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Theoretical and experimental studies on concerted elimination of 1, 2-bromochloroethane monocation to C2H4+ and BrCl
  • +7
  • Hua Wu,
  • Mengdi An,
  • Junqing Wen,
  • Lihua Bai,
  • Dongming Li,
  • Junkun Liu,
  • Ruijuan Sun,
  • Wanlin He,
  • Lin Lin,
  • Yumei Li
Hua Wu
Xi'an Shiyou University
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Mengdi An
Xi’an Shiyou University
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Junqing Wen
Xi’an Shiyou University
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Lihua Bai
Xi’an Shiyou University
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Dongming Li
Xi’an Shiyou University
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Junkun Liu
Shanghai Institute of Technology
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Ruijuan Sun
Xi'an Shiyou University
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Wanlin He
Xi’an Shiyou University
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Lin Lin
Xi’an Shiyou University
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Yumei Li
Xi’an Shiyou University
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Peer review status:UNDER REVIEW

27 Feb 2020Submitted to International Journal of Quantum Chemistry
28 Feb 2020Submission Checks Completed
28 Feb 2020Assigned to Editor
02 Mar 2020Reviewer(s) Assigned
04 May 2020Review(s) Completed, Editorial Evaluation Pending
04 May 2020Editorial Decision: Revise Major
27 May 20201st Revision Received
28 May 2020Submission Checks Completed
28 May 2020Assigned to Editor
10 Jun 2020Reviewer(s) Assigned

Abstract

We calculate the concerted pathway of 1, 2-bromochloroethane monocation to C2H4+ and BrCl using the Minnesota density functional M06-2X and the def2-TZVP basis set. We also calculate the elimination channel of 1, 2-bromochloroethane monocation to C2H4 and BrCl+ for the reason that positive charge can be assigned to either moiety in the fragmentation process of 1,2-C2H4BrCl+. Our results demonstrate that the elimination channel of 1, 2-bromochloroethane monocation to C2H4+ and BrCl is preferred, and the singly charged 1,2-bromochloroethane ions surpass two energy barriers and then separate into C2H4+ + BrCl by an asynchronous concerted process. Experimentally, we confirm that this elimination channel is from the dissociative ionization process of 1,2-bromochloroethane monocation by dc-slice imaging technique. Besides, we can see in laser-induced time-of-flight mass spectra of 1,2-bromochloroethane that fragment ion C2H4+ occur at the laser intensity of 6.0×1013 W/cm2 while BrCl+ occur at a higher laser intensity, which is consistent with the theoretical results that appearance energy of ion C2H4+ should be lower than that of BrCl+, and this is the reason why the low-velocity component of ion BrCl+ is absent from our sliced images.