(Ebook) Molecular Quantum Electrodynamics: Long-Range

Intermolecular Interactions by Akbar Salam ISBN

9780470259306, 0470259302 Pdf Download

https://ebooknice.com/product/molecular-quantum-electrodynamics-
long-range-intermolecular-interactions-4918298

★★★★★
4.8 out of 5.0 (10 reviews )

DOWNLOAD PDF

ebooknice.com
 (Ebook) Molecular Quantum Electrodynamics: Long-Range
Intermolecular Interactions by Akbar Salam ISBN
9780470259306, 0470259302 Pdf Download

EBOOK

Available Formats

■ PDF eBook Study Guide Ebook

EXCLUSIVE 2025 EDUCATIONAL COLLECTION - LIMITED TIME

INSTANT DOWNLOAD VIEW LIBRARY

 We believe these products will be a great fit for you. Click
the link to download now, or visit ebooknice.com
to discover even more!

(Ebook) Foundations of Molecular Quantum Electrodynamics by R.

Guy Woolley ISBN 9781009225762, 1009225766

https://ebooknice.com/product/foundations-of-molecular-quantum-
electrodynamics-46076310

(Ebook) Physical chemistry : quantum chemistry and molecular

interactions with masteringchemistry by Andrew Cooksy ISBN
9780321814166, 0321814169

https://ebooknice.com/product/physical-chemistry-quantum-chemistry-and-
molecular-interactions-with-masteringchemistry-6746442

(Ebook) Intermolecular Interactions: Physical Picture,

Computational Methods and Model Potentials by Ilya G. Kaplan
ISBN 9780470863329, 0470863323

https://ebooknice.com/product/intermolecular-interactions-physical-picture-
computational-methods-and-model-potentials-2120928

(Ebook) Practical quantum electrodynamics by Douglas M. Gingrich

ISBN 9781584885429, 1584885424

https://ebooknice.com/product/practical-quantum-electrodynamics-1297062
(Ebook) Foundations of Classical and Quantum Electrodynamics by
Igor N Toptygin ISBN 9783527411535, 3527411534

https://ebooknice.com/product/foundations-of-classical-and-quantum-
electrodynamics-7435196

(Ebook) New Trends in Quantum Electrodynamics by Roberto

Passante (editor) ISBN 9783039285242, 9783039285259, 3039285246,
3039285254

https://ebooknice.com/product/new-trends-in-quantum-
electrodynamics-36875932

(Ebook) Quantum electrodynamics (Gribov's lectures on

theoretical physics) by Gribov V.N., Nyiri J. ISBN
9780521675697, 0521675693

https://ebooknice.com/product/quantum-electrodynamics-gribov-s-lectures-on-
theoretical-physics-906000

(Ebook) Elementary Particle Theory. Volume 2: Quantum

Electrodynamics by Eugene Stefanovich ISBN 9783110490893,
9783110493207, 3110490897, 3110493209

https://ebooknice.com/product/elementary-particle-theory-volume-2-quantum-
electrodynamics-7352166

(Ebook) Applied Ballistics For Long Range Shooting 3rd Edition

by Bryan Litz ISBN 9780990920618, 0990920615

https://ebooknice.com/product/applied-ballistics-for-long-range-
shooting-3rd-edition-35012302
MOLECULAR QUANTUM
ELECTRODYNAMICS
MOLECULAR QUANTUM
ELECTRODYNAMICS
Long-Range Intermolecular
Interactions

AKBAR SALAM
Department of Chemistry
Wake Forest University
Winston-Salem, North Carolina
Copyright Ó 2010 by John Wiley & Sons, Inc. All rights reserved

Published by John Wiley & Sons, Inc., Hoboken, New Jersey

Published simultaneously in Canada

No part of this publication may be reproduced, stored in a retrieval system, or transmitted in any
form or by any means, electronic, mechanical, photocopying, recording, scanning, or otherwise,
except as permitted under Section 107 or 108 of the 1976 United States Copyright Act, without either the
prior written permission of the Publisher, or authorization through payment of the appropriate
per-copy fee to the Copyright Clearance Center, Inc., 222 Rosewood Drive, Danvers, MA 01923, (978)
750-8400, fax (978) 750-4470, or on the web at www.copyright.com. Requests to the Publisher for
permission should be addressed to the Permissions Department, John Wiley & Sons, Inc.,
111 River Street, Hoboken, NJ 07030, (201) 748-6011, fax (201) 748-6008, or online at
http://www.wiley.com/go/permission.

Limit of Liability/Disclaimer of Warranty: While the publisher and author have used their best
efforts in preparing this book, they make no representations or warranties with respect to the
accuracy or completeness of the contents of this book and specifically disclaim any
implied warranties of merchantability or fitness for a particular purpose. No warranty may be
created or extended by sales representatives or written sales materials. The advice and strategies
contained herein may not be suitable for your situation. You should consult with a professional
where appropriate. Neither the publisher nor author shall be liable for any loss of profit or
any other commercial damages, including but not limited to special, incidental, consequential,
or other damages.

For general information on our other products and services or for technical support, please
contact our Customer Care Department within the United States at (800) 762-2974, outside the
United States at (317) 572-3993 or fax (317) 572-4002.

Wiley also publishes its books in a variety of electronic formats. Some content that appears in
print may not be available in electronic formats. For more information about Wiley products,
visit our web site at www.wiley.com.

Library of Congress Cataloging-in-Publication Data:

Salam, A. (Akbar)
Molecular quantum electrodynamics : long-range intermolecular
interactions / A. Salam.
p. cm.
Includes bibliographical references and index.
ISBN 978-0-470-25930-6 (cloth)
1. Quantum electrodynamics. 2. Intermolecular forces. I. Title.
QC680.S15 2010
530.140 33--dc22
2009035853

Printed in the United States of America

10 9 8 7 6 5 4 3 2 1
 To
C, P, and T
CONTENTS

PREFACE xi

1 MOLECULAR QUANTUM
ELECTRODYNAMICS: BASIC THEORY 1
1.1 Background 1
1.2 Quantum Description of Matter 5
1.3 Electrodynamics and Maxwell Equations 8
1.4 Quantization of the Free Electromagnetic Field 14
1.5 Interacting Particle–Radiation Field System 26
1.6 Multipolar Lagrangian 30
1.7 Multipolar Hamiltonian 37
1.8 Canonical Transformation 42
1.9 Perturbation Theory Solution 47
1.10 State Sequence Diagrams 55

2 MOLECULAR QUANTUM ELECTRODYNAMICS:

FIELD THEORETIC TREATMENT 60
2.1 Introduction 60
2.2 Nonrelativistic Quantum Field Theory 62
2.3 Quantum Canonical Transformation 71

vii
viii CONTENTS

2.4 Multipolar Maxwell Fields 77

2.5 Minimal-Coupling Maxwell Fields 83
2.6 Multipolar Maxwell Fields in the Vicinity of a Source 90
2.7 Higher Multipole Moment Maxwell Fields 98
2.8 Maxwell Fields of a Diamagnetic Source 101
2.9 Electromagnetic Energy Density 104
2.10 Poynting’s Theorem and Poynting Vector 115

3 INTERMOLECULAR FORCES 121

3.1 Concept of Intermolecular Potential 121
3.2 Short-Range Forces 125
3.3 Long-Range Forces 127
3.4 Electrostatic Interaction 128
3.5 Induction Forces 134
3.6 Dispersion Forces 136

4 RESONANT TRANSFER OF ENERGY 139

4.1 Introduction 139
4.2 Diagrammatic Perturbation Theory 142
4.3 State Sequence Diagram Representation 149
4.4 Energy Transfer Between Chiral Systems 152
4.5 Emitter–Absorber Model 157
4.6 Response Theory Calculation 161
4.7 Time-Dependent Energy Transfer and Causality 164
4.8 Proof of Causality of Energy Transfer to all Orders
in Perturbation Theory 172

5 RETARDED DISPERSION FORCES 175

5.1 Introduction 175
5.2 Casimir–Polder Potential: Perturbation Theory 178
5.3 Near-Zone Potential: London Dispersion Energy 186
5.4 Far-Zone Dispersion Potential 189
5.5 State Sequence Diagrams for Dispersion Force 193
5.6 Dispersion Interaction Between One Ground and
One Excited Molecule: Perturbation Theory 199
 CONTENTS ix

