Hydrogen Atom

Atomic Structure
Periodic Table of Elements
 Potential Energy for the Hydrogen Atom (1)
 How do we describe the hydrogen
atom quantum mechanically? U(r)

 We need to specify U, the potential r

energy of the electron: 0
We assume that the Coulomb force
between the electron and the nucleus
is the force responsible for binding
the electron in the atom

e 2
U( r )   1
r   9  10 9 Nm2 / C 2
40

This spherically symmetric problem must be solved in

spherical coordinates.
SEQ in spherical coordinates

SEQ is separated into 2 parts:

What is wave function ?
 Product Wavefunction in Spherical Coordinates
 The solution to the SEQ in spherical coordinates
is a product wave function of the form:

 nlm ( r ,  ,  )  R nl ( r )Y lm ( ,  ) r z
y
with quantum numbers: n l and m
x 
principal orbital magnetic
(angular
momentum)
Rnl is the ‘radial part’, and Ylm are “spherical harmonics.” The
Schrödinger equation in spherical coordinates is complicated. An
appreciation of the problem can be gained by considering only spherically
symmetric states (wavefunctions with no angular dependence). For these
“s-states”, l = 0 and m = 0, and the ‘radial SEQ’ takes the form:
  2 1 2 s-state
e2 
 r  Rn0 ( r )  En Rn0 ( r ) Wavefunction:
 2m r r 2 r 
  ( r , , )  Rn0 ( r )
KE term PE term
 Radial Eigenstates of H
 The radial eigenstates, Rno(r) , for the electron in the Coulomb
potential of the proton are plotted below:

“s-state” wavefunctions
The zeros in the subscripts below are a reminder that these
are states with zero angular momentum.
1 1 1 1 3

R10
2
0.5 R20 d4( x)
R30
f( x) 0.5 h( x)

0 0
0 00 .2 0 .50
00 00 10a 00 r 15a
4a4 0
5 10 15 0
rx rx
2 5 10
0
0 4 0 10 0 x 15

  2r  r  2 
r   r / 2a0 R3,0 (r )   3   2  e r / 3a0
R1,0 ( r )  e  r / a0 R2,0 ( r )  1  e 
 2a0  
a0  3a0  

2
a0  = “Bohr radius” = 0.053 nm
me 2  e 2 1  13.6 eV
En  
Plug these into radial SEQ (Appendix)  2ao n 2 n2
 Probability Density of Electrons
Probability density = Probability per unit volume = 2  Rn02 for s-states
The density of dots plotted below is proportional to Rn02.
“1s state” “2s state”

1 1 1 1

R10 0.5 R20

f( x) 0.5 h( x)

0
.2 0
0 00
00 10a
00 rx
5 10
0
rx
2
4a4 0 0 10
0 4
 Radial Probability Densities for s-states
 Summary of wave functions and radial probability densities for some
s-states:

1 1
1 1
P10
R10
f( x) 0.5 g( x) 0.5
Question: If the
classical planetary
model were
00 0 0 00
0 0

00 r
2
4a 0
4
00 r
2
x
4a
4
4 0
correct, then
what would you
x 4
1 1

R20 .5
P20
0.4 expect for P(r)?
0.5
h( x)
h2( x)
0.2

00
00 0
.2

000 10a
0

r 0 rx5 10a
5 10
10 0
10
x
0 10
0
3

2 R30 P30
d4( x)

0
.5
0
0 00 5
rx
10
15a
15
15 0 0 r 20a0
radial wave functions radial probability densities, P(r)
 Optical Transitions in H -- Example
 An electron, initially excited to the n = 3 r/a0
energy level of the hydrogen atom, falls 00 5 10 15
20
20

to the n = 2 level, emitting a photon in 00

the process. What are the energy and E3
wavelength of the photon emitted?
-5 E2
E (eV)
U(r)
-10

-15-15 E1

Atomic hydrogen


l (nm)

Answer: 656 nm
 Optical Transitions in H --Example
 An electron, initially excited to the n = 3 r/a0
energy level of the hydrogen atom, falls to 00 5 10 15
20
20
the n = 2 level, emitting a photon in the
00
process. What are the energy and wavelength
of the photon emitted? E3
-5 E2
E (eV)
U(r)
-10

Therefore:
 1 1 
Eni n f  13.6  2  2  eV -15-15 E1
n n 
 i f 
1 1 Atomic hydrogen
E photon  E32  13.6    eV  1.9eV
9 4
1240eV  nm
l
hc
  656nm 
l (nm)
E photon 1.9eV

You will experimentally measure several transitions in Lab.

