First-Principles Thermochemistry for the Thermal Decomposition of Titanium Tetraisopropoxide

The thermal decomposition of titanium
tetraisopropoxide (TTIP)
is investigated using quantum chemistry, statistical thermodynamics,
and equilibrium composition analysis. A set of 981 Ti-containing candidate
species are proposed systematically on the basis of the thermal breakage
of bonds within a TTIP molecule. The ground state geometry, vibrational
frequencies and hindrance potentials are calculated for each species
at the B97-1/6-311+G­(d,p) level of theory. Thermochemical data are
computed by applying statistical thermodynamics and, if unknown, the
standard enthalpy of formation is estimated using balanced reactions.
Equilibrium composition calculations are performed under typical combustion
conditions for premixed flames. The thermodynamically stable decomposition
products for different fuel mixtures are identified. A strong positive
correlation is found between the mole fractions of Ti species containing
carbon and the TTIP precursor concentration.