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SCATTERING METHODS AND THEIR
APPLICATION IN COLLOID
AND INTERFACE SCIENCE
SCATTERING
METHODS AND THEIR
APPLICATION IN
COLLOID AND
INTERFACE SCIENCE
Otto Glatter
Department of Inorganic Chemistry,
Graz University of Technology,
Graz, Austria
Elsevier
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Preface
Scattering methods like small-angle X-ray and neutron scattering (SAXS and SANS), as
well as static and dynamic light scattering (SLS and DLS), have become leading techniques
for the characterization of structure and dynamics in soft matter. Scattering methods are
integral techniques; this means that the investigated area, the scattering volume, is several
orders of magnitude larger than the structures of interest. In most cases, the scattering vol-
ume has dimensions in the regime of millimeters, while the structures of interest can range
from nanometers to several micrometers. This means that typically one measures the con-
tribution of a larger number of scattering centers or particles, even in the case of dilute
systems. This method has the advantage of a relatively strong signal, quick acquisition of
statistically relevant data, and the experiments give a representative overview of the exist-
ing structure. The disadvantage is that no information about individual particles is avail-
able, and that the systems are in most cases not oriented. Complementary techniques with
a high spatial resolution like electron microscopy or atomic force microscopy are, there-
fore, of great importance to get a complete picture of the systems under investigation, but
will not be discussed here.
Soft matter, also called soft condensed matter, includes a wide range of systems and
materials. It is maybe easiest to define what is not included in soft matter: solids, gases,
simple fluids, and crystals. However, liquid crystalline systems are also soft matter, as
well as many complex fluids, colloidal dispersions, and gels. Soft matter science includes
colloids, polymers, and surfactant systems. Surfactants and other amphiphilic systems are
of increasing importance, due to their ability to form self-assembled systems, a key point
in the formation of nanostructured materials and nanotechnology. Molecular self-assembly
leads automatically to nanostructured systems. However, the length scales of interest
range from nanometers up to several micrometers, and to macroscopic dimensions in hier-
archically organized systems. This also leads to a wide range of interesting time-scales of
dynamic behavior, ranging from nanoseconds to several hours when fluid systems show
arrested dynamics. Soft matter science has a strong overlap with biosciences, physics, and
chemistry, especially with polymer research and more generally, with materials sciences.
One or the other aspect of these fields is taught in most universities, but scattering meth-
ods are hardly part of the curriculum.
It is impossible to cover all aspects of scattering methods and their application to soft
matter in one book. Here, I want to give a somewhat detailed introduction into SAXS,
SANS, SLS, and DLS based on my personal experience in these fields over more than 40
years, including typical examples manifesting the possibilities and limitations of these
methods. This contribution is not meant as a review of the existing literature, and is cer-
tainly biased by my personal view. Therefore, some related research fields are completely
missing, like grazing-incidence small-angle scattering (GISAXS and GISANS), inelastic
ix
x PREFACE
neutron scattering, reflectivity measurements, Fraunhofer scattering, and diffusive wave

spectroscopy. This is not because I consider these fields less important, but because of my
missing knowhow.
The limitation to my personal experience is maybe also the main difference to multiau-
thor books in this area, in which recognized experts in the different subsections give an
overview from different viewing angles. A typical example of this is the book edited by P.
Lindner and Th. Zemb (Lindner, P.; Zemb, T. Neutrons, X-rays and Light: Scattering Methods
Applied to Soft Condensed Matter. Elsevier Science: Amsterdam, 2002.).
This book is based on my experience in teaching in this field. I have to thank genera-
tions of students for their interest and challenging questions. This is not restricted to my
students in Graz, Austria, but also in many places all over the world. In the first place I
would like to mention all the participants of the, until now, 13 “Bombannes Schools” on
“Scattering Methods Applied to Soft Condensed Matter” but I should mention also my
students in Leuven, Belgium; Roskilde, Denmark; Turku, Finland; Ystad, Sweden;
Yokohama, Japan; Singapore; and Berlin, Germany.
Of course I also have to thank my undergraduate, graduate students, and postdocs over
the many years. Either they have contributed to one or another methodical detail of the
scattering and evaluation techniques, or they have helped to gain a deeper understanding
of these methods in various applications. So my thanks go to Heribert Fuchs, Michael
Hofer, Elisabeth Maurer- Spurej, Heimo Schnablegger, Norbert Maurer, Karl Gruber,
Judith Brunner-Popela, Dieter Lehner, Sabina Haber-Pohlmeier, Bertram Weyerich, Gerd
Kroner, Gerhard Popovski-Fritz, Alexander Bergmann, Doris Orthaber, Anna Stradner,
Rainer Mittelbach, Helmut Lindner, Josef Innerlohinger, Andrej Jamnik, Thomas Röder,
Thomas Frühwirt, Liliana de Campo, Anan Yaghmur, Christian Moitzi, Norbert
Freiberger, Martin Medebach, Samuel Guillot, Stefan Salentinig, François Muller, Anniina
Salonen, Matija Tomšič, Sandra Engelskirchen, Martin Dulle, Angela Chemelli, Patrizia
Foditsch, Roman Geier, Manuela Maurer, Chandrashekhar Kulkarni, Silvia Ahualli,
Guillermo Iglesias Salto, and Franz Pirolt.
In Chapter 1, Interference, Rayleigh Debye Gans Theory, the principles of scattering
are discussed. Similarities and differences to spectroscopic experiments will be summa-
rized briefly, and then the interference of the scattering wavelets, resulting in the scattered
field, will be discussed. This section includes two important steps: as we cannot measure
electric fields at these high frequencies, we have to proceed to the measurable scattering
intensities, including the averaging process necessary for isotropic, nonoriented samples,
followed by a section on the Rayleigh Debye Gans Theory. Here, we start off from the
simplest case: dilute and monodisperse systems. The important concept of the pair 2 dis-
tance distribution function, PDDF, the Fourier transform of the scattering intensities, is
introduced. The correlation length and chord distribution are of less practical importance,
but are added for the sake of completeness.
In Chapter 2, General Theorems and Special Cases, several general theorems are pre-
sented and special cases are discussed. The theorems include the concept of the Guinier
approximation, which results in the radius of gyration—or Guinier radius, and the Porod
law, which gives access to the surface of the particles. The special cases of spherical sym-
metry, elongated, rod-like particles, and flat lamellar particles are discussed in this section,
followed by the cases of aggregates and polydisperse systems.
PREFACE xi
In Chapter 3, The Inverse Scattering Problem, the inverse scattering problem for dilute,
noninteracting systems is discussed in some detail. The scattering problem is concerned
with the calculation of the scattering function (scattering curve and the PDDF) for particles
of known size, shape, and internal structure. The inverse scattering problem deals with the
recognition of structural details of unknown particles from their scattering pattern. There
is no unambiguous way to calculate the three-dimensional structure of a scatterer from the
one-dimensional scattering function. In this chapter, a series of examples of different
shapes of homogeneous scatterers will be given in real (PDDF) and reciprocal space (scat-
tering function), in order to introduce the possibilities of extracting simple structural
details. This concept is also extended to hollow and inhomogeneous structures. For spheri-
cal, cylindrical, and lamellar symmetry, there is no loss of information and the PDDF can
be deconvoluted into the radial scattering length density profile, i.e., a direct structure
analysis is possible. A short overview describes the special situation for polymer chains.
Several parameters can be extracted directly from the scattering data.
In Chapter 4, Concentration Effects, Interactions, the condition of dilute systems is abol-
ished, i.e., particle interactions are no longer negligible. In such systems, we have to con-
sider intra- and interparticle contributions to the scattering process. This situation can be
described by the so-called form and structure factors. This concept can be applied to
spherical or globular particles, to lamellar stacks or hexagonally ordered rods.
In Chapter 5, Absolute Intensity, SAXS, and SANS, we discuss how experimental SAXS
and SANS data can be put on an absolute scale to make the results independent of the
actual experimental situation. The special case of light scattering will be discussed later in
Chapter 9, Static Light Scattering From Small Particles.
Chapter 6, Contrast Variation, is dedicated to contrast variation, and discusses the pos-
sibility of varying the contrast between the scatterers and the surrounding medium. This
can help to optimize the absolute scattering intensity, to highlight the contrast of special
regions in the sample or to avoid multiple scattering. This topic is of special importance
for SANS.
In Chapter 7, Instrumentation for SAXS and SANS, the possible instrumentation for
SAXS and SANS experiments is discussed in some detail, together with the instrumental
broadening effects. The instrumental broadening functions are important for necessary
corrections in the evaluation procedures. Again, instrumentation for light scattering
experiments will be discussed later in the specialized Chapters 9 2 11.
Chapter 8, Numerical Methods, gives an overview of the different evaluation schemes
necessary for data treatment. After some primary data handling, data can be approxi-
mated (smoothing of statistical fluctuations), corrected for instrumental broadening, and
Fourier transformed into real space (PDDF) in one process by using the indirect Fourier
transformation (IFT) method. This technique can be extended to a concentrated interactive
system as the so-called generalized indirect Fourier transformation (GIFT) technique. In
the case of special symmetry, the PDDF can be deconvoluted into the radial density distri-
bution by using a convolution square root (or simply speaking, deconvolution) technique.
Finally, simple methods for model calculations are presented.
Static light scattering (SLS) from small particles—small compared to the wavelength—is
discussed in Chapter 9, Static Light Scattering From Small Particles. This chapter includes
sections on absolute scale and contrast, as well as parameter determination.
xii PREFACE
Chapter 10, Light Scattering From Large Particles: Lorenz 2 Mie Theory, discusses SLS
from large particles. Large means their size is in the order of the wavelength of light.
Interaction of light is much more complicated in this case, as there exist possibilities of
surface resonances. The corresponding theory—known as Lorenz Mie theory—is dis-
cussed in some detail. Such large particles have a very high scattering power, and there-
fore multiple scattering is an important issue here. Finally, design principles of SLS
instruments are discussed.
The last scattering technique, DLS, is discussed extensively in Chapter 11, Dynamic
Light Scattering (DLS), including basic principles, experimental details, and evaluation
techniques. DLS is mostly used as a fast technique for particle sizing in dilute systems,
using translational diffusion measured in a homodyne experiment. However, it is also pos-
sible to learn about particle interactions from concentration series, and finally one can
study solidifying systems with a so-called ergodic-to-nonergodic transition (also some-
times called glass transition, jamming, or gelation). Rotational diffusion can be measured
for nonisotropic scatterers like rod-like particles by depolarized DLS (DDLS), measuring
only the depolarized component of the scattered light. The electrophoretic mobility is
accessible from electrophoretic DLS (EDLS) measurements performed in a so-called het-
erodyne mode. Moving or flowing samples, like soot particles in a flame, can be measured
in specialized DLS setups.
Even though some examples have been given throughout the previous chapters, the
subsequent two chapters will give more examples to demonstrate the applicability of the
scattering techniques. Chapter 12, Dilute Systems: Practical Aspects—Applications, is
restricted to dilute systems, while in Chapter 13, Concentrated, Interacting Systems:
Practical Aspects, Applications, examples of applications to interacting dense systems are
given.
Glasses, liquid crystals, and gels are typical examples of dense and highly viscous sys-
tems. Some applications in this direction are discussed in Chapter 14, Glasses, Liquid
Crystals, and Gels.
In the Appendix the basic principles of statistical thermodynamics and their relation-
ship to particle correlation functions are summarized to assist the theoretical description
of the structure factor in Chapter 4, Concentration Effects, Interactions.
As already mentioned, this presentation is far from complete, but it should give a good
entry into and overview of the scientific field of scattering techniques, and their applica-
tion to soft matter. Finally, the reference list should help the reader to find the relevant
original literature for further in-depth studies.
C H A P T E R
1
Interference,
RayleighDebyeGans Theory
INTERFERENCE OF SCATTERED WAVES
When an electromagnetic wave is sent through a thin slab of material, the electric field
will introduce a polarization of the atoms, leading to the formation of little dipoles. The elec-
tric field oscillates with a frequency that is defined by the wavelength of the radiation sent
into the material, so the dipoles will oscillate in a forced motion with the same frequency.
Around the turn of the last century, H.A. Lorentz1 developed a classical theory of the
optical properties of matter. He treated electrons and ions as simple harmonic oscillators
(springs), which are moved by the driving force of the electromagnetic field. The results of
this procedure are qualitatively identical to those resulting from a quantum mechanical
treatment of these problems, even though quantities are interpreted differently in the clas-
sical and in quantum mechanical theory.2 The principles of the Lorentz model are essential
to understand the connections between spectroscopy and scattering, but we want to focus
here on the scattering process only. The interested reader will find an excellent overview
of the Lorentz model in Marshall (1978).2
It can be shown that a wave is not only partially absorbed by matter when passing
through a thin slab of material (exponential decrease), but also gives rise to a scattering
field, as every accelerated electric charge emits an electric field with an amplitude propor-
tional to the acceleration.3 In spectroscopic experiments we are interested in absorption
phenomena, i.e., we check the frequency-dependent absorption of radiation to find the
resonances of the systems. This frequency range close to the resonance is called the
Lorentz limit. In scattering methods we try to stay far away from these resonance frequen-
cies, ω0. For low frequencies, i.e., ω{ω0, we are dealing with the Rayleigh limit, which
holds for visible light, and for high frequencies, i.e., ωcω0, we are dealing with the
Thomson limit, which holds for X-rays. In both regimes we are interested in the scattering
wavelets that are emitted from these oscillating dipoles.
At the moment, it is only important to notice that the energy of X-rays is high enough
to be above the resonance regime ω0 for most soft matter materials and to polarize all
Scattering Methods and their Application in Colloid and Interface Science

