Two-Dimensional Partial-Covariance Mass Spectrometry of Large Molecules Based on Fragment Correlations

Covariance mapping [L. J. Frasinski, K. Codling, and P. A. Hatherly, Science 246, 1029 (1989)SCIEAS0036-807510.1126/science.246.4933.1029] is a well-established technique used for the study of mechanisms of laser-induced molecular ionization and decomposition. It measures statistical correlations be...

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Autores principales:	Taran Driver, Bridgette Cooper, Ruth Ayers, Rüdiger Pipkorn, Serguei Patchkovskii, Vitali Averbukh, David R. Klug, Jon P. Marangos, Leszek J. Frasinski, Marina Edelson-Averbukh
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Lenguaje:	EN
Publicado:	American Physical Society 2020
Materias:	Physics QC1-999
Acceso en línea:	https://doaj.org/article/7b17f06c1b364a06b05b0221e0c212a8
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spelling	oai:doaj.org-article:7b17f06c1b364a06b05b0221e0c212a82021-12-02T11:22:27ZTwo-Dimensional Partial-Covariance Mass Spectrometry of Large Molecules Based on Fragment Correlations10.1103/PhysRevX.10.0410042160-3308https://doaj.org/article/7b17f06c1b364a06b05b0221e0c212a82020-10-01T00:00:00Zhttp://doi.org/10.1103/PhysRevX.10.041004http://doi.org/10.1103/PhysRevX.10.041004https://doaj.org/toc/2160-3308Covariance mapping [L. J. Frasinski, K. Codling, and P. A. Hatherly, Science 246, 1029 (1989)SCIEAS0036-807510.1126/science.246.4933.1029] 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 10^{3}–10^{4} Da, 2 orders of magnitude above the state of the art. This opens new opportunities for mechanistic studies of large molecule decompositions through revealing their fragment-fragment correlations. Moreover, we demonstrate that self-correcting partial covariance is applicable to solving the inverse problem: reconstruction of a molecular structure from its fragment spectrum, within two-dimensional partial-covariance mass spectrometry.Taran DriverBridgette CooperRuth AyersRüdiger PipkornSerguei PatchkovskiiVitali AverbukhDavid R. KlugJon P. MarangosLeszek J. FrasinskiMarina Edelson-AverbukhAmerican Physical SocietyarticlePhysicsQC1-999ENPhysical Review X, Vol 10, Iss 4, p 041004 (2020)
institution	DOAJ
collection	DOAJ
language	EN
topic	Physics QC1-999
spellingShingle	Physics QC1-999 Taran Driver Bridgette Cooper Ruth Ayers Rüdiger Pipkorn Serguei Patchkovskii Vitali Averbukh David R. Klug Jon P. Marangos Leszek J. Frasinski Marina Edelson-Averbukh Two-Dimensional Partial-Covariance Mass Spectrometry of Large Molecules Based on Fragment Correlations
description	Covariance mapping [L. J. Frasinski, K. Codling, and P. A. Hatherly, Science 246, 1029 (1989)SCIEAS0036-807510.1126/science.246.4933.1029] 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 10^{3}–10^{4} Da, 2 orders of magnitude above the state of the art. This opens new opportunities for mechanistic studies of large molecule decompositions through revealing their fragment-fragment correlations. Moreover, we demonstrate that self-correcting partial covariance is applicable to solving the inverse problem: reconstruction of a molecular structure from its fragment spectrum, within two-dimensional partial-covariance mass spectrometry.
format	article
author	Taran Driver Bridgette Cooper Ruth Ayers Rüdiger Pipkorn Serguei Patchkovskii Vitali Averbukh David R. Klug Jon P. Marangos Leszek J. Frasinski Marina Edelson-Averbukh
author_facet	Taran Driver Bridgette Cooper Ruth Ayers Rüdiger Pipkorn Serguei Patchkovskii Vitali Averbukh David R. Klug Jon P. Marangos Leszek J. Frasinski Marina Edelson-Averbukh
author_sort	Taran Driver
title	Two-Dimensional Partial-Covariance Mass Spectrometry of Large Molecules Based on Fragment Correlations
title_short	Two-Dimensional Partial-Covariance Mass Spectrometry of Large Molecules Based on Fragment Correlations
title_full	Two-Dimensional Partial-Covariance Mass Spectrometry of Large Molecules Based on Fragment Correlations
title_fullStr	Two-Dimensional Partial-Covariance Mass Spectrometry of Large Molecules Based on Fragment Correlations
title_full_unstemmed	Two-Dimensional Partial-Covariance Mass Spectrometry of Large Molecules Based on Fragment Correlations
title_sort	two-dimensional partial-covariance mass spectrometry of large molecules based on fragment correlations
publisher	American Physical Society
publishDate	2020
url	https://doaj.org/article/7b17f06c1b364a06b05b0221e0c212a8
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Two-Dimensional Partial-Covariance Mass Spectrometry of Large Molecules Based on Fragment Correlations

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