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QUANTUM MECHANICS
(PHYS4010) LECTURE NOTES
2011
YORK UNIVERSITY
2
CONTENTS
V. Hermitian Operators 10
IX. Commutators 16
XIV. Tunneling 24
XVII. Hydrogen 32
XIX. Spin 45
XXI. Entanglement 51
1. To every observable there corresponds an operator. For example to the observable A(e.g. energy,momentum,
position, etc.) there corresponds an operator Â. Every measurement of A gives a value, a, s.t. a is an eigenvalue
of the operator Â. i.e. for an eigenfunction of A, φ, Âφ = aφ.
2. Measurement of observable A yields the value a, and then leaves the state in the state φa . i.e.
Aφa = aφa
∂Ψ(r, t)
i~ = ĤΨ(r, t) (I.1)
∂t
B. Important Properties
Experimentally this would be done by preparing an ensemble of identical initial states Ψ(r, 0) and measure C at time
t. This will generate a set of values, c1 , c2 , c3 , ..., cN (where N is the number of measurements)
N
1 X
hCi = ci (I.3)
N i=1
probability to find
particle at point x
z }| {
|Ψ|2 dx = P (x)dx (I.7)
ˆ
Suppose Ĥ doesn’t depend on time. (i.e. Ĥ = H(r). Assume Ψ(r, t) = φ(r)T (t)) Plugging this result into the
SWE:
∂(φT )
i~ = ĤφT (I.9)
∂t
∂T
i~φ = T Ĥφ (I.10)
∂t
Divide both sides by ψ:
f g
z }| { z }| {
1 ∂T 1
i~ = Ĥφ (I.11)
T ∂t φ
Thus f (t) = g(r) (regardless of t and r) The only way this can be true is if f (t) = g(r) = E where E is some constant.
This generates two equations
∂T
i~ = ET (I.12)
∂t
and
Ĥ φ̂ = Eφ (I.13)
Notice that equation I.13 contains all the physics of the problem while the time equation contains no physics (does
not contain the Hamiltonian). Equation I.12 can be solved by:
Thus if the problem is seperable then the time dependance is always given by the above equation. All this term does
is changes the phase of the wavefunction (shifts the magnitude of the wavefunction from the real and complex part
of the wavefunction). This time dependence is often referred to as trivial time dependence.
Equation I.13 is an eigenvalue problem. E is the eigenvalue and φ is the eigenfunction of the operator Ĥ. There
are typically infinitely many solutions:
Ĥφn = En φn (I.15)
With
∂Ψ
i~ = ĤΨ (I.18)
∂t
∂Ψ −i
⇒ = ĤΨ (I.19)
∂t ~
∂Ψ Ĥ
⇒ +i ψ =0 (I.20)
∂t ~
∂
⇒ exp(itĤf /~)Ψ(r, t) = 0 (I.21)
∂t
1. Notice that in the factor exp( it~Ĥ ), Ĥ is an operator (could be a matrix). This can be understood by the real
definition of the exponential function (a power series expansion):
itĤ (itĤ)2
exp(itĤ/~) = 1 + + 2 + ... (I.22)
~ ~ 2!
This operator is defined as:
!
−1 itĤ
Û ≡ exp (I.23)
~
Hence in this special case the time ordering operator is just the trivial phase found earlier.
Lecture 3
Step 1:
Write down the potential
(
V =0 0<x<a
V (x) = (II.1)
V (x) = ∞ x ≤ 0, x ≥ a
Step 2:
Write down the S.E.
~2 ∂ 2 ∂Ψ
− Ψ + V (x)Ψ = i~ (II.2)
2m ∂x2 ∂t
The time portion is given by (assuming a separable solution)
~2 ∂ 2
− φ(x) + V (x)φ(x) = Eφ(x) (II.4)
2m ∂x2
Step 3:
Outside the box the solution is trivial. It is zero.
Inside the box the equation is given by
∂2
φ(x) = −k 2 φ(x) (II.5)
∂x2
Where k is given by
2mE
k2 = (II.6)
~2
The solution is given by
φ(x) = A sin(kx) + B cos(kx) (II.7)
Step 4:
Check the boundary conditions
φ(0) = 0 = B (II.8)
φ(a) = 0 = Asin(ka) (II.9)
(II.10)
Hence we have the trivial solution (no particle) unless
ka = nπ ( n is an integer) (II.11)
r
2mE
a = nπ (II.12)
~2
nπ 2 ~2
⇒ En = (II.13)
a 2m
Hence E developed an index and energy quantization came out. Note that k also has an index:
nπ
kn = The wave-number is also quantized (II.14)
a
nπx
φn (x) = A sin (II.15)
a
Note the energy levels rise rapidly they go as n2 . Note we were dealing with a homogeneous differential equation and
hence isn’t fixed yet. This can be done using the normalization condition:
(II.16)
Z ∞ Z a nπx
|φn |2 dx = A2 sin2 dx (II.17)
−∞ 0 a
a
A2 =1 (II.18)
2
Hence
r
2
A= (II.19)
a
Notice that the normalization constant is independent of the particular quantum number n.
Therefore
r
2 nπx n2 ~2 π 2
φn (x) = sin , En = (II.20)
a a 2ma2
7
Since the energy increases with decreasing a it means that quantum mechanics opposes this motion. This can be
thought of as a quantum mechanical pressure on the outside of the box.
Note that n can equal any integer
n = 1, 2, ... ( Infinity many bound states) (II.21)
√
Note the dimensions of φ are 1/ L and the dimensions of the P (the probability density) is 1/L. The energy levels
FIG. 1. The Wavefunctions of the Square Well and Their Corresponding Probability Densities
as well as the corresponding wavefunctions are shown in figure 1. Typically there are as many quantum numbers as
dimensions of the problem.
Def 1. In any problem as ~ → 0 we recover classical physics. Equivalently we can recover classical physics as E → ∞.
In our problem as E becomes large we should recover the classical distribution. The classical distribution is given
by
(
1/a 0<x<a
P (x) = (II.22)
0 x ≤ 0, x ≥ a
In the limit of large E, we have a highly oscillating function from 0 to 2/a. For any experiment that tries to measure
how likely it is we will get to any finite region it will be 1/a.
Assignment: Demonstrate by direct substitution that the first 5 eigenfunctions of the 1d well are indeed eigenfunctions
of the potential. Plot the first 5 eigenfunctions as well as the first 5 probability distributions. Due date: Wednesday.
The Dirac notation is a more abstract notation then was used up till now though it is more powerful. There is a
corresponding notation in geometry referred to as coordinate free notation. The idea is a vector has a meaning before
a coordinate system is assigned to it. Similarly in quantum mechanics we have states which are independent of a
particular representation.
