(eBook PDF) Atkins' Physical

Chemistry 11e: Volume 2: Quantum

Chemistry, Spectroscopy, and
Statistical Thermodynamics 11th
Edition
Visit to download the full and correct content document:
https://ebooksecure.com/download/ebook-pdf-atkins-physical-chemistry-11e-volume-
2-quantum-chemistry-spectroscopy-and-statistical-thermodynamics-11th-edition/
 Using the book vii

Presenting the mathematics

How is that done?

You need to understand how an equation is derived from rea-
sonable assumptions and the details of the mathematical steps
involved. This is accomplished in the text through the new
‘How is that done?’ sections, which replace the Justifications of
earlier editions. Each one leads from an issue that arises in the
text, develops the necessary mathematics, and arrives at the
equation or conclusion that resolves the issue. These sections
maintain the separation of the equation and its derivation
so that you can find them easily for review, but at the same
time emphasize that mathematics is an essential feature of
physical chemistry.
How is that done? 4A.1 Deducing the phase rule
The argument that leads to the phase rule is most easily appre-
ciated by first thinking about the simpler case when only one
component is present and then generalizing the result to an
arbitrary number of components.
Step 1 Consider the case where only one component is present
When only one phase is present (P = 1), both p and T can be
varied independently, so F = 2. Now consider the case where
two phases α and β are in equilibrium (P = 2). If the phases
are in equilibrium at a given pressure and temperature, their
chemical potentials must be equal:

The chemist’s toolkits The chemist’s toolkit 2 Properties of bulk matter

The chemist’s toolkits, which are much more numerous in this
edition, are reminders of the key mathematical, physical, and
chemical concepts that you need to understand in order to
follow the text. They appear where they are first needed. Many
of these Toolkits are relevant to more than one Topic, and a
compilation of them, with enhancements in the form of more
information and brief illustrations, appears on the web site.
www.oup.com/uk/pchem11e/
The state of a bulk sample of matter is defined by specifying the
values of various properties. Among them are:
The mass, m, a measure of the quantity of matter present
(unit: kilogram, kg).
The volume, V, a measure of the quantity of space the sam-
ple occupies (unit: cubic metre, m3).
The amount of substance, n, a measure of the number of
specified entities (atoms, molecules, or formula units) pre-
sent (unit: mole, mol).

Annotated equations and equation labels

d(1/f )/dx = −(1/f 2)df/dx
We have annotated many equations to help you follow how Um(T) = Um(0) + NA 〈εV〉 used twice
they are developed. An annotation can take you across the 2 V
dN A 〈ε V 〉 d 1  θV  eθ /T
equals sign: it is a reminder of the substitution used, an CVV,m = = Rθ V = R   θ /T
dT dT eθ /T −1 V
T
  (e −1)2
V

approximation made, the terms that have been assumed

constant, an integral used, and so on. An annotation can By noting that eθ
V
/T
= (eθ
V
/2T 2
) , this expression can be rearranged
also be a reminder of the significance of an individual term into
in an expression. We sometimes colour a collection of num- 2 2
 θ V   e −θ /2T 
V

bers or symbols to show how they carry from one line to the CVV,m = Rf (T ) f (T ) =   
 T   1− e −θ /T 
V

next. Many of the equations are labelled to highlight their

significance. Vibrational contribution to CV,m (13E.3)

Checklists of equations
A handy checklist at the end of each topic summarizes the Checklist of equations
most important equations and the conditions under which
they apply. Don’t think, however, that you have to memorize Property Equation
every equation in these checklists. Gibbs energy of mixing ΔmixG = nRT(xA ln xA + xB ln xB)
Entropy of mixing ΔmixS = −nR(xA ln xA + xB ln xB)
viii Using the book
Setting up and solving problems
Brief illustrations
A Brief illustration shows you how to use an equation or con-
cept that has just been introduced in the text. It shows you
how to use data and manipulate units correctly. It also helps
you to become familiar with the magnitudes of quantities.
Examples
Worked Examples are more detailed illustrations of the appli-
cation of the material, and typically require you to assemble
and deploy the relevant concepts and equations.
We suggest how you should collect your thoughts (that is a
new feature) and then proceed to a solution. All the worked
Examples are accompanied by Self-tests to enable you to test
your grasp of the material after working through our solution
as set out in the Example.
Discussion questions
Discussion questions appear at the end of every Focus, and are
organised by Topic. These questions are designed to encour-
age you to reflect on the material you have just read, to review
the key concepts, and sometimes to think about its implica-
tions and limitations.
Exercises and problems
Exercises and Problems are also provided at the end of every
Focus and organised by Topic. Exercises are designed as
relatively straightforward numerical tests; the Problems are
more challenging and typically involve constructing a more
detailed answer. The Exercises come in related pairs, with
final numerical answers available online for the ‘a’ questions.
Final numerical answers to the odd-numbered Problems are
also available online.
Integrated activities
At the end of every Focus you will find questions that span
several Topics. They are designed to help you use your knowl-
edge creatively in a variety of ways.
Brief illustration 3B.1
When the volume of any perfect gas is doubled at constant
temperature, Vf/Vi = 2, and hence the change in molar entropy
of the system is
ΔSm = (8.3145 J K−1 mol−1) × ln 2 = +5.76 J K−1 mol−1
Example 1A.1 Using the perfect gas law
In an industrial process, nitrogen gas is introduced into
a vessel of constant volume at a pressure of 100 atm and a
temperature of 300 K. The gas is then heated to 500 K. What
pressure would the gas then exert, assuming that it behaved
as a perfect gas?
Collect your thoughts The pressure is expected to be greater
on account of the increase in temperature. The perfect gas
FOCUS 3 The Second and Third Laws
Assume that all gases are perfect and that data refer to 298.15 K unless otherwise stated.
TOPIC 3A Entropy
Discussion questions
D3A.1 The evolution of life requires the organization of a very large number D3A.2 Discuss the significance of the terms ‘dispersal’ and ‘disorder’ in the
of molecules into biological cells. Does the formation of living organisms context of the Second Law.
violate the Second Law of thermodynamics? State your conclusion clearly and
D3A.3 Discuss the relationships between the various formulations of the
present detailed arguments to support it.
Second Law of thermodynamics.
Exercises
E3A.1(a) Consider a process in which the entropy of a system increases by gas of mass 14 g at 298 K doubles its volume in (a) an isothermal reversible
125 J K−1 and the entropy of the surroundings decreases by 125 J K−1. Is the
process spontaneous?
E3A.1(b) Consider a process in which the entropy of a system increases by
expansion, (b) an isothermal irreversible expansion against pex = 0, and (c) an
adiabatic reversible expansion.
E3A.4(b) Calculate the change in the entropies of the system and the
105 J K−1 and the entropy of the surroundings decreases by 95 J K−1. Is the
process spontaneous?
surroundings, and the total change in entropy, when the volume of a sample
of argon gas of mass 2.9 g at 298 K increases from 1.20 dm3 to 4.60 dm3 in (a)
an isothermal reversible expansion, (b) an isothermal irreversible expansion
E3A.2(a) Consider a process in which 100 kJ of energy is transferred reversibly
and isothermally as heat to a large block of copper. Calculate the change in
entropy of the block if the process takes place at (a) 0 °C, (b) 50 °C.
against pex = 0, and (c) an adiabatic reversible expansion.
E3A.5(a) In a certain ideal heat engine, 10.00 kJ of heat is withdrawn from the
E3A.2(b) Consider a process in which 250 kJ of energy is transferred reversibly
and isothermally as heat to a large block of lead. Calculate the change in
hot source at 273 K and 3.00 kJ of work is generated. What is the temperature
of cold sink?
entropy of the block if the process takes place at (a) 20 °C, (b) 100 °C. E3A.5(b) In an ideal heat engine the cold sink is at 0 °C. If 10.00 kJ of heat
E3A.3(a) Calculate the change in entropy of the gas when 15 g of carbon dioxide
gas are allowed to expand isothermally from 1.0 dm3 to 3.0 dm3 at 300 K.
is withdrawn from the hot source and 3.00 kJ of work is generated, at what
temperature is the hot source?
E3A.3(b) Calculate the change in entropy of the gas when 4.00 g of nitrogen is
3 3
allowed to expand isothermally from 500 cm to 750 cm at 300 K.
E3A.6(a) What is the efficiency of an ideal heat engine in which the hot source
is at 100 °C and the cold sink is at 10 °C?
E3A.6(b) An ideal heat engine has a hot source at 40 °C. At what temperature
E3A.4(a) Calculate the change in the entropies of the system and the
must the cold sink be if the efficiency is to be 10 per cent?
surroundings, and the total change in entropy, when a sample of nitrogen
Problems
P3A.1 A sample consisting of 1.00 mol of perfect gas molecules at 27 °C is transferred to or from the gas. (d) Explain why the work done is equal to the
expanded isothermally from an initial pressure of 3.00 atm to a final pressure difference between the heat extracted from the hot source and that deposited
of 1.00 atm in two ways: (a) reversibly, and (b) against a constant external in the cold sink. (e) Calculate the work done over the cycle and hence the
pressure of 1.00 atm. Evaluate q, w, ΔU, ΔH, ΔS, ΔSsurr, and ΔStot in each case. efficiency η. (f) Confirm that your answer agrees with the efficiency given by
eqn 3A.9 and that your values for the heat involved in the isothermal stages
P3A.2 A sample consisting of 0.10 mol of perfect gas molecules is held by a
are in accord with eqn 3A.6.
piston inside a cylinder such that the volume is 1.25 dm3; the external pressure
is constant at 1.00 bar and the temperature is maintained at 300 K by a P3A.4 The Carnot cycle is usually represented on a pressure−volume
thermostat. The piston is released so that the gas can expand. Calculate (a) the diagram (Fig. 3A.8), but the four stages can equally well be represented
volume of the gas when the expansion is complete; (b) the work done when on temperature−entropy diagram, in which the horizontal axis is entropy
the gas expands; (c) the heat absorbed by the system. Hence calculate ΔStot. and the vertical axis is temperature; draw such a diagram. Assume that the
P3A.3 Consider a Carnot cycle in which the working substance is 0.10 mol of
perfect gas molecules, the temperature of the hot source is 373 K, and that
temperature of the hot source is Th and that of the cold sink is Tc, and that the
volume of the working substance (the gas) expands from VA to VB in the first
isothermal stage. (a) By considering the entropy change of each stage, derive
of the cold sink is 273 K; the initial volume of gas is 1.00 dm3, which doubles
an expression for the area enclosed by the cycle in the temperature−entropy
over the course of the first isothermal stage. For the reversible adiabatic stages
diagram. (b) Derive an expression for the work done over the cycle. (Hint: The
it may be assumed that VT 3/2 = constant. (a) Calculate the volume of the gas
work done is the difference between the heat extracted from the hot source
after Stage 1 and after Stage 2 (Fig. 3A.8). (b) Calculate the volume of gas after
and that deposited in the cold sink; or use eqns 3A.7 and 3A.9) (c) Comment
Stage 3 by considering the reversible adiabatic compression from the starting
on the relation between your answers to (a) and (b).
point. (c) Hence, for each of the four stages of the cycle, calculate the heat
 Using the book ix

