Microsolvation of electrons by a handful of ammonia molecules.

Microsolvation of electrons in ammonia is studied here via anionic NH3 n - clusters with n = 2-6. Intensive samplings of the corresponding configurational spaces using second-order perturbation theory with extended basis sets uncover rich and complex energy landscapes, heavily populated by many local minima in tight energy windows as calculated from highly correlated coupled cluster methods. There is a marked energetical preference for structures that place the excess electron external to the molecular frame, effectively coordinating it with the three protons from a single ammonia molecule. Overall, as the clusters grow in size, the lowest energy dimer serves as the basic motif over which additional ammonia molecules are attached via unusually strong charge-assisted hydrogen bonds. This is a priori quite unexpected because, on electrostatic grounds, the excess electron would be expected to be in contact with as many protons as possible. Accordingly, a full quantum mechanical treatment of the bonding interactions under the tools provided by the quantum theory of atoms in molecules is carried out in order to dissect and understand the nature of intermolecular contacts. Vertical detachment energies reveal bound electrons even for n = 2.

Structure, energy, and bonding in anionic water tetramers obtained by exhaustive search.

An analysis of the structures, some energy related properties, and key aspects of the bonding nature of the microsolvated electron with four water molecules is presented. The study is based on an exhaustive potential energy surface scan of the ground state of (H2O)4 - at the UCCSD(T)/6-311(3+,4+)G(d,p)//UMP2/6-311(3+,4+)G(d,p) level. A total of 18 structures, most of them not reported before, spanning in an energy range of 8.8 kcal mol-1 were found. The energetic stability of the clusters is dictated by the effect of the excess electron on their structures, on their partial fragmentation, and on the hydrogen bonds' framework. Vertical detachment energies depend on the number of water molecules holding the excess electron in "direct contact" to their two protons at the same time and, to a lesser extent, also depend on the hydrogen bond sequence in the rest of the structure. In general, hydrogen bonds in (H2O)4 - are of closed shell character, and there are other less common interactions assisted by the excess electron.

Exotic species with explicit noble metal-noble gas-noble metal linkages.

We present a study of the isoelectronic Pt2Ng2F4 and [Au2Ng2F4]2+ species with noble gas atoms (Ng = Kr, Xe, Rn) acting as links bridging the two noble metal atoms. The stability of the species is investigated using several thermodynamic, kinetic and reactivity indicators. The results are compared against [AuXe4]2+, which is thermodynamically unstable in the gas phase but is stabilized in the solid state to the point that it has been experimentally detected as [AuXe4](Sb2F11)2 (S. Seidel and K. Seppelt, Science, 2000, 290, 117-118). Our results indicate that improving upon [AuXe4]2+, these exotic combinations between the a priori non-reactive noble metals and noble gases lead to metastable species, and, therefore, they have the possibility of existing in the solid state under adequate conditions. Our calculations include accurate energies and geometries at both the CCSD/SDDALL and MP2/SDDALL levels. We offer a detailed description of the nature of the bonding interactions using orbital and density-based analyses. The computational evidence suggests partially covalent and ionic interactions as the stabilization factors.

Spin-Orbit Coupling Effects in AumPtn Clusters (m + n = 4).

A study of AumPtn(m + n = 4) clusters with and without spin-orbit (SO) coupling using scalar relativistic (SR) and two component methods with the ZORA Hamiltonian was carried out. We employed the PW91 functional in conjunction with the all-electron TZ2P basis set. This paper offers a detailed analysis of the SO effects on the cluster geometries, on the LUMO-HOMO gap, on the charge distribution, and on the relative energies for each relativistic method. In general, SO coupling led to an energetic rearrangement of the species, to changes in geometries and structural preferences, to changes in the structural identity of the global minimum for the Au3Pt, AuPt3 and Pt4 cases, and to a reduction of relative energies among the clusters, an effect that appears stronger as the amount of Pt increases.

Types and characteristics of drinking water for hydration in the elderly.

The role of hydration in the maintenance of health is increasingly recognized. Hydration requirements vary for each person, depending on physical activity, environmental conditions, dietary patterns, alcohol intake, health problems, and age. Elderly individuals have higher risk of developing dehydration than adults. Diminution of liquid intake and increase in liquid losses are both involved in causing dehydration in the elderly. The water used for drinking is provided through regular public water supply and the official sanitary controls ensure their quality and hygiene, granting a range of variation for most of its physical and chemical characteristics, being sometimes these differences, though apparently small, responsible for some disorders in sensitive individuals. Hence, the advantages of using bottled water, either natural mineral water or spring water, are required by law to specify their composition, their major components, and other specific parameters. It is essential to take this into account to understand the diversity of indications and favorable effects on health that certain waters can offer.