A Tug of War between the Self‐ and Cross‐associating Hydrogen Bonds in Neutral Ammonia‐Water Clusters: Energetic Insights by Molecular Tailoring Approach. Issue 24 (17th October 2022) - Patkar, Deepak
Abstract: In the present work, the energies of various types of individual HBs observed in neutral (NH3 )m (H2 O)n, (m+n=2 to 7) clusters were estimated using the molecular tailoring approach (MTA)‐based method. The calculated individual HB energies suggest that the O−H…N HBs are the strongest (1.21 to 12.49 kcal mol −1 ). The next ones are the O−H…O (3.97 to 9.30 kcal mol −1 ) HBs. The strengths of N−H…N (1.09 to 5.29 kcal mol −1 ) and N−H…O (2.85 to 5.56 kcal mol −1 ) HBs are the weakest. The HB energies in dimers also follow this rank ordering. However, the HB energies in dimers are much smaller than those obtained by the MTA‐based method due to the loss in cooperativity contribution in the dimers. Thus, the calculated cooperativity contributions, for different types of HBs, fall in the range 0.64 to 5.73 kcal mol −1 . We wish to emphasize based on the energetic rank ordering obtained by the MTA‐based method that the O−H of water is a better HB donor than the N−H of ammonia. The reasons for the observed energetic rank ordering are two folds: (i) intrinsically stronger O−H…N HBs than the O−H…O ones as revealed by dimer energies and (ii) the higher cooperativity contribution in the former than the later ones. Indeed, the MTA‐based method is useful in providing the missing energetic rank ordering of various type of HBs in neutral (NH3 )m (H2 O)n clusters, in the literature. Abstract : The molecular tailoring approach reveals the energetics of self‐ and cross‐associating hydrogen bonds and cooperativity in ammonia‐water clusters.