skip to main content
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Ultrafast X-ray scattering reveals vibrational coherence following Rydberg excitation

Abstract

The coherence and dephasing of vibrational motions of molecules constitute an integral part of chemical dynamics, influence material properties, and underpin schemes to control chemical reactions. Significant progress has been made in understanding vibrational coherence through spectroscopic measurements, but the precise direct measurement of the structure of a vibrating excited-state polyatomic organic molecule has remained elusive. Here, we measure the time-evolving molecular structure of optically excited N-methyl morpholine through scattering with ultrashort X-ray pulses. The scattering signals are corrected for the different electron density in the excited electronic state of the molecule compared to the ground state. In conclusion, the experiment maps the evolution of the molecular geometry with femtosecond resolution, showing coherent motion that survives electronic relaxation and appears to persist for longer than previously seen using other methods.

Authors:
 [1]; ORCiD logo [1];  [2];  [1];  [2];  [3];  [3];  [3];  [3];  [3];  [1];  [1];  [1];  [3]; ORCiD logo [3]; ORCiD logo [2]; ORCiD logo [1]
  1. Brown Univ., Providence, RI (United States)
  2. Univ. of Edinburgh, Edinburgh (United Kingdom)
  3. SLAC National Accelerator Lab., Menlo Park, CA (United States)
Publication Date:
Research Org.:
SLAC National Accelerator Lab., Menlo Park, CA (United States); Brown Univ., Providence, RI (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Chemical Sciences, Geosciences & Biosciences Division
Contributing Org.:
SLAC National Laboratory; University of Edinburgh
OSTI Identifier:
1526046
Alternate Identifier(s):
OSTI ID: 1596774
Grant/Contract Number:  
AC02-76SF00515; SC0017995
Resource Type:
Accepted Manuscript
Journal Name:
Nature Chemistry
Additional Journal Information:
Journal Volume: 11; Journal Issue: 8; Journal ID: ISSN 1755-4330
Publisher:
Nature Publishing Group
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Stankus, Brian, Yong, Haiwang, Zotev, Nikola, Ruddock, Jennifer M., Bellshaw, Darren, Lane, Thomas J., Liang, Mengning, Boutet, Sébastien, Carbajo, Sergio, Robinson, Joseph S., Du, Wenpeng, Goff, Nathan, Chang, Yu, Koglin, Jason E., Minitti, Michael P., Kirrander, Adam, and Weber, Peter M. Ultrafast X-ray scattering reveals vibrational coherence following Rydberg excitation. United States: N. p., 2019. Web. doi:10.1038/s41557-019-0291-0.
Stankus, Brian, Yong, Haiwang, Zotev, Nikola, Ruddock, Jennifer M., Bellshaw, Darren, Lane, Thomas J., Liang, Mengning, Boutet, Sébastien, Carbajo, Sergio, Robinson, Joseph S., Du, Wenpeng, Goff, Nathan, Chang, Yu, Koglin, Jason E., Minitti, Michael P., Kirrander, Adam, & Weber, Peter M. Ultrafast X-ray scattering reveals vibrational coherence following Rydberg excitation. United States. doi:10.1038/s41557-019-0291-0.
Stankus, Brian, Yong, Haiwang, Zotev, Nikola, Ruddock, Jennifer M., Bellshaw, Darren, Lane, Thomas J., Liang, Mengning, Boutet, Sébastien, Carbajo, Sergio, Robinson, Joseph S., Du, Wenpeng, Goff, Nathan, Chang, Yu, Koglin, Jason E., Minitti, Michael P., Kirrander, Adam, and Weber, Peter M. Mon . "Ultrafast X-ray scattering reveals vibrational coherence following Rydberg excitation". United States. doi:10.1038/s41557-019-0291-0. https://www.osti.gov/servlets/purl/1526046.
@article{osti_1526046,
title = {Ultrafast X-ray scattering reveals vibrational coherence following Rydberg excitation},
author = {Stankus, Brian and Yong, Haiwang and Zotev, Nikola and Ruddock, Jennifer M. and Bellshaw, Darren and Lane, Thomas J. and Liang, Mengning and Boutet, Sébastien and Carbajo, Sergio and Robinson, Joseph S. and Du, Wenpeng and Goff, Nathan and Chang, Yu and Koglin, Jason E. and Minitti, Michael P. and Kirrander, Adam and Weber, Peter M.},
abstractNote = {The coherence and dephasing of vibrational motions of molecules constitute an integral part of chemical dynamics, influence material properties, and underpin schemes to control chemical reactions. Significant progress has been made in understanding vibrational coherence through spectroscopic measurements, but the precise direct measurement of the structure of a vibrating excited-state polyatomic organic molecule has remained elusive. Here, we measure the time-evolving molecular structure of optically excited N-methyl morpholine through scattering with ultrashort X-ray pulses. The scattering signals are corrected for the different electron density in the excited electronic state of the molecule compared to the ground state. In conclusion, the experiment maps the evolution of the molecular geometry with femtosecond resolution, showing coherent motion that survives electronic relaxation and appears to persist for longer than previously seen using other methods.},
doi = {10.1038/s41557-019-0291-0},
journal = {Nature Chemistry},
number = 8,
volume = 11,
place = {United States},
year = {2019},
month = {7}
}

