Photoinduced charge transfer in Zn(II) and Au(III)-ligated symmetric and asymmetric bacteriochlorin dyads: A computational study

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dc.authoridDunietz, Barry D/0000-0002-6982-8995
dc.authoridAksu, Huseyin/0000-0001-9463-3236
dc.contributor.authorAksu, Huseyin
dc.contributor.authorMaiti, Buddhadev
dc.contributor.authorPtaszek, Marcin
dc.contributor.authorDunietz, Barry D.
dc.date.accessioned2025-01-27T20:51:50Z
dc.date.available2025-01-27T20:51:50Z
dc.date.issued2020
dc.departmentÇanakkale Onsekiz Mart Üniversitesi
dc.description.abstractThe excited-state properties and photoinduced charge-transfer (CT) kinetics in a series of symmetrical and asymmetrical Zn- and Au-ligated meso-meso-connected bacteriochlorin (BChl) complexes are studied computationally. BChl derivatives, which are excellent near-IR absorbing chromophores, are found to play a central role in bacterial photosynthetic reaction centers but are rarely used in artificial solar energy harvesting systems. The optical properties of chemically linked BChl complexes can be tuned by varying the linking group and involving different ligated metal ions. We investigate charge transfer in BChl dyads that are either directly linked or through a phenylene ring (1,4-phenylene) and which are ligating Zn or Au ions. The directly linked dyads with a nearly perpendicular arrangement of the BChl units bear markedly different properties than phenylene linked dyads. In addition, we find that the dielectric dependence of the intramolecular CT rate is very strong in neutral Zn-ligated dyads, whereas cationic Au-ligated dyads show negligible dielectric dependence of the CT rate. Rate constants of the photo induced CT process are calculated at the semiclassical Marcus level and are compared to fully quantum mechanical Fermi's golden rule based values. The rates are calculated using a screened range separated hybrid functional that offers a consistent framework for addressing environment polarization. We study solvated systems in two solvents of a low and a high scalar dielectric constant.
dc.description.sponsorshipDepartment of Energy, Basic Energy Sciences [DE-SC0016501, PAA-0213]; College of Arts and Sciences, Kent State University
dc.description.sponsorshipB.D.D. is grateful for support from the Department of Energy, Basic Energy Sciences (Grant No. DE-SC0016501). Computing facilities were provided by the Ohio Supercomputer Center110 (Project No. PAA-0213) and from the College of Arts and Sciences, Kent State University.
dc.identifier.doi10.1063/5.0023609
dc.identifier.issn0021-9606
dc.identifier.issn1089-7690
dc.identifier.issue13
dc.identifier.pmid33032416
dc.identifier.scopus2-s2.0-85092438113
dc.identifier.scopusqualityQ1
dc.identifier.urihttps://doi.org/10.1063/5.0023609
dc.identifier.urihttps://hdl.handle.net/20.500.12428/25537
dc.identifier.volume153
dc.identifier.wosWOS:000578502400003
dc.identifier.wosqualityQ1
dc.indekslendigikaynakWeb of Science
dc.indekslendigikaynakScopus
dc.indekslendigikaynakPubMed
dc.language.isoen
dc.publisherAmer Inst Physics
dc.relation.ispartofJournal of Chemical Physics
dc.relation.publicationcategoryinfo:eu-repo/semantics/openAccess
dc.rightsinfo:eu-repo/semantics/openAccess
dc.snmzKA_WoS_20250125
dc.subjectPhotosynthetic Reaction Centers
dc.subjectDensity-Functional Theory
dc.subjectElectron-Transfer
dc.subjectEnergy-Transfer
dc.subjectSpecial Pair
dc.subjectTransfer States
dc.subjectRhodobacter-Sphaeroides
dc.subjectRhodopseudomonas-Viridis
dc.subjectSpectroscopic Properties
dc.subjectPhotophysical Properties
dc.titlePhotoinduced charge transfer in Zn(II) and Au(III)-ligated symmetric and asymmetric bacteriochlorin dyads: A computational study
dc.typeArticle

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