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We study the resistance switching mechanism of rutile TiO2 using ab initio calculations based on DFT. Ordering of the oxygen vacancies substantially increases the conductivity of TiO2 by forming a conductive channel, i.e. “ON”-state. We find that the diffusion of either oxygen or hydrogen atoms into the conductive channel causes the rupture of the conductive filament resulting in the transition from “ON”-state to “OFF”-state.