Abstract
Using third-order perturbation theory, effective London dispersion forces between two molecules in a medium are evaluated. The reduction in the pair interaction is calculated for spherical and polymeric bodies at various separations. For nearest neighbors in pure liquids, pair potentials decrease by 1.8% in helium, and 32% in carbon tetrachloride. The contribution to the total energy of the liquid is one-third of this. The dispersion forces between lateral base pairs in a single DNA double helix decrease by about 28% due to third- and fourth-order perturbations involving the four neighboring bases of each pair. Solvent effects cause an additional decrease of 14% (in water) to 18% (in formamide). The guanine-cytosine and adenine-thymine pairs change similarly. In general between segments of any two typical linear polymer chains (ionization potential of 10 V), dispersion forces decrease between 17% and 22% in water. In the theoretical sections, operator and diagrammatic techniques are presented which simplify the calculation of higher-order effects. We also show that dispersion forces do not decrease as the square of the high-frequency dielectric constant of the solvent, since this does not include the attractive many-body correlations which reduce the effect of the medium on the pair potential.
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Dates
Type | When |
---|---|
Created | 20 years, 7 months ago (Jan. 9, 2005, 1:59 a.m.) |
Deposited | 1 year, 6 months ago (Feb. 8, 2024, 4:33 p.m.) |
Indexed | 1 year, 6 months ago (Feb. 10, 2024, 9:29 a.m.) |
Issued | 62 years, 4 months ago (April 1, 1963) |
Published | 62 years, 4 months ago (April 1, 1963) |
Published Print | 62 years, 4 months ago (April 1, 1963) |
@article{Kestner_1963, title={Effective Intermolecular Pair Potentials in Nonpolar Media}, volume={38}, ISSN={1089-7690}, url={http://dx.doi.org/10.1063/1.1776947}, DOI={10.1063/1.1776947}, number={7}, journal={The Journal of Chemical Physics}, publisher={AIP Publishing}, author={Kestner, Neil R. and Sinanoğlu, Oktay}, year={1963}, month=apr, pages={1730–1739} }