General remarks As already mentioned in the Introduction, the exact solution of the main equation of quantum mechanics – the Schrödinger equation – lies beyond the potentialities of modern mathematics and computer technology. But a number of important inferences about the behaviour, structure and properties of a given quantum-mechanical many-particle system can be drawn without solving this equation, just by examining its symmetry properties. Symmetry concepts come about in physics in two ways. First, since any physical process occurs in a real space, we have to make use of one or another coordinate system. The isotropy and homogeneity of space make physically meaningful only those mathematical relationships that remain unchanged under rotations of the axes of the coordinate system, and that impose fairly rigorous constraints on the possible physical laws. Second, every physical object and process features a symmetry which should be taken into account by the physical theory. A common idea underlying particular forms of symmetry is the invariance of a system under a certain set (group) of transformations. The normally considered forms of symmetry are rotational symmetry, which is based on the equivalence of all directions in space, and permutation symmetry, which is caused by identical particles. The operations of the geometrical symmetry group are responsible for appropriate conservation laws. So, the rotational symmetry of a closed system gives rise to the law of conservation of angular momentum. The group of rotations of a three-dimensional space stands apart in atomic spectroscopy. This is mostly due to the high accuracy of the central field approximation, on which the entire modern theory of complex atoms and ions is based.
General remarks As already mentioned in the Introduction, the exact solution of the main equation of quantum mechanics – the Schrödinger equation – lies beyond the potentialities of modern mathematics and computer technology. But a number of important inferences about the behaviour, structure and properties of a given quantum-mechanical many-particle system can be drawn without solving this equation, just by examining its symmetry properties. Symmetry concepts come about in physics in two ways. First, since any physical process occurs in a real space, we have to make use of one or another coordinate system. The isotropy and homogeneity of space make physically meaningful only those mathematical relationships that remain unchanged under rotations of the axes of the coordinate system, and that impose fairly rigorous constraints on the possible physical laws. Second, every physical object and process features a symmetry which should be taken into account by the physical theory. A common idea underlying particular forms of symmetry is the invariance of a system under a certain set (group) of transformations. The normally considered forms of symmetry are rotational symmetry, which is based on the equivalence of all directions in space, and permutation symmetry, which is caused by identical particles. The operations of the geometrical symmetry group are responsible for appropriate conservation laws. So, the rotational symmetry of a closed system gives rise to the law of conservation of angular momentum. The group of rotations of a three-dimensional space stands apart in atomic spectroscopy. This is mostly due to the high accuracy of the central field approximation, on which the entire modern theory of complex atoms and ions is based.
A symmetry is an equivalence of different physical situations, and is therefore strictly associated with the concept of invariance . One of the main aims of physics is the search in nature for symmetries and, therefore, for observables that are invariant under certain classes of transformation. In this context, it becomes particularly interesting to look for the conditions under which a certain symmetry is eventually broken. We have already discussed some symmetries of quantum mechanics: time translations (Ch. 3), space translations (Ch. 2) and rotations (Ch. 6). Another example of invariance is represented by the indistinguishability of identical particles, which we discussed in the previous chapter. Symmetries are induced by physical transformations that generate some invariant properties (see Sec. 8.1). In Sec. 8.2, the continuous transformations induced by rotations and space translations are analyzed, whereas in Sec. 8.3, space reflection and time reversal ( discrete symmetries) are discussed. As we shall see in the next chapter, time reversibility is lost in the measurement process. The rigorous mathematical framework of a theory of transformations and of their invariance is called group theory (the subject of Sec. 8.4). Quantum transformations and symmetries Active and passive transformations We have seen that time evolution may be represented either in the Schrödinger picture (state vectors evolve and observables are kept constant) or in the Heisenberg picture (states vectors remain constant and observables evolve) (see Subsec. 3.6.1 and Sec. 5.3).
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.
Symmetries play a central role in physics. They dictate what one can change in a physical system without affecting any of its properties. You might have encountered symmetries like translational symmetry, where a system remains unchanged if it is spatially translated by an arbitrary distance. A system with rotational symmetry, however, is invariant under rotations. Some symmetries, like the ones mentioned above, give information about the structure of the system. Others have to do with the more fundamental physical framework that we adopt. An example for this is the invariance under Lorentz transformations in relativistic physics. Other types of symmetries can be even more subtle. For example, it is rather self-evident that physics should remain unchanged if we exchange two identical point-like particles. Nevertheless, this fundamental property that we call statistical symmetry gives rise to rich and beautiful physics. In three spatial dimensions it dictates the existence of bosons and fermions. These are particles with very different quantum mechanical properties. Their wave function acquires a +1 or a -1 phase, respectively, whenever two particles are exchanged. A direct consequence of this is that bosons can actually occupy the same state. In contrast, fermions can only be stacked together with each particle occupying a different state. When one considers two spatial dimensions, a wide variety of statistical behaviours is possible. Apart from bosonic and fermionic behaviours, arbitrary phase factors, or even non-trivial unitary evolutions, can be obtained when two particles are exchanged (Leinaas and Myrheim, 1977).
