EPR spectroscopy and DFT calculations of the g tensors of {VO}~1/ZSM-5,{CuNO}~(II)/ZSM-5 and {NaNO}~1/ZSM-5 intrazeolitic complexes

摘要

The relation between the structure and magnetic properties of VO~(2+) (d~1) species and nitrosyl adducts of Cu~+ (d~(10)) and Na~+(d~0) ions exchanged in the ZSM-5 zeolite was studied by DFT and EPR methods.Electronic g tensors were predicted using the spin-unrestricted zero order relativistic approximation (ZORA) and the scalar relativistic Pauli Hamiltonian calculations.The main purpose was to reproduce theoretically the g tensor components of the investigated intrazeolite paramagnets and to interpret the observed DELTA g_(ii) shifts in terms of the associated molecular orbital contributions.