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Annalen der Physik

Äquivalente Operatoren der Wechselwirkung zwischen Atomen und elektromagnetischem Feld

Heinz Steudel

Published Jan 1, 1972• 1 citation
Publisher

Abstract

Abstract As well‐known the dynamical interaction theory of molecules or atoms with the electromagnetic field may be based alternatively on one of two HAMILTONians, IH or IIH. where the vector potential appears in the interaction term of IH while this of IIH is expressed in terms of the electric and the magnetic field strength coupled to atomic multipoles. Using a calculus of transversal functional derivation with respect to a vector function we show that we can go from IH to IIH by a comperatively simple canonical transformation which may be interpreted within the classical theory as well as within as the quantized theory. The equivalence of both HAMILTONians is lost if, as customary in quantum optics, only a few atomic levels are taken into account. We give a plausible argument that in this case the multipole HAMILTONian IIH is more suitable.

DOI
10.1002/andp.19724830109

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Abstract As well‐known the dynamical interaction theory of molecules or atoms with the electromagnetic field may be based alternatively on one of two HAMILTONians, IH or IIH. where the vector potential appears in the interaction term of IH while this of IIH is expressed in terms of the electric and the magnetic field strength coupled to atomic multipoles. Using a calculus of transversal functional derivation with respect to a vector function we show that we can go from IH to IIH by a comperatively simple canonical transformation which may be interpreted within the classical theory as well as within as the quantized theory. The equivalence of both HAMILTONians is lost if, as customary in quantum optics, only a few atomic levels are taken into account. We give a plausible argument that in this case the multipole HAMILTONian IIH is more suitable.
Abstract A canonical transformation is performed on the conventional Hamiltonian for the electromagnetic radiation field and an assemblage of neutral molecules in interaction. The new Hamiltonian has interaction energies expressed in terms of the electromagnetic fields alone and these energies have direct physical significance. The terms linear in e are the multipole interactions, both electric and magnetic, and the term quadratic in e is a generalization of the elementary diamagnetic energy shift. The intermolecular Coulomb energies have cancelled with transverse polarization fields in the new Hamiltonian, although the intramolecular Coulomb potentials are left unaffected. The equations of motion that follow from the new Hamiltonian are deduced. They are the so-called atomic-field equations for the Maxwell fields and Schrödinger equation for an electron wave in a transverse electromagnetic field. The former are the microscopic analogues of Maxwell’s equations in a medium (not restricted to dipole polarization fields) and the latter are dependent on the field strengths alone (not explicit functions of the vector potential).
The Hamiltonian of a system of charged particles interacting with the electromagnetic field is investigated. For an arbitrary system the multipole expansion of the interaction between the system and the field is derived by means of a suitable canonical transformation. The transformed Hamiltonian is obtained from the Hamiltonian of the system by replacing the momenta by the transformed kinetic momenta and by adding to the Hamiltonian a term representing the interaction of the system with the electric component of the field. By expanding this interaction term, as well as the transformed momenta, in powers of the dimension of the system over the wavelength, the multipole expansion of the Hamiltonian is obtained. For a system interacting with a classical field the multipole form of the Hamiltonian is exactly equivalent to the original Hamiltonian. For a quantized field this is not true, and the multipole form of the transformed Hamiltonian is shown to be equivalent to the original Hamiltonian only for first-order radiation processes.
A recent investigation of the interaction between the Maxwell radiation field and neutral atoms or molecules has led us to consider the relation between the straightforward interaction Hamiltonian between particle (k) and the radiation field, and the more physical, and explicitly gauge invariant, couplings of the form q. E and µ. H, etc., where q and µ are the electric and magnetic dipole moments of a system of particles. That these latter form of interaction energies follow from well-formulated approximations for atoms in external fields has been known for many years (Goeppert-Mayer(1); see also Rosenfeld(2)). When the Maxwell field is an internal and dynamical field further discussion is necessary, especially concerning the Coulomb interactions. Their advantage has recently been shown in dealing with dipole interactions in the long range Van der Waals force between two neutral systems where the complete coupling, in dipole approximation, is given by — q.ET for each neutral system, where ET is the transverse electric field. The short-range London limit is contained in this coupling despite the absence of longitudinal electric fields (Power and Zienau (3)). In this note we extend these arguments to higher electric multipoles and magnetic multipoles. We also demonstrate their use in the quantum theory of scattering of light, and in particular the derivations of Stephen (4) of the phase angle between emergent beams in optical double refraction phenomena are shown to follow immediately.
Abstract The interaction between atoms or molecules and electromagnetic (EM) fields underlies all spectroscopic techniques and a great variety of desirable molecular properties. EM fields and EM waves are introduced via the famous Maxwell equations. The scalar and vector potential are defined, and the gauge freedom is outlined. The Coulomb gauge is adopted. The classical Hamiltonian for a charged particle in an EM field is derived, and from this the ‘minimal substitution’ rules for incorporating the fields in the quantum Hamiltonian are obtained. The operators describing the interaction of an electron with static electric and magnetic fields, including the magnetic fields from nuclear spins, are derived, followed by the derivation of the interaction between an electron and an EM wave.
Abstract Previous calculations [1] yielding the frequency spectrum of a one‐mode radiation field interacting with a single atom are extended to the case of M atoms. Under the assumption M „N (N mean photon number) the total Hamiltonian is diagonalized, and the correlation function 〈𝔈̂(t1 𝔈̂(t2)〉 revealing the frequency spectrum of the interacting field calculated quite generally. The following special initial conditions are discussed in detail: a) Any atom is either in the upper or the lower state, and b) the electric dipole moment of the ensemble of atoms is oscillating in phase or with a phase difference of π with respect to the electric field strength. In case a) the initial monochromatic line is broadened, and in case b) a frequency shift appears.
It is shown that Mandel's argument that the electric dipole interaction in quantum electrodynamics is inconsistent with Maxwell's equations relies on the use of the wrong canonical momenta in the multipolar form of the Hamiltonian; the field conjugate to the vector potential in the Coulomb gauge is proportional to the transverse displacement vector and not, as in the minimal-coupling form of the Hamiltonian, to the transverse electric field, and similarly the canonical momenta of the charged particles differ in the two cases. Some consequences of this for time-dependent perturbation theory are discussed.