Frequency-dependent second hyperpolarizabilities using coupled cluster cubic response theory

Christof Hättig, Ove Christiansen, and Poul Jørgensen
Department of Chemistry, Århus University, DK-8000 Århus C, Denmark

Chem. Phys. Lett. 282, 139-146 (1998)
(Received 27 June 1997; revised 22 October 1997; accepted 24 October 1997)

The coupled cluster cubic response function is derived using a time-averaged quasienergy Lagrangian and Fourier component variational perturbation theory. The obtained expressions are in accord with the 2n+1 and 2n+2 rules. The first implementation of the cubic response function is reported for frequency-dependent second hyperpolarizabilities for a coupled cluster singles and doubles wavefunction and sample calculations are presented for hyperpolarizabilities of N2 for several third-order optical processes. The results are in excellent agreement with recent experiments for electric field induced second harmonic generation.


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