Ab initio free energy of vacancy formation and mass-action kinetics in vis-active TiO2

Abstract

Recent reports have identified bulk defects such as oxygen vacancies as key players in visible-light photoactive TiO2. This would imply greater visible light absorption rates may be possible provided effective defect engineering can be achieved. To further this we have developed methods to simulate vacancy formation in bulk TiO2 using ab initio techniques. Initial results of these methods show an entropic reduction in the free energy of vacancy formation of 2.3 eV over a range of 266 K. The use of this result is illustrated by a 'toy' mass-action kinetics model which offers insight into vacancy concentration, rate constants, and enthalpy of reaction.

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