AB-INITIO MOLECULAR-ORBITAL CALCULATIONS ON THE ASSOCIATED COMPLEXES OF LITHIUM CYANIDE WITH AMMONIA

Ab initio molecular orbital (Mo) calculations with the 3-21G and 6-31G basis sets are carried out on a series of complexes of NH3 with Li+, C=N-, LiCN, and its isomer LiNC. The BSSE-corrected interaction energies, geometrical parameters, internal force constants, and harmonic vibrational frequencies are evaluated for 15 species. Complexes with trifurcated (C-3 upsilon) structures are calculated to be saddle points on the potential energy surfaces and have one imaginary frequency each. Calculated energies, geometrical parameters, internal force constants, and harmonic vibrational frequencies of the various species considered are discussed in terms of the nature of association of LiCN with ammonia. The vibrational frequencies of the relevant complexed species are compared with the experimental frequencies reported earlier for solutions of lithium cyanide in liquid ammonia. (C) 1995 John Wiley & Sons, Inc.