V(x) = k x2/2
Quantization -
Nodes -
Symmetry of ψ -
52
ACTUALLY,
En = (k/m)1/2(n + ½ ) n = 0,1,2,3, . . .
β x2
Ψ n (x) = N n H n (β x) e −
2
Again, to get a sense of the wavefunctions and the time dependence, look at the falstad website
http://www.falstad.com/qm1d/ and select “Setup: Harmonic Oscillator” from the drop down
menu.
53
What about various integrals of the harmonic oscillator functions?
ψ i ψ j = δ ij (WHY??)
Note that both the particle in a box and the harmonic oscillator eigenfunctions have a
definite parity and that it alternates with the quantum number. This result has to do with the
symmetry of V(x).
We can generalize this result with operators. Let the parity operator  be such that
Âf(x) = f(-x)
What is f g ? WHY??
54
Three Dimensional Harmonic Oscillator
Now let's quickly add dimensions to the problem. Consider a three dimensional harmonic
oscillator for a particle of mass m with different force constants kx, ky, and kz in the x, y and z
2 2 2
kx x ky y kz z
directions. The potential energy is V(x, y, z) = + +
2 2 2
and the Hamiltonian is given by
∂ 2 − 2 ∂ 2 − 2 ∂ 2 + kxx 2 + k yy + kzz2
2 2
Hˆ = − .
2 m ∂ x 2 2 m ∂ y2 2 m ∂ z 2 2 2 2
This Hamiltonian is clearly separable into x-, y- and z- equations, each of which looks
just like the one we have already solved. Thus the solutions are
kx 1 ky F1 I
kz 1 F I F I
En , n , n =
x
m
nx +
y z
2
+
m H
ny + +
2 mK nz +
2 H K H K
with n x = 0,1,2,.. n y = 0,1,2,.. n z = 0,1,2,...
It's really that simple! Now consider the isotropic 3-D oscillator with all three force constants
k
equal. Then kx=ky=kz=k and we have V(x, y, z) = x2 + y + z2 =
2
2 k 2
2
r . Here c h
r = x 2 + y2 + z 2 , the distance from the origin. The result is
k F n + n + n + 3I F 3 I
En , n , n =
x y z
m H x y
2K
z
H
= h ν class n x + n y + n z +
2 K
with n x = 0,1,2,. . n y = 0,1,2,.. n z = 0,1,2,...
Now we see new energy degeneracies since the problem has high symmetry.
Consider the level E= (9/2) hνclass . Then (nx + ny + nz +3/2) = 9/2
or nx + ny + nz = 3 . The possibilities are as follows:
55
nx ny nz
3 0 0
2 1 0
2 0 1
1 2 0
1 0 2
1 1 1
0 2 1
0 1 2
0 3 0
0 0 3
56
Separation Of Center Of Mass Motion
Consider as a concrete example an ideal spring with masses m1 and m2 at the ends of the
spring, and constrained to move only in the z-direction. Let 0 be the unstretched (equilibrium)
length of the spring. We have the following picture.
m1 m
2
z
z1 z2
57
2 2
pz k pZ
H ( z1, z 2 ) = H(z, Z) = + (z − 0) 2 +
2μ 2 2( m1 + m 2 )
−
d φ(z)
22
+
k z− a f φ(z)
0
2
= E φ(z)
2μ dz2 2
with the known solutions, now simply centered about 0 rather than zero. This same procedure
will always work in 3 dimensions, and the motion of the center of mass reduces by three the
number of internal quantum numbers. These center of mass motions when the "particle" is
confined to a box give rise to the translational heat capacity expression we will derive in the
statistical mechanic portion of the course.
We will always implicitly separate out the center of mass motion in the future.
Soon we will see that when the 3 dimensional potential V(x,y,z) depends only on
the distance from the origin, i.e. V(x,y,z) = V(r), a central potential, then the Hamiltonian will
be separable in spherical polar coordinates, (r, θ, φ). The θ and φ parts of the solution will be
the same for any radial potential: coulomb, harmonic, rigid rotor or whatever!!
