Theoretical investigations of reactions between AlH((1)Sigma) and X-H (X =Cl, OH)

Reaction paths of AlH((1)Sigma) 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, respective ly; energies of reactions and barriers are calculated by the G2 level of th eory and MP4SDQ/6-31G(d)//MP2(fc)/6-31G(d). The calculations show that ther e are two parallel reaction channels: one is an addition reaction to give H 2AlX via the three-membered ring transition state (TS); the other is a dehy drogenation reaction to give (AlX + H-2) via the four-membered ring TS. Gen eral statistical thermodynamics (GST) and Eyring transition state theory (T ST) with Wigner correction are also used to compute the thermodynamic funct ions, equilibrium constants, A factors, and rate constants of these reactio n channels at 100-1100 K. The results show that the unique product (AlX + H -2) is to be obtained.