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Cambridge University Press eBooks

Basic Concepts of Quantum Mechanics

M. Nisoli

Published Nov 10, 2022• 0 citations
Publisher

Abstract

Basic concepts of quantum mechanics: Schroedinger equation; Dirac notation; the energy representation; expectation value; Hermite operators; coherent superposition of states and motion in the quantum world; perturbation Hamiltonian. Time-dependent perturbation theory: harmonic perturbation. Transition rate: Fermi’s golden rule. The density matrix; pure and mixed states. Temporal dependence of the density operator: von Neuman equation. Randomizing Hamiltonian. Longitudinal and transverse relaxation times. Density matrix and entropy.

DOI
10.1017/9781009106153.004

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Basic concepts of quantum mechanics: Schroedinger equation; Dirac notation; the energy representation; expectation value; Hermite operators; coherent superposition of states and motion in the quantum world; perturbation Hamiltonian. Time-dependent perturbation theory: harmonic perturbation. Transition rate: Fermi’s golden rule. The density matrix; pure and mixed states. Temporal dependence of the density operator: von Neuman equation. Randomizing Hamiltonian. Longitudinal and transverse relaxation times. Density matrix and entropy.
Table of Contents 1. The Origins of Quantum Mechanics 1.1 Introduction 1.2 Blackbody Radiation The Problem with Blackbody Radiation 1.3 The Nature of Light The Photoelectric Effect The Compton Effect Is it a Particle or a Wave? 1.4 TheWave Nature of Matter 1.5 The Bohr Atom 1.6 Where do we Stand? 2. Math Interlude A: Complex Numbers and Linear Operators 2.1 Complex Numbers 2.2 Operators Definition of an Operator Eigenfunctions and Eigenvalues 3. The Schrodinger Equation 3.1 Derivation of the Schrodinger Equation 3.2 The Meaning of theWave Function 3.3 The Time-Independent Schrodinger Equation Derivation of the Time-Independent Schrodinger Equation Qualitative Solutions and the Origin of Quantization 4. One-Dimensional Time-Independent Schrodinger Equation 4.1 Unbound States: Scattering and Tunneling Scattering From Step-Function Potentials 4.2 Bound Systems The Infinite SquareWell The Harmonic Oscillator Potential 5. Math Interlude B: Linear Algebra 5.1 Properties of Linear Operators 5.2 Vector Spaces Inner Products Adjoint and Hermitian Operators Basis Sets 6. The Three-Dimensional Time-Independent Schrodinger Equation 6.1 Solution in Rectangular Coordinates 6.2 Angular Momentum 6.3 The Schrodinger Equation in Spherical Coordinates 6.4 The Hydrogen Atom 7. Math Interlude C: Matrices, Dirac Notation, and the Dirac Delta Function 7.1 The Matrix Formulation of Linear Operators 7.2 Dirac Notation 7.3 The Dirac Delta Function 8. Spin Angular Momentum 8.1 Spin Operators 8.2 Evidence for Spin 8.3 Adding Angular Momentum 8.4 The Matrix Representation of Spin 8.5 The Stern-Gerlach Experiment 8.6 Spin Precession 8.7 Spin Systems with Two Particles Noninteracting Spins Interacting Spins 8.8 Measurement Theory Hidden Variables The ManyWorlds Interpretation of Quantum Mechanics 9. Time-Independent Perturbation Theory 9.1 Derivation of Time-Independent Perturbation Theory 9.2 Perturbations to the Atomic Energy Levels Fine Structure The Lamb Shift 9.3 The Atom in External Electric or Magnetic Fields The Atom in an Electric Field: The Stark Effect The Atom in a Magnetic Field: The Zeeman Effect 10. The Variational Principle 10.1 Variational Principle: Theory 10.2 Variational Principle: Application to the Helium Atom 11. Time-Dependent Perturbation Theory 11.1 Derivation of Time-Dependent Perturbation Theory 11.2 Application: Selection Rules for Electromagnetic Radiation 12. Scattering Theory 12.1 Definition of the Cross Section 12.2 The Born Approximation 12.3 PartialWaves 13. The Multiparticle Schrodinger Equation 13.1 Wave Function for Identical Particles 13.2 Multielectron Atoms 14. Some Modern Applications of Quantum Mechanics 14.1 Magnetic Resonance Imaging 14.2 Quantum Computing 15. What Comes Next? Relativistic Quantum Mechanics 15.1 The Klein-Gordon Equation Derivation of the Klein-Gordon Equation Probability Densities and Currents 15.2 The Dirac Equation Answers and Hints for Selected End-of-Chapter Exercises Index