Angular Momentum,
Atomic States,
&
the Pauli Principle
 Quantized Angular Momentum
 The  dependence of our
wavefunction must have the form
Re() r
im
Yl ,m ( ,  )  e
Reminder: eim= cos(m) + i sin(m)

 Semi-classical ‘argument’ for angular momentum quantization: An integer
number, m, of wavelengths must fit around the circle (radius r) above!

2r = ml m = 0, 1,  2,  3, ... m = ‘orbital’ magnetic quantum

number
Quantization arises because only certain wavelengths fit around path.
But, l= h/pt, where pt is the tangential momentum of ‘orbiting’ electron:

pt r = Lz = m The angular momentum along a given axis

can have only quantized values:
m = 0, 1,  2,  3, ... Lz = 0, ,  2,  3, ...
 The “l” Quantum Number
 The quantum number m reflects the component of angular momentum
about a given axis.

Lz  m where m  0,  1,  2, ...
 The quantum number l in the angular wave function Ylm(,) tells the
total angular momentum L.
L2 = Lx2 + Ly2 + Lz2 is quantized. The possible values of L2 are:

L2  l( l  1 ) 2 where l  0 , 1, 2 , ..
Summary of quantum numbers for the H-atom:

Principal quantum number:

n = 1, 2, 3, ….
Orbital quantum number:
l = 0, 1, 2, …, n-1
Orbital magnetic quantum number:
m = -l, -(l-1), … 0, … (l-1), l ( = ml )
 Classical Picture of L-Quantization

e.g., l = 2 L  l( l  1 ) 2  2( 2  1 ) 2  6 
Lz L = 6 
+2

+ Classically, the
angular momentum
0 vector precesses
around the z axis.
- Lrp
-2

Why can’t the orbital angular momentum vector simply point in a

specific direction, e.g., along z?
If it did, then that would mean that r and p must both be in the x-y
plane. But that means that there would be no position uncertainty
z in the z-direction, nor any momentum uncertainty pz, i.e., z =
pz =0, in violation of the Uncertainty Principle.
 Probability Density of Electrons
Probability density = Probability per unit volume = nlm2  Rnl2 Ylm2
The density of dots plotted below is proportional to nlm2.

“1s state” “2s state” “2p states”

n= 1 2 2
l = 0 0 1
ml = 0 0 0, ±1
 The Angular Wavefunction, Ylm(,)
 The angular wavefunction may be written: Ylm(,) = P()eimwhere P()
are polynomial functions of .
 To get some feeling for these angular distributions, we make polar plots
of the -dependent part of |Ylm(,)| (i.e., P()):
(Length of the dashed arrow is the magnitude of Ylm as a function of .)
z z
z
l =0
Parametric Curve Parametric Curve

l =1
1.2 1.2

1 1

  Y10
|Y00
y( t )
|0 0 |Yx10(10t ) |0 0
y

Y0,0 
1
1.2 1
Y1,0  cos
1.2 1 x
4 1 0 1 1 0 1
1.2 z
x( t ) 1.2
1.2
1.2 y10( t )Curve
Parametric 1.2
z
1

Y00 
Re{Y11}
0  |Y110|
x11( t )
0
y
y

x Y1,1  sin 
1.2 1

1 0 1 x
The Angular Wavefunction, Ylm(,)
z
z
l=2
Parametric Curve
2 2

 Y20
|Yx20(20t )|0 y
x

Y2,0  3 cos 2   1 
z
2
1.2 2
Parametric Curve
2 0 2
1 2 y20( t ) 2

|Yx21(21t ) |0
Re{Y21}
y
Y2,1  sin  cos1.2 1
x
1.2
Parametric Curve
1 0 1
1 1.2 y21( t ) 1.2

 z
|Yx(22
t)
0| + -
Re{Y22} y
Y2, 2  sin  2
1.2 1
x - +
1 0 1
1.2 y( t ) 1.2
 The Angular Wavefunction, Ylm(,)
Why are these distributions important?

 They govern the bonding and chemistry of atoms.

