We will summarize recent advances in First-principles based methods for predicting interfacial entropy and free energy with applications to reactions at surfaces of water containing various electrolytes. At Caltech, we have recently adapted an electrospray ionization mass spectrometer to selectively probe physicochemical phenomena on liquid surfaces. Thus, together with theory and experiments we have demonstrated that (1) anions present at air-water interface can electrostatically preorganize surrounding water molecules to facilitate proton transfer events, (2) the negative charge of the air-water interface is due to the presence of excess OH- at the aerial interface with a point-of-zero-charge at pH ~ 3, and (3) rate enhancements observed in the proton catalyzed reactions at fluctuating aqueous interfaces is due to inadequate hydration of hydronium, H3O+. These findings should further our understanding of atmospheric chemistry, colloidal science, 'on-water' and enzymatic catalysis and proton transfer reactions along and across membranes, including fuel cells and cellular processes.

First principles based theory complemented with electrospray ionization mass spectrometry to address environmental abiotic and biotic reactions

245th National Meeting (2013)

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