Marcus cross relation in the space of H-atom abstraction reactions boosted through off-diagonal thermodynamics

Result code in IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61388963%3A_____%2F25%3A00640180" target="_blank" >RIV/61388963:_____/25:00640180 - isvavai.cz</a>

Alternative codes found

RIV/61388955:_____/25:00640180 RIV/68407700:21340/25:00386244

Result on the web

<a href="https://pubs.aip.org/aip/jcp/article/163/14/144105/3366960/Marcus-cross-relation-in-the-space-of-H-atom" target="_blank" >https://pubs.aip.org/aip/jcp/article/163/14/144105/3366960/Marcus-cross-relation-in-the-space-of-H-atom</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1063/5.0289063" target="_blank" >10.1063/5.0289063</a>

Result language

angličtina

Original language name

Marcus cross relation in the space of H-atom abstraction reactions boosted through off-diagonal thermodynamics

Original language description

Proton-coupled electron transfer (PCET) and hydrogen-atom transfer (HAT) reactions, collectively called H-atom abstraction (HAA) reactions, play critical roles in biological processes and modern organic synthesis. The kinetics of these processes can align with the principles described in the renowned Marcus cross relation (MCR), a framework initially formulated to describe electron transfer mechanisms. The MCR provides an outstanding link between the kinetics of HAA reactions involving two distinct reactants and two related auxiliary self-exchange reactions—each between a molecule of one of the reactants and its conjugated radical. In this study, we investigate the applicability and limitations of the canonical MCR across over 300 HAA reactions, providing a comprehensive theoretical analysis. Our findings reveal the need for an enhanced framework that incorporates “off-diagonal” thermodynamic factors—asynchronicity and frustration. Of these factors, asynchronicity, which quantifies the imbalance between the proton vs electron transfer components of the reaction, is identified as the dominant contributor to the improved predictive accuracy of the MCR. Notably, the incorporation of off-diagonal thermodynamics yields a more pronounced enhancement for HAT reactions than for PCET-like HAA reactions. As a corollary, the model also describes a so-called pseudoinverted region, in which more exergonic reactions feature higher free energy barriers even though the thermodynamic driving force is not so large as it is required for the proper inverted region well-known from the original Marcus theory. This advancement offers a refined theoretical basis for understanding H-atom abstraction mechanisms and underscores the importance of off-diagonal effects in HAA chemistry.

Czech name

—

Czech description

—

Type

J_imp - Article in a specialist periodical, which is included in the Web of Science database

CEP classification

—

OECD FORD branch

10403 - Physical chemistry

Project

Result was created during the realization of more than one project. More information in the Projects tab.

Continuities

I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Publication year

2025

Confidentiality

S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů

Name of the periodical

Journal of Chemical Physics

ISSN

0021-9606

e-ISSN

1089-7690

Volume of the periodical

163

Issue of the periodical within the volume

14

Country of publishing house

US - UNITED STATES

Number of pages

13

Pages from-to

144105

UT code for WoS article

001591299000001

EID of the result in the Scopus database

2-s2.0-105018173913