Theoretical investigations of reactions between AlH(1Σ) and XνH (X=Cl, OH)

Abstract

Reaction paths of AlH(¹Σ) with X–H (X=Cl, OH) are characterized by the HF/6-31G(d), MP2(fc)/6-31G(d) and MP2(full)/6-31G(d) levels, respectively; energies of reactions and barriers are calculated by the G2 level of theory and MP4SDQ/6-31G(d)//MP2(fc)/6-31G(d). The calculations show that there are two parallel reaction channels: one is an addition reaction to give H₂AlX via the three-membered ring transition state (TS); the other is a dehydrogenation reaction to give (AlX+H₂) via the four-membered ring TS. General statistical thermodynamics (GST) and Eyring transition state theory (TST) with Wigner correction are also used to compute the thermodynamic functions, equilibrium constants, A factors, and rate constants of these reaction channels at 100–1100 K. The results show that the unique product (AlX+H₂) is to be obtained.