The initial reaction mechanismof atomic layer deposited TiO2 thin film on the silicon surface using Cp*Ti(OCH3)(3) as the metal precursor has been investigated by using the density functional theory. We find that Cp*Ti(OCH3)(3) adsorbed state can be formed via the hydrogen bonding interaction between CH3O ligands and the Si-OH sites, which is in good agreement with the quadrupole mass spectrometry (QMS) experimental observations. Moreover, the desorption of adsorbed Cp*Ti(OCH3)(3) is favored in the thermodynamic equilibrium state. The elimination reaction of CH3OH can occur more readily than that of Cp*H during the Cp*Ti(OCH3)(3) pulse. This conclusion is also confirmed by the QMS experimental results. (C) 2012 Elsevier B. V. All rights reserved.