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Bohr-Sommerfeld Quantization
Bohr-Sommerfeld Quantization
This course summary organizes the basic ideas contained in the lecture notes, the textbook, and the course
handouts. It is not intended as a substitute for these materials, and it skips many important details. Any discussion
of core concepts is necessarily abridged. The emphasis is on putting most of the important equations and concepts
in one place, to serve as a launching point for further study.
1 Bohr-Sommerfeld Quantization
1.1 Quanta
Planck introduced the constant that now bears his name to eliminate the ultraviolet divergence in the black-body
radiation spectrum. It defines a fundamental scale of action, that allows us to relate kinematic and wave properties
of quantum mechanical objects.
Quantum mechanical waves obey the superposition principle, and therefore may exhibit quantum mechanical
interference.
Experimentally, the emission and absorption spectra of atoms were known to exhibit discrete lines, which satis-
fied the Rydberg-Ritz combination principle, that ν = Ai − Aj , where the Ai and Aj were empirically determined
terms. This discrete spectrum could not be explained by classical models, and we now understand these terms as
the energy levels of the atom. The arithmetic relationships among certain groups of lines were identified as early
as 1885, when Balmer showed that certain lines were predicted by the formula hν = Ry(1/22 − 1/n2 ) (Balmer,
unaware of h, focused on the wavelength). Similar series are associated with Lyman, Paschen, Brackett, and Pfund.
Other experimental indications of quantization:
where p is the momentum and q is the position coordinate of an electron in three-dimensional space; the integral
is performed over some closed orbit in phase space {p, q}. Considering the electron as a wave with wavelength
λ = h/p, this Bohr-Sommerfeld quantization condition ensures that the wave is described by a function that is
single-valued.
Although the Bohr atom is a crude approximation of the full solution to the Schrödinger equation in a central
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Spring 2001 PHYS 385 Quantum Physics Course Summary
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Spring 2001 PHYS 385 Quantum Physics Course Summary
2 Wave Mechanics
2.1 The Wave Function
Wave mechanics refers to Schrödinger’s formalism of quantum mechanics, in which a quantum mechanical state is
represented by a complex wave function, which is frequently denoted by ψ(r, t). Born interpreted the wave function
as a complex probability amplitude. Given an ensemble of particles, all described by the same wave function, the
probability density for finding one particle at position r at time t is given by the norm squared of the wave function:
|ψ(r, t)|2
P(r, t) ≡ R . (4)
dr |ψ(r, t)|2
The integral in the denominator is taken to be over all space. The wave function may be multiplied by an arbitrary
complex constant, and this probability density will remain invariant; therefore, we are generally free to choose a
proper normalization of the wave function, such that
Z Z
dr P(r, t) = dr |ψ(r, t)|2 = 1. (5)
This normalization condition will set the magnitude of the wave function at every point in space, but it still leaves
us free to choose the complex phase of the wave function. In general, we choose this phase to simplify calculations
in any particular problem.
The wave function obeys the superposition principle, and therefore exhibits quantum interference: if one possible
state of a particle is given by ψ1 = |ψ1 |eiφ1 , and another possible state is given by ψ2 = |ψ2 |eiφ2 , so that the total
wave function is given by ψ = ψ1 + ψ2 ,
|ψ|2 = |ψ1 + ψ2 |2 = |ψ1 |2 + |ψ2 |2 + 2|ψ1 | |ψ2 | cos(φ1 − φ2 ). (6)
These plane waves are simultaneous eigenfunctions of the Hamiltonian, H = p2 /2m, and the momentum operator,
p = (h/i)∂/∂x. This is possible because [H, p] = 0. The energy eigenvalues of the plane wave states are doubly
degenerate: Ep = E−p . By labeling a state according to its momentum quantum number, we have a unique basis
in which to expand any one-dimensional wave function. Thus, we have expressed the wave function as a function
of x, t, and labelled it by its (continuous) momentum quantum number p. We did not use this notation at the time
that we developed Fourier analysis, but now you have seen other basis sets labelled by other quantum numbers,
and the meaning here is the same.
It is important to remember that any individual plane-wave basis function has a constant amplitude over all
space, and so is not actually normalizable. Thus, it is not a legitimate candidate for a physically admissible quantum
mechanical wave function. To construct a normalizable wave function, we must truncate the wave function in space,
which necessarily implies that the wave function is a superposition of plane waves with different p values. We write
such a superposition as ψ(p), calling it the momentum-space representation of the wave function. It is the Fourier
transform of the real-space, or coordinate, representation ψ(x):
Z ∞ Z ∞
1 ipx/~ 1
ψ(x) = √ dp e ψ(p) ψ(p) = √ dx e−ipx/~ ψ(x), (15a)
2π~ −∞ 2π~ −∞
Z ∞ Z ∞
ψ(x) = dp ψ(p)ϕp (x) ψ(p) = dx ϕp∗ (x)ψ(x). (15b)
−∞ −∞
Written in this way, we may understand ψ(p) as the coefficients of ψ(x) in the basis ϕp (x).
