Gabriel Kotliar Physics Department and Center for Materials Theory Rutgers University

1. Dynamical Mean Field Theory from Model Hamiltonian Studies of the Mott Transition to Electronic Structure Calculations Gabriel Kotliar Physics Department and Center for Materials Theory Rutgers University 11 Conference on Recent Progress in Many Body Physics UMIST July 9-15th 2001

2. What is DMFT, when is it useful and how is it done. What has been accomplished. Ex. model Hamiltonian studies of the finite temperature Mott transition. How to combine DMFT and band structure, formal aspects. Results for some real materials. Outline THE STATE UNIVERSITY OF NEW JERSEY RUTGERS

3. Review: A. Georges, G. Kotliar, W. Krauth and M. Rozenberg Rev. Mod. Phys. 68,13 (1996)] Finite T Mott endpoint: Kotliar Lange and Rozenberg PRL 84, 5180 (2000)) Realistic Calculations:S. Savrasov and GK cond-mat 0106308. Application to Pu, S.Savrasov GK and E. Abrahams Nature 410, 793 (2001). Fe and Ni A. Lichtenstein M. Katsnelson and GK (PRL in press). References, Collaborators THE STATE UNIVERSITY OF NEW JERSEY RUTGERS

4. DMFT Review: A. Georges, G. Kotliar, W. Krauth and M. Rozenberg Rev. Mod. Phys. 68,13 (1996)] Weissfield THE STATE UNIVERSITY OF NEW JERSEY RUTGERS

5. Solving the DMFT equations • Wide variety of computational tools (QMC, NRG,ED….)Analytical Methods THE STATE UNIVERSITY OF NEW JERSEY RUTGERS

6. Exact in large dimensions [Metzner and Vollhardt 89] Trick to sum all LOCAL skeleton graphs, [Muller Hartman 89]. Can be used for susceptibilities, ordered states etc.. Non perturbative construction, works even when skeleton expansion fails. Comments on the DMFT construction THE STATE UNIVERSITY OF NEW JERSEY RUTGERS

7. Evolution of the electronic structure between the atomic limit and the band limit. Basic solid state problem. Solved by band theory when the atoms have a closed shell. Mott’s problem: Open shell situation. The “”in between regime” is ubiquitous central them in strongly correlated systems. Some unorthodox examples Fe, Ni, Pu. Solution of this problem should lead to advances in electronic structure theory (LDA +DMFT) Good method to study the Mott phenomena THE STATE UNIVERSITY OF NEW JERSEY RUTGERS

8. A time-honored example: Mott transition in V2O3 under pressure or chemical substitution on V-site THE STATE UNIVERSITY OF NEW JERSEY RUTGERS

9. Phase Diag: Ni Se2-x SxG. Czek et. al. J. Mag. Mag. Mat. 3, 58 (1976) THE STATE UNIVERSITY OF NEW JERSEY RUTGERS

10. Mott transition in layered organic conductors Ito et al. (1986) Kanoda (1987) Lefebvre et al. (2001) THE STATE UNIVERSITY OF NEW JERSEY RUTGERS

11. Schematic DMFT phase diagram one band Hubbard (half filling, semicircular DOS, role of partial frustration) Rozenberg et.al PRL (1995) THE STATE UNIVERSITY OF NEW JERSEY RUTGERS

12. Insights into the Mott phenomena • The Mott transition is driven by transfer of spectral weight from low to high energy as we approach the localized phase • Control parameters: doping, temperature,pressure… THE STATE UNIVERSITY OF NEW JERSEY RUTGERS

13. Evolution of the Spectral Function with Temperature Anomalous transfer of spectral weight connected to the proximity to an Ising Mott endpoint (Kotliar et.al.PRL 84, 5180 (2000)) THE STATE UNIVERSITY OF NEW JERSEY RUTGERS

14. Expt. Ni Se S Matsuura et. Al. THE STATE UNIVERSITY OF NEW JERSEY RUTGERS

15. Singular part of the Weiss field is proportional to h a Max{ (p-pc) ,(T- Tc)}1/d d=3 in mean field and 5 in 3d h couples to all physical quantities which then exhibit a kink at the Mott endpoint. Resistivity, double occupancy,photoemission intensity, integrated optical spectral weight, etc. Divergence of the the compressibility ,in particle hole asymmetric situations e.g. Furukawa and Imada Ising character of Mott endpoint THE STATE UNIVERSITY OF NEW JERSEY RUTGERS

