Chapter 40/41: Quantum Mechanics

Wave Functions & 1D

Schrodinger Eq
Particle in a Box
Wave function
Energy levels
Potential Wells/Barriers &
Tunneling
The Harmonic Oscillator
The H-atom
Wave Equation for a String
For a wave on a string (1D) moving with speed , any wave function
must satisfy the wave equation (Ch. 15):
( )
, y x t
( ) ( )
2 2
2 2 2
, ,
1
y x t y x t
x v t
c c
=
c c
( )
, y x t
v
It has the following sinusoidal wave function as its fundamental solution:
( ) ( ) ( )
, cos sin y x t A kx t B kx t e e = +
where is the wave number and is the angular frequency
of the wave. [A and B determines the amplitude and phase of the wave.]
2 k t =
2 f e t =
By substituting the fundamental wave function into the PDE, we arrived at
the algebraic relation (dispersion relation) that and must satisfy:
Wave Equation for a String
2
2
2
k
v
e
=
( )
( ) ( ) ( ) ( )
,
cos sin sin cos k
y x t
A kx t B kx t A kx t B x
x
k k t
x
e e e e
c
c
= + = + (

c c
e
or vk e =
k
check...
1. Each spatial derivative of will pull out one k: ( )
, y x t
So, the 2
nd
order spatial derivative gives,
( )
( ) ( )
2
2
2
2
,
cos sin
y x t
A kx t x t k B k
x
k e e
c
=
c
(Obviously, dont
forget the signs.)
Wave Equation for a String
( )
( ) ( ) ( ) ( ) ( ) ( )
,
cos sin sin cos
y x t
A kx t B kx t A kx t B kx t
t t
e e e e e e
c
c
= + = + (

c

c
check...
2. Each time derivative of will pull out one : ( )
, y x t
So, the 2
nd
order time derivative gives,
( )
( ) ( )
2
2
2
2
,
cos sin
y x t
A kx t B kx t
t
e e e e
c
=
c
(Again, dont forget
the signs.)
e
Putting these back into the wave equation, we then have,
( ) ( )
2 2
2 2 2
, ,
1
y x t y x t
x v t
c c
=
c c
( ) ( )
( ) ( )
2
2 2
2 2
cos sin
1
cos sin
k k A kx t B kx t
A kx t B kx t
v
e
e
e
e e e

( =

2
2
2
k
v
e
=
Thus, the fundamental property of a mechanical wave
Wave Equation for a String
Putting the definitions for and back into the Dispersion relation, we
have the familiar relation for wavelength, frequency, and wave speed.
( ) ( )
2 2
2 2 2
, ,
1
y x t y x t
x v t
c c
=
c c
v f =
2t
2
f v
t
=

e k
2
2
2
or v f k
v
e

| |
= =
|
\ .
is intimately linked to the form of the wave equation !
Now, we will now try to use the same argument to find a wave equation for a
quantum wave function.
Now, from the de Broglie relations, the energy and momentum of this
quantum free particle must be related to its wave number and angular
frequency through:
Since the reference point for is arbitrary, we can simply take .
Then, the energy E of a free particle will simply be its kinetic energy,
Wave Equation for a Quantum Free
Particle
A free particle has no force acting on it. Equivalently, the potential energy
( ) U x
e
k
( )
0
x
F dU x dx = =
( ) U x
( ) 0 U x =
2 2 2
2
1
2 2 2
m v p
E mv
m m
= = =
must be a constant for all x, i.e.,
2
2
h
E hf f t e
t
= = =
2
2
h h
p k
t
t
= = =
2 2
2
k
m
e =

2
2
p
E
m
=
(non-relativistic)
We now assume the same fundamental sinusoidal form for the wave function of
a quantum free particle with mass m, momentum and energy :
Wave Equation for a Quantum Free
Particle
Thus, a correct quantum wave function for this free particle must satisfy this
quantum dispersion relation for and : e
k
E e =
( )
2 2
*
2
k
m
e =

