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Combining rules

2011-11-18T10:55:26Z

128.178.234.123: /* Kong rules */

The '''combining rules''' (also known as ''mixing rules'') are geometric expressions designed to provide the interaction energy between two dissimilar non-bonded atoms (here labelled <math>i</math> and <math>j</math>). Most of the rules are designed to be used with a specific [[Idealised models| interaction potential]] in mind.
==Admur and Mason==
For the [[second virial coefficient]] of a mixture
<ref>[http://dx.doi.org/10.1063/1.1724353 I. Amdur and E. A. Mason "Properties of Gases at Very High Temperatures", Physics of Fluids '''1''' pp. 370-383 (1958)]</ref>
:<math>B_{ij} = \frac{\left(B_{ii}^{1/3}+B_{jj}^{1/3}\right)^3}{8}</math>
==Böhm-Ahlrichs==
<ref>[http://dx.doi.org/10.1063/1.444057 Hans‐Joachim Böhm and Reinhart Ahlrichs "A study of short‐range repulsions", Journal of Chemical Physics '''77''' pp. 2028- (1982)]</ref>
==Diaz Peña-Pando-Renuncio==
<ref>[http://dx.doi.org/10.1063/1.442726 M. Diaz Peña, C. Pando, and J. A. R. Renuncio "Combination rules for intermolecular potential parameters. I. Rules based on approximations for the long-range dispersion energy", Journal of Chemical Physics '''76''' pp. 325- (1982)]</ref>
<ref>[http://dx.doi.org/10.1063/1.442727 M. Diaz Peña, C. Pando, and J. A. R. Renuncio "Combination rules for intermolecular potential parameters. II. Rules based on approximations for the long-range dispersion energy and an atomic distortion model for the repulsive interactions", Journal of Chemical Physics '''76''' pp. 333- (1982)]</ref>
==Fender-Halsey==
The Fender-Halsey combining rule for the [[Lennard-Jones model]] is given by <ref>[http://dx.doi.org/10.1063/1.1701284 B. E. F. Fender and G. D. Halsey, Jr. "Second Virial Coefficients of Argon, Krypton, and Argon-Krypton Mixtures at Low Temperatures", Journal of Chemical Physics '''36''' pp. 1881-1888 (1962)]</ref>
:<math>\epsilon_{ij} = \frac{2 \epsilon_i \epsilon_j}{\epsilon_i + \epsilon_j}</math>
==Gilbert-Smith==
The Gilbert-Smith rules for the [[Born-Huggins-Meyer potential]]<ref>[http://dx.doi.org/10.1063/1.1670463 T. L. Gilbert "Soft‐Sphere Model for Closed‐Shell Atoms and Ions", Journal of Chemical Physics '''49''' pp. 2640- (1968)]</ref><ref>[http://dx.doi.org/10.1063/1.431848 T. L. Gilbert, O. C. Simpson, and M. A. Williamson "Relation between charge and force parameters of closed‐shell atoms and ions", Journal of Chemical Physics '''63''' pp. 4061- (1975)]</ref><ref>[http://dx.doi.org/10.1103/PhysRevA.5.1708 Felix T. Smith "Atomic Distortion and the Combining Rule for Repulsive Potentials", Physical Review A '''5''' pp. 1708-1713 (1972)]</ref>.
==Good-Hope rule==
The Good-Hope rule for [[Mie potential |Mie]]–[[Lennard-Jones model |Lennard‐Jones]] or [[Buckingham potential]]s <ref>[http://dx.doi.org/10.1063/1.1674022 Robert J. Good and Christopher J. Hope "New Combining Rule for Intermolecular Distances in Intermolecular Potential Functions", Journal of Chemical Physics '''53''' pp. 540- (1970)]</ref> is given by (Eq. 2):

:<math>\sigma_{ij} = \sqrt{\sigma_{ii} \sigma_{jj}}</math>
==Hudson and McCoubrey==
<ref>[http://dx.doi.org/10.1039/TF9605600761 G. H. Hudson and J. C. McCoubrey "Intermolecular forces between unlike molecules. A more complete form of the combining rules", Transactions of the Faraday Society '''56''' pp. 761-766 (1960)]</ref>
==Kong rules==
<ref>[http://dx.doi.org/10.1063/1.1680358 Chang Lyoul Kong "Combining rules for intermolecular potential parameters. II. Rules for the Lennard-Jones (12–6) potential and the Morse potential", Journal of Chemical Physics '''59''' pp. 2464-2467 (1973)]</ref>

