Prediction of pressure-induced redshift of f1-->d(t2g)1 excitations in Cs2NaYCl6:Ce3+ and its connection with bond-length shortening.
Quantum chemical calculations including embedding, scalar relativistic, and dynamic electron correlation effects on Cs(2)NaYCl(6):(CeCl(6))(3-) embedded clusters predict (i) redshifts of the f(1)-->d(t(2g))(1) transition with pressure and (ii) bond-length shortening upon f-->d(t(2g)) 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.
Ruipérez
Fernando
F
Departamento de Química, C-XIV, Universidad Autónoma de Madrid, 28049 Madrid, Spain.
Seijo
Luis
L
Barandiarán
Zoila
Z