• Accepted Paper

Observation of pronounced spin-phonon coupling in spin-driven ferroelectrics Mn4X2O9 (X = Nb, Ta)

Rajesh Jana, Alka Garg, Mayuresh Mukadam, Rekha Rao, and Thomas Meier

Phys. Rev. B - Accepted 28 September, 2026

DOI: https://doi.org/10.1103/rl7s-xyzt

Abstract

We report detailed Raman spectroscopic and magnetic susceptibility studies on the spin-driven ferroelectric compounds Mn4Nb2O9 (MNO) and Mn4Ta2O9 (MTO). Both systems exhibit strong spin–phonon coupling below the short-range magnetic ordering temperature (Tsro∼220 K), followed by further anomalous changes in several Raman modes at the long-range magnetic ordering temperatures (TN = 120 K for MNO and 110 K for MTO). Distinct low-temperature evolutions of Raman mode shift, linewidth, and integrated intensity in MNO and MTO highlight the role of the nonmagnetic cation in tuning spin–lattice coupling, driven by differences in spin–orbit coupling and orbital hybridization between Nb5+ (4d) and Ta5+ (5d). By combining Raman spectroscopy with nuclear magnetic resonance, and diffuse reflectance spectroscopy, we further show that Mn-based systems possess a more distorted local structure than their Co analogues, while their electronic structures differ despite comparable band gaps. These results provide a comprehensive understanding of spin–lattice coupling in Mn- and Co-based A4X2O9 (A = Fe, Co, Mn; X = Nb, Ta) magnetoelectric systems.

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