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This is a series of slides prepared by Heather Kulik (http://www.stanford.edu/~hkulik or email hkulik at stanford dot edu) for a talk given at the University of Pennsylvania in February 2012. It covers a basic introduction to DFT+U and related approaches for improving descriptions of transition metals and other systems with localized electrons.
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Slides created by Heather Kulik intended for educational use only. Visit http://www.stanford.edu/~hkulik for more info.
Recent developments in Hubbard-augmented DFT
Heather Kulik02/03/12
Slides created by Heather Kulik intended for educational use only. Visit http://www.stanford.edu/~hkulik for more info.
Nicola MarzariMIT/EPFL
Matteo CococcioniU Minnesota
Quantum-ESPRESSO
http://www.quantum-espresso.orgOpen source plane-wave, pseudopotential codeOther codes with similar implementations: VASP, ONETEP, Qbox, others?Coming soon: TeraChem, GPAW?
Slides created by Heather Kulik intended for educational use only. Visit http://www.stanford.edu/~hkulik for more info.
http://www.stanford.edu/~hkulik
Slides created by Heather Kulik intended for educational use only. Visit http://www.stanford.edu/~hkulik for more info.
Density functional theory
Exact…in theory One-to-one mapping of many-body interacting system onto a non-interacting one.Quantum mechanis becomes computationally tractable.
Slides created by Heather Kulik intended for educational use only. Visit http://www.stanford.edu/~hkulik for more info.
Density functional theory
Exact…in theory
Approximations in practice
One-to-one mapping of many-body interacting system onto a non-interacting one.Quantum mechanis becomes computationally tractable.
Slides created by Heather Kulik intended for educational use only. Visit http://www.stanford.edu/~hkulik for more info.
Density functional theory
Exact…in theory
Approximations in practiceCharge transfer (short or long range)Electron delocalizationWrong dissociations…all some form of self-interaction error.
One-to-one mapping of many-body interacting system onto a non-interacting one.Quantum mechanis becomes computationally tractable.
Slides created by Heather Kulik intended for educational use only. Visit http://www.stanford.edu/~hkulik for more info.
Electronic structure methods
A density worldview
higher derivatives of the densityadding in Hartree-Fock exchangeparameterizing until the end of time
A “sophisticated” condensed matter electronic structure worldview
Density matrix renormalization groupDynamical mean field theoryGW approximationQuantum Monte Carlo
A wavefunction worldview
Hartree-Fock/MCSCFPerturbative theories + RAS/CAS/etc.
Coupled cluster methods(Some approximation to) Full CI
Slides created by Heather Kulik intended for educational use only. Visit http://www.stanford.edu/~hkulik for more info.
But I just want results…
My (slightly different) density worldview
Physics-based, parameter free methods to alleviate self-interaction
For 1-1000 atoms (or more with GPUs), approaches that balance accuracy with computational efficiency.
Slides created by Heather Kulik intended for educational use only. Visit http://www.stanford.edu/~hkulik for more info.
DFT+U
Slides created by Heather Kulik intended for educational use only. Visit http://www.stanford.edu/~hkulik for more info.
DFT+U DFT+U+V
Slides created by Heather Kulik intended for educational use only. Visit http://www.stanford.edu/~hkulik for more info.
DFT+U DFT+U+V
DFT+U(R)
Slides created by Heather Kulik intended for educational use only. Visit http://www.stanford.edu/~hkulik for more info.
DFT+U DFT+U+V
DFT+U(R)in practice
Slides created by Heather Kulik intended for educational use only. Visit http://www.stanford.edu/~hkulik for more info.
DFT+U
Slides created by Heather Kulik intended for educational use only. Visit http://www.stanford.edu/~hkulik for more info.
Basic Hubbard model Hamiltonian
Conductor to insulator transition
Slides created by Heather Kulik intended for educational use only. Visit http://www.stanford.edu/~hkulik for more info.
Basic Hubbard model Hamiltonian
Conductor to insulator transition
Slides created by Heather Kulik intended for educational use only. Visit http://www.stanford.edu/~hkulik for more info.
Basic Hubbard model Hamiltonian
Conductor to insulator transition
DFT conductors to DFT+U insulators
Slides created by Heather Kulik intended for educational use only. Visit http://www.stanford.edu/~hkulik for more info.
