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Challenges and Advances
in Computational Chemistry and Physics 26
Series Editor: Jerzy Leszczynski
Andrzej Koleżyński
Magdalena Król Editors
Molecular
Spectroscopy—
Experiment and
Theory
From Molecules to Functional Materials
Challenges and Advances in Computational
Chemistry and Physics
Volume 26
Series editor
Jerzy Leszczynski
Department of Chemistry and Biochemistry
Jackson State University, Jackson, MS, USA
This book series provides reviews on the most recent developments in computa-
tional chemistry and physics. It covers both the method developments and their
applications. Each volume consists of chapters devoted to the one research area.
The series highlights the most notable advances in applications of the computa-
tional methods. The volumes include nanotechnology, material sciences, molecular
biology, structures and bonding in molecular complexes, and atmospheric
chemistry. The authors are recruited from among the most prominent researchers
in their research areas. As computational chemistry and physics is one of the most
rapidly advancing scientific areas such timely overviews are desired by chemists,
physicists, molecular biologists and material scientists. The books are intended for
graduate students and researchers.
More information about this series at http://www.springer.com/series/6918

Andrzej Koleżyński Magdalena Król
•
Editors
Molecular Spectroscopy—
Experiment and Theory
From Molecules to Functional Materials
123
Editors
Andrzej Koleżyński Magdalena Król
Faculty of Materials Science and Ceramics Faculty of Materials Science and Ceramics
AGH University of Science and Technology AGH University of Science and Technology
Kraków, Poland Kraków, Poland
ISSN 2542-4491 ISSN 2542-4483 (electronic)

Challenges and Advances in Computational Chemistry and Physics
ISBN 978-3-030-01354-7 ISBN 978-3-030-01355-4 (eBook)
https://doi.org/10.1007/978-3-030-01355-4
Library of Congress Control Number: 2018955928
© Springer Nature Switzerland AG 2019

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Preface
The idea of this book originated in some discussions we carried out during one
of the conference we had the pleasure to organize, namely XIVth International
Conference on Molecular Spectroscopy, Kraków-Białka Tatrzańska, Poland in
2017, which was the last conference in a series. The history of these conferences
spans over 20 years. In 1991, Prof. Henryk Ratajczak from Wroclaw University,
Poland, the originator of the idea, organized the first one in a series (as a national
conference with international participation) with the intention to have the following
ones every two years. Similar conferences devoted to Vibrational Spectroscopy in
Materials Science were initiated in 1996 by Prof. Mirosław Handke from AGH
University of Science and Technology in Krakow, Poland. For a few years, these
conferences were organized independently and in 2009 were merged into a single
one, organized every two years, alternately by University of Wrocław and AGH
University of Science and Technology. The last conference was organized in 2017
in Białka Tatrzańska and gathered above three hundred participants (almost a third
from abroad) and was devoted to practical application of various spectroscopic
methods to study different types of materials and showed that modern spectroscopy
is an invaluable tool in recent scientific endeavor to understand the structure and
properties of various natural and synthetic materials as well as to create new or to
modify existing ones in order to obtain better suited (functionalized) materials
required by modern industry.
There are a lot of books devoted to various issues related to either spectroscopic
methods themselves or their use in the characterization of diverse classes of
materials exhibiting often very different properties. However, the books containing
comprehensive, up-to-date description of theory, experimentation, and simultane-
ous use of different spectroscopic methods to study the properties of a given type of
materials, provided by leading specialists in the field for various classes of materials
are still rare and sought after.
This book is intended to provide such comprehensive description of materials
characterization by means of a wide spectrum of modern spectroscopic methods
and is aimed at scientists interested in theory and practical application of various
spectroscopic methods in their work. It starts with a short introduction to theoretical
v
vi Preface
foundations and description of fundamentals of computational methods commonly

used in spectroscopy, followed by a series of chapters presenting the results
obtained using various spectroscopy methods combined with theoretical calcula-
tions. Consecutive chapters are devoted to the studies of a broad range of materials
(starting from organic molecules and biological systems, through quantum dots and
nanomaterials, to crystalline and amorphous inorganic solids) using various spec-
troscopic methods, like the most popular vibrational spectroscopy (IR and Raman),
Mossbauer spectroscopy, and UV–Vis electron spectroscopy.
Kraków, Poland Andrzej Koleżyński

Magdalena Król
Contents
1 Computational Methods in Spectroscopy . . . . . . . . . . . . . . . . . . . . 1

2 Scaling Procedures in Vibrational Spectroscopy . . . . . . . . . . . . . . . 49
Olga Bąk and Piotr Borowski
3 Quantum Dot and Fullerene with Organic Chromophores
as Electron-Donor-Acceptor Systems . . . . . . . . . . . . . . . . . . . . . . . 97
Danuta Wróbel and Bolesław Barszcz
4 Material Analysis Using Raman Spectroscopy . . . . . . . . . . . . . . . . 123
Animesh K. Ojha and H. Michael Heise
5 Ligand-Core NLO-Phores . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 139
Rodolphe Antoine
6 Small and Large Molecules Investigated by Raman
Spectroscopy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 161
Krzysztof Czamara, Ewelina Szafraniec, Ewelina Wiercigroch,
Szymon Tott, Grzegorz Zając, Ewa Machalska, Monika Dudek,
Dominika Augustynska, Kamilla Malek, Agnieszka Kaczor
and Malgorzata Baranska
7 Hydantoins and Mercaptoimidazoles: Vibrational Spectroscopy
as a Probe of Structure and Reactivity in Different Environments,
from the Isolated Molecule to Polymorphs . . . . . . . . . . . . . . . . . . . 199
Rui Fausto, Gulce O. Ildiz, Elisa M. Brás and Bernardo A. Nogueira
8 Vibrational Spectroscopy in Analysis of Stimuli-Responsive
Polymer–Water Systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 223
Marcin Kozanecki, Marcin Pastorczak and Krzysztof Halagan
9 Mössbauer Spectroscopy of Magnetoelectric Perovskite
Oxides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 273
Paweł Stoch and Agata Stoch
vii
viii Contents
10 Vibrational Spectroscopy of Zeolites . . . . . . . . . . . . . . . . . . . . . . . . 301

Magdalena Król, Andrzej Koleżyński, Andrzej Mikuła
and Włodzimierz Mozgawa
11 In Situ and Operando Techniques in Catalyst Characterisation
and Design . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 333
Przemysław Jodłowski and Joanna Łojewska
12 Application of Spectroscopic Methods in the Studies of
Polysiloxanes, Cubic Oligomeric Silsesquioxanes, and
Spherosilicates Modified by Organic Functional Groups
via Hydrosilylation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 361
Aleksandra Chechelska-Noworyta, Jan Mrówka, Maria Owińska
and Magdalena Hasik
13 Spectroscopic Aspects of Polydimethylsiloxane (PDMS) Used
for Optical Waveguides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 401
Dengke Cai and H. Michael Heise
14 The Luminescent Properties of Photonic Glasses and Optical
Fibers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 427
Jacek Zmojda, Marcin Kochanowicz, Piotr Miluski
and Dominik Dorosz
15 Spectroscopic Characterization of Silicate Amorphous
Materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 457
Włodzimierz Mozgawa, Maciej Sitarz and Magdalena Król
16 Spectroscopy in the Analysis of Artworks . . . . . . . . . . . . . . . . . . . . 483
Tomasz Łojewski and Barbara Łydżba-Kopczyńska
Index . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 519
Contributors
Rodolphe Antoine Institut Lumière Matière, UMR5306 Université Claude

Bernard Lyon1-CNRS, Université de Lyon, Villeurbanne Cedex, France
Dominika Augustynska Jagiellonian Centre for Experimental Therapeutics,
Jagiellonian University, Krakow, Poland
Olga Bąk Faculty of Chemistry, Maria Curie-Skłodowska University, Lublin,
Poland
Malgorzata Baranska Faculty of Chemistry, Jagiellonian University, Krakow,
Poland; Jagiellonian Centre for Experimental Therapeutics, Jagiellonian University,
Krakow, Poland
Bolesław Barszcz Faculty of Technical Physics, Institute of Physics, Poznan
University of Technology, Poznań, Poland; Institute of Molecular Physics Polish
Academy of Sciences, Poznań, Poland
Piotr Borowski Faculty of Chemistry, Maria Curie-Skłodowska University,
Lublin, Poland
Elisa M. Brás CQC, Department of Chemistry, University of Coimbra, Coimbra,
Portugal
Dengke Cai Laboratory of Micro-Structure Technology, Department of Electrical
Engineering and Information Technology, TU Dortmund University, Dortmund,
Germany
Aleksandra Chechelska-Noworyta Faculty of Materials Science and Ceramics,
AGH University of Science and Technology, Krakow, Poland
Krzysztof Czamara Faculty of Chemistry, Jagiellonian University, Krakow,
Krakow, Poland
ix
x Contributors
Dominik Dorosz Faculty of Materials Science and Ceramics, AGH University of