There is a lot of additional material on the web

IMPAC T 1 …ON ENVIRONMENTAL SCIENCE: A DEEPER LOOK 2 The fugacity

The gas laws and the weather
At various stages in the development of physical chemistry In this expression, f1 is the fugacity when the pressure is
it is necessary to switch from a consideration of ideal- p1 and f2 is the fugacity when the pressure is p2. That is,
The biggest sample of gas readily accessible to us is the 25 ized systems to real systems. In many cases it is desirable from eqn 3b,
atmosphere, a mixture of gases with the composition to preserve the form of the expressions that have been
derived for an idealized system. Then deviations from the
p2 f2
summarized in Table 1. The composition is maintained
moderately constant by diffusion and convection (winds,
20
idealized behaviour can be expressed most simply. For
∫ p1
Vm d p = RT ln
f1 (4a)
Altitude, h/km
particularly the local turbulence called eddies) but the 15 instance, the pressure-dependence of the molar Gibbs
For a perfect gas,
pressure and temperature vary with altitude and with energy of a perfect gas is
the local conditions, particularly in the troposphere (the 10
p2
 p  p2
‘sphere of change’), the layer extending up to about 11 km. Gm = G m + RT ln  −○−  ∫ Vperfect ,mdp = RT ln (4b)
−−
○
(1a)
p  p1 p1

‘Impact’ sections Group theory tables

‘Impact’ sections show how physical chemistry is applied in a
variety of modern contexts. They showcase physical chemistry
as an evolving subject. www.oup.com/uk/pchem11e/
A deeper look
These online sections take some of the material in the text
further and are there if you want to extend your knowledge
and see the details of some of the more advanced derivations
www.oup.com/uk/pchem11e/
Comprehensive group theory tables are available to download.
Molecular modelling problems
Files containing molecular modelling problems can be down-
loaded, designed for use with the Spartan Student™ software.
However they can also be completed using any modelling
software that allows Hartree–Fock, density functional, and
MP2 calculations. The site can be accessed at www.oup.com/
uk/pchem11e/.

To the instructor
We have designed the text to give you maximum flexibility in
the selection and sequence of Topics, while the grouping of
Topics into Focuses helps to maintain the unity of the subject.
Additional resources are:
Figures and tables from the book
Lecturers can find the artwork and tables from the book in
ready-to-download format. These may be used for lectures
without charge (but not for commercial purposes without
specific permission).
Key equations
Supplied in Word format so you can download and edit them.
Lecturer resources are available only to registered adopters of
the textbook. To register, simply visit www.oup.com/uk/pchem11e/
and follow the appropriate links.

Solutions manuals
Two solutions manuals have been written by Peter Bolgar, The Instructor’s Solutions Manual provides full solutions
Haydn Lloyd, Aimee North, Vladimiras Oleinikovas, Stephanie to the ‘b’ Exercises and to the even-numbered Problems
Smith, and James Keeler. (available to download online for registered adopters of the
The Student’s Solutions Manual (ISBN 9780198830085) book only).
provides full solutions to the ‘a’ Exercises and to the odd-
numbered Problems.
about the authors

Peter Atkins is a fellow of Lincoln College, Oxford, and was Professor of Physical Chemistry in the
University of Oxford. He is the author of over seventy books for students and a general audience. His
texts are market leaders around the globe. A frequent lecturer in the United States and throughout the
world, he has held visiting professorships in France, Israel, Japan, China, Russia, and New Zealand.
He was the founding chairman of the Committee on Chemistry Education of the International Union
of Pure and Applied Chemistry and was a member of IUPAC’s Physical and Biophysical Chemistry
Division.

Photograph by Natasha
Ellis-Knight.

Julio de Paula is Professor of Chemistry at Lewis & Clark College. A native of Brazil, he received a
B.A. degree in chemistry from Rutgers, The State University of New Jersey, and a Ph.D. in biophysical
chemistry from Yale University. His research activities encompass the areas of molecular spectroscopy,
photochemistry, and nanoscience. He has taught courses in general chemistry, physical chemistry, bio-
physical chemistry, inorganic chemistry, instrumental analysis, environmental chemistry, and writ-
ing. Among his professional honours are a Christian and Mary Lindback Award for Distinguished
Teaching, a Henry Dreyfus Teacher-Scholar Award, and a Cottrell Scholar Award from the Research
Corporation for Science Advancement.

James Keeler is a Senior Lecturer in Chemistry at the University of Cambridge, and Walters Fellow in
Chemistry at Selwyn College, Cambridge. He took his first degree at the University of Oxford and con-
tinued there for doctoral research in nuclear magnetic resonance spectroscopy. Dr Keeler is Director of
Teaching for undergraduate chemistry, and teaches courses covering a range of topics in physical and
theoretical chemistry.

