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Alkali-ion microsolvation with benzene molecules.

J M C Marques¹, J L Llanio-Trujillo, M Albertí

¹Departamento de Química, Universidade de Coimbra, 3004-535 Coimbra, Portugal. qtmarque@ci.uc.pt

The Journal of Physical Chemistry. A

|April 21, 2012

Summary

Alkali ions solvated with benzene molecules form stable structures. The number of benzene molecules in the first solvation shell increases with ion size, revealing "magic numbers" for specific cluster sizes.

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Area of Science:

Physical Chemistry
Computational Chemistry
Biophysical Chemistry

Background:

Understanding ion solvation in nonpolar environments is key to biochemical selectivity.
Aromatic rings play a crucial role in the solvation shells of alkali ions.

Purpose of the Study:

Characterize alkali-ion solvation shells in nonpolar environments using benzene.
Investigate the influence of cation size on solvation structure and stability.

Main Methods:

Employed an evolutionary algorithm to find global minima of alkali-ion-benzene clusters (M+-(Bz)n).
Utilized a potential model based on benzene's molecular polarizability to decompose intermolecular interactions.
Studied microsolvation of Na+, K+, and Cs+ with up to 21 benzene molecules.

Main Results:

Observed that the first solvation shell size increases with cation size (3 for Na+, 4 for K+ and Cs+).
Identified particularly stable cluster structures ("magic numbers") at specific benzene molecule counts (n=2, 3, 4 for Na+, K+, Cs+).
Found weaker "magic numbers" for larger cluster sizes, independent of the specific ion.

Conclusions:

The structure of the first solvation shell is primarily determined by cation size and remains stable as more solvent is added.
The concept of "magic numbers" highlights specific stable configurations in alkali-ion-benzene clusters.
This study provides insights into ion-aromatic interactions relevant to biochemical processes.