Non‐bonded interatomic potential functions and crystal structure. Correction of the functions for use with macromolecules and application to polypeptide helixes

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Abstract
On the basis of a set of nonbonded interatomic potential functions derived earlier from heats of sublimation and experimental crystal structures, we derive a second, less repulsive, set which is to be used in the absence of the expansion caused by thermal motion and in particular in macromolecular systems where thermal motion is much reduced compared with crystals of small molecules. Working with a pair of octane molecules, we calculate the intermolecular potential (U) in the presence of thermal motion from potentials U° (in the absence of thermal motion), by letting a system of pairs of molecules assume a Boltzmann distribution over the intermolecular distance, in the presence of a force of varied magnitude applied to obtain different equilibrium distances. The potential U° is adjusted until the calculated and the empirical potentials U agree. Finally, best interatomic Lennard‐Jones potentials which reproduce the function U° are calculated. The resulting functions are tested by calculating the crystal structure of benzene and comparing it with experimental data at low temperature, by energy minimization of the crystal structure of polyethylene and of the β‐structure of poly‐L‐alanine, and by comparing the energy of the α‐helix and the β‐structure of poly‐L‐alanine. In all cases, the corrected functions give more satisfactory results than the uncorrected set.