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Günter Ludyk

Quantum
Mechanics in
Matrix Form
Quantum Mechanics in Matrix Form
Günter Ludyk

Quantum Mechanics
in Matrix Form

123
Günter Ludyk
Physics and Electrical Engineering
University of Bremen
Bremen
Germany

ISBN 978-3-319-26364-9 ISBN 978-3-319-26366-3 (eBook)

https://doi.org/10.1007/978-3-319-26366-3
Library of Congress Control Number: 2017954872

© Springer International Publishing AG 2018

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In memory of my parents

Martha and Paul Ludyk

Preface and Introduction

Though this be madness, yet there is method in’t.

Hamlet, William Shakespeare

Matrix mechanics was introduced in 1925 by the German physicist Werner

Heisenberg1 [13]. However, the American Nobel laureate Steven Weinberg2 writes
about this publication [26]:
If the reader is mystified at what Heisenberg was doing, he or she is not alone. I have tried
several times to read the paper that Heisenberg wrote on returning from Helgoland, and,
although I think I understand quantum mechanics, I have never understood Heisenberg’s
motivations for the mathematical steps in his paper.

For years, Heisenberg and his colleagues had been struggling with a problem that
had been raised in 1913 by Niels Bohr3 in his atomic theory: why do electrons in
atoms occupy only certain permitted orbits with certain well-defined energies?
Heisenberg took a completely new approach to this question. Because the trajectory
of an electron in an atom cannot be directly observed, he decided to deal only with
measurable quantities (namely the allowed energies for the quantum states of all
electrons in the atom, as well as the frequencies with which an atom spontaneously
jumps from one of these quantum states to a different state while emitting a light
particle, i.e., a photon). Heisenberg introduced a sort of “table” of these frequencies.
He performed mathematical operations on it, which led to new tables for the various
physical quantities such as position, velocity, or the square of the velocity of an
electron.
To be more precise, the table entries were the so-called transition amplitudes,
that is, quantities whose squares specify a transition probability. When returning

1
Werner Heisenberg, 1901–1976, German physicist, Nobel Prize 1932.
2
Steven Weinberg, * 1933, American physicist, Nobel Prize 1979.
3
Niels Bohr, 1885–1962, Danish physicist, Nobel Prize 1922.

vii
viii Preface and Introduction

from Helgoland (where he first had this crucial idea) to Göttingen, Heisenberg
found out that the operations he applied to these tables were well known to
mathematicians. The tables were called matrices, and the operations that he used to
get from the table representing the electron velocity to the table representing the
square was named matrix multiplication. Starting from the known dependence
between the energy of a particle and its velocity and position in a simple system,
Heisenberg could calculate a table of the system’s energies in its different quantum
states, similar to Newton’s4 calculation of the energy of a planet based on its
position and velocity.
At the time, Heisenberg was constantly in touch with some influential theoretical
physicists, including the German researchers Max Born5 and Pascual Jordan6 and
the English physicist Paul Dirac.7 Until the end of the year 1925, they transformed
Heisenberg’s ideas into a comprehensive and systematic version of quantum
mechanics, which today we refer to as matrix mechanics. With the help of the new
matrix mechanics, the German physicist Wolfgang Pauli8 managed in the following
January to solve the paradigmatic problem in atomic physics, namely the calcula-
tion of the energy levels of the hydrogen atom. His calculations proved the earlier
ad hoc results of Bohr.
H.S. Green, an employee of Max Born, writes in [12]:
Most books on quantum theory emphasize the wave mechanical approach (of Schrödinger9),
probably because it is supposed to be easier to understand for those who already have a solid
knowledge on differential equations.

In this book, however, we restrict ourselves to the algebraic method using matrices
and only briefly describe Schrödinger’s wave mechanics in order to show the
equivalence with Heisenberg’s matrix mechanics. By implementing numerical
algorithms in standard software such as MAPLE or MATHEMATICA, matrices
and matrix equations are easy to handle these days [23].
I would like to thank Dr. Claus Ascheron from Springer for his kind assistance
during the compilation of this manuscript. Last but not least, I would like to express
my gratitude towards my wife Renate, without whom this book would have never
been published.