 In particular, they determine the angles at which different atoms
“bond”. The structure of molecules & solids

Historical Labeling of Orbitals

Angular momentum quantum # Notation from spectroscopy

l=0 s “sharp”

l=1 p “principle”

l=2 d “diffuse”

l=3 f “fundamental”
Effect of l on Radial Wavefunctions Rn,l

General properties:
n=2 n=3
(1) l < n
Total energy must
always be larger than
l=0 l=0 rotational part
(2) Number of ‘wiggles’ in Rnl(r)
(i.e., radial kinetic energy term)
increases with decreasing l
l=1 l=1
More total energy E in
translational than rotation
E = Ttrans + Trot + U(r)
l=2
(3) # of zero-crossings
= (n – 1) - l
 Hydrogen Atom States: Summary
 Key Points:
 n: principal quantum # r/a0 20
0 5 10 15
 l: orbital quantum # 0
 ml: orbital magnetic quantum # n=3

 Energy depends only upon n n=2

-5
 e2 1 me 2e4 1
En  2

2a0 n 2 2 n2
E
U(r)
 For a given value of n, there -10
are n possible ang. momentum
states: l = n-1, n-2,..., 2, 1, 0
n=1

 For a given angular momentum -15

state l, there are 2l + 1
possible orientations with z-
axis ml = -l, -(l -1),…0,…(l -1), l Therefore, a level with quantum
number n has n2 degenerate states.
 Hydrogen Atom States: Summary

r/a0
0 5 10 15 20
(n,l,ml)
0
n=3 (3,0,0), (3,1,-1), (3,1,0), (3,1,1), (3,2,-2),
(3,2,-1), (3,2,0), (3,2,1), (3,2,2)
n=2 (2,0,0), (2,1,-1), (2,1,0), (2,1,1)
-5
n = 1, 2, 3,...
E
U(r) l = 0, 1, 2, .. n-1

-10
ml = -l, -(l - 1), ..0,… (l -1),
l
n=1 (1,0,0)

-15
 Stern-Gerlach Experiment
 In 1922, Stern and Gerlach shot a beam of Ag atoms through a non-
uniform magnetic field and detected them at a screen.

spin

You will analyze this experiment in detail in your discussion section.

The amazing result:

The beam split in two! This marked the discovery of the
electron spin. A new type of angular momentum, with a
quantum number that can take on only two values:
(s = ½)
ms = ±½
 B-field
B-field on:
off: No
Two peaks!
splitting

Gerlach's postcard, dated 8 February 1922, to Niels Bohr. It shows

a photograph of the beam splitting, with the message, in translation:
“Attached [is] the experimental proof of directional quantization. We
congratulate [you] on the confirmation of your theory.”
 Electron Spin - Zeeman effect
 The new kind of angular momentum is called the electron SPIN. Why
call it spin?
 If the electron were spinning on its axis, it would have angular
momentum and a magnetic moment regardless of its spatial motion.
 However, this “spinning” ball picture is not realistic, because it
would require that the tiny electron be spinning so fast that
parts would travel faster than c !
 So we can’t picture the spin in any simple way … the electron’s
spin is simply another degree-of-freedom available to electron

B0 EmB mzBz

B=0 meB
E 2meB| B
meB
me  9.2848 1024 J/Tesla -- electron magnetic moment
 mB = e /2me  9.27411024 J/Tesla (the "Bohr Magneton" related to orbital motion)
Note: All particles have spin (e.g., protons, neutrons, quarks, photons
 Electron Spin and Nuclear Spin
 So, we need FOUR quantum numbers to specify the electronic state
of a hydrogen atom
 n, l, ml, ms (where ms = - /2 and + /2)
1 1

 Actually, the proton in the H atom ALSO has a spin, which is

described by an additional quantum number, mp

 The energy difference between the two proton spin states in a

magnetic field is 660 times smaller than for electron spin states!
 But… There are many more unpaired proton spins than unpaired

electron spins in ordinary matter. Our bodies have many unpaired

protons in H2O. Detect them …...
 Nuclear Spin and MRI: Example
 Magnetic resonance imaging (MRI) depends on the absorption of
electromagnetic radiation by the nuclear spin of the hydrogen atoms
in our bodies. The nucleus is a proton with spin ½, so in a magnetic
field B there are only two possible spin directions with definite
energy. The energy difference between these states is E=2mpB,
with mp= 1.41 x 10-26 J /Tesla.
B0
B=0
E 2mpB B

Question 1: The person to be scanned by an

MRI machine is placed in a strong magnetic
field, with B=1 T being a typical value. What
is the energy difference between spin-up and
spin-down proton states in this field?