Photograph by Nathan Pitt,

©University of Cambridge.
acknowledgements
A book as extensive as this could not have been written with-
out significant input from many individuals. We would like to
reiterate our thanks to the hundreds of people who contrib-
uted to the first ten editions. Many people gave their advice
based on the tenth edition, and others, including students,
reviewed the draft chapters for the eleventh edition as they
emerged. We wish to express our gratitude to the following
colleagues:
Andrew J. Alexander, University of Edinburgh
Stephen H. Ashworth, University of East Anglia
Mark Berg, University of South Carolina
Eric Bittner, University of Houston
Melanie Britton, University of Birmingham
Eleanor Campbell, University of Edinburgh
Andrew P. Doherty, Queen’s University of Belfast
Rob Evans, Aston University
J.G.E. Gardeniers, University of Twente
Ricardo Grau-Crespo, University of Reading
Alex Grushow, Rider University
Leonid Gurevich, Aalborg University
Ronald Haines, University of New South Wales
Patrick M. Hare, Northern Kentucky University
John Henry, University of Wolverhampton
Karl Jackson, Virginia Union University
Carey Johnson, University of Kansas
George Kaminski, Worcester Polytechnic Institute
Scott Kirkby, East Tennessee State University
Kathleen Knierim, University of Louisiana at Lafayette
Jeffry Madura, University of Pittsburgh
David H. Magers, Mississippi College
Kristy Mardis, Chicago State University
Paul Marshall, University of North Texas
Laura R. McCunn, Marshall University
Allan McKinley, University of Western Australia
Joshua Melko, University of North Florida
Yirong Mo, Western Michigan University
Gareth Morris, University of Manchester
Han J. Park, University of Tennessee at Chattanooga
Rajeev Prabhakar, University of Miami
Gavin Reid, University of Leeds
Chad Risko, University of Kentucky
Nessima Salhi, Uppsala University
Daniel Savin, University of Florida
Richard W. Schwenz, University of Northern Colorado
Douglas Strout, Alabama State University
Steven Tait, Indiana University
Jim Terner, Virginia Commonwealth University
Timothy Vaden, Rowan University
Alfredo Vargas, University of Sussex
Darren Walsh, University of Nottingham
Collin Wick, Louisiana Tech University
Shoujun Xu, University of Houston
Renwu Zhang , California State University
Wuzong Zhou, St Andrews University
We would also like to thank Michael Clugston for proofread-
ing the entire book, and Peter Bolgar, Haydn Lloyd, Aimee
North, Vladimiras Oleinikovas, Stephanie Smith, and James
Keeler for writing a brand new set of solutions. Last, but by
no means least, we acknowledge our two commissioning
­editors, Jonathan Crowe of Oxford University Press and Jason
Noe of OUP USA, and their teams for their assistance, advice,
­encouragement, and patience.
brief contents

PROLOGUE 1 FOCUS 12 Magnetic resonance 255

FOCUS 7 Quantum theory 3 FOCUS 13 Statistical thermodynamics 299

FOCUS 8 Atomic structure and spectra 71 Resource section

1 Common integrals 352
FOCUS 9 Molecular structure 109 2 Units 354
3 Data 355
4 Character tables 363
FOCUS 10 Molecular symmetry 155
Index367
FOCUS 11 Molecular spectroscopy 185
Full Contents

Conventionsxix (a) The acceptable solutions 31

(b) The properties of the wavefunctions 32
List of tables xx
(c) The properties of the energy 33
List of The chemist’s toolkitsxxi
7D.3 Confined motion in two and more dimensions 34
List of material provided as A deeper lookxxii (a) Energy levels and wavefunctions 34
List of Impactsxxiii (b) Degeneracy 35
7D.4 Tunnelling 36

PROLOGUE Energy, temperature, Checklist of concepts 39

and chemistry 1 Checklist of equations 40

TOPIC 7E Vibrational motion 41

FOCUS 7 Quantum theory 3 7E.1 The harmonic oscillator 41
(a) The energy levels 42
TOPIC 7A The origins of quantum mechanics 5
(b) The wavefunctions 43
7A.1 Energy quantization 5
7E.2 Properties of the harmonic oscillator 45
(a) Black-body radiation 5
(a) Mean values 45
(b) Heat capacity 8
(b) Tunnelling 46
(c) Atomic and molecular spectra 9
Checklist of concepts 47
7A.2 Wave–particle duality 10
(a) The particle character of electromagnetic radiation 10 Checklist of equations 48
(b) The wave character of particles 12
TOPIC 7F Rotational motion 49
Checklist of concepts 13
7F.1 Rotation in two dimensions 49
Checklist of equations 13
(a) The solutions of the Schrödinger equation 51
(b) Quantization of angular momentum 52
TOPIC 7B Wavefunctions 14
7F.2 Rotation in three dimensions 53
7B.1 The Schrödinger equation 14
(a) The wavefunctions and energy levels 53
7B.2 The Born interpretation 15
(b) Angular momentum 56
(a) Normalization 16
(c) The vector model 56
(b) Constraints on the wavefunction 17
Checklist of concepts 58
(c) Quantization 18
Checklist of equations 58
Checklist of concepts 18
Checklist of equations 18
FOCUS 8 Atomic structure and spectra 71
TOPIC 7C Operators and observables 19
7C.1 Operators 19 TOPIC 8A Hydrogenic atoms 72
(a) Eigenvalue equations 19 8A.1 The structure of hydrogenic atoms 72
(b) The construction of operators 20 (a) The separation of variables 72
(c) Hermitian operators 21 (b) The radial solutions 73
(d) Orthogonality 22 8A.2 Atomic orbitals and their energies 76
7C.2 Superpositions and expectation values 23 (a) The specification of orbitals 76

7C.3 The uncertainty principle 25 (b) The energy levels 76

(c) Ionization energies 77
7C.4 The postulates of quantum mechanics 27
(d) Shells and subshells 77
Checklist of concepts 28
(e) s Orbitals 78
Checklist of equations 28 (f) Radial distribution functions 79
(g) p Orbitals 81
TOPIC 7D Translational motion 29
(h) d Orbitals 82
7D.1 Free motion in one dimension 29
Checklist of concepts 82
7D.2 Confined motion in one dimension 30
Checklist of equations 83
xvi Full Contents

TOPIC 8B Many-electron atoms 84 9C.2 Photoelectron spectroscopy 130

8B.1 The orbital approximation 84 Checklist of concepts 131
8B.2 The Pauli exclusion principle 85 Checklist of equations 132
(a) Spin 85
(b) The Pauli principle 86
TOPIC 9D Molecular orbital theory: ­heteronuclear
8B.3 The building-up principle 87
diatomic molecules 133
(a) Penetration and shielding 87
9D.1 Polar bonds and electronegativity 133
(b) Hund’s rules 89 9D.2 The variation principle 134
(c) Atomic and ionic radii 91 (a) The procedure 135
(d) Ionization energies and electron affinities 92 (b) The features of the solutions 137

8B.4 Self-consistent field orbitals 93 Checklist of concepts 138

Checklist of concepts 93 Checklist of equations 138
Checklist of equations 94
TOPIC 9E Molecular orbital theory: ­polyatomic
TOPIC 8C Atomic spectra 95 molecules 139
8C.1 The spectra of hydrogenic atoms 95 9E.1 The Hückel approximation 139
(a) An introduction to the method 139
8C.2 The spectra of many-electron atoms 96
(b) The matrix formulation of the method 140
(a) Singlet and triplet terms 96
(b) Spin–orbit coupling 97 9E.2 Applications 143
(c) Term symbols 100 (a) π-Electron binding energy 143

(d) Hund’s rules 103 (b) Aromatic stability 144

(e) Selection rules 103 9E.3 Computational chemistry 145

Checklist of concepts 104 (a) Semi-empirical and ab initio methods 146
(b) Density functional theory 147
Checklist of equations 104
(c) Graphical representations 147
Checklist of concepts 148
FOCUS 9 Molecular structure 109 Checklist of equations 148
PROLOGUE The Born–Oppenheimer approximation 111
FOCUS 10 Molecular symmetry 155
TOPIC 9A Valence-bond theory 112
9A.1 Diatomic molecules 112 TOPIC 10A Shape and symmetry 156
9A.2 Resonance 114 10A.1 Symmetry operations and symmetry elements 156

9A.3 Polyatomic molecules 114 10A.2 The symmetry classification of molecules 158
(a) Promotion 115 (a) The groups C1, Ci, and Cs 160

(b) Hybridization 115 (b) The groups Cn, Cnv, and Cnh 160

(c) The groups Dn, Dnh, and Dnd 161
Checklist of concepts 118
(d) The groups S n 161
Checklist of equations 118
(e) The cubic groups 161
(f) The full rotation group 162
TOPIC 9B Molecular orbital theory:
the hydrogen molecule-ion 119 10A.3 Some immediate consequences of symmetry 162
(a) Polarity 162
9B.1 Linear combinations of atomic orbitals 119
(b) Chirality 163
(a) The construction of linear combinations 119
(b) Bonding orbitals 121 Checklist of concepts 163
(c) Antibonding orbitals 122 Checklist of operations and elements 164
9B.2 Orbital notation 124
TOPIC 10B Group theory 165
Checklist of concepts 124
10B.1 The elements of group theory 165
Checklist of equations 124
10B.2 Matrix representations 166
TOPIC 9C Molecular orbital theory: homonuclear (a) Representatives of operations 166
(b) The representation of a group 167
diatomic molecules 125
(c) Irreducible representations 168
9C.1 Electron configurations 125
(d) Characters 169
(a) σ Orbitals and π orbitals 125
(b) The overlap integral 127
10B.3 Character tables 169
(a) The symmetry species of atomic orbitals 170
(c) Period 2 diatomic molecules 128
 Full Contents xvii