Basic Hubbard model Hamiltonian
Conductor to insulator transition
DFT conductors to DFT+U insulators
DFT
E
conductors
Slides created by Heather Kulik intended for educational use only. Visit http://www.stanford.edu/~hkulik for more info.
Basic Hubbard model Hamiltonian
Conductor to insulator transition
DFT conductors to DFT+U insulators
DFT
E
DFT+U
E
conductors
Slides created by Heather Kulik intended for educational use only. Visit http://www.stanford.edu/~hkulik for more info.
Basic Hubbard model Hamiltonian
Conductor to insulator transition
DFT conductors to DFT+U insulators
DFT
E
DFT+U
E
conductorsconductors insulators
V.I. Anisimov, J. Zaanen and O.K. Andersen. Phys. Rev. B, (1991).M. Cococcioni and S. de Gironcoli. Phys. Rev. B, (2005).
Slides created by Heather Kulik intended for educational use only. Visit http://www.stanford.edu/~hkulik for more info.
DFT+U for moleculesUGE Perera, HJK et al Phys. Rev. Lett. (2010).
HJK et al J. Am. Chem. Soc. (2009).
HJK et al Phys. Rev. Lett. (2006). HJK et al J. Chem. Phys. (2008).
HJK et al Phys. Rev. Lett. (2006). HJK et al Fuel Cell Science (2010).
Slides created by Heather Kulik intended for educational use only. Visit http://www.stanford.edu/~hkulik for more info.
Physical meaning of DFT+U
N-1 N N+1
Energ
y
# of Electrons
M. Cococcioni and S. de Gironcoli. PRB, 71: 2005.
Energy of an atom
J.P. Perdew, R.G. Parr, M. Levy, and J. L. Balduz, Jr. Phys. Rev. Lett. (1982).
Slides created by Heather Kulik intended for educational use only. Visit http://www.stanford.edu/~hkulik for more info.
Physical meaning of DFT+U
N-1 N N+1
Energ
y
# of Electrons
M. Cococcioni and S. de Gironcoli. PRB, 71: 2005.
Energy of an atom
J.P. Perdew, R.G. Parr, M. Levy, and J. L. Balduz, Jr. Phys. Rev. Lett. (1982).
Slides created by Heather Kulik intended for educational use only. Visit http://www.stanford.edu/~hkulik for more info.
Physical meaning of DFT+U
N-1 N N+1
Energ
y
# of Electrons
M. Cococcioni and S. de Gironcoli. PRB, 71: 2005.
Energy of an atom
J.P. Perdew, R.G. Parr, M. Levy, and J. L. Balduz, Jr. Phys. Rev. Lett. (1982).
Slides created by Heather Kulik intended for educational use only. Visit http://www.stanford.edu/~hkulik for more info.
Physical meaning of DFT+U
N-1 N N+1
Energ
y
# of Electrons
exact
M. Cococcioni and S. de Gironcoli. PRB, 71: 2005.
Energy of an atom
J.P. Perdew, R.G. Parr, M. Levy, and J. L. Balduz, Jr. Phys. Rev. Lett. (1982).
Slides created by Heather Kulik intended for educational use only. Visit http://www.stanford.edu/~hkulik for more info.
Physical meaning of DFT+U
N-1 N N+1
Energ
y
# of Electrons
exact
M. Cococcioni and S. de Gironcoli. PRB, 71: 2005.
Energy of an atom
J.P. Perdew, R.G. Parr, M. Levy, and J. L. Balduz, Jr. Phys. Rev. Lett. (1982).
LDA/GGA
Slides created by Heather Kulik intended for educational use only. Visit http://www.stanford.edu/~hkulik for more info.
Physical meaning of DFT+U
N-1 N N+1
Energ
y
# of Electrons
exact
M. Cococcioni and S. de Gironcoli. PRB, 71: 2005.
Energy of an atom
J.P. Perdew, R.G. Parr, M. Levy, and J. L. Balduz, Jr. Phys. Rev. Lett. (1982).
LDA/GGA
+U
Slides created by Heather Kulik intended for educational use only. Visit http://www.stanford.edu/~hkulik for more info.
Physical meaning of DFT+U
N-1 N N+1
Energ
y
# of Electrons
M. Cococcioni and S. de Gironcoli. PRB, 71: 2005.
Energy of an atom
J.P. Perdew, R.G. Parr, M. Levy, and J. L. Balduz, Jr. Phys. Rev. Lett. (1982).
