dc.contributor.author
Dalton, Benjamin A.
dc.contributor.author
Kiefer, Henrik
dc.contributor.author
Netz, Roland R.
dc.date.accessioned
2024-05-07T10:36:53Z
dc.date.available
2024-05-07T10:36:53Z
dc.identifier.uri
https://refubium.fu-berlin.de/handle/fub188/43475
dc.identifier.uri
http://dx.doi.org/10.17169/refubium-43192
dc.description.abstract
Molecular isomerization kinetics in liquid solvent depends on a complex interplay between the solvent friction acting on the molecule, internal dissipation effects (also known as internal friction), the viscosity of the solvent, and the dihedral free energy profile. Due to the absence of accurate techniques to directly evaluate isomerization friction, it has not been possible to explore these relationships in full. By combining extensive molecular dynamics simulations with friction memory-kernel extraction techniques we consider a variety of small, isomerising molecules under a range of different viscogenic conditions and directly evaluate the viscosity dependence of the friction acting on a rotating dihedral. We reveal that the influence of different viscogenic media on isomerization kinetics can be dramatically different, even when measured at the same viscosity. This is due to the dynamic solute-solvent coupling, mediated by time-dependent friction memory kernels. We also show that deviations from the linear dependence of isomerization rates on solvent viscosity, which are often simply attributed to internal friction effects, are due to the simultaneous violation of two fundamental relationships: the Stokes-Einstein relation and the overdamped Kramers prediction for the barrier-crossing rate, both of which require explicit knowledge of friction.
dc.format.extent
10 Seiten
dc.rights.uri
https://creativecommons.org/licenses/by/4.0/
dc.subject
Chemical physics
en
dc.subject
Molecular dynamics
en
dc.subject
Physical chemistry
en
dc.subject.ddc
500 Naturwissenschaften und Mathematik::530 Physik::530 Physik
dc.title
The role of memory-dependent friction and solvent viscosity in isomerization kinetics in viscogenic media
dc.type
Wissenschaftlicher Artikel
dcterms.bibliographicCitation.articlenumber
3761
dcterms.bibliographicCitation.doi
10.1038/s41467-024-48016-7
dcterms.bibliographicCitation.journaltitle
Nature Communications
dcterms.bibliographicCitation.volume
15
dcterms.bibliographicCitation.url
https://doi.org/10.1038/s41467-024-48016-7
refubium.affiliation
Physik
refubium.funding
Springer Nature DEAL
refubium.note.author
Die Publikation wurde aus Open Access Publikationsgeldern der Freien Universität Berlin gefördert.
refubium.resourceType.isindependentpub
no
dcterms.accessRights.openaire
open access
dcterms.isPartOf.eissn
2041-1723