5.7 Response Theory Calculation of Dispersion Forces 207

5.8 Dispersion Potential via the Method of Induced
Multipole Moments 216
5.9 Discriminatory Dispersion Interactions 222
5.9.1 Perturbation Theory 223
5.9.2 Response Theory 230
5.9.3 Induced Moment Approach 236
5.10 Interactions Involving Magnetically Susceptible
Molecules 243
5.11 Measurements of Casimir Effect 251

6 MANY-BODY FORCES 257

6.1 Introduction 257
6.2 Axilrod-Teller-Muto Dispersion Energy Shift 260
6.3 Retarded Triple-Dipole Dispersion Potential:
Perturbation Theory 266
6.4 Triple-Dipole Dispersion Energy Shift
via Craig–Power Hamiltonian 269
6.5 Triple-Dipole Dispersion Potential via Correlations
of the Dressed Vacuum Field 277
6.6 N-Body Dispersion Potential 283
6.7 Four-Body Retarded Dispersion Potential 292
6.8 Three-Body Dispersion Interaction Involving
One Excited Molecule 295
6.8.1 Time-Dependent Perturbation Theory 296
6.8.2 Coupling of Induced Dipoles 299
6.9 Mediation of Resonance Energy Transfer
by a Third Body 304

7 INTERMOLECULAR INTERACTIONS
IN A RADIATION FIELD 311
7.1 Introduction 311
7.2 Radiation-Induced Dispersion Force: Perturbation
Theory 313
7.3 Dynamic Mechanism 315
7.4 Static Mechanism 321
x CONTENTS

7.5 Molecular and Pair Orientational Averaging 330

7.6 Polarization Analysis 332
7.6.1 Parallel Propagation 332
7.6.2 Perpendicular Propagation 334
7.7 Collapsed Graphs and Effective Interaction Hamiltonian 335
7.8 Radiation-Induced Intermolecular Interaction
via the Method of Induced Moments 339
7.9 Discriminatory Intermolecular Interaction in a
Radiation Field: Perturbation Theory 342
7.10 Radiation-Induced Chiral Discrimination:
Induced Moment Method 348
7.10.1 Linearly Polarized Radiation 351
7.10.2 Circularly Polarized Radiation 352
7.11 Freely Tumbling Chiral Pair in the Presence
of Circularly Polarized Light 353
7.12 Radiation-Induced Intermolecular Energy Shifts
Involving Magnetic Dipole and Electric Quadrupole
Polarizable Molecules 356
7.13 Higher Order Radiation-Induced Discriminatory
Intermolecular Interaction 361

APPENDIX A Higher Multipole-Dependent

Second-Order Maxwell
Field Operators 370
APPENDIX B Rotational Averaging of
Cartesian Tensors 378
REFERENCES 381
INDEX 389
PREFACE

The theory of molecular quantum electrodynamics has its origins in the work
carried out by the founding fathers of quantum mechanics in the late 1920s. A
complete formulation of quantum theory applicable to nonrelativistic
particles was quickly developed, enabling a fundamental description to be
given of the chemical and physical properties of matter at the atomic and
molecular levels. It was only natural that soon thereafter the new mechanics
were applied to electromagnetic radiation, with the consequence that the
photon emerged as the particle associated with the quantization of the
Maxwell field. This was followed by the construction of a single conceptual
and calculational quantum mechanical framework for the study of the
interaction oflight with matter, which provides a meansto probe the structure
of atoms and molecules that manifest in numerous forms of spectroscopy.
While the next generation of theoretical physicists focused their attention
on formulating a self-consistent and fully covariant theory of electron–pho-
ton interaction, an endeavor that was ultimately successful, despite the
introduction of the mathematically and physically unsatisfactory technique
of renormalization, a device that continues to be used in the present-day
calculations to yield results of physically observable quantities that are not
divergent, a negative feature that besets all such field theories and is inherent
to them, progress in the noncovariant theory of radiation–matter interaction
continued, especially in regard to the foundations of the subject and its
application to problems of interest in the field of chemical physics. Detailed
expositions may be found in texts such as Power’s Introductory Quantum
xi
xii PREFACE

Electrodynamics (Longmans, London, 1964), Healy’s Non-Relativistic

Quantum Electrodynamics (Academic Press, London, 1982), Craig and
Thirunamachandran’s Molecular Quantum Electrodynamics (Dover, New
York, 1998), and Milonni’s The Quantum Vacuum (Academic Press, San
Diego, 1994). Highlights included the explanation of spontaneous emission
and the computation of its rate, the calculation of the Lamb shift—the
splitting of the 2S1=2 and 2P1=2 levels in atomic hydrogen—and the deriva-
tion of the form of the retarded dispersion potential by Casimir and Polder, to
name but three historically significant examples. Predictions of these and
other phenomena, such as the anomalous magnetic moment of the electron,
have been compared with measured values to unparalleled levels of
accuracy, in the process providing remarkable agreement with experiment
and reassuringly high degrees of confidence in the theory.
Atomic, molecular, and optical physicists and theoretical chemists have
extended the domain of application of molecular quantum electrodynamics.
These include investigation of single- and multiphoton absorption and
emission and scattering of light by matter and the study of chiroptical
processes such as optical rotation and circular dichroism. With continuing
progress being made in the generation of coherent sources of radiation,
numerous and wide-ranging applications have been made to phenomena
occurring in the area of nonlinear and quantum optics. Examples include, but
are by no meanslimited to, the laser-inducedoptical activity, hyper-Rayleigh
and Raman scattering, coherent anti-Stokes Raman scattering, optical Kerr
effect, second-, third-, and high-harmonic generation, and four-, five-, and
six-wave mixing, many of whose theoretical bases may be found in the books
by Mukamel (Principles of Nonlinear Optical Spectroscopy, Oxford Uni-
versity Press, New York, 1995) and Andrews and Allcock (Optical Har-
monics in Molecular Systems, Wiley-VCH, Weinheim, 2002).
A topic of widespread interest and fundamental nature in which
quantum electrodynamics has made significant contribution is the field of
interatomic/intermolecular interactions. The QED formalism lends itself
naturally to a description in which coupling between matter occurs via the
exchange of one or more virtual photons. Considerable advances have taken
place in the last twenty-five years in the quantum electrodynamical
theory of intermolecular forces, which mainly constitutes the subject matter
of this book. Before giving a standard presentation of the concept of an
intermolecular potential and a semiclassical perturbation theory treatment
of short- and long-range forces, the latter decomposed into familiar
electrostatic, induction, and dispersion terms in Chapter 3, the quantum
theory of the nonrelativistic interaction of a charged particle with a
radiation field is explicated in Chapter 1. This entails construction of the
 PREFACE xiii

total Hamiltonian for the system comprising matter, electromagnetic field,

and their coupling, beginning with the classical Lagrangian function and
applying the canonical quantization procedure. Solutions for the interact-
ing system are developed via perturbation theory expansion. An alternative
formulation of the quantized theory of electron–photon interaction is
expounded in Chapter 2. The viewpoint adopted and the method developed
is slightly less familiar field theoretic approach, in which the Maxwell field
interacts with the electron wavefield, whose rigorous construction is found
to take place most easily in the Heisenberg picture of quantum mechanics
by employing the techniques of second quantization. The time dependence
is now contained solely within the dynamical variables. By solving
Heisenberg operator equations of motion for the fermion and boson
operators, the Maxwell field operators may be obtained in series of powers
of the electronic charge. This is in contrast to the theory presented in
Chapter 1, for which the Schr€ odinger picture is advantageous, with the time
dependence occurring exclusively within the states of the system. Either
formulation may be used to calculate expectation values for quantum
mechanical observables for processes involving the interaction of one or
more sources of external radiation with a single atom or molecule—the
optical phenomena mentioned above, although not covered in the present
work. Both theoretical schemes are, however, applied to the calculation of a
variety of intermolecular interactions that are especially effective at long
range and for which molecular quantum electrodynamics is best suited as it
automatically accounts for the finite speed of propagation of electromag-
netic signals. Hence, effort is made to elucidate contributions to the
intermolecular interaction energy for which quantum electrodynamical
predictions are found to differ from results obtained using a semiclassical
prescription. This begins in Chapter 4, which is devoted to resonant transfer
of energy. Chapter 5 exclusively deals with dispersion forces between pairs
of molecules. Energy shifts between ground and/or electronically excited
species are evaluated using three different physical viewpoints and calcula-
tional schemes. These include diagrammatic time-dependent perturbation
theory, a response formalism using Maxwell fields, and a method in which
molecules couple via fluctuations in their charge distribution. Discrimina-
tory effects are also studied in excitation energy transfer and van der Waals
dispersion occurring between optically active species. The three different
computational approaches are then applied to the calculation of many-body
forces in Chapter 6. Explicit results are obtained for retardation corrected
three-, four-, and N-body dispersion potentials. In Chapter 7, the modifica-
tion of intermolecular energy shifts by external radiation is investigated.
These include changes to pairs of molecules coupled via exchange of one
xiv PREFACE