DOI: http://dx.doi.org/10.1016/B978-0-12-813580-8.00001-8 1 © 2018 Elsevier Inc. All rights reserved.
2 1. INTERFERENCE, RAYLEIGHDEBYEGANS THEORY
electrons, also those in the innermost shells of the atoms, and therefore every electron in
the illuminated volume will give rise to a scattered wave. In the case of visible light the
situation is very different. The energy is lower than that of X-rays by a factor of about
4.000 (defined by the ratio of the wavelengths). This lower energy corresponds to lower
frequencies (ω , ω0), and can only polarize the electrons in the outer shell, typically the
valence electrons. Fortunately we have easy access to this polarizability as it is propor-
tional to the refractive index of the material. This fact will be discussed in more detail in
Chapter 9, Static Light Scattering From Small Particles. Here, we focus on X-ray scattering
and we ignore all prefactors relating the amplitude of the scattered wave to the amplitude
of the incoming plane wave. We set the scattered field amplitude as equal to one, because
we are not interested in the amplitude of the single scattering waves, but we want to dis-
cuss how they sum up (interfere) to the total scattering field. We discuss a virtual particle
in a vacuum with a volume V and a distribution of electrons that results in an electron den-
sity ρ(r) (number of electrons per volume element dV) at position r.
We now let a plane wave hit this particle. All scattering waves are coherent, i.e., there is
a fixed phase relation between the incident radiation and the scattered waves, and both
fields have the same frequency. Incoherent (Compton) scattering can be neglected for our
scattering process with X-rays, but is important in the case of neutrons.
The different waves will differ only in their relative phases ϕ, which will depend on the
position of the scattering centers relative to each other. The phase difference relative to an
arbitrary reference beam is given by the difference of the path lengths multiplied by the
wave number k 5 2π/λ, where λ is the wavelength of the radiation in the material. For a
traveling wave, the wave number gives the change in phase per length. This phase change
is, of course, equal to 2π if the wave has traveled one wavelength.
We choose an arbitrary reference point O in the body, and consider a beam through
this point as a reference beam. The direction of the incident beam is defined by the unit
- -
vector s0 s0 ; the direction of the scattered beam is given by s s (see Fig. 1.1). The
path-length difference of the reference beam and a beam through the point P is:
a 2 b 5 rs0 2 rs 5 2 r ðs 2 s0 Þ; (1.1)
so we get the phase difference ϕ by multiplication with the wave number:
ϕ 5 2 ð2π=λÞ r ðs 2 s0 Þ (1.2)
We now introduce the scattering vector q with:
q 5 ð2π=λÞ ðs 2 s0 Þ: (1.3)
FIGURE 1.1 Path-length difference of two rays.
SCATTERING METHODS AND THEIR APPLICATION IN COLLOID AND INTERFACE SCIENCE

INTERFERENCE OF SCATTERED WAVES 3
FIGURE 1.2 The scattering vector q.
and so we get:
ϕ 5 2qr (1.4)
The difference vector (s 2 s0) lies symmetrically with the incident and the scattered
beam, or orthogonal to the “mirror plane” (dashed line in Fig. 1.2) and its magnitude is
2sin(θ/2), where θ is the scattering angle. Contrary to what older textbooks on small-angle
scattering tell us, we do not use 2θ as the scattering angle; such a definition would contra-
dict the usual definition in light scattering!
The scattering vector q has the same direction as (ss0), and its magnitude is given by
the magnitude of (s 2 s0), 2sin(θ/2) (see Fig. 1.2) multiplied by the wave number 2π/λ:
4π θ
q q 5 sin (1.5)
λ 2
For small angles sinθ/2 may be replaced by θ/2, i.e., q, the magnitude of q is propor-
tional to the scattering angle θ (to be given in radians). The dimension is [length]21,
depending on the choice of λ. We use nanometers for the wavelength, so q has the dimen-
sion nm21. It should be noted that many other symbols are used in literature for the scat-
tering vector, like h, k, s, Q, etc., sometimes with a slightly different definition (missing
factor 2π). For all theoretical considerations, we shall use the scattering vector instead of
the scattering angle. This makes all our results independent of the wavelength used. It
should be kept in mind, however, that a certain q value will lead to different scattering
angles for different wavelengths! To summarize: the scattering vector has a magnitude
proportional to the scattering angle θ, has the dimension nm21, and its direction is not the
direction of the detector but points into the bisecting line between the incoming beam and
the detector direction.
Now let us come back to the phase difference ϕ. The scalar vector product qr in
Eq. (1.4) means that only the component of r that is in the direction of q is relevant for the
phase. This implies that all points in a plane perpendicular to q will have the same phase.
Scattering might, therefore, be regarded as a “reflection” by a set of planes (dashed line in
Fig. 1.2). This concept, though of great importance in crystallography, will not be used in
the following.
The product ks 5 k is often used as wave vector and the wave vector change q 5 k 2 k0 is
also called momentum transfer. According to de Broglie the relationship between the wave

properties and the particulate properties can be expressed by the wavelength λ that is
associated with a particle of mass m and velocity v:
h
λ5 (1.6)
mv
where h is Plank’s constant. So we see that the momentum, mv, can be written as:
mv 5
h
5
λ 2π
h
2πλ 5 h̄ k (1.7)
where h̄ 5 h/2π. This equation holds for neutrons as well as for photons and for any elec-
tromagnetic radiation. We see that the momentum of the field or of the neutron is a vector
pointing in the direction of propagation and its magnitude is h̄ω=c 5 h̄k. The elastically
scattered wave has the same energy or wavelength as before and so the same wave num-
ber k, but the direction of the wave vector has changed from s0 to s. The corresponding
momentum transfer is h̄q (see Fig. 1.3). We may even think of a completely classical anal-
ogy of a billiard ball moving in s0 direction with a momentum of h̄k0 5 h̄ks0 (whatever h̄k
might be). In order to change its direction into s with the same speed, i.e., momentum, as
h̄k 5 h̄ks we have to knock it with another ball with momentum h̄q, i.e., we have to trans-
fer the momentum h̄q to our ball.
We can now calculate the total scattered field from our particle by summing up all sec-
ondary waves considering their relative phases. This can easily be done by using complex
notation. A complex number with magnitude 1 and phase ϕ is represented by eiϕ or
e2iqr. The number of electrons (and the number of wavelets) per unit volume is given
by the electron density ρ(r). A small volume element dr (or dV) at position r will contain
ρ(r)dr electrons. So the summation can be replaced by integration over the whole vol-
ume V of the particle:
ð
Es ðqÞ 5 ρðrÞe2iqr dr (1.8)
V
In mathematical terms, the scattered field is the Fourier transformation of the electron-
density distribution of the object.
We call the space containing all position vectors r the real space, and the space contain-
ing the vectors q the reciprocal space. This is a direct consequence of the similarity theorem
of Fourier transformation.4 The reciprocity between real and reciprocal space can also be
explained by using Eq. (1.8). The two spaces are connected by the phase qr only; the result
would be the same if r were enlarged and q diminished by the same factor. So large
FIGURE 1.3 Momentum transfer.

RAYLEIGHDEBYEGANS THEORY 5
particles (large compared to the wavelength λ) will give a scattering pattern concentrated
at small angles.
In the field of X-ray and neutron scattering the wavelength is in the order of 1021 nm,
while the structures under investigation have a dimension of at least several nanometers.
This results in small scattering angles, and therefore in the names small-angle X-ray and
small-angle neutron scattering (SAXS and SANS).
As the connection between the spatial structure and the angular dependence of the scat-
tering amplitude is given by a Fourier transformation, the most important definitions and
theorems of Fourier transformations can be found in Bracewell (1986).4
RAYLEIGHDEBYEGANS THEORY
The so-called RayleighDebyeGans (RDG) theory of scattering is nothing other than the
rigorous application of the idea of coherent interference to scattering, assuming that the
electromagnetic wave propagates into and through the particle regularly and homo-
geneously, i.e., the magnitude of the electric field is the same in all parts of the particle.
The RDG theory describes well SAXS and SANS, as well as static light scattering of small
particles (size much smaller than the wavelength) and low contrast. The name small angle
comes from the fact that the wavelength of X-rays and neutrons is usually much smaller
than the size of the particles under investigation.
In the following we are no longer interested in the scattering of a particle in vacuum,
as we are dealing with soft matter, but in scattering from scattering centers embedded
in a homogeneous medium such as surfactants or macromolecules and their aggregates
in solution, and also defects in glasses, and pores in noncrystalline amorphous solids,
i.e., soft condensed matter where the scattering centers exist in a surrounding medium
of (nearly) constant electron density ρ. The incident field is a plane wave in the direc-
tion s0:
E1 ðr; tÞ 5 E0 eiðks0 r2ωtÞ (1.9)
The scattered waves have a spherical wave form:
eiðkR2ωtÞ
Es ðR; tÞ 5 Es0
R

sinϑ Φ q; t (1.10)
where R is the vector from the scattering center O to the point-like detector; and sinϑ is
the polarization term for polarized light, where ϑ is the angle between the direction of
polarization and the direction to the detector. This polarization factor is mostly relevant
for light-scattering experiments such as those that are usually performed with a polar-
ized laser source. In order to detect the scattered light intensity in a horizontal plane
the laser must be vertically polarized, i.e., ϑ 5 90 degrees, and therefore sinϑ 5 1.0. For
unpolarized light this factor has to be replaced by (1 1 cos2θ)/2, with θ being the scat-
tering angle. Most X-ray sources emit unpolarized light. However, in SAXS experiments
the scattering angle is small enough so this factor can be neglected, but it must be
considered for SWAXS (combined small- and wide-angle X-ray scattering) experiments.

