Predicting the structure and NMR coupling constant 1J(129Xe–19F) of XeF6 using quantum mechanics methods

Abstract

The XeF₆ molecule exists as a monomer in the gas phase and as the (XeF₆)₄ tetramer in solution. Herein we used distinct quantum mechanics methods to study the conformational equilibrium for the XeF₆ monomer, which is represented mainly by O_h and C_3v symmetric geometries, and for the (XeF₆)₄ structure found in condensate phases. The NMR ¹J(¹²⁹Xe–¹⁹F) coupling constant is predicted using our own NMR-DKH basis set, designed for NMR properties. The C_3v conformer of XeF₆ was stable only with HF, CCSD, and hybrid DFT functionals with at least 28% exact HF exchange. Increasing the % of HF exchange improves the description of the geometry and the O_h → C_3v equilibrium. The BMK, BHandHLYP and LC-ωPBE functionals produce results in excellent agreement with experiments and high-level calculations for the XeF₆ molecule. When it comes to the ¹J(¹²⁹Xe–¹⁹F) coupling constant, the (XeF₆)₄ structure must be considered. For that compound, BHandHLYP leads to the best structure, and BMK leads to the best coupling constant; therefore, the generalized protocol BMK/NMR-DKH//BHandHLYP/def2-SVP is recommended to study the XeF₆ molecule in the gas phase and solution.