DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Time-resolved molecular dynamics of single and double hydrogen migration in ethanol

Abstract

Being the lightest, most mobile atom that exists, hydrogen plays an important role in the chemistry of hydrocarbons, proteins and peptides and most biomolecules. Hydrogen can undergo transfer, exchange and migration processes, having considerable impact on the chemical behavior of these molecules. Although much has been learned about reaction dynamics involving one hydrogen atom, less is known about those processes where two or more hydrogen atoms participate. Here we show that single and double hydrogen migrations occurring in ethanol cations and dications take place within a few hundred fs to ps, using a 3D imaging and laser pump-probe technique. For double hydrogen migration, the hydrogens are not correlated, with the second hydrogen migration promoting the breakup of the C–O bond. The probability of double hydrogen migration is quite significant, suggesting that double hydrogen migration plays a more important role than generally assumed. The conclusions are supported by state-of-the-art molecular dynamics calculations.

Authors:
 [1]; ORCiD logo [2]; ORCiD logo [1];  [1];  [1];  [1]; ORCiD logo [1];  [1];  [1];  [1];  [3]; ORCiD logo [4];  [1]
  1. Univ. of Connecticut, Storrs, CT (United States)
  2. Universidad Autónoma de Madrid (Spain)
  3. SLAC National Accelerator Lab., Menlo Park, CA (United States)
  4. Universidad Autónoma de Madrid (Spain); Instituto Madrileño de Estudios Avanzados en Nanociencia (IMDEA-Nano), Madrid (Spain); Donostia International Physics Center (DIPC), Donostia-San Sebastián (Spain)
Publication Date:
Research Org.:
SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1546973
Grant/Contract Number:  
AC02-76SF00515
Resource Type:
Accepted Manuscript
Journal Name:
Nature Communications
Additional Journal Information:
Journal Volume: 10; 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; 08 HYDROGEN

Citation Formats

Kling, Nora G., Díaz-Tendero, S., Obaid, R., Disla, M. R., Xiong, H., Sundberg, M., Khosravi, S. D., Davino, M., Drach, P., Carroll, A. M., Osipov, T., Martín, F., and Berrah, N. Time-resolved molecular dynamics of single and double hydrogen migration in ethanol. United States: N. p., 2019. Web. doi:10.1038/s41467-019-10571-9.
Kling, Nora G., Díaz-Tendero, S., Obaid, R., Disla, M. R., Xiong, H., Sundberg, M., Khosravi, S. D., Davino, M., Drach, P., Carroll, A. M., Osipov, T., Martín, F., & Berrah, N. Time-resolved molecular dynamics of single and double hydrogen migration in ethanol. United States. https://doi.org/10.1038/s41467-019-10571-9
Kling, Nora G., Díaz-Tendero, S., Obaid, R., Disla, M. R., Xiong, H., Sundberg, M., Khosravi, S. D., Davino, M., Drach, P., Carroll, A. M., Osipov, T., Martín, F., and Berrah, N. Thu . "Time-resolved molecular dynamics of single and double hydrogen migration in ethanol". United States. https://doi.org/10.1038/s41467-019-10571-9. https://www.osti.gov/servlets/purl/1546973.
@article{osti_1546973,
title = {Time-resolved molecular dynamics of single and double hydrogen migration in ethanol},
author = {Kling, Nora G. and Díaz-Tendero, S. and Obaid, R. and Disla, M. R. and Xiong, H. and Sundberg, M. and Khosravi, S. D. and Davino, M. and Drach, P. and Carroll, A. M. and Osipov, T. and Martín, F. and Berrah, N.},
abstractNote = {Being the lightest, most mobile atom that exists, hydrogen plays an important role in the chemistry of hydrocarbons, proteins and peptides and most biomolecules. Hydrogen can undergo transfer, exchange and migration processes, having considerable impact on the chemical behavior of these molecules. Although much has been learned about reaction dynamics involving one hydrogen atom, less is known about those processes where two or more hydrogen atoms participate. Here we show that single and double hydrogen migrations occurring in ethanol cations and dications take place within a few hundred fs to ps, using a 3D imaging and laser pump-probe technique. For double hydrogen migration, the hydrogens are not correlated, with the second hydrogen migration promoting the breakup of the C–O bond. The probability of double hydrogen migration is quite significant, suggesting that double hydrogen migration plays a more important role than generally assumed. The conclusions are supported by state-of-the-art molecular dynamics calculations.},
doi = {10.1038/s41467-019-10571-9},
journal = {Nature Communications},
number = 1,
volume = 10,
place = {United States},
year = {2019},
month = {6}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 26 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