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

Citation Metrics:
Cited by: 12 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

Electron Transfer Reactions in Chemistry: Theory and Experiment (Nobel Lecture)
journal, August 1993

  • Marcus, Rudolph A.
  • Angewandte Chemie International Edition in English, Vol. 32, Issue 8
  • DOI: 10.1002/anie.199311113

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


Spectral encoding method for measuring the relative arrival time between x-ray/optical pulses
journal, August 2014

  • Bionta, M. R.; Hartmann, N.; Weaver, M.
  • Review of Scientific Instruments, Vol. 85, Issue 8
  • DOI: 10.1063/1.4893657

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


Capturing Chemistry in Action with Electrons: Realization of Atomically Resolved Reaction Dynamics
journal, May 2017


Imaging CF 3 I conical intersection and photodissociation dynamics with ultrafast electron diffraction
journal, July 2018


Pixel array detector for X-ray free electron laser experiments
journal, September 2011

  • Philipp, Hugh T.; Hromalik, Marianne; Tate, Mark
  • Nuclear Instruments and Methods in Physics Research Section A: Accelerators, Spectrometers, Detectors and Associated Equipment, Vol. 649, Issue 1
  • DOI: 10.1016/j.nima.2010.11.189

Simplicity Beneath Complexity: Counting Molecular Electrons Reveals Transients and Kinetics of Photodissociation Reactions
journal, April 2019

  • Ruddock, Jennifer M.; Zotev, Nikola; Stankus, Brian
  • Angewandte Chemie International Edition, Vol. 58, Issue 19
  • DOI: 10.1002/anie.201902228

Determining Orientations of Optical Transition Dipole Moments Using Ultrafast X-ray Scattering
journal, October 2018

  • Yong, Haiwang; Zotev, Nikola; Stankus, Brian
  • The Journal of Physical Chemistry Letters, Vol. 9, Issue 22
  • DOI: 10.1021/acs.jpclett.8b02773

First lasing and operation of an ångstrom-wavelength free-electron laser
journal, August 2010


Quantum beats and dephasing in isolated large molecules cooled by supersonic jet expansion and excited by picosecond pulses: Anthracene
journal, December 1981

  • Lambert, Wm. R.; Felker, P. M.; Zewail, A. H.
  • The Journal of Chemical Physics, Vol. 75, Issue 12
  • DOI: 10.1063/1.442052

Bound-State Eigenfunctions of Classically Chaotic Hamiltonian Systems: Scars of Periodic Orbits
journal, October 1984


Molpro: a general-purpose quantum chemistry program package: Molpro
journal, July 2011

  • Werner, Hans-Joachim; Knowles, Peter J.; Knizia, Gerald
  • Wiley Interdisciplinary Reviews: Computational Molecular Science, Vol. 2, Issue 2
  • DOI: 10.1002/wcms.82

Ab Initio Calculation of Molecular Diffraction
journal, October 2014

  • Northey, Thomas; Zotev, Nikola; Kirrander, Adam
  • Journal of Chemical Theory and Computation, Vol. 10, Issue 11
  • DOI: 10.1021/ct500096r

On the interpretation of time-resolved anisotropic diffraction patterns
journal, November 2010


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

  • Budarz, J. M.; Minitti, M. P.; Cofer-Shabica, D. V.
  • Journal of Physics B: Atomic, Molecular and Optical Physics, Vol. 49, Issue 3
  • DOI: 10.1088/0953-4075/49/3/034001

X-Ray Diffraction from Isolated and Strongly Aligned Gas-Phase Molecules with a Free-Electron Laser
journal, February 2014


Oscillatory Photoelectron Signal of N -Methylmorpholine as a Test Case for the Algebraic-Diagrammatic Construction Method of Second Order
journal, November 2018

  • Dsouza, Raison; Cheng, Xinxin; Li, Zheng
  • The Journal of Physical Chemistry A, Vol. 122, Issue 50
  • DOI: 10.1021/acs.jpca.8b10241

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

  • Northey, Thomas; Moreno Carrascosa, Andrés; Schäfer, Steffen
  • The Journal of Chemical Physics, Vol. 145, Issue 15
  • DOI: 10.1063/1.4962256

Symmetry controlled excited state dynamics
journal, January 2019

  • Waters, Max D. J.; Skov, Anders B.; Larsen, Martin A. B.
  • Physical Chemistry Chemical Physics, Vol. 21, Issue 5
  • DOI: 10.1039/C8CP05950K

Nonadiabatic dynamics: The SHARC approach
journal, May 2018

  • Mai, Sebastian; Marquetand, Philipp; González, Leticia
  • Wiley Interdisciplinary Reviews: Computational Molecular Science, Vol. 8, Issue 6
  • DOI: 10.1002/wcms.1370

Coherence in nonradiative transitions: internal conversion in Rydberg-excited N-methyl and N-ethyl morpholine
journal, January 2017

  • Zhang, Yao; Jónsson, Hannes; Weber, Peter M.
  • Phys. Chem. Chem. Phys., Vol. 19, Issue 38
  • DOI: 10.1039/C7CP05244H

