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Physical Review A

Photon Wave Functions and the Exact Electromagnetic Matrix Elements for Hydrogenic Atoms

H. E. Moses

Published Oct 1, 1973• 83 citations
Publisher

Abstract

After reviewing the properties of the photon considered as a quantized particle of zero mass, positive energy, and unit spin, the expansion of the unquantized and quantized electromagnetic fields and vector and scalar potentials in terms of the photon wave functions and creation and destruction operators is reviewed and extended. The most general vector and scalar potentials are obtained through the use of the eigenfunctions of the curl operator. The dichotomy between the photon and wave picture of electromagnetic radiation is discussed and resolved. The results are applied to the calculation of the exact electromagnetic matrix elements and transition probabilities (i.e., with retardation taken into account exactly) for hydrogenic atoms. The exact matrix elements are very simple in form. The notion of multipole radiation of the usual treatments is irrelevant. However, it is shown how multipoles appear as an approximation.

DOI
10.1103/physreva.8.1710

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After reviewing the properties of the photon considered as a quantized particle of zero mass, positive energy, and unit spin, the expansion of the unquantized and quantized electromagnetic fields and vector and scalar potentials in terms of the photon wave functions and creation and destruction operators is reviewed and extended. The most general vector and scalar potentials are obtained through the use of the eigenfunctions of the curl operator. The dichotomy between the photon and wave picture of electromagnetic radiation is discussed and resolved. The results are applied to the calculation of the exact electromagnetic matrix elements and transition probabilities (i.e., with retardation taken into account exactly) for hydrogenic atoms. The exact matrix elements are very simple in form. The notion of multipole radiation of the usual treatments is irrelevant. However, it is shown how multipoles appear as an approximation.
The present Rapid Communication makes two points. (1) The exact matrix elements for the transitions between two hydrogenic states accompanied by the emission or absorption of one photon has been calculated in closed form without resorting to multiple expansions. Thus, retardation is taken into account exactly. (2) In addition to using these exact matrix elements to calculate transition probabilities, one can make estimates of the contribution to second-order processes of these matrix elements. In particular, it can be shown that the total contribution of bound-state matrix elements to the electromagnetic shift of the ground state is finite without renormalization.
The present work is concerned with de Broglie's quantum theory of light. It is assumed that the photon is described by a Hermitian wave function with 16 components. Using this wave function it is shown that the 32 of de Broglie's equations are reduced to one set of 16 equations in the form: [equation] where the [alpha]'[rho] are Dirac matrices and [psi] is a matrix with 16 components. The electromagnetic quantities associated with the photon are described by means of the Dirac matrices operating on [psi] in a specified way. It is shown also that these electromagnetic quantities satisfy Maxwell's equations as a result of the equation the interaction between an electron and a photon is developed and the matrix elements for the radiation transitions are calculated. It is further shown that the above wave equation can be considered as the superposition of two similar wave equations, one for the positive energy photons and the other for the negative energy photons. To each of these states there corresponds electromagnetic quantities defined by the above method. It is the superposition of these fields which gives rise to the reality of the electromagnetic field, found in experience. The wave mechanics of the positive energy photon is discussed and the method of second quantization is applied to its wave function, from which we deduce the commutation relations for the complex fields.
We develop practical formulas for the calculation of the matrix elements of the interaction of the electromagnetic field with an atomic state, beyond the long-wavelength approximation. The atom-plus-field Hamiltonian is chosen to have the multipolar form, containing the electric, paramagnetic, and diamagnetic operators. The final workable expressions include the interactions to all orders and are derived by first expanding the fields in partial waves. The electric-field operator reaches a constant value as the radial variable becomes large, contrary to the result of the electric-dipole approximation (EDA) where the value of the corresponding operator increases indefinitely. Applications are given for Rydberg states of hydrogen up to n=50n=50n=50 and for free-free transitions in a Coulomb potential. Such matrix elements are relevant to a number of real and virtual processes occurring during laser-atom interactions. The computation is done numerically, using a combination of analytic with numerical techniques. By comparing the results of the EDA with those of the exact treatment, it is shown that the former is inadequate in such cases. This finding has repercussions on the theory and understanding of the physics of quantum systems in high-lying Rydberg levels and wave packets or in scattering states.
