Quantum mechanical study of optical emission spectra of Rydberg-excited H₃ and its isotopomers

Abstract

Optical emission spectra of Rydberg-excited H₃, D₃, H₂D, and D₂H, in the range 200–400 nm, are investigated theoretically and compared with the experimental findings of Bruckmeier et al. [Phys. Rev. Lett. 72, 2550 (1994)]. The time-dependent wave packet method combined with the vibronic coupling theory for ( E×ε) Jahn-Teller systems is utilized in order to calculate the corresponding Franck-Condon emission profiles from the upper n=3 electronic state to the degenerate (2p)1E′ ground electronic manifold of those species. We obtain bimodal spectra with two maxima 9600cm^-1 apart in good agreement with the experimental result.