The location of Brønsted-acid sites (bridging OH groups, b-OH) at different crystallographic positions of zeolite catalysts influences their reactivity due to varying confinement. Selecting the most stable b-OH conformers at each of the 12 T-sites (T=Si/Al) of H-MFI, a representative set of 26 conformers is obtained which includes free b-OH groups pointing into the empty pore space and b-OH groups forming H-bonds across five- or six-membered rings of TO4 tetrahedra. Chemically accurate coupled-cluster-quality calculations for periodic models show that the strength of internal H-bonds and, hence, the OH bond length vary substantially with the framework position. For 11 of the 19 H-bonded b-OH groups examined, our predictions fall into the full width at half maximum range of the experimental signals at 3250±175 cm-1 and 7.0±1.4 ppm which supports previously debated assignments of these signals to H-bonded b-OH sites.

Department of Chemistry Humboldt University Berlin 10099 Berlin Germany

Department of Interface Science Fritz Haber Institute of the Max Planck Society 14195 Berlin Germany

Department of Physical and Macromolecular Chemistry and Charles University Center of Advanced Materials Charles University 12843 Prague Czech Republic

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