DOE OSTI2018
A priori rate predictions for gas phase reactions have undergone a gradual but dramatic transformation, with current predictions often rivaling the accuracy of the best available experimental data. The utility of such kinetic predictions would be greatly magnified if they could more readily be implemented for large numbers of systems. Here, we report the development of a new computational environment, namely, EStokTP, that reduces the human effort involved in the rate prediction for single channel reactions essentially to the specification of the methodology to be employed. The code can also be used to obtain all the necessary master equation building blocks for more complex reactions. In general, the prediction of rate constants involves two steps, with the first consisting of a set of electronic structure calculations and the second in the application of some form of kinetic solver, such as a transition state theory (TST)-based master equation solver. EStokTP provides a fully integrated treatment of both steps through calls to external codes to perform first the electronic structure and then the master equation calculations. It focuses on generating, extracting, and organizing the necessary structural properties from a sequence of calls to electronic structure codes, with robust automatic failure recovery options to limit human intervention. The code implements one or multidimensional hindered rotor treatments of internal torsional modes (with automated projection from the Hessian and with optional vibrationally adiabatic corrections), Eckart and multidimensional tunneling models (such as small curvature theory), and variational treatments (based on intrinsic reaction coordinate following). This focus on a robust implementation of high-level TST methods allows the code to be used in high accuracy studies of large sets of reactions, as illustrated here through sample studies of a few hundred reactions. At present, the following reaction types are implemented in EStokTP: abstraction, addition, isomerization, and beta-decomposition. Finally, preliminary protocols for treating barrierless reactions and multiple-well and/or multiple-channel potential energy surfaces are also illustrated.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