IR-induced and tunneling reactions in cryogenic matrices: the (incomplete) story of a successful endeavor.

In this article, IR-induced and tunneling-driven reactions observed in cryogenic matrices are described in a historical perspective, the entangling of the two types of processes being highlighted. The story of this still ongoing fascinating scientific endeavor is presented here following closely our own involvement in the field for more than 30 years, and thus focuses mostly on our work. It is, because of this reason, also an incomplete story. Nevertheless, it considers a large range of examples, from very selective IR-induced conformational isomerizations to IR-induced bond-breaking/bond-forming reactions and successful observations of rare heavy atom tunneling processes. As a whole, this article provides a rather general overview of the major progress achieved in the field.

Molecular structure, infrared spectra, photochemistry, and thermal properties of 1-methylhydantoin.

The structural, vibrational, and photochemical study of 1-methylhydantoin (1-MH, C4H6N2O2) was undertaken by matrix isolation infrared spectroscopy (in argon matrix; 10 K), complemented by quantum chemical calculations performed at the DFT(B3LYP)/6-311++G(d,p) level of approximation. The theoretical calculations yielded the Cs symmetry structure, with planar heavy atom skeleton, as the minimum energy structure on the potential energy surface of the molecule. The electronic structure of this minimum energy structure of 1-MH was then studied in detail by means of the natural bond orbital (NBO) and atoms in molecules (AIM) approaches, allowing for the elucidation of specific characteristics of the molecule's σ and π electronic systems. The infrared spectrum of the matrix-isolated 1-MH was fully assigned, also with the help of the theoretically predicted spectrum of the compound, and its UV-induced unimolecular photochemistry (λ ≥ 230 nm) was investigated. The compound was found to fragment to CO, isocyanic acid, methylenimine, and N-methyl-methylenimine. Finally, a thermal behavior investigation on 1-MH samples was carried out using infrared spectroscopy (10 K until melting), differential scanning calorimetry and polarized light thermal microscopy. A new polymorph of 1-MH was identified. The IR spectra of the different observed phases were recorded and interpreted.