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Cambridge University Press eBooks

The problem of the structure of matter

Jorge José Kohanoff

Published Jun 29, 2006• 0 citations
Publisher

Abstract

The description of the physical and chemical properties of matter is a central issue that has occupied the minds of scientists since the age of the ancient Greeks. In their route to dissect matter down to what cannot be divided any further, they coined the term atom , the indivisible . Matter became then a collection of atoms. More than twenty centuries had to pass until the development of a more precise concept of atom, thanks, amongst others, to the systematic studies of Mendeleyev and the establishment in 1869 of the periodic table of the elements (Mendeleyev, 1869). The discovery of the electron in 1897 and the first modern model of the atomic structure by Sir Joseph Thomson were soon refined by his student, Sir Ernest Rutherford, who in 1910 showed that an atom was made of a positively charged small nucleus and a number of negatively charged electrons that neutralize the nuclear charge. Much in the spirit of planetary systems, and drawing from the analogy between gravitational and electrostatic interactions, scientists in the beginning of the twentieth century built an image of the atom that consisted of a number Z of electrons – of elementary charge – e – orbiting around the nucleus of charge Ze . A number of experimental observations, though, were incompatible with this idea of orbiting electrons. In particular, according to the successful electromagnetic theory, charged electrons in orbital (radially accelerated) motion should radiate energy, thus decelerating and eventually collapsing onto the nucleus. Clearly, such a picture would imply that matter is essentially unstable, in flagrant contradiction with our everyday experience of the very existence of matter.