A state labeled by a quantum number α is denoted by a “ket”. The symbol for the ket of α
|αi (III.1)
In the spatial representation the state |αi is given by Ψα (x). For example
Z ∞
hα|βi = ψβ∗ (x)ψa (x)dx (III.2)
−∞
8
A·B (III.3)
Thus the wavefunctions are infinite dimension vectors. In coordinate free notation equation III.2 is given by
hβ|αi (III.5)
hβ| (III.6)
This makes sense since this expression reads what is the amplitude that a state |x0 i coincides with the state |x|. These
two states are distinctly different unless x = x0 . The overlap of a position with the state α is
This expression can be read as what is the amplitude that a state α is at x. Suppose you have a complete set of states
labeled by integers (an orthonormal set):
X
|ni hn| = Iˆ (III.14)
n
1
Ψ(x, t) = √ φ1 (x)e−iω1 t + φ2 (x)e−iω2 t
(III.20)
2
~2 π 2
E1 = ~ω1 = (III.21)
2ma2
Continuing with the lecture
Dual vectors are the objects that come from the scalar product with kets.
Z
hα|βi = ψα∗ (x)ψβ (x)dx (III.26)
Aside (Cultural):The place where these are completely different objects are in differential geometry (general relativity).
The objects dual to vectors are called one-forms. Maxwell’s equals can be written in differential geometry language
as:
dF = 0 (III.27)
d∗F =J (III.28)
v = (vx , vy , vz ) (IV.1)
v = êx vx + êy vy + êz vz (IV.2)
We say that (êx , êy , êz ) form a basis that spans the vector space. In other words we can build any vector in the vector
space by a linear combination of the basis vectors.
Inner Product:
v · u = vx ux + vy uy + vz uz (IV.3)
Length:
√
v · u = |v| (IV.4)
Def 2. Cauchy Sequence: A sequence that as we go on in the sequence the difference gets smaller and smaller
between neighboring number.
X
|αi = am |mi (IV.8)
m
X
hn|αi = hn |am | mi (IV.9)
m
X
= am hn|mi (IV.10)
m
X
= am δn,m (IV.11)
m
= an (IV.12)
Word of warning: Sometimes we choose basis sets in H that are labeled by a continuous valued label. An example of
this is the wave number: |ki. This can be used as:
hx|ki = eikx (IV.13)
Z Z ∞
k| |x| hx| k dx = (1)dx = ∞ (IV.14)
x −∞
The reason the overlap is infinity is because the plane waves are non-normalizable.
V. HERMITIAN OPERATORS
D E
Consider the operator  such that  |αi is also in H and β|Â|α . If there is another operator designated by †
such that
D E D E
† β|α = β|Âα (V.1)
Then we say that † is the Hermitian adjoint of  (It does not mean that  is hermitian).
Simplest possible operator  = a (where a is some number)
†
a β|α = hβ|aαi = a hβ|αi = ha∗ β|αi
(V.2)
Hence a† = a∗ . i.e. the hermitian adjoint of a complex number is its complex conjugate.
∂
Consider the operator D̂ = ∂x .
D E Z ∞ ∂
β|D̂α = dxψβ∗ (x) ψα (x) (V.3)
−∞ ∂x
11
By integration by parts:
∞ 0 Z ∞
∗
:
∂ ∗
−
= ψβ(x)ψ β (x)
dx ψ (x) ψα (x) (V.4)
−∞ −∞ ∂x β
† =  (V.6)
∂ ∂ † ∂
Lecture 7 - Sept 21, 20111 Recall ∂x is not Hermitian, but ∂x = − ∂x .
Consider
Then
D E
n  n = hn |an | ni (V.8)
= an hn|ni (V.9)
(V.10)
= an hm|ni (V.14)
But
D E D E
m  n = † m|n (V.15)
D E
= Âm|n (V.16)
= ham m|ni (V.17)
= a∗m hm|ni = am hm|ni (V.18)
Therefore
If an 6= am then
hm|ni (V.20)
Suppose f (x) is periodic with period 2. i.e. For some a and all n:
f (x + na) = f (x) (VI.1)
Then we can write
( P∞
a0
2 + n=1 an cos(nx) for odd f
f (x) = P∞ (VI.2)
n=1 bn sin(nπx) for odd f
Where for all n:
Z 2 Z 2
an = f (t) cos(nπt)dt bn = f (t) sin(nπt)dt (VI.3)
0 0
Exercise: Prove that any function can be written as a Fourier expansion
For any interval -L to L for a general periodic function:
∞
a0 X nπx nπx
f (x) = + an cos + bn sin (VI.4)
2 n=1
L L
Where
Z L
1 nπt
an = f (t) cos dt (VI.5)
L −L L
1 L
Z
nπt
bn = f (t) sin dt (VI.6)
L −L L
For an example consider the square wave:
(
0 −π <x<0
f (x) = (VI.7)
1 0<x<π
a0 = 1 (VI.8)
1 π
Z
an = cos (nt) dt = 0 It is an odd function shifted upwards (VI.9)
π 0
1 π
Z
bn = sin (nt) dt (VI.10)
π 0
1 1 cos nπ
= − (VI.11)
π n n
1
= (1 − (−1)n ) (VI.12)
nπ
Therefore
(
2
nπ odd n
bn = (VI.13)
0 even n
1 2 sin 3x
f (x) = + sin x + + ... (VI.14)
2 π 3
The orthogonality statement
Z 2π
sin (mx) sin (nx) = πδnm Unless m = n = 0 (VI.15)
0
Z 2π
cos (mx) cos (nx) = πδnm (VI.16)
0
Z 2π
sin (mx) cos (nx) = πδnm = 0 Unless m = n = 2π (VI.17)
0
13
Where
Z L
1 nπt
an = f (t) cosdt (VII.2)
L
−L l
1 L
Z
nπt
bn = f (t) sin dt (VII.3)
L −L L
Explicitly:
πnx Z L ∞ nπx Z ∞
1 1 nπt 1X nπt
f (x) = f (t)dt + cos f (t) cos dt + sin f (t) sin dt (VII.4)
2L L L −L L L n= L −L L
Z L ∞ Z
1 1X L nπ
= f (t)dt + f (t) cos (t − x) dt (VII.5)
2L −L L n= −L L
Notice that in the integrand we have an even function of ω. Therefore we can divide by 2 and change the ω integral
to:
Z ∞ Z ∞
1
f (x) = dω f (t) cos (ω (t − x)) dt (VII.9)
2π −∞ −∞
Now notice that the limits are symmetric so we can add an odd function of ω in the integrand (it will just go to zero
anyways)
Z ∞ Z ∞
1
f (x) = dω f (t) cos (ω (t − x)) + if (t) sin (ω (t − x)) dt (VII.10)
2π −∞ −∞
Z ∞ Z ∞
1
= dω f (t)e−iω(t−x) dt (VII.11)
2π −∞ −∞
F −1 (x) F (ω)
zZ }| {Z
z }| {
∞ ∞
1
= eiωx dω f (t)e−iωt dt (VII.12)
2π −∞ −∞
Each of these F are transformations on the function f (t). Whatever the first one does, the second one undoes. F is
called the Fourier transform of f (t). F −1 (x) is the inverse Fourier transform of g(ω).