Question 2: What is the frequency f of photons

that can be absorbed by this energy difference?
 Nuclear Spin and MRI: Example
 Magnetic resonance imaging (MRI) depends on the absorption of
electromagnetic radiation by the nuclear spin of the hydrogen atoms
in our bodies. The nucleus is a proton with spin ½, so in a magnetic
field B there are the only two possible spin directions with definite
energy. The energy difference between these states is E=2mpB,
with mp= 1.41 x 10-26 J/Tesla.
B0
B=0
E 2mpB| B

Question 1: The person to be scanned by an

MRI machine is placed in a strong magnetic
field, with B=1 T being a typical value. What
is the energy difference between spin up and
down proton states in this field?
Solution:
E 2mpB = 2 x (1.41 x 10-26 J/T) x 1 T

= 2.82 x 10-26 J

= 2.82 x 10-26 J x 1 eV/ 1.6 x 10-19 J = 1.76 x 10-7 eV

 Nuclear Spin and MRI: Example
 Magnetic resonance imaging (MRI) depends on the absorption of
electromagnetic radiation by the nuclear spin of the hydrogen atoms
in our bodies. The nucleus is a proton with spin ½, so in a magnetic
field B there are the only two possible spin directions with definite
energy. The energy difference between these states is E=2mpB,
with mp= 1.41 x 10-26 J/Tesla.
B0
B=0
E 2mpB B

Question 2: What is the frequency f of photons

that can be absorbed by this energy difference?
 Nuclear Spin and MRI: Example
 Magnetic resonance imaging (MRI) depends on the absorption of
electromagnetic radiation by the nuclear spin of the hydrogen atoms
in our bodies. The nucleus is a proton with spin ½, so in a magnetic
field B there are the only two possible spin directions with definite
energy. The energy difference between these states is E=2mpB,
with mp= 1.41 x 10-26 J/Tesla.
B=0 B0

E 2mpB| B

Question 2: What is the frequency f of photons

that can be absorbed by this energy difference?
Solution:
Energy conservation: Ephoton = hf = E

so: f = E / h
= 2.82 x 10-26 J / 6.626 x 10-34 J-sec = 42 MHz

Radio waves
 Pauli Exclusion Principle - The Periodic Table
We now want to start building more complicated atoms to
study the Periodic Table. For atoms with many electrons (e.g.,
carbon: 6, iron: 26, etc.) - what energies do they have?

From spectra of complex atoms, Wolfgang Pauli (1925) deduced a new rule:

“Pauli Exclusion Principle”

“In a given atom, no two electrons* can be in the same quantum state,
i.e. they cannot have the same set of quantum numbers n, l, ml , ms”
-- I.e., every “atomic orbital with n,l,ml” can hold 2 electrons: ()

 Therefore, electrons do not pile up in the lowest energy state, i.e,

the (1,0,0) orbital.
 They are distributed among the higher energy levels according to

the Pauli Principle.

 Particles that obey the Pauli Principle are called “fermions”

*Note: More generally, no two identical fermions (any particle with

spin of ħ/2, 3ħ/2, etc.) can be in the same quantum state.
 Building Atoms and Molecules
+e +e
r

even
Plane of
hydrogen atoms

odd
Filling the atomic orbitals according to the
Pauli Principle
n s p d f g  13.6 eV 2
l=0 1 2 3 4
Energy En  Z

n2
is valid only for one electron in
4 the Coulomb potential of Z
3 protons. The energy levels shift
as more electrons are added,
due to electron-electron
2
interactions. Nevertheless, this
hydrogenic diagram helps us
keep track of where the added
electrons go.
Example: Na
l label #orbitals (2l+1)
0 s 1
Z = 11
1 p 3
1s22s22p63s1 2 d 5
3 f 7
1

Z = atomic number = number of protons

 exercise 1: Pauli Exclusion Principle
1. Which of the following states (n,l,ml,ms) is/are NOT
allowed?
(a). (2, 1, 1, -1/2)
(b). (4, 0, 0, 1/2)
(c). (3, 2, 3, -1/2)
(d). (5, 2, 2, 1/2)
(e). (4, 4, 2, -1/2)

2. Which of the following atomic electron configurations

violates the Pauli Exclusion Principle?

