The Functional Form of Angular Forces around Transition Metal Ions in Biomolecules

Physics – Condensed Matter – Soft Condensed Matter

Scientific paper

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Latex source, 9 postscript figures

Scientific paper

10.1016/S0006-3495(01)75675-5

A method for generating angular forces around $\sigma$-bonded transition metal ions is generalized to treat $\pi$-bonded configurations. The theoretical approach is based on an analysis of a ligand-field Hamiltonian based on the moments of the electron state distribution. The functional forms that are obtained involve a modification of the usual expression of the binding energy as a sum of ligand-ligand interactions, which however requires very little increased in CPU time. The angular interactions have simple forms involving sin and cos functions, whose relative weights depend on whether the ligands are $\sigma$- or $\pi$-bonded. They describe the ligand-field stabilization energy to an accuracy of about 10%. The resulting force field is used to model the structure of small clusters, including fragments of the copper blue protein structure. Large deviations from the typical square copper coordination are found when $\pi$-bonded ligands are present.

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