Science and Technology, Krakow, Poland
Monika Dudek Faculty of Chemistry, Jagiellonian University, Krakow, Poland
Rui Fausto CQC, Department of Chemistry, University of Coimbra, Coimbra,
Portugal
Krzysztof Halagan Faculty of Chemistry, Department of Molecular Physics, Lodz
University of Technology, Lodz, Poland
Magdalena Hasik Faculty of Materials Science and Ceramics, AGH University of
H. Michael Heise Interdisciplinary Center for Life Sciences, South-Westphalia
University of Applied Sciences, Iserlohn, Germany
Gulce O. Ildiz CQC, Department of Chemistry, University of Coimbra, Coimbra,
Portugal; Department of Physics, Faculty of Sciences and Letters, Istanbul Kultur
University, Istanbul, Turkey
Przemysław Jodłowski Faculty of Chemical Engineering and Technology,
Cracow University of Technology, Kraków, Poland
Agnieszka Kaczor Faculty of Chemistry, Jagiellonian University, Krakow,
Krakow, Poland
Marcin Kochanowicz Faculty of Electrical Engineering, Bialystok University of
Technology, Białystok, Poland
Andrzej Koleżyński Faculty of Materials Science and Ceramics, AGH University
of Science and Technology, Krakow, Poland
Marcin Kozanecki Faculty of Chemistry, Department of Molecular Physics, Lodz
University of Technology, Lodz, Poland
Magdalena Król Faculty of Materials Science and Ceramics, AGH University of
Joanna Łojewska Faculty of Chemistry, Jagiellonian University, Kraków, Poland
Tomasz Łojewski Faculty of Materials Science and Ceramics, AGH University of
Barbara Łydżba-Kopczyńska Faculty of Chemistry, University of Wroclaw,
Wroclaw, Poland
Ewa Machalska Faculty of Chemistry, Jagiellonian University, Krakow, Poland
Contributors xi
Kamilla Malek Faculty of Chemistry, Jagiellonian University, Krakow, Poland;

Jagiellonian Centre for Experimental Therapeutics, Jagiellonian University,
Krakow, Poland
Andrzej Mikuła Faculty of Materials Science and Ceramics, AGH University of
Piotr Miluski Faculty of Electrical Engineering, Bialystok University of
Włodzimierz Mozgawa Faculty of Materials Science and Ceramics, AGH
University of Science and Technology, Krakow, Poland
Jan Mrówka Faculty of Materials Science and Ceramics, AGH University of
Bernardo A. Nogueira CQC, Department of Chemistry, University of Coimbra,
Coimbra, Portugal
Animesh K. Ojha Department of Physics, Motilal Nehru National Institute of
Technology, Allahabad, India
Maria Owińska Faculty of Materials Science and Ceramics, AGH University of
Marcin Pastorczak Institute of Physical Chemistry, Polish Academy of Sciences,
Warsaw, Poland
Maciej Sitarz Faculty of Materials Science and Ceramics, AGH University of
Agata Stoch Institute of Electron Technology Krakow Division, Krakow, Poland
Paweł Stoch Faculty of Materials Science and Ceramics, AGH University of
Ewelina Szafraniec Faculty of Chemistry, Jagiellonian University, Krakow,
Poland
Szymon Tott Faculty of Chemistry, Jagiellonian University, Krakow, Poland
Ewelina Wiercigroch Faculty of Chemistry, Jagiellonian University, Krakow,
Poland
Danuta Wróbel Faculty of Technical Physics, Institute of Physics, Poznan
University of Technology, Poznań, Poland
Grzegorz Zając Faculty of Chemistry, Jagiellonian University, Krakow, Poland
Jacek Zmojda Faculty of Electrical Engineering, Bialystok University of
Chapter 1
Computational Methods in Spectroscopy
Abstract Spectroscopy investigates the interaction of electromagnetic radiation

with matter. Along with the development of theoretical methods, increasingly
effective numerical algorithms and computational methods as well as computer
technologies and resulting growing computer power available for scientists, the
so-called in silico experiments—computer simulations of materials and their prop-
erties in computer—have become an irreplaceable tool supporting experimental
research, often allowing a better understanding of phenomena taking place during
these interactions, and associated material properties. As a result, it becomes pos-
sible in growing number of cases to effectively design new materials with desired
properties and to modify existing ones, to improve their properties. This chapter is
devoted to a brief introduction to issues related to theoretical foundations of quantum
mechanics and density functional theory, both in stationary and time-dependent
form. The key assumptions of these theories are presented, together with the
description of various approximations and simplifications necessary for their prac-
tical application to the calculation of properties examined by spectroscopic methods.
The most important practical problems encountered during calculations, resulting
from the complexity of real materials and typical ways of dealing with these prob-
lems by means of various simplifications, idealizations, and abstractions in designed
structural models corresponding to real materials, are also presented.
1.1 Introduction
A broadly understood spectroscopy is devoted to the studies of the interactions of

electromagnetic radiation with matter. There are many different spectroscopic
techniques, but all of these techniques are based on the assumption that—when
certain conditions are fulfilled—each material emits or absorbs energy, usually in
A. Koleżyński (&)
Faculty of Materials Science and Ceramics, AGH University of Science
and Technology, 30 Mickiewicza Av., 30-059 Krakow, Poland
e-mail: andrzej.kolezynski@agh.edu.pl
© Springer Nature Switzerland AG 2019 1

A. Koleżyński and M. Król (eds.), Molecular Spectroscopy—Experiment
and Theory, Challenges and Advances in Computational Chemistry
and Physics 26, https://doi.org/10.1007/978-3-030-01355-4_1
2 A. Koleżyński
the form of electromagnetic radiation. The spectrum of electromagnetic radiation

