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research article

Temperature Dependent Properties of the Aqueous Electron

Lan, Jinggang  
•
Rybkin, Vladimir V.
•
Pasquarello, Alfredo  
August 8, 2022
Angewandte Chemie-International Edition

The temperature-dependent properties of the aqueous electron have been extensively studied using mixed quantum-classical simulations in a wide range of thermodynamic conditions based on one-electron pseudopotentials. While the cavity model appears to explain most of the physical properties of the aqueous electron, only a non-cavity model has so far been successful in accounting for the temperature dependence of the absorption spectrum. Here, we present an accurate and efficient description of the aqueous electron under various thermodynamic conditions by combining hybrid functional-based molecular dynamics, machine learning techniques, and multiple time-step methods. Our advanced simulations accurately describe the temperature dependence of the absorption maximum in the presence of cavity formation. Specifically, our work reveals that the red shift of the absorption maximum results from an increasing gyration radius with temperature, rather than from global density variations as previously suggested.

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Type
research article
DOI
10.1002/anie.202209398
Web of Science ID

WOS:000837589500001

Author(s)
Lan, Jinggang  
Rybkin, Vladimir V.
Pasquarello, Alfredo  
Date Issued

2022-08-08

Publisher

WILEY-V C H VERLAG GMBH

Published in
Angewandte Chemie-International Edition
Article Number

e202209398

Subjects

Chemistry, Multidisciplinary

•

Chemistry

•

ab initio molecular dynamics

•

aqueous electron

•

hybrid functional

•

machine learning

•

hydrated electron

•

supercritical water

•

solvated electron

•

excess electrons

•

resonance raman

•

spectroscopy

•

spectrum

•

dynamics

•

simulation

•

mechanism

Editorial or Peer reviewed

REVIEWED

Written at

EPFL

EPFL units
CSEA  
Available on Infoscience
August 29, 2022
Use this identifier to reference this record
https://infoscience.epfl.ch/handle/20.500.14299/190296
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