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Lecture Notes in Chemistry 104

Kazuya Saito

Chemical Physics
of Molecular
Condensed
Matter
Lecture Notes in Chemistry

Volume 104

Series Editors
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Eva Perlt, Bonn, Germany
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Reiner Salzer, Dresden, Germany
The series Lecture Notes in Chemistry (LNC), reports new developments in
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Kazuya Saito

Chemical Physics
of Molecular Condensed
Matter

123
Kazuya Saito
Department of Chemistry
Faculty of Pure and Applied Sciences
University of Tsukuba
Tsukuba, Japan

ISSN 0342-4901 ISSN 2192-6603 (electronic)

Lecture Notes in Chemistry
ISBN 978-981-15-9022-1 ISBN 978-981-15-9023-8 (eBook)
https://doi.org/10.1007/978-981-15-9023-8

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Preface

I started my research activity as an undergraduate student in a chemical school

under the supervision of Profs. Hideaki Chihara and Tooru Atake. My research
object was a phase transition exhibited by the crystal of an organic compound,
and our experimental setup was a laboratory-made calorimeter constructed by
Tooru. The measurement itself of the heat capacity was not difficult (but very
time-consuming) because of the state-of-the-art calorimeter. On the other hand, my
knowledge was deficient in analyzing the results and even catching their meaning.
The situation forced me to read textbooks of statistical and solid-state physics.
I found the necessity to generalize the content if we intended to utilize them for
molecular crystals. Indeed, the inclusion of rotational and even deformational
degrees of freedom into the lattice-dynamical treatment was necessary.
After graduation with my doctoral degree, I joined the group headed by
Prof. Isao Ikemoto. The group was active in synthesizing and characterizing organic
conductors, including some superconductors. My knowledge in solid-state physics
was undoubtedly useful in this period of ca. 10 years. The important lesson I
learned was that most of the interesting properties were well (although only par-
tially) described without molecular languages. Although crystal structures were
essential, the properties were analyzed using an effective Hamiltonian, which did
not retain “molecular” properties. On the other hand, the complete oblivion of the
molecular nature sometimes irritated the research community.
After returning to the university of my graduation as a member of Prof. Michio
Sorai’s group, I started studying liquid crystals and have continued it besides other
issues at the other place till now. Through the whole period of my research, I have
been more convinced that the essential feature of molecular systems is the
molecular shape. The other belief I have acquired is that many attractive and
challenging puzzles are in molecular systems as critical issues of condensed matter
physics.
The three preceding paragraphs give the background of my idea of writing this
book. I intended to fill a gap in the knowledge about the properties of macroscopic
(bulk) material between chemistry- and physics-trained persons and to illustrate the
appeal of molecular systems without stepping into every detail. Although many

v
vi Preface

good textbooks are available on solid-state (or condensed matter) physics, they
generally treat simple systems such as metals and crystals consisting of atoms. On
the other hand, in solid-state chemistry, textbooks give a diverse variety of fasci-
nating examples but often avoid descriptions of theoretical background even at the
simplest level. This book gives a coherent description starting from intermolecular
interaction up to properties of condensed matter ranging from the isotropic liquid to
molecular crystals in terms of molecular language. The contents should serve as a
starting point based on the current status for further study.
It may be useful to give some comments about the adoption of subjects. The
book highlights the effects of molecular properties, i.e., the presence of the shape
and its deformation, on structure and properties. However, I omitted details for
specific subjects for which a comprehensive monograph is available. Linear and
branched polymers correspond to the case though they well fit the category. Many
specialized textbooks are available. Besides, they need specific treatment as a string
or ribbon. This coarse-grained treatment mostly throws the identity of molecules
away. It is a kind of idealization of a higher order. On the other hand, even if the
subject remains, the topic non-relevant to molecular nature is excluded. The con-
tinuum theory of liquid crystals is an example.
Other subjects omitted from the content are systems, for which effective theories
usually do not incorporate molecular natures. These include optical properties,
molecular conductor and magnets, and properties of liquid solutions. Although the
optical properties are directly related to spectroscopies of molecular systems, their
effective theories, i.e., quantum-mechanical models, treat molecules only indirectly.
Molecular conductors and magnets are spreading research fields, but their argu-
ments rely on anisotropic and exotic crystal structures and the resulting effective
Hamiltonians. For solutions, it seems difficult to give a coherent molecular
description at present. When the researches in these fields begin to involve
molecular natures of systems, a new version should be necessary.
I assumed the pieces of knowledge of classical and quantum mechanics, ther-
modynamics, and statistical mechanics at the elementary level, for which under-
graduate classes are available in chemical school. Mathematics behind them is
implicitly assumed. It contains analysis including partial derivatives of multivari-
able functions, linear algebra, and group theory. However, the manipulation in the
text does not go far beyond the very elementary level. I explicitly included
step-by-step derivations for many issues because such examples seem valuable for
practical applications to specific problems by readers. This necessity for particular
treatments to case by case reflects the diverse nature of molecular systems.
Concerning chemistry, on the other hand, I only assumed the meaning of chemical
formulas and the fact that the bulk substance consists of a vast number of mole-
cules! In total, this book should be readable for graduate students majoring in either
chemistry or physics. However, I am grateful if the book is enjoyable to established
researchers in physical chemistry and condensed matter physics.
This book stands on my research/teaching activity with many colleagues.
Drs. H. Chihara, T. Atake, Ichiro Hatta, and M. Sorai were my professors, and they
guided directly or indirectly with their profound insights and broad perspective on
Preface vii

condensed matter science. Dr. Yasuhisa Yamamura was a student at first and has
been the most effective collaborator. Encouragement by Prof. Mary Anne White, a
respected friend who has worked in a similar field, in an early stage of writing
convinced me of some merit of books of this kind. My friends, Prof. Tadeus
Wasiutyński, Maria Massalska-Arodź, Robert Pełka, and Kiku Ishii, read some
parts of the draft and gave me valuable comments and suggestions for correcting
faults and improving writing. Especially, Robert checked most of the math.
Prof. Takehiko Mori provided information on polymorphism of organic conductors.
Still, I declare to be solely responsible for all of the mistakes and faults in this book.
Without people irrespective of the mentioned above or not, I could not prepare this
book. It is my great pleasure to express my sincere thanks to all of them.

Tsukuba, Japan Kazuya Saito

June 2020
Contents

1 Molecules and Intermolecular Interactions . . . . . . . . . . . . . . . . . . . 1

1.1 Hierarchy of Materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
1.1.1 Energetic Overview of Nature . . . . . . . . . . . . . . . . . . . 1
1.1.2 Molecular World . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
1.2 Intermolecular Interaction . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
1.2.1 Charge Distribution in a Molecule . . . . . . . . . . . . . . . . 5
1.2.2 Electrostatic Interaction . . . . . . . . . . . . . . . . . . . . . . . . 9
1.2.3 Polarizability and Dispersion Interaction . . . . . . . . . . . 10
1.2.4 Repulsion: Pauli’s Exclusion Principle . . . . . . . . . . . . . 16
1.2.5 Practical Representation . . . . . . . . . . . . . . . . . . . . . . . 18
1.2.6 Other Interactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21
1.3 What the Interaction Brings . . . . . . . . . . . . . . . . . . . . . . . . . . . 23
1.3.1 Equation of State of Gas . . . . . . . . . . . . . . . . . . . . . . . 23
1.3.2 Liquefaction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 25
1.3.3 Crystallization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 27
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 28
2 Phase Transitions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 31
2.1 Background . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 31
2.1.1 Thermodynamic Aspects . . . . . . . . . . . . . . . . . . . . . . . 31
2.1.2 Entropy and Boltzmann’s Principle . . . . . . . . . . . . . . . 34
2.1.3 Interface and Phase Growth . . . . . . . . . . . . . . . . . . . . 36
2.2 Landau’s Phenomenology . . . . . . . . . . . . . . . . . . . . . . . . . . . . 39
2.2.1 Power Expansion of Thermodynamic Potential . . . . . . . 39
2.2.2 Order Parameter . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 40
2.2.3 Simplest Case: Continuous Transition . . . . . . . . . . . . . 40
2.2.4 Discontinuous Transition . . . . . . . . . . . . . . . . . . . . . . 43
2.2.5 Plural Equivalent Order Parameters . . . . . . . . . . . . . . . 45
2.2.6 Implication and Outcome . . . . . . . . . . . . . . . . . . . . . . 47