16. Phase diagram 1 band model THE STATE UNIVERSITY OF NEW JERSEY RUTGERS

17. Divergent compressibility U=2.4 THE STATE UNIVERSITY OF NEW JERSEY RUTGERS

18. QMC two band model, U=3 Compressibility THE STATE UNIVERSITY OF NEW JERSEY RUTGERS

19. Rapid variation has been observed in optical measurements in vanadium oxide (Thomas) and Ni mixtures(Miyasaka and Takgai) Experimental questions: width of the critical region. Ising exponents or classical exponents, validity of mean field theory Building of coherence in other strongly correlated electron systems. condensation of doubly occupied sites and onset of coherence . Mott transition endpoint THE STATE UNIVERSITY OF NEW JERSEY RUTGERS

20. Optical Conductivty Miyasaka Takagi (2000) THE STATE UNIVERSITY OF NEW JERSEY RUTGERS

21. Insights from DMFT: think in term of spectral functions , the density is not changing! Resistivity near the metal insulator endpoint ( Rozenberg et.al 1995) exceeds the Mott limit THE STATE UNIVERSITY OF NEW JERSEY RUTGERS

22. Insights from DMFT • High temperature behavior around Mott endpoint, more universal regime, captured by simple models treated within DMFT • Low temperatures several competing phases . Their relative stability depends on chemistry and crystal structure, LRO etc.. THE STATE UNIVERSITY OF NEW JERSEY RUTGERS

23. Two Roads for calculations of the electronic structure of correlated materials Crystal Structure +atomic positions Model Hamiltonian Correlation functions Total energies etc. THE STATE UNIVERSITY OF NEW JERSEY RUTGERS

24. The light, SP (or SPD) electrons are extended, well described by LDA The heavy, D (or F) electrons are localized,treat by DMFT. LDA already contains an average interaction of the heavy electrons, substract this out by shifting the heavy level (double counting term) The U matrix can be estimated from first principles of viewed as parameters LDA+DMFT THE STATE UNIVERSITY OF NEW JERSEY RUTGERS

25. DFT, consider the exact free energy as a functional of an external potential. Express the free energy as a functional of the density by Legendre transformation. GDFT[r(r)] Introduce local orbitals, caR(r-R)orbitals, and local GF G(R,R)(i w) = The exact free energy can be expressed as a functional of the local Greens function and of the density by introducing sources for r(r) and G and performing a Legendre transformation, G[r(r),G(R,R)(iw)] Spectral Density Functional : effective action construction (Fukuda, Valiev and Fernando , Chitra and GK). THE STATE UNIVERSITY OF NEW JERSEY RUTGERS

26. The exact functional can be built in perturbation theory in the interaction (well defined diagrammatic rules )The functional can also be constructed from the atomic limit, but no explicit expression exists. DFT is useful because good approximations to the exact density functional GDFT[r(r)] exist, e.g. LDA, GGA A useful approximation to the exact functional can be constructed, the DMFT +LDA functional. Spectral Density Functional THE STATE UNIVERSITY OF NEW JERSEY RUTGERS

27. LDA+DMFT functional F Sum of local 2PI graphs with local U matrix and local G THE STATE UNIVERSITY OF NEW JERSEY RUTGERS

28. LDA+DMFTConnection with atomic limit Weiss field THE STATE UNIVERSITY OF NEW JERSEY RUTGERS

29. Functional approach THE STATE UNIVERSITY OF NEW JERSEY RUTGERS

30. Static limit of the functional reduces to LDA+U Removes inconsistencies of this approach, Only in the orbitally ordered Hartree Fock limit, the Greens function of the heavy electrons is fully coherent Gives the local spectra and the total energy simultaneously, treating QP and H bands on the same footing. Comments on LDA+DMFT THE STATE UNIVERSITY OF NEW JERSEY RUTGERS

31. V. Anisimov, A. Poteryaev, M. Korotin, A. Anokhin and G. Kotliar, J. Phys. Cond. Mat. 35, 7359-7367 (1997). A Lichtenstein and M. Katsenelson Phys. Rev. B 57, 6884 (1988). S. Savrasov and GK full self consistent implementation cond-mat 0106308. Application to Pu, S.Savrasov GK and E. Abrahams Nature 410, 793 (2001) LDA+DMFT References THE STATE UNIVERSITY OF NEW JERSEY RUTGERS

32. LDA+DMFT Self-Consistency loop E U DMFT THE STATE UNIVERSITY OF NEW JERSEY RUTGERS

33. Archetypical itinerant ferromagnets LSDA predicts correct low T moment Band picture holds at low T Case study Fe and Ni THE STATE UNIVERSITY OF NEW JERSEY RUTGERS

34. Iron and Nickel: crossover to a real space picture at high T THE STATE UNIVERSITY OF NEW JERSEY RUTGERS

35. Photoemission Spectra and Spin Autocorrelation: Fe (U=2, J=.9ev,T/Tc=.8) (Lichtenstein, Katsenelson,GK prl 2001) THE STATE UNIVERSITY OF NEW JERSEY RUTGERS