Preface. 1. Origins of Quantum Physics. 1.1 Historical Note. 1.2 Particle Aspect of Radiation. 1.3 Wave Aspect of Particles. 1.4 Particles versus Waves. 1.5 Indeterministic Nature of the Microphysical World. 1.6 Atomic Transitions and Spectroscopy. 1.7 Quantization Rules. 1.8 Wave Packets. 1.9 Concluding Remarks. 1.10 Solved Problems. Exercises. 2. Mathematical Tools of Quantum Mechanics. 2.1 Introduction. 2.2 The Hilbert Space and Wave Functions. 2.3 Dirac Notation. 2.4 Operators. 2.5 Representation in Discrete Bases. 2.6 Representation in Continuous Bases. 2.7 Matrix and Wave Mechanics. 2.8 Concluding Remarks. 2.9 Solved Problems. Exercises. 3. Postulates of Quantum Mechanics. 3.1 Introduction. 3.2 The Basic Postulates of Quantum Mechanics. 3.3 The State of a System. 3.4 Observables and Operators. 3.5 Measurement in Quantum Mechanics. 3.6 Time Evolution of the System's State. 3.7 Symmetries and Conservation Laws. 3.8 Connecting Quantum to Classical Mechanics. 3.9 Solved Problems. Exercises. 4. One-Dimensional Problems. 4.1 Introduction. 4.2 Properties of One-Dimensional Motion. 4.3 The Free Particle: Continuous States. 4.4 The Potential Step. 4.5 The Potential Barrier and Well. 4.6 The Infinite Square Well Potential. 4.7 The Finite Square Well Potential. 4.8 The Harmonic Oscillator. 4.9 Numerical Solution of the Schrodinger Equation. 4.10 Solved Problems. Exercises. 5. Angular Momentum. 5.1 Introduction. 5.2 Orbital Angular Momentum. 5.3 General Formalism of Angular Momentum. 5.4 Matrix Representation of Angular Momentum. 5.5 Geometrical Representation of Angular Momentum. 5.6 Spin Angular Momentum. 5.7 Eigen functions of Orbital Angular Momentum. 5.8 Solved Problems. Exercises. 6. Three-Dimensional Problems. 6.1 Introduction. 6.2 3D Problems in Cartesian Coordinates. 6.3 3D Problems in Spherical Coordinates. 6.4 Concluding Remarks. 6.5 Solved Problems. Exercises. 7. Rotations and Addition of Angular Momenta. 7.1 Rotations in Classical Physics. 7.2 Rotations in Quantum Mechanics. 7.3 Addition of Angular Momenta. 7.4 Scalar, Vector and Tensor Operators. 7.5 Solved Problems. Exercises. 8. Identical Particles. 8.1 Many-Particle Systems. 8.2 Systems of Identical Particles. 8.3 The Pauli Exclusion Principle. 8.4 The Exclusion Principle and the Periodic Table. 8.5 Solved Problems. Exercises. 9. Approximation Methods for Stationary States. 9.1 Introduction. 9.2 Time-Independent Perturbation Theory. 9.3 The Variational Method. 9.4 The Wentzel Kramers Brillou in Method. 9.5 Concluding Remarks. 9.6 Solved Problems. Exercises. 10. Time-Dependent Perturbation Theory. 10.1 Introduction. 10.2 The Pictures of Quantum Mechanics. 10.3 Time-Dependent Perturbation Theory. 10.4 Adiabatic and Sudden Approximations. 10.5 Interaction of Atoms with Radiation. 10.6 Solved Problems. Exercises. 11. Scattering Theory. 11.1 Scattering and Cross Section. 11.2 Scattering Amplitude of Spinless Particles. 11.3 The Born Approximation. 11.4 Partial Wave Analysis. 11.5 Scattering of Identical Particles. 11.6 Solved Problems. Exercises. A. The Delta Function. A.1 One-Dimensional Delta Function. A.2 Three-Dimensional Delta Function. B. Angular Momentum in Spherical Coordinates. B.1 Derivation of Some General. B.2 Gradient and Laplacianin Spherical Coordinates. B.3 Angular Momentum in Spherical Coordinates. C. Computer Code for Solving the Schrodinger Equation. Index.
