The role of water molecules in the dissociation of an electron-molecule contact pair

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61388955%3A_____%2F25%3A00618181" target="_blank" >RIV/61388955:_____/25:00618181 - isvavai.cz</a>

Výsledek na webu

<a href="https://hdl.handle.net/11104/0365167" target="_blank" >https://hdl.handle.net/11104/0365167</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1038/s41467-025-57403-7" target="_blank" >10.1038/s41467-025-57403-7</a>

Jazyk výsledku

angličtina

Název v původním jazyce

The role of water molecules in the dissociation of an electron-molecule contact pair

Popis výsledku v původním jazyce

The hydrated electron, e-(aq), is a potent reducing agent and a prototypical quantum solute. Reactions of e-(aq) often involve a contact pair comprised of a molecule and electron that are hydrated within a single sphere. However, a molecular-level understanding of the solvent-driven coordinate that links the contact pair to the free dissociated e-(aq) remains elusive. Here, we study this coordinate by kinetically trapping representative metastable intermediates as gas-phase clusters and probing them using photoelectron spectroscopy. We apply this methodology to uracil-water anion clusters, where key intermediates are identified with supporting quantum chemical calculations. Just a single water molecule drives the parent molecule and non-valence electron apart, thereby inhibiting geminate recombination to form the more stable valence-bound uracil anion. The electron-water binding is akin to bare water cluster anions, highlighting the link to larger clusters and e-(aq). Our results provide a molecular-level view of quantum solute hydration and, more broadly, of how water-driven electron-transfer reactions proceed.

Název v anglickém jazyce

The role of water molecules in the dissociation of an electron-molecule contact pair

Popis výsledku anglicky

The hydrated electron, e-(aq), is a potent reducing agent and a prototypical quantum solute. Reactions of e-(aq) often involve a contact pair comprised of a molecule and electron that are hydrated within a single sphere. However, a molecular-level understanding of the solvent-driven coordinate that links the contact pair to the free dissociated e-(aq) remains elusive. Here, we study this coordinate by kinetically trapping representative metastable intermediates as gas-phase clusters and probing them using photoelectron spectroscopy. We apply this methodology to uracil-water anion clusters, where key intermediates are identified with supporting quantum chemical calculations. Just a single water molecule drives the parent molecule and non-valence electron apart, thereby inhibiting geminate recombination to form the more stable valence-bound uracil anion. The electron-water binding is akin to bare water cluster anions, highlighting the link to larger clusters and e-(aq). Our results provide a molecular-level view of quantum solute hydration and, more broadly, of how water-driven electron-transfer reactions proceed.

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10403 - Physical chemistry

Projekt

<a href="/cs/project/EH22_008%2F0004649" target="_blank" >EH22_008/0004649: Kvantové inženýrství a nanotechnologie</a><br>

Návaznosti

I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Rok uplatnění

2025

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

2041-1723

Svazek periodika

16

Číslo periodika v rámci svazku

1

Stát vydavatele periodika

GB - Spojené království Velké Británie a Severního Irska

Počet stran výsledku

8

Strana od-do

2113

Kód UT WoS článku

001437303700014

EID výsledku v databázi Scopus

2-s2.0-85219599997