( ) ( ) ( )
, cos sin x t A kx t B kx t e e + = +
p k =
(non-relativistic)
Recall from our discussion on the mechanical wave, we have the following:
t
c

c x
c

c
take out an over all k
factor from
( )
, x t +
take out an over all
factor from
( )
, x t +
e
2 2
2
k
m
e =

We can deduce that the PDE for the quantum wave function for this free particle
must involves:
Wave Equation for a Quantum Free
Particle
So, from the quantum dispersion relation,
Putting in the other constants and one additional fitting constant C, we have,
t
c

c
2
2
x
c
c
( ) ( )
2
2
2
, ,
2
x t x t
C
m x t
c + c+
=
c c

Wave Equation for a Quantum Free

Particle
Now, we substitute into our quantum wave function
into the proposed wave equation to solve for the fitting constant:
( ) ( ) ( )
, cos sin x t A kx t B kx t e e + = +
( )
( ) ( )
2
2 2
2 2
2
,
cos sin
2 2
x t
Ak kx t Bk kx t
m x m
e e
c +
( =

c

( ) ( )
2 2
cos sin
2
k
A kx t B kx t
m
e e = (

( )
( ) ( ) ( ) ( )
,
sin cos
x t
C C A kx t B kx t
t
e e e e
c+
= + (

c

( ) ( )
cos sin CB kx t CA kx t e e e = (

Wave Equation for a Quantum Free

Particle
Equating the two terms and using the equality , we have,
2 2
2
k
m

( ) ( )
cos sin A kx t B kx t e e (

e =
( ) ( )
cos sin CB kx t CA kx t e e (

A CB
B CA
=

In order for this equality to be true for all , all coeffs for cos and sin
must equal to each other,
( )
, x t
Substituting the first eq into the second, we have,
( )
2
1 B C CB C = =
Thus, the fitting constant is where .
2 2
2
k
m
e =

1 i =
C i =
With , the free particle quantum wave function can also be
written in a compact exponential form using the Eulers formula,
Wave Equation for a Quantum Free
Particle
Then, finally, putting everything together, we have the desired wave equation
for a quantum free particle,
B CA iA = =
( ) ( )
2
2
2
, ,
2
x t x t
i
m x t
c + c+
=
c c

( ) ( ) ( )
, cos sin x t A kx t i kx t e e + = + (

( )
( )
,
i kx t
x t Ae
e
+ =
This is the 1D Schrodingers Equation for a free particle.
(quantum wave function for a free particle)
Free Particle Wave Function &
Uncertainty Principle
The wave function for a free particle is
a complex function with sinusoidal real
and imaginary parts
A free particle exists in all space ,
| |
, +
& (wave function extends into all space & time)
but 0 & 0 (energy and momentum is fixed)
x t
p E
A = A =
A = A =
Note:
2 x p A A >
can still be satisfied. 2 t E A A >
&
More Realistic Particle (Wave Packets)
Under more practical circumstance, a particle
will have a relatively well defined position
and momentum so that both Ax and Ap will
be finite with limited spatial extents.
A more localized quantum particle can not be a
pure sine wave and it can be described by a
wave packet with a combination of many sine
waves.
( )
( , ) ( )
i kx t
x t A k e dk
e

+ =
}
(a linear combination
of many sine waves.)
The coefficient A(k) gives the relative proportion of
the various sine waves with diff. k (wave number).
Wave Packets
Recall: Combination of two sine waves
more localized than a pure sine wave.
Wave Packets (characteristic)
Ap smaller Ax bigger
Wave Packets (characteristic)
Ap bigger
Ax smaller
The is consistent with:
! x p A A >
Quantum Wave Function
In QM, the matter wave postulated by de Broglie is described by a complex-
valued wavefunction +(x,t) which is the fundamental descriptor for a quantum
particle.
x,t
Re/Im +(x,t)
+(x,t) is a complex-valued function of
space and time.
1. Its absolute value squared
gives the probability of finding the
particle in an infinitesimal volume dx
at time t.
2. For any Q problem:
The goal is to find for the
particle for all time.
Physical interactions involves
operations (A) on this wave
function:
Experimental measurements will
involve the products,
2
( , ) x t dx +
( , ) x t +
( , ) A x t +
( , ) A x t + ( , ) x t
-
+
Since is a probability, it has to be normalized !
Wave Function and Probability
2
*
( , ) ( , ) ( , ) x t x t x t + = + +
is called the probability distribution function (or probability density)
In other words,
2
+
x dx
is the probability in finding the particle in
the interval at time t. [ , ] x x dx +
(shaded area)
2
( ) ( , ) p x dx x t dx +
2
( ) ( , ) 1 p x dx x t dx
+ +