F F −1
f (t) −→ g(ω) f (t) ←−−− g(ω) (VII.13)
g(ω) is analogous to an .
14
Definitions:
Z ∞
1
g(ω) = √ f (t)e−iωt dt (VII.15)
2π −∞
We say that g(ω) is the Fourier transform of the function f (t). The function
Z ∞
1
f (t) = √ g(ω)eiωt dω (VII.16)
2π −∞
(
sinω0 t |t| < Nω0π
f (t) = (VII.17)
0 |t| Nω0π
Nπ
The reason it is ω0 is because sin ω0 t → sin ωNω0
π
= 0. Note that this is an odd function. Remember that
This is equal to probability amplitude to find a particle at position x for the state |αi. Analogously,
is the probability amplitude to find a particle with momentum p for the state |αi. The functions ψα (x) and φα (p)
are Fourier transforms of one another
FT
ψα (x) −−→ φα (p) (VIII.3)
The dimensionless quantity that represents the probability of finding the particle with momentum between p and
p + dp is:
Pα (p)dp (VIII.5)
In three dimensions:
Z Z Z
1
φα (p) = 3/2
ψα (r)ei(r·p)/~ dr (VIII.6)
(2π~)
16
1/2
1
ψ1s (r) = e−r/a0 (VIII.7)
πa30
2
~
Where a0 = me 2 is the Bohr radius. Notice that the wave function is spherically symmetrical. Note if we want to
The representations of the harmonic oscillator (ground?) state in position and momentum space are given by
√
mk/(2~))x2
ψ(x) ∝ e−( (VIII.13)
−1
√ p2
φ(p) ∝ e 2~ mk (VIII.14)
Notice the functional forms are the same but one gets narrower as the other gets wider with α.
IX. COMMUTATORS
h i
Â, B̂ = ÂB̂ − B̂ Â (IX.1)
h i
If Â, B̂ = 0 we say the operators commute.
~ ∂
[x̂, p̂] = x, (IX.2)
i ∂x
~ ∂ ∂ ~ ∂
= x − + x = i~ (IX.3)
i ∂x ∂x i ∂x
17
h i
If Â, B̂ = 0 then one can find simultaneous eigenfunctions of  and B̂. I.e.
Âψ = λψ (IX.4)
0
B̂ψ = λ ψ (IX.5)
h i
If Â, B̂ 6= 0 then one cannot find simultaneous eigenfunctions.
The expectation value of the distance from the average value is given by
D E2
∆2A ≡ Â − Â (IX.6)
This value is referring the uncertainty. To avoid confusion lets expand this definition:
D E2 D D E E
 −  = Â2 − 2  + Â2 (IX.7)
D E D E2 D E
= Â2 − 2 Â + Â2 (IX.8)
D E D E2
= Â2 − Â (IX.9)
Remember its implied that there is some state α at either end. i.e.
D D E D E E
∆2A = α Â − Â Â − Â α (IX.10)
D D E D E E
= Â − Â α Â − Â α (IX.11)
likewise
2
hf |f i hg|gi ≥ |hf |gi| (IX.14)
Therefore
2
∆2A ∆2β = hf |f i hg|gi ≥ |hf |gi| (IX.15)
remember that in general hf |gi is in general a complex number. Lets call this number z. Then
2
z − z∗
2 2 2 2
|z| = (<z) + (=z) ≥ (=z) = (IX.16)
2i
Thus
2
1
∆2A ∆2B ≥ [hf |gi − hg|f i] (IX.17)
2i
Consider
D D E D EE
hf |gi = Â − Â B̂ − B̂ (IX.18)
D D E D E D E D EE
= ÂB̂ − Â B̂ − Â B̂ + Â B̂ (IX.19)
D E D ED E
= ÂB̂ − Â B̂ (IX.20)
18
D E D ED E
hg|f i = B̂ Â − B̂ Â (IX.21)
D E D E
hf |gi − hg|f i = ÂB̂ − B̂ Â (IX.22)
D E
= ÂB̂ − B̂ Â (IX.23)
Dh iE
= Â, B̂ (IX.24)
Hence
2
1 Dh iE
∆2A ∆2β ≥ Â, B̂ (IX.25)
2i
Example:
Equivalently:
~2
∆2x ∆2p ≥ (IX.28)
4
~
∆ x ∆p ≥ (IX.29)
2
When none commuting operators correspond to observables, we can them incompatible observables.
F = −kx (X.1)
2
d x
m = −kx (X.2)
dt2
⇒ x = A sin ωt + B cos ωt (X.3)
2
kx
V = (X.4)
2
The use of the harmonic oscillator model is that almost any potential can be approximated as a harmonic oscillator.
Now lets work with the quantum analogue. The Hamiltonian is given by
~2 ∂ 2 ψ 1
H=− + mω 2 x2 ψ (X.5)
2m ∂x2 2
The S.E. is given by
1
p2 + (mωx)2 ψ = Eψ
(X.6)
2m
19
The key idea is to factor the operator p2 + (mωx)2 . Consider if we were factoring two numbers u and v:
Lets define
1 1
a− ≡ √ (ip + mωx) ; a+ ≡ √ (−ip + mωx) (X.8)
2~mω 2~mω
Now if everything commuted then we would have H = a− a+ . However this is not the case as shown below:
1
a− a+ = (ip + mωx) (−ip + mωx) (X.9)
2~mω
1
p2 + m2 ω 2 x2 + imω (px − xp)
= (X.10)
2~mω
1
p2 + m2 ω 2 x2 − imωi~
= (X.11)
2~mω
1 1
= H+ (X.12)
~ω 2
In the future we require a+ a− so we may as well calculate it here:
1
a+ a− = (−ip + mωx) (ip + mωx) (X.13)
2~mω
1
p2 + m2 ω 2 x2 − imω (px − xp)
= (X.14)
2~mω
1 1
= H − iω (i~) (X.15)
~ω 2
1 1
= H− (X.16)
~ω 2
Rearranging gives
1
H = ~ω a+ a− + (X.17)
2
The commutator of a+ , a− is
1 1 1 1
[a+ , a− ] = H− − H+ (X.18)
~ω 2 ~ω 2
= −1 (X.19)
Hence
Hψ = Eψ (X.20)
1
~ω a+ a− + ψ = Eψ (X.21)
2
Hence the energy of the state acted on or “raised” by a+ is increased by a factor of ~ω.