DOI
10.1017/cbo9780511755613.002

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The description of the physical and chemical properties of matter is a central issue that has occupied the minds of scientists since the age of the ancient Greeks. In their route to dissect matter down to what cannot be divided any further, they coined the term atom , the indivisible . Matter became then a collection of atoms. More than twenty centuries had to pass until the development of a more precise concept of atom, thanks, amongst others, to the systematic studies of Mendeleyev and the establishment in 1869 of the periodic table of the elements (Mendeleyev, 1869). The discovery of the electron in 1897 and the first modern model of the atomic structure by Sir Joseph Thomson were soon refined by his student, Sir Ernest Rutherford, who in 1910 showed that an atom was made of a positively charged small nucleus and a number of negatively charged electrons that neutralize the nuclear charge. Much in the spirit of planetary systems, and drawing from the analogy between gravitational and electrostatic interactions, scientists in the beginning of the twentieth century built an image of the atom that consisted of a number Z of electrons – of elementary charge – e – orbiting around the nucleus of charge Ze . A number of experimental observations, though, were incompatible with this idea of orbiting electrons. In particular, according to the successful electromagnetic theory, charged electrons in orbital (radially accelerated) motion should radiate energy, thus decelerating and eventually collapsing onto the nucleus. Clearly, such a picture would imply that matter is essentially unstable, in flagrant contradiction with our everyday experience of the very existence of matter.
​Richard Feynman, in his famous Lectures on Physics, toyed with the idea of all scientific knowledge being wiped out and facing the choice of passing one single idea down to future generations (Feynman et al. 1989). He believed it should be the hypothesis that all things are made of atoms. The idea that matter is built up from discrete fundamental units can be traced back to several ancient cultures (the word atom deriving from the Greek word atomos ‘cannot be divided’). It is only within the last century or so, however, that theories for atomic structure were developed to explain a series of phenomena observed throughout the 18th–19th Centuries. Many of these phenomena were optical, such as Melvill’s observation in 1752 that a mixture of sea salt and alcohol would burn with a yellow flame (see Figure 1) or Wollaston’s observation in 1802 that sunlight contains black lines in its spectrum (Cajori 1962). Further refinement and characterisation from people like Fraunhofer, Kirchoff, Bun-sen, Balmer, and Zeeman followed, but it was not until 1913, with the introduction of the Rutherford-Bohr atomic model, that a cornerstone was laid for what would become a quantum mechanical description of the atom.
A few days later, while finishing his dinner, Mr Tompkins remembered that it was the night of the professor's lecture on the structure of the atom, which he had promised to attend. But he was so fed up with his father-in-law's interminable expositions that he decided to forget the lecture and spend a comfortable evening at home. However, just as he was getting settled with his book, Maud cut off this avenue of escape by looking at the clock and remarking, gently but firmly, that it was almost time for him to leave. So, half an hour later, he found himself on a hard wooden bench in the university auditorium together with a crowd of eager young students. ‘Ladies and gentlemen,’ began the professor, looking at them gravely over his spectacles, ‘In my last lecture I promised to give you more details concerning the internal structure of the atom, and to explain how the peculiar features of this structure account for its physical and chemical properties. You know, of course, that atoms are no longer considered as elementary indivisible constituent parts of matter, and that this role has passed now to much smaller particles such as electrons, protons, etc. ‘The idea of elementary constituent particles of matter, representing the last possible step in divisibility of material bodies, dates back to the ancient Greek philosopher DEMOCRITUS who lived in the fourth century B.C. Meditating about the hidden nature of things, Democritus came to the problem of the structure of matter and was faced with the question whether or not it can exist in infinitely small portions.
PREFACE PART I: THE STRUCTURE OF MATTER 1. THE MICROSCOPIC WORLD: ATOMS AND MOLECULES 1.1 Development of the Atomic Theory: Relative Atomic Weights 1.2 Atomic Magnitudes 1.3 The Charge-to-Mass Ratio of the Electron: Thomson's Method 1.4 The Charge of the Electron: Millikan's Method 1.5 Mass Spectrometry 1.6 The Atomic Mass Scale and the Mole 1.7 The Periodic Table 2. ORIGINS OF THE QUANTUM THEORY OF MATTER 2.1 The Franck-Hertz Experiment 2.2 The Photoelectric Effect 2.3 X-rays and Matter 2.4 The Emission Spectra of Atoms 2.5 The Nuclear Atom 2.6 The Problem of Black-Body Radiation 2.7 The Concept of Action 2.8 The Harmonic Oscillator 2.9 Action Quantized: The Heat Capacity of Solids 2.10 Some Orders of Magnitude 2.11 Bohr's Model of the Atom Appendix 2A: Rutherford Scattering 3. MATTER WAVES IN SIMPLE SYSTEMS 3.1 The de Broglie Hypothesis 3.2 The Nature of Waves 3.3 Dispersion Relations and Wave Equations: The Free Particle 3.4 Operators 3.5 Eigenfunctions and Eigenvalues 3.6 The Particle in a One-Dimensional Box 3.7 The Indeterminacy or Uncertainty Principle 3.8 Expectation Values Summary of Postulates 3.9 Particles in Two- and Three-Dimensional Boxes 3.10 Particles in Circular Boxes 3.11 Particles in Spherical Boxes 3.12 The Rigid Rotor Appendix 3A: More on Circular Coordinates and the Circular Box 4. PARTICLES IN VARYING POTENTIAL FIELDS TRANSITIONS 4.1 Finite Potential Barriers 4.2 The Quantum Mechanical Harmonic Oscillator 4.3 The Hydrogen Atom 4.4 The Shapes of Orbitals 4.5 Transitions between Energy Levels 5. THE STRUCTURE OF ATOMS 5.1 Electron Spin