On the theory of oxidation-reduction reactions involving electron transfer. I

Marcus, R. A. (1956). On the theory of oxidation-reduction reactions involving electron transfer. I. The Journal of Chemical Physics, 24(5), 966-978.

Type

Journal article

Intellectual base

Primary research

Year

1956

Volume

24

Issue

5

Pages

966-978

DOI

10.1063/1.1742723

DOI registrant

AIP Publishing

Link

https://doi.org/10.1063/1.1742723

Cited from

chemistry_materials, physics

Cited by

2 citations across 2 artifacts.

Each citation links to the sentence it supports in the citing article.

Primes

• Activation Energy
  • Activation energy specifically denotes the energy-cost barrier—not just any crossing point, but the energetic price of initiation, as Marcus (1956) made precise by formulating the activation barrier in terms of reorganization energy and Gibbs free energy.

    This sourceFormalizes the activation barrier in terms of reorganization energy and Gibbs free energy (the Marcus two-parabola picture); sharpens the distinction between an energetic-cost barrier and a generic threshold. SUPPORTS the claim that Marcus made the activation barrier precise via reorganization energy and Gibbs free energy.

    Supported in partVerified against the work's full text

    Marcus 1956 treats the electron-transfer barrier as the free energy of solvent reorganization, dF*, which supports the barrier-as-free-energy-cost idea but not the 'specifically denotes' definitional point.

    “An object of the present paper is to devise a method of calculating the free energy of reorganization of the solvent molecules about the reactants prior to the electronic jump process”

    Read by an automated reader; not a human review. How support was checked

• Hidden Path and Barrier Crossing
  • However, many enzymes achieve additional rate enhancement via hydrogen tunneling: a proton or hydride ion tunnels through a classically forbidden region of the reaction coordinate, shortcutting the top of the activation barrier.

    This sourceFormalizes the activation barrier in terms of reorganization energy and Gibbs free energy; sharpens the distinction between an energetic-cost barrier and a generic threshold.

Verification

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Registry ID ref:3617f24f532a · see in the full table