Introduction The application of group theory to study physical problems and their solutions provides a formal method for exploiting the simplifications made possible by the presence of symmetry. Often the symmetry that is readily apparent is the symmetry of the system/object of interest, such as the three-fold axial symmetry of an NH 3 molecule. The symmetry exploited in actual analysis is the symmetry of the Hamiltonian. When alluding to symmetry we usually include geometrical, time-reversal symmetry, and symmetry associated with the exchange of identical particles. Conservation laws of physics are rooted in the symmetries of the underlying space and time. The most common physical laws we are familiar with are actually manifestations of some universal symmetries. For example, the homogeneity and isotropy of space lead to the conservation of linear and angular momentum, respectively, while the homogeneity of time leads to the conservation of energy. Such laws have come to be known as universal conservation laws. As we will delineate in a later chapter, the relation between these classical symmetries and corresponding conserved quantities is beautifully cast in a theorem due to Emmy Noether. At the day-to-day working level of the physicist dealing with quantum mechanics, the application of symmetry restrictions leads to familiar results, such as selection rules and characteristic transformations of eigenfunctions when acted upon by symmetry operations that leave the Hamiltonian of the system invariant.
The structures are physical systems and/or their mathematical descriptions consisting of elements such as particles, fields, observables, operators etc and of relations between these elements: the equations of motion and the rules of quantum mechanics. Examples of symmetries are reflections, permutations of particles, time reversal. The physical system has a symmetry group means, then, that there is a group of transformations leaving the equations of motion and the rules of quantum mechanics invariant. The discrete symmetries lead to conservation laws frequently expressible in terms of quantum numbers, but sometimes requiring a more elaborate description. The observables corresponding to the super-selection quantum numbers can be measured without disturbing any other measurement; their values are always sharp. The chapter shows that the invariant subspace may be labelled by continuous quantum numbers (for instance momentum) when the direct sum becomes a direct integral.
Chapter 4 deals with Quantum Mechanical (QM) phenomena. The first section describes the first attempts at quantization of energy, momentum, angular momentum, etc. We start with Plank's solution to the black-body problem, introducing the concept of photons: discrete packets of electromagnetic energy. We show how Plank's description of black-body radiation is perfectly fit by the cosmic microwave radiation, providing the strongest evidence for the Big-Bang at the origin of the Universe. We then describe Bohr's solution to the paradoxical stability of atoms, introducing quantization of angular momentum (or action) and correctly predicting the energy levels of the hydrogen atom. We show how Einstein used Plank's idea to explain the photo-electric effect (an effect exploited in CCD cameras and solar cells) and how he used Bohr's understanding of energy levels in atoms to provide an intuitive explanation of Plank's law. Einstein insight opened the way to the field of spectroscopy and the development of the laser. In the second section, following the lead of Dirac, we show that QM is equivalent to Linear Algebra in the space of complex functions (which describe the state of the system). We show that Schrödinger's equation is a natural consequence of that description, once the relation between energy and frequency established by Plank (for photons) and de Broglie (for particles) is taken into account. In the context of the chiral ammonia molecule we discuss the queerness of QM which describes physical systems as superposition of states (such as left and right chirality state of a molecule, dead and alive cat). We show that this queerness is nonetheless supported by experiments and is behind much of our technology: masers and lasers, atomic clocks, semiconductors (diodes, transistors, etc.). In the following section we introduce the representation of operators in QM (the equivalent of matrices in linear algebra): momentum, position, energy, etc. which correspond to measurements on the system. We show that the non-commutability of some operators (common with matrix operations) leads to Heisenberg uncertainty principle: the position and momentum of a particle cannot be determined with absolute precision. We discuss the solution of Schrödinger's equation for free particles demonstrating their equivalence with EM phenomena: particles undergo refraction and diffraction, exemplifying the particle/wave duality inherent to QM systems. We discuss QM tunneling and its use in the Scanning Tunneling Microscope. In the following section we study Dirac's equation: the successful attempt by Dirac to unify QM with Einstein's relativity, with the resulting prediction of anti-particles and spin. We then solve for the energy levels of electrons in the hydrogen atom (from Schrödinger's equation) and show that the existence of spin profoundly affects the behavior of electrons in an atom: they cannot share the same energy level, a rule known as Pauli's exclusion principle. Pauli's principle is central to the understanding of the chemical properties of atoms and fully explains Mendeleev's periodic table of the elements. In the next section we discuss along with two exactly soluble systems (diatomic rotational and vibrational levels), various approximations used to study systems (e.g. molecules) for which there are no analytical solutions. In particular, we introduce Pauling's variational approach, Hückel molecular orbital theory and time independent perturbation theory. We apply those approaches to determine the energy levels in alkenes, in multi-electron atoms and in systems under constant electric or magnetic field (such as in Magnetic Resonance Imaging). In the last section we discuss time dependent perturbation theory. We use it to establish the rules allowing for transitions between energy levels and revisit Einstein description of absorption/emission phenomena.