Park, Kyoung-Won Kolpak, Alexie M. 2024-01-19T19:33:27Z 2024-01-19T19:33:27Z 2021-09-02 2019-07-03 2399-3669 https://pubs.kist.re.kr/handle/201004/119784 The conduction and valence band edges (EC and EV) of a material relative to the water redox potential levels are critical factors governing photocatalytic water splitting activity. Here we discuss the large discrepancy in the experimentally measured EC and EV of various transition metal oxides (TMOs) in vacuum and in an aqueous solution. We speculate that the discrepancy stems from the different degree of electron transfer across the surface due to the different environment at the surface of the TMOs in vacuum and water. Accurately modeling the electronic structure at TMO/water interfaces is a significant challenge, however. Using first-principles density functional theory calculations on rutile titanium dioxide and cobalt monoxide model systems, here we identify the optimal approaches to accurately predict the band edge positions in vacuum and water. We then validate the optimized schemes on other TMOs, demonstrating good agreement with experimental measurements in both vacuum and water. English NATURE PUBLISHING GROUP RUTILE TIO2(110) SURFACE 1ST-PRINCIPLES CALCULATIONS ELECTRON-TRANSFER WATER SEMICONDUCTOR ENERGETICS INTERFACES ALIGNMENT COO FLUORESCENCE Optimal methodology for explicit solvation prediction of band edges of transition metal oxide photocatalysts Article 10.1038/s42004-019-0179-3 1 COMMUNICATIONS CHEMISTRY, v.2 COMMUNICATIONS CHEMISTRY 2 scie scopus 000473720600003 2-s2.0-85071151541 Chemistry, Multidisciplinary Chemistry Article RUTILE TIO2(110) SURFACE 1ST-PRINCIPLES CALCULATIONS ELECTRON-TRANSFER WATER SEMICONDUCTOR ENERGETICS INTERFACES ALIGNMENT COO FLUORESCENCE