Ultrafast isomerization in acetylene dication after carbon K-shell ionization
Abstract
Ultrafast proton migration and isomerization are key processes for acetylene and its ions. However, the mechanism for ultrafast isomerization of acetylene [HCCH]2+ to vinylidene [H2CC]2+ dication remains nebulous. Theoretical studies show a large potential barrier ( > 2 eV) for isomerization on low-lying dicationic states, implying picosecond or longer isomerization timescales. However, a recent experiment at a femtosecond X-ray free-electron laser suggests sub-100 fs isomerization. Here we address this contradiction with a complete theoretical study of the dynamics of acetylene dication produced by Auger decay after X-ray photoionization of the carbon atom K shell. We find no sub-100 fs isomerization, while reproducing the salient features of the time-resolved Coulomb imaging experiment. This work resolves the seeming contradiction between experiment and theory and also calls for careful interpretation of structural information from the widely applied Coulomb momentum imaging method.
- Authors:
-
[1];
[6];
[7];
[8]
- SLAC National Accelerator Lab., Menlo Park, CA (United States); Stanford Univ., CA (United States). PULSE Inst. Dept. of Chemistry
- Deutsches Elektronen-Synchrotron (DESY), Hamburg (Germany). Center for Free-Electron Laser Science; Hamburg Center for Ultrafast Imaging (Germany)
- SLAC National Accelerator Lab., Menlo Park, CA (United States); Stanford Univ., CA (United States). Dept. of Physics
- Deutsches Elektronen-Synchrotron (DESY), Hamburg (Germany). Center for Free-Electron Laser Science; Czech Academy of Sciences, Prague (Czech Republic). Inst. of Physics. Dept. of Radiation and Chemical Physics; Czech Academy of Sciences, Prague (Czech Republic). Inst. of Plasma Physics. Laser Plasma Dept.
- SLAC National Accelerator Lab., Menlo Park, CA (United States)
- Czech Republic
- Harvard-Smithsonian Center for Astrophysics, Cambridge, MA (United States)
- SLAC National Accelerator Lab., Menlo Park, CA (United States); SLAC National Accelerator Lab., Menlo Park, CA (United States). Photon Ultrafast Laser Science and Engineering Inst. (PULSE). Dept. of Chemistry
- Publication Date:
- Research Org.:
- SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities Division
- OSTI Identifier:
- 1624044
- Grant/Contract Number:
- AC02-76SF00515
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Nature Communications
- Additional Journal Information:
- Journal Volume: 8; Journal Issue: 1; Journal ID: ISSN 2041-1723
- Publisher:
- Nature Publishing Group
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSICS; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Science & Technology - Other Topics
Citation Formats
Li, Zheng, Inhester, Ludger, Liekhus-Schmaltz, Chelsea, Curchod, Basile F. E., Snyder, James W., Medvedev, Nikita, Cryan, James, Osipov, Timur, Pabst, Stefan, Vendrell, Oriol, Bucksbaum, Phil, and Martinez, Todd J. Ultrafast isomerization in acetylene dication after carbon K-shell ionization. United States: N. p., 2017.
Web. doi:10.1038/s41467-017-00426-6.
Li, Zheng, Inhester, Ludger, Liekhus-Schmaltz, Chelsea, Curchod, Basile F. E., Snyder, James W., Medvedev, Nikita, Cryan, James, Osipov, Timur, Pabst, Stefan, Vendrell, Oriol, Bucksbaum, Phil, & Martinez, Todd J. Ultrafast isomerization in acetylene dication after carbon K-shell ionization. United States. https://doi.org/10.1038/s41467-017-00426-6
Li, Zheng, Inhester, Ludger, Liekhus-Schmaltz, Chelsea, Curchod, Basile F. E., Snyder, James W., Medvedev, Nikita, Cryan, James, Osipov, Timur, Pabst, Stefan, Vendrell, Oriol, Bucksbaum, Phil, and Martinez, Todd J. Wed .
"Ultrafast isomerization in acetylene dication after carbon K-shell ionization". United States. https://doi.org/10.1038/s41467-017-00426-6. https://www.osti.gov/servlets/purl/1624044.
@article{osti_1624044,
title = {Ultrafast isomerization in acetylene dication after carbon K-shell ionization},
author = {Li, Zheng and Inhester, Ludger and Liekhus-Schmaltz, Chelsea and Curchod, Basile F. E. and Snyder, James W. and Medvedev, Nikita and Cryan, James and Osipov, Timur and Pabst, Stefan and Vendrell, Oriol and Bucksbaum, Phil and Martinez, Todd J.},
abstractNote = {Ultrafast proton migration and isomerization are key processes for acetylene and its ions. However, the mechanism for ultrafast isomerization of acetylene [HCCH]2+ to vinylidene [H2CC]2+ dication remains nebulous. Theoretical studies show a large potential barrier ( > 2 eV) for isomerization on low-lying dicationic states, implying picosecond or longer isomerization timescales. However, a recent experiment at a femtosecond X-ray free-electron laser suggests sub-100 fs isomerization. Here we address this contradiction with a complete theoretical study of the dynamics of acetylene dication produced by Auger decay after X-ray photoionization of the carbon atom K shell. We find no sub-100 fs isomerization, while reproducing the salient features of the time-resolved Coulomb imaging experiment. This work resolves the seeming contradiction between experiment and theory and also calls for careful interpretation of structural information from the widely applied Coulomb momentum imaging method.},
doi = {10.1038/s41467-017-00426-6},
journal = {Nature Communications},
number = 1,
volume = 8,
place = {United States},
year = {Wed Sep 06 00:00:00 EDT 2017},
month = {Wed Sep 06 00:00:00 EDT 2017}
}
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