How Well Does a Solvated Octa-acid Capsule Shield the Embedded Chromophore? A Computational Analysis Based on an Anisotropic Dielectric Continuum Model

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dc.authoridHerbert, John/0000-0002-1663-2278
dc.authoridDunietz, Barry D/0000-0002-6982-8995
dc.authoridAksu, Huseyin/0000-0001-9463-3236
dc.contributor.authorAksu, Huseyin
dc.contributor.authorPaul, Suranjan K.
dc.contributor.authorHerbert, John M.
dc.contributor.authorDunietz, Barry D.
dc.date.accessioned2025-01-27T20:51:49Z
dc.date.available2025-01-27T20:51:49Z
dc.date.issued2020
dc.departmentÇanakkale Onsekiz Mart Üniversitesi
dc.description.abstractThe optical properties of chromophores embedded in a water-solvated dimer of octa-acid that forms a molecular-shaped capsule are investigated. In particular, we address the anisotropic dielectric environment that appears to blue-shift excitation energies compared to the free aqueous chromophores. Recently we reported that using an effective scalar dielectric constant epsilon approximate to 3 appears to reproduce the measured spectra of the embedded coumarins, suggesting that the capsule provides a significant, albeit not perfect, screening of the aqueous dielectric environment. Here, we report absorption energies using a theoretical treatment that includes continuum solvation affected by an anisotropic dielectric function reflecting the high-dielectric environment outside of the capsule and the low-dielectric region within. We report time-dependent density functional theory calculations using a range-separated functional with the Poisson boundary conditions that model the anisotropic dielectric environment. Our calculations find that the anisotropic environment due to the water-solvated hydrophobic capsule is equivalent to a homogeneous effective dielectric constant of approximate to 3. The calculated values also appear to reproduce measured absorption of the embedded coumarin, where we study the effect of the hydrophobic capsule on the excited state.
dc.description.sponsorshipOhio Super-computer Center63 [PAA-0003, PAA-0213]; National Science Foundation [CHE-1665322]; Department of Energy, basic energy sciences grant [DE-SC0016501]
dc.description.sponsorshipComputing facilities were provided by the Ohio Super-computer Center63 (projects PAA-0003 and PAA-0213 awarded to J.M.H. and B.D.D., respectively) and by the Kent State University College of Arts and Sciences. Work by S.K.P. and J.M.H. was supported by National Science Foundation grant no. CHE-1665322. Work by H.A. and B.D.D. was supported by the Department of Energy, basic energy sciences grant no. DE-SC0016501.
dc.identifier.doi10.1021/acs.jpcb.0c04032
dc.identifier.endpage7004
dc.identifier.issn1520-6106
dc.identifier.issn1520-5207
dc.identifier.issue32
dc.identifier.pmid32787071
dc.identifier.scopus2-s2.0-85089494431
dc.identifier.scopusqualityQ2
dc.identifier.startpage6998
dc.identifier.urihttps://doi.org/10.1021/acs.jpcb.0c04032
dc.identifier.urihttps://hdl.handle.net/20.500.12428/25529
dc.identifier.volume124
dc.identifier.wosWOS:000562943100006
dc.identifier.wosqualityQ3
dc.indekslendigikaynakWeb of Science
dc.indekslendigikaynakScopus
dc.indekslendigikaynakPubMed
dc.language.isoen
dc.publisherAmer Chemical Soc
dc.relation.ispartofJournal of Physical Chemistry B
dc.relation.publicationcategoryinfo:eu-repo/semantics/openAccess
dc.rightsinfo:eu-repo/semantics/closedAccess
dc.snmzKA_WoS_20250125
dc.subjectPhotoinduced Electron-Transfer
dc.subjectDensity-Functional Theory
dc.subjectSupramolecular Photochemistry
dc.subjectAcceptor
dc.subjectExcitations
dc.subjectEnergies
dc.subjectViologen
dc.subjectSolutes
dc.subjectSurface
dc.subjectDonors
dc.titleHow Well Does a Solvated Octa-acid Capsule Shield the Embedded Chromophore? A Computational Analysis Based on an Anisotropic Dielectric Continuum Model
dc.typeArticle

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