Introduction to the tight binding

approximation—implementation by
diagonalisation

Anthony T Paxton

Atomistic Simulation Centre

School of Mathematics and Physics
Queen’s University Belfast

http://titus.phy.qub.ac.uk/group/Tony/WSMS2009
 WSMS–Jülich, March 4, 2009

Outline
1. Tight binding approximations
2. Bond integrals and Slater Koster table
3. Energy bands and DOS in the simple cubic structure
4. Self consistent tight binding
5. Tight binding in small molecules—some new results

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WSMS–Jülich, March 4, 2009 Energy bands in Ge

pseudopotential tight binding free electron

One electron dispersion relations in germanium (after Harrison)

2 / 27
 WSMS–Jülich, March 4, 2009 Tight binding approximation—I
The Bloch sum of s–orbitals at N sites {R}

1 X ik·R
ψk (r) = √ e ϕs (r − R)
N R

obeys Bloch’s theorem because if R0 is another atomic site

0 1 ik·R0
X ik·R00 ` 00 ´ ik·R0
ψk (r + R ) = √ e e ϕs r − R =e ψk (r)
N 00
R =R−R0

If ψk is an eigenstate of the Schrödinger equation H 0 ψk = εk ψk then its eigenvalue will

be
dr ψ̄k H 0 ψk
R
εk = R
dr ψ̄k ψk

3 / 27
 WSMS–Jülich, March 4, 2009 Tight binding approximation—II

0 ~2 2 X 00
H =− ∇ + Veff (r) Veff (r) = v(r − R )
2m
R00

In which case we have

2 3
1 X ik·(R−R0 ) ~2 2 X
Z Z
0 ` 0´ 4 00 5
ψ̄k H ψk = e ϕ̄s r − R − ∇ + v(r − R ) ϕs (r − R)
N 2m
R,R0 R00

1 X ik·(R−R0 )
Z Z
` 0´
ψ̄k ψk = e ϕ̄s r − R ϕs (r − R)
N 0
R,R

The tight binding approximations

1. Neglect three centre integrals—i.e., those for which R 6= R0 6= R00

2. Neglect overlap integrals (except those for which R = R0 )

3. Don’t even attempt to calculate the remaining integrals—treat them as disposable

parameters of the TB model, retaining only nearest neighbours.

4 / 27
 WSMS–Jülich, March 4, 2009 Tight binding approximation—III
Then we find
2 3
Z X X Z
ik·R
εk = εs + ϕ̄s (r) 4 v (r − R)5 ϕs (r) + e ϕ̄s (r)v(r)ϕs (r − R)
R6=0 R6=0

" #
~2 2
Z
εs = ϕ̄s (r) − ∇ + v(r) ϕs (r)
2m

If we neglect the crystal field terms,

X ik·R
εk = εs + e h(R)
R6=0

+ + h(R) = h = ssσ
R

So, given some hopping (or transfer) integrals and a crystal structure we can construct the
energy bands.

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WSMS–Jülich, March 4, 2009 Bond integrals

+ + + − +
ssσ spσ

+ +
− + − +
ppσ
− ppπ − −

sdσ + + +
− +
−
+ −
+ + + − − +
pdσ pdπ

+
− − + +
− + − −
+ −
+ − − + − −
− + − +
ddσ +
ddπ ddδ

6 / 27
 WSMS–Jülich, March 4, 2009 The simple cubic s–band
For example in the simple cubic s–band with lattice constant a
{R} = { [±a, 0, 0] [0, ±a, 0] [0, 0, ±a] }
X ik·R
εk = εs + e h(R)
R6=0

= εs + 2ssσ (cos kx a + cos ky a + cos kz a)

π π
Plot this along high symmetry lines in the Brillouin zone, Γ: (000), R: a (111), X: a (100)

6
−(ε−εs) / ssσ

−6
R Γ X
n(ε)

7 / 27
 WSMS–Jülich, March 4, 2009 p–orbitals—I
The three p-orbitals are ϕx (r − R), ϕy (r − R) and ϕz (r − R). The expansion of a trial
wavefunction or Bloch sum is

