Identification of HOC^•HC(O)H, HOCH₂C^•O, and HOCH₂CH₂O^• Intermediates in the Reaction of H + Glycolaldehyde in Solid <i>Para</i>-Hydrogen and Its Implication to the Interstellar Formati

Glycolaldehyde [HOCH₂C(O)H, GA], the primitive sugar-like molecule detected in the interstellar medium (ISM), is a potential precursor for the synthesis of complex sugars. Despite its importance, the mechanism governing the formation of these higher-order sugars from GA under interstellar circumstances remains elusive. Radical intermediates HOCH₂CH₂O^• (<b>1</b>), HOCH₂C^•HOH (<b>2</b>), HOCH₂C^•O (<b>3</b>), HOC^•HC(O)H (<b>4</b>), and O^•CH₂C(O)H (<b>5</b>) derived from GA could be potential precursors for the formation of glyceraldehyde (aldose sugar), dihydroxyacetone (ketose sugar), and ethylene glycol (sugar alcohol) in dark regions of ISM. However, the spectral identification of these intermediates and their roles were little investigated. We conducted reactions involving H atoms and the <i>Cis</i>-<i>cis</i> conformer of GA (<i>Cc</i>-GA) in solid <i>p</i>-H₂ at 3.2 K and identified IR spectra of radicals <i>Cc</i>-HOCH₂C^•O (<b>3</b>) and <i>Cc</i>-HOC^•HC(O)H (<b>4</b>) produced from H abstraction as well as closed-shell HOCHCO (<b>6</b>) produced via consecutive H abstraction of GA. In addition, <i>Cc</i>-HOCH₂CH₂O^• (<b>1</b>) and C^•H₂OH + H₂CO (<b>7</b>) were produced through the H addition and the H-induced fragmentation channels, respectively. In darkness, when only H-tunneling reactions occurred, the formation of (<b>3</b>) was major and that of (<b>1</b>) was minor. In contrast, during IR irradiation to produce H atoms with higher energy, the formation of (<b>4</b>) and C^•H₂OH + H₂CO (<b>7</b>) became important. We also successfully converted most <i>Cc-</i>GA to the second-lowest-energy conformer <i>Trans</i>-<i>trans</i>-GA (<i>Tt</i>-GA) by prolonged IR irradiation at 2827 nm to investigate H + <i>Tt</i>-GA; <i>Tt</i>-HOCH₂C^•O (<b>3'</b>), <i>Tt</i>-HOC^•HC(O)H (<b>4'),</b> HOCHCO (<b>6</b>), <i>Tt</i>-HOCH₂CH₂O^• (<b>1'</b>), and C^•H₂OH + H₂CO (<b>7</b>) were observed. We discuss possible routes for the formation of higher-order sugars or related compounds involving (<b>7</b>), (<b>1</b>), (<b>3</b>), and (<b>4</b>), but neither (<b>2</b>), which was proposed previously, nor (<b>5</b>) plays a significant role in H + GA. Such previously unreported rich chemistry in the reaction of H + GA, with four channels of three distinct types, indicates the multiple roles that GA might play in astronomical chemistry.