Vogel, Yan BZhang, LongDarwish, NadimGoncales, Vinicius R.Le Brun, AntonGooding, J JustinMolina, Angelawallace, GordonCoote, MichelleGonzalez, JoaquinCiampi, Simone2021-09-102021-09-102041-1723http://hdl.handle.net/1885/247764Predicting or manipulating charge-transfer at semiconductor interfaces, from molecular electronics to energy conversion, relies on knowledge generated from a kinetic analysis of the electrode process, as provided by cyclic voltammetry. Scientists and engineers encountering non-ideal shapes and positions in voltammograms are inclined to reject these as flaws. Here we show that non-idealities of redox probes confined at silicon electrodes, namely full width at half maximum <90.6 mV and anti-thermodynamic inverted peak positions, can be reproduced and are not flawed data. These are the manifestation of electrostatic interactions between dynamic molecular charges and the semiconductor's space-charge barrier. We highlight the interplay between dynamic charges and semiconductor by developing a model to decouple effects on barrier from changes to activities of surface-bound molecules. These findings have immediate general implications for a correct kinetic analysis of charge-transfer at semiconductors as well as aiding the study of electrostatics on chemical reactivity.This work was supported by grants from the Australian Research Council (ARC, DE160100732 (S.C.), DE160101101 (N.D.)). J.G.S. and A.M. greatly appreciate the financial support provided by the Fundación Séneca de la Región de Murcia (Projects 19887/GERM/15 and 18968/JLI/13) and by the Ministerio de Economía y Competitividad (projects CTQ-2015-65243-P and CTQ-2015-71955-REDT Network of excellence “Sensors and Biosensors”). L.Z., M.L.C., and G.G.W. acknowledge funding from the ARC Centre of Excellence Scheme (Project No. CE 140100012). J.J.G. and G.G.W. are under ARC Laureate Fellowships (FL150100060 and FL110100196).application/pdfen-AU© The Author(s) 2017https://creativecommons.org/licenses/by/4.0/201710.1038/s41467-017-02091-12020-11-23Creative Commons License (Attribution 4.0 International)