Bremen, Germany Günter Ludyk

4
Isaac Newton, 1642–1727.
5
Max Born, 1882–1970, German physicist, Nobel Prize 1954.
6
Pascual Jordan, 1902–1980, German physicist.
7
Paul Dirac, 1902–1984, English physicist, Nobel Prize 1933.
8
Wolfgang Pauli, 1900–1958, German physicist, Nobel Prize 1945.
9
Erwin Schrödinger, 1887–1961, Austrian physicist, Nobel Prize 1933.
Notations

Important definitions, facts, and theorems are shown in boxes. Important in-
termediate results are double underlined.

Scalars are written in normal font:

a; b; c; a; b; °; . . .

Vectors are written as lowercase letters in bold font:

x, p, v, …
Vectors in four-dimensional spacetime (R4 ) are written as bold lowercase letters
with an arrow:

~
x;~
v;~
u; . . .

Matrices are written as uppercase letters in bold font:

X; P; R; I; . . .

Matrix vectors are written as uppercase letters in bold Fraktur font:

<; X; B; . . .

Matrix vectors are block matrices:

0 1
X1
def @
<¼ X 2 A:
X3

The identity matrix In of size n is an n-by-n matrix in which all the elements on the
main diagonal are equal to 1 and all other elements are equal to 0:

ix
x Notations

0 1
1 0 0 0
B0 1 0 0C
I4 ¼ B
@0
C
0 1 0A
0 0 0 1

If the components are real numbers (R), the transpose of a vector x or a matrix A is
written as xT and AT, respectively. If the components are complex numbers (C), the
transpose is written as xy and Ay , respectively. In this case, the components of the
transpose row vector are the complex conjugate. Note that this is necessary in order
for the scalar product xy x to be a real number. The same reasoning applies to the
transpose matrix elements.
Contents

1 Quantum Theory Prior to 1925 . . . ..... . . . . . . . . . . . . . . . . . . . 1

1.1 Bohr–Sommerfeld Quantization Rule . . . . . . . . . . . . . . . . . . . . 1
1.2 Sommerfeld’s Derivation . . . . . ..... . . . . . . . . . . . . . . . . . . . 2
1.3 Bohr’s Postulates . . . . . . . . . . ..... . . . . . . . . . . . . . . . . . . . 7
1.4 Atom Sizes . . . . . . . . . . . . . . . ..... . . . . . . . . . . . . . . . . . . . 7
2 Heisenberg’s Year 1925 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
2.1 Spectral Lines . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
2.2 Introduction of Matrices . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
2.3 Problems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20
3 Expansion of the Matrix Method . ........... . . . . . . . . . . . . . . 23
3.1 Commutation Relation . . . . . ........... . . . . . . . . . . . . . . 23
3.2 Systems with Several Degrees of Freedom . . . . . . . . . . . . . . . . 28
3.3 Transformations . . . . . . . . . . ........... . . . . . . . . . . . . . . 29
3.4 Problems . . . . . . . . . . . . . . . ........... . . . . . . . . . . . . . . 31
4 Observables and Uncertainty Relations . . . . . . . . . . . . . . . . . . . . . . 33
4.1 State Vector . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 33
4.2 The Stern-Gerlach Experiment . . . . . . . . . . . . . . . . . . . . . . . . . 34
4.3 States and Postulates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 35
4.4 Projection Matrices . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 36
4.5 Probabilistic Interpretation . . . . . . . . . . . . . . . . . . . . . . . . . . . . 38
4.6 Density Matrix . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 39
4.6.1 Definitions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 39
4.6.2 Mixed States . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 40
4.6.3 Examples . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 42
4.7 Time Evolution of the Expectation Value . . . . . . . . . . . . . . . . . 43
4.8 Heisenberg’s Uncertainty Principle . . . . . . . . . . . . . . . . . . . . . . 44
4.9 Problems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 46

