a) Scheme of SFG experimental setup, SFG measurements were performed at the air/liquid interface in 1.0-inch diameter Teflon dish placed inside a tightly sealed chamber with two KBr windows for the input and output laser beams. b) ssp-SFG spectra collected at the air/100 mM aqueous K₃VO₄ interface with (red) and without (black) excess CO₂ from 2,200 to 2,400 cm⁻¹. The 2,336 cm⁻¹ peak observed upon CO₂ infusion is assigned to the CO₂ asymmetric stretching mode, indicating adsorption of CO₂ at the air/liquid interface. c) Schematic of CO₂ adsorption at the air/liquid interface, showing the direct interaction of the hydroxyl group of protonated orthovanadate with CO₂. d) Time-dependent ssp-SFG spectra collected at the air/100 mM aqueous K₃VO₄ interface before and after excess CO₂ are introduced at t = 0 from 2,200 to 2,400 cm⁻¹. d) Inset: Amplitude of the 2,336 cm⁻¹ peak normalized to the maximum amplitude at 60 min of CO₂ exposure from spectra in (d). The SFG spectra (and amplitude) collected after CO₂ purging stopped (after 60 min) show that the CO₂ 2,336 cm⁻¹ peak persists, demonstrating an indicative of a long-lived population, possibly kinetically trapped in this metastable state. e) CO₂ bond angle, Raman activity, and ʋ₃ symmetric stretch peak frequency from DFT calculations, showing enhanced Raman activity with CO₂ bending, which can be achieved through molecular interactions with the orthovanadate anions.