Ab initio investigation on blue shift and red shift of C–H stretching vibrational frequency in NH 3⋯CH nX 4– n ( n=1,3, X=F, Cl, Br, I) complexes

Abstract

Ab initio quantum mechanics methods are employed to investigate CH⋯N intermolecular interactions between NH 3 as the proton acceptor and CH n X 4− n ( n=1,3, X=F, Cl, Br, I) as the proton donor. For the NH 3⋯CH 3X complexes, C–H⋯N blue-shifting H-bonds are identified and the blue shifts are about 11–26 cm −1. For the NH 3⋯CHX 3 complexes, the stronger hydrogen bonds are found, but they are all classical H-bonds with red shifts of about 100–183 cm −1. The reason of the different shift directions in different halomethanes can be successfully explained by natural bond orbital analysis. The way in which the electron density is transferred for the NH 3⋯CH 3X complexes differs from that for the NH 3⋯CHX 3 complexes, which are responsible for the blue shifts in the NH 3⋯CH 3X complexes but the red shifts in the NH 3⋯CHX 3 complexes.