| Abstract: | Thermodynamic equilibrium and kinetics of the gas‐phase reaction between TiCl4 and NH3 have been studied computationally using results from recent quantum mechanical calculations of titanium tetrachloride ammonolysis. 1 These calculations were based upon the transition state theory for the direct reactions and RRKM theory for the reactions proceeding via intermediate complex. Rate constants for the barrierless reactions were expressed through the thermodynamic characteristics of the reagents and products using a semiempirical variational method. The kinetic simulation of the gas‐phase steps of CVD was performed within a model of a well‐stirred reactor at temperatures 300–1200 K and residence times between 0.1–2 s. At temperatures below 450 K formation of donor–acceptor complexes between TiCl4 and NH3 is the dominating process. At higher temperatures sequential direct ammonolysis takes place. At typical LPCVD conditions the only product of the first step of ammonolysis, TiCl3NH2, is formed in substantial amount. © 2001 John Wiley & Sons, Inc. J Comput Chem 22: 1366–1376, 2001 |