extends in a very wide range of energy (and thus radiation frequencies). Various
spectroscopic techniques, when investigating the interaction of electromagnetic
radiation with a matter (absorption or emission, primary or secondary, by the matter
of a part of energy in the form of electromagnetic radiation), use different frequency
ranges of electromagnetic radiation, depending on the studied spectroscopic pro-
cesses and characteristic for them magnitude of the energy changes (in Fig. 1.1, a
schematic spectrum of electromagnetic radiation with the assignment of radiation
ranges to individual spectroscopic techniques is shown). For example, nuclear
magnetic resonance (NMR) technique [1–3] uses radio frequency radiation of about
108 Hz, recording changes in the spin of atomic nucleus (with very small energy
change) in atoms with a nonzero nuclear spin, e.g., 1H, 2H, 6Li, 7Li, 13C, 29Si.
Under the influence of the applied external magnetic field, there is a split of energy
levels in these atoms into two groups, depending on whether the nuclear spins are
directed parallel or antiparallel to the direction of the magnetic field. This level
separation is very small, of the order of 0.01 J/mol for the applied field of 1 T,
which corresponds to the radiation frequency of approximately 500 MHz. The
magnitude of energy changes and the associated frequency of electromagnetic
radiation strongly depends on the type of atom and its chemical environment, so
one can get a lot of relevant information about the structure of the material under
investigation.
The method closely related to the NMR is EPR/ESR method (electron param-
agnetic resonance/electron spin resonance) [4, 5]—the difference is that in this
method the change in the configuration of the electron spins, and not nuclei, is
studied. The EPR method is based on the presence of permanent magnetic dipoles,
i.e., unpaired electrons (as is the case, e.g., in many transition metals), and examines
the change in spins of such unpaired electrons under the influence of an external
magnetic field. Similarly to NMR, the observed energy changes are also small
(although about 2 orders of magnitude larger) and they are approximately 1 J/mol,
which corresponds to the microwave radiation frequency of approximately
3 1010 Hz. The obtained data allow analyzing direct environment of a given
atom and hence provide the information on the oxidation state, electron configu-
ration and coordination number of the paramagnetic ion, structural distortions due
Fig. 1.1 Main regions of electromagnetic spectrum with related spectroscopic techniques
1 Computational Methods in Spectroscopy 3
to, e.g., Jahn–Teller effect, or the degree of covalence of bonds formed by the ion
with surrounding atoms or ligands.
With the increase of radiation frequency, the energy of photons increases and
hence the possibility appears of studying phenomena in which energy changes are
higher and correspond to radiation with frequencies of about 1011–1013 Hz, e.g.,
molecular rotations and atomic vibrations in molecules and solids (the domain of IR
and Raman spectroscopy). While rotational spectra can only be obtained for
molecules (those with a permanent dipole moment) and thus provide the infor-
mation on the structure of such molecules (lengths of bonds and angles between
bonds), atomic vibrations are present in both, molecules and solids (amorphous and
crystalline), hence the vibrational spectroscopy (IR and Raman) [6] is a universal
method of studying the local structure of materials (force constants, bonds lengths,
angles, etc.) by analyzing normal modes of vibrations and changes in absorption
(IR) or scattering (Raman) of infrared radiation associated with structural changes
resulting, for example, from phase transitions or changes in chemical composition
(defects, admixtures, etc.).
The next group of spectroscopic methods is UV-Vis [7, 8] techniques related to
electronic transitions between different energy levels and the corresponding radi-
ation range, from near infrared, through visible region, to ultraviolet (about 1014–
1015 Hz). Various types of electronic transitions are possible, both between the low
lying localized levels of the internal shells of individual atoms and the levels of the
outermost valence shells (either localized on atoms or delocalized, forming bands).
Generally, there are four basic types of electron transitions:
• Excitation of an electron from a localized orbital to another localized orbital on
the same atom but with higher energy: The examples are d-d or f-f transitions in
compounds containing transition metals, transitions on outer shells in heavy
metals compounds (e.g., 6s–6p in lead(II) compounds), or transitions related to
defects (trapped electrons or holes, color centers);
• Excitation of an electron from a localized orbital on one atom to a higher energy
orbital localized on an adjacent atom (charge transfer processes, e.g., from
oxygen to chromium in tetrahedral [CrO4]2− anion);
• Excitation of an electron from a localized orbital on an atom to a delocalized
conduction band (e.g., photoconductive materials);
• Electron transitions from valence band to conduction band (e.g., in
semiconductors).
UV-Vis spectroscopy has a very wide range of applications related to the study
of the local structure of materials, because the positions of absorption bands are
very sensitive to the immediate surroundings and the nature of chemical bonding.
For example, by adding a small amount of spectroscopically active elements, such
as transition metals or p-block heavy metals (e.g., Pb2+), a number of information
on the local structure of amorphous materials can be obtained. Materials for lasers
often contain transition metal ions as active species, e.g., Al2O3 doped with Cr3+
(ruby laser) or Nd3+-doped glass (neodymium laser), and UV-Vis spectroscopy
4 A. Koleżyński
allows obtaining detailed knowledge about energy levels and possible transitions—
a key information from the point of view of effective laser working. UV-Vis
spectroscopy is also widely used in analytical chemistry, e.g., to determine the
concentration of ions, molecules, or functional groups responsible for individual
absorption peaks.
Electron spectroscopy methods [9–12] (XPS—X-ray photoelectron spec-
troscopy, UPS—ultraviolet photoelectron spectroscopy, or AES—Auger electron
spectroscopy) measure the kinetic energy of electrons emitted from the material as a
result of exposure to high energy ionizing radiation or high energy particles
bombardment. The main difference between XPS and UPS methods is in the atomic
shells which can be studied: The inner shells electrons can be ejected using higher
energy X-rays (frequencies around 1018 Hz), while valence shells electrons can be
ionized using lower energy ultraviolet light with the frequencies about 1016 Hz. The
kinetic energy of electrons measured by these methods is equal to the difference
between the energy ht of the used incident radiation and the binding energy
(ionization potential) of the emitted electron and depends strongly on the type of
atom from which the electron was emitted, its oxidation state, and its immediate
environment; whereby it is possible to use these techniques to identify the atoms of
a given element in the material, providing the basis for electron spectroscopy for
chemical analysis (ESCA) developed by Siegbahn et al. [13].
The method directly related to the XPS and UPS spectroscopy is the Auger
electron spectroscopy [11, 14], in which emitted electrons are not the electrons
primary ionized by X-ray or ultraviolet radiation, but the product of secondary
processes, i.e., decay of ionized atoms from excited states to lower energy states
associated with emission of a photon, which can be emitted (and measured by XPS
or UPS) or absorbed by the electron from outer shells, resulting in the emission of
such secondary ionized electron (called the Auger electron). Electron spectroscopy
methods are very important and useful methods to determine energy levels in atoms
and molecules. In the case of solids, they are particularly useful for studying the
local structure of the surface of materials, since due to the relatively low energy of
emitted electrons and their strong dissipation in the material, in practice it is pos-
sible to observe only electrons ejected from the surface layer with a thickness of up
to 5 nm.
Even higher energies than those used in electron spectroscopy require processes
of transitions between energy levels of atomic nuclei (around 1019 Hz). The method
that examines such processes is the Mössbauer spectroscopy [15, 16], based on the
Mössbauer effect (i.e., resonant and recoil-free emission and absorption of c-rays by
atomic nuclei in a solid). In Mössbauer spectroscopy, three types of nuclear
interactions are observed:
• Isomer shift (energy shift of the absorption peak resulting from the modification
of the energy levels of the nucleus by changes in the distribution of electron
density in the atom, due to the changes in the local environment of the atom; this
shift may, e.g., correlate with the electron density at atomic nucleus of the outer
s shells electrons);
• Quadrupole splitting (in the case of nuclei with nuclear spin I > ½, the distri-
bution of positive charge in the nucleus is not spherically symmetrical resulting
in quadrupole moment Q, which in turn results in the split of the nuclear energy
levels and hence the split of the corresponding absorption bands in the
Mössbauer spectrum);
• Magnetic hyperfine Zeeman splitting (when the atomic nucleus with spin I will
be subjected to the magnetic field, then each nuclear energy level splits into
2I + 1 levels).
The source of radiation in this method is a highly monochromatic gamma-ray
beam whose energy is changed using the Doppler effect: The sample is fixed and
the radiation source moves at a constant velocity toward or away from the sample,
and as a result, the energy of radiation incident on the sample increases or decreases
with respect to the primary energy of radiation. In this way, an absorption spectrum
of gamma radiation is created, the analysis of which allows obtaining information
about the local structure (oxidation state, coordination number, nature of binding,
etc.) and precisely measuring—due to a high energy and extremely narrow line
widths of c-rays—small energy changes in nuclei, atoms, and crystals induced by
electrical, magnetic, or gravitational field. The studies of hyperfine splitting,
especially as a function of temperature, allow additionally obtaining information on
the ordering of magnetic materials.
Theoretical studies on the above-mentioned spectroscopic methods are cur-
rently conducted in practice only with the help of methods based on the for-
malism of quantum mechanics. In practice, only in the case of vibrational
spectroscopy, it is possible to use classical methods (both stationary-molecular
mechanics and dynamical—molecular dynamics), in which atoms are treated as
charged particles, and their interactions are described by means of analytic two
and more center functions, the so-called interatomic potentials. It is then possible
to calculate the total potential energy of such a classical system, hence the forces
acting on individual atoms and their minimization (relaxation of the structure),
and then calculating (for the relaxed structure) the frequencies of normal modes
of vibrations and simulation of vibrational spectra. However, due to the lack of a
correct description of the electron density, such an approach does not allow to
analyze the processes dealt with by other spectroscopic methods mentioned
above, and therefore, in remaining parts of this chapter, classical methods will not
be further discussed.
1.2 Theoretical Foundations for Modeling of Real Systems

and Processes Studied by Spectroscopic Methods
The physical reality that surrounds us is extremely complex and impossible to be

accurately described using available physical theories. This applies in particular to
the micro-world and the structure and properties of materials of various sizes and
6 A. Koleżyński
level of complexity, starting with the simplest atoms, through molecules and
clusters, to amorphous and periodic solids. In the past, experimental studies were
the main and, in some cases, practically the only source of knowledge about the
properties of materials. The development of computer technology and theoretical
methods leads gradually to the increasing use of computer calculations and simu-
lations (the so-called in silico experiments) in materials research, which in many
cases becomes an equivalent (and sometimes also the first, preliminary) tool
allowing understanding of the properties of materials and their modification and
functionalization.
Among the theoretical methods used in material research, the so-called ab initio
methods (methods from the first principles), whose basic idea is to treat
multi-atomic systems as systems of many bodies composed of atomic nuclei and
electrons and to analyze them employing quantum mechanics—the arguably most
important contemporary physical theory, without using any empirical parameters.
In the following few sections, the most important ingredients of quantum
mechanics formalism as well as the density functional theory, rooted in this
formalism (and nowadays the dominant approximation used in theoretical cal-
culations), required for their practical application in modeling of the properties of
complex many-body systems will be presented. Apart from the above-mentioned
“static” methods, i.e., methods based on the solutions of appropriate equations
formulated for stationary states, there are also other, computationally much more
complex and demanding, dynamic (ab initio molecular dynamics allowing to
study the changes of system state with time) and statistical approaches (ab initio
quantum Monte Carlo, allowing going beyond the mean field theory and
independent electrons approximations and direct treatment and description of
complex interactions in many-body systems). However, due to the limited volume
of the chapter and still relatively rare use of these methods, they will not be
presented here and interested readers are referred to the rich literature devoted to
this topic [e.g., 17–21].
1.2.1 Ab Initio Methods
1.2.1.1 Schrödinger Equation
The physical theory describing the phenomena occurring in the micro-world, and
therefore also the processes studied by various spectroscopic methods, is quantum
mechanics. The most popular formulation of quantum theory is the formalism of
wave mechanics proposed by Erwin Schrödinger [22–27]. The starting point in
Schrödinger’s formulation is a number of postulates regarding the wave function of
complex values (representing the state of the system), linear Hermitian operators
and their eigenvalues (mathematical representations of observable quantities, the
so-called observables), a recipe enabling finding an operator associated with a given
observable, a description of the measurement process and a way of predicting its
possible results (measurement problem, collapse of the wave function), which

culminates in the formulation of the equation describing the evolution of the state of
the system, the so-called time-dependent Schrödinger equation (TDSE):
@Wðr; tÞ ^
ih ¼ HWðr; tÞ ð1:1Þ
@t
where W—wave function describing the state of the system and h—Planck’s
^
constant h, divided by 2p. The Hamiltonian H of the system (the total energy
operator) used in the Schrödinger equation is defined as:
2 2
^ ¼ h @ þ @ þ @ þ Vðr; tÞ ¼
h2 2
2 2
^ ¼ T^ þ V
H r þ Vðr; tÞ ð1:2Þ
2m @x2 @y2 @z2 2m
and the time-dependent Schrödinger equation takes its final form:
@Wðr; tÞ h2 2
ih ¼ r Wðr; tÞ þ V ðr; tÞWðr; tÞ ð1:3Þ
@t 2m
In the vast majority of cases, when we model a given system we are interested in
its properties at stationary state (ground or excited), which is why we are usually
interested in solving the so-called time-independent Schrödinger equation (TISE). If
we assume that in the stationary state the external potential is constant, independent
of time V ðr; tÞ ¼ VðrÞ, then we can perform a mathematical operation of separating
the variables and write the function of the state of the system as:
Wðr; tÞ ¼ wðrÞTðtÞ ð1:4Þ
The Schrödinger equation then takes the form:

h2 2 @
h ½wðrÞTðtÞ
r þ VðrÞ wðrÞTðtÞ ¼ i ð1:5Þ
2m @t
which after the transformation gives the equation:
h2 1 1 dTðtÞ
r2 wðrÞ þ VðrÞ ¼ i
h ð1:6Þ
2m wðrÞ TðtÞ dt
true for all r and t, so both sides must be equal to constant E, called the separation
constant. In this way, we obtain two independent equations describing the depen-
dence of the wave function, first on the position:
h2 1 ^
r2 wðrÞ þ VðrÞ ¼ E ) HwðrÞ ¼ EwðrÞ ð1:7Þ
2m wðrÞ
8 A. Koleżyński
and second on time:
1 dT ðtÞ
ih ¼E ð1:8Þ
T ðtÞ dt
The solution of the latter has the form T ðtÞ ¼ AeiEt=h , where E, is energy of
stationary state, one of the eigenvalues of the Hamiltonian operator defined for the
system in time-independent (stationary) state. Finally, the solution to the
Schrödinger equation has the form:
Wðx; tÞ ¼ wðxÞTðtÞ ¼ wðxÞeiEt=h ð1:9Þ
One can easily see that although the potential of V(r) is independent of time, the
wave function oscillates in time with the frequency depending on the energy cor-
responding to the current stationary state of the system (however, at the same time,
the probability distribution Pðx; tÞ ¼ jWðx; tÞj2 ¼ jwðxÞj2 , and therefore also the
distribution of total electron density, is constant in time).
Since the solution of the time-dependent part of Schrödinger equation is identical
in each case, in order to obtain full information about the system’s state and its
evolution over time, it is sufficient to find a solution for time-independent
Schrödinger equation, of the general form:
^
Hwðr 1 ; r2 ; . . .; rn ; Ra ; Rb ; . . .; Rm Þ ¼ Ewðr1 ; r2 ; . . .; ri ; Ra ; Rb ; . . .; Rm Þ ð1:10Þ
where ri and Ra—the coordinates of electrons and atomic nuclei, respectively, n—

number of electrons, m—number of atomic nuclei, and respective total energy
operator assumes the form:
X 1 h2 X 2 X X Za Zb e2
b ¼ h
2
b ¼T
H bþV r2a ri þ
2 a
ma 2me i a a[b
rab
ð1:11Þ
X X Za e2 X X e2
þ
a i
ria j
r
i [ j ij
Except for a few simplest cases, finding an exact, analytical solution of this
equation is impossible, and thus, some simplifications are usually necessary to be
used and solutions are obtained in numerical form.
1.2.1.2 Born–Oppenheimer Approximation, Potential Energy

Hypersurface
The first simplification, bringing us closer to the solution of the time-independent

Schrödinger equation for a multi-electron system, is called Born–Oppenheimer
approximation (BOA). This approximation is rooted directly in the simple observation
that since nuclei are much heavier then electrons (approximately 103–105 times,
depending on the number of protons and neutrons making up particular nucleus), they
move much slower than electrons which have a response time of the order of fem-
toseconds and can adjust themselves almost instantaneously to the new atomic con-
figuration (thus—from electrons’ point of view—nuclei seem to be clamped and the
idea goes, we can treat the motions of electrons and nuclei as independent). In this
case, the effective interactions between the atoms take place via electrons, and we
carry out the calculations looking for a solution for the ground state of the electron
cloud, for the assumed, fixed spatial configuration of motionless atoms. The
assumption of the independent movement of the atomic nuclei and electrons allows
separation of the variables describing their positions and writing the multi-electron
wave function as a productof two functions: one dependent only on nuclei positions
(nuclei wave function wN Ra ; Rb ; . . .; Rm ) and the other on positions of electrons

(electronic wave function wel r1 ; r2 ; . . .; rn ; Ra ; Rb ; . . .; Rm ) and current geometry
(nuclei positions):

w r1 ; r2 ; :::; rn ; Ra ; Rb ; :::; Rm ¼ wel r1 ; r2 ; :::; rn ; Ra ; Rb ; :::; Rm wN Ra ; Rb ; :::; Rm
ð1:12Þ
This enables us to solve the electron and nuclear Schrödinger equation sepa-
rately, starting with the one for electrons:
^ el wel ðr; RÞ ¼ Eel wel ðr; RÞ
H ð1:13Þ
where
2 X X X Za e2 X X e2
^ el ¼ h
H r2i þ ð1:14Þ
2me i a i
ria r
j i [ j ij
The Born–Oppenheimer approximation leads to a very important concept—the

potential energy hypersurface U(R):
X X Za Zb e2
UðRÞ ¼ Eel þ VNN ¼ Eel þ ð1:15Þ
a a[b
rab
Once we have the potential energy surface (PES), we can solve the nuclear
Schrödinger equation:
^ N wN ðRÞ ¼ E N wN ðRÞ
H ð1:16Þ
where
X 1
^ N ¼ h
2
H r2 þ U ðRÞ ð1:17Þ
2 a
ma a
10 A. Koleżyński
The solution of this equation allows obtaining information on the quality of the
initially adopted geometry of the studied system (spatial configuration of atoms).
Usually, the assumed geometry deviates from the equilibrium geometry and the
atoms are subjected to the forces that can be easily calculated (as a potential energy
gradient with respect to the atomic position). Information about forces acting on
atoms allows the geometry modification (optimization) by changing the positions of
all atoms according to the direction and magnitude of the respective forces and
repeating the total energy calculations, another forces estimation, geometry modi-
fication according to new forces calculated, and repeating the whole procedure until
the calculated forces on the atoms are smaller than the assumed precision. In
most cases, the relaxation of the structure (minimization of forces on atoms) is a
necessary step in the calculation, because the majority of physical quantities that are
of interest is defined for systems that are in the minimum of potential energy well
(relaxed, equilibrium geometry).
1.2.1.3 Hartree–Fock Method and Post-HF Extensions
The solution of the nuclear time-independent Schrödinger equation allows deter-

mination of a large variety of molecular properties (e.g., vibrational energy levels,
phonon dispersion in crystals). But this is just the first step, since by employing
Born–Oppenheimer approximation we have simplified our Hamiltonian a little; but
we still have to solve electronic TISE for our multi-electron system, which is
impossible to be done exactly (the reason being the last term in electronic
Hamiltonian, namely electron–electron interactions) and we need to make further
approximations. Since we cannot calculate exactly very complicated electron–
electron interactions, let us assume that electrons are independent from each other
and every single electron is moving in an effective single-particle potential due to
all fixed nuclei and the average electron density distribution of all remaining
electrons. This simple idea, called independent electrons approximation (IEA) , was
first formulated by Hartree [28] and led to the development of famous Hartree–
Fock SCF method, consisting of a set of self-consistent single-particle equations
with multi-electron wave function defined as a product of one-electron wave
functions (Hartree product).
wel ðr1 ; r2 ; . . .; rN Þ ¼ /1 ðr1 Þ/2 ðr2 Þ /N ðrN Þ ð1:18Þ
Since such simple product does not fulfill the requirement for electronic wave
function of the system to be antisymmetric (due to Pauli’s Exclusion Principle,
which electrons—as indistinguishable fermions—have to obey) while the linear
combination of different products does, the original Hartree product was replaced
later by antisymmetric-by-definition Slater determinant (with (spin)orbitals as its
elements) of the form:

/1 ðr1 Þ /1 ðr2 Þ /1 ðrN Þ

1 /2 ðr1 Þ /2 ðr2 Þ /2 ðrN Þ
wel ðr1 ; . . .ri ; . . .; rj ; . . .; rN Þ ¼ pffiffiffiffiffi . .. .. ð1:19Þ
N! .. . .

/ ðr1 Þ /N ðr2 Þ /N ðrN Þ
N
In the general case, the wave function for the N-electron system can be written in
the form of a linear combination of Slater determinants (including in the determi-
nants also partially occupied spinorbitals for excited states, empty in the ground
state):
X
wel ¼ di Ui ¼ d0 U0 þ d1 U1 þ d2 U2 þ ð1:20Þ
i
^ el of the form (1.14)

A more detailed analysis of the electron energy operator H
shows that it consists of two types of contributions:
• One-electron contribution (depending on the coordinates of only one electron):
P
n P
m
^hi where ^hi ¼ Tê þ V
^Ne ¼ h2 r2i Za e 2
ð1:21Þ
2me ria
i¼1 a¼1
• Two-electron contribution (depending on the coordinates of two electrons):
X X e2
^ ee ¼
V ð1:22Þ
j
r
i [ j ij
The former can be calculated accurately, whereas the two-electron contributions

can only be approximated, due to the complexity of interelectronic interactions. The
potential energy associated with two-electron interactions is equal to:
n X
X n
Vee ¼ Jee Kee ¼ ðJij Kij Þ ð1:23Þ
i j[i
where Jij is a Coulomb integral defined as:

ZZ
1
Jee ¼ /2i ð1Þ /2j ð2Þdr1 dr2 ð1:24Þ
r12
describing Coulomb repulsion between electron 1 on orbital i and electron 2 on

orbital j, while Kij is the exchange integral (nonzero only for like-spin electrons),
12 A. Koleżyński
with no classical interpretation—this integral is entirely a quantum mechanical

effect resulting from fermions’ antisymmetry.
ZZ
1
Kee ¼ /i ð1Þ/j ð2Þ /i ð2Þ/j ð1Þdr1 dr2 ð1:25Þ
r12
In order to be able to solve this Schrödinger equation, we must replace the

êe with an approximate, effective, one-electron operator
electron–electron operator V
êff :
V
X
n
êff ðiÞ ¼
V 2^Jj ðiÞ K
^ j ðiÞ ð1:26Þ
j
where
Z
^Jj ð1Þ ¼ 1
uj ð2Þ u ð2Þdr2 ð1:27Þ
r12 j
Z
^ j ð1Þui ð1Þ ¼ 1
K uj ð2Þ u ð2Þdr2 uj ð1Þ ð1:28Þ
r12 i
and as a result, the so-called one-electron Fock operator is obtained:
X
^fi ¼ h r2
2 m
Za e2 ^
þ V eff ðiÞ ð1:29Þ
2me i a¼1
ria
Using variational principle:

w Hw ^ trial w Hw ^ trial
hEtrial i ¼ trial Eexact ; d trial ¼0 ð1:30Þ
wtrial wtrial wtrial wtrial
to the problem of energy minimization, we get a set of appropriate one-electron

