F Ef about b2 – 1/2 = 0, and truncation to 1st order lead toE = Ef max 1 + E4(6.18)The following conclusions are drawn in the Marcus formulation of electron, proton, and atom transfer reactions: (i) If the reaction free power is tiny sufficient when compared with the reorganization energy, eqs six.7, six.eight apply to both ET and atom transfer, soon after inclusion of the relevant degrees of freedom and evaluation of the proper absolutely free energy 118974-02-0 Purity & Documentation quantities. (ii) As a consequence of point i, the cross-relation (eqs six.4-6.six or eqs six.9-6.10) remains intact (furthermore, it might also be improved to account for steric and statistical effects232), assisting with all the interpretation of experimental data. Failure of your cross-relation has also been observed and associated for the presence of considerable contributions for the activation barrier that happen to be independent of your degree-of-reaction parameter.232 (iii) Marcus’ treatment enables interpretion and quantification with the Br sted slope241 as a measure of your proximity of your activated complex towards the items of the reaction,247 which assists with interpreting atom transfer and PCET reaction data. (iv) The cross-relation along with the Br sted coefficient inside the extended Marcus theory allow the investigation of intrinsic reactions barriers and isotopic effects of wide experimental relevance. These four points guide the successful application with the extended Marcus theory, which has broad relevance to interpretation of charge transfer information, which includes multiple-site concerted electron-proton transfer reaction information.six.2. Implications on the Extended Marcus Theory: Br sted Slope, Kinetic Isotope Impact, and Cross-RelationFor a homologous set of reactions with approximately equal reorganization energies and perform terms,230 the Br sted241 (or the Leffler247) slopedx.doi.org/10.1021/cr4006654 | Chem. Rev. 2014, 114, 3381-Chemical Reviews= G/G= G/GR (six.21)Reviewcorrelates the reaction price with equilibrium properties on the systems,249 due to the partnership involving Gand the equilibrium continuous (see section 3 of the Supporting Facts). Equation six.21 is usually rewritten with regards to the adjustments in G and Ginduced by structural variation:G = G(six.22)which shows how reflects the fraction of change inside the reaction absolutely free energy which is observable as a transform in the activation barrier.247,250 Equations 6.20a and six.20b imply that= bt(6.23)which hyperlinks the Br sted coefficient towards the degree-of-reaction parameter b at Qt, and hence for the productlike character with the activated complicated. In certain, is definitely the order of your bond being formed as outlined by the BEBO model. In weak-overlap reactions in solution, will be the 592542-59-1 supplier contribution from the items for the prospective energy function that determines the distribution of activated complex coordinates. Furthermore, includes a comparable meaning in strong-overlap ET, proton, and HAT reactions (see ref 232 and also the discussion under). If eq 5.29 could be utilised, 1 obtains= GR 1 1 +(6.24)outcome from very simple application of eq six.24. For example, eq six.24 is inappropriate to describe the deprotonation of substituted nitroalkanes260 or hydride transfer reactions.250 The activation cost-free energies obtained in ref 250 in the extended Marcus theory agree nicely with ab initio values obtained in the MP2261,262 degree of theory. Normally, eqs six.24 and six.25 are applicable to reaction mechanisms exactly where the totally free power landscape near the activated complex and along one (or extra) appropriate reaction coordinate(s) can be decomposed int.