1 X X ik·R
ψk (r) = cα e ϕα (r − R)
N α=x,y,z R

The Schrödinger equation becomes a secular problem

˛ ˛
˛ ˛
˛ (εp − εk ) δ 0 + T 0 ˛ = 0
˛ αα αα ˛

X Z
ik·R
Tαα0 = e ϕ̄α (r)v(r)ϕα0 (r − R)
R6=0

8 / 27
 WSMS–Jülich, March 4, 2009 p–orbitals—II

Z
ϕ̄α (r)v(r)ϕα0 (r − R) = h(R)

− +

R
h(R) = ppσ cos2 θ + ppπ sin2 θ
θ
− +

generally, if l, m and n are the direction cosines of R

Z “ ”
2 2
ϕx vϕx = l ppσ + 1 − l ppπ
Z
ϕx vϕy = lm ppσ − lm ppπ
Z
ϕx vϕz = ln ppσ − ln ppπ

Bond Integrals 9 / 27
WSMS–Jülich, March 4, 2009 The Slater–Koster table, s–p block

10 / 27
WSMS–Jülich, March 4, 2009 The Slater–Koster table, sp–d block

11 / 27
WSMS–Jülich, March 4, 2009 The Slater–Koster table, d–d block

12 / 27
 WSMS–Jülich, March 4, 2009 The simple cubic p–band—I
You don’t even need to diagonalise the secular matrix in the simple cubic crystal structure
since it’s already diagonal!!
Tαα0 = Tαα δαα0

and

Txx = 2 ppσ cos kx a + 2 ppπ (cos ky a + cos kz a)

Tyy = 2 ppσ cos ky a + 2 ppπ (cos kz a + cos kx a)
Txx = 2 ppσ cos kz a + 2 ppπ (cos kx a + cos ky a)

In the (100) direction, Γ → X, k = (kx 00) there are three bands,

8
<2 ppσ cos kx a + 4 ppπ
>
εk = εp + 2 ppπ + 2 (ppσ + ppπ)
>
:2 ppπ + 2 (ppσ + ppπ)
8
<2 ppσ cos kx a
>
≈ εp + 2 ppσ
>
:2 ppσ

13 / 27
WSMS–Jülich, March 4, 2009 The simple cubic p–band—II

(ε−εp) / ppσ
0

−2

R Γ X
n(ε)
8
<2 ppσ cos kx a
>
Γ → X : εk ≈ εp + 2 ppσ
>
:2 ppσ

14 / 27
WSMS–Jülich, March 4, 2009 Bands of Strontium Oxide
SrO lmf SrO TB
0.8
0.4
0.6
0.2
Energy (Ry)

Energy (Ry)
0.4
0
0.2
−0.2
0
−0.4
−0.2
Γ M X R Γ XM R Γ M X R Γ XM R

8
<2 ppσ cos kx a
>
Γ → X : εk ≈ εp + 2 ppσ
>
:2 ppσ

15 / 27
 WSMS–Jülich, March 4, 2009 Further. . .
• d–bands

• hybridisation

• non orthogonal tight binding

• total energy and force

• self consistent tight binding

• magnetic tight binding

• small molecules

• time dependent tight binding

”Fools rush in where angels fear to tread,” Alexander Pope 1711

16 / 27
 WSMS–Jülich, March 4, 2009 self consistent tight binding
There are components of the electrostatic potential at site R due to all multipoles at sites R0 :

2
X
VRL = e B̃RL R0 L0 QR0 L0
R0 L0

B̃ is a sort of generalised Madelung matrix, proportional to ˛R − R0 ˛−1 for point charges.

˛ ˛
They induce electrostatic shifts in the hamiltonian matrix elements which are on site and off
diagonal:

0
X
HRL0 RL00 = UR ∆qR δL0 L00 + VRL ∆`0 `00 ` CL0 L00 L
L

The Hubbard–U acts to resist charge accumulation.

