Simplicity Beneath Complexity: Counting Molecular Electrons Reveals Transients and Kinetics of Photodissociation Reactions

Ruddock, Jennifer M.; Zotev, Nikola; Stankus, Brian; Yong, Haiwang; Bellshaw, Darren; Boutet, Sébastien; Lane, Thomas J.; Liang, Mengning; Carbajo, Sergio; Du, Wenpeng; Kirrander, Adam; Minitti, Michael; Weber, Peter M.

doi:10.1002/ange.201902228

Title: Simplicity Beneath Complexity: Counting Molecular Electrons Reveals Transients and Kinetics of Photodissociation Reactions

Abstract

Abstract Time‐resolved pump–probe gas‐phase X‐ray scattering signals, extrapolated to zero momentum transfer, provide a measure of the number of electrons in a system, an effect that arises from the coherent addition of elastic scattering from the electrons. This allows to identify reactive transients and determine the chemical reaction kinetics without the need for extensive scattering simulations or complicated inversion of scattering data. We examine the photodissociation reaction of trimethylamine and identify two reaction paths upon excitation to the 3p state at 200 nm: a fast dissociation path out of the 3p state to the dimethyl amine radical (16.6±1.2 %) and a slower dissociation via internal conversion to the 3s state (83.4±1.2 %). The time constants for the two reactions are 640±130 fs and 74±6 ps, respectively. Additionally, it is found that the transient dimethyl amine radical has a N−C bond length of 1.45±0.02 Å and a C−N−C bond angle of 118°±4°.

Authors:

^[1]; Zotev, Nikola ^[2]; Stankus, Brian ^[3]; Yong, Haiwang ^[3]; Bellshaw, Darren ^[2]; Boutet, Sébastien ^[4]; Lane, Thomas J. ^[4]; Liang, Mengning ^[4]; Carbajo, Sergio ^[4]; Du, Wenpeng ^[3]; Kirrander, Adam ^[2];

^[4];

^[3]

Department of Chemistry Brown University 324 Brook St Providence RI 02912 USA, SLAC National Accelerator Laboratory 2575 Sandhill Rd Menlo Park CA 94025 USA
EaStCHEM School of Chemistry University of Edinburgh David Brewster Road Edinburgh EH9 3FJ UK
Department of Chemistry Brown University 324 Brook St Providence RI 02912 USA
SLAC National Accelerator Laboratory 2575 Sandhill Rd Menlo Park CA 94025 USA

Publication Date:: Mon May 06 00:00:00 EDT 2019

Sponsoring Org.:: USDOE

OSTI Identifier:: 1504297

Grant/Contract Number:: AC02-76SF00515

Resource Type:: Publisher's Accepted Manuscript

Journal Name:: Angewandte Chemie

Additional Journal Information:: Journal Name: Angewandte Chemie Journal Volume: 131 Journal Issue: 19; Journal ID: ISSN 0044-8249

Publisher:: Wiley Blackwell (John Wiley & Sons)

Country of Publication:: Germany

Language:: English

Citation Formats


                    Ruddock, Jennifer M., Zotev, Nikola, Stankus, Brian, Yong, Haiwang, Bellshaw, Darren, Boutet, Sébastien, Lane, Thomas J., Liang, Mengning, Carbajo, Sergio, Du, Wenpeng, Kirrander, Adam, Minitti, Michael, and Weber, Peter M. Simplicity Beneath Complexity: Counting Molecular Electrons Reveals Transients and Kinetics of Photodissociation Reactions.  Germany: N. p., 2019. 
Web.  doi:10.1002/ange.201902228.

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                    Ruddock, Jennifer M., Zotev, Nikola, Stankus, Brian, Yong, Haiwang, Bellshaw, Darren, Boutet, Sébastien, Lane, Thomas J., Liang, Mengning, Carbajo, Sergio, Du, Wenpeng, Kirrander, Adam, Minitti, Michael, & Weber, Peter M. Simplicity Beneath Complexity: Counting Molecular Electrons Reveals Transients and Kinetics of Photodissociation Reactions.  Germany.  https://doi.org/10.1002/ange.201902228

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                    Ruddock, Jennifer M., Zotev, Nikola, Stankus, Brian, Yong, Haiwang, Bellshaw, Darren, Boutet, Sébastien, Lane, Thomas J., Liang, Mengning, Carbajo, Sergio, Du, Wenpeng, Kirrander, Adam, Minitti, Michael, and Weber, Peter M. Mon .  
"Simplicity Beneath Complexity: Counting Molecular Electrons Reveals Transients and Kinetics of Photodissociation Reactions".  Germany.  https://doi.org/10.1002/ange.201902228.

