Mott insulators

Introduction Cluster-model description Chemical trend Band description Self-energy correction

Mott insulators
Introduction

Lattice models for transition-metal compounds

Anderson-lattice model or p-d model

Hubbard model

Transition metal ion (with d orbitals) Non-metal anion (with p orbitals)

Lattice models for transition-metal compounds

(degenerate) Hubbard model Anderson-lattice or p-d model

t-J model
no double occopancy

Band gap excitation and localized excitation

Photoemission Inverse-photoemission

EN-1 - EN

EN+1 - EN

E*N - EN

Band gap excitation energy: Eg = EN+1 + EN-1 - 2EN

Relevant to charge transport

Localized excitation (d-d excitation, exciton, ...)

Band gap excitations - relevant to charge transport

Excitation energy: Eg = EN+1 + EN-1 - 2EN

EN-1 - EN

EN+1 - EN

Charge transfer energy: on-site Coulomb energy: L: ligand (p) hole

Photoemission spectroscopy

Lattice models for transition-metal compounds

Anderson-lattice model or p-d model

Hubbard model

Transition metal ion (with d orbitals) Non-metal anion (with p orbitals)

Mott-Hubbard-type insulators vs charge-transfer-type insulators

Inversephotoemission Photoemission spectra spectra

chemical potential

U<

U>

Mott-Hubbard gap ~U-W

Charge-transfer gap ~-W

Charge-transfer energy: On-site Coulomb energy: L: ligand (p) hole Band width: W

Resonant photoemission

discrete level

continuous level

Resonant photoemission
Fano line shape
discrete level

continuous level

q = [g.st.-discr.]/[discr.-contin.]

Effectively enhances the 3d photoionization cross-section

Photoemission spectra of NiO

XPS spectrum
main peaks

LDA band calc.

satellite

Ligand-field theory

T. Oguchi et al., PRB 83

Resonant photoemission spectra of NiO

main peaks satellite

Ni 3p core abs.
S.-J. Oh et al., PRB 82

Mott insulators
Cluster-model description

Cluster model for transition-metal oxides

BO6 cluster model

AB2O4 spinel
perovskite

treated as adjustable parameters

atomic d and p orbitals, molecular orbitals on the cluster

Atomic d orbitals

Crystal-field splitting

atomic d and p orbitals, molecular orbitals on the cluster

Molecular orbitals composed of atomic p orbitals

Atomic d orbitals

Many-electron energy level scheme for BO6 cluster

Optical absorption
n o i iss m e to o Ph

ph In ot ve oe rs m e iss ion

Ground state

: Band gap = EN+1 + EN-1 - 2EN

Multiplet effects

Many-electron energy levels vs single-particle energy level

ph In ot ve oe rs m e iss ion

ion s is m e to o Ph

EN+1 Eg
N-1

Inversephotoemission spectra Photoemission spectra E

Ground state

: chemical potential Eg : band gap

Mott-Hubbard-type insulators vs charge-transfer-type insulators

Inversephotoemission Photoemission spectra spectra

chemical potential

U<

U>

Mott-Hubbard gap ~U-W

Charge-transfer gap ~-W

Charge-transfer energy: On-site Coulomb energy: L: ligand (p) hole Band width: W

Mott-Hubbard type versus charge-transfer type many-electron energy level scheme

Charge-transfer type insulator U>

Mott-Hubbard type insulator U<

N

Configuration-interaction cluster-model analysis of d-electron photoemission spectra

Ground state

Final states

ion s is m oe t o Ph

satellite

main

Ground state

Intensities

Configuration-interaction cluster-model analysis of d-electron photoemission satellites

dn-1 final state dnL final state

U- charge-transfer type U>

-U

Mott-Hubbard type U<

Configuration-interaction cluster-model analysis vs LDA band theory for NiO

LDA band calc.

t2g

satellite

O 2p

t2g

eg eg

O 2p

T. Oguchi et al., PRB 83 G.A. Sawatzky and J.W. Allen, PRL 84 A. Fujimori and F. Minami, PRB 83

Configuration-interaction cluster-model analysis of core-level satellite

satellite
with core hole

Ground state

main

Final states

photoemission

without core hole

Intensities
ground state
I.H. Inoue et al., PRB 92 G. van der Laan et al., PRB 81