A graphical representation of the polarizing factors can be seen in Figs. 15.115.3 in

Marshall (1978).2 Phi (Φ) is a phase factor describing the interference of all scattered
wavelets. This will be the most interesting part of Eq. (1.10). Before we can focus on Φ
we have to discuss the amplitude factor Es0 which defines the strength of the scattered
radiation.
For this part of our discussion we start from:
1 d2 ðexÞ sinϑ
Es 5 (1.11)
c2 dt2 R
This equation tells us that the scattered field is proportional to the second derivative of
the induced dipole moment ex. If we consider scattering of X-rays (Thomson limit, ωcω0)
we get:
2
e
Es0 51E0 51 E0 r0 (1.12)
mc2

where the factor r0 5 e2/mc2 5 2.82 10213 cm is the classical electron radius (in cgs units, or

r0 5 (1/4πε0) e2/mc2 5 2.82 10215 m in SI units).5 In the case of light scattering it is conve-
nient to express the magnitude of the electric dipole moment, ex, which results from the
application of the electric field E0 in terms of the molecular polarizability, α, as:
ex 5 αE (1.13)
This polarizability α is proportional to the refractive index of the particles, as we shall
discuss in detail in Chapter 9, Static Light Scattering From Small Particles. In general we
get6,7:
k2
Es0 51E0 δεr (1.14)
4π
where δεr 5 ε/ε0 2 1 and ε is the dielectric constant of the particle. In the Thomson limit
(ωcω0), which holds for X-rays, we obtain the field dEs(R, t) at the detector in a
distance R due to scattering by the infinitesimal volume element dV 5 dr with electron
density ρ(r, t):
eiðkR2ωtÞ e2
dEs ðR; tÞ 5 E0
R mc2
ρðr; tÞe2iqr dr (1.15)
where we have omitted the polarization term since (1 1 cos2θ)/2 is close enough to 1 for
the usual range of scattering angles in SAXS. In order to find the total scattered field we
have to integrate over the whole illuminated volume V:
ð
e2 eiðkR2ωtÞ
Es ðR; tÞ 5 E0 2
mc

R V
ρðr; tÞe2iqr dr: (1.16)
We can now express the density ρ(r, t) by its mean ρ and its fluctuations Δρ(r, t):
ρðr; tÞ 5 ρ 1 Δρðr; tÞ (1.17)

RAYLEIGHDEBYEGANS THEORY 7
The Fourier integral in Eq. (1.16) is a linear operation (an integral over a series of terms
can be replaced by the series of the integrals over these terms), so we can rewrite
Eq. (1.16) using Eq. (1.17):
ð ð
e2 eiðkR2ωtÞ
Es ðR; tÞ 5 E0 2
mc
R V

ρ e2iqr
dr 1 Δρðr; tÞe
V
2iqr
dr (1.18)
The contribution of the first term, caused by the mean ρ integrated over the whole scat-
tering volume V, peaks strongly at q 5 0, as the typical size of the scattering volume is in
the order of millimeters; this is huge compared to the wavelength λ. Therefore, this term
is hidden in the primary beam which has to be blocked in the experiment by a beam stop.
So we are left with the second term only, and for the scattering at q 6¼ 0 we get only the
contributions of the fluctuations Δρ(r, t) around the mean ρ:
ð
e2 eiðkR2ωtÞ
Es ðR; tÞ 5 E0 2 Δρðr; tÞe2iqr dr (1.19)
mc R V
So we see that the scattered field Es is the Fourier transformation of the density fluctua-
tions Δρ. This result leads to the fact that the contrast can also be negative (whenever the
density of a particle is lower than that of the solvent).
Inhomogeneities of the solvent are usually very small, and their contributions are taken
into account experimentally by subtracting the scattering of the pure solvent from the scat-
tering of the solution (see Chapter 8: Numerical Methods).
In addition, we should keep in mind that ρ is the electron density of X-rays, but repre-
sents the scattering-length density of neutrons (see Chapter 5: Absolute Intensity, SAXS,
and SANS) and the refractive index for light scattering (see Chapter 9: Static Light
Scattering From Small Particles) (Fig. 1.4).
FIGURE 1.4 Assembly of discrete particles, Rk(t) is the posi-

tion relative to an arbitrary origin O of the center of mass of
particle k at time t; rk is the vector from the center to a volume
element drk inside this particle.

Assembly of Discrete Scatterers

We can describe the density distribution Δρ(r,t) by:
X
N
Δρðr; tÞdr 5 δ½r 2 Rk ðtÞ 2 rk Δρðrk ; tÞdrk (1.20)
k51
Now we omit for simplicity all prefactors (including the fixed value of R) from
Eq. (1.19), replace the vector R pointing to the detector by the corresponding scattering
vactor q, and get:
N ð
X
Es q; t ~ Δρðrk ; tÞe2iq½Rk ðtÞ1rk drk
k51 Vk
XN ð
5 Δρðrk ; tÞe2iqrk drk e2iqRk ðtÞ (1.21)
k51 Vk
XN
5 Fk q; t e2iqRk ðtÞ
k51
where we have introduced the field Fk scattered by the particle k with volume Vk as:
ð
Fk ðq; tÞ 5 Δρðrk ; tÞe2iqrk drk (1.22)
Vk
In static scattering experiments we measure the scattered intensity as:

Is ðq; tÞ 5 jEs ðq; tÞj2
averaged over time or, for a nonergodic medium, ensemble averaged:
2 2 X
D 2 E e N XN D 2iqðR 2R Þ E

Is q 5 Es ðqÞ 5 I0 Fk ðqÞF
q e k l
(1.23)
I
mc2 k51 I51
At this step one might wonder what happened to the time-dependent phase factor
ei(kRωt). The time average over any periodic function with arbitrary frequency is
/2 (hcos2 (ωt 1 ϕ)it 5 1/2), so the intensity of the incident field I0 is simply equal to E02/2;
1
this holds for any electric field.

The double sum in Eq. (1.23) is the general result for an assembly of discrete scatterers;
the factor Fk(q) represents the scattering amplitudes of the kth particle, the phase factor exp
[ 2 iq(Rk 2 Rl)] depends on the vector between the centers of mass of particles k and l. This
equation is, as most basic equations, difficult to analyze in general. So we will start off
from this equation and discuss several special cases.
DILUTE SYSTEMS
We start with the simplest possible case; a very dilute system of scatterers. This
assumption not only guarantees that the condition of single scattering is fulfilled automati-
cally, but also leads to a situation in which all scatterers are uncorrelated, i.e., every particle

DILUTE SYSTEMS 9
of the system can be regarded as independent in respect to translation and orientation,
and no long-range order exists. So we assume that no interparticle interaction exists at all.
This condition can often be met by colloidal systems of globular particles with a low vol-
ume fraction (typically below 1%), but we have to keep in mind that high particle charges
or long thin cylinders and large vesicles may necessitate much higher dilutions. The condi-
tion of a very dilute system also leads to the situation in which ρ is equal to the density of
the solvent and Δρ is just the difference between the density of the particle and the den-
sity of the solvent (or surrounding medium).
We rewrite Eq. (1.23) and omit the constant prefactor:
XN 2 XX
Is q 5 Fk q 1 Fk q e2iqRk Fl q e2iqRl (1.24)
k51 k6¼l
If the system is very dilute and the scatterers are uncorrelated, the phase factors in the
double sum go through many multiples of 2π, and so these contributions cancel each other
and we get:
XN
Is q 5 jFk q j2 ; (1.25)
k51
i.e., the scattered intensity is simply the sum over the average intensities scattered by all N
individual particles, and contains information about structure and shape of these particles
averaged over orientations and particle sizes and shapes.
Monodisperse, Dilute Systems: Form Factor

If all particles are identical (monodisperse) we get:

Is q 5 N jFðqÞj2 5 N F20 P0 q 5 NP q (1.26)
where we have introduced the normalized averaged form factor P0(q) with the normaliza-
tion factor F20 :

jFðqÞj2 jFðqÞj2

P q
P0 q 5 5 5 2 or PðqÞ 5 F20 P0 ðqÞ (1.27)
jFð0Þj2 F20 F0
with P0(0) 5 1. For simplicity in the following, we use the symbol I(q) for the form factor
P(q) for dilute systems. We shall come back to the notation P(q) when were are dealing
with concentrated systems (see Chapter 4: Concentration
2 Effects, Interactions). Now we
have a closer look at the averaging process FðqÞ :
From Fields to Intensities and Spatial Averaging

Due to the high frequency of our radiation (10151018 Hz) it is impossible to measure
the field, i.e., the amplitude and the phase. We can only measure the intensity. In the next
step we have to take into account that our scattering centers in soft matter are not oriented
within the scattering volume. So we have to calculate the spatially averaged intensity.

First we recall Eq. (1.22), neglecting any time dependence:

ð
FðqÞ 5 ΔρðrÞe2iqr dr (1.28)
V
ð ð

2

jFðqÞj 5 F q F ðqÞ 5
V
Δρðr1 ÞΔρðr2 Þ e2iqðr1 2r2 Þ dr1 dr2 (1.29)
with V as the particle volume. We put r1 2 r2 5 r and use r2 5 r1 2 r:

ð ð
jFðqÞj 5
2
Δρ ðr1 Þ Δρ ðr1 2 rÞ e2iqr dr1 dr (1.30)
V
Now we introduce the convolution square Δ~ρ2 ðrÞ of the density fluctuations:
ð
γðrÞ Δρ~2 ðrÞ 5 Δρ ðr1 Þ Δρ ðr1 2 rÞ dr1 (1.31)
V
(Please note the difference in notation

when comparing to existing literature. Porod
(1982)8 uses the notation γ ðrÞ 5 V1 Δρ~2 ðrÞ!)
This function is, when normalized to γ(0) 5 1, also called the spatial autocorrelation func-
tion (ACF). For more details, see the excellent textbook on Fourier transformation and
related topics by Bracewell (1986).4 Introducing Eq. (1.31) into (1.30) gives:
ð
jFðqÞj2 5 Δρ~2 ðrÞ e2iqr dr (1.32)
V
So we see that the scattered intensity is essentially the Fourier transformation of the
spatial ACF of the density fluctuations ΔρðrÞ of the particle.
Now we have to perform the spatial averaging process. This means that the autocorrela-
tion function depends only on the magnitude of the distance r 5 |r|, and the scattering
intensity is a function of the magnitude q of the scattering vector q only. It is obvious that
information about the system is lost by this averaging process; a point that is important
for the evaluation and interpretation of scattering experiments. Also, the three-
dimensional Fourier transformation (Eq. 1.32) reduces to the one-dimensional, centro-
symmetric form. The phase factor must be replaced by its average taken over all directions
of r and so we get:
ð
γðrÞ 5 ρ~2 ðrÞ 2 VðρÞ2 5 Δρ~2 ðrÞ 5 Δρ ðr1 Þ Δρ ðr1 2 rÞ dr1 (1.33)
V
The convolution square Δρ~ ðrÞ is calculated as the overlap between a particle fixed in
2
space and its identical ghost shifted by r. If Δρ(r) is constant inside the particle, Δρ~2 ðrÞ is
given by the square of this contrast, (Δρ)2 times the overlap volume between the particle
and its shifted ghost, see Porod (1948).9
The spatially averaged convolution square γ ðrÞ 5 Δρ~2 ðrÞ results from the same process;
the ghost is shifted by a distance r 5 |r|, but we have to average over all possible direc-
tions in space. This correlation function γ(r) was introduced in the field of small-angle
scattering by Debye and Bueche (1949),10 and in its normalized form as the characteristic
function γ 0(r) by Porod (1951)11 (Fig. 1.5).

DILUTE SYSTEMS 11
FIGURE 1.5 The convolution square. If the electron density
Δρ(r) is constant inside the particle thenΔ~ρ2 ðrÞ describes the over-
lapping volume between the particle and its ghost, shifted by r.
For homogeneous particles we find immediately that:

ð
γ ð0Þ 5 ðΔρÞ 2
dr5 ðΔρÞ2 V
V
(1.34)
After normalization we have:

γ ð rÞ γ ðrÞ
γ 0 ð rÞ 5 5 (1.35)
γ ð0Þ ðΔρÞ2 V
The spatial average of the phase factor in Eq. (1.32) can be expressed by the fundamen-
tal formula also given by Debye (1915)12:
sin qr
e2iqr 5 (1.36)
qr
found by averaging over all possible directions of r (see also Guinier and Fournet (1955)13,
p. 8) (Fig. 1.6).
FIGURE 1.6 Spatially averaged convolution square γðrÞ 5 Δρ~2 ðrÞ: here we
shift the ghost again over the distance r 5 |r|, but take the average over all
directions in space.