The θ and φ parts will refer to the angular momentum properties of the system, no
matter what system V(r) describes. For example, if V(r) is the 1/r Coulomb potential (H atom),
then the quantum numbers arising from the θ and φ parts give rise to the and m quantum
numbers we know well.
Before that time, however we make a short foray into commutation relations and the
basics of angular momentum.
58
Commutation Relationships
We have seen something of commutation relations. We need to say a little more about
why they are important.
First remember that if a state function is an eigenfunction of operator Â, then every
measurement of the A property gives the eigenvalue ai. This means that the property A is an
exact description of that aspect of the system. (energy, angular momentum, whatever) We wish
to find as many sharp properties of the system as possible.
In our 3D harmonic oscillator we saw that the function
-βx2/2 -βy2/2 -βz2/2
Ψnx,ny.nz(x,y,z) = Nn Hn(βx)e Hn(βy)e Hn(βz)e
is simultaneously an eigenfunction of [KEx, + V(x)] , [KEy +V(y)] and [KEz +V(z)]. The
harmonic oscillator Hamiltonian commutes with all of these operators. The properties are all
"sharp", i.e., characterized by zero standard deviation in a measurement. We will always want
to utilize such sharp such properties to characterize a system.
For an H atom, they might be total energy, total angular momentum and one component
of angular momentum. How do we identify such properties?
Theorem 1: If  commutes with Ô ( i.e., [Ô,Â] = 0), then there exists a complete set of
functions which are simultaneously eigenfunctions of Ô and Â.
Theorem 2: If two operators Ô and  have a common, complete set of eigenfunctions, then
they commute, i.e. [Ô,Â] = 0.
The proof follows from the fact that any function can be expanded in the common,
complete set of eigenfunctions.
Theorem 3: If Hermitian operator  commutes with Ô, and if φ1 and φ2 are eigenfunctions of Â
with eigenvalues a1 and a2 , then the MATRIX ELEMENT O1,2 vanishes unless a1 = a2..
Here O1,2 = φ1 O φ 2 , the definition of a matrix element.
Proof:
First Âφ1 = a1φ1 and Âφ2 = a2φ2
Now φ1 OA φ 2 = a2 φ1 O φ 2 .
Also φ1 OA φ 2 = φ1 AO φ 2 since they commute
φ1 AO φ 2 = Aφ1 O φ 2 = a1 φ1 O φ 2
Thus a2 φ1 O φ 2 = a1 φ1 O φ 2
or (a2-a1 ) φ1 O φ 2 = 0.
59
Since a1 ≠ a2, the matrix element must vanish. This theorem will be extremely useful in
applying symmetry to assist in obtaining wavefunctions. It also begins to show the importance
of matrix elements in quantum mechanics.
As a follow up, consider the harmonic oscillator problem
2 2 2
Hˆ = − d + kx
2 μ dx 2 2
with state functions ψn (x) as we know.
Now Hij ≡ ψ i Hˆ ψ j
2μ
If we start with rectangular (x,y,z) coordinates, we must transform this expression to spherical
polar coordinates, r, θ, φ where 0 ≤r<∞ , 0≤θ≤π and 0≤φ≤2π. This is easily done as shown:
We can transform the x, y and z derivatives into r, θ, and φ terms. After much
manipulation, sweat, blood and tears, we would obtain the time independent Schrödinger
60
equation for a central field. Alternatively, we look up the form of ∇2 in spherical polar
coordinates.
In either case, we finally obtain the time independent Schrödinger equation for a central
field:
LM 1 ∂ F r ∂ I + 1 ∂ F sin θ ∂ I OPψ(r, θ, φ)
2
2μ N r ∂ r H ∂ r K r sin θ ∂θ H ∂θ K Q
− 2
2
2
∂
2
1
+ 2 2 2 ψ (r, θ, φ ) + V(r)ψ (r, θ, φ ) = E ψ (r, θ, φ )
r sin θ ∂ φ
Various forms of V(r) give us important problems:
V(r) Problem
61
Angular Momentum
Thus L , Lx, Ly, and Lz are constant in this case. They are "Constants of the Motion" Think
about tops or gyroscopes!
