Direct Experimental Observation of the Tetrabromine Cluster Br4 by Synchrotron Photoionization Mass Spectrometry

McClish, Rory; Meloni, Giovanni

doi:10.1002/open.202300266

Direct Experimental Observation of the Tetrabromine Cluster Br₄ by Synchrotron Photoionization Mass Spectrometry

Journal Article · Thu Feb 01 23:00:00 EST 2024 · ChemistryOpen

DOI:https://doi.org/10.1002/open.202300266· OSTI ID:2471042

McClish, Rory ^[1]; ^[2]

University of San Francisco, San Francisco, CA (United States)
University of San Francisco, San Francisco, CA (United States); New York Institute of Technology, Old Westbury, NY (United States)

We present a first spectroscopic characterization of the homoatomic polyhalogen tetrabromine, Br₄, in the gas phase. Photolysis of CHBr₃ at 248 nm is used to generate atomic bromine radicals in a flow tube reactor. Resulting combination products are detected by photoionization mass spectrometry at the Advanced Light Source of the Lawrence Berkeley National Laboratory. Interpretation of the experimental mass spectra is informed by calculated adiabatic ionization energies carried out at the CCSD(T)/aug-cc-pVTZ//M06-2X/aug-cc-pVTZ and CCSD(T)/aug-cc-pVTZ//cam-B3LYP/6-311++g** levels of theory. Tunable VUV synchrotron radiation enables the collection of the mass-selected photoionization spectra by which Br₄ is assigned using Franck-Condon simulations of a Br₂ dimer with a stretched tetrahedral geometry.

View Accepted Manuscript (DOE)

Research Organization:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). Advanced Light Source (ALS)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB)

Grant/Contract Number:: AC02-05CH11231

OSTI ID:: 2471042

Journal Information:: ChemistryOpen, Journal Name: ChemistryOpen Journal Issue: 7 Vol. 13; ISSN 2191-1363

Publisher:: ChemPubSoc EuropeCopyright Statement

Country of Publication:: United States

Language:: English

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Direct Experimental Observation of the Tetrabromine Cluster Br4 by Synchrotron Photoionization Mass Spectrometry

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Direct Experimental Observation of the Tetrabromine Cluster Br₄ by Synchrotron Photoionization Mass Spectrometry