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 (alpha(alphabeta)) 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 alpha(alphabeta) invariants change rapidly around R-e = 1.444 Angstrom as alpha(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) Deltaalpha(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 (dalpha/dR)(e) and (dDeltaalpha/R)(e). (C) 2004 Elsevier B.V. All rights reserved.