The “+U” contribution to standard DFT:exact
LDA+U
+U
U is the extent of curvature: we calculate this uniquely for each system.
Slides created by Heather Kulik intended for educational use only. Visit http://www.stanford.edu/~hkulik for more info.
Choosing occupations1) Select the localized manifold or manifolds for each atom “site”
2) Choose the projections
Results in this talk: Other options:Wannier/Boys functionsPopulation schemes
Slides created by Heather Kulik intended for educational use only. Visit http://www.stanford.edu/~hkulik for more info.
Linear response U
6+ MXae
n
n’
U is the curvature: We calculate it from linear response:
In lieu of constrained occupations
Bare response due to rigid potential shift on localized manifold
Converged response (from an SCF calculation)
Slides created by Heather Kulik intended for educational use only. Visit http://www.stanford.edu/~hkulik for more info.
U is a system-dependent property
MXU
(eV)
FeO+ 5.50FeN 4.38MnO 3.41CrO- 2.85CrF 2.00Isoelectronic
Series
Less co
vale
nt
HJK and N. Marzari, J. Chem. Phys. (2010).
6+ MXA property that should be calculated
Electron configurationCovalency/ionicitySpin states/charge statesElement identityCoordination numbers
Slides created by Heather Kulik intended for educational use only. Visit http://www.stanford.edu/~hkulik for more info.
A self-consistent U
HJK et al., Phys. Rev. Lett. (2006).
Calculate U self-consistently on the DFT+U system:
x7
Most key for when DFT and DFT+U ground states differ
Slides created by Heather Kulik intended for educational use only. Visit http://www.stanford.edu/~hkulik for more info.
DFT+U+V
Slides created by Heather Kulik intended for educational use only. Visit http://www.stanford.edu/~hkulik for more info. Extending the Hubbard model
Slides created by Heather Kulik intended for educational use only. Visit http://www.stanford.edu/~hkulik for more info. Extending the Hubbard model
Slides created by Heather Kulik intended for educational use only. Visit http://www.stanford.edu/~hkulik for more info. Extending the Hubbard model
IJ K
UIIVIJ VIK
V favors intersite interactions
J. Hubbard Proc. R. Soc. A 285 (1965).J. Hubbard Proc. R. Soc. A 296 (1967).
V. I. Anisimov, I. S. Elfimov, N. Hamada, and K. Terakura Phys. Rev. B 54 (1996).
Slides created by Heather Kulik intended for educational use only. Visit http://www.stanford.edu/~hkulik for more info.
Functional formExtended Hubbard Model
Campo and Cococcioni, J. Phys. Cond. Matt. (2010).
Slides created by Heather Kulik intended for educational use only. Visit http://www.stanford.edu/~hkulik for more info.
Functional formExtended Hubbard Model Generalized FLL double counting
Campo and Cococcioni, J. Phys. Cond. Matt. (2010).
Slides created by Heather Kulik intended for educational use only. Visit http://www.stanford.edu/~hkulik for more info.
Functional formExtended Hubbard Model Generalized FLL double counting
Campo and Cococcioni, J. Phys. Cond. Matt. (2010).
Slides created by Heather Kulik intended for educational use only. Visit http://www.stanford.edu/~hkulik for more info.
Generalized occupations
m and m’ defined by interacting manifolds
Connection to atomic projections is clear. Wannier basis less so (already bond-centered?)
nII nIJ
nJI nJJ
Block diagonals: on-site standard occupations.
Slides created by Heather Kulik intended for educational use only. Visit http://www.stanford.edu/~hkulik for more info.
What happens to states
nII nIJ
nJI nJJ
Internal competition
Slides created by Heather Kulik intended for educational use only. Visit http://www.stanford.edu/~hkulik for more info.
What happens to states
nII nIJ
nJI nJJ
Standard U: Favors integer occupations in block diagonals, weak off-site blocks.
Internal competition
Slides created by Heather Kulik intended for educational use only. Visit http://www.stanford.edu/~hkulik for more info.
What happens to states
nII nIJ
nJI nJJ
Standard U: Favors integer occupations in block diagonals, weak off-site blocks.
New V term: strong intersite occupations in off diagonal.
Internal competition
Slides created by Heather Kulik intended for educational use only. Visit http://www.stanford.edu/~hkulik for more info.
MO2 bent linear
Gong, Chem. Rev. 2009 and references therein.
