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Physical Review A

Effects of Molecular Interactions on Coherent Electric Quadrupole Radiation Processes

Helen S. Freedhoff

Published Jan 1, 1972• 7 citations
Publisher

Abstract

The theory of the line shape in coherent electric quadrupole absorption and emission processes involving $N$ interacting molecules is developed, both quantum mechanically and with the use of a classical model. The theory is applied to small clusters and to linear chains of molecules. As in the dipole case, the effects of the interaction include in general a splitting of each molecular transition line into a number of components, a shift of each component from the molecular transition frequency, and a broadening or narrowing of each component relative to the width of the molecular line.

DOI
10.1103/physreva.5.126

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The theory of the line shape in coherent electric quadrupole absorption and emission processes involving NNN interacting molecules is developed, both quantum mechanically and with the use of a classical model. The theory is applied to small clusters and to linear chains of molecules. As in the dipole case, the effects of the interaction include in general a splitting of each molecular transition line into a number of components, a shift of each component from the molecular transition frequency, and a broadening or narrowing of each component relative to the width of the molecular line.
The theory of the line shape in coherent resonant absorption and emission in the infrared and optical region is developed. The Dicke spin model and the Lorentz oscillator model of a radiating molecule are discussed in detail, and the complications arising for degenerate levels are analyzed. The absorption and emission spectra are expressed in terms of the damped normal modes of the system of equivalent oscillators interacting via the retarded dipole–dipole interaction, and the results are shown to be identical with those derived using Heitler's quantum theory of radiation damping. The theory is applied to small clusters and linear chains of molecules. For a chain that is small compared with the wavelength, the natural line width is proportional to the total number of molecules, whereas for a long chain the width approaches a constant value. The discussion of three-dimensional systems, and the application to the zero-phonon lines in the infrared spectrum of solid hydrogen will be given in a separate paper.
Various characteristics of molecules have been clarified by spectroscopic methods in which the interactions of molecules with the radiation field were investigated. A stationary response of a molecule excited by a radiation field appears as a spectral line. Information on molecules may be obtained from position (resonance frequency), intensity, and shape and width of the spectral line. So far the interaction of molecules with the radiation field has been studied primarily in a “frequency domain.” Although molecular spectroscopy is one of the research fields in modern science which has the longest history, a variety of important aspects have been demonstrated very recently in this field as radiation sources have been improved. When the radiation field is “weak,” the photon nature of the radiation field is dominant in the interaction with a molecule, such as in the cases of emission, absorption, and scattering of photons. When the radiation field is “strong,” in the sense that many photons exist in a proper mode of the radiation field, the wave nature of the field plays an important role in the interaction. In this case the radiation may be described in the form of the classical field, say, a sinusoidal function of the time and spatial coordinates, coherently interacting with the molecule, which is described quantum mechanically. Here nonlinear properties would appear in the interactions: saturation in absorption, induced scattering, multiphoton processes, coherent transients, etc.
The classical theory of the interaction of light with the electron clouds of atoms and molecules will be discussed in this chapter. The discussion will begin with the interaction of a steady electric field with a collection of point charges, leading to the development of terms describing the electric dipole and quadrupole moments. The classical Lorentz model is then introduced to describe interaction of an oscillating electric field with the electron cloud of an atom, and the concepts of absorption and emission are introduced. The propagation of a light wave through a medium with electric dipoles is then discussed. Finally, the classical theory of radiation from an oscillating dipole is discussed.
The processes of absorption and emission of radiation by a system of two interacting atoms is investigated. Separation between the atoms is assumed to be much larger than the atomic diameter, and interactions considered are those between the individual atoms and the radiation field and the electrostatic interaction between the atoms. Calculations include those for the time-dependent probability amplitude of the intermediate and final states as well as that of the emission line shape. The line shape of the emitted radiation consists of two peaks whose amplitude, separation, and half-width are functions of both the internuclear separation R of the atoms and the energy difference of the excited states of the two atoms. For a large energy difference, the peaks are distinct; for small energy differences, the peaks are distinct at smaller separations, but merge toward the line shape characteristic of a single, isolated atom as R increases.
The development of the theory of the interaction of electromagnetic radiation with atoms and molecules is outlined. A fully classical analysis of absorption and emission is formulated in which particular attention is paid to questions of detailed balance and to the sum rules obeyed by the susceptibility. Collision broadening is introduced through time-dependent dipole moment correlation functions, and brief discussions of interruption broadening and various frequency modulation models are given. The corresponding quantum mechanical analysis is presented with emphasis on the points in common with the classical approach. The importance of correspondence principles in bridging the gap between classical and quantum mechanical theories is stressed.
Abstract A general and exact formalism is developed that permits the calculation of the line shape in all line-breadth phenomena, in principle to any order of approximation. Expansions for the line breadth and the numerator occurring in the line-shape formula are given. Corrections to the classical line shape include: (i) radiative corrections to the line breadth, (ii) a level shift additional to the usual radiative shift for levels with finite transition probability, (iii) radiative corrections to the numerator and (iv) a slight frequency dependence of the numerator. All these corrections, with the exception of (iv), are exceedingly small. The case of radio-frequency transitions is discussed.