(b) The symmetry species of linear combinations of orbitals 171 (b) The Birge–Sponer plot 213
(c) Character tables and degeneracy 172 11C.4 Vibration–rotation spectra 214
Checklist of concepts 173 (a) Spectral branches 215
Checklist of equations 173 (b) Combination differences 216
11C.5 Vibrational Raman spectra 216
TOPIC 10C Applications of symmetry 174 Checklist of concepts 217
10C.1 Vanishing integrals 174 Checklist of equations 218
(a) Integrals of the product of functions 175
(b) Decomposition of a representation 176 TOPIC 11D Vibrational spectroscopy of polyatomic
10C.2 Applications to molecular orbital theory 177 molecules 219
(a) Orbital overlap 177 11D.1 Normal modes 219
(b) Symmetry-adapted linear combinations 177 11D.2 Infrared absorption spectra 220
10C.3 Selection rules 179 11D.3 Vibrational Raman spectra 221
Checklist of concepts 179 Checklist of concepts 222
Checklist of equations 179 Checklist of equations 222

TOPIC 11E Symmetry analysis of vibrational

FOCUS 11 Molecular spectroscopy 185 spectra 223
TOPIC 11A General features of molecular 11E.1 Classification of normal modes according to symmetry 223
spectroscopy 187 11E.2 Symmetry of vibrational wavefunctions 225
11A.1 The absorption and emission of radiation 188 (a) Infrared activity of normal modes 225
(a) Stimulated and spontaneous radiative processes 188 (b) Raman activity of normal modes 226
(b) Selection rules and transition moments 189 (c) The symmetry basis of the exclusion rule 226
(c) The Beer–Lambert law 189 Checklist of concepts 226
11A.2 Spectral linewidths 191
(a) Doppler broadening 191
TOPIC 11F Electronic spectra 227
(b) Lifetime broadening 193 11F.1 Diatomic molecules 227
(a) Term symbols 227
11A.3 Experimental techniques 193
(b) Selection rules 229
(a) Sources of radiation 194
(c) Vibrational fine structure 230
(b) Spectral analysis 194
(d) Rotational fine structure 233
(c) Detectors 196
(d) Examples of spectrometers 196 11F.2 Polyatomic molecules 234
(a) d-Metal complexes 235
Checklist of concepts 197
(b) π* ← π and π* ← n transitions 236
Checklist of equations 197
Checklist of concepts 237
TOPIC 11B Rotational spectroscopy 198 Checklist of equations 237
11B.1 Rotational energy levels 198
(a) Spherical rotors 200
TOPIC 11G Decay of excited states 238
(b) Symmetric rotors 200 11G.1 Fluorescence and phosphorescence 238
(c) Linear rotors 202 11G.2 Dissociation and predissociation 240
(d) Centrifugal distortion 202 11G.3 Lasers 241
11B.2 Microwave spectroscopy 203 Checklist of concepts 242
(a) Selection rules 203
(b) The appearance of microwave spectra 204
11B.3 Rotational Raman spectroscopy 205
FOCUS 12 Magnetic resonance 255
11B.4 Nuclear statistics and rotational states 207 TOPIC 12A General principles 256
Checklist of concepts 209 12A.1 Nuclear magnetic resonance 256
Checklist of equations 209 (a) The energies of nuclei in magnetic fields 256
(b) The NMR spectrometer 258
TOPIC 11C Vibrational spectroscopy of diatomic 12A.2 Electron paramagnetic resonance 259
molecules 210 (a) The energies of electrons in magnetic fields 259
11C.1 Vibrational motion 210 (b) The EPR spectrometer 260
11C.2 Infrared spectroscopy 211 Checklist of concepts 261
11C.3 Anharmonicity 212 Checklist of equations 261
(a) The convergence of energy levels 212
xviii Full Contents

­TOPIC 12B Features of NMR spectra 262 (d) The electronic contribution 315

12B.1 The chemical shift 262 Checklist of concepts 316

12B.2 The origin of shielding constants 264 Checklist of equations 316

(a) The local contribution 264
(b) Neighbouring group contributions 265
TOPIC 13C Molecular energies 317
(c) The solvent contribution 266
13C.1 The basic equations 317

12B.3 The fine structure 267 13C.2 Contributions of the fundamental modes of motion 318
(a) The translational contribution 318
(a) The appearance of the spectrum 267
(b) The rotational contribution 318
(b) The magnitudes of coupling constants 269
(c) The vibrational contribution 319
(c) The origin of spin–spin coupling 270
(d) The electronic contribution 320
(d) Equivalent nuclei 271
(e) The spin contribution 320
(e) Strongly coupled nuclei 272
12B.4 Exchange processes 273 Checklist of concepts 321

12B.5 Solid-state NMR 274 Checklist of equations 321

Checklist of concepts 275

TOPIC 13D The canonical ensemble 322
Checklist of equations 276
13D.1 The concept of ensemble 322
(a) Dominating configurations 323
TOPIC 12C Pulse techniques in NMR 277
(b) Fluctuations from the most probable distribution 323
12C.1 The magnetization vector 277
13D.2 The mean energy of a system 324
(a) The effect of the radiofrequency field 278
(b) Time- and frequency-domain signals 279
13D.3 Independent molecules revisited 324

12C.2 Spin relaxation 281 13D.4 The variation of the energy with volume 325
(a) The mechanism of relaxation 281 Checklist of concepts 326
(b) The measurement of T1 and T2 282 Checklist of equations 326
12C.3 Spin decoupling 283
TOPIC 13E The internal energy and the entropy 327
12C.4 The nuclear Overhauser effect 284
13E.1 The internal energy 327
Checklist of concepts 286
(a) The calculation of internal energy 327
Checklist of equations 286
(b) Heat capacity 328

TOPIC 12D Electron paramagnetic resonance 287 13E.2 The entropy 329
(a) Entropy and the partition function 329
12D.1 The g-value 287
(b) The translational contribution 331
12D.2 Hyperfine structure 288
(c) The rotational contribution 331
(a) The effects of nuclear spin 288
(d) The vibrational contribution 332
(b) The McConnell equation 289
(e) Residual entropies 333
(c) The origin of the hyperfine interaction 290
Checklist of concepts 334
Checklist of concepts 291
Checklist of equations 334
Checklist of equations 291
TOPIC 13F Derived functions 335
FOCUS 13 Statistical thermodynamics 299 13F.1 The derivations 335
13F.2 Equilibrium constants 338
TOPIC 13A The Boltzmann distribution 300 (a) The relation between K and the partition function 338
13A.1 Configurations and weights 300 (b) A dissociation equilibrium 338
(a) Instantaneous configurations 300 (c) Contributions to the equilibrium constant 339
(b) The most probable distribution 301
Checklist of concepts 341
(c) The values of the constants 303
Checklist of equations 341
13A.2 The relative population of states 304
Checklist of concepts 304
Checklist of equations 305 Resource section 351
1 Common integrals 352
TOPIC 13B Molecular partition functions 306 2 Units 354
13B.1 The significance of the partition function 306
3 Data 355
13B.2 Contributions to the partition function 308
4 Character tables 363
(a) The translational contribution 308
(b) The rotational contribution 310
(c) The vibrational contribution 314
Index367
CONVENTIONS

To avoid intermediate rounding errors, but to keep track of Blue terms are used when we want to identify a term in
values in order to be aware of values and to spot numerical an equation. An entire quotient, numerator/denominator, is
errors, we display intermediate results as n.nnn… and round coloured blue if the annotation refers to the entire term, not
the calculation only at the final step. just to the numerator or denominator separately.
LIST OF TABLES

Table 7E.1 The Hermite polynomials 43 Table 11F.1 Colour, frequency, and energy of light 227