ix
x Contents

2.3 Critical Phenomena and Universality . . . . . . . . . . . . . . . . . . . . 48

2.4 Formation Versus Collapse of Order . . . . . . . . . . . . . . . . . . . . 50
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 51
3 Molecular Liquids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 53
3.1 Liquid Structure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 53
3.1.1 Scattering from Molecular Liquid . . . . . . . . . . . . . . . . 53
3.1.2 Case Study . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 57
3.2 Molecular Association . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 60
3.3 Ionic Liquids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 62
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 64
4 Molecular Crystals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 65
4.1 Crystallization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 65
4.1.1 Alder Transition . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 65
4.1.2 Landau Theory of Weak Crystallization . . . . . . . . . . . . 66
4.2 Diffraction and Modern Definition of Crystals . . . . . . . . . . . . . 68
4.3 Molecular Shape and Crystal Structure . . . . . . . . . . . . . . . . . . . 71
4.3.1 Within Landau Theory . . . . . . . . . . . . . . . . . . . . . . . . 71
4.3.2 Close Packing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 73
4.3.3 Polymorphism . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 74
4.4 Cohesive Energy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 76
4.4.1 Experimental Information . . . . . . . . . . . . . . . . . . . . . . 76
4.4.2 Lattice Sum . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 78
4.4.3 Crystal Engineering . . . . . . . . . . . . . . . . . . . . . . . . . . 81
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 82
5 Lattice Dynamics of Molecular Crystals . . . . . . . . . . . . . . . . . . . . . 85
5.1 Scope of This Chapter . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 85
5.2 Atomic Case . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 85
5.2.1 Atomic Array . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 86
5.2.2 Atomic Crystals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 91
5.3 Crystals of Rigid Molecules . . . . . . . . . . . . . . . . . . . . . . . . . . 94
5.3.1 Formulation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 94
5.3.2 Properties of Problems . . . . . . . . . . . . . . . . . . . . . . . . 97
5.4 Crystals of Deformable Molecules . . . . . . . . . . . . . . . . . . . . . . 100
5.5 Related Issues and Examples . . . . . . . . . . . . . . . . . . . . . . . . . . 102
5.5.1 Heat Capacity and Debye Temperature . . . . . . . . . . . . 102
5.5.2 Debye–Waller Factor . . . . . . . . . . . . . . . . . . . . . . . . . 105
5.5.3 Lattice Instability and Structural Phase Transition . . . . 106
5.5.4 Anharmonicity and Thermal Expansion . . . . . . . . . . . . 109
5.5.5 Large Amplitude Motion . . . . . . . . . . . . . . . . . . . . . . 113
5.5.6 Degrees of Freedom for Membrane Dynamics . . . . . . . 115
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 116
Contents xi

6 Melting of Molecular Crystals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 119

6.1 Melting in Reality . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 119
6.2 Plastic Crystals and Liquid Crystals . . . . . . . . . . . . . . . . . . . . . 124
6.2.1 Mean-Field Theory of Ising Model . . . . . . . . . . . . . . . 124
6.2.2 Simple Theory of Melting of Atomic Crystal . . . . . . . . 129
6.2.3 Translational and Orientational Melting . . . . . . . . . . . . 133
6.3 Molecular Deformation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 136
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 139
7 Liquid Crystals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 143
7.1 Classification . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 143
7.1.1 Thermotropic Versus Lyotropic . . . . . . . . . . . . . . . . . . 143
7.1.2 Various Thermotropics . . . . . . . . . . . . . . . . . . . . . . . . 144
7.2 Effects of Molecular Anisotropy . . . . . . . . . . . . . . . . . . . . . . . 149
7.2.1 Liquid Crystal of Hard Particles: Onsager Theory . . . . 149
7.2.2 Maier–Saupe Theory . . . . . . . . . . . . . . . . . . . . . . . . . 152
7.3 Effects of Molecular Shape . . . . . . . . . . . . . . . . . . . . . . . . . . . 155
7.4 Molecular Shape and Aggregation in Lyotropics . . . . . . . . . . . . 157
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 160
8 Molecular Glasses . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 161
8.1 Glass as Frozen-in State . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 161
8.1.1 Simple View on Glass Transitions . . . . . . . . . . . . . . . . 161
8.1.2 Structural Chemistry of Glass Transitions . . . . . . . . . . 168
8.2 Properties of Glasses . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 169
8.2.1 Fragility . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 169
8.2.2 Step in Heat Capacity at Tg . . . . . . . . . . . . . . . . . . . . 170
8.2.3 Residual Entropy . . . . . . . . . . . . . . . . . . . . . . . . . . . . 171
8.2.4 Effects of Structural Inhomogeneity . . . . . . . . . . . . . . . 173
8.3 Possibility of Ideal Glass Transitions . . . . . . . . . . . . . . . . . . . . 174
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 175
9 Molecular Flexibility and Material Properties . . . . . . . . . . . . . . . . . 177
9.1 Single-Particle or Extended Scheme . . . . . . . . . . . . . . . . . . . . . 177
9.2 Glass Transitions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 177
9.3 Phase Transitions Related to Molecular Deformation . . . . . . . . 178
9.4 Conformational Disordering of Alkyl Groups . . . . . . . . . . . . . . 180
9.4.1 Odd-Even Effect . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 180
9.4.2 Systematics as Indispensable Tool . . . . . . . . . . . . . . . . 182
9.4.3 Entropy Reserver . . . . . . . . . . . . . . . . . . . . . . . . . . . . 184
9.4.4 Chains in Liquid Crystals . . . . . . . . . . . . . . . . . . . . . . 186
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 196
xii Contents

10 Importance of Molecular Crystals . . . . . . . . . . . . . . . . . . . . . . . . . . 199

10.1 Motional Correlation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 199
10.1.1 Significance and Difficulty . . . . . . . . . . . . . . . . . . . . . 199
10.1.2 Entropic Detection . . . . . . . . . . . . . . . . . . . . . . . . . . . 200
10.1.3 Dynamics in Quasi-one-dimensional Systems . . . . . . . . 202
10.2 Molecular Crystals as Tunable Model System . . . . . . . . . . . . . . 204
10.2.1 Basis of Tunability . . . . . . . . . . . . . . . . . . . . . . . . . . . 204
10.2.2 Unified Description of Structural Phase
Transitions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 205
10.2.3 Impurity Effects on Structural Phase Transitions . . . . . . 208
10.3 Molecular Crystals as Stage for Novelties . . . . . . . . . . . . . . . . 210
10.3.1 Coupling Between Molecular Dynamics
and Electronic System . . . . . . . . . . . . . . . . . . . . . . . . 210
10.3.2 Phenomena Involving Molecular Flexibility . . . . . . . . . 211
10.3.3 Dipolar Ising System . . . . . . . . . . . . . . . . . . . . . . . . . 211
10.3.4 Exotic Superstructure . . . . . . . . . . . . . . . . . . . . . . . . . 212
10.3.5 Molecular Aggregation in a Gyroid Phase . . . . . . . . . . 214
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 218
Chapter 1
Molecules and Intermolecular
Interactions

1.1 Hierarchy of Materials

1.1.1 Energetic Overview of Nature

This book deals with the structure and properties of an ensemble of molecules.
Before proceeding into details, let us see the typical magnitude of energies involved
in various phenomena. It will be clear why such a description based on the identity
of molecules is appropriate and what extent it is to.
It is reasonable to start with nuclei of atoms. They are formed by nucleons (protons
and neutrons) through the strong interaction. Although hadrons, including nucleons,
are composed of quarks, the decomposition to quarks is impossible (known as the
quark confinement). The minimal nuclear reaction is the formation of a deuteron
from a proton and a neutron. This reaction accompanies the emission of a photon
(γ-ray) with the energy of ca. 2.2 MeV (1 eV is ca. 96.5 kJ mol−1 ). According to
the equivalence of mass and energy revealed by Einstein, E = mc2 (c is the speed
of light in vacuum), the binding energy ΔE for an arbitrary nucleus with Z protons
and N neutrons can be calculated from its mass defect ΔM as

ΔE = ΔMc2
 
= Z Mp + N Mn − M c 2 , (1.1)

where Mp , Mn , and M are masses of proton, neutron, and the nucleus, respectively.
Figure 1.1 shows the binding energy per nucleon (ΔE/(Z + N )). As seen in Fig. 1.1,
the binding energy is typically several MeV and shows the maximum (≈ 8.7 MeV)
for the nucleus of 56 Fe.
Each neutral atom consists of a nucleus and electrons, the number of latter which
accords to the charge compensation. The energy necessary to remove an electron from
an atom in the ground state is the (first) ionization energy. The ionization energy is,
within an excellent approximation, dependent not on the atom’s mass number but
© The Editor(s) (if applicable) and The Author(s), under exclusive license 1
to Springer Nature Singapore Pte Ltd. 2020
K. Saito, Chemical Physics of Molecular Condensed Matter,
Lecture Notes in Chemistry 104,
https://doi.org/10.1007/978-981-15-9023-8_1
2 1 Molecules and Intermolecular Interactions

[ΔE / (Z+N)] / MeV

8

6
0 20 40 60 80
Z

Fig. 1.1 Binding energy per nucleon of most stable nuclei (having the longest half life) of elements
as a function of atomic number

30
He
Ne
20
Ar
ΔE1 /eV

Kr

Zn
10

0
10 20 30
Z

Fig. 1.2 First ionization energy of neutral atom as a function of atomic number

solely on the atomic number Z . The ionization energy is shown in Fig. 1.2. The figure
indicates the energy scale of several eV, which is much (ca. 10−5 ) smaller than that
of nuclear reactions.
Atoms may bind through a chemical bond, resulting in the formation of a molecule.
It has often been assumed that the energy gain upon the molecular formation is well
approximated by a sum of those of formed chemical bonds, though some fundamental
1.1 Hierarchy of Materials 3

