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DYNAMICS OF
MOLECULAR EXCITONS
DYNAMICS OF
MOLECULAR EXCITONS
SEOGJOO J. JANG
Queens College, City University of New York
Department of Chemistry and Biochemistry
Queens, NY, United States
Elsevier
Radarweg 29, PO Box 211, 1000 AE Amsterdam, Netherlands
The Boulevard, Langford Lane, Kidlington, Oxford OX5 1GB, United Kingdom
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noted herein).
Notices
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changes in research methods, professional practices, or medical treatment may become necessary.
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Typeset by VTeX
To my wife
Contents vii
Contents
About the author . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . xi
Preface . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . xiii
Acknowledgments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . xv
Chapter 1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
1.1 Motivation and objective. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
1.2 Frenkel and Wannier excitons . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
1.3 Disorder, fluctuations, and measure of delocalization. . . . . . . . . . . . 16
1.4 Utility and limitations of exciton models . . . . . . . . . . . . . . . . . . . . . . . 18
Chapter 2 Microscopic derivation of Frenkel exciton-bath Hamiltonian. 21
2.1 Aggregates of chromophores. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23
2.2 Aggregates of chromophores embedded in host media . . . . . . . . . 45
2.3 Summary and additional remarks. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 50
Chapter 3 Linear spectroscopy of molecular excitons . . . . . . . . . . . . . . . . 53
3.1 Absorption lineshape . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 57
3.2 Stimulated emission lineshape . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 72
3.3 Model calculations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 76
3.4 Summary and additional remarks. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 79
Chapter 4 Exciton transfer rates and hopping dynamics . . . . . . . . . . . . . . . 83
4.1 Transfer between two exciton states: Förster theory’s and its
generalizations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 84
4.2 Transfer between groups of exciton states. . . . . . . . . . . . . . . . . . . . . . 93
4.3 Master equation approaches and long range exciton hopping
dynamics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 101
4.4 Summary and additional remarks. . . . . . . . . . . . . . . . . . . . . . . . . . . . . 105
Chapter 5 Quantum dynamics of molecular excitons. . . . . . . . . . . . . . . . . 107
5.1 Projection operator formalism . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 109
5.2 Second order approximations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 118
5.3 Fourth order approximations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 124
viii Contents
5.4 Harmonic oscillator bath with linear coupling. . . . . . . . . . . . . . . . . . 132

Chapter 6 Excitons and quantum light. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 149

6.1 Interaction of materials with quantum light . . . . . . . . . . . . . . . . . . . . 150
6.2 Microscopic derivation of Förster’s spectral overlap expression . 152
6.3 Polariton. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 157
Chapter 7 Time-resolved nonlinear spectroscopy of excitons. . . . . . . . . 161

7.1 General assumption of material Hamiltonian . . . . . . . . . . . . . . . . . . 162
7.2 Two-pulse spectroscopy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 164
7.3 Four wave mixing spectroscopy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 171
Chapter 8 Examples and applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 181

8.1 Excitons in natural light harvesting complexes. . . . . . . . . . . . . . . . . 182
8.2 Excitons for photovoltaic devices . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 186
8.3 Excitons for structural determination. . . . . . . . . . . . . . . . . . . . . . . . . . 188
Chapter 9 Summary and outlook. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 195

Appendix A Useful mathematical identities and solutions. . . . . . . . . . . . 199
A.1 Solution of eigenvalue problems for the simple Frenkel exciton
models . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 199
A.2 Some identities for averages involving harmonic oscillator
models . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 201
Appendix B Interaction between matter and classical
electromagnetic fields . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 207
B.1 Maxwell equations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 207
B.2 Classical Hamiltonian for matter and radiation interaction . . . . . . 213
B.3 Quantum mechanical Hamiltonian for matter-radiation
interaction in the weak field limit with Coulomb gauge . . . . . . . . . 214
Contents ix
B.4 Interaction with a plane wave radiation and dipole

approximation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 215
Bibliography . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 219
Index . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 223
About the author xi
About the author

Seogjoo J. Jang is a Professor of Chemistry at Queens College of
the City University of New York (CUNY), and is a doctoral fac-
ulty of both Chemistry and Physics PhD programs at the Graduate
Center of CUNY. He obtained his BS (1989) and MS (1993) degrees
in Chemistry from Seoul National University, and a PhD degree
(1999) in Chemistry from the University of Pennsylvania. He then
worked as a postdoctoral associate at MIT (1999–2002) and as a
Goldhaber Distinguished Fellow (2003–2005) at Brookhaven Na-
tional Laboratory before starting his faculty position at Queens
College, CUNY in 2005. His research expertise is in quantum dy-
namics theories and computational modeling. In particular, he
has pioneered modern theories of resonance energy transfer that
are now being incorporated into theoretical analyses of experi-
mental data on complex molecular systems, and has made key
contributions to understanding the role of delocalized excitons
in photosynthetic light harvesting complexes. He is a recipient of
the National Science Foundation CAREER Award (2009) and the
Camille Dreyfus Teacher Scholar Award (2010).
Preface xiii
Preface
Writing a book on exciton is an act of significant courage given

that there are already many authoritative classic books on this
topic that are hard to match. However, when Prof. David Andrews
invited me to write a book on molecular excitons as one of the
Nanophotonics Series, I accepted the offer without much hesi-
tation. I hoped writing such a book would be a great chance to
organize the information and knowledge I have cumulated over
about two decades of research. In addition, throughout my inter-
actions with colleagues and students, I have indeed experienced
the necessity for a new kind of monograph on excitons that can
address current computational and experimental need, in partic-
ular concerning the dynamics.
This book is intended for general readers who have completed
standard graduate level quantum mechanics or quantum chem-
istry courses. I tried to make this book as a kind of self contained
theoretical reference for those who try to understand theories of
exciton dynamics. This book can help non-experts who would
like to get into this field of research and also experts by offering
new details and perspectives that are not often discussed explic-
itly. I tried to also address applications as much as possible, but I
should admit that the account of applications in this book is quite
limited.
There are three major issues this book is particularly focused
on. The first is to understand the assumptions and approxima-
tions implicit in conventional models for molecular excitons and
their interactions with environments. Most of consideration is at
formal level, which will form the basis for more detailed numerical
investigations in the future. In addition, this part can be consid-
ered as an extension of standard molecular quantum mechanics,
and can be used as supplemental reading for a quantum chem-
istry class. The second is to offer as comprehensive description
as possible of most dynamics theories of molecular excitons. The
main focus was on explaining the derivation of these theories and
methods. The rate theories and quantum dynamics methods de-
scribed here are in fact much more general and are applicable to
other quantum dynamical processes. Finally, detailed theoretical
description is provided for the spectroscopy of excitons. Again, the
major focus is on theoretical aspects of these spectroscopic meth-
xiv Preface
ods and understanding their capability as a tool for probing the

exciton dynamics.
Seogjoo J. Jang
New York
December 6, 2019
Acknowledgments xv
Acknowledgments
I thank the late Bob Silbey who taught me a great deal about
molecular excitons when I was a postdoctoral researcher at MIT.
He also continued inspiring me for many years afterwards as a
colleague. Interactions with him were always special. He could
easily explain important ideas and issues in a few minutes, which
helped me understand their implications so quickly and pursue
new ideas efficiently. Writing this book gave me another chance
to interact with him indirectly through his publications, and I am
still learning from works he has completed decades ago.
Although not directly related to this topic, I am heavily in-
debted to Marshall Newton, one of the best critical thinker and
theoretician I am aware of. His broad knowledge and expertise in
electron transfer theories helped me envision a roadmap for de-
veloping theories of exciton transfer and dynamics, which have
remained relatively unexplored in comparison to the field of elec-
tron transfer theories. Communications and interactions with him
helped me evolve through my early formative period as an inde-
pendent theoretician.
There are also many others that I should not forget mention-
ing names for various contributions related to this book. I am
indebted to my mentors at Seoul National University, Sangyoub
Lee and Kook Joe Shin, who first introduced me to Förster theory
and guided my first research on this topic, and to my PhD mentor
Gregory Voth from whom I learned the fundamentals of quantum
dynamics. I would like to thank Jeff Cina, David Reichman, Chris
Bardeen, Yuan-Chung Cheng, Benedetta Mennucci, Joe Subotnik,
Dorthe Eisele, Greg Scholes, Young Min Rhee, David Coker, Jian-
shu Cao, Jasper Knoester, Graham Fleming, and K. Birgitta Whaley
for discussions and help at various stages leading to this work,
and Frank Spano, Ari Chakraborty, Qiang Shi, and Andrew Mar-
cus for allowing me use their images. Support from National Sci-
ence Foundation, the Department of Energy, and Camille Dreyfus
Foundation have made it possible to continue projects that con-
stitute various parts of this book.
I am grateful to the editor of the Nanophotonics Series, Prof.
David Andrews, and the editorial office of Elsevier for support. Fi-
nally, I cannot thank enough my wife who has been truly support-
ive of writing this book. I am happy to dedicate this book to her.
Seogjoo J. Jang
January 28, 2020
Introduction
1
Contents
1.1 Motivation and objective 1
1.2 Frenkel and Wannier excitons 3
1.2.1 A brief overview 3
1.2.2 Model Hamiltonians for Frenkel excitons 6
1.2.2.1 Linear chain 7
1.2.2.2 Circular chain 11
1.2.3 Semiclassical model Hamiltonians for Wannier excitons 15
1.3 Disorder, fluctuations, and measure of delocalization 16
1.4 Utility and limitations of exciton models 18
1.1 Motivation and objective

An exciton represents a quantum mechanical state of elec-
tronic excitation or a bound pair of an electron and its hole.1
Any electronic excitation of a molecule can be viewed as an ex-
citon confined within the molecule. However, the real benefit of
the concept of exciton is that it helps generalizing the excitation
beyond molecular boundaries in a simple manner. For example,
excitons can be formed across the confines of molecules and exist
in quantum mechanical superposition states. These represent col-
lective quantum states distinctive from independent sums of ele-
mentary molecular excitations, which can exhibit unique quan-
tum mechanical properties of collective nature. One well-known
example is the super-radiance, a collective emission phenomenon
that applies to any atomic [1] or molecular systems [2–6].
Direct experimental confirmation of molecular excitons was
difficult in early days of quantum mechanics. Although well-
established conceptually, their practical significance was not
clearly recognized either. Through decades of research and devel-
opment, excitons have steadily become established as essential
objects for solar light harvesting, imaging, sensing, lasing, and
light-emitting devices. Applications of excitons for quantum infor-
mation processing devices and novel photonic materials are also
emerging areas of research. Thanks to these advances, excitons
are now well supported by many computational and experimental
1 The hole itself is a quasi-particle and refers to the absence of electron.
Dynamics of Molecular Excitons. https://doi.org/10.1016/B978-0-08-102335-8.00009-0 1

2 Chapter 1 Introduction
data, and are perceived as important objects for a few key applica-
tions. However, while data informing the existence and contribu-
tion of excitons abound, accurate and complete information on
excitons is still difficult to get in general. In particular, accurate
measurement of both spatial patterns and temporal dynamics of
excitons, which is crucial for satisfactory microscopic characteri-
zation, remains a challenging area of research even to date.
The difficulty in detailed microscopic characterization of ex-
citons stems in part from their indefinite spatial extents (in
nanometer length scales) and transient dynamical nature (in time
scales typically as short as tens of femtoseconds). Resolving this
issue requires experimental tools that can simultaneously probe
nanometer length scales at femtosecond time resolution, which
remain challenging despite recent advances. The other reason, al-
though less appreciated, is the fact that exciton has often been
perceived by experimentalists as a loosely defined simple object of
semi-empirical nature. This is in contrast to the current status of
computational molecular quantum mechanics, which has come a
long way of constructing sophisticated methods and rigorous mi-
croscopic formulations that can account for various many-body
quantum effects. The gap between these modern practices of
molecular quantum mechanics and the conceptual basis of most
experimental investigation based on old exciton theories, is often
the source of confusion and miscommunication.
For both practical and fundamental reasons, there is increas-
ing demand for accurate characterization and control of excitons
in complex environments. However, for many interesting systems,
the scale and accuracy of calculations necessary for reliable com-
putation of excitonic properties is in general beyond the reach of
rigorous computational methods at present. Significant theoreti-
cal progress is needed for more accurate and microscopic descrip-
tion of excitons as well as for further advances in experimental
probe techniques. In promoting the theoretical progress, it is im-
portant to establish a general theoretical framework for excitons
that is both rigorous and practical. This is one of the main motiva-
tions for this book.
The first objective of this book is to help consolidating many
versions and ideas of excitons into a single theoretical formalism.
While this is an ambitious objective difficult to achieve at present,
this book can set the stage for initiating a long term effort of such
nature. In addition, many assumptions and approximations clar-
ified in this book will help gain better understanding of the dy-
namics and spectroscopic data. The second objective is to offer
comprehensive description of various theories of exciton dynam-
ics along with their applications. There are multiple approaches
Chapter 1 Introduction 3
possible for achieving this goal. The approach taken in this book
is to begin with molecular Hamiltonians. This approach makes
it straightforward to clarify assumptions and approximations im-
plicit in different forms of excitons from the outset. The formal
foundation for this will be provided in the next chapter. In the
rest of this chapter, for motivational purposes, a brief overview of
Frenkel and Wannier excitons is presented. This is then followed
by introduction of simple model Hamiltonians used for describ-
ing such excitons.
A few words on the convention of notations. For exciton states
and Hamiltonians, the first order quantization and the Dirac no-
tation for states and operators will be used in most cases. The sec-
ond quantization will be primarily reserved only for the descrip-
tion of electromagnetic radiation within the quantum electrody-
namics formalism. When appropriate, semiclassical description
of electromagnetic radiation will also be used for the description
of matter-radiation interaction.
1.2 Frenkel and Wannier excitons

