The main purpose of this paper is to address the issue of crystallographic transitions related to magnetic/electronic phenomena in strongly correlated transition metal (TM) compounds in a regime of very high static density. The experimental tools used were: synchrotron X-ray diffraction, Mossbauer spectroscopy and electrical resistivity. We focus on the following cases: (i) high-spin to low-spin transition which could lead to a significant reduction of the TM ionic radii and therefore even a structural transition; (ii) sluggish structural phase transitions in antiferromagnetic insulators FeI2 and FeCl2 attributed to the onset of a Mott transition; (iii) volume dependence of the orbital term of the moment in FeI2 and FeCl2 resulting in its eventual collapse, which is accompanied by a significant lattice distortion; and (iv) pressure-induced metal–metal intervalence charge transfer in the antiferromagnetic Cu1+Fe3+O2 as a result of the increase in overlap of atomic orbitals.

Crystallographic transitions related to high-pressure magnetic and electronic phenomena in Fe-based compounds

Many of the Transition Metal (TM) compounds, because of exchange and correlation interactions within the narrow and poorly overlapping d-bands, become antiferromagnetic insulators, the Mott Insulators (MI). The properties of the MI and their gradual transition into the non-correlated metallic state (the Mott Transition) are of crucial important for the elucidation of HTS materials features in particular and to magnetism in general. The transition of the MI into a metal can be achieved either by doping or by high pressure. To yield the definitive data on the Mott transition high pressure work on well characterized materials should be sought. The present studies provide for the first time extensive information on the Mott-Hubbard gap closure induced by high pressure. High pressure studies using Diamond Anvil Cells were conducted in several (TM)I{sub 2} compounds. They all have layered structures and other antiferromagnetically at ambient pressure. {sup 129}I Moessbauer Spectroscopy (MS) was used to study the properties of the (TM){sup 2+} sublattice magnetization as a function of pressure and temperature, and X-ray diffraction was used to look for possible crystallographic transitions and to obtain the equation of state. Results show that the high pressure transition at P{sub c} from a magnetic to amore » non-magnetic state is not accompanied by crystallographic changes. Previous studies{sup 1} with NiI{sub 2} have confirmed the presence of a metallic state at P > P{sub c}. Inherent to the pressure behavior of the magnetic state is the gradual increase of T{sub N} in all cases and a slight increase in the TM{sup 2+} moments with pressure increase. The collapse of the magnetic state is abrupt for some cases (NiI{sub 2}) and gradual for others (CoI{sub 2}), indicative of different band-overlap mechanisms. 2 refs., 5 figs.« less

R.D. Taylor

Papers

The pressure-induced Mott Transition in transition-metal iodides