화학공학소재연구정보센터
Journal of Chemical Physics, Vol.115, No.11, 5066-5075, 2001
On the effects of spin-orbit coupling on conical intersection seams in molecules with an odd number of electrons. II. Characterizing the local topography of the seam
Characteristic of conical intersections of Born-Oppenheimer potential energy surfaces is eta, the dimension of the branching space, the space in which the degeneracy is lifted linearly. In molecules with an odd number of electrons, eta =2 for the nonrelativistic Coulomb Hamiltonian, while eta =3(5) when the spin-orbit interaction is included and the molecule has (does not have) C-s symmetry. In the eta =2 case, the branching space is defined by two vectors: the energy difference gradient vector, g, and the interstate coupling vector, h. g and h can, without loss of generality, be chosen orthogonal. gxh is invariant under the unitary wave function transformation that orthogonalizes g and h. The orthogonal g and h can be used to define an optimal set of coordinates for describing the vicinity of the conical intersection. Here these ideas are generalized to eta =3 intersections. In particular, it is shown that g, the energy difference gradient vector, and h(r) and h(i), the real and imaginary parts of the interstate coupling vector, which define the eta =3 space, can without loss of generality be chosen orthogonal. It is also shown that gxh(r).h(i) is invariant under the unitary wave function transformation that orthogonalizes these vectors. These ideas are illustrated using a portion of the OH(A (2)Sigma (+)(1/2),X (2)Pi (3/2,1/2)) + H-2 seam of conical intersection.