Hydrocarboxyl Radical as a Product of α-Alanine Ultraviolet Photolysis.

UV photodissociation of α-alanine was studied by parahydrogen matrix isolation infrared spectroscopy. The temporal behavior of Fourier transform infrared spectra revealed that UV irradiation at 213 nm yielded the HOCO radical as a direct photoproduct from the S2 excited state. The concentration of HOCO quickly approached a steady state due to secondary photodissociation of HOCO to produce CO2 + H or CO + OH. On the other hand, no photoproducts were detected by S1 excitation at 266 nm. Irradiation of fully deuterated α-alanine at 213 nm yielded ∼2 times more cis-DOCO radicals than the lower energy isomer trans-DOCO, indicating that the conformation of the hydroxyl group is fairly well-preserved upon photodissociation of α-alanine. The present study suggests that HOCO may be a good tracer species in the search for amino acids in interstellar space.

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.