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 (Delta alpha) of the polarizability, and the first and second hyperpolarizabilities (beta(0) and gamma(0), respectively) for four lithium-bond dimers (LiCN center dot center dot center dot LiCN, LiNC center dot center dot center dot LiNC, H4C2 center dot center dot center dot LiF, and H3N center dot center dot center dot 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 center dot center dot center dot LiCN, by 204.8% for LiNC center dot center dot center dot LiNC, by 75.5% for H4C2 center dot center dot center dot LiF, and by 24.0% for H3N1 center dot center dot center dot LiF), and also considerably decrease the second hyperpolarizabilities of the Li-bond dimers investigated (by 52.7% for LiCN center dot center dot center dot LiCN, by 43.7% for LiNC center dot center dot center dot LiNC, by 16.4% for H4C2 center dot center dot center dot LiF, and by 62.6% for H3N center dot center dot center dot LiF).