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

  • Minitti, Michael P.; Budarz, James M.; Kirrander, Adam
  • Faraday Discuss., Vol. 171
  • DOI: 10.1039/C4FD00030G

Clocking transient chemical changes by ultrafast electron diffraction
journal, March 1997

  • Williamson, J. Charles; Cao, Jianming; Ihee, Hyotcherl
  • Nature, Vol. 386, Issue 6621
  • DOI: 10.1038/386159a0

The Coherent X-ray Imaging instrument at the Linac Coherent Light Source
journal, April 2015

  • Liang, Mengning; Williams, Garth J.; Messerschmidt, Marc
  • Journal of Synchrotron Radiation, Vol. 22, Issue 3
  • DOI: 10.1107/S160057751500449X

Electronically Driven Structure Changes of Si Captured by Femtosecond Electron Diffraction
journal, April 2008


SHARC: ab Initio Molecular Dynamics with Surface Hopping in the Adiabatic Representation Including Arbitrary Couplings
journal, March 2011

  • Richter, Martin; Marquetand, Philipp; González-Vázquez, Jesús
  • Journal of Chemical Theory and Computation, Vol. 7, Issue 5
  • DOI: 10.1021/ct1007394

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


Diffractive Imaging of Coherent Nuclear Motion in Isolated Molecules
journal, October 2016


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

  • Moreno Carrascosa, Andrés; Northey, Thomas; Kirrander, Adam
  • Physical Chemistry Chemical Physics, Vol. 19, Issue 11
  • DOI: 10.1039/C6CP06793J

Observation of Structural Wavepacket Motion: The Umbrella Mode in Rydberg-Excited N -Methyl Morpholine
journal, July 2017

  • Zhang, Yao; Deb, Sanghamitra; Jónsson, Hannes
  • The Journal of Physical Chemistry Letters, Vol. 8, Issue 16
  • DOI: 10.1021/acs.jpclett.7b01274

Optimal control of quantum-mechanical systems: Existence, numerical approximation, and applications
journal, June 1988

  • Peirce, Anthony P.; Dahleh, Mohammed A.; Rabitz, Herschel
  • Physical Review A, Vol. 37, Issue 12, p. 4950-4964
  • DOI: 10.1103/PhysRevA.37.4950

Ultrafast Electron Diffraction: Oriented Molecular Structures in Space and Time
journal, November 2005


4d Ultrafast Electron Diffraction, Crystallography, and Microscopy
journal, May 2006


Femtochemistry: Atomic-Scale Dynamics of the Chemical Bond Using Ultrafast Lasers (Nobel Lecture)
journal, August 2000


    Works referencing / citing this record:

    Femtochemistry: Atomic-Scale Dynamics of the Chemical Bond Using Ultrafast Lasers (Nobel Lecture)
    journal, August 2000


    Electron Transfer Reactions in Chemistry: Theory and Experiment (Nobel Lecture)
    journal, August 1993

    • Marcus, Rudolph A.
    • Angewandte Chemie International Edition in English, Vol. 32, Issue 8
    • DOI: 10.1002/anie.199311113

    Simplicity Beneath Complexity: Counting Molecular Electrons Reveals Transients and Kinetics of Photodissociation Reactions
    journal, April 2019

    • Ruddock, Jennifer M.; Zotev, Nikola; Stankus, Brian
    • Angewandte Chemie International Edition, Vol. 58, Issue 19
    • DOI: 10.1002/anie.201902228

    Ultrafast Electron Diffraction: Oriented Molecular Structures in Space and Time
    journal, November 2005


    Nonadiabatic dynamics: The SHARC approach
    journal, May 2018

    • Mai, Sebastian; Marquetand, Philipp; González, Leticia
    • Wiley Interdisciplinary Reviews: Computational Molecular Science, Vol. 8, Issue 6
    • DOI: 10.1002/wcms.1370

    Molpro: a general-purpose quantum chemistry program package: Molpro
    journal, July 2011

    • Werner, Hans-Joachim; Knowles, Peter J.; Knizia, Gerald
    • Wiley Interdisciplinary Reviews: Computational Molecular Science, Vol. 2, Issue 2
    • DOI: 10.1002/wcms.82

    Pixel array detector for X-ray free electron laser experiments
    journal, September 2011

    • Philipp, Hugh T.; Hromalik, Marianne; Tate, Mark
    • Nuclear Instruments and Methods in Physics Research Section A: Accelerators, Spectrometers, Detectors and Associated Equipment, Vol. 649, Issue 1
    • DOI: 10.1016/j.nima.2010.11.189

    Capturing Chemistry in Action with Electrons: Realization of Atomically Resolved Reaction Dynamics
    journal, May 2017


    Oscillatory Photoelectron Signal of N -Methylmorpholine as a Test Case for the Algebraic-Diagrammatic Construction Method of Second Order
    journal, November 2018

    • Dsouza, Raison; Cheng, Xinxin; Li, Zheng
    • The Journal of Physical Chemistry A, Vol. 122, Issue 50
    • DOI: 10.1021/acs.jpca.