Now if we apply a− continuously to some state ψ then at one point you will get the state with no particle there at all
(zero)
a − ψo = 0 (X.26)
Hence
1
√ (ip + mωx) ψ0 = 0 (X.27)
2~mω
∂ψ
~ + mωxψ = 0 (X.28)
∂x
∂ψ ω
= −m xψ (X.29)
∂x ~
−mω 2
ψ = e 2~ x (X.30)
F = ma (XI.1)
−kx = ma (XI.2)
d2 x
m + kx = 0 (XI.3)
dt2
d2 x
+ ωo2 x = 0 (XI.4)
dt2
1 1
E(t) = mA2 ωo2 sin2 ωo t + kA2 cos2 ωo t (XI.7)
2 2
1 2
= kA (XI.8)
2
1 1 1
mẋ2 + kx2 = kA2 (XI.9)
2 2 2 p
ẋ = ωo A2 − x2 (XI.10)
dt
P (x)dx = (XI.11)
T /2
21
2π
Where T is the period of oscillation. The period is given by T = ωo . Thus:
dt
P (x)dx = (XI.12)
T /2
2ωo dt
= (XI.13)
2π
2ωo dx
= (XI.14)
2π ẋ
2ωo dx
= √ (XI.15)
2π ωo A2 − x2
dx
= √ (XI.16)
π A2 − x 2
The probability of finding the particle everywhere should be 1. Hence:
Z A
= P (x)dx (XI.17)
−A
Z A
1 dx
= √ =1 (XI.18)
−A π A2 − x2
Let x = Ay, dx = Ady.
Z A
A dy
= p (XI.19)
−A π A − A2 y 2
2
Z A
1 dy
= p (XI.20)
−A π 12 − y 2
=1 (XI.21)
Note that the probability density is infinite at x = A, however its not a problem since the probability is finite (as it
must be since our probability density is normalized)
Consider
D E
 (XII.1)
In the x-representation for example we integrate this over all positions x. Hence the expectation value isn’t a function
of x. In other words:
D E D E
d  ∂ Â
= (XII.2)
dt ∂t
D E
∂ Â ∂
Z ∞
= ψ ∗ (x)Âψα (x)dx (XII.3)
∂t ∂t −∞ α
Z ∞
∂ ∗
= ψα (x)Âψα dx (XII.4)
−∞ ∂t
Z ∞
∂ψα∗ (x) ∂ Â ∂ψα (x)
= Âψα (x) + ψα∗ (x) ψα (x) + ψα∗ (x)Â dx (XII.5)
−∞ ∂t ∂t ∂t
Now the Schrodinger equation says that:
∂ψ ∂ψ ∗
i~ = Ĥψ; −~ = Hψ ∗ (XII.6)
∂t ∂t
22
Thus
!
∞ ∞
∂ψ ∗ Âψ
Z Z
i ∗ ∗ h ∗ ∂ Â
dx = Ĥψ Âψ − ψ ÂĤψ + ψ ψ dx (XII.7)
−∞ ∂t −∞ ~ i ∂t
but
d hp̂i i Dh iE
= Ĥ, p̂ (XII.23)
dt ~
d hp̂i ∂V
=− (XII.24)
dt ∂x
This is Newton’s second law!
• In classical physics one can show that the invariance of physics under time translations leads to energy conser-
vation.
• In a previous lecture we have derived the time evolution operator:
!
−iĤt
U = exp ; U † = U −1 (XIII.1)
~
hU α |H| U αi = α U † HU α
(XIII.2)
Note that
2
Ht −iHt 1
U = exp (−iHt/~) = 1 − i + + ... (XIII.3)
~ ~ 2
Hence U commutes with H. Thus
Therefore
dp̂
=0 (XIII.11)
dt
This operator rotates the function by an amount ∆φ. If the rotation operator commutes with the Hamiltonian then
angular momentum will be conserved. i.e.
d hLz i
[Lz , H] = 0 ⇒ =0 (XIII.16)
dt
Next consider the parity operator (P).
If f (x) = f (−x) then we say f (x) even. If f (x) = −f (−x) then we say that f (x) is odd. For even f the eigenvalue of
P is 1 if f is odd then the eigenvalue of P is −1. If
d hPi
[P, H] = 0 ⇒ =0 (XIII.18)
dt
Weak interactions violate parity conservation.
XIV. TUNNELING
Test 1: November 1
Make up lecture is in room HNE on Nov. 1st, Nov 8th
Consider the potential
x < −a
V =0
V = −a < x < a V = Vo (XIV.1)
x>a V =0
−~2 d2 ψ
+ V ψ = Eψ (XIV.2)
2m dx2
For x < a:
−~2 d2 ψ
= Eψ (XIV.3)
2m dx2
25
The points where the transmission is one are called transmission resonances. The transmission function in different
regimes is shown in figure 2.
26
FIG. 2. The transmission function in different regimes T (η, y). The greater the value of η the more classical the transmission
function
Classically:
L=r×p (XV.1)
x̂ ŷ ẑ
= det x y z (XV.2)
px py pz
= x̂ (ypz − ypy ) + ŷ (zpx − xpz ) + ẑ (xpy − ypx ) (XV.3)
(XV.4)
Quantumly:
h ∂ ~ ∂
Lx = y −z (XV.5)
i ∂z i ∂y
~
L= r×∇ (XV.6)
i
In order to find the following commutator makes use the the commutator:
[Lx , Ly ] = Lx Ly − Ly Lx (XV.9)
= (ypz − zpy ) (zpx − xpz ) − (zpx − xpz ) (ypz − zpy ) (XV.10)
~ ~
= ypx − xpy (XV.11)
i i
~
= (−Lz ) (XV.12)
i
= i~Lz (XV.13)
Lx , L2 = 0
(XV.17)
Ly , L2 = 0
(XV.18)
Lz , L2 = 0
(XV.19)
28
J+ = Jx + iJy (XV.21)
†
J− = Jx − iJy = J+ (XV.22)
~2 K 2 ≥ ~2 m2 (XV.47)
and hence
|K| ≥ |m| (XV.48)
This means that a given sequence of m’s must lie between |K| and − |K|. Therefore
J+ |mmax i = 0 (XV.49)
J− |mmin i = 0 (XV.50)
We could proceed in this way but its more natural to move to spherical coordinates. The coordinate system is shown
in figure 3 Exercise: Transform Lz into spherical coordinates. This can be found by finding the transformation from
theta
phi
x r
y→θ (XVI.4)
z φ
and then taking the inverse of the transformation. This gives the following
∂ ∂ sin θ sin φ ∂ cos θ ∂
= (sin θ sin φ) + + (XVI.5)
∂y ∂r r ∂θ r sin θ ∂φ
∂ ∂ cos θ cos φ ∂ sin φ ∂
= (sin θ cos φ) + − (XVI.6)
∂x ∂r r ∂θ r sin θ ∂φ
Hence
e2imπ = 1 (XVI.20)
In other words m ∈ Z. In order to keep the φ component normalized we require that the φ component is
1
√ eimφ (XVI.21)
2π
Now subbing into the spherical harmonics says that
eimφ Θ(θ)
Ylm (θ, φ) = √ (XVI.22)
2π
Plugging this into
µ = cos θ (XVI.25)
1 dl l
Pl (µ) = l l
µ2 − 1 (XVI.28)
2 l! dµ
The first few Legendre Polynomials are
Po (µ) = 1 (XVI.29)
P1 (µ) = µ (XVI.30)
1 d2 4 2
3µ2 − 1
P2 (µ) = µ − 2µ + 1 = (XVI.31)
8 dµ2 2
32
P0
P1
-1 1
P2
1/2
2l + 1 (l − m)!
