This chapter begins with a discussion of radiation by a microscopic classical oscillator with radiative damping. It then turns to the Schrödinger equation for the hydrogen atom, and an extended analysis of the solutions to the Schrödinger equation for the hydrogen atom in polar coordinates is then presented. Real orbitals are constructed from linear combinations of the complex Schrödinger equation solutions. The significance of real orbitals for molecular structure and the consequent introduction of rotating and vibrating dipoles are then introduced. A semiclassical model (quantal atom and classical E-M field) for the absorption and emission of radiation is developed and compared to the Einstein A and B coefficients. It is shown how the time-dependence of the radiatively coupled non-stationary states of the hydrogen atom are analogous to the classical harmonic oscillator. The essentials of atomic transitions, as well as molecular rotational, vibrational, and electronic spectroscopy complete the chapter.
This chapter begins with a discussion of radiation by a microscopic classical oscillator with radiative damping. It then turns to the Schrödinger equation for the hydrogen atom, and an extended analysis of the solutions to the Schrödinger equation for the hydrogen atom in polar coordinates is then presented. Real orbitals are constructed from linear combinations of the complex Schrödinger equation solutions. The significance of real orbitals for molecular structure and the consequent introduction of rotating and vibrating dipoles are then introduced. A semiclassical model (quantal atom and classical E-M field) for the absorption and emission of radiation is developed and compared to the Einstein A and B coefficients. It is shown how the time-dependence of the radiatively coupled non-stationary states of the hydrogen atom are analogous to the classical harmonic oscillator. The essentials of atomic transitions, as well as molecular rotational, vibrational, and electronic spectroscopy complete the chapter.
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.
In this chapter, the authors solve the Schrodinger equation for a harmonic oscillator using two methods, analytical method and algebraic method. They discuss the quantum properties of the harmonic oscillator. A harmonic oscillator is a system that exhibits simple harmonic motion or periodic motion, a motion that repeats itself after equal intervals of time. Many systems such as spring, simple pendulum, vibrating string and molecular vibration can be approximated as simple harmonic oscillators. The authors consider a simple harmonic oscillator, a spring whose spring constant is "k" attached to a mass "m" as a simple harmonic oscillator. They describe the Schrodinger equation in spherical coordinates. The authors also solve the three-dimensional Schrodinger equation for the hydrogen atom. For the hydrogen atom, the potential energy function is dependent only on radial distance and is independent of angular variables. The hydrogen atom consists of a positively charged proton surrounded by an electron that orbits around it.
Radiation can change the energy state of matter via three optical processes: spontaneous emission, absorption and stimulated emission. In spontaneous emission, an excited atomic or molecular state decays to a lower energy state with the emission of a photon of energy equal to the difference in the quantum state energies. Photon absorption is the reverse process, with a photon causing excitation from a lower to an excited quantum state. Stimulated emission was first proposed by Einstein in a paper published in 1917. He attempted to balance spontaneous emission and photon absorption, but could not get the correct balance without the postulated process of stimulated emission (see Section 4.2). With stimulated emission, an excited quantum state is stimulated to decay to a lower quantum state by an impinging photon. The existing photon survives with another identical photon being created (so that energy is conserved). The rates at which radiative transitions occur can be calculated using quantum mechanics. The time-dependent Schrodinger equation is used with the system wavefunction comprising time-varying linear combinations of the two wavefunctions for the lower and upper quantum states. In semi-classical treatments, an atom is treated quantum mechanically with the radiation field treated classically. There is a perturbation in energy associated with, say, the electric field of the radiation interacting with the electric dipole of the atom, though other interactions can be significant if the electric dipole interaction energy is small. In absorption, for example, a differential equation representing the change in ‘weighting’ of the wavefunction from the lower to upper state is obtained. A ‘time constant’ for the speed of change represents the rate of the radiative process. We examine the quantum mechanical nature of radiation absorption in Section 10.1 before discussing (Section 10.3) another important parameter arising with radiative transitions between discrete bound quantum states: the lineshape function. Quantum Theory of the Atom–Radiation Interaction An expression for the Einstein B-coefficient for photo-absorption is derived using quantum mechanics in this section. Einstein determined the detailed balance relationship between the rates of spontaneous emission, photo-absorption and stimulated emission when light interacts with an atom by considering an atomic system of two energy levels which are in equilibrium with a black-body radiation field. We use a semi-classical treatment where the atom is treated quantum mechanically and the radiation field is treated as a classical oscillating electric field.
