Ultrafast Proton Transfer Pathways Mediated by Amphoteric Imidazole

Abstract

Imidazole, being an amphoteric molecule, can act both as an acid and as a base. This property enables imidazole, as an essential building block, to effectively facilitate proton transport in high-temperature proton exchange membrane fuel cells and in proton channel transmembrane proteins, enabling those systems to exhibit high energy conversion yields and optimal biological function. We explore the amphoteric properties of imidazole by following the proton transfer exchange reaction dynamics with the bifunctional photoacid 7-hydroxyquinoline (7HQ). We show with ultrafast ultraviolet-mid-infrared pump−probe spectroscopy how for imidazole, in contrast to expectations based on textbook knowledge of acid−base reactivity, the preferential reaction pathway is that of an initial proton transfer from 7HQ to imidazole, and only at a later stage a transfer from imidazole to 7HQ, completing the 7HQ tautomerization reaction. An assessment of the molecular distribution functions and first-principles calculations of proton transfer reaction barriers reveal the underlying reasons for our observations.

Detailed Complementary Consistency: Wave Function Tells Particle How to Hop, Particle Tells Wave Function How to Collapse

“…In chemistry, physics, biology, and materials science, many important processes (e.g., proton transfer, [1][2][3] charge transport, [4][5][6] exciton diffusion, [7][8][9] energy relaxation, [10][11][12][13] and singlet fission [14][15][16][17] ) all belong to the category of nonadiabatic dynamics. Due to the presence of quantum transitions, the traditional Born-Oppenheimer approximation is no longer valid, and the electronic and nuclear dynamics become strongly coupled.…”

Detailed Complementary Consistency: Wave Function Tells Particle How to Hop, Particle Tells Wave Function How to Collapse

“…In chemistry, physics, biology, and materials science, many important processes (e.g., proton transfer, − charge transport, − exciton diffusion, − energy relaxation, − and singlet fission − ) all belong to the category of nonadiabatic dynamics. Due to the presence of quantum transitions, the traditional Born–Oppenheimer approximation is no longer valid, and the electronic and nuclear dynamics become strongly coupled.…”