Conformational Analysis and Ultraviolet Photodissociation of Valine in Solid Parahydrogen: Conformer-Specific Photolysis and Product Identification

The conformational composition and ultraviolet photochemistry of neutral valine isolated in solid parahydrogen were investigated using high-resolution infrared spectroscopy, ultraviolet photolysis, and density functional theory calculations. The observed infrared spectrum was analyzed by combining calculated vibrational frequencies, relative infrared intensities, and conformer-specific photolysis kinetics. Four distinct photolysis-rate categories were identified experimentally, providing direct evidence for the presence of at least four valine conformers in the parahydrogen matrix. The combined spectroscopic and kinetic analysis enabled assignment of the major absorption bands to the six lowest-energy conformers and revealed pronounced conformer-dependent photostability of valine. Upon irradiation at 213 nm, valine undergoes predominantly α-carbonyl C–C bond cleavage, producing the hydrocarboxyl (HOCO) radical and 2-methylpropan-1-imine as the major photoproducts. The formation of HOCO is consistent with previous studies of amino acids isolated in solid parahydrogen and supports a common photodissociation pathway among aliphatic amino acids. The hydrogen-bonded Type II conformer exhibits significantly slower photodepletion than the Type I conformers, indicating that intramolecular hydrogen bonding enhances ultraviolet photostability of valine. These results establish a direct relationship between molecular conformation and photochemical stability in isolated amino acids while further demonstrating the unique capability of solid parahydrogen matrix isolation for conformer-specific photochemical investigations.