Journal of Chemical Physics, Vol.103, No.8, 2839-2849, 1995
The Structure, Spectroscopy, and Excited-State Predissociation Dynamics of Geh2
The spectroscopy and excited state dynamics of ($) over tilde A B-1(1) germylene (GeH2) have been investigated experimentally and theoretically. Jet-cooled laser-induced fluorescence spectra of GeH2 were obtained by subjecting germane (GeH4) to an electric discharge at the exit of a pulsed nozzle. The band origins of ten vibronic transitions were determined, giving values for the upper state fundamentals of v(1)=783.0 cm(-1) and v(2)=1798.4 cm(-1). Sufficient numbers of 0(0)(0) band rovibronic transitions were observed to give the ground and excited state structures as r "=1.591(7) Angstrom, theta "=91.2(8)degrees and r’=1.553(12) Angstrom, theta’=123.4(19)degrees. Fluorescence lifetime measurements show that the 0(0,0), rotational levels decay radiatively; higher J rotational states in the 0(0) vibronic level decay much faster, due to a heterogeneous predissociation in the excited state. High quality ab initio studies are consistent with a model in which the lower vibronic levels of the ($) over tilde A state predissociate through the ($) over tilde a B-3(1) state to produce Ge(P-3)+H-2((1) Sigma(g)(+)). The transition state for this process has been located and the barrier to dissociation is 15.2 kcal/mol above the ($) over tilde A B-1(1) state, so that tunneling through the barrier must occur. Above 4000 cm(-1) of vibrational energy in the ($) over tilde A state, a breaking off of fluorescence is observed as a second predissociation channel involving GeH2(($) over tilde A B-1(1))-->Ge(D-1)+H-2((1) Sigma(g)(+)) becomes accessible. This process is also found to have a barrier, in contrast to previous theoretical studies of SiH2, where the analogous dissociation was predicted to be barrierless.
Keywords:GAUSSIAN-BASIS SETS;QUANTUM-CHEMICAL CALCULATIONS;PYROLYSIS JET SPECTROSCOPY;HARTREE-FOCK CALCULATIONS;ATOMIC NATURAL ORBITALS;VIBRATION ENERGY-LEVELS;ANO BASIS-SETS;ELECTRONIC-SPECTRUM;GENERAL CONTRACTION;SIMPLE GERMYLENES