Correction to the Clausius-Mosotti equation: The dielectric constant of nonpolar fluids from Monte Carlo simulations.

We examine the dielectric constant of nonpolar fluids by direct Monte Carlo simulations on the basis of the polarizable hard sphere (PHS) model, where the spheres carry molecular polarizabilities. Point dipoles are induced in the spheres partly by an external electric field and partly by other molecules. It has been known that the Clausius-Mosotti equation needs a correction due to mutual polarization between molecules. We reproduce the qualitative behavior found in experiments: the correction increases with increasing density, reaches a maximum, and decreases at high densities. We show that the classic theory of Kirkwood and Yvon is quantitatively correct for the PHS model.

[1]  Paul Madden,et al.  A Consistent Molecular Treatment of Dielectric Phenomena , 2007 .

[2]  L. Frommhold Collision‐Induced Scattering of Light and the Diatom Polarizabilities , 2007 .

[3]  D. Boda,et al.  Monte Carlo simulation and renormalized perturbation theory study of the dielectric properties of mixtures of polarizable hard spheres and polarizable dipolar hard spheres , 2006 .

[4]  D. Boda,et al.  Relative permittivity of polar liquids. Comparison of theory, experiment, and simulation. , 2005, The journal of physical chemistry. B.

[5]  I. Szalai,et al.  A systematic Monte Carlo simulation and renormalized perturbation theoretical study of the dielectric constant of the polarizable Stockmayer fluid , 2003 .

[6]  J. Godet,et al.  Multipolar Polarizabilities from Interaction‐induced Raman Scattering , 2002 .

[7]  P. Cummings,et al.  Pair approximation for polarization interaction: efficient method for Monte Carlo simulations of polarizable fluids , 2001 .

[8]  Weis,et al.  Chain formation in low density dipolar hard spheres: A Monte Carlo study. , 1993, Physical review letters.

[9]  T. Bose,et al.  Determination of the quadrupole moment of nitrogen from the dielectric second virial coefficient , 1991 .

[10]  T. Bose Dielectric properties of non dipolar gases , 1987 .

[11]  Martin Neumann,et al.  Dipole moment fluctuation formulas in computer simulations of polar systems , 1983 .

[12]  P. Madden,et al.  On the dielectric constant of non-polar fluids , 1982 .

[13]  Franz J. Vesely,et al.  N-particle dynamics of polarizable Stockmayer-type molecules , 1977 .

[14]  G. S. Rushbrooke,et al.  On the dielectric constant of non-polar Lennard-Jones fluids according to the Kirkwood-Yvon theory , 1975 .

[15]  G. S. Rushbrooke,et al.  On the dielectric constant of nonpolar fluids , 1974 .

[16]  T. Bose,et al.  Dielectric and Pressure Virial Coefficients of Imperfect Gases. V. Octopole Moments of CH4 and CF4 , 1972 .

[17]  T. Bose,et al.  Dielectric and Pressure Virial Coefficients of Imperfect Gases. IV C2H4 and C2H4–Ar Mixtures , 1971 .

[18]  J. Barker,et al.  Perturbation Theory and Equation of State for Fluids. II. A Successful Theory of Liquids , 1967 .

[19]  R. Cole,et al.  Dielectric Constants of Imperfect Gases. III. Atomic Gases, Hydrogen, and Nitrogen , 1967 .

[20]  P. Tseng,et al.  Neutron Total Cross Section of Arsenic at 14 Mev. , 1963 .

[21]  R. Cole,et al.  Dielectric Constants of Imperfect Gases. I. Helium, Argon, Nitrogen, and Methane , 1960 .

[22]  L. Jansen Molecular Theory of the Dielectric Constant , 1958 .

[23]  J. Pople,et al.  Electric Quadrupole Moments and Dielectric Constants , 1957 .

[24]  L. Jansen,et al.  Molecular Theory of the Dielectric Constant of Nonpolar Gases , 1956 .

[25]  R. Zwanzig Influence of Molecular Electric Quadrupole Moments on Dielectric Constants , 1956 .

[26]  C. A. T. Seldam,et al.  The dielectric constant of argon at 25 °C and 125 °C for pressures up to 2700 atmospheres , 1951 .

[27]  W. Brown Dielectric Constants of Non‐Polar Fluids. I. Theory , 1950 .

[28]  C. Böttcher Die Druckabhängigkeit Der Molekularpolarisation Von Dipolfreien Gasen Und Flüssigkeiten , 1942 .

[29]  L. Kleerekoper,et al.  Measurements on the dielectric constant of CO2 at 25°, 50° and 100°C up to 1700 atmospheres , 1939 .

[30]  J. V. Vleck On the Role of Dipole‐Dipole Coupling in Dielectric Media , 1937 .

[31]  J. Kirkwood On the Theory of Dielectric Polarization , 1936 .

[32]  W. E. Danforth The Dielectric Constant of Liquids under High Pressure , 1931 .

[33]  F. G. Keyes,et al.  The Intramolecular Field and the Dielectric Constant , 1931 .

[34]  B. Alder,et al.  Depolarization of Light in Atomic Fluids , 1973 .

[35]  M. Wertheim Dielectric constant of non-polar fluids , 1973 .

[36]  T. Bose,et al.  Dielectric and Pressure Virial Coefficients of Imperfect Gases. II. CO2–Argon Mixtures , 1970 .

[37]  J. Pople,et al.  The dielectric constant of an imperfect non-polar gas , 1955 .

[38]  P. Mazur,et al.  On the theory of molecular polarization in gases: I. Effect of molecular interactions on the polarizability of spherical nonpolar molecules , 1954 .

[39]  P. Mazur,et al.  On the theory of molecular polarization in gases: II. Effect of molecular interactions on the Clausius-Mosotti function for systems of spherical nonpolar molecules , 1954 .

[40]  J. D. Boer,et al.  The molecular polarisation of compressed non-polar gases , 1953 .

[41]  William Fuller Brown,et al.  Theory of electric polarisation , 1952 .

[42]  M. V. D. Meij The theory of electrons , 1917 .