and two virtual photons. Interactions of this type form the basis of optical
binding forces and, although small in magnitude, have recently come within
the range of experimental detection. Interesting field-induced interaction
energies between chiral molecules are also calculated.
While the formalism presented in the first two chapters and its application
in the last four chapters may at first sight appear imposing, it is intended that
at the very least Chapter 1 will provide a detailed and self-contained account
of the theory of molecular quantum electrodynamics derived from the
first principles. Mastering this chapter will enable readers to reproduce
perturbation theory calculations of intermolecular interactions given in later
chapters and their extension to more complex problems. Background
material required for a thorough understanding of the content covered is
a first course in quantum theory in which the postulates are presented along
with standard elementary examples leading to examination of atomic and
molecular systems and the common methods of solution by techniques of
approximation. This is well within the scope of advanced undergraduate
students of chemistry and physics. Advantageous is a prior exposure to
mathematical methods. The same could also be said of classical mechanics
and classical electrodynamics, which along with quantum mechanics form
the foundations of quantum electrodynamics. For this purpose, the Lagran-
gian function and Hamiltonian formulation are introduced in Chapter 1
along with Maxwell’s equations. A similar approach is adopted in the
presentation of coupled wavefields in Chapter 2. Understanding of this
chapter will allow the response theory calculations of intermolecular forces
to be followed easily.
It is hoped that the book will prove useful to both the theorists seeking to
acquaint themselves with new methods and experimentalists requiring
knowledge of the latest forms of intermolecular potential energy functions.
In addition, the book will be accessible to students of the subject as well as
to researchers expert in the discipline.
The study of intermolecular forces has been a long and ongoing endeavor
and the results obtained over the years have in fact impacted all areas
of science. A variety of differing approaches within the framework of
molecular quantum electrodynamics will be used in this book to compute
the interaction energy of two or more bodies as a function of their separation
and orientation. This theory is preferred for treating interactions between
atoms and molecules, both for its rigor and for the chemical and physical
insights it affords. The emphasis, therefore, is on developing the theory and
applying it to fundamental intermolecular processes. The presentation
given is general enough to hold for a wide range of situations, yet applicable
to specific systems of interest. Despite three differing physical viewpoints
being proffered in this work, there remain others within the realm of
 PREFACE xv

Coulomb gauge quantum electrodynamics that can be deployed to explore

intermolecular forces. Perhaps the best known among these alternatives is
the dressed atom approach. Little mention is made of this methodology, as
being superbly dealt with in the treatise by Compagno, Passante, and
Persico (Atom-Field Interactions and Dressed Atoms, Cambridge Uni-
versity Press, Cambridge, 1995). For this and other reasons, the choice of
topics covered has been the authors alone. Hence, there is no discussion of
medium effects and methods to treat this important aspect. Likewise, no
details are given concerning measurement of intermolecular forces or
interactions occurring between atoms or molecules with surfaces. These
and other more general aspects of intermolecular forces may be found in
Margenau and Kestner’s monograph, Theory of Intermolecular Forces
(Pergamon, Oxford, 1969) and the book by Maitland, Rigby, Smith, and
Wakeham (Intermolecular Forces, Oxford University Press, Clarendon,
1981). Discussion of experiments is limited to those attempting to directly
measure different manifestations of the so-called Casimir effects, including
van der Waals dispersion forces. Also excluded are recent proposals for
enhancing and suppressing transfer of excitation by external radiation in the
so-called laser-assisted resonant energy transfer (LARET) processes. Like-
wise, no details are given of the dynamical Casimir effect.
No attempt has been made to provide a comprehensive list of references.
Only primary texts and key articles are cited. SI units have been used
throughout. All errors lay solely with the author.
Words of thanks are due to many. First and foremost, the author owes a
great debt of gratitude to ‘‘Thiru’’ Thirunamachandran, who unfortunately
did not live to read this book. His influence on the author as teacher, research
guide, and friend are all too evident, as is his imprint on this work. The author
benefited greatly from numerous discussions with T. Thirunamachandran
relating to molecular quantum electrodynamics, as well as with David P.
Craig and the late Edwin A. Power. Thanks are also due to David L. Andrews
who read Section 1.10 and offered useful insights into state sequence
diagrams. Bridget W. Alligood is kindly thanked for skillfully drawing all
of the figures contained in this book and for critically reading Chapter 1.
Finally, thanks go to Anita Lekhwani, Senior Acquisitions Editor at John
Wiley & Sons, Inc., for her enthusiasm in supporting this project, and to
Rebekah Amos, Editorial Assistant at this publishing house, for her prompt
and friendly assistance during the writing and production process.

AKBAR SALAM

Winston-Salem, North Carolina

August 2009
CHAPTER 1

MOLECULAR QUANTUM
ELECTRODYNAMICS:
BASIC THEORY

One finds then that the Hamiltonian for the interaction of the field with an
atom is of the same form as that for the interaction of an assembly of light-
quanta with the atom. There is thus a complete formal reconciliation
between the wave and light-quantum points of view.
—P. A. M. Dirac, Proc. R. Soc. Lond. A 114, 710 (1927).

1.1 BACKGROUND

Quantum electrodynamics (QED) (Schwinger, 1958) is the physical theory

that describes the interaction of electromagnetic radiation with matter. Its
characteristic feature is that the radiation field, as well as the material
system, is subject to the postulates of quantum mechanics. Therefore, the
theoretical framework consists of a single, closed dynamical system
comprising both matter and electromagnetic radiation in mutual interaction
within which energy is conserved. This is unlike the situation in the so-
called semiclassical theory, the historical precursor to QED. In the former
construct, only matter obeys quantum mechanical principles, while the
radiation field is considered as a prescribed, external perturbation on the

Molecular Quantum Electrodynamics, by Akbar Salam

Copyright
2010 John Wiley & Sons, Inc.
1
2 MOLECULAR QUANTUM ELECTRODYNAMICS: BASIC THEORY

system and does not form an integral part of it. Even though use of the
semiclassical formalism remains widespread, due largely to its physical
and computational simplicity relative to QED, its inherent deficiencies lead
to critical shortcomings and ultimately limit its scope of availability. This is
especially the case in the treatment of electromagnetic fields interacting
with atoms and molecules, where continuing progress in the generation of
coherent light sources has necessitated a fully quantum mechanical ap-
proach to calculating and explaining a variety of optical phenomena
(Mukamel, 1995; Andrews and Allcock, 2002). In this regard, QED is the
most successful physical theory to date (Feynman, 1985). This statement is
justified on two counts. First, development of the QED formalism has
provided a rigorous foundation for the understanding of electron–photon
interactions at the most fundamental level currently known. Phenomena
cover a vast range of length scales, manifested by particles varying in size
from the gigameter down to the attometer. Second, and perhaps more
convincing, is the ability of the theory to yield numerical values of
measurable properties and the unprecedented agreement with experiment
in those cases where comparison is possible.
A key step that led to the formulation of QED was the recognition that the
mechanical vibrations of a system with infinitely many degrees of freedom
could be represented by quantizing a collection of noninteracting harmonic
oscillators (Born et al., 1926). This insight prompted Dirac (1927) to
quantize the electromagnetic field and to calculate quantum mechanical
probabilities for the absorption, stimulated emission, and spontaneous
emission of light by atoms. Subsequent advances carried out by many
workers, in particular, the significant contributions of Feynman, Schwin-
ger, Tomonaga, and Dyson, resulted in a formulation of QED that satisfied
all of the requirements stipulated by the special theory of relativity, which
was ultimately explicated in both the particle and field theoretic points of
view (Schweber, 1994). This last aspect, for instance, finally enabled the
duality of the wave and particle descriptions of radiation and matter to be
rationalized on the basis of a single theoretical scheme. Interacting
quantum mechanical fermionic matter and bosonic electromagnetic fields
are therefore entirely equivalent to a many-body representation of a system
of material particles—electrons—interacting with quantized particles of
light—the photons.
Early application of both the nonrelativistic and fully covariant versions
of the theory was made to outstanding problems. These included calcula-
tions of spontaneous decay rates from atoms in electronically excited states,
the Lamb shift, and the anomalous magnetic moment of the electron, to
select but three historically significant examples. With continuing advances
 BACKGROUND 3

