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Frank Hoffmann
Solid-State Chemistry
De Gruyter Textbook
Frank Hoffmann
Solid-State Chemistry
ISBN 9783110657241
e-ISBN (PDF) 9783110657296
e-ISBN (EPUB) 9783110657500
Bibliographic information published by the Deutsche
Nationalbibliothek
The Deutsche Nationalbibliothek lists this publication in the
Deutsche Nationalbibliografie; detailed bibliographic data are
available on the Internet at http://dnb.dnb.de.
© 2023 Walter de Gruyter GmbH, Berlin/Boston
Contents
Preface
1 Introduction
2 Categorizing and description of crystal structures
2.1 Symmetry
2.2 Sphere (and rod) packings
2.3 Coordination polygons/polyhedra and the five Pauling
rules
2.3.1 The five Pauling rules
2.3.2 Effective coordination numbers, linking coordination
polyhedra, and Niggli notation
2.4 Prototypical compounds – structure types
2.5 Networks (nets)
3 Symmetry of crystals
3.1 The concept of the unit cell
3.1.1 The metric and the stoichiometry
3.1.2 Lattice points and motifs/bases
3.1.3 The seven crystal systems
3.2 The 14 Bravais lattices – centring of unit cells
3.3 Crystallographic point groups (crystal classes) – the
morphology of crystals
 3.3.1 Point symmetry elements
3.3.2 The 32 crystal classes
3.4 Further (micro-) translations – glide planes and screw
axes
3.4.1 Glide planes
3.4.2 Screw axes
3.5 The 230 space groups
3.5.1 Nomenclature of space groups
3.5.2 Deriving point groups from space groups
3.5.3 International tables for crystallography
4 Densest sphere packings
4.1 The hexagonal closest packing
4.2 The cubic closest packing
4.3 Voids in the hcp and ccp packing
4.4 Locations of interstitial sites along the packing
direction
4.5 Stacking variants/polytypes
5 Some important structure types
5.1 Metal structures – sphere packings in action
5.1.1 Cu (ccp or fcc) (Strukturbericht type A1)
5.1.2 Mg (hcp) (Strukturbericht type A3)
5.1.3 Lanthanoids and actinoids – stacking variants
5.1.4 W (bcc) (Strukturbericht type A2)
 5.1.5 α-Polonium
5.1.6 Special metal structures
5.2 (Ionic) compounds based on densest sphere packings
5.3 Compounds based on a cubic closest packing
5.3.1 NaCl (Strukturbericht type B1)
5.3.2 CdCl2 (Strukturbericht type C19)
5.3.3 CrCl3, AlCl3, and RhBr3
5.3.4 CaF2 (Strukturbericht type C1)
5.3.5 MgAl2O4 (spinel) (Strukturbericht type H11)
5.3.6 CaTiO3 (perovskite, Strukturbericht type E21)

5.4 Compounds based on a hexagonal closest packing

5.4.1 NiAs (Strukturbericht type B8)
5.4.2 CdI2 (Strukturbericht type C6)
5.4.3 β-V2N (Strukturbericht type L’32)
5.4.4 CaCl2 (Strukturbericht type C35), TiO2 (rutile)
(Strukturbericht type C4), and FeS2 (marcasite)
(Strukturbericht type C18)
5.4.5 BiI3 (Strukturbericht type D05)
5.4.6 β-TiCl3 and MoBr3/ZrI3/RuBr3
5.4.7 α-Al2O3 (corundum, Strukturbericht type D51) and
FeTiO3 (ilmenite, type E22)
5.4.8 ZnS (wurtzite) (Strukturbericht type B4)
5.4.9 Olivine (Mg,Mn,Fe)2SiO4 (Strukturbericht type S12)

5.5 Other important structure types not based on densest

packings
 5.5.1 CsCl (Strukturbericht type B2)
5.5.2 MoS2 (Strukturbericht type C7)

6 Defects in solids
6.1 Point defects
6.1.1 Point defects in crystals of elements
6.1.2 Point defects in ionic compounds
6.1.3 Kröger-Vink notation for point defects
6.1.4 Colour centres – a special kind of point defects
6.1.5 Swapping places – order-disorder phenomena and
the relation between superstructures and sublattices
6.1.6 Non-stoichiometric compounds and defect clusters
6.1.7 Substitutional and interstitial solid solutions
6.2 Line defects – dislocations
6.2.1 Edge dislocations
6.2.2 Screw dislocations
6.2.3 Movement of dislocations – plastic deformation
6.2.4 Crystallographic shear planes
6.3 Planar defects
6.3.1 Stacking faults, turbostratification, and
interstratification
6.3.2 Internal boundaries in single crystals – mosaicity
6.3.3 Grain boundaries
6.3.4 Twin boundaries
6.4 Volume defects
7 Phase diagrams
 7.1 One-component systems
7.2 Two-component systems
7.2.1 Complete miscibility – solid solutions
7.2.2 Singly eutectic systems
7.2.3 Systems with compound formation that melt
congruently
7.2.4 Systems with compound formation but incongruent
melting
7.2.5 Systems with compound formation with an upper or
lower limit of stability
8 Electronic structure of solid-state compounds
8.1 Bloch functions, Bloch’s theorem, the quantum
number k, and crystal orbitals
8.2 Bandwidth, density of states, and the Fermi level
8.3 The Peierls distortion
8.4 Band structures in two- and three-dimensional
systems
8.5 Examples of real band structures
8.5.1 ReO3 – a d1 compound with metallic properties
8.5.2 MoS2 – a d2 semiconductor with an indirect band
gap
8.6 Direct and indirect band gaps
9 Magnetic properties of solid-state compounds
 9.1 Diamagnetism and paramagnetism
9.1.1 Quantifying the magnetic moments of paramagnetic
substances
9.1.2 Pauli paramagnetism
9.2 Cooperative magnetic phenomena
The reason for the magnetically ordered states: exchange
interactions and band structure
9.2.1 Ferromagnetism
9.2.2 Antiferromagnetism and superexchange
interactions
9.2.3 Ferrimagnetism and double exchange
9.3 Some magnetic materials
9.3.1 Cubic spinel ferrites
9.3.2 Garnets
9.3.3 Hexagonal ferrites – magnetoplumbites
10 Phosphors, lamps, lasers, and LEDs
10.1 Phosphors
10.1.1 Fluorescent lamps
10.1.2 Phosphors for CRTs of TVs and computer screens
10.2 (Solid-state) lasers
10.2.1 Operation conditions
10.2.2 The ruby and the He-Ne laser
10.2.3 Classification of lasers
10.3 LEDs
11 Superconductivity
 11.1 From the metallic to the superconducting state
11.1.1 The Meissner-Ochsenfeld effect and type I and type
II superconductors
11.1.2 The BCS theory
11.2 Superconducting materials
11.2.1 The elements
11.2.2 Binary compounds, alloys, and intermetallics
11.2.3 Oxo cuprates – the high-temperature
superconducting revolution
1 Further superconducting compounds
12 Ceramics
12.1 Definition and classification of ceramics and the
ceramic method
12.2 (Alumo)silicate ceramics (traditional ceramics)
12.3 Binary oxide ceramics
12.3.1 α-Al2O3
12.3.2 ZrO2
12.3.3 TiO2, MgO, and BeO