= + =
} }
(At any instance of time t, the particle must be somewhere in space !)
2
( , ) x t dx +
(Similar to the intensity of an electric field:
being proportional to the #of photons.)
2
I E
The Schrodinger Equation
In Classical Mechanics, we have the Newtons equation which describes the
trajectory x(t) of a particle:
m = F x
In EM, we have the wave equation for the propagation of the E, B fields:
2 2
2 2 2
, 1 , E B E B
x c t
c c
=
c c
(derived from Maxwells eqns)
In QM, Schrodinger equation prescribes the evolution of the wavefunction
for a particle in timet and space x under the influence of a potential energy U(x),
2 2
2
( , ) ( , )
( ) ( , )
2
x t x t
U x x t i
m x t
c + c+
+ + =
c c

(general 1D Schrdinger equation)

U(x)
The 1D Schrodinger Equation
As we have see,
- the first term (2
nd
order spatial derivative term) in the Schrodinger equation
is associated with the Kinetic Energy of the particle
- the last term (the 1
st
order time derivative term) is associated with the total
energy of the particle
- together with the Potential Energy term U(x)+ (x)
the Schrodinger equation is basically a statement on the conservation of
energy.
KE PE Total E + =
2 2
2
( , ) ( , )
( ) ( , )
2
x t x t
U x x t i
m x t
c + c+
+ + =
c c

Stationary States
For most problems, we can factor out the time dependence by assuming the
following harmonic form for the time dependence,
( , ) ( )
i t
x t x e
e

+ =
(Recall the free particle case: .)
( , )
ikx i t
x t Ae e
e
+ =
With , we can rewrite the time exponent in terms of E,
/
( , ) ( )
iEt
x t x e

+ =

/ E e =
is a state with a definite energy E and is called astationary state. ( , ) x t +
Note that,
2
* * / /
( , ) ( , ) ( , ) ( ) ( )
iEt iEt
x t x t x t x e x e

+ = + + =

2
* ( / / ) *
( ) ( ) ( ) ( ) ( )
i Et Et
x x e x x x
+
= = =

( ) x
is called the time-independent wave function.
The Time-Independent Schrdinger
Equation
Substituting this factorization into the general time-dependent Schrodinger
Eq, we have
( )
/ / /
( , )
( ( ) ) ( )
iEt iE iE t t
x t iE
i i i x x e E x e e
t t


c+ c
| |
= = =
|
c c
\ .

and,
2 2
2 2
/
( , ) ( )
iEt
x t d x
e
x dx

c +
=
c

RHS
LHS
2
/
2
2
( )
2
iEt
d x
e
dx m

/
( ) ( )
iEt
x e U x

+
/
( )
iEt
E x e

=

2 2
2
( )
( ) ( ) ( )
2
d x
U x x E x
m dx

+ =

(time dependence can

be cancelled out !)
More on Wavefunction
In general, the probability in finding the particle in the interval [a,b] is given
by:
2
( )
b
ab
a
p x dx =
}
Note: is not the probability density
is the probability density.
( ) x
Other physical observables can be obtained from (x) by the following operation:
2
( ) x
a b
x
p(x)
example (position x):
2
( ) ( ) x xp x dx x x dx


= =
} }
is called the expectation value (of x): it is the experimental
value that one should expect to measure in real experiments !
x
More on Wavefunction
In general, any experimental observable (position, momentum, energy, etc.)
O(x) will have an expectation value given by:
2
( ) ( ) O O x x dx

