By combined studies of electron spin resonance and optical absorption
at low temperatures, the charge-transfer bands of Rh5+ and Rh4+ are id
entified to be peaked near 1.6 and 1.9 eV, respectively. On this basis
, the light-induced charge-transfer processes in BaTiO3:Rh are unravel
ed at room temperature. It is shown that three charge states of Rh are
involved, leading to two levels: the shallow Rh-4+/5+ and the deeper
Rh-3+/4+ level. The optical behaviour of these two levels corresponds
to those expected from a 'two-center' model. The present paper represe
nts the first atomic-scale identification of three charge states of on
e element leading to optical 'two-level' response.