Reactive mode composition factor analysis of transition states: the case of coupled electron–proton transfers

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61388955%3A_____%2F19%3A00511366" target="_blank" >RIV/61388955:_____/19:00511366 - isvavai.cz</a>

Nalezeny alternativní kódy

RIV/61388963:_____/19:00517835 RIV/68407700:21340/19:00337853

Výsledek na webu

<a href="http://hdl.handle.net/11104/0301649" target="_blank" >http://hdl.handle.net/11104/0301649</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1039/C9CP05131G" target="_blank" >10.1039/C9CP05131G</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Reactive mode composition factor analysis of transition states: the case of coupled electron–proton transfers

Popis výsledku v původním jazyce

A simple method for the evaluation of the kinetic energy distribution within the reactive mode of a transition state (TS), denoted as the Reactive Mode Composition Factor (RMCF), is presented. It allows one to directly map the barrier properties onto the atomic-motion components of the reaction coordinate at the TS, which has potential to shed light onto some mechanistic features of a chemical process. To demonstrate the applicability of RMCF to reactivity, we link the kinetic energy distribution within a reactive mode with the asynchronicity (η) in C–H bond activation, as they both evolve in a series of coupled proton–electron transfer (CPET) reactions between FeIVO oxidants and 1,4-cyclohexadiene. RMCF shows how the earliness or lateness of a process manifests as a redistribution of kinetic energy in the reactive mode as a function of the free energy of reaction (ΔG0) and η. Finally, the title analysis can be applied to predict H-atom tunneling contributions and kinetic isotope effects in a set of reactions, yielding a transparent rationalization based on the kinetic energy distributions in the reactive mode.

Název v anglickém jazyce

Reactive mode composition factor analysis of transition states: the case of coupled electron–proton transfers

Popis výsledku anglicky

A simple method for the evaluation of the kinetic energy distribution within the reactive mode of a transition state (TS), denoted as the Reactive Mode Composition Factor (RMCF), is presented. It allows one to directly map the barrier properties onto the atomic-motion components of the reaction coordinate at the TS, which has potential to shed light onto some mechanistic features of a chemical process. To demonstrate the applicability of RMCF to reactivity, we link the kinetic energy distribution within a reactive mode with the asynchronicity (η) in C–H bond activation, as they both evolve in a series of coupled proton–electron transfer (CPET) reactions between FeIVO oxidants and 1,4-cyclohexadiene. RMCF shows how the earliness or lateness of a process manifests as a redistribution of kinetic energy in the reactive mode as a function of the free energy of reaction (ΔG0) and η. Finally, the title analysis can be applied to predict H-atom tunneling contributions and kinetic isotope effects in a set of reactions, yielding a transparent rationalization based on the kinetic energy distributions in the reactive mode.

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10403 - Physical chemistry

Projekt

Výsledek vznikl pri realizaci vícero projektů. Více informací v záložce Projekty.

Návaznosti

P - Projekt vyzkumu a vyvoje financovany z verejnych zdroju (s odkazem do CEP)

Rok uplatnění

2019

Kód důvěrnosti údajů

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

Název periodika

Physical Chemistry Chemical Physics

ISSN

1463-9076

e-ISSN

—

Svazek periodika

21

Číslo periodika v rámci svazku

OCT 2019

Stát vydavatele periodika

GB - Spojené království Velké Británie a Severního Irska

Počet stran výsledku

7

Strana od-do

24912-24918

Kód UT WoS článku

000506841300003

EID výsledku v databázi Scopus

2-s2.0-85075619564