To solve the problems of the classical model of the atom of both the atom's instability and the fact that it does not emit a line at a well-defined wavelength, we introduce the necessary quantum-mechanical ideas of angular momentum and energy quantization and provide a simple description of the hydrogen atoms. We go on to consider how to build up the structure of more complicated atoms. We also consider what quantum mechanics has to say about the exchange of energy between atoms in collisions and in interaction with light. This description includes collisional excitation and deexcitation and radiative processes (spontaneous and stimulated emission, absorption).
To solve the problems of the classical model of the atom of both the atom's instability and the fact that it does not emit a line at a well-defined wavelength, we introduce the necessary quantum-mechanical ideas of angular momentum and energy quantization and provide a simple description of the hydrogen atoms. We go on to consider how to build up the structure of more complicated atoms. We also consider what quantum mechanics has to say about the exchange of energy between atoms in collisions and in interaction with light. This description includes collisional excitation and deexcitation and radiative processes (spontaneous and stimulated emission, absorption).
The absorbed/emitted radiation will be treated classically, as a monochromatic plane wave, whereas the atomic system that can absorb/emit such radiation will be described quantum-mechanically. However, no incident radiation beam is needed, and the atom “falls down” after a certain time interval to the ground state without any external reason. In the spontaneous emission processes the emitting atom can be thought of as a classical oscillating dipole, whose amplitude decreases due to the energy loss through the radiation. If an ensemble of identical atoms is considered and if, for simplicity, each atom emits radiation with the same spectral shape and full width at half maximum, it is impossible to ascribe a definite spectral component with intensity to a definite atom. In this case, such a broadening is identical for all atoms in the ensemble. On the microscopic scale, absorption of radiation is reduced to the transitions between pairs of energy levels of a discrete atomic spectrum.
The whole realm of phenomena at the atomic or subatomic level is the special province of quantum theory. When isolated from radiation and other atoms, most atoms remain stable indefinitely: they neither collapse nor explode. When atoms are excited electrically or by collisions or otherwise, they emit radiation of discrete wavelengths characteristic of the kind of atoms excited. The simplest model of the atom is a hard, tiny, electrically neutral sphere—just the smallest possible fragment of the bulk material that possesses the identity of a given chemical element. Neils Bohr's theory was built primarily on the photon concept of radiation, which was understood as an hypothesis but was not yet unambiguously verified when Bohr did his early work. Bohr's first solution of the hydrogen-atom problem in his historic 1913 paper depended on a rather arbitrary combination of classical and quantum ideas.
This chapter provides a brief overview of quantum mechanics and light. It begins with a discussion on the purpose and practice of spectroscopy, which involves the investigation of the interaction of light with matter. It then breaks down the nature of electromagnetic radiation, expounding on the classical theory of light before turning to photons and how they make up light. Next, the chapter elaborates on the properties of lasers and how these same remarkable properties are achieved largely from the process of stimulated emission. Afterward, the chapter presents the wave mechanical description of an atom, and considers the Schrödinger equation and the Hamiltonian operator. Lastly, angular momentum is explored.
Some preliminaries We have, until now, thought of atoms as tiny hard spheres that feel a force of attraction towards one another. We ignored the fact that an atom consists of a nucleus surrounded by one or more electrons. If we stopped at this, we would make little progress towards understanding the properties of solids, other than that the atoms may form crystals. We must therefore go on and take a look at the internal structure of the atom itself, and see how this changes when the atom is surrounded by other atoms in a crystal. We shall then find that we need a description that is somewhat removed from our everyday experience. There is a name for this description, quantum mechanics : mechanics, because it deals with the motion of objects, and quantum, because features of the motion, such as energy, are quantized , meaning that they can only have any one of a set of distinct values, and no other value in between. Imagine for example a car which is so constructed that it can travel only at speeds of 10, or 50, or 100 km per hour, and not at any other speed. Then we could say that the speed of the car is quantized. This idea of quantization is something alien to our usual way of thinking. After all, a car is able to go at any speed we like up to its maximum speed.
Chapter 12 introduces light–matter interaction at the atomic scale and at interaction energies less than, or comparable to, the chemical bond. The classical electrodynamics treatment for fields is retained, but a very simple quantum atomic structure with electric dipole transitions among atomic and molecular internal states is introduced. The correspondence between classical and quantal electron orbital angular momentum states in atoms is developed in detail for the hydrogen atom, and the difference between quantised orbital states and real, space-directed orbitals is explained. A wave mechanical quantum representation brings out the analogies between classical light waves, quantum matter waves, classical dipole radiation, and atomic radiative emission. The intrinsic electron spin, that has no classical analogue, is introduced and discussed. The chapter ends with a discussion of the rigid rotor, harmonic oscillator model to interpret rotational and vibrational diatomic molecular spectra. Finally rovibronic states complete the picture with the introduction of diatomic molecular electronic transitions.
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.