Ylm (θ, φ) = Plm (cos θ) eimφ (XVI.37)
4π (l + m)!
XVII. HYDROGEN
~2 2 1 q2 Z
H=− ∇ − (XVII.1)
2m 4πo r
33
~2 2 1 q2 Z
H=− ∇ − (XVII.2)
2m 4πo r
L2
z }| !{
2
1 ∂2
2 1 ∂ 2 ∂ 1 1 ∂ ∂
∇ = 2 r + 2 sin θ + (XVII.3)
r ∂r ∂r r sin θ ∂θ ∂θ sin2 θ ∂θ
~2 2 ~2 1 ∂ 2 ∂ L2
− ∇ =− r + (XVII.4)
2m 2m r2 ∂r ∂r 2mr2
p2r L2
= + (XVII.5)
2m 2mr2
34
Theorem: The ground state of a system has the full symmetry of the problem.
This lovely coincidence that L2 showed up was of course not actually a coincidence.
2
L2 = (r × p) (XVII.6)
2 2 2
= r p − (r · p) (XVII.7)
2 2 2 2
r p = (r · p) + L (XVII.8)
2 2
p (r · p)
= + L2 r2 (XVII.9)
2m r2
2 L
= (r̂ · p) + (XVII.10)
2mr2
2 2
p L
= r + (XVII.11)
2m 2mr2
Thus
p2r L2 Ze2
+ − ψ (r, θ, φ) = Eψ (r, θ, φ) (XVII.12)
2m 2mr2 r
Using the relation L2 , H = 0 (easy to see by looking at the Hamiltonian term by term), we know that they share
eigenfunctions. Hence
ψ (r, θ, φ) = R(r)Ylm (θ, φ) (XVII.13)
Note it is always the case that if V = V (r) then ψ = R(r)Ylm (θ, φ).
Angular momentum
Coloumb
Centrifugal Barrier
So we know that
α+β+γ =0 (XVII.21)
−β − 2γ = 0 (XVII.22)
2β + 2γ = 1 (XVII.23)
The solution of this set of equations is
α = −1 (XVII.24)
β=2 (XVII.25)
γ = −1 (XVII.26)
Thus
4πo ~2
[L] = = 0.53 × 10−10 m ≡ ao (XVII.27)
me2
Note that with little work we already know the natural scale for atomic systems (Å).
Its also convenient to introduce
r
−2mE 2
κ≡ ; ρ ≡ κr; ρo = (XVII.28)
~ ao κ
With these changes we get
d2 v
ρo l (l + 1)
= 1− + v (XVII.29)
dρ2 ρ ρ2
Consider ρ → ∞.
d2 v
=v (XVII.30)
dρ2
⇒ u(ρ) = Ae−ρ + ρ
Be (XVII.31)
36
d2 v l (l + 1)
2
= v (XVII.32)
dρ ρ2
−l
u(ρ) = Cρl+1 +
Dρ (XVII.33)
Where for normalization we require D = 0. Substitute u(ρ) = ρl+1 e−l v(ρ) into the radial equation
d2 v dv
ρ + 2 (l + 1 − ρ) + (lo − 2 (l + 1)) v = 0 (XVII.34)
dρ2 dρ
Frobenius method gives that the result is the associated Laguerre polynomials.
p d p
Lpq−p (x) ≡ (−1) dx Lq (x)
d q
(e−x xq )
Lq ≡ ex dx
L0 = 1
L1 = 1 − x
L2 = x2 − 4x + 2
L00 = 1
L01 = −x + 1
L02 = x2 − 4x + 2
E1
En = (XVII.36)
n2
Where
1 e2 1
E1 = − mc2 α2 ; α≡ ≈ (XVII.37)
2 4πo ~c 137
α is called the fine structure constant. It is a measure of the electromagnetic interaction.
~2 1 ∂ e2 1
2 ∂ 2 l (l
+ 1)
− r +~ − R(r) = ER(r) (XVII.38)
2m r2 ∂r ∂r 2mr2 4πo r
Notice that the only place were we have l dependence is in the middle term. Also notice that there is no m dependence
in the Schrodinger equation. This reflects the fact that our problem is rotationally invariant. m measures the projection
of l into the z axis and our choice of z is arbitrary. We can break this rotational symmetry (by for example adding a
magnetic field) in this case the energy would depend on m. Note there has been a change in notation (at least with
his online notes):
√
4πo ~2 −2mE
ρ ≡ 2κr; ao = = 0.53 Å; κ = (XVII.39)
me2 ~
The new differential equation is
d2 u
1 n l(l + 1)
= − + (XVII.40)
dρ2 4 ρ ρ2
37
1
Where n = ao κ . The result is
have the same eigenvalues! This mysterious degeneracy in the eigenvalues is due to a hidden symmetry in the problem.
R10
R21
R20
Z
ψn∗ 0 l0 m0 ψnlm r2 sin θdrdθdφ = δn0 n δl0 l δm0 m (XVII.47)
38
hn|αi = an (XVIII.6)
X
|αi = an |ni (XVIII.7)
n
a01
a1 F11 F12 ...
a F F
2 = 21 22 ...
a02
(XVIII.15)
.. .. .. .. ..
. . . . .
We also call Fqn the matrix representation of the operator F.
Consider
G |ni = gn |ni (XVIII.16)
This is an eigenvalue equation.
g1 0 0
G = 0 g2 0 (XVIII.17)
.
0 0 ..
The eigenfunctions are just
0
.
..
0
|ni = 1 (XVIII.18)
0
..