0 0
H =H +H

Crystal field 17 / 27
 WSMS–Jülich, March 4, 2009 Zirconia bands
Fluorite (LDA) Fluorite (TB)

0.2
1.4
0
t2
1.2
−0.2 e
Energy (Ry)

Energy (Ry)
1
−0.4
0.8
−0.6
0.6
−0.8
0.4
−1
0.2
XUK Γ X W L Γ XUK Γ X W L Γ

Rutile (LDA) Rutile (TB)

0.2
1.4
0 e
1.2
−0.2
t2
Energy (Ry)

Energy (Ry)

1
−0.4
0.8
−0.6
0.6
−0.8
0.4
−1
0.2
Γ Z R A M Γ X Γ Z R A M Γ Z

18 / 27
 -0.2
0 0.2 -0.4 -0.005 T=50 K
u.) 0.4 WSMS–Jülich, March 4, 2009 Zirconia phase transition
-0.01
0 0 0.1 0.2 0.3 0.4 0.5 0.6
5 10 15 20 25
ν (THz)
urfaces for a tetragonal cell with the
<0,0,δ> (a.u.)

a) section in the y ; x plane, (b) sec-

The isoenergetic contours are plotted FIG.6310. Temperature evolution of the free energy p
S. Fabris, A. T. Paxton and M. W. Finnis,
FIG. 4.2 .Temperature dependence of the macroscopic
Ry/ZrO order
calcu-the order parameter direction h00i.
PRB, 094101 (2001)

arameter z . The symbols () are the results of thealong
projected
tions. The continuous symbols () in
(b) solid eye-line is extrapolated arethethe 0 K calculations, the thick solid lin
gion near Tc where the large uctuations
∆U (mRy) theinresult of thethethermodynamic integration and corre
z make
to the temperatures 50, 500, 1000, 1500, and 2000 K.
1
eraging procedure inaccurate.
0
-1
-2
0.6 2
1.5 T=2000 K
0.4 0.5
0.2 1 T
0.4 0 0.4

∆F (mRy/ZrO2)
2 δx 0.2 0.5
0.4-0.2
<δ> (a.u.)

0
-0.4 -0.2 δz
-0.4 0
0.3 -0.5

0.2 -1
-1.5
y of the 0 0.1K energy-expansion co- -2 T=0 K
nt tetragonal0 cells with the tetrag- -2.5
ections of the600corresponding energy
800 1000 1200 1400 1600 1800 2000 2200
-0.6 -0.4 -0.2 0 0.2 0.4 0.6

ymmetry order-parameter directionsT (K) <0,0,δ> (a.u.)

(b)
FIG. 5. Calculation results of the frequencyFIG.
=1.00 squared
19 / 11.
z2 vs. well in the internal energy along the
27 Double

=1.01 1
WSMS–Jülich, March 4, 2009 TB model for water

Finding TB parameters for water

20 / 27
WSMS–Jülich, March 4, 2009 Water monomer
q q = δe
p(δ)
d
θ
pind

−2q
point charge model dipole polarisable model

p(δ) = 2dδe cos 1θ = 5.65δ (Debye) ; e>0

2
2eδ 1θ
pind αO (δ)
pind = −αO (δ) 2 cos 2
; =−
d p(δ) d3
pexp = p(δ) + pind = 1.86 (D)
αO (δ) ≈ 0.8 − 0.23δ → δ ≈ 0.9 ; (N → O → F → Ne)

δ αO ν1 ν2 ν3 αH2 O Ecoh
3 3
model (Å ) —force constants (au)— (Å ) (Ry)
point 0.33 — 1.029 0.099 1.002 1.3 0.79
dipole 0.45 0.31 1.029 0.104 0.847 1.2 0.84
exp. — 0.7 1.029 0.100 1.062 1.4 0.75

