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α-Ga2O3has the corundum structure analogous to that of α-Al2O3. The bandgap energy of α-Ga2O3is 5.3 eV and is greater than that of β-Ga2O3, making the α-phase attractive for devices that benefit from its wider bandgap. The O–H and O–D centers produced by the implantation of H+and D+into α-Ga2O3have been studied by infrared spectroscopy and complementary theory. An O–H line at 3269 cm−1is assigned to H complexed with a Ga vacancy (VGa), similar to the case of H trapped by an Al vacancy (VAl) in α-Al2O3. The isolated VGaand VAldefects in α-Ga2O3and α-Al2O3are found by theory to have a “shifted” vacancy-interstitial-vacancy equilibrium configuration, similar to VGain β-Ga2O3, which also has shifted structures. However, the addition of H causes the complex with H trapped at an unshifted vacancy to have the lowest energy in both α-Ga2O3and α-Al2O3.