=
}
Expectation values of physically measurable functions are
the only experimentally accessible quantities in QM.
Wavefunction itself is not a physically measureable
quantity.
( ) x
Note:
O can be x, p, E, etc.
Standard Procedure in Solving QM
Problems with Schrodinger Equation
(with the time-independent Schrodinger Equation)
Given: A particle is moving under the influence of a
potential U(x).
Examples:
Free particle: U(x) =0
Particle in a box:
Barrier:
HMO:
0, 0
( )
,
x L
U x
elsewhere
s s

0
, 0
( )
0,
U x L
U x
elsewhere
s s

2
1
( ) '
2
U x k x =
Standard Procedure in Solving QM
Problems with Schrodinger Equation
Solve time-independent Schrodinger equation for (x) as a function of energy E,
with the restrictions:
and are continuous everywhere for smooth U(x).
is normalized, i.e.,
Bounded solution:
( ) x
( ) d x
dx

( ) x
2
( ) 1 x dx

=
}
( ) 0 x as x
Then, expectation values of physical measurable quantities can be calculated.
Particle in a Box
A 1-D box with hard walls:
(0) ( ) U U L = = (non-penetrable)
A free particle inside the box:
( ) 0 U x = (inside box)
No forces acting on the particle
except at hard walls.
P (in x) is conserved between
bounces
|P| is fixed but P switches
sign between bounces.
Classical Picture
Particle in a Box (Quantum Picture)
The situation can be described by the following potential energy U(x):
0, 0
( )
,
x L
U x
elsewhere
< <

2 2
2
( )
( ) ( ) ( )
2
d x
U x x E x
m dx

+ =

The time-independent Schrodinger equation is:

Recall, this is basically
KE PE Total E + =
Problem statement: For a given U(x), what are the possible wave functions (x)
and their corresponding energies E ?
Inside the box, , U(x) =0, and the particle is free. From before,
we know that the wave function for a free particle has the following form:
Wave functions for a Particle in a Box
0 x L < <
1 2
( )
ikx ikx
inside
x A e A e

= +
(linear combination of the two
possible solutions.)
where A
1
and A
2
are constants that will be determined later.
Outside the box, , and the particle cannot exist outside the box and ( ) U x =
( ) 0
outside
x = (outside the box)
At the boundary, x =0 and x =L,the wavefunction has to be continuous:
(0, ) (0, ) 0
inside outside
L L = =
2 2
2
k
E
m
| |
=
|
\ .

Wavefunctions for a Particle in a Box

Let see how this boundary condition imposes restrictions on the two
constants, A
1
and A
2
, for the wave function.
Using the Eulers formula, we can rewrite the interior wave function in terms
of sine and cosine:
( ) ( )
( ) ( )
1 2
1 2 1 2
( ) cos sin cos sin
cos sin
inside
x A kx i kx A kx i kx
A A kx i A A kx
= + +
= + +
Imposing the boundary condition at x =0,
( ) ( )
1 2 1 2
(0) cos0 sin0
inside
A A i A A = + +
( )
1 2
0 A A = + =
1 2
A A =
1
( ) 2 sin sin
inside
x iA kx C kx = =
(where C=2iA
1
)
ikx
e
+
ikx
e

Wavefunctions for a Particle in a Box

Now, consider the boundary condition at x =L:
( ) sin 0
inside
L C kL = =
For a non-trivial solution ( ), only certain sine waves with a
particular choice of wave numbers (k) can satisfy this condition:
0 C=
or , 1,2,3,
n n
n
k L n k n
L
t
t = = =
This implies that the wavelengths within the box is quantized !
2
2
n
n
k
t
t = =
L
nt
2
, 1,2,3,
L
n
n
= =
Allowed wavelengths are the ones which can fit within the box !
Wavefunction for a Particle in a Box
2 2
, 1,2,3,
n
n
L
n
k n
t
= = =
/ 2

3 / 2
L must fit an integral number of
half-wavelengths: 2
n
L n =
So,
( )
( ) sin sin ,
1,2,3,
n n
n
x C k x C x
L
n
t

| |
= =
|
\ .
=
(similar to standing waves on a cramped string)
2
5 / 2
Quantized Energies for a Particle in a
Box
Since the wave number k
n
is quantized, the energy for the particle in the box is
also quantized:
2
2 2 2 2 2 2 2 2
2 2
or , 1,2,3,
2 2 2 8
n
n
k n n n h
E n
m m L mL mL
t t | |
| |
= = = = =
| |
\ .
\ .