12.4 Mixed oxide ceramics

12.4.1 Aluminium titanate
12.4.2 Barium titanate and lead zirconate titanate
12.5 Boride ceramics
12.6 Carbide ceramics
12.6.1 Boron carbide
 12.6.2 Silicon carbide
12.7 Silicide ceramics
12.8 Nitride ceramics
12.8.1 Boron nitride
12.8.2 Aluminium nitride
12.8.3 Silicon nitride and SiALONs
12.8.4 Aluminium oxynitride
12.9 Glass-ceramics
13 Intermetallic phases
13.1 Classification scheme
13.2 Ordered solid solutions – superstructures
13.2.1 Superstructures of the bcc packing
13.2.2 Superstructures derived from densest packings
(ccp or hcp)
13.3 Hume-Rothery phases
13.3.1 The γ-brass structure
13.4 Zintl phases
13.5 Packing-dominated phases (Frank-Kasper and Laves
phases)
13.5.1 The geometrical principles in FK phases and the FK
coordination polyhedra
13.5.2 Laves phases
13.5.3 Variants of Laves phases
13.5.4 σ-, µ-, M, P, and R phases
 13.5.5 The Cr3Si structure (Strukturbericht type A15)

14 Porous crystals, reticular chemistry, and the net

approach
14.1 Zeolites and zeotypes
14.1.1 Structural chemistry and building units of zeolites
14.1.2 Technically important zeolites
14.2 Metal-organic frameworks
14.2.1 Carbon capture and sequestration
14.2.2 Hydrogen storage
14.2.3 Methane storage
14.2.4 Water harvesting from air
14.2.5 Other (potential) applications
14.3 Networks and topology
14.3.1 Graphs and nets
14.3.2 Turning crystal structures into their underlying nets
14.3.3 Topology and net descriptors
14.3.4 Characterizing and identifying nets
Appendix A: Strukturbericht designations and Pearson
symbols
References
Subject index
Formula index

Preface
Dear reader,
You might ask: another book about solid-state chemistry!
Why? The first answer could be: Because the author just could
not resist the publisher’s invitation to write a textbook on that
subject. But that is not the whole story. It is not that there is a
shortage of books on this topic, but the cross-cutting nature and
the vast amount of research make it a worthy subject.
It might be also justified to ask whether textbooks are still
needed at all. Aren’t Wikipedia and the latest generation of AI
tools like ChatGPT, Dall-e, and Midjourney sufficient? If you
prompt ChatGPT for a short definition of solid-state chemistry,
you will get the following answer:

Solid-state chemistry is the study of the chemical and physical properties

of solids, including their synthesis, structure, bonding, and reactivity, with
a focus on understanding the relationship between these properties and
their applications.

That’s an excellent answer, no question! But if you ask

Midjourney to generate a picture of a “fancy crystal structure
composed of various types of atoms, mainly colored in blue and
orange, render look”, this is what you get:
An interesting and beautiful image, indeed, but not a picture of a
crystal structure. Maybe in the near future, the fusion of AI
language tools with AI art creation tools is the answer to all
questions! But I think that the decisive question is: Who will train
the students to ask the right questions and to be able to
evaluate the quality and correctness of the answers given by
ChatGPT? And in this sense, this book should serve as a
contribution to this goal.
 You are invited to delve into fascinating structures and
astonishing phenomena that occur in the solid state. You will
gain a basic understanding of the systematics and principles of
structures and their electronic, magnetic, and optical properties.
In any case, special emphasis was placed on clear, high-quality
illustrations and figures.
This small compendium offers a special selection of subjects,
covering relevant topics, but without repeating all the basics
from general chemistry that are already very well covered in
many textbooks. The choice of the presented topics and the
extent of their presentation have been made according to
merely subjective assessments and may please some experts in
the field as well as disappoint others – this cannot be avoided.
And, last but not least, two topics in the area of solid-state
chemistry that may be regarded as essential by others are not
covered at all. Silicates except for zeolites are left out, because
on the one hand it is a very comprehensive topic that deserves
its own presentation, but is, on the other hand, from a
conceptual point of view not very productive. Furthermore,
lithium-ion batteries are not covered. However, I am always
happy to receive wishes and ideas for updates in future editions.

