Abstract
Infrared spectra of the mass selected ionic complexes H2–HCO+ and D2–DCO+ have been recorded in the vicinity of their ν1 vibrations (H2/D2 stretch) by means of photofragmentation spectroscopy. The anomalous rotational constants obtained by fitting the observed line positions to a semirigid Watson A-type Hamiltonian reflect the appreciable zero-point excursions of the H2/D2 molecule. Barriers for this internal motion are estimated utilizing a simple atom–diatom hindered rotor Hamiltonian. According to this one-dimensional model, the barrier increases by about 15% upon vibrational excitation which is mainly attributed to electrostatic effects.
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