Journal of Physical Chemistry A, Vol.108, No.11, 1930-1937, 2004
Rotationally resolved infrared laser spectroscopy of (H-2)(n)-HF and (D-2)(n)-HF (n=2-6) in helium nanodroplets
Rotationally resolved vibrational spectra are reported for a total of 15 hydrogen-HF clusters formed in helium nanodroplets, each with a different size (up to 6 hydrogens), or isotopic (H-2/D-2) or ortho/para composition. All of these spectra correspond to H-F stretch excitation and are well represented as symmetric or near symmetric prolate tops; fitted rotational constants are presented. Symmetry breaking in the mixed ortho/para complexes gives rise to both parallel and perpendicular transitions in the (H-2)(n)-HF complexes, whereas only parallel transitions are observed in the spectra of the mixed ortho/para (D-2)(n)-HF complexes. This difference, as well as the general trends in the rotational constants, can be understood in terms of the relative zero-point energies of the H2 and D2 complexes. Evidence of significant delocalization of the solvating hydrogen molecules is presented for larger pure para hydrogen clusters (n = 4-6).