I feel deeply indebted to a number of people who have been

very supportive in the preparation of the manuscript: First of all,
of course, Ria Sengbusch from De Gruyter, whom I thank for her
great supervision of the project and her patience, then Michael
Fischer, because he is simply the best content checker,
proofreader, and discussion partner in the world, then Ninja
Reineke for her support and for making sure that the author’s
thoughts were put into a better linguistic form, and finally my
boss, Michael Fröba, who allowed me to partially use my working
hours with textbook writing.
Frank Hoffmann
Hamburg, Germany, March 2023
1 Introduction
The question, what solid-state chemistry actually is, cannot
readily be answered, but the term already implies some obvious
characteristics: solid state refers to the aggregate state of the
matter that is involved and chemistry is defined as the study of
the structure, composition, properties, and behaviour of
substances, in particular, their changes during chemical
reactions.
It is not easy to discriminate solid-state chemistry from
related disciplines or from certain subdisciplines of other fields.
There is considerable overlap with solid-state physics, inorganic
structural chemistry, metallurgy, materials science, mineralogy,
and crystallography. A sharp distinction between solid-state
chemistry and these disciplines is not possible.
There are two types of matter in the solid state: crystalline
and amorphous substances. Crystals are homogeneous,
anisotropic solid-state bodies that show a strictly periodic order of
their constituents. Different approaches of categorizing and
describing crystal structures are presented in Chapter 2, while
the most important aspects of the symmetry of crystals are
described in Chapter 3. Amorphous substances also show a
certain order on the short range but lack the strict periodic order
(long-range order). Examples of amorphous materials are
glasses, wood, some types of ceramics, or plastics, although
some types of plastics are at least partially crystalline (for
instance, polyethylene terephthalate, PET). Wood also has a
structure that is not completely chaotic but shows a certain
repetition of some of its underlying constituents (in particular,
the biopolymer lignin) but they do not possess a strictly periodic
order.
 In this introduction to solid-state chemistry, we will deal
mainly with crystals, because we are interested in basic
structure-property relations, for which a regular and, to some
extent, also idealized structure is a prerequisite. However, some
important properties of real crystalline materials depend on the
kind and number of so-called defects, i.e., deviations from the
ideal structure. Therefore, the most important types of defects
will be presented in Chapter 6.
In our considerations of crystals, we will focus even more: we
assume that they are single crystals, although many solid-state
bodies, in particular metals and alloys, are polycrystalline, i.e.,
consist of an aggregate of smaller and differently oriented
crystallites, which are also called grains. The properties of many
technically important materials are in particular dependent on
this microstructure and are rather the subject of material science
and metallurgy.
Why is there a dedicated chemical discipline that refers to
the solid state of matter, while no explicit subcategory like
“liquid chemistry” or “gas-phase chemistry” exists? The author
would argue that these subcategories exist, but that they are not
called that way: chemical reactions are happening usually in a
fluid-like medium; in solution or in the gas phase! Only in fluid-
like media it is easy to ensure an intimate mixing between the
reaction partners. This is obviously different in a solid-state
body: we should be aware of the fact that in an ideal, defect-free
solid body, reactions can take place only at the interface and that
inside the body there are usually no transport pathways. This
often requires special synthesis methods, the oldest of which
have been known for thousands of years and are used in the
production of porcelain and ceramics; ceramics are discussed in
Chapter 12. In this context, the renaissance of mechanochemistry
is worth mentioning, which has meanwhile fallen into oblivion,
and which is also leading to new synthesis products and
materials in the field of solid-state chemistry. A good
introduction to this topic can be found in Ref. [1].
In order to understand the processes taking place during a
chemical reaction and to explore new pathways to hitherto
unknown compounds or materials, knowledge about the
structures of the compounds involved is a prerequisite.
Therefore, a large body of the book is devoted to the
presentation of prototypical structure types (Chapter 5) and
forms the basis for the understanding of more advanced
structures. The preparation and examination of new solid-state
compounds has led to technical advances as well as enormous
progress in understanding of the properties of materials. The
basics of electronic and magnetic properties of solid-state
compounds are presented in Chapters 8 and 9, respectively.
Optical properties and devices to generate light are the topic of
Chapter 10. It is fascinating to observe that there are still new
developments in the field of superconductivity and how different
the classes of compounds that show this phenomenon can be.
Superconductors are discussed in Chapter 11.
The book closes with a more detailed description of two
further material classes. Intermetallics are covered in Chapter
13, a topic that is often only very briefly presented, although they
represent a very large class of compounds and comprise those
with equally complex, astonishing, and appealing structures.
Finally, Chapter 14 deals with porous crystals, which, in addition
to classical zeolites, comprise the class of metal-organic
frameworks that could not be ignored in view of the rapid
developments taking place in this field.
2 Categorizing and description of
crystal structures
Crystals, i.e., chemical entities that show a strictly periodic order
of their constituents in two or three dimensions, can be
described and categorized in many different ways, all of which
emphasize a certain aspect of the crystal structure and
complement each other. The most important ones are the
following: (a) to describe the symmetry of the crystal, (b) to look
at the structure if it can be derived from a rather geometrical
aspect, if we assume that atoms or ions behave like hard
spheres, i.e., to emphasize the way the spheres (or rods) are
packed together, (c) to explore the neighbouring species around
a certain atom in the form of their coordination polyhedra, (d) to
categorize crystals according to prototypical compounds of a
certain type of structure (structure types), and (e) to specify the
way in which the atoms are connected (bonded) to other atoms,
i.e., to describe the network that a structure forms.

2.1 Symmetry
In crystallography, the most important aspect of a crystal
structure is its symmetry. The presence (or absence) of certain
symmetry elements leads to one of the 17 possible plane groups
(for two-periodic systems) or to one of the 230 possible space
groups (for three-periodic structures). A plane/space group is, in
principle, nothing more than stating which symmetry elements
are present in a structure. While the symmetry aspect is
completely covered with this specification, it ignores all other
aspects, like the nature of the constituents of a structure and
how they are held together. Therefore, also other objects, even
everyday objects, can be classified according to their symmetry:
from a symmetry point of view, a hexagonal tiling in your
bathroom is identical to a single graphene sheet of graphite.
Disparate substances like the pure metal copper, held together
by metallic bonds, the prototypical ionic compound NaCl (i.e.,
simple rock salt), held together by electrostatic interactions, noble
gases (except helium) at very low temperatures, and the solid
Buckminsterfullerene (at least at room temperature [→2]),
consisting of discrete C60 molecules (the famous football
molecule), which are interacting only via dispersion forces, all
have the same cubic symmetry: they all belong to the space
group Fm3¯m (space group no. 225; for an explanation of the
nomenclature of space groups, see below). What is different is,
of course, (i) the base (also called motif) and (ii) the dimension of
the unit cell; but the symmetry elements that are acting on this
base are the same. The crystallographic description then will be
completed by specifying the (i) lattice parameters and (ii) the
nature and position of the atomic species of the base, i.e., their
atomic (fractional) coordinates and sometimes their Wyckoff
letter, this means their multiplicity and site symmetry. We will
recap the most important aspects of the symmetry framework of
crystals in Chapter 3.

