Topology of Conical Intersection Seams and the Geometric Phase.

Abstract

In this paper, we demonstrate two topological properties of crossing seams, that is, the sets of points in the N-dimensional space of nuclear coordinates where two electronic eigenstates are degenerate. We shall examine the typical case of states of the same spin with accidental degeneracies, whereby the crossing seam is of dimension N - 2. The first property we demonstrate is that a crossing seam has no boundary, therefore, it must either extend asymptotically to infinite values of one or more coordinates or wrap on itself. The second property is that two (or more) crossing seams can intersect each other but in such a way that neither of them ends at the intersection. When N = 3, the crossing seam is a line in a 3D space; this is so in triatomic molecules but also in reduced dimensionality treatments of larger polyatomics. The above-mentioned rules then mean that the crossing seam is a line of infinite length or a closed loop and can split into three branches but not in two. The example of the first two excited 1A' states of H2Cl+ illustrates these rules and shows their usefulness for computational search and characterization of crossing seams.