Table 7F.1 The spherical harmonics 54 Table 11F.2 Absorption characteristics of some groups and
molecules 235
Table 8A.1 Hydrogenic radial wavefunctions 74
Table 11G.1 Characteristics of laser radiation and their
Table 8B.1 Effective nuclear charge 88
chemical applications 241
Table 8B.2 Atomic radii of main-group elements, r/pm 91
Table 12A.1 Nuclear constitution and the nuclear spin
Table 8B.3 Ionic radii, r/pm 92 quantum number 256

Table 8B.4 First and second ionization energies 93 Table 12A.2 Nuclear spin properties 257

Table 8B.5 Electron affinities, Ea/(kJ mol−1) 93 Table 12D.1 Hyperfine coupling constants for atoms, a/mT 290

Table 9A.1 Some hybridization schemes 117 Table 13B.1 Rotational temperatures of diatomic molecules 312

Table 9C.1 Overlap integrals between hydrogenic orbitals 127 Table 13B.2 Symmetry numbers of molecules 313

Table 9C.2 Bond lengths 130 Table 13B.3 Vibrational temperatures of diatomic
molecules 315
Table 9C.3 Bond dissociation energies 130
Table A.1 Some common units 354
Table 9D.1 Pauling electronegativities 134
Table A.2 Common SI prefixes 354
Table 10A.1 The notations for point groups 158
Table A.3 The SI base units 354
Table 10B.1 The C2v character table 170
Table A.4 A selection of derived units 354
Table 10B.2 The C3v character table 170
Table 0.1 Physical properties of selected materials 356
Table 10B.3 The C4 character table 173
Table 0.2 Masses and natural abundances of selected
Table 11B.1 Moments of inertia 199
nuclides 357
Table 11C.1 Properties of diatomic molecules 215
LIST OF THE CHEMIST’S TOOLKITS

Number Topic Title

13 7A Electromagnetic radiation 5
14 7B Complex numbers 15
15 7C Integration by parts 22
16 7C Euler’s formula 24
17 7D Vectors 30
18 7E The classical harmonic oscillator 41
19 7F Cylindrical coordinates 49
20 7F Angular momentum 50
21 7F Spherical polar coordinates 54
22 8C The manipulation of vectors 98
23 9D Determinants 136
24 9E Matrices 141
25 9E Matrix methods for solving eigenvalue equations 143
26 11A Exponential and Gaussian functions 192
27 12B Dipolar magnetic fields 265
28 12C The Fourier transform 280
LIST OF MATERIAL PROVIDED AS
A DEEPER LOOK

Number Title
1 The Debye–Hückel theory
2 The fugacity
3 Separation of variables
4 The energy of the bonding molecular orbital of H2+
5 Rotational selection rules
6 Vibrational selection rules
7 The van der Waals equation of state
8 The electric dipole–dipole interaction
9 The virial and the virial equation of state
10 Establishing the relation between bulk and molecular properties
11 The random walk
12 The RRK model
13 The BET isotherm
LIST OF IMPAC TS

Number Focus Title

11 7 . . .on technology: Quantum computing
12 7 . . .on nanoscience: Quantum dots
13 8 . . .on astrophysics: The spectroscopy of stars
14 9 . . .on biochemistry: The reactivity of O2, N2, and NO
15 9 . . .on biochemistry: Computational studies of biomolecules
16 11 . . .on astrophysics: Rotational and vibrational spectroscopy of interstellar species
17 11 . . .on environmental science: Climate change
18 12 . . .on medicine: Magnetic resonance imaging
19 12 . . .on biochemistry and nanoscience: Spin probes
20 13 . . .on biochemistry: The helix–coil transition in polypeptides
Another random document with
no related content on Scribd:
were unsatisfactory to several of the concerted Powers, and
were sharply criticised in the British and German press. The
German government, especially, was disposed to insist upon
stern and strenuous measures in dealing with that of China,
and it addressed the following circular note, on the 18th of
September, to all the Powers:

"The Government of the Emperor holds as preliminary to

entering upon diplomatic relations with the Chinese Government
that those persons must be delivered up who have been proved
to be the original and real instigators of the outrages
against international law which have occurred at Peking. The
number of those who were merely instruments in carrying out
the outrages is too great. Wholesale executions would be
contrary to the civilized conscience, and the circumstances of
such a group of leaders cannot be completely ascertained. But
a few whose guilt is notorious should be delivered up and
punished. The representatives of the powers at Peking are in a
position to give or bring forward convincing evidence. Less
importance attaches to the number punished than to their
character as chief instigators or leaders. The Government
believes it can count on the unanimity of all the Cabinets in
regard to this point, insomuch as indifference to the idea of
just atonement would be equivalent to indifference to a
repetition of the crime. The Government proposes, therefore,
that the Cabinets concerned should instruct their
representatives at Peking to indicate those leading Chinese
personages from whose guilt in instigating or perpetrating
outrages all doubt is excluded."

The British government was understood to be not unwilling to

support this demand from Germany, but little encouragement
seems to have been officially given to it from other quarters,
and the government of the United States was most emphatic in
declining to approve it. The reply of the latter to the German
circular note was promptly given, September 21, as follows:
"The government of the United States has, from the outset,
 proclaimed its purpose to hold to the uttermost accountability
the responsible authors of any wrongs done in China to
citizens of the United States and their interests, as was
stated in the Government's circular communication to the
Powers of July 3 last. These wrongs have been committed not
alone in Peking, but in many parts of the Empire, and their
punishment is believed to be an essential element of any
effective settlement which shall prevent a recurrence of such
outrages and bring about permanent safety and peace in China.
It is thought, however, that no punitive measures can be so
effective by way of reparation for wrongs suffered and as
deterrent examples for the future as the degradation and
punishment of the responsible authors by the supreme Imperial
authority itself, and it seems only just to China that she
should be afforded in the first instance an opportunity to do
this and thus rehabilitate herself before the world.

"Believing thus, and without abating in anywise its deliberate

purpose to exact the fullest accountability from the
responsible authors of the wrongs we have suffered in China,
the Government of the United States is not disposed, as a
preliminary condition to entering into diplomatic negotiations
with the Chinese Government, to join in a demand that said
Government surrender to the Powers such persons as, according
to the determination of the Powers themselves, may be held to
be the first and real perpetrators of those wrongs. On the
other hand, this Government is disposed to hold that the
punishment of the high responsible authors of these wrongs,
not only in Peking, but throughout China, is essentially a
condition to be embraced and provided for in the negotiations
for a final settlement.
{139}
It is the purpose of this Government, at the earliest
practicable moment, to name its plenipotentiaries for
negotiating a settlement with China, and in the mean time to
authorize its Minister in Peking to enter forthwith into
conference with the duly authorized representatives of the
Chinese Government, with a view of bringing about a
preliminary agreement whereby the full exercise of the
Imperial power for the preservation of order and the
protection of foreign life and property throughout China,
pending final negotiations with the Powers, shall be assured."

On the same day on which the above note was written the
American government announced its recognition of Prince Ching
and Li Hung-chang, as plenipotentiaries appointed to represent
the Emperor of China, in preliminary negotiations for the
restoration of the imperial authority at Peking and for a
settlement with the foreign Powers.

Differences between the Powers acting together in China, as to

the preliminary conditions of negotiation with the Chinese
government, and as to the nature and range of the demands to
be made upon it, were finally adjusted on the lines of a
proposal advanced by the French Foreign Office, in a note
dated October 4, addressed to the several governments, as
follows:

"The intention of the Powers in sending their forces to China

was, above all, to deliver the Legations. Thanks to their
union and the valour of their troops this object has been
attained. The question now is to obtain from the Chinese
Government, which has given Prince Ching and Li Hung-chang
full powers to negotiate and to treat in its name, suitable
reparation for the past and serious guarantees for the future.
Penetrated with the spirit which has evoked the previous
declarations of the different Governments, the Government of
the Republic has summarized its own sentiments in the
following points, which it submits as a basis for the
forthcoming negotiations after the customary verification of
powers:

(1) The punishment of the chief culprits, who will be

designated by the representatives of the Powers in Peking.
(2) The maintenance of the embargo on the importation of arms.

(3) Equitable indemnity for the States and for private

persons.

(4) The establishment in Peking of a permanent guard for the

Legations.

(5) The dismantling of the Ta-ku forts.

(6) The military occupation of two or three points on the

Tien-tsin-Peking route, thus assuring complete liberty of
access for the Legations should they wish to go to the coast
and to forces from the sea-board which might have to go up to
the capital.