2.2 Sphere (and rod) packings

Nature generally tends to avoid structures with pronounced
voids. The reason for this is that the creation of surfaces or
interfaces requires energy. Therefore, there is a trend to realize
structures that are as compact as possible by minimizing the
surface area and thus reducing energy. In particular, for systems
composed of spheres (or rods, i.e., infinite cylinders; for an early
overview of crystal structures based on rod packings, see, for
instance, Ref. [→3]) structures are realized by the guiding
principle of how efficient and to which degree space can be
filled, so that a minimum of unfilled space is left. In the case of
only one type of spheres there are two equivalent densest
sphere packings: the cubic closest packing (ccp) and the
hexagonal closest packing (hcp).
A large number of metals crystallize in one of these two
structures (ccp, for instance, by Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, and
hcp, for instance, by Mg, Ti, Zr, Re, Ru, Os, Co, Cd). In both cases
the volume is filled by approx. 74%. And in both arrangements,
there are tetrahedral and octahedral voids, which can potentially
be occupied by some other, smaller atoms or ions; depending on
the composition of the (binary/ternary…) compound and the size
and charge of the counterions, a fraction or all of these voids are
filled. The structure of many ionic compounds can be described
by sphere packings, in which usually the smaller cations are
located in the voids of a ccp or hcp arrangement of the larger
anions. However, interestingly, there are also a significant
number of (simple) structures – although based on spheres –
where not densest packings are formed and the principle of
realizing structures that are as compact as possible seems to be
violated: in elements with a body-centred cubic structure (bcc),
for instance, V, Nb, Ta, Cr, Mo, W, α-Fe, the packing density is
only 68%, and in primitive cubic (pcu) arrangements, like in α-Po,
only 52% of the space is filled. And this means, of course, that
atoms are not hard spheres that behave like billiard balls.
The packing density and specifications of the coordination of
different kinds of sphere packings are gathered in →Table 2.1. A
more detailed view on densest sphere packings and their
crystallographic descriptions are given in Chapter 4.
Table 2.1: Packing density and coordination in different sphere
packings.
Sphere packing Packing Coordination Relative distance of the
density number of shell coordination shells
1 2 3 4 d2/d1 d3/d1 d4/d1
Primitive cubic 0.52 6 12 8 6 1.41 1.73 2
(pcu)
Body-centred 0.68 8 6 12 8 1.15 1.63 1.91
cubic (bcc)
Cubic closest 0.74 12 6 24 12 1.41 1.73 2
packing (ccp)
Hexagonal closest 0.74 12 6 8 24 1.41 1.63 1.73
packing (hcp)

2.3 Coordination polygons/polyhedra and

the five Pauling rules
A slightly extended and complementary approach to
categorizing crystal structures, mostly for compact and ionic
crystalline compounds, is based on the specification of
coordination polyhedra. Here, the coordination environments of
the cations and/or anions are specified together with
information on how these regular or also slightly distorted
polyhedra are connected to each other (i.e., if they are corner-
or/and edge- or/and face-connected). The advantage is that
structures, which are not based on a densest packing of one of
the components, can also be categorized and that polyhedra of
any kind can be considered (not only tetrahedral or octahedral
ones as in the case of sphere packings). Furthermore, this
concept also allows, at least partly, predicting and rationalizing
the crystal structure of ionic compounds. As early as 1929, Linus
Carl Pauling (1901–1994, American chemist, awarded the Nobel
Prize in chemistry in 1954 and the Nobel Peace Prize in 1962)
published his seminal work on the principles on which the
structure of complex ionic crystals is based, known as the five
Pauling rules (see below).
The most important coordination environments, their
names, and short symbols are shown in →Figure 2.1.

Figure 2.1: Important coordination polyhedra; l =

collinear/coplanar, n = non-collinear/non-coplanar (redrawn and
adapted from Ref. [→4]).

2.3.1 The five Pauling rules

In 1929, Pauling published five rules for predicting and
rationalizing the crystal structure of ionic compounds [→5].
First rule: the critical radius ratio
Pauling’s first rule is about the fact that the coordination
number and geometry of a coordination polyhedron that is
formed around a cation or anion by the respective other species
can be deduced from the cation-anion radius ratio, i.e., rc/ra,
assuming that the cation is smaller than the anion, which is
usually the case. (Of course, if the cation is larger than the anion
the quotient has to be inverted). Stable arrangements result
when cations or anions are surrounded by a number of the other
species, where the cations and anions are in contact with each
other. Pauling mathematically derived the minimum or critical
radius ratio for which the cation is in contact with a given
number of anions (considering the ions as rigid spheres). If the
cation and therefore the radius ratio is smaller, it will not be in
contact with the anions, resulting in instability and leading to a
lower coordination number. The critical radius ratios that
Pauling derived for different coordination numbers (CN) and
corresponding regular coordination polyhedra are shown in
→Table 2.2. Note that more irregular coordination environments
are not possible if only electrostatic forces and rigid spheres are
assumed. Note further that the limiting radii have to be
considered in such a way that the coordination number must
decrease if they are below the given value, but not in such a way
that the coordination number must necessarily increase if the
value is larger than the next limiting value.
Table 2.2: Overview of the critical radius ratios for selected
coordination numbers and polyhedra in ionic compounds, as
geometrically derived by Pauling.
Coordination Coordination Critical radius
number polygon/polyhedra ratio
3 Triangle 0.155
4 Tetrahedron 0.225
6 Octahedron 0.414
7 Capped octahedron 0.592
8 Square antiprism 0.645
8 Cube 0.732
9 Tricapped triangular prism 0.732
12 Cuboctahedron 1.000

