27Al quadrupole interaction in zeolites loaded with probe molecules -: a quantum-chemical study of trends in electric field gradients and chemical bonds in clusters

The electric field gradient (EFG) has been calculated in zeolite clusters at the aluminium site surrounded by four SiO4 tetrahedra. Density functional theory (DFT) with the 6-31G * * basis set has been employed. Formation of a Bronsted acid site by protonation of one oxygen atom of the AlO4 tetrahedron perturbs the coordination of aluminium, i.e., the corresponding Al-O bond is considerably weaker than in the unprotonated case. This leads to a large EFG, and the calculated quadrupole coupling constant (QCC) for Al-27 is 18.2 MHz. Different probe molecules were adsorbed on the Bronsted site. The hydrogen bond formed between the acid proton and the probe molecule weakens the zeolitic O-H bond. For conservation of the overall bond order of the oxygen atom, its bonds to the neighboring tetrahedral atoms (Si, Al) become stronger. As a consequence, the perturbation of the AlO4 tetrahedron and the EFG at the aluminium position decrease depending on the strength of the hydrogen bond. Perturbation of an oxygen atom of the AlO4 tetrahedron by accepting a hydrogen bond from the base molecule also affects the corresponding Al-O bond order. A linear correlation is found between the calculated QCC constants for Al-27 and the Al-O bond orders of the oxygen atoms which are perturbed by protonation or by hydrogen bonds. A geometrical shear strain parameter and a simple electrostatic point charge model are less successful at predicting the trends in EFG which clearly shows the importance of the chemical bonds. Published by Elsevier Science B.V.