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Thermochemical Studies of NiII and ZnII Ternary Complexes Using Ion Mobility-Mass Spectrometry

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Benchmark Experimental Gas-Phase Intermolecular Dissociation Energies by the SEP-R2PI Method.

Richard Knochenmuss¹, Rajeev K Sinha², Samuel Leutwyler¹

¹Department of Chemistry and Biochemistry, University of Bern, 3012 Bern, Switzerland;

Annual Review of Physical Chemistry

|February 20, 2020

Summary

This study presents experimental measurements of intermolecular interaction strengths for 55 (hetero)aromatic-solvent complexes. The data provides a valuable database for understanding noncovalent interactions and refining theoretical models.

Keywords:

London dispersion hydrogen bond intermolecular binding energy intermolecular dissociation energy noncovalent interactions

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Area of Science:

Physical Chemistry
Chemical Physics
Spectroscopy

Background:

Gas-phase ground-state dissociation energy (D₀(S₀)) quantifies intermolecular interaction strength.
Accurate D₀ values are crucial for theoretical calculations and model parameterization in various scientific fields.

Purpose of the Study:

To review experimental measurements of D₀(S₀) and D₀(S₁) for 55 (hetero)aromatic-solvent complexes.
To establish a comprehensive experimental database of accurate noncovalent interactions.

Main Methods:

Utilizing the triply resonant SEP-R2PI laser method for electronic excitation and stimulated emission.
Inducing vibrational predissociation at high vibrational energy levels within the M⋅S complex.

Main Results:

Experimental D₀ values were determined for 55 M⋅S complexes, where M is a (hetero)aromatic molecule and S is a solvent.
49 dissociation energies were precisely bracketed to within ≤1.0 kJ/mol.

Conclusions:

The study provides a substantial experimental dataset of accurate noncovalent interaction energies.
This database serves as a benchmark for theoretical chemistry and aids in developing predictive models for molecular interactions.