All-Atom Force Field for Molecular Dynamics Simulations on Organotransition Metal Solids and Liquids. Application to M(CO)_<i>n</i> (M = Cr, Fe, Ni, Mo, Ru, or W) Compounds

Abstract

A previously developed OPLS-based all-atom force field for organometallic compounds was extended to a series of first-, second-, and third-row transition metals based on the study of M­(CO)<i>_n</i> (M = Cr, Fe, Ni, Mo, Ru, or W) complexes. For materials that are solid at ambient temperature and pressure (M = Cr, Mo, W) the validation of the force field was based on reported structural data and on the standard molar enthalpies of sublimation at 298.15 K, experimentally determined by Calvet-drop microcalorimetry using samples corresponding to a specific and well-characterized crystalline phase: Δ_sub<i>H</i>_m^° = 72.6 ± 0.3 kJ·mol^–1 for Cr­(CO)₆, 73.4 ± 0.3 kJ·mol^–1 for Mo­(CO)₆, and 77.8 ± 0.3 kJ·mol^–1 for W­(CO)₆. For liquids, where problems of polymorphism or phase mixtures are absent, critically analyzed literature data were used. The force field was able to reproduce the volumetric properties of the test set (density and unit cell volume) with an average deviations smaller than 2% and the experimentally determined enthalpies of sublimation and vaporization with an accuracy better than 2.3 kJ·mol^–1. The Lennard-Jones (12-6) potential function parameters used to calculate the repulsive and dispersion contributions of the metals within the framework of the force field were found to be transferable between chromium, iron, and nickel (first row) and between molybdenum and ruthenium (second row)