The two-photon decay mode of hydrogenic atoms from an arbitrary state (n1{n}_{1}n1​, l1{l}_{1}l1​, m1{m}_{1}m1​) to an arbitrary state (n2{n}_{2}n2​, l2{l}_{2}l2​, m2{m}_{2}m2​) is studied within the framework of nonrelativistic quantum mechanics. In the dipole approximation, these decay rates, which involve infinite summation over intermediate states, are derived exactly via a general second-order matrix element obtained by Kelsey and Macek and an implicit technique introduced by Dalgarno and Lewis. The results are expressed in terms of hypergeometric functions. For transitions ${n}_{1}s\ensuremath{\rightarrow}{n}_{2}s$, our results reduce to those of Klarsfeld whose starting point is the Coulomb Green's function. For transitions to the ground state, an alternative expression involving a simple one-dimensional integral is presented. The decay rate of the 2s2s2s metastable state of atomic hydrogen is calculated as an illustration of the method. The result, $\frac{1}{\ensuremath{\tau}}=8.2284$ ${\mathrm{sec}}^{\ensuremath{-}1}$, agrees with Klarsfeld. For transitions of ${n}_{1}s\ensuremath{\rightarrow}1s$ and ${n}_{1}d\ensuremath{\rightarrow}1s ({n}_{1}\ensuremath{\ge}3)$, the transition rates exhibit interesting and unexpected structures. In particular, "zeros" are found in the two-photon emission spectrum indicating that two-photon emission is not possible at certain frequencies. Physically, these "zeros" are the result of destructive interference between the radiating dipole terms associated with the sum over intermediate states. In addition to the emission spectrum the expected coincidence signal between two detectors monitoring the two photons simultaneously emitted during a two-photon transition is calculated as a function of the angle between the detectors. The angular distribution for the ${n}_{1}d\ensuremath{\rightarrow}1s$ transitions is shown to be significantly different from the ${n}_{1}s\ensuremath{\rightarrow}1s$ transitions. Finally, a possible experiment is suggested to test the results presented in this paper.
In this paper, we extend to three-photon radiative transitions in hydrogenic ions our fully relativistic multipole approach [Z. Bona et al., Phys. Rev. A 89, 022514 (2014)], which has proven so far to yield extremely accurate results for two-photon emission processes. Closed-form formulas of double and single differential frequency distributions as well as total emission probabilities are derived for arbitrary multipole channels by using the Dirac-Coulomb Sturmian functions of the first order. Two cases of atomic systems are considered in the study, namely, ions with a spinless nucleus and those with a nonzero nuclear spin to check the validity of the Bose-Einstein statistics for three-photon emission investigated by Zalialiutdinov et al. [J. Phys. B: At. Mol. Opt. Phys. 49, 055001 (2016)]. In an effort to assess relativistic effects and the influence of the negative spectrum of the set of Dirac-Coulomb Sturmians, we formulate two nonrelativistic schemes that involve Schr\"odinger-Coulomb Sturmians, a transition operator with retardation, on one hand, and a transition operator in the long wavelength approximation, on the other hand. An application of these theories is made for the relativistic and nonrelativistic atomic transitions $2{s}_{1/2}\ensuremath{\rightarrow}1{s}_{1/2}, 2{p}_{1/2}\ensuremath{\rightarrow}1{s}_{1/2}, 2{p}_{3/2}\ensuremath{\rightarrow}2{s}_{1/2}$ and $2s\ensuremath{\rightarrow}1s, 2p\ensuremath{\rightarrow}1s$, respectively, with nuclear charge ranging from 1 to 100. Some of our numerical values are compared with the scarce data available in the literature and they enable us to draw inferences as to the improvements obtained with our approach, while the others are additional results that we provide as a further step for more investigations of three-photon decays.
We employ here the enhancement of the vector potential amplitude quantization at a single photon state. The analysis of the general solution of the vector potential, obtained by resolving Maxwell’s equations, implies that the amplitude is proportional to the angular frequency. The photon vector potential function αkλ(r,t) can be written in the plane wave representation satisfying the classical wave propagation equation, Schrödinger’s equation for the energy with the relativistic massless field Hamiltonian and a linear time-dependent equation for the vector potential amplitude operator. Thus, the vector potential αkλ(r,t) with the quantized amplitude may play the role of a real wave function for the photon in a nonlocal representation that can be suitably normalized. We then deduce that the amplitudes of the electric and magnetic fields, respectively, of a single free photon are proportional to the square of the angular frequency. This might open perspectives for the development of nondestructive photon detection methods based on the influence of the electric and/or magnetic fields of photons on the energy levels of atoms and molecules.