Note: the lowest energy

is not zero:
2
1
2
0
8
h
E
mL
= >
n =0 gives (x) =0
and it means no particle.
(n is called the
quantum number)
Probability and Wavefunction
Recall that | (x)|
2
(and not the wavefunction itself (x)) is the probability
density function. In particular,
2
2 2
( ) sin
n x
x dx C dx
L
t
=
gives the probability in finding the particle in an interval [x, x+dx] within the box.
Probability in Finding the Particle
Notes:
The positions for the particles are
probabilistic. We just know that it
has to be in the box but the exact
location within the box is uncertain.
Not all positions between x =0 and
L are equally likely. In CM, all
positions are equally likely for the
particle in the box.
There are positions where the
particle has zero probability to be
found.
Probability and Normalization
Although we dont know exactly where the particle might be inside the box,
we know that it has to be in the box. This means that,
2
( ) 1 x dx

=
}
2 2 2
0
sin 1
2
L
n L
C x dx C
L
t
| |
= =
|
\ .
}
(normalization condition)
So, the normalization condition fixes the final free constant C in the
wavefunction, . This then gives, 2 C L =
2
( ) sin
n
n x
x
L L
t
= (particle in a box)
Time Dependence
Note that with (x) found, we can write down the full wavefunction for the
time-dependent Schrodinger equation as:
/
( , ) ( )
iEt
n n
x t x e + =

Note that the absolute value for is unity, i.e.,
/
2
( , ) sin
iEt
n
n x
x t e
L L
t
| |
+ =
|
\ .

/ iEt
e

2
/ / / 0
1
iEt iEt iEt
e e e e

= = =

so that |+
n
(x,t)|
2
=| (x)|
2
is independent of time and probability density in
finding the particle in the box is also independent of time.
recall E hf e = =
Finite Square-Well Potential
Square-well with finite height
0
,
( )
0, 0
U elsewhere
U x
x L

=

s s

In Newtons mechanics, a particle

will be trapped inside the well if
E <U
0
. In QM, such a trapped
state is called a bound state.
If E >U
0
, then the particle is not bound.
For the infinitely deep well (as in the
particle in a box problem), all states
are bound states.
For a finite square-well, there will
typically be only a finite number of
bound states.
Finite Square-Well Potential
Similar to the particle in a box problem, U(x) =0 inside the well, we have
2
2
2
1 2
( ) 2
( ), where
( )
ikx ikx
d x mE
k x k
dx
x Ae A e

= =
= +

and A, B are constants to be determined by boundary conditions and normalization.
(inside the well)
But for a finite square-well potential, the wavefunction is not identically zero
outside the well. The Schrodinger equation is given by:
( )
( )
2
2
2
0
0
2
2
( )
( ) ( ), where
m
U E
m U E
d x
x x
dx
k

k

= = =

(outside the well)
( ) cos sin
inside
x A kx B kx = + or,
Finite Square-Well Potential
( )
x x
x Ce De
k k

= +
Since U
0
>E, k is positive and the wavefunction outside the well is given in
terms of exponentials instead of harmonic functions:
where C and D are constants to be determined by B.C. and normalization again.
wavefunction must remain finite (not blowing up) at large |x|
For this problem, there is a new type of B.C. at large distances from the origin:
0
( ) and ( )
x x
x x L
x Ce x De
k k


< >
= =
Finite Square-Well Potential
As in the particle in a box problem, both and must also be
continuous at x =0 and x =L.
( ) x ( )/ d x dx
Matching
0
( ), ( ), and ( )
x inside x L
x x x
< >
at x =0 and x =L will enforce a certain
set of allowed functions to be fitted within the well and the bound state
energy is correspondingly quantized.
Example: e in a Square-Well/Quantum
Dot
An electron trapped in a Square-Well potential with width L =0.5nm (~size of
an atom)
a) What is ground state energy if this
well is infinitely deep U
0
= instead ?
b) Now, back to a finite well with

