title: Exceptional isotopic-substitution effect: breakdown of collective proton tunneling in hexagonal ice due to partial deuteration.
abstract: Multiple proton transfer controls many chemical reactions in hydrogen-bonded networks. However, in contrast to well-understood single proton transfer, the mechanisms of correlated proton transfer and of correlated proton tunneling in particular have remained largely elusive. Herein, fully quantized ab initio simulations are used to investigate H/D isotopic-substitution effects on the mechanism of the collective tunneling of six protons within proton-ordered cyclic water hexamers that are contained in proton-disordered ice, a prototypical hydrogen-bonded network. At the transition state, isotopic substitution leads to a Zundel-like complex, [HO⋅⋅⋅D⋅⋅⋅OH], which localizes ionic defects and thus inhibits perfectly correlated proton tunneling. These insights into fundamental aspects of collective proton tunneling not only rationalize recent neutron-scattering experiments, but also stimulate investigations into multiple proton transfer in hydrogen-bonded networks much beyond ice.
authors.affiliation: Lehrstuhl für Theoretische Chemie, Ruhr-Universität Bochum, 44780 Bochum (Germany). Christof.Drechsel-Grau@theochem.rub.de.
authors.forename: Christof
authors.initials: C
authors.lastname: Drechsel-Grau
authors.forename: Dominik
authors.initials: D
authors.lastname: Marx
keywords: ab initio calculations; collective tunneling; hexagonal ice; isotope effects; proton transfer