RT Journal Article
T1 Charge analysis in (RE)CrO4 scheelites by combined Raman spectroscopy and computer simulations
A1 García Baonza, Valentín
A1 Lobato Fernández, Álvaro
A1 Recio, J. Manuel
A1 Taravillo Corralo, Mercedes
AB The quest for structure-property relationships in scheelite-type (RE)CrO4 compounds (where RE is a rare earth element) is a difficult task due to the number of exceptions found in RE empirical trends and the uncommon Cr(V) oxidation state. In this work, we experimentally and computationally analyse how the stretching vibrational frequencies ν1(Ag) and ν3(Eg) associated with the [CrO4] tetrahedral units evolve in the (RE)CrO4 crystal family (RE ¼ Nd, Gd, Dy, Ho, and Lu). Since previously reported Cr–O distances and volume changes along with the RE series are not sufficiently accurate to explain the monotonic decrease observed for the ν1(Ag) and ν3(Eg) frequencies, a deeper analysis was performed involving the well-known fact that the bond strength (force constant) decreases as the interatomic distance increases. Our results demonstrates that structural and spectroscopic parameters can be reconciled with classical solid state chemistry ideas when charge effects are considered. This analysis provides a new method for predicting chromium oxidation states from Raman spectroscopy that can be generalised to the study of other crystal families.
PB Elsevier
SN 0022-4596
YR 2022
FD 2022-09-30
LK https://hdl.handle.net/20.500.14352/72607
UL https://hdl.handle.net/20.500.14352/72607
LA eng
NO CRUE-CSIC (Acuerdos Transformativos 2022)
NO Ministerio de Ciencia e Innovación (MICINN)
DS Docta Complutense
RD 25 jul 2024