H/D Isotope Effects Accompanying Electrolysis of Water as Studied by Molecular Orbital Calculations

Abstract

H/D isotope effects accompanying the electrolysis of liquid water based on the evaluation of the RPFRs of involved hydrogen species were studied using molecular orbital (MO) methods at the B3LYP/6-31G (d, p) level of theory. Our purpose is understanding the isotope effects; thus, taking into consideration the H/D isotope exchange equilibriums between the hydrogen species absorbed on surfaces of electrodes and H₂O or H₃O⁺ seems a better approach than simply considering the equilibrium between H₂ and H₂O.