The momentum and coordinate representations of the wave function obey Parseval’s theorem:
Z ∞ Z ∞
dx |ψ(x)|2 = dp |ψ(p)|2 . (16)
−∞ −∞
The Fourier transform relations between x and p representations of the wave function lead directly to the Heisenberg
Uncertainty Relation:
~
(∆x)rms (∆p)rms ≥ . (17)
2
Additional Fourier transform relations exist between the time and frequency (or energy) domain, and between
real-space and momentum-space in d > 1 dimensions:
Z ∞ Z ∞
1 −iωt 1
f (t) = √ dω e F (ω) F (ω) = √ dt eiωt f (t), (18a)
2π −∞ 2π −∞
Z ∞ Z ∞
1 1
f (t) = √ dω e−iEt/~ F (E) F (E) = √ dt eiEt/~ f (t), (18b)
2π~ −∞ 2π~ −∞
Z Z
1 ip·x/~ 1
ψ(x) = p dp e ψ(p) ψ(p) = p dx e−ip·x/~ ψ(x). (18c)
(2π~)d (2π~)d
all all
space space
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Spring 2001 PHYS 385 Quantum Physics Course Summary
In d > 1, the Heisenberg Uncertainty Relation applies only to xi and pi , where i indicates a particular coordinate
axis. There is no problem with performing a measurement of the position along the x-axis and the momentum
along the y-axis, for example.
A wavepacket evolves in time according to the time-dependent Schödinger equation. To characterize the motion
of the wavepacket, two velocities prove useful,
ω ∂ω
vϕ = vg = , (19)
k ∂k
where vϕ is called the phase velocity and vg is called the group velocity. The group velocity of the wavepacket
corresponds to the classical motion of the particle.
We found that a 1D gaussian wavepacket is a wavepacket of minimum uncertainty, and will remain a gaussian
as it evolves, though with a time-dependent width. If the state at t = 0 has a real-space representation
Then, if we want to know the real-space width of the wavepacket, we back-transform to get ψ(x, t), which we may
write in the form
ψ(x, t) = {π[a(t)]2 }−1/4 exp{−(x − vg t)2 /2[a(t)]2 } exp[ip0 (x − vϕ t)/~], (24)
where [a(t)]2 = a2 + i~t/m. Thus, the envelope of the wavepacket moves at the group velocity vg = p0 /m, while
the underlying wavefronts move at the phase velocity vϕ = p0 /2m. The probability distribution |ψ(x, t)|2 will then
spread in time, according to s 2
a ~t
(∆x)rms = √ 1+ . (25)
2 ma2
For t ma/~, the width remains approximately constant,√growing only quadratically with time. However, for
t ma/~, the width grows linearly with time, at a rate ~/ 2ma = ~/2m(∆x)rms ' (∆p)rms /m = (∆v)rms .
The general solution of Schödinger’s equation in the infinite well is of the form:
∞
X
ψ(x) = cn ψn (x). (28)
n=1
If we are given some wave function ψ(x), then we can find the coefficient cn of ψn (x) by taking the inner product
of ψ(x) with ψn (x): Z ∞
cn = dx ψn∗ (x)ψ(x). (29)
−∞
Once we have found the spectral decomposition of the wave function ψ(x), we can find the time dependence of the
state by multiplying each basis state by the appropriate exponential factor e−iEt/~ :
∞
X
ψ(x, t) = cn e−iEn t/~ ψn (x). (30)
n=1
The probability density for finding the particle at position x at time t will be
∞
X
P(x, t) = |ψ(x, t)|2 = c∗m cn e−i(En −Em )t/~ ψm
∗
(x)ψn (x), (31)
m,n=1
which is oscillatory whenever the state ψ(x, t) involves more than one eigenstate of the Hamiltonian.
An exception to this general methodology is spin, which has no classical analogue, and is naturally represented in
terms of states in an abstract vector space, not as functions of spatial coordinates. Even here, however, the analysis
from point (3) onward may be employed with a simple substitution of Dirac kets (|+i, |−i for S = 1/2) instead of
eigenfunctions.
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Spring 2001 PHYS 385 Quantum Physics Course Summary
We can also write a general state |ψi in terms of some basis of states |ϕn i, usually the eigenstates of the Hamiltonian:
X
|ψi = cn |ϕn i. (33)
all
states
Here, as before, we write the spectral decomposition for a discrete basis; for a continuous basis we replace the sums
by integrals over the appropriate variable(s).
