Imperial College London
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ProfessorDavidKlug

Faculty of Natural Sciences, Department of Chemistry

Associate Dean for Enterprise for FoNS & Professor
 
 
 
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Contact

 

+44 (0)20 7594 5806d.klug

 
 
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Location

 

Molecular Sciences Research HubWhite City Campus

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Summary

 

Publications

Citation

BibTex format

@article{Driver:2020:10.1103/PhysRevX.10.041004,
author = {Driver, T and Cooper, B and Ayers, R and Pipkorn, R and Patchkovskii, S and Averbukh, V and Klug, D and Marangos, J and Frasinski, L and Edelson-Averbukh, M},
doi = {10.1103/PhysRevX.10.041004},
journal = {Physical Review X},
pages = {041004  1--041004  13},
title = {Two-dimensional partial covariance mass spectrometry of large molecules based on fragment correlations},
url = {http://dx.doi.org/10.1103/PhysRevX.10.041004},
volume = {10},
year = {2020}
}
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RIS format (EndNote, RefMan)

TY  - JOUR
AB  - Covariance mapping [L. J. Frasinski, K. Codling, and P. A. Hatherly, Science 246, 1029 (1989)] is a well-established technique used for the study of mechanisms of laser-induced molecular ionization and decomposition. It measures statistical correlations between fluctuating signals of pairs of detected species (ions, fragments, electrons). A positive correlation identifies pairs of products originating from the same dissociation or ionization event. A major challenge for covariance-mapping spectroscopy is accessing decompositions of large polyatomic molecules, where true physical correlations are overwhelmed by spurious signals of no physical significance induced by fluctuations in experimental parameters. As a result, successful applications of covariance mapping have so far been restricted to low-mass systems, e.g., organic molecules of around 50 daltons (Da). Partial-covariance mapping was suggested to tackle the problem of spurious correlations by taking into account the independently measured fluctuations in the experimental conditions. However, its potential has never been realized for the decomposition of large molecules, because in these complex situations, determining and continuously monitoring multiple experimental parameters affecting all the measured signals simultaneously becomes unfeasible. We introduce, through deriving theoretically and confirming experimentally, a conceptually new type of partial-covariance mapping—self-correcting partial-covariance spectroscopy—based on a parameter extracted from the measured spectrum itself. We use the readily available total ion count as the self-correcting partial-covariance parameter, thus eliminating the challenge of determining experimental parameter fluctuations in covariance measurements of large complex systems. The introduced self-correcting partial covariance enables us to successfully resolve correlations of molecules as large as
AU  - Driver,T
AU  - Cooper,B
AU  - Ayers,R
AU  - Pipkorn,R
AU  - Patchkovskii,S
AU  - Averbukh,V
AU  - Klug,D
AU  - Marangos,J
AU  - Frasinski,L
AU  - Edelson-Averbukh,M
DO  - 10.1103/PhysRevX.10.041004
EP  - 1
PY  - 2020///
SN  - 2160-3308
SP  - 041004
TI  - Two-dimensional partial covariance mass spectrometry of large molecules based on fragment correlations
T2  - Physical Review X
UR  - http://dx.doi.org/10.1103/PhysRevX.10.041004
UR  - https://journals.aps.org/prx/abstract/10.1103/PhysRevX.10.041004
UR  - http://hdl.handle.net/10044/1/82399
VL  - 10
ER  -
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