Structures, binding energies, temperature effects, infrared spectroscopy of [Mg(NH₃)_{n = 1−10}]⁺ clusters from DFT and MP2 investigations

Abstract

The possible isomers of [Mg(NH3)n = 1 − 10]+ clusters have been investigated using both M06‐2X/6‐31++G(d,p) and MP2/6‐31++G(d,p) levels of theory. The isomeric distribution for each n size has been studied as a function of temperatures ranging from 25 to 400 K. To the best of our knowledge, for clusters size n > 6, this is the first theoretical study available in the literature. From the calculated values in the considered clusters and using a fitting procedure, we have evaluated the binding energies (−14.0 kcal/mol), clustering energies (−10.1 kcal/mol), clustering free energies (−2.8 kcal/mol), and clustering enthalpies (−10.3 kcal/mol). On the basis of our structural and infrared (IR) spectroscopy outcomes, we find that the first solvation shell can hold up to six ammonia molecules. © 2019 Wiley Periodicals, Inc.

A fresh perspective on metal ammonia molecular complexes and expanded metals: opportunities in catalysis and quantum information

“…one ammonia is placed in the second solvation shell and the electron is on the metal. 69 Based on the PEPs of Fig. 3, the displacement of the more diffuse valence s-electron of Ca + (compared to Be + and Mg + ) is smoother but leads to smaller metal-ammonia binding energies due to the smaller charge density of the Ca 2+ core.…”