Given a particular orthonormal basis {|ϕn i} for the state space, we may write a general state in terms of the
coefficients cn in its spectral decomposition, just as we write a three-dimensional vector in terms of its coefficients
(vx , vy , vz ) in the expression v = vx x̂ + vy ŷ + vz ẑ. For kets, we write the coefficients as a column vector, and for
bras, we write them as a row vector:
c1 hϕ1 |ψi
c2 hϕ2 |ψi
hψ| = c∗1 c∗2 c∗3 . . . = hψ|ϕ1 i hψ|ϕ2 i hψ|ϕ3 i . . . , |ψi = c3 = hϕ3 |ψi . (34)
.. ..
. .
By writing them in this way, the inner product is just the matrix product of the row vector with the column vector:
cb1
∗ cb2 X
hψa |ψb i = ca1 ca2∗
c∗a3 . . . cb3 = c∗an cbn . (35)
.. n
.
We can describe the relationship between the bra and the ket by saying that one is the adjoint of the other,
where the adjoint operator is written as a superscript dagger:
In the matrix representation of the states (row and column vectors are 1xN and Nx1 matrices, respectively), the
adjoint of a matrix is the complex conjugate of its transpose:
†
M † = (M T )∗ Mij ∗
= Mji . (37)
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Spring 2001 PHYS 385 Quantum Physics Course Summary
These operators are associative under multiplication and addition, and commutative under addition, but they are
not commutative under multiplication: Ô1 Ô2 =
6 Ô2 Ô1 .
The projection operator is a particularly simple example of an operator, that projects an arbitrary state onto
some subspace of the state space. For a one-dimensional subspace of all states proportional to |ψS i, the projection
operator P̂ψS may be written as
P̂ψS = |ψS ihψS |. (39)
This has a matrix representation given by multiplying the column vector representation of |ψS i by the row vector
representation of hψS |. If |ψS i is one of the basis states, |ϕn i, then the matrix representation of P̂ψS has only one
nonzero element at position (n, n).
An orthonormal basis of a quantum mechanical state space satisfies the closure relation, which we write below
for different types of bases:
X
1̂ = |ϕn ihϕn | Discrete (40a)
n
Z
1̂ = dα |ϕ(α)ihϕ(α)| Continuous (40b)
X Z
1̂ = |ϕn ihϕn | + dα|ϕ(α)ihϕ(α)| Mixed (40c)
n
Mixed bases include the states of the finite potential well and of the hydrogen atom (where the continuum corre-
sponds to ionized states).
In quantum mechanics, each observable property of a physical system must be represented mathematically by
a Hermitian operator, which is self-adjoint; that is, given an inner product (ψa , ψb ) between two states in our state
space, a Hermitian operator Ĥ satisfies (ψa , Ĥψb ) = (Ĥψa , ψb ). Alternatively, we have
Ĥ = Ĥ † , ∗
Hij = Hji . (41)
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Spring 2001 PHYS 385 Quantum Physics Course Summary
The matrix elements are arranged in matrix format in the usual way,
A11 A12 ... A1j ...
A21 A22 ... A2j . . .
.. ... ..
A= . . (45)
Ai1 Ai2 ... Aij . . .
... ..
. ...
In a continuous basis (plane waves, for example) the matrix elements A(p, p0 ) are functions of continuous variables
p and p0 , and the matrix representation of operators becomes more awkward. The idea, nonetheless, is the same,
and the term “matrix element” continues to be used.
Linear operators may be characterized by their eigenvalues, and their corresponding eigenvectors. For a general
linear operator A, an eigenvector |ϕλ i of A, with eigenvalue λ, satisfies the eigenvalue equation
A|ϕλ i = λ|ϕλ i. (46)
Given a matrix representation of A, the eigenvalues λ of A will be given by the following characteristic equation:
A11 − λ
A12 . . .
det[A − λ1̂] = A21 A22 − λ . . . = 0. (47)
.. .
.
. .
A defining characteristic of Hermitian operators is that they have real eigenvalues. This is the reason that observ-
ables must be represented by them. Once we know the eigenvalues of A by solving its characteristic equation, we
may find an eigenvector |ϕn i associated with a particular eigenvalue λn by solving the system of equations given
by Eq. 46:
A11 A12 . . . c1 c1
A21 A22 . . . c2 c2
= λn . (48)
.. .. .. .
.
. . . .
If two eigenvectors of a Hermitian operator have different eigenvalues, then these eigenvectors are orthogonal.
We say that two states are distinct if they are not parallel; that is, they are not related by a simple constant factor.
