Analysis of the intermolecular interactions between CH₃OCH₃, CF₃OCH₃, CF₃OCF₃, and CH₂F₂, CHF₃

Abstract

Abstract The intermolecular interaction energy curves of CH 3 OCH 3 CH 2 F 2 , CF 3 OCH 3 CH 2 F 2 , CF 3 OCF 3 CH 2 F 2 , CH 3 OCH 3 CHF 3 , CF 3 OCH 3 CHF 3 , and CF 3 OCF 3 CHF 3 complexes were calculated by the MP2 level ab initio molecular orbital method using the 6‐311G** basis set augmented with diffuse polarization functions. We investigate the fluorine substitution effects of both methane and dimethyl ether on intermolecular interactions. In addition, orientation dependence of intermolecular interaction energies is also studied with utilizing eight types of orientations. Our analyses demonstrate that partial fluorinations of methane make electrostatic interaction dominant, and consequently enhance attractive interaction at several specific orientations. On the contrary, fluorine substitutions of dimethyl ether substantially decrease the electrostatic interaction between ether and CH 2 F 2 or CHF 3 ; thus, there is no such characteristic interaction between the CH of fluorinated methane and ether oxygen of CF 3 OCF 3 as conventional hydrogen bonding, due to reduced polarity of fluorinated ether. The combination of different pairs of the electrostatic interaction is therefore responsible for the intermolecular interaction differences among the complexes investigated herein and also their orientations. © 2003 Wiley Periodicals, Inc. J Comput Chem 25: 447–459, 2004