Colossal Negative Magnetoresistance Research Articles

Electronic structure of CMR manganites (invited)

A “colossal” negative magnetoresistance (CMR) occurs in manganites at a first-order ferromagnetic transition. The Mn4+ and high-spin Mn3+ ions each contain localized t3 configurations; the t3–pπ–t3 superexchange interactions are antiferromagnetic. The orbital degeneracy of localized Mn3+:t3e1, Eg5 configurations is lifted by cooperative static or dynamic Jahn–Teller deformations. Strong e-electron coupling to oxygen displacements, static or dynamic, introduces ferromagnetic e1–pσ–e0 interactions either via superexchange or, for fast Mn3+ to Mn4+ electron transfer relative to the spin-relaxation time (τh<τs), via a stronger double exchange. At the first-order ferromagnetic transition, a change from τh≈ℏ/Wσ>ωR−1 to τh<ωR−1 occurs within mobile molecular units, where Wσ is the bandwidth for states of e-orbital parentage and ωR−1 is the period of the optical-mode lattice vibration that traps a mobile hole as a small-polaron Mn4+ ion. TC increases with the fraction of double-exchange couplings, and this fraction increases with Wσ and ωR at the transition from polaronic to itinerant-electron behavior below TC. The bandwidth Wσ∼εσλσ2 cos φ〈cos(θij/2)〉 depends on the covalent mixing parameter λσ, which increases with pressure, as well as on the Mn–O–Mn bond angle (180°−φ), which increases with the tolerance factor t that measures the equilibrium bond-length mismatch, and on the angle θij between neighboring spins so that Wσ increases with the spontaneous magnetization on cooling below TC. In the compositions Ln0.7A0.3MnO3 with A=Ca or Sr, TC increases with t over the range 0.96⩽t⩽0.98 where the transition at TC is first order. The CMR is greatest near t≈0.96; it reflects a trapping out of mobile holes with decreasing temperature in the paramagnetic phase and their progressive release with decreasing temperature in the ferromagnetic phase where spin entropy is exchanged for configurational entropy.