Repozytorium Uniwersytetu Jagiellońskiego

On the nature of spin- and orbital-resolved Cu^{+}-NO charge transfer in the gas phase and at Cu(I) sites in zeolites

On the nature of spin- and orbital-resolved Cu^{+}-NO ...

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dc.contributor.author Kozyra, Paweł [SAP11017716] pl
dc.contributor.author Radoń, Mariusz [SAP14000880] pl
dc.contributor.author Datka, Jerzy [SAP11003748] pl
dc.contributor.author Brocławik, Ewa [SAP14000006] pl
dc.date.accessioned 2015-09-17T15:33:01Z
dc.date.available 2015-09-17T15:33:01Z
dc.date.issued 2012 pl
dc.identifier.issn 1040-0400 pl
dc.identifier.uri http://ruj.uj.edu.pl/xmlui/handle/item/15707
dc.language eng pl
dc.rights Udzielam licencji. Uznanie autorstwa 4.0 Międzynarodowa *
dc.rights.uri http://creativecommons.org/licenses/by/4.0/pl/legalcode *
dc.title On the nature of spin- and orbital-resolved Cu^{+}-NO charge transfer in the gas phase and at Cu(I) sites in zeolites pl
dc.type JournalArticle pl
dc.description.physical 1349-1356 pl
dc.identifier.weblink http://link.springer.com/article/10.1007%2Fs11224-012-0050-y pl
dc.abstract.en Electronic factors essential for NO activation by Cu(I) sites in zeolites are investigated within spin-resolved analysis of electron transfer channels (natural orbitals for chemical valence). NOCV analysis is performed for three DFT-opti- mized models of Cu(I)–NO site in ZSM-5: [CuNO] ? , (T1)CuNO, and (M7)CuNO. NO as a non-innocent, open- shell ligand reveals significant differences between inde- pendent deformation density components for a and b spins. Four distinct components are identified: (i) unpaired electron donation from NO p k * antibonding orbital to Cu s,d ; (ii) backdonation from copper d yz to p \ * antibonding orbital; (iii) donation from occupied p k and Cu d xz to bonding region, and (iv) donation from nitrogen lone-pair to Cu s,d . Channel (i), corresponding to one-electron bond, shows-up solely for spin majority and is effective only in the interaction of NO with naked Cu ? . Channel (ii) dominates for models b and c: it strongly activates NO bond by populating antibonding p * orbital and weakens the N–O bond in contrast to channel (i), depopulating the antibonding orbital and strengthening N–O bond. This picture perfectly agrees with IR experiment: interaction with naked Cu ? imposes small blue-shift of N stretching frequency while it becomes strongly red-shifted for Cu(I) site in ZSM-5 due to enhanced backdonation. pl
dc.subject.en NO activation pl
dc.subject.en donation and backdonation pl
dc.subject.en Cu(I) sites pl
dc.subject.en natural orbitals for chemical valence pl
dc.subject.en charge transfer pl
dc.description.volume 23 pl
dc.description.number 5 pl
dc.description.points 25 pl
dc.identifier.doi 10.1007/s11224-012-0050-y pl
dc.identifier.eissn 1572-9001 pl
dc.title.journal Structural Chemistry pl
dc.language.container eng pl
dc.date.accession 2015-09-17 pl
dc.affiliation Wydział Chemii : Zakład Chemii Nieorganicznej pl
dc.subtype Article pl
dc.rights.original CC-BY; inne; ostateczna wersja wydawcy; w momencie opublikowania; 0 pl
dc.identifier.project ROD UJ / P pl
.pointsMNiSW [2012 A]: 25


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