Determining the molecular Aharonov-Bohm phase angle: A rigorous approach employing a molecular properties based adiabatic to diabatic states transformation

摘要

Recently there has been considerable interest, not to mention controversy, concerning a key aspect of the molecular Aharonov-Bohm (MAB) effect: the construction of the phase angle, induced by geometric phase effect, whose gradient is the vector potential characteristic of MAB theory. In the past this angle was constructed from explicit knowledge of the locus of the seam of conical intersection. Here it is shown how a phase angle that satisfies the requirements of MAB theory can be determined without a priori knowledge of the locus of points of conical intersection. This approach has important implications for direct dynamics. It is a corollary of a recent analysis that showed that diagonalizing the matrix of virtually any symmetric (real-valued-Hermitian) electronic property operator in the subspace of states that intersect conically generates a transformation that removes all of the singularity of the derivative coupling at a conical intersection. Key aspects of this method are illustrated by considering the dipole moment operator near a point on the 1 ~3A"-2 ~3A" seam of conical intersection in CH_2.