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

Abstract

We have calculated the effect of the symmetric stretching on the dipole polarizability ( α αβ ) of the cyclic form of ozone, O 3(D 3h). We have used both conventional ab initio and density functional theory methods. All basis sets have been especially designed for polarizability calculations on O 3(D 3h). At the CCSD(T)/[9s6p5d1f] level of theory the α αβ invariants change rapidly around R e = 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 . The B3LYP, B3P86 and B3PW91 density functional theory methods agree quite well with the most accurate conventional ab initio values for the mean polarizability at R e 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 (dΔ α/ R) e.