.
0
Recall some matrix properties
40
1. Matrix multiplication:
X
(AB)nq = Anp Bpq (XVIII.19)
p
2. Inverse:
A−1 A = I (XVIII.20)
1 i+j
A−1 = Aadj ; Aadj = ATcof actor ; Acof = (−1) Mij (XVIII.21)
det A
3. Determinant:
X n
Y
det(A) = sgn(σ) Ai,σ(n) (XVIII.22)
σ∈Sn i=1
Where σ is the particular permutation. Sn is the set of permutations. sgn(σ) = +1, −1 depending on if we have
an even or odd permutation.
4. Symmetry: If
AT = A (XVIII.23)
Then A is symmetric. If
AT = −A (XVIII.24)
Then A is antisymmetric.
5. Trace:
X
Tr (A) = Ann (XVIII.25)
n
6. Hermitian Adjoint:
A† = A∗T (XVIII.26)
A† = A (XVIII.28)
The proof of Hermitian operators corresponding to real numbers in terms of matrices is straightforward. It also
shows that Hermitian operators correspond to Hermitian matrices. Exercise try this!
7. Unitary:
U † = U −1 (XVIII.29)
e−iHt/~ (XVIII.30)
F U −1 |α0 i = U −1 |β 0 i (XVIII.35)
−1 0 −1 0
UFU |α i = U U |β i (XVIII.36)
F |α0 i = |β 0 i
0
(XVIII.37)
Hence
F 0 = U F U −1 (XVIII.38)
2
B = e−ξ /2
(Ao Ho (ξ), A1 H1 (ξ), ...) (XVIII.40)
mωo
Where ξ 2 = β 2 x2 , β 2 = ~ . Another way to denote the basis is
1/2
a+ |ni = (n + 1) |n + 1i (XVIII.48)
a− |ni = n1/2 |n − 1i (XVIII.49)
42
1 1
x= √ (a− + a+ ) (XVIII.50)
2β
Angular momentum:
2
L , Lz = 0 (XVIII.59)
0 0 00 0 0
0 2 00 0 0
0 0 20 0 0
2 2
L =~ (XVIII.62)
0 0 00 2 0
0 0 00 0 6
..
0 0 0 0 0 .
43
0 0 0 00 0
0 1 0 00 0
0 0 0 00 0
2
Lz = ~ (XVIII.63)
0 0 0 −1
0 0
0 0 0 00 2
..
0 0 0 0 0 .
L+ = Lx + iLy (XVIII.64)
L− = Lx − iLy (XVIII.65)
1/2
L± |l, mi = ((l ∓ m) (l ± m + 1)) |l, m ± 1i (XVIII.66)
1/2
hl, m| L± |l0 m0 i = (l0 ∓ m0 ) (l0 ± m0 + 1) ~δll0 δn,m0 ±1 (XVIII.67)
0 1 0
~
Lx = √ 1 0 1 (XVIII.69)
2
0 1 0
−i 0
~
Lx = √ i 0 −i (XVIII.70)
2
0 i 0
1 0 0
Lz = ~ 0 0 0 (XVIII.71)
0 0 −1
• Tunneling
• Angular momentum
• Hydrogen
44
The eigenvalues of L2 are 2~2 (the same for all m). To diagonalize Lx is to
Lx v = λv (XVIII.73)
(Lx − λ) v = 0 (XVIII.74)
One solution is the trivial solution v = 0, but this isn’t interesting. To get interesting solutions:
−λ ~
√
2
0
= 0 − λ λ2 − ~2 /2 + λ~2 /2
det
~
√
2
−λ ~
√
2 =0 (XVIII.76)
0 ~
√
2
−λ
This gives eigenvalues are 0, ±~. To get eigenvectors plug λ’s back in. Plugging in λ = ~:
−~ ~
√ 0
~ 2 v1
√ −~ √~ v2 =0
(XVIII.77)
2 2
0 √~
−~ v3
2
−1 √12 0
1 v1
√ −1 √1 v =0 (XVIII.78)
~
2 2 2
1 v
0 √
2
−1 3
In order to diagonalize Lx :
√ √
1 2 1 0 1 0 1 2 1
1√ √ ~ 1√ √
U Lx U −1 = 2 0 − 2√ 1 0 1 2 0 − 2 (XVIII.83)
2 √ 2 2 √
1 − 2 1 0 1 0 1 − 2 1
1 0 0
= ~ 0 0 0 (XVIII.84)
0 0 −1
45
In terms of spherical harmonics what are the eigenvectors? Thus the eigenvector for λ = ~:
1 √
1√ 1
2 → = Y1,1 (φ, θ) + 2Y1,0 (φ, θ) + Y1,−1 (φ, θ) (XVIII.85)
2 2
1
r
1 3
sin θe−iφ + 2 cos θ + sin θeiφ
= (XVIII.86)
4 2π
r
1 3
= (cos θ + −i sin θ sin φ) (XVIII.87)
2 2π
1 3
cos2 θ + sin2 θ sin2 φ sin θ
P (φ, θ) = (XVIII.88)
4 2π
Z
P (φ, θ)dθdφ = 1 (XVIII.89)
Notice that since these aren’t eigenfunctions of z we know longer have rotational
symmetry of φ! Now we can check
∂ ∂
whether this truly is an eigenfunction of Lx = i~ sin φ ∂θ + cos θ cos φ ∂φ . Notice that finding the eigenfunction of
this operator is very difficult without the matrix formulation.
XIX. SPIN
Spin is the intrinsic angular momentum of a particle. There is no coordinate representation for spin since it doesn’t
exist in real space. We will construct the matrix representation. We still expect the angular momentum commutation
relations to hold. For example
We can define
Where ms = (−s, −s + 1, ..., s − 1, s). Pions, mesons, etc all carry s = 0. Electrons, protons, neutrons, neutrinos, etc.
all carry s = 12 . The force carriers such as photons, W and Z bosons, gluons, carry s = 1. The graviton (if it exists)
carries s = 2. We will focus on spin half objects since all stable matter is mostly made up of spin half particles.
1 1 13 2 1 1
S2 | , i = ~ | , i (XIX.7)
2 2 22 2 2
1 1 1 1 1
Sz | , i = ~| , i (XIX.8)
2 2 2 2 2
46
Recall
1/2
L± |l, mi = ~ (l (l + 1) − m (m ± 1)) |l, m ± 1i (XIX.9)
1/2
1 1 1 1 1 1
S− | , i = +1 − −1 (XIX.10)
2 2 2 2 2 2
1 1
= ~| ,− i (XIX.11)
2 2
1 1
S+ | , i = 0 (XIX.12)
2 2
1 1 3 1 1
S 2 | , − i = ~2 | , − i (XIX.13)
2 2 4 2 2
1 1 1 1 1
Sz | , − i = − ~ | , − i (XIX.14)
2 2 2 2 2
1 1 1 1
S+ | , − i = ~ | , i (XIX.15)
2 2 2 2
1 1
S− | , − i = 0 (XIX.16)
2 2
Lets denote |↑i → |αi, |↓i → |βi.