xi
xii Contents

5 The Harmonic Oscillator . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 47

5.1 Physics of the Harmonic Oscillator . . . . . . . . . . . . . . . . . . . . . 47
5.2 Expectation Values and Variances . . . . . . . . . . . . . . . . . . . . . . 56
5.3 Problems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 57
6 Angular Momentum . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 59
6.1 The Matrix Vector of the Angular Momentum . . . . . . . . . . . . . 59
6.2 Eigenvalues and Eigenvectors of L2 and L3 . . . . . . . . . . . . . . . 63
6.2.1 Commutativity of L2 and L3 . . . . . . . . . . . . . . . . . . . . 63
6.2.2 Eigenvalues and Eigenvectors . . . . . . . . . . . . . . . . . . . 64
6.2.3 Maximum and Minimum Eigenvalues . . . . . . . . . . . . . 65
6.2.4 Orientation of the Angular Momentum Vectors . . . . . . 68
6.2.5 The Matrices L2 and L3 . . . . . . . . . . . . . . . . . . . . . . . 69
6.2.6 The Matrices L þ , L , L1 and L2 . . . . . . . . . . . . . . . . . 71
6.3 Problems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 75
7 Wolfgang Pauli and the Hydrogen Atom . . . . . . . . . . . . . . . . . . . . 77
7.1 Basic Matrices and Matrix Vectors . . . . . . . . . . . . . . . . . . . . . 77
7.2 Introduction of the Matrix Vector A . . . . . . . . . . . . . . . . . . . . 79
7.3 The Hydrogen Spectrum . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 83
7.4 Problems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 84
8 Spin . ..................................... . . . . . . . . . . . 85
8.1 Magnetic Fields and Light . . . . . . . . . . . . . . . . . . . . . . . . . . . . 85
8.2 Derivation of the Zeeman Effect (Without Spin) . . . . . . . . . . . . 85
8.3 Symmetry Considerations . . . . . . . . . . . . . . . . . . . . . . . . . . . . 87
8.4 Symmetry and the Spin . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 91
8.5 Spin-12 Systems and Spinors . . . . . . . . . . . . . . . . . . . . . . . . . . . 93
8.6 Adding Angular Momenta . . . . . . . . . . . . . . . . . . . . . . . . . . . . 94
8.6.1 Clebsch–Gordan Coefficients . . . . . . . . . . . . . . . . . . . . 94
8.6.2 Clebsch–Gordan Coefficients on the Internet . . . . . . . . 98
8.7 Spin-Orbit Coupling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 98
8.8 Problems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 104
9 Atoms in Electromagnetic Fields . . . . . . . . . . . . . . . . . . . . . . . . . . . 105
9.1 Normal Zeeman Effect . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 105
9.2 Anomalous Zeeman Effect . . . . . . . . . . . . . . . . . . . . . . . . . . . . 105
9.2.1 Weak Field Limit . . . . . . . . . . . . . . . . . . . . . . . . . . . . 105
9.2.2 Strong Magnetic Field . . . . . . . . . . . . . . . . . . . . . . . . 109
9.3 Problem . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 109
10 Many Particle Systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 111
10.1 Composed Systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 111
10.1.1 Systems with Two Distinguishable Particles . . . . . . . . . 111
10.1.2 Systems with N Distinguishable Subsystems . . . . . . . . 113
Contents xiii

