Raman and infrared study of 4f electron-phonon coupling in HoVO3.
First-order Raman scattering and multiphonons are studied in RVO3 (R  =  Ho and Y) as a function of temperature in the orthorhombic and monoclinic phases. Raman spectra of HoVO3 and YVO3 unveil similar features since both compounds have nearly identical R-radii. However, the most important difference lies in the transition temperature involving the V(3+) orbitals, the V(3+) magnetic moments as well as the crystallographic structure. Particularly, the magnetic and orbital reorientations occur at T N2  =  40 K for HoVO3 instead T N2  =77 K in the case of YVO3. For both systems, anomalous phonon shifts which are related to spin-phonon coupling are observed below the V(3+) magnetic ordering temperature (T N1  ≈  110 K) while additional phonon anomalies are exclusively observed in HoVO3 around T (*)  ≈  15 K. On the other hand, infrared (IR) transmittance measurements as a function of temperature reveal Ho(3+5)I8  →  (5)I7 excitations and additional excitations assigned as vibronics. These latter combined with drastic changes in Ho(3+5)I8  →  (5)I7 excitations at T N2, are indicative of a strong coupling between the Ho(3+) ions and the ligand field. This could explain the large magnetocaloric capacity shown by HoVO3.
Regroupement Québecois sur les matériaux de pointe, Département de physique, Université de Sherbrooke, J1K 2R1, QC, Canada.
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