In →Figure 2.2, the first Pauling rule is illustrated for the

coordination number 6 starting with a cation-anion arrangement
in which the radius ratio is actually larger than 0.414. This
arrangement is more stable than at the critical value of 0.414
since the cation is still in contact with six anions, but the anions
are further away from each other, so that their mutual
electrostatic repulsion is reduced. If, however, the ratio rises
above 0.732, a cubic geometry with a coordination number of 8
is favourable. If the radius ratio is below the critical value of
0.414, the stability limit is reached and a tetrahedral coordination
environment will be realized.
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Title: Redemption

Author: Robert F. Young

Illustrator: Ed Emshwiller

Release date: December 17, 2023 [eBook #72441]

Language: English

Original publication: New York, NY: Ziff-Davis Publishing Company,

1963

Credits: Greg Weeks, Mary Meehan and the Online Distributed

Proofreading Team at http://www.pgdp.net

*** START OF THE PROJECT GUTENBERG EBOOK

REDEMPTION ***
 REDEMPTION

By ROBERT F. YOUNG

Illustrated by EMSH

To love a saint is hard. To be one, that is harder.

But rejoice, now in the search of Capt. Nathaniel
Drake for Saint Annabelle Leigh. For you will read
this story many times in the future, as it assumes
what will be its rightful reputation as a classic.

[Transcriber's Note: This etext was produced from

Amazing Stories July 1963.
Extensive research did not uncover any evidence that
the U.S. copyright on this publication was renewed.]
They called him "The Jet-propelled Dutchman", but he was neither
Dutch nor jet-propelled. He was neo-Terran. In common with all
interplanetary spaceships of his day, his ship employed the Lamarre
displacement-drive. His name was Nathaniel Drake.
Legend has it that whenever he put into port he searched for a certain
woman in the hope of redeeming himself through love, but the
makers of legends are prone to draw parallels where no true parallels
exist. Nathaniel Drake searched for a certain woman—yes; but the
woman for whom he searched was even more of a ghost than he
was, and it was not love through which he hoped to redeem himself,
but hate.
His story begins in a region of space off the orbital shores of Iago
Iago, not long after the "Suez Canal" sprang its first "leak." In those
days, the Sirian Satrapy was at the height of her industrial career. Her
globular merchant ships busily plied her interplanetary seas, and her
Suez Canal freighters left Wayout almost daily for the ravenous marts
of Earth. Her planets prospered and her peoples dwelled in peace
and plenty and her politicians lived high on the hog. Only one of her
ten eco-sphere worlds knew not the blessings of civilization. This one
—Iago Iago—had been set aside for displaced indigenes in
accordance with section 5, paragraph B-81, of the Interstellar Code,
and was out of bounds to poet and pillager alike.
Nathaniel Drake was transporting a cargo of pastelsilk from Forget
Me Not to Dior. Forget Me Not and Dior, as any schoolboy will tell
you, are Sirius VIII and X respectively. Between their orbits lies the
orbit of Sirius IX, or Iago Iago. Now at the time of Drake's run, these
three planets were in conjunction, and consequently, in order to avoid
the gravitic pull of Iago Iago, he had programmed the automatic pilot
to swing the one-man ship into a wide detour. Although he did not
know it at the time, this detour had already brought the Fly by Night
into an area of space seldom "trodden by the foot of man."
When the "Suez Canal warp-process" proved impracticable for
interplanetary runs, interplanetary spacemen accepted their lot once
and for all and adopted three standard measures to combat solitude.
In the order of their importance, these measures were (1) girlie reali-
tapes, (2) girlie stereo-comics, and (3) hangoverless gin. Nathaniel
Drake had nothing against watered-down voyeurism, but he believed
in slaking a thirst, not in tantalizing it; hence during most of his runs
he concentrated on measure number three—i.e., hangoverless gin.
The present run was no exception, and he was in the middle of his
fifth fifth when the knock sounded on his cabin door.

He was not a man who took fright easily, and he never panicked. He
finished filling the glass he had just emptied, and set the bottle back
down on the chart table. He could hear the faint creaking of the hull
re-enforcing beams and the subdued murmuring of the grav
generator in the power room below him. For a while, there were no
other sounds. Then the knock came again.
Deliberately Drake got up, removed his ion gun from the rack above
his bunk, and laid it on the table. He sat back down again. "Come in,"
he said.
The door opened, and a girl entered.
She was quite tall. Her hair was light-brown, and her brown eyes
were set wide-apart in a thin, rather high-cheekboned face. They
were strange eyes. They seemed to be looking both outward and
inward at the same time. Atop her head sat a small kepi, its hue
strictly in keeping with the blue-grayness of her coatblouse and skirt.
Army of the Church of the Emancipation uniforms were noted for their
severity, and hers was no exception. In her case, however, the
severity seemed to have been lost in the shuffle, and catching the
sweep of her thighs as she moved into the room, Drake guessed why.
She was stacked, this girl was—stacked so stunningly that the fact
would have been self-evident even if she had been wearing a
blanket.
The thoroughness of his scrutiny neither escaped nor disconcerted
her. She did seem somewhat taken aback by his appearance,
however. Small wonder: he needed a haircut, and the side-burns and
chin whiskers that symbolized his captaincy had spread out into an
unkempt beard that made him look fifty years of age instead of the
thirty-two he actually was. "I—I imagine you're surprised to see me,"
she said.
Her voice was husky, but rich and full, and lent her words a
resonance that words seldom get to know. Drake dug up another
glass, poured it half full of gin, and offered it to her. She declined it, as
he had known she would. "No thank you," she said.
He drank the gin himself, then sat back in his chair and waited. While
waiting, he pondered the why and the whereby of her presence. The
whereby gave him no trouble: the starboard storeroom provided
sufficient space for a penurious passenger to stow away, and venality
was certainly a common enough ailment among port officials. The
why, however, was a horse of a different dimension.
She tethered it herself. "I want you to put me down on Iago Iago," she
said. "I'll pay you—pay you well. It would have been impractical for
me to take a passenger ship—with so many witnesses, the pilot
wouldn't have dared to land me. I—I gambled that a loner like
yourself might. Iago Iago's in conjunction now, and you won't lose
more than a few hours, and no one will ever know."
He was staring at her. "Iago Iago! Why should you want me to put you
down in Iago Iago?"
"The Polysirians are expecting the resurrection of their supreme saint.
I—I want to be on hand to witness it."
"Nonsense!" Drake said. "When you're dead, you're dead, and that
goes for saints and sinners alike."
Golden flecks danced briefly in her brown eyes. "Does it, Mr. Drake?
Then how do you explain the Potomac Peregrination?"
"I don't have to explain it because I don't believe in it. But to get back
to specifics: even assuming that there is a resurrection about to take
place on Iago Iago, there would be no way for the news to have
reached you."
"We have ways. Call it an interplanetary grapevine, if you like.... The
supreme saint prophesied that he would rise from the dead before the
passing of a single year and appear in the heavens for all to see, and
then descend among the people."

