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The Effect of Conformers on Free Energies of Atmospheric Complexes.

Research paper by Lauri Johannes LJ Partanen, Hanna H Vehkamaki, Klavs K Hansen, Jonas J Elm, Henning H Henschel, Theo T Kurtén, Roope R Halonen, Evgeni E Zapadinsky

Indexed on: 05 Oct '16Published on: 05 Oct '16Published in: Journal of Physical Chemistry A



Abstract

In this article we show how to calculate free energies for atmospherically relevant complexes when multiple conformers and/or isomers are present. We explain why the thermal averaging methods used in several published works are not correct. Based on our two sample cases, the sulfuric acid - pinic acid complex and the (H2SO4)3(NH3)3(H2O)4 cluster,we provide numerical evidence that the use of these incorrect formulae can result in errors larger than one kcal/mol. We recommend that if vibrational frequencies and thus Gibbs free energies of the individual conformers are unavailable, one should not attempt to correct for the presence of multiple conformers and instead use only the global minimum conformers for both reactants and products. On the other hand, if the free energies for the conformers are calculated for both reactants and products, their effect can be accounted for by the statistical mechanical methods presented in this article.