,1
E

0 ,1
6 9.0 U E eV

= =
( )
( )( )
2
2 34
2 2
,1
2 2
31 9
19
1.055 10
2
2 9.11 10 0.50 10
2.4 10 1.50
J s
E
mL
kg m
J eV
t
t

= =

= =

The energy levels for the finite well are

given as shown on the next slide.
(not derived here)
Example: e in a Square-Well/Quantum
Dot
=0.94eV
=3.6eV
=7.6eV
What is the wavelength of light released if
the electron was originally at the 1
st
excited state (n=2) and relaxed back to the
ground state (n=1)?
( )
( )
2 1
2 1
1240
460
3.6 0.94
hc
hf E E
eV s
hc
nm
E E eV eV

= =

= = =

Example: e in a Square-Well/Quantum
Dot
D
Qdot
Application: Quantum dots are nanometer-sized
particles of a semi-conductor (such as cadmium
selenide or gallium arsenide).
An electron within a quantum dot behaves much
like a particle in a finite square well potential.
When a quantum dot is illuminated by a
ultraviolet light, the electron within the quantum
dot can be excited to a higher energy state (let say, n=3) from ground state (n=1).
When it relaxed back to the ground state thru the intermediate state (n=2): [32
and 21] photons with lower energy (longer wavelengths in the visible range)
can be observed (fluorescence) !
Tunneling Through a Barrier
Consider the following potential barrier:
0
, 0
( )
0,
U x L
U x
elsewhere
s s

A quantum particle with mass m and energy

E is traveling from the left to the right.
Classical Expectation(with E <U
0
):
In the region x <0, the particle is free but when it reaches x =0, the particle will
hit a wall since its E is less than the potential at x =0. It will be reflected back
and it could not penetrate the barrier!
Tunneling Through a Barrier
Quantum Picture:
x <0 andx >L (free space):
The wavefunction for a free
particle with definite E and
P is sinusoidal, e
ikx
or e
-ikx
.
(inside the barrier): 0 x L s s
0
E U <
wavefunction is a
decaying exponential e
-kx
.
exponential function within barrier
Tunneling Through a Barrier
If the energy is high enough and the barrier is not too wide so that the
exponential decay does not significantly diminish the amplitude of the
incidence wave, then there is a non-zero probability that a quantum particle
might penetrate the barrier.
(reduced amplitude reduced probability but not zero probability !)
The transmission probability T can be solved from the Schrodinger equation
by enforcing the boundary conditions:
( )
0
2
0 0
2
, , 16 1
L
m U E
E E
T Ge G
U U
k
k

| |
= = =
|
\ .

(for E/U
0
small)
Application of Tunneling (STM)
Scanning Tunneling Microscope (STM):
In a STM, an extremely sharp conducting needle is
brought very close to a surface that one wants to
image.
When the needle is at a positive potential with
respect to the surface, electrons from the surface can
tunnel through the surface-potential energy barrier.
The tunneling current
detected will vary
sensitively on the
separation L of the
surface gap and
these variations can be used to map surface features.
The Harmonic Oscillator
Classically, the harmonic oscillator can be envisioned as a mass m acted on by
a conservative force: (Hookes Law: mass on a spring). Its associated
potential energy is the familiar:
' F k x =
2
1
( ) '
2
U x k x =
For a classical particle with energy E,
the particle will oscillate sinusoidally
about x =0 with an amplitude A and
angular frequency . ' k m e =
where k is the spring constant.
The Harmonic Oscillator
The Harmonic Oscillator is important since it is a good approximation for
ANY potential near the bottom of the well. ( ) U x
The Harmonic Oscillator
For the Quantum analysis, we will use the same form of the potential energy
for a quantum Harmonic Oscillator.
2 2
2
2
( ) 1
' ( ) ( )
2 2
d x
k x x E x
m dx

+ =

And we have the following quantized energies:

2
2
2 2
( ) 2 1
' ( )
2
d x m
k x E x
dx

| |
=
|
\ .