Visualizing Recurrently Migrating Hydrogen in Acetylene Dication by Intense Ultrashort Laser Pulses
journal, December 2007


Fragmentation Dynamics of Doubly Charged Methionine in the Gas Phase
journal, February 2014

  • Ha, Dang Trinh; Wang, Y.; Alcamí, M.
  • The Journal of Physical Chemistry A, Vol. 118, Issue 8
  • DOI: 10.1021/jp4113238

Formation of H 3 O + from alcohols and ethers induced by intense laser fields
journal, March 2010

  • Shirota, Tatsuro; Mano, Narutoshi; Tsuge, Masashi
  • Rapid Communications in Mass Spectrometry, Vol. 24, Issue 5
  • DOI: 10.1002/rcm.4438

Formation of fragment ions (H+, H3+, CH3+) from ethane in intense femtosecond laser fields – from understanding to control
journal, January 2013

  • Schirmel, Nora; Reusch, Nicola; Horsch, Philipp
  • Faraday Discussions, Vol. 163
  • DOI: 10.1039/c3fd20152j

Tabletop imaging of structural evolutions in chemical reactions demonstrated for the acetylene cation
journal, July 2014

  • Ibrahim, Heide; Wales, Benji; Beaulieu, Samuel
  • Nature Communications, Vol. 5, Issue 1
  • DOI: 10.1038/ncomms5422

Intramolecular hydrogen atom migration along the backbone of cationic and neutral radical tripeptides and subsequent radical-induced dissociations
journal, January 2012

  • Zhao, Junfang; Song, Tao; Xu, Minjie
  • Physical Chemistry Chemical Physics, Vol. 14, Issue 24
  • DOI: 10.1039/c2cp40708f

Formation of H 3 O + from alcohols and ethers induced by intense laser fields
journal, March 2010

  • Shirota, Tatsuro; Mano, Narutoshi; Tsuge, Masashi
  • Rapid Communications in Mass Spectrometry, Vol. 24, Issue 5
  • DOI: 10.1002/rcm.4438

Fragmentation Dynamics of Doubly Charged Methionine in the Gas Phase
journal, February 2014

  • Ha, Dang Trinh; Wang, Y.; Alcamí, M.
  • The Journal of Physical Chemistry A, Vol. 118, Issue 8
  • DOI: 10.1021/jp4113238

Control of Electron Localization in Molecular Dissociation
journal, April 2006


Formation of fragment ions (H+, H3+, CH3+) from ethane in intense femtosecond laser fields – from understanding to control
journal, January 2013

  • Schirmel, Nora; Reusch, Nicola; Horsch, Philipp
  • Faraday Discussions, Vol. 163
  • DOI: 10.1039/c3fd20152j

Infrared Photoactivation Reduces Peptide Folding and Hydrogen-Atom Migration following ETD Tandem Mass Spectrometry
journal, October 2009

  • Ledvina, Aaron R.; McAlister, Graeme C.; Gardner, Myles W.
  • Angewandte Chemie, Vol. 121, Issue 45
  • DOI: 10.1002/ange.200903557

Rapid formation of H + 3 from ammonia and methane following 4 MeV proton impact
journal, April 2009

  • Jochim, Bethany; Lueking, Amy; Doshier, Laura
  • Journal of Physics B: Atomic, Molecular and Optical Physics, Vol. 42, Issue 9
  • DOI: 10.1088/0953-4075/42/9/091002

Ab initio molecular dynamics: Propagating the density matrix with Gaussian orbitals
journal, June 2001

  • Schlegel, H. Bernhard; Millam, John M.; Iyengar, Srinivasan S.
  • The Journal of Chemical Physics, Vol. 114, Issue 22
  • DOI: 10.1063/1.1372182

