Structural properties and nonlinear optical responses of superatom compounds BF₄‐M (M = Li, FLi₂, OLi₃, NLi₄)

Abstract

Abstract A new type of superhalogen‐(super)alkali compound, BF 4 ‐M (M = Li, FLi 2 , OLi 3 , NLi 4 ), is theoretically characterized at the MP2/6‐311+G(3df) level. The interaction between superhalogen BF 4 and different shaped (super)alkali M is found to be strong and ionic in nature. Bond energies of these BF 4 ‐M species are in the range of 200.0–226.7 kcal/mol at the CCSD(T)/6‐311+G(3df) level, which are much larger than the traditional ionic bond energy of 130.1 kcal/mol of FLi. In addition, different from the alkali halides, the BF 4 ‐M compounds prefer to dissociate into ions rather than neutral fragments. The energetic properties of BF 4 ‐M are found to be closely related to the size of the M subunit. The different effects of superalkali and superhalogen subunits on the nonlinear optical (NLO) properties of such superatom compounds are also revealed. © 2011 Wiley Periodicals, Inc. Int J Quantum Chem, 2011