1. Electronic Structure of Cubic Copper Monoxides*
Paul M. Grant
Stanford (Visiting Scholar)
Wolter Siemons
Stanford (U. Twente)
Gertjans Koster
Stanford (U. Twente)
Robert H. Hammond
Stanford
Theodore H. Geballe
Y , 12:51 PM, Friday, 14 March
Session Y23: Electronic Structure of Complex Oxides
2008 APS March Meeting, New Orleans, LA
* Research Funded by US AFOSR & EPRI

2. Tenorite (Monoclinic CuO)
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3. Comparison of Tenorite (111) to CuO – MgO Proxy (100)
This figure shows the possible growth interface for the lattice of monoclinic CuO matched to an MgO substrate. The Cu and O “yellow lines” on the “unfolded” interface suggest how the growth of cubic CuO might indeed begin on the (100) surface of MgO. The terms (111) and (100) are the “Miller indices” describing the intersection of symmetry planes with the crytallographic axes of tenorite and MgO respectively.
(111) Tenorite
(100) MgO

4. Néel Temperature vs. TMO Atomic Number

5. “CuO – MgO Proxy” Converged Energies
Observe the lowest energy is possessed by monoclinic CuO, tenorite.

6. Proto-TMO AF Rock Salt
[111]

7. Proto-TMO AF Rock Salt
[-1-1-1]

11. Extended Hubbard Hamiltonian
Qualitative Description of the Physical Properties of Antiferromagnetic Insulators
On-site “Hubbard” double occupation coulomb repulsion
Off-site repulsion
One-electron “band” term
Hubbard Hamiltonian
CuO and NiO, as well as undoped high temperature superconductors and a number of other transition metal oxides, are members of a class of compounds known as “Mott insulators,” named after Sir Neville Mott who first described their properties. They “should be” metals, inasmuch as their primitive atomic lattice cells contain an odd number of electrons, one of the defining properties of metals such as sodium, copper, aluminum, gold, along with many other examples. John Hubbard constructed an empirical model, shown above, to describe why this rule of thumb was violated in Mott insulators. The term on the left can be thought of as the “free electron” energy, that which arises in metals and within the valence and conduction bands of semiconductors where the electrons are delocalized from their atomic orbitals and can move more or less freely. It is essentially this energy which density functional theory describes in crystals and which contains its “binding” or “ground state” energy.
In Mott insulators, the “odd electrons” derive from atomic d-orbitals whose wave functions are intrinsically more localized than the s and p electrons typically conducting current in most other metals.
To explain the effect of the local character of otherwise free-to-move d-electrons, Hubbard introduced the second term in the above equation. Using nickel oxide as an example, this term contains the repulsive force between two electrons of opposite spin (as allowed by the Pauli Principle) occupying the same d-orbital on a given Ni ion. This repulsive force is also present for s and p electrons, is much weaker than the delocalization energy of the first term. For d-electrons, the repulsive energy, U, is of the order of t, and thus an energy gap, the Hubbard gap, is created that supersedes the formation of a metallic state. It has qualitative characteristics similar to the “band gap” of a semiconductor, but arises from very different physical origins. For NiO, both t and U are of the order of 2 eV (a crystal of NiO appears green and barely transparent to the human eye).

12. Mott-Hubbard Insulator
After Imada, et al, RMP 70, 1039 (1998)

13. Charge Transfer Insulator
After Imada, et al, RMP 70, 1039 (1998)

14. Cu2+ 3d Multiplet Splitting (Cubic)
t2g eg
Cu2+ Ion
Cubic

15. DFT & (LDA + U)
Implemented in LMTO by Anisimov, et al, JPCM 2, 3973 (1990)
Applied to NiO, MnO, FeO, CoO and La2CuO4
Plane-Wave Pseudopotential Implementation by Cococcioni and de Gironcoli, PRB 71, (2005)
Applied to FeO and NiO
Download open-source package from

16. On Seeking Insight from Numbers
“The computer is a tool for clear thinking.” Freeman Dyson
“Garbage In, Garbage Out” Anon., IBM ca. 1954
Q: “Pray, Mr. Babbage, if you put into the machine wrong figures, will the right answers come out?”
A: “I am not able rightly to comprehend the kind of confusion of ideas that could provoke such a question.”

