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2023-07-10Zeitschriftenartikel DOI: 10.3390/molecules28145319
Valence and Core Photoelectron Spectra of Aqueous I3− from Multi-Reference Quantum Chemistry
dc.contributor.authorKochetov, Vladislav
dc.contributor.authorAhsan, Md Sabbir
dc.contributor.authorHein, Dennis
dc.contributor.authorWilkinson, Iain
dc.contributor.authorBokarev, Sergey
dc.date.accessioned2023-08-17T13:02:22Z
dc.date.available2023-08-17T13:02:22Z
dc.date.issued2023-07-10none
dc.date.updated2023-08-08T15:39:50Z
dc.identifier.urihttp://edoc.hu-berlin.de/18452/27778
dc.description.abstractThe I3− molecule is known to undergo substantial structural reorganization upon solvation by a protic solvent, e.g., water. However, the details of this process are still controversially discussed in the literature. In the present study, we combined experimental and theoretical efforts to disentangle this controversy. The valence (5p), N4,5 (4d), and M4,5 (3d) edge photoelectron spectra were measured in an aqueous solution and computed using high-level multi-reference methods. Our previous publication mainly focused on obtaining reliable experimental evidence, whereas in the present article, we focused primarily on theoretical aspects. The complex electronic structure of I3− requires the inclusion of both static and dynamic correlation, e.g., via the multi-configurational perturbation theory treatment. However, the resulting photoelectron spectra appear to be very sensitive to problems with variational stability and intruder states. We attempted to obtain artifact-free spectra, allowing for a more reliable interpretation of experiments. Finally, we concluded that the 3d Photoelectron Spectrum (PES) is particularly informative, evidencing an almost linear structure with a smaller degree of bond asymmetry than previously reported.eng
dc.description.sponsorshipDeutsche Forschungsgemeinschaft
dc.language.isoengnone
dc.publisherHumboldt-Universität zu Berlin
dc.rights(CC BY 4.0) Attribution 4.0 Internationalger
dc.rights.urihttps://creativecommons.org/licenses/by/4.0/
dc.subjectphotoelectron spectraeng
dc.subjectshake-up bandseng
dc.subjectmulti-reference methodseng
dc.subjecttriiodide anioneng
dc.subject.ddc540 Chemie und zugeordnete Wissenschaftennone
dc.titleValence and Core Photoelectron Spectra of Aqueous I3− from Multi-Reference Quantum Chemistrynone
dc.typearticle
dc.identifier.urnurn:nbn:de:kobv:11-110-18452/27778-5
dc.identifier.doi10.3390/molecules28145319none
dc.identifier.doihttp://dx.doi.org/10.18452/27110
dc.type.versionpublishedVersionnone
local.edoc.pages20none
local.edoc.type-nameZeitschriftenartikel
local.edoc.container-typeperiodical
local.edoc.container-type-nameZeitschrift
dc.description.versionPeer Reviewednone
dc.identifier.eissn1420-3049
dcterms.bibliographicCitation.journaltitleMoleculesnone
dcterms.bibliographicCitation.volume28none
dcterms.bibliographicCitation.issue14none
dcterms.bibliographicCitation.articlenumber5319none
dcterms.bibliographicCitation.originalpublishernameMDPInone
dcterms.bibliographicCitation.originalpublisherplaceBaselnone
bua.departmentMathematisch-Naturwissenschaftliche Fakultätnone

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