On the (E ⊗ e) -Jahn-Teller conical intersections in the 3p (E′) and 3d (E″) Rydberg electronic states of triatomic hydrogen

Abstract

The static and dynamic aspects of the Jahn-Teller (JT) interactions in the 3p (E′) and 3d (E″) Rydberg electronic states of H3 are analyzed theoretically. The static aspects are discussed based on recent ab initio quantum chemistry results, and the dynamic aspects are examined in terms of the vibronic spectra and nonradiative decay behavior of these states. The adiabatic potential-energy surfaces of these degenerate electronic states are derived from extensive ab initio calculations. The calculated adiabatic potential-energy surfaces are diabatized following our earlier study on this system in its 2p (E′) ground electronic state. The nuclear dynamics on the resulting conically intersecting manifold of electronic states is studied by a time-dependent wave-packet approach. Calculations are performed both for the uncoupled and coupled state situations in order to understand the importance of nonadiabatic interactions due to the JT conical intersections in these excited Rydberg electronic states. © 2005 American Institute of Physics.