There is a newer version of the record available.

Published December 10, 2025 | Version v1
Journal article Open

Critical Chemical Equivalence(CCE): The SymC Principle Governing Catalysis and Reactivity

Description

The ratio χ = Γ/(2Ω) — damping rate to characteristic frequency — organizes chemical reactivity across multiple domains. This paper demonstrates that (i) adiabatic versus nonadiabatic electron transfer corresponds to χ > 1 versus χ < 1, (ii) concerted versus stepwise proton-coupled electron transfer reflects whether χ remains within or oscillates through the critical window, and (iii) catalytic bond activation occurs when the catalyst tunes the substrate toward χ ≈ 1. This framework unifies Marcus theory, proton-coupled electron transfer mechanism selection, and the Sabatier principle under a single stability criterion derived from the Symmetrical Convergence (SymC) postulate. Illustrative comparisons with TEMPO self-exchange kinetics showing k_et ∝ 1/τ_L across solvents, and N₂ dissociation on Fe surfaces where barrier reduction from 1.1 eV (Fe(110)) to 0.3 eV (Fe(111)) tracks χ moving toward unity, are consistent with the framework’s predictions. The approach yields falsifiable predictions for solvent effects, isotope effects, and spectroscopic signatures across all three domains.

Files

SymC_CCE.pdf

Files (2.3 MB)

Name Size Download all
md5:3796e478ac945074a59cfbed70dd320a
931.0 kB Preview Download
md5:9276640ac0e84ead0930007960e65b86
1.1 MB Preview Download
md5:4457f827791c12ba9ec659b63c2917d9
201.2 kB Preview Download

Additional details

References

  • Kramers, Hendrik A. (1940). Brownian motion in a field of force and the diffusion model of chemical reactions. Physica, 7(4), 284–304. https://doi.org/10.1016/S0031-8914(40)90098-2
  • Marcus, Rudolph A. (1956). On the theory of oxidation-reduction reactions involving electron transfer. I. The Journal of Chemical Physics, 24(5), 966–978. https://doi.org/10.1063/1.1742723
  • Zusman, Lev D. (1980). Outer-sphere electron transfer in polar solvents. Chemical Physics, 49(2), 295–304. https://doi.org/10.1016/0301-0104(80)85267-0
  • Pollak, Eli, & Talkner, Peter. (2005). Reaction rate theory: What it was, where is it today, and where is it going? Chaos: An Interdisciplinary Journal of Nonlinear Science, 15(2), 026116. https://doi.org/10.1063/1.1858782
  • Kumpulainen, Tatu, Lang, Bernhard, Rosspeintner, Arnulf, & Vauthey, Eric. (2017). Ultrafast elementary photochemical processes of organic molecules in liquid solution. Chemical Reviews, 117(16), 10826–10939. https://doi.org/10.1021/acs.chemrev.6b00423
  • Grampp, Günter, & Rasmussen, Kenneth. (2002). Solvent dynamical effects on the electron self-exchange rate of the TEMPO•/TEMPO+ couple. Physical Chemistry Chemical Physics, 4(22), 5546–5549. https://doi.org/10.1039/B208076G
  • Jimenez, Ralph, Fleming, Graham R., Kumar, P. V., & Maroncelli, Mark. (1994). Femtosecond solvation dynamics of water. Nature, 369, 471–473. https://doi.org/10.1038/369471a0
  • Barbara, Paul F., Meyer, Thomas J., & Ratner, Mark A. (1996). Contemporary issues in electron transfer research. The Journal of Physical Chemistry, 100(31), 13148–13168. https://doi.org/10.1021/jp9605663
  • Hammes-Schiffer, Sharon, & Stuchebrukhov, Alexei A. (2010). Theory of coupled electron and proton transfer reactions. Chemical Reviews, 110(12), 6939–6960. https://doi.org/10.1021/cr1001436
  • Newns, Dennis M. (1969). Self-consistent model of hydrogen chemisorption. Physical Review, 178(3), 1123–1135. https://doi.org/10.1103/PhysRev.178.1123
  • Nørskov, Jens K., Bligaard, Thomas, Rossmeisl, Jan, & Christensen, Claus H. (2009). Towards the computational design of solid catalysts. Nature Chemistry, 1, 37–46. https://doi.org/10.1038/nchem.121
  • Whitman, Lloyd J., Bartosch, Charles E., Ho, Wilson, Strasser, Gottfried, & Grunze, Michael. (1986). Alkali-metal promotion of a dissociation precursor: N2 on Fe(111). Physical Review Letters, 56(18), 1984–1987. https://doi.org/10.1103/PhysRevLett.56.1984
  • Brathwaite, Antonio D., Ricks, Allen M., & Duncan, Michael A. (2013). Infrared spectroscopy of iron carbonyl cations. The Journal of Physical Chemistry A, 117(46), 11695–11703. https://doi.org/10.1021/jp409405n
  • Liu, Hong, Wang, Yang, Gong, Xue-Qing, & Wang, Yi. (2022). Breaking the linear relation in the dissociation of nitrogen on iron clusters. ChemPhysChem, 23(16), e202200191. https://doi.org/10.1002/cphc.202200191
  • Maurer, Reinhard J., Jiang, Bin, Guo, Hua, & Tully, John C. (2017). Mode specific electronic friction in dissociative chemisorption on metal surfaces: H2 on Ag(111). Physical Review Letters, 118(25), 256001. https://doi.org/10.1103/PhysRevLett.118.256001