1.2.1 A brief overview
Frenkel [7–9] and Wannier excitons [10,8] represent two well-
known forms of collective excitations that are applicable in two
opposing limits and are amenable for simple quantum mechani-
cal description.
Frenkel exciton theory has been successful for describing the
spectroscopy of molecular crystals and aggregates [8,11,12], where
molecules are bound together by weak interactions. In this case,
electronic properties of individual molecules remain mostly in-
tact. Thus, collective excitation processes can be described still
in terms of properties characterizing the excitation of individual
molecules. Application of the Frenkel exciton theory has since
been expanded to macromolecular and supramolecular systems.
Most recently, Frenkel excitons were shown to play a major role in
natural photosynthetic light harvesting complexes [13].
On the other hand, Wannier excitons [10,8] are appropriate for
inorganic insulating or semiconducting solid materials where the
band theory serves as a successful framework to describe delocal-
ized electrons and holes. The concept of Wannier exciton played
a key role in the development of inorganic photovoltaic and solid
state laser devices. To a certain extent, Wannier excitons can be
used to describe electronic excitation processes in highly confined
systems such as quantum dots.
The basis set of quantum mechanical states used for Frenkel

exciton is the direct product of individual molecular orbitals,
which are typically assumed to be orthogonal to each other. To be
more specific, consider an example of N aggregates of molecules,
where the j th molecule has the ground electronic state |gj , and
a single excited state |ej . Then, the ground electronic state of the
aggregate is
|g = |g1 ⊗ |g2 · · · ⊗ |gN , (1.1)
where ⊗ represents direct product. One can then introduce N or-

thogonal states forming the basis of single exciton states, each of
which is denoted as |sj . This represents a state where only the
j th molecule is in the excited state |ej while all others are in the
ground electronic state. Thus,
|sj = |g1 ⊗ · · · |gj −1 ⊗ |ej ⊗ |gj +1 · · · ⊗ |gN . (1.2)
Higher order excitons such as double and triple excitons can also
be defined in a similar manner.
The original formulation of Frenkel exciton [7,9] used a single
orbital to define each state |ej . However, this is not in fact an es-
sential assumption. Each electronic state at molecule j can be any
general molecular electronic state accounting for all many-body
electronic correlations within the molecule as has been suggested
by Agranovich [14]. The only assumption necessary for the con-
struction of Frenkel exciton basis, as will become clear in the next
chapter, is that ej |ek = 0 for j = k. Consequently,
sj |sk = 0, for j = k . (1.3)
Despite the assumption of weak interactions implicit in

Eq. (1.3), the electronic excitation |ej at the molecule j can still
cause perturbation of electrons in the ground electronic state
|gk of another molecule k. Such interaction is dominated by ex-
change interaction at short range and becomes mainly Coulombic
at moderate to long distances. These interactions couple the ex-
citation of electrons at the j th molecule with that of electrons at
the kth molecule, and are often called resonance interactions. In
other words, given the electronic Hamiltonian of the aggregate Ĥe ,
there is a non-vanishing resonance term
Jj k = sj |Ĥe |sk , for j = k . (1.4)
These resonance interactions, Jj k ’s, cause eigenstates of Ĥe to be

coherent superpositions of |sj ’s. The resulting N eigenstates form
the exciton basis, which is different from the site excitation basis.
The exciton states are fully delocalized and also form a band of vir-
tually continuous states in the limit of large N . This exciton band
is however constructed out of two electron processes and is differ-
ent from the conduction and valance band of the single electron
picture that form the basis of the Wannier excitons as described
below.
The concept of Wannier exciton is built on the band theory
of electronic states in semiconducting/insulating solid materials,
which represent almost continuum states of delocalized electrons
(conduction band) and holes (valance band). Namely, it is based
on the following effective electronic Hamiltonian:

Ĥe = Ec (k)ek† êk + Ev (k)ĥ†k hk
k
1
+ V (p, k, k )êk+p
†
ĥ†p−k ĥp−k êp+k , (1.5)
Nt
p,k,k
where Ec (k) and Ev (k) are energies of conduction and valance

bands corresponding to wave vector k, êk† (êk ) and ĥ†k (ĥk ) are
creation (annihilation) operators of an electron and hole, respec-
tively. Nt is the total number of lattice sites and V (p, k, k ) is the
Coulomb potential between electron and hole represented in the
momentum space.
For electrons and holes localized near the band edges, semi-
classical wave packets consisting of the superposition of the
nearby band states can provide reasonable description of their
properties. These wave packets behave in almost classical man-
ner with effective masses reflecting the dispersion relationships
of respective bands. Given that the distance between the cen-
ters of electron and hole wave packets is much larger than lattice
spacings of the solids, their effective interaction can be modeled
by simple Coulomb attraction screened by the average dielectric
constant of the medium. Within this picture, the energy levels of
excitons (in the simplest case) have the same structure as the elec-
tronic energy of the hydrogen atom, but with effective charges
and masses that are different from bare ones. In the presence
of confinement or boundary effects, the effective potential de-
viates significantly from a simple Coulombic behavior. Accurate
theoretical understanding of such deviation is necessary for the
determination of the exciton binding energy.
The manner of localization/delocalization is different for
Frenkel and Wannier excitons. In the former case, the delocal-
ization occurs only through quantum mechanical superposition
Figure 1.1. Illustration of the formation of a Frenkel exciton. Each ellipse with +
and − represents intramolecular excitation, and the whole exciton state (black
line) is formed as a linear combination of these localized excitations. C1 , · · · , CN
are complex coefficients such that |C1 |2 + |C2 |2 + · · · + |CN |2 = 1.
Figure 1.2. Illustration of the formation of Wannier exciton. Localized

wavepackets of electron in the conduction band and hole in the valance band are
formed and are bound to each other via Coulomb interaction.
of originally localized excitation states, namely, formation of

delocalized exciton states. Fig. 1.1 provides illustration of such
states. On the other hand, in the latter case, formation of exci-
tons amount to partial localization of band states, which are fully
delocalized effective single electron and hole states. Fig. 1.2 de-
picts this process. The sources of localization can vary but are
most likely the combination of disorder, dynamic relaxation, and
thermalization effect. The Coulombic binding potential between
electron and hole also contributes to the localization as well.
1.2.2 Model Hamiltonians for Frenkel excitons

For more concrete understanding, it is instructive to consider
two well-known models of Frenkel excitons formed by N identical
molecular units. One is a linear chain with only nearest neigh-
bor interactions. The other is a circular chain with arbitrary non-
nearest neighbor interactions satisfying cyclic symmetry. In the

absence of any disorder or dynamical fluctuations, these models
have simple analytic expressions for their eigenvalues and eigen-
states. Detailed consideration of these states can be used to illus-
trate key concepts and languages of molecular excitons. In the two
models described below, it is assumed that the level spacings of
excited states within each molecular unit are much larger than the
resonance coupling. Under this condition, one can focus on only
one excited state of each molecule with energy E as far as single
exciton is concerned.
1.2.2.1 Linear chain

Consider a linear chain of N identical molecules, with only the
nearest neighbor resonance interaction denoted as J . Then, the
single exciton Hamiltonian in the basis of |sj , with j = 1, · · · , N ,
can be represented as

N
N−1

Ĥe = E |sj sj | + J |sj sj +1 | + |sj +1 sj | . (1.6)
j =1 j =1
The eigenstates and eigenvalues of this Hamiltonian are as fol-

lows:

pπ
Ep = E + 2J cos , (1.7)
N +1
1/2 N
2 pnπ
|ϕp = sin |sj , (1.8)
N +1 N +1
n=1
where p = 1, · · · , N . Detailed mathematical steps leading to these

expressions are provided in Appendix A.
For J < 0, the lowest value of the exciton energy and its eigen-
state correspond to p = 1 in Eqs. (1.7) and (1.8) as follows:

π
E1 = E + 2J cos , (1.9)
N +1
1/2
N
2 nπ
|ϕ1 = sin |sj . (1.10)
N +1 N +1
n=1
On the other hand, the highest value of the exciton energy and the
corresponding eigenstate correspond to p = N as follows:

π
EN = E − 2J cos , (1.11)
N +1
1/2
N
2 nπ
|ϕN = sin (−1)n+1 |sj . (1.12)
N +1 N +1
n=1
Therefore, the energies of all the exciton states are within a band
of the following width:

π
= 4|J | cos ≤ 4|J | , (1.13)
N +1
which are distributed symmetrically2 around E. Thus, the exciton

band width is characteristic of the nearest neighbor coupling.
For J > 0, the order of eigenstates is reversed. In other words,
Eq. (1.11) becomes the lowest exciton energy and Eq. (1.9) the
highest exciton energy. Except for this, other features remain the
same as in the case of J < 0.
Let us now consider a more concrete model for transition
dipoles. Assume that the j th molecular unit has the following
transition dipole moment:

μj = μ sin θj cos φj , sin θj sin φj , cos θj , (1.14)
where it is assumed that the linear chain is along the z-direction.

Thus, θj is the axial angle and φj is the azimuthal angle of the di-
rection of the transition dipole μj . Let us also assume that J is
given by a sum of constant nearest neighbor term and an effective
transition dipole interaction as follows:
μ2
J = J0 + 3
sin θj sin θj +1 cos(φj − φj +1 ) − 2 cos θj cos θj +1 ,
d
(1.15)
where is an effective optical dielectric constant and d is the dis-

tance between nearest neighbors. This assumption is reasonable
if the distance d is large enough such that μ2 /(8d 3 ) << |J0 |. Here,
J0 represents all the higher order Coulomb and exchange interac-
tions that are significant only between nearest neighbors.
In order for Eq. (1.15) to be independent of j , φj − φj +1 = δφ.
For θj , there are two possibilities, θj = θj +1 or θj + θj +1 = π. As
representative examples, it is useful to consider the following four
cases: (i) φj = 0, θj = 0; (ii) φj = 0, θ2j −1 = 0, θ2j = π; (iii) φj = 0,
θj = π/2; (iv) φj +1 − φj = π with φ1 = 0, θj = π/2, which are de-
picted in Fig. 1.3. Detailed description of each case is provided
below.
2 This symmetry gets broken if there are non-nearest neighbor interactions.
Figure 1.3. Depiction of four examples of linear aggregates.
(i) In this case where all the transition dipoles are along the
z direction in head-to-tail, Eq. (1.15) simplifies to J = J0 −
2μ2 /(d 3 ). Assume that J0 < 0. Then, J < 0, and Eqs. (1.9)
and (1.10) represent the lowest exciton energy and eigen-
state. The corresponding transition dipole of each exciton
state has zero components along the x and y directions, but
only the following z-component:

N
μ̃p,z = μ ϕp |sj
j =1
1/2
N
2 pj π
=μ sin
N +1 N +1
j =1

(1 − (−1)p ) pπ
=μ √ cot , (1.16)
2(N + 1) 2(N + 1)
where p = 1, · · · , N . In
√ the large N limit and for p << N , this
approaches μ̃p,z ≈ μ 2(N + 1)(1 − (−1)p )/(pπ).
(ii) In this configuration of an alternating head-to-head and
tail-to-tail configuration along the z direction, Eq. (1.15)
simplifies to J = J0 + 2μ2 /(d 3 ). Depending on the sign of
J0 and its magnitude relative to 2μ2 /(d 3 ), the order of exci-
ton energy levels may or may not be the same as case (i). Let
us assume for now that J > 0. Then, Eqs. (1.11) and (1.12)
represent the lowest single exciton energy and eigenstate.
As in case (i), the transition dipole of each exciton state has
zero components along the x and y directions, and has the
following component along the z-direction:

N
μ̃p,z = μ (−1)j −1 ϕp |sj
j =1
1/2
N
2 pj π
=μ sin + (j − 1)π
N +1 N +1
j =1

(1 − (−1)p ) pπ
=μ √ tan . (1.17)
2(N + 1) 2(N + 1)
By introducing p = N + 1 − p, it is easy to find that this case

becomes nearly equivalent to (i). In the large N √ limit and for
N − p << N, Eq. (1.17) approaches μ̃p,z ≈ μ 2(N + 1)(1 −
(−1)p )/((N + 1 − p)π). For even N , the lowest exciton level
(p = N ) has zero intensity, whereas the second lowest ex-
citon state has the maximum intensity. On the other hand,
for odd N , the lowest exciton state has the maximum in-
tensity, but the second lowest one has zero intensity. Except
for these fine details depending on even or odd N , the level
spacings and the fact that major intensities are in the lower
exciton states are the same as in case (ii).
(iii) In this case corresponding to a parallel arrangement of tran-
sition dipoles along the x-direction, Eq. (1.15) simplifies to
J = J0 + μ2 /(d 3 ). Let us assume that J > 0 as in case (ii).
Then, Eqs. (1.11) and (1.12), the case with p = N , repre-
sent the lowest exciton energy and eigenstate. The transi-
tion dipole of each exciton state has zero components along
the y and z directions, but has the following x-component:

(1 − (−1)p ) pπ
μ̃p,x = μ √ cot . (1.18)
2(N + 1) 2(N + 1)
Note that this has the same expression as Eq. (1.16) except
that the direction is now along the x-direction. This is ex-
pected because the transition dipoles are parallel in both
cases and exactly the same expression is used for summing
up the contribution to the transition dipole of the exciton
state. However, there is major difference from case (i) in that
the order of exciton state is reversed here, as in case (ii). For
even N , the transition dipole of the lowest exciton state is
zero. For odd N , the transition dipole of the lowest exciton
state is finite but of the minimum magnitude.
√ In the limit of
large odd N , it approaches μ̃N,x ∼ π 2μ/(N + 1)3/2 , which is
vanishingly small. Thus, the lowest single exciton state has
either zero or almost zero transition dipole in this case.
(iv) In this case corresponding to antiparallel arrangement of

transition dipoles along the x-direction, Eq. (1.15) simpli-
fies to J = J0 − μ2 /(d 3 ). Let us assume that J < 0. Then,
Eqs. (1.9) and (1.10) represent the lowest exciton energy and
eigenstate. The transition dipole of each exciton state has
zero components along the y and z directions, but has the
following x-component:

(1 − (−1)p ) pπ
μ̃p,x = μ √ tan . (1.19)
2(N + 1) 2(N + 1)
Note that this has the same expression as Eq. (1.17) except
that it is now along the x-direction. However, note the dif-
ference of exciton energy ordering in this case. While the
transition√dipole of the lowest exciton state is nonzero, its
value is π 2μ/(N + 1)3/2 , which is vanishingly small.
The details described above for the cases (i) and (ii) are al-
most equivalent except for the phase factor, which can be incor-
porated into the definition of each state |sj . The same is true for
the cases (iii) and (iv). Thus, both the cases (i) and (ii) correspond
to J -aggregates [8,15,16] in the sense that the major oscillator
strength are concentrated on the lowest exciton state. On the other
hand, the cases (iii) and (iv) correspond to H -aggregates [8,15,16]
in the sense the lowest exciton state has virtually zero oscillator
strength. These also serve as counter examples for often referred
simple picture for J - and H aggregates, i.e., the former as result-
ing from “head-to-tail” and the latter from “parallel” configura-
tion of transition dipoles. For example, (ii) is not in “head-to-tail”
but the pattern of transition dipoles will empirically classify it as
J -aggregate. On the other, (iv) is not “parallel” but its pattern of
transition dipoles also makes it an example of H -aggregate.
The summary provided above is of course based on the as-
sumption that the sign of J0 is the same as that of the transition
dipole interaction. If the sign of J0 is different and plays a domi-
nant role, the classification given above should be altered. In addi-
tion, for more general values of θj and φj − φj +1 = δφ, the division
into J or H aggregates will be less clear.
1.2.2.2 Circular chain

As the second example, consider a ring of identical N molecu-
lar units with the following exciton Hamiltonian:

N
N
Ĥe = J (j − k)|sj sk | , (1.20)
j =1 k=1
where J (j − k) satisfies the cyclic boundary condition with period

N and J (0) = E, which is the energy of each state |sj . This cyclic
symmetry leads to the following states to be eigenstates of Ĥe .
1 2πipj/N
N
|ϕp = √ e |sj , (1.21)
N n=1
where p = 0, · · · , N − 1. This can be demonstrated easily by the

following identity:
1
N N

ϕp |Ĥe |ϕp = sj |Ĥ0 |sk e2πipj /N e−2πip j/N
N
j =1 j =1
1
N N

= J (j − j )e2πip(j −j )/N e2πi(p−p )j/N
N
j =1 j =1
⎛ ⎞
N
1 N

= J (k)e−2πipk/N ⎝ e2πi(p−p )j/N ⎠
N
k=1 j =1

N
= δpp J (k)e−2πipk/N , (1.22)
k=1
where the index k = j − j was introduced in the third line and the
fact that J (j ) = J (j + N ) and e−2πipj/N = e−2πip(j +N )/N was used to
replace j < 0 with N + j in the summation. As a result, the exciton
Hamiltonian and eigenvalue can be expressed as

N −1
Ĥe = Ep |ϕp ϕp | , (1.23)
p=0

N −1
Ep = E + J (k)e−2πipk/N . (1.24)
k=1
Equivalently, p can be rearranged to be centered around zero,

which is often more convenient. For odd N , p = 0, ±1, · · · ,
±(N −1)/2 can be used. For even N , p = 0, ±1, · · · , ±(N −2)/2, N/2,
can be used.
Let us now consider a more detailed specification of the po-
sitions and transition dipoles of molecules forming the ring. As-
sume that the ring is in the xy-plane and that its radius is R. Then,
assume that the position and transition dipole of the nth molecule
are given by
rj = R (cos(2πj/N), sin(2πj/N), 0) , (1.25)

μj = μ sin θμ cos φμ + 2πj/N ,

sin θμ sin φμ + 2πj/N , cos θμ , (1.26)
where θμ and φμ are fixed reference angles of the transition

dipoles. Then, assuming additional non-transition dipole interac-
tion only for nearest neighbors, it is straightforward to show that
J (j − k) for j = k can be expressed as
J (j − k) = J0 δ[(j −k)/N ],±1

2 2 cos θμ + sin θμ 3 cos 2φμ − cos (2π(j − k)/N)
2 2
+μ ,
16R 3 | sin(π(j − k)/N )|3
(1.27)
where [(j − k)/N] in the subscript of the delta function denotes

mod function of j −k with respect N . Inserting this expression into
Eq. (1.24) and utilizing the fact that J (k) = J (N − k), we obtain the
following general expression:

2πp
Ep = E + 2J0 cos
N

μ2 2 cos2 θμ + sin2 θμ 3 cos(2φμ ) − cos(2πk/N )
N−1
+
R 3 16| sin(πk/N )|3
k=1

2πpk
× cos . (1.28)
N
Note that the energy levels of ±|p|’s are degenerate.

On the other hand, for the definition given by Eq. (1.26), the
transition dipole of the pth exciton state becomes

N
1 2πipk/N
N
μ̃p = ϕp |sk μk = √ e μk
k=1
N k=1
√
N
=μ sin θμ eiφμ δp,−1 (1, −i, 0) + e−iφμ δp,1 (1, i, 0)
2√
+ μ Nδp,0 cos θμ (0, 0, 1) . (1.29)
Unlike the case with the linear chain, non-zero values of transition
dipoles in this model are confined to only p = 0 and ±1. Whether
these correspond to low-lying or high-lying exciton states depend
on details such as J0 , θμ , φμ , and N .
Let us consider three simple cases as follows: (i) θμ = 0;

(ii) θμ = π/2, φμ = 0; (iii) θμ = π/2, φμ = π/2. These three cases
are depicted in Fig. 1.4 for N = 8. More detailed description of en-
ergies and transition dipoles for each case are provided below.
(i) In this case of transition dipoles aligned in parallel along the
z direction, the exciton energy level is given by

μ2 cos(2πpk/N)
N−1
2πp
Ep = E + 2J0 cos + . (1.30)
N 8R 3 | sin(πk/N )|3
k=1
The transition dipole has nonzero component only for the

z-direction and p = 0 state as follows:
√
μ̃p,z = μ Nδp,0 . (1.31)
(ii) In this case of transition dipoles aligned along the radial di-
rection of the circle in the x − y plane, the exciton energy
level is given by

2πp
Ep = E + 2J0 cos
N
2 (3 − cos(2πk/N ))
N−1
μ 2πpk
+ cos .
16R 3 | sin(πk/N )|3 N
k=1
The transition dipoles are confined in the x − y plane and

have the following components:
√
N
μ̃p = μ δp,−1 (ex − iey ) + δp,1 (ex + iey ) . (1.32)
2
(iii) In this case of transition dipoles aligned along the tangential
direction of the circle in the x − y plane, the exciton energy
level is given by

2πp
Ep = E + 2J0 cos
N
2 (3 + cos(2πk/N ))
N−1
μ 2πpk
− cos .
16R 3 | sin(πk/N )|3 N
k=1
The transition dipoles are confined in the x − y plane and

have the following components:
√
N
μ̃p = μ δp,−1 (iex + ey ) + δp,1 (−iex + ey ) . (1.33)
2
Figure 1.4. Circular arrangement of molecules for N = 8.
1.2.3 Semiclassical model Hamiltonians for Wannier

excitons
Wannier excitons are formed in inorganic solid materials and
various interfacial areas promoting the separation of electron and
hole [10]. As explained briefly in Sec. 1.2.1, Eq. (1.5) represents
electrons and holes formed in the band theory and are bound by
Coulomb interactions. Given that a pair of electron and hole are
spatially localized due to disorder, electron–phonon coupling, or
fluctuations and that they can be presented as superposition of
states near the band edges, they can be described by the following
effective Hamiltonian:
p̂2e p̂2h e2
Ĥe = ∗
+ ∗ + Ve (r̂e ) + Vh (r̂h ) − + Vnc (r̂e , r̂h ) , (1.34)
2me 2mh |r̂e − r̂h |
where m∗e and m∗h are effective masses of electron and hole that are
determined by the dispersion relations of respective bands, Ve (r̂e )
and Vh (r̂h ) are effective confining potentials, and is the effective
dielectric constant of the medium, and Vnc (re , rh ) represent other
contributions. Even at this two-particle picture, exact analytic so-
lution is not possible in general.
In the simplest case where the boundary effects and Vnc (re , rh )
can be ignored, Eq. (1.34) reduces to that of hydrogen-like Hamil-
tonian with effective reduced mass μ∗ = m∗e m∗h /(m∗e + m∗h ). How-
ever, this is no longer true if anisotropy due to crystalline environ-
ments need to be taken into consideration. An elegant way to solve
this is to map the Hamiltonian to an isotropic one in fractional-
dimension [17]. Solution of this leads to the following expression
for the energy of bound exciton state:
Ee
En = Eg − , (1.35)
(n + (α − 3)/2)2
where Eg is the electron-hole band gap, Ee = μ∗ e4 /(8 2 h3 c), and

1 < α < 3 is the fractional dimension.
In recent years, research on two dimensional materials and

perovskites have raised renewed interest in the effects of con-
finement and dielectric response on Wannier excitons. The long
standing issue of calculating charge separation rates at inter-
faces of organic bulk heterojunction materials also requires un-
derstanding major factors influencing the nature of such interfa-
cial excitons.
For two dimensional excitons, the dielectric response becomes
nonlocal and the screened electron-hole potential deviates signif-
icantly from the original form. For example, even in the simple
case, it was shown that [18] the electron-hole screened potential
is given by V (r) ∼ H0 (r) − Y0 (r), where H0 (r) and Y0 (r) are the
Struve function and the Bessel function of the second kind. This
has logarithmic dependence for short r and decays exponentially
for large r.
In three dimensionally confined systems such as quantum
dots, with sizes comparable or smaller than the average electron-
hole pair distance, it also becomes necessary to take explicit con-
fining potentials Ve (r̂e ) and Vh (r̂h ) into consideration. Transla-
tional invariance no longer holds in this case, and the problem in
general requires numerical solution.
1.3 Disorder, fluctuations, and measure of

delocalization
Disorder and fluctuations in general cause excitons to be local-
ized. The detailed manner of localization depends on the type of
excitons, which in turn requires different measures to quantify the
extent of localization or delocalization.
For Frenkel excitons, each eigenstate of a purely electronic and
symmetric Hamiltonian such as shown in Secs. 1.2.2.1 and 1.2.2.2
can be viewed as fully delocalized over the entire system. Ex-
cept for the fact that the probability density varies in association
with nodal patterns, such states represent excitons that are spread
across the entire system with virtual uniformity. In the presence
of static disorder only, eigenstates of the resulting exciton Hamil-
tonian for each realization of the disorder still remains stationary.
However, the probability density for such state is more dominant
in certain region of the system than the other. The extent of local-
ization/delocalization in this case should be treated as the prop-
erty of the entire ensemble of the disorder and is associated with
how much the static disorder breaks the symmetry of the original
Hamiltonian.
A well-known measure of delocalization is the following in-

verse participation ratio (IPR):
1
LIDP R = , (1.36)
p wp j |Ujp |4
where wp is the Boltzman factor for each eigenstate |ϕp and Ujp =
sj |ϕp , which is the component of the unitary transformation be-
tween the exciton state and site excitation state. For the case where
|Ujp |2 = 1/N , which is true for the lowest exciton state of the linear
chain in Sec. 1.2.2.1 and for all exciton states for the circular chain
in Sec. 1.2.2.2, LIDP R = N . For the case where the disorder signif-
icantly lowers the energy of a specific site j such that Ujp = δjj ,
LIDP R = 1. Thus, LIDP R approaches correct values in the two oppos-
ing limits. In between, the value of LIDP R serves as a reasonable
quantitative measure for the average size of Frenkel excitons, but
its exact physical meaning is not always clear.
The measure of delocalization is not in fact unique and there
are many other alternatives. One simple alternative measure is the
following one [19]:

LD =
J DS
wp min 1, N |Ujp |2
. (1.37)
p j
This produces the same values as LIDP R in the two fully localized
and delocalized limits. However, Eqs. (1.36) and (1.37), and also
other alternative measures, in general have different values in the
intermediate situation.
In fact, it is not unexpected that there is no unique value for the
measure of delocalization in the intermediate situation consider-
ing that it is typically used to give qualitative or semi-quantitative
estimate of the size of the exciton. This leaves the possibility for
the definition of a new delocalization length with clear opera-
tional implication in quantum mechanical sense. However, this is
again expected to depend on a specific type of measurement.
In the presence of additional time dependent fluctuations or
dynamical interactions with environments, Eqs. (1.36) and (1.37)
can be used in the same manner. The quantity being averaged over
the static disorder now becomes a dynamical variable in this case
and it offers information on the spatio-temporal evolution of the
extent of delocalization.
For Wannier excitons, the contribution of disorder and fluc-
tuations enter at two stages. The first is at the level of forming
the semiclassical electron and hole quasiparticles near the band
edges, which in general become realized through the interplay of

disorder and dynamical fluctuations. The sizes of these electron
and hole quasiparticles are assumed to be much smaller (although
they may even be larger than typical sizes of Frenkel excitons)
than the actual sizes of Wannier excitons. Instead, the actual delo-
calization length or size of the Wannier exciton is conventionally
understood as the average distance between the electron and hole
quasiparticles, namely, the Bohr radius for the exciton model. This
delocalization length is mainly determined by the effective masses
of electron and hole, which reflect their dispersion relationship
at their band edges, and the dielectric screening of the medium.
The role of disorder and fluctuation at this stage can be critical
but is in general of secondary importance. In other words, it is
generally believed that the delocalization of Wannier exciton is
primarily determined by the effective binding energy of the pair
of electron and hole quasiparticles, and the disorder and fluctua-
tions affect the former primarily through the latter. At interfaces
and confined systems, boundary effects become another factors
determining the electron-hole binding energy and thus the result-
ing size of exciton.
1.4 Utility and limitations of exciton models

The simplicity and conceptual clarity of simple exciton models
have made it possible to describe collective electronic excitation
process in an effective manner. However, such models cannot be
justified based on phenomenological success alone. For better mi-
croscopic understanding of the success or failure of such models,
both high level computational studies and comprehensive spec-
troscopic studies are necessary. Fig. 1.5 shows representative ex-
amples for which such efforts have been actively pursued. I will
conclude this chapter by addressing three issues that are impor-
tant in this context.
(i) Many-body quantum correlation: This effect is largely ignored in
simple Frenkel and Wannier exciton models. Within the frame-
work of the Frenkel exciton theory, this can be accounted for by
including charge transfer states and expanding the basis set to
include different configurations of charge transfer states. While
this systematic approach is feasible in principle, the additional
terms that are needed to account for necessary phenomena ex-
pand rapidly with the system size, which pose serious numerical
challenges. From the Wannier exciton point of view, such effect
can be accounted for going beyond independent electron-hole
picture. One of the most successful approach in addressing this is-
Figure 1.5. Examples of exciton hosting systems. (A) Dithiaanthracenophane (DTA) – a dimeric exciton system
(adapted with permission from [20]. © (2010) American Chemical Society); (B) Light harvesting 2 (LH2) complex of
purple bacteria (reprinted with permission from [13]. © (2018) by the American Physical Society); (C) Self-assembled
nanotube consisting of a double layer (adapted with permission from [21]. © (2012) Springer Nature); (D) Dimeric
exciton on a DNA scaffold (adapted with permission from [22]. © (2018) AIP Publishing.); (E) Two-dimensional
herringbone lattice of oligothiophenes (adapted with permission from [23]. © (2007) AIP Publishing); (F) Cd1012 Se1063
quantum dot (adapted with permission from [24]. © (2013) American Chemical Society).
sue is the Bethe–Salpeter equation, which can be used to calculate

the two-particle electron-hole Green function. However, solving
this equation numerically is nontrivial and often suffers from con-
vergence issue.
(ii) Nonadiabatic effects: There are various nonadiabatic effects ne-
glected in simple exciton models. It is important to clarify the
physical basis for such simplification because some of them may
be responsible for certain exciton processes that have not been
clearly understood yet. These include dark processes that influ-
ence the lifetime of an exciton and spin-forbidden processes. In-
vestigation of these issues requires detailed theoretical consid-
eration at the level of microscopic molecular Hamiltonian and
extensive computational analysis. While this involves somewhat
complicated formal consideration, as will become clear in the next
chapter, it will help develop more general models offering qualita-

tively correct and quantitatively accurate description.
(iii) Coupling to molecular vibrations and environmental degrees of free-
dom: Accurate modeling of these effects is essential for quantita-
tive description of the spectroscopy and the dynamics of excitons.
To what extent this can be accounted for at the level of first prin-
ciples calculation or employing parameterized Hamiltonian is not
always clear. The former approach, while appears to be straight-
forward, requires efficient high precision electronic structure cal-
culation method at the minimum and is limited to only small sys-
tems at present. The latter approach of employing parametrized
model Hamiltonian is applicable to a broad range of systems. This
approach separates the two issues of different nature, one accu-
rate modeling of parameters for the Hamiltonian and the other of
quantum dynamics employing the determined Hamiltonian. This
approach makes the theoretical and computational challenges
more tractable. However, the assumption of certain form of model
Hamiltonians in this approach often does not have solid founda-
tion but is rather based on intuition and/or constraint of actual
quantum dynamics calculation. How to overcome this issue is an
important theoretical challenge.
This book is focused on the dynamics of molecular excitons,
and thus will be mostly devoted to (iii). However, in order to clar-
ify (i) and (ii) at least at a formal level for the case of molecular
excitons, the next chapter will provide a detailed account of how
conventional exciton-bath models can be constructed and how
further extension of such models can be made.
Microscopic derivation of
2
Frenkel exciton-bath
Hamiltonian
Contents
2.1 Aggregates of chromophores 23
2.1.1 Preliminary step: Hamiltonian of each chromophore in the
adiabatic basis 25
2.1.2 Inter-chromophore interaction Hamiltonian terms in the adiabatic
basis of each chromophore 32
2.1.3 Single exciton Hamiltonian in the site excitation basis 35
2.1.3.1 General expression 35
2.1.3.2 Crude adiabatic approximation 41
2.1.3.3 Minimal Frenkel exciton-bath model 44
2.2 Aggregates of chromophores embedded in host media 45
2.2.1 General consideration 45
2.2.2 Linearly coupled harmonic oscillator bath model 48
2.3 Summary and additional remarks 50
From the point of view of modern molecular quantum mechanics,

the assumptions behind the Frenkel exciton theory are extremely
simple [9,8]. This is understandable considering that the Frenkel
exciton theory was developed in early days of quantum mechan-
ics. Nonetheless, the Frenkel-type exciton Hamiltonian has been
very versatile and used in systems for which the original assump-
tions do not necessarily hold. This chapter will provide some in-
sight into why this is the case by clarifying the minimal assump-
tions and approximations necessary for constructing the Frenkel-
type exciton Hamiltonian.
One major assumption used in the original Frenkel exciton the-
ory was that the excitation at each molecule can be accounted for
by a single molecular orbital [9,8]. As has been well recognized by
many practitioners, this assumption is not in fact essential. An-
other key assumption is the crude adiabatic approximation for the
electronic states of individual molecules that form the basis set of
the exciton Hamiltonian. While this approximation can also be re-
moved at formal level [25], its numerical feasibility has not been
fully demonstrated yet.
Dynamics of Molecular Excitons. https://doi.org/10.1016/B978-0-08-102335-8.00010-7 21
22 Chapter 2 Microscopic derivation of Frenkel exciton-bath Hamiltonian
Figure 2.1. The procedure of deriving exciton-bath Hamiltonian starting from the
microscopic molecular Hamiltonian.
Within the crude adiabatic approximation, the effects of the

molecular vibrations and environmental effects can be incor-
porated by introducing phenomenological fluctuations of pa-
rameters of the exciton Hamiltonian or supplementing the exci-
ton Hamiltonians with terms that represent couplings to vibra-
tional/bath modes. While these exciton-bath models can account
for rich physical processes and have been successful, it remains
challenging to determine the parameters of such models from cal-
culations based on first principles.
The objective of this chapter is to examine the theoretical steps
that lead to Frenkel exciton-bath model Hamiltonians from the
standard molecular Hamiltonians. Particular focus of this account
will be clarifying the types of non-adiabatic terms that are often
neglected but can have potential significance for more general sit-
uations. To this end, the formulation will start from the standard
expression for the molecular Hamiltonian, and will go through ex-
plaining all the detailed steps that lead to the exciton Hamiltonian.
While this involves repeating some of well-established textbook
level procedures, it is a worthwhile exercise for clarifying all the as-
sumptions implicit in conventional Frenkel exciton-bath Hamil-
tonian. This will also ultimately help developing a more accurate
way to describe the dynamics of excitons in general. Fig. 2.1 sum-
marizes the overall procedure of derivation. Readers who are not
interested in or are already well aware of these details can skip this
chapter and move to the next chapter.
In order to make the formulation applicable to as broad cases
as possible, the role of molecule in the original Frenkel exciton
theory will be replaced by chromophore in this chapter. The con-
cept of chromophore is well-known in molecular spectroscopy,
Chapter 2 Microscopic derivation of Frenkel exciton-bath Hamiltonian 23
and is defined here as either a molecule or part of a molecule

with well characterized electronic excitation. For molecular crys-
tals, each molecule can be identified as a chromophore. For a
system of pigment molecules embedded in host media, it is syn-
onymous with the pigment molecule. For extended molecules
such as conjugated polymers, the definition of chromophore be-
comes somewhat ambiguous but in general represents a section
of the molecule within which the coherence of excitation remains
mostly intact.
2.1 Aggregates of chromophores

Consider an aggregate of Nc chromophores interacting with
each other. The total molecular Hamiltonian representing the ag-
gregate can be expressed as

Nc
1c
N c N
Ĥc = Ĥj + Ĥj k , (2.1)
2
j =1 j =1 k=j
where Ĥj is the full molecular Hamiltonian of the j th chro-

mophore, and Ĥj k is the interaction Hamiltonian between the j th
and the kth chromophores. For the j th chromophore, the three
dimensional position and momentum of the ith electron are de-
noted as rj,i and pj,i , and those of the lth nucleus as Rj,l and Pj,l .
Given that the j th chromophore has Lj nuclei and Nj electrons,
Ĥj in Eq. (2.1) can be expressed as
Ĥj = T̂j,n + V̂j,nn + T̂j,e + V̂j,en + V̂j,ee

Lj Lj Lj
P̂2j,l 1 Zj,l Zj,l e2
= +
l=1
2Mj,l 2 |R̂j,l − R̂j,l |
l=1 l =l
Nj Lj Nj Nj N j
p̂2j,i Zj,l e2 1 e2
+ − + ,
i=1
2me
l=1 i=1 |R̂j,l − r̂j ,i | 2 i=1 i =i |r̂j,i − r̂j,i |
(2.2)
where, in the first line on the right hand side, T̂ and V̂ represent
kinetic and potential energy operators. The subscripts n and e in
these terms respectively refer to nuclear and electronic degrees of
freedom. For example, T̂j,n represents the kinetic energy opera-
tor of the nuclei of the j th chromophore, and V̂j,nn the nuclear-
nuclear potential energy operator of the j th nuclei. The second
Figure 2.2. Schematic of an aggregate with 4 chromophore units (Nc = 4). Each
chromophore can be a separate molecule embedded in a host media or part of a
supramolecular system with well defined number of electrons and nuclei.
and third lines of the above equation represent standard expres-

sions for all of these terms written in the same order.
The second term in Eq. (2.1) represents interactions between
all chromophores. These are pairwise at the level of explicit de-
scription of all the Coulomb interactions among electrons and
nuclei. Each component Ĥj k consists of four potential terms as
follows:
Ĥj k = V̂j k,nn + V̂j k,ne + V̂j k,en + V̂j k,ee