Table 1.1 Energy scales in nature

Phenomenon Energy scale Environmental energy
Nuclear reaction (binding energy of 10 MeV
atomic nucleus per nucleon)
Ionization energy of atom 10 eV
Energy of chemical bond > 3 eV
≤ 3 eV Photon of visible light
Hydrogen bond 10−1 eV
26 meV Thermal energy (kB T ) at
300 K
Intermolecular interaction 10−2 eV

difficulties have been recognized.1 The binding energy assigned to a bond is called
the bond energy. Generally, bond energies are parallel to the order of chemical bonds.
Indeed, the triple bond in a nitrogen molecule accompanies large bond energy of ca.
10 eV. Single bonds have about half of this. Thus, the energy scale of chemical
bonding is smaller than the atomic ionization by about one order of magnitude.
Ubiquitous interaction between molecules is of the dispersion character workable
even between neutral molecules, as discussed in the next section. This interaction is
approximately additive for interatomic contributions. The interaction energy itself
may become significant when molecules are large (with a large number of atoms),
accordingly. However, it seems adequate to see the interaction between two atoms
as an element of this interaction. The order of magnitude is estimated as ca. 10−2
eV based on the lattice energies of solids of rare gas elements. On the other hand, a
relatively strong interaction is known, such as the hydrogen bond. Its energy is ca.
10−1 eV. Thus, even considering this strong interaction, the energy of the intermolec-
ular interaction is smaller than that of chemical bonds by one order of magnitude.
However, note that, under the additivity of interactions, the molecular aggregation
might compete with the chemical stability of substances if molecules are sufficiently
large.
Finally, environmental energy is to be considered. Although the light originally
emitted at the surface of the sun (at ca. 6,000 K) contains notably components of
ultraviolet light, a large portion of the component is absorbed by some components
in the air (mainly by ozone). On the earth, thus, the visible light is dominant. Its
energy lies between ca. 3 eV (violet) and 2 eV (red). The thermal energy is given by
kB T . At 300 K, it is ca. 26 meV. Table 1.1 summarizes the energy scales mentioned.

1 Forexample, the localized nature of chemical bonds is violated for delocalized π electrons in
aromatic molecules. Even if the localization seems acceptable, the energy necessary to break a C–H
bond of methane (CH4 ) is not a quarter of that to break all of its four bonds.
4 1 Molecules and Intermolecular Interactions

1.1.2 Molecular World

It is evident from Table 1.1 that the energy involved in a nuclear reaction is much
larger than those of other phenomena. The separation of the process from other
processes is almost complete, accordingly. Nuclear synthesis (syntheses of elements
below nickel) proceeds in stars. Indeed, the pressure and temperature at the solar
core are, respectively, 2.5 · 1011 atm and 1.5 · 107 K, the thermal energy of the latter
amounts to ca. 1.3 keV. Although this energy is still smaller than the binding energies
of atomic nuclei, the extreme density caused by the high pressure facilitates the
synthesis of helium nuclei from protons. Under the complete separation in the energy
scale, any low-energy process is almost impossible to affect the nuclear process. This
separation is the basis of the possibility of chemistry, a science of the diversity and
“inhomogeneity” of the materials world.
Note that the relevant energy to be compared with average translational energy,
i.e., thermal energy, is not biding energies but the energy barrier to be overcome
necessary for nuclear reactions. A similar situation is also encountered in molecular
syntheses.
The ignorance of nuclear reaction automatically offers a way of understanding
materials based on atoms. This is the way traditionally developed in condensed
matter physics, and certainly possible. However, for example, in the interpretation of
temperature dependence of heat capacity of crystals, the analysis in this way assuming
the number of atoms in a unit cell yields a high characteristic temperature (Debye
temperature described in Sect. 5.5.1), which is practically useless because of too
high value in comparison with melting temperatures. Although the separation in the
energy scale is not complete in contrast with the above case, the energies of electronic
processes such as ionization and formation of chemical bonds involve larger energy
by, at least, about one order of magnitude than intermolecular interactions. Thus, it
is reasonable and even better to consider this separation for understanding molecular
materials. Indeed, returning to the example of heat capacity, we can readily explain
even an apparent saturation of heat capacity to 6R if the number of degrees of freedom
is adequately assumed (such as 6 for a rigid molecule).
The last case exemplifies the benefit of the understanding of materials based on
the molecular description. In some cases, this is done by replacing “atoms” with
“molecules.” For example, in discussing electronic or magnetic properties of molec-
ular systems (molecular conductor and magnet), their properties are interpreted based
on a complicated (and often anisotropic) arrangement of sites. On the other hand,
such a replacement cannot work for, for example, the issue of melting. The intrinsic
difference between atoms and molecules lies in the necessity to take their anisotropy
into account (except for cases of monatomic molecules, i.e., rare gasses). A partial
melting, e.g., the melting of solely the positional degrees of freedom but the orien-
tational ones, is only possible in cases of crystals consisting of molecules because
atoms have no rotational degrees of freedom detectable from the outside. The possi-
bility of molecular deformation is also an intrinsic difference. The main body of this
1.1 Hierarchy of Materials 5

monograph is devoted to showing how analysis and understanding of materials are

possible based on molecules.
Before concluding this introductory section, it is reminded that the separation
in the energy scale is not perfect between intermolecular interaction and chemical
phenomena. There exist some examples that reflect this incompleteness. There exist
rare instances of phase transitions, in which molecular structures change with rear-
rangement of chemical bonds, include the melting of PCl4 ·PCl6 [1, 2] to molecular
liquid and that in liquid sulfur (changing from S8 to linear polymer) [3].

1.2 Intermolecular Interaction

1.2.1 Charge Distribution in a Molecule

Among the four fundamental interactions between particles in nature, i.e., strong
and weak interactions, electrostatic interaction, and gravity, those workable between
atoms and molecules are the two latter of them, which have no characteristic length
scale. The interaction energy of both is inversely proportional to the distance between
two interacting subjects. The gravity is always attractive, whereas the electricity can
have not only attractive but also repulsive character depending on the signs of the elec-
tric charge. Because of the large difference in their magnitudes, however, the consid-
eration only on the electric term is sufficient in molecular physics. Indeed, the gravi-
tational and electrostatic interactions between two electrons (with the mass m ≈ 9.1 ·
10−31 kg and the charge q ≈ −1.6 · 10−19 C) 1 Å apart are −5.5 · 10−61 J and 2.3 ·
10−18 J, respectively. The electrostatic interaction between charges of molecules is
dominant if they carry net charges, i.e., if they are ions.
Even if molecules are neutral, electrostatic interaction governs the interaction
between them. We can easily imagine that the antiparallel arrangement is more stable
than the parallel arrangement for a pair of dipolar but neutral molecules because the
head with the positive partial charge of each molecule is closer to the negatively
charged tail of the other molecule. Thus, the consideration of charge distribution in
a molecule, ρ(r), is necessary. Even for ions, a similar consideration is necessary
to validate the naïve expectation that the interaction between them resembles that
between point charges when the molecular size is non-negligible compared to their
separation.
The following identity is known as the multipole expansion for |R| > |r| in the
three-dimensional space:
∞
 |r|n
1
= Pn (cos θ Rr ), (1.2)
|R − r| n=0
|R|n+1

where Pn (·) is n-th order Legendre polynomial, and θ Rr the angle between vectors R
and r (cos θ Rr = R · r/|R||r|). Suppose that the center of gravity of a molecule with
6 1 Molecules and Intermolecular Interactions

the charge distribution ρ(r) be at the origin and that ρ(r) is negligible for |r| > rmol .
Since the electrostatic potential is additive, that at R (outside the molecule) produced
by the charge distribution ρ(r) in the molecule is a superposition of those formed by
component charge elements. Thus, for |R| > rmol ,
∞ 
1  1
V (R) = |r|n Pn (cos θ Rr )ρ(r)dv, (1.3)
4πε0 n=0 |R|n+1

where the integration is over the volume of the molecule. It is essential to notice that
a successive term becomes smaller in the power of |R|. Thus, the first non-vanishing
term is of primary importance. Let’s see some leading terms. Suppose first the term
with n = 0 is non-vanishing with the total charge of q. Since P0 (·) = 1,

1 1
V (R) ≈ ρ(r)dv
4πε0 |R|
1 q
= . (1.4)
4πε0 |R|

This is precisely the same as the electrostatic potential produced by a point charge
q. In other words, any charge distribution looks like a point charge if viewed from
a point far away from the molecule. This guarantees the validity of the intuitive
expectation mentioned before.
When the net charge is null (q = 0), the leading term would be of n = 1. Since
P1 (x) = x, the term is given by

1 1
V1 (R) = |r| cos θ Rr ρ(r)dv,
4πε0 |R|2

1 R
= · rρ(r)dv. (1.5)
4πε0 |R|3

In the second identity, the relation cos θ Rr = R · r/|R||r| is used. By defining2 the
dipole moment p as

p= rρ(r)dv (1.6)
⎛ ⎞
 r x ρ(r)dv
= ⎝  r y ρ(r)dv ⎠ ,
r z ρ(r)dv

Equation 1.5 is rewritten as

2 Inthis book, a resultant object consisting of components, such as a vector and matrix, after inte-
grating components is simply expressed like Eq. 1.6.
1.2 Intermolecular Interaction 7

a) b1)

b2) c)

Fig. 1.3 Examples of dipolar (a), quadrupolar (b1 and b2) and octopolar (c) distributions of charge
on a sphere. While b1 is axially symmetric similarly to the dipolar case (a), b2 has the twofold
symmetry

1 R· p
V1 (R) = . (1.7)
4πε0 |R|3

A dipole moment is a vectorial quantity characterizing the polarization of the molec-

ular charge distribution (for primarily neutral molecules). The electric field E asso-
ciated with this potential is obtained in accordance with standard static electromag-
netism as a gradient for R,

