Lithium bonding interaction hyperpolarizabilities of various li-bond dimers.

The effects of intermolecular interaction on dipole moment (mu(z)), the mean (alpha(0)) and anisotropy (Deltaalpha) of the polarizability, and the first and second hyperpolarizabilities (beta(0) and gamma(0), respectively) for four lithium-bond dimers (LiCN...LiCN, LiNC...LiNC, H(4)C(2)...LiF, and H(3)N...LiF) have been investigated in the finite-field approach. The electric properties were obtained at the CCSD(T)/6-311++G(2df, 2p) level. For the four dimers, electron correlation contributions are very important to the total and interaction static electric properties. Different from the H bond interaction effects on hyperpolarizabilities of H-bond dimers, the Li-bond interactions significantly decrease the beta(0) values of the four Li-bond dimers (by 73.6% for LiCN...LiCN, by 204.8% for LiNC...LiNC, by 75.5% for H(4)C(2)...LiF, and by 24.0% for H(3)N...LiF), and also considerably decrease the second hyperpolarizabilities of the Li-bond dimers investigated (by 52.7% for LiCN...LiCN, by 43.7% for LiNC...LiNC, by 16.4% for H(4)C(2)...LiF, and by 62.6% for H(3)N...LiF).