Infrared multiple photon dissociation spectroscopy of sodium and potassium chlorate anions

Ryan P. Dain; Christopher M. Leavitt; Jos Oomens; Jeffrey D. Steill; Gary S. Groenewold; Michael J. van Stipdonk

doi:10.1002/rcm.4379

Infrared multiple photon dissociation spectroscopy of sodium and potassium chlorate anions

Ryan P. Dain, Christopher M. Leavitt, Jos Oomens, Jeffrey D. Steill, Gary S. Groenewold, Michael J. van Stipdonk

Energy & Environmental Science & Technology

Research output: Contribution to journal › Article › peer-review

2 Scopus citations

Abstract

The structures of gas-phase, metal chlorate anions with the formula [M(ClO₃)₂], M 1/4Na and K, were determined using tandem mass spectrometry and infrared multiple photon dissociation (IRMPD) spectroscopy. Structural assignments for both anions are based on comparisons of the experimental vibrational spectra for the two species with those predicted by density functional theory (DFT) and involve conformations that feature either bidentate or tridentate coordination of the cation by chlorate. Our results strongly suggest that a structure in which both chlorate anions are bidentate ligands is preferred for [Na(ClO₃)₂]. However, for [K(ClO₃)₂] the best agreement between exper-imental and theoretical spectra is obtained from a composite of predicted spectra for which the chlorate anions are either both bidentate or both tridentate ligands. In general, we find that the overall accuracy of DFT calculations for prediction of IR spectra is dependent on both functional and basis set, with best agreement achieved using frequencies generated at the B3LYP/6-311Rg(3df) level of theory.

Original language	English
Pages (from-to)	232-238
Number of pages	7
Journal	Rapid Communications in Mass Spectrometry
Volume	24
Issue number	2
DOIs	https://doi.org/10.1002/rcm.4379
State	Published - Jan 30 2010

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@article{2a7fe4e47c4b4e16ae6ace15241000e1,

title = "Infrared multiple photon dissociation spectroscopy of sodium and potassium chlorate anions",

abstract = "The structures of gas-phase, metal chlorate anions with the formula [M(ClO3)2], M 1/4Na and K, were determined using tandem mass spectrometry and infrared multiple photon dissociation (IRMPD) spectroscopy. Structural assignments for both anions are based on comparisons of the experimental vibrational spectra for the two species with those predicted by density functional theory (DFT) and involve conformations that feature either bidentate or tridentate coordination of the cation by chlorate. Our results strongly suggest that a structure in which both chlorate anions are bidentate ligands is preferred for [Na(ClO3)2]. However, for [K(ClO3)2] the best agreement between exper-imental and theoretical spectra is obtained from a composite of predicted spectra for which the chlorate anions are either both bidentate or both tridentate ligands. In general, we find that the overall accuracy of DFT calculations for prediction of IR spectra is dependent on both functional and basis set, with best agreement achieved using frequencies generated at the B3LYP/6-311Rg(3df) level of theory.",

author = "Dain, {Ryan P.} and Leavitt, {Christopher M.} and Jos Oomens and Steill, {Jeffrey D.} and Groenewold, {Gary S.} and {van Stipdonk}, {Michael J.}",

note = "Funding Information: We thank the staff of the Fishing Federation of Vauc-luse and of the Fontanelle fish-farm, D. Beaudou and L. Blanc for efficient help in trout sampling, E. Desmarais and F.J. Garcia de Leon for technical assistance and G. Cattaneo-Berrebi who performed some of the protein electrophoresis analyses. We thank A. Ferguson, M. Monnerot and J.L. Garcia-Marin for useful comments on an earlier version of the manuscript. We wish to thank two anonymous reviewers and J.L Nielsen for many useful suggestions. This work was supported by grant 93–179 from the Conseil Sup{\'e}rieur de la P{\^e}che and EC contract EV5VCT920097.",

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T1 - Infrared multiple photon dissociation spectroscopy of sodium and potassium chlorate anions

AU - Dain, Ryan P.

AU - Leavitt, Christopher M.

AU - Oomens, Jos

AU - Steill, Jeffrey D.

AU - Groenewold, Gary S.

AU - van Stipdonk, Michael J.

N1 - Funding Information: We thank the staff of the Fishing Federation of Vauc-luse and of the Fontanelle fish-farm, D. Beaudou and L. Blanc for efficient help in trout sampling, E. Desmarais and F.J. Garcia de Leon for technical assistance and G. Cattaneo-Berrebi who performed some of the protein electrophoresis analyses. We thank A. Ferguson, M. Monnerot and J.L. Garcia-Marin for useful comments on an earlier version of the manuscript. We wish to thank two anonymous reviewers and J.L Nielsen for many useful suggestions. This work was supported by grant 93–179 from the Conseil Supérieur de la Pêche and EC contract EV5VCT920097.

PY - 2010/1/30

Y1 - 2010/1/30

N2 - The structures of gas-phase, metal chlorate anions with the formula [M(ClO3)2], M 1/4Na and K, were determined using tandem mass spectrometry and infrared multiple photon dissociation (IRMPD) spectroscopy. Structural assignments for both anions are based on comparisons of the experimental vibrational spectra for the two species with those predicted by density functional theory (DFT) and involve conformations that feature either bidentate or tridentate coordination of the cation by chlorate. Our results strongly suggest that a structure in which both chlorate anions are bidentate ligands is preferred for [Na(ClO3)2]. However, for [K(ClO3)2] the best agreement between exper-imental and theoretical spectra is obtained from a composite of predicted spectra for which the chlorate anions are either both bidentate or both tridentate ligands. In general, we find that the overall accuracy of DFT calculations for prediction of IR spectra is dependent on both functional and basis set, with best agreement achieved using frequencies generated at the B3LYP/6-311Rg(3df) level of theory.

AB - The structures of gas-phase, metal chlorate anions with the formula [M(ClO3)2], M 1/4Na and K, were determined using tandem mass spectrometry and infrared multiple photon dissociation (IRMPD) spectroscopy. Structural assignments for both anions are based on comparisons of the experimental vibrational spectra for the two species with those predicted by density functional theory (DFT) and involve conformations that feature either bidentate or tridentate coordination of the cation by chlorate. Our results strongly suggest that a structure in which both chlorate anions are bidentate ligands is preferred for [Na(ClO3)2]. However, for [K(ClO3)2] the best agreement between exper-imental and theoretical spectra is obtained from a composite of predicted spectra for which the chlorate anions are either both bidentate or both tridentate ligands. In general, we find that the overall accuracy of DFT calculations for prediction of IR spectra is dependent on both functional and basis set, with best agreement achieved using frequencies generated at the B3LYP/6-311Rg(3df) level of theory.

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JO - Rapid Communications in Mass Spectrometry

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ER -

Infrared multiple photon dissociation spectroscopy of sodium and potassium chlorate anions

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