dc.contributor.author
Rinne, Klaus F.
dc.contributor.author
Gekle, Stephan
dc.contributor.author
Netz, Roland R.
dc.date.accessioned
2018-06-08T03:35:03Z
dc.date.available
2015-01-13T14:45:23.798Z
dc.identifier.uri
https://refubium.fu-berlin.de/handle/fub188/15494
dc.identifier.uri
http://dx.doi.org/10.17169/refubium-19682
dc.description.abstract
Using extensive equilibrium molecular dynamics simulations we determine the
dielectric spectra of aqueous solutions of NaF, NaCl, NaBr, and NaI. The ion-
specific and concentration-dependent shifts of the static dielectric constants
and the dielectric relaxation times match experimental results very well,
which serves as a validation of the classical and non-polarizable ionic force
fields used. The purely ionic contribution to the dielectric response is
negligible, but determines the conductivity of the salt solutions. The ion-
water cross correlation contribution is negative and reduces the total
dielectric response by about 5%-10% for 1 M solutions. The dominating water
dielectric response is decomposed into different water solvation shells and
ion-pair configurations, by this the spectral blue shift and the dielectric
decrement of salt solutions with increasing salt concentration is demonstrated
to be primarily caused by first-solvation shell water. With rising salt
concentration the simulated spectra show more pronounced deviations from a
single-Debye form and can be well described by a Cole-Cole fit, in
quantitative agreement with experiments. Our spectral decomposition into ionic
and different water solvation shell contributions does not render the
individual contributions more Debye-like, this suggests the non-Debye-like
character of the dielectric spectra of salt solutions not to be due to the
superposition of different elementary relaxation processes with different
relaxation times. Rather, the non-Debye-like character is likely to be an
inherent spectral signature of solvation water around ions.
en
dc.rights.uri
http://publishing.aip.org/authors/web-posting-guidelines
dc.subject.ddc
500 Naturwissenschaften und Mathematik::530 Physik
dc.title
Dissecting ion-specific dielectric spectra of sodium-halide solutions into
solvation water and ionic contributions
dc.type
Wissenschaftlicher Artikel
dcterms.bibliographicCitation
Journal of Chemical Physics. - 141 (2014), 21, Artikel Nr. 214502
dcterms.bibliographicCitation.doi
10.1063/1.4901927
dcterms.bibliographicCitation.url
http://dx.doi.org/10.1063/1.4901927
refubium.affiliation
Physik
de
refubium.mycore.fudocsId
FUDOCS_document_000000021578
refubium.resourceType.isindependentpub
no
refubium.mycore.derivateId
FUDOCS_derivate_000000004365
dcterms.accessRights.openaire
open access