Experiments:
Can theory predict transition?
180
100
Slides created by Heather Kulik intended for educational use only. Visit http://www.stanford.edu/~hkulik for more info.
MnO2: Single or double well?
r
Slides created by Heather Kulik intended for educational use only. Visit http://www.stanford.edu/~hkulik for more info.
MnO2: Single or double well?
r
Slides created by Heather Kulik intended for educational use only. Visit http://www.stanford.edu/~hkulik for more info.
MnO2 hybridization
r
Slides created by Heather Kulik intended for educational use only. Visit http://www.stanford.edu/~hkulik for more info.
O-M-O Structures
2
2
2
DFT+U+U|r0
+U+VExpt.
DFT +U +U+V
MnO2 1.61 1.70 1.59FeO2 1.59 1.67 1.58CoO2 1.55 1.63 1.56
Angles Bonds
+U|r0: angle from M-O bond fixed to DFT value.
HJK and N. Marzari, J. Chem. Phys. 134, 094103 (2011).
Slides created by Heather Kulik intended for educational use only. Visit http://www.stanford.edu/~hkulik for more info.
O-M-O Structures
2
2
2
DFT+U+U|r0
+U+VExpt.
DFT +U +U+V
MnO2 1.61 1.70 1.59FeO2 1.59 1.67 1.58CoO2 1.55 1.63 1.56
Angles Bonds
+U|r0: angle from M-O bond fixed to DFT value.
HJK and N. Marzari, J. Chem. Phys. 134, 094103 (2011).
Slides created by Heather Kulik intended for educational use only. Visit http://www.stanford.edu/~hkulik for more info.
FeO2 Splitting and Angle
+U +V
Expt GS
GS ∠
U = 0 V = 0
U = 5 V = 0
U = 5 V = 2
Slides created by Heather Kulik intended for educational use only. Visit http://www.stanford.edu/~hkulik for more info.
Solid state applicationsLDA+DMFT+V for VO2
A. S. Belozerov, et al. PRB (2012).
Monoclinic M1
Magnetic susceptibilities
Cheaper than cluster DMFT but yields similar results.
Slides created by Heather Kulik intended for educational use only. Visit http://www.stanford.edu/~hkulik for more info.
Solid state applicationsLDA+DMFT+V for VO2
A. S. Belozerov, et al. PRB (2012).
Monoclinic M1
Magnetic susceptibilities
Cheaper than cluster DMFT but yields similar results.
Slides created by Heather Kulik intended for educational use only. Visit http://www.stanford.edu/~hkulik for more info.
Solid state applicationsNiOCubic rock-salt structure
Si and GaAs
Campo and Cococcioni, J. Phys. Cond. Matt. (2010).
Slides created by Heather Kulik intended for educational use only. Visit http://www.stanford.edu/~hkulik for more info.
DFT+U(R)
Slides created by Heather Kulik intended for educational use only. Visit http://www.stanford.edu/~hkulik for more info.
Inspiration for a variable U
re we De DE
Erro
r
GGAGGA+U
Errors for 22 MX (X=H,C,N,O,F)
(eV)(eV)(cm-
1/100)
(Åx10)
HJK and N. Marzari. J. Chem. Phys. (2010).HJK and N. Marzari, J. Chem. Phys. (2011).
Slides created by Heather Kulik intended for educational use only. Visit http://www.stanford.edu/~hkulik for more info.
Inspiration for a variable U
re we De DE
Erro
r
GGAGGA+U
Errors for 22 MX (X=H,C,N,O,F)
(eV)(eV)(cm-
1/100)
(Åx10)
HJK and N. Marzari. J. Chem. Phys. (2010).
In DFT+U, we average U over all points. Works well most of the time!!
HJK and N. Marzari, J. Chem. Phys. (2011).
Slides created by Heather Kulik intended for educational use only. Visit http://www.stanford.edu/~hkulik for more info.
Inspiration for a variable U
re we De DE
Erro
r
GGAGGA+U
Errors for 22 MX (X=H,C,N,O,F)
(eV)(eV)(cm-
1/100)
(Åx10)
HJK and N. Marzari. J. Chem. Phys. (2010).
Electronic structure in differing bonding regimes
In DFT+U, we average U over all points. Works well most of the time!!
HJK and N. Marzari, J. Chem. Phys. (2011).