<math>\epsilon_{ij}\sigma_{ij}^{6}=\left(\epsilon_{ii}\sigma_{ii}^{6}\epsilon_{jj}\sigma_{jj}^{6}\right)^{\frac{1}{2}}</math>

<math> \epsilon_{ij}\sigma_{ij}^{12} = \frac{\epsilon_{ii}\sigma_{ii}^{12}}{2^{13}}\left[ 1+\left( \frac{\epsilon_{jj}\sigma_{jj}^{12}}{\epsilon_{ii}\sigma_{ii}^{12}} \right)^{\frac{1}{13}}\right]^{13} </math>

==Lorentz-Berthelot rules==
The Lorentz rule is given by <ref>[http://dx.doi.org/10.1002/andp.18812480110 H. A. Lorentz "Ueber die Anwendung des Satzes vom Virial in der kinetischen Theorie der Gase", Annalen der Physik '''12''' pp. 127-136 (1881)]</ref>
:<math>\sigma_{ij} = \frac{\sigma_{ii} + \sigma_{jj}}{2}</math>

which is only really valid for the [[hard sphere model]].

The Berthelot rule is given by <ref>[http://visualiseur.bnf.fr/Document/CadresPage?O=NUMM-3082&I=1703 Daniel Berthelot "Sur le mélange des gaz", Comptes rendus hebdomadaires des séances de l’Académie des Sciences, '''126''' pp. 1703-1855 (1898)]</ref>

:<math>\epsilon_{ij} = \sqrt{\epsilon_{ii} \epsilon_{jj}}</math>

These rules are simple and widely used, but are not without their failings <ref>[http://dx.doi.org/10.1080/00268970010020041 Jérôme Delhommelle; Philippe Millié "Inadequacy of the Lorentz-Berthelot combining rules for accurate predictions of equilibrium properties by molecular simulation", Molecular Physics '''99''' pp. 619-625 (2001)]</ref>
<ref>[http://dx.doi.org/10.1080/00268970802471137 Dezso Boda and Douglas Henderson "The effects of deviations from Lorentz-Berthelot rules on the properties of a simple mixture", Molecular Physics '''106''' pp. 2367-2370 (2008)]</ref>
<ref>[http://dx.doi.org/10.1063/1.1610435 W. Song, P. J. Rossky, and M. Maroncelli "Modeling alkane+perfluoroalkane interactions using all-atom potentials: Failure of the usual combining rules", Journal of Chemical Physics '''119''' pp. 9145- (2003)]</ref>.

==Mason-Rice rule==
The Mason-Rice rule for the [[Exp-6 potential]] <ref>[http://dx.doi.org/10.1063/1.1740100 Edward A. Mason and William E. Rice "The Intermolecular Potentials of Helium and Hydrogen", Journal of Chemical Physics '''22''' pp. 522- (1954)]</ref>.
==Sikora rules==
The Sikora rules for the [[Lennard-Jones model]] <ref>[http://dx.doi.org/10.1088/0022-3700/3/11/008 P. T. Sikora "Combining rules for spherically symmetric intermolecular potentials", Journal of Physics B: Atomic and Molecular Physics '''3''' pp. 1475- (1970)]</ref>.
==Tang and Toennies==
<ref>[http://dx.doi.org/10.1007/BF01384663 K. T. Tang and J. Peter Toennies "New combining rules for well parameters and shapes of the van der Waals potential of mixed rare gas systems", Zeitschrift für Physik D Atoms, Molecules and Clusters '''1''' pp. 91-101 (1986)]</ref>
==Waldman-Hagler rules==
<ref>[http://dx.doi.org/10.1002/jcc.540140909 M. Waldman and A. T. Hagler "New combining rules for rare-gas Van der-Waals parameters", Journal of Computational Chemistry '''14''' pp. 1077-1084 (1993)]</ref>
==References==
<references/>
'''Related reading'''
*[http://dx.doi.org/10.1021/ja00046a032 Thomas A. Halgren "The representation of van der Waals (vdW) interactions in molecular mechanics force fields: potential form, combination rules, and vdW parameters", Journal of the American Chemical Society '''114''' pp. 7827-7843 (1992)]
[[category: mixtures]]

