dc.contributor.author
Bredtmann, Timm
dc.contributor.author
Diestler, Dennis J.
dc.contributor.author
Li, Si-Dian
dc.contributor.author
Manz, Jörn
dc.contributor.author
Pérez-Torres, Jhon Fredy
dc.contributor.author
Tian, Wen-Juan
dc.contributor.author
Wu, Yan-Bo
dc.contributor.author
Yang, Yonggang
dc.contributor.author
Zhai, Hua-Jin
dc.date.accessioned
2018-06-08T04:04:36Z
dc.date.available
2016-11-10T11:01:07.742Z
dc.identifier.uri
https://refubium.fu-berlin.de/handle/fub188/16534
dc.identifier.uri
http://dx.doi.org/10.17169/refubium-20715
dc.description.abstract
An elementary molecular process can be characterized by the flow of particles
(i.e., electrons and nuclei) that compose the system. The flow, in turn, is
quantitatively described by the flux (i.e., the time-sequence of maps of the
rate of flow of particles though specified surfaces of observation) or, in
more detail, by the flux density. The quantum theory of concerted electronic
and nuclear fluxes (CENFs) associated with electronically adiabatic
intramolecular processes is presented. In particular, it is emphasized how the
electronic continuity equation can be employed to circumvent the failure of
the Born–Oppenheimer approximation, which always predicts a vanishing
electronic flux density (EFD). It is also shown that all CENFs accompanying
coherent tunnelling between equivalent “reactant” and “product” configurations
of isolated molecules are synchronous. The theory is applied to three systems
of increasing complexity. The first application is to vibrating, aligned
H2+(2Σg+), or vibrating and dissociating H2+(2Σg+, J = 0, M = 0). The EFD maps
manifest a rich and surprising structure in this simplest of systems; for
example, they show that the EFD is not necessarily synchronous with the
nuclear flux density and can alternate in direction several times over the
length of the molecule. The second application is to coherent tunnelling
isomerization in the model inorganic system B4, in which all CENFs are
synchronous. The contributions of core and valence electrons to the EFD are
separately computed and it is found that core electrons flow with the nuclei,
whereas the valence electrons flow obliquely to the core electrons in
distinctive patterns. The third application is to the Cope rearrangement of
semibullvalene, which also involves coherent tunnelling. An especially
interesting discovery is that the so-called “pericyclic” electrons do not
behave in the manner typically portrayed by the traditional Lewis structures
with appended arrows. Indeed, it is found that only about 3 pericyclic
electrons flow, in contrast to the 6 predicted by the Lewis picture. It is
remarkable that the time scales of these three processes vary by 18 orders of
magnitude: femtoseconds (H2+(2Σg+)); picoseconds (B4); kilosceconds
(semibullvalene). It is emphasized that results presented herein are appearing
in the literature for the first time.
en
dc.rights.uri
http://www.rsc.org/journals-books-databases/open-access/green-open-access/
dc.subject.ddc
500 Naturwissenschaften und Mathematik::540 Chemie
dc.title
Quantum theory of concerted electronic and nuclear fluxes associated with
adiabatic intramolecular processes
dc.type
Wissenschaftlicher Artikel
dcterms.bibliographicCitation
Physical Chemistry Chemical Physics. - 17 (2015), 44, S. 29421-29464
dcterms.bibliographicCitation.doi
10.1039/C5CP03982G
dcterms.bibliographicCitation.url
http://pubs.rsc.org/en/Content/ArticleLanding/2015/CP/C5CP03982G#!divAbstract
refubium.affiliation
Biologie, Chemie, Pharmazie
de
refubium.mycore.fudocsId
FUDOCS_document_000000025687
refubium.resourceType.isindependentpub
no
refubium.mycore.derivateId
FUDOCS_derivate_000000007335
dcterms.accessRights.openaire
open access