arbitrary but p is equal to 2. The various derivations as well as the final results are accompanied by numerical examples extracted from three- to five-state ab initio calculations for the H + H-2 system.