Mott band filling from

In a category of materials known as Mott insulators, like MnO, CoO or NiO, with band gaps of 4.8, 3.4, and 1.8 eV, respectively ([2], and references therein), the upper energy band made from 3d states is partially occupied resulting in metallic conduction. The insulating behaviour of these compounds is attributed to a strong intra-atomic Coulomb interaction, which results in the formation of a gap between the filled and empty 3d states [35]. 

When the cores are approached, the sub-bands split, acquiring a bandwidth, and decreasing the gap between them (Fig. 14 a). At a definite inter-core distance, the subbands cross and merge into the non-polarized narrow band. At this critical distance a, the narrow band has a metallic behaviour. At the system transits from insulator to metallic (Mott-Hubbard transition). Since some electrons may acquire the energies of the higher sub-band, in the solid there will be excessively filled cores containing two antiparallel spins and excessively depleted cores without any spins (polar states). 

As a remark, it should be noted that a single electron ground state from a filled band (which would be the case of americium within a band description because the 5 f band is spin-orbit splitted into a filled 5/2 sub-band and an empty 7/2 sub-band) is equivalent to a localized state and thus a spin-polarized band description leads to the same conclusion as a simple Mott description. 

Hubbard (13) elucidated a mathematical description of the change from one situation to another for the simplest case of a half-filled s band of a solid. His result is shown in Figure 11. For ratios of W/U greater than the critical value of 2/ /3 then a Fermi surface should be found and the system can be a metal. This critical point is associated with the Mott transition from metal to insulator. At smaller values than this parameter, then, a correlation, or Hubbard, gap exists and the system is an antiferromagnetic insulator. Both the undoped 2-1 -4 compound and the nickel analog of the one dimensional platinum chain are systems of this type. At the far left-hand side of Figure 11 we show pictorially the orbital occupancy of the upper and lower Hubbard bands. 

The possibility to vary the parameters governing the physical properties of (TM>2X compounds (nature of cation or anion, pressure and application of a magnetic field) allows an exploration moving continuously from half-filled band 1-D Mott insulators in sulfur based compounds to conducting systems in selenium or strongly pressurized sulfur based compounds (Fig. 4). 

It should be added that the expansion of the tr-conjugating system and/or the introduction of Se atoms with greater polarizability (as shown in BETS or TTPs) reduce the effective on-site Coulomb energy U. For example, the V values for the TTP-type donors estimated from electrochemical and optical measurements are considerably small. (TTM-TTP)l3 is a 1 1 salt with a highly one-dimensional half-filled band. Although 1 1 salts were believed to be non-metal due to the Coulomb interaction (Mott-insulator), this salt shows metallic behavior down to about 160 K. This system is regarded as a small-f/ case of a one-dimensional conductor with an inherently half-filled band [27]. 

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