Prediction of pressure-induced redshift of f 1 →d (t 2g) 1 excitations in Cs 2NaYCl 6: Ce 3+ and its connection with bond-length shortening

Abstract

Quantum chemical calculations including embedding, scalar relativistic, and dynamic electron correlation effects on Cs2 NaY Cl6: (Ce Cl6) 3- embedded clusters predict (i) redshifts of the f1 →d (t2g) 1 transition with pressure and (ii) bond-length shortening upon f→d (t2g) excitation. Both effects are found to be connected which suggests that new high-pressure spectroscopic experiments could reveal the sign of the bond-length change. © 2005 American Institute of Physics.