Mixed ortho-H2 and para-H2 clusters studied by vibrational coherent anti-Stokes Raman spectroscopy

The search for macroscopic quantum effects, including superfluidity, in molecular hydrogen is mostly focused on its parahydrogen (p-H-2) nuclear spin modification because of weaker intermolecular interaction compared to orthohydrogen (o-H-2), both modifications being bosonic. In this work, mixed clusters of o-H-2 and p-H-2 containing similar to 10(4) molecules are prepared by supersonic expansion with helium and studied by vibrational coherent anti-Stokes Raman scattering (CARS) spectroscopy. At similar experimental conditions the neat p-H-2 clusters avoid freezing and remain fluid at 1-2 K, which is predicted to be the realm of their superfluid behavior [Phys. Rev. Lett. 101, 205301 (2008)]. Dependence of the vibrational frequencies and intensities of the main CARS peaks due to o-H-2 and p-H-2 versus the ratio of the o-H-2 and p-H-2 concentrations in the expanding gas suggests that o-H-2 and p-H-2 molecules are uniformly mixed in the interior of the clusters. A weak spectral feature at 4157 cm(-1) that appears independent of the concentration ratio is assigned to the outer shell of the clusters enriched with p-H-2 molecules. Although the phase of the mixed clusters could not be unambiguously identified, the shift of the vibrational frequencies with respect to the bulk solid is consistent with the liquid state of the clusters.