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Where are the limits of ADO theory in relation to reaction rate calculation?

Equilibrium constant

Proton affinity

Bond-dissociation energy

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The ADO theory predicts reaction rates within 40% agreement for proton transfer reactions to neutral molecules with dipole moments up to 2.98 D . However, for reactions involving CH3+ transfer, the classical theories predict higher values than observed, indicating the presence of energy barriers in the potential surface . The ADO theory may not be accurate for exothermic reactions involving C-, C2-, and C2H- with various molecules due to multiple bond rearrangement or close range electrostatic interaction . Theoretical treatments for ternary ion-molecule association reactions may be ineffective without ab initio quantum-chemical calculations to determine the formation of isomeric product ions . Therefore, the limits of the ADO theory in relation to reaction rate calculation are evident in its accuracy for proton transfer reactions and its inability to account for energy barriers and isomeric forms of product ions .

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Journal Article•DOI A new approach to diffusion-limited reaction rate theory M. S. Veshchunov, M. S. Veshchunov - Show less +1 more 03 Aug 2011-Journal of Engineering Thermophysics 6 Citations	The traditional diffusion approach to calculation of reaction rates is limited to reactions with a large reaction radius, and becomes inappropriate for reactions with a relatively small reaction radius.
Journal Article•DOI Flowing afterglow studies at york university Harold I. Schiff, Diethard K. Bohme - Show less +1 more 01 Jan 1975-International Journal of Mass Spectrometry and Ion Physics 42 Citations	The ADO theory predicts reaction rates within 40% agreement for proton transfer reactions with molecules having dipole moments up to 2.98 D.
Journal Article•DOI Association reactions. Theoretical shortcomings Eric Herbst, David Smith, Nigel G. Adams, Bruce J. McIntosh - Show less +3 more 01 Jan 1989-Journal of the Chemical Society, Faraday Transactions 39 Citations	Theoretical treatments can be ineffective in predicting reaction rates when there are multiple isomeric forms of the product ions.
Journal Article•DOI Calculation of the Rate of Elementary Association Reactions Eugene P. Wigner 01 Sep 1937-Journal of Chemical Physics 535 Citations	The paper discusses the upper limit of the rate of association reactions and the discrepancy between calculated values and experimental measurements.
Journal Article•DOI Reaction rate theory for non-Markovian systems Fernando A. Oliveira 15 Aug 1998-Physica A-statistical Mechanics and Its Applications 6 Citations	The paper discusses the limits of the ADO theory in explaining reaction rates for systems with long-range memories.

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