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Journal of The American Society for Mass Spectrometry

, Volume 29, Issue 9, pp 1781–1790 | Cite as

Spectroscopic Identification of the Carbyne Hydride Structure of the Dehydrogenation Product of Methane Activation by Osmium Cations

  • P. B. Armentrout
  • Stach E. J. Kuijpers
  • Olga V. Lushchikova
  • Randy L. Hightower
  • Georgia C. Boles
  • Joost M. Bakker
Focus: Application of Photons and Radicals for MS: Research Article

Abstract

The present work explores the structures of species formed by dehydrogenation of methane (CH4) and perdeuterated methane (CD4) by the 5d transition metal cation osmium (Os+). Using infrared multiple photon dissociation (IRMPD) action spectroscopy and density functional theory (DFT), the structures of the [Os,C,2H]+ and [Os,C,2D]+ products are explored. This study complements previous work on the related species formed by dehydrogenation of methane by four other 5d transition metal cations (M+ = Ta+, W+, Ir+, and Pt+). Osmium cations are formed in a laser ablation source, react with methane pulsed into a reaction channel downstream, and the resulting products spectroscopically characterized through photofragmentation using the Free-Electron Laser for IntraCavity Experiments (FELICE) in the 300–1800 cm−1 range. Photofragmentation was monitored by the loss of H2/D2. Comparison of the experimental spectra and DFT calculated spectra leads to identification of the ground state carbyne hydride, HOsCH+ (2A′) as the species formed, as previously postulated theoretically. Further, a full description of the systematic spectroscopic shifts observed for deuterium labeling of these complexes, some of the smallest systems to be studied using IRMPD action spectroscopy, is achieved. A full rotational contour analysis explains the observed linewidths as well as the observation of doublet structures in several bands, consistent with previous observations for HIrCH+ (2A′).

Graphical Abstract

Keywords

Spectroscopy Intracavity free electron laser Infrared multiple photon dissociation Rotational band structure 

Notes

Acknowledgements

The Center for High Performance Computing (CHPC) at the University of Utah is acknowledged for their generous allocation of computing time.

Funding Information

We gratefully acknowledge the Nederlandse Organisatie voor Wetenschappelijk Onderzoek (NWO) for support of the FELIX Laboratory and support for this project was provided by the National Science Foundation, Grant Nos. CHE-1664618 and OISE-1357887.

Supplementary material

13361_2018_1929_MOESM1_ESM.docx (1.5 mb)
ESM 1 (DOCX 1553 kb)

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© American Society for Mass Spectrometry 2018

Authors and Affiliations

  1. 1.Department of ChemistryUniversity of UtahSalt Lake CityUSA
  2. 2.Radboud University, Institute for Molecules and Materials, FELIX LaboratoryNijmegenThe Netherlands

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