of bonds and bands how to understand mo theory for extended solids?
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Of bonds and bands How to understand MO theory for extended solids?. What does this mean?. Linear chain of hydrogen atoms. Polyene. Energy. The strongest attraction is found for the configuration with the smallest number of nodes. - PowerPoint PPT PresentationTRANSCRIPT
Of bonds and bandsHow to understand MO theory for
extended solids?
What does this mean?
Linear chain of hydrogen atoms
Polyene
Energy
The strongest attraction is found for the configuration with the smallest number of nodes.
The distances between the nodes is the reciprocal of their number. If there are no nodes, the distance is infinite. If there is a node between every atom the distance is a.
E
No nodes, k=0
Nodes between all atoms, k=/a
k=/2a
0
1
2
3
4
5
6
7
8
Linear chain of hydrogen atoms
a
n exp(ikna) n - What is this?
kn exp(ikna) n - what is this?
n are basis functions, orbitals for H
k is an index related to the number of nodes, or rather times the reciprocal of the distance between the nodes. If there are no nodes k=0. If there are nodes between all atoms, k=/a
kn exp(ikna) n
0n n 0 + 1 + 2 + 2 +…
Strongly bonding
No nodes, k=0
/an exp(i /a na) n
n exp(in) n (alternating signs)
/a0 - 1 + 2 - 2 +…
Strongly anti-bonding
Nodes between all atoms, k=/a
E
/a k /2a
E(k)
Band widthIf the hydrogen atoms are at large
distances, they do not interact: a=5Å
E
/a k /2a
E
/a k /2a
a=0.5Å
A stack of square planar platinum PtL4
MonomerE
Pt PtL4 L4
p
s
d 4L
x2-y2
z
z2
yz
xz
xy
MonomerE
Pt PtL4 L4
p
s
d 4L
x2-y2
z
z2
yz
xz
xy
MonomerE
Pt PtL4 L4
p
s
d 4L
x2-y2
z
z2
yz
xz
xy
MonomerE
Pt PtL4 L4
p
s
d 4L
x2-y2
z
z2
yz
xz
xy
MonomerE
Pt PtL4 L4
p
s
d 4L
x2-y2
z
z2
yz
xz
xy
MonomerE
Pt PtL4 L4
p
s
d 4L
x2-y2
z
z2
yz
xz
xy
MonomerE
Pt PtL4 L4
p
s
d 4L
x2-y2
z
z2
yz
xz
xy
MonomerE
Pt PtL4 L4
p
s
d 4L
x2-y2
z
z2
yz
xz
xy
Dispersion – z2
Strongly bonding –strongly antibonding
Dispersion – z
Strong bonding –antibonding
Dispersion – z
Strong bonding – antibonding
Dispersion – xz, yz
Intermediate bonding – antibonding
Dispersion – x2-y2
Weak bonding – antibonding
PolymerE
x2-y2
z
z2
yz
xz
xy
PolymerE
x2-y2
z
z2
yz
xz
xy
PolymerE
x2-y2
z
z2
yz
xz
xy
PolymerE
Pt is d8
EF
k
EF
In oxidised systems, the Pt-Pt distance shortens. Why?
BS DOS COOP
Linear chain of hydrogen atoms
E
a
Linear chain of hydrogen atoms
E
k
Dispersion
a
Peierls distortion - H2
E
k
a-
a+
/a/2a
Peierls distrotion
E
k
/2a
The Brillouin zone
The Brillioun zone is the primitive cell of the reciprocal lattice. Special points in the Brillioun zone have particular properties and are therefore given special symbolms
Special points of the Brillouin zone
Two dimensions - Graphene
Face center Body centre Edge centre Face centre
All Pz orbitals in-phase, , Strongly -bonding
All Pz orbitals out-of-phase, , Strongly anti -bonding
Two dimensions - Graphene
Face center Body centre Edge centre Face centre
Pz, , K: non-bonding
Pz, *, : non-bonding
Pz, , : bonding
Pz, , : anti-bonding
bands –no gap at gap at
Px, , : strongly bonding, weakly anti-bonding
Px, *, : strongly anti-bonding, weakly bonding
Px, , : strongly bonding, weakly bonding
Px, *, : strongly anti-bonding, weakly anti-bonding
interactions in graphene
bands run down away from .
*bands run up away from
What’s the use?
Bonding and electronics. Graphene is strongly bonded. It is a zero bandgap semiconductor.
Copper – A Metal
DOS
E
EF
e-
e-
e-
Si has four valence electrons and achieves octet by bonding to four neighbours.
All electrons are taking part in bonding and the electronic conductivity is low
Silicon –A semiconductor
DOS
E
EF
Si Semiconductor
Fermi-Dirac: f(E) =[e(E-EF)/kT+1]-1
k≈8.6*10-5 eV/K
Eg in silicon ≈1eV
f(Eg+Ef)300K ≈ [e1/0.025+1]-1 ≈ e-40 ≈ 4*10-18
Silicon – Extrinsic (K,) excitation
DOS
E
EF
Excited electrons
Hole
e-
Silicon - Doping
DOS
E
EF