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Thermochemistry of gas-phase species relevant to titanium nitride CVD

Conference ·
OSTI ID:95424
; ; ; ; ;  [1];  [2]
  1. Sandia National Labs., Livermore, CA (United States)
  2. Sandia National Labs., Albuquerque, NM (United States)
In this work, three different ab initio methods are used to predict bond dissociation enthalpies (BDE) and atomization energies for TiCl{sub n} (n = 1-4) and Ti(NH{sub 2})n (n = 1-4) compounds, as well as for the complex TiCl{sub 4}:NH{sub 3}. There is considerable variation in the predicted BDES, even for highly electron-correlated methods. However, bond-additivity corrections applied to coupled-cluster calculations at the CCSD(T) level, expected to be the most reliable of the three methods, yield Ti-Cl BDEs in good agreement with experimental results. An experimental estimate of the TiCl{sub 4} BDE is also reported that is consistent with the ab initio results and recent experiments by others indicating that the TiCl{sub 3} heat of formation reported in the JANAF Tables is too low. Finally, the predicted BDEs indicate that the gas-phase reaction of TiCl{sub 4} and NH{sub 3} to form the complex Cl{sub 4}Ti:NH{sub 3} is exothermic by 17 kcal mol{sub {minus}1}. In addition, decomposition of the complex to form Cl{sub 3}TiNH{sub 2} and HCl is endothermic by 20 kcal mol{sup {minus}1}.
Research Organization:
Sandia National Labs., Livermore, CA (United States)
Sponsoring Organization:
USDOE, Washington, DC (United States); Department of Defense, Washington, DC (United States)
DOE Contract Number:
AC04-94AL85000
OSTI ID:
95424
Report Number(s):
SAND--95-8636; CONF-9505243--1; ON: DE95014353
Country of Publication:
United States
Language:
English

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