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Spectroscopic current‐voltage (I‐V) curves taken with a scanning tunneling microscope on a synthetic, boron‐doped diamond single crystal indicate that the diamond, boiled in acid and baked to 500 °C in vacuum, does not exhibit ideal Schottky characteristics. These I‐V curves taken in ultrahigh vacuum do not fit the traditional theory of thermionic emission; however, the deviation from ideal can be accounted for by charge screening at the diamond surface. At ambient pressure, the I‐V curves have a sharp threshold voltage at 1.7 eV above the valence band edge indicating pinning of the Fermi energy. This measurement is in excellent agreement with the 1/3 band gap rule of Mead and Spitzer [Phys. Rev. 134, A713 (1964)].