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Title: H2 roaming chemistry and the formation of H3+ from organic molecules in strong laser fields

Abstract

Roaming mechanisms, involving the brief generation of a neutral atom or molecule that stays in the vicinity before reacting with the remaining atoms of the precursor, are providing valuable insights into previously unexplained chemical reactions. Here in this paper, the mechanistic details and femtosecond time-resolved dynamics of H 3 + formation from a series of alcohols with varying primary carbon chain lengths are obtained through a combination of strong-field laser excitation studies and ab initio molecular dynamics calculations. For small alcohols, four distinct pathways involving hydrogen migration and H 2 roaming prior to H 3 + formation are uncovered. Despite the increased number of hydrogens and possible combinations leading to H 3 + formation, the yield decreases as the carbon chain length increases. The fundamental mechanistic findings presented here explore the formation of H 3 +, the most important ion in interstellar chemistry, through H 2 roaming occurring in ionic species.

Authors:
ORCiD logo [1];  [2]; ORCiD logo [1];  [1];  [1];  [2];  [2];  [2];  [2];  [2];  [2];  [2];  [2];  [2];  [1]; ORCiD logo [1];  [2]; ORCiD logo [3]
  1. Michigan State Univ., East Lansing, MI (United States). Dept. of Chemistry
  2. Kansas State Univ., Manhattan, KS (United States). J. R. Macdonald Lab., Physics Dept.
  3. Michigan State Univ., East Lansing, MI (United States). Dept. of Chemistry, and Dept. of Physics and Astronomy
Publication Date:
Research Org.:
Michigan State Univ., East Lansing, MI (United States); Kansas State Univ., Manhattan, KS (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1490277
Grant/Contract Number:  
SC0002325; FG02-86ER13491
Resource Type:
Accepted Manuscript
Journal Name:
Nature Communications
Additional Journal Information:
Journal Volume: 9; Journal Issue: 1; Journal ID: ISSN 2041-1723
Publisher:
Nature Publishing Group
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Ekanayake, Nagitha, Severt, Travis, Nairat, Muath, Weingartz, Nicholas P., Farris, Benjamin M., Kaderiya, Balram, Feizollah, Peyman, Jochim, Bethany, Ziaee, Farzaneh, Borne, Kurtis, Raju P., Kanaka, Carnes, Kevin D., Rolles, Daniel, Rudenko, Artem, Levine, Benjamin G., Jackson, James E., Ben-Itzhak, Itzik, and Dantus, Marcos. H2 roaming chemistry and the formation of H3+ from organic molecules in strong laser fields. United States: N. p., 2018. Web. doi:10.1038/s41467-018-07577-0.
Ekanayake, Nagitha, Severt, Travis, Nairat, Muath, Weingartz, Nicholas P., Farris, Benjamin M., Kaderiya, Balram, Feizollah, Peyman, Jochim, Bethany, Ziaee, Farzaneh, Borne, Kurtis, Raju P., Kanaka, Carnes, Kevin D., Rolles, Daniel, Rudenko, Artem, Levine, Benjamin G., Jackson, James E., Ben-Itzhak, Itzik, & Dantus, Marcos. H2 roaming chemistry and the formation of H3+ from organic molecules in strong laser fields. United States. doi:10.1038/s41467-018-07577-0.
Ekanayake, Nagitha, Severt, Travis, Nairat, Muath, Weingartz, Nicholas P., Farris, Benjamin M., Kaderiya, Balram, Feizollah, Peyman, Jochim, Bethany, Ziaee, Farzaneh, Borne, Kurtis, Raju P., Kanaka, Carnes, Kevin D., Rolles, Daniel, Rudenko, Artem, Levine, Benjamin G., Jackson, James E., Ben-Itzhak, Itzik, and Dantus, Marcos. Sat . "H2 roaming chemistry and the formation of H3+ from organic molecules in strong laser fields". United States. doi:10.1038/s41467-018-07577-0. https://www.osti.gov/servlets/purl/1490277.
@article{osti_1490277,
title = {H2 roaming chemistry and the formation of H3+ from organic molecules in strong laser fields},
author = {Ekanayake, Nagitha and Severt, Travis and Nairat, Muath and Weingartz, Nicholas P. and Farris, Benjamin M. and Kaderiya, Balram and Feizollah, Peyman and Jochim, Bethany and Ziaee, Farzaneh and Borne, Kurtis and Raju P., Kanaka and Carnes, Kevin D. and Rolles, Daniel and Rudenko, Artem and Levine, Benjamin G. and Jackson, James E. and Ben-Itzhak, Itzik and Dantus, Marcos},
abstractNote = {Roaming mechanisms, involving the brief generation of a neutral atom or molecule that stays in the vicinity before reacting with the remaining atoms of the precursor, are providing valuable insights into previously unexplained chemical reactions. Here in this paper, the mechanistic details and femtosecond time-resolved dynamics of H3 + formation from a series of alcohols with varying primary carbon chain lengths are obtained through a combination of strong-field laser excitation studies and ab initio molecular dynamics calculations. For small alcohols, four distinct pathways involving hydrogen migration and H2 roaming prior to H3 + formation are uncovered. Despite the increased number of hydrogens and possible combinations leading to H3 + formation, the yield decreases as the carbon chain length increases. The fundamental mechanistic findings presented here explore the formation of H3 +, the most important ion in interstellar chemistry, through H2 roaming occurring in ionic species.},
doi = {10.1038/s41467-018-07577-0},
journal = {Nature Communications},
number = 1,
volume = 9,
place = {United States},
year = {2018},
month = {12}
}

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Cited by: 9 works
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Figures / Tables:

Fig. 1 Fig. 1: Primary H3+ formation pathways from methanol (CH3OH) and ethanol (CH3CH2OH). Formation occurs via the neutral H2 roaming mechanism under strong-field laser ionization. In both molecules, the carbon atom attached to the hydroxyl functional group is referred to as the α-carbon and the corresponding hydrogen atoms are referred tomore » as α-hydrogens. In the case of ethanol, the terminal carbon atom and hydrogen atoms are referred to as the β-carbon and the β-hydrogen atoms, respectively« less

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