화학공학소재연구정보센터
Journal of Physical Chemistry B, Vol.110, No.38, 19031-19039, 2006
On the characterization of three-state conical intersections using a group homomorphism approach: The two-state degeneracy spaces
Second-order degenerate perturbation theory, in conjunction with the group homomorphism method for describing a similarity transformation, are used to characterize the subspace of two-state conical intersections contained in the branching space of a three-state conical intersection. It is shown by explicit calculation, using the lowest three-state conical intersection of (CH)(3)N-2, that a second-order treatment yields highly accurate absolute energies, even at significant distances from the reference point of three-state intersection. The excellent agreement between the second order and ab initio results depends on the average energy component, which is computed using 5 first-order terms and 15 second-order terms. The second-order absolute energy change over the range rho = 0.0-0.3 au, where F is the distance from the three-state conical intersection in the branching space coordinates, is approximately 6500 and 9500 cm(-1) for the E-1=2 and E-2=3 seams, respectively, with the maximum ab initio energy deviation from degeneracy of 200 cm(-1) occurring at rho = 0.3 au. The characteristic parameters g(IJ) and h(IJ) are also predicted to great accuracy, even at large rho, with the error growing to only 10-15% at rho = 0.3 au.