The frequency-dependent dipole polarizability of the mercury dimer from four-component relativistic density-functional theory.
The frequency-dependent dipole polarizability of Hg(2) is calculated using response theory within four-component relativistic density-functional theory [using the local-density approximation (LDA) and the hybrid functional B3LYP] including corrections for the basis-set superposition error. The anisotropic component of the polarizability tensor agrees well with the values obtained from collision-induced Raman spectroscopy carried out at a wavelength of 488 nm. The values obtained from the two density functionals agree closely with the experimentally derived anisotropy component of the dipole polarizability, despite their rather large differences in the dimer potential-energy curves (LDA is strongly overbinding while B3LYP is purely repulsive). The first two refractivity virial coefficients for the generalized Clausius-Mossotti function are derived.
Gaston
Nicola
N
Institute of Fundamental Sciences, Massey University (Albany Campus), Private Bag 102904, North Shore MSC, Auckland, New Zealand.
Schwerdtfeger
Peter
P
Saue
Trond
T
Greif
Jörn
J