title: Adsorption of dioxygen to copper in CuHY zeolite.
abstract: The adsorption of dioxygen to copper in CuHY zeolites has been studied by means of FTIR spectroscopy and model calculations at the quantum mechanical/molecular mechanics (QM/MM) level. Different Si/Al ratios, substitution patterns and adsorption sites within the cavities of the zeolite lead to a large number of different isomers to be studied. In addition, these parameters control the end-on vs. side-on adsorption of dioxygen. High-level multireference benchmark calculations for the singlet and triplet states of such adsorption complexes corroborate the use of density functional theory for the investigation of these systems. Comparison of the experimental and computed data allows for the identification of a preferred adsorption site and a small number of isomers which appear to be most relevant for the adsorption process. Redshifts of >250 cm(-1) are obtained for the vibrational frequencies of adsorbed O(2).
authors.affiliation: Institute of Theoretical Chemistry, University of Stuttgart, Pfaffenwaldring 55, 70569 Stuttgart, Germany.
authors.forename: Shampa
authors.initials: S
authors.lastname: Santra
authors.forename: Tanja
authors.initials: T
authors.lastname: Archipov
authors.forename: Augusta B
authors.initials: AB
authors.lastname: Ene
authors.forename: Helena
authors.initials: H
authors.lastname: Komnik
authors.forename: Hermann
authors.initials: H
authors.lastname: Stoll
authors.forename: Emil
authors.initials: E
authors.lastname: Roduner
authors.forename: Guntram
authors.initials: G
authors.lastname: Rauhut
mesh_terms: D000327:Adsorption; D003300:Copper / Q000737:chemistry*; D056004:Molecular Dynamics Simulation; D010100:Oxygen / Q000737:chemistry*; D011789:Quantum Theory; D017550:Spectroscopy, Fourier Transform Infrared; D013499:Surface Properties; D017641:Zeolites / Q000737:chemistry*
chemical_list: D017641:Zeolites; D003300:Copper; D010100:Oxygen