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dc.contributor.author
Weser, Oskar
dc.contributor.author
Freitag, Leon
dc.contributor.author
Guther, Kai
dc.contributor.author
Alavi, Ali
dc.contributor.author
Li Manni, Giovanni
dc.date.accessioned
2021-01-08T15:55:24Z
dc.date.available
2020-11-01T08:20:38Z
dc.date.available
2020-11-02T11:10:11Z
dc.date.available
2021-01-08T15:55:24Z
dc.date.issued
2021-02-05
dc.identifier.other
10.1002/qua.26454
en_US
dc.identifier.uri
http://hdl.handle.net/20.500.11850/448987
dc.identifier.doi
10.3929/ethz-b-000448987
dc.description.abstract
Stochastic‐CASSCF and DMRG procedures have been utilized to quantify the role of the electron‐correlation mechanisms that, in an Fe‐porphyrin model system, are responsible for the differential stabilization of the 3Eg over the 5A1g state. Orbital entanglement diagrams and CI coefficients of the wave function in a localized orbital basis allow for an effective interpretation of the role of charge‐transfer configurations. A preliminary version of the Stochastic Generalized Active Space Self‐Consistent Field method has been developed and is here introduced to further assess the π backdonation stabilizing effect. By the new method, excitations between metal and ligand orbitals can selectively be removed from the complete CI expansion. It is demonstrated that these excitations are key to the differential stabilization of the triplet, effectively leading to a quantitative measure of the correlation‐enhanced π backdonation.
en_US
dc.format
application/pdf
en_US
dc.language.iso
en
en_US
dc.publisher
Wiley
en_US
dc.rights.uri
http://creativecommons.org/licenses/by/4.0/
dc.subject
sigma donation/pi backdonation
en_US
dc.subject
DMRG
en_US
dc.subject
FCIQMC
en_US
dc.subject
Fe-porphyrin
en_US
dc.subject
stochastic-CASSCF
en_US
dc.subject
stochastic-GASSCF
en_US
dc.title
Chemical insights into the electronic structure of Fe(II) porphyrin using FCIQMC, DMRG, and generalized active spaces
en_US
dc.type
Journal Article
dc.rights.license
Creative Commons Attribution 4.0 International
dc.date.published
2020-10-10
ethz.journal.title
International Journal of Quantum Chemistry
ethz.journal.volume
121
en_US
ethz.journal.issue
3
en_US
ethz.pages.start
e26454
en_US
ethz.size
14 p.
en_US
ethz.version.deposit
publishedVersion
en_US
ethz.identifier.wos
ethz.identifier.scopus
ethz.publication.place
Hoboken, NJ
en_US
ethz.publication.status
published
en_US
ethz.date.deposited
2020-11-01T08:20:45Z
ethz.source
WOS
ethz.eth
yes
en_US
ethz.availability
Open access
en_US
ethz.rosetta.installDate
2021-01-08T15:55:32Z
ethz.rosetta.lastUpdated
2021-02-15T23:02:28Z
ethz.rosetta.versionExported
true
ethz.COinS
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