10.1.3 Entangled Systems . . . . . . . . . . . . . . . . . . . . . . . . . . . 114

10.2 Indistinguishable Subsystems . . . . . . . . . . . . . . . . . . . . . . . . . . 115
10.2.1 Interchanging Two Particles . . . . . . . . . . . . . . . . . . . . 119
10.2.2 Interchanging Three Identical Particles . . . . . . . . . . . . . 124
10.2.3 Interchanging N Identical Particles . . . . . . . . . . . . . . . 125
10.3 Problems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 128
11 Equivalence of Matrix and Wave Mechanics . . . . . . . . . . . . . . . . . 129
11.1 The De Broglie Wavelength . . . . . . . . . . . . . . . . . . . . . . . . . . 129
11.2 Operators in the Schrödinger Formalism . . . . . . . . . . . . . . . . . . 130
11.3 Schrödinger’s Wave Mechanics . . . . . . . . . . . . . . . . . . . . . . . . 131
11.4 Equivalence of Heisenberg and Schrödinger Pictures . . . . . . . . 134
11.5 Example: The Harmonic Oscillator . . . . . . . . . . . . . . . . . . . . . 139
11.6 Problems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 140
12 Relativistic Quantum Mechanics . . . . . . . . . . . . . . . . . . . . . . . . . . . 141
12.1 Special Relativity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 141
12.1.1 Four-Dimensional Spacetime . . . . . . . . . . . . . . . . . . . . 141
12.1.2 Lorentz Transformation . . . . . . . . . . . . . . . . . . . . . . . . 142
12.1.3 Velocity and Its Lorentz Transformation . . . . . . . . . . . 143
12.1.4 Momentum and Its Lorentz Transformation . . . . . . . . . 144
12.1.5 Equation of Motion and Force . . . . . . . . . . . . . . . . . . 144
12.1.6 Energy and Rest Mass . . . . . . . . . . . . . . . . . . . . . . . . 146
12.2 The Dirac Equation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 147
12.2.1 The Wave Equation for a Free Particle . . . . . . . . . . . . 147
12.2.2 Invariant Form of the Dirac Equation . . . . . . . . . . . . . 150
12.2.3 Solution of the Dirac Equation . . . . . . . . . . . . . . . . . . 151
12.2.4 Dirac’s Interpretation of the Negative Energy . . . . . . . . 153
12.3 Problems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 154
Appendix A: Solutions to Problems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 155
Appendix B: The Kronecker Product . . . . . . . . . . . . . . . . . . . . . . . . . . . . 183
Appendix C: Fourier Decomposition of Periodic Functions . . . . . . . . . . . 185
Appendix D: Laplace–Runge–Lenz Vector . . . . . . . . . . . . . . . . . . . . . . . . 187
Appendix E: Permutation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 191
Appendix F: Determinants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 193
Appendix G: Dirac’s Bra-Ket Notation . . . . . . . . . . . . . . . . . . . . . . . . . . . 195
Appendix H: Proofs of Pauli’s Formulas . . . . . . . . . . . . . . . . . . . . . . . . . . 197
Appendix I: Physical Quantities and Units . . . . . . . . . . . . . . . . . . . . . . . . 207
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 209
Index . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 211
Chapter 1
Quantum Theory Prior to 1925

Abstract A description is given of the “Older Quantum Mechanics” as introduced

by Nils Bohr and Arnold Sommerfeld in the years before 1925. Bohr’s postulates
are formulated and the atom size is derived from them.

1.1 Bohr–Sommerfeld Quantization Rule

Before the behavior of atoms could be described with the help of quantum mechan-
ics, Bohr and Sommerfeld1 explained the spectra of simple atoms based on Bohr’s
atom model (“Older Quantum Mechanics”). In this model, spectral lines appear as
energy differences between two “discrete” electron orbits. The Bohr–Sommerfeld
quantization rule requires that not only the equation of motion holds for the orbit of
the electron around the nucleus, but that for each additional circulation

p dx = nh (n = 1, 2, . . . ) (1.1)

applies, where p is the momentum, and the position x runs through one complete
circle. As does the angular momentum, this integral has the dimension location times
moment and is an action. The constant

h = 2π ·  = 2π · 1.054572 · 10−34 J s = 6.6260755 · 10−34 J s

is the Planck quantum of action or Planck’s constant.2 In other words, the action of
each stationary electron orbit in the atom is quantized. The action can only occur as
an integer multiple of Planck’s constant. A detailed derivation of this principle by
Sommerfeld [22] is presented in the following section.

