Prediction of pressure-induced red shift of f->d(t2g) excitations in Cs2NaYCl6:Ce(3+) and its connection with bond length shortening

Abstract

Quantum chemical calculations including embedding, scalar relativistic, and dynamic electron correlation effects on Cs2NaYCl6:(CeCl6)3- embedded clusters predict: (i) red shifts of the 4f->5d(t2g) transition with pressure and (ii) bond length shortening upon 4f->5d(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.Comment: 6 pages text; 1 table; 3 figures; to be published in J.Chem.Phy