17. c-CuO (U = 0) eV
c-CuO
U = 0
PP = PMG Y G Z K U K

18. c-CuO (U = 5 eV) eV
c-CuO
U = 5
PP = PMG
SNE = 1,1,1,1 Y G Z K U K

19. c-CuO Density-of-StatesEF
N(E) (eV-1)
E (eV)

20. DOS Projected on PP Orbitals
U = 0 Projections
DOS Projected on PP Orbitals
N(E) (eV-1)
E (eV)

21. Tetragonal CuO c/a = 1.36 Measurements 2-4 ML epi on STO No Fermi Edge
No Exchange Bias on ferro-SRO (Tc ~ K)
5.320
3.905
3.905

23. Cu2+ 3d Multiplet Splitting (Tetra)
Cu2+ Ion
Cubic
Tetragonal
t2g eg

24. t-CuO (U = 0) eV
t-CuO
U = 0
PP = PMG Y G Z K U K

25. t-CuO (U = 5 eV) eV
t-CuO
U = 5
PP = PMG
SNE = 1,1,1,1 Y G Z K U K

26. t-CuO (U = 7.5 eV) eV
t-CuO
U = 7.5
PP = PMG
SNE = 1,1,1,1 Y G Z K U K

27. Spin-DOS Projected on Cu 3d-Orbitals As Function of Hubbard U
U = 0 d-pdos Cu1
N(E) (eV-1)
E (eV)

28. Spin Composition of Cu 3d pDOS as fn(Hubbard)
U = 0 d-spin-pdos Cu1
U = 5 d-spin-pdos Cu1

29. t-CuO Density-of-States
He I UPS Spectrum
W. Siemons (PhD Thesis, Stanford) EF
N(E) (eV-1)
E (eV)

30. Conclusions & Homework
If you could make it, cubic rock salt copper monoxide would be a metal!
Distortions (J-T?) are necessary to “spread” the Cu 3d10 multiplet allowing Hubbard to separate spins creating the 3d9 AF ground state and thus HTS.
To-do
Check the LDA+U PW-PP package on tenorite
Compute “tetragonal supercell” to get to CuO plane properties.
Then “dope” and perform e-p calculation to “see what happens.”

41. EF

42. Insight from Numbers
“The universe is of two indivisible elements…tiny particles and the void.” Democritos, after Leucippus, 4th Century BC
“The computer is a tool for clear thinking.” Freeman Dyson, 20th Century AD
“Garbage In, Garbage Out” Anon., IBM ca. 1954
Q: “Pray, Mr. Babbage, if you put into the machine wrong figures, will the right answers come out?”
A: “I am not able rightly to comprehend the kind of confusion of ideas that could provoke such a question.”

43. t-CuO Density-of-States
He I UPS Spectrum
W. Siemons (PhD Thesis, Stanford) EF
N(E) (eV-1)
E (eV)

44. t-CuO Density-of-States
He I UPS Spectrum
W. Siemons (PhD Thesis, Stanford) EF
N(E) (eV-1)
E (eV)

46. 3d Multiplet
3d9
t2g eg
Cu2+ Ion
Cubic

48. Extended Hubbard Hamiltonian
Qualitative Description of the Physical Properties of Antiferromagnetic Insulators
This term represents the repulsive force between two electrons on the same ionic site. It tends to separate spins of opposite sign on nearest neighbor ions, thus producing an antiferromagnetic state. “U” is the repelling energy, and “n” is the occupation number (either ) or 1) for each spin direction on ion “i”. It is independent of bond length, and thus is a simple constant for all crystallographic configurations involving the same elements.
This term is the repulsive energy between two electrons on separate ionic sites and thus dependent on bond length, but not included in the DFT formalism, and thus may play a role in setting the absolute value of the Ground State Energy for a given crystallographic configuration.
This is the energy calculated in DFT which describes the physical properties of uncorrelated systems such as semiconductors and metals. This energy depends strongly on the interatomic bond length. “t” is the energy to transfer an electron from atom to atom, and the “c’s” create and annihilate electrons as they move from site to site.
Hubbard Hamiltonian
CuO and NiO, as well as undoped high temperature superconductors and a number of other transition metal oxides, are members of a class of compounds known as “Mott insulators,” named after Sir Neville Mott who first described their properties. They “should be” metals, inasmuch as their primitive atomic lattice cells contain an odd number of electrons, one of the defining properties of metals such as sodium, copper, aluminum, gold, along with many other examples. John Hubbard constructed an empirical model, shown above, to describe why this rule of thumb was violated in Mott insulators. The term on the left can be thought of as the “free electron” energy, that which arises in metals and within the valence and conduction bands of semiconductors where the electrons are delocalized from their atomic orbitals and can move more or less freely. It is essentially this energy which density functional theory describes in crystals and which contains its “binding” or “ground state” energy.
In Mott insulators, the “odd electrons” derive from atomic d-orbitals whose wave functions are intrinsically more localized than the s and p electrons typically conducting current in most other metals.
To explain the effect of the local character of otherwise free-to-move d-electrons, Hubbard introduced the second term in the above equation. Using nickel oxide as an example, this term contains the repulsive force between two electrons of opposite spin (as allowed by the Pauli Principle) occupying the same d-orbital on a given Ni ion. This repulsive force is also present for s and p electrons, is much weaker than the delocalization energy of the first term. For d-electrons, the repulsive energy, U, is of the order of t, and thus an energy gap, the Hubbard gap, is created that supersedes the formation of a metallic state. It has qualitative characteristics similar to the “band gap” of a semiconductor, but arises from very different physical origins. For NiO, both t and U are of the order of 2 eV (a crystal of NiO appears green and barely transparent to the human eye).
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