Understanding the Hydrogen-Bonded Clusters of Ammonia (NH3)n (n = 3–6): Insights from the Electronic Structure Theory

Although it is well known that hydrogen bonds commonly exist in ammonia clusters and play an important role, there are still many challenges in understanding the electronic structure properties of hydrogen bonds. In this paper, the geometric and electronic structure properties of cyclic ammonia clusters are investigated by using first-principles density functional theory (DFT) and the Møller-Plesset perturbation theory (MP2). The calculation results show that the pentamer and hexamer have deviated from the perfect plane, while the trimer and tetramer present planarization that has been confirmed by infrared (IR) spectra. The electronic structure analysis further shows that the covalent properties play a non-negligible role in hydrogen bonding. The results also indicate that the electronic structure facilitates structure planarization. Our work not only provides insight into the role and nature of hydrogen bonds in ammonia clusters but also provides a theoretical basis for frontier science in fields such as atmospheric haze and biomolecular functions.