Control of Electron Localization in Molecular Dissociation
journal, April 2006


Influence of Peptide Composition, Gas-Phase Basicity, and Chemical Modification on Fragmentation Efficiency:  Evidence for the Mobile Proton Model
journal, January 1996

  • Dongré, Ashok R.; Jones, Jennifer L.; Somogyi, Árpád
  • Journal of the American Chemical Society, Vol. 118, Issue 35
  • DOI: 10.1021/ja9542193

Structure and function of a novel antioxidant peptide from the skin of tropical frogs
journal, February 2018


Ultrafast isomerization initiated by X-ray core ionization
journal, September 2015

  • Liekhus-Schmaltz, Chelsea E.; Tenney, Ian; Osipov, Timur
  • Nature Communications, Vol. 6, Issue 1
  • DOI: 10.1038/ncomms9199

Ultrafast isomerization initiated by X-ray core ionization
journal, September 2015

  • Liekhus-Schmaltz, Chelsea E.; Tenney, Ian; Osipov, Timur
  • Nature Communications, Vol. 6, Issue 1
  • DOI: 10.1038/ncomms9199

An intramolecular model for the enzymic insertion of coenzyme B12 into unactivated carbon-hydrogen bonds
journal, March 1976

  • Breslow, Ronald; Khanna, Pyare L.
  • Journal of the American Chemical Society, Vol. 98, Issue 5
  • DOI: 10.1021/ja00421a060

Electron Capture Dissociation Proceeds with a Low Degree of Intramolecular Migration of Peptide Amide Hydrogens
journal, January 2008

  • Rand, Kasper D.; Adams, Christopher M.; Zubarev, Roman A.
  • Journal of the American Chemical Society, Vol. 130, Issue 4
  • DOI: 10.1021/ja076448i

Femtochemistry:  Atomic-Scale Dynamics of the Chemical Bond
journal, June 2000

  • Zewail, Ahmed H.
  • The Journal of Physical Chemistry A, Vol. 104, Issue 24
  • DOI: 10.1021/jp001460h

Hydrogen migration in methanol studied under asymmetric fs laser irradiation
journal, June 2014


Infrared Photoactivation Reduces Peptide Folding and Hydrogen-Atom Migration following ETD Tandem Mass Spectrometry
journal, October 2009

  • Ledvina, Aaron R.; McAlister, Graeme C.; Gardner, Myles W.
  • Angewandte Chemie International Edition, Vol. 48, Issue 45
  • DOI: 10.1002/anie.200903557

Hydrogen migration in acetonitrile in intense laser fields in competition with two-body Coulomb explosion
journal, December 2004

  • Hishikawa, Akiyoshi; Hasegawa, Hirokazu; Yamanouchi, Kaoru
  • Journal of Electron Spectroscopy and Related Phenomena, Vol. 141, Issue 2-3
  • DOI: 10.1016/j.elspec.2004.06.009

A Multicoincidence Study of Fragmentation Dynamics in Collision of γ-Aminobutyric Acid with Low-Energy Ions
journal, June 2012

  • Capron, Michael; Díaz-Tendero, Sergio; Maclot, Sylvain
  • Chemistry - A European Journal, Vol. 18, Issue 30
  • DOI: 10.1002/chem.201103922

Energetics and Mechanism of Hydronium ion Formation by Electron Impact
journal, December 1963

  • Raalte, D. Van; Harrison, A. G.
  • Canadian Journal of Chemistry, Vol. 41, Issue 12
  • DOI: 10.1139/v63-455

Formation of H3O+ from ethanol clusters induced by intense femtosecond laser fields
journal, April 2010


Wave packet bifurcation in ultrafast hydrogen migration in CH3OH+ by pump-probe coincidence momentum imaging with few-cycle laser pulses
journal, March 2015


The structures, conversions and fragmentations of C2H6O2+ isomers: An ab initio study
journal, October 2006


Two-body Coulomb explosion in methylacetylene in intense laser fields: double proton migration and proton/deuteron exchange
journal, January 2012

