Theoretical study of the insertion reactions of aluminum with H₂O, NH₃, HCl, and Cl₂

Abstract

Stationary points on the potential energy surfaces describing the reactions between Al and H2O, NH3, HCl, and Cl2 respectively, have been optimized at the ab initio MP2 and QCISD levels as well as by density functional theory (DFT) using the B3LYP functional and the 6-31G(d,p) basis set. Reaction energies were computed using the MP2 and B3LYP methods and the QCISD and CCSD(T) methods in conjunction with the 6-311+G(2df,p) and 6-31G(d,p) bases, respectively. Isotropic hyperfine coupling constants (hfcc's) of Al, N, Cl, and H were computed using the MP2, B3LYP, and QCISD methods in conjunction with the 6-311+G(2df,p) basis, and at the PWP86/IGLO-III level for isotropic and anisotropic coupling constants. For HAlCl and AlCl2, the theoretical study predicts positive isotropic Cl hyperfine coupling constants at variance with the previously reported experimental values. A revised analysis of the experimental ESR spectra led to new assignments of the Cl hyperfine coupling tensors, in agreement with the computed results.