Collision-induced light scattering spectra of the inert gases and hydrogen at high densities provide evidence of nonadditive three-body interaction effects, for which a quantitative theory is needed. In this work, we derive and evaluate the three-body polarizability for interacting molecules with negligible electronic overlap. Our results, based on nonlocal response theory, account for dipole-induced-dipole (DID) interactions, quadrupolar induction, dispersion, and concerted induction-dispersion effects. The contribution of leading order comes from a DID term that scales as in the molecular polarizability α and a representative distance d between the molecules in a cluster. Quadrupolar induction effects are also large, however, ranging from ∼35% to 104% of the leading DID terms for equilateral triangular configurations of the species studied in this work, at separations approximately 1 a.u. beyond the van der Waals minima in the isotropic pair potentials. For the same configurations, the dispersion terms range from 2% to 7% of the total The dispersion and induction-dispersion contributions are derived analytically in terms of integrals over imaginary frequency, with integrands containing the polarizability and the γ hyperpolarizability. For H, He, and the integrals have been evaluated accurately by 64-point Gauss–Legendre quadrature; for heavier species, we have developed approximations in terms of static polarizabilities, static hyperpolarizabilities, and van der Waals interaction energy coefficients and In the isotropic interaction-induced polarizability the three-body terms are comparable in magnitude to the two-body terms, due to a cancellation of the first-order, two-body DID contributions to For the heavier species in this work (Ar, Kr, Xe, and in the configurations studied, the three-body contributions to range from −7 to −9% of the two-body terms for equilateral triangular arrays and from 35% to 47% of the two-body terms for linear, centrosymmetric systems.
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22 January 2000
Research Article|
January 22 2000
Nonadditive three-body polarizabilities of molecules interacting at long range: Theory and numerical results for the inert gases, and
M. H. Champagne;
M. H. Champagne
Department of Chemistry, Michigan State University, East Lansing, Michigan 48824
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X. Li;
X. Li
Department of Chemistry, Michigan State University, East Lansing, Michigan 48824
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K. L. C. Hunt
K. L. C. Hunt
Department of Chemistry, Michigan State University, East Lansing, Michigan 48824
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J. Chem. Phys. 112, 1893–1906 (2000)
Article history
Received:
August 11 1999
Accepted:
October 04 1999
Citation
M. H. Champagne, X. Li, K. L. C. Hunt; Nonadditive three-body polarizabilities of molecules interacting at long range: Theory and numerical results for the inert gases, and . J. Chem. Phys. 22 January 2000; 112 (4): 1893–1906. https://doi.org/10.1063/1.480753
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