HYPERPOLARIZABILITIES AND POLARIZABILITIES OF LI- AND B+ - FINITE-FIELD COUPLED-CLUSTER CALCULATIONS

The finite-field coupled-cluster doubles (CCD) model, supplemented by fourth-order and triples contributions computed with CCD amplitudes, is used to calculate the dipole-dipole-quadrupole (B) and second dipole (γ) hyperpolarizabilities, and the dipole (α1) and quadrupole (α2) polarizabilities of Li- and B+ using large, optimized basis sets. Electron correlation effects are huge; correlation reduces B for Li- to less than a third of its SCF value. The Li-1 results are α1 = 793.1 e2 a2 0 E- h, α2=4.59×104 e2 a4 0 E- h, B = 3.04 × 106 e3 a4 0 E-2 h, and γ = 1.27 × 109 e4 a4 0 E-3 h. The B+ results are α1 = 9.566 e2 a2 0 E- h, α2=26.91 e2 a4 0 E-1 h, B = -93.04 e3 a4 0 E-2 h, and γ = 589 e4 a4 0 E-2 h, and γ = 589 e4 a4 0 E-3 h. These values are likely to be the best currently available theoretical estimates. © 1990.