For example, when we choose a baisis of N states to span an N -dimensional state space, each of the N states must
be distinct. An eigenvalue that is associated with one and only one distinct eigenvector is called nondegenerate, and
when we solve the system of equations given by Eq. 48, we will get N − 1 equations in N unknowns that completely
constrains the relationship among the coefficients {cn }. When several distinct eigenvectors satisfy the eigenvalue
equation, Eq. 46 for the same eigenvalue, the eigenvalue is called degenerate, and its degeneracy g is given by the
number of distinct eigenvectors associated with it. Eq. 48 then gives N − g equations in N unknowns, and we must
choose an appropriate basis for the degenerate subspace. In general, we must use the Gramm-Schmidt procedure
to find an orthogonal basis for the degenerate subspace:
1. Pick arbitrary coefficients {c1 , c2 , . . . }.
(1)
2. Normalize this state. This will be the first basis vector, |ϕn i, corresponding to eigenvalue λn .
3. Pick new, different coefficients {c01 , c20 , . . . }. Call the state defined by these coefficients |ψi.
(1)
4. From |ψi, create a new state |ψ 0 i that is orthogonal to |ϕn i, by projecting out any component parallel to it:
|ψ 0 i = (1̂ − Pψ(1) )|ψi.
n
(2)
5. Normalize |ψ 0 i to get the next basis vector, |ϕn i:
|ψ 0 i
|ϕ(2)
n i= p .
hψ 0 |ψ 0 i
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Spring 2001 PHYS 385 Quantum Physics Course Summary
6. Repeat steps (3)-(5) until you have found an orthonormal basis for the degenerate subspace.
Frequently, however, we may find an orthogonal basis for some degenerate subspace of A by identifying some
other Hermitian operator B that commutes with A. The plane wave basis for a free particle provides a particularly
simple example: |ψp i and |ψ−p i have the same eigenvalue in H = p2 /2m, but have different eigenvalues under p,
so they form an orthogonal basis for the two-fold degenerate subspace corresponding to eigenvalues p2 /2m of the
Hamiltonian. Similarly, we chose the 2` + 1 degenerate eigenstates of L2 to simultaneously satsify an eigenvalue
equation with Lz , each with a different eigenvalue m, so they were necessarily orthogonal.
5. If the measurement of A on |ψi gives the result an , the state immediately after the measurement is the
normalized projection of |ψi onto the subspace associated with an ,
Pϕan |ψi
p .
hψ|Pϕan |ψi
6. The time evolution of |ψ(t)i is given by the time dependent Schrödinger equation,
d
i~ |ψ(t)i = H|ψ(t)i,
dt
where H is the Hamiltonian of the system.
where the cn are the coefficients that define |ψi in terms of the eigenstates of A, and the an are the associated
eigenvalues of A. In wave mechanics, it is sometimes more straightforward to use the form
Z
hAi = dxψ ∗ (x)Aψ(x). (50)
It is important to recognize that the expectation value of an operator may not be an eigenvalue of the operator, so
that an individual measurement will never produce the expectation value as a result. The expectation value of the
operator is what would be obtained on average in a measurement on a large number of identically prepared states.
When two operators do not commute, it is not possible to perform their associated measurements with infinite
precision. This is related to the projection postulate (5). If [A, B] 6= 0, then the eigenstates of B can not be made
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Spring 2001 PHYS 385 Quantum Physics Course Summary
parallel to the eigenstates of A for all circumstances, and the order in which we perform our projection operations
will matter. We know from the Fourier analysis of wave mechanics that x and p can not be measured simultaneously
with infinite precision, and in fact their associated operators do not commute:
We may generalize the Heisenberg Uncertainty Principle to other observables by defining for an operator A an
rms uncertainty (∆A)rms , defined as the expectation value of the measurement error:
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Spring 2001 PHYS 385 Quantum Physics Course Summary
4 One-Dimensional Problems
4.1 General Features
If we consider a particle of mass m in an arbitrary one-dimensional (1D) potential, there are a few things that we
can say about it without actually solving the TISE. As shown in Fig. 1,
for a potential that is bounded above on the left by V =
0, on the right by V = Vmax , and bounded from below by V(x)
V = Vmin , there are four characteristic energy scales, each
with different types of states: a E
1. E > Vmax (Ea ): the eigenvalues of the TISE form a con- Vmax
tinuum, which is two-fold degenerate, with one rightward
travelling state and one leftward travelling state. Eb
2. 0 < E < Vmax (Eb ): the eigenvalues of the TISE form a
Ec x
nondegenerate continuum.
~2 d2 ψ(x)
− = (E − V )ψ(x), x ∈ D, (56)
2m dx2
which has three different categories of solution:
3. E = V , linear solutions:
ψ(x) = Cx + D. (59)
At the boundaries between domains with different constant potentials, the wave function must satisfy boundary
conditions. At the discontinuities in the potential, the wave function must be both continuous and differentiable.