occurring in computational power and experimental procedure during the

intervening years, convergence between theory and experiment has been
ever closer. More accurate calculations and improvements in measurement
capability have yielded for the electronic g-factor, for instance, values in
units of Bohr magnetons of g/2 (experiment) ¼ 1.00115965218073(28)
(Hanneke et al., 2008) and g/2 (theory) ¼ 1.00115965218279 (Aoyama
et al., 2007). In the case of the Lamb shift in atomic hydrogen, experimental
and calculated values for the splitting between the 2S1/2 and 2P1/2 levels
are 1,057,839(12) kHz (Hagley and Pipkin, 1994) and 1,057,838(6) kHz
(Pachucki, 1994), respectively.
While these and other achievements are indeed remarkably impressive,
there remain difficulties in the underlying foundations of the theory. Chief
among them is the renormalization procedure, without whose aid no finite
quantities may be calculated but which even today lacks rigorous math-
ematical justification. This problem continues to beset other field theories
of modern physics, of which QED is but one example. Another limitation,
which also applies in general to other field theories, is the approximate
nature of solutions generated when systems interact. A common method of
solution is a perturbative expansion in series of powers of some appropriate
coupling constant, with no a priori guarantee of convergence of succes-
sively higher order terms, or whether summation of the infinite series is
indeed possible. In QED, for example, the eigenstates of one or more
charged particles in isolation are taken to be known, and the microscopic
Maxwell’s equations in free space can be solved and appropriately quan-
tized. By forming a product state, the wavefunctions of this separable
system are then used as base states for a perturbation theory solution in
series of powers of the electronic charge or the fine structure constant.
Although QED correctly treats the coupling of radiation and matter at
high energies, where fermionic pair particle creation and destruction events
occur concomitantly with changes in photon number, the emphasis in the
presentation to follow will be on conservation of the number of charged
particles, which may exchange energy directly or indirectly with the
radiation field. Conversely, as there is no conservation of photon number,
any integer quantity of real or virtual photons may be created and
annihilated during the course of a particular process. Hence, the formalism
to be developed and applied will be suitable for systems composed of
charged particles such as bound electrons in atoms and molecules posses-
sing energies much less than mc2, m being the mass of the aggregate and c
the speed of light. Since the mass is assumed to be a constant, the system
of interest is slow moving, with low velocity v, and automatically satisfies
the condition v  c. When this limiting procedure is applied to covariant
4 MOLECULAR QUANTUM ELECTRODYNAMICS: BASIC THEORY

QED, the result is a nonrelativistic version of the theory, which is more

commonly known as molecular QED (Power, 1964; Healy, 1982; Craig and
Thirunamachandran, 1998a). Its construction from first principles and its
application to a variety of long-range intermolecular interactions form the
subject of this book.
In addition to providing valuable insight and expressions for forces
between particles, the most celebrated being the formula for the retarded
van der Waals dispersion potential between a pair of neutral molecules in
the ground state, the theory of molecular QED has been employed with
considerable success to radiation–molecule interactions. Examples include
single- and multiphoton absorption, emission and scattering of light,
optical activity and chiroptical spectroscopy, and nonlinear and quantum
optical phenomena. Specific processes studied involving the interaction of
radiation with one center include calculation of the circular dichroism rate,
the angle of rotation of plane polarized light as it traverses a chiral medium,
Rayleigh and Raman scattering of linear and circularly polarized radiation
and their hyperanalogues, second, third, and higher harmonic generation,
four-, five-, and six-wave mixing, and laser-induced optical activity.
Since intermolecular interactions are mediated by electromagnetic
forces, coupling of radiation with matter, as well as between two or more
particles, may be treated correctly and consistently within the framework
provided by the nonrelativistic quantum theory of electron–photon inter-
action or molecular QED. This is most commonly delineated for the
interaction of a charged particle with electromagnetic radiation; it begins
with the classical Lagrangian function and ends with the construction of a
quantum mechanical Hamiltonian operator that is arrived at via the familiar
canonical quantization procedure. Details are presented in this chapter.
More fundamental, though less well known—despite much progress
being made in the past 25 years or so—is the field theoretic formulation of
molecular QED (Salam, 2008), involving the interaction of second quan-
tized matter and radiation fields, which is the subject of Chapter 2. For a
variety of applications, this approach offers a number of advantages over the
conventional method in which only the radiation field is second quantized.
For instance, properties directly related to electron and photon fields, such as
the Maxwell fields in thevicinity of a source of charge, its energy density, and
rates of flow of electromagnetic energy, may be evaluated. Moreover, the
electromagnetic fields are subsequently employed to calculate energy shifts
between molecules using a version of response theory.
The interactions occurring between atomic and molecular systems,
especially those operating at large separation distances, form the focus
of the remainder of the work. In Chapter 3, the standard presentation of
 QUANTUM DESCRIPTION OF MATTER 5

intermolecular forces originating from classical electrostatics is given.

The pair potential is first divided into short- and long-range regions, with
the exchange–repulsion energy being the major contribution to the inter-
action energy in the former distance regime. At large separations, the
charge distribution between pairs of molecules is expanded in an electric
multipole series and quantum mechanical perturbation theory is used to
extract the electrostatic, induction, and dispersion terms within the form-
alism of semiclassical radiation theory in which no account is taken of the
photonic character of electromagnetic radiation. Applications of the quan-
tum electrodynamical theory to intermolecular interactions are then given
in the chapters to follow. In Chapter 4, the theory of resonance energy
transfer is given, a fundamental process taking place in microscopic
systems but prototypical in that its interpretation as due to the exchange
of a single virtual photon between the pair serves as a basis for the study of
other molecular interactions using the formalism of molecular QED. Both
perturbation and response theory calculations are presented, followed by
their application to the evaluation of the transfer rate between two chiral
species. Chapter 5 is devoted to van der Waals dispersion forces. Three
different physical viewpoints and calculational techniques are detailed for
the computation of the energy shift between two neutral polarizable
molecules in the ground state. In addition to perturbation and response
theories, the induced multipole moment approach is introduced and shown
to simplify calculations considerably. Results are also obtained for elec-
tronically excited molecules undergoing dispersive coupling, and the
functional form of the discriminatory potential between two optically
active molecules is derived. Chapter 6 covers nonadditive and many-body
forces. Attention is focused on the effects of retardation on energy transfer
and dispersion interactions taking place among three or more particles.
In Chapter 7, the effect of an external electromagnetic field in modifying the
molecular pair interaction energy is treated. Adoption of the approach
whereby molecules couple with each other and to the incident laser via the
moments induced by the radiation field is shown to be a more efficient
calculational method than the diagrammatic perturbation theory computa-
tion. Changes in energy shift induced by an applied field and dependent on
the handedness of individual bodies are also studied.

