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Online text: goldbook.iupac.org/terms/view/P04811

Online text: goldbook.iupac.org/terms/view/A00446

Cited passages: IUPAC Gold Book: Arrhenius equation.

Online text: old.goldbook.iupac.org/html/E/E01990.html

Cited passages: IUPAC Gold Book, E01990: Mulliken average and relative Pauling scale; indexed definition, full entry unavailable during verification.

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Cited passages: definition and symbols: standard molar enthalpy for homolysis, Δdiss H°.

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Cited passages: definition of bond-dissociation energy: molar enthalpy for homolysis of a specified molecular entity.

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Cited passages: IUPAC Gold Book entry for acid dissociation constant, definition and notes 1–2: standard concentration, conditional constants and dimensionless thermodynamic constant.

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Cited passages: IUPAC Gold Book, atomic mass: ground-state rest mass of an atom.

Online text: goldbook.iupac.org/terms/view/A00102

Cited passages: IUPAC Gold Book, activation energy: empirical derivative definition and threshold-energy qualification; IUPAC Gold Book, activation energy: operational temperature-derivative definition; IUPAC Gold Book: activation energy.

Online text: goldbook.iupac.org/terms/view/C01458

Cited passages: IUPAC Gold Book, current efficiency: definition and exception for simultaneous anodic and cathodic reactions; IUPAC Gold Book, current efficiency: partial electrode currents and product yield; conditions excluding consecutive product-consuming reactions.

Online text: www.msterms.org/wiki/index.php/Aston_1922/Chapter_5

Cited passages: Chapter V, §§33–40: apparatus and photographic procedure; §§43 and 45–46: calibration, aperture comparisons, and accuracy.

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 $d$, entrance ion $i$, and Maxwellian electrons, ${\alpha }_d=(g_d/(2g_i))(h^2/(2\pi mkT){)}^{3/2}{e}^{-E_d/kT}{A}_{di}^a{A}_{\mathrm{stab}}^r/(A_{\mathrm{tot}}^a+A_{\mathrm{tot}}^r)$. Detailed balance determines the capture rate; a steady population balance determines the survival factor. The rate coefficient has dimensions volume per time.