E 1 (R) = −∇ R V1 (R)
1 1 1
=− R · p∇ R + ∇R R · p
4πε0 |R|3 |R|3
1 1
= [3(R · p)R − |R|2 p]. (1.8)
4πε0 |R|5

To characterize the charge distribution of symmetrical molecules such as nitrogen

having the charge distribution essentially similar to b1 in Fig. 1.3, terms with n = 0
and n = 1 is insufficient because q = 0 and | p| = 0. The next term (n = 2) having
the form

1 1
V2 (R) = |r|2 P2 (cos θ Rr )ρ(r)dv
4πε0 |R|3

2 3 cos θ Rr − 1
2
1 1
= |r| ρ(r)dv
4πε0 |R|3 2
1 1 t
= RQR (1.9)
4πε0 |R|5
8 1 Molecules and Intermolecular Interactions

is called a quadrupolar term. Here, Q is a tensor of order 2, i.e., 3 × 3 matrix,

characteristic of a molecule called quadrupole moment given by

1  
Qi j = 3ri r j − |r|2 δi j ρ(r)dv (1.10)
2

with i, j = x, y, z. Since Q is symmetric and traceless, its largest eigenvalue is often

used to characterize the molecule. An example of the charge distribution relevant for
this term is shown in Fig. 1.3.
Higher-order terms are necessary for highly symmetric molecules such as the
tetragonal ones like methane, and the octahedral ones like SF6 . The electrostatic
potential is given by

1 1
Vn (R) = |r|n Pn (cos θ Rr )ρ(r)dv. (1.11)
4πε0 |R|n+1

The associated electric field is calculated using

1 
∇ R cos θ Rr = |R|2 r − (R · r)R (1.12)
|R| |r|
3

as

E n (R) = −∇ R Vn (R)
  
1 1
=− ∇R |r| n
Pn (cos θ Rr )ρ(r)dv
4πε0 |R|n+1

1 1
=− |r|n Pn (cos θ Rr )ρ(r)dv∇ R
4πε0 |R|n+1
 
1
+ n+1 |r|n ρ(r)Pn (cos θ Rr )∇ R cos θ Rr dv
|R|

n+1
= Vn (R)R (1.13)
|R|2
 
1 1 
− |R| W n − (R·W n )R ,
2
4πε0 |R|n+4

where
d Pn (x)
Pn (x) = (1.14)
 dx
Wn = r|r|n−1 ρ(r)Pn (cos θ Rr )dv. (1.15)
1.2 Intermolecular Interaction 9

The molecular characteristic that is tensor of the order n emerges in these terms.
They are called a 2n -pole moment for arbitrary n. The first few are dipole (n = 1),
quadrupole (n = 2), octopole (n = 3), hexadecapole (n = 4), etc.

1.2.2 Electrostatic Interaction

In this section, we calculate electrostatic interactions while placing the charge distri-
bution of another molecule in the electrostatic potential produced by a molecule (such
as Eq. 1.3). It is noteworthy that only interactions involving up to dipole moments
are necessary to consider in most real cases in comparison with the shape effects of
molecules discussed later.
When molecules are spherical, the interaction is simply of that between point
charges
1 q0 q R
E mm (R) = , (1.16)
4πε0 |R|

where q0 and q R are their charges. For non-spherical molecules, the calculation can
be performed as in the following example of the dipolar interaction. Suppose one
molecule is at the origin and the other at R with the electron density ρ (R + r  )
around R. We expand |R + r  |−3 in r  assuming |R|  |r  | as

1 1 (r  ·R)
≈ − 3 . (1.17)
|R + r  |3 |R|3 |R|5

Thus, the interaction between two dipoles ( p0 at the origin and p R at R) is given by
the integration over a space around R:
  
1 1 (r · R) 
E dd (R) ≈ − 3 (R + r  ) · p0 ρ (r  )dv 
4πε0 |R| 3 |R| 5
    
1 1    1    
≈ ( p · R) ρ (r )dv + p · r ρ (r )dv
4πε0 |R|3 0 |R|3 0
  
1
−3 5 ( p0 · R) R · Rρ (r  )dv 
|R|
 
1 ( p0 · p R ) 3( p0 · R)( p R · R)
= − . (1.18)
4πε0 |R|3 |R|5

Note that the second line is obtained while neglecting the second-order term in r  ,
and the
 last equality assumes the vanishing net charge for the molecule at R, i.e.,
q R = ρ (r  )dv  = 0 in the first term in the second line. This term is the interaction
between a point charge and a dipole p0 . The last expression is exact for point dipoles
irrespective of their species.
10 1 Molecules and Intermolecular Interactions

a) b)

Fig. 1.4 Comparison of dipolar interaction (interaction between two dipoles) given by Eq. 1.18
( p = | p| and R = |R|). Parallel arrangement has a lower energy than antiparallel one in tandem (a)
(Vpara = −2 p 2 R −3 /4πε0 < 2 p 2 R −3 /4πε0 = Vanti ) while in (b) the relation is reversed (Vanti =
− p 2 R −3 /4πε0 < p 2 R −3 /4πε0 = Vpara )

The interaction between a quadrupole and one of a point charge, dipole and
quadrupole can be calculated similarly by truncating the series expansion of |R +
r|−n up to the second-order in r. Note that the second-order term neglected in Eq. 1.18
is only a part of the interaction between a dipole and a quadrupole.
Since 2n -pole moment has the form of [charge]×[length]n while the interaction
between point charges has [charge]2 ×[length]−1 apart from the common prefactor
(4πε0 )−1 , the interaction between a 2n -pole and a 2m -pole depends on their separa-
tion R as R −(n+m+1) . The interaction between two dipoles given by Eq. 1.18 indeed
has the power of −(1 + 1 + 1) = −3. The interaction between them depends not
only on the distance in between but also on their mutual orientations because 2n -
pole moments are tensorial quantities. Equation 1.18, for example, indicates that
the interaction prefers parallel arrangement if two dipoles are in line (tandem) in
Fig. 1.4a while it does antiparallel one if they are side-by-side as in Fig. 1.4b. It is
interesting to see that not only the preferred arrangement but also the strength of the
preference exhibits the anisotropy. There is a report that a seemingly isotropic (three-
dimensional) crystal exhibits the anisotropy (low-dimensionality) arising from the
anisotropy of the dipolar interaction [4].

1.2.3 Polarizability and Dispersion Interaction

In this section, we derive the dependence of the interaction between neutral molecules
on their separation in two steps [5].

1.2.3.1 Dispersion of Polarizability

Consider a neutral molecule that is spherically symmetric and has a closed-shell

electronic structure. The electronic wave function satisfies the following Schrödinger
equation:
∂
H0 Φ = i Φ, (1.19)
∂t
1.2 Intermolecular Interaction 11

where H0 is a Hamiltonian operator of the molecule. Normalized stationary states

are denoted by φn exp(−iωn t) (n = 0, 1, 2, . . .). Then,

H0 φn = ωn φn . (1.20)

This indicates that φn are eigen functions of the time-independent Schrödinger equa-
tion.
Suppose the weak electric field is exerted on the molecules in the ground state
(n = 0) along the x-axis. The time dependence of the field is assumed to be E x cos ωt.
Then, the total Hamiltonian H is given by

H = H0 − Px E x cos(ωt)
= H0 + H , (1.21)

where Px is the operator corresponding to the x component of the molecular dipole

moment. The wave function should fulfill the following time-dependent Schrödinger
equation:
  ∂
H0 + H Φ = i Φ. (1.22)
∂t
Considering the weak filed, we assume the proportionality between the electric field
and the dipole moment. Thus,

Φ ∗ Px Φdv = α(ω)E x cos ωt, (1.23)

where α(ω) is the frequency-dependent polarizability of the molecule.

Assuming |H | |H0 |, we proceed with the time-dependent perturbation theory.
We write the wave function as

Φ = φ0 exp(−iω0 t) + φn exp(−iωn t)an (t). (1.24)
n

Here, |an (t)| 1 is assumed for n ≥ 1. Putting this expansion into Eq. 1.22 yields
 
∂ 
H0 − i φ0 exp(−iω0 t) + φn exp(−iωn t)an (t)
∂t n
 

= −H φ0 exp(−iω0 t) + φn exp(−iωn t)an (t) . (1.25)
n

Considering Eq. 1.20, we have

 d
− i φn exp(−iωn t) an (t) (1.26)
n
dt
12 1 Molecules and Intermolecular Interactions

for the left-hand side.3 Considering the smallness of |H | and |an (t)|, the second term
in the right-hand side can be ignored. Then, we have
 d
− i φn exp(−iωn t) an (t) = −H φ0 exp(−iω0 t)
n
dt
= Px E x cos(ωt)φ0 exp(−iω0 t) (1.27)

By introducing ωn0 = ωn − ω0 , Eq. 1.27 is rewritten as

 d
− i φn exp(−iωn0 t) an (t) = Px E x cos(ωt)φ0 . (1.28)
n
dt

Integration after multiplying φ∗n from the left yields


d
− i exp(−iωn0 t) an (t) = E x cos ωt φ∗n Px φ0 dv (1.29)
dt

because of the orthonormality of φn ’s


φ∗m φn dv = δmn . (1.30)