To gain time for reflection, Drake dropped the subject and asked her
name. "Annabelle," she said. "Saint Annabelle Leigh."
"And how old are you?"
"Twenty-three. Please put me down on Iago Iago, Mr. Drake."
"You said you were prepared to pay. How much?"
She turned her back on him, did something to her coatblouse, and
swung around a moment later with a money belt in her hands. She
held it out to him. "It contains two thousand credits. Count them, if
you like."
He shook his head. "Put it back on. I wouldn't risk losing my pilot's
license for ten times that amount."
"But there isn't any risk. I'm certainly not going to tell anyone that you
violated the code."
He regarded her speculatively. "Credits aren't the only form of
negotiable cash," he said.
She did not even blush. "I am prepared to pay in that kind of cash
too."
He was dumbfounded. Sex was not forbidden to Church of the
Emancipation girls, but usually at the merest hint of it they ran away
and hid somewhere. For a moment, remembering the sweep of her
thighs when she had entered the room, he was tempted; but only for
a moment. Recovering himself, he said, "I'm afraid that kind of cash
won't suffice either. My pilot's license is my bread and butter, and I
value my bread and butter highly." He stood up. "In my capacity as
captain of this vessel I hereby place you under arrest and order you
to return to your self-chosen quarters and to remain there for the
duration of this voyage."
Disbelief darkened her wide-apart brown eyes. Then golden motes of
anger came and chased the darkness away. She made a wild grab
for the ion gun on the table. He thwarted her easily, seized her arm
and, towering above her, escorted her out of the cabin and down the
companionway to the starboard storeroom. The starboard storeroom
adjoined the hull, and in common with all hull compartments, it was
equipped with a lock instead of a door. After shoving Saint Annabelle
Leigh inside, he adjusted the sealing mechanism so that the lock
could be opened only from the outside, then he turned to go.
She ran forward and caught his arm. There was desperation in her
brown eyes. "Please put me down on Iago Iago."
He freed his arm, stepped out into the corridor, and closed the lock
behind him.
An hour later, his ship passed through a Lambda-Xi field.

