Photodynamics of Gas‐Phase Pyruvic Acid Following Light Absorption in the Actinic Region

The photochemistry of pyruvic acid has received a large attention due to its relevance atmospheric chemistry. Pyruvic is produced in the troposphere from both biogenic and anthropogenic sources prototypical model for family -dicarbonyls. What makes particularly interesting gas-phase perceptive expected decarboxylation upon sunlight absorption. exact photodynamics leading this release CO2 remains elusive. In work, we used combination excited- ground-state ab initio molecular dynamics unravel possible mechanisms acid. Our calculations highlight importance proton-coupled electron transfer mechanism taking place first excited electronic state triggering nonadiabatic molecule ground state. takes ground-electronic with concomitant formation methylhydroxycarbene. We also calculate photoabsorption cross-section wavelength-dependent quantum yields acid, highlighting limits our theoretical formalism.