Ab initio calculation of the refractivity and hyperpolarizability second virial coefficients of neon gas

Christof Hättig1, Javier López Cachiero2, Berta Fernández2, and Antonio Rizzo3*
1 Forschungszentrum Karlsruhe, Institute of Nanotechnology, PO Box 3640, D-76021 Karlsruhe, Germany
2 Department of Physical Chemistry, Faculty of Chemistry, University of Santiago de Compostela, E-15782 Santiago de Compostela, Spain
3Istituto per i Processi Chimico-Fisici del Consiglio Nazionale delle Ricerche, Area della Ricerca, via G. Moruzzi 1, loc. S. Cataldo, I-56124 Pisa, Italy

Mol. Phys. 101, 1983-1995 (2003).
(Received 23 October 2002; accepted 1 February 2003)

Second virial coefficients for the density dependence of a number of electric properties are calculated for neon gas. Employing an accurate CCSD(T) potential for the Ne2 van der Waals dimer and interaction-induced polarizabilities and hyperpolarizabilities obtained from CCSD response theory, we evaluated the dielectric, refractivity, Kerr and ESHG second virial coefficients using both a semiclassical and a quantum statistical approach. The results cover a wide range of temperatures and are expected to be more reliable than the available experimental and empirical data. Quantum effects are found to be important only for temperatures below 100 K. The frequency-dependence of the refractivity virial coefficient is found to be small, but not negligible. For frequencies in the visible region it accounts for a few percent of the final results. For the ESHG virial coefficient of neon, frequency dependence is found to be very important, accounting for 20-25% of the second virial coefficient at the typical frequencies employed in experiments.

*Author for correspondence. email: rizzo@icpf.cnr.it; Web: http://www.icqem.pi.cnr.it/rizzo/ar.html

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