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dc.contributor.authorMoilanen, Jani
dc.contributor.authorKarttunen, Antti
dc.contributor.authorTuononen, Heikki
dc.contributor.authorChivers, Tristram
dc.date.accessioned2015-11-25T12:02:16Z
dc.date.available2015-11-25T12:02:16Z
dc.date.issued2012
dc.identifier.citationMoilanen, J., Karttunen, A., Tuononen, H., & Chivers, T. (2012). The Nature of Transannular Interactions in E4N4 and E82+ (E = S, Se). <i>Journal of Chemical Theory and Computation</i>, <i>8</i>(11), 4249-4258. <a href="https://doi.org/10.1021/ct300627p" target="_blank">https://doi.org/10.1021/ct300627p</a>
dc.identifier.otherCONVID_21747301
dc.identifier.otherTUTKAID_53111
dc.identifier.urihttps://jyx.jyu.fi/handle/123456789/47828
dc.description.abstractThe electronic structures of tetrachalcogen tetranitrides, E4N4, and octachalcogen dications, E82+, and the nature of their intramolecular E···E interactions (E = S, Se) was studied with high-level theoretical methods. The results reveal that the singlet ground states of both systems have a surprisingly large correlation contribution which functions to weaken and therefore lengthen the cross-ring E–E bond. The observed correlation effects are primarily static in E4N4, whereas in E82+ the dynamic part largely governs the total correlation contribution. The presented description of bonding is the first that gives an all-inclusive picture of the origin of cross-ring interactions in E4N4 and E82+; not only does it succeed in reproducing all experimental structures but it also offers a solid explanation for the sporadic performance of different computational methods that has been reported in previous studies. Furthermore, the theoretical data demonstrate that E···E bonds in E4N4 and E82+ are unique and fundamentally different from, for example, dispersion that plays a major role in weak intermolecular chalcogen···chalcogen contacts.
dc.language.isoeng
dc.publisherACS
dc.relation.ispartofseriesJournal of Chemical Theory and Computation
dc.subject.otherrikki-typpi -yhdisteet
dc.subject.otherkalkogeenikationit
dc.subject.otherelektronirakenne
dc.subject.othersulfur-nitrogen compounds
dc.subject.otheroctachalcogen dications
dc.subject.otherelectronic structure
dc.titleThe Nature of Transannular Interactions in E4N4 and E82+ (E = S, Se)
dc.typearticle
dc.identifier.urnURN:NBN:fi:jyu-201511243787
dc.contributor.laitosKemian laitosfi
dc.contributor.laitosDepartment of Chemistryen
dc.contributor.oppiaineEpäorgaaninen ja analyyttinen kemiafi
dc.contributor.oppiaineInorganic and Analytical Chemistryen
dc.type.urihttp://purl.org/eprint/type/JournalArticle
dc.date.updated2015-11-24T10:15:23Z
dc.type.coarjournal article
dc.description.reviewstatuspeerReviewed
dc.format.pagerange4249-4258
dc.relation.issn1549-9618
dc.relation.numberinseries11
dc.relation.volume8
dc.type.versionacceptedVersion
dc.rights.copyright© 2012 American Chemical Society. This is a final draft version of an article whose final and definitive form has been published by ACS. Published in this repository with the kind permission of the publisher.
dc.rights.accesslevelopenAccessfi
dc.relation.doi10.1021/ct300627p


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