title: Adsorption of NH(3) and H(2)O in acidic chabazite. Comparison of ONIOM approach with periodic calculations.
abstract: The adsorption of NH(3) and H(2)O in acidic chabazite has been studied with the B3LYP method within the cluster approach (5T, 48T clusters) and the periodic approach adopting a Si/Al = 11/1 chabazite and a basis set of polarized double-zeta quality. The 5T cluster has been treated fully ab initio at the B3LYP level whereas the 48T cluster has been treated with the ONIOM2 scheme using B3LYP as the high level of theory and the MNDO, AM1, and HF/3-21G methods as low levels of theory. Periodic calculations show that the adsorption of NH(3) in acidic chabazite takes place through an ion pair (NH(4)(+)-CHA(-)) structure, the computed adsorption energy being -32 kcal/mol. The adsorption of H(2)O leads to a hydrogen bonded (H(2)O-HCHA) complex with the computed adsorption energy of -20 kcal/mol. All ONIOM combinations provide similar structures to those obtained with periodic calculations. Adsorption energies, however, are sensitive to the low level used, especially for NH(3). The ONIOM B3LYP:HF/3-21G method is the one that provides more satisfactory results. Present results show that, for larger zeolites, the ONIOM scheme can be successfully applied while drastically reducing the cost of a fully ab initio treatment.
authors.affiliation: Departament de Quimica, Universitat Autonoma de Barcelona, Bellaterra 08193, Spain.
authors.forename: Xavier
authors.initials: X
authors.lastname: Solans-Monfort
authors.forename: Mariona
authors.initials: M
authors.lastname: Sodupe
authors.forename: Vicenç
authors.initials: V
authors.lastname: Branchadell
authors.forename: Joachim
authors.initials: J
authors.lastname: Sauer
authors.forename: Roberto
authors.initials: R
authors.lastname: Orlando
authors.forename: Piero
authors.initials: P
authors.lastname: Ugliengo