  • Okino, Tomoya; Watanabe, Anri; Xu, Huailiang
  • Physical Chemistry Chemical Physics, Vol. 14, Issue 12
  • DOI: 10.1039/c2cp23880b

Intramolecular Hydrogen Migration in Alkylperoxy and Hydroperoxyalkylperoxy Radicals: Accurate Treatment of Hindered Rotors
journal, May 2010

  • Sharma, Sandeep; Raman, Sumathy; Green, William H.
  • The Journal of Physical Chemistry A, Vol. 114, Issue 18
  • DOI: 10.1021/jp9098792

Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density
text, January 1988

  • Robert, Parr,; Chengteh, Lee,; Weitao, Yang,
  • The University of North Carolina at Chapel Hill University Libraries
  • DOI: 10.17615/zrp0-ry04

Intramolecular Hydrogen Migration in Alkylperoxy and Hydroperoxyalkylperoxy Radicals: Accurate Treatment of Hindered Rotors
journal, May 2010

  • Sharma, Sandeep; Raman, Sumathy; Green, William H.
  • The Journal of Physical Chemistry A, Vol. 114, Issue 18
  • DOI: 10.1021/jp9098792

Ultrafast hydrogen migration in allene in intense laser fields: Evidence of two-body Coulomb explosion
journal, February 2009


Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density
journal, January 1988


The structures, conversions and fragmentations of C2H6O2+ isomers: An ab initio study
journal, October 2006


Mechanisms and time-resolved dynamics for trihydrogen cation (H3 +) formation from organic molecules in strong laser fields
journal, July 2017


Strong fields induce ultrafast rearrangement of H-atoms in H$_2$O
text, January 2008


Ab initio molecular dynamics: Propagating the density matrix with Gaussian orbitals. III. Comparison with Born–Oppenheimer dynamics
journal, November 2002

  • Schlegel, H. Bernhard; Iyengar, Srinivasan S.; Li, Xiaosong
  • The Journal of Chemical Physics, Vol. 117, Issue 19
  • DOI: 10.1063/1.1514582

Energetics and Mechanism of Hydronium ion Formation by Electron Impact
journal, December 1963

  • Raalte, D. Van; Harrison, A. G.
  • Canadian Journal of Chemistry, Vol. 41, Issue 12
  • DOI: 10.1139/v63-455

Dynamics of Glycine Dications in the Gas Phase: Ultrafast Intramolecular Hydrogen Migration versus Coulomb Repulsion
journal, November 2013

  • Maclot, Sylvain; Piekarski, Dariusz Grzegorz; Domaracka, Alicja
  • The Journal of Physical Chemistry Letters, Vol. 4, Issue 22
  • DOI: 10.1021/jz4020234

A review on reforming bio-ethanol for hydrogen production
journal, October 2007


Production of doubly-charged highly reactive species from the long-chain amino acid GABA initiated by Ar 9+ ionization
journal, January 2017

  • Piekarski, Dariusz Grzegorz; Delaunay, Rudy; Mika, Arkadiusz
  • Physical Chemistry Chemical Physics, Vol. 19, Issue 30
  • DOI: 10.1039/C7CP00903H

Encoding of vinylidene isomerization in its anion photoelectron spectrum
journal, October 2017

  • DeVine, Jessalyn A.; Weichman, Marissa L.; Laws, Benjamin
  • Science, Vol. 358, Issue 6361
  • DOI: 10.1126/science.aao1905

Unusual hydroxyl migration in the fragmentation of β-alanine dication in the gas phase
journal, January 2015

  • Piekarski, Dariusz Grzegorz; Delaunay, Rudy; Maclot, Sylvain
  • Physical Chemistry Chemical Physics, Vol. 17, Issue 26
  • DOI: 10.1039/c5cp01628b

Strong fields induce ultrafast rearrangement of H-atoms in H$_2$O
text, January 2008


Ab initio molecular dynamics: Propagating the density matrix with Gaussian orbitals. III. Comparison with Born–Oppenheimer dynamics
journal, November 2002

  • Schlegel, H. Bernhard; Iyengar, Srinivasan S.; Li, Xiaosong
  • The Journal of Chemical Physics, Vol. 117, Issue 19
  • DOI: 10.1063/1.1514582