Slides created by Heather Kulik intended for educational use only. Visit http://www.stanford.edu/~hkulik for more info.
Inspiration for a variable U
re we De DE
Erro
r
GGAGGA+U
Errors for 22 MX (X=H,C,N,O,F)
(eV)(eV)(cm-
1/100)
(Åx10)
HJK and N. Marzari. J. Chem. Phys. (2010).
Electronic structure in differing bonding regimes
In DFT+U, we average U over all points. Works well most of the time!! DFT+U(R), changes
in U incorporated directly for key cases.
!HJK and N. Marzari, J. Chem. Phys. (2011).
Slides created by Heather Kulik intended for educational use only. Visit http://www.stanford.edu/~hkulik for more info.
Even better with DFT+U(R)
Slides created by Heather Kulik intended for educational use only. Visit http://www.stanford.edu/~hkulik for more info.
Even better with DFT+U(R)
DFT+U Forces
Interpolated
Slides created by Heather Kulik intended for educational use only. Visit http://www.stanford.edu/~hkulik for more info.
Even better with DFT+U(R)
DFT+U Forces
Interpolated
CC value
Slides created by Heather Kulik intended for educational use only. Visit http://www.stanford.edu/~hkulik for more info.
Even better with DFT+U(R)
DFT+U Forces
Interpolated
CC value
In practice, interpolate over forces or interpolate over energies with a common physical reference.
Slides created by Heather Kulik intended for educational use only. Visit http://www.stanford.edu/~hkulik for more info.
U variation from occupations
Slides created by Heather Kulik intended for educational use only. Visit http://www.stanford.edu/~hkulik for more info.
U variation from occupations
Slides created by Heather Kulik intended for educational use only. Visit http://www.stanford.edu/~hkulik for more info.
U variation from occupations
Slides created by Heather Kulik intended for educational use only. Visit http://www.stanford.edu/~hkulik for more info.
U variation from occupations
Component of forces gradient
Slides created by Heather Kulik intended for educational use only. Visit http://www.stanford.edu/~hkulik for more info.
U variation from occupations
From linear response
Component of forces gradient
Slides created by Heather Kulik intended for educational use only. Visit http://www.stanford.edu/~hkulik for more info.
U variation from occupations
4F FeO+: U vs. R
1.6 2.6R (Å)
U (eV
)
6
0
ActualPredicted
Slides created by Heather Kulik intended for educational use only. Visit http://www.stanford.edu/~hkulik for more info.
U variation from occupations
4F FeO+: U vs. R
1.6 2.6R (Å)
U (eV
)
6
0
ActualPredicted
Slides created by Heather Kulik intended for educational use only. Visit http://www.stanford.edu/~hkulik for more info.
Predicting U variation from forces
Slides created by Heather Kulik intended for educational use only. Visit http://www.stanford.edu/~hkulik for more info.
Predicting U variation from forces
Slides created by Heather Kulik intended for educational use only. Visit http://www.stanford.edu/~hkulik for more info.
Predicting U variation from forces
Slides created by Heather Kulik intended for educational use only. Visit http://www.stanford.edu/~hkulik for more info.
Predicting U variation from forces
Slides created by Heather Kulik intended for educational use only. Visit http://www.stanford.edu/~hkulik for more info.
Predicting U variation from forces
Exiting linear regime for derivatives of forces is a numerical challenge.
Slides created by Heather Kulik intended for educational use only. Visit http://www.stanford.edu/~hkulik for more info.
Numerical noise in practice
Predicted U trends for 4F FeO+
Slides created by Heather Kulik intended for educational use only. Visit http://www.stanford.edu/~hkulik for more info.
Numerical noise in practice
Slides created by Heather Kulik intended for educational use only. Visit http://www.stanford.edu/~hkulik for more info.
Numerical noise in practice
In principle, the force-based approach is more exact. In practice, it suffers from a greater degree of numerical noise.
Slides created by Heather Kulik intended for educational use only. Visit http://www.stanford.edu/~hkulik for more info.
When U(R) matters
A metric: when is U ½ of lin.resp. U?
Slides created by Heather Kulik intended for educational use only. Visit http://www.stanford.edu/~hkulik for more info.
When U(R) matters
A metric: when is U ½ of lin.resp. U?
