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Aqueous Solutions and Heats of Hydration

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Updated: May 30, 2026

Computation of Atmospheric Concentrations of Molecular Clusters from ab initio Thermochemistry

Computation of Atmospheric Concentrations of Molecular Clusters from ab initio Thermochemistry

Published on: April 8, 2020

Ion-water clusters, bulk medium effects, and ion hydration.

Safir Merchant¹, Purushottam D Dixit, Kelsey R Dean

¹Department of Chemical and Biomolecular Engineering, The Institute of NanoBioTechnology, Johns Hopkins University, Baltimore, Maryland 21218, USA.

The Journal of Chemical Physics

|August 10, 2011

Summary

This summary is machine-generated.

The bulk medium significantly impacts ion-water cluster stability and hydration free energy calculations. Accounting for the bulk medium is crucial for accurately determining ion hydration thermodynamics, especially for soft ions.

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Computation of Atmospheric Concentrations of Molecular Clusters from ab initio Thermochemistry

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From Molecules to Materials: Engineering New Ionic Liquid Crystals Through Halogen Bonding

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Controlling the Size, Shape and Stability of Supramolecular Polymers in Water

Controlling the Size, Shape and Stability of Supramolecular Polymers in Water

Published on: August 2, 2012

Area of Science:

Physical Chemistry
Computational Chemistry
Chemical Thermodynamics

Background:

Hydration free energy calculations often employ continuum solvent models.
The primitive quasichemical approximation offers a framework for these calculations.
Understanding the influence of the bulk medium on ion-water clusters is essential.

Purpose of the Study:

To evaluate approximations in the primitive quasichemical approach.
To elucidate the role of the bulk medium in ion-water cluster thermochemistry.
To assess the impact of the bulk medium on hydration free energy calculations.

Main Methods:

Utilizing thermochemistry of gas-phase ion-water clusters.
Estimating hydration free energy of clusters and water ligands.
Applying the primitive quasichemical approximation to quasichemical theory.
Analyzing the influence of the bulk medium on cluster configurations and ion chemical potential.

Main Results:

The bulk medium stabilizes normally unobserved cluster configurations.
The bulk medium lowers the excess chemical potential of ions, particularly soft ions.
Discrepancies arise in optimal cluster size and hydration thermodynamics with and without bulk medium consideration for soft ions.

Conclusions:

The primitive quasichemical approach requires careful evaluation of bulk medium effects.
Accurate determination of hydrated ion thermodynamics necessitates accounting for the bulk medium's influence on clustering.
Findings are relevant for experimental and theoretical studies linking ion-water cluster thermochemistry to hydrated ion thermodynamics.