By matching up the solutions for each domain using these boundary conditions, the complete solution to the TISE
for the piecewise constant potential may be obtained. Where the potential is symmetric about some point, then
the wave functions of the particle in the potential may have well-defined parity, and this may be used to provide
further conditions on the wave functions in different domains.
The basic potentials that we considered were:
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Spring 2001 PHYS 385 Quantum Physics Course Summary
1. The finite potential well. This has both bound state solutions, which we found by solving a transcendental
equation with a graphical method. The continuum solutions behave similarly to the scattering solutions of
the barrier potential, discussed below.
2. The potential step. This has a continuum of solutions, and we found the coefficients of transmission and
reflection at the step. If we consider the left hand side of the step Region 1, and the right hand side Region 2,
then the transmission and reflection coefficients for a particle moving from left to right are
(+) 2 (−) 2
k2 A2 A1
T = and R = (+) . (60)
k1 A(+) A
1 1
The factor of k2 /k1 in the transmission coefficient arises because the coefficient is defined in terms of a ratio
of the probability current density S on each side of the step. The current density is proportional to the speed,
which is different on either side of the step, so the transmission coefficient includes the ratio of the speeds in
addition to the square of the ratio of the amplitudes.
3. The barrier potential. We discussed two types of solutions: scattering for E > V0 , and tunnelling for E < V0 ,
where V0 is the potential height of the barrier. The scattering solutions are valid for both positive and negative
values of V0 . We found that for the scattering solutions, the transmission coefficient of the barrier exhibited
resonances, like the resonances of a Fabry-Perot cavity in optics:
4E(E − V0 )
T = p . (61)
4E(E − V0 ) + V02 sin2 [ 2m(E − V0 )L/~]
For the tunneling solutions are given by this equation, after some manipulation to account for the fact that
the argument of the sine function becomes imaginary:
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Spring 2001 PHYS 385 Quantum Physics Course Summary
[a, a† ] = 1. (69)
By examining the properties of N , a, a† , and their various commutation relations, we were able to prove that
n ∈ N. Thus, the energy spectrum of the harmonic oscillator Hamiltonian is
1
En = n + ~ω n ∈ N. (73)
2
We found that in the basis of Hamiltonian eigenstates, the matrix elements of a and a† are
√
amn = nδm,n−1 , (74a)
√
a†mn = n + 1δm,n+1 . (74b)
Thus, given an arbitrary state |ϕn i, we can use the creation and annihilation operators to generate all other
eigenstates of the Hamiltonian. Writing Eqs. 68 in the differential operator form of wave mechanics allows us to
calculate the wave functions ϕn (x), first by solving a|ϕ0 i = 0, then using the creation operator to generate the
higher energy states, via
1
|ϕn i = √ (a† )n |ϕ0 i. (75)
n!
The first few eigenfunctions are
mω 1/4
1 mω 2
ϕ0 (x) = exp − x , (76a)
π~ 2 ~
1/4
4 mω 3 1 mω 2
ϕ1 (x) = x exp − x (76b)
π ~ 2 ~
mω 1/4 mω
1 mω 2
ϕ2 (x) = 2 x2 − 1 exp − x (76c)
4π~ ~ 2 ~
By inverting Eqs. 68, we can also find the matrix elements of x and p in the same basis:
r
~ √ √
xmn = n + 1 δm,n+1 + n δm,n−1 , (77a)
2mω
r
m~ω √ √
pmn = i n + 1 δm,n+1 − n δm,n−1 , (77b)
2
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Spring 2001 PHYS 385 Quantum Physics Course Summary
In addition to the operator method for finding the eigenfunctions of the harmonic p
oscillator, we solved the
differential equation given by the TISE in wave mechanics. With the substitutions ξ = mω/~x and ε = E/~ω,
this differential equation is
d2 ψ(ξ)
+ (2ε − ξ 2 )ψ(ξ) = 0. (78)
dξ 2
2
We solved this equation in the limit ξ → 0 first, to find solutions of the gaussian form ψ(ξ) ∝ e−ξ /2 . We then
2
wrote the general solution as a product of this gaussian with a polynomial function, ψ(ξ) = h(ξ)e−ξ /2 , with
∞
X
h(ξ) = am ξ m , (79)
m=0
and where h(ξ) dominates the behavior of the eigenfunction for ξ → 0. The differential equation then yields a
recursion relation that relates the am for different values of m:
From the recursion relation we were able to find the eigenfunctions of even and odd parity, for a discrete set of
εm = m + 1/2 that terminate the polynomial sum in Eq. 79.
