An integrated protocol to study hydrogen abstraction reactions by atomic hydrogen in flexible molecules: application to butanol isomers.

ABSTRACT

This work presents a protocol designed to study hydrogen abstraction reactions by atomic hydrogen in molecules with multiple conformations. The protocol starts with the search and location of the conformers of the equilibrium structures using the TorsiFlex program. By a simple modification of the starting geometry of reactants, a Python script generates the input for the hydrogen abstraction transition states. Initially, the search of the stationary points (reactants and transition states) is carried out at a low-level employing firstly a preconditioned search and secondly a random search. The low-level conformers were reoptimized using a higher level electronic structure method. This information allows the evaluation of the multistructural harmonic-oscillator partition functions, which are corrected for zero-point energy anharmonicity by the hybrid degeneracy-corrected second-order vibrational perturbation theory and for torsional anharmonicity by the multistructural torsional method, as implemented in the MsTor program. The structural information of the stationary points is used by Pilgrim to evaluate the multipath canonical variational transition state theory thermal rate constants with multidimensional small-curvature corrections for tunneling. Therefore, the thermal rate constants include variational (recrossing) and tunneling effects in addition to the effect of multiple conformations on the thermal rate constants. These features grant the applicability of the method to a wide range of temperatures. The method was applied to each of the hydrogen abstraction sites of the four isomers of butanol. The methodology employed allowed us to calculate the thermal rate constants in the temperature range of 250-2500 K and to accurately fit them to analytical expressions. The variety of abstraction sites shows that the protocol is robust and that it can be employed to study hydrogen abstraction reactions in molecules containing carbon and oxygen as heavy atoms.