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Strategies to tune electrode potentials using molecular dipoles adsorbed to the semiconductor surface have been pursued for decades but are often based on weak interactions and quickly react to desorb the molecule under conditions relevant to sustained photoelectrolysis. Here, we show that covalent attachment of fluorinated, aromatic molecules to p\u2010GaAs(1\u20090\u20090) surfaces can be employed to tune the photocurrent onset potentials of p\u2010GaAs(1\u20090\u20090) photocathodes and reduce the external energy required for water splitting. Results indicate that initial photocurrent onset potentials can be shifted by nearly 150\u2005mV in pH \u22120.5 electrolyte under 1\u2005Sun (1000\u2005W\u2009m<jats:sup>\u22122<\/jats:sup>) illumination resulting from the covalently bound surface dipole. Though X\u2010ray photoelectron spectroscopy analysis reveals that the covalent molecular dipole attachment is not robust under extended 50\u2005h photoelectrolysis, the modified surface delays arsenic oxide formation that results in a p\u2010GaAs(1\u20090\u20090) photoelectrode operating at a sustained photocurrent density of \u221220.5\u2005mA\u2009cm<jats:sup>\u22122<\/jats:sup> within \u22120.5\u2005V of the reversible hydrogen electrode.<\/jats:p>","DOI":"10.1002\/cssc.201601408","type":"journal-article","created":{"date-parts":[[2016,12,12]],"date-time":"2016-12-12T18:36:24Z","timestamp":1481567784000},"page":"767-773","update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":28,"title":["Covalent Surface Modification of Gallium Arsenide Photocathodes for Water Splitting in Highly Acidic Electrolyte"],"prefix":"10.1002","volume":"10","author":[{"given":"Logan E.","family":"Garner","sequence":"first","affiliation":[{"name":"Chemistry &amp; Nanoscience Center National Renewable Energy Laboratory  Golden Colorado 80401 United States"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"K. 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