How chemistry controls electron localization in 3d1 perovskites: A Wannier-function study

Abstract

In the series of 3d1 t2g perovskites, SrVO3--CaVO3--LaTiO3--YTiO3 the transition-metal d electron becomes increasingly localized and undergoes a Mott transition between CaVO3 and LaTiO3. By defining a low-energy Hubbard Hamiltonian in the basis of Wannier functions for the t2g LDA band and solving it in the single-site DMFT approximation, it was recently shown[1] that simultaneously with the Mott transition there occurs a strong suppression of orbital fluctuations due to splitting of the t2g levels. The present paper reviews and expands this work, in particular in the direction of exposing the underlying chemical mechanisms by means of ab initio LDA Wannier functions generated with the NMTO method. The Wannier functions for the t2g band exhibit covalency between the transition-metal t2g, the large cation-d, and the oxygen-p states; this covalency, which increases along the series, turns out to be responsible not only for the splittings of the t2g levels, but also for non-cubic perturbations of the hopping integrals, both of which are decisive for the Mott transition. We find good agreement with the optical and photoemission spectra, with the crystal-field splittings and orbital polarizations recently measured for the titanates, and with the metallization volume for LaTiO3. The metallization volume for YTiO3 is predicted. Using super-exchange theory, we reproduce the observed magnetic orders in LaTiO3 and YTiO3, but the results are sensitive to detail, in particular for YTiO3 which, without the Jahn-Teller distortion, would be AFM C- or A-type, rather than FM. Finally, we show that it possible to unfold the orthorhombic t2g LDA bandstructure to a pseudocubic zone. In this zone, the lowest band is separated from the two others by a direct gap and has a width, W_I, which is significantly smaller than that, W, of the entire t2g band. The progressive GdFeO3-type distortion favours electron localization by decreasing W, by increasing the splitting of the t2g levels and by decreasing W_I. Our conclusions concerning the roles of GdFeO3-type and JT distortions agree with those of Mochizuki and Imada [2].

Published version, final. For high resolution figures see http://www.fkf.mpg.de/andersen/docs/pub/abstract2004+/pavarini_02.pdf

References in corpus (39)

• Ab initio calculations of quasiparticle band structure in correlated systems: LDA++ approach
• First-principles Calculations of the Electronic Structure and Spectra of Strongly Correlated Systems: Dynamical Mean-field Theory
• Muffin Tin Orbitals of Arbitrary Order
• Mott transition and suppression of orbital fluctuations in orthorhombic 3$d^1$ perovskites
• Full orbital calculation scheme for materials with strongly correlated electrons
• The Hubbard Model at Infinite Dimensions: Thermodynamic and Transport Properties
• Orbital liquid in three dimensional Mott insulator: $LaTi{O}_3$
• Mutual Experimental and Theoretical Validation of Bulk Photoemission Spectra of Sr1-xCaxVO3
• Crystal and magnetic structure of LaTiO3 : evidence for non-degenerate $t_{2g}$-orbitals
• Spin Dynamics and Orbital State in LaTiO_3
• Band-width control in a perovskite-type 3d^1 correlated metal Ca_{1-x}Sr_xVO_3. I. Evolution of the electronic properties and effective mass
• Interplay between orbital ordering and lattice distortions in LaMnO3, YVO3, and YTiO3
• Mott Transition in Degenerate Hubbard Models: Application to Doped Fullerenes
• Interplay of Mott Transition and Ferromagnetism in the Orbitally Degenerate Hubbard Model
• Orbital Physics in the Perovskite Ti Oxides
• The alpha to gamma transition in Ce: a theoretical view from optical spectroscopy
• Surface vs. bulk Coulomb correlations in photoemission spectra of perovskites
• Electronic structure of Ca${}_{1-x}$Sr${}_x$VO${}_3$: a tale of two energy-scales
• Magnetic Order and Dynamics in an Orbitally Degenerate Ferromagnetic Insulator
• Orbital-Spin Structure and Coupling to Lattice in RTiO${}_3$ with R=La,Pr,Nd and Sm
• Quantum behavior of Orbitals in Ferromagnetic Titanates: Novel Orderings and Excitations
• Order from disorder: Quantum spin gap in magnon spectra of LaTiO_3
• Band-width control in a perovskite-type 3d^1 correlated metal Ca_1-xSr_xVO_3. II. Optical spectroscopy investigation
• Evidence for Jahn-Teller distortions at the antiferromagnetic transition in LaTiO${}_3$
• Mott transition at large orbital degeneracy: dynamical mean-field theory
• Determination of the orbital moment and crystal field splitting in LaTiO${}_3$
• Calculation of photoemission spectra of the doped Mott insulator La_{1-x}Sr_xTiO_3 using LDA+DMFT(QMC)
• Presence of 3d Quadrupole Moment in LaTiO3 Studied by 47,49Ti NMR
• Optical study of orbital excitations in transition-metal oxides
• Theory of orbital state and spin interactions in ferromagnetic titanates
• Mott-Hubbard insulators for systems with orbital degeneracy
• Estimates of electronic interaction parameters for La$M$O${}_3$ compounds ($M$=Ti-Ni) from ab-initio approaches
• Fermi Surface of 3d^1 Perovskite CaVO3 Near the Mott Transition
• Magnetic and Orbital States and Their Phase Transition of the Perovskite-Type Ti Oxides: Strong Coupling Approach
• Sensitivity of the Mott Transition to Non-cubic Splitting of the Orbital Degeneracy: Application to NH3 K3C60
• Origin of G-type Antiferromagnetism and Orbital-Spin Structures in ${\mathrm{LaTiO}}_3$
• G-type antiferromagnetism and orbital ordering due to the crystal field from the rare-earth ions induced by the GdFeO_3-type distortion in RTiO_3 with R=La, Pr, Nd and Sm
• Filling dependence of the Mott transition in the degenerate Hubbard model
• Phonons and Magnetic Excitations in Mott-Insulator LaTiO${}_3$

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