It appears impossible to the Government of the Republic that

these so legitimate conditions, if collectively presented by
the representatives of the Powers and supported by the
presence of the international troops, will not shortly be
accepted by the Chinese Government."

On the 17th of October, the French Embassy at Washington

announced to the American government that "all the interested
powers have adhered to the essential principles of the French
note," and added: "The essential thing now is to show the
Chinese Government, which has declared itself ready to
negotiate, that the powers are animated by the same spirit;
that they are decided to respect the integrity of China and
the independence of its Government, but that they are none the
less resolved to obtain the satisfaction to which they have a
right. In this regard it would seem that if the proposition
which has been accepted as the basis of negotiations were
communicated to the Chinese plenipotentiaries by the Ministers
of the powers at Peking, or in their name by their Dean, this
step would be of a nature to have a happy influence upon the
determinations of the Emperor of China and of his Government."
The government of the United States approved of this
suggestion from France, and announced that it had "instructed
its Minister in Peking to concur in presenting to the Chinese
plenipotentiaries the points upon which we are agreed." Other
governments, however, seem to have given different
instructions, and some weeks were spent by the foreign
Ministers at Peking in formulating the joint note in which
their requirements were to be presented to Prince Ching and
Earl Li.

The latter, meantime, had submitted, on their own part, to the

allied plenipotentiaries, a draft of what they conceived to be
the just preliminaries of a definitive treaty. They prefaced
it with a brief review of what had occurred, and some remarks,
confessing that "the throne now realizes that all these
calamities have been caused by the fact that Princes and high
Ministers of State screened the Boxer desperados, and is
accordingly determined to punish severely the Princes and
Ministers concerned in accordance with precedent by handing
them over to their respective Yamêns for the determination of
a penalty." The "draft clauses" then submitted were as
follows:

"The siege of the Legations was a flagrant violation of the

usages of international law and an utterly unpermissible act.
China admits the gravity of her error and undertakes that
there shall be no repetition of the occurrence. China admits
her liability to pay an indemnity, and leaves it to the Powers
to appoint officers who shall investigate the details and make
out a general statement of claims to be dealt with
accordingly.

"With regard to the subsequent trade relations between China

and the foreign Powers, it will be for the latter to make
their own arrangements as to whether former treaties shall be
 adhered to in their entirety, modified in details, or
exchanged for new ones. China will take steps to put the
respective proposals into operation accordingly.

"Before drawing up a definitive treaty it will be necessary

for China and the Powers to be agreed as to general
principles. Upon this agreement being arrived at, the
Ministers of the Powers will remove the seals which have been
affixed to the various departments of the Tsung-li-Yamên and
proceed to the Yamên for the despatch of business in matters
relating to international questions exactly as before.

"So soon as a settlement of matters of detail shall have been

agreed upon between China and the various nations concerned in
accordance with the requirements of each particular nation,
and so soon as the question of the payment of an indemnity
shall have been satisfactorily settled, the Powers will
respectively withdraw their troops. The despatch of troops to
China by the Powers was undertaken with the sole object of
protecting the Ministers, and so soon as peace negotiations
between China and the Powers shall have been opened there
shall be a cessation of hostilities.

{140}

"The statement that treaties will be made with each of the

Powers in no way prejudices the fact that with regard to the
trade conventions mentioned the conditions vary in accordance
with the respective powers concerned. With regard to the
headings of a definitive treaty, questions of nomenclature and
precedence affecting each of the Powers which may arise in
framing the treaty can be adjusted at personal conferences."
Great Britain and Germany were now acting in close accord,
having, apparently, been drawn together by a common distrust
of the intentions of Russia. On the 16th of October, Lord
Salisbury and Count Hatzfeldt signed the following agreement,
which was made known at once to the other governments
concerned, and its principles assented to by all:

"Her Britannic Majesty's Government and the Imperial German

Government, being desirous to maintain their interests in
China and their rights under existing treaties, have agreed to
observe the following principles in regard to their mutual policy
in China:—

"1. It is a matter of joint and permanent international

interest that the ports on the rivers and littoral of China
should remain free and open to trade and to every other
legitimate form of economic activity for the nationals of all
countries without distinction; and the two Governments agree
on their part to uphold the same for all Chinese territory as
far as they can exercise influence.

"2. The Imperial German Government and her Britannic Majesty's

Government will not, on their part, make use of the present
complication to obtain for themselves any territorial
advantages in Chinese dominions, and will direct their policy
towards maintaining undiminished the territorial condition of
the Chinese Empire.

"3. In case of another Power making use of the complications

in China in order to obtain under any form whatever such
territorial advantages, the two Contracting Parties reserve to
themselves to come to a preliminary understanding as to the
eventual steps to be taken for the protection of their own
interests in China.

"4. The two Governments will communicate this Agreement to the

other Powers interested, and especially to Austria-Hungary,
France, Italy, Japan, Russia, and the United States of
America, and will invite them to accept the principles
recorded in it."

The assent of Russia was no less positive than that of the

other Powers. It was conveyed in the following words: "The
first point of this Agreement, stipulating that the ports
situated on the rivers and littoral of China, wherever the two
Governments exercise their influence, should remain free and
open to commerce, can be favorably entertained by Russia, as
this stipulation does not infringe in any way the 'status quo'
established in China by existing treaties. The second point
corresponds all the more with the intentions of Russia, seeing
that, from the commencement of the present complications, she
was the first to lay down the maintenance of the integrity of
the Chinese Empire as a fundamental principle of her policy in
China. As regards the third point relating to the eventuality
of an infringement of this fundamental principle, the Imperial
Government, while referring to their Circular of the 12th
(25th) August, can only renew the declaration that such an
infringement would oblige Russia to modify her attitude
according to circumstances."

On the 13th of November, while the foreign plenipotentiaries

at Peking were trying to agree in formulating the demands they
should make, the Chinese imperial government issued a decree
for the punishment of officials held responsible for the Boxer
outrages. As given the Press by the Japanese Legation at
Washington, in translation from the text received there, it
was as follows;

"Orders have been already issued for the punishment of the

officials responsible for opening hostilities upon friendly
Powers and bringing the country into the present critical
condition by neglecting to suppress and even by encouraging
the Boxers. But as Peking and its neighborhood have not yet
been entirely cleared of the Boxers, the innocent people are
still suffering terribly through the devastation of their
fields and the destruction of their houses, a state of affairs
which cannot fail to fill one with the bitterest feelings
against these officials. And if they are not severely
punished, how can the anger of the people be appeased and the
 indignation of the foreign Powers allayed?

"Accordingly, Prince Tuan is hereby deprived of his title and

rank, and shall, together with Prince Chwang, who has already
been deprived of his title, be delivered to the Clan Court to
be kept in prison until the restoration of peace, when they
shall be banished to Sheng-King, to be imprisoned for life.
Princes Yi and Tsai Yung, who have both been already deprived
of their titles, are also to be delivered to the Clan Court
for imprisonment, while Prince Tsai Lien, also already
deprived of title and rank, is to be kept confined in his own
house, Duke Tsai Lan shall forfeit his ducal salary, but may
be transferred with the degradation of one rank. Chief Censor
Ying Nien shall be degraded two ranks and transferred. As to
Kang Yi, Minister of the Board of Civil Appointment, upon his
return from the commission on which he had been sent for the
purpose of making inquiries into the Boxer affair he
memorialized the Throne in an audience strongly in their
favor. He should have been severely punished but for his death
from illness, and all penalties are accordingly remitted. Chao
Shuy Yao, Minister of the Board of Punishment, who had been
sent on a mission similar to that of Kang Yi, returned almost
immediately. Though such conduct was a flagrant neglect of his
duties, still he did not make a distorted report to the
Throne, and therefore he shall be deprived of his rank, but
allowed to retain his present office. Finally, Yu Hsien,
ex-Governor of Shan-Se, allowed, while in office, the Boxers
freely to massacre the Christian missionaries and converts.
For this he deserves the severest punishment, and therefore he
is to be banished to the furthermost border of the country, and
there to be kept at hard labor for life.

