Effect of the symmetric stretch on the dipole polarizability of the cyclic form of the ozone molecule: a study based on high-level ab initio and density functional theory calculations

We have calculated the effect of the symmetric stretching on the dipole polarizability (ααβ) of the cyclic form of ozone, O3(D3h). We have used both conventional ab initio and density functional theory methods. All basis sets have been especially designed for polarizability calculations on O3(D3h). At the CCSD(T)/[9s6p5d1f] level of theory the ααβ invariants change rapidly around Re = 1.444 Å as α ¯ ( R ) / e 2 a 0 2 E h - 1 = 16.49 + 8.68 ( R - R e ) + 0.38 ( R - R e ) 2 - 2.63 ( R - R e ) 3 + 0.51 ( R - R e ) 4 , Δ α ( R ) / e 2 a 0 2 E h - 1 = - 6.79 - 7.93 ( R - R e ) + 0.32 ( R - R e ) 2 + 2.15 ( R - R e ) 3 . LYP, B3P86 and B3PW91 density functional theory methods agree quite well with the most accurate conventional ab initio values for the mean polarizability at Re but tend to overestimate the magnitude of the anisotropy. The same trend is very much obvious for the derivatives ( d α ¯ / d R ) e and (dΔα/R)e.