Clusters of solvated ferrous ion in water-ammonia mixture: Structures and noncovalent interactions.

The behavior of metal ions is commonly studied in pure solvent although, in our daily life, these metals are involved in mixtures of solvents. In the present study, we investigated structures, relative stabilities and temperature dependance of solvated ferrous ion in water-ammonia mixture solvent at 0K and at various temperatures ranging from 25K to 400K. All the calculations are performed at the MN15 level of theory associated with the aug-cc-pVDZ basis set. For deep understanding of binding patterns in solvated ferrous ion in water-ammonia mixture solvent, noncovalent interactions are presented based on the QTAIM analysis using AIMAll. Our results prove that the ferrous ion is more stable when it is solvated by ammonia instead of water. In addition, hydrogen bonds are weakened by the presence of ammonia molecules. The temperature dependence of the different obtained geometries indicates that from s=6 (s is the sum of water and ammonia molecules around the ferrous ion), when the number of water molecules is almost equal to that of ammonia, the structures with coordination number 5 are dominant. However, the coordination number is six when there are a maximum water molecules (rich water solution) or maximum ammonia molecules (rich ammonia solution) around the ferrous ion (for s≥6). The QTAIM analysis shows that there are two coordination bondings and four hydrogen bondings. Furthermore, it is found that the Fe2+⋯N coordination bondings are stronger than the Fe2+⋯O confirming that the ferrous ion prefers to be solvated by ammonia instead of water.

Solvation energies of the ferrous ion in water and in ammonia at various temperatures.

CONTEXT: The solvation of metal ions is crucial to understanding relevant properties in physics, chemistry, or biology. Therefore, we present solvation enthalpies and solvation free energies of the ferrous ion in water and ammonia. Our results agree well with the experimental reports for the hydration free energy and hydration enthalpy. We obtained [Formula: see text] kJ mol[Formula: see text] for the hydration free energy and [Formula: see text] kJ mol[Formula: see text] for the hydration enthalpy of ferrous ion in water at room temperature. At ambient temperature, we obtained [Formula: see text] kJ mol[Formula: see text] as the [Formula: see text] ammoniation free energy and [Formula: see text] kJ mol[Formula: see text] for the ammoniation enthalpy. In addition, the free energy of solvation is deeply affected when the temperature increases. This pattern can be attributed to the rise of entropy when the temperature rises. Besides, the temperature does not affect the ammoniation enthalpies and the hydration enthalpy of the [Formula: see text] ion. METHOD: All the geometry optimizations are performed at the MP2 methods associated with the 6-31++g(d,p) basis set of Pople. solvated phase structures of [Formula: see text] ion in water or in ammonia are performed using the PCM model. The [Formula: see text] program suite was used to perform all the calculations. The program TEMPO was also used to evaluate the temperature sensitivity of the different obtained geometries.