The first data on the relative single-particle energies outside the doubly magic Sn100 nucleus were obtained. A prompt 171.7(6)keV γ-ray transition was correlated with protons emitted following the β decay of Sn101 and is interpreted as the transition between the single-neutron g7/2 and d5/2 orbitals in Sn101. This observation provides a stringent test of current nuclear structure models. The measured νg7/2-νd5/2 energy splitting is compared with values calculated using mean-field nuclear potentials and is used to calculate low-energy excited states in light Sn isotopes in the framework of the shell model. The correlation technique used in this work offers possibilities for future, more extensive spectroscopy near Sn100
