  We have investigated the temperature-dependent changes in the near-$E$$_F$
occupied and unoccupied states of Pr$_{0.67}$Ca$_{0.33}$MnO$_3$ which shows the
presence of ferromagnetic and antiferromagnetic phases. The
temperature-dependent changes in the charge and orbital degrees of freedom and
associated changes in the Mn 3$d$ - O 2$p$ hybridization result in varied O
2$p$ contributions to the valence band. A quantitative estimate of the charge
transfer energy ($E$$_{CT}$) shows a larger value compared to the earlier
reported estimates. The charge localization causing the large $E$$_{CT}$ is
discussed in terms of different models including the electronic phase
separation.