The solutions for this ordinary differential equation with the boundary
condition are called the Hermite functions:
or
( ) 0 x as x
Boundary condition consideration: U(x) increases without bound as
x
so that the wavefunction for particle with a given energy E must vanish at large x.
2
' 2
( )
mk x
x Ce

=

1
, 0,1,2,
2
n
E n n e
| |
= + =
|
\ .

(ground state n=0)
The Harmonic Oscillator
Hermite Functions
note: similar to previous
examples, the lowest E
state is not zero.
note: wavefunction penetration into
classically forbidden regions.
1
, 0,1,2,
2
n
E n n e
| |
= + =
|
\ .

The Harmonic Oscillator
Probability Distribution Function:
Classically, the particle with energy E
will slow down as it climbs up on both
side of the potential hills and it will
spend most of its time near . x A =
The bluecurve depicts this classical
behavior and the QM ~CM as the
quantum number n increases.
The H-atom
Important pre-notes:
e
-
does not exist in well-defined circular orbits around
the nucleus as in the Bohrs model.
e
-
in a H-atom should be envisioned as a cloud or
probability distribution function.
The size and shape of this cloud is described by the wavefunction for the H-
atom and it can be explicitly calculated from the Schrodinger equation:
2 2 2 2 2
2 2 2
0
1
2 4
e
E
m x y z r


tc
| | c c c
+ + =
|
c c c
\ .

(in 3D)
The H-atom
In the Schrodinger equation, we have
explicitly included the Coulomb potential
energy term under which the electron
interacts with the nucleus at the origin:
2
0
1
( ) ,
4
e
U r
r tc
=
2 2 2
r x y z = + +
is the radius in
spherical coordinates.
Electron Probability Distributions
In 3D, the probability in finding the electron in a given volume dV is given by,
2
( , , ) x y z dV
A good way to visualize this 3D probability distribution is to consider a
thin spherical shell with radius r and thickness dr as our choice for dV:
2
4 dV r dr t =
We denote the probability of finding the electron within this
thin radial shell as the radial probability distribution
function P(r) with:
2 2
2
( ) 4 P r dr dV r dr t = =
r
dr
Electron Probability Distributions
Examples of the 3-D probability distribution function | |
2
(electron cloud):
2
11
0
2
4
5.29 10 a m
me
tc

= =

is the Bohrs radius which we

have seen previously.
The corresponding radial probability distribution function P(r):
More Electron Probability
Distributions
Quantum Number
Recall that for a particle in a 1D box, we have one quantum number for the total
energy of the particle.
It arises from fitting the
wavefunction [sin (ntx/L)] within a
box of length L (quantization).
/ 2

