Autoionization 2026-10-13
An excited atom or ion above an electron-emission threshold can decay without a photon by ejecting an electron and leaving a more highly charged ion. This is autoionization. Its rate competes with radiative stabilization in dielectronic recombination; the inverse electron-capture channel is dielectronic capture.
A free Electron is resonantly captured while exciting the ionic core, producing a doubly excited state above the parent-ion threshold. Capture becomes permanent recombination only if the state undergoes radiative stabilization rather than autoionization. For resonance , entrance ion , and Maxwellian electrons, . Detailed balance determines the capture rate; a steady population balance determines the survival factor. The rate coefficient has dimensions volume per time.
The Boltzmann distribution for two atomic levels at thermodynamic equilibrium is
where is the statistical weight of an atomic level. For a resolved level of total angular momentum , when magnetic substates are unresolved.
To extend this counting to the continuum, assume an ideal, nondegenerate plasma with classical free Electrons and neglect the small difference between the translational masses of the two heavy ionic species. Let be the electron fugacity in the Saha equation, with the Electron chemical potential measured relative to its rest energy. The two Electron spin states and the phase-space cell volume give
Chemical equilibrium for capture equates the bound species' chemical potential to the sum for its parent ion and free Electron. Thus applying Boltzmann factors to a bound level at energy gives . Eliminating the Electron fugacity proves the level-specific Saha ionization equation:
The factor two is the Electron spin multiplicity; the factor with power is the inverse free-electron translational state density. A total-ionization Saha equation sums the bound states into an internal partition function, whereas this expression refers to one specified level.
For dielectronic recombination, write the entrance ion as in ground state , and the intermediate state of as . Capture excites the core from to while binding the incident Electron. The resonance energy relative to the entrance continuum is . The doubly excited state can eject the Electron by autoionization, or undergo radiative stabilization to a bound state.
Let be the partial autoionization rate back to the entrance ion, the total autoionization rate, the total radiative decay rate, and the rate of radiative decays that stabilize into bound levels. For an isolated narrow resonance, the Saha-Boltzmann equilibrium ratio has the bound-state energy replaced by the positive resonance energy:
At equilibrium, inverse dielectronic capture and autoionization fluxes balance: . This establishes the capture coefficient even when the actual plasma is not in local thermodynamic equilibrium. In the low-density, weak-radiation recombining plasma, the intermediate level instead has the stationary balance
Multiplying its population by the successful stabilization rate gives the actual recombination coefficient
Here the equilibrium population was used only to determine the capture rate by detailed balance; it was not assumed to equal the intermediate population when photons escape. This is precisely why the competing decay probabilities appear.
Use the supplied core-transition relation between the Einstein coefficients and atomic oscillator strength,
Here is the fine-structure constant and the Bohr radius, not a recombination coefficient. Factor out and define
Substitution yields
This definition accommodates several entrance and decay channels. In the common spectator-electron approximation with one autoionization channel and stabilization by the core transition, and . If all coupled substates of the captured Electron are summed, , giving
For an intermediate state resolved by fine structure, retain its actual instead of that summed weight. The stabilization probability itself is ; the requested is not just this branching probability, because the prefactor has already factored out the core radiative rate and statistical weights of atomic levels. Radiative transitions to another still-autoionizing state require that state's eventual survival probability, rather than automatically counting every emitted photon as stabilization.
The total dielectronic recombination coefficient sums all accessible positive-energy resonances. In this isolated-resonance approximation it has the form
with atomic factors included in . The resonance-temperature dependence of dielectronic recombination follows by differentiating a single term's logarithm:
Thus low temperatures suppress a positive-energy resonance, although resonances very near threshold can still matter; at sufficiently high temperature a fixed set of resonances falls as . Several core-excitation series can produce several peaks. When autoionization is much faster than radiation, the capture-and-survival product is limited by the stabilizing radiative rate; when capture is weak, autoionization is the limiting inverse-capture rate. For a fixed Rydberg angular channel, autoionization typically decreases at high principal quantum number while the core radiative rate changes little. Capture into very high levels is vulnerable to subsequent collisional or field ionization, so finite-density survival can suppress the total rate. dielectronic recombination is resonant and strongly temperature-selective; its magnitude can be important in coronal ionization balance.