Ab initio calculation of entropy and heat capacity of gas-phase n-alkanes with hetero-elements O and S: Ethers/alcohols and sulfides/thiols

P. Vansteenkiste, T. Verstraelen, V. Van Speybroeck, M. Waroquier
Chemical Physics
328 (1-3), 251-258
2006
A1

Abstract 

In this paper, the performance of the one-dimensional hindered rotor approach (1D-HR) is evaluated for n-alkanes with hetero-elements O or S. The internal rotations in these molecules show a behavior distinct from those in n-alkanes, for which 1D-HR is a cost-efficient method to describe the thermochemical features (entropy and heat capacity). It turns out that also for ethers, alcohols, sulfides and thiols this approach gives a satisfactory experimental agreement. This work confirms earlier results, and consolidates the assumption that the 1D-HR model is highly suitable for reproducing thermodynamic properties of single chain molecules, and that multi-dimensional coupled hindered rotor approaches (nD-HR) are not necessarily required for attaining high accuracy. Moreover, it seems that the 1D-HR results are almost independent of the details of the level of theory.