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Spring 2001 PHYS 385 Quantum Physics Course Summary
5 Angular Momentum
5.1 General Properties
We define angular momentum in quantum mechanics just as we do in classical mechanics,
L = r × p. (81)
Due to the nonzero commutators among the various components of L, it is impossible to measure all three
components of the angular momentum simultaneously. In fact, if we measure the component of L along one axis, in
general the projection of the state along that axis will disrupt any subsequent measurements of L along a different
axis. This is known as spatial quantization. By convention, we choose Lz to be the quantization axis of angular
momentum, and express states of angular momentum in terms of the simultaneous eigenvectors of Lz and L2 , which
commutes with Lz . The eigenvalue equations are
Through operator methods similar to those that we used to solve the harmonic oscillator, we found the following
conditions on `, m:
2` ∈ N, m1 − m2 ∈ Z, (85a)
` ≥m ≥ −`, 2` + 1 allowed values. (85b)
We found that the L± operators act much as the operators a and a† act in the state space of the harmonic oscillator,
by transforming the states |ϕ`m i into the states |ϕ`m±1 i. The matrix elements are
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Spring 2001 PHYS 385 Quantum Physics Course Summary
and the first few normalized spherical harmonics obtained from this procedure are
r
1 15
Y00 = √ Y22 = sin2 θe2iφ
4π 32π
r r
3 iφ 15
Y11 = − sin θe Y21 = − sin θ cos θeiφ (95)
8π 8π
r r
3 5
Y10 = cos θ Y20 = (3 cos2 θ − 1),
4π 16π
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Spring 2001 PHYS 385 Quantum Physics Course Summary
and
Y` −m = (−1)m Y`m . (96)
We may express any function of angular coordinates in terms of the spherical harmonics, according to the usual
expansion:
∞ X̀
X
f (θ, φ) = a`m Y`m (θ, φ), (97a)
`=0 m=−`
Z
∗
a`m = dΩ Y`m (θ, φ)f (θ, φ) (97b)
Z 2π Z π
∗
= dφ dθ sin θ Y`m (θ, φ)f (θ, φ) (97c)
0 0
Since there are now two quantum numbers, ` and m, the probability of obtaining `(` + 1)~2 in a measurement
of L2 is a sum,
X̀
P (`) = |a`m |2 , (98)
m=−`
We also have expressions for expectation values that involve double summations:
∞ X̀
X
hL2 i = `(` + 1)~2 |a`m |2 (100a)
`=0 m=−`
∞ X̀
X
hLz i = m~ |a`m |2 (100b)
`=0 m=−`
pr2 L2
H= + + V (r) (101a)
2m 2mr2
~2 1 ∂ 2 ∂ L2
=− 2
r + + V (r), (101b)
2m r ∂r ∂r 2mr2
and if we write ψ(r, θ, φ) = R(r)Y`m (θ, φ), then the TISE may be transformed, using the eigenvalue equation for
L2 Y`m , into an ordinary differential equation for R(r),
~2 1 d 2 d ~2 `(` + 1)
− r + + V (r) Rk` (r) = Ek` Rk` (r), (102)
2m r2 dr dr 2mr2
where we have introduced the subscripted Ek` and Rk` (r) to identify the eigenvalue equation that is being solved
(`) as well as the particular eigenvalue associated with that solution (k).
By introducing a new function,
uk` (r) = rRk` (r), (103)
we can convert Eq. 102 into another, simpler equation,
~2 d2 ~2 `(` + 1)
− + + V (r) uk` (r) = Ek` uk` (r), (104)
2m dr2 2mr2
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Spring 2001 PHYS 385 Quantum Physics Course Summary
which looks just like the 1D TISE except that we have an effective potential
`(` + 1)~2
Veff (r) = V (r) + , (105)
2mr2
and we have an additional boundary condition,
uk` (r → 0) → 0. (106)
~2 2 e~ e2
H=− ∇ − A·∇+ A2 + V (r). (111)
2m imc 2mc2
For a constant magnetic field, the vector potential in the Coulomb gauge is A = (r × B)/2, and for a field B = Bz ẑ,
the Hamiltonian becomes
~2 2 e e2
H=− ∇ − Lz Bz + B 2 (x2 + y 2 ) + V (r). (112)
2m 2mc 8mc2 z
The second and third terms on the right hand side of Eq. 112 are responsible for paramagnetism and diamagnetism,
respectively. Since Lz is in units of ~, the paramagnetic term provides the basis for quantizing the magnetic moment
of a charged particle with angular momentum. The quantum of magnetic moment is the Bohr magneton, and is
written as
e~
µB = . (113)
2mc
For electrons, this is a negative number, and the magnetic moment points antiparallel to the magnetic field.
The Hamiltonian of a particle with spin in a magnetic field is analagous to the paramagnetic term in Eq. 112:
gµB
Hspin = − S · B, (114)
~
where the gyromagnetic ratio or g-factor g = 2.0023 ' 2 for electrons. For an orbital magnetic moment the g-factor
is g = 1.
