We will review computational and physical aspects of the ionization of an atom by N photons with N>P, where P is the minimum number of photons required to ionize the atom. In perturbation theory the matrix element, M(N), for N-photon absorption can be decomposed as M+(N) + M−(N), which results from the decomposition of the stationary wave of the emergent photoelectron into its outgoing ( + ) and ingoing (−) parts. Each of the M±(N)are N-dimensional integrals over N radial coordinates ri, i=1,…,N. Although these integrals are not formally convergent for N>P, the integrand of M+(N) consists of functions that either decay exponentially or are outgoing waves for ri~∞.
We show how the inclusive rate of decay of an atomic system by absorption of any number N of photons can be calculated at
Nth order of perturbation theory without employing the final-state (continuum) wave function. We give a computationally useful formula which involves only the response function for a system perturbed by absorption of N photons. In the case of a two-electron system, the contributions to the inclusive rate from individual channels can be separated using projection operators.
A perturbation theory of the ionization of atoms by simultaneous absorption of several photons, each of whose energy is less than the ionization potential, is developed from the evolution-operator formalism. A precise computation is made for the hydrogen atom, giving transition rates as a function of photon energy for two- through twelve-photon photoionization. The eighth-order ionization rate (in cgs units) at the 1.78-eV ruby-laser line is found to be \ensuremath{\sim}${10}^{\ensuremath{-}244}$\ifmmode\times\else\texttimes\fi{}
(photonflux)8 and should be observable using available techniques. Good agreement is obtained with Zernik's exact calculation of the two-photon ionization rate of metastable
2S hydrogen. Approximate calculations are made for the rare gases. Assuming "typical" experimental conditions of a gas density of \ensuremath{\sim}
1020 atoms ${\mathrm{cm}}^{\ensuremath{-}3}$ and a ruby laser focused into a volume of \ensuremath{\sim}${10}^{\ensuremath{-}8}$
cm3, we find that the flux required to liberate one electron during a 10-nsec pulse is \ensuremath{\sim}
1029 ${\mathrm{cm}}^{\ensuremath{-}2}$ ${\mathrm{sec}}^{\ensuremath{-}1}$ for Xe, Kr, and Ar and \ensuremath{\sim}5\ifmmode\times\else\texttimes\fi{}
1030 photons ${\mathrm{cm}}^{\ensuremath{-}2}$ ${\mathrm{sec}}^{\ensuremath{-}1}$ for Ne and He. These gases ionize with the simultaneous absorption of 7, 8, 9, 13, and 14 photons, respectively. The predicted rate for Xe is found to be in excellent agreement with the recent direct measurements of Voronov and Delone. We conclude that multiphoton ionization provides the initial electrons required for the optical breakdown of gases, though it does not account for the over-all growth of the discharge except possibly at very low pressures. Impurity atoms (particularly heavy rare gases) may be the source of "initiating" electrons in Ne and He.
The general theory of multiphoton ionization of hydrogen atoms by simultaneous absorption of several photons is discussed. In the nonrelativistic dipole approximation, the calculations lead to a recursion relationship concerning angular functions and involve radial matrix elements containing many summations over intermediate states. A general method for exactly evaluating several sums is described in detail and applied to the photo-ionization of atomic hydrogen in the ground state. Numerical results are presented as dispersion curves of the transition rate $\frac{{\ensuremath{\sigma}}_{n}}{{I}^{N\ensuremath{-}1}}$ for a range of wavelengths from 1000 up to 7200 \AA{}.