At least Drake thought it was a Lambda-Xi field. Certainly its effect

upon himself and the Fly by Night fitted the hypothetical description
given in section 3, chapter 9 of The Pilot's Handbook—a prose-work
which all spacemen were required to know by heart. The bulkheads
"shimmered"; the artificial atmosphere took on a "haze-like aspect";
the deck "desolidified". As for Drake himself, he experienced a
"painful prickling of nerve-ends and a slight vertigo". Then
translucence—"the prelude to total disintegration" came to ship and
master alike.
The handbook went on to state that in view of the fact that no one
had ever passed through a Lambda-Xi field and survived, all
knowledge pertaining to the preliminary effects of such a passage
had had to be extrapolated. It then added reassuringly that since
such fields were exceedingly rare, the danger they represented was
virtually negligible. The handbook said nothing, however, about any
handwriting on the wall. Handwriting there was, though, just the
same. Standing in his ship, through the translucent bulkheads and
hull of which he could make out the stars, Drake read the single word:
DEATH.
And yet death did not come. Neither did total disintegration—if a
distinction can be drawn. The Fly by Night went right on being
translucent, and so did Nathaniel Drake.
He took a tentative step. He took another. The deck supported him,
even though he could look down through it and through the decks
beneath it and through the hull and dimly see the stars—yes, and in
the nearer distance, the green globe of Iago Iago. He raised his hand,
and found that he could see through his flesh too. He got a mirror and
hung it on the wall and stared into his translucent face. He could see
right through his reflected eyes to the reflected wall behind him. He
could see right through his reflected cheeks and chin. Looking down
at himself, he found that he could see through his body. Through his
clothes. The translucence was such that the combination of clothes
and flesh cancelled out nakedness; nevertheless, his spaceshoes
and his spaceslacks and his thigh-length spacecoat were as
unquestionably spectral as he was.
And yet he felt whole. His body had solidity. He lived and breathed.
His ghostly ship still sped on its way to the distant shores of Dior.
Maybe he was dead, but he did not feel dead. I think, therefore I
am....
He got out the log and set down the co-ordinates of the field. Abruptly
he remembered his passenger, and ran down the companionway to
the starboard storeroom. However, he did not throw open the lock. If
he had he really would have been dead. Beyond the translucent
bulkhead lay the utter airlessness of space. The storeroom was gone.
So were all the other starboard compartments. So was the starboard
hull.
So was Saint Annabelle Leigh.
Nathaniel Drake sought out Madame Gin, only to find that she too
was a ghost of her former self. Nevertheless, she had not lost her
sixty-proof personality, and he consulted her at considerable length—
throughout the rest of the voyage, in fact—beseeching her to close up
the rather raw wound that had appeared in the side of his hitherto
impregnable conscience. This, Madame Gin obstinately refused to
do.
Between consultation he put his mind to work on a pair of pressing
problems. The first problem had to do with his cargo. It had come
through, every yard of it, but it had come through the way the ship
itself had come through—with the exception, of course, of the
starboard side, which had apparently passed through the center of
the field and been disintegrated altogether. It was ironic that a vessel
so effective when it came to nullifying thermo-nuclear devices could
be so utterly helpless against Lambda-Xi bombardment. Translucent
to begin with, the pastelsilk was now virtually transparent and
undoubtedly would be rejected by Dernier Cri Garments, the New
Paris firm that had ordered it. Worse, he was bonded for it, and if the
bonding company had to stand the entire loss, his ship would have to
be forfeited, and his career as an independent merchant spaceman
would be over.
The second problem had to do with his ghosthood. He did not have to
ask himself how people would react to his appearance because he
knew how he himself reacted to it whenever he looked into the mirror.
And it was no good arguing that the mirror was a ghost of its former
self too. He had merely to glance down at his hands to prove that the
degree of emphasis was negligible.
Invariably his thoughts reverted to the wound in his conscience,
whereupon he would rejoin Madame Gin at the chart table. Oh, he
had a hundred arguments in his favor. He had not asked Saint
Annabelle Leigh to stow away on his ship, had he? He had not known
that the ship was going to undergo Lambda-Xi bombardment, had
he? He had not known that the starboard section was doomed, had
he? But, while each question could be answered with a resounding
"no", the cold cruel truth marched inexorably on: If he had acceded to
Annabelle Leigh's request and put in for Iago Iago, she would still be
alive, and by not acceding to her request and by locking her in the
starboard storeroom, he had afforded Fate a very large assist.
"I wash my hands of it," he told Madame Gin. "I'm no more to blame
for her death than Pilate was to blame for the death of Christ the
First."
Madame Gin was silent.
"It's not my fault she was a saint," he said. "That's what makes it
seem worse than it really is—her being a saint, I mean."
Madame Gin said nothing.
"If she hadn't been a saint, it wouldn't be half so bad," Drake went on.
"If she'd been some bum peddling her posterior, it probably wouldn't
bother me at all. Why the hell should I care just because she was a
saint? It's crazy, I tell you. Hell, she wasn't even a good saint. Good
saints don't go around making the kind of proposition she made me,
no matter what the cause. Saint Annabelle Leigh isn't quite as noble
as you might think."
"Wasn't," said Madame Gin.
"All right then, I killed her. I'll even admit it. All I'm trying to say is that
her being a saint makes it worse."
"Murderer," said Madame Gin.
Nathaniel Drake seized her around the neck, whereupon she turned
into an empty bottle. He smashed the bottle on the edge of the table,
and spectral splinters flew in all directions. "I'm not a murderer!" he
screamed. "I'm not, I'm not, I'm not."

The first person to set eyes on "The Jet-propelled Dutchman" was the
pilot of the New Paris sewage barge. He saw the ghost ship rather
than its ghostly occupant, but this is of small consequence in view of
the fact that the same looseness of terminology that marks the
original legend also marks the second. He took one long look, then
dumped his cargo into orbit post-haste and put back into port. The
word spread rapidly, and when Nathaniel Drake put down some
fifteen minutes later the New Paris streets and rooftops were jammed
with jaded curiosity-seekers hopefully waiting to be scared out of their
wits. They were not disappointed.
It is one thing to scare people who have no chestnuts in the fire that
frightens them; it is quite another to scare people who have. The Fly
by Night had barely settled itself on its anti-grav jacks when a ground
car came skimming across the spacestrip and drew up before the
cargo dock. Out of the car stepped Thaddeus P. Terringer, president
of Dernier Cri Garments, Dorrel Numan, vice president of Dernier Cri
Garments, and the mayor of New Paris, who had his finger in the pie
à la mode somewhere but exactly where not even the IRS troopers
had been able to find out. Nathaniel Drake did not keep his visitors
waiting, but donned his anti-grav belt, opened the ventral lock, and
came drifting down to the dock. He had not shaved in two weeks, his
unkempt hair hung over his forehead, and he was as translucent as
tissue paper. They gaped.
The dock, rising as it did some five feet above the spacestrip, gave
him an eminence of sorts, and the eminence, in turn, gave him
confidence. "First time I ever rated a welcoming party," he said.
"Where's the red carpet?"
Thaddeus P. Terringer was the first of the tongue-tied trio to recover
his voice. He was a tall portly man, and he was attired as were his
companions in the latest of Dernier Cri Garments' creations for the
modern male: a pink tophat, a green, form-fitting suit of hand-twilled
thrip fuzz, and high-heeled plastigator shoes. "Drake," he said,
"you're drunk."
"No I'm not—I'm disintegrated."
Terringer took a backward step. So did Dorrel Numan and the mayor.
"You went through a Lambda-Xi field!" Numan exclaimed.
"That's about the size of it."
"Nonsense," Terringer said. "No one could survive Lambda-Xi
bombardment."
"You call this survival?" Drake asked.
"The cargo," groaned the mayor. "What about the cargo?"
Drake answered him. "With a little luck, it might make good wrapping
material for invisible bread. Put on your belt and go up and take a
look."
By this time, the port master had arrived upon the scene. "I don't want
anyone to board that ship till I've run a radiation check on it," he said.
"Meanwhile Drake, take it up and park it on the five-hundred foot
level. I don't know what happened to it and I don't know what
happened to you, but I'm not taking any chances."
"Bring back a sample bolt," Terringer said. "We won't be
contaminated if we look at it from a distance."

