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Quantum chemical electron impact mass spectrum prediction for de novo structure elucidation: Assessment against experimental reference data and comparison to competitive fragmentation modeling


We investigate the success of the quantum chemical electron impact mass spectrum (QCEIMS) method in predicting the electron impact mass spectra of a diverse test set of 61 small molecules selected to be representative of common fragmentations and reactions in electron impact mass spectra. Comparison with experimental spectra is performed using the standard matching algorithms, and the relative ranking position of the actual molecule matching the spectra within the NIST‐11 library is examined. We find that the correct spectrum is ranked in the top two matches from structural isomers in more than 50% of the cases. QCEIMS, thus, reproduces the distribution of peaks sufficiently well to identify the compounds, with the RMSD and mean absolute difference between appropriately normalized predicted and experimental spectra being at most 9% and 3% respectively, even though the most intense peaks are often qualitatively poorly reproduced. We also compare the QCEIMS method to competitive fragmentation modeling for electron ionization, a training‐based mass spectrum prediction method, and remarkably we find the QCEIMS performs equivalently or better. We conclude that QCEIMS will be very useful for those who wish to identify new compounds which are not well represented in the mass spectral databases.

The accurate prediction of electron impact mass spectra would greatly expedite the process of unknown compound identification or de‐novo structure elucidation. The capabilities of ab‐initio methods and a machine learning methods as compared to reference to experimental spectra, demonstrate great potential for future practical applications in de‐novo structure elucidation.

Authors:   Peter R. Spackman, Björn Bohman, Amir Karton, Dylan Jayatilaka
Journal:   International Journal of Quantum Chemistry
Year:   2017
Pages:   n/a
DOI:   10.1002/qua.25460
Publication date:   26-Aug-2017
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