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Assessment of model chemistries for hydrofluoropolyethers: A DFT/M08‐HX benchmark study
Author(s) -
Viegas Luís P.
Publication year - 2017
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/qua.25381
Subject(s) - benchmark (surveying) , work (physics) , computational chemistry , conformational isomerism , reduction (mathematics) , chemistry , computer science , mathematical optimization , mathematics , statistical physics , physics , molecule , thermodynamics , organic chemistry , geometry , geodesy , geography
In this work, we report the first detailed theoretical comparative conformational investigation between two different classes of hydrofluoropolyethers: dihydro‐ and dimethoxyfluoropolyethers. The main objective was to determine a cost‐effective computational methodology that could accurately reproduce the energetic rankings and thermal weight factors of the simplest examples of those two classes calculated with M08‐HX/triple‐ ζ //M08‐HX/double‐ ζ benchmark model chemistries. Between the tested methodologies, M08‐HX/aug‐pcseg‐2//M08‐HX/pcseg‐1 was found to be the most appropriate, exhibiting a good accuracy and considerable reduction in computational cost with respect to the benchmark, being more than three times faster than M08‐HX/aug‐pcseg‐2//M08‐HX/aug‐pcseg‐1. This cost‐effective approach will be essential in future work when studying larger hydrofluoropolyethers, where the computational complexity associated with increasing number of conformers will require such approximations.