Competition between proton transfer and intermolecular Coulombic decay in water

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F60461373%3A22340%2F18%3A43916702" target="_blank" >RIV/60461373:22340/18:43916702 - isvavai.cz</a>

Výsledek na webu

<a href="https://www.nature.com/articles/s41467-018-07501-6" target="_blank" >https://www.nature.com/articles/s41467-018-07501-6</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1038/s41467-018-07501-6" target="_blank" >10.1038/s41467-018-07501-6</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Competition between proton transfer and intermolecular Coulombic decay in water

Popis výsledku v původním jazyce

Intermolecular Coulombic decay (ICD) is a ubiquitous relaxation channel of electronically excited states in weakly bound systems, ranging from dimers to liquids. As it is driven by electron correlation, it was assumed that it will dominate over more established energy loss mechanisms, for example fluorescence. Here, we use electron-electron coincidence spectroscopy to determine the efficiency of the ICD process after 2a(1) ionization in water clusters. We show that this efficiency is surprisingly low for small water clusters and that it gradually increases to 40-50% for clusters with hundreds of water units. Ab initio molecular dynamics simulations reveal that proton transfer between neighboring water molecules proceeds on the same timescale as ICD and leads to a configuration in which the ICD channel is closed. This conclusion is further supported by experimental results from deuterated water. Combining experiment and theory, we infer an intrinsic ICD lifetime of 12-52 fs for small water clusters.

Název v anglickém jazyce

Competition between proton transfer and intermolecular Coulombic decay in water

Popis výsledku anglicky

Intermolecular Coulombic decay (ICD) is a ubiquitous relaxation channel of electronically excited states in weakly bound systems, ranging from dimers to liquids. As it is driven by electron correlation, it was assumed that it will dominate over more established energy loss mechanisms, for example fluorescence. Here, we use electron-electron coincidence spectroscopy to determine the efficiency of the ICD process after 2a(1) ionization in water clusters. We show that this efficiency is surprisingly low for small water clusters and that it gradually increases to 40-50% for clusters with hundreds of water units. Ab initio molecular dynamics simulations reveal that proton transfer between neighboring water molecules proceeds on the same timescale as ICD and leads to a configuration in which the ICD channel is closed. This conclusion is further supported by experimental results from deuterated water. Combining experiment and theory, we infer an intrinsic ICD lifetime of 12-52 fs for small water clusters.

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10403 - Physical chemistry

Projekt

<a href="/cs/project/GA18-23756S" target="_blank" >GA18-23756S: Transformace molekul rentgenovým zářením: Ab initio simulace v kapalinách</a><br>

Návaznosti

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

Rok uplatnění

2018

Kód důvěrnosti údajů

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

Název periodika

Nature Communications

ISSN

2041-1723

e-ISSN

—

Svazek periodika

9

Číslo periodika v rámci svazku

1

Stát vydavatele periodika

GB - Spojené království Velké Británie a Severního Irska

Počet stran výsledku

8

Strana od-do

4988

Kód UT WoS článku

000451176100013

EID výsledku v databázi Scopus

2-s2.0-85057284813