This chapter begins by developing the relation between the quantum theory and the linear algebra. It discusses the most fundamental postulates of the theory and provides a phenomenological development of the Schrödinger wave equation (SWE) although the results might be gleaned from the classical Lagrangian and Hamiltonian with the Poisson bracket relations. Afterward some simple examples for the infinitely and finitely deep wells help clarify the basic postulates. The simple harmonic oscillator has perhaps the most sweeping implications and applications for the quantum theory. For this reason, we present the most applicable formalism for the Harmonic oscillator that uses the operator approach rather than the classical method of partial differential equations. The angular momentum and spin are presented for the study of the atom and for applications for nanodevices, and quantum computing. Next the representation formalism clarifies the distinction between the dynamical operators and the wave functions and their interrelations. The chapter discusses both timeindependent and time-dependent perturbation theories. The density operator combines the quantum theory with the classical theory for finding the behavior of a system. The density operator represents one of the basic concepts in the quantum theory. The remainder of the chapter introduces the more advanced material meant to introduce the quantum field theory starting with the second quantization and the propagator.
This text presents a rigorous mathematical account of the principles of quantum mechanics, in particular as applied to chemistry and chemical physics. Applications are used as illustrations of the basic theory. The first two chapters serve as an introduction to quantum theory, although it is assumed that the reader has been exposed to elementary quantum mechanics as part of an undergraduate physical chemistry or atomic physics course. Following a discussion of wave motion leading to Schrödinger's wave mechanics, the postulates of quantum mechanics are presented along with essential mathematical concepts and techniques. The postulates are rigorously applied to the harmonic oscillator, angular momentum, the hydrogen atom, the variation method, perturbation theory, and nuclear motion. Modern theoretical concepts such as hermitian operators, Hilbert space, Dirac notation, and ladder operators are introduced and used throughout. This text is appropriate for beginning graduate students in chemistry, chemical physics, molecular physics and materials science.
1. Wave-Particle Duality and Schroedinger Equation. 2. Introduction to Bound States. 3. Rotationally Invariant Potentials: Hydrogen Atom and Beyond. 4. Wave Packets and Uncertainty Relations. 5. Scattering by Simple Barriers. 6. WKB Approximations. 7. Expectation Values and Operators. 8. Electrons in a Magnetic Field. 9. Beyond Hermitian Operators. 10. Harmonic Oscillator: Full Operator Treatment. 11. Composite Systems. 12. Variational Principle. 13. Expansion Principle and Matrix Formulation. 14. Perturbation Theory, I: Degenerate Perturbation Theory. 15. Perturbation Theory, II: Non-Degenerate Perturbation Theory. 16. Symmetry. 17. Electrons in Periodic Crystal Potentials. 18. Rotational Invariance and Angular Momentum. 19. Time-Dependent Perturbation Theory. 20. Elements of Field Quantization. 21. Electron Spin. 22. Indistinguishable Particles: Fermions and Bosons. Appendices: Dirac ...d-Function. Poisson-Distributed Events. Spherical Harmonics. Hydrogen Radial Eigenfunctions. Fourier Integral. Construction of Two Group Character Tables. Selected General References. Fundamental Constants. Index.