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Title: Bond-rearrangement and ionization mechanisms in the photo-double-ionization of simple hydrocarbons (C2H4, C2H3F, and 1,1-C2H2F2) near and above threshold

Abstract

We investigate bond-rearrangement driven by photo-double-ionization (PDI) near and above the double-ionization threshold in a sequence of carbon-carbon double-bonded hydrocarbon molecules: ethylene, fluoroethylene, and 1,1-difluoroethylene. We employ the kinematically complete cold target recoil ion momentum spectroscopy method to resolve all photo-double-ionization events leading to two-ion fragments. We observe changes in the branching ratios of different dissociative ionization channels depending on the presence of no, one, or two fluorine atoms. The role of the fluorine atom in the bond-rearrangement channels is intriguing, as evident by the reordering of the threshold energies of the PDI in the fluorinated molecules. These effects offer a compelling argument that the electronegativity of the fluorine (or the polarity of the molecule) strongly influences the potential energy surfaces of the molecules and drives bond rearrangement during the dissociation process. The energy sharing and the relative angle between the three-dimensional momentum vectors of the two electrons enable us to distinguish between knockout and other ionization mechanisms of the PDI processes.

Authors:
 [1];  [1];  [2];  [2];  [3];  [3];  [4];  [5];  [5];  [4];  [1];  [1]
  1. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
  2. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Goethe Univ., Frankfurt (Germany)
  3. Goethe Univ., Frankfurt (Germany)
  4. Auburn Univ., AL (United States)
  5. Kansas State Univ., Manhattan, KS (United States)
Publication Date:
Research Org.:
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1339563
Alternate Identifier(s):
OSTI ID: 1324498; OSTI ID: 1377491
Report Number(s):
LBNL-1005182
Journal ID: ISSN 2469-9926; ir:1005182; TRN: US1701640
Grant/Contract Number:  
AC02-05CH11231; FG02-86ER13491
Resource Type:
Accepted Manuscript
Journal Name:
Physical Review A
Additional Journal Information:
Journal Volume: 94; Journal ID: ISSN 2469-9926
Publisher:
American Physical Society (APS)
Country of Publication:
United States
Language:
English
Subject:
74 ATOMIC AND MOLECULAR PHYSICS

Citation Formats

Gaire, B., Gatton, A. S., Wiegandt, F., Neff, J., Janke, C., Zeller, S., Reedy, D., Rajput, J., Ben-Itzahk, I., Landers, A. L., Belkacem, A., and Weber, Th. Bond-rearrangement and ionization mechanisms in the photo-double-ionization of simple hydrocarbons (C2H4, C2H3F, and 1,1-C2H2F2) near and above threshold. United States: N. p., 2016. Web. doi:10.1103/PhysRevA.94.033412.
Gaire, B., Gatton, A. S., Wiegandt, F., Neff, J., Janke, C., Zeller, S., Reedy, D., Rajput, J., Ben-Itzahk, I., Landers, A. L., Belkacem, A., & Weber, Th. Bond-rearrangement and ionization mechanisms in the photo-double-ionization of simple hydrocarbons (C2H4, C2H3F, and 1,1-C2H2F2) near and above threshold. United States. https://doi.org/10.1103/PhysRevA.94.033412
Gaire, B., Gatton, A. S., Wiegandt, F., Neff, J., Janke, C., Zeller, S., Reedy, D., Rajput, J., Ben-Itzahk, I., Landers, A. L., Belkacem, A., and Weber, Th. Wed . "Bond-rearrangement and ionization mechanisms in the photo-double-ionization of simple hydrocarbons (C2H4, C2H3F, and 1,1-C2H2F2) near and above threshold". United States. https://doi.org/10.1103/PhysRevA.94.033412. https://www.osti.gov/servlets/purl/1339563.
@article{osti_1339563,
title = {Bond-rearrangement and ionization mechanisms in the photo-double-ionization of simple hydrocarbons (C2H4, C2H3F, and 1,1-C2H2F2) near and above threshold},
author = {Gaire, B. and Gatton, A. S. and Wiegandt, F. and Neff, J. and Janke, C. and Zeller, S. and Reedy, D. and Rajput, J. and Ben-Itzahk, I. and Landers, A. L. and Belkacem, A. and Weber, Th.},
abstractNote = {We investigate bond-rearrangement driven by photo-double-ionization (PDI) near and above the double-ionization threshold in a sequence of carbon-carbon double-bonded hydrocarbon molecules: ethylene, fluoroethylene, and 1,1-difluoroethylene. We employ the kinematically complete cold target recoil ion momentum spectroscopy method to resolve all photo-double-ionization events leading to two-ion fragments. We observe changes in the branching ratios of different dissociative ionization channels depending on the presence of no, one, or two fluorine atoms. The role of the fluorine atom in the bond-rearrangement channels is intriguing, as evident by the reordering of the threshold energies of the PDI in the fluorinated molecules. These effects offer a compelling argument that the electronegativity of the fluorine (or the polarity of the molecule) strongly influences the potential energy surfaces of the molecules and drives bond rearrangement during the dissociation process. The energy sharing and the relative angle between the three-dimensional momentum vectors of the two electrons enable us to distinguish between knockout and other ionization mechanisms of the PDI processes.},
doi = {10.1103/PhysRevA.94.033412},
journal = {Physical Review A},
number = ,
volume = 94,
place = {United States},
year = {Wed Sep 14 00:00:00 EDT 2016},
month = {Wed Sep 14 00:00:00 EDT 2016}
}

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