Let us take a vector r with magnitude r that takes all orientations with equal probability. We
define the angle between q and r with ϕ. This angle varies between 0 and π radians. Any rota-
tion of r around q with fixed ϕ is described by the angle ψ. For any possible direction r we shall
find a direction r so that hsinqri 5 0, and we can deal with hcosqri instead of he2iqri (remember
Euler’s identity: e2iqr 5 cosqr 2 i sinqr). The product qr can therefore be described as qr cos ϕ,
and the probability of finding the endpoint of r between ϕ and ϕ 1 dϕ is sinϕdϕ.
So we have:
ð ð
1 2π π
hcosqri 5 cos qr cos ϕ sin ϕ dϕ dψ
4π Ψ50 ϕ50
ð
1 π
5 cos qr cos ϕ sin ϕ dϕ
2 ϕ50
Substitution of u 5 qr cos ϕ leads to:

ð0
21 sin ðqrÞ
cosqr 5 cosudu 5
qr qr qr
The Pair 2 Distance Distribution Function

By inserting Eqs. (1.33) and (1.36) into (1.27) and (1.32) we get:
ð
IðqÞ 5 jFðqÞj2 5 Δρ~2 ðrÞ e2iqr dr
V
ðN
sinqr 2
5 4π Δ~ρ2 ðrÞ r dr (1.37)
0 qr
ðN
sinqr
5 4π γ ðrÞ r2 dr
0 qr
and by introducing the pair 2 distance distribution function (PDDF) p(r) as:
ð
2
2 2

pðrÞ 5 r γ ðrÞ 5 r Δρ~ ðrÞ 5 r 2

Δρ ðr1 Þ Δρ ðr1 2 rÞ dr1
V
(1.38)
we obtain:
ðN
sin ðqrÞ
IðqÞ 5 4π pðrÞ dr: (1.39)
0 qr
The correlation function and the PDDF p(r) can, in principle, be calculated from I(q) by
the inverse transformation:
ð
1 N sinqr
γ ðrÞ 5 IðqÞq2 dq (1.40)
2π 0 qr

DILUTE SYSTEMS 13
or:
ðN
1
pð r Þ 5 IðqÞ qr sinqr dq (1.41)
2π2 0
In practice, we cannot use these two equations directly for the calculation of the real-
space functions as I(q) cannot be measured in the full regime 0 # q # N, but the equations
will be helpful for some theoretical considerations.
We can summarize the above findings as follows: the scattering amplitude F(q) depends
on the electron-density difference Δρ(r), they are Fourier transformation pairs and the
scattering intensity I(q) is the Fourier transformation of the correlation function γ(r) aver-
aged over all directions in space, or with an equivalent transformation, of the PDDF p(r).
This averaging process leads to a loss of information. The whole information of the scatter-
ing experiment is contained in the two functions I(q) and p(r). In principle, the information
content of these two functions is exactly the same, as they are linked to each other by the
unique Fourier transformation. We see in the following that most of the special features in
one space can also be found by special Fourier theorems in the corresponding reciprocal
space, however, the possibility to recognize the features may be quite different in the two
spaces. Such a problem does not exist in theoretical considerations, but can be of great
importance for practical applications.
Now we want to discuss some of the above defined quantities in more detail. Let us start
with the correlation function γ(r). For a homogeneous particle with constant contrast Δρ we
have shown that γ(0) is given by the square of this contrast multiplied by the particle vol-
ume (Eq. 1.34). If we have density fluctuations inside the particle we use Eq. (1.33) and get:
ð ð
γ ð 0Þ 5 Δρðr1 Þ Δρðr1 Þ dr1 5 ðΔρðr1 ÞÞ2 dr1 5 Δρ2 V
V
(1.42)
So we see that we simply have to replace the square of the contrast by the mean of the
squared fluctuations. By combining Eqs. (1.42) and (1.40), we get:
ð
1
γ ð0Þ 5 V Δρ 5 2 IðqÞ q2 dq
2 (1.43)
2π
This equation shows that the second moment of the intensity over the reciprocal space is
directly related to the mean square fluctuation of the densityΔρ2 , irrespective of structural
special features. If, e.g., parts of the system were shifted or deformed, the scattering pattern
might be altered considerably, but the integral in Eq. (1.43) must remain invariant.11
ðN
Invariant Q 5 q2 IðqÞdq 5 2π2 VΔρ2 (1.44)
0
By virtue of its invariance, it will play an important role later.

From Eqs. (1.37) and (1.39) follows:
ðN ðN
Ið0Þ 5 4π γðrÞr dr 5 4π
2
pðrÞdr (1.45)
0 0

In the forward direction, at exactly q 5 0, all secondary waves are in phase, so that we
expect I(0) to be equal to the square of the total number of difference electrons:
2
Ið0Þ 5 V 2 Δρ 5 Δn2e (1.46)
I(0) should be regarded as an extrapolated value, rather than a measurable quantity.
For homogeneous particles the function γ 0(r) can be interpreted as the probability of
finding a point inside the particle when starting from another point inside the particle,
within a distance r, where we have to average over all possible starting points. This func-
tion only depends on the geometry of the particle. If we choose r 5 0, then all endpoints
must be inside the particle, i.e., γ 0(0) 5 1, and the function must be zero for all distances
r $ D, where D is the maximum dimension of the particle.
We now want to move on from probabilities to number of distances. This number can
be found if we multiply the probability with the possible number of endpoints, i.e., the
volume of the spherical shell with radius r and the thickness dr. The number of distances
is therefore proportional to:
4πγðrÞr2 dr 5 4πpðrÞdr
We see that we can view the PDDF p(r) as a distance histogram, if the particles are homo-
geneous. The height of p(r) is proportional to the number of distances found inside the
particle within the interval r and r 1 dr (see Fig. 1.7).
If we now leave the assumption of homogeneous densities in the particles we come to
the (difference-electron) pair 2 distance distribution. This situation is very common for
SAXS data from surfactant micelles, where the electron density of the hydrophilic head-
groups is higher (Δρ . 0) than that of water, and for the hydrophobic tails it is lower than
water (Δρ , 0). Here, p(r) is proportional to the number of difference-electron pairs in the
interval r and r 1 dr. Still, the orientation of all connection lines is irrelevant due to the
spatial averaging process. We can understand the PDDF for inhomogeneous particles as
follows: we subdivide the particle into many small volume elements (small compared to
the local density fluctuations). The p(r) function is proportional (factor 4π) to the product
of the number of difference electrons nink of two volume elements i and k (where
ni 5 Δρ(ri)dV) with a center-to-center distance between r and r 1 dr, and we sum over all
pairs with this distance (see Fig. 1.8).
FIGURE 1.7 Definition of the PDDF p(r): the

height of this function is proportional to the num-
ber of possible connection lines with a length
between r and r 1 dr.

DILUTE SYSTEMS 15
FIGURE 1.8 Definition of the PDDF p(r) of inhomo-

geneous particles. Each line is weighted by ni nk.
The difference density may be either positive or negative. Whenever we combine volume
elements with opposite signs of density, we get negative contributions to p(r) that lead in some
cases to minima and even to negative values of the PDDF at this distance. It will be shown in
the following chapter that the PDDF of monodisperse, homogeneous particles allows an easy
shape analysis. However, this is no longer the case for inhomogeneous particles.
With Eq. (1.39) we understand that the scattering intensity I(q) can be understood as the
sum over many two-center interference terms [sin(qri)/(qri) 2 functions] with the ampli-
tude p(ri). The definition of p(r) guarantees that the total intensity is positive for all q
values (Fig. 1.9).
Correlation Length and Chord Distribution

For homogeneous particles we can also introduce the correlation length, lc, as the mean
width of the correlation function:
ðD
lc 5 2 γ 0 ðrÞ dr (1.47)
0
where we use the fact that γ(r) is an even function of r. This quantity can also be estimated
in reciprocal space. From Eqs. (1.40) and (1.42) we get:
ð
1 N 2 sin qr
γ 0 ð rÞ 5
1
Δρ2 V 2π2 0
I q q
qr
dq
and so:
ð N ð N
1 sin qr
lc 5 qdr IðqÞqdq
π2 Δρ2 V 0 0 qr

FIGURE 1.9 Relation between the scattering intensity I(q) and the PDDF p(r). The intensity is the sum over
many sin(qr)/qr functions with the corresponding height p(r). Here the contributions for r 5 5, 9, and 13 are
shown as dashed, dotted and dash-dotted lines.
We substitute x 5 qr, dx 5 qdr and take into account that the integral over sin(x)/x is
simply π/2, and get:
ðN
1
lc 5 I ðqÞ qdq (1.48)
2πΔρ2 V 0
and with Eq. (1.44) we finally have:
ðN ðN
I ðqÞ qdq I ðqÞ qdq
lc 5 π ð N
0
5π 0
(1.49)
Q
I ðqÞ q2 dq
0
We see that lc is proportional to the quotient of the first and the second moment of the
scattering curve and can be estimated without calibration to an absolute scale. It is easy to
show that the numerator in Eq. (1.49) is proportional to the total scattered energy of the
small-angle scattering experiment (Guinier and Fournet,13 1955, p. 18). In a distance R
from the sample, we have an area dσ for all rays between the angles θ and θ 1 dθ:
λ2 2
dσC2πR2 θdθ 5 R qdq (1.50)
2π

DILUTE SYSTEMS 17
With Eqs. (1.18) and (1.23) we get:
2 2 ð
e2 λ
I 5 I0 2
I q q dq
mc 2π
2 2 (1.51)
e
5 I0 λ2 Δρ2 V lc
mc2
Now we want to introduce the concept of chords through a homogeneous particle. If we

draw narrow parallel lines of equal spacing into a particle, the particle is cut into rods of
varying length, l, which we call chords. The group of chords for all directions may be con-
sidered by using a chord distribution G(l),13,14 such that G(l)dl is the probability that a chord
chosen at random is of length between l and (l 1 dl). Now we come back to the picture of
the particle and its ghost, which we introduced for the explanation of the correlation func-
tion (see Fig. 1.5).
We can see from Fig. 1.10 that for each chord with l . r, a piece (l 2 r) is in the overlap
volume. With the mean chord length, l, defined as:
ðD
l5 l ðGðlÞdl (1.52)
0
where D is the maximum particle dimension, we get:

ð
1 D
γ 0 ðrÞ 5 ðl 2 rÞ G ðlÞ dl (1.53)
l r
By differentiation we find:
ðD
dγ 0 ðrÞ 1 d2 γ 0 ðrÞ 1
52 GðlÞdl and 5 GðrÞ (1.54)
dr l r dr2 l
FIGURE 1.10 Particle (full line) and ghost (dashed line) with
chords. Source: Adapted from Porod, G. General Theory. In Small-Angle
X-ray Scattering; Glatter, O.; Kratky, O., Eds.; Academic Press: London,
1982; pp 1751, Fig. 3 with permission.

or:
d2 γ 0 ðrÞ
GðrÞ 5 l (1.55)
dr2
Thus the chord distribution, G(r), is closely related to the correlation function, γ 0(r), and
represents the particle features. Many attempts have been made to develop this concept
further.1417 There are serious difficulties, however, in treating more complicated cases,
such as hollow or composite particles, or densely packed systems.
The crucial point is the practical application of this concept. It is difficult enough to
calculate the correlation function γ(r) or the PDDF p(r) from experimental data
(see Chapter 8: Numerical Methods), but we would have to take the second derivative of
γ(r) to find G(r), which can be not straightforward.
OTHER BOOKS COVERING THIS FIELD
The following books also offer detailed descriptions of different aspects of this chapter:
A. Guinier and G. Fournet: Small-Angle Scattering of X-rays13; H. Brumberger:
Small-Angle X-ray Scattering18; O. Glatter and O. Kratky: Small Angle X-ray Scattering19;
L.A. Feigin and D.I. Svergun: Structure Analysis by Small-Angle X-Ray and Neutron
Scattering20; A.G. Marshall: Biophysical Chemistry2; H. Brumberger: Modern Aspects of
Small-Angle Scattering21; P. Lindner and T. Zemb: Neutrons, X-rays and Light: Scattering
Methods Applied to Soft Condensed Matter22; R.N. Bracewell: Fourier Transform and Its
Applications.4

