The subject of this chapter is the quantum mechanical analysis of the interaction of electromagnetic radiation with atomic transitions. The analysis is based on the Schrödinger wave equation, and in the first section, the gauge-invariant form of the external electromagnetic field is introduced. The electric dipole interaction and the long-wavelength approximation for the analysis of this interaction are discussed. The perturbative analysis of both single-photon and two-photon electric dipole interactions is presented, and density matrix analysis is introduced. The interaction of radiation with the resonances of atomic hydrogen is then discussed. The analysis is performed for both coupled and uncoupled representations. In the last section of the chapter, the radiative interactions for multielectron atoms are discussed. The Wigner–Eckart theorem and selection rules for transitions between levels characterized by coupling are developed. The effect of hyperfine splitting on radiative transitions is also briefly discussed.
The subject of this chapter is the quantum mechanical analysis of the interaction of electromagnetic radiation with atomic transitions. The analysis is based on the Schrödinger wave equation, and in the first section, the gauge-invariant form of the external electromagnetic field is introduced. The electric dipole interaction and the long-wavelength approximation for the analysis of this interaction are discussed. The perturbative analysis of both single-photon and two-photon electric dipole interactions is presented, and density matrix analysis is introduced. The interaction of radiation with the resonances of atomic hydrogen is then discussed. The analysis is performed for both coupled and uncoupled representations. In the last section of the chapter, the radiative interactions for multielectron atoms are discussed. The Wigner–Eckart theorem and selection rules for transitions between levels characterized by coupling are developed. The effect of hyperfine splitting on radiative transitions is also briefly discussed.
In this chapter a quantum mechanical treatment of atomic response to the fields of an electromagnetic wave is presented. Absorption and emission of energy by atoms involves transition between their quantized energy levels driven by an interaction Hamiltonian. Schrodinger equation is used to derive the equations of motion for the density matrix of the atom, which is better suited to include the effects of mechanisms other than the interaction Hamiltonian – collisions, level decays, level shifts, etc. that also affect the state of the atom. Using the density matrix equation of motion and focusing on two atomic levels, induced dipole moment for a single two-level atom and polarization and susceptibility for a collection of two-level atoms, including the effects of level decays, and collisions, are calculated. Equations of motion for level populations are also derived. These expressions naturally predict stimulated emission as well as absorption. Expressed in terms of spontaneous emission rate they confirm the validity of equations derived in Chapter 5 using the dipole oscillator model of atomic response. The limit in which quantum mechanical equations for atomic response reduce to the classical dipole oscillator equations is also discussed.
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.
We treat the interaction between an electromagnetic radiation bath and a material system in the semi-classical picture: the radiation is treated according to the Maxwell equations, but the process of emission/absorption is described through the concept of a photon; on the other hand, the material system is modelled according to quantum mechanics, assuming a discrete two-level energy spectrum. This very simple model allows one to elaborate the elementary theory of the absorption/emission coefficients, both for the spontaneous and for the stimulated processes which will be described within the electric dipole approximation. Selection rules for allowed transitions are eventually obtained and the nature of high-order transition is briefly outlined. Finally, a qualitative description of the light amplification by stimulated emission of radiation is presented.
In Chap. 1 we introduced the Schrodinger equation and gave solutions for a number of simple cases. The general solution was then obtained by a linear superposition of these solutions. In our work, we are particularly concerned with the way in which atomic systems interact with electromagnetic radiation. These systems are still described by wave functions given by superpositions of simple solutions, but the expansion coefficients Cn (probability amplitudes) become functions of time. In this chapter we derive equations of motion for the expansion coefficients using Schrddinger’s equation and introduce the electric-dipole interaction energy. Then, specializing to a two-level system and a monochromatic electromagnetic field, we solve the equations of motion both by time-dependent perturbation theory and by the more exact Rabi method.
Abstract The atom-field interaction is treated in semiclassical radiation theory, starting from the transformation from the minimal coupling Hamiltonian to the electric dipole form used extensively in quantum optics. The Heisenberg and density matrix approaches are developed and applied to two-state atoms, Bloch equations, Rabi oscillations, Maxwell-Bloch equations, and transition rates for absorption and emission. Einstein’s theory of blackbody radiation based on momentum fluctuations and dissipation is reviewed. The Einstein fluctuation formula is derived and used to introduce wave-particle duality, Hanbury Brown-Twiss correlations, and photon bunching.
In continuation of our earlier works, we present results concerning the computation of matrix elements of the multipolar Hamiltonian (MPH) between extended wave functions that are obtained numerically. The choice of the MPH is discussed in connection with the broader issue of the form of radiation-atom (or -molecule) interaction that is appropriate for the systematic solution of various problems of matter-radiation interaction. We derive analytic formulas, in terms of the sine-integral function and spherical Bessel functions of various orders, for the cumulative radial integrals that were obtained and calculated by Komninos, Mercouris, and Nicolaides [Phys. Rev. A 71, 023410 (2005)]. This development allows the much faster and more accurate computation of such matrix elements, a fact that enhances the efficiency with which the time-dependent Schr\"odinger equation is solved nonperturbatively, in the framework of the state-specific expansion approach. The formulas are applicable to the general case where a pair of orbitals with angular parts $|{\ensuremath{\ell}}_{1},\phantom{\rule{1.0pt}{0ex}}\phantom{\rule{1.0pt}{0ex}}{m}_{1}\ensuremath{\rangle}$ and $|{\ensuremath{\ell}}_{2},\phantom{\rule{1.0pt}{0ex}}\phantom{\rule{1.0pt}{0ex}}{m}_{2}\ensuremath{\rangle}$ are coupled radiatively. As a test case, we calculate the matrix elements of the electric field and of the paramagnetic operators for on- and off-resonance transitions, between hydrogenic circular states of high angular momentum, whose quantum numbers are chosen so as to satisfy electric dipole and electric quadrupole selection rules. Because of the nature of their wave function (they are nodeless and the large centrifugal barrier keeps their overwhelming part at large distances from the nucleus), the validity of the electric dipole approximation in various applications where the off-resonance couplings must be considered becomes precarious. For example, for the transition from the circular state with n = 20 to that with n = 21, for which $\ensuremath{\langle}r\ensuremath{\rangle}\ensuremath{\approx}400$ a.u., the dipole approximation starts to fail already at XUV wavelengths ($\ensuremath{\lambda}<125\phantom{\rule{0.28em}{0ex}}\mathrm{nm}$).