{141}

"We have a full knowledge of the present trouble from the very
beginning, and therefore, though no impeachment has been brought
by Chinese officials at home or abroad against Princes Yi,
Tsai Lien and Tsai Yung, we order them to be punished in the
same manner as those who have been impeached. All who see this
edict will thus perceive our justice and impartiality in
inflicting condign penalties upon these officials," It was not
until the 20th of December that the joint note of the
plenipotentiaries of the Powers, after having been submitted
in November to the several governments represented, and
amended to remove critical objections, was finally signed and
delivered to the Chinese plenipotentiaries. The following is a
precis of the requirements set forth in it:

"(1) An Imperial Prince is to convey to Berlin the Emperor's

regret for the assassination of Baron von Ketteler, and a
monument is to be erected on the site of the murder, with an
inscription, in Latin, German, and Chinese, expressing the
regret of the Emperor for the murder.

"(2) The most severe punishment fitting their crimes is to be

inflicted on the personages designated in the Imperial decree
of September 21, whose names—not mentioned—are Princes Tuan
and Chuang and two other princes, Duke Lan, Chao Shu-chiao,
Yang-yi, Ying-hien, also others whom the foreign Ministers
shall hereafter designate. Official examinations are to be
suspended for five years in those cities where foreigners have
been assassinated or cruelly treated.

"(3) Honourable reparation is to be made to Japan for the

murder of M. Sugiyama.

"(4) Expiatory monuments are to be erected in all foreign

cemeteries where tombs have been desecrated.

"(5) The importation of arms or 'materiel' and their

manufacture are to be prohibited.

"(6) An equitable indemnity is to be paid to States,

societies, and individuals, also to Chinese who have suffered
injury because of their employment by foreigners. China will
adopt financial measures acceptable to the Powers to guarantee
the payment of the indemnity and the service of the loans.

"(7) Permanent Legation guards are to be maintained, and the

diplomatic quarter is to be fortified.

"(8) The Ta-ku forts and those between Peking and the sea are
to be razed.

"(9) There is to be a military occupation of points necessary

to ensure the safety of the communications between Peking and
the sea.

"(10) Proclamations are to be posted during two years

throughout the Empire threatening death to any person joining
an anti-foreign society and enumerating the punishment
inflicted by China upon the guilty ringleaders of the recent
outrages. An Imperial edict is to be promulgated ordering
Viceroys, Governors, and Provincial officials to be held
responsible for anti-foreign outbreaks or violations of
treaties within their jurisdiction, failure to suppress the
same being visited by the immediate cashiering of the
officials responsible, who shall never hold office again.

"(11) China undertakes to negotiate a revision of the

commercial treaties in order to facilitate commercial
relations.

"(12) The Tsung-li-Yamên is to be reformed, and the Court

ceremonial for the reception of foreign Ministers modified in
the sense indicated by the Powers.

"Until the foregoing conditions are complied with ('se

conformer à') the Powers can hold out no expectation of a
limit of time for the removal of the foreign troops now
occupying Peking and the provinces."
CHINA: A. D. 1900 (November).
Russo-Chinese agreement relating to Manchuria.

See (in this volume)

MANCHURIA.

CHINA: A. D. 1900 (December).

Russo-Chinese agreement concerning the Manchurian
province of Fêng-tien.

See (in this volume)

MANCHURIA: A. D. 1900.

CHINA: A. D. 1900-1901 (November-February).

Seizure of grounds at Peking for a large Legation Quarter.
Extensive plans of fortification.

In February, 1901, the following from a despatch written in

the previous November by Mr. Conger, the American Minister at
Peking, was given to the Press by the State Department at
Washington: "I have the honor to report that in view of the
probability of keeping large legation grounds in the future,
and because of the general desire on the part of all the
European representatives to have extensive legations, all of
the Ministers are taking possession of considerable areas
adjoining their legations—property belonging either to the
Chinese Government or to private citizens, and having been
abandoned by the owners during the siege—with the intention to
claim them as conquest, or possibly credit something for them
on their account for indemnity. I have as yet not taken formal
possession of any ground for this purpose, nor shall I without
instructions, but I shall not for the present permit any of the
owners or other persons to reoccupy any of the property
between this legation and the canal to the east of it. While
this area will be very small in comparison with the other
legations, yet it will be sufficient to make both the legation
 personnel and the guard very comfortable, and will better
comport with our traditional simplicity vis-a-vis the usual
magnificence of other representatives.

"It is proposed to designate the boundaries of a legation

quarter, which shall include all the legations, and then
demand the right to put that in a state of defence when
necessary, and to prohibit the residence of Chinese there,
except by permission of the Ministers. If, therefore, these
ideas as to guards, defence, etc:., are to be carried out, a
larger legation will be an absolute necessity. In fact, it is
impossible now to accommodate the legation and staff in our
present quarters without most inconvenient crowding.

"There are no public properties inside the legation quarter

which we could take as a legation. All the proposed property
to be added, as above mentioned, to our legation, is private
ground, except a very small temple in the southeast corner,
and I presume, under our policy, if taken, will be paid for
either to the Chinese owners or credited upon account against
the Chinese Government for indemnity, although I suspect most
of the other Governments will take theirs as a species of
conquest. The plot of ground adjoining and lying to the cast
of the legation to which I have made reference is about the
size of the premises now occupied by us."

Before its adjournment on the 4th of March, 1901, the Congress

of the United States made an appropriation for the purchase of
grounds for its Legation at Peking, and instructions were sent
to make the purchase.

{142}

By telegram from Peking on the 14th of February it was

announced that a formidable plan of fortification for this
Legation Quarter had been drawn up by the Military Council of
the Powers at Peking, and that work upon it was to begin at
once. The correspondent of the "London Times" described the
plan and wrote satirically of it, as follows; "From supreme
contempt for the weakness of China armed we have swayed to
exaggerated fear of the strength of China disarmed. The
international military experts have devised a scheme for
putting the Legation quarter in a state of defence which is
equivalent to the construction of an International fortress
alongside the Imperial Palace. The plan requires the breaching
of the city wall at the Water-gate, the levelling of the Ha-ta
Mên and Chien Mên towers, the demolition of the ramparts
giving access to them, the sweeping clear of a space 150 to
300 yards wide round the entire Legation area, and the
construction of walls, glacis, moats, barbed wire defences,
with siege guns, Maxims, and barracks capable of holding 2,000
troops, with military stores and equipment sufficient to
withstand a siege of three months. All public buildings,
boards, and civil offices between the Legations and the
Imperial walls are to be levelled, while 11,000 foreign troops
are to hold the communications between Peking and the sea, so
that no Chinese can travel to Peking from the sea without the
knowledge of the foreign military authorities.

"The erection of the defences is to begin at once, before the

return of the Court to Peking. They are no doubt devised to
encourage the Court to return to Peking, it being apparently
the belief of the foreign Ministers that an Imperial Court
governing an independent empire are eager to place themselves
under the tutelage of foreign soldiers and within the reach of
foreign Maxims.

"Within the large new Legation area all the private property
of Chinese owners who years before sought the advantages of
vicinity to the Legations has been seized by the foreign
Legations. France and Germany, with a view to subsequent
commercial transactions, have annexed many acres of valuable
private property for which no compensation is contemplated,
while the Italian Legation, which boasts a staff of two
 persons, carrying out the scheme of appropriation to a logical
absurdity, has, in addition to other property, grabbed the
Imperial Maritime Customs gardens and buildings occupied for
so many years by Sir Robert Hart and his staff."

CHINA: A. D. 1901 (January-February).

Famine in Shensi.

A Press telegram from Peking, late in January, announced a

fearful famine prevailing in the province of Shensi, where
thousands of natives were dying. The Chinese government was
distributing rice, and there was reported to be discrimination
against native Christians in the distribution. Mr. Conger, Sir
E. Satow, and M. Pichon protested to Prince Ching and Li
Hung-chang against such discrimination. A Court edict was
therefore issued on the 26th instant ordering all relief
officials and Chinese soldiers to treat Christians in exactly
the same way as all other Chinese throughout the Empire, under
penalty of decapitation. Another despatch, early in February,
stated: "Trustworthy reports received here from Singan-fu [the
temporary residence of the fugitive Chinese court] all agree
that the famine in the provinces of Shen-si and Shan-si is one
of the worst in the history of China. It is estimated that
two-thirds of the people are without sufficient food or the
means of obtaining it. They are also suffering from the bitter
cold. As there is little fuel in either province the woodwork
of the houses is being used to supply the want. Oxen, horses,
and dogs have been practically all sacrificed to allay hunger.
Three years of crop failures in both provinces and more or less
of famine in previous seasons had brought the people to
poverty when winter began. This year their condition has
rapidly grown worse. Prince Ching stated to Mr. Conger, the
United States Minister, that the people were reduced to eating
human flesh and to selling their women and children.
Infanticide is alarmingly common."

