Magnetism and charge ordering in high- and low-temperature phases of Nb2O2F3

To sum up, we show in the present paper that magnetic response in Nb$_2$O$_2$F$_3$ at the high-temperatures ($T>$90 K) is related to the orbital selective regime, when part of the electrons form molecular orbitals while other electrons have local magnetic moments. The charge disproportionation, which occurs at $T\sim$90 K is seen in the GGA calculations, but its degree ($δn \sim 0.1$ electron) is far from what one would expect from naive expectations based on the formal ionic valences. The mechanism of the charge ordering is argued to be related with a sizable kinetic energy gain due to formation of two molecular orbitals in short Nb$³⁺$-Nb$³⁺$ dimers caused by a strong nonlinearity of the distance dependence on electron hopping. We think that this mechanism of charge ordering, stabilized not by decrease of interaction energy, but rather by the gain in kinetic energy, may be operative in many other systems, especially consisting of structural dimers.