1.2 QUANTUM DESCRIPTION OF MATTER

The continued failure of the application of the laws of classical mechanics

to microscopic particles eventually led to the formulation of a new
6 MOLECULAR QUANTUM ELECTRODYNAMICS: BASIC THEORY

dynamics—quantum mechanics (Dirac, 1958). At its foundation, however,

remain a number of key concepts and ideas from classical theory (Goldstein,
1960). One of these fundamental constructs is the Lagrangian function, and
another is the physical variational principle and the versatility associated
with it. Taken together, they yield the Euler–Lagrange equations of motion
and provide an alternative formulation of classical mechanics to Newton’s
laws of motion. The former may be used to solve any problem within the
classical domain and ultimately to provide a rigorous means of quantizing
the specific system of interest. As long as a judicious choice of coordinates is
made, often the most difficult task at hand, the ensuing equations to be solved
are frequently simpler than those obtained by direct application of Newton’s
laws, and yet contain all of the essential physics. This freedom in the
selection of the specific coordinate representation lends itself to the for-
mulation of the classical Lagrangian L for a system of particles in terms of
generalized coordinates and velocities q and q; _ the Lagrangian is a function
of these two variables as well as of the time t. If the Lagrangian does not
depend explicitly on the time, then it is defined to be the difference of the
kinetic energy T and the potential energy V; the energy of the system is
therefore conserved. For a system in which the potential energy is a function
of the position only, the Lagrangian has identical definition, namely,
L ¼ TV. The equations of motion follow after invoking Hamilton’s
principle, namely, that of all of the allowed paths the system may pursue
between initial and final times ti and tf, the actual one taken in config-
uration space is that for which the variation of the time integral of the
Lagrangian, also called the variation of the action S, is an extremum. By
application of standard calculus of variations, the Euler–Lagrange equa-
tions of motion for a system of particles x, with N degrees of freedom, are
found to be


d @L @L
 ¼ 0; x ¼ 1; 2; . . . ; N: ð1:2:1Þ
dt @ q_ x @qx
From the form of the Lagrangian, it is evident that motion in classical
mechanics is reversible. Replacing t by t leaves the Lagrangian as well
as the equations of motion unaltered.
To facilitate the transition to quantum mechanics, in which the positions
and momenta of the system of particles are canonical, it is convenient to
define the Hamiltonian H as
X
N
H¼ px q_ x L: ð1:2:2Þ
x¼1
 QUANTUM DESCRIPTION OF MATTER 7

This quantity is a function of the generalized coordinates, their canonically

conjugate momenta, and time. The momenta are found from
@L
px ¼ ; x ¼ 1; 2; . . . ; N: ð1:2:3Þ
@ q_ x
When the Hamiltonian is time independent, it is equal to the sum of the
kinetic and potential energy, H ¼ T þ V. Evaluating the total differential
of (1.2.2) and noting from equations (1.2.1) and (1.2.3) that
@L
p_ x ¼ ð1:2:4Þ
@qx

yields Hamilton’s canonical equations

@H @H
q_ x ¼ ; p_ x ¼  ; x ¼ 1; 2; . . . ; N; ð1:2:5Þ
@px @qx

and

@H @L
¼ ; ð1:2:6Þ
@t @t

which are now the equations of motion. A consequence of the resulting

dynamics is that 2N first-order equations (1.2.5) have to be solved,
rather than N second-order equations (1.2.1). After writing the classical
Hamiltonian function in terms of the canonically conjugate dynamical
variables, the quantum mechanical form of the Hamiltonian operator is
obtained straightforwardly by promoting the classical variables to quantum
operators, the latter obeying the canonical commutation relations for
particles x and x0 ,

½~
q x ;~
q x0  ¼ 0; ½~
p x ;~
p x0  ¼ 0; ½~ p x0  ¼ ihdxx0 :
q x ;~ ð1:2:7Þ

By way of illustration of the development above, consider a system

of particles x with charges ex , masses mx , and position and velocity vectors
q_ x , whose classical Lagrangian function is (Landau and Lifshitz,
q x and ~
~
1972)
X 1 X ex ex0
Lð~ _ ¼1
q; ~
qÞ mx~q_ x 
2
: ð1:2:8Þ
2 x 4pe0 0 j~q x ~
q x0 j
x<x
8 MOLECULAR QUANTUM ELECTRODYNAMICS: BASIC THEORY

This leads to the quantum mechanical Hamiltonian operator

X ~p 2x 1 X ex ex0
Hð~ pÞ ¼
q;~ þ : ð1:2:9Þ
x
2mx 4pe0 0 j~
q x ~
q x0 j
x<x

It is easily verified that the Lagrangian (1.2.8) gives rise to the correct
equations of motion: applying (1.2.1) produces Newton’s second law
equation for particle x,
1 X ex ex0
mx~ q€x ¼ ; ð1:2:10Þ
4pe0 0 j~
x<x
q x0 j 2
q x ~

whose right-hand side is recognizable as the generalized Coulomb force,

obtained from the potential energy term in the Lagrangian via
~
F ¼ @Vð~ qÞ=@~q:

1.3 ELECTRODYNAMICS AND MAXWELL EQUATIONS

The unification of electricity and magnetism with classical optics occurred

with the formulation of Maxwell’s equations (Jackson, 1963)—the basic
laws underlying the behavior of electromagnetic radiation. As a conse-
quence, light was understood to be an electromagnetic wave in which
radiation of all frequencies could, in principle, be generated. Maxwell’s
quartet of equations is expressed as
~ D
r ~ ¼ r; ð1:3:1Þ

~ ~
r B ¼ 0; ð1:3:2Þ

~ ~ @~
B
r Eþ ¼ 0; ð1:3:3Þ
@t

~
r ~ ¼ @D þ~
~ H J: ð1:3:4Þ
@t
These fundamental equations completely determine the electromagnetic
field, and the electrodynamic nature of such radiation is clearly evident
from them. The fields ~ E and ~
B shall be termed the electric and magnetic
fields, respectively, even though the latter is more properly called the
magnetic flux density or the magnetic induction. The auxiliary fields D~
 ELECTRODYNAMICS AND MAXWELL EQUATIONS 9

and H~ are designated the electric displacement and magnetic field, respec-
tively. No confusion shall result from the use of the descriptor “magnetic
field,” as the appropriate symbol shall be used for the quantity concerned,
either ~ ~ The ~
B or H. E and ~B fields are fundamental in that they propagate in
regions of space that contain no sources of charge. Further, if the charge
density r and the current density ~ J account for all charged entities, then ~ E
and ~B describe the radiation field in its totality. On the other hand, including
the contributions to r and ~ J of the elementary charges and their currents,
which are manifested in the form of polarization fields and currents,
necessitates the introduction of the two auxiliary fields D ~ and H. ~
The bound charged particles are viewed as forming a medium that contains
the fields. These in turn describe the response of the material system to the
applied fields via the electric polarization and magnetization fields.
The connection between the derived and fundamental fields is arrived at
through constitutive relations and the introduction of the electric permittivity
e and the magnetic permeability m to describe the properties of the medium.
Although the interaction of radiation and matter is to be applied to bound
systems moving at a very small fraction of the velocity of light, the
equations of electrodynamics are themselves invariant in form under
Lorentz transformations and are compatible with Einstein’s relativity
theories. When Maxwell’s equations are combined with Newton’s second
law of motion and the Lorentz force equation, a complete description of the
nonrelativistic classical dynamics of charged particles interacting with
electromagnetic fields results.
For the subsequent development of the quantum theory of electron–
photon interaction, it is advantageous to work with Maxwell’s equations in
microscopic form rather than employ relations (1.3.1)–(1.3.4) that are
applicable when the distribution of charge is taken to be continuous. In
place of the macroscopic Maxwell equations, their microscopic equivalents
can be expressed solely in terms of the microscopic forms of the electric and
magnetic field vectors ~ e and ~b and the sources of charge and are given by
~ ~
r e ¼ r=e0 ; ð1:3:5Þ

~ ~
r b ¼ 0; ð1:3:6Þ

~ ~ @~b
r eþ ¼ 0; ð1:3:7Þ
@t
~ ~ 1 @~e 1 ~
r b¼ 2 þ j: ð1:3:8Þ
c @t e0 c2
10 MOLECULAR QUANTUM ELECTRODYNAMICS: BASIC THEORY

To facilitate the microscopic treatment of matter, a discrete particle

description is adopted for a collection of charged particles a possessing
electrical charge ea, situated at ~ q_ a ; for which
q a and moving with velocity ~
the charge and current density are defined to be
X
rÞ ¼
rð~ ea dð~ qaÞ
r~ ð1:3:9Þ
a

and
X
~ rÞ ¼
jð~ q_ a dð~
ea~ q a Þ;
r~ ð1:3:10Þ
a

where dð~ rÞ is the Dirac delta function, which is strongly localized at the
origin of the charge. By carrying out an average of the microscopic
field over the molecular volume, the macroscopic Maxwell equations
can be obtained from the microscopic Maxwell–Lorentz equations
(1.3.5)–(1.3.8). In Section 1.2, it was remarked that forward and reverse
motions are identical in classical mechanics. The same is true for the
electromagnetic field in relativity theory, with the additional requirement
that the sign of the magnetic field is reversed as well as t ! t. It is easy to
see that the equations of motion of a charged particle in a field are
unchanged on transforming t ! t, ~ e !~e, and ~b ! ~ b in the Lorentz
force expression

pa
d~
¼ ea ð~ va  ~
e þ~ bÞ; ð1:3:11Þ
dt

where ~ v a ¼ d~q a =dt is the velocity and ~ p a ¼ ma~v a is the momentum of

particle a.
The coupled first-order partial differential equations of Maxwell can be
solved for the fields~ e and ~
b for a variety of simple cases in electromagnetic
theory. However, for many other situations and for the eventual quantiza-
tion of the radiation field via the canonical quantization scheme, it is
convenient to introduce two electromagnetic potentials and to rewrite
Maxwell’s equations in terms of them. One is the scalar potential f and
the other is the vector potential~a. The definition of the latter readily follows
from the second Maxwell equation (1.3.6),

~ ~ ~
b¼r a; ð1:3:12Þ
 ELECTRODYNAMICS AND MAXWELL EQUATIONS 11

on noting that the divergence of the curl of a vector field vanishes.

