Relaxation Processes in Aqueous Systems upon X-ray Ionization: Entanglement of Electronic and Nuclear Dynamics

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F60461373%3A22340%2F16%3A43902480" target="_blank" >RIV/60461373:22340/16:43902480 - isvavai.cz</a>

Výsledek na webu

<a href="http://pubsdc3.acs.org/doi/full/10.1021/acs.jpclett.5b02665" target="_blank" >http://pubsdc3.acs.org/doi/full/10.1021/acs.jpclett.5b02665</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1021/acs.jpclett.5b02665" target="_blank" >10.1021/acs.jpclett.5b02665</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Relaxation Processes in Aqueous Systems upon X-ray Ionization: Entanglement of Electronic and Nuclear Dynamics

Popis výsledku v původním jazyce

The knowledge of primary processes following the interaction of high-energy radiation with molecules in liquid phase is rather limited. In the present Perspective, we report on a newly discovered type of relaxation process involving simultaneous autoionization and proton transfer between adjacent molecules, so-called proton transfer mediated charge separation (PTM-CS) process. Within PTM-CS, transients with a half-transferred proton are formed within a few femtoseconds after the core-level ionization event. Subsequent nonradiative decay of the highly nonequilibrium transients leads to a series of reactive species, which have not been considered in any high-energy radiation process in water. Nonlocal electronic decay processes are surprisingly accelerated upon proton dynamics. Such strong coupling of electronic and nuclear dynamics is a general phenomenon for hydrogen-bonded systems, however, its probability correlates strongly with hydration geometry. We suggest that the newly observed processes will impact future high-energy radiation-chemistry-relevant modeling, and we envision application of autoionization spectroscopy for identification of solution structure details.

Název v anglickém jazyce

Relaxation Processes in Aqueous Systems upon X-ray Ionization: Entanglement of Electronic and Nuclear Dynamics

Popis výsledku anglicky

The knowledge of primary processes following the interaction of high-energy radiation with molecules in liquid phase is rather limited. In the present Perspective, we report on a newly discovered type of relaxation process involving simultaneous autoionization and proton transfer between adjacent molecules, so-called proton transfer mediated charge separation (PTM-CS) process. Within PTM-CS, transients with a half-transferred proton are formed within a few femtoseconds after the core-level ionization event. Subsequent nonradiative decay of the highly nonequilibrium transients leads to a series of reactive species, which have not been considered in any high-energy radiation process in water. Nonlocal electronic decay processes are surprisingly accelerated upon proton dynamics. Such strong coupling of electronic and nuclear dynamics is a general phenomenon for hydrogen-bonded systems, however, its probability correlates strongly with hydration geometry. We suggest that the newly observed processes will impact future high-energy radiation-chemistry-relevant modeling, and we envision application of autoionization spectroscopy for identification of solution structure details.

Druh

J_x - Nezařazeno - Článek v odborném periodiku (Jimp, Jsc a Jost)

CEP obor

CF - Fyzikální chemie a teoretická chemie

OECD FORD obor

—

Projekt

<a href="/cs/project/GA13-34168S" target="_blank" >GA13-34168S: Ab initio simulace rentgenové fotodynamiky a spektroskopie ve vodných roztocích</a><br>

Návaznosti

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

Rok uplatnění

2016

Kód důvěrnosti údajů

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

Název periodika

Journal of Physical Chemistry Letters

ISSN

1948-7185

e-ISSN

—

Svazek periodika

7

Číslo periodika v rámci svazku

2

Stát vydavatele periodika

US - Spojené státy americké

Počet stran výsledku

10

Strana od-do

234-243

Kód UT WoS článku

000368652700005

EID výsledku v databázi Scopus

2-s2.0-84955437983