1 Arnold Sommerfeld, 1868–1951, German physicist.

2 Max Planck, 1858–1947, German physicist, Nobel Prize 1919.
© Springer International Publishing AG 2018 1
G. Ludyk, Quantum Mechanics in Matrix Form,
https://doi.org/10.1007/978-3-319-26366-3_1
2 1 Quantum Theory Prior to 1925

1.2 Sommerfeld’s Derivation

Let us consider an arbitrarily moving point mass with momentum

p = mv. (1.2)

With v = q̇ we get
p = m q̇. (1.3)

It is important to note that the dynamic triple of the momentum coordinates p is

considered in addition to the geometric triple of the position coordinates q. Newton
supplies
∂ E pot
ṗ = f = − , (1.4)
∂q

where it was assumed that the force f can be derived from a potential energy E pot
(which is a function of the position coordinates q). Using (1.3), the kinetic energy is
obtained as
m  1 
E kin = q̇ q̇ = p p.
2 2m
The total energy as a function of the qk and pk is also called the Hamilton function
or Hamiltonian H . We hence have
∂H ∂ E pot ∂H ∂ E kin p
H (q, p) = E kin + E pot , = , = = .
∂q ∂q ∂p ∂p m

As a result, the basic (1.3) and (1.25) can be written as

dq ∂H dp ∂H
= , =− . (1.5)
dt ∂p dt ∂q

Assuming that the kinetic energy is expressed as a function of q and q̇, the equation

∂ E kin
p= (1.6)
∂ q̇

is identical to (1.3).
The values of the coordinates q and p determine the state of the system. To
understand how the state of motion of the system depends on the location q and
the speed/momentum p, let us imagine a single mass point with three degrees of
freedom. Its three location coordinates and its three momentum coordinates can be
plotted as Cartesian coordinates in a state space of six dimensions, such that each
point of this state space represents a potential state of our mass point. Accordingly,
for a system with d degrees of freedom one gets a state space with 2d dimensions.
1.2 Sommerfeld’s Derivation 3

In a first step, we can restrict ourselves to systems with only one degree of freedom.
In this case, the general state space is a simple (two-dimensional) state plane. In this
state plane, we can introduce q and p as orthogonal coordinates. Afterwards, we
can construct state trajectories in this state plane, that is, the sequence of points
corresponding to the successive states of motion of the system. Taking each point
as the initial condition, we could draw such state trajectories and cover the entire
state plane with them, whereby the trajectories are arbitrarily close to each other. It is
characteristic for quantum theory, however, that a discrete subset of state trajectories
is singled out from the infinite amount of potential trajectories. For defining this
subset, we first consider a surface area of the state plane that is bounded by any two
state trajectories, and we associate this area with the corresponding state. Afterwards
we construct our bundle such that the area of the state between two neighboring
curves is always equal to Planck’s constant h. In other words, h has the meaning of
an elementary area of the state. Let us from now on consider this meaning the true
definition of Planck’s quantum h.
We illustrate these abstract ideas with the help of two important special cases,
namely the oscillator and the rotator. The linear oscillator is a spring attached to
a point mass m at rest position, whereby the mass can only move in one direction
x = q from its rest position. Due to the spring, the mass experiences a restoring
force, but no damping. The oscillator is the simplest model of a vibration center, as it
is used in optics to describe a “quasi-elastically bounded electron.” The oscillator is
specified as a harmonic oscillator if we want to emphasize that only a certain eigen-
oscillation is allowed. The oscillation frequency of the oscillator (i.e., the number of
free vibrations in one time unit) is ν. The oscillation process then looks like

x = q = a sin 2πνt, (1.7)

where a is the amplitude of the oscillation. In this case, the momentum p is simply
m q̇; that is,
p = 2π ν m a cos 2πνt. (1.8)

Eliminating t from (1.7) and (1.8), we obtain an ellipse as the state trajectory in the
p, q-plane:
q2 p2
2
+ 2 = 1, (1.9)
a b
where the semi-minor axis b has the value

b = 2π ν m a. (1.10)

The area of the ellipse is

a b π = 2π 2 ν m a 2 .
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