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2004-09-22Zeitschriftenartikel DOI: 10.1063/1.1781122
Electron hole formation in acidic zeolite catalysts
dc.contributor.authorSolans-Monfort, Xavier
dc.contributor.authorBranchadell, Vicenç
dc.contributor.authorSodupe, Mariona
dc.contributor.authorSierka, Marek
dc.contributor.authorSauer, Joachim
dc.date.accessioned2017-06-17T00:07:02Z
dc.date.available2017-06-17T00:07:02Z
dc.date.created2005-11-28
dc.date.issued2004-09-22
dc.date.submitted2004-01-01
dc.identifier.urihttp://edoc.hu-berlin.de/18452/9781
dc.description.abstractThe formation of an electron hole on an AlO4H center of the H-ZSM-5 zeolite has been studied by a hybrid quantum mechanics/shell-model ion-pair potential approach. The Becke-3-Lee-Yang-Parr (B3LYP) and Becke-Half&Half-Lee-Yang-Parr (BHLYP) hybrid density functionals yield electron holes of different nature, a delocalized hole for B3LYP and a hole localized on one oxygen atom for BHLYP. Comparison with coupled cluster calculations including single and double substitutions and with perturbative treatment of triple substitutions CCSD(T) and with experimental data for similar systems indicate that the localized description obtained with BHLYP is more accurate. Generation of the electron hole produces a substantial geometry relaxation, in particular an elongation of the Al-O distance to the oxygen atom with the unpaired electron. The zeolite framework stabilizes the positive charge by long-range effects. Our best estimates for the vertical and adiabatic ionization energies are 9.6–10.1 and 8.4–8.9 eV, respectively. Calculations for silicalite, the all-silica form of ZSM-5, also yield a localized electron hole, but the energy cost of the process is larger by 0.6–0.7 eV. The deprotonation energy of H-ZSM-5 is found to decrease from 12.86 to 11.40 eV upon electron hole formationeng
dc.language.isoeng
dc.publisherHumboldt-Universität zu Berlin, Mathematisch-Naturwissenschaftliche Fakultät I
dc.rights.urihttp://rightsstatements.org/vocab/InC/1.0/
dc.subjectdensity functional theoryeng
dc.subjectaluminium compoundseng
dc.subjectzeoliteseng
dc.subjectionisation potentialeng
dc.subjectbond lengthseng
dc.subjectdissociation energieseng
dc.subjectquantum theoryeng
dc.subjectcatalystseng
dc.subject.ddc540 Chemie
dc.titleElectron hole formation in acidic zeolite catalysts
dc.typearticle
dc.identifier.urnurn:nbn:de:kobv:11-10054325
dc.identifier.doi10.1063/1.1781122
dc.identifier.doihttp://dx.doi.org/10.18452/9129
local.edoc.container-titleThe Journal of Chemical Physics
local.edoc.type-nameZeitschriftenartikel
local.edoc.institutionMathematisch-Naturwissenschaftliche Fakultät I
local.edoc.container-typeperiodical
local.edoc.container-type-nameZeitschrift
local.edoc.container-eventconference
local.edoc.container-eventconference
local.edoc.container-volume2004
local.edoc.container-volume121
local.edoc.container-volume121
local.edoc.container-issue12
local.edoc.container-issue12
local.edoc.container-year2004
local.edoc.container-firstpage6034
local.edoc.container-lastpage6041
dc.description.versionPeer Reviewed

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