Automated Transition State Theory Calculations for High-Throughput Kinetics

A scarcity
of known chemical kinetic parameters leads to the use
of many reaction rate estimates, which are not always sufficiently
accurate, in the construction of detailed kinetic models. To reduce
the reliance on these estimates and improve the accuracy of predictive
kinetic models, we have developed a high-throughput, fully automated,
reaction rate calculation method, AutoTST. The algorithm integrates
automated saddle-point geometry search methods and a canonical transition
state theory kinetics calculator. The automatically calculated reaction
rates compare favorably to existing estimated rates. Comparison against
high level theoretical calculations show the new automated method
performs better than rate estimates when the estimate is made by a
poor analogy. The method will improve by accounting for internal rotor
contributions and by improving methods to determine molecular symmetry.