AbstractPhotochemical behaviors of pyruvic acid in multiple phases have been extensively studied, while those of its conjugate base, the pyruvate anion (CH3COCOO-, PA-) are less understood and remain contradictory in gaseous versus aqueous phases. Here in this article, we report a joint experimental and theoretical study combining cryogenic, wavelength-resolved negative ion photoelectron spectroscopy (NIPES) and high-level quantum chemical computations to investigate PA- actinic photochemistry and its dependence on microsolvation in the gas phase. PA–·nH2O (n = 0–5) clusters were generated and characterized, with their low-lying isomers identified. NIPES conducted at multiple wavelengths across the PA– actinic regime revealed the PA– photochemistry extremely sensitive to its hydration extent. While bare PA– anions exhibit active photoinduced dissociations that generate the acetyl (CH3CO–), methide (CH3 –) anions, their corresponding radicals, and slow electrons, one single attached water molecule results in significant suppression with a subsequent second water being able to completely block all dissociation pathways, effectively annihilating all PA– photochemical reactivities. The underlying dissociation mechanisms of PA–·nH2O (n = 0–2) clusters are proposed involving np* excitation, dehydration, decarboxylation, and further CO loss. Since the photoexcited dihydrate does not have sufficient energy to overcome the full dehydration barrier before PA? could fragmentate, the PA? dissociation pathway is completely blocked, with the energy most likely released via loss of one water and internal electronic and vibrational relaxations. The insight unraveled in this work provides a muchneeded critical link to connect the seemingly conflicting PA– actinic chemistry between the gas and condensed phases.
Published: November 4, 2022