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

TL;DR

This study uses advanced quantum chemical calculations to predict how pressure affects electronic excitations and bond lengths in a cerium-doped crystal, suggesting experimental verification of these effects.

Contribution

It provides the first detailed theoretical prediction linking pressure-induced electronic shifts with bond length changes in Cs2NaYCl6:Ce(3+).

Findings

Pressure causes red shifts in 4f->5d(t2g) transitions.

Bond length shortens upon excitation.

Predicted effects can be tested with high-pressure spectroscopy.

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.