### Abstract

In this work a complete and consistent set of 95 Benson group additive values (GAVs) for standard entropies S° and heat capacities Cp° of hydrocarbons and hydrocarbon radicals is presented. These GAVs include 46 groups, among which 25 radical groups, which, to the best of our knowledge, have not been reported before. The GAVs have been determined from a set of B3LYP/6-311G(d,p) ideal gas statistical thermodynamics values for 265 species, consistently with previously reported GAVs for standard enthalpies of formation. One-dimensional hindered rotor corrections for all internal rotations are included. The computational methodology has been compared to experimental entropies (298 K) for 39 species, with a mean absolute deviation (MAD) between experiment and calculation of 1.2 J mol−1 K−1, and to 46 experimental heat capacities (298 K) with a resulting MAD = 1.8 J mol−1 K−1. The constructed database allowed evaluation of corrections on S° and Cp° for non-nearest-neighbor effects, which have not been determined previously. The group additive model predicts the S° and Cp° within 5 J mol−1 K−1 of the ab initio values for 11 of the 14 molecules of the test set, corresponding to an acceptable maximal deviation of a factor of 1.6 on the equilibrium coefficient. The obtained GAVs can be applied for the prediction of S° and Cp° for a wide range of hydrocarbons and hydrocarbon radicals. The constructed database also allowed determination of a large set of hydrogen bond increments, which can be useful for the prediction of radical thermochemistry.