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AbstractAbstract
[en] The problem of the highly correlated electron gas V2O3 consisting of a filled a/sub 1g/ and a quarterly full e/sub g/ band is treated on the basis of a Hartree-Fock calculation with spin and orbit unrestriction. The values of the effective hopping integrals which include covalency effects (due to the overlap of the 2p/sub π/ orbitals of the oxygens with the 3d wave functions of the vanadium atoms) are assessed on the bases of available band-structure calculations and experimental results measuring covalency contributions. For reasonable values of the Hubbard parameters U/sub m/m approx. = 2 eV, U/sub m/n approx. = 1.6 eV, and J/sub m/n approx. = 0.2 eV [the interatomic Coulomb repulsion of electrons on the same orbit (m, m) on different orbits (m, n) and the exchange integral J/sub m/n] it is found that the observed spin structure of V2O3 together with an antiferromagnetic orbital order gives the lowest Hartree-Fock ground-state energy amongst a large class of solutions which we considered and shows a gap in the density of states of the order of 0.2--0.3 eV. Since this gap appears already in the trigonal phase, we feel confident that the monoclinic distortion in the low-temperature phase is of magnetostrictive origin and not a primary cause of the metal-insulator transition. The peculiar value of 1.2μ/sub B/ per V atom as observed by neutron scattering is interpreted as a strongly covalency-enhanced moment on the V atom. The atomic limit value of 1μ/sub B/ due to one magnetic e/sub g/ electron per V atom is reduced to approx. = 0.75μ/sub B/ in an itinerant picture. The covalency mechanism providing the extra 0.4μ/sub B/ is known as back-bonding effect and leads at the same time to a negative spin density on the oxygen ions which are therefore no longer diamagnetic. Negative 17O NMR shift in the insulating antiferromagnetic phase should be able to verify this conjecture
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Journal Article
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Phys. Rev., B; v. 18(9); p. 4967-5000
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