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Raman study of the Verwey transition in Magnetite at high-pressure and low-temperature; effect of Al doping

We report high-pressure low-temperature Raman studies of the Verwey transition in pure and Al-doped magnetite (Fe_3O_4). The low temperature phase of magnetite displays a number of additional Raman modes that serve as transition markers. These transition markers allow one to investigate the effect of hydrostatic pressure on the Verwey transition temperature. Al-doped magnetite Fe_2.8Al_0.2O_4 (TV=116.5K) displays a nearly linear decrease of the transition temperature with an increase of pressure yielding dP/dT_V = -0.096 GPa/K. In contrast pure magnetite displays a significantly steeper slope of the PT equilibrium line with dP/dT_V = -0.18 GPa/K. The slope of the PT equilibrium lines is related to the changes of the molar entropy and molar volume at the transition. We compare our spectroscopic data with that obtained from the ambient pressure specific heat measurements and find a good agreement in the optimally doped magnetite. Our data indicates that Al doping leads to a smaller entropy change and larger volume expansion at the transition. Our data displays the trends that are consistent with the mean field model of the transition that assumes charge ordering in magnetite.