Cations Strongly Reduce Electron-Hopping Rates in Aqueous Solutions
(2011) In Journal of the American Chemical Society 133(34). p.13489-13495- Abstract
- We study how the ultrafast intermolecular hopping of electrons excited from the water O1s core level into unoccupied orbitals depends on the local molecular environment in liquid water. Our probe is the resonant Auger decay of the water O1s core hole (lifetime similar to 3.6 fs), by which we show that the electron-hopping rate can be significantly reduced when a first-shell water molecule is replaced by an atomic ion. Decays resulting from excitations at the O1s post-edge feature (similar to 540 eV) of 6 m LiBr and 3 m MgBr2 aqueous solutions reveal electron-hopping times of similar to 1.5 and 1.9 fs, respectively; the latter represents a 4-fold increase compared to the corresponding value in neat water. The slower electron-hopping in... (More)
- We study how the ultrafast intermolecular hopping of electrons excited from the water O1s core level into unoccupied orbitals depends on the local molecular environment in liquid water. Our probe is the resonant Auger decay of the water O1s core hole (lifetime similar to 3.6 fs), by which we show that the electron-hopping rate can be significantly reduced when a first-shell water molecule is replaced by an atomic ion. Decays resulting from excitations at the O1s post-edge feature (similar to 540 eV) of 6 m LiBr and 3 m MgBr2 aqueous solutions reveal electron-hopping times of similar to 1.5 and 1.9 fs, respectively; the latter represents a 4-fold increase compared to the corresponding value in neat water. The slower electron-hopping in electrolytes, which shows a strong dependence on the charge of the cations, can be explained by ion-induced reduction of water-water orbital mixing. Density functional theory electronic structure calculations of solvation geometries obtained from molecular dynamics simulations reveal that this phenomenon largely arises from electrostatic perturbations of the solvating water molecules by the solvated ions. Our results demonstrate that it is possible to deliberately manipulate the rate of charge transfer via electron-hopping in aqueous media. (Less)
Please use this url to cite or link to this publication:
https://lup.lub.lu.se/record/2208199
- author
- Ottosson, Niklas ; Odelius, Michael ; Spangberg, Daniel ; Pokapanich, Wandared ; Svanqvist, Mattias ; Öhrwall, Gunnar LU ; Winter, Bernd and Bjorneholm, Olle
- organization
- publishing date
- 2011
- type
- Contribution to journal
- publication status
- published
- subject
- in
- Journal of the American Chemical Society
- volume
- 133
- issue
- 34
- pages
- 13489 - 13495
- publisher
- The American Chemical Society (ACS)
- external identifiers
-
- wos:000295551600049
- scopus:80052081471
- pmid:21755940
- ISSN
- 1520-5126
- DOI
- 10.1021/ja204100j
- language
- English
- LU publication?
- yes
- id
- ed415467-2d2b-423a-9e74-cd70362f605f (old id 2208199)
- date added to LUP
- 2016-04-01 13:17:06
- date last changed
- 2022-01-27 18:24:14
@article{ed415467-2d2b-423a-9e74-cd70362f605f, abstract = {{We study how the ultrafast intermolecular hopping of electrons excited from the water O1s core level into unoccupied orbitals depends on the local molecular environment in liquid water. Our probe is the resonant Auger decay of the water O1s core hole (lifetime similar to 3.6 fs), by which we show that the electron-hopping rate can be significantly reduced when a first-shell water molecule is replaced by an atomic ion. Decays resulting from excitations at the O1s post-edge feature (similar to 540 eV) of 6 m LiBr and 3 m MgBr2 aqueous solutions reveal electron-hopping times of similar to 1.5 and 1.9 fs, respectively; the latter represents a 4-fold increase compared to the corresponding value in neat water. The slower electron-hopping in electrolytes, which shows a strong dependence on the charge of the cations, can be explained by ion-induced reduction of water-water orbital mixing. Density functional theory electronic structure calculations of solvation geometries obtained from molecular dynamics simulations reveal that this phenomenon largely arises from electrostatic perturbations of the solvating water molecules by the solvated ions. Our results demonstrate that it is possible to deliberately manipulate the rate of charge transfer via electron-hopping in aqueous media.}}, author = {{Ottosson, Niklas and Odelius, Michael and Spangberg, Daniel and Pokapanich, Wandared and Svanqvist, Mattias and Öhrwall, Gunnar and Winter, Bernd and Bjorneholm, Olle}}, issn = {{1520-5126}}, language = {{eng}}, number = {{34}}, pages = {{13489--13495}}, publisher = {{The American Chemical Society (ACS)}}, series = {{Journal of the American Chemical Society}}, title = {{Cations Strongly Reduce Electron-Hopping Rates in Aqueous Solutions}}, url = {{http://dx.doi.org/10.1021/ja204100j}}, doi = {{10.1021/ja204100j}}, volume = {{133}}, year = {{2011}}, }