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Computation of Atmospheric Concentrations of Molecular Clusters from ab initio Thermochemistry

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Highly Structured Water Networks in Microhydrated Dodecaborate Clusters.

Yanrong Jiang^1,2, Zhaojie Cai¹, Qinqin Yuan³

¹State Key Laboratory of Precision Spectroscopy, School of Physics and Electronic Science, East China Normal University, Shanghai 200241, China.

The Journal of Physical Chemistry Letters

|December 14, 2022

Summary

The study reveals how water molecules arrange around dodecaborate clusters (B12X12(2-)) based on the cluster type. B12H12(2-) forms highly structured water networks due to strong B-H···H-O bonds.

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Area of Science:

Physical Chemistry
Inorganic Chemistry
Computational Chemistry

Background:

Dodecaborate clusters (B12X12(2-)) are unique anionic species.
Understanding microsolvation is crucial for aqueous borate chemistry.

Purpose of the Study:

To investigate the structural arrangements of water clusters around dodecaborate anions.
To elucidate the role of solute specificity in microsolvation dynamics.

Main Methods:

Combined photoelectron spectroscopy and theoretical calculations.
Investigation of size-selected hydrated dodecaborate clusters (B12X12(2-)·nH2O).

Main Results:

Distinct water cluster structures (n=1-6) observed, dependent on the B12X12(2-) base (X=H, F, I).
B12H12(2-) forms highly structured water networks via strong B-H···H-O dihydrogen bonds.
B12F12(2-) and B12I12(2-) show different water binding modes and network similarities to free water.

Conclusions:

Provides a molecular-level understanding of microsolvation in aqueous borate systems.
Highlights the structural diversity of hydrogen bonding networks in microhydrated dodecaborates.
Demonstrates significant solute specificity in water cluster formation.