The role of relative rate constants in determining surface state phenomena at semiconductor–liquid interfaces
Literature Information
Asif Iqbal, Md. Sazzad Hossain, Kirk H. Bevan
In this work, we present a theoretical study of surface state occupation statistics at semiconductor–liquid interfaces, as it pertains to the evolution of H2 and O2 through water splitting. Our approach combines semiclassical charge transport and electrostatics at the semiconductor–liquid junction, with a master rate equation describing surface state mediated electron/hole transfer. As a model system we have studied the TiO2–water junction in the absence of illumination, where it is shown that surface states might not always equilibrate with the semiconductor. Non-trivial electrostatics, for example including a shifting of the Mott–Schottky plateau in capacitive measurements, are explored when deep-level surface states partially equilibrate with the liquid. We also endeavor to explain observations of non-linearity present in Mott–Schottky plots, as they pertain to surface state occupation statistics. In general, it is intended that the results of this work will serve to further the use and development of quantitative device modeling techniques in the description of H2 evolution at semiconductor–liquid junctions.
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Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.