21 / 27
 Rapid progress has recently been made in the precise determi- geometry optimizations u
nation of the equilibrium geometry and binding energy of the reported by Hobza et al.
water dimer
WSMS–Jülich, March 4, 2009 by ab initio methods.1h33 Apart from advances Water
in using Dimer
conventional basis
hardware and software the progress has been stimulated by energy, *E(FC), approache
the availability of basis sets which (in principle) allow a sys- around [20.5 kJ mol~1,
tematic approach to the basis set limit at a given level of [20.28 kJ mol~1 (ref. 25)
theory, and by a growing consensus that the basis set super- 32). Corresponding MP2-
position error (BSSE) can rigorously be avoided by applying taken to represent the basis
the counterpoise method (CP), so that the user can focus on a Relaxing the monomer geo
good description of the interaction without having to worry kJ mol~1 (refs. 21 and 2
about the size of the BSSE. A survey of recent studies, giving valence correlation e†ects
details of the geometries (cf. Fig. 1) obtained or explored, is mol~1.24,31,32 Thus the Ðn
given
non self consistent in Table 1. point charge model
model dipole polarisable model
all these contributions into
A fairly complete set of results converging to the basis set mol~1.
limit is now R availablerfat the rdMP2/CPα level of βtheory. At higher levels of the
Xantheas21
TB has291
converged
95.4the OÉ 8.8◦
É ÉO equilibrium
97.3 97.6◦ Re
distance Halkier et al.25,33 have s
◦ ◦ geometry, the step from M
CCSD 291 95.7 96.4 5.5 124.4
monomer *E(FC) by amou
for the aug-cc-pVDZ basi
pVQZ, and their extrapola
an increase to [0.27 kJ m
mated the increase to [
monomer relaxation e†e
lengthening is exaggerated
expects a smaller relaxatio
the coreÈvalence correction
been studied.
The aim of the present p
CCSD(T) level of theory in
W.
Fig. Klopper et al., PCCP,
1 The equilibrium structure2, 2227
of the (2000)
water dimer. result as is technically poss
currently feasible to gene
accurate as those availabl
¤ Dedicated to Professor Reinhart Ahlrichs on the occasion of his out CCSD(T) geometry o
60th birthday.
22 / 27 aug-cc-pV5Z, with 572 fun
WSMS–Jülich, March 4, 2009 Water Tetramer

—dipole moment (D)—

monomer 1.82
dimer 1.97 1.98
trimer 2.22 2.23 2.24
tetramer 2.25 2.25 2.27 2.27
.
.
.
bulk water ≈ 2.66 (point charge model)

23 / 27
 WSMS–Jülich, March 4, 2009 Polarisability of small molecules
azulene p-nitroaniline
3 12

2 10
dipole moment (Debye)

dipole moment (Debye)

1 8 O
−
+
H

− N N+
O
H

0 6

−1 4
− H
O +
N N

−2 2
O
H

−3 0
−2 −1 0 1 2 −4 −2 0 2 4
electric field (GV/m) electric field (GV/m)

24 / 27
 WSMS–Jülich, March 4, 2009 Time dependent TB
0.02

0.01
∆q (electrons)

−0.01

30

20
π−bond current (µA)

10

−10

−20

−30
0 500 1000 1500 2000 2500 770 780 790
time (fs) time (fs)

dρ̂ 1 2e X
= [H, ρ̂] − Γ (ρ̂ − ρ̂0 ) ; jRR0 = HR0 L0 RL Im ρRL R0 L0
dt i~ ~ 0
LL

25 / 27
 WSMS–Jülich, March 4, 2009 Ehrenfest dynamics
0.02

0.01
∆q (electrons)

−0.01

30

20
π−bond current (µA)

10

−10

−20

−30
0 500 1000 1500 2000 2500 560 570 580
time (fs) time (fs)

d2 R X 0
X
MR =− 2ρRL R0 L0 ∇R HR0 L0 RL − QRL ∇R VRL − ∇R Epair
dt2
RL R0 L0 L
R0 6=R

26 / 27
WSMS–Jülich, March 4, 2009 Acknowledgements

Thanks to

Catherine Walsh
Alin Elena
Jorge Kohanoff
Tchavdar Todorov
Mike Finnis

27 / 27