Supramolecular ordering of PTCDA molecules : the key role of dispersion forces in an unusual transition from physisorbed into chemisorbed state

2012
journal article
article
47
dc.abstract.enAdsorption and self-assembly of large $\pi$-conjugated 3,4,9,10-perylene tetracarboxylic dianhydride (PTCDA) molecules on rutile $TiO_{2}$(110) surface have been investigated using a combination of high-resolution scanning tunneling microscopy (STM), low-energy electron diffraction, and density functional theory calculations with inclusion of Grimme treatment of the dispersion forces (DFT-D). Evolution of the STM images as a function of PTCDA coverage Is owed by transition of the adsorption mode from physisorbed single adspecies and meandering stripes into spontaneously ordered chemisorbed molecular assemblies. This change in the adsorption fashion is accompanied by significant bending of the intrinsically flat, yet elastic, PTCDA molecule, which allows for strong electronic coupling of the dye adspecies with the $TiO_{2}$ substrate. Extensive DFT-D modeling has revealed that adsorption is controlled by interfacial and intermolecular dispersion forces playing a dominant role in the adsorption of single PTCDA species, their self-organization into the meandering stripes, and at the monolayer coverage acting collectively to surmount the chemisorption energy barrier associated with the molecule bending. Analysis of the resulting density of states has revealed that alignment of the energy levels and strong electronic coupling at the PTCDA/$TiO_{2}$ interface are beneficial for dye sensitization purposes.pl
dc.affiliationWydział Fizyki, Astronomii i Informatyki Stosowanej : Instytut Fizyki im. Mariana Smoluchowskiegopl
dc.affiliationWydział Chemii : Zakład Chemii Nieorganicznejpl
dc.contributor.authorGodlewski, Szymon - 140233 pl
dc.contributor.authorTekiel, Antonipl
dc.contributor.authorPiskorz, Witold - 131426 pl
dc.contributor.authorZasada, Filip - 200610 pl
dc.contributor.authorPrauzner-Bechcicki, Jakub - 160675 pl
dc.contributor.authorSojka, Zbigniew - 131982 pl
dc.contributor.authorSzymoński, Marek - 132296 pl
dc.date.accessioned2015-01-26T11:12:03Z
dc.date.available2015-01-26T11:12:03Z
dc.date.issued2012pl
dc.description.admin[AB] Tekiel, Antoni 50000139
dc.description.number10pl
dc.description.physical8536-8545pl
dc.description.publication1pl
dc.description.volume6pl
dc.identifier.doi10.1021/nn303546mpl
dc.identifier.eissn1936-086Xpl
dc.identifier.issn1936-0851pl
dc.identifier.urihttp://ruj.uj.edu.pl/xmlui/handle/item/2740
dc.languageengpl
dc.language.containerengpl
dc.rightsDodaję tylko opis bibliograficzny*
dc.rights.licenceBez licencji otwartego dostępu
dc.rights.uri*
dc.subject.othersupramolecular orderingpl
dc.subject.othertitanium dioxidepl
dc.subject.other$TiO_{2}$pl
dc.subject.otherPTCDApl
dc.subject.otherdye sensitizationpl
dc.subject.otherphotovoltaicspl
dc.subject.otherSTMpl
dc.subject.otherDFT-Dpl
dc.subject.othervan der Waalspl
dc.subject.othersemi-empirical dispersionpl
dc.subject.otheradsorptionpl
dc.subject.otherDOSpl
dc.subject.othersurface functionalizationpl
dc.subtypeArticlepl
dc.titleSupramolecular ordering of PTCDA molecules : the key role of dispersion forces in an unusual transition from physisorbed into chemisorbed statepl
dc.title.journalACS Nanopl
dc.typeJournalArticlepl
dspace.entity.typePublication
dc.abstract.enpl
Adsorption and self-assembly of large $\pi$-conjugated 3,4,9,10-perylene tetracarboxylic dianhydride (PTCDA) molecules on rutile $TiO_{2}$(110) surface have been investigated using a combination of high-resolution scanning tunneling microscopy (STM), low-energy electron diffraction, and density functional theory calculations with inclusion of Grimme treatment of the dispersion forces (DFT-D). Evolution of the STM images as a function of PTCDA coverage Is owed by transition of the adsorption mode from physisorbed single adspecies and meandering stripes into spontaneously ordered chemisorbed molecular assemblies. This change in the adsorption fashion is accompanied by significant bending of the intrinsically flat, yet elastic, PTCDA molecule, which allows for strong electronic coupling of the dye adspecies with the $TiO_{2}$ substrate. Extensive DFT-D modeling has revealed that adsorption is controlled by interfacial and intermolecular dispersion forces playing a dominant role in the adsorption of single PTCDA species, their self-organization into the meandering stripes, and at the monolayer coverage acting collectively to surmount the chemisorption energy barrier associated with the molecule bending. Analysis of the resulting density of states has revealed that alignment of the energy levels and strong electronic coupling at the PTCDA/$TiO_{2}$ interface are beneficial for dye sensitization purposes.
dc.affiliationpl
Wydział Fizyki, Astronomii i Informatyki Stosowanej : Instytut Fizyki im. Mariana Smoluchowskiego
dc.affiliationpl
Wydział Chemii : Zakład Chemii Nieorganicznej
dc.contributor.authorpl
Godlewski, Szymon - 140233
dc.contributor.authorpl
Tekiel, Antoni
dc.contributor.authorpl
Piskorz, Witold - 131426
dc.contributor.authorpl
Zasada, Filip - 200610
dc.contributor.authorpl
Prauzner-Bechcicki, Jakub - 160675
dc.contributor.authorpl
Sojka, Zbigniew - 131982
dc.contributor.authorpl
Szymoński, Marek - 132296
dc.date.accessioned
2015-01-26T11:12:03Z
dc.date.available
2015-01-26T11:12:03Z
dc.date.issuedpl
2012
dc.description.admin
[AB] Tekiel, Antoni 50000139
dc.description.numberpl
10
dc.description.physicalpl
8536-8545
dc.description.publicationpl
1
dc.description.volumepl
6
dc.identifier.doipl
10.1021/nn303546m
dc.identifier.eissnpl
1936-086X
dc.identifier.issnpl
1936-0851
dc.identifier.uri
http://ruj.uj.edu.pl/xmlui/handle/item/2740
dc.languagepl
eng
dc.language.containerpl
eng
dc.rights*
Dodaję tylko opis bibliograficzny
dc.rights.licence
Bez licencji otwartego dostępu
dc.rights.uri*
dc.subject.otherpl
supramolecular ordering
dc.subject.otherpl
titanium dioxide
dc.subject.otherpl
$TiO_{2}$
dc.subject.otherpl
PTCDA
dc.subject.otherpl
dye sensitization
dc.subject.otherpl
photovoltaics
dc.subject.otherpl
STM
dc.subject.otherpl
DFT-D
dc.subject.otherpl
van der Waals
dc.subject.otherpl
semi-empirical dispersion
dc.subject.otherpl
adsorption
dc.subject.otherpl
DOS
dc.subject.otherpl
surface functionalization
dc.subtypepl
Article
dc.titlepl
Supramolecular ordering of PTCDA molecules : the key role of dispersion forces in an unusual transition from physisorbed into chemisorbed state
dc.title.journalpl
ACS Nano
dc.typepl
JournalArticle
dspace.entity.type
Publication
Affiliations

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