The excitation of surface-localized polaronic states has recently been discussed as an additional photocatalytic channel to band gap excitation for rutile $\mathrm{Ti}{\mathrm{O}}_2$. A contribution from photoexcitation of bulk polarons could, in principle, provide a greater contribution because of their higher number and their protection from oxidation. However, determining such a contribution to the photoyield is challenging and has not been achieved thus far. Here we use two photon photoemission spectroscopy measurements to separate bulk and surface polaron photoexcitation. We find that bulk polarons are less bound by 0.2 eV compared with polarons at the surface, consistent with our results of hybrid density functional theory calculations. Because the excited state is also shifted to higher energy, bulk polarons have the same photoexcitation resonance energy as at the surface (3.6 eV) with a threshold at 3.1 eV. This is degenerate with the band gap, suggesting that bulk polarons could also provide an additional contribution to the photoyield.

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• Density of states
• First-principles calculations
• Photoinduced effect
• Polarons
• Energy materials
• Density functional theory
• Two-photon photoelectron spectroscopy