C H A P T E R
2
General Theorems and Special Cases
THE RADIUS OF GYRATION AND THE GUINIER APPROXIMATION
The radius of gyration, Rg, is one of the most important parameters in the field of
small-angle scattering (others will be discussed at the end of this chapter). In full analogy
to the radius of inertia in mechanics it is defined as:
Ð
Δρ ðri Þ r2i dVi
Rg 5 VÐ
2
(2.1)
V Δρ ðri Þ dVi
According to the momentum theorem of Fourier transformation,4 the second moment

of a function in one space is related to the second derivative (curvature) of its Fourier
transform at the origin. This relation is the basis of the so-called Guinier approximation for
the description of I(q) for low values of q.
The scattering curve I(q) can be expanded in a McLaurin series of the type:

IðqÞ 5 Ið0Þ a0 1 a2 q2 1 a4 q4 1 ? (2.2)
It can be shown that this series starts with:
Ð
q2 Δρ ðri Þ r2i dVi
IðqÞ 5 Ið0Þ 1 2 Ð 1?
3 Δρ ðri Þ dVi
With Eq. (2.1), we can rewrite the above equation to give:
" #
q2 R2g
IðqÞ 5 Ið0Þ 1 2 1? (2.3)
3
R2g
i.e., a2 5 2
3
The higher-order terms are a complicated function of the shape of the particle. If we
perform a similar series expansion for a Gaussian we get:
e2aq 5 1 2 aq2 1 a2 q4 2 1 ?
2
Scattering Methods and their Application in Colloid and Interface Science

DOI: http://dx.doi.org/10.1016/B978-0-12-813580-8.00002-X 19 © 2018 Elsevier Inc. All rights reserved.
20 2. GENERAL THEOREMS AND SPECIAL CASES
and by setting a equal to R2g =3 we get the famous result of Guinier:

q2 R2
g
IðqÞ 5 Ið0Þ e2 3 ; (2.4)
which tells us that the innermost part of a scattering function can always be approximated
by a Gaussian function. However, it should be kept in mind that this approximation is cor-
rect only for the q2 term in Eq. (2.2) (see also discussion by Porod,8 and Guinier and
Fournet13). This approximation can be used to determine Rg with a so-called Guinier plot.
By plotting ln[I(q)] vs. q2 we get a straight line with a slope proportional to R2g .
Now we start from Eq. (1.39) and use the McLaurin series for sin x/x:
sin ðqrÞ q 2 r2 q4 r4
512 1 2 1?
qr 6 120
Insertion into Eq. (1.39) gives:
ð N ð ð
q2 N q4
IðqÞ 5 4π p ðrÞ dr 2 p ðrÞ r2 dr 1 p ðrÞ r4 dr? (2.5)
0 6 0 120
By comparing Eqs. (2.3) and (2.5) we get another important and useful relation for the
radius of gyration:
Ð
p ðrÞ r2 dr
Rg 5 Ð
2
(2.6)
2 p ðrÞ dr
We can see from Eq. (1.39) and Eq. (2.6) that the scattering intensity in the forward
direction I(0) is proportional to the area under the p(r) function, while the radius of gyra-
tion is proportional to its normalized second moment. The radius of gyration is an interest-
ing parameter for homogeneous particles, and it is related to the geometrical parameters
of simple homogeneous bodies (see Eq. 3.24). These relationships allow for the possibility
of estimating the size of a scatterer with a shape from the radius of gyration. This simple
method of particle sizing depends highly on the assumed shape, and is only possible for
homogeneous scatterers.
FINAL SLOPE OF THE SCATTERING CURVE, POROD LAW
We have already seen how different parameters of the particles such as V, Rg, and lc
can be determined from the scattering data. These parameters may be termed integral
parameters, as they are characteristic of the overall dimension of the particle.
Correspondingly, they are mainly related to the central part of I(q). If we now proceed to
discuss the final slope of the scattering curve, we may expect this to depend mainly on the
fine structure of the particle, which is expressed by the behavior of γ 0(r) at small r values.
We follow Porod8 and expand γ 0(r) into a power series:
γ 0 ðrÞ 5 1 2 ar 1 br2 1 cr3 (2.7)

PARTICLES WITH SPHERICAL SYMMETRY 21
where the coefficients a, b, c . . . may be termed differential parameters.14 The first of these
coefficients is immediately related to the chord distribution by Eq. (1.54). If we look for the
overlap volume for a small shift in r, we see from Fig. 1.5 that it differs from V only by the
shift of the surface. The contribution of a surface element dS to this shell is dSr cos ϑ where
ϑ is the
angle between r and the surface normal. Averaging over all directions leads to
cos ϑ 5 1/2. Further, it must be considered that only the part of r directed inwards makes
a contribution, which results in a second factor 1/2. Each surface element will, therefore,
diminish by dSr/4 on average, which gives 1/4 Sr for the total surface. So we have the first
term of the series:
1
VðrÞ CV 2 Sr 1 ? or (2.8)
4
S S
γ 0 ðrÞC1 2 r 1 ? with a 5 : (2.9)
4V 4V
Now we substitute Eq. (2.9) into Eq. (1.37) and get:
ðD
S sin qr
IðqÞCðΔρÞ2 V4π r2 1 2 r1? dr (2.10)
0 4V qr
An integration by parts leads to a series of negative powers in q, the pseudo-periodic
terms fall off rapidly for nonspherical particles, and for the final slope of the scattering
curve we find the Porod law:
IðqÞq-N 5 ðΔρÞ2 2π
q4
S (2.11)
This fourth-power law was derived by Porod11 under the assumption of a sharp phase
boundary between the particle and the surrounding medium.
PARTICLES WITH SPHERICAL SYMMETRY
Here we discuss particles with spherical symmetry, i.e., particles with a spherical shape
and Δρ(r)Δρ(r). There should be no angular dependence of the density fluctuations, Δρ.
With this condition we can express the scattering amplitude F(q) as a function of the mag-
nitude q of the scattering vector q. From Eq. (1.22) follows:
ðN
sin qr
FðqÞ 5 FðqÞ 5 4π Δρ ðrÞ r2 dr (2.12)
0 qr
with the inverse transformation:
ðN
1 sin qr
Δρ ðrÞ 5 FðqÞ q2 dq (2.13)
2π2 0 qr

22 2. GENERAL THEOREMS AND SPECIAL CASES
For a homogeneous sphere with radius R we get:

ð
4πΔρ R
FðqÞ 5 r:sin ðqrÞdr (2.14)
q 0
and by straightforward partial integration we get:

$ %
4πR3 3ðsin qR 2 qR cos qRÞ
FðqÞ 5 Δρ (2.15)
3 ðqRÞ3
The scattered intensity I(q) is the square of the amplitude, i.e.:
" #2
3ðsin qR2qR cos qR
IðqÞ 5 ðΔρÞ V P0 ðqÞ 5 ðΔρÞ V
2 2 2 2
(2.16)
ðqRÞ3
with the normalized form factor, P0(q):
" #2
3ðsin qR2qR cos qR
P0 ðqÞ 5 (2.17)
ðqRÞ3
This form factor is simply the square of the Bessel function of order 3/2 J3/2(qR). This
function has zeros for qR 5 4.493, 7.725, . . . (see also Fig. 2.1). These zeros allow the estima-
tion of the size of the sphere from the scattering function. But this procedure may be dan-
gerous, because we have to assume that the particles are homogeneous spheres.
FIGURE 2.1 Form factor P0(q) for homogeneous spheres in a semilog plot, log(P0(q)) vs. qR.