S+ |αi = 0 (XIX.17)
S− |αi = ~ |βi (XIX.18)
S+ |βi = ~ |αi (XIX.19)
S− |βi = 0 (XIX.20)
S± = Sx ± iSy (XIX.21)
~
Sx |αi = |βi (XIX.22)
2
~
Sy |αi = i |βi (XIX.23)
2
~
Sz |αi = |αi (XIX.24)
2
~
Sx |βi = |αi (XIX.25)
2
~
Sy |βi = −i |αi (XIX.26)
2
−~
Sz |βi = |βi (XIX.27)
2
To construct the Sx matrix:
!
hα|Sx i α hα|Sx i β
Sx = (XIX.28)
hβ|Sx i α hβ|Sx i β
!
~ 0 1
(XIX.29)
2 1 0
!
~ 0 −i
Sy = (XIX.30)
2 i 0
!
~ 1 0
Sz = (XIX.31)
2 0 −1
47
! !
1 0
|αi → ; |βi → (XIX.32)
0 1
σ = (σx , σy , σz ) (XIX.33)
Hence any two component vector is an eigenstate of S 2 . Note that these spinors are not a vector in the sence of R3
or R2 . Of course its a vector in Hilbert space. The geometrical meaning is not a 2D or 3D geometrical vector but its
a new geometric object called a spinor. Geometrically there are scalars, vectors, and tensors. Spinors fit in between
scalars and vectors. Under rotations spinors do not behave trasnform like vectors but like spinors.
! ! ! !!
~2 0 1 0 −i 0 −i 0 1
Sx Sy + Sy Sx = + (XIX.37)
4 1 0 i 0 i 0 1 0
=0 (XIX.38)
{Sx , Sy } = 0 (XIX.39)
V = −µ · B (XIX.40)
Where
e
µ= S (XIX.41)
mc
But
is the rotation operator for rotations. If θ = π2 then this is just the U !. This makes sence since the matrix that
diagonalizes Lx can be interpreted as a rotation about the y axis.
48
Examples
An electron with both orbital and spin angular momentum:
J=L+S (XX.1)
J = S1 + S2 (XX.2)
[S1 , S2 ] = 0 (XX.4)
but
2
(S1 + S2 ) = S12 + S22 + 2S1 · S2 (XX.6)
Hence
! !
0 1 0 0
S+ = ~ ; S− = ~ (XX.9)
0 0 1 0
Hence
J 2 |↑↑i = S12 + S22 + S+,1 S−,2 + S−,1 S+,2 + 2Sz,1 Sz,2 |↑↑i (XX.12)
2
3 2 3 ~
= ~ |↑↑i + ~2 |↑↑i + |↑↑i (XX.13)
4 4 2
= 2~2 |↑↑i (XX.14)
= J (J + J) ; Where J = 1 (XX.15)
J 2 |↑↓i = S12 + S22 + S+,1 S−,2 + S−,1 S+,2 + 2Sz,1 Sz,2 |↑↓i (XX.16)
~2
3 2 3 2
= ~ + ~ |↑↓i + 0 + ~2 |↓↑i − |↑↓i (XX.17)
4 4 2
= ~2 (|↑↓i + |↓↑i) (XX.18)
This gives us the spin singlet and the spin triplet states. Thus electrons in Helium can be in both spin singlet and
spin singlet.
Exercise: take L = 1 and S = 21 and find the eigenfunctions of J = L + S. Also try S1 + S2 + S3 .
In general if we do
J = L1 + L2 (XX.23)
l1
X l2
X
|l1 l2 , jmi = |l1 m1 i |l2 m2 i hl1 m1 , l2 m2 |jmi (XX.24)
m1 =−l1 m2 =−l2
|↑↑i (XX.29)
1
√ (|↑↓i + |↓↑i) (XX.30)
2
|↓↓i (XX.31)
1 1
Jz √ (|↑↓i + |↓↑i) = Sz1 + Sz2 √ (|↑↓i + |↓↑i) (XX.33)
2 2
1 ~ ~ ~ ~
= √ |↑↓i − |↓↑i − |↑↓i + |↓↑i (XX.34)
2 2 2 2 2
=0 (XX.35)
h↑ | ↑i = 1 (XX.36)
h↓ | ↓i = 1 (XX.37)
h↑ | ↓i = 0 (XX.38)
h↓ | ↑i (XX.39)
50
!
~ 0 1
Lets find the matrix U that diagonalizes the Sx = 2 matrix.
1 0
!
−λ ~ ~
det 2 =0⇒λ=± (XX.40)
~
2 −λ 2
! !
~ −1 1 1
=0 (XX.41)
2 1 −1 1
Hence the eigenvector is (after normalization)
!
1 1
√ (XX.42)
2 1
The other eigenvector (easy to check) is
!
1 1
√ (XX.43)
2 −1
Thus the transformation matrix is
!
1 1 −1
U† = √ = U −1 (XX.44)
2 1 1
Here we are changing the quantization axis from z to x. So the rotation matrix is (rotation about the y axis)
2 3
iθσy (iθ) σy2 (iθ) σy3
eiθSy /~ = 1 + + + 3 ... (XX.45)
2 4 2 2 6
But the squares the Pauli spin matrices are 1!. Thus
iθσy θ2 1 θ3 σy 1
eiθSy /~ = 1 + − − 3 + ... (XX.46)
2 4 2 2 6
= cos (θ/2) + i sin (θ/2) σy (XX.47)
!
cos (θ/2) sin (θ/2)
= (XX.48)
− sin (θ/2) cos (θ/2)
For θ = π/2:
!
iπSy /2~ 1 1 1
e =√ (XX.49)
2 −1 1
Notice that for θ = 2π
!
−1 0
U (θ = 2π) = (XX.50)
0 −1
Thus when we rotate by 2π we don’t get the identity!
We can split the eigenstates of Sx into eigenstates of Sz :
!
1 1 1
√ = √ (|↑i + |↓i) (XX.51)
2 1 2
One notation for this vector is
1
|→i = √ (|↑i + |↓i) (XX.52)
2
XXI. ENTANGLEMENT
The idea of entanglement first came out in the paper called the “EPR paper” by Einstein, Podolsky, and Rosen
(1935). This paper discussed the philosophy of entanglement but never thought that the different interpretations of
quantum mechanics could really be proved right or wrong. However a paper by Bell showed that they could and
Bell produced Bell’s inequalities. Einstein’s problem with quantum mechanics ws that he thought that “Quantum
mehanics is not complete, it doesn’t describe objective reality”.
