Allene and pentatetraene cations as models for intramolecular charge transfer: Vibronic coupling Hamiltonian and conical intersections

Abstract

We consider the vibronic coupling effects involving cationic states with degenerate components that can be represented as charge localized at either end of the short cumulene molecules allene and pentatetraene. Our aim is to simulate dynamically the charge transfer process when one component is artificially depopulated. We model the Jahn-Teller vibronic interaction within these states as well as their pseudo-Jahn-Teller coupling with some neighboring states. For the manifold of these states, we have calculated cross sections of the ab initio adiabatic potential energy surfaces along all nuclear degrees of freedom, including points at large distances from the equilibrium to increase the physical significance of our model. Ab initio calculations for the cationic states of allene and pentatetraene were based on the fourth-order Møller-Plesset method and the outer valence Green's function method. In some cases we had to go beyond this method and use the more involved third-order algebraic diagrammatic construction method to include intersections with satellite states. The parameters for a five-state, all-mode diabatic vibronic coupling model Hamiltonian were least-square fitted to these potentials. The coupling parameters for the diabatic model Hamiltonian are such that, in comparison to allene, an enhanced preference for indirect charge transfer is predicted for pentatetraene.