Updating the Molecular–Mechanical Force Field for Organic Halides

In extension of previous molecular mechanical studies of organic halides, we examine three pathways to enlarge the scope of the force field. These are: adaptation of the constants to a new formulation of the basic force field; substitution of the monopole for the dipole approximation, in evaluating the electrostatic strain; estimation of solvation energies and conformational equilibria in solution. The structures studied are mono‐ and non‐geminal dihaloalkanes, and monohaloketones (fluorides, chlorides, bromides). We discuss the quantitative separation of steric and electrostatic effects in halocyclohexanones, and identity the minimum‐energy rotamers in haloacetones.