Ab initio molecular orbital calculations on ion-molecule and ion-pair-molecule complexes of formamide with LiF and LiCl

Mohandas, P. ; Singh, Surjit (1996) Ab initio molecular orbital calculations on ion-molecule and ion-pair-molecule complexes of formamide with LiF and LiCl Journal of Molecular Structure: Theochem, 361 (1-3). pp. 229-242. ISSN 0166-1280

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Official URL: http://linkinghub.elsevier.com/retrieve/pii/016612...

Related URL: http://dx.doi.org/10.1016/0166-1280(95)04322-5

Abstract

Ab initio molecular orbital (MO) calculations are reported on a series of ion-molecule and ion-pair-molecule complexes of (HCONH2)n+Li+X- (n=1, 2; X=F, Cl) systems using 3-21G, 6-31G and 6-31G∗∗ basis sets. Stabilization energies, optimized geometrical parameters, internal force constants and harmonic vibrational frequencies are evaluated for 28 structures of interest. Interaction of Li+, F- and Cl- ions with formamide (FA) leads to highly stabilized complexes. The FA---F- complex reveals a proton transfer. The calculated properties of the solvated contact ion-pair complexes follow patterns similar to those noted for the corresponding ion-molecule complexes. However, the presence of the counterion reduces the interaction energies significantly. The interaction of FA with Li+ ions as well as with F- and Cl- ions results in a red shift in the CO and NH stretching frequencies and a blue shift in the CN stretching frequency. The CH stretching frequency is found to be influenced by the ions in a different manner, cations causing a substantial blue shift and anions a red shift. The variations in the harmonic frequencies are compared with the trends observed in the experimental results for the corresponding systems as reported in the literature.

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ID Code:39153
Deposited On:09 May 2011 08:09
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