Hartree–Fock equations:
^fi /ðiÞ ¼ ei /ðiÞ; i ¼ 1; 2; . . .; N ð1:31Þ
One-electron Fock operator ^fi depends, through effective potential V

êff ðiÞ, on the
one-electron wave functions /ðiÞ of all other electrons, and the Hartree–Fock
equations, despite the form resembling a classical eigenvalue problem, are not
possible to be solved directly; hence, it is necessary to perform calculations itera-
tively (using the so-called self-consistent field—SCF method):
• A set of one-electron initial functions (orbitals) is defined and respective Fock
operator is calculated;
• Next, the system of Hartree–Fock equations is solved;

• The set of new orbitals being the solution of the HF equations is used in the next
cycle of calculations to determine a new Fock operator;
• The system of Hartree–Fock equations with the new Fock operator is solved;
• The last two steps are repeated until the orbitals used to define the Fock operator
and the orbitals obtained as a result of solving the system of HF equations with
this operator (or total energies) differ by less than the predetermined, required
maximum error (i.e., until we get a self-consistent solution).
By applying these two approximations (BOA and IEA) to initial TISE, we have
made a big step toward the practical applicability of QM to real systems. But one
thing remains unresolved—we have assumed electrons to be independent particles,
but we have to define yet the functions describing (spin)orbitals in Slater deter-
minant—the state vectors of these electrons. Since we do not know the exact form
of such functions, we are forced to make some assumptions about their shape and
usually define these functions as a linear combination of some analytical functions
and search for the best form (best expansion coefficients for chosen set of analytical
functions) employing variational principle. In principle, one can choose any
functions, but in practice, due to the numerical efficiency, only limited set of various
analytical functions is used—depending on the system of interest, the functions
which “mimic” the electron distribution of real system best, are chosen, since this
can greatly decrease the number of calculation cycles and thus the time necessary to
carry out the calculations. For molecular system, the usual choice are atomic
orbitals (AO)—one can safely assume that when atoms approach each other and
start to form the molecule, the resulting electron density distribution will change,
but will resemble, even in case of valence electrons, the original atomic distribution
and thus the linear combination of such atomic orbitals, defining the shape of
molecular orbital should be the most efficient one in molecular system. But again—
since the exact form of atomic orbitals is not known, one can further approximate
AO by means of linear combination of some simple analytical functions. Originally
Slater-type orbitals were used, but later, due to their numerical inefficiency, they
were substituted in most quantum chemical codes by Gaussian-type orbitals,
functions poorly describing the density distribution (so we need more of them in
linear combination), but definitely more efficient numerically, which more than
enough compensates their inefficient shape. Such Gaussian-type orbitals can be
single Gaussian functions (primitives) or their linear combination (contracted).
Currently, many predefined basis sets (depending on a definition of atomic orbitals
by means of Gaussian functions) is available, and the user is responsible for a
choice of the basis set (theory level) best suited for the system being studied. In case
of periodic solids, where one can find both extreme cases (metals and molecular
crystals) and a whole lot of intermediate ones, electrons can be described by plane
waves (best suited for metals) or atomic orbitals (best for molecular crystal). One
can use either of them (having in mind that their efficiency will be quite different
depending on the crystal studied) or some kind of hybrid functions like (L)APW,
ASW, (L)ASO, (L)MTO, to name the few—see, e.g., [29] for more details.
14 A. Koleżyński
Since the original HF method does not (by definition) take into account electron
correlation effects, in order to get the results in better agreement with experiment, a
few extensions, the so-called post-HF methods, have been proposed in following
years, e.g., CI—Configuration interaction [30–32], MP2 [33, 34], MP3 [35, 36],
and MP4 [37] Møller–Plesset Perturbation Theory, CC—Coupled Cluster Theory
[38, 39], QCI—Quadratic Configuration Interaction [40], CASSCF—Complete
Active Space Self-Consistent Field calculation [41, 42], MRSDCI—
Multi-Reference Single and Double Configuration Interaction [43] or Quantum
Chemistry Composite methods, like Gaussian G1 [44, 45], G2 [46], G3 [47], and
G4 [48], FPD Feller–Peterson–Dixon approach [49, 50], ccCA—correlation con-
sistent Composite Approach [51], or CBS—Complete Basis Set methods [52]. Such
extensions improved considerably the quality of calculations, but at the expense of
significantly higher demand for computer resources and calculation time (in the
worst-case scenario, calculation time increases fivefold with the size of the system,
comparing to original HF method).
1.2.1.4 Density Functional Theory
HF method with post-HF extensions is still commonly used (especially by chemists

interested in molecular compounds), but in recent years the Density Functional
Theory (DFT) approach became to dominate in computational physics and in great
part of computational chemistry. The origins of density functional theory go back to
the first years of the twentieth century and the works of Thomas [53] and Fermi [54],
describing the properties of multi-electron systems using total electron density,
extended in following years by Dirac [55] (exchange energy term) and Weizsäcker
[56] (first-order correction for kinetic energy functional). These attempts turned out,
however, to be unsatisfactory, due to, inter alia, approximate character of the
expression for kinetic and exchange energy and complete neglect of electron corre-
lation resulting in fundamentally wrong description of chemical bonding: The cal-
culated total energy of any molecule was higher than the sum of the energies of
isolated atoms, and therefore, Thomas–Fermi–Dirac model predicted molecules to be
unstable [57]. The problem of inaccurate description of kinetic energy in the Thomas–
Fermi–Dirac–Weizsäcker model was circumvented in Kohn–Sham’s Density
Functional Theory (with electron density as a key variable in the description of the
properties of non-uniform electron gas in multi-electron systems) for which firm
mathematical foundation was given in 1964 in two Hohenberg–Kohn theorems [58].
The starting point in density functional theory is the Born–Oppenheimer
approximation, resulting in constant external Coulomb potential Vext(r), generated
by motionless atomic nuclei, in which all electrons move:
X Za e2
Vext ðrÞ ¼ ð1:32Þ
a
j r ra j
Hence, the system Hamiltonian is defined as the sum of two operators:

X 1XX 1
^ ¼ 1
F r2i þ ð1:33Þ
2 i
2 i j6¼i ri rj
And
X
êxt ¼
V Vext ðri Þ ð1:34Þ
i
Functional F^ is the same for each N-electron system; therefore, the Hamiltonian
and the ground state W are completely defined by N and Vext(r), and the W
eigenstate corresponds to the electron density n(r), expressed as:
Z
nðrÞ ¼ N jWðr; r2 ; . . .; rN j2 dr2 . . .drN ð1:35Þ
According to the first Hohenberg–Kohn theorem, the ground state properties of

such multi-electron system are uniquely determined by the total electron density
and there is an unequivocal mapping Vext(r) $ n(r) (one-to-one correspondence)
between the external potential Vext(r) and the total electron density of the ground
state n(r) (and therefore, the electron density of the ground state is uniquely
determined by the external potential and at the same time this potential is uniquely
determined by the total electron density distribution of the ground state).
The second Hohenberg–Kohn theorem states that the total energy of the system
of N interacting electrons, subjected to the external potential Vext(r), is a functional
of the total electron density n(r):
Z
E½nðrÞ ¼ F½nðrÞ þ nðrÞVext ðrÞdr ð1:36Þ
and reaches the minimum for the total N-electron density of the ground state in the
external potential Vext(r). The ground state energy of such a system can be calcu-
lated using the variational method, since for each density n′(r) that is not eigenstate
of the external potential Vext(r), Ev[n′(r)] > Ev[n(r)], where the electron density that
minimizes the total energy of the system is the exact density of the ground state
(however, this is true only for the exact functional Ev[n(r)]).
An extraordinary result of DFT is the demonstration of the existence of a uni-
versal functional F[n(r)], independent of external potential, which means that instead
of dealing with the N-electron wave function, we operate on the electron density, i.e.,
three-dimensional spatial coordinates function. The level of complexity of the
problem is thus dramatically reduced and scales linearly with the size of the system
(compare the HF method, where the problem scales with second– third power).
Unfortunately, the exact form of the functional F[n(r)] is unknown and the practical
16 A. Koleżyński
problem faced by DFT (finding an approximate function) results directly from the
complexity of the problem of interacting electrons in many-body system.
Kohn and Sham [59] have reformulated the above problem by replacing the
system of N interacting electrons with a special reference system—the system of
N non-interacting electrons, having the same ground electron density. In the case of
such a reference system, this electron density is equal to the sum over the
one-electron wi(r) orbitals (Kohn–Sham orbitals):
X
N=2
nðrÞ ¼ 2 jwi ðrÞj2 ð1:37Þ
i¼1
being a solution to the following Schrödinger equations:
1
r2 þ VKS ðrÞ wi ðrÞ ¼ ei wi ðrÞ ð1:38Þ
2
and satisfying the orthonormality condition:

Z

w ðrÞw ðrÞdr ¼ dij ð1:39Þ
i j
The existence of a uniquely determined VKS(r) potential for the ground state
electron density n(r) is a direct consequence of the first Hohenberg–Kohn theorem.
Therefore, we have a situation in which the problem of finding a universal func-
tional F[n(r)] was replaced by the problem of finding an effective VKS[n(r)] func-
tional. This problem can be solved using the variational principle. Lets write down
the energy in the form:
Z
E ¼ TS ½nðrÞ þ EH ½nðrÞ þ EXC ½nðrÞ þ nðrÞVext ðrÞdr ð1:40Þ
The first part is the kinetic energy of the system of non-interacting electrons:
Z
h2 X
N=2
TS ½nðrÞ ¼ 2 wi ðrÞr2 wi ðrÞdr ð1:41Þ
2m i¼1
The second is Hartree energy, classic electrostatic energy:

Z
e2 nðrÞnðr 0 Þ
EH ½nðrÞ ¼ drdr 0 ð1:42Þ
2 jr r 0 j
and the last term is the classical Coulomb energy of electron interactions with
external potential. The key element in the expression for the energy of the system is
the third term whose exact form is unknown—this is the exchange and correlation
energy EXC[n(r)], containing non-classical electrostatic interactions and the differ-

ence in kinetic energy of the interacting and non-interacting particles systems. The
purpose of such energy partitioning is to separate the first two and the last, which
can be calculated accurately, giving together most of the total energy and third term,
a small part of the total energy, which contains the complex quantum effects of
multi-electron interactions (here our entire ignorance about the system is hidden).
According to the second H-K theorem, the energy of the ground state can be
calculated by minimizing the energy functional. The appropriate variational prob-
lem for the H-K density functional, when imposing the constraints on the number of
electrons N, takes the form:
R R
d F½nðrÞ þ nðrÞVext ðrÞdr k nðrÞdr N ¼ 0;
ð1:43Þ
F½nðrÞ ¼ Ts ½nðrÞ þ EH ½nðrÞ þ EXC ½nðrÞ
where k is undetermined Lagrange multiplier associated with constraints on the

number of electrons N, and the corresponding Euler equation has the form:
dF½nðrÞ
l¼ þ Vext ðrÞ ð1:44Þ
dnðrÞ
In Kohn–Sham’s formulation, respective Euler’s equation transforms into:
dTS ½nðrÞ
l¼ þ VKS ðrÞ ð1:45Þ
dnðrÞ
where
VKS ðrÞ ¼ Vext ðrÞ þ VH ðrÞ þ Vxc ðrÞ ð1:46Þ
and
Z
dEH ½nðrÞ nðrÞ dEXC ½nðrÞ
VH ðrÞ ¼ ¼ dr 0 ; VXC ðrÞ ¼
dnðrÞ jr r 0 j dnðrÞ ð1:47Þ
Both Euler equations are equivalent, which means that the density obtained as a
solution to the variational problem for the KS reference system is identical to the
density obtained for the original system of N interacting electrons and can be in
practice obtained by solving a system of N one-electron Schrödinger equations
(Kohn–Sham equations):

1
r2 þ VKS ðrÞ wi ðrÞ ¼ ei wi ðrÞ ð1:48Þ
2
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service. Accordingly, kings not infrequently made demands upon
the abbey to use its buildings. Thus the chapter house became a
frequent place for meetings of parliament, and at a later time it
was used and continued to be used till the nineteenth century, for
the storage of official records. In the same way Edward secured
the crypt underneath the chapter house as one of the
storehouses of his Wardrobe. When the crypt was first used for
this purpose I do not know, but records show us that it was
already in use in 1291, at which date it was newly paved. It was
not the only storehouse of the Wardrobe. There was another
“treasury of the wardrobe” in the Tower of London, but this was
mainly used for bulky articles, arms and armour, cloth, furs,
furniture, and the like. Most of what we should call treasure was
deposited in the Westminster crypt, and we are fortunate in
having still extant a list of the jewels preserved there in 1298, the
time when the court began to establish itself for its five years’
sojourn in the north. In 1303 jewels and plate were still the chief
treasures preserved there. Some money was there also, notably
a store of “gold florins of Florence,” the only gold coins currently
used in England at a time when the national mints limited
themselves to the coinage of silver. But I do not think there could
have been much money, for Edward’s needs were too pressing,
his financial policy too much from hand to mouth, for the crypt at
Westminster to be a hoard of coined money, like the famous
Prussian Kriegsschatz at Spandau, which, we now rejoice to
learn, is becoming rapidly depleted. Whatever its contents,
Edward estimated that their value was £100,000, a sum
equivalent to a year’s revenue of the English state in ordinary
times. Unluckily mediaeval statistics are largely mere guess-work.
But the amount of the guess at least suggests the feeling that
the value of the treasures stored in the crypt was very
considerable.
The crypt under the chapter house is one of the most
interesting portions of the abbey buildings at Westminster. It is
little known because it is not, I think, generally shown to visitors.
I am indebted to the kindness of my friend, Bishop Ryle, the
present dean, for an opportunity of making a special inspection of
it. It is delightfully complete, and delightfully unrestored. The chief
new thing about it seems the pavement, but the dean’s well-
informed verger told me that it was within living memory that this
pavement had replaced the flooring of 1291. Numerous windows
give a fair amount of light to the apartment; though the enormous
thickness of the walls, some thirteen feet, it was said, prevent the
light being very abundant, even on a bright day. The central
column, the lower part of the great pillar from which radiates the
high soaring vaults of the chapter house above, alone breaks the
present emptiness of the crypt. Considerable portions of the
column are cut away to form a series of neatly made recesses,
and there are recesses within these recesses, which suggest in
themselves careful devices for secreting valuables, for it would be
easy to conceal them by the simple expedient of inserting a
stone here and there where the masonry had been cut away, and
so suggesting to the unwary an unbroken column. I should not
like to say that these curious store-places already existed in
1303; but there is no reason why they should not. Certainly they
fit in admirably with the use of the crypt as a treasury.
One other point we must also remember about the
dispositions of this crypt. There is only one access to it, and that
is neither from the chapter house above nor from the adjacent
cloister, but from the church itself. A low, vaulted passage is
entered by a door at the south-east corner of the south transept
of the abbey, now for many centuries the special burial place for
poets, eminent and otherwise. This passage descends by a flight
of steep steps to the crypt itself, and the flight originally seems, I
am told—doubtless as another precaution against robbery—to
have been a broken one suggesting that a steep drop,
presumably spanned by a short ladder, further barred access to
the crypt. We must remember, too, that this sole access to the
treasury was within a few feet of the sacristy of the abbey. The
sacristy was the chapel to the south of the south transept, and
communicating with it where the sacrist kept the precious vessels
appropriated to the service of the altar. Altogether it looks as if
the crypt were originally intended as a storehouse for such
church treasure as the sacrist did not need for his immediate
purposes. From this use it was diverted, as we have seen, to the
keeping of the royal treasures. Nowadays the sacristy is called
the chapel of St. Faith and is used for purposes of private
devotion. We must not forget the close connexion in our period of
the sacristy and the crypt. The connexion becomes significant
when we remember that among Pudlicott’s monastic boon
companions at the palace-keeper’s lodge was the sacrist of the
abbey, Adam of Warfield.
Pudlicott had made up his mind to steal the king’s treasure.
The practical problem was how to get access to it. If we examine
the evidence collected at the enquiry, we find that there are two
discrepant accounts as to how the robber effected his purpose.
The one is warranted by the testimony of a large number of
sworn juries of reputable citizens of every ward in the city of
London, of burgesses of Westminster, and of the good men of
every hundred in the adjacent shires of Middlesex and Surrey. It
is—like much truthful evidence—rather vague, but its general
tendency is, while recognizing that Pudlicott is the prime offender,
to make various monks and palace officers his accomplices. Of
the latter category William of the Palace seems to have been the
most active, while of the many monks Adam Warfield the sacrist
was the most generally denounced. But the proved share of both
Adam and William was based largely on the discovery of stolen
property in their possession. The evidence of the juries suggests
theories as to how the crime may have been perpetrated; it does
not make the methods of the culprits clear and palpable. But it
suggests that masons and carpenters were called in, so that
some breaking in of the structure was attempted, and in particular
it suggests that the churchyard was the thoroughfare through
which the robbers removed their booty.
Let us turn next to Pudlicott’s own confession, that remarkable

document from which I have already borrowed many details,
though seldom without a word of warning. According to his
confession, Pudlicott, having resolved to rob the treasury, came to
the conclusion that the best way to tackle the business was to
pierce a hole through the wall of thirteen feet of stone that
supported the lower story of the chapter house. For so colossal a
task time was clearly needed. Richard accordingly devoted
himself during the dark nights of winter and early spring to drilling
through the solid masonry. He attacked the building from the
churchyard or eastern side, having access thereto from the
palace. But the churchyard was open to the parish and the thrifty
churchwardens of St. Margaret’s had let to a neighbouring
butcher the right of grazing his sheep in it. Now the butcher was
told that his privilege was withdrawn, and passers-by were sent
round by another path. This was a precaution against the casual
wayfarer seeing the hole which was daily growing larger. To hide
from the casual observer the great gash in the stonework,
Richard tells us that he sowed hempseed in the churchyard near
the hole, and that this grew so rapidly that the tender hemp
plants not only hid the gap in the wall, but provided cover for him
to hide the spoils he hoped to steal from the treasury. When the
hole was complete on 24 April, Pudlicott went through and found
to his delight that the chamber was full of baskets, chests, and
other vessels for holding valuables, plate, relics, jewels, and gold
florins of Florence. Richard remained in the crypt gloating over
the treasure surrounding him from the evening of 24 April to the
morning of 26 April. Perhaps he found it impossible to tear
himself away from so much wealth; or perhaps the intervening
day, being the feast of St. Mark, there were too many people
about, and too many services in the abbey to make his retreat
secure. However, he managed on the morning of 26 April to get
away, taking with him as much as he could carry. He seems to
have dropped, or to have left lying about, a good deal that he
was unable to carry, possibly for his friends to pick up.
Such is Pudlicott’s story. It is the tale of a bold ruffian who

