Ab Initio Description of the Structure and Interaction Energy of Perhalomethane Dimers
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The intermolecular interactions in (CX4)2 dimers (X = H, F, Cl, Br, I) were studied by the ab initio methods. The calibration values of the energies and bond lengths of the dimers were obtained by the coupled-cluster method taking into account single and double excitations and the non-iterative correction for triple excitations (CCSD(T)) with Dunning’s basis sets complemented with bond functions centered between the carbon atoms, followed by extrapolation to the infinite basis set limit. An analysis of the constructed PES cross sections of the (CX4)2 dimers allowed us to substantially refine the dissociation energies for (CCl4)2 and (CBr4)2 from previous calculations and to evaluate the dissociation energy of the (CI4)2 dimer. The constructed correlations between the calculated dissociation energies of the (CX4)2 dimers and the polarizabilities of CX4 revealed the critical role of polarizability of individual molecules in the variation of the physical properties of CX4 dimers with X changed from fluorine to iodine.
Keywords:dimers van der Waals interaction bond functions polarizability
We are grateful to N.F. Stepanov for useful discussion of the results, to D.A. Shulga for discussing the interaction in halogenated systems, and to T.M. Ro-shchina for discussing the importance of describing the interaction during the adsorption of perfluorinated compounds. This study was financially supported by the Russian Scientific Foundation (grant no. 17-13-01466). The calculations were performed using the computer resources of the Research Computing Center, Moscow State University, and of the Skolkovo Institute of Science and Technology.
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