Eyringpy is a modular program for calculating thermochemical properties and rate constants for reactions in the gas phase and in solution. The code is written in Python and it has a user‐friendly interface and a simple input format. Unimolecular and bimolecular reactions with one and two products are supported. Thermochemical properties are estimated through canonical ensemble and rate constants are computed according to the transition state theory. One‐dimensional Wigner and Eckart tunneling corrections are also available. Rate constants of bimolecular reactions involving the formation of pre‐reactive complexes are also estimated. To compute rate constants in solution, Eyringpy uses the Collins–Kimball theory to include the diffusion‐limit, the Marcus theory for electron transfer processes, and the molar fractions to account for the solvent pH effect.

Unlike other atoms, a planar tetracoordinate fluorine atom is elusive. So far, there are no theoretical or experimental reports suggesting their existence. Herein, we introduce the first six combinations (FIn4+,...

Hindered rotations are common in nature and can greatly affect thermodynamic properties. Typically, the standard rigid-rotor harmonic-oscillator approximation is used to compute thermodynamic properties; however, it often leads to serious errors, particularly for molecules with hindered rotations. Hence, to reach accurate thermodynamic predictions for such cases, the hindered rotor approximation must be applied. Different methods to compute thermodynamic properties for molecules with hindered rotations are available. Herein, we review the theoretical basis of different methods, their accuracy, and applicability. We also present the different algorithms to identify hindered rotors and obtain the input parameters for the hindered rotor model, and the software available to compute thermodynamic properties under this scheme.

The mechanism for the walk rearrangement in Dewar thiophenes has been clarified theoretically by studying the evolution of chemical bonds along the intrinsic reaction coordinates. Substituent effects on the overall mechanism are assessed by using combinations of the ring (R = H, CF3) and traveling (X = S, S = O, and CH2) groups. The origins of fluxionality in the S–oxide of perfluorotetramethyl Dewar thiophene are uncovered in this work. Dewar rearrangements are chemical processes that occur with a high degree of synchronicity. These changes are directly related to the activation energy.