glories in his crime, and is proud to declare “I alone did it”. But
there was a touch of heroism and of devotion in our hero thus
taking on himself the whole blame. He voluntarily made himself
the scapegoat of an offence for which scores were charged, and
in particular he took on his own shoulders the heavy share of
responsibility which belonged to the negligent monks of
Westminster. Now as to the credibility of Pudlicott’s story, we
must admit that some of the juries accepted evidence that
corroborated some parts of it. Sworn men declared their belief
that the crypt was approached from the outside; that masons and
carpenters were employed on the business; that the churchyard
was closely guarded, and access refused, even to the butcher
who rented the grazing. It is clear too that the booty was got rid
of through the churchyard, and that piecemeal. There is evidence
even that hemp was sown, though the verdict of a jury cannot
alter the conditions of vegetable growth in an English winter. We
must allow too that it is pretty certain that Warfield had not the
custody of the keys of the crypt; though he was doubtless able to
give facilities for tampering with the door or forcing the lock. Yet
Pudlicott’s general story remains absolutely incredible. It was
surely impossible to break through the solid wall, and no
incuriousness or corruption would account for wall-piercing
operations being unnoticed, when carried on in the midst of a
considerable population for three months on end. Some of
Pudlicott’s lies were inconceivable in their crudity. Is it likely that
hemp, sown at Christmas-time, would, before the end of April,
afford sufficient green cover to hide the hole in the wall, and to
secrete gleaming articles of silver within its thick recesses? And
how are we to believe that there was a great gaping hole in the
wall of the crypt when nothing was heard of the crime for several
weeks after its perpetration, and no details of the king’s losses
were known until two months after the burglary, when the keeper
of the Wardrobe unlocked the door of the treasury and examined
its contents? A more artistic liar would have made his confession
more convincing.
What really happened seems to me to have been something
like this. I have no doubt that Pudlicott got into the treasury by
the simple process of his friend, Adam of Warfield, giving him
facilities for forcing the door or perhaps breaking a window. He
remained in the crypt a long time so that he might hand out its
contents to confederates who, as we learn from the depositions,
ate, drank, and revelled till midnight for two nights running in a
house within the precincts of the Fleet prison, and then went
armed and horsed to Westminster, returning towards daybreak
loaded with booty. But not only the revellers in Shenche’s
headquarters, but many monks, many abbey servants, the
custodians of the palace, the leading goldsmiths of the city, and
half the neighbours must have been cognisant of, if not
participating in, the crime. It speaks well for honour among
thieves, that it was not until deplorable indiscretions were made
in the disposal of the booty that any news of the misdeed
reached the ears of any of the official custodians of the treasure.
Suspicion of the crime was first excited by the discovery of
fragments of the spoil in all sorts of unexpected places. A
fisherman, plying his craft in the then silver Thames, netted a
silver goblet which had evidently been the property of the king.
Passers-by found cups, dishes, and similar precious things hidden
behind tombstones and other rough hiding-places in
St. Margaret’s Churchyard. Boys playing in the neighbouring fields
found pieces of plate concealed under hedgerows. Such
discoveries were made as far from Westminster as Kentish Town.
Moreover, many other people lighted upon similar pieces of
treasure trove. Foreign money found its way into the hands of the
money-changers at London, York, and Lymm, and other remote
parts. The city goldsmiths were the happy receivers of large
amounts of silver plate, among them, I regret to say, being
William Torel, the artist-goldsmith, whose skill in metal work has
left such an abiding mark in the decorations of the abbey church.
There were, too, scandalous stories whispered abroad. One of
them was that a woman of loose life explained her possession of
a precious ring by relating that it was given her by Dom Adam
the sacrist “so that she should become his friend”.
Such tales soon made the story of the robbery common

property. At last it came to the ears of the king and his ministers,
then encamped at Linlithgow for the Scottish war. Thereupon, on
6 June, the king appointed a special commission of judges to
investigate the matter. On 20 June, John Droxford, the keeper of
the wardrobe, came to Westminster with the keys of the crypt,
and then and only then did any official examination of the
treasury take place. An entry was made into the crypt and the
damage which had been done was inspected. The result is still to
be read in an inventory of the treasures lost and the treasures
found which Droxford drew up, and which may now be studied in
print.
It is pleasant to say that by the time Droxford went to work
much of the treasure, which had been scattered broadcast, was
being brought back and that more was soon to follow. The first
investigations as to where the treasure had been carried led to
fruitful results. A good deal of it was found hidden beneath the
beds of the keeper of the palace and of his assistant. Still more
was found in the lodgings of Richard Pudlicott and his mistress.
Adam the sacrist, and some of his brother monks and their
servants, were discovered to be in possession of other missing
articles. Altogether, when Droxford had finished his inventory, a
large proportion of the articles which had been lost were
reclaimed. Ultimately it seems that the losses were not very
severe.
Wholesale arrests were now made. Richard Pudlicott was
apprehended on 25 June, and William of the Palace soon
experienced the same fate. Before long the connexion which the
monks had had with the business seemed so well established
that the whole convent, including the abbot and forty-eight monks,
were indicted and sent to the Tower, where they were soon
joined by thirty-two other persons. This time the king’s net had
spread rather too widely, and the indiscriminate arrest of guilty
and innocent excited some measure of sympathy, even for the
guilty. The majority of the clerical prisoners were released on bail,
but some half-dozen laymen and ten monks were still kept in
custody. Both the released and the imprisoned culprits raised a
great outcry, sending petitions to the king demanding a further
enquiry into the whole matter.
The first commission meanwhile had been empanelling juries

and collecting evidence. But the matter was so serious that in
November a second royal commission was appointed to hear and
determine the matter. The members of this second commission
were chosen from among the most eminent of the king’s judges,
including the chief justice of the king’s bench, Sir Roger
Brabazon and the shrewdest judge of the time, William Bereford,
afterwards chief justice of common pleas.
I have already indicated in outline the result of the
investigations of the two judicial commissions. I have told you
how juries were empanelled from every hundred in the counties
of Middlesex and Surrey, and from the wards of the city of
London and from Westminster. The details of the evidence are
worthy of more special treatment than I can give them here,
because they afford a wonderful picture of the loose-living, easy-
going, slack, negligent, casual, and criminal doings of mediaeval
men and women. I must, however, be content to restate the
general result of the trials. Richard of Pudlicott was found guilty.
Various other people, including William of the Palace, and certain
monks, were declared accomplices, while Adam Warfield was
shrewdly suspected to be at the bottom of the whole business.
More than a year was spent in investigations, and it was not until
March, 1304, eleven months after the burglary, that William of the
Palace and five other lay culprits were comfortably hanged.
The great problem was how to deal with the clerical offenders
without adding to the king’s difficulties by rousing the sleeping
dogs of the church, always ready to bark when the state
meditated any infringement of the claim of all clerks to be subject
solely to the ecclesiastical tribunals. Accordingly Richard of
Pudlicott, and ten monks were reserved for further treatment.
Pudlicott, as we have seen, had been a tonsured person in his
youth, and he probably claimed, as did the monks, benefit of
clergy. It was probably now that Pudlicott nobly tried to shield his
monastic allies by his extraordinary confession. His heroism,
however, availed him nothing. But whatever his zeal for the
church, Edward I was upon adequate occasion ready to ride
rough-shod over clerical privileges, and he always bitterly
resented any attempt of a culprit, who had lived as a layman,
trying to shield himself on the pretext that he had been a clerk in
his youth. His corrupt chief justice, Thomas Weyland, had sought
to evade condemnation by resuming the tonsure and clerical garb
which he had worn before he abandoned his orders to become a
knight, a country squire, and the founder of a family of landed
gentry. But Weyland’s subdiaconate did not save him from exile
and loss of land and goods. Pudlicott’s sometime clerical
character had even less power to preserve him. He also paid
tardily the capital penalty for his misdeed. But it was surely his
clergy that kept him alive in prison for more than two years after
the date of the commission of his crime.
The Outrage at Westminster.
The fate of the incriminated clerks still hung in the balance
when in the spring of 1305 Edward came back in triumph to
London, rejoicing that at last he had effected the thorough
conquest of Scotland. His cheerful frame of mind made him listen
readily to the demands of the monks of Westminster to have pity
on their unfortunate brethren, and to comply with the more
general clerical desire that ecclesiastical privilege should be
respected. Only a few months after the burglary, the news of the
outrage on pope Boniface VIII at Anagni had filled all
Christendom with horror. At the instance of Philip the Fair, king of
France, and his agents in Italy the pope was seized, maltreated,
and insulted. In the indignant words of Dante, “Christ was again
crucified in the person of his vicar”. The universal feeling of
resentment against so wanton a violation of ecclesiastical
privilege was ingeniously used in favour of the monks of
Westminster. Among the monks, arrested at first, but soon
released with the majority of their brethren, were two men who
had some reputation as historians. One of these was
magnanimous enough to write, two or three years afterwards, a
sort of funeral eulogy of Edward, but the other, Robert of
Reading, who, in my opinion, kept the official chronicle of the
abbey from 1302 to 1326, set forth the Westminster point of view
very effectively in the well-known version of the chronicle called
Flores Historiarum, the original manuscript of which is now in the
Chetham Library. In this is given what may be regarded as the
official account of Richard’s burglary. The robbery of the king of
England was a crime only comparable to the robbery of the
treasure of Boniface VIII, six months later at Anagni. The
chronicler is most indignant at the suggestion that the monks had
anything to do with the matter, and laments passionately their
long imprisonment and their unmerited sufferings. He relies in
substance on the story as told in Pudlicott’s confession. The
burglary was effected by a single robber.
So lacking in humour was the Westminster annalist that he
did not scruple to borrow the phraseology and the copious
Scriptural citations of a certain “Passion of the monks of
Westminster according to John,” the whole text of which is
unfortunately not extant. I may say, however, that the species of
composition called a “Passion” was particularly in vogue at the
turn of the thirteenth and fourteenth centuries, and is mainly
characterised by its extraordinary skill in parodying the words of
the Scripture in order to describe in mock heroic vein some
incident of more or less undeserved suffering. For profanity, grim
humour, and misapplied knowledge of the Vulgate the “passions”
of this period have no equal. They are a curious illustration of the
profane humour of the mediaeval ecclesiastic in his lighter
moments.
The Westminster annalist did not stand alone. Other monastic
chroniclers took up and accepted his story. It became the
accepted monastic doctrine that one robber only had stolen the
king’s treasure, and that therefore the monks of Westminster
were unwarrantably accused. One writer added to his text a
crude illustration of how, it was imagined, Pudlicott effected his
purpose. You may see opposite this page his rude pictorial
representation of the “one robber” kneeling on the grass in the
churchyard, and picking up by a hand and arm extended through
the broken window the precious stores within. But Pudlicott’s arm
must have been longer than the arm of justice to effect this
operation, and must have been twice or thrice the length of a tall
man. This same chronicler was not contented with repeating the
parallel now recognised between the sufferings of the monks of
Westminster, under their unjust accusations, and the passion of
pope Boniface, five months later, at the hands of the robbers
hired by the ruthless king of France. He must give a picture of
the Anagni outrage as well as of the orthodox version of the
Westminster burglary. How far he has succeeded, you may
gather from the rude sketch figured on the opposite page. Not
only does he give us so vivid a picture of pope Boniface’s
sufferings from the rude soldiery that the drawing might well be
used as a representation of a martyrdom, like that of St. Thomas
of Canterbury. His sketch of three other sacrilegious warriors,
rifling the huge chest that contained the papal treasures, skilfully
suggests that robbery was the common motive that united the
outrage at Anagni to the outrage at Westminster. He leaves us to
draw the deeper moral that the sinful desire of unhallowed
laymen to bring holy church and her ministers into discredit was
the ultimate root of both these scandals.
Edward was satisfied with his Scottish campaign; he was

