Statistical mechanics of chemical equilibria and intramolecular structures of nonrigid molecules in condensed phases

David Chandler; Lawrence R. Pratt

doi:10.1063/1.433529

journal article Oct 15, 1976

Statistical mechanics of chemical equilibria and intramolecular structures of nonrigid molecules in condensed phases

David Chandler

Lawrence R. Pratt

The Journal of Chemical Physics Vol. 65 No. 8 pp. 2925-2940 · AIP Publishing

View at Publisher Save 10.1063/1.433529

Abstract

An exact classical statistical mechanical theory is developed which describes how intermolecular forces alter the average intramolecular structures of nonrigid molecules and how these forces affect the equilibrium constant of chemically reacting species. The theory lends itself to computationally convenient approximations. Three illustrative applications of the theory are given. First, the equilibrium constant for the reaction N2O2?2NO2 is studied. Second, the shift in the chemical bond lengths of N2 and O2 from their gas phase values to those in the liquid are calculated from the theory. Third, the average conformational structure of n-butane in various dense fluid solvents is predicted. The basic methods used in the derivation of the theory are the techniques of physical cluster series (as opposed to the usual Mayer ’’mathematical’’ cluster expansions), and topological reductions. The formalism gives rise to a renormalization of chemical bonding Boltzmann factors so that the theoretical expressions are not swamped by essentially infinite and unnormalized cluster functions. Along with the results on chemical equilibria and intramolecular structures, the interaction site cluster series for intermolecular correlation functions is rederived in a more general manner than the derivation originally presented by Ladanyi and Chandler.

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References

39

[1]

Ann. Rev. Phys. Chem. (1973) 10.1146/annurev.pc.24.100173.001505

[2]

Mol. Phys. (1973) 10.1080/00268977300102411

[3]

Mol. Phys. (1974) 10.1080/00268977400101181

[4]

J. Chem. Phys. (1974) 10.1063/1.1681931

[5]

J. Chem. Phys. (1974) 10.1063/1.1682485

[6]

J. Chem. Phys. (1975) 10.1063/1.431339

[7]

J. Chem. Phys. (1976) 10.1063/1.432458

[8]

[9]

Optimized Cluster Expansions for Classical Fluids. II. Theory of Molecular Liquids

David Chandler, Hans C. Andersen

The Journal of Chemical Physics 1972 10.1063/1.1678513

[10]

J. Chem. Phys. (1973)

[11]

J. Chem. Phys. (1973) 10.1063/1.1680038

[12]

J. Chem. Phys. (1975) 10.1063/1.430278

[13]

J. Chem. Phys. (1974) 10.1063/1.1681868

[14]

[15]

Chem. Phys. (1976) 10.1016/0301-0104(76)80039-0

[16]

J. Chem. Phys. (1975) 10.1063/1.431001

[17]

Mol. Phys. (1976) 10.1080/00268977600100941

[18]

J. Chem. Phys. (1976) 10.1063/1.432793

[19]

[20]

[21]

J. Chem. Phys. (1939) 10.1063/1.1750413

[22]

J. Chem. Phys. (1939) 10.1063/1.1750444

[23]

J. Chem. Phys. (1963) 10.1063/1.1776907

[24]

J. Chem. Phys. (1968) 10.1063/1.1669709

[25]

J. Chem. Phys. (1968) 10.1063/1.1669710

[26]

J. Chem. Phys. (1971) 10.1063/1.1675356

[27]

J. Chem. Phys. (1971) 10.1063/1.1675357

[28]

Progr. Theor. Phys. (1961) 10.1143/ptp.25.537

[29]

[30]

J. Chem. Phys. (1968) 10.1063/1.1669587

[31]

Mol. Phys. (1972) 10.1080/00268977200101431

[32]

[33]

J. Phys. Chem. (1961) 10.1021/j100829a037

[34]

J. Chem. Soc. (1891) 10.1039/ct8915901076

[35]

J. Chem. Soc. (1895) 10.1039/ct8956700794

[36]

[37]

Mol. Phys. (1975) 10.1080/00268977500100491

[38]

[39]

Conformational Analysis of Macromolecules. II. The Rotational Isomeric States of the Normal Hydrocarbons

Roy A. Scott, Harold A. Scheraga

The Journal of Chemical Physics 1966 10.1063/1.1727180

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Citations

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References

Details

Published: Oct 15, 1976
Vol/Issue: 65(8)
Pages: 2925-2940

Authors

D

David Chandler

School of Chemical Sciences, University of Illinois, Urbana, Illinois 61801

L

Lawrence R. Pratt

School of Chemical Sciences, University of Illinois, Urbana, Illinois 61801

Cite This Article

David Chandler, Lawrence R. Pratt (1976). Statistical mechanics of chemical equilibria and intramolecular structures of nonrigid molecules in condensed phases. The Journal of Chemical Physics, 65(8), 2925-2940. https://doi.org/10.1063/1.433529

Statistical mechanics of chemical equilibria and intramolecular structures of nonrigid molecules in condensed phases

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