Lj Lk Lj Nk
Zj,l Zk,l e2 Zj,l e2
= −
l=1 l =1 |R̂j,l − R̂k,l | l=1 i=1 |R̂j,l − r̂k,i |
Nj Nj N k

Lk
Zk,l e2 e2
− + , (2.3)
|R̂k,l − r̂j,i | |r̂j,i − r̂k,i |
l=1 i=1 i=1 i =1
where, each term with subscript n/e on the right hand side of the
first line represents the interaction potential term between nu-
clei/electrons of the j th chromophore and nuclei/electrons of the
kth chromophore. The expressions in the second and third lines
above again show detailed expressions of all these terms in the
same order. Fig. 2.2 shows a schematic of an aggregate with 4 chro-
mophore units, for which there are 6 distinctive Ĥj k ’s.
2.1.1 Preliminary step: Hamiltonian of each

chromophore in the adiabatic basis
Let us consider a quantum state representing all the electrons
and nuclei of chromophore j as |j , and abbreviate the collec-
tion of all 3Lj nuclear coordinates as Rj . The position state for
the collection of all the nuclear coordinates for chromophore j
is given by |Rj ≡ |Rj,1 · · · |Rj,Lj , where direct product sign has
been omitted. Projection of Ĥj |j onto this nuclear position state
results in

Rj |Ĥj |j = Tj,n (∇j ) + Vj,nn (Rj ) + Ĥj,e (Rj ) Rj |j , (2.4)
where
Lj
2
Tj,n (∇j ) = − ∇2 , (2.5)
2Mj,l j,l
l=1
the position representation of the nuclear kinetic energy, and

Vj,nn (Rj ) is the position representation of the nuclear-nuclear po-
tential energy. This is the same as V̂j,nn defined in Eq. (2.2) except
that R̂j,l and R̂j,l are replaced with Rj,l and Rj,l . The operator
Ĥj,e (Rj ) in Eq. (2.4) is the adiabatic electronic operator represent-
ing the rest of Ĥj in the position representation of the nuclei
Ĥj,e (Rj ) = T̂j,e + V̂j,en (Rj ) + V̂j,ee , (2.6)
where T̂j,e and V̂j,ee have been defined by Eq. (2.2), and
Lj Nj
Zj,l e2
V̂j,en (Rj ) = − , (2.7)
|Rj,l − r̂j,i |
l=1 i=1
which is the same as V̂j,en defined in Eq. (2.2) except that R̂j,l has
been replaced with Rj,l . All the terms presented above are stan-
dard quantum mechanical expressions.
Let us denote the αj th eigenstate of Eq. (2.6) with eigenvalue
Eαj (Rj ) as |Eαj (Rj ), which is an adiabatic electronic state of the
j th chromophore defined at Rj . Thus,
Ĥj,e (Rj )|Eαj (Rj ) = Eαj (Rj )|Eαj (Rj ) . (2.8)
The index αj above represents the collection of all the compatible

quantum numbers needed to define the eigenstate.
In general, the projection of |j onto the nuclear position
state |Rj can be represented as a linear combination of |Eαj (Rj )’s
as follows:

Rj |j = Cαj αj (Rj )|Eαj (Rj ) , (2.9)
αj
where αj (Rj ) is a normalized nuclear wave function, and Cαj

is
a complex coefficient satisfying the normalization condition,
αj |C αj |2 = 1. Note that (R ) and C are arbitrary otherwise.
αj j αj
Employing Eq. (2.9) on the right-hand side of Eq. (2.4), one can
obtain the following expression:

Cαj Tj,n (∇j ) + Vj,nn (Rj ) + Ĥj,e (Rj ) αj (Rj )|Eαj (Rj )
αj

= Cαj |Eαj (Rj ) Tj,n (∇j ) + Uαj (Rj ) αj (Rj )
αj
Lj
2
− ∇j,l αj (Rj ) · ∇j,l |Eαj (Rj )
Mj,l
l=1
2
+ 2
α (Rj )∇j,l |Eαj (Rj ) , (2.10)
2Mj,l j
where Uαj (Rj ) is the effective nuclear potential energy for the αj th
adiabatic state of the pigment j defined as
Uαj (Rj ) = Vj,nn (Rj ) + Eαj (Rj ) , (2.11)
which is the sum of the nuclear potential energy and the elec-
tronic energy for the αj th state. The terms in the third line in
Eq. (2.10) represent intrachromophore nonadiabatic couplings.
For closely packed molecular aggregates and natural light harvest-
ing pigment-protein complexes, displacements of nuclear degrees
of freedom from their equilibrium coordinates are small in gen-
eral. Therefore, the contribution of these nonadiabatic terms are
expected to be insignificant. The success of simple exciton models
in the interpretation of recent experimental results, where these
nonadiabatic terms are not taken into consideration, indeed val-
idate this assumption. At least, such nonadiabatic terms do not
appear to be explicitly needed for modeling the spectroscopy or
exciton dynamics. However, for flexible macromolecules in flexi-
ble environments, there can be significant displacements in nu-
clear degrees of freedom following excitation, making regions of
significant nonadiabatic effects as illustrated in Fig. 2.3 more ac-
cessible. Intra-chromophore nonadiabatic effects in such systems
can influence the formation, energetics, and dynamics of excitons
Figure 2.3. Illustration of electronic energies for two different electronic states for
one dimensional nuclear coordinate. R0 is the most likely position for the nuclear
coordinate where the non-adiabatic effect is expected to be insignificant. The
region marked by dot-dashed line is the region where nonadiabatic effects can be
significant.
in a nontrivial manner. For quantitative understanding of these ef-

fects, detailed numerical calculation of all the terms in Eq. (2.10)
is necessary. To this end, further formal consideration of all the
nonadiabatic terms is worthwhile.
The equation governing the quantum states for the nuclear de-
grees of freedom can be obtained by taking an inner product of
Eq. (2.4) with Eαj (Rj )| and also employing Eq. (2.10). This results
in the following equation:

Eαj (Rj )|Rj |Ĥj |j = Cαj Tj,n (∇j ) + Uαj (Rj ) αj (Rj )
Lj
2
− Cαj ∇j,l αj (Rj ) · Eαj (Rj )| ∇j,l |Eαj (Rj )
αj
Mj,l
l=1
1
+ αj (Rj )Eαj (Rj )| ∇j,l
2
|Eαj (Rj ) . (2.12)
2
This is the standard expression for the nuclear wave function

αj (Rj )’s for the chromophore j . The left-hand side represents the
projection of |j onto the nuclear position state |Rj and then
onto the αj th adiabatic electronic state at the fixed position. For
the case where |j is an eigenstate of Ĥj with eigenvalue Ej , the
left hand side of Eq. (2.12) becomes Ej Cαj αj (Rj ). The resulting
equation is a well-known one for the nuclear wavefunctions cou-
pled by nonadiabatic interactions.
For the derivation of a more compact operator expression, it is

useful to recast the nonadiabatic terms in a more symmetric form.
For this, the following identity can be used.
1
αj (Rj )Eαj (Rj )| ∇j,l
2
|Eαj (Rj )
2
1
= ∇j,l · αj (Rj )Eαj (Rj )| ∇j,l |Eαj (Rj )
2
1
− (∇j,l (αj (Rj )) · Eαj (Rj )| ∇j,l |Eαj (Rj )
2
1
− (αj (Rj ))(∇j,l Eαj (Rj )|) · ∇j,l |Eαj (Rj ) . (2.13)
2
Employing the above identity, Eq. (2.12) can be recast into the fol-
lowing form:

Lj
2
− Cαj ∇j,l αj (Rj ) · Eαj (Rj )| ∇j,l |Eαj (Rj )
αj
2Mj,l
l=1

+ ∇j,l · αj (Rj )Eαj (Rj )| ∇j,l |Eαj (Rj )

− αj (Rj ) ∇j,l Eαj (Rj )| · ∇j,l |Eαj (Rj ) . (2.14)
For further simplification, let us introduce the following new

terms for the non-adiabatic couplings:

Gαj αj ,l (Rj ) = Eαj (Rj )| ∇j,l |Eαj (Rj ) , (2.15)
2
Lj

Sαj αj (Rj ) = ∇j,l Eαj (Rj )| · ∇j,l |Eαj (Rj ) . (2.16)
2Mj,l
l=1
The above terms should satisfy symmetry properties due to the

orthogonality of adiabatic states. Taking gradient of Eαj (Rj )|
Eαj (Rj ) = δαj αj , it is straightforward to show that
G∗α αj ,l (Rj ) = −Gαj αj ,l (Rj ) . (2.17)

j
In addition, directly from the definition of Eq. (2.16), it is easy to

confirm the following property:
Sα∗ αj (Rj ) = Sαj αj (Rj ) . (2.18)

j
For more concrete description, it is also worthwhile to consider

representation of these terms in the position space of electrons.
Let us introduce ψαj (r; Rj ) = r|Eαj (Rj ), where r represents all
the collection of electron coordinates. Then, Eqs. (2.15) and (2.16)
are equivalent to the following expressions:

G αj αj ,l (Rj ) = dr ψα∗ (r; Rj )∇j,l ψαj (r; Rj ) , (2.19)
j
Lj

2 ∗

Sαj αj (Rj ) = dr ∇j,l ψα (r; Rj ) · ∇j,l ψαj (r; Rj ) .
2Mj,l j
l=1
(2.20)
In the above expression, note that ∇j,l is the gradient with respect
to Rj , which serves as the parameter of the electronic wavefunc-
tion. For the case where ψαj (r; Rj ) is a real valued function, which
can be assumed to be true for bound states in the absence of mag-
netic field, the combination of Eq. (2.19) and the condition (2.17)
shows that Gαj αj ,l (Rj ) = 0. If not, Gαj αj ,l (Rj ) is not necessarily
zero. On the other hand, Sαj αj (Rj ) is nonzero in general according
to Eq. (2.20). Because the formulation here is for all possible situ-
ations, from now on, I will assume that Gαj αj ,l (Rj ) is also nonzero.
Employing Eqs. (2.15) and (2.16), Eq. (2.14) can be expressed as

Lj
2
+ Cαj − Gαj αj ,l (Rj ) · ∇j,l αj (Rj )
αj
2Mj,l
l=1

+ ∇j,l · Gαj αj ,l (Rj )αj (Rj )
+ Sαj αj (Rj )αj (Rj ) . (2.21)
In the above expression, each nuclear wave function is a position

representation of a nuclear quantum state |αj and can be ex-
pressed as
αj (Rj ) = Rj |αj . (2.22)

Then, Eq. (2.21) can be recast into the following form:

Eαj (Rj )|Rj |Ĥj |j = Cαj Rj | T̂j,n + Uαj (R̂j ) |αj
Lj
i
+ Cαj − Rj | Gαj αj ,l (R̂j ) · P̂j,l
α
2Mj,l
j l=1
+ P̂j,l · Gαj αj ,l (R̂j ) |αj + Rj |Sαj αj (R̂j )|αj . (2.23)
Note that Eαj (Rj )|Rj |Ĥj |j = Rj |Eαj (R̂j )|Ĥj |j , where
Eαj (R̂j )| or |Eαj (R̂j ) represents the adiabatic state in the space
of electronic degrees of freedom except that nuclear coordinate
Rj is replaced with R̂j . Employing this in Eq. (2.23) and using the
fact that the equation remains true for arbitrary value of Rj , it sim-
plifies to

Eαj (R̂j )|Ĥj |j = Cαj T̂j,n + Uαj (R̂j ) |αj
Lj
i
+ Cαj − Gαj αj ,l (R̂j ) · P̂j,l + P̂j,l · Gαj αj ,l (R̂j )
α
2Mj,l
j l=1
+ Sαj αj (R̂j ) |αj . (2.24)
Let us also note that Eq. (2.9) can be expressed as

|j = Cαj |Eαj (R̂j )|αj . (2.25)
αj
The above expression is valid only for the order shown on the right
hand side because |Eαj (R̂j ) function as an operator with respect
to the nuclear state.
Since the set of all the eigenstates |Eαj (R̂j )’s form a complete
basis in the electronic space of the chromophore j , in a simi-
lar manner, we can define the identity operator in the electronic
space of the chromophore j as follows:

1̂j,e = |Eαj (R̂j )Eαj (R̂j )| . (2.26)
αj
It is important to note that the completed sum in the above ex-

pression is independent of the nuclear coordinate operators R̂j ,
whereas each component is not. Using this completeness relation
and Eq. (2.25), Eq. (2.24) can be expressed as