We shall see that quantum mechanically only the square of the total angular
momentum and one component can be constants of the motion. That is to say, they have
commuting operators. Thus we will look at the QM operators, their commutation relations
and their representation in spherical polar coordinates.
Looking at the quantum mechanical operator,
i j k
Lop = x y z = Lx i + L y j + Lz k
pˆ x pˆ y pˆ z
where
⎡ ∂ ∂ ⎤
Lx = − i ⎢ y −z
⎣ ∂z ∂ y ⎥⎦
⎡ ∂ ∂ ⎤
Ly = − i ⎢ z −x ⎥
⎣ ∂x ∂z⎦
⎡ ∂ ∂ ⎤
Lz = − i ⎢ x −y
⎣ ∂y ∂ x ⎥⎦
Also,
L2 = L ⋅ L = L2x + L2y + L2z
62
Let us look at commutation relations, e.g., ⎡⎣ L x , L y ⎤⎦
⎛ ∂f ∂f ⎞
First L x L y f = L x ⎜ − i ⎡⎢ z − x ⎤⎥ ⎟
⎝ ⎣ ∂x ∂z⎦ ⎠
Then evaluate L y L x f and subtract. After a bunch of algebra, we obtain the commutator
⎡Lx , L y ⎤ = i Lz
⎣ ⎦
By cyclic permutation of variables (x→y, y→z, z→x), we also get
⎡Lx , L y ⎤ = i Lz
⎣ ⎦
⎡L y , Lz ⎤ = i Lx
⎣ ⎦
⎡Lz , Lx ⎤ = i Ly
⎣ ⎦
Since none of these commutators are zero, we have that
No two components of angular momentum commute.
Thus we cannot specify two components of angular momentum at the same time!
We also find that [ L2 , L x ] = [ L2 , L y ] = [ L2 , L z ] = 0
So we can find functions that are simultaneously eigenfunctions of L2 and any one component
of the angular momentum.
We switch to spherical polar coordinates (r, θ, φ) and find that we can write the operators L2
and L z in the following form:
⎡ 1 ∂ ⎛ ∂ ⎞ 1 ∂2 ⎤
Li L ≡ L = − ⎢ ⎜ sin θ
2 2
⎟+ 2 2⎥
⎣ sin θ ∂θ ⎝ ∂θ ⎠ sin θ ∂φ ⎦
∂
Lz = − i
∂φ
63
So finally we obtain
2
[ L , Lx ] = 0 [ H cent , L y ] = 0 [ Lx , Ly ] = i Lz
[ L2 , L y ] = 0 [ H cent , L z ] = 0 [Ly, L z ] = i L x
[ L2 , L z ] = 0 [ H cent , L x ] = 0
[ L z , L x ] = i Ly
[ H cent , L ] = 0
2
So we can find eigenfunctions of the central field Hamiltonian, H cent , that are
simultaneously eigenfunctions of H cent , L2 and one component of the total angular momentum.
Conventionally, and for mathematical simplicity this is taken to be the unique axis (z). Thus
we add L z to our list of eigenfunctions. Since there are only three possible quantum numbers
for this system (WHY??), our list is complete. We now go on our way about solving the three
eigenvalue equations for L z , L2 and H cent .
Note that our solutions for the first two must be valid for any central field problem.
I. Z - Component
We can readily solve the L z eigenvalue equation,
∂Φ
L z Φ (φ ) = − i = CΦ (φ ) ,
∂φ
to obtain Φ( φ ) = e imφ for 0 ≤ φ ≤ 2π with the eigenvalues C being m .
In order for Φ(φ) to be single valued, we must satisfy the boundary condition Φ(0) =
Φ(2π). This restriction requires that m = 0, ±1, ±2, . . . . Thus the z-component of total angular
momentum is quantized. This quantum number will turn out to be the m quantum number we
have seen before in the hydrogen atom.
Show that the corresponding eigenvalues are m . Note that this must mean that has
units of angular momentum.
64
II. Square of Total Angular Momentum
The solution to the L2 eigenvalue equation is not so straightforward, and we will not go
through it. However, the solution is a standard function of mathematical physics called the
spherical harmonics, Y ,m(θ,φ). These are tabulated in the text (and in any standard quantum
mechanics text). The key properties of these functions are summarized by their eigenvalues:
2
L2 Y ,m(θ,φ)= ( )( +1) Y ,m(θ,φ) = 0, 1, 2 , . . .
and
L z Y ,m(θ,φ)= m Y ,m(θ,φ) m= - , - +1 , . . . , 0 , . . . ,
Lz
L
z z z
√2 √2
√2
65
Some of the spherical harmonics are listed below:
2 1
Y0,0 (θ, φ ) =
4 2π
3 1
Y1,0 (θ, φ ) = cos θ
2 2π
3 1 ± iφ
Y1, ±1 (θ, φ ) = sin θ e
4 2π
Y2,0 (θ, φ ) =
5
8
c
3 cos2 θ − 1 h 1
2π
15 1 ± iφ
Y2, ±1 (θ, φ ) = sin θ cos θ e
4 2π
15 2 1 ±2iφ
Y2, ±2 (θ, φ ) = sin θ e
16 2π
What about nodes in these functions?
III. Radial Part
Now back to the central potential problem. We had previously obtained the Schrödinger
equation for a central force as
2
∂ ⎛ 2∂ ⎞ L2
− ⎜r ⎟ψ (r,θ , φ ) + ψ (r,θ , φ ) + V(r)ψ (r,θ , φ ) = Eψ (r,θ , φ )
2μ r 2 ∂ r ⎝ ∂ r ⎠ 2μ r 2
Let a solution be of the form ψn, ,m(r,θ,φ) = Rn, (r)Y ,m(θ,φ).
When we make this substitution, we can explicitly carry out the angular momentum operation,
and bring the Y ,m(θ,φ) terms through the r - derivatives and the V(r) Rn, (r) term through the
angular momentum operator. We then divide through by Y ,m(θ,φ).
The Rn, (r) must satisfy the following ordinary differential equation :
2
FG
d 2 dR n, IJ + LMV(r) + b + 1g OP R
2
−
2μr dr
2 r
dr H K N 2μr Q 2 n, (r) = E R n , ( r )
−
2
FG 2 dR 2
d R n, IJ LM 2
( + 1) OP
2μ H r dr K N
n,
+
dr 2
+ V(r) +
2μr 2 Q
R n, (r) = E R n , ( r )
66
electron atom problems. This is the starting point for ANY system, and is the reason that the
solutions of the hydrogen atom problem play such a key role in our understanding of atomic and
molecular structure!
Rigid Rotor Energies and Wavefunctions
The rigid rotor consists of a pair of particles of masses M1 and M2 (reduced mass μ)
separated by a fixed distance Ro. With this model, we can set the central potential to be V(r) =
0 for R =Ro, and infinite otherwise. The R(r) derivatives in the preceding equation can be can
be shown to be zero, basically for the same reasons as for the infinite square well solved earlier.
Thus at r = Ro, the radial Schrödinger equation becomes
2
⎛ ( + 1) ⎞
⎜ ⎟ Y ,m (θ , φ ) = EY ,m (θ ,φ )
2 μ ⎝ Ro2 ⎠
By convention, the quantum number in the rotor problem is replaced by j. Thus the allowed
energies are given by
2 2
E j,m = j(j+ 1) = j(j+ 1) = B j(j+ 1)
2μ R 2o 2I
67