The second hyperpolarizability of the N2 molecule calculated using the approximate coupled cluster triples model CC3

The static and frequency-dependent hyperpolarizabilities of the N2 molecule have been calculated using the coupled cluster approximate triples model CC3. The CC3 basis-set limit of the hyperpolarizability has been estimated. Considering the zero-point vibrational correction and neglecting the relativistic contributions (which are found to be small) the best estimate of the static hyperpolarizability is 912.9 ± 4.3 a.u. (the uncertainty of 4.3 a.u. does not account for correlation effects beyond CC3). The effect of triples is important and increases with frequency. The hyperpolarizabilities calculated at the CC3 level agree well with experiment, the discrepancies being of 0.1–2.2%. The largest CC3 calculations employed 326 basis functions.