Determination of Energy-Transfer Distributions in Ionizing Ion-Molecule Collisions
journal, August 2016


Ultrafast hydrogen migration in allene in intense laser fields: Evidence of two-body Coulomb explosion
journal, February 2009


Ab initio molecular dynamics: Propagating the density matrix with Gaussian orbitals. II. Generalizations based on mass-weighting, idempotency, energy conservation and choice of initial conditions
journal, January 2001

  • Iyengar, Srinivasan S.; Schlegel, H. Bernhard; Millam, John M.
  • The Journal of Chemical Physics, Vol. 115, Issue 22
  • DOI: 10.1063/1.1416876

Wave packet bifurcation in ultrafast hydrogen migration in CH3OH+ by pump-probe coincidence momentum imaging with few-cycle laser pulses
journal, March 2015


Hydrogen Atom Scrambling in Selectively Labeled Anionic Peptides Upon Collisional Activation by MALDI Tandem Time-of-Flight Mass Spectrometry
journal, December 2008

  • Bache, N.; Rand, K.; Roepstorff, P.
  • Journal of the American Society for Mass Spectrometry, Vol. 19, Issue 12
  • DOI: 10.1016/j.jasms.2008.05.021

Hydrogen migration in acetonitrile in intense laser fields in competition with two-body Coulomb explosion
journal, December 2004

  • Hishikawa, Akiyoshi; Hasegawa, Hirokazu; Yamanouchi, Kaoru
  • Journal of Electron Spectroscopy and Related Phenomena, Vol. 141, Issue 2-3
  • DOI: 10.1016/j.elspec.2004.06.009

Efficient ejection of H3+ from hydrocarbon molecules induced by ultrashort intense laser fields
journal, September 2008

  • Hoshina, Kennosuke; Furukawa, Yusuke; Okino, Tomoya
  • The Journal of Chemical Physics, Vol. 129, Issue 10
  • DOI: 10.1063/1.2973588

Hydrogen scrambling in ethane induced by intense laser fields: Statistical analysis of coincidence events
journal, May 2012

  • Kanya, Reika; Kudou, Tatsuya; Schirmel, Nora
  • The Journal of Chemical Physics, Vol. 136, Issue 20
  • DOI: 10.1063/1.4720503

An intramolecular model for the enzymic insertion of coenzyme B12 into unactivated carbon-hydrogen bonds
journal, March 1976

  • Breslow, Ronald; Khanna, Pyare L.
  • Journal of the American Chemical Society, Vol. 98, Issue 5
  • DOI: 10.1021/ja00421a060

Visualization of bond rearrangements in acetylene using near single-cycle laser pulses
journal, January 2016

  • Burger, Christian; Kling, Nora G.; Siemering, Robert
  • Faraday Discussions, Vol. 194
  • DOI: 10.1039/C6FD00082G

Strong fields induce ultrafast rearrangement of H atoms in H2O
journal, June 2009

  • Rajgara, F. A.; Dharmadhikari, A. K.; Mathur, D.
  • The Journal of Chemical Physics, Vol. 130, Issue 23
  • DOI: 10.1063/1.3157234

Steering Proton Migration in Hydrocarbons Using Intense Few-Cycle Laser Fields
journal, May 2016


Hydrogen migration in methanol studied under asymmetric fs laser irradiation
journal, June 2014


Infrared Photoactivation Reduces Peptide Folding and Hydrogen-Atom Migration following ETD Tandem Mass Spectrometry
journal, October 2009

  • Ledvina, Aaron R.; McAlister, Graeme C.; Gardner, Myles W.
  • Angewandte Chemie International Edition, Vol. 48, Issue 45
  • DOI: 10.1002/anie.200903557

Observation of the Hydrogen Migration in the Cation-Induced Fragmentation of the Pyridine Molecules
journal, February 2016

  • Wasowicz, Tomasz J.; Pranszke, Bogusław
  • The Journal of Physical Chemistry A, Vol. 120, Issue 7
  • DOI: 10.1021/acs.jpca.5b11298

Formation of H3O+ from ethanol clusters induced by intense femtosecond laser fields
journal, April 2010


