Hyperpolarizability of H2O revisited:: accurate estimate of the basis set limit and the size of electron correlation effects

A large (18s 13p 8d 5f/ 12s 7p 3d2f) basis set consisting of 256 uncontracted gaussian-type functions is expected to yield values near the Hartree-Fock limit for the static hyperpolarizability of H2O: beta(zxx) = - 9.40, beta(zyy) = - 1.35, beta(zzz) = -7.71 and <(beta)over bar> = -11.07 for beta(alpha beta gamma) (e(3)a(0)(3)E(h)(-2)) and gamma(xxxx) = 569, gamma(yyyy) = 1422, y(zzzz) = 907, gamma(xxyy) = 338, gamma(yyzz) = 389, (zzxx) = 287 and <(gamma)over bar> = 985 for gamma(alpha beta gamma delta) (e(4)a(0)(4)E(h)(-3)) at the experimental equilibrium geometry (with z as the C-2 axis, molecule on the xz plane). The respective electron correlation corrections obtained with the single, double and perturbatively linked triple excitations coupled-cluster method and a [9s 6p 6d 3f / 6s 4p 2d 1f] basis set are beta(zxx) = - 0.45, beta(zyy) = - 4.19, beta(zzz) = - 6.09, <(beta)over bar> = - 6.44 and gamma(xxxx) = 267, gamma(yyyy) = 1228, gamma(zzzz) = 574, gamma(xxyy) = 295, gamma(yyzz) = 322, gamma(zzxx) = 152, <(gamma)over bar> = 721. For the static limit we propose <(beta)over bar> = - 17.5 +/- 0.3 e(3)a(0)(3)E(h)(-2) and <(beta)over bar>= (171+/-6) x 10(1 )e(4)a(0)(4)E(h)(-3), in near agreement with the experimental findings of <(beta)over bar> = - 19.2 +/- 0.9 e(3)a(0)(3)E(h)(-2) and <(gamma)over bar> = 1800 +/- 150 e(4)a(0)(4)E(h)(-3) deduced from EFISH measurements at 1064 nm by Kaatz et al. [P. Kaatz, E.A. Donley, D.P. Shelton, J. Chem. Phys. 108 (1998) 849]. (C) 1998 Elsevier Science B.V. All rights reserved.