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Isotopic Substitution as a Strategy to Control Non-Adiabatic Dynamics in Photoelectrochemical Cells: Surface Complexes between TiO2 and Dicyanomethylene Compounds

We investigate the effect of deuteration on geminate recombination in photoelectrochemical cells operating by interfacial charge transfer absorption bands. The trend in recombination in surface complexes of tetracyanoethylene (TCNE), 7,7,8,8-tetracyanoquinodimethane (TCNQ), and 11,11,12,12-tetracyanonaphtho-2,6-quinodimethane (TCNAQ) with TiO2 is treated as internal conversion (IC) in the model compounds TCNX–O–Ti(OH)3-. The deuteration of TCNQ and TCNAQ significantly modifies the spectrum of vibronic coupling constants for many vibrational modes, but affects little the modes with the strongest contribution to IC. As a result, the overall effect on recombination/internal conversion is expected to be limited, slightly increasing its rate. We also consider the influence on the recombination of vibrational modes of the Ti(OH)3 moiety which only crudely models the oxide surface. We conclude that even as the model is sensitive to the motions of Ti(OH)3, the predicted trend in recombination in the series TCNE–TCNQ–TCNAQ holds under different treatments of Ti(OH)3 modes.