Drake nodded, adjusted his belt and guided himself up through the
ventral lock. He extended the anti-grav jacks to five hundred feet,
then, after getting a bolt of pastelsilk out of the hold, he drifted down
to the dock again. He unrolled the bolt a little ways and held it up so
that Terringer, Numan and the mayor, all of whom had retreated to a
safer distance, could get a good look at it. It was as tenuous as mist,
and owed what little visibility it still possessed to the exquisite
blueness which the worms of Forget Me Not had imparted to it.
Terringer groaned. So did Numan. So did the mayor.
"And it's all like that?" Terringer asked.
Drake nodded. "Every last yard."
"Take it back to Forget Me Not," Terringer said.
Drake stared at him. "Why? They won't make it good."
"Of course they won't. But they may be able to induce their worms to
reprocess it, or be able to salvage it in some other way. Meanwhile,
we'll just have to order another shipment." He regarded Drake
shrewdly. "You'd better hope they can salvage it. If they can't, your
bonding company will be liable, and you know what that means." He
glanced skyward to where the maimed and ghostly Fly by Night
hovered like an awry balloon. "Although how a ship in that condition
can be auctioned off is beyond me."
He turned, and together with Numan and the mayor re-entered the
ground car and skimmed away. Drake felt suddenly, desperately
sober. "Before you run a radiation check on my ship, run one on me,"
he told the port master. "I'm going into town and tie a good one on."
The port master grinned sympathetically. "Will do, Mr. Drake. I'll have
the doc take a look at you too."
He was as good as his word, and both the Fly by Night and Drake
checked out satisfactorily. Drake then went to see the port doctor,
who gave him a complete physical and finally confessed in a rather
awed voice that he could find nothing wrong with him. Afterward,
Drake visited the Port Exchange Bank, turned in his translucent credit
notes for a less spectral species, and withdrew his savings—-a
matter of some five hundred Rockefellows. However, he did not tie a
good one on. He did not tie any kind of a one on. He had barely set
foot outside the port when it all began. People looked at him and ran
away, or, even worse, stared at him and followed him wherever he
went. The first lush lair he went into emptied almost as soon as he
stepped in the door. In the next, the bartender refused to serve him.
He said hello to a pretty girl walking down the street, and she fainted
right before his eyes. He had gotten a haircut and a beard-trim by that
time in one of the automatic barberbooths scattered strategically
throughout the city, but apparently neither concession to propriety
had made his appearance any the less ghastly. Finally, in
desperation, he visited one of New Paris' leading physicists. The
physicist ran a lengthy series of tests on him, stared at him for a long
time, then asked, "Are you of Dutch descent by any chance?"
"No," Drake said, and left.
He bought ten fifths of gin and returned to his ship. It had already
been recharged and reprovisioned. Repairing it, of course, had been
out of the question. He thumbed his nose at the city as he soared
spaceward. Soon he was beyond the sewage belt and free among
the stars.
 Forget Me Not

In Nathaniel Drake's day, the worms of Forget Me Not were legion. All
over Silk City you could hear the sad susurrus of their tiny bodies as
they spun their colorful cocoons in the long low sheds thoughtfully
provided for them by the good folk of Pastelsilks, Inc. Toward twilight,
the whispering would fade away, then, with the timid twinkling of the
first star, it would come to life again and build up and up and up until
the night would be one great vast whispering of worms at work—-pink
worms, green worms, blue worms, yellow worms, spinning silk such
as had never been known before and will never be known again, for
now the worms of Forget Me Not are dead.
Raise one more monument to the onward march of mankind. Place it
beside the statue of the buffalo. You know where the statue of the
buffalo stands. It stands right next to the statue of the blue whale.
Nathaniel Drake was well acquainted with the whispering. Forget Me
Not was his birthplace, and his father had brought him to the fabled
city-farm when Drake was a small boy. In his capacity as merchant
spaceman, Drake had been there many times since, but it was the
first time that stood out the most vividly in his memory. His father had
been a grower of multi-pastels, a Forget Me Not plant genus whose
mulberry-like leaves formed the worms' main diet, and had
occasionally come to Silk City on business. On one of these
occasions he had brought the boy Nathaniel with him and taken him
through several of the long low sheds, hoping that the experience
might help the boy to forget about his mother, who had died the
spring before and about whom he had been brooding ever since.
There had been the sad susurrus of the worms working, and the
glowing of colorful cocoons in the gloom, and in the processing sheds
there had been the relentless turning of the automatic reels and the
tiny corpses falling to the floor, one by one, and the boy Nathaniel,
obsessed with thoughts of death, had wondered why more of the
larvae were not spared the ignominy of the heat-treatment ovens and
allowed to attain the apotheosis that was their birthright, not knowing
then the senseless selfishness of mankind.
The man Nathaniel had not wondered. The man Nathaniel had not
cared. The ghost of the man Nathaniel cared even less.
"Hello," said the ghost to a pretty girl as it passed her on the street.
The girl screamed, and ran away.
An old woman looked at him with horror in her eyes, then looked the
other way. An IRS trooper stopped and stared.
Nathaniel Drake went on.
Behind him in the Silk City spaceport, a trio of reluctant techs from
Pastelsilks, Inc. were conducting various tests upon his cargo in order
to determine whether or not it could be salvaged. As their findings
would have to be processed through the executive echelons of the
company and would not be made known to him till later in the day, he
had a few hours to kill.
He did not intend to kill them in lush lairs, however. He had a wound
to take care of.

It was the wound that had appeared in the side of his conscience. It
had festered on the trip in from Dior, and now it was so painful that he
could barely endure it. Madame Gin had only made it worse.
Conscience-wounds are different from physical wounds. In treating
physical wounds, you attack the effect. In treating conscience-
wounds, you attack the cause. Once the cause is eliminated, the
wound automatically closes. This is rarely possible, but quite often
the cause can be weakened, in which case the wound, while it will
never completely close, will at least be less painful. In Nathaniel
Drake's case, the cause was Saint Annabelle Leigh. If he could prove
to himself that his suspicions were correct and that she had been
something less than her sainthood would seem to indicate, a quantity
of his pain might go away, and if he could discredit her sainthood
altogether, his wound might close completely.