becoming old and tired; he was pleased to know that a great
deal of the lost treasure had been recovered; and he was always
anxious to avoid scandal, and to minimise any disagreement with
the monks of his father’s foundation. He, therefore, condoned
what he could not remedy. He soon released all the monks from
prison. He even restored Shenche to his hereditary office of the
keepership of the palace. Richard of Pudlicott alone was offered
up to vengeance. In October, 1305, Richard was hanged,
regardless of his clergy.
The Outrage at Anagni.
Affairs at the monastery of Westminster were not improved
after these events. There was much quarrelling among the
monks. Walter of Wenlock died. There were disputes as to his
succession; an unsatisfactory appointment was made, and there
was a considerable amount of strife for a generation. The feeling
against the king was shown equally against his son, and is
reflected in the bitter Westminster chronicle of the reign of
Edward II. One result of the demonstration of the futility of storing
valuables within the precincts of the abbey was that the chief
treasury of the wardrobe was bodily transferred to the Tower of
London.
Some obvious morals might be drawn from this slight but not
unpicturesque story; but I will forbear from printing them. One
generalisation I will, however, venture to make by way of
conclusion. The strongest impression left by the records of the
trial is one of the slackness and the easy-going ways of the
mediaeval man. The middle ages do not often receive fair
treatment. Some are, perhaps, too apt to idealise them, as an
age of heroic piety, with its statesmen, saints, heroes, artists, and
thinkers; but such people are in all ages the brilliant exceptions.
The age of St. Francis of Assisi, of Dante, of Edward I, of
St. Louis of France, of St. Thomas Aquinas, the age in which the
greatest buildings of the world were made, was a great time and
had its great men. But the middle ages were a period of strange
contrasts. Shining virtues and gross vices stood side by side. The
contrasts between the clearly cut black and white of the thirteenth
century are attractive to us immersed in the continuous grey of
our own times. But we find our best analogies to mediaeval
conditions in those which are nowadays stigmatised as Oriental.
Conspicuous among them was a deep pervading shiftlessness
and casualness. Mediaeval man was never up to time. He
seldom kept his promise, not through malice, but because he
never did to-day what could be put off till to-morrow or the next
day.
Pudlicott then is a typical mediaeval criminal. He was

doubtless a scamp, but most of the people with whom he had
dealings were loose-thinking, easy-going folk like himself. Of
course there are always the exceptions. But Edward I, with his
gift of persistence, was a peculiarly exceptional type in the middle
ages, and even Edward I found it convenient to let things slide in
small matters. Thus on this occasion Edward began his
investigation with great show of care and determination to sift the
whole matter; but when he found that thorny problems were
being stirred up, he determined—not for the first time—to let
sleeping dogs lie, and avoid further scandal.
We must not, however, build up too large a superstructure of
theory on this petty story of the police courts, plus a mild
ecclesiastical scandal. Nor must we emphasize too much or
generalise too largely from the signs of slackness and negligence
shown in mediaeval trials. I become more and more averse to
facile generalisation about the middle ages or mediaeval man.
They may, moreover, be made in both directions. On the one
side we have the doctrine of our greatest of recent scholars,
bishop Stubbs, that the thirteenth century was the greatest
century of the middle ages, the flowering type of mediaeval
christianity and so on. But on the other hand there is the
contradictory generalisation of students, like my friend
Mr. Coulton, who surveys the time from St. Francis to Dante with
the conviction that the so-called great days of faith were the days
of unrestrained criminality and violence. Both these views can be
argued; but neither are really convincing. They seem to me to be
obtained by looking at one side of the question only. A more
fruitful doctrine is surely the view that ordinary mediaeval men
were not so very unlike ourselves, and that their virtues and
vices were not those of saints or ruffians, but were not wholly out
of relation to the ordinary humdrum virtues and vices that are
found to-day.
1 A lecture delivered in the John Rylands Library on 20 January, 1915.

Return to text
NOTES.
I. Note on Authorities.
The accounts of the robbery of the king’s treasury in the

Chronicles are vitiated by the obvious desire of the writers, who
were mainly monks, to minimise the scandal to “religion” involved
in the suspected complicity of the Westminster monks. This is
seen even in the moderate account originating at St. Alban’s
Abbey, and contained in William Rishanger’s Chronicle (Rolls
Series), pp. 222 and 225, and also in the other St. Alban’s
version in Gesta Edwardi Primi, published in the same volume,
pp. 420–1. The bias is naturally at its worst in the Westminster
Abbey Chronicle, printed in Flores Historiarum, iii. 115, 117, 121,
and 131 (Rolls Series), which is more valuable perhaps as an
index of Westminster opinion than as a dispassionate statement
of the facts. The chief manuscript of this chronicle is preserved in
the Chetham Library, Manchester [MS. Chetham No. 6712]. It
was certainly written by a Westminster monk, and, perhaps after
1302, by Robert of Reading, who undoubtedly was the author of
the account of the reign of Edward II. If Robert wrote the story of
the robbery, it should be remembered that he was one of the
forty-nine monks indicted and sent to the Tower on a charge of
complicity in it. There are useful and more impartial notices in the
non-monastic Annales Londonienses in Stubbs’ Chronicles of
Edward I and Edward II, i. 130, 131, 132, and 134 (Rolls Series).
These date the robbery on 2 May.

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Molecular Spectroscopy—Experiment

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foundations and description of fundamentals of computational methods commonly

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1 Computational Methods in Spectroscopy . . . . . . . . . . . . . . . . . . . . 1

10 Vibrational Spectroscopy of Zeolites . . . . . . . . . . . . . . . . . . . . . . . . 301

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the form of electromagnetic radiation. The spectrum of electromagnetic radiation

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and second on time:

Wðx; tÞ ¼ wðxÞTðtÞ ¼ wðxÞeiEt=h ð1:9Þ

where ri and Ra—the coordinates of electrons and atomic nuclei, respectively, n—

1.2.1.2 Born–Oppenheimer Approximation, Potential Energy

The ﬁrst simpliﬁcation, bringing us closer to the solution of the time-independent

The Born–Oppenheimer approximation leads to a very important concept—the

1.2.1.3 Hartree–Fock Method and Post-HF Extensions

The solution of the nuclear time-independent Schrödinger equation allows deter-

wel ðr1 ; r2 ; . . .; rN Þ ¼ /1 ðr1 Þ/2 ðr2 Þ    /N ðrN Þ ð1:18Þ

^ el of the form (1.14)

• Two-electron contribution (depending on the coordinates of two electrons):

The former can be calculated accurately, whereas the two-electron contributions

where Jij is a Coulomb integral deﬁned as:

describing Coulomb repulsion between electron 1 on orbital i and electron 2 on

with no classical interpretation—this integral is entirely a quantum mechanical

In order to be able to solve this Schrödinger equation, we must replace the

and as a result, the so-called one-electron Fock operator is obtained:

Using variational principle:

to the problem of energy minimization, we get a set of appropriate one-electron

^fi /ðiÞ ¼ ei /ðiÞ; i ¼ 1; 2; . . .; N ð1:31Þ

One-electron Fock operator ^fi depends, through effective potential V

• Next, the system of Hartree–Fock equations is solved;

1.2.1.4 Density Functional Theory

HF method with post-HF extensions is still commonly used (especially by chemists

Hence, the system Hamiltonian is deﬁned as the sum of two operators:

According to the ﬁrst Hohenberg–Kohn theorem, the ground state properties of

being a solution to the following Schrödinger equations:

and satisfying the orthonormality condition:

The second is Hartree energy, classic electrostatic energy:

wel ðr1 ; r2 ; . . .; rN Þ ¼ /1 ðr1 Þ/2 ðr2 Þ /N ðrN Þ ð1:18Þ