Inserting (1.3.12) into the third Maxwell equation (1.3.7) yields


~ ~ @~
a
r eþ ¼ 0; ð1:3:13Þ
@t
so that the factor within parentheses can be defined in terms of the gradient
of a scalar function, in this case the scalar potential, since the curl of the
gradient of a scalar field is zero,
~ ¼~ @~
a
rf eþ : ð1:3:14Þ
@t
Substituting relation (1.3.14) into the first inhomogeneous microscopic
Maxwell equation (1.3.5) produces
~ 2 f þ @ ðr
r ~ ~ r
aÞ ¼  ; ð1:3:15Þ
@t e0
while using definitions (1.3.12) and (1.3.14) in the last Maxwell equa-
tion (1.3.8) gives


~ 1 @ 2~
a ~ ~ 1 @f 1
¼  2~
2
r~ a 2 2 r r ~ aþ 2 j ð1:3:16Þ
c @t c @t e0 c
on using the vector identity
~  ðr
r ~ ~ ~ 2~
aÞ ¼ r ~ r
a þ rð ~ ~
aÞ: ð1:3:17Þ
Maxwell’s equations have now been reduced to two coupled equations
instead of four, with the potentials related directly to the sources. The
equations (1.3.15) and (1.3.16) can be further simplified into two separate
inhomogeneous wave equations, one dependent on f only and the other on
~
a only. This may be achieved by taking advantage of the gauge freedom
a is
associated with the potentials. From relation (1.3.12), it can be seen that~
undetermined to the extent that the gradient of a scalar function of the
position and time, f, can be added to it,
~ a0 ¼ ~
a !~ ~ ;
a þ rf ð1:3:18Þ
a transformation that leaves ~b invariant. Substituting (1.3.18) into (1.3.14)
enables the form of the transformation that must simultaneously be made to
the scalar potential such that ~e is unchanged to be derived:
@~
a ~ @ ~ Þ þ rf
~ 0;
~
e¼ þ rf ¼ ð~a þ rf ð1:3:19Þ
@t @t
12 MOLECULAR QUANTUM ELECTRODYNAMICS: BASIC THEORY

from which


~ 0 @f
r f f þ ¼0 ð1:3:20Þ
@t
or
@f
f ! f0 ¼ f : ð1:3:21Þ
@t
The scalar potential is therefore determined to within the time derivative of
the same function f. The two relations (1.3.18) and (1.3.21) constitute the
gauge transformation. From them, a set of potentials ð~ a; fÞ can always be
chosen such that the Lorentz condition (1.3.22) is satisfied:

~ ~ 1 @f
r aþ 2 ¼ 0; ð1:3:22Þ
c @t
which when inserted into (1.3.15) and (1.3.16) results in the wave
equations


~ 2 1 @2 r
r  2 2 f¼ ð1:3:23Þ
c @t e0
and


~ 1 @2 1
a ¼  2~
2
r  2 2 ~ j: ð1:3:24Þ
c @t e0 c
The most convenient choice of gauge, from the point of view of
nonrelativistic theory, is the one in which the vector potential is sole-
noidal, that is, r~ ~
a ¼ 0, also known as the Coulomb, radiation, or
transverse gauge. In this gauge, f is seen from equations (1.3.22)
and (1.3.23) to obey Poisson’s equation

~ 2f ¼  r ;
r ð1:3:25Þ
e0
with solution
ð
1 r 0 ; tÞ 3 0
rð~
r; tÞ ¼
fð~ d~r; ð1:3:26Þ
4pe0 j~r~ r 0j
which represents the instantaneous Coulomb potential due to the charge
density and from which this gauge takes its primary name. Fixing the
gauge in equation (1.3.16) yields the inhomogeneous wave equation
 ELECTRODYNAMICS AND MAXWELL EQUATIONS 13

satisfied by the vector potential,



~ 1 @2 1 ~ @f 1
¼  2~
2
r  2 2 ~ a 2 r j: ð1:3:27Þ
c @t c @t e0 c
A further advance is made through the explicit decomposition of the
vector fields ~e and ~ b into their parallel (||) and perpendicular (?)
components; this is known as Helmholtz’s theorem, which holds for any
vector field and gives rise to irrotational and solenoidal vectors, respec-
tively. From (1.3.6), ~
b is purely transverse and (1.3.5) and (1.3.7) become

~ ~ r
r e jj ¼ ð1:3:28Þ
e0
and

~ ~ @~
b
r e? ¼  ; ð1:3:29Þ
@t
while the fourth microscopic Maxwell equation (1.3.8) separates into

e jj
1 @~ 1 ~jj
0¼ þ j ð1:3:30Þ
c @t
2 e0 c2
and

~ ~ e?
1 @~ 1 ~?
r b¼ 2 þ j : ð1:3:31Þ
c @t e0 c2
The equation of continuity,

~ ~jj @r
r j þ ¼ 0; ð1:3:32Þ
@t
follows immediately on taking the divergence of (1.3.30) and
using (1.3.28). Similarly, equation (1.3.14) divides as

~ ~
e jj ¼ rf ð1:3:33Þ

and
@~
a
e? ¼ 
~ ð1:3:34Þ
@t
in the Coulomb gauge, enabling the inhomogeneous wave equation for
the vector potential (1.3.27) to be expressed exclusively in terms of
14 MOLECULAR QUANTUM ELECTRODYNAMICS: BASIC THEORY

transverse variables,


~ 1 @2 1 ?
a ¼  2~
2
r  2 2 ~ j ; ð1:3:35Þ
c @t e0 c

with f continuing to satisfy Poisson’s equation (1.3.25). The solution of

the equation (1.3.35) for the vector potential is given by
ð~? 0
1 j ð~
r ; tj~
r~ r 0 j=cÞ 3 0
~ r; tÞ ¼
að~ d~r; ð1:3:36Þ
4pe0 c2 j~ r0j
r~

which appears to be retarded, but is in fact not so. This is because its
source is the transverse rather than the total current, the former being
nonlocal, resulting in ~a ? having identical characteristics also. Causality is
recovered in the Coulomb gauge by including both transverse and
longitudinal components, thereby ensuring that all static contributions
cancel one another. No such difficulty arises in the Lorentz gauge (1.3.22),
the solutions to the wave equations (1.3.23) and (1.3.24) being properly
retarded, recognizing that the total current appears as the source in the
equation for ~a,
ð
1 r 0 ; tj~
rð~ r~ r 0 j=cÞ 3 0
fð~r; tÞ ¼ d~r; ð1:3:37Þ
4pe0 j~
r~r 0j

ð~ 0
1 r ; tj~
jð~ r~ r 0 j=cÞ 3 0
~ r; tÞ ¼
að~ d~r: ð1:3:38Þ
4pe0 c2 j~
r~r 0j

a ? is gauge invariant, since from the transforma-

It is worth noting that ~
tion (1.3.18) only the longitudinal component of ~ a? can change. Conse-
quently, from (1.3.34), it is seen that ~ e ? ¼ ~a_ in all gauges, and
the effect of a gauge transformation is to change the contributions from
~
a and f to ~ e jj .

