over time, followed more recently by an exploration of the strong influence of the alkali counterions on the CO 2 capture rate thereof by Arteaga et al. As for tetraperoxometalates, Ma et al. demonstrated the reversible formation of the peroxycarbonate species [Ta(O 2 ) 3 (CO 4 )] 3 -from [Ta(O 2 ) 4 ] 3 -as the anion of an ionic liquid under high CO 2 pressures. A distinguishing feature of the [Ta(O 2 ) 4 ] 3 -study was the use of computational results with up-to-date methodologies that supported the observed spectroscopybased explanations. Prominent among these results were thermochemical calculations performed using Density-Functional Theory (DFT), the most widely used electronic structure method nowadays, that provided a molecular-level framework for understanding how the reaction proceeds. The authors of the current work have with others studied the DAC reactivity of a mononuclear tetraperoxovanadate, K 3 [V(O 2 ) 4 ], with extensive experimental and computational characterization. Included in that study was the description of the overall reaction of