Density Functional Theory Study of the Properties of N−H···N, Noncooperativities, and Intermolecular Interactions in Linear trans-Diazene Clusters up to Ten Molecules

Abstract

We investigate aspects of N-H...N hydrogen bonding in the linear trans-diazene clusters (n=2-10) such as the N...H and N-H lengths, n(N) --> sigma(N-H) interactions, N...H strengths, and frequencies of the N-H stretching vibrations utilizing the DFT/B3LYP theory, the natural bond orbital (NBO) method, and the theory of atoms in molecules (AIM). Our calculations indicate that the structure and energetics are qualitatively different from the conventional H-bonded systems, which usually exhibit distinct cooperative effects, as cluster size increases. First, a shortening rather than lengthening of the N-H bond is found and thus a blue rather than red shift is predicted. Second, for the title clusters, any sizable cooperative changes in the N-H and N...H lengths, n(N) --> sigma(N-H) charge transfers, N...H strengths, and frequencies of the N-H stretching vibrations for the linear H-bonded trans-diazene clusters do not exist. Because the n(N) --> sigma(N-H) interaction hardly exhibits cooperative effects, the capability of the linear trans-diazene cluster to localize electrons at the N...H bond critical point is almost independent of cluster size and thereby leads to the noncooperative changes in the N...H lengths and strengths and the N-H stretching frequencies. Third, the dispersion energy is sizable and important; more than 30% of short-range dispersion energy not being reproduced by the DFT leads to the underestimation of the interaction energies by DFT/B3LYP. The calculated nonadditive interaction energies show that, unlike the conventional H-boned systems, the trans-diazene clusters indeed exhibit very weak nonadditive interactions.