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Journal of Mathematical Physics

Nth order perturbation theory for hydrogen

Edward J. Kelsey, J. H. Macek

Published Jul 1, 1976• 34 citations
Publisher

Abstract

This paper presents a simple reformulation of second order perturbation theory for hydrogen. We calculate first the perturbed wavefunction and then the perturbed matrix element. This procedure is repeated to obtain the nth order matrix element in terms of n−1 integrals. The parameters in the nth order matrix element are defined recursively. Schwinger’s representation of the Coulomb Green’s function follows immediately from our expression for the second order matrix element.

DOI
10.1063/1.523028

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Acta Physica Sinica•Jan 1, 1988•0 citations
This paper presents a simple reformulation of second order perturbation theory for hydrogen. We calculate first the perturbed wavefunction and then the perturbed matrix element. This procedure is repeated to obtain the nth order matrix element in terms of n−1 integrals. The parameters in the nth order matrix element are defined recursively. Schwinger’s representation of the Coulomb Green’s function follows immediately from our expression for the second order matrix element.
The Schrodinger-Coulomb Green function is discussed as a tool for evaluating terms in bound-state perturbation theory. As an example the energy shift of the ground state of hydrogen in a uniform electric field is considered. The Green function is used in an evaluation of the second-order perturbation theory expression for this energy shift. For comparison a direct numerical approach to the evaluation of this energy shift is also described. The Green function approach is simpler and more elegant, and leads to an exact result.
The infinite summations over the complete set of unperturbed atomic states appearing in the Nth-order time-dependent perturbation theory are performed using the Green's function formalism. In order to test the method extended calculations of the cross section for two- and three-photon ionization for atomic hydrogen are made and numerical comparison is shown with the values obtained by different methods. The resonant character of the process is made evident since the poles of the radial part of the Green's function represent the actual energy spectrum of the atom. The relevant transition matrix elements are written in closed form and then computed exactly without averaging over the intermediate states. The cross sections vanish for circularly polarized light near some energies which explains the form of the cross sections for circularly and linearly polarized light.
By mapping the perturbation scheme onto the ladder operator formalism, the field of application of the Schrodinger-Infeld-Hull factorisation method is enlarged. It is shown how, at each order of the perturbation, perturbed ladder operators can be constructed. Thus, without having to calculate explicitly either the excited unperturbed functions or any matrix element, one obtains analytical expressions of the perturbed eigenvalues in terms of the quantum numbers of the factorisable unperturbed problem. A three-terms recurrence relation, valid at any rank of the perturbation, is derived and leads to closed form expressions of the perturbed eigenfunctions. Consequently, a closed form expression of any matrix element on the basis of the perturbed eigenfunctions is easily obtained from the calculation of one unique particular integral.
A general method is presented for calculating the higher-order terms of series in powers of the DC field for the hydrogen Stark-state wavefunctions, dipole transition matrix elements and corresponding line intensities. Analytical expressions are derived for the second-order Stark effect on the matrix elements and intensities of the Stark lines. Simple formulae for transitions to states with zero parabolic quantum numbers are given. The numerical data for the Lyman and Balmer series and for some transitions between Rydberg levels are analysed in detail.
The variationally stable procedure for Nth-order perturbative-transition-matrix elements introduced by the authors [Phys. Rev. Lett. 61, 404 (1988)] is presented here in detail. Its key features are that it is noniterative, involves only two unknown functions regardless of the value of N, is stable even near intermediate-state resonances (due to the presence of energy numerators rather than energy denominators), and uses the inverse of the perturbation operator for N\ensuremath{\ge}3. Explicit formulas are presented for application to high-order multiphoton processes in atomic hydrogen. Numerical results for multiphoton-ionization cross sections (for two, three, and seven photons), for the frequency dependence of the nonlinear susceptibilities for harmonic generation (for the third, fifth, and seventh harmonics), and for harmonic-generation transition rates up to 11th order for \ensuremath{\lambda}=1064 nm are presented for the atomic hydrogen ground state and compared with results of others by more standard procedures. We also present detailed analyses of the Z scaling of our results for hydrogenic systems, of the use of the imaginary part of the appropriate 2N-photon nonlinear susceptibility to obtain N-photon-ionization cross sections, and of the relation of the variational principle presented here to variational principles for scattering processes of Nuttall and Cohen [Phys. Rev. 188, 1542 (1969)] and of Schwinger [Phys. Rev. 72, 742 (1947)].