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@article{osti_1504297,

  title        = {Simplicity Beneath Complexity: Counting Molecular Electrons Reveals Transients and Kinetics of Photodissociation Reactions},

  author       = {Ruddock, Jennifer M. and Zotev, Nikola and Stankus, Brian and Yong, Haiwang and Bellshaw, Darren and Boutet, Sébastien and Lane, Thomas J. and Liang, Mengning and Carbajo, Sergio and Du, Wenpeng and Kirrander, Adam and Minitti, Michael and Weber, Peter M.},

  abstractNote = {Abstract Time‐resolved pump–probe gas‐phase X‐ray scattering signals, extrapolated to zero momentum transfer, provide a measure of the number of electrons in a system, an effect that arises from the coherent addition of elastic scattering from the electrons. This allows to identify reactive transients and determine the chemical reaction kinetics without the need for extensive scattering simulations or complicated inversion of scattering data. We examine the photodissociation reaction of trimethylamine and identify two reaction paths upon excitation to the 3p state at 200 nm: a fast dissociation path out of the 3p state to the dimethyl amine radical (16.6±1.2 %) and a slower dissociation via internal conversion to the 3s state (83.4±1.2 %). The time constants for the two reactions are 640±130 fs and 74±6 ps, respectively. Additionally, it is found that the transient dimethyl amine radical has a N−C bond length of 1.45±0.02 Å and a C−N−C bond angle of 118°±4°.},

  doi          = {10.1002/ange.201902228},

  journal      = {Angewandte Chemie},

  number       = 19,

  volume       = 131,

  place        = {Germany},

  year         = {Mon May 06 00:00:00 EDT 2019},

  month        = {Mon May 06 00:00:00 EDT 2019}

}

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Similar Records

Title: Simplicity Beneath Complexity: Counting Molecular Electrons Reveals Transients and Kinetics of Photodissociation Reactions

Abstract

Citation Formats

Imaging Molecular Motion: Femtosecond X-Ray Scattering of an Electrocyclic Chemical Reaction journal, June 2015

Molecular Imaging Using X-Ray Free-Electron Lasers journal, April 2013

Ultra-fast and ultra-intense x-ray sciences: first results from the Linac Coherent Light Source free-electron laser journal, August 2013

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Photodissociating trimethylamine at 193 nm to probe dynamics at a conical intersection and to calibrate detection efficiency of radical products journal, September 1999

Toward structural femtosecond chemical dynamics: imaging chemistry in space and time journal, January 2014

The role of novel Rydberg-valence behaviour in the non-adiabatic dynamics of tertiary aliphatic amines journal, January 2016

X-ray diffraction assisted spectroscopy of Rydberg states journal, October 2012

Self-Referenced Coherent Diffraction X-Ray Movie of Ångstrom- and Femtosecond-Scale Atomic Motion journal, October 2016

Electron Diffraction of Molecules in Specific Quantum States: A Theoretical Study of Vibronically Excited s -Tetrazine journal, February 2004

Ab Initio Calculation of Molecular Diffraction journal, October 2014

Imaging rotations and vibrations in polyatomic molecules with X-ray scattering journal, January 2017

Resolved: Electronic states underneath broad absorptions journal, July 2007

Pump–probe diffraction imaging of vibrational wave functions journal, May 1998

Electronic Spectroscopy and Ultrafast Energy Relaxation Pathways in the Lowest Rydberg States of Trimethylamine journal, October 2008

Observation of femtosecond molecular dynamics via pump–probe gas phase x-ray scattering journal, January 2016

Characterization of nitrogen-containing radical products from the photodissociation of trimethylamine using photoionization detection journal, August 2000

Elastic X-ray scattering from state-selected molecules journal, October 2016

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The effects of symmetry and rigidity on non-adiabatic dynamics in tertiary amines: a time-resolved photoelectron velocity-map imaging study of the cage-amine ABCO journal, January 2016

Imaging Molecular Motion: Femtosecond X-Ray Scattering of an Electrocyclic Chemical Reaction
journal, June 2015

Molecular Imaging Using X-Ray Free-Electron Lasers
journal, April 2013

Ultra-fast and ultra-intense x-ray sciences: first results from the Linac Coherent Light Source free-electron laser
journal, August 2013

Direct imaging of excited electronic states using diffraction techniques: theoretical considerations
journal, November 1996

The Coherent X-ray Imaging (CXI) instrument at the Linac Coherent Light Source (LCLS)
journal, March 2010

Photodissociating trimethylamine at 193 nm to probe dynamics at a conical intersection and to calibrate detection efficiency of radical products
journal, September 1999

Toward structural femtosecond chemical dynamics: imaging chemistry in space and time
journal, January 2014

The role of novel Rydberg-valence behaviour in the non-adiabatic dynamics of tertiary aliphatic amines
journal, January 2016

X-ray diffraction assisted spectroscopy of Rydberg states
journal, October 2012

Self-Referenced Coherent Diffraction X-Ray Movie of Ångstrom- and Femtosecond-Scale Atomic Motion
journal, October 2016

Electron Diffraction of Molecules in Specific Quantum States: A Theoretical Study of Vibronically Excited s -Tetrazine
journal, February 2004

Ab Initio Calculation of Molecular Diffraction
journal, October 2014

Imaging rotations and vibrations in polyatomic molecules with X-ray scattering
journal, January 2017

Resolved: Electronic states underneath broad absorptions
journal, July 2007

Pump–probe diffraction imaging of vibrational wave functions
journal, May 1998

Electronic Spectroscopy and Ultrafast Energy Relaxation Pathways in the Lowest Rydberg States of Trimethylamine
journal, October 2008

Observation of femtosecond molecular dynamics via pump–probe gas phase x-ray scattering
journal, January 2016

Characterization of nitrogen-containing radical products from the photodissociation of trimethylamine using photoionization detection
journal, August 2000

Elastic X-ray scattering from state-selected molecules
journal, October 2016

Mapping the Complete Reaction Path of a Complex Photochemical Reaction
journal, May 2018

The effects of symmetry and rigidity on non-adiabatic dynamics in tertiary amines: a time-resolved photoelectron velocity-map imaging study of the cage-amine ABCO
journal, January 2016