Physics of atoms

and molecules
2nd edition

B.H. Bransden and C.J. Joachain

Prentice
Hall
An imprint of Pearson Education
Harlow, England London New York Boston San Francisco Toronto Sydney Singapore Hong Kong
Tokyo Seoul Taipei New Delhi Cape Town Madrid Mexico City Amsterdam Munich Paris Milan

Contents

Preface to the second edition

Preface to the first edition

xi

Acknowledgements

xii

1j Electrons, photons and atoms

1.1
1.2
1.3

The atomic nature of matter

The electron
Black body radiation

1.4

The photoelectric effect

14

1.5
1.6

X-rays and the Compton effect

The nuclear atom

18
23

1.7

Atomic spectra and the Bohr model of hydrogen

27

1.8
1.9

The Stern-Gerlach experiment - angular momentum and spin

de Broglie's hypothesis and the genesis of wave mechanics
Problems

41
48
54

2j The elements of quantum mechanics

2.1
2.2
2.3
2.4
2.5
2.6
2.7
2.8

Waves and particles, wave packets and

the uncertainty principle
The Schrodinger equation
Expansions, operators and observables
One-dimensional examples
Angular momentum
Central forces
Several-particle systems
Approximation methods
Problems

| j One-electron atoms

1
3
9

59
59
68
73
81
89
103
108
114
142

147

3.1
3.2

The Schrodinger equation for one-electron atoms

Energy levels

147
152

3.3

The eigenfunctions of the bound states

155

vi E3 Contents

3.4
3.5

Expectation values. The virial theorem

One-electron atoms in parabolic coordinates

164
168

3.6

Special hydrogenic systems: positronium; muonium;

antihydrogen; muonic and hadronic atoms; Rydberg atoms
Problems

1 73
180

4 Interaction of one-electron atoms with

electromagnetic radiation
4.1 The electromagnetic field and its interaction with
charged particles
4.2 Transition rates
4.3 The dipole approximation
4.4 The Einstein coefficients
4.5 Selection rules and the spectrum of one-electron atoms
4.6 Line intensities and the lifetimes of excited states
4.7 Line shapes and widths
4.8 The photoelectric effect
4.9 The scattering of radiation by atomic systems
Problems

5 One-electron atoms: fine structure and

hyperfine structure
5.1 Fine structure of hydrogenic atoms
5.2 The Lamb shift
5.3 Hyperfine structure apd isotope shifts
Problems

6 Interaction of one-electron atoms with external

electric and magnetic fields
6.1 The Stark effect
6.2 The Zeeman effect
Problems

3ij|j Two-electron atoms

7.1 The Schrodinger equation for two-electron atoms.
Para and ortho states
7.2 Spin wave functions and the role of the Pauli
exclusion principle
7.3 Level scheme of two-electron atoms
7.4 The independent particle model

183
184
189
195
201
203
212
215
225
230
234

237
237
249
254
270

271
271
287
304

307
307
309
313
316

Contents tJ vii

7.5
7.6

The ground state of two-electron atoms

Excited states of two-electron atoms

325
337

7.7

Doubly excited states of two-electron atoms.

Auger effect (autoionisation). Resonances

344

Problems

347

8 Many-electron atoms
8.1

The central field approximation

349

8.2
8.3
8.4
8.5

The periodic system of the elements

The Thomas-Fermi model of the atom
The Hartree-Fock method and the self-consistent field
Corrections to the central field approximation. Correlation
effects. L-S coupling and j-j coupling
Density functional theory
Problems

361
369
382
401
416
419

9j Interaction of many-electron atoms with

electromagnetic radiation and with static electric
and magnetic fields

423

8.6

9.1

Many-electron atoms in an electromagnetic field

9.2

Selection rules for electric dipole transitions. Oscillator and

line strengths
Retardation effects. Magnetic dipole and electric quadrupole
transitions

435

9.4

The spectra of the alkalis

440

9.5
9.6

Helium and the alkaline earths

Atoms with several optically active electrons.
Multiplet structure
X-ray spectra
The Stark effect
The Zeeman effect. The Hanle effect and level-crossing
spectroscopy
Problems

446

9.3

9.7
9.8
9.9

\...

349

10 Molecular structure

423
429

450
457
462
468
475

477

10.1
10.2

General nature of molecular structure

The Bom-Oppenheimer separation for diatomic molecules

477
480

10.3
10.4
10.5

Electronic structure of diatomic molecules

The rotation and vibration of diatomic molecules
The electronic spin and Hund's cases

485
513
522

viii D Contents

10.6

The structure of polyatomic molecules

529

Problems

539

11 Molecular spectra

541

11.1

Rotational spectra of diatomic molecules

541

11.2

Vibrational-rotational spectra of diatomic molecules

543

11.3
11.4
11.5
11.6

Electronic spectra of diatomic molecules

Spin-dependent interactions and electric dipole transitions
The nuclear spin
The inversion spectrum of ammonia "
Problems

549
558
561
564
568

12 Atomic collisions: basic concepts and potential

scattering

571

12.1

Types of collisions, channels, thresholds and cross-sections

571

12.2
12.3
12.4

Potential scattering. General features

The method of partial waves
The integral equation of potential scattering

575
579
599

12.5
12.6
12.7
12.8

The Coulomb potential

Scattering of two identical particles
Approximation methods
Absorption processes and scattering by a complex potential
Problems

606
612
619
657
663

13 Electron-atom collisions and atomic photoionisation

13.1
13.2
13.3
13.4
13.5

Electron-atom collisions. General features

Elastic and inelastic electron-atom collisions at low energies
Elastic and inelastic electron-atom collisions at high energies
Electron impact ionisation of atoms
Atomic photoionisation

Problems

14 Atom-atom collisions

669
669
673
705
731
745
761

765

14.1

Collisions at very low energies

766

14.2

Elastic collisions at low velocities

769

14.3
14.4

Non-elastic collisions between atoms

The impact parameter method

778
782

14.5

Atom-atom collisions at high velocities

Problems

801
810

Contents

15: Masers, lasers and their interaction with atoms

and molecules
15.1
15.2
15.3
15.4
15.5
15.6

Masers and lasers

Lasers and spectroscopy
Atoms in intense laser fields
Laser cooling and trapping of neutral atoms
Bose-Einstein condensation
Atom lasers

16 Further developments and applications of atomic

and molecular physics
16.1
16.2
16.3
16.4
16.5
1
2
3
4
5
6
7
8
9
10
11
12
13
14

ix

813
814
837
846
881
892
897

901

Magnetic resonance
Atom optics
Atoms in cavities and ions in traps
Atomic clocks
Astrophysics

901
914
940
952
967

Appendices

979

Classical scattering by a central potential

The laboratory and centre of mass systems
Evaluation of integrals by using generating functions
Angular momentum - useful formulae and results
Hydrogenic wave functions in momentum space
The Hamiltonian for a charged particle in an
electromagnetic field
The Dirac equation and relativistic corrections to the
Schrodinger equation
Separation of the centre of mass coordinates for an
N-electron atom
The space-fixed and body-fixed frames for a diatomic molecule
Evaluation of two-centre integrals
The rotational wave functions of a diatomic molecule
Dalitz integrals
Solutions of selected problems
Fundamental constants, atomic units and conversion factors

981
989
996
1000
1009

References
Author Index
Subject Index

1016
1018
1029
1032
1035
1037
1040
1044
1072

1077
1083
1093