Molecule U dU/dR DrU½
2S+ CoC 4.8 -4.0 0.62S- CrN 4.3 -2.3 0.94F+ FeO+ 6.3 -5.0 0.65S+ MnF 2.4 -4.8 0.26S+ CrF 2.0 -0.1 9.0
Slides created by Heather Kulik intended for educational use only. Visit http://www.stanford.edu/~hkulik for more info.
When U(R) matters
A metric: when is U ½ of lin.resp. U?
Molecule U dU/dR DrU½
2S+ CoC 4.8 -4.0 0.62S- CrN 4.3 -2.3 0.94F+ FeO+ 6.3 -5.0 0.65S+ MnF 2.4 -4.8 0.26S+ CrF 2.0 -0.1 9.0
Including more variables
Slides created by Heather Kulik intended for educational use only. Visit http://www.stanford.edu/~hkulik for more info.
When U(R) matters
A metric: when is U ½ of lin.resp. U?
Molecule U dU/dR DrU½
2S+ CoC 4.8 -4.0 0.62S- CrN 4.3 -2.3 0.94F+ FeO+ 6.3 -5.0 0.65S+ MnF 2.4 -4.8 0.26S+ CrF 2.0 -0.1 9.0
Including more variables
Some matter more than others
Slides created by Heather Kulik intended for educational use only. Visit http://www.stanford.edu/~hkulik for more info. Ordering multiple U(R) surfaces
Expt.
Slides created by Heather Kulik intended for educational use only. Visit http://www.stanford.edu/~hkulik for more info. Ordering multiple U(R) surfaces
Aligned at the effectiveunited atom limit
Expt.
Slides created by Heather Kulik intended for educational use only. Visit http://www.stanford.edu/~hkulik for more info.
DFT+U(R) Improvements
re (Å)
we (cm-1)
De(eV)
1) Binding curves: Errors on worst case subset from MX DFT+U
2) Reaction coordinates: H2 on FeO+
CC value
3) Work in progress: Molecular adsorbates on TM surfaces. Preliminary evidence: U(R) improves binding energies.
Slides created by Heather Kulik intended for educational use only. Visit http://www.stanford.edu/~hkulik for more info.
in practice
Slides created by Heather Kulik intended for educational use only. Visit http://www.stanford.edu/~hkulik for more info.
Numerical instabilities
Full manifolds or integer occupations
Unperturbed or rigid occupations
a
Example:
Slides created by Heather Kulik intended for educational use only. Visit http://www.stanford.edu/~hkulik for more info.
Numerical instabilities
c
c-1
Slides created by Heather Kulik intended for educational use only. Visit http://www.stanford.edu/~hkulik for more info.
Numerical instabilities
c
c-1
Slides created by Heather Kulik intended for educational use only. Visit http://www.stanford.edu/~hkulik for more info.
Projection dependence
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Projection dependence
DFT: significant PSP dependence
Slides created by Heather Kulik intended for educational use only. Visit http://www.stanford.edu/~hkulik for more info.
Projection dependence
DFT: significant PSP dependence
+U: Different Us, less PSP dependence
Slides created by Heather Kulik intended for educational use only. Visit http://www.stanford.edu/~hkulik for more info.
Multiple manifoldsStrong hybridization between 3d and 4s in TM hydrides
dd ds
sd ss
U3d=(0-1--1)dd
U4s=(0-1--1)ss
In the solid state: Ce 4f/5d/6s, MOFs?
Slides created by Heather Kulik intended for educational use only. Visit http://www.stanford.edu/~hkulik for more info. Angle dependence of n and c
linear
bent
Slides created by Heather Kulik intended for educational use only. Visit http://www.stanford.edu/~hkulik for more info. Angle dependence of n and c
linear
bent
Slides created by Heather Kulik intended for educational use only. Visit http://www.stanford.edu/~hkulik for more info. Angle dependence of n and c
Slides created by Heather Kulik intended for educational use only. Visit http://www.stanford.edu/~hkulik for more info.
A renormalized U
An equivalent U along a coordinate:
Redefining response functions:
All dependence of U on O-Mn-O angle is from filling/emptying d states!
Slides created by Heather Kulik intended for educational use only. Visit http://www.stanford.edu/~hkulik for more info.
Conclusions
For transition metals and materials with localized electrons:
DFT+U-works well in most casesDFT+U+V-a balance of localization/delocalization, more general cases like semiconductorsDFT+U(R)-bond breaking for chemical applicationsIn practice, things don’t always go according to plan (method is still not a black box).