This is the equation an (t) should fulfill. By introducing


x
Pmn = φ∗m Px φn dv, (1.31)

the equation is expressed as

d
− i exp(−iωn0 t) an (t) = E x Pn0
x
cos ωt (1.32)
dt
Considering the forced nature of the oscillation of the electric field, we can assume the
periodic oscillation for an (t). Then, the solution is obtained by integrating Eq. 1.32
as
1 x eiωt e−iωt
an (t) = Pn0 E x exp(iωn0 t) + . (1.33)
2 ωn0 + ω ωn0 − ω

The expectation value of the dipole moment is calculated to the first order in an (t)
as

3 We changed the derivative symbol to the normal one from the partial one because an (t) depends
solely on t.
1.2 Intermolecular Interaction 13

Φ ∗ Px Φdv
 
≈ exp(iωn0 t)an∗ (t)Pn0
x
+ x ∗
exp(−iω0n t)an (t)(P0n )
n n
2  |Pn0 | ωn0
x 2
= E x cos ωt (1.34)
 n ωn0 − ω 2
2

because of P00x
= 0 derived from the spherical symmetry of the ground state of the
spherical molecule with the closed-shell electronic structure. In the second equality,
x ∗
the relation (Pn0 ) = P0nx
is assumed. A comparison with Eq. 1.23 yields

2  |Pn0 | ωn0
x 2
α(ω) = . (1.35)
 n ωn0
2
− ω2

This formula indicates the frequency dependence of the polarizability. The depen-
dence of a dielectric property (such as a polarizability) on the applied frequency is
generally called its dispersion.

1.2.3.2 Dispersion Interaction

Consider two spherical molecules, each of which is the same as the one in the
previous section. When their separation is large enough compared to molecular size,
it is natural to treat two independent molecules as the unperturbed system. The
interaction between them corresponds to the perturbation term. Since we discuss the
system consisting of two neutral molecules, the interaction should arise from not the
term involving net charges of the molecules but their higher-order moments.
Let us see what is the lowest order term using two hydrogen atoms as an example.
When two atoms are very distant, we may label protons and electrons. Using capitals
for protons and lower case letters for electrons, the total Hamiltonian is written as

2  2  2  2 
Hk = − ∇I + ∇II2 − ∇1 + ∇22 (1.36)
2M 2m
q2 1 1
Hp = − + (1.37)
4πε0 |r 1 − RI | |r 2 − RII |
q2 1 1
− +
4πε0 |r 1 − RII | |r 2 − RI |
q2 1 1
+ + .
4πε0 |RI − RII | |r 1 − r 2 |

On the other hand, the Hamiltonian of atom 1 is given by

14 1 Molecules and Intermolecular Interactions

2 2 2 2 q2 1
HH = − ∇I − ∇1 − . (1.38)
2M 2m 4πε0 |r 1 − RI |

Thus, Hk and the first line of H p are in the Hamiltonian of two independent atoms.
Then, the perturbation term is

q2 1 1 1 1
HH = + − − . (1.39)
4πε0 |RI − RII | |r 1 − r 2 | |r 1 − RII | |r 2 − RI |

Using the multipole expansion, it can be confirmed that the lowest order term is of
the form

q2 3[(r 1 − RI ) · (RII − RI )][(r 2 − RII ) · (RII − RI )]
−
4πε0 |RII − RI |5

(r 1 − RI ) · (r 2 − RII )
− (1.40)
|RII − RI |3

This is just the interaction between two dipoles p j = q(r j − R j ) ( j = 1, 2) with

the distance |RII − RI |.
Having seen the lowest order term in the perturbation being the dipolar interaction,
we return to the general case. The operator of the dipole interaction is denoted by
J . Then the total Hamiltonian is

H = H0 + J (1.41)
H0 = HH1 + HH2 (1.42)
1 1
J = [(P1 · P2 ) − 3(P1 · e)(P2 · e)] (1.43)
4πε0 |R|3
1 1 t
= P1 TP2 ,
4πε0 |R|3
T = I − 3et e. (1.44)

where R is the vector between two molecular centers and e = R/|R|. Ignoring the
necessity of antisymmetry for permutation of two electrons, the normalized eigen
functions of the unperturbed Hamiltonian is given by

ψmn = φ1m φ2n (1.45)

which satisfies
H0 ψmn = (ωm + ωn )ψmn . (1.46)

Note that φ1m and φ2n in ψmn are around different centers.
According to the standard treatment of the time-independent perturbation theory,
the change in energy of the ground level is
1.2 Intermolecular Interaction 15

∗
ΔE 1 = ψ00 J ψ00 dv1 dv2 (1.47)

in the lowest order. However, this term vanishes because, for example,
  
∗
ψ00 P1x ψ00 dv1 dv2 = φ∗10 P1x φ10 dv1 φ∗20 φ20 dv2

= φ∗10 P1x φ10 dv1
=0 (1.48)

because of the spherical symmetry of the molecule. Therefore, the interaction comes
from the second order term:
  J00mn Jmn00
ΔE 2 = − (1.49)
m =0 n =0
ωm0 + ωn0

J jklm = ψ ∗jk J ψlm dv1 dv2 (1.50)

Since J jklm is proportional to |R|−3 , the interaction is attractive with the leading
dependence of |R|−6 .4
To see the numerical factor, we write the interaction energy as
2
1 1
ΔE 2 = − μ (1.51)
4πε0 |R|6
  t00mn tmn00
μ= (1.52)
m =0 n =0
ωm0 + ωn0

t jklm = 4π 0 |R|3 J jklm (1.53)


= ψ ∗jk t P1 TP2 ψlm dv1 dv2

jα
Since P0m (α = x, y, z and j = 1, 2) are quantities related to a spherical molecule,
finally, we obtain
  |P 1x |2 |P 2x |2
μ=6 0m 0n
. (1.54)
m =0 n =0
ω m0 + ω n0

Using the identity

 ∞
1 2 ab
= du, (1.55)
a+b π 0 (a 2 + u 2 )(b2 + u2)

4 The series is in terms of |R|−1 .

16 1 Molecules and Intermolecular Interactions

Equation 1.54 is rewritten as

 ∞
3
μ= α1 (iω)α2 (iω)dω, (1.56)
π 0

where αi (ν) is the polarizability of atom i at a real frequency ν (given by Eq. 1.35)
although the integration should be taken along the imaginary axis. This formula
implies a close connection between the dispersion interaction and the molecular
polarizability.
For the interaction between unlike molecules, 1 and 2, some estimates have been
proposed [6, 7]. Among them, the following form is often adopted:
√
μ12 ≈ μ11 μ22 . (1.57)

This approximation is a basis for combination rules often assumed in the atom–atom
potential method described later.

1.2.4 Repulsion: Pauli’s Exclusion Principle

The theory governing the microscopic world is the quantum mechanics, which has
revealed a wavy nature of any moving body. The wavy nature becomes obvious and
significant for microscopic particles. Thus, two microscopic particles are indistin-
guishable. A wave function expresses the state of such a system. Suppose that a
state with two particles, a and b, in respective “coordinates,” α and β, is specified
by a wave function ϕ(α, β). If two particles are interchanged, the expression should
become ϕ(β, α). According to the indistinguishability of two particles, the two states
are equivalent. This implies

ϕ(α, β) = cϕ(β, α) (1.58)

with a non-vanishing constant c. The repetition of the interchange of two particles

once more yields
ϕ(α, β) = c2 ϕ(α, β), (1.59)

leading to
c = ±1. (1.60)

This simple argument shows that the indistinguishability gives an important classi-
fication of microscopic particles. Particles with c = 1 are called bosons while those
with c = −1 are fermions. Electrons with a half-integer spin (s = ± 21 ) are fermions.
1.2 Intermolecular Interaction 17

Fig. 1.5 Schematic

representation of

interaction energy / arbitrary unit

intermolecular interaction
energy as a function of their
distance

Fermions have a notable property known as Pauli’s exclusion principle. Starting

from the state where two particles have identical “coordinates,” the interchange of
two particles yields
ϕ(α, α) = −ϕ(α, α). (1.61)

This forces ϕ(α, α) = 0. This result should be understood as an indication of the

absence of such states. Namely, two electrons are not allowed to have the same
coordinates.
The exclusion principle imposes a critical effect on the intermolecular interaction.
When two molecules in respective ground states approach, the overlap of electron
distributions follows. The overlap causes the deformation of electron distributions.
The deformation is achieved by the mixing of excited states’ wave functions to the
ground state one, resulting in a significant increase in total energy. Thus, when the
distance of two molecules is small enough to cause the overlap of electron distribu-
tions in the ground state, repulsive interaction becomes dominant. The increase in
energy is steep in comparison with attractive interactions. The dependence on the
distance (r ) is usually expressed as an exponential function (∝ exp(−r/r0 ) with a
characteristic distance r0 ) or a power-law (∝ r −m ) with an index m ≥ 6). Total inter-
action between two molecules consists of both attractive and repulsive contributions
and has a minimum, as shown in Fig. 1.5.
It is noteworthy that the ground state wavefunction mostly determines the spatial
range of the strong repulsive interaction except the details of energy increase, in
contrast to other interactions. This property is the basis for practical van der Waals
radii of atoms and ionic radii, both of which are defined as minimum distances found
in crystals. The so-called excluded volume effects are also understood in terms of the
repulsive interaction.
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 CHAPTER VI.
REPTON’S MERRY BELLS.

