Raman scattering and microwave dielectric studies of the structural phase transition in the quasi-one-dimensional ferromagnet (CH3)4NNiBr3

Abstract

We report polarized Raman spectra and 9.6 GHz dielectric constant measurements of the quasi-one-dimensional ferromagnet (CH3)4NNiBr3 (TMNB) at temperatures above and below the 134 K structural phase transition (Tc). The dielectric response is typical of materials for which a structural phase transition occurs, rising upon approach to Tc and decreasing sharply at Tc; ε1 falls gradually in the low temperature phase. There is a small hysteresis in the dielectric constant at Tc, indicative of the first order nature of the transition. The Raman spectra display striking changes through the structural phase transition as well. At room temperature, we observe the weak signature of four of the five Raman active BX3 modes. Below Tc, we observe splitting in several degenerate vibrational modes, one of which is a BX3 chain mode. This suggests that the phase transition is related to a symmetry breaking structural distortion in which the NiBr3 chains are intimately involved. The behavior of TMNB through Tc is in contrast to that of many other hexagonal magnetic materials, most notably TMNC, where the phase transition occurs with a doubling of the unit cell and an ordering of the tetramethylammonium counterions. We suggest that this difference is related to a combination of electrostatic and lattice expansion effects. Small frequency shifts of the phonons and a variation of the slope in the dielectric constant also provide evidence for a second phase transition near 95 K, which we relate to complete counterion ordering as in the case of TMCC.