Faradaic phase transition of dibenzyl viologen on an HOPG electrode surface studied by in situ electrochemical STM and electroreflectance spectroscopy.

Phase transitions of an adsorption layer of dibenzyl viologen (dBV) as a typical diaryl viologen on a basal plane of a highly oriented pyrolytic graphite (HOPG) electrode are described using voltammetry, in situ electrochemical scanning tunneling microscopy (EC-STM), and electroreflectance (ER) spectroscopy. A monolayer redox process at less negative potential than the bulk redox process was found to be the first-order faradaic phase transition between a gaslike adsorption layer of dication (dBV2+) and a 2D condensed monolayer of radical cation (dBV•+). Comparison of the results of cyclic voltammetry and potential step chronoamperometry was made with those of heptyl viologen (HV), which also undergoes a faradaic phase transition of the first order. It suggested that the contribution of intermolecular π–π interaction between benzyl groups of dBV to the phase transition is minor and apparently equivalent to interchain interaction between the heptyl chains of HV. In situ EC-STM images of the 2D condensed mon...