Combining rules

2011-11-18T10:49:18Z

128.178.234.123: /* Kong rules */

The '''combining rules''' (also known as ''mixing rules'') are geometric expressions designed to provide the interaction energy between two dissimilar non-bonded atoms (here labelled <math>i</math> and <math>j</math>). Most of the rules are designed to be used with a specific [[Idealised models| interaction potential]] in mind.
==Admur and Mason==
For the [[second virial coefficient]] of a mixture
<ref>[http://dx.doi.org/10.1063/1.1724353 I. Amdur and E. A. Mason "Properties of Gases at Very High Temperatures", Physics of Fluids '''1''' pp. 370-383 (1958)]</ref>
:<math>B_{ij} = \frac{\left(B_{ii}^{1/3}+B_{jj}^{1/3}\right)^3}{8}</math>
==Böhm-Ahlrichs==
<ref>[http://dx.doi.org/10.1063/1.444057 Hans‐Joachim Böhm and Reinhart Ahlrichs "A study of short‐range repulsions", Journal of Chemical Physics '''77''' pp. 2028- (1982)]</ref>
==Diaz Peña-Pando-Renuncio==
<ref>[http://dx.doi.org/10.1063/1.442726 M. Diaz Peña, C. Pando, and J. A. R. Renuncio "Combination rules for intermolecular potential parameters. I. Rules based on approximations for the long-range dispersion energy", Journal of Chemical Physics '''76''' pp. 325- (1982)]</ref>
<ref>[http://dx.doi.org/10.1063/1.442727 M. Diaz Peña, C. Pando, and J. A. R. Renuncio "Combination rules for intermolecular potential parameters. II. Rules based on approximations for the long-range dispersion energy and an atomic distortion model for the repulsive interactions", Journal of Chemical Physics '''76''' pp. 333- (1982)]</ref>
==Fender-Halsey==
The Fender-Halsey combining rule for the [[Lennard-Jones model]] is given by <ref>[http://dx.doi.org/10.1063/1.1701284 B. E. F. Fender and G. D. Halsey, Jr. "Second Virial Coefficients of Argon, Krypton, and Argon-Krypton Mixtures at Low Temperatures", Journal of Chemical Physics '''36''' pp. 1881-1888 (1962)]</ref>
:<math>\epsilon_{ij} = \frac{2 \epsilon_i \epsilon_j}{\epsilon_i + \epsilon_j}</math>
==Gilbert-Smith==
The Gilbert-Smith rules for the [[Born-Huggins-Meyer potential]]<ref>[http://dx.doi.org/10.1063/1.1670463 T. L. Gilbert "Soft‐Sphere Model for Closed‐Shell Atoms and Ions", Journal of Chemical Physics '''49''' pp. 2640- (1968)]</ref><ref>[http://dx.doi.org/10.1063/1.431848 T. L. Gilbert, O. C. Simpson, and M. A. Williamson "Relation between charge and force parameters of closed‐shell atoms and ions", Journal of Chemical Physics '''63''' pp. 4061- (1975)]</ref><ref>[http://dx.doi.org/10.1103/PhysRevA.5.1708 Felix T. Smith "Atomic Distortion and the Combining Rule for Repulsive Potentials", Physical Review A '''5''' pp. 1708-1713 (1972)]</ref>.
==Good-Hope rule==
The Good-Hope rule for [[Mie potential |Mie]]–[[Lennard-Jones model |Lennard‐Jones]] or [[Buckingham potential]]s <ref>[http://dx.doi.org/10.1063/1.1674022 Robert J. Good and Christopher J. Hope "New Combining Rule for Intermolecular Distances in Intermolecular Potential Functions", Journal of Chemical Physics '''53''' pp. 540- (1970)]</ref> is given by (Eq. 2):

:<math>\sigma_{ij} = \sqrt{\sigma_{ii} \sigma_{jj}}</math>
==Hudson and McCoubrey==
<ref>[http://dx.doi.org/10.1039/TF9605600761 G. H. Hudson and J. C. McCoubrey "Intermolecular forces between unlike molecules. A more complete form of the combining rules", Transactions of the Faraday Society '''56''' pp. 761-766 (1960)]</ref>
==Kong rules==
<ref>[http://dx.doi.org/10.1063/1.1680358 Chang Lyoul Kong "Combining rules for intermolecular potential parameters. II. Rules for the Lennard-Jones (12–6) potential and the Morse potential", Journal of Chemical Physics '''59''' pp. 2464-2467 (1973)]</ref>

