The purpose of the present investigation is to calculate partition functions and thermodynamic quantities, viz., entropy, enthalpy, heat capacity, and Gibbs free energies, for 1-butanol, 2-methyl-1-propanol, and butanal in the vapor phase. We employed the multi-structural (MS) anharmonicity method and electronic structure calculations including both explicitly correlated coupled cluster theory and density functional theory. The calculations are performed using all structures for each molecule and employing both the local harmonic approximation (MS-LH) and the inclusion of torsional anharmonicity (MS-T). The results obtained from the MS-T calculations are in excellent agreement with experimental data taken from the Thermodynamics Research Center data series and the CRC Handbook of Chemistry and Physics, where available. They are also compared with Bensons empirical group additivity values, where available; in most cases, the present results are more accurate than the group additivity values. In other cases, where experimental data (but not group additivity values) are available, we also obtain good agreement with experiment. This validates the accuracy of the electronic structure calculations when combined with the MS-T method for estimating the thermodynamic properties of systems with multiple torsions, and it increases our confidence in the predictions made with this method for molecules and temperatures where experimental or empirical data are not available.
|Original language||English (US)|
|Journal||Journal of Chemical Physics|
|State||Published - Jan 21 2012|
Bibliographical noteFunding Information:
The authors are grateful to Jingjing Zheng for valuable contributions to this work. This work was supported in part by the US Department of Energy, Office of Science, Office of Basic Energy Science, as part of the Combustion Energy Frontier Research Center under Award Number DE-SC0001198. Some of the computations were performed as part of a Computational Grand Challenge grant at the Molecular Science Computing Facility in the William R. Wiley Environmental Molecular Sciences Laboratory, a national scientific user facility sponsored by the US Department of Energy's Office of Biological and Environmental Research and located at the Pacific Northwest National Laboratory, operated for the Department of Energy by Battelle.