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Notable failures of LDA/GGA: transition-metal oxides introduction to correlation LDA+U: general formulation Examples and applications Computing U from first-principles
Oxygen
Antiferromagnetic ground state: OK crystal structure (cubic): OK Crystal field produces a band gap, but
Mott insulators: U vs W
Two quantities are to be considered: U W on-site electron-electron repulsion bandwidth (hopping amplitude, related to kinetic energy)
Two different regimes: W/U >> 1: the energy is minimized making the kinetic term as small as possible through delocalization (little price is paid on the occupied atomic sites to overcome repulsion U) W/U << 1: the kinetic energy of electrons is not large enough to overcome the on-site repulsion. Electrons undergo a Mott localization
I. G. Austin and N. F. Mott, Science 168, 71 (1970)
LDA/GGA approximations to DFT always tend to over-delocalize electrons: U is not well accounted for electronic energy functionals are affected by self-interaction
H2 molecule in DFT
Lets consider the spherically and system-averaged pair electronic density:
where
At very large internuclear distances each electron is still split between the two sites!
(1,2) = N [ a (1) a (2 )]
ionic terms
2) d > 0: H molecule
2) d >> 0: distinct H atoms each electron is on the 1s ground state of each H atom:
(i ) = 1s ( i )
c c
instead of
E Hub
I I + ( m, m' ' | Vee | m' , m' ' ' m, m' ' | Vee | m' ' ' , m' ) nmm ' nm''m '''
Edc n
[{ }]
k ,v
U I I J I I = n n 1 n n 1 I 2 I , 2
)
n I = n I
Occupations:
I I I nmm ' = f kv kv | m ' m | kv
I n I = nmm m
Electronic interactions
Hartree-Fock formalism (for d states): from the expansion of 1/|r-r| in spherical harmonics we get:
|r-r'|
4 k * ak (m, m' , m' ' , m' ' ') = lm | Ykq | lm' lm' ' | Ykq | lm' ' ' 2k + 1 q = k
The double counting term is evaluated as the Mean Field Approximation of the Hubbard one. So in the expression of EHub we put
I nmm ' = mm '
and get
1 Tr n I 2l + 1
[ ]
1 ' m, m' Vee m, m' = F 0 (2l + 1)2 m,m F2 + F4 1 J= ' m, m'| Vee | m' , m = 14 2l (2l + 1) m ,m U=
k
A simplified approach
First order approximation: lets neglect the exchange interaction J:
We get:
J = F2 = F4 = 0
I I EU nmm ' = EHub nmm ' Edc n I =
[{ }]
[{ }]
[{ }]
U = 2
Tr n I ( 1 n I )
I ,
Note: a) U is the only interaction parameter in the functional Note: b) the rotational invariance is preserved. This is the formula implemented in PWscf. We have
ELDA+U
Tr n I ( 1 n I )
I ,
where
U EU = 2
I n I v m = m v m
I, m
I I m ( 1 m )
I I I m = f kv kv | m m | kv k, v
Potential:
EU U = VU | kv = * kv 2
I I I 1 2m ) | m m | kv ( I , m
I m
I m
There is a different U for each distinct type of Hubbard atom U is in eV Typical values: U is rarely larger than 7-8 eV (in most cases 0<U<5 eV)
There might be need of using finer k-points grids for a better evaluation of on-site occupations.
FeO
Does it work?
NiO
structural parameters
M. Cococcioni and S. de Gironcoli PRB 71, 035105 (2005)
V=
H2 addition-elimination to FeO+
O2
Magnetic ground state Exp GGA B3LYP HF GGA+U quintuplet (S=2) triplet triplet quintuplet quintuplet singlet (S=0) singlet singlet quintuplet singlet
H. J. Kulik, M. Cococcioni, D. Scherlis and N. Marzari, submitted for publication
I, m
I I m ( 1 m )
The +U correction is the one needed to recover the exact behavior of the energy. What is the physical meaning of U?
Evaluation of U
U is the unphysical curvature of the DFT total energy We want effective interactions: we evaluate U from the DFT ground state A free-electron contribution (due to rehybridization) is to be subtracted in crystals:
2 GGA 2 GGA 0 I 2
d E d E U= I 2 d (n ) d (n )
Second derivatives
Second derivatives of the energy are not directly accessible We apply a potential shift to the d states of each Hubbard atom I and use a Legendre transform:
Legendre transform
d E nJ = I n J d nI
[{ }]
({ })
d 2E nJ
I 2
[{ }] = d ({n }) dn d (n )
J I I
Linear response
Using I as perturbation parameters we can easily evaluate the response matrices:
dn = d J
0 IJ
I 0
dn IJ = d J
Run a self consistent (unperturbed) calculation. Starting from saved potential and wavefunction add the perturbation The response 0 is evaluated at the first iteration (at fixed potential) The response is evaluated at self consistency
d I d I = 0 1 1 U = I + I dn d n0
II
What screening?
U = 0 1 1
U = 0 1 0 1 0 1
is equivalent to
= 0 + 0U
= 0 + 0U 0
diagrammatic representation:
U is a bare interaction; U is the dressed (effective) one. We use U and let the electrons perform the screening through the relaxation to their self-consistent ground state. But werent we looking for screened effective interactions? What screening are we including?
Vext (r )
n(r )
where:
n(r ) = (r, r ' )Vext (r ' )dr ' = 0 (r, r ' )V (r ' )dr '
(1) (2)
v xc (r ) n(r' ) V (r ) = Vext + n(r ' )dr ' dr '+ n(r ' ) | r r'|
V (r ) = 0 1 (r, r ' )n(r ' )dr ' Vext (r ) = (r, r ' )n(r ' )dr '
(3)
xc kernel
unperturbed run
&system . . . lda_plus_u = .true., Hubbard_U(1) = 1.d-20, Hubbard_U(2) = 1.d-20, . . Hubbard_U(ntype) = 1.d-20, . . / Hubbard_alpha values are symmetrically distributed around 0 (typically from 0.1 to 0.1 eV) the perturbed atom has to be treated as of different kind the series of perturbed runs at different Hubbard_alpha is repeated for every different kind of Hubbard atom diago_thr_init is chosen close to the last ethr of the unperturbed run (ethr_conv)
Importance of computing U
Consistency with the expression of the +U functional and with the choice of localized basis set: the computed U is exactly the one needed Sensitiveness to spin states, chemical/physical environments, structural changes (important in studying e.g. chemical reactions, phase transitions) FeO rhombohedral distorsion under pressure (MgxFe1-x)O HS to LS transition under pressure
T. Tsuchiya, R. M. Wentzcovitch, C. R. S. da Silva and S. De Gironcoli, Phys. Rev. Lett. 96, 198501 (2006)
Work in progress
Compute J better functionals (for better energetics) auto-consistent calculation of U (from a LDA+U ground state) on-the-fly evaluation of U inter-site interactions phonon+U