(a). 1s2, 2s2, 2p6, 3d10

(b). 1s2, 2s2, 2p6, 3d4
(c). 1s2, 2s2, 2p8, 3d8
(d). 1s1, 2s2, 2p6, 3d5
(e). 1s2, 2s2, 2p3, 3d11
 exercise 1: Pauli Exclusion Principle
1. Which of the following states (n,l,ml,ms) is/are NOT
allowed?
(a). (2, 1, 1, -1/2) ml = -l, -(l -1), … (l-1), l
(b). (4, 0, 0, 1/2)
(c). (3, 2, 3, -1/2)
(d). (5, 2, 2, 1/2) n>l
(e). (4, 4, 2, -1/2)

2. Which of the following atomic electron configurations

violates the Pauli Exclusion Principle?

(a). 1s2, 2s2, 2p6, 3d10 2(2l +1) = 6 allowed electrons

(b). 1s2, 2s2, 2p6, 3d4
(c). 1s2, 2s2, 2p8, 3d8
2(2l +1) = 10 allowed electrons
(d). 1s1, 2s2, 2p6, 3d5
(e). 1s2, 2s2, 2p3, 3d11
 Filling Procedure for Atomic Orbitals
Due to electron-electron interactions, the hydrogen levels fail to give us the
correct filling order as we go higher in the periodic table.
The actual filling order is given in the table below
As you learned in chemistry, the various behaviors of all the elements
(and all the molecules made up from them) is all due to the way the
electrons organize themselves, according to quantum mechanics.
 Optical Transitions between Atomic Levels
Consider the
hydrogenic picture:
r
U(r)
E c
n = 2
f  
E h l
n = 1
photon
hc 1240 eV  nm
l 
E E
In the field of a photon, the electron may be considered as being in a
superposition of two stationary states. The time-dependent solution of the SEQ
shows the wave function oscillating between the two eigenstates. Not all
transitions are possible  must conserve angular momentum (and photon has ħ!)
Superpositions
Stationary States: :
No electric- Forbidden
1s ± 2s
dipole moment transition
l = 0

1s ± 2p Oscillating Allowed
1s 2s 2p
electric-dipole transition
couples to l = ±1
www.falstad.com/qmatomrad photons

Each photon carries 1ħ of angular momentum

 Allowed Transitions for H
(You observed some of these transitions )
s p d f g
n Energy (eV)
l=0 1 2 3 4
 0.00
4 -0.85
3 -1.51
Selection Rule for
electric-dipole
transitions:
2 -3.40
l  1
(A few representative
transitions are shown.)
 13.6 eV
En 
n2
Selection Rule on m:
m  0, 1
photon is photon is
linearly circularly
polarized polarized
1 -13.6 eV
 Bonding between atoms
-- How can two neutral objects bind together?
H + H  H2

Continuum of
+e free electron
Let’s represent the atom r states.
in space by its Coulomb n=3
n=2
potential centered on the
proton (+e): e 2
n=1 U( r )  
r

In this picture the +e +e

potential energy of r
the two protons in an
H2 molecule look e 2 e 2
something like this: U( r )   
r  r1 r  r2

The energy levels for this potential are more complicated, so we consider a
simpler potential that we already know a lot about.
 Particle in a box
-- Finite square well potential
(analogue to Molecular binding)

Continuum of
If this were the free electron
‘atomic’ potential, Bound
states.

states

then this would be

the ‘molecular’
potential:

Again, we don’t know exactly what the energy levels are, but
 Just consider the ground state:

Let’s say that the

lowest energy level is
about equal to that of E
1.505 eV  nm 2
 0.4 eV
an infinite well: (2L)2

L = 1 nm

For convenience, we are going

to plot the electronic A
wavefunction with the energy
level as a baseline:
 ‘Molecular’ Wavefunctions and Energies
‘Atomic’
L = 1 nm
Wavefunctions:

A
1.505 eV  nm 2
E 2
 0.4 eV
(2L)

‘Molecular’ Wavefunctions: 2 ‘atomic’ states  2 ‘molecular’ states

even

odd

When the wells are far apart, ‘atomic’ functions don’t overlap. The
single electron can be in either well with equal probability, and E =
 ‘Molecular’ Wavefunctions and Energies
d L = 1 nm
Wells far apart:

even 1.505 eV  nm 2
E  0.4 eV
(2L)2

odd 1.505 eV  nm 2
E 2
 0.4 eV
(2L)

(“Degenerate” states)
Wells closer together:
d
‘Atomic’ states are
beginning to overlap and
even distort. 2even and 2odd are
not the same (note center
point). Energies for these
two states are not equal.
odd
(The degeneracy is
broken.)
 filling energy states in solids

Atom Solid
+e
r

n=3
E
n=2 F
n=1

Discrete atomic states  band of crystal states  Fill according to Paul

Principle
Why do some solids conduct current
and others don’t?

