Molecular dynamics simulations of organolithium aggregates in solution are reported for the first time. We use a combined
quantum/classical force field (the so-called QM/MM approach) and study ethyl-lithium aggregates in dimethyl ether (DME) solvent.
The solutes are described at the Density Functional Theory level while solvent molecules are described using molecular mechanics.
NVT Molecular Dynamics simulations at 200 K are carried out in the Born–Oppenheimer approximation. After equilibration, the
production phase was run for 80 ps (monomer), 40 ps (dimer) and 26 ps (tetramer). The analysis of the results focuses on Li
coordination as a function of aggregate size and we show that the total Li coordination number is always 4. No decoordination
has been observed along the simulations. Fluctuations of the structures are predicted to be large in some cases and possible
implications on reactivity are discussed.
Keywords Organolithium compounds - QM/MM - Molecular dynamics simulations - Solvent effects