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Physical Review A

Maxwell fields and Poynting vector in the proximity of a chiral molecule

Akbar Salam, T. Thirunamachandran

Published Dec 1, 1994• 17 citations
Publisher

Abstract

The electromagnetic field operators for a chiral (optically active) molecule are calculated in the Heisenberg picture, using the multipolar Hamiltonian. Interactions involving electric-dipole, magnetic-dipole, and electric-quadrupole moments are taken into account. The operators are expanded in powers of moments, and expressions correct to quadratic powers in the moments are given. Comparable contributions from diamagnetic interactions are also presented. The properties of these operators are discussed. Terms that are linear in the moments are found to act in the electron space alone; those quadratic in the moments act in both the electron and photon spaces. The operators are used to calculate the Poynting vector, from which the spontaneous emission rates for magnetic-dipole and electric-quadrupole transitions are obtained. Attention is drawn to the inverse square dependence of the Poynting vector on the distance of the field point from the source. This behavior is shown to be consistent with the requirement of local conservation of energy. The operators are used in the following paper [J. K. Jenkins, A. Salam, and T. Thirunamachandran, Phys. Rev. A 50, 4767 (1994)] to calculate dispersion energies between two optically active molecules.

DOI
10.1103/physreva.50.4755

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The electromagnetic field operators for a chiral (optically active) molecule are calculated in the Heisenberg picture, using the multipolar Hamiltonian. Interactions involving electric-dipole, magnetic-dipole, and electric-quadrupole moments are taken into account. The operators are expanded in powers of moments, and expressions correct to quadratic powers in the moments are given. Comparable contributions from diamagnetic interactions are also presented. The properties of these operators are discussed. Terms that are linear in the moments are found to act in the electron space alone; those quadratic in the moments act in both the electron and photon spaces. The operators are used to calculate the Poynting vector, from which the spontaneous emission rates for magnetic-dipole and electric-quadrupole transitions are obtained. Attention is drawn to the inverse square dependence of the Poynting vector on the distance of the field point from the source. This behavior is shown to be consistent with the requirement of local conservation of energy. The operators are used in the following paper [J. K. Jenkins, A. Salam, and T. Thirunamachandran, Phys. Rev. A 50, 4767 (1994)] to calculate dispersion energies between two optically active molecules.
The electromagnetic field operators and the electron field operators for the coupled system governed by the multipolar Hamiltonian are obtained within the Heisenberg picture. Their causal behavior and their relationship to the minimal-coupling forms are discussed. The basic fields of the multipolar theory, namely, the displacement vector and the magnetic field, are calculated up to terms quadratic in the multipole moment sources. The terms linear in the transition moments are the quantum counterparts of the classical fields and do not change the photon occupation number. The quadratic terms have no classical analogs: they act in both the photon and electron occupation-number spaces. It is shown that it is necessary to include these second-order terms in the calculation of the Poynting vector for an emitting dipole, thus demonstrating their role in the transport of radiative energy.
The quantized electromagnetic field in interaction with nonrelativistic sources, i.e., atoms and molcules, has been the subject of study in the previous papers in this series. The Heisenberg formalism is used to calculate the electric- and magnetic-field operators arising from charges and currents expressed in multipolar form. In this paper, quadratic operators in these fields such as the Thompson energy density and the Poynting vector and their expectation values for specified states are found. The expectation values are, in general, time dependent. For initial conditions given at t=0 it is shown that the fields are causal, i.e., for tr/c the source-dependent fields are zero and the quadratic operators have only their zero-point contributions. For t>r/c they have both time-independent and time-dependent terms. The time-dependent terms, though transient, are shown to obey Poynting's theorem. The steady-state part of the Poynting vector is related to the Einstein coefficients. The corresponding electric-energy density is related to the Casimir-Polder potential for a polarizable test body in the field of the source molecules. Similarly the magnetic-energy density is derived and is used in the calculation of energy shifts. Quadratic operators referring to different field points are also discussed.
Spontaneous emission in dipole approximation is studied theoretically using both source-field theory and a Schrodinger picture approach. Using source-field theory we obtain formal equations for the Poynting vector and energy density without making the rotating wave approximation (RWA) and Weisskopf-Wigner approximation (WWA). The initial condition at t=0 is one in which the atom is in an excited state and the field in the vacuum state. The source-field expressions are evaluated within the the RWA and WWA and are found to satisfy Poynting's theorem. To explore the consequences of not making the RWA and WWA, the Poynting vector and energy density are calculated using perturbation theory. We use a Schrodinger picture approach and essentially reproduce and complement the results of Compagno, Passante, and Persico [J. Mod. Optics 37:8, 1377 (2007)] and those of Power and Thirunamachandran [Phys. Rev. A 45, 54 (1992)] obtained using a Heisenberg picture approach. The theory involves a sum over field mode frequencies and both finite cutoffs and convergence factors are used to carry out the sums. It is shown that the perturbation theory calculation leads to unphysical values for atomic state populations for all times when a sum over all field frequencies is taken, even if a convergence factor is used. It is also proved that the fields calculated using source-field theory always satisfy Poynting's theorem for ct not equal to R, where R is the distance from the atom.
The electromagnetic field operators in the Heisenberg picture are found in both the minimal and multipolar forms of nonrelativistic quantum electrodynamics within the electric dipole approximation. These are made up of free- and source-field terms. The free electric- and magnetic-field operators in the two formalisms differ since the creation/annihilation operators are manifestly distinct. Their explicit forms in the Heisenberg picture are given. However, the source fields are formally the same when expressed in terms of dipole moment operators at positive retarded time. The cancellations that lead to this equivalence are presented. In many applications it is necessary to express the operators at retarded time in terms of creation and annihilation operators at the initial time. Explicit expressions for the fields up to second order in terms of the transition dipole moments are given. These enable the formulas for induced dipole moments to be derived within the context of quantum electrodynamics whereas previous derivations have been based on semiclassical electrodynamics.
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).
A multipolar semi-classical hamiltonian for magneto-optical intensities is derived by a canonical transformation taking Feynman's formulation of the conventional Pauli hamiltonian as the point of departure. Only interactions up to the order of electric quadrupole and magnetic dipole terms are retained. The resulting hamiltonians are divided into their respective time-independent, single photon and double photon parts, and the difference in the appearance of magnetic field dependent contributions in the perturbation terms is analysed. On the basis of this analysis it is argued that the magnetic field dependent term in the magnetic dipole transition moment operator may lead to a unique single photon process with an amplitude proportional to the static magnetic field. This process leads, amongst others, to transitions between totally symmetric atomic states, in contrast to the standard multipolar selection rules of ordinary spectroscopy.