A force field for MD simulations on rhenium organometallic compounds developed from enthalpy of sublimation and X-ray diffraction measurements

Abstract

The standard (p° = 0.1 MPa) molar enthalpies of sublimation, at 298.15 K, of methyltrioxorhenium(VII), ΔsubHmo[CH3ReO3] = 70.2 ± 0.4 kJ mol−1, and dirhenium decacarbonyl, ΔsubHmo[Re2(CO)10] = 97.4 ± 0.9 kJ mol−1, corresponding to well characterized crystalline phases, were determined by Calvet microcalorimetry. These results, along with structural information obtained in this work by single crystal X-ray diffraction for CH3ReO3, or previously reported for Re2(CO)10, tetramethylammonium perrhenate(VII), [N1111][ReO4], and hexamethylrhenium(VI), Re(CH3)6, were used to extend our previously developed all-atom force field for organometallic compounds, to rhenium species. The new parametrization was able to reproduce the enthalpies of sublimation and unit cell parameters of the test set with maximum absolute deviations of 3.3 kJ⋅mol−1 and <3.8%, respectively. The transferability of the interaction (ε) and atomic diameter (σ) parameters of the Lennard-Jones (12–6) potential function, observed for first and second-row transition metals, was also found to be valid for rhenium and tungsten (third-row metals).