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 3d 2f) 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: βzxx=−9.40, βzyy=−1.35, βzzz=−7.71 and β̄=−11.07 for βαβγ (e3a03Eh−2) and γxxxx=569, γyyyy=1422, γzzzz=907, γxxyy=338, γyyzz=389, γzzxx=287 and γ̄=985 for γαβγδ (e4a04Eh−3) at the experimental equilibrium geometry (with z as the C2 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 βzxx=−0.45, βzyy=−4.19, βzzz=−6.09, β̄=−6.44 and γxxxx=267, γyyyy=1228, γzzzz=574, γxxyy=295, γyyzz=322, γzzxx=152, γ̄=721. For the static limit we propose β̄=−17.5±0.3 e3a03Eh−2 and γ̄=(171±6)×101 e4a04Eh−3, in near agreement with the experimental findings of β̄=−19.2±0.9 e3a03Eh−2 and γ̄=1800±150 e4a04Eh−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].