Nuclear motion on the orbitally degenerate electronic ground state of fully deuterated triatomic hydrogen

Abstract

Nuclear motion in the vicinity of conical intersections of the degenerate electronic ground state of fully deuterated triatomic hydrogen, D3, is investigated with the aid of a time-dependent wavepacket approach in hyperspherical coordinates. Vibronic energy level spectra and the eigenfunctions are examined by including, for example, (1) geometric phase (GP) correction, (2) diagonal Born-Huang (BH) correction, and (3) both GP and BH corrections to the Born-Oppenheimer adiabatic Hamiltonian and finally by considering the nonadiabatic coupling between the two electronic surfaces explicitly. It emerges from this study that inclusion of both the GP and BH corrections is insufficient to explain the spectral features observed in the experiment. The latter are recovered by considering the complete two-states coupled Hamiltonian only. This study shows that both the GP and BH corrections constitute a minor part of the surface coupling effects, in particular, on the dynamics of the upper adiabatic sheet. Most importantly, we add that the experimental signature of the GP effect appears only in the observed shift of the eigenlevels of the electronic state when compared to those obtained from a completely Born-Oppenheimer Hamiltonian. The detail fine structure of the observed band of the electronic state is shaped by the off-diagonal derivative coupling elements of the nonadiabatic coupling operator. © 2011 American Institute of Physics.