Abstract
A split diabatic representation is proposed as a technique for generating diabatic potential curves with the maximal physical content and favorable computational characteristics. This method is a mixed adiabatic-diabatic representation, in which smoothly varying couplings appear in both the kinetic- and potential-energy matrices. It requires the solution of the first-order differential equation for the transformation matrix of the standard strict diabatic representation for which an efficient numerical scheme is also presented. A transformation propagator, akin to the Cayley-Hamiltonian time evolution operator, is employed to obtain the diabatic states while preserving unitarity. Several examples illustrate the advantages of the proposed split diabatic representation.
- Received 30 June 2003
DOI:https://doi.org/10.1103/PhysRevA.68.042706
©2003 American Physical Society