Electronic spectroscopy of Mg-phthalocyanine embedded in cold hydrogen clusters produced by a pulsed nozzle.

Cold clusters of molecular hydrogen were created using a pulsed nozzle. The thermodynamical states of the clusters were characterized by measuring the cluster beam velocity and the laser-induced fluorescence (LIF) spectra of embedded molecules. Two distinct velocity components were identified in the beam that originates from different clustering mechanisms. The fast velocity component corresponds to the expansion of H2 from the gas phase, while the slow velocity component corresponds to the expansion from the liquid phase. The velocity distribution of these two components showed no significant difference between the expansions of para and normal hydrogen. In this study, LIF spectroscopy of single Mg-phthalocyanine molecules embedded in the H2 clusters consisting of 105 H2 molecules was used to investigate the properties of the fast component. The observed peak frequencies of the LIF signals, compared to those observed in helium droplets, were used to infer the possible presence of the liquid phase in the fast component of the H2 clusters below 5 K. The shift, linewidth, and splitting in the spectra, which strongly depend on the ortho/para ratio, are attributed to the local configurations of hydrogen in the vicinity of the probe molecules.

VUV photochemistry and nuclear spin conversion of water and water-orthohydrogen complexes in parahydrogen crystals at 4 K.

Samples of H2O, HDO, and D2O were isolated in solid parahydrogen (pH2) matrices and irradiated by vacuum ultraviolet (VUV) radiation at 147 nm. Fourier-Transform Infrared (FTIR) spectra showed a clear depletion of D2O and an enrichment of both HDO and H2O by 147 nm irradiation. These irradiation-dependent changes are attributed to the production of OH and/or OD radicals through photodissociations of H2O, HDO, and D2O. The radicals subsequently react with the hydrogen matrix, leading to the observed enrichment of H2O. No trace of isolated OH or OD was detected in the FTIR spectra, indicating that the OH/OD radicals react with the surrounding matrix hydrogen molecules via quantum tunneling within our experimental timescale. The observed temporal changes in concentrations, especially the increase of HDO concentration during VUV irradiation, can be interpreted by a model with a rapid conversion from orthohydrogen (oH2) to pH2 in water-oH2 complexes upon VUV photodissociation, indicating either the acceleration of the nuclear spin conversion (NSC) of H2 due to the magnetic moment of the intermediate OH/OD radical, or the preferential reaction of the OH/OD radical with a nearby oH2 molecule over other pH2 molecules. We have also identified and quantified an anomalously slow NSC of H2O and D2O complexed with oH2 in solid pH2.