title: Relativistic density functional calculations of EPR g tensor for eta1{CuNO}(11) species in discrete and zeolite-embedded states.
abstract: Spin-unrestricted zeroth order regular approximation (ZORA) and the scalar relativistic method based on Pauli Hamiltonian implemented in the Amsterdam Density Functional suite were used to calculate the electronic g tensor for isolated covalent {CuNO}(11) and electrostatic {q-NO}(1) species and for various model molecular and nonmolecular {CuNO}(11)-containing systems, epitomizing copper nitrosyl cage adducts in the ZSM-5 zeolite. The predicted g tensor values using the ZORA/VWN scheme were in satisfactory agreement with experimental EPR results. Relativistic, diamagnetic, and paramagnetic contributions to the calculated g tensor were quantified. The nature of the observed Deltag shifts was discussed in terms of the molecular orbital contributions due to the magnetic field-induced couplings and their structure sensitivity. The influence of basis set and exchange-correlation functional on the results was also briefly evaluated.
authors.affiliation: Faculty of Chemistry, Jagiellonian University, Ingardena 3, 30-060 Cracow, Poland.
authors.forename: Piotr
authors.initials: P
authors.lastname: Pietrzyk
authors.forename: Zbigniew
authors.initials: Z
authors.lastname: Sojka
mesh_terms: D000465:Algorithms; D002384:Catalysis; D055598:Chemical Phenomena; D002627:Chemistry, Physical; D003198:Computer Simulation; D003300:Copper / Q000737:chemistry*; D004578:Electron Spin Resonance Spectroscopy; D008958:Models, Molecular; D008968:Molecular Conformation; D009569:Nitric Oxide / Q000737:chemistry*; D009589:Nitrogen Oxides / Q000737:chemistry; D017641:Zeolites / Q000737:chemistry*
chemical_list: D009589:Nitrogen Oxides; D017641:Zeolites; D009569:Nitric Oxide; D003300:Copper