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constitute the royal livery, was also lying prone on the floor with his
head towards the east. Their orisons, if praying they were, were
extremely short, for in a trice both men were on their feet and all
attention to my wants. I mean to speak later of the minutiæ of my
daily life, but at this point I wish to hasten my reader and not to
weary or detain him with petty diurnal details that I have settled to
describe in another place. Let it suffice to say that I bathed, dressed
and breakfasted to my complete satisfaction, and that having duly
performed these matutinal duties I was glad to find myself at leisure
to contemplate by the brilliant light of morning the veiled scene of the
previous night.
From the vantage ground of my exterior gallery I obtained a superb
and intimate view of the great city of Tamarida and its surroundings.
Imagine a compound of Naples, Algiers and Amalfi, each of these
Mediterranean cities being built on steep slopes descending to the
sea-shore, and yet such compound resulting in something totally
dissimilar from any earthly town of my acquaintance. In size and
arrangement Tamarida somewhat resembled the older portions of
Naples that stretch from Sant' Elmo to the Monte di Dio; in setting I
was reminded of Amalfi with its craggy headlands, though here on a
grander scale; whilst in general character the cascade of dazzling
white flat-roofed square houses of the Arab native town in Algiers
suggested many points of comparison in this case. But though it was
evident that my capital was very extensive, and that much of its area
was thickly populated, nevertheless there seemed to be abundance
of parks and gardens in all directions, forming oases of vivid
greenery amongst the dense masses of small low squat dwellings.
Roughly speaking, the city was divided into three portions, that were
formed by two deep valleys, down each of which flowed a rapid clear
torrent fed from the mountainous regions above. The two outer
sections of this curving site were wholly occupied, as I have said, by
houses and gardens of the citizens, apparently both rich and poor
intermingled; whilst the central slope between the two streams was
reserved for the palace and the main temple and other official
buildings. Of these the palace took up a considerable space about
half-way up the hillside, and below it, stretching to the harbour, was a
large tract of tilth and orchard, well sprinkled with tiny white cottages
and long low barns that were presumably used by the labourers and
other servants of the palace. The royal residence itself was an
immense rambling structure, built without plan and at various
periods, though it was hard to classify its many architectural features
or to guess which were the older or more recent portions of the
fabric. Above the palace and its adjacent enclosures could be seen
hanging-gardens traversed by immense flights of broad shallow
steps, beyond which was another conspicuous group of buildings
situated at different levels. This pile I rightly concluded to be the chief
—it was the only—temple of the city, both from its more ornate style
of architecture and from a circular tower which crowned the main
edifice. On this tower upreared a tall column whereon rested a gilded
copper representation of the sun in splendour, making a brilliant
mass of golden light under the fierce rays of its great original, and
offering a prominent landmark for many miles around. Of the
residential districts of Tamarida on the two flanking slopes I have
omitted to mention that two main streets or arteries for traffic could
be distinctly traced by me, running irregularly through the crowded
quarters and parks alike, and ending in the broad quays alongside
the waters of the harbour. Many ships of various shapes and sizes,
but mostly appearing to be fishing vessels, lined these quays and
were also visible in numbers on the placid surface of the circular
harbour itself, which was contained by two outlying rocky
promontories crowned on either tip by a low light-house.
CITY & HARBOUR OF TAMARIDA
I was interrupted in the midst of my many interesting discoveries and
observations by the sudden entrance of one of my equerries, who
was followed by the Arch-priest demanding an audience. Left alone
together, I instinctively put myself on my guard, assuming as well as
I could an air of naive simplicity. Despite his deferential words and
attitude, I could not fail to detect the deep-set twinkle in his eye as he
proceeded to inform me of the object of his mission. At the same
time, however, I felt certain that I must have produced a favourable
impression on the previous day, and from my deportment both now
and in the future I warmly hoped to be able to hold the old man's
approval, for something in my inner consciousness, a species of
sixth sense, assured me he was ready to show himself my friend,
though doubtless a friend within certain limits that I had yet to learn.
The Arch-priest opened our talk with an apology for thus invading the
privacy of my apartments without previous warning, excusing himself
for his intrusion by the urgent necessity of the occasion. He then
informed me that on the next day the ceremony of my coronation
was fixed to take place in the temple, which he pointed out to me
from the balcony. "You are in the eyes of your subjects, as you know,
the Child of the Sun, whom alone we worship in Meleager, and who
sends you as a king to rule over his favoured people. You will
therefore be presented in public by myself and my colleagues of the
Sacred College to the populace; you will be robed and crowned; you
will extend your formal blessing to them; you will offer incense at the
crystal altar of your Father the Sun, in the great courtyard of the
temple; and after that you will mount the sacred white horse so as to
ride in full majesty through the streets of the city in the presence of
your subjects. It will be a long and tedious series of ceremonies, yet I
flatter myself that each one of these rites will not be without interest
to you, seeing the lengthy spell of authority amongst us that lies
ahead of you. I myself shall be at your side throughout, and you may
rely with safety on my tutelage in any event."
Other advice and suggestions the Arch-priest likewise imparted to
me, amongst the rest that Hiridia would in course of time teach me
the spoken language of Meleager. "Ever since your immersion in the
mystical well," so my companion proceeded, "you will experience an
acceleration of all the faculties, which in your case were already
highly developed when on Earth. Moreover, the tongue of the
Meleagrians, which under Hiridia's teaching you will soon acquire, is
not a written language, and none outside our hierarchy of the Temple
of the Sun can read or write at all. Indeed, our only archives are in
Latin, since for reasons which it is not expedient for me to mention at
this point we have always vigorously opposed the casting of the
popular speech into a literary form." This last statement the old man
made in a very solemn manner, looking me full in the face as though
to catch any motion or expression of surprise or disapproval. But I
had set my countenance unflinchingly, and received his confidences
with perfect outward composure, whereupon the Arch-priest leaned
back in his chair with a faint sigh of relief which by no means
escaped my watchful notice. Having received this minor secret of
Meleagrian state craft so calmly and suitably, I was hoping to glean
yet more information on the traditional polity of the governing cabal
of my kingdom, but on this occasion I was doomed to be
disappointed. For the Arch-priest arose abruptly, and leading me to
the balustrade of the gallery began to point out and explain to me the
various buildings and salient features that were discernible from this
spot. In most cases I found I had already guessed correctly, my
intelligence and perspicacity evidently serving to strengthen the
favourable impression I had already created. The Arch-priest then
led me to the other side of the building and introduced me to the
private gardens of the palace, a delightful pleasance, full of
subtropical verdure and flowers and overshadowed by tall palms and
cypresses. Fountains with marble basins were frequent, and their
constant plashing made an agreeable sound in the intense quiet of
this retreat. I noted too that every fountain was circular in shape, and
that everywhere were to be seen endless representations of the sun,
whilst the many lackeys or slaves attached to the royal service bore
the same design woven in gold and blue on their breasts. Returning
to the gallery overlooking the town and harbour, my companion bade
me listen to the hum of voices and the din of traffic that rose from
below into the warm air, striking on my ears with the mingled sounds
of a teeming city.
"Tamarida is filled to overflowing with your loyal subjects,"
commented the Arch-priest; "who are all agog to behold to-morrow's
function; and even now the town is hourly receiving innumerable
visitors from the country districts and from your Majesty's second city
of Zapyro, which is ever jealous of the capital for its possession of
the person of the Child of the Sun." He paused for a moment to give
me another of those arch glances from his kindly, humorous old
eyes; but I only nodded and smiled amiably. "Thousands of faithful
citizens too from your Majesty's colonies on the wild rocky coasts of
Barbaria yonder to the north (and he waved his arm to indicate some
distant land beyond the enclosing hills) are hastening hither to
behold the reincarnation of the Child of the Sun, concerning whom
their parents have doubtless told them wonderful tales. See those
boats with bellying sails that are even now entering the harbour's
mouth; they are all freighted with excited pilgrims, men, women and
children, drawn hither to assist at a spectacle of outward splendour
and interior sanctity that your Earth, notwithstanding its illimitable
wealth and its superior population, cannot produce. They tell me
(and here the old man's eyes again twinkled mischievously) that one
of your own many religious cults is ruled by a priest who claims and
receives divine honours. He is said to be elected by a college of
saintly and venerable brother priests, and to be borne aloft with
pomp and acclamation on the shoulders of men of noble birth. I
have, of course, never seen the ceremonies of modern Rome (which
city I hold in especial esteem as having been in ancient times the
origin of our official written language), but in this one crucial instance
this consecration of an earthly high priest must yield to ours. For
there is (so I am informed) no unanimity of opinion, no universal
acceptance of the chosen pontiff; whilst here the King who is
provided by our hierarchy is acknowledged by all without hesitation
or limit as the connecting link between the divine and the human,
whose presence is absolutely essential to the welfare of his subjects.
Our King is the peculiar guerdon of our sole Deity the Sun to his
favoured people, on whom from time to time he deigns to bestow a
member of his own family for guidance and example."
At length the Arch-priest took his departure, and I spent the
remainder of the day agreeably enough in the society of Hiridia,
whom I set to teach me the names of every object in sight. I had
already requested the Arch-priest for pen and ink and paper, and
after a visible tendency to demur he had yielded to my demand, a
plentiful supply of beautifully prepared rolls of vellum, an ink-horn
and some quill pens being brought me. I now wrote down
phonetically the name of each thing supplied me by Hiridia, placing
its English equivalent opposite. I was quite astonished at my
progress in the course of a few hours' application of this nature, and
the sun was low in the western sky when my patient tutor made
respectful signs to me to rise and follow him. I soon grasped his
intention, for he led me through the gardens to an open court where
two young nobles were playing at some sort of hand-ball. A slave
now removed my mantle and tunic, to exchange them for a short
linen garment, whilst a pair of hard leather gloves were likewise
supplied me. We four now fell to play with zest a game that was so
reminiscent of the hand-fives of my school-days that I learned the
science, the rules and the method of scoring in a very short space. I
thoroughly enjoyed the healthy exercise, which in due course
produced a copious perspiration, and thus we amused ourselves till
the final sinking of the sun brought our game to a close for lack of
light. At this moment I heard the prolonged blare of a distant trumpet,
and straightway perceived my three companions sink to their knees
for a short but silent prayer. Then they rose and led me to the
thermal baths attached to the palace, where I indulged in a further
bout of sweating followed by a plunge in cool water. After resting I
dressed myself again, and with an excellent appetite made my way
to the banqueting hall, where I partook of the last meal of the day.
On this occasion a band of professional players with unfamiliar
instruments provided us with music, which I found neither better nor
worse than many of the concerts I had been obliged to attend at
various times upon Earth. Pleasantly fatigued, at last I sought my
bed-chamber to ponder over my late experiences of the first twenty-
four conscious hours I had spent on the planet of Meleager.
Early on the following morning there were abundant signs to warn