We need to consider
the how electrons fill

The Energy Bands in Solids

 Insulators, Semiconductors
and Metals
Energy bands and the gaps between them determine the
conductivity and other properties of solids.

 Insulators have a valence band which is full and a

large energy gap (few eV) E
 apply an electric field - no states of higher

energy available for electron

 Semiconductors are insulators at T = 0. They have a

small energy gap (~1 eV) between valence and
conduction bands, so they become conducting at
higher T.
insulators semi- metals
 Metals have an upper band which is only partly full
conductors
 apply an electric field - lots of states of higher

energy available for electron

 Electronic Conduction in Metals
--example: Na
Z = 11 1s22s22p63s1

3s N states

4N states
2s, 2p
N states
1s

The 2s and 2p bands overlap.

Basis # Bloch
functions Since there is only one electron in the n = 3 shell, we don’t states
(atomic states) need to consider the 3p or 3d bands of states, which
partially overlap the 3s band.

Fill the crystal states with

N = # atoms 11N electrons
 Electronic Conduction in Metals
--example: Na
Fill the Bloch states according to Total # atoms = N Total #
Pauli Principle: electrons = 11N
Z = 11
1s22s22p63s1

3s N states

4N states
2s, 2p
N states
1s
2N electrons fill these 8N electrons fill these
states. states.

These electrons are easily

The 3s band is only half promoted to higher states in
filled (N orbital states and N the band. Therefore, Na is a
electrons) good conductor.

Partially filled band  good conductor

 What about silicon?
Fill the Bloch states according Total # atoms = N
to Pauli Principle
Z = 14 1s22s22p63s23p2
Total # electrons = 14N

3s, 3p 4N states

2s, 2p 4N states

N states
1s
2N electrons fill these 8N electrons fill these
states. states.

By this analysis, Si should be a

It appears that, like Na, Si
good metal, just like Na.
will also have a half filled
band: The 3s3p band has But something special
4N orbital states and 4N happens for Group IV
electrons. elements.
 Energy Bands in Si
Fill the Bloch states according Total # atoms = N
to Pauli Principle Z = 14 1s22s22p63s23p2
Total # electrons = 14N

3s, 3p 4N states

2s, 2p 4N states

N states
1s
2N electrons fill these 8N electrons fill these
states. states.

In Si, the atomic states are There are 2 superpositions The s-p band splits into two:
hybrid combinations of s between neighbors:
and p states: Antibonding
states
Antibonding
Bonding
states
sp hybrid state
(Actually s + px + py + pz) Bonding
 Electronic Conduction in a Semiconductor
--example: Si Z = 14 1s22s22p63s23p2

Empty band at T = 0. valence electrons

(Conduction Band)

3s/3p Energy Gap  Poor conductor at T = 0

band Egap ≈ 1 eV

Filled band at T = 0
(Valence band)

The electrons in a filled band cannot contribute to conduction, because with

reasonable E fields they cannot be promoted to a higher kinetic energy. Therefore,
at T = 0, Si is an insulator. At higher temperatures, however, electrons are thermally
promoted into the conduction band:
Metal: scattering time t gets
Resistivity shorter with increasing T
1 m
  2 Semiconductor: number n of free
 ne t electrons increases rapidly with T
(much faster than t decreases)
Temperature, T (This graph only shows trends. A semiconductor has
much higher resistance than a metal.)
 Insulators, Semiconductors
and Metals
Energy bands and the gaps between them determine the
conductivity and other properties of solids.

 Insulators have a valence band which is full and a

large energy gap (few eV) E
 apply an electric field - no states of higher

energy available for electron

 Semiconductors are insulators at T = 0. They have a

small energy gap (~1 eV) between valence and
conduction bands, so they become conducting at
higher T.

insulators semi- metals

 Metals have an upper band which is only partly full
conductors
 apply an electric field - lots of states of higher

energy available for electron

 Summary
 Ability to conduct electricity is useful and common way to classify
different types of solids

Resistivity is defined by: I 1

J  E


A 
where J = current density and E = applied electric field
 Resistivity depends on the scattering time for electrons.

