ISSN:
1089-7690
Source:
AIP Digital Archive
Topics:
Physics
,
Chemistry and Pharmacology
Notes:
For atoms or molecules of D∞h or higher symmetry, this work gives equations for the long-range, collision-induced changes in the first (Δβ) and second (Δγ) hyperpolarizabilities, complete to order R−7 in the intermolecular separation R for Δβ, and order R−6 for Δγ. The results include nonlinear dipole-induced-dipole (DID) interactions, higher multipole induction, induction due to the nonuniformity of the local fields, back induction, and dispersion. For pairs containing H or He, we have used ab initio values of the static (hyper)polarizabilities to obtain numerical results for the induction terms in Δβ and Δγ. For dispersion effects, we have derived analytic results in the form of integrals of the dynamic (hyper)polarizabilities over imaginary frequencies, and we have evaluated these numerically for the pairs H...H, H...He, and He...He using the values of the fourth dipole hyperpolarizability ε(−iω; iω, 0, 0, 0, 0) obtained in this work, along with other hyperpolarizabilities calculated previously by Bishop and Pipin. For later numerical applications to molecular pairs, we have developed constant ratio approximations (CRA1 and CRA2) to estimate the dispersion effects in terms of static (hyper)polarizabilities and van der Waals energy or polarizability coefficients. Tests of the approximations against accurate results for the pairs H...H, H...He, and He...He show that the root mean square (rms) error in CRA1 is ∼20%–25% for Δβ and Δγ; for CRA2 the error in Δβ is similar, but the rms error in Δγ is less than 4%. At separations ∼1.0 a.u. outside the van der Waals minima of the pair potentials for H...H, H...He, and He...He, the nonlinear DID interactions make the dominant contributions to Δγzzzz (where z is the interatomic axis) and to Δγxxxx, accounting for ∼80%–123% of the total value. Contributions due to higher-multipole induction and the nonuniformity of the local field (Qα terms) may exceed 15%, while dispersion effects contribute ∼4%–9% of the total Δγzzzz and Δγxxxx. For Δγxxzz, the α term is roughly equal to the nonlinear DID term in absolute value, but opposite in sign. Other terms in Δγxxzz are smaller, but they are important in determining its net value because of the near cancellation of the two dominant terms. When Δγ is averaged isotropically over the orientations of the interatomic vector to give Δγ¯, dispersion effects dominate, contributing 76% of the total Δγ¯ (through order R−6) for H...H, 81% for H...He, and 73% for He...He. © 1996 American Institute of Physics.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1063/1.472867
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