Derivation of the electronic nonadiabatic coupling field in molecular systems:An algebraic-vectorial approach

摘要

In this Communication it is suggested that various elements of the nonadiabatic coupling matrix,tau_(jk)(s) are created by the singular nonadiabatic coupling terms of the system.Moreover,given the spatial distribution of these coupling terms in the close vicinity of their singularity points yields,according to this approach,the integrated intensity of the field at every point in the region of interest.To support these statements we consider the conical intersections of the three lower states of the H+H_2 system:From an ab initio treatment we obtain the nonadiabatic coupling terms around each conical intersection separately (at its close vicinity) and having those,create the field at every desired point employing vector-algebra.This approach is also used to calculate the intensity of the Curl of those matrix elements that lack their own sources [tau_(13)(s) in the present case].The final results are compared with relevant ab initio calculations.