Femtochemistry:  Atomic-Scale Dynamics of the Chemical Bond
journal, June 2000

  • Zewail, Ahmed H.
  • The Journal of Physical Chemistry A, Vol. 104, Issue 24
  • DOI: 10.1021/jp001460h

Dynamics of Glycine Dications in the Gas Phase: Ultrafast Intramolecular Hydrogen Migration versus Coulomb Repulsion
journal, November 2013

  • Maclot, Sylvain; Piekarski, Dariusz Grzegorz; Domaracka, Alicja
  • The Journal of Physical Chemistry Letters, Vol. 4, Issue 22
  • DOI: 10.1021/jz4020234

CXII. On the analysis of τ-meson data and the nature of the τ-meson
journal, October 1953

  • Dalitz, R. H.
  • The London, Edinburgh, and Dublin Philosophical Magazine and Journal of Science, Vol. 44, Issue 357
  • DOI: 10.1080/14786441008520365

A review on reforming bio-ethanol for hydrogen production
journal, October 2007


Hydrogen Atom Scrambling in Ion‐Molecule Reactions of Methane and Ethylene
journal, May 1972

  • Huntress, Wesley T.
  • The Journal of Chemical Physics, Vol. 56, Issue 10
  • DOI: 10.1063/1.1676996

Mechanisms and time-resolved dynamics for trihydrogen cation (H3 +) formation from organic molecules in strong laser fields
journal, July 2017


Efficient ejection of H3+ from hydrocarbon molecules induced by ultrashort intense laser fields
journal, September 2008

  • Hoshina, Kennosuke; Furukawa, Yusuke; Okino, Tomoya
  • The Journal of Chemical Physics, Vol. 129, Issue 10
  • DOI: 10.1063/1.2973588

Ab initio molecular dynamics: Propagating the density matrix with Gaussian orbitals. II. Generalizations based on mass-weighting, idempotency, energy conservation and choice of initial conditions
journal, January 2001

  • Iyengar, Srinivasan S.; Schlegel, H. Bernhard; Millam, John M.
  • The Journal of Chemical Physics, Vol. 115, Issue 22
  • DOI: 10.1063/1.1416876

Tabletop imaging of structural evolutions in chemical reactions demonstrated for the acetylene cation
journal, July 2014

  • Ibrahim, Heide; Wales, Benji; Beaulieu, Samuel
  • Nature Communications, Vol. 5, Issue 1
  • DOI: 10.1038/ncomms5422

Influence of Peptide Composition, Gas-Phase Basicity, and Chemical Modification on Fragmentation Efficiency:  Evidence for the Mobile Proton Model
journal, January 1996

  • Dongré, Ashok R.; Jones, Jennifer L.; Somogyi, Árpád
  • Journal of the American Chemical Society, Vol. 118, Issue 35
  • DOI: 10.1021/ja9542193

Rapid formation of H + 3 from ammonia and methane following 4 MeV proton impact
journal, April 2009

  • Jochim, Bethany; Lueking, Amy; Doshier, Laura
  • Journal of Physics B: Atomic, Molecular and Optical Physics, Vol. 42, Issue 9
  • DOI: 10.1088/0953-4075/42/9/091002

Theories and simulations of roaming
journal, January 2017

  • Bowman, Joel M.; Houston, Paul L.
  • Chemical Society Reviews, Vol. 46, Issue 24
  • DOI: 10.1039/c7cs00578d

Density‐functional thermochemistry. III. The role of exact exchange
journal, April 1993

  • Becke, Axel D.
  • The Journal of Chemical Physics, Vol. 98, Issue 7, p. 5648-5652
  • DOI: 10.1063/1.464913

Works referencing / citing this record:

Ultrafast dissociation dynamics of singly and doubly ionized N 2 O in strong laser fields
journal, January 2020


Strong-field control of H3+ production from methanol dications: Selecting between local and extended formation mechanisms
journal, February 2020

  • Iwamoto, Naoki; Schwartz, Charles J.; Jochim, Bethany
  • The Journal of Chemical Physics, Vol. 152, Issue 5
  • DOI: 10.1063/1.5129946