An informative subtlety of itemperature-jump or coulostatic responses for surface-attached species

Theoretical relationships are developed to describe the open-circuit responses associated with the indirect laser-induced temperature-jump (ILIT) method, a method for measuring fast electron-transfer rate constants of surface-attached redox species. The analysis is also applicable to data obtained using the coulostatic charge-injection method. The unique relationship between km, the relaxation rate constant for the ILIT (or coulostatic) response, and Ei, the potential at which the system is initially poised, exhibits a surprising sensitivity to the values of k0, Ei0ʹ (the standard rate constant and formal potential for the redox couple), alpha (the transfer coefficient in the Butler¯Volmer equation) and gamma (a dimensionless parameter which is directly proportional to the total surface concentration of the redox moiety). ILIT data for several examples of surface-attached ferrocene moieties confirm the theoretically predicted km vs Ei behavior. Values of Ei0ʹ and gamma extracted from the ILIT data agree well with the values obtained from cyclic voltammetric data thereby confirming that the ILIT and cyclic voltammogram (CV) experiments are sampling the same ferrocene population.