Diabolical conical intersections

Abstract

In the Born-Oppenheimer approximation for molecular dynamics as generalized by Born and Huang, nuclei move on multiple potential-energy surfaces corresponding to different electronic states. These surfaces may intersect at a point in the nuclear coordinates with the topology of a double cone. These conical intersections have important consequences for the dynamics. When an adiabatic electronic wave function is transported around a closed loop in nuclear coordinate space that encloses a conical intersection point, it acquires an additional geometric, or Berry, phase. The Schr\"odinger equation for nuclear motion must be modified accordingly. A conical intersection also permits efficient nonadiabatic transitions between potential-energy surfaces. Most examples of the geometric phase in molecular dynamics have been in situations in which a molecular point-group symmetry required the electronic degeneracy and the consequent conical intersection. Similarly, it has been commonly assumed that the conical intersections facilitating nonadiabatic transitions were largely symmetry driven. However, conical intersections also occur in the absence of any symmetry considerations. This review discusses computational tools for finding and characterizing the conical intersections in such systems. Because these purely accidental intersections are difficult to anticipate, they may occur more frequently than previously thought and in unexpected situations, making the geometric phase effect and the occurrence of efficient nonadiabatic transitions more commonplace phenomena. [S0034-6861(96)00404-7]