 Resistivity depends on the number of free electrons (carriers).

Example properties at room temperature:

Material Resistivity Carrier Type

(Wm) Density (cm-3)
Cu 2x10-8 1023 conductor
Si 3x103 1010 semiconductor
Diamond 2x1016 small insulator

 The structure as well as the bonding type determine the properties of a solid. Take
Physics 489 to learn all about the properties of solids.
 Bonding between atoms
-- How can two neutral objects bind together?
H + H  H2

Continuum of free
+e electron states.
We represented an atom r
n=3
by its Coulomb potential n=2
e 2
centered on the proton U( r )  
n=1 r
(+e):

+e +e
The potential r
energy of the two
protons in an H2 e 2 e 2
U( r )   
molecule look r  r1 r  r2
schematically like
this:
The wavefunctions for the molecule were the sum of 2 atomic
 Molecular Wavefunctions and Energies -- H2

+e
r
Atomic ground state: e 2
U( r )  
A r
n=1  ( r )  er / a 0

Molecular states:
+e +e +e +e
r r
even odd

Bonding state Antibonding state

Remember: These are single-electron states. Now we

will use the Pauli Exclusion principle to fill these states.
 Molecular Wavefunctions and Energies -- H2
The splitting between even and odd states increases as atoms get closer together:

Eodd Remember
 example from 2
square wells.
Eeven
d
d d
+e +e +e +e
r r

Anti-bonding
Eodd
Bonding Eeven

Now we fill these states with the 2 available electrons (one Pauli Principle puts
from each hydrogen atom) both electrons in the
bonding orbital.
 Simple model of a crystal
with covalent bonding
+e
r
Again start with
simple atomic state: A
n=1

Bring N atoms together forming a 1-d crystal (a periodic lattice).

(N atomic states N crystal states):

Energy
band

What do these crystal states look like?

 Simple model of a crystal
with covalent bonding

N

Highest energy orbital (N-1 nodes)

1

Lowest energy orbital (zero nodes)

 The “in between" states
Length of crystal, L
n
Lattice spacing, a

Envelope: eikx

The wave vector k has N possible values from k = /L to k = /a.

n
kn  n  1,2, ..... L/a N = L/a states
L
u(x) depends on the
Bloch Wavefunction for
 n (x)  u(x)e ikn x
atomic states involved:
electron in a solid:
2s-states

u(x) x

1s-states
x
 Bloch Wavefunctions and the Energy Band
For N = 6 there are six different
 n (x)  u(x)eikn x
superpositions of the atomic states that
form the crystal states
Highest energy wavefunction
Energy
6

5
4

3

2
Closely spaced
 energy levels in
1 this “1s-band”
Lowest energy wavefunction
Bloch Wavefunctions and the Free Electron Model
 n (x)  u(x)eik x n

2

Envelope: eikx

 Bloch wavefunction acts almost like free electron wavefunction:

2k 2  p2 
Free electron:  (x)  Ae ikx
Energy E   
 2m 
2m  
 2 kn2
Bloch wave:  n (x)  u(x)e ik n x
Energy E  m*  " effective mass"
2m *

 In a perfectly periodic lattice, an electron e-

moves freely without scattering from the
atomic cores !!
It’s in a stationary state –- the Bloch
wavefunction.
 Free Electron Model
 (x)  u(x)eikx (Bloch wavefunction)

 Electron in a periodic potential has a well defined wavevector and

momentum:
p  k (  h/l )
even though it is traveling in a complicated potential.

 If there is a defect in the crystal, the electron may scatter to another Bloch
state:

e-
 Also lattice vibrations break the periodicity – electrons in metals scatter
more at higher temperatures.
 Semi-classical Picture of Conduction

n = # free electrons/volume t =
time between scattering events
e-
E
Wire with
cross section J  nevdrift J = current density = I/A
A F = force = -eE
F eE
vdrift  at  t  t a = acceleration = F/m
m m
ne 2t ne 2t
J E  E   conductivity
m m
Metal: scattering time gets shorter
Resistivity with increasing T
1 m
  2
 ne t

Temperature, T
Introduction to the
Physics of Solids
U(r) a
r

6
5
4

3
2


1