⎛ ⎞

Ĥj ⎝ Cαj |Eαj (R̂j )|αj ⎠
αj

= Cαj |Eαj (R̂j ) T̂j,n + Uαj (R̂j ) |αj
αj

+ Cαj |Eαj (R̂j ) Fαj αj (R̂j , P̂j ) + Sαj αj (R̂j ) |αj ,
αj αj
(2.27)
where
Lj
i
Fαj αj (R̂j , P̂j ) = − Gαj αj ,l (R̂j ) · P̂j,l + P̂j,l · Gαj αj ,l (R̂j ) .
2Mj,l
l=1
(2.28)
Since G†α α ,l (R̂j ) = −Gαj αj ,l (R̂j ), as can be seen from Eq. (2.17), it
j j
is straightforward to show that Fα† α (R̂j , P̂j ) = Fαj αj (R̂j , P̂j ). From
j j
Eq. (2.18), it is also clear that Sα† α (R̂j ) = Sαj αj (R̂j ).
j j
Eq. (2.27) can now be converted to an operator identity em-
ploying the fact that Eαj (R̂j )|Eαj (R̂j ) = δαj αj . Inserting this iden-
tity along with dummy indices in front of |αj ’s on the right hand
side of Eq. (2.27), we find that
⎛ ⎞

Ĥj ⎝ Cαj |Eαj (R̂j )|αj ⎠
αj

= |Eαj (R̂j ) T̂j,n + Uαj (R̂j ) Eαj (R̂j )|
αj

+ |Eαj (R̂j ) Fαj αj (R̂j , P̂j ) + Sαj αj (R̂j ) Eαj (R̂j )|
αj αj
⎛ ⎞

×⎝ Cαj |Eαj (R̂j )|αj ⎠ . (2.29)
αj
The above equation is true for arbitrary Cαj ’s and |αj ’s. This im-
plies that the Hamiltonian operator for the chromophore j can be
expressed as:

Ĥj = |Eαj (R̂j ) T̂j,n + Uαj (R̂j ) Eαj (R̂j )|
αj

+ |Eαj (R̂j ) Fαj αj (R̂j , P̂j ) + Sαj αj (R̂j ) Eαj (R̂j )| .
αj αj
(2.30)
It is easy to show that the above expression is Hermitian as ex-

pected.
Eq. (2.30) is equivalent to what has been derived before in a dif-
ferent manner [25] except for some difference in notations. While
the primary purpose of deriving Eq. (2.30) was to facilitate the
derivation of the exciton Hamiltonian, as will be detailed in the
rest of this chapter, it is in fact a general expression that can be ap-
plied to any molecular systems. Therefore, it may be of utility for
other cases where the nonadiabatic effects become important. In
fact, theoretical and computational study of nonadiabatic effects
remains one of the key issues in excited state quantum chemistry
and quantum dynamics of molecular systems, for which there
have been numerous works during the past decade. Most of these
works have been based on the wave function approach where all
the effects of environmental decoherence cannot be accounted
for in a natural manner. In this sense, the direct expression for
the Hamiltonian Eq. (2.30), which includes nonadiabatic terms as
operators that couple different adiabatic states, can be useful for
more general density operator description. A preliminary formu-
lation of this nature has been presented in a recent work [25].
2.1.2 Inter-chromophore interaction Hamiltonian

terms in the adiabatic basis of each
chromophore
Given that there is no exchange or transfer of electrons be-
tween two chromophores j and k, the direct products of the elec-
tronic states for independent j th and kth chromophore forms the
identity resolution for the electronic degrees of freedom as fol-
lows:

1̂j k,e = |Eαj (R̂j )Eαj (R̂j )| ⊗ |Eαk (R̂k )Eαk (R̂k )|
αj αk

= |Eαj (R̂j )|Eαk (R̂k )Eαj (R̂j )|Eαk (R̂k )| , (2.31)
αj αk
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nor to be blamed. We do not wish to speak disrespectfully of the
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The morning’s sport was not good, and therefore the worthy
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uttering of a single profane oath being, in the eye of our most
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When the baronet had relieved his bursting heart, and vented his
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“Could you believe it, Spoonbill?—You know the pains I have
taken with that wood—I say, could you believe it, after all the
expense I have been at about it—after having six men sitting up
night after night to watch it, that in one afternoon, and that in broad
daylight, it should be almost cleared by those infernal villains?”
Here the baronet became angry again, and no wonder; it was
beyond all endurance. Not only did he as a magistrate feel grieved at
the violation of the laws, but as a gentleman and a man he was
pained at the loss of those birds which he seemed born to shoot.
The birds were gone and the poachers were gone; the first he could
not shoot, and the last he could not commit. And what is the use of
living in the country, if there are no birds to be shot and no poachers
to be sent to gaol?
Pitying the sorrows of the magistrate, Colonel Crop replied, “Too
bad, ’pon my honor.”
But Lord Spoonbill having recently quitted the university, in which
he had been taught to investigate and seek out the connection of
cause and effect, enquired:—
“But how could the rascals do all this without being detected, if you
had men to keep the wood by night and day?”
“I will tell you,” said the baronet, whose violence seemed a little
abated by the kind sympathy of his friends: “it was entirely owing to a
rascally gamekeeper of mine, who, no longer ago than last Sunday
week, instead of attending to his duty, must needs go sneaking to
church. I saw the fellow there myself. He absolutely had the
impudence to come into church when he knew I was there. I
dismissed him however at a short notice. I was determined to have
no church-going gamekeepers.”
“That going to church was abominable,” said the colonel.
“But I thought you had always guns in your plantations, Sir
George?” said Lord Spoonbill.
“So I have,” replied the magistrate; “but unfortunately the guns had
been discharged in the morning on some boys and girls who had
gone to look for nuts; and as one of the boys was nearly killed, the
under keeper took it into his fool’s head that he would not charge the
guns again; so I gave him his discharge.”
“You have been very unfortunate in your servants, Sir George.” So
spake the colonel, who was more than usually eloquent and voluble;
and Sir George was especially delighted with him, for he seemed to
enter so fully into all the magistrate’s feelings upon the subject of
game and poaching.
It is astonishing that, notwithstanding all the pains which the
legislature has taken upon the subject of the game laws, which are
so essential to national prosperity and the Protestant succession, still
there is a possibility that gentlemen may be deprived of their sport by
the intervention of a poacher. The laws are too lenient by half; and till
it is made felony without benefit of clergy to be suspected of
poaching, we shall never be free from this dreadful calamity. Our
legislators have done a great deal, certainly; but they ought to take
up the subject with as much zeal as if the cause were their own.
Now while Colonel Crop was sympathising with Sir George
Aimwell on his great and serious calamity, Lord Spoonbill was
gradually withdrawing himself from his companions, and moving
towards the side of the field which lay nearest to the road, and
looking with great earnestness in the direction of the village of
Neverden. It was not long before his eye caught the object for which
he had been looking. There came clumsily cantering towards him a
quadruped, the appearance of which would have puzzled Buffon,
and on its back there sat a biped as unclassable as the beast on
which he rode. The two were usually called Nick Muggins and his
pony. Lord Spoonbill took great pains to see Nick by accident.
“Have you any letters for the castle, Muggins?” said the heir of
Smatterton.
“Isser,” replied Muggins, and forthwith he produced two letters,
one of which was addressed to the Right Honorable the Earl of
Smatterton, and the other to the Right Honorable Lord Spoonbill.
“I will take charge of them,” said his lordship.
To which proposal Nick Muggins made no objection. His lordship
then, just by way of condescendingly noticing the humble post-boy,
said—
“There now, I have saved you the trouble of riding any farther,
unless you have any letters for the parsonage?”
“Here is one, sir, for the young lady as lives at Parson Grindle’s.”
Muggins looked rather significantly at Lord Spoonbill when he thus
spoke, and his lordship replied—
“You may give that to me, and I will take care of it.”
What arguments were used to induce this breach of trust in the
guardian of the Smatterton post-bag, is not stated, nor known, but
conjectured. Muggins, when he had given the letter to his lordship,
looked rather hesitatingly, and as if he wished to speak; his lordship
interpreted his looks, and said, “Well, what are you waiting for?”
To this interrogation Muggins replied with a cunning simper, “Why,
please, sir, my lord, on case of any questions being axed, perhaps
your lordship, sir, will just-like get a poor boy off, you know, my lord.”
“Bah!” replied his lordship, “leave that to me.” And thereupon those
arguments were used which had been of such great and decided
efficacy in previous cases of the same nature. The undescribable
rider of the undescribable beast then turned about and went
homewards, and the heir of Smatterton soon rejoined his sporting
companions.
Lord Spoonbill was now in possession of two letters more than did
of right belong to him; and though he had taken great pains to
become possessed of at least one of them, and though he was glad
that he could prevent the information which they contained from
reaching the destined point, still he was not altogether comfortable.
Once or twice he determined that the letter designed for the
parsonage of Smatterton should reach its destination, and then he
as often changed his mind again. It may seem strange, and perhaps
be thought not true, that an hereditary legislator should descend to
such meanness as to intercept a letter. It is indeed strange, and but
for its strangeness it would not be here recorded. But Lord Spoonbill
was one of those decided characters that do not let trifles deter them
from pursuing their schemes. He was rather proud of the dexterity
and address with which he pursued any object on which he had fixed
his mind, and he mistook, as many other prigs do, obstinacy for
firmness. He had fully made up his mind to a certain end, and he
was not choice as to the means. Yet he was a man of honor, a man
of the nicest honor, a man of the most sensitive and susceptible
honor. If any one had been capable of calling him mean, if any one
so bold as to have expressed the slightest idea that his lordship was
a contemptible fellow, with what indignation would he have heard
and repelled the suspicion. His notions of honor must have been
very curious and quite unique. We wish it were in our power to
present to our readers an analysis of those views which Lord
Spoonbill took of the principles of honor. We are not equal to a task
so truly philosophical: we can only say that his lordship did descend
to the meanness of intercepting a letter, and did call and think
himself a man of honor. If any of our readers think that this is very
paradoxical and altogether improbable, we congratulate them on
their ignorance.
We cannot help at this part of our narrative shifting the scene for a
little moment, just enough to shew our readers the effect produced in
another quarter by the conduct of the above-named man of honor.
From the sportsmen at Neverden we turn to the rectory of
Smatterton and its inhabitants. Dr Greendale was in his study as
usual, not kept away by any weariness of the preceding evening.
Mrs Greendale felt more acutely the trouble of company departed
than of company coming, and Mrs Greendale was not selfish in her
sorrows, but communicated them to all about her. Penelope
Primrose felt the full weight of her aunt’s troubles; and as the good
lady of the rectory had been rather disappointed the preceding
evening she was not in one of her best humours. Patiently as
possible did Penelope bear with those ill humours, for her mind was
buoyed up with hopes of pleasing intelligence from abroad. The hour
arrived which usually brought the postman, but no postman arrived.
It was possible the clocks at Smatterton were too fast. The hour was
gone by, a full hour was past. It was not probable that the Smatterton
clocks were an hour too fast. There was a little hope that Mr Darnley
might be at Smatterton in the course of the morning; but the morning
passed away and Mr Darnley did not come. But a messenger came
from the rectory of Neverden with enquiries after Dr and Mrs
Greendale. Penelope asked very particularly after the rector of
Neverden and Mrs Darnley, and hoped that they arrived safely
home, and that they had taken no cold, and—and—just as a matter
of curiosity, had they heard from their son lately? The answer was,
that a letter from Mr Robert Darnley had arrived the very hour before
the messenger set out. Penelope turned pale, and then blushed
most intemperately, because she felt how pale she looked; and then
she thought—“Now I know he has forgotten me.” Immediately after
however she thought again, and then it occurred to her that, as
Robert Darnley was remarkable for his great filial affection, it was
possible that he might have had no time to write by that conveyance
more than one letter. But she still could not help thinking that he
might have sent her one small letter: if it had been but short, it might
have been a memorial of his thoughts still dwelling upon her. She felt
hurt, but would not be angry; and hoped, very earnestly hoped, that
she was not cherishing a foolish and fond passion for one who had
relinquished all fondness for her. It was very strange and altogether
unaccountable. It was so very much unlike the usual frankness and
openness of mind for which Robert Darnley was so remarkable.
These were painful thoughts, and the more painful because so very
perplexing. It is somewhat wearying to exert the mind very diligently
and perseveringly, even in solving problems and guessing riddles
which are mere abstractions; but when, in addition to the perplexity,
there is personal and deep interest and moral feeling, then the
agitation and weariness of the mind is at the highest.
Penelope found her accustomed resource in trouble, and her
consolation under life’s perplexities, in the kind and paternal
attention of her uncle. She spent the greatest part of the afternoon of
that day in Dr Greendale’s study, and listened with great pleasure to
the fatherly exhortations of that most excellent man; and, as she was
afterwards heard to observe, she thought that he spoke more like an
angel than a man. She treasured up in her heart the hope that the
morrow would bring tidings from the beloved one.
CHAPTER V.
Sir George Aimwell and his companions found but little sport in the
field, and it was not unpleasant to Colonel Crop to hear that it was
now high time to leave the birds and to adjourn to dinner. This was a
relief also to the baronet himself; for though he was a keen
sportsman he never suffered the amusements of the field to interfere
with the duties of the dinner table. Colonel Crop was aware of this
laudable peculiarity in the manners of Sir George of Neverden, and
therefore enjoyed a day’s sport with him far more than he would
have done with another.
Those of our readers who know the worthy baronet need not be
informed of the superior style of his culinary arrangements. It was
very well for him that his table had this attraction, for it is very certain
it had no other. His own conversation was by no means the most
brilliant. Lady Aimwell might indeed be capable of conversing, but
the guests of Sir George never heard her voice, excepting so far as it
was absolutely necessary that some words must be uttered by the
lady who presides at the head of a table.
Speaking of the intellectual accomplishments of the magistrate of
Neverden, we may not be considered as making a needless
digression if we narrate an anecdote, or rather expression, a critical
expression, of the worthy baronet. Mr Peter Kipperson, the wise and
knowing agriculturist of Smatterton, one day dined at the table of Sir
George of Neverden hall. Now Peter was a very literary man, who
thought there was nothing worth living for but science and literature;
and having somewhere read that it was impossible to take shelter in
a shower of rain with such a man as Burke, without discovering him
to be a man of genius, Peter was desirous of continually showing off,
and was instant in season and out of season. Therefore when sitting
at the table of the worthy baronet, he assailed the magistrate with
various scientific subjects, but all to no purpose; there was no
response from his worthy host. Endeavouring to adapt himself to the
moderate talents and circumscribed reading of the baronet, he next
started the subject of novels and novel reading, taking care to
insinuate that, though Sir George might not read the trash of
circulating libraries, he might be acquainted with some of our best
novels. To this at last the baronet replied—
“Oh, yes; I remember many years ago reading a novel called Tom
Jones, written by a Bow-street officer. I recollect something about it
—it was very low stuff—I forget the particulars, but it was written in
the manner of servants.”
Hereupon Mr Peter Kipperson set it down as an indisputable fact
that baronets and magistrates were the most ignorant creatures on
the face of the earth, and he congratulated himself that neither he
nor Sir Isaac Newton were baronets.
Our readers may therefore very well imagine that if we pass over
in silence the dinner at Neverden hall, where sat Sir George and
Lady Aimwell, and Colonel Crop, and my Lord Spoonbill, we are not
transgressing the truth of history. Soon after the cloth was removed,
Lady Aimwell made herself invisible, and Sir George made himself
what he called comfortable.
“Now, my good friends,” said he, “you know my way. Pray take
care of yourselves. Pass the bottle. There—now—well—you know—I
—sometimes—it is very rude—you—I know you will—excuse”—
Saying, or muttering as above, the guardian of laws and game
sank to sleep in his easy chair, and left Lord Spoonbill and Colonel
Crop to amuse each other. They were however very bad company,
for one had no good in his head, and the other had nothing at all
there.
Lord Spoonbill smiled at the baronet in his easy chair, and Colonel
Crop smiled also. Colonel Crop looked at his lordship most
imploringly, as if to beg that he would say something to which yes or
no might be replied; but the heir of Smatterton was more deeply
engaged in his own thoughts. Colonel Crop filled his glass and
emptied it, and cracked nuts, and picked his teeth, and took snuff,
and yawned, and looked at the pictures, and looked at his own
fingers, and put them into the finger glass, and took them out and
wiped them. Lord Spoonbill filled his glass, and did not empty it, and
did not look at the pictures, and he took out his watch and put it into
his pocket without looking at it. Of many events it is said, that they
are no sooner said than done. But all these movements took up a
much longer time in doing than they have in the reporting. It was a
great relief to the colonel that Lord Spoonbill looked at his watch, for
that enabled the man-of-war to say, “What time is it?”
Lord Spoonbill answered by guess, and the colonel was not very
particular. When about half an hour more had elapsed, the heir of
Smatterton rang to order his horse, and he said to the colonel, “Crop,
I shall leave you to play at backgammon with Sir George. Make my
apologies. I have some matters to attend to at the castle.”
Lord Spoonbill then took his departure from Neverden hall. It was
a fine moonlight night, and the road from Neverden to Smatterton
was peculiarly well calculated for the enjoyment of a moonlight ride.
The domain of Neverden was for the most part on low and level
ground; and the road from the hall towards Smatterton lay partly by
the side of the park, over the low fence of which a person on
horseback might have a most beautiful view of plantation scenery,
and a distant glimpse of lofty and swelling hills, dark with abundant
foliage, but softened by indistinctness and remoteness. The ground
then gradually rose, and on the left hand might be seen at no great
distance a broad and gracefully undulating river, far indeed from the
sea, but bearing on its bosom the sails of commerce and the barks
of pleasure. And there ran rippling by the side of the road a little
prattling infant streamlet, bounding along its bright pebbly channel as
in haste to reach the calmer and more majestic expanse of waters.
On the right hand a dense and dark plantation of firs skirted an
abruptly rising ground, at the end of which the road brought the
traveller by a sudden turn to an immediate and full view of the
massive and whitened towers of Smatterton castle. The castle rose,
as some writers would say, but stood, we think, is the most proper,
majestically towering above all surrounding objects, and enjoying
from its lofty turrets a view of four counties; what these counties
were we will not say,—we dislike personalities.
Now as Lord Spoonbill rode along under the bright light of the
moon, undisturbed by any earthly sound but the tinkling of the
sheep-bell, or the barking of some cottage curs, he did seem to
himself to enjoy the beauty of the scenery and the pleasant balm of
the autumnal air. And as a feeling of scenic beauty penetrated his
soul, there entered also with that a thought of moral beauty, and he
felt that his mind did not harmonize with the repose and beauty
which surrounded him. The feeling was not strong enough to be
called remorse, it was not serious enough to border upon
repentance. He felt conscious that he had acted with meanness, that
he had been guilty of a piece of cruelty. He had used a most
contemptible and debasing artifice to produce alienation between too
worthy and excellent young persons, loving and beloved, confiding
and hoping amidst their doubts and difficulties. These feelings were
unpleasant, and he endeavoured to soothe himself by sophistry.
After all, what injury had he done to Robert Darnley? It would be a
pity that so fine a woman as Penelope Primrose should be sacrificed
to such a dull, plodding, common-place man as the younger Darnley.
Common-place men are not worthy of the notice of men of fashion,
nor deserving of the ordinary privileges of humanity. His lordship had
some recollection of Mr Darnley as being a very poor creature, and
he thought that it was not probable that he should have gained any
great degree of improvement by commercial pursuits and habits of
business; for, as everybody knows, these things tend very much to
degrade and to cramp the mind; while on the other hand those
pursuits in which his lordship had been engaged had quite the
contrary effect. It must be very ennobling to the mind to be engaged
in gambling, horse-racing, lounging, bird-shooting, fox-hunting, and
seduction; and any woman of sense and spirit must infinitely prefer a
protector of this description, to a common-place man who knows
nothing of the world. As to Penelope then, his lordship very naturally
concluded that he was designing her an essential service. Poor,
simple, artless creature, she knew nothing of society, all her days
had been passed in a sequestered village; and as Robert Darnley
was almost the only person she was acquainted with, at all likely to
make her an offer, she fancied that she must of necessity be in love
with him. Lord Spoonbill had not according to his own account been
much of a reader, but he had read the Sorrows of Werter, and he
had read many other compositions of that nature; and he invariably
found that the lovers of the betrothed and the married were men of
genius, fine feeling, elegant manners, and every species of
sentimentality; and he observed that they were induced to the very
laudable practice of seducing the affections of young women from
their husbands or lovers, by a mere principle of compassion. It was a
pity that so much sense and sensibility should be so ill met, and then
how kind and considerate for some high-minded young gentleman,
like my Lord Spoonbill, to save them from the stupidity of a common-
place husband, and consign them to infamy and a broken heart.
Nothing of course can be a greater manifestation and proof of
sensibility and fine feeling, than seducing engaged affections, and, if
Lord Spoonbill had written his own history, we should have heard of
as much sympathy being expressed for him as there has been for
Werter and such like coxcombs; but as we do not suffer his lordship
to speak for himself, our readers must be content to contemplate his
character in all the baldness of truth.
While thoughts as above described were occupying the mind of
his lordship, he drew nearer to the domain of Smatterton, and as the
view of the castle and village opened upon him, he saw more lights
in the cottages than usual at that time in the evening, and he heard
at a little distance sounds of more than ordinary movements. And
presently there came galloping towards him a servant from the
castle. Thinking that it was a messenger sent for himself, he stopped
the man to ask what was the matter. The man drew up his horse just
for a moment, and in hurried accents replied that Dr Greendale had
been taken seriously ill, and that the Earl had given orders to ride
over to M—— to fetch his lordship’s own physician. Waiting for no
further interrogations the messenger rode off as fast as before.
Will it be believed that at this moment one of the first and
promptest thoughts that occurred to Lord Spoonbill was the idea,
that should this illness terminate fatally, the event might facilitate his
designs upon Penelope? Yet so it was. This was his first and
strongest feeling. He had forgotten all the fatherly kindness of that
good man. He was insensible to any impression from the
numberless acts and words of friendship received from the pious and
holy rector. Dr Greendale had been for many years an intimate friend
of the family at the castle. The Earl, though a haughty man and of
very strong aristocratic feelings, had never regarded the worthy
rector with any other feeling than friendship and respect; and the
Countess, though not insensible to the charms and fascinations of
fashionable life, yet delighted in the moral repose and the sober
beauties of the pastor’s character. The Earl and Countess did not
condescend to visit at the rectory, but the doors of the castle were
most cheerfully open for the doctor, and there was sincerity in their
language, when the noble inhabitants of the mansion declared that a
more welcome guest never crossed their threshold. There must have
been something good and pre-eminently good in the character of a
man who could thus as it were command the moral homage of minds
in the highest walks of society. The doctor was not a man of fortune
or of family. His respectability was altogether personal and individual.
This good man had taken very especial notice of the heir of
Smatterton, and had endeavoured, according to the best of his
ability, to impress upon the mind of the young lord those principles
which, in after-life, might become a blessing to him; and when he
could not but observe with all his natural disposition to candor and
charity, that there were bad principles at work within, he
endeavoured to hope for the best, and in his pastoral admonitions to
the youth he did not assume the sternness of the censor, but
adopted the gentle insinuating language of a friend to a friend. He
was grieved, indeed, when he saw that Lord Spoonbill was likely to
become a frivolous character, but he was spared the bitter
mortification of knowing that he was decidedly profligate.
Miserably degraded must have been the mind of Lord Spoonbill
when intelligence of the good man’s illness reached him, that he
could think only, or chiefly, of the vicious benefit likely to accrue from
the fatal termination of that illness. There was indeed another
thought in his lordship’s mind. He could not but notice the hurry in
which the messenger seemed to be, and he was also struck with the
obvious sensation which the illness of the rector had created in the
village. And this thought was more powerfully impressed as he rode
past a few cottages near the park-gate. He there heard the
comments and commendations of the humblest of the humble, and
the poorest of the poor. He heard the aged tremulously uttering their
lamentations; these lamentations were perhaps rather selfish, but
still they were such as did honour to him for whom they were
expressed, if not to those by whom they were used. Then his
lordship thought within himself of the power and efficacy of moral
worth; and he himself began to be almost sorry; but his more
degrading and vicious thoughts had the ascendancy; and he was
fully resolved not to be moved or melted by the sorrows of ignorant
rustics.
He rode up to the castle, and having dismounted he proceeded
immediately to the magnificent saloon, in which the Earl was so fond
of sitting even when alone. As Lord Spoonbill entered the apartment,
the Earl raised his eyes from a book which he was reading, and said,
“You are soon returned, Spoonbill; did you find Sir George’s
company not very inviting? Or, have you left Crop to enjoy the sole
benefit of the worthy baronet’s wit and humour?”
“I left the baronet taking his nap after dinner, and desired Crop to
stay and amuse him with his backgammon when he should wake.
My visits at Neverden, you know, are never long.”
The Earl was about to resume his book, when Lord Spoonbill
added, “But pray, sir, what is this account I hear from one of your
people about Dr Greendale? I hope the old gentleman is not
seriously ill.”
By this interrogation the Earl seemed to be roused to a recollection
of what might otherwise have passed away from his mind. Laying
down his book, he said:
“Oh!—ay—right: I am very sorry to tell you that the poor man is
very ill. That is, so I understand—I sent immediately for my
physician, and I also said that, if it were necessary, I myself would go
down to the rectory and see the good man. He will be a very great
loss to the village. The poor people are very much attached to him,
and I believe he is very conscientiously attentive to his duties. We
must do all we can for him.”
“Certainly, we must. I am sure I should be extremely sorry to lose
him. What is the nature of his complaint? I was at the rectory last
night, and he seemed perfectly well.”
“They tell me,” replied the Earl, “that it is a fit of apoplexy, and that
the poor man is in a state of total insensibility. I would certainly go
down and see him, late as it is, if I thought it would do him any good.
I shall hear what my physician says.”
“If you will give me leave, sir, I will walk down to the rectory, and
bring you word how the doctor is. That will save you the necessity of
going out so late.”
“Very good, very good, do so, I am anxious to hear some more
particular account.”
Lord Spoonbill then departed for the rectory. And, when having
heard what was the nature of the rector’s illness, he had reason to
apprehend that the hand of death was upon him, the young lord was
more deeply moved. He really did make anxious haste to the
parsonage. It is a great pity that he did not pay more attention to
these frequent admonitions which he received as it were from his
better genius, and by which he was reminded that good principles
were not altogether foreign to his nature; but he resisted them—he
felt “a dread of shame among the spirits beneath.”
CHAPTER VI.
When his lordship arrived at the rectory, he found the door
standing open, and the lower apartments of the house deserted.
While he was hesitating whether he should seek his way to the
doctor’s apartment, one of the domestics made her appearance, and
his lordship very earnestly inquired after the afflicted pastor. With
deep and unaffected feeling she replied, that her dear master was
very, very ill, and with increased emotion continued—
“Oh, my lord, if you will see him, perhaps he may know you—he
may try to speak.”
“Certainly I will see him. How long is it since he was taken?”
“Only two hours, my lord. He was quite well this afternoon at five
o’clock, and then he went into his study, where he always goes
about that time, and we heard nothing of him till about two hours
since; his bell rang, and I went, your lordship, to see what my master
wanted, and there I saw him sitting in his great chair quite
speechless.”
The poor woman was overcome with her own emotion, and Lord
Spoonbill hastened to the room into which the patient had been
removed. When he entered the apartment, he saw by the light of one
dim candle, and a recently kindled fire, the figure of Dr Greendale
sitting in an easy chair, in a state of apparent insensibility, and on
one side of him sat Mrs Greendale, grasping his hand with
convulsive eagerness, and looking anxiously on his still and frozen
features: how like and how unlike what he was! On the other side
Penelope was kneeling, holding him also by the hand, and hiding her
face, that its expression of deep feeling might not needlessly distress
her aunt. Gentle sobbings were heard, and the hard breathings of
the death-stricken man. His lordship stood for a few seconds as if
rivetted to the spot where his eye first caught the sight of the
melancholy group. Mrs Greendale first noticed the presence of a
stranger, and recognised his lordship, who then advanced with slow
and gentle step towards the sick man, and silently took the hand of
Mrs Greendale, whose tears then flowed afresh, as with louder
sobbings she exclaimed—
“Oh, my lord, what a sight is here! Those dear eyes have been
fixed as they are now for hours. He was a good man, my lord; such a
heart! such tenderness! Oh, he cannot, he cannot continue long! Oh,
that I should live to see this!”
As Mrs Greendale spoke, Penelope rose from her kneeling
posture, and turning round, then first saw that Lord Spoonbill was in
the room. His lordship intreated Mrs Greendale to compose herself,
and then turning again towards the sick man’s chair, he held out his
hand to Penelope, who resigned to his lordship the hand the dying
man, which she had been holding. Lord Spoonbill took the offered
hand, and kneeling on one knee pressed the hand to his lips, and
looked with searching earnestness to the face of the patient, as if
endeavouring to rouse him into consciousness and recollection. The
eyes were fixed and motionless, and their brightness was passing
away. After a few moments there appeared a convulsive movement
of the lips, and there seemed to be a gleam of consciousness in the
eye, and the hand which Lord Spoonbill had been holding was lifted
up and placed on his lordship’s head, from whence it fell in a
moment, and the breathing, after one long sigh, died away and was
heard no more. At the instant of the change, Mrs Greendale uttered
a piercing shriek, and fell senseless to the floor. Penelope, as if
unconscious of the distress of her aunt and the presence of Lord
Spoonbill, knelt gently down, and lifting up her hands and her eyes,
murmured a prayer, which relieved for a moment her bursting heart;
for tears came copiously to her aid, and her presence of mind was
soon restored, and she assisted the domestics in removing Mrs
Greendale into another apartment.
Lord Spoonbill then took his leave, and as he quitted the house of
mourning he felt as he had never felt before. He had seen life in
many of its varieties, but death had been to his eye and thoughts a
stranger. He had now witnessed such a scene as he never had
before. His mind was deeply and powerfully moved. But yesterday,
and he had seen Dr Greendale in the fullness of strength and the
vigour of health, and life was bright about him, and he was in its
enjoyments and sympathies. One day, one little day, produced an
awful change. The music of the tongue was mute, the benevolence
of the look had fled, the animation of the intellect had vanished, and
the beatings of the kind heart had ceased. Then did the young lord
call to mind many kind expressions which the good man had used
towards him. He thought of the day when he went at the desire of the
Earl his father, rather than by any prompting of his own inclination, to
call at the rectory and take leave of the doctor, previously to setting
out on his journey to Cambridge, when he first entered the
University. He recollected that on that occasion he had been
received in the doctor’s study, and the good man carefully laid aside
his books, and drew his chair round and conversed with him most
cheerfully and most wisely; and he remembered how very tenderly
he hinted at the possibility of juvenile follies, and how like a friend
and companion he endeavoured to guard his mind against the
fascinations of vice. He remembered also the fervent prayer which
the good man uttered at parting, and the words seemed to live again,
and he heard afresh the pious rector pray, “May God bless you, my
dear young friend, and keep you from the evil that is in the world,
and make you an ornament to that station which you are destined to
fill.” Then came to his mind the sad neglect of all the kind precepts
which the holy man had given him, and he felt that as yet the
pastor’s prayer had not been answered by the event. Now, had
these feelings been followed by that sobriety and steadiness of
thought which should be the natural fruit of such emotions, it had
been well for him; but unfortunately he had so much satisfaction in
these emotions, and looked upon them as being virtue, and not
merely the means of virtue, so that they failed to produce any lasting
effect upon his mind, or to cause any change in his conduct. He was
proud of his remorse and pleased with his regrets, and so the virtue
which had its birth in a tear, evaporated when that tear was dry.
Before Lord Spoonbill had left the rectory many minutes, he met
the medical gentleman on his way to the house. He stopped the
physician and told him that all was over.
With due solemnity, and professional solemnity is very solemn
indeed, the medical attendant of the Earl of Smatterton shook his
head and replied—
“Indeed! Aye, I thought I should find it so, from the account which
the messenger gave me. However, my lord, as I am thus far, I may
as well just look in. There is a possibility, perhaps, that even yet the
use of the lancet may not be too late.”
Lord Spoonbill did not oppose the physician’s wish, though he had
no expectation of any benefit to be derived from it. He therefore
returned and waited the report. The man of medicine soon rejoined
his lordship, and pronounced the patient beyond the reach of
professional skill.
“The spirit, my lord, has left the body,” continued he, “according to
the vulgar expression.”
No man could more heartily enjoy the reprobation of vulgar
phraseology than could Lord Spoonbill, generally speaking; but at
this moment he was not disposed to be critical, and he answered the
medical man rather pettishly. He was not for his own part able so
quickly to make the transition from the grave to the gay as persons
more accustomed to such scenes. It is also not very uncommon for
the imperfectly virtuous to be exceedingly morose when under the
impression of serious or religious feelings. The physician was very
much surprised at the manner in which his lordship received the
above-quoted speech; for it is a great absurdity in these enlightened
days to imagine that there is any such thing as a soul. If there had
been any such thing, the medical gentlemen, who have very
minutely dissected the human body, certainly must have found it. But
as they have not seen it, clearly it has no existence, and that which
we take for the soul is only a sort of a kind of a something that is not
a soul, but is only a word of four letters. Many of the Newmarket
students indeed had discovered this fact before the dissectors had
revealed it.
When the medical philosopher observed that Lord Spoonbill did
not express any approbation of the phraseology whereby a doubt of
the existence of a soul was intimated, he did not consider that the
disapprobation might be more from feeling than from opinion, and
therefore he proceeded to the discussion of the subject in a regular
and systematic method. His lordship was, however, not at all
disposed to listen to his arguments, and the two walked side by side
in silence to the castle.
When the Earl saw his medical oracle, he directed his inquiries
first to him—
“Doctor, you will be seated,” having been uttered with its usual
majesty of condescension, the Earl then proceeded to ask—
“And now, doctor, what report do you bring of our worthy rector?”
“Dr Greendale, my lord, is no more. Life was extinct before I could
reach him; and I am of opinion that nothing could have saved him.”
“Indeed! you don’t say so! It is a sad loss. The doctor was a most
excellent man. I had a very high opinion of him. I gave him the living
purely for his moral worth. He had nothing else to recommend him. I
always make it an invariable rule to distribute the church preferment
which is in my power, purely on the ground of merit. I am never
influenced by any political feeling.”
“Your lordship,” replied the physician, who understood his
lordship’s mind as well as his body, and perhaps better; “your
lordship is remarkable for the good judgment which you always
exercise in these matters, and indeed in everything else where the
public good is concerned. It would be well for the country if the
distribution of public and responsible offices were in such good
hands. We should not hear so much the language of dissatisfaction.”
“Doctor, you are disposed to compliment. But it is not very easy to
prevent the language of dissatisfaction. It is too common and too
indiscriminate. It is not proper that the common people should
acquire a habit of carping at all the acts of the government. The
multitude cannot understand these things. Now I have studied the
science of government with great and close attention, and I think I do
know something which even the ministers themselves do not rightly
understand. They are engaged in the dry details of office, and they
have been brought up in the trammels of prejudice. For my part I

