Primary photodissociation mechanisms of pyruvic acid on S1: observation of methylhydroxycarbene and its chemical reaction in the gas phase

• Published in: Physical chemistry chemical physics : PCCP 2021-01, Vol.23 (7), p.4107-4119
• Main Authors: Samanta, B R, Fernando, R, Rösch, D, Reisler, H, Osborn, D L
• Format: Article
• Language: English
• Subjects: Acetaldehyde; Acids; Atmospheric models; Carboxylic acids; Chemical reactions; Decarboxylation; Excitation; Fluence; Free radicals; Hydrogen bonds; INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Isomerization; Mass spectrometry; Organic chemistry; Photodissociation; Photoionization; Solar radiation; Thermochemistry; Troposphere; Vapor phases
• ISSN: 1463-9076; 1463-9084
• DOI: 10.1039/d0cp06424f

Pyruvic acid, a representative alpha-keto carboxylic acid, is one of the few organic molecules destroyed in the troposphere by solar radiation rather than by reactions with free radicals. To date, only its stable final products were identified, often with contribution from secondary chemistry, making it difficult to elucidate photodissociation mechanisms following excitation to the lowest singlet excited-state (S1) and the role of the internal hydrogen bond in the most-stable Tc conformer. Using multiplexed photoionization mass spectrometry we report the first direct experimental evidence, via the observation of singlet methylhydroxycarbene (MHC) following 351 nm excitation, supporting the decarboxylation mechanism previously proposed. Decarboxylation to MHC + CO2 represents 97–100% of product branching at 351 nm. We observe vinyl alcohol and acetaldehyde, which we attribute to isomerization of MHC. We also observe a 3 ± 2% yield of the Norrish Type I photoproducts CH3CO + DOCO, but only from d1-pyruvic acid. At 4 Torr pressure, we measure a photodissociation quantum yield of 1.0−0.4+0, consistent with IUPAC recommendations. However, our measured product branching fractions disagree with IUPAC. In light of previous calculations, these results support a mechanism in which hydrogen transfer on the S1 excited state occurs at least partially by tunneling, in competition with intersystem crossing to the T1 state. We present the first evidence of a bimolecular reaction of MHC in the gas phase, where MHC reacts with pyruvic acid to produce a C4H8O2 product. This observation implies that some MHC produced from pyruvic acid in Earth's troposphere will be stabilized and participate in chemical reactions with O2 and H2O, and should be considered in atmospheric modeling.