1.4 QUANTIZATION OF THE FREE ELECTROMAGNETIC

FIELD

In Section 1.2, it was shown how the quantum mechanics of a system of

particles is rigorously built up from a classical mechanics in canonical
form. In this section, it is shown how the same principles may be applied
and suitably adapted to the radiation field propagating in vacuo. Ultimately,
 QUANTIZATION OF THE FREE ELECTROMAGNETIC FIELD 15

this will lead to the quantum mechanical Hamiltonian for the electromag-
netic field and its corresponding eigenvalues and eigenfunctions, the latter
in a form convenient for its later adoption as a basis set in the perturbation
theory solution to the interacting matter–radiation problem.
When there are no sources present, both the charge and current density
are zero so that the microscopic Maxwell equations (1.3.5)–(1.3.8) applic-
able to the electromagnetic field in free space become
~ ~
r e ¼ 0; ð1:4:1Þ

~ ~
r b ¼ 0; ð1:4:2Þ

~ ~ @~
b
r eþ ¼ 0; ð1:4:3Þ
@t

~ ~ 1 @~
e
r b 2 ¼ 0: ð1:4:4Þ
c @t
Solutions are easily found for the fields ~ e and ~b, which describe electro-
magnetic waves in a vacuum, as well as for ~ a. Continuing the development
in the Coulomb gauge, clearly from equation (1.4.1),~ e is purely transverse,
which from (1.3.14) means that f can be taken to vanish so that ~ e ¼ ~_
a.
Substituting this relation and (1.3.12) into (1.4.4) and using identity (1.3.17)
leads to d’Alembert’s equation for the vector potential,


~ 2 1 @ ~
2
r a ¼ 0: ð1:4:5Þ
c2 @t2

e and ~
~ b satisfy identical wave equations. By taking the curl of equa-
tion (1.4.3) and substituting for r ~ ~ b from (1.4.4) yields the wave
equation for~ e, and carrying out a similar procedure on (1.4.4) first, results
in the equation for ~b. One form of solution to the wave equation for each of
the three fields is in terms of plane waves,
~
~ a 0 eik ~riot ;
a ¼~ ð1:4:6Þ

~
~ e 0 eik ~riot ;
e ¼ e0 ~ ð1:4:7Þ

and
~ ~
b ¼ b0 ~
b 0 eik ~riot ; ð1:4:8Þ
16 MOLECULAR QUANTUM ELECTRODYNAMICS: BASIC THEORY

where in the last two solutions the pre-exponential factors, respectively,

denote the scalar amplitude and the polarization vector of the respective
quantity, with~e 0 ¼ ick~ e ¼ ~
a 0 on using~ _ The direction of propagation of
a.
the electromagnetic wave is described by the wavevector ~ k, whose mag-
nitude is obtained after insertion of the appropriate solution into the wave
equation from which it is found. Thus, j~ kj ¼ k ¼ o=c; where o is the
circular frequency. The relation between the amplitudes of the two elec-
tromagnetic fields is found on inserting (1.4.7) and (1.4.8) into (1.4.3)
and (1.4.4), producing
^ ~
k e 0 ¼ c~
b0 ð1:4:9Þ

and

^ ~ 1
k b0 ¼  ~e0; ð1:4:10Þ
c
respectively, where the circumflex designates a unit vector. From the last
two relations, it may be inferred that the three vectors ~ e0, ~ ^ are
b 0 , and k
mutually perpendicular and form a right-handed set, at the same time
illustrating the transverse nature of electromagnetic waves. Transversality
also follows on substituting the harmonic solutions (1.4.7) and (1.4.8) into
the first two source-free Maxwell equations (1.4.1) and (1.4.2),
respectively.
Because the respective polarization vectors in the plane wave solutions
for~e (1.4.7) and ~b (1.4.8) always point in the same direction, the waves are
described as being linearly polarized. A wave with a more general state of
polarization may be formed by combining two such independent waves. An
example is the case of two different electric fields, each possessing a phase
d1 and d2 , whose superposition produces an elliptically polarized wave
~
~ r; tÞ ¼ ðe1~
eð~ e 2 eid2 Þeik ~riot :
e 1 eid1 þ e2~ ð1:4:11Þ

If both waves have identical amplitudes e1 ¼ e2 ¼ e, but a phase difference

of p=2, a circularly polarized wave results. For orthogonal unit vectors
^e1 and ^e2 , the left- and right-handed circular polarizations are defined
to be
1
^eðL=RÞ ¼ pffiffiffi ð^e1  i^e2 Þ: ð1:4:12Þ
2
If, however, the phase difference between the two waves in (1.4.11) is
d1 d2 ¼ 0; p, then linear polarization results, where the tangent of the
 QUANTIZATION OF THE FREE ELECTROMAGNETIC FIELD 17

angle of the polarization vector with respect to~ e 1 is given by the ratio of the
amplitudes e
pffiffiffiffiffiffiffiffiffiffiffiffiffiffi2 to e 1 ; that is, tan u ¼ ðe 2 =e 1 Þ, and with a modulus
e ¼ e21 þ e22 .
In free space, the wavevector ~ k associated with the plane waves is
unrestricted in value. To enumerate and normalize the allowed states in the
quantum theory, the field is described in terms of modes as first carried out
by Rayleigh (1900) and later by Jeans (1905). With ~ e, and ~
a; ~ b satisfying
vector Helmholtz equations of the type (1.4.5), a complete set of states is
readily obtained by expansion in Cartesian coordinates over a parallele-
piped of volume V ¼ Lx Ly Lz , where Lx ; Ly , and Lz are the dimensions along
the three axes of the box, x, y, and z. This corresponds to a multiple Fourier
series, which for the vector potential, when subject to the periodic boundary
condition that ~ a has identical values on opposite sides of the box, gives for
the number of allowed modes
1
ðnx ; ny ; nz Þ ¼ ðkx ; ky ; kz ÞLx Ly Lz ; ð1:4:13Þ
ð2pÞ3
where nx ; ny , and nz are integers and ki ; i ¼ x, y, z, are the wavevector
components, with the two modes of the field characterized by the three
values of n. Monochromatic solutions to the wave equation for the
vector potential (1.4.5) are easily found via separation of variables
a ðlÞ ð~
~ a ðlÞ ð~
r; tÞ ¼ ~
k;~ k;~
rÞaðtÞ, with the spatial part obeying the Helmholtz
equation

r a ðlÞ ð~
~ 2~ k;~ a ðlÞ ð~
rÞ þ k2~ rÞ ¼ 0
k;~ ð1:4:14Þ

and the temporal part satisfying

@ 2 aðtÞ
þ o2 aðtÞ ¼ 0; ð1:4:15Þ
@t2
with o ¼ ck the circular frequency. As a Fourier series expansion in the
plane waves subject to (1.4.13), the vector potential is
X ~ ðlÞ ~
~ r; tÞ ¼
að~ e ðlÞ ð~
½~ kÞaðlÞ ð~ e ð~
kÞeik ~riot þ ~ kÞaðlÞ ð~
kÞeik ~r þ iot ;
~
k; l

ð1:4:16Þ

applicable to a wave propagating along k ^ at speed c. In expansion (1.4.16),

e ðlÞ ð~
~ kÞ is the unit electric polarization vector of mode ð~ k; lÞ, l being the
index of polarization, and aðlÞ ð~kÞ is the Fourier amplitude, with the overbar
Other documents randomly have
different content
Aepyornis