“Barrow’s big boulders, Repton’s merry bells,

Foremark’s cracked pancheons, and Newton’s egg shells.”

Thus does a local poet compare Repton bells with those of

neighbouring parishes. It is not intended to defend the comparison,
for as Dogberry says, “Comparisons are odorous”! but to write an
account of the bells, derived from all sources, ancient and modern.
Llewellynn Jewitt, in Vol. XIII. of the Reliquary, describing the bells
of Repton, writes, “at the church in the time of Edward VI. there were
iij great bells & ij small.” Unfortunately “the Churchwardens’ and
Constables’ accounts of the Parish of Repton” only extend from the
year 1582 to 1635. I have copied out most of the references to our
bells entered in them, which will, I hope, be interesting to my
readers.
Extracts from “the Churchwardens’ and Constables’ accounts of the
Parish of Repton.”

A.D. 1583. The levy for the bell vjˡⁱ ixˢ 0

It’ spent at takying downe the bell xvjᵈ
It’ payd to the Bellfounder xxxiijˢ iijᵈ
It’ bestowed on the s’vants at casting
of ye bell xvjᵈ
It’ expensys drawing up the bell vijᵈ
It’ to the ryngers the xviiᵗʰ day of
november xijᵈ
A.D. 1584. Recevyd of the levy for the bell vjˡⁱ xˢ vijᵈ
It’ of Bretby towards the bell vjˢ viijᵈ
It’ spent at taking downe ye bell viijᵈ
 It’ bestowed on the bell founder ijᵈ
It’ Payd to Bellfounder for weight, i.e.,
iiij score & ij pounds iijˡⁱ xiˢ viijᵈ
A.D. 1585. It’ for a bell rope for the great bell ijˢ
It’ to John Pratt for makinge iiij newe
bellropes vˢ
It’ the day before Saynt Hew’s day for
mendyng the bels, & for nayles viijᵈ
A.D. 1586. It’ of our ladie’s even, given to the
ringers for the preservation of
our Queene xijᵈ
Our ladie’s even, eve of the
Annunciation of the Blessed
Virgin Mary (March 25th).
Preservation of our Queene Elizabeth
from the Babington Conspiracy.
A.D. 1587. It’ given unto the ringers uppon
coronation daye iijᵈ
A.D. 1589. It’ for a bell rope ijˢ viijᵈ
A.D. 1590. It’ payde to francis Eaton for
mendynge the irons aboutt the
bells ijˢ iijᵈ
A.D. 1592. It’ payde to Ralphe Weanwryghte for
trussynge the bells agyne the
Coronacyon daye iijˢ
A.D. 1600. It’ spent in takinge downe ye beell xijᵈ
It’ payd to John Welsh fordowne
takinge hitt donne vjᵈ
It’ spent in lodinge hitt iiijᵈ
It’ spent in charges going with the
beell to Nottingham, being towe
days and one night vjˢ viijᵈ
It’ payd to ye bellfounder for castinge
ye beell iiijˡⁱ xviijˢ
It’ spent with him ijᵈ
It’ payd for yookeinge ye Beell and ijˢ viijᵈ
 for greysse
It’ spent uppon them that holpe with
the beell xᵈ
A.D. 1603. It’ given to the ringers uppon New
yeares daye morninge vjᵈ
It’ given to ye ringers upon St. James
daye (July 25th) xijᵈ
It’ given to ye ringers the v daye of
August xijᵈ
A.D. 1605. It’ payd at hanginge up ye greatte bell vjᵈ
It’ bestowed of ye Ringers at ye first
Ringinge of ye bells vijᵈ
It’ payd for greese for ye bells viijᵈ
A.D. 1607. It’ given to ye Ringers uppon
Christmas daye morning iiijᵈ
A.D. 1614. It’ towe bellclappers
A.D. 1615. The names of them that gave money
to bye the newe beell 80
(Repton, 62. Milton, 18.)
Sum gathered xijˡⁱ viijˢ viijᵈ
A.D. 1623. First paide for castinge the bell vˡⁱ
It’ given to the Ringers at the time of
Prince Charlles his comminge
forth of spaine. (Oct. 1623). xijᵈ

Extract from the diary of Mr. George Gilbert.

“A.D. 1772, Oct. 7th. The third bell was cracked, upon ringing
at Mr. John Thorpe’s wedding. The bell upon being taken
down, weighed 7 cwt. 2 qr. 18lb., clapper, 24lb. It was
sold at 10d. per lb., £35. 18s. Re-hung the third bell, Nov.
21st, 1774. Weight 8 cwt. 3 qr. 24lb., at 13d. per lb., £54.
7s. 8d., clapper, 1 r. 22 lb., at 22d., £1. 2s. 10d. £55. 9s
6½d.”
 This is all the information I can gather about “Repton’s merry bells”
from ancient sources.
For some time our ring of six bells had only been “chimed,” owing
to the state of the beams which supported them, it was considered
dangerous to “ring” them.
During the month of January, 1896, Messrs. John Taylor and Co.,
of Loughborough, (descendants of a long line of bell-founders),
lowered the bells down, and conveyed them to Loughborough,
where they were thoroughly cleansed and examined. Four of them
were sound, but two, the 5th and 6th, were found to be cracked, the
6th (the Tenor bell) worse than the 5th. The crack started in both
bells from the “crown staple,” from which the “clapper” hangs; it (the
staple) is made of iron and cast into the crown of the bell. This has
been the cause of many cracked bells. The two metals, bell-metal
and iron, not yielding equally, one has to give way, and this is
generally the bell metal. The “Canons,” as the projecting pieces of
metal forming the handle, and cast with the bell, are called, and by
which they are fastened to the “headstocks,” or axle tree, were found
to be much worn with age. All the “Canons” have been removed,
holes have been drilled through the crown, the staples removed, and
new ones have been made which pass through the centre hole, and
upwards through a square hole in the headstocks, made of iron, to
replace the old wooden ones. New bell-frames of iron, made in the
shape of the letter H, fixed into oak beams above and below, support
the bells, which are now raised about three feet above the bell
chamber floor, and thus they can be examined more easily.
During the restoration of the Church in 1886, the opening of the
west arch necessitated the removal of the ringers’ chamber floor,
which had been made, at some period or other, between the ground
floor and the groined roof, so the ringers had to mount above the
groined ceiling when they had to ring or chime the bells. There,
owing to want of distance between them and the bells, the labour
and inconvenience of ringing was doubled, the want of sufficient
leverage was much felt: now the ringers stand on the ground floor,
and with new ropes and new “sally-guides” their labour is lessened,
and the ringing improved.
 When the bells were brought back from Loughboro’ I made careful
“rubbings” of the inscriptions, legends, bell-marks, &c., before they
were raised and fixed in the belfry. The information thus obtained,
together with that in Vol. XIII. of the Reliquary, has enabled me to
publish the following details about the bells.
The “rubbings” and “squeezes” for the article in the Reliquary were
obtained by W. M. Conway (now Sir Martin Conway) when he was a
boy at Repton School.
 Plate 6.

REPTON BELL MARKS AND ORNAMENTS.

The 1st (treble) Bell.

On the haunch, between three lines, one above, two below,
 FRAVNCIS THACKER OF LINCOLNS INN ESQᴿ, 1721.

a border: fleurs-de-lis (fig. 7): Bell-mark of Abraham Rudhall, (a

famous bell-founder of Gloucester): border (fig. 7).
A catalogue of Rings of Bells cast by A. R. and others, from 1684-
1830, is in the Bodleian Library, Oxford: this bell is mentioned as the
gift of Francis Thacker.
At the east end of the north aisle of our Church there is a mural
monument to his memory.
The 2nd Bell.
On the crown a border of fleurs-de-lis (fig. 9). Round the haunch,

Is sweetly toling men do call to taste on meats that feed the soule

between two lines above and below, then below the same border
(fig. 9) inverted.

1622 Godfrey Thacker Iane Thacker

This bell is referred to in the Churchwardens’ accounts under

dates 1615 and 1623.
The 3rd Bell.
Round the haunch, between two lines,
THOˢ. GILBERT & IOHN TETLEY CHVRCH WARDENS 1774 PACK & CHAPMAN
OF LONDON FECIT

Below, a border, semicircles intertwined.

This is the bell referred to in the extract quoted above from George
Gilbert’s diary.
The 4th Bell.
Round the haunch, between six lines (3 above and 3 below),

✠ Melodie Nomen Tenet Magdelene

a shield: three bells (two and one), with a crown between them (fig.
1), (Bell mark of Richard Brasyer, a celebrated Norwich Bell founder,
who died in 1513) a lion’s head on a square (fig. 2): a crown on a
square (fig. 3); and a cross (fig. 5).
The 5th Bell.
Round the haunch, between two lines, one above, one below,

✠ Vox du̅ i̅ ihū x̅ r̅ i̅ vox exultarionis

same marks (except the crown) as No. 4 Bell: a king’s head crowned
(fig. 4): and a cross (fig. 6). Below this, round the haunch, a beautiful
border composed of a bunch of grapes and a vine leaf (fig. 8),
alternately arranged.
 Below, the Bell mark of John Taylor and Co. within a double circle,
a triangle interlaced with a trefoil, and a bell in the centre. Above the
circle the sacred emblem of S. John Baptist, the lamb, cross, and
flag. The name of the firm within the circle.
RECAST 1896.
The 6th Bell (the tenor Bell).
Round the haunch, between four lines, two above, and two below,

Hec Campana Sacra Fiat Trinitate Beata GILB THACKAR ESQ IC MW CH

WARDENS 1677

(no bell marks).