Configuration-interaction cluster-model analysis of core-level satellite

Mn 2p3/2 Mn 2p1/2 Mn 2p3/2

2+

satellite = 9 eV satellite
3+

= 6.5 eV

= 4.5 eV

= 4.5 eV

4+

= 3.2 eV

= 2.0 eV

J. Park et al., PRB 88 G. van der Laan et al., PRB 86

A.E. Bocquet et al., PRB 92

Mott insulators
Chemical trend

Systematic variation of band gaps in transition-metal oxides

Ueff, eff Ueff, eff: Eestimated from ionic model

T. Arima et al., PRB 93

Systematic materials dependence of charge-transfer energy

v
A.E. Bocquet et al., PRB 92

~ 23 eV, 22.5 eV for selenides, tellurides

Systematic materials dependence of on-site Coulomb energy U

v
A.E. Bocquet et al., PRB 92

Systematic materials dependence of p-d transfer integral

Tpd 3(pd), 2(pd)

A.E. Bocquet et al., PRB 92

Zaanen-Sawatzky-Allen diagram

=W Eg ~ W charge-transfer regime
3+

2+

charge-transfer 2+ regime
3+

2+

2+ 3+

p-metal

Mott-Hubbard regime Eg ~ U - W d-metal U=W

negative- regime

4+

4+ 3+ 3+

3+

5+

3+ 3+ 2+

4+ 4+

Mott-Hubbard regime
3+

3+

J. Zaanen, G.A. Sawatzky, J.W. Allen, PRL 85

A.E. Bocquet et al., PRB 96

Systematic variation of band gaps in transition-metal oxides

Ueff, eff Ueff, eff: Eestimated from ionic model

T. Arima et al., PRB 93

Multiplet corrections for Mott-Hubbard gap and charge-transfer gap

Correction for charge-transfer energy: eff Multiplet corrections for and U

CT gap is reduced

Correction for on-site Coulomb energy: U Ueff

d4

d5
M-H and CT gap is enhanced

T. Saitoh et al., PRB 95

Multiplet corrections for Mott-Hubbard gap and charge-transfer gap

Optical gaps Calculated band gaps

d3 d3

T. Arima et al., PRB 93

T. Saitoh et al., PRB 95

Zaanen-Sawatzky-Allen diagram

=W Eg ~ W charge-transfer regime
3+

2+

charge-transfer 2+ regime
3+

2+

2+ 3+

p-metal

Mott-Hubbard regime Eg ~ U - W d-metal U=W

negative- regime

4+

4+ 3+ 3+

3+

5+

3+ 3+ 2+

4+ 4+

Mott-Hubbard regime
3+

3+

J. Zaanen, G.A. Sawatzky, J.W. Allen, PRL 85

A.E. Bocquet et al., PRB 96

Negative- (covalent) insulator

p-p gap
determined by p-d hybridization strength

Modified Zaanen-Sawatzky-Allen diagram

Ex.) NaCu3+(d8)O2
ground state:
T. Mizokawa et al., PRL 94

cf) Covalent insulator: S. Nimkar et al., PRB 93

Mott insulators
Band description

Hartree-Fock and LDA+U band calculations - failure of LDA in NiO

Hartree-Fock band calc.
t2g eg t2g O 2p Eg ~ 4 eV eg

Local-density-approximation (LDA) band calc.

eg O 2p t2g eg Eg ~ 0.2 eV t2g

T. Mizokawa and A.F., PRB 96 eg t2g

O 2p

LDA+U band calc.

O 2p eg Eg ~ 4 eV

t2g

CoO, FeO: metallic !

V.I. Anisimov et al., PRB 91 T. Oguchi et al., PRB 83

Failure of LDA in Mott insulators

Hartree-Fock potential energy (also for LDA+U)

: occupation number of orbital i

orbital-dependent self-consistent potential positive feedback toward orbital polarization

Local-density approximation (LDA) potential energy

: total occupation number (local density)

spherically averaged potential, unphysical self-interaction orbital polarization suppressed

Orbital magnetic moments in Fe3O4

Fe3+ (d5 : t2g3 eg2 ) <LZ> = 0 Fe2+ (d6 : t2g3 eg2 t2g ) <LZ> ~ -1 Fe 3p MCD

Fe 2p MCD

D.J. Huang et al., unpublished

T. Koide et al., PRB 91

Magnetic circular dichroism (MCD) in core-level absorption

Orbital ordering in perovskite-type ABO3 compounds

orbital 1 orbital 2

ex) LaMn3+O3 d4: t2g3 eg

Jahn-Teller distortion

Charge and orbital ordering in R0.5A0.5MnO3

3+

2+

Mn3.5+ (d3.5 : t2g3 eg0.5 )

Jahn-Teller distortion

Breathing-type distortion
TMizokawa and A.F., PRB 97

Mott insulators
Self-energy correction

Hartree-Fock band calculation + self-energy correction ()

expt

expt

Greens function:

Spectral function:

calculated with 2nd order perturbation T. Mizokawa and A. Fujimori, PRB 96 Hartree-Fock eigenvalue

CI cluster model, Hartree-Fock band theory and photoemission spectra

Experimental input

band gaps magnetic moment hybridization strength