Fig. 3: Effect of cell potential on diabatic free energies at fixed z.
From: Insights into solvent and surface charge effects on Volmer step kinetics on Pt (111)
A solvent reorganization λ; B equilibrium \(\Delta e\) value for \({{{{{{\rm{H}}}}}}}^{+}\), \(\Delta {e}_{{{\min }}\,}^{{{{{{{\rm{H}}}}}}}^{+}};\) C free energy to reach the diabatic crossing with the effect of overpotential subtracted off, \(\Delta {F}_{\eta=0\,}^{{{\ddagger}} }\); and D reduction free energy change, \(\Delta F\), for the diabatic curves where \({F}^{{{{{{\rm{H}}}}}}}\left(\Delta e\right)={F}^{{{{{{{\rm{H}}}}}}}^{+}}\left(\Delta e\right)+\Delta e\). The blue, red, green, and purple curves are computed from diabatic free energy curves at electrode voltages relative to PZC of \(V-{V}_{{{{{{\rm{pzc}}}}}}}=0{{{{{\rm{V}}}}}},-0.5{{{{{\rm{V}}}}}},-1{{{{{\rm{V}}}}}},-2{{{{{\rm{V}}}}}}\), respectively.