CHINA: A. D. 1901 (January-February).

Submission to the demands of the Powers
by the Imperial Government.
Punishments inflicted and promised.
A new Reform Edict.

With no great delay, the Chinese plenipotentiaries at Peking

were authorized by the Emperor and Empress to agree to the
demands of the Powers, which they did by formally signing the
Joint Note. Prince Ching gave his signature on the 12th of
January, 1901, and Li Hung-chang, who was seriously ill,
signed on the following day. Discussion of the punishments to
be inflicted on guilty officials was then opened, and went on
for some time. On the 5th of February, the foreign Ministers
submitted the names of twelve leading officials, against whom
formal indictments were framed, and who were considered to be
deserving of death. Three of them, however (Kang Yi, Hsu Tung,
and Li Ping Heng), were found to be already deceased. The
remaining nine were the following: Prince Chuang,
commander-in-chief of the Boxers; Prince Tuan, who was held to
be the principal instigator of the attack on foreigners; Duke
Lan, the Vice-President of Police, who admitted the Boxers to
the city; Yu Hsien, who was the governor of Shan-Si Province,
promoter of the Boxer movement there, and director of the
massacres in that province; General Tung Fu Siang, who led the
attacks on the Legations, Ying Nien, Chao Hsu Kiao, Hsu Cheng
Yu, and Chih Siu, who were variously prominent in the
murderous work. In the cases of Prince Tuan and Duke Lan, who
were related to the Imperial family, and in the case of
General Tung Fu Siang, whose military command gave him power
to be troublesome, the Chinese court pleaded such difficulties
in the way of executing a decree of death that the Ministers
at Peking were persuaded to be satisfied with sentences of
exile, or degradation in rank, or both. On the 21st of
February the Ministers received notice that an imperial edict
had been issued, condemning General Tung Fu Siang to be
degraded and deprived of his rank; Prince Tuan and Duke Lan to
be disgraced and exiled; Prince Chuang, Ying Nien and Chao Hsu
 Kiao to commit suicide; Hsu Cheng Yu, Yu Hsien and Chih Siu to
be beheaded. Hsu Cheng Yu and Chih Siu were then prisoners in
the hands of the foreign military authorities at Peking, and
the sentence was executed upon them there, on the 26th of
February, in the presence of Japanese, French, German and
American troops. A despatch from Peking reporting the
execution stated that, while it was being carried out, "the
ministers held a meeting and determined on the part of the
majority to draw a curtain over further demands for blood.
United States Special Commissioner Rockhill sided strongly
with those favoring humane methods, who are Sir Ernest Satow
and MM. Komura, De Cologan and De Giers, respectively British,
Japanese, Spanish and Russian ministers. Others believe that
China has not been sufficiently punished, and that men should
be executed in every city, town and village where foreigners
were injured."

{143}

While the subject of punishments was pending, and with a view,

it was said, of quickening the action of the Chinese
government, Count von Waldersee, the German Field-Marshal
commanding the allied forces in China, ordered preparations to
be made for an extensive military expedition into the
interior. The government of the United States gave prompt
directions that its forces at Peking should not take part in
this movement, and the remonstrances of other Powers more
pacifically inclined than the Germans caused the project to be
given up.

Meantime, three Imperial edicts of importance, if faithfully

carried out, had been issued. One, on the 5th of February,
commanded new undertakings of reform, accounting for the
abandonment of the reform movement of 1898 by declaring that
it was seditionary and would have resulted in anarchy, and
that it was entered upon when the Emperor was in bad health;
for all which reasons he had requested the Empress Dowager to
 resume the reins of government. Now, it was declared, since
peace negotiations were in progress, the government should be
formed on a basis for future prosperity. Established good
methods of foreign countries should be introduced to supply
China's deficiencies. "China's greatest difficulty," said the
edict, "is her old customs, which have resulted in the
insincere dispatch of business and the promoting of private
gain. Up to the present time those who have followed the
Western methods have had only superficial knowledge, knowing
only a little of foreign languages and foreign inventions,
without knowing the real basis of the strength of foreign
nations. Such methods are insufficient for real reform."

In order to obtain a true basis, the Emperor commanded a

consultation between the ministers of the privy council, the
six boards, nine officers, the Chinese ministers to foreign
countries and all the viceroys and governors. Those were
instructed to recommend reforms in the seven branches of
government, namely, the central government, ceremonies,
taxation, schools, civil-service examinations, military
affairs and public economies. They were also to recommend what
part of the old system can be used and what part needs changing.
Two months were given them in which to prepare their report.

On the following day, two edicts, in fulfilment of demands

made in the Joint Note of the Powers, were promulgated. The
first provided, in accordance with article 3 of the Joint
Note, for the suspension of official examinations for five
years in places where foreigners are killed. The second edict
forbade anti-foreign societies, recited the punishment of
guilty parties and declared that local officials will be held
responsible for the maintenance of order. If trouble occurs
the officials would be removed without delay and never again
allowed to hold office.

CHINA: A. D. 1901 (March).

The murdered Christian missionaries and native converts.
Varying statements and estimates of their number.

To the time of this writing (March, 1901), no complete

enumeration of the foreign Christian missionaries and members
of missionary families who were killed during the Boxer
outbreak of the past year has been made. Varying estimates
have appeared, from time to time, and it is possible that one
of the latest among these, communicated from Shanghai on the
1st of March, may approach to accuracy. It was published in
the "North China Daily News," and said to be founded on the
missionary records, according to which, said the "News," "a
total of 134 adults and 52 children were killed or died of
injuries in the Boxer rising of 1899 and 1900."

On the 13th of March, the "Lokal Anzeiger," of Berlin,

published a statistical report from its Peking correspondent
of "foreign Christians killed during the troubles, exclusive
of the Peking siege," which enumerated 118 Englishmen, 79
Americans, Swedes and Norwegians, 26 Frenchmen, 11 Belgians,
10 Italians and Swiss, and 1 German. The total of these
figures is largely in excess of those given by the "North
China Daily News," but they cover, not missionaries alone, but
all foreign Christians. It is impossible, however, not to
doubt the accuracy of both these accounts. Of native
Christians, the German writer estimated that 30,000 had
perished. In September, 1900, the United States Consul-General
at Shanghai, Mr. Goodnow, "after making inquiries from every
possible source," placed the number of British and American
missionaries who had probably been killed at 93, taking no
account of a larger number in Chih-li and Shan-si whose fate
was entirely unknown. Of those whose deaths he believed to be
absolutely proved at that time, 34 were British, including 9
men, 15 women and 10 children, and 22 were American, 8 of
these being men, 8 women and 6 children.

In December, 1900, a private letter from the "Association for

the Propagation of the Faith, St. Mary's Seminary," Baltimore,
 Maryland, stated that up to the end of September 48 Catholic
missionaries were known to have been murdered. A pastoral
letter issued in December by Cardinal Vaughan, in London,
without stating the numbers killed, declared that all work of
the Catholic church, throughout the most of China, where 942
European and 445 native priests had been engaged, was
practically swept away.

A private letter, written early in January, 1901, by the

Reverend Dr. Judson Smith, one of the corresponding
secretaries of the American Board of Commissioners for Foreign
Missions, contains the following statement: "The American
Board has lost in the recent disturbances in China 13
missionaries, 6 men and 7 women, and 5 children belonging to
the families who perished. The number of native converts
connected with the mission churches of the American Board who
have suffered death during these troubles cannot be stated
with accuracy. It undoubtedly exceeds 1,000; it may reach a
much larger figure; but some facts that have come to light of
late imply that more of those who were supposed to be lost
have been in hiding than was known. If we should reckon along
with native converts members of their families who have
suffered death, the number would probably be doubled."

There seems to be absolutely no basis of real information for

any estimate that has been made of the extent of massacre
among the native Christian converts. Thousands perished,
without doubt, but how many thousands is yet to be learned. As
intimated by Dr. Smith, larger numbers than have been supposed
may have escaped, and it will probably be long before the true
facts are gathered from all parts of the country.

{144}

In any view, the massacre of missionaries and their families

was hideous enough; but fictions of horror were shamefully
added, it seems, in some of the stories which came from the