36. Photoemission and T/Tc=.8 Spin Autocorrelation: Ni (U=3, J=.9 ev) THE STATE UNIVERSITY OF NEW JERSEY RUTGERS

37. Iron and Nickel:magnetic properties (Lichtenstein, Katsenelson,GK cond-mat 0102297) THE STATE UNIVERSITY OF NEW JERSEY RUTGERS

38. m( T=.9 Tc)/ mB ordered moment Fe 1.5 ( theory) 1.55 (expt) Ni .3 (theory) .35 (expt) meff / mB high T moment Fe 3.1 (theory) 3.12 (expt) Ni 1.5 (theory) 1.62 (expt) Curie Temperature Tc Fe 1900 ( theory) 1043(expt) Ni 700 (theory) 631 (expt) Ni and Fe: theory vs exp THE STATE UNIVERSITY OF NEW JERSEY RUTGERS

39. Satellite in minority band at 6 ev, 30 % reduction of bandwidth, exchange splitting reduction .3 ev Spin wave stiffness controls the effects of spatial flucuations, it is about twice as large in Ni and in Fe Mean field calculations using measured exchange constants(Kudrnovski Drachl PRB 2001) right Tc for Ni but overestimates Fe , RPA corrections reduce Tc of Ni by 10% and Tc of Fe by 50%. Fe and Ni THE STATE UNIVERSITY OF NEW JERSEY RUTGERS

40. Case study in f electrons, Mott transition in the actinide series THE STATE UNIVERSITY OF NEW JERSEY RUTGERS

41. Small amounts of Ga stabilize the d phase THE STATE UNIVERSITY OF NEW JERSEY RUTGERS

42. f electrons in Th Pr U Np are itinerant . From Am on they are localized. Pu is at the boundary. Pu has a simple cubic fcc structure,the d phase which is easily stabilized over a wide region in the T,p phase diagram. The d phase is non magnetic. Many LDA , GGA studies ( Soderlind et. Al 1990, Kollar et.al 1997, Boettger et.al 1998, Wills et.al. 1999) give an equilibrium volume of the d phaseIs 35% lower than experiment This is one of the largest discrepancy ever known in DFT based calculations. Delocalization-Localization across the actinide series THE STATE UNIVERSITY OF NEW JERSEY RUTGERS

43. DFT in the LDA or GGA is a well established tool for the calculation of ground state properties. Many studies (Freeman, Koelling 1972)APW methods ASA and FP-LMTO Soderlind et. Al 1990, Kollar et.al 1997, Boettger et.al 1998, Wills et.al. 1999) give an equilibrium volume of the d phaseIs 35% lower than experiment This is the largest discrepancy ever known in DFT based calculations. Problems with LDA THE STATE UNIVERSITY OF NEW JERSEY RUTGERS

44. LSDA predicts magnetic long range order which is not observed experimentally (Solovyev et.al.) If one treats the f electrons as part of the core LDA overestimates the volume by 30% LDA predicts correctly the volume of the a phase of Pu, when full potential LMTO (Soderlind and Wills). This is usually taken as an indication that a Pu is a weakly correlated system Problems with LDA THE STATE UNIVERSITY OF NEW JERSEY RUTGERS

45. Pu: DMFT total energy vs Volume THE STATE UNIVERSITY OF NEW JERSEY RUTGERS

46. Lda vs Exp Spectra THE STATE UNIVERSITY OF NEW JERSEY RUTGERS

47. Pu Spectra DMFT(Savrasov) EXP (Arko et. Al) THE STATE UNIVERSITY OF NEW JERSEY RUTGERS

48. The character of the localization delocalization in simple( Hubbard) models within DMFT is now fully understood, nice qualitative insights. This has lead to extensions to more realistic models, and a beginning of a first principles approach interpolating between atoms and band, encouraging results for simple elements Conclusion THE STATE UNIVERSITY OF NEW JERSEY RUTGERS

49. Systematic improvements, short range correlations. Take a cluster of sites, include the effect of the rest in a G0 (renormalization of the quadratic part of the effective action). What to take for G0: DCA (M. Jarrell et.al) , CDMFT ( Savrasov GK Palsson and Biroli ) include the effects of the electrons to renormalize the quartic part of the action (spin spin , charge charge correlations) E. DMFT (Kajueter and GK, Si et.al) Outlook THE STATE UNIVERSITY OF NEW JERSEY RUTGERS

50. Extensions of DMFT implemented on model systems, (e.g. Motome and GK ) carry over to more realistic framework. Better determination of Tcs. First principles approach: determination of the Hubbard parameters, and the double counting corrections long range coulomb interactions E-DMFT Improvement in the treatement of multiplet effects in the impurity solvers, phonon entropies, ……… Outlook THE STATE UNIVERSITY OF NEW JERSEY RUTGERS