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CRC Press eBooks

Quantum Mechanics of Atomic Response

Surendra Singh

Published Sep 23, 2026• 0 citations
Publisher

Abstract

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.

DOI
10.1201/9781003584179-6

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Nonlinear Optics•May 4, 2018•1 citation
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.
This chapter presents the electron oscillator model of light-matter interaction. It models atomic response to the fields in an electromagnetic wave after a classical driven charged (dipole) oscillator. It is used to calculate atomic polarization and dielectric susceptibility and derive an equation of motion for atomic polarization for a collection of atoms. By replacing the oscillator number density in this equation with the level population density difference and interpreting oscillator frequency with transition frequency and decay rate with spontaneous emission rate a quantum mechanically correct equation for atomic polarization is obtained. Poynting theorem on energy exchange between light and atoms in an EM wave then yields quantum mechanically correct rate equations for population densities. These equations together with the equation for atomic polarization provide a complete description of atomic response to light. Modifications to the atomic response due to finite atomic lifetimes, collisions, atomic motion, local variation of resonance frequency and other factors are also discussed in terms of lineshape function and cross-section.
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.
Abstract The quantum mechanical description of the interaction of light with atoms treats absorption, gain, and recombination as upward and downward induced transitions of electrons between two states by perturbation due to the optical electric field. This provides the basis for a quantitative theory of diode lasers. The chapter begins with Einstein’s description of absorption, stimulated emission, and spontaneous emission, setting the scene for calculation of the transition probability by solving the time-dependent Schrödinger equation for a coherent superposition of the wavefunctions of two states. The resulting absorption spectrum has a Lorentzian lineshape due to dephasing of these wavefunctions. Expressions for the optical absorption cross section and Einstein coefficients are derived in terms of the dipole matrix element, and the dipole is illustrated using a hypothetical one-dimensional atom. Fermi’s Golden Rule for transitions to a continuum of states (as in quantum wells) is introduced in terms of the momentum matrix element.
Bohr’s correspondence principle is that associated with each observable in classical mechanics is an observable in quantum mechanics that follows certain quantization axioms which can be used to explain the energy spectra of atoms and quantum oscillators. In Schrodinger’s wave mechanics, the state of the system at any time is described by a density operator in a Hilbert space. The chapter describes how the Pauli equation can be used to calculate the average electric dipole moment and average magnetic dipole moment of an atom in an external electromagnetic field. This calculation enables to calculate the electric polarization field and the magnetization field of a material.
This chapter considers an atom as a quantum mechanical system. But the electromagnetic radiation will be treated as classical waves described by the Maxwell equations. The treatment is called semi-classical. Quantum mechanics describes an atom as a quantized system with a set of discrete energy levels. Each energy level is designated by a set of quantum numbers like the principal quantum of the Rydberg level and the quantum numbers representing the orbital, spin and total angular momentum. A molecule will have a different set of quantum numbers arising from its rotational and vibrational motions. Atoms in a solid have energy levels in the form of a band. The observed spectrum due to spontaneous emission from a collection of atoms is not monochromatic, but it is spread over a certain range of frequencies. The absorption spectrum also shows that the atom does not absorb at a single frequency, but it is spread over a band of frequencies around the resonance frequency.
A detectable nonlinear response between light and matter depends on one of two key ingredients: Either there is a resonance between the light wave and some natural oscillation mode of the material, or the light is sufficiently intense. In this chapter, the authors let the matter variables themselves play active roles and derive coupled nonlinear differential equations for the electric and matter fields. They outline the use of Schrodinger's equation to derive the Bloch equations, which describe the dynamics of the oscillators of matter and help to derive the Maxwell equation for the envelope of an almost monochromatic electromagnetic wave. The authors analyse the case of two distinct co- or counter-propagating waves interacting with a three-level medium where both waves excite separate quantum transitions sharing a common level. They also help to derive an effective two-level atom model that describes two-photon absorption and stimulated Raman scattering.