me of the great impending event. All was bustle and animation within
the palace, and at an early hour the Arch-priest himself was
announced to give me some final instructions. Soon afterwards a
litter was brought, borne by a number of servants dressed in what
was evidently their gala livery, and in this equipage I was placed,
behind carefully closed curtains, and was thus conveyed up many
long flights of steps to the precincts of the temple above. Here on my
arrival I found the Arch-priest and several members of the hierarchy
awaiting me, and was informed that first of all it was necessary for
me to hold a levée of the whole of the ruling Council of the Seventy. I
cannot say that this prospect afforded me any pleasure; still, I
prepared to comport myself with the necessary amount of calm
dignity I deemed fitting for the occasion. I was next ushered into a
large hall, where in a semicircle were seated a large number of these
all-powerful patriarchs clad in their robes of flowing white. I was
directed to a throne opposite them, and at once began to hold my
formal reception, each member of the Council being presented to me
in turn by the Arch-priest. In every case, mindful of our royal Court
procedure on Earth, I proffered my right hand for a kiss of salutation,
and at the same time set my face to exhibit no sign of anxiety or self-
consciousness, for I realised that I was amongst the keenest and
most critical intellects of the kingdom, who regarded me not in the
light of a true monarch, but rather as their own creature, a thing
raised by their choice and efforts from mere nothingness to a
position of extreme though false magnificence. Nevertheless, I was
not so much preoccupied with the mastery of my feelings that I failed
to note carefully the face and expression of each individual member
as the councillors filed before me in a long moving stream that
seemed to flow interminably past the throne, so prolix and lengthy
was the Arch-priest in his style of presentation. Vainly did I look for
the appearance of my Herthian friend Signor Arrigo d'Aragno
amongst their number, but either he was absent or else was so
skilfully disguised that I failed to detect his presence. One little
circumstance I observed was that whereas all the Meleagrian men I
had hitherto seen wore moustaches, these grandees of the
governing caste were all either clean-shaven or else owned beards
of an imposing length. Nearly two hours were consumed in this
fatiguing occupation, and thankful I was when the last sharp-eyed
senator had returned to his seat.
I now arose of my own motion, and expressed a desire to quit the
chamber of the councillors, whose atmosphere somehow oppressed
and irritated me. The Arch-priest accordingly led me into a closet
adjoining, where I sat down on the pretence of fatigue. Ere long
however to my relief I saw Hiridia approach, followed by my two
equerries and by some servants of the palace bearing large bundles,
which I perceived contained the regal robes of state. A priest
certainly stood beside me, but he made no attempt to interfere with
Hiridia's arrangements. First of all, I was stripped to my inner
vesture, after which gorgeous blue leather buskins with heavy gold
tassels and laces were fitted to my feet. Next a tunic far more
elaborate than my usual one was donned; then a mantle of an
appalling weight but of a surpassing splendour was hung from my
yielding shoulders. On the mantle itself was embroidered a device of
the blazing sun in heavy gold thread, whilst the rest of the surface of
the cloak was thickly patined with golden stars. The mantle was
fastened by a clasp composed of a huge cabochon sapphire of
perfect water set in a circle of flashing diamonds. At this moment the
Arch-priest returned, resplendent in festal robes of white silk fringed
with gold and with a tall golden mitre on his head. Thus habited, he
appeared a striking and venerable figure, for his superior height, his
flowing white beard, his pleasant brown eyes and his delicate
complexion all combined to make a most favourable impression on
the beholder. On a cushion he carried the regal crown, of the type
known to heraldry as "palisaded," and not unlike the diadem worn by
the Medicean Grand Dukes of Tuscany, as shown in their pictures
and effigies. My crown was all of gold with the exception of one large
oval sapphire surrounded by brilliants for its central ornament. This
object the Arch-priest now carefully placed on my head, not a little to
my trepidation until I realised that, whether by accident or as the
result of forethought, the heavy circle fitted my cranium to a nicety.
The finishing touch consisted in fastening solid gold armillæ, or
bracelets, set with sapphires on my wrists.
Thus gloriously apparelled, I must on standing up have presented a
truly noble and imposing appearance, and I say so without shame of
conceit or vanity. I was many inches taller than the tallest of my
companions; thanks to my bath in the Fountain of Rejuvenation I had
a clear white skin, a sparkling eye, and an elegance of carriage that
have rarely been seen by mortal man; whilst the extreme fairness of
my complexion and the sheen of my long locks in contrast with so
many dusky skins and black heads of hair seemed to attract to
themselves some kind of shadowy semi-divine aureole, such as
Benvenuto Cellini describes as investing his person after his
colloquy with the Blessed Virgin and St Peter in his cell of the castle
of Sant'Angelo. I was well aware of the sensation I aroused in all
present, even in the Arch-priest; and a thrill of elation, of confidence
in the future, possessed me through and through. Whether or no
these saturnine priests of the Temple of the Sun chose to regard me
as their puppet, their slave, what was that to me? I realised that my
marvellous beauty at this moment was an asset whereof nothing
they could say or do would lessen my influence in the eyes of the
mass of the people I was about to face. All misgivings and tremors
left me, as I prepared boldly to move forward and take my part in the
coming pageant.
To a terrific blast of trumpets and to the explosions of some
antiquated-looking mortars that stood on the temple parapet, our
procession filed through a narrow doorway on to a broad marble
platform. First emerged the nobles attached to the Court in their
crimson gala robes, then the priests, a long sinuous line of snowy
white; behind them walked the Arch-priest, whilst last of all appeared
myself, a tall commanding majestic figure with my equerries to
uphold my glittering mantle. My entry into sight of the vast multitude
that thronged the courtyard below the platform on which we stood
was first greeted by a spell of perfect silence, which in time changed
to a long low murmur of approval and awe, and finally to a
resounding roar of satisfied delight. Slowly did our long train of
nobles, priests, choristers and attendants unwind and fall into proper
groups in their assigned places, the whole scene reminding me of
some wonderful ballet on an immense stage, with its blending and
massing and dividing of the colours of white, red, gold and blue, like
the intricate movements of some stately dance.
At last only the Arch-priest and myself remained standing in the
central space of the platform, when the former, after an obeisance of
a cringing humility of which I had hitherto deemed him incapable,
conducted me to a throne beneath a canopy of blue and gold. From
this point, during the performance of some singing, I was enabled
surreptitiously to examine the component parts of the huge crowd
beneath. Immediately under the dais were numbers of persons who
were all characterised by wearing green in some form or other, either
green tunics or mantles or scarves. As these seemed to occupy the
better and reserved space in the courtyard I concluded (and rightly
so) that they were members of the middle or mercantile class, who
were given precedence over the general populace. The latter were
farther away, and were consequently more difficult for me to
distinguish. But it was a picturesque throng in any case, and
brilliantly coloured, for the robes were mostly in tints of yellow,
orange, violet, pink, cinnamon and other shades, though the four
colours of blue, white, red and green were conspicuously absent.
Men, women and children were visible in the crowd, all of them being
small dark people of the type already exemplified in the few persons
I had hitherto seen. Part of the court was enclosed by double
colonnades that supported upper chambers screened by lattice-work
from inquisitive eyes, like the discreet convent windows I used to
observe in the highest storeys above the streets of Naples and
Palermo. Behind these screens were evidently many spectators, and
from the shrillness of the voices issuing hence and from other
indications I gathered that the occupants of these galleries were
mostly women. As a matter of fact, one side was reserved for the
ladies and children of the nobility, and the other for the female
inmates of the college of nuns or recluses attached to the Temple of
the Sun, of whose duties I mean to speak later.
After a long interval of chanting, at a sign from the Arch-priest I rose
and gave a benediction to the assembled crowd by raising my right
arm and slowly turning round so as to envisage the whole assembly.
This was made the excuse for more applause, and when this had
subsided more canticles were intoned. Again I imparted the required
blessing, after which a golden censer was brought me and I was
assisted to advance towards a small altar, formed apparently of solid
crystal, whereon the sun's rays were falling in blinding coruscations
of light. Here I offered up clouds of incense in the direction of my
supposed Parent, the whole multitude kneeling in the most profound
silence and in the most decorous attitude of rapt attention. For fully
ten minutes I must have been swaying that heavy censer, and what
with the weight of my robes, the scorching heat of the sun's beams,
and the extreme tension caused by the magnificence and novelty of
my situation, I felt almost at last ready to drop from sheer
exhaustion, when the Arch-priest again came to my rescue and
relieved me of the smoking thurible. More cheering, more intoning,
more ceremonious movements, till ultimately I found myself with the
Arch-priest on one side of me and Hiridia on the other, making my
way off the platform. I was forthwith led to a chamber furnished with
long tables whereon was served a collation of which I stood
considerably in need. I then learned I was being entertained thus by
the body of the hierarchy, so that once more I felt the necessity of
exhibiting no sign of fatigue or of astonishment. The meal was of
brief duration, for the day was well advanced by this time, and there
still remained the important state entry and procession through the
streets of the capital. Quitting the temple precincts I found a
cavalcade, or guard of honour, awaiting me, whilst some pages were
holding a horse in readiness for me. My steed of state was of a
remarkable aspect, for he was pure white with a strong tint of flesh
pink showing through his coat, and with pink ears and muzzle. His
flowing mane and tail had also been dyed of a blue colour, and, most
marvellous thing of all, his eyes showed of a clear light blue.
Afterwards I learned that this animal belonged to a breed that is
specially reserved for the use of the Child of the Sun on state
occasions, and that certain families possess hereditary rights in
connection with the breeding and training of these uncanny
quadrupeds. With a saddle and bridle of blue leather richly
ornamented with gold this white stallion stood ready caparisoned for
my person, and with some assistance owing to the weight of my
cloak I managed to mount without conscious loss of dignity. My long
mantle with its gorgeous devices was deftly spread over the horse's
back; my feet were fixed in the clumsy bucket-like stirrups, and the
reins placed in my hand. Thus seated, with Hiridia and other nobles
walking beside me, I was ready to start, whereupon my mounted
escort in their picturesque chain-armour led the way with a clanking
sound.
Leaving the temple gates we soon crossed a bridge spanning a
rushing river whose precipitous banks were thickly clothed with rich
vegetation of palm ferns, poinsettias and other tropical plants.
Pursuing our course we turned sharply to the right, whereupon I
almost immediately found myself in the streets of the capital with the
prospect of descending a very narrow steep paved roadway that led
eventually to the beach below. The streets themselves being too
narrow to permit of the presence of spectators, every window and
flat house-roof, and indeed every possible coign of vantage, was
occupied by the citizens of Tamarida, who all evinced the liveliest
enthusiasm in thus beholding their new sovereign in his progress.
Much to my relief my horse contrived to pick his way without mishap
down that fearful lane, which now and again broke into actual steps,
like the dingy mediæval streets of old Naples. Every second I was
dreading a stumble on the part of my queer-coloured steed, and a
consequent loss of majesty to myself; each moment I feared for the
fate of my weighty diadem. Mechanically I continued to smile and to
scatter benisons upon the vociferous crowds of loyal subjects, the
while I trusted to my own good luck as well as to Hiridia's careful
guidance; and it was with a sense of unspeakable gratitude that
eventually I reached the water-side that was lined with shipping of
which every yard-arm was positively bristling with eager brown
humanity. For some little distance we now pursued the curved line of
the shore, and then crossing another archway entered a gate
opening into the lower portion of the palace gardens. Here a large
number of servants, gardeners and labourers, with their families,
was drawn up to cheer and to prostrate themselves before me, and I
concluded my ride had drawn to an end. But it was not so, for I had
to cross the gardens and by means of another bridge or viaduct to
enter the southern quarter of the city and to repeat my previous
experience, with the important difference that this time I had to
ascend instead of descend the long narrow winding streets. This at
any rate was an improvement on my former trial, and I carried it
through with apparent unconcern, although it seemed an
interminable time before I was finally quit of the crowds and the
streets and was once more on my feet and in the purlieus of the
palace. Thus did I accomplish successfully the not inconsiderable
task allotted me on my second day in Meleager, and albeit hot and
exhausted by my exertions, I flattered myself internally that I had
borne the long ordeal of my coronation ceremonies with distinction.
It was almost dark when I dismounted from my peculiar but
trustworthy palfrey, to seek the peace and privacy of my bed-
chamber, where I was assisted to unrobe. A warm bath and a cool
plunge soon refreshed me, so that I felt capable of facing any further
demands on my bodily or mental strength that might be required of
me that night. There was a grand banquet with music and some
display of dancing and conjuring, but nothing more occurred of
special interest, though I was glad to observe and feel that I had won
the warm approval of the nobles of the Court, who sat feasting round
me. Thus ended my coronation day, and right glad I was to retire to
my bed and to sleep off the fatigue and excitement of its many
strange incidents.
I trust I have not wearied or disgusted the reader with my lengthy
account of all these events that took place during the first two days
of my reign in Meleager. Portions of what I have thus described will, I
fear, seem somewhat disjointed and obscure, but in excuse I can
plead that so did they also seem disjointed and obscure to myself at
the time, for at this early stage I had naturally learned next to nothing
of the peculiar conditions prevailing in my new kingdom. These I
intend to treat of in my subsequent chapters, whereby I hope to
throw some light on my own anomalous position as a semi-divine
monarch, on the composition and aims of the hierarchy, on the social
status of the various classes composing the realm, and on the daily
life of myself and of my people.
V
At this very early stage I had naturally not acquired the native
language of Meleager, and my sole communication was carried on
with the Arch-priest in a classical tongue. Besides this, apart from
the restricted nature of our intercourse, it was tolerably clear to me
that the members of the hierarchy as a whole showed themselves
anxious to suppress rather than to explain to me their guiding
principles of polity. With this impression firmly fixed in my mind, I
became more than ever eager and determined to learn the native
language with all speed, so that for the next few weeks I abandoned
myself with the greatest diligence to this object. What with my
sharpened wits and with my close application I made unexpectedly
rapid progress; nor should I omit to pay my tribute of gratitude to
Hiridia's pains and patience in this matter. For many hours daily we
engaged in our task, and, with the exception of taking the exercise
necessary for health, practically all my working time was occupied in
linguistic efforts. My toil was well rewarded, for after no very great
length of time I had the satisfaction of perceiving that daily I grew
more and more proficient in my subject, so that I was able to
converse with Hiridia with some degree of fluency and mutual
understanding.
This interval of vigorous study must have lasted about three months
in all, and in spite of many hints from the Arch-priest I firmly refused
to leave the precincts of the palace until I had gained the mastery of
the native tongue. As to whether this attitude of close seclusion
caused disappointment in the capital or annoyance among the
members of the council I paid no heed, but only showed my inflexible
resolution on this head. Having once succeeded completely in my
design, I made every effort to draw from Hiridia all conceivable
information about the land and people I had been called upon to rule,
my questions ranging over the whole field of possible inquiry. I
certainly did in this way contrive to amass a certain amount of
valuable knowledge, although I was by no means satisfied with all
the answers and explanations I received. For, if it was plain that the
Arch-priest and his colleagues were averse to supplying the required
details, it was equally plain that poor Hiridia with all the good
intentions possible was excessively ignorant of his own
surroundings; for instance, he could tell me next to nothing of the
mode of life, the general conditions and the interior affairs of any
class of the realm save that of the nobility to which he himself
belonged. As to the hierarchy, on which subject I plied him with the
greatest tact, I had to conclude that, whilst regarding the ruling caste
with unmeasured awe and respect, he was at the same time in
nowise intimate with any of that elusive body, though its members
were drawn solely from his own class and were in some cases his
own relations. Thus was I compelled to build my edifice of
knowledge and discovery of bricks without straw, so that often I was
fain to lose my temper in my fruitless endeavours to attain the truth;
happily, however, my patience and perseverance triumphed over my
natural exasperation. Daily I made careful notes in English on my
parchment, altering or adding to these notes from time to time, as
further inquiry or observation served to throw more light on the main
subject of my study. And it always amused me to observe the look of
profound admiration, even of alarm, wherewith Hiridia used to regard
the cabalistic scrolls I daily annotated on my table, which stood in the
long gallery facing the sea. At the same time I grew to learn that my
tutor's reverence was mingled with an intense feeling of loyalty and
devotion to myself, so that I instinctively knew that his life would be
willingly risked in my service, should any evil chance arise. Thus my
reputation of semi-divinity in this instance certainly carried some
advantages with it! As to the Arch-priest, who always insisted on
speaking in Latin to me, I did not indeed look for the same
unwavering fidelity as I found in Hiridia, yet with that curious extra
sixth sense of mine, that is never at fault, I knew he was pleased
with my painstaking efforts, and that he was for the present at least
very much my sincere friend and champion.
I think I had better at this point in my narrative offer a brief

