Electric (hyper)polarizability derivatives for the symmetric stretching of carbon dioxide

We have relied on finite-field Coupled Cluster calculations with carefully designed basis sets to obtain the bond length dependence of the static electric (hyper)polarizability for the symmetric stretching of carbon dioxide. We find that around the experimental bond length of R-e/a(0) the mean and the anisotropy ((alpha) over bar) of the dipole polarizability and the mean hyperpolarizability (gamma) vary at the CCSD(T) level of theory as [(x) over bar (R) - (alpha) over bar (R-e)]/e(2)a(0)(2)E(h)(-1) = 13.81 (R - R-c) + 3.78(R - R-e)(2) - 0.83(R - R-e)(3) + 0.44(R - R-e)(4), [Deltaalpha(R) - Deltaalpha(R-e)]/e(2)a(0)(2)E(h)(-1) = 19.35(R - R-e) + 11.23(R - Re)(2) + 1.06(R - R-e)(3) + 0.17(R - Re)(4), [(gamma) over bar (R) - (gamma) over bar (Re)/]e(4)a(0)(4)E(h)(-3) = 1493(R - R-e) + 1041 (R - Re)(2) - 433(R - R-e)(3) - 350(R - R-e)(4). Our values for the derivatives (d (alpha) over bar /dR)(e), (d(2)(alpha) over bar /dR(2))(c), and the anisotropy Deltaalpha agree quite well with the recent experimental findings. (C) 2003 Elsevier Science B.V. All rights reserved.