3 / 2
2
5 / 2
In the H-atom case, we are in 3D, the fitting of the wavefunction in
space will result in 2 additional quantum numbers (a total of 3).
Quantum Numbers
1. n Principle Quantum Number: related to the quantization of the main energy
levels in the H-atom (as in the Bohrs model).
2
13.6
, 1,2,3,
n
eV
E n
n
= =
The other two related to the quantization of the orbital angular momentum of
the electron. Only certain discrete values of the magnitude and the component
of the orbital angular momentum are permitted:
Quantum Numbers
2. l Orbital Quantum Number: related to the quantization of the magnitude of
the e
-
s orbital angular momentum.
( ) ( )
1 , 0,1,2, , 1 L l l l n = + =
(note: in Bohrs model, each energy level (n) corresponds to a single value of
angular momentum. In the correct QM description, for each energy level (n), there
are n possible values for L.)
3. m
l
Magnetic Quantum Number: related to the quantization of the direction
of the e
-
s orbital angular momentumvector.
, 0, 1, 2, ,
z l l
L m m l = =
(By convention, we pick the z-direction be the relevant direction for this
quantization. Physically, there are no preference in the z-direction. The other
two directions are not quantized.)
Magnetic Quantum Number
Illustrations showing the relation between L and L
z
.
Zeeman Effect
Experimentally, it was found that under a magnetic field, the energy levels of
the H-atom will split according to the magnetic quantum number m
l
.
Semi-classical explanation:
e
-
B
L
e
-
orbits around the nucleus and it forms a
current loop. L
z
measures the orientation of
L with respect to B and thus affects the
energy level of the H-atom.
Anomalous Zeeman Effect
Additional experiments shows that some of the Zeeman lines are further split.
Predicted with
alone
l
m
Electron Spins
In 1925, using again semi-classical model, Samuel Goudsmidt and George
Uhlenbech demonstrate that this fine structure splitting is due to the spin
angular momentum of the electron and this introduces the 4
th
quantum number.
4. Spin Quantum Number: The electron has another intrinsic physical
characteristic akin to spin angular momentum associated with a spinning top.
Pauli and Bohr
This quantum characteristic did not come out from
Schrodingers original theory. Its existence requires
the consideration of relativistic quantum effects
(Diracs Theory).
1
,
2
z s s
S m m = =
The direction of the spin angular momentum S
z
of the
electron is quantized:
1
( 1) ,
2
s
S s s s m = + = =
Pauli Exclusion Principle
In order to understand the full electronic structures of the all the elements beyond
the simple single-electron H-atom, we need another quantum idea. In 1925,
Wolfgang Pauli proposed the Paulis Exclusion Principle:
no two electrons can occupy the same quantum-mechanical
state in a given system, i.e., no two electrons in an atom can
have the same set of value for all four quantum numbers (n, l,
m
l
, m
s
).
The Paulis Exclusion Principle +the set of the four quantum numbers give the
complete prescription in identifying the ground state configuration of e
-
s for all
elements in the Periodic Table. Then, all chemical properties for all atoms
follow !
Additional electrons cannot all crowded into the n =1 state due to the
Paulis Exclusion Principle and they must distribute to other higher levels
according to the ordering of the four quantum numbers.
Wavefunction Labeling Scheme
We have identified 4 separate quantum numbers for the H-atom (n, l, m
l
, m
s
).
For a given principal quantum number n, the H-atom has a given energy and
there might be more than one distinct states (with additional choices for the
other three quantum numbers). The fact that there are more than one distinct
states for the same energy is call degeneracy.
And, states with different orbital
quantum numbers are labeled as:
0:
1:
2:
3:
4:
5:
l s subshell
l p subshell
l d subshell
l f subshell
l g subshell
l h subshell
=
=
=
=
=
=
Historically, states with different
principal quantum numbers are
labeled as:
1:
2:
3:
4:
n K shell
n L shell
n M shell
n N shell
=
=
=
=
Wavefunction Labeling Scheme
m
l
andm
s
are
not labeled by
this scheme.
Filling in the Ground State: Example
1 filled, 1
free space
H-atom (Z =1 one e
-
)
n =1, l =0
E
Helium (Z =2 two e
-
)
n =1, l =0
E the lowest
level is
now full
Lithium (Z =3 three e
-
)
n =1, l =0
E
Last electron must go to n=2, l=0
level by Paulis Exclusion
Principle.
n =2, l =0
n =2, l =1
}
n =2 level
1 0 1
l
m = +
Filling in the Ground State: Example
Sodium (Z =11)
n =1, l =0
E
n =2, l =0
n =2, l =1
n =3, l =0
1 0 1
l
m = +
Spectroscopic Notation in the Periodic
Table
Typically, only the outer most shell (including the subshells within the outer
most shell) is labeled.
1
2
2 4
1
1
2 2
H s
He s
O s p

#of e
-
in that subshell
shell n value subshell l value
Z = 8
outer shell
is n =2
two subshells
(l =0 and l =1)
s p
( 0): 0
( 1): 1,0,1
l
l
s l m
p l m
= =

= =

only 2 max slots

6 max slots with
4 taken
8 electrons to fill, 2 will fill K shell
and 6 remaining will need to go to L shell:
Ground-State Electron Configurations