Magnetic Phenomena 5.2 The Pauli Exclusion Principle the Aufbau Principle 5.3 Electronic Configurations of Atoms 5.4 Calculation of Atomic Structures 5.5 Atomic Structure and Periodic Behavior 5.6 Term Splitting and the Vector Model 5.7 Fine Structure and Spin-Orbit Interactions Appendix 5A: The Stern-Gerlach Experiment 6. THE CHEMICAL BOND IN THE SIMPLEST MOLECULES: H[2+ AND H[2 6.1 Bonding Forces between Atoms 6.2 The Simplest Molecule: The Hydrogen Molecule-Ion, H[2+ 6.3 H[2+: Molecular Orbitals and the LCAO Approximation 6.4 H[2+: Obtaining the Energy Curve 6.5 H[2+: Correlation of Orbitals Excited States 6.6 The H[2 Molecule: Simple MO Description 6.7 Symmetry Properties of Identical Particles 6.8 H[2: The Valence Bond Representation 6.9 H[2: Beyond the Simple MO and VB Approximations 6.10 H[2: Excited Electronic States Appendix 6A: Orthogonality Appendix 6B: Hermitian Operators 7. MORE ABOUT DIATOMIC MOLECULES 7.1 Vibrations of Diatomic Molecules 7.2 Rotations of Diatomic Molecules 7.3 Spectra of Diatomic Molecules 7.4 The Ionic Bond 7.5 Homonuclear Diatomic Molecules: Molecular Orbitals and Orbital Correlation 7.6 Homonuclear Diatomic Molecules: Aufbau Principle and Structure of First-Row Molecules 7.7 Introduction to Heteronuclear Diatomic Molecules: Electronegativity 7.8 Bonding in LiH: Crossing and Noncrossing Potential Curves 7.9 Other First-Row Diatomic Hydrides 7.10 Isoelectronic and Other Series Appendix 7A: Perturbation Theory 8. TRIATOMIC MOLECULES 8.1 Electronic Structure and Geometry in the Simplest Cases: H[3 and H[3+ 8.2 Dihydrides: Introduction to the Water Molecule 8.3 Hybrid Orbitals 8.4 Delocalized Orbitals in H[2O: The General MO Method 8.5 Bonding in More Complex Triatomic Molecules 8.6 Normal Coordinates and Modes of Vibration 8.7 A Solvable Example: The Vibrational Modes of CO[2 8.8 Transitions and Spectra of Polyatomic Molecules: Rotations and Vibrations 8.9 Transitions and Spectra of Polyatomic Molecules: Magnetic Transitions 8.10 Transitions and Spectra of Polyatomic Molecules: Electronic Transitions 9. LARGER POLYATOMIC MOLECULES 9.1 Small Molecules 9.2 Catenated Carbon Compounds Transferability 9.3 Other Extended Structures 9.4 Some Steric Effects 9.5 Complex Ions and Other Coordination Compounds: Simple Polyhedra 9.6 Chirality and Optical Rotation 9.7 Chiral and Other Complex Ions 9.8 Magnetic Properties of Complexes 9.9 Electronic Structure of Complexes Appendix 9A: Schmidt Orthogonalization 10. INTERMOLECULAR FORCES 10.1 Long-Range Forces: Interactions between Charge Distributions 10.2 Empirical Intermolecular Potentials 10.3 Weakly Associated Molecules 11. THE STRUCTURE OF SOLIDS 11.1 Some General Properties of Solids 11.2 Space Lattices and Crystal Symmetry 11.3 X-ray Diffraction from Crystals: The Bragg Model 11.4 The Laue Model 11.5 Determination of Crystal Structures 11.6 Techniques of Diffraction 11.7 Molecular Crystals 11.8 Structures of Ionic Crystals 11.9 Binding Energy of Ionic Crystals 11.10 Covalent Solids 11.11 The Free-Electron Theory of Metals 11.12 The Band Theory of Solids 11.13 Conductors, Insulators, and Semiconductors 11.14 Other Forms of Condensed Matter APPENDICES I. Systems of Units II. Partial Derivatives III. Glossary of Symbols IV. Searching the Scientific Literature INDEX
What was Bohr's response to the problem of wave-particle duality? Before considering this question in detail it will be useful to survey briefly Bohr's work in physics between 1911 and 1923. Bohr and the ‘old’ quantum theory In 1911 Bohr completed his doctoral dissertation on the classical electron theory of metals. Developed by Sir J.J. Thomson and Lorentz, the theory explained electrical, magnetic and thermal properties of metals in terms of the motions of free electrons. Although Bohr made no use of the quantum hypothesis in his dissertation, he noted that classical electrodynamics was incapable of explaining Planck's radiation law and entailed the ultraviolet catastrophe. After completing his dissertation Bohr pursued his post-graduate studies under Thomson at Cambridge University. Finding that Thomson was little interested in his work, Bohr went on to Manchester University in March 1912, to work under Ernest Rutherford. Bohr's move to Manchester was very opportune: the quantum hypothesis was just beginning to receive a wider recognition, thanks largely to the first Solvay Conference in 1911, which Rutherford attended; Rutherford's laboratory, moreover, was one of the most active centres in the investigation of radio-activity. In order to explain the results of experiments on the passage of alpha and beta particles through matter Rutherford had revived Hantaro Nagaoka's (1904) planetary model of the atom. On this model an atom consists of a positively charged nucleus which is orbited by negatively charged electrons, the number of which corresponds to the number of charges on the nucleus.
In 1897, Thomson demonstrated that cathode rays (observed to be emitted from the cathodes of vacuum tubes) were in fact charged particles which he called electrons. Thomson proposed that the atom consisted of a positively charged sphere in which were embedded negatively charged electrons. Rutherford subsequently found in 1911 that the electrons orbited at some distance from a central positively charged nucleus. Rutherford proposed that electrostatic attraction between the nucleus and the electron was balanced by the centrifugal force arising from the orbital motion. However, if this were the case, then the electrons (being accelerated inwards towards the center of rotation) would continuously radiate all their energy as electromagnetic waves and very quickly fall into the nucleus. In 1913, Bohr postulated two important additions to Rutherford’s theory of atomic structure: 1. Electrons can orbit the nucleus in what are called stationary states in which no emission of radiation occurs and in which the angular momentum L is constrained to have values: 2. Electrons can make transitions from one state to another accompanied by the emission or absorption of a single photon of energy E = hf thus leading to absorption and emission spectra.