Conformational Properties of Macromolecules by A. J. Hopfinger

By A. J. Hopfinger

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Such a nonspherical distribution of " b u l k " in atoms probably is a contributing factor to the variations found in the contact distances. Inherently related to the shape of the atom is the electron density found on the atom. Since each atom has a unique characteristic electronegativity it HI. Nonbonded Potential Functions 43 follows that in a bonded system of atoms the distribution of charge is not uniform. T h u s molecules are found to have dipole moments. Realistic conformational calculations should include the energy contributions due to the interaction of the charge distribution (s) on a given molecule or set of molecules.

L n e j and rj ^2j e,X. nj *-< r, m «-Σ (n) ejYnj J=l t,Z. nj mz A = ^11 ^12 ^13 ^21 ^22 ^23 \Anl where A n2 An3 ··· SXij — ru Ί 0 0^ 4, = |0 1 0|, [0 0 1, ^4n SYijXij 'SZijXij 'u AiJ = -ai 3 ^ 0 ' ^ij J Yi2f — rf ,· * *ij Zij 'ij 'ij 3^u ^u 3 Ytj Zij 2 "ij — 'U 'ij VI. The Concept of a Dielectric on the Molecular Level 59 W e can solve these simultaneous equations by any n u m b e r of methods, some of which will be discussed later, for the set of triplets {m

However, we do know t h a t atoms, and groups of atoms, are polarizable and thus rc-body (n > 2) interactions must be considered. T o begin a n analysis of the rc-body interactions let us divide each of the types of inter­ actions into two separate classes, namely, bonded interactions and nonbonded interactions. I n other words we can write the terms in (2-1) as Vtj = VU(B) + vu(NB) (2-2) Vijk=ViJk(B)+viJk(NB) (2-3) Vijkl=Vijkl(B)+viJkl(NB) (2-4) 44 2. Conformational Energies and Potential Functions (B indicates bonded and NB nonbonded).

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