Interaction of bihalogen anions with nitrogen: Matrix-isolation study and first principle calculations of the (ClHCl)(-)center dot center dot center dot N-2 and (BrHBr)(-)center dot center dot center dot N-2 complexes

摘要

The N-2 complexes of (CIHCl)(-) and (BrHBr)(-) are studied both experimentally using IR absorption spectroscopy and computationally. Two computational [MP2(full)/6-311++G(2d,2p)] geometries for the systems were found, and the cross-like structure is energetically the more stable for both of the systems. The BSSE-corrected interaction energies for the cross-like structures are -500 to -600 cm(-1). The matrix-isolation experiments support the formation of this complex structure, and the experimental complexation-induced shift is +4.8 and +7.1 cm(-1) for the (CIHCI)(-)center dot center dot center dot N-2 and (BrHBr)(-)center dot center dot center dot N-2 complexes, respectively. The HArCl and HKrBr molecules do not appear upon annealing of the photolyzed HCl/Ar and HBr/Kr matrices probably suggesting instability of these molecules. (c) 2005 Elsevier B.V. All rights reserved.