This chapter focuses on the hydrogen atom, which is the most important chemical application of the quantum theory. The hydrogen atom was Erwin Schrödinger's immediate goal when he developed his equation, and the solution obtained in 1926 persuaded him and indeed most interested physicists that his theory was successful. Indeed, the solutions of Schrödinger's equation — known as atomic orbitals — form the basis of our understanding, not only of atomic structure, but also of chemical bonding in molecules and solids. The chapter begins by considering the Rutherford–Bohr atom. It then looks at hydrogenic ions. The solutions described in the chapter are 'exact', in the mathematical sense that they can be obtained from the Schrödinger's equation without approximation. However, they are not quite 'correct', because this equation does not truly describe a real hydrogen atom.
Chapter 11 presents the simplest and most intuitive approach to atom-optical interactions: the atom is modelled as a damped harmonic oscillator with spontaneous emission as the damping agent. The semiclassical viewpoint, in which the atom is treated as a quantum object but the fields are classical, is adopted throughout the chapter. Next, the two-level atom is introduced, which sets the stage for establishing light forces at the atomic level: the dipole-gradient force and the radiation pressure force. The Einstein B coefficient is revisited as stimulated dipole emission. Finally, the optical Bloch equations are used to reformulate more generally the appearance of optical forces and to describe the existence of atom Doppler cooling.
This paper develops and verifies a physics-first description of the hydrogen-atom transition from the L shell (n = 2) to the K shell (n = 1) by combining the historical Bohr model of atomic structure with classical Maxwell electrodynamics. Beginning with the Coulomb force, centripetal dynamics, and Bohr’s angular-momentum quantization condition, the analysis derives the allowed orbital radii, electron velocities, angular momenta, kinetic energies, electrostatic potential energies, and total bound-state energies of the hydrogen atom. For the n = 2 → n = 1 transition, the calculated energy difference is approximately 10.2 eV, corresponding through the Planck–Einstein relation ΔE = hν to a frequency of approximately 2.47 × 10¹⁵ Hz and a wavelength near 121.6 nm, consistent with the hydrogen Lyman-α transition. The emitted radiation is then examined through Maxwell’s equations and the vacuum constitutive relations. The resulting electromagnetic-wave description yields the transverse electric and magnetic fields together with the associated electromagnetic energy density, Poynting energy flux, momentum density, radiation pressure, and Maxwell stress tensor. In this way, the atomic energy difference obtained from the Bohr model is connected quantitatively to the classical propagation properties of the outgoing electromagnetic radiation. The derivation is mathematically consistent as a historical Bohr–Maxwell reconstruction, but it does not constitute a closed dynamical theory of spontaneous emission. The essential bridge between discrete atomic energy levels and the continuous Maxwell field is supplied by the quantum frequency condition ΔE = hν. Neither classical Maxwell electrodynamics nor Newtonian orbital mechanics independently derives this relation, and classical Maxwell theory does not by itself quantize the emitted radiation energy into individual photons. A complete treatment of spontaneous emission, transition probabilities, radiative lifetimes, and photon-field quantization requires quantum mechanics and ultimately quantum electrodynamics. Accordingly, the framework is presented as a verified correspondence between established limiting descriptions rather than as a replacement for Schrödinger wave mechanics, Dirac theory, or quantum electrodynamics. By clearly separating the atomic bound-state calculation, the quantum energy-frequency bridge, and the classical electromagnetic propagation problem, the analysis provides a rigorous conceptual and mathematical foundation for subsequent Maxwell–Schrödinger, Dirac–Maxwell, quantum-electrodynamic, Maxwell–Scretching, and Scretching Quantum Chain formulations of hydrogenic radiative transitions.