Two-Dimensional Analysis of the Diabatic Transition of a General Vectorial Physical Observable Based on Adiabatic-to-Diabatic Transformation.

We present a full analysis of the magnitude and orientation of the diabatic transition matrix element of a general vectorial physical observable during the adiabatic-to-diabatic transformation. The diabatic transition is a function of the adiabatic-to-diabatic transformation angle and the two basic vectors of the adiabatic states, which are the off-diagonal matrix element and the difference between the two diagonal matrix elements. To the best of our knowledge, this is the first time that the transformation has been accomplished in a more general two-dimensional scale for a vectorial physical observable. All possible extreme values of a diabatic transition are deduced for systems with different features. By using an approximate diabatic transition dipole, the pilot implementation of the analysis produces an electronic coupling curve nearly identical to that obtained by the generalized Mulliken-Hush method for the testing molecule. Evidently, this complete analysis of a diabatic transition will be very useful in determining the adiabatic-to-diabatic transformation angle by using a physical observable and can also be used to evaluate the quality of various approximations for constructing the diabatic states.