Below, a border like that on the fifth Bell.

RECAST 1896.

G. WOODYATT, VICAR.
J. ASTLE, }
CHURCHWARDENS.
T. E. AUDEN, }

Bell mark of J. Taylor and Co. on the opposite side.

(Owing to the difference of the type of the inscription, and names,
it is supposed that this bell was recast in 1677, so it may have been
one of the “three great bells” in Edward VI.’s time.)
The following particulars of the bells have been supplied by
Messrs. John Taylor & Co.

Diameter. Height. Note. Weight.

ft. in. ft. in. cwt. qr. lbs.
No. I. 2 9½ 2 3 C♯ 7 3 19
 ” II. 2 10¾ 2 4½ B 7 2 27
” III. 3 0½ 2 4½ A 8 1 18
” IV. 3 2 2 6½ G♯ 9 2 21
” V. 3 6 2 10 F♯ 12 2 26
” VI. 3 11 3 1 E 17 3 0

Total 3 tons 4 cwts. 0 qrs. 27 lbs.

Key-note E major.
To complete the octave, two more bells are required, D ♯ and E,
then indeed Repton will have a “ring” second to none.
 CHAPTER VII.
THE PRIORY.

THE PRIORY FOUNDED, &c.

Before we write an account of the next most important event in the
history of Repton, viz., the founding of Repton Priory, we must go
back to the year 1059, when Calke Abbey is supposed to have been
founded by Algar, Earl of Mercia. Dr. Cox is of opinion that it was
founded later, at the end of the reign of William (Rufus), or at the
beginning of that of Henry I. circa 1100. About that date a Priory of
Canons regular of St. Augustine, dedicated to St. Giles, was
founded. Many benefactors made grants of churches, lands, &c., a
list of all these will be found in Cox’s Derbyshire Churches, vol. iii., p.
346. There is a curious old Chronicle, written in Latin, by one
T(h)omas de Musca, Canon of Dale Abbey. Each section of the
Chronicle begins with a letter which, together, form the Author’s
name, a monkish custom not uncommon. The section beginning with
an E. (Eo tempore) records the arrival, at Deepdale, of the Black
Canons, as they were called, from Kalc (Calke). Serlo de Grendon,
Lord of Badeley or Bradeley, near Ashbourne, “called together the
Canons of Kalc, and gave them the place of Deepdale.” Here, about
1160, the Canons “built for themselves a church, a costly labour, and
other offices,” which became known as Dale Abbey, in which they
lived for a time, “apart from the social intercourse of men,” but “they
began too remissly to hold themselves in the service of God; they
began to frequent the forest more than the church; more to hunting
than to prayer or meditation, so the King ordered them to return to
the place whence they came,” viz., Calke. During the reign of Henry
II., Matilda, widow of Randulf, 4th Earl of Chester, who died 1153,
granted to God, St. Mary, the Holy Trinity, and to the Canons of
Calke, the working of a quarry at Repton, (Repton Rocks), together
with the advowson of the church of St. Wystan at Repton, &c., &c.,
on condition that as soon as a suitable opportunity should occur, the
Canons of Calke should remove to Repton, which was to be their
chief house, and Calke Abbey was to become subject to it. “A
suitable opportunity occurred” during the episcopate of Walter
Durdent, Bishop of Coventry only, at first, afterwards of Lichfield. He
died at Rome, Dec. 7th, 1159. The usual date given for the founding
of Repton Priory is a.d. 1172, but this must be wrong for the simple
reason that Matilda addresses the Charter of Foundation to Bishop
Walter Durdent, who died, as we saw, in 1159: moreover, the
“remains” of the Priory belong to an earlier date; probably the date
1172 refers to the coming of the Canons from Calke to Repton, as
Dugdale writes, “About the year 1172, Maud, widow of Randulf,
removed the greater part of them here (Repton), having prepared a
church and conventual buildings for their reception.” To those
interested in Charters, copies of the original, and many others, can
be read in Bigsby’s “History of Repton,” Dugdale’s “Monasticon,” and
Stebbing-Shaw’s Article in Vol. II. of “the Topographer,” in which he
has copied several “original Charters, not printed in the Monasticon,”
which were in the possession of Sir Robert Burdett, Bart., of
Foremark, and others.
 Plate 7.

Repton Priory.

The Charters, containing grants, extend from Stephen’s reign,

(1135-1154), to the reign of Henry V., (1413-1422), and include the
church of St. Wystan, Repton, with its chapels of Newton Solney,
Bretby, Milton, Foremark, Ingleby, Tickenhall, Smisby, and Measham,
the church at Badow, in Essex, estates at Willington, including its
church, and Croxall.
In 1278 a dispute arose between the Prior of Repton and the
inhabitants of the Chapelry of Measham, which had been granted to
the Priory about 1271. The chancel of Measham Church was “out of
repair,” and the question was, who should repair it? After
considerable debate, it was settled that the inhabitants would re-
build the chancel provided that the Priory should find a priest to
officiate in the church, and should keep the chancel in repair for ever
after, both of which they did till the dissolution of the Priory.
 In the year 1364 Robert de Stretton, Bishop of Lichfield (1360-
1386), was holding a visitation at Repton in the Chapter House of the
Priory. For some reason or other, not known, the villagers, armed
with bows and arrows, swords and cudgels, with much tumult, made
an assault on the Priory gate-house. The Bishop sent for Sir Alured
de Solney, and Sir Robert Francis, Lords of the Manors of Newton
Solney and Foremark, who came, and quickly quelled this early
“town and gown” row, without any actual breach of the peace. The
monument in the crypt of Repton Church, where it was placed during
the “restoration” of 1792, is supposed to be an effigy of Sir Robert
Frances. “The Bishop proceeded on his journey, and, on reaching
Alfreton, issued a sentence of interdict on the town and Parish
Church of Repton, with a command to the clergy, in the neighbouring
churches, to publish the same under pain of greater
excommunication.” See Lichfield Diocesan Registers.
On October 26th, 1503, during the reign of Henry VII., an
inquisition was held at Newark. A complaint was heard against the
Prior of Repton for not providing a priest “to sing” the service in a
chapel on Swarkeston Bridge, “nor had one been provided for the
space of twenty years, although a piece of land between the bridge
and Ingleby, of the annual value of six marks, had been given to the
Prior for that purpose.”

THE PRIORY DISSOLVED AND DESTROYED.

The Priory of Repton was dissolved in the year 1538. By the
advice of Thomas Cromwell—malleus monachorum—the hammer of
the monks—Henry VIII. issued a commission of inquiry into the
condition, &c., of the monasteries in England. A visitation was made
in 1535, the results were laid before the House of Commons, in a
report commonly known as the “Black Book.” In 1536 an Act was
passed for the suppression of all monasteries possessing an income
of less than £200. a year. By this Act 376 monasteries were
dissolved, and their revenues, £32,000. per annum, were granted to
the King, by Divine permission Head of the Church! Repton Priory
was among them. In the Valor Ecclesiasticus (27 Henry VIII.) the
gross annual value of the temporalities and spiritualities is given as
£167. 18s. 2½d. In 1535, Dr. Thomas Leigh and Dr. Richard Layton,
visited Repton and gave the amount as £180. Also they reported, as
they were expected, that the Canons were not living up to their vows,
&c., &c., and “Thomas Thacker was put in possession of the scite of
the seid priory and all the demaynes to yᵗ apperteynying to oʳ
sov’aigne lorde the Kynges use the xxvj day of October in the xxx
yere of oʳ seid sov’aigne lorde Kyng henry the viijᵗʰ.” There is a very
full inventory of the goods and possessions in the Public Record
Office, Augmentation Office Book, 172. A transcript of this inventory
is given by Bigsby in his History of Repton, also by W. H. St. John
Hope, in Vol. VI. of the Derbyshire Archæological Journal. From this
inventory, and Mr. St. John Hope’s articles in the journal, a very good
account and description can be given of the Priory as it was at the
time of its dissolution.
The dissolved Priory was granted to Thomas Thacker in 1539, he
died in 1548, leaving his property to his son Gilbert. He, according to
Fuller (Church History, bk. vi., p. 358), “being alarmed with the news
that Queen Mary had set up abbeys again (and fearing how large a
reach such a precedent might have), upon a Sunday (belike the
better day, the better deed) called together the carpenters and
masons of that county, and plucked down in one day (churchwork is
a cripple in going up, but rides post in coming down) a most beautiful
church belonging thereto, saying “he would destroy the nest, for fear
the birds should build therein again”.” The destruction took place in
the year 1553. How well he accomplished the work is proved by the
ruins uncovered during the years 1883-4.
This Gilbert died in 1563, as set forth on the mural tablet in the
south aisle of Repton Church, a copy of which I have made, so that
my readers may see what sort of a person he was who “wrought
such a deed of shame.” Gilbert sold the remains of the Priory to the
executors of Sir John Port in 1557, he and his descendants lived at
the Hall till the year 1728, when Mary Thacker, heiress of the Manor
of Repton Priory, left it, and other estates, to Sir Robert Burdett, of
Foremark, Bart. Since that time the Hall has been occupied by the
Headmasters of Repton School.
 REPTON PRIORY DESCRIBED.
The Priory followed the usual plan of monastic buildings, differing
chiefly in having the cloister on the north of its church, instead of the
south. This alteration was necessary owing to the river Trent being
on the north. In choosing a site for monasteries the water supply was
of the first consideration, as everything, domestic and sanitary,
depended on that. The Conventual buildings consisted of Gate-
house, Cloister, with Church on its south side, Refectory or Fratry on
its north. The Chapter Rouse, Calefactorium, with Dormitory above
them, on its east side. Kitchens, buttery, cellars, with Guest Hall over
them, on its west side. The Infirmary, now Repton Hall, “beside the
still waters” of the Trent, on the north of the Priory. The Priory
precincts, (now the Cricket ground), were surrounded by the existing
wall on the west, south, and east sides; on the north flowed, what is
now called, “the Old Trent,” and formed a boundary in that direction.