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Dynamics of Molecular Excitons:

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5.4 Harmonic oscillator bath with linear coupling. . . . . . . . . . . . . . . . . . 132

Chapter 6 Excitons and quantum light. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 149

Chapter 7 Time-resolved nonlinear spectroscopy of excitons. . . . . . . . . 161

Chapter 8 Examples and applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 181

Chapter 9 Summary and outlook. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 195

B.4 Interaction with a plane wave radiation and dipole

About the author

Writing a book on exciton is an act of significant courage given

ods and understanding their capability as a tool for probing the

1.1 Motivation and objective

Dynamics of Molecular Excitons. https://doi.org/10.1016/B978-0-08-102335-8.00009-0 1

1.2 Frenkel and Wannier excitons

The basis set of quantum mechanical states used for Frenkel

|g = |g1 ⊗ |g2 · · · ⊗ |gN , (1.1)

where ⊗ represents direct product. One can then introduce N or-

|sj = |g1 ⊗ · · · |gj −1 ⊗ |ej ⊗ |gj +1 · · · ⊗ |gN . (1.2)

sj |sk = 0, for j = k . (1.3)

Despite the assumption of weak interactions implicit in

Jj k = sj |Ĥe |sk , for j = k . (1.4)

These resonance interactions, Jj k ’s, cause eigenstates of Ĥe to be

where Ec (k) and Ev (k) are energies of conduction and valance

Figure 1.2. Illustration of the formation of Wannier exciton. Localized

of originally localized excitation states, namely, formation of

1.2.2 Model Hamiltonians for Frenkel excitons

nearest neighbor interactions satisfying cyclic symmetry. In the

1.2.2.1 Linear chain

The eigenstates and eigenvalues of this Hamiltonian are as fol-

where p = 1, · · · , N . Detailed mathematical steps leading to these

which are distributed symmetrically2 around E. Thus, the exciton

where it is assumed that the linear chain is along the z-direction.

where  is an effective optical dielectric constant and d is the dis-

Figure 1.3. Depiction of four examples of linear aggregates.

following component along the z-direction:

By introducing p = N + 1 − p, it is easy to find that this case

(iv) In this case corresponding to antiparallel arrangement of

1.2.2.2 Circular chain

where J (j − k) satisfies the cyclic boundary condition with period

where p = 0, · · · , N − 1. This can be demonstrated easily by the

Equivalently, p can be rearranged to be centered around zero,

rj = R (cos(2πj/N), sin(2πj/N), 0) , (1.25)

where θμ and φμ are fixed reference angles of the transition

J (j − k) = J0 δ[(j −k)/N ],±1

where [(j − k)/N] in the subscript of the delta function denotes

Note that the energy levels of ±|p|’s are degenerate.

Let us consider three simple cases as follows: (i) θμ = 0;

The transition dipole has nonzero component only for the

The transition dipoles are confined in the x − y plane and

The transition dipoles are confined in the x − y plane and

Figure 1.4. Circular arrangement of molecules for N = 8.

sj |sk = 0, for j = k . (1.3)

Jj k = sj |Ĥe |sk , for j = k . (1.4)

where is an effective optical dielectric constant and d is the dis-

By introducing p = N + 1 − p, it is easy to find that this case

where Eg is the electron-hole band gap, Ee = μ∗ e4 /(8 2 h3 c), and

αj (Rj ) = Rj |αj . (2.22)

+ P̂j,l · Gαj αj ,l (R̂j ) |αj + Rj |Sαj αj (R̂j )|αj . (2.23)