description of the average day that I spend, so as to afford the
reader some notion of my duties, my pleasures and my occupations
—that is, of course, after I had succeeded in mastering the language
of my kingdom. The course of time being reckoned in Meleager after
the old Italian mode of counting the twenty-four hours from the
uprising of the sun, at the first streak of dawn watchers in the temple
proclaim the new-born day, by firing a piece of ordnance. This is
succeeded by loud trumpet calls in the barracks of the soldiery, and
the whole city awakens. Every one leaps from bed, and kneeling
repeats the following short prayer to the Sun:
"O Sun, mighty King, Father of Lights, I bless thee and thank thee for
another day! It is Thou alone that canst gladden our hearts, warm
our homes, nourish our crops, sweeten our grass, ripen our fruits. By
Thy Light alone Thy servants can live and adore Thee. Blessed be
Thy Face once more appearing!"
This simple formula is the universal morning prayer on Meleager,
whose inhabitants are true sun-worshippers, in the sense that they
attribute all good and all gifts to the sun's visible power and majesty
that are daily revealed to them. As for myself, however, being
deemed the Child of the Sun, I do not consider it incumbent on me to
indulge in this matutinal act of worship, though each dawn I wake to
see my servant lying prostrate on the floor with face turned
reverently towards the east. The act of prayer performed, he
approaches my couch with a goblet filled with some sort of mineral
water of a slightly bitter flavour, that is invariably swallowed before
arising. I then have a rather perfunctory bath in an adjoining room,
submitting myself to a rapid ablution with water slightly perfumed
with verbena, a scent that is reserved exclusively for the royal use. I
dress in the manner previously described, and am then ready for my
breakfast, which is usually set out in the open gallery that is already
flooded by the warm early sunlight. My repast consists of coffee
(which is extensively cultivated here), together with thick cream, a
manchet of fine white bread, and a platter heaped with superb fruit. I
leisurely enjoy these dainties and then (what on my first
acquaintance afforded me equal pleasure and surprise) I proceed to
smoke a cigar, or large cigarette, consisting of coarse granular
tobacco rolled in maize leaf, like the type of cigarette affected by the
natives of Brazil. For tobacco is largely grown here, and its leaves
are put to many uses, including this last-mentioned agreeable
purpose.
Whilst I am enjoying my fragrant cigarette, Hiridia invariably appears,
bringing me the news of the day, and thus conversing we soon stroll
into the gardens that are still fresh and gleaming with the dew. As I
stand about six feet three inches, and perhaps a trifle more, and my
tutor is of the average Meleagrian height of five foot five inches, I
used at first to find our walks on the terrace rendered unsatisfactory
by reason of our disparity in stature. To remedy this, I have caused a
low platform of stone to be constructed the whole of its length some
ten inches above the ground, and along this erection Hiridia now
walks beside me so that we can chat at a convenient level. I thought
the Arch-priest rather inclined to boggle at this suggestion, but I
contrived to carry my point all the same.
At the third hour of the day begins my work. First of all I hold an
audience, which is attended by the Arch-priest and some other
members of the hierarchy, whereat various matters of state
concerning the needs of the community, or the colonies, or the
troops are broached and discussed. An hour or more is generally
exhausted in this business, and by the fourth hour or a little later I
issue from the palace with a military escort and shadowed by the
umbrella of state to the judgment hall of the people, which is situated
in the city itself. (Or rather, to be quite explicit, I visit thus the two
courts of the northern and southern quarters of Tamarida on
alternate mornings.) Here I take my seat on a dais, and dispense
justice and advice to all and sundry in a fashion that constantly
reminds me of the multitudinous duties of a London stipendiary
magistrate, though the conditions of the two cases are happily very
diverse. My suppliants are drawn almost wholly from the lowest
estate of the realm, and sometimes the points submitted to my
judgment are of the most trivial character. But I sit and listen with all
the patience I can command, and then announce my verdict with all
the care and circumspection whereof I am capable. It is pathetic to
observe the intense faith my people have in my decisions; a suitor
who has lost his plea may perhaps feel disappointment, but he is
obviously fully resigned to my judgment, and accepts my award as
absolutely just and final. In short, the popular confidence in my
wisdom and sense of equity is unbounded, as the large and ever-
increasing roll of my daily petitioners can testify.
At noon a discharge of cannon, such as one still hears in the large
Italian cities at midday, resounds through the air, and the business of
the court is hurried to a conclusion. Everyone now retires to dine and
sleep, for at least two hours' space of rest is allotted to the whole
community. I return to the palace with my escort, quite ready for my
midday meal, which usually consists of eggs, fish, bread and fruit,
with plenty of the rough red or white Meleagrian wine, that is both
palatable and wholesome. To this repast I am in the habit of inviting
various members of the nobility, and I always find these small
informal parties far preferable to the rather dreary public supper of
the Court, which takes place each evening soon after sundown. After
eating, I sometimes play at chess (which is a very popular game
here) with one of my invited friends, whilst my other guests amuse
themselves as best they may; or at other times I listen to tales or
poems recited by such as aspire to become distinguished in this
department of Meleagrian social life. About the ninth or tenth hour I
walk in the gardens, and after that I change my clothes so as to
enjoy a vigorous game of hand-ball, which usually lasts till dusk.
After my exercise follows the bath, a lengthy but delightful daily
experience, for after the usual sweating and course of rubbing in the
heated chambers, one can plunge into a deep basin of cool water.
This pool also contains a cascade of artificial construction that one
shoots, in the manner employed by some of the islanders of the
South Seas, the bather being hurled over the falling volume of water
into another deep pool below. By swimming rapidly for a few strokes
beneath the surface one emerges farther on in the calm clear water
of a large natural basin that is fringed with ferns and verdure. A rapid
stream flowing down from the mountain-tops above through a
precipitous channel has at some time or other been cleverly utilised
in the construction of this cataract and lower pool, which have been
incorporated in these bathing arrangements for the palace.
Afterwards, I rest a while before dressing, when I proceed at my own
convenience to the large banqueting hall, though not before a salvo
of trumpets has given the signal that the workaday phase of
Meleagrian daily life is ended. All toil save that of domestic service
now ceases, and the whole city of Tamarida willingly resigns itself to
rest and recreation until the morrow's dawn. At the evening meal
eaten in public I remain but a short time, and then retire to my own
apartments, whither I summon, if so disposed, such persons as I feel
inclined to honour with an interview. Often however I sit or pace
alone for hours in the darkened or moonlit solitude of my loggia,
meditating on my strange fate and concocting plans for my future
course of conduct.
Such is the outline of my average day, but this programme is often
varied. In the first place, every seventh day being a public day of
thanks-giving and rest from labour, I have to attend the necessary
ceremonies in the temple instead of holding my informal court in the
city. On these days, too, I usually ride afield with some of my
courtiers, generally to go hunting into the wild mountainous region
behind the temple, where the keen air and the wide views over sea
and land seem to freshen my body and my spirits. Occasionally I pay
a visit on horseback to the seat of some hospitable nobleman,
whence we return late at night. At other times I honour some country
village with my presence, much to the delight and surprise of its
inhabitants. There are no books, as I have already explained, so that
in reality my life is necessarily compounded of action and meditation,
which on the whole has not hitherto caused me weariness or disgust.
Whether or no I shall always rest thus contented with this
monotonous routine of splendour and duty is a disagreeable and
anxious question that I try, with only moderate success, to thrust into
the background of my thoughts.
VI
Not a day passes here but that I lament my crass ignorance of even
the elementary principles of astronomy. In my school-days I was
never taught the use of the celestial globe, though my young brains
were burdened with the problems and theorems of Euclid, with
Greek enclitics and other scholastic lumber, dear to the dry-as-dust
soul of the English pedagogue. Such books dealing with the heavens
as I chanced to read in later life failed to leave an abiding impression
on my adult mind, with the result that now I can only bewail uselessly
the gaps in my early education. I mention this defect for a special
reason—namely, to crave allowance for the tentative character and
amateurish account of the features of my planet, which I want to
present to the reader.
From such calculations as I have made for myself and by myself I
believe the planet of Meleager to be insignificant in comparison with
the Earth. Possibly I may be mistaken in stating that its whole
surface is barely equal to the area of Australia, yet that is my
opinion. Its climate is subtropical in the central zone, gradually
tapering to temperate and cold towards its poles. Roughly speaking,
the "Regio Solis," the spreading peninsula that forms the main
portion of the kingdom of the Child of the Sun, possesses the climate
of Egypt or Mexico. Its summers are long and warm, though never
disagreeably torrid; its winter is of brief duration and normally wet
rather than cold, snow rarely falling near the coast. The changes of
spring and autumn are little marked, so that the whole course of the
year seems to consist of an extended warm season followed by a
spell of wet and cold. Southward of the Region of the Sun there
extends an apparently trackless ocean, on whose waters, I am told,
there is no land visible save a few barren islets and rocky reefs. But
then exploration for exploration's sake is wholly alien to the
Meleagrian outlook, and I much doubt whether the light sailing
vessels of the fishermen (who alone tempt these southern seas)

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Scattering Methods and their

Application in Colloid and Interface

For Information on all Elsevier publications

Publisher: John Fedor

neutron scattering, reflectivity measurements, Fraunhofer scattering, and diffusive wave

INTERFERENCE OF SCATTERED WAVES

Scattering Methods and their Application in Colloid and Interface Science

FIGURE 1.1 Path-length difference of two rays.

SCATTERING METHODS AND THEIR APPLICATION IN COLLOID AND INTERFACE SCIENCE

SCATTERING METHODS AND THEIR APPLICATION IN COLLOID AND INTERFACE SCIENCE

FIGURE 1.3 Momentum transfer.

SCATTERING METHODS AND THEIR APPLICATION IN COLLOID AND INTERFACE SCIENCE

SCATTERING METHODS AND THEIR APPLICATION IN COLLOID AND INTERFACE SCIENCE

A graphical representation of the polarizing factors can be seen in Figs. 15.115.3 in

SCATTERING METHODS AND THEIR APPLICATION IN COLLOID AND INTERFACE SCIENCE

FIGURE 1.4 Assembly of discrete particles, Rk(t) is the posi-

SCATTERING METHODS AND THEIR APPLICATION IN COLLOID AND INTERFACE SCIENCE

Assembly of Discrete Scatterers

In static scattering experiments we measure the scattered intensity as:

this holds for any electric field.

SCATTERING METHODS AND THEIR APPLICATION IN COLLOID AND INTERFACE SCIENCE

Monodisperse, Dilute Systems: Form Factor

From Fields to Intensities and Spatial Averaging

SCATTERING METHODS AND THEIR APPLICATION IN COLLOID AND INTERFACE SCIENCE

First we recall Eq. (1.22), neglecting any time dependence:

with V as the particle volume. We put r1 2 r2 5 r and use r2 5 r1 2 r:

(Please note the difference in notation

SCATTERING METHODS AND THEIR APPLICATION IN COLLOID AND INTERFACE SCIENCE

For homogeneous particles we find immediately that:

After normalization we have:

SCATTERING METHODS AND THEIR APPLICATION IN COLLOID AND INTERFACE SCIENCE

Substitution of u 5 qr cos ϕ leads to:

The Pair 2 Distance Distribution Function

SCATTERING METHODS AND THEIR APPLICATION IN COLLOID AND INTERFACE SCIENCE

By virtue of its invariance, it will play an important role later.

SCATTERING METHODS AND THEIR APPLICATION IN COLLOID AND INTERFACE SCIENCE

FIGURE 1.7 Definition of the PDDF p(r): the

SCATTERING METHODS AND THEIR APPLICATION IN COLLOID AND INTERFACE SCIENCE

Correlation Length and Chord Distribution

SCATTERING METHODS AND THEIR APPLICATION IN COLLOID AND INTERFACE SCIENCE

SCATTERING METHODS AND THEIR APPLICATION IN COLLOID AND INTERFACE SCIENCE

Now we want to introduce the concept of chords through a homogeneous particle. If we

where D is the maximum particle dimension, we get:

SCATTERING METHODS AND THEIR APPLICATION IN COLLOID AND INTERFACE SCIENCE

OTHER BOOKS COVERING THIS FIELD

SCATTERING METHODS AND THEIR APPLICATION IN COLLOID AND INTERFACE SCIENCE

THE RADIUS OF GYRATION AND THE GUINIER APPROXIMATION

According to the momentum theorem of Fourier transformation,4 the second moment

Scattering Methods and their Application in Colloid and Interface Science

and by setting a equal to R2g =3 we get the famous result of Guinier:

FINAL SLOPE OF THE SCATTERING CURVE, POROD LAW

SCATTERING METHODS AND THEIR APPLICATION IN COLLOID AND INTERFACE SCIENCE

PARTICLES WITH SPHERICAL SYMMETRY

SCATTERING METHODS AND THEIR APPLICATION IN COLLOID AND INTERFACE SCIENCE

For a homogeneous sphere with radius R we get:

and by straightforward partial integration we get:

SCATTERING METHODS AND THEIR APPLICATION IN COLLOID AND INTERFACE SCIENCE

Early on the following morning there were abundant signs to warn