<math> \epsilon_{ij}\sigma_{ij}^{12} = \frac{\epsilon_{ii}\sigma_{ii}^{12}}{2^{13}}\left[ 1+\left( \frac{\epsilon_{jj}\sigma_{jj}^{12}}{\epsilon_{ii}\sigma_{ii}^{12}} \right)^{\frac{1}{13}}\right]^{13} </math>

==Lorentz-Berthelot rules==
The Lorentz rule is given by <ref>[http://dx.doi.org/10.1002/andp.18812480110 H. A. Lorentz "Ueber die Anwendung des Satzes vom Virial in der kinetischen Theorie der Gase", Annalen der Physik '''12''' pp. 127-136 (1881)]</ref>
:<math>\sigma_{ij} = \frac{\sigma_{ii} + \sigma_{jj}}{2}</math>

which is only really valid for the [[hard sphere model]].

The Berthelot rule is given by <ref>[http://visualiseur.bnf.fr/Document/CadresPage?O=NUMM-3082&I=1703 Daniel Berthelot "Sur le mélange des gaz", Comptes rendus hebdomadaires des séances de l’Académie des Sciences, '''126''' pp. 1703-1855 (1898)]</ref>

:<math>\epsilon_{ij} = \sqrt{\epsilon_{ii} \epsilon_{jj}}</math>

These rules are simple and widely used, but are not without their failings <ref>[http://dx.doi.org/10.1080/00268970010020041 Jérôme Delhommelle; Philippe Millié "Inadequacy of the Lorentz-Berthelot combining rules for accurate predictions of equilibrium properties by molecular simulation", Molecular Physics '''99''' pp. 619-625 (2001)]</ref>
<ref>[http://dx.doi.org/10.1080/00268970802471137 Dezso Boda and Douglas Henderson "The effects of deviations from Lorentz-Berthelot rules on the properties of a simple mixture", Molecular Physics '''106''' pp. 2367-2370 (2008)]</ref>
<ref>[http://dx.doi.org/10.1063/1.1610435 W. Song, P. J. Rossky, and M. Maroncelli "Modeling alkane+perfluoroalkane interactions using all-atom potentials: Failure of the usual combining rules", Journal of Chemical Physics '''119''' pp. 9145- (2003)]</ref>.

==Mason-Rice rule==
The Mason-Rice rule for the [[Exp-6 potential]] <ref>[http://dx.doi.org/10.1063/1.1740100 Edward A. Mason and William E. Rice "The Intermolecular Potentials of Helium and Hydrogen", Journal of Chemical Physics '''22''' pp. 522- (1954)]</ref>.
==Sikora rules==
The Sikora rules for the [[Lennard-Jones model]] <ref>[http://dx.doi.org/10.1088/0022-3700/3/11/008 P. T. Sikora "Combining rules for spherically symmetric intermolecular potentials", Journal of Physics B: Atomic and Molecular Physics '''3''' pp. 1475- (1970)]</ref>.
==Tang and Toennies==
<ref>[http://dx.doi.org/10.1007/BF01384663 K. T. Tang and J. Peter Toennies "New combining rules for well parameters and shapes of the van der Waals potential of mixed rare gas systems", Zeitschrift für Physik D Atoms, Molecules and Clusters '''1''' pp. 91-101 (1986)]</ref>
==Waldman-Hagler rules==
<ref>[http://dx.doi.org/10.1002/jcc.540140909 M. Waldman and A. T. Hagler "New combining rules for rare-gas Van der-Waals parameters", Journal of Computational Chemistry '''14''' pp. 1077-1084 (1993)]</ref>
==References==
<references/>
'''Related reading'''
*[http://dx.doi.org/10.1021/ja00046a032 Thomas A. Halgren "The representation of van der Waals (vdW) interactions in molecular mechanics force fields: potential form, combination rules, and vdW parameters", Journal of the American Chemical Society '''114''' pp. 7827-7843 (1992)]
[[category: mixtures]]