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Unimolecular Fragmentation Properties of Thermometer Ions from Chemical Dynamics Simulations

preprint
revised on 06.10.2020 and posted on 07.10.2020 by Abdul Malik, Riccardo Spezia, William L. Hase
Thermometer ions are widely used to calibrate the internal energy of the ions produced by electrospray ionization in mass spectrometry. Commonly used ions are benzylpyridinium ions with different substituents. More recently benzhydrylpyridinium ions were proposed for their lower bond dissociation energies. Direct dynamics simulations using M06-2X/6-31G(d), DFTB, and PM6-D3 are performed to characterize the activation energies of two representative systems; para-methyl-benzylpyridinium ion (p-Me-BnPy+) and methyl,methylbenzhydrylpyridinium ion (Me,Me-BhPy+). The theoretical bond dissociation energies match closely with the experiment. Simulation results are used to calculate rate constants for the two systems. These rate constants and their uncertainties are used to find the Arrhenius activation energies and RRK fitted threshold energies which give reasonable agreement with calculated bond dissociation energies at the same level of theory. There is only one fragmentation mechanism observed for both systems, which involves C-N bond dissociation via a loose transition state, to generate either benzylium or benzhydrylium ion and a neutral pyridine molecule. For p-Me-BnPy+ using DFTB and PM6-D3 the formation of tropylium ion, from rearrangement of benzylium ion, was observed but only at higher excitation energies and for longer simulation times. These observations suggest that there is no competition between reaction pathways that could affect the reliability of internal energy calibrations.

Funding

Robert A. Welch Foundation under Grant No. D-0005

History

Email Address of Submitting Author

riccardo.spezia@sorbonne-universite.fr

Institution

Sorbonne Université & CNRS

Country

France

ORCID For Submitting Author

0000-0001-5160-489X

Declaration of Conflict of Interest

No conflict of interest

Version Notes

V1 - 26/05/2020

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