Plate 8.
 Sir John Porte Knt. The Founder of Repton School. (F. C. H.) (Page 62.)

Gilbert Thacker. (Page 54.)

On the east side of the Priory was the Mill. The wall, with arch-
way, through which the water made its way across the grounds in a
north-westerly direction, is still in situ in the south-east corner of the
Cricket ground. The Priory, and well-stocked fish ponds, were thus
supplied with water for domestic, sanitary, and other purposes.
The bed of the stream was diverted to its present course, outside
the eastern boundary wall, by Sir John Harpur, in the year 1606.
The Gate-house (now represented by the School Arch, which was
its outer arch, and wall) consisted of a square building with an upper
chamber, and other rooms on the ground floor for the use of the
porter. Two “greate gates,” with a wicket door let into one of them, for
use when the gates were closed, or only pedestrians sought for
admission, provided an entrance to the Priory. Proceeding through
the arch-way of the Gate-house, we find ourselves in the precincts.
In the distance, on our left hand, was the Parish Church of St.
Wystan, on our right the Priory Church and conventual buildings.
The Priory Church consisted of nave, with north and south aisles,
central tower, north and south transepts, choir, with aisles, and a
south chapel, and a presbytery to the east of the choir. The Nave (95
ft. 6 in. long, and, with aisles, 51 ft. 8 in. wide) “was separated from
the aisles by an arcade of six arches, supported by clustered pillars
of good design, and must have been one of the most beautiful in this
part of the country, all of exceptionally good character and design,
and pertained to the transitional period of architecture which
prevailed during the reign of Edward I., (1272-1307), when the
severe simplicity of the Early English was merging into the more
flowing lines of the Decorated.” In the north aisle the foundations of
an older church, perhaps the original one, were discovered in 1883-
4.
There were several Chapels in the Nave, two of which are named,
viz., “Oʳ lady of petys Chapell” and the “Chapell of Saint Thomas,”
with images, “reredoses, of wood gylte, and alebaster,” “and a
partition of tymber seled ouerin seint Thom’s Chapell.” “vij. peces of
tymber and lytell oulde house of tymber,” probably the remains of a
shrine, and “xij. Apostells,” i.e. images of them. “j sacrying bell,”
sanctus bell, used during the celebration of the mass. In the floor, in
front of the central tower arch, a slab was discovered, (6 ft. 4 in. by 3
ft. 2 in.), bearing a rudely cut cross, with two steps, and an
inscription, in Old English letters, partly obliterated, round the margin
“(Orate pro) anima magistri edmundi duttoni quondam canonici huius
ecclisie qui obiit ... januarii anno diu mcccclᵒ cui’ ppic (deus Amen).”
This slab is now lying among the ruins at the east end of the Pears
School.
Central Tower (25 ft. by 21 ft. 6 in.) supported by four large piers.
Between the two eastern piers there was a pulpitum, a solid stone
screen (5 ft. 4½ in. deep), with a door in the centre (4 ft. 4½ in.
wide). In the northern half was a straight stone stair leading to the
organ loft above, where was “j ould pair of Organs,” a phrase often
met with in old inventories, and church accounts, in describing that
instrument of music. Through the passage under the screen we
enter the Choir. The step leading down to the choir floor, much worn
by the feet of the canons and pilgrims, is still in situ. The Choir (26 ft.
wide, 31 ft. long) was separated from the south Choir aisle, by an
arcade of five arches, from the north choir aisle, by an arcade of
three arches. All traces of the Canons’ stalls have gone, but there
was room for about thirty-four, thirteen on each side, and four
returned at the west end of the Choir. In the Choir was the High Altar
with “v. great Images” at the back of which was a retable, or ledge of
alabaster, with little images, (on a reredos with elaborate canopies
above them). “iiij lytle candlestyks” and “a laumpe of latten,” i.e., a
metal chiefly composed of copper, much used in church vessels,
also “j rode” or cross.
On the south of the choir was a chapel dedicated to St. John, with
his image, and alabaster table, similar to that in the choir. To the
south of St. John’s Chapel was the “Chapel our Lady” similarly
ornamented, these two chapels were separated from the south
transept by “partitions of tymber,” or screens, the holes in which the
screens were fixed are still to be seen in the bases of the pillars. On
the east of the choir was the Presbytery. In the South Transept was
the Chapel of St. Nicholas with images of St. John and St. Syth, (St.
Osyth, daughter of Frithwald, over-lord of the kingdom of Surrey, and
Wilterberga daughter of King Penda). Of the North Choir Aisle
nothing remains: it is supposed that in it was the shrine of St.
Guthlac, whose sanctus bell is thus referred to by the visitors in their
report “superstitio—Huc fit peregrinatio ad Sanctum Guthlacum et ad
eius campanam quam solent capitibus imponere ad restinguendum
dolorem capitis.” “Superstition. Hither a pilgrimage is made to (the
shrine of) St. Guthlac and his (sanctus) bell, which they were
accustomed to place to their heads for the cure of headache.” The
North Transept was separated from the north choir aisle by an
arcade of three arches, immediately to the east of which the
foundations of a wall, about six feet wide, were discovered, which,
like those in the north nave aisle, belonged to an older building.
Many beautiful, painted canopies, tabernacle work, &c., were found
among the débris of the north transept and aisle, which no doubt
adorned the shrines, and other similar erections, which, before the
suppression of the monasteries, had been destroyed, and their relics
taken away—that is, probably, the reason why we find no mention of
the shrines of St. Guthlac, or St. Wystan in the Inventory.
In the western wall of the North Transept there was a curious
recess (13 ft. 10 in. by 4 ft. 10 in.) which may have been the
armarium, or cupboard of the Vestry, to hold the various ornaments,
and vestments used by the Canons, “j Crosse of Coper, too tynacles,
(tunicles), ij albes, ij copes of velvet, j cope of Reysed Velvet, iiij
towels & iiij alter clothes, ij payented Alterclothes,” &c., &c.
Leaving the Church, we enter the Cloister, through the door at the
east end of the Nave, it opened into the south side of the Cloister (97
ft. 9 in. long by 95 ft. wide). Here were “seats,” and “a lavatory of
lead,” but, owing to alterations, very little indeed is left except the
outside walls. Passing along the eastern side we come to the
Chapter House, the base of its entrance, divided by a stone mullion
into two parts, was discovered, adjoining it on the north side was a
slype, or passage, through which the bodies of the Canons were
carried for interment in the cemetery outside. The slype (11¾ ft. wide
by 25½ ft. long) still retains its roof, “a plain barrel vault without ribs,
springing from a chamfered string course.” Next to the slype was the
Calefactorium or warming room. Over the Chapter House, Slype,
and Calefactorium was the Dormitory or Dorter, which was
composed of cells or cubicles.
The Fratry or Refectory occupied the north side of the Cloister,
here the Canons met for meals, which were eaten in silence,
excepting the voice of the reader. A pulpit was generally built on one
of the side walls, from which legends, &c., were read. Underneath
the Fratry was a passage, leading to the Infirmary, and rooms, used
for various purposes, Scriptorium, &c. At the east end of the Fratry
was the Necessarium, well built, well ventilated, and well flushed by
the water from the Mill race.
At the west end of the Fratry was the Buttery. The west side of the
Cloister was occupied by the Prior’s Chamber, and five others called,
in the Inventory, “the Inner,” “Gardyn,” “Next,” “Halle,” and “Hygh
Chambers.” All were furnished with “fether bedds, &c., &c.,” for the
use of guests, who were received and entertained in this part of the
Priory. Underneath these rooms were “the Kychenn,” “Larder,”
“Bruhouse,” &c., called the Cellarium, over which the Cellarer had
supreme authority. Originally the Cellarium was divided into three
parts, Kitchen, Cellar, and Slype or passage into the south side of
the Cloister. The part assigned to the Kitchen was sub-divided into
three rooms, one on the east side, two on the west. One of these two
(the south) has a vaulted roof, with plain square ribs, the boss where
they meet has been carved, and a part of one of the ribs has been
ornamented with the dog tooth moulding, for about 18 inches, there it
stopped unfinished, in the walls are many recesses for the reception
of “plate,” &c.
The Cellar was a long room (89 ft. by 26 ft.), divided into two
“alleys” by a row of six massive Norman columns, four of which
remain, one has a scollopped capital, the others are plain. The floor
above was divided in a similar manner, with the Prior’s Chamber at
the north end, the Guest Hall, divided into the various rooms
mentioned above, and a chamber over the slype, which was
probably used as a parlour by the guests.