The EPR experiment is as follows. Consider a π 0 particle which has spin J = 0. It decays through
π 0 → e+ + e− (XXI.1)
Angular momentum is conserved and therefore the e+ , e− pair has total J = 0. Hence the spin configuration is
1
|0, 0i = √ (↑↓ − ↓↑) (XXI.2)
2
Entanglement is displayed in figure 8
e- e+
z z
50%
x x
z
x
x
Def 3. Entanglement: We say a state is entangled if it cannot be written a as a simple product of one particle
states.
For example: If we could write the Helium atom as
L R
G R G R
1 1
2 3 2 3
3 Switch Positions
2 Lights
Recall that
J 2 χ = 0χ (XXI.8)
We want to know that correlator:
hχ| S1z S2z |χi (XXI.9)
First lets do the simpler correlator
11
S1z S2z |↑↓i = −~2 |↑↓i (XXI.10)
22
~2
S1z S2z |↓↑i = − |↓↑i (XXI.11)
4
Now
~2
S1z S2z χ = − (XXI.12)
4
We can finally compute the normalized correlator:
hχ| S1z S2z |χi
q = −1 (XXI.13)
2 2
hχ| (S1z ) |χi hχ| (S2z ) |χi
This tells you that the spins in this state are perfectly anti-correlated. Now consider the operators in the x direction
hχ| S1x S2x |χi
q (XXI.14)
2 2
hχ| (S1x ) |χi hχ| (S2x ) |χi
~2
S1x S2x χ = − χ (XXI.18)
4
Thus
hχ| S1x S2x |χi
q = −1 (XXI.19)
2 2
hχ| (S1x ) |χi hχ| (S2x ) |χi
The same is true for the S1y S2y we have perfect anti-correlation.
C (S1x S2z ) |↑↓i = (S1x ↑) (S2z ) (XXI.20)
! ! ! !
~ 0 1 1 ~ 1 0 0
= (XXI.21)
2 1 0 0 2 0 −1 1
~2
=− |↓↓i (XXI.22)
4
Similarly
~2
S1x S2z |↓↑i = |↑↑i (XXI.23)
4
54
~2 1
S1x S2z χ = − √ (↓↓ + ↑↑) (XXI.24)
4 2
π 0 → e+ + e− (XXI.26)
1
π 0 → √ (↑↓ − ↓↑) ≡ χ; J = 0, Jz = 0 (XXI.27)
2
The three pointers in the experiment
√
are actually
√
the directions in which we are actually meauring the spin: The
vectors are (nˆ1 = eˆz , nˆ2 = 23 eˆx − 12 eˆz , nˆ3 = − 23 eˆx − 21 eˆz ). Recall the definition of S
~
S= σ (XXI.28)
2
Where σ 1 is the spin matrix corresponding to particle 1. To find the correlator we first find the relations:
−~2
S1z S2z ↑↓= ↑↓ (XXI.29)
4
The correlator of S1 · n̂1 S2 · nˆ1 (without normalization) is
! !
~ 0 1 1
Sx ↑ = (XXI.35)
2 1 0 0
!
~ 0
(XXI.36)
2 1
55
Sx ↓ = − ↑ (XXI.37)
√ √ !
~2 3 1 3 3
O ↑↓ = ↓↑ − ↑↓ − ↑↑ + ↓↓ (XXI.38)
4 4 4 4 4
√ √ !
~2 3 1 3 3
O ↓↑ = ↑↓ − ↓↑ + ↓↓ − ↑↑ (XXI.39)
4 4 4 4 4
Finally
1
Oχ = O √ (↑↓ − ↓↑) (XXI.40)
2
~2
=− χ (XXI.41)
4
Thus these are perfectly anti-correlated.
If we don’t pay any attention to the spin then we should get zero for the following: (i 6= j)
X X X
hχ| S1 · n̂i S2 · n̂j |χi = hχ| S1 · n̂i S2 · n̂j |χi (XXI.42)
i,j i j
!
X X
= hχ| S1 · n̂i S2 · n̂j |χi (XXI.43)
i j
=0 (XXI.44)
Since the vector sum over all the three vectors is trivially zero. To summarize: Bell’s inequality follows from classical
thinking. Bell’s inequality is violated by experiment and quantum mechanics. Bell’s inequality is a statistical state-
ment. In other words you have to do many measurements and sum the results. This is the way things stood until
GHZ came along (Greenburger, Horne, and Zolnger) and they proposed an experiment and carried it out which is
not a statistical experiment (one-shot experiment). In this experiment 100% of the time quantum mechanics predicts
one thing and classical mechanics predicts another. You are responsible for this experiment for the exam.
We have solved most of the exactly solvable problems in quantum mechanics but we have approximation schemes for
the others.
• WKB approximation
• Variational method
Hψ = Eψ (XXII.1)
56
Then we consider
hα |H| αi (XXII.2)
As an apprimation to the energy. To get the trial state we make an educated guess. There is no way we’ll get the
exact solution. If we minimize
hα| H |αi (XXII.3)
this quantity with respect to a parameter then we assured of getting as closed as possilbe the exact solution. Mathe-
matically:
d hα| H |αi
=0 (XXII.4)
da
For some parameter a is the best possible solution. We call a a variational parameter and we use it to parametrize
our wavefunction. e.g. ψ(x, a). Why does it work? This works because
X
|αi = an |ni (XXII.5)
n
X
hα| H |αi = an a∗n0 hn0 | H |ni (XXII.6)
n,n0
∞
~2 e2
Z
2 1
ha| H |ai = γ 2 r2 dr − − + 2 −Z e−r/a (XXII.15)
o 2m ar a r
Z ∞ 2
e2 ~2 2 −r/a
4 ~ −r/a
= 3 −Z re − r e dr (XXII.16)
a 0 ma r 2ma2
57
but
∞
a3
Z
r2 e−r/a dr = (XXII.17)
0 4
and
∞
a2
Z
re−r/a dr = (XXII.18)
0 4
2 2
~2 a3
4 ~ 2 a
ha| H |ai = 3 − Ze − (XXII.19)
a ma 4 2ma2 4
2 2 2
4 ~ a e a
= 3 −Z (XXII.20)
a 8m 1 4
2
e2
~
= − Z (XXII.21)
2ma2 a
(XXII.22)
~2 e2
E(a) = − Z (XXII.23)
2ma2 a
The Coloumb term is pushing the electron inwards while the Quantum mechanics forms the repulsive term pushing
Quantum Mechanics
Coloumb Term