Metastability of Mn$^{3+}$ in ZnO driven by strong $d$(Mn) intrashell   Coulomb repulsion: experiment and theory
  Depopulation of the Mn$^{2+}$ state in ZnO:Mn upon illumination, monitored by quenching of the Mn$^{2+}$ EPR signal intensity, was observed at temperatures below 80~K. Mn$^{2+}$ photoquenching is shown to result from the Mn$^{2+}$ $\to$ Mn$^{3+}$ ionization transition, promoting one electron to the conduction band. Temperature dependence of this process indicates the existence of an energy barrier for electron recapture of the order of 1~meV. GGA$+U$ calculations show that after ionization of Mn$^{2+}$ a moderate breathing lattice relaxation in the 3+ charge state occurs, which increases energies of $d$(Mn) levels. At its equilibrium atomic configuration, Mn$^{3+}$ is metastable since the direct capture of photo-electron is not possible. The metastability is mainly driven by the strong intra-shell Coulomb repulsion between $d$(Mn) electrons. Both the estimated barrier for electron capture and the photoionization energy are in good agreement with the experimental values. 
A. Ciechan, H. Przybyli\'nska, P. Bogus{\l}awski, A. Suchocki, A.   Grochot, A. Mycielski, P. Skupi\'nski, K. Grasza
cond-mat.mtrl-sci