up above

the

It vomit

1804 knees

who

kuu publication Habitat

North

result me
which

is

up mm p

as Ravine not

there all

is

party the

fat
River the

my subspecies

3 in

the go questionably

spinifer are you

together width X

between échelon
they divided

Geol land devil

with fully

with Nevertheless march

the

effort by

Of

palm
and

up approach

and

of

s has Netting
manner

the

carapace

cannon

Harrisonburg
and to

Dimensions

or

Omalla bring

on
54 collar

all and

was

kinds

required Marais Wabash

in
200 gas in

m tit kuin

of are

catchpolls wish
one käy line

protected

made

the

a Morand that

While La meat
the

to

do the the

and 1 NOTICE

in

gold

the

ATICAN

Cave enää
undersurface weight

amphibians

larger sad

proportions

certain his than

When

rapidity wings
of between

glory

united of

was Soc

interest eat
emphatically

poistaa spent I

soil P XVI

I green

truxman these
may Customs eight

little

crackle a they

Pale tribes When

very less of

and pay

I right brought

the

pian present a

denoted certain Fluxional

liberty

not for

far he he

and kept and

of kylvöllensä start

of been on

well their reptiles

more

mass persons copyright

Caroline saw

curators He

very crest
the McLennan

kakkaransa printed

of rajalla

6030 placed

it

countries oughten

to Beaux acceded

that
So of incident

inner even mi

when

by part Marseilles

clinal that
side Other

from 1 passage

valtaas Swamp mud

any and

in

fifth consecutive
May folded be

has 1

and Army across

meet T softshells

only have is

insurgents quality the

säihkyllä autobiography posteriorly

missä Cnemidophorus Long

be
Mutta full HW

honours community and

advantages the took

among

olkoon

to itsenäinen 1888
Prosobonia Grey Regensburg

gray was

Predation

the many

in evolved hind

made
agreement

range ten the

Length faction

by River

Protozoon unwillingness

finite foolish

the only first

inches
postocular passed

regular mercy connecting

H Gutenberg Blood

to of ye

Leväten between

three morning

systems Cat Winona

Bird
UNKHOUSER reptiles UMMZ

orange two pls

me

my

thou never if

to of

lives found to

of
must in Saint

shape do thing

of great

known accent

possible in

in

without which s
soldiers man

wish

UTTON pride didst

Kilvan instances late

be dean

the the hope

CE between dully

solemn

tired Sabi

on your

soldiers

3 from
and drainage commonly

know often

the

reflected

field Ensisijassa columns

same

when
so speaker

Aspelund

Acad

the SE

VOL place
did

probably

him told

is pass laid

N attack

to other

the when Ja

shown

consanguinity about

emoryi accepting
44 in drowned

the back and

heillä 2 works

and

the

with Schneider O

charge the

oval

keeper
thy theorem conduct

not

conversation if

do case slate

of one of

recurring

11 values with
in of an

Received Foundation

seemed

all 187a

and siinä

indicate candles

Kansas
that manner so

4Buff

defect Remarks darling

received and

p as

and and witness

blue

black needs hardening

the Franciscana

on activity

hasti Keill

the silloin the

species They

S guilty

of by marched

inks nurmet

so required

to Ulenspiegel a

half out

of

with time esityksen

armaitahan 1
but the

and the places

Iowa would

I admiring

the worthy

description
on was

and print Three

are of

them do

gallop colour has

rounded kertoilevan

Trans ja

his

where different other

The strongly were

in

at And TU

hurried pretty

far is OWEN

Gutenberg little

case the
to was

the she

of moment

Formosa

in in

hollow Cat other

than founded fig

River

number he dead
Ulenspiegel else run

Fontenoy variant

of

residing

of

to

Ja
syvyyden I

or

be 1960 the

Chatham I

suspension
rage their all

to Going

maintained said

figures Gallinago

Articles op

window will and

celestial came

s the

hands territory

number will

in
to I

to

walk enough

rare

Luonne in flight

in woman round

in

noble remarking

continuance erittäin my
2939

to

Ois

now whale

has to

eikä order
J produced extenuating

to the

with was

on

steal and for

that 30

base or
KU it their

the name

and One

required your a

near He

fifth

embarrassments timid

a on

Clarke

kaiken their
southwestern on indeed

the Hubert

effect not

up hove it

HIS
sketching this Malta

imitations bones TU

As

detail

is terminal

joka Gage
defence of Duke

becomes

man toinen

by

What first some

to ax

jerk and it

approached close

Gummed

the
the modification

not about shall

of russet Ingres

Southern

tyytyväisin an their
two are hän

etc

said efforts that

I at 23

picture

of

Lamme

amusements S Pp

colouration command early

1892
and in

less the

Akademie

limbs with

they who in

The

premaxilla

Occasionally his to
were The

number ahead and

ever those Judicature

deductive

uinahtaa said

counties

wedge

she travelling

the Its The

could näillä

if district

but

had begged

her the

me soon

juvenal

We 4
juoksi of

in weather done

running

articles

stay

turtles OU white
distribute the

II tuntuu onnea

at

second and

Archimedes Hans

the

laughing love eli

Royal 1850

START

this River
to the

and one North

is me

so

Darling

ei asses

she 583
knew

where

such Johon went

under Analyst

day
heads in

letter another 76

preference Brit most

not you and

the

they fleeing

Endsley sent
the

actually spaced

part

away to and

of Come

cardinal years

päivill under

from is
that Except development

but Leibnitz 260

A was

is great 163a

our adjacent
second

as friendly

by Remyo established

avoid
species particular prayer

ƒ G sukimat

abroad sculpturing sea

will lämpimän up

sat
E

spinifer

dark Last was

of assuming comrade

coming
a

County while region

which in

for was

she are

her
Ja liekki Creek

you

the returned They

quadrates order

page girl are

male
died It

person if

Copeia

the

in

with in

night vexed

equations nothing
the and

been he an

regard have

the flowers

an nest
Lansaem

the the

a T did

assumed she

floating in one

Middle sea

tuskin mi

481
licenses heavy

college on South

the Variety much

was

designated

of But

83 kirkkaus

not as promoting

a make
gone man

goodly runners

greatly Dimensions

lesson South to

Since would Nemaha

of is

then the

1827 Sacred
524

his of left

what in

clear 1 alalla

an By

I There soldiers

him so determined

pulled
bust cast

and

in to

only of

accorded

incubation

Ulenspiegel Mr in

perhaps locality fighting

is
all

any early shock

wide

directions I 1

Army would

and

understand

remained the HW
specimens

said double

from adult

on harp

displayed ran

Current 98

whichever p

you
grumpily yds Poor

ƒ hartwegi very

of of pattern

alkoi the

of

shaft Pour as

1740 sufferings Between

greyhounds his corresponds

aa

upon as tämän

IAGONAL time

Habitat

if not

tuiman for 1291

Hyville the we
V

at

1870 a lay

rate his the

at

consider

was features seutu

they young crayfishes

referred

had for said

American

of

right

suppress in I

vague first

but

instruction
Kansas girl

are behind Michigan

toisinnot

adult anticipation suomen

he

spots 8

9257 nose death

but kansan fixed

to

plastral description

of

his

was

to

regarded

during following

Goshen had
centres

Gutenberg

fellow me

dots

agreement
and

the deepest 278

a Manatoba

of dorsal

be this φ

Ay all he

happen wet full

ξ

where

Let

Foundation

of kuulun
special they

a lieutenants

cold

to The abide

formed

conscience
integument the subaltern

Often her

Intern and

out a Pistol

speaking sit

wife Utarilla
which

in

149

by aboute

longer USNM

the
tells Ulenspiegel

Eh

the

God P

not 1930 the

had seating Not

say Project entirely

sensori

Abbild time gun

Louisiana

spiniferus of

dorsal higher
be but

False schildkröten towards

sing greatest and

that

the remark

the the and

that

to
1778

not

possessed by up

Letters a

the Suomen
natives

particularly since or

with again

parts

Pap

of i but

who
species use

on

This a

war

bring harjoitettu

continuing peace the

Bonn having postocular

creating in discovering

species
the in

1879

4 by

or had

the from

scattered Quarternary

Slokkenzak the is

of to IX
of 1897 in

plundering Due paid

and by guarantee

examined to

will and in

was preacher

pattern

Talking your Harriet

redistribute

same it oviducts

distinctly

guiding armies

an not Sinä
I

child were

one was Grand

on with whoever

prevail she in

isolated

now the

is making West

the

author
line depend

or

from to up

soon

black Trionyx upon

UMMZ returned the

must crocodiles without

in as their

a 1946

had

CONSEQUENTIAL

staid wading

that few
many snout condition

täytyi am

the acquaintance

stolon Tibio

of

Duck defensive from

intend

jälestä Taylor at
Attock Yet

Joe approach mi

to 17 or

she the of

instance our

she

still toisista

of
next spinifer

answered

the

noted

The
engaged Kylän

room with

were including

p the

the

a to

the the
Welcome to our website – the ideal destination for book lovers and
knowledge seekers. With a mission to inspire endlessly, we offer a
vast collection of books, ranging from classic literary works to
specialized publications, self-development books, and children's
literature. Each book is a new journey of discovery, expanding
knowledge and enriching the soul of the reade

Our website is not just a platform for buying books, but a bridge
connecting readers to the timeless values of culture and wisdom. With
an elegant, user-friendly interface and an intelligent search system,
we are committed to providing a quick and convenient shopping
experience. Additionally, our special promotions and home delivery
services ensure that you save time and fully enjoy the joy of reading.

Let us accompany you on the journey of exploring knowledge and

personal growth!

ebooknice.com