Benchmark data for interactions in zeolite model complexes and their use for assessment and validation of electronic structure Methods

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We present benchmark binding energies for five zeolite model complexes, with four of the adsorbates bound noncovalently and one covalently. The binding energies were determined as the sum of the infinite-basis-set limit of Møller-Plesset second-order perturbation theory (MP2) energies and a CCSD(T) correction term evaluated with the aug-cc-pVDZ basis set. The basis set limit of MP2 energies was determined by two-point extrapolation using the aug-cc-pVXZ basis sets for X = D and T and separate extrapolation of the Hartree-Fock and correlation energies. We found that correlation contributions beyond MP2 to the final binding energies are small; their magnitude is in the range of 0.02-1.0 kcal/mol. For the MP2 method to describe the interactions in these zeolite model systems accurately, one needs to use a basis set at least the size of aug-cc-pVTZ in conjunction with counterpoise corrections. Final binding energies (kcal/mol) of the model complexes are in the range of 3.5-19.5 kcal/mol, and they were used as reference data to test 6 wave function methods and 41 density functionals. Among the tested density functional methods, M06-L/6-31+G(d,p) gives a mean unsigned error (MUE) without counterpoise correction of 0.87 kcal/mol. With counterpoise corrections, the M06-2X and M05-2X functionals give the best performance. The MUE with counterpoise corrections for the M06-2X/6-311+G(2df,2p)//MP2/6-311+G(2df,2p) level of theory is 0.39 kcal/mol. With the DFT/6-31 +G-(d,p) geometries and the 6-311+G(2df,2p) basis set, M05-2X and M06-2X give MUEs with counterpoise corrections of 0.40 and 0.52 kcal/mol, respectively. Tests against the binding energies of four complexes (two noncovalent and two covalent) of the adsoption of isobutene on a large 16T zeolite model cluster confirmed that M06-L, M06, M05-2X, and M06-2X are very promising quantum mechanical methods for hybrid quantum mechanical/molecular mechanical (QM/MM) simulations of zeolites. In fact the performance of these four Minnesota functionals, as compared to other high-quality functionals, is relatively even better for the larger 16T clusters than for the smaller 3T ones.

Original languageEnglish (US)
Pages (from-to)6860-6868
Number of pages9
JournalJournal of Physical Chemistry C
Issue number17
StatePublished - May 1 2008

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