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Spring 2001 PHYS 385 Quantum Physics Course Summary
To find the solutions of the TISE, it is useful to make a coordinate transformation into center-of-mass-coordinates,
m1 m2
M = m1 + m2 µ= (117a)
m1 + m2
m1 r1 + m2 r2
R= r = r1 − r2 (117b)
m1 + m2
m2 p1 − m1 p2
P = p1 + p2 p= (117c)
m1 + m2
The transformed Hamilton is then
P2 p2
H= + + V (r), (118)
2M 2µ
√
which has solutions of the form ψ(R, r) = ϕP (R)ψµ (r) where ϕP (R) = eiP·R / 2π~ are just the eigenfunctions
of a free particle (which is the whole hydrogen atom). This reduces the two-particle Hamiltonian to an effective
single-particle Hamiltonian, the eigenfunctions of which are the internal states of the hydrogen atom.
~2 e2 r 2 En`
a0 = , EI = , ρ= , λn` =− , (120)
µe2 2a0 a0 EI
where we have changed the radial quantum number from k to n in anticipation of the integer values of n. With
these substitutions, the radial equation becomes
2
d `(` + 1) 2Z 2
− + − λn` uk` (ρ) = 0, (121)
dρ2 ρ2 ρ
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Spring 2001 PHYS 385 Quantum Physics Course Summary
where
∞
X
T (ρ) = ρs aq ρq . (125)
q=0
We obtain s = ` + 1 from the boundary condition of Eq. 106. When we plug Eq. 124 into Eq. 121, we get the
recursion relation
q(q + 2` + 1)aq = 2[λn` (` + q) − Z]aq−1 . (126)
This recursion relation will generate a series T (ρ) that will not be normalizable if it is not terminated. Thus, the
only good solutions to the radial equation are those for which aq = 0 for some q, for this to occur we must have
λn` (` + q) − Z = 0. Returning to the dimensionful quantities in Eq. 120, we have
Z 2 e2
En` = − , n ∈ N, n ≥ ` + 1. (127)
n2 2a0
Thus we have solved for the energy spectrum of the hydrogen atom, which has levels that are n2 -fold degenerate
for each value of n, due to the multiplicity of angular momentum states for each radial quantum number.
A few of the properly normalized solutions to the radial equation are listed below, together with its name in
spectroscopic notation.
3/2
Z
1s R10 (r) = 2 exp(−Zr/a0 ) (128a)
a0
3/2
Z Zr
2s R20 (r) = 2− exp(−Zr/2a0 ) (128b)
2a0 a0
3/2
Z 1 Zr
2p R21 (r) = √ exp(−Zr/2a0 ) (128c)
2a0 3 a0
3/2 " 2 #
Z 2 Zr 2 Zr
3s R30 (r) = 2 1− + exp(−Zr/3a0 ) (128d)
3a0 3 a0 27 a0
3/2 √
Z 4 2 Zr 1 Zr
3p R31 (r) = 1− exp(−Zr/3a0 ) (128e)
3a0 3 a0 6 a0
3/2 r 2
Z 2 2 Zr
3d R32 (r) = exp(−Zr/3a0 ) (128f)
3a0 27 5 a0
(128g)
The spherical symmetry of the 1/r potential implies that the eigenfunctions of the Hamiltonian will have well-
defined parity, where in three dimensions the parity operator changes the sign of all three cartesian coordinate
axes: P ψ(r) = ψ(−r). We have
P |ψn`m i = (−1)` |ψn`m i (131)
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Spring 2001 PHYS 385 Quantum Physics Course Summary
If an operator has well-defined parity, also, then we may immediately identify nonzero matrix elements as those
which do not change sign when the parity operator acts on both the operator and the states. In particular, the
interaction of electromagnetic radiation with atoms is dominated by the interaction of the electric field with the
electric dipole of the atom. For the atom to possess an electric dipole, it must be in a superposition of states which
have opposite parity, since the electric dipole operator is odd under parity. This is an example of a selection rule
on atomic transitions. Upon further analysis of the properties of the electric dipole operator, we may obtain the
following electric dipole selection rules:
∆` = ±1 (132)
∆m = 0, ±1. (133)
These selection rules, together with the principle of the conservation of angular momentum, imply that electro-
magnetic carries angular momentum, and that it is quantized in units of Lz = ±~, where we choose z to be along
the direction of propogation.
Here, the αn are the quantum numbers that identify the particular single-particle state, including the spin projection
quantum number. The fully antisymmetric state may be written as a determinant of a matrix of single-particle
wave functions, called a Slater determinant:
ψα1 (1) ψα1 (2) . . . ψα1 (N )
ψα2 (1) ψα2 (2) . . . ψα2 (N )
(a)
ψ (1, 2, . . . , N ) = . .. .. (137)
.. . .
ψα (1) ψα (2) . . . ψα (N )
N N N
The Pauli Exclusion Principle is expressed here by the fact that if any two single-particle states in this determinant
are the same, then two rows of the matrix will be identical, and the determinant will be zero.
One of the many consequences of the Pauli exclusion principle is the structure of the periodic table. As the
nuclear charge increases, so that we need to add more electrons for charge neutrality, each new electron must go into
a different quantum state. Since the spin projection quantum number of an electron may take two different values,
each hydrogenic wave function may hold two electrons. For low Z atoms, the electronic states fill up “in order,”
22
Spring 2001 PHYS 385 Quantum Physics Course Summary
that is, 1s, 2s, 2p, 3s, 3p. But beyond this, the interaction of the electrons with each other become important, and
in the transition metal series and beyond, the structure is more complicated (or richer, depending on the eye of the
beholder).
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Spring 2001 PHYS 385 Quantum Physics Course Summary
In this basis, we may write S = ~2 σ, where the components of σ are the three Pauli matrices:
0 1 0 −i 1 0
σx = σy = σz = (139)
1 0 i 0 0 −1
The Pauli matrices exhibit commutation relations that are similar to the operators of angular momentum,
Spatial quantization results from these commutation relations. That is, if we know that the system is in an
eigenstate of Sz , say |+i, then it must be in a superposition of eigenstates of Sx , or of any other operator that
projects the spin along an axis different from z. Consequently, if we apply a magnetic field along an axis that is
different from the original quantization axis, the spin will precess around the magnetic field, and oscillat between |+i
and |−i with a frequency ω = ∆E/~ = 2µB B/~. Our treatment of this precession followed the general methodology
laid out in Sec. 2.5.
Although in any particular case it is fairly straightforward to solve for the eigenvalues and eigenvectors of a
2 × 2 Hermitian matrix, we discussed a general method of solution. We can write the Hamiltonian matrix as a sum
of two matrices, one proportional to 1̂ and the other proportional to a traceless matrix that we denote by K,
1 1
H= (H11 + H22 )1̂ + (H11 − H22 )K, (141)
2 2
where !
2H12
1 H11 −H22
K= 2H21 . (142)
H11 −H22 −1
The all states are eigenstates of 1̂, so the eigenstates of the Hamiltonian are determined by the eigenstates of K:
with solutions p
1 (H11 − H22 )2 + 4|H12 |2
κ± = ± =± . (147)
cos θ H11 − H22
Thus the energy eigenvalues are
1 1p
E± = (H11 + H22 ) ± (H11 − H22 )2 + 4|H12 |2 , (148)
2 2
with associated eigenvectors
cos 2θ e−iφ/2 − sin θ2 e−iφ/2
|ψ+ i = |ψ− i = (149)
sin θ2 eiφ/2 cos θ2 eiφ/2
Note that the angles θ, φ may be interpreted as the azimuthal and meridional angles, respectively, of a fictitious
spin with respect to the quantization axis. For θ = 0, |ψ+ i = |+i, while for θ = π, |ψ+ i = |−i.
The Pauli matrices, together with 1̂, form a basis for the space of all 2 × 2 Hermitian matrices. Thus, any
two-state system may be described by the formalism that we have developed for spin. We discussed how this
formalism could be applied to a variety of physical systems, including the inversion oscillations of the ammonia
molecule, the bonding and antibonding states of the H+ ion, and the resonating valence bond of benzene. In each
of these examples, we identified two states of the system, {|+i, |−i}, which would be degenerate if the Hamiltonian
exhibited no coupling between them. As we turned on some coupling, however, represented by off-diagonal matrix
elements in the Hamiltonian, we found that the eigenstates of the Hamiltonian became superpositions of the original
two states, {|ψ+ i, |ψ− i} and the energy of one state rose while the other fell in energy; for H11 = H22 = E and
H12 = −V , we found energy levels E± = E ± V . We saw that if the system is placed in a superposition of states
with different energies, then the system will precess, just as the spin system does in a magnetic field, at a frequency
ω = ∆E/~.
We also discussed the phenomenon of level anticrossing in the application of an electric field to the ammonia
molecule. Here, the effect of an electric field may be represented as a diagonal matrix in basis {|+i, |−i}, but
it has off-diagonal matrix elements in the basis {|ψ+ i, |ψ− i}. Thus, when the field is zero, the eigenstates of
the Hamiltonian are {|ψ+ i, |ψ− i}, but as the field is turned on, the eigenstates of the Hamiltonian transform
continuously into {|+i, |−i} at high fields, E V /d, where E is the electric field, V is the intrinsic coupling
between the two states |+i and |−i, and d is the electric dipole strength of the ammonia molecule.
25