As known, small HCl-water nanoclusters display a particular dissociation behaviour, whereby at least four water molecules are required for the ionic dissociation of HCl. In this work, we examine how intermolecular interactions promote the ionic dissociation of such nanoclusters. To this end, a set of 45 HCl-water nanoclusters with up to four water molecules is introduced. Energy decomposition analysis based on absolutely localized molecular orbitals (ALMO-EDA) is employed in order to study the importance of frozen interaction, dispersion, polarization, and charge-transfer for the dissociation. The vertical ALMO-EDA scheme is applied to HCl-water clusters along a proton-transfer coordinate varying the amount of spectator water molecules. The corresponding ALMO-EDA results show a clear preference for the dissociated cluster only in the presence of four water molecules. Our analysis of adiabatic ALMO-EDA results reveals a push-pull mechanism for the destabilization of the HCl bond based on the synergy between forward and backward charge-transfer.

Cooperative or nonadditive effects contribute to the pairwise noncovalent interaction of two molecules in a cluster or the condensed phase in ways that depend on the specific arrangements and interactions of the other surrounding molecules that constitute their environment. General expressions for an effective two-body interaction are presented, which are correct to increasing orders in the many-body expansion. The simplest result, correct through third order, requires only seven individual calculations, in contrast to a linear number of three-body contributions. Two applications are presented. First, an error analysis is performed on a model (H₂O)₈ cluster which completes the first solvation shell of a central water-water hydrogen bond. Energy decomposition analysis is performed to show that the largest effects of cooperativity on the central hydrogen bond arise from electrical polarization. Second, the nature of cooperative effects on proton transfer in an HCl + (H₂O)₄ cluster is characterized.

This article summarizes technical advances contained in the fifth major release of the Q-Chem quantum chemistry program package, covering developments since 2015. A comprehensive library of exchange-correlation functionals, along with a suite of correlated many-body methods, continues to be a hallmark of the Q-Chem software. The many-body methods include novel variants of both coupled-cluster and configuration-interaction approaches along with methods based on the algebraic diagrammatic construction and variational reduced density-matrix methods. Methods highlighted in Q-Chem 5 include a suite of tools for modeling core-level spectroscopy, methods for describing metastable resonances, methods for computing vibronic spectra, the nuclear-electronic orbital method, and several different energy decomposition analysis techniques. High-performance capabilities including multithreaded parallelism and support for calculations on graphics processing units are described. Q-Chem boasts a community of well over 100 active academic developers, and the continuing evolution of the software is supported by an "open teamware" model and an increasingly modular design.