Microsolvation versus Encapsulation in Mono, Di, and Trivalent Cations.

The effects of the formal charge in the stability and bonding of water cavities when solvating a cation are studied here using [X(H2 O)20 ]q+ clusters starting with the well known 512 isomer of (water)20 , placing a single mono, di, or trivalent Xq+ cation at the interior, and then optimizing and characterizing the resulting clusters. Highly correlated interaction and deformation energies are calculated using the CCSD(T)-DLPNO formalism. Bonding interactions are characterized using the tools provided by the quantum theory of atoms in molecules, natural bond orbitals, and non-covalent surfaces. Our results indicate that water to water hydrogen bonds are sensibly strengthened resulting in strong cooperative effects, which amount to ≈ 2 ${ \approx 2}$  kcal/mol per hydrogen bond in the bare cavity and to larger values for the systems including the cations. Approximate encapsulation, that is, surrounding the cation by a network of hydrogen bonds akin to the well known methane clathrate seems to be preferred by cations with smaller charge densities while microsolvation, that is, cluster structures having explicit X⋯O contacts seem to be preferred by cations with larger charge densities which severely deform the cavity.

To Be or Not To Be? that is the Entropic, Enthalpic, and Molecular Interaction Dilemma in the Formation of (Water)20 Clusters and Methane Clathrate.

A detailed analysis under a comprehensive set of theoretical and computational tools of the thermodynamical factors and of the intermolecular interactions behind the stabilization of a well known set of (water)20 cavities and of the methane clathrate is offered in this work. Beyond the available reports of experimental characterization at extreme conditions of most of the systems studied here, all clusters should be amenable to experimental detection at 1 atm and moderate temperatures since 280 K marks the boundary at which, ignoring reaction paths, formation of all clusters is no longer spontaneous from the 20H2 O→(H2 O)20 and CH4 +20H2 O→CH4 @512 processes. As a function of temperature, a complex interplay leading to the free energy of formation occurs between the destabilizing entropic contributions, mostly due to cluster vibrations, and the stabilizing enthalpic contributions, due to intermolecular interactions and the PV term, is best illustrated by the highly symmetric 512 cage consistently showing signs of stronger intermolecular bonding despite having smaller binding energy than the other clusters. A fluxional wall of attractive non-covalent interactions, arising because of the cumulative effect of a large number of tiny individual charge transfers to the interstitial region, plays a pivotal role stabilizing the CH4 @512 clathrate.

On the strength of hydrogen bonding within water clusters on the coordination limit.

Hydrogen bonds (HB) are arguably the most important noncovalent interactions in chemistry. We study herein how differences in connectivity alter the strength of HBs within water clusters of different sizes. We used for this purpose the interacting quantum atoms energy partition, which allows for the quantification of HB formation energies within a molecular cluster. We could expand our previously reported hierarchy of HB strength in these systems (Phys. Chem. Chem. Phys., 2016, 18, 19557) to include tetracoordinated monomers. Surprisingly, the HBs between tetracoordinated water molecules are not the strongest HBs despite the widespread occurrence of these motifs (e.g., in ice Ih ). The strongest HBs within H2 O clusters involve tricoordinated monomers. Nonetheless, HB tetracoordination is preferred in large water clusters because (a) it reduces HB anticooperativity associated with double HB donors and acceptors and (b) it results in a larger number of favorable interactions in the system. Finally, we also discuss (a) the importance of exchange-correlation to discriminate among the different examined types of HBs within H2 O clusters, (b) the use of the above-mentioned scale to quickly assess the relative stability of different isomers of a given water cluster, and (c) how the findings of this research can be exploited to indagate about the formation of polymorphs in crystallography. Overall, we expect that this investigation will provide valuable insights into the subtle interplay of tri- and tetracoordination in HB donors and acceptors as well as the ensuing interaction energies within H2 O clusters.

The structure of {[Co(pht)(bpy)(H2O)]·3H2O}n (pht is phthalate and bpy is 4,4'-bipyridine) and the role of solvent water clusters in structure stability.

The Co(II) cation in poly[[aqua(µ-benzene-1,2-dicarboxylato-κ(3)O(1),O(2):O(1))(µ-4,4'-bipyridine-κ(2)N:N')cobalt(II)] trihydrate], {[Co(C8H4O4)(C10H8N2)(H2O)]·3H2O}n, is octahedrally coordinated by two N atoms of two 4,4'-bipyridine ligands, three O atoms from phthalate anions and a fourth O atom from a coordinated water molecule. The packing consists of planes of coordination polymers linked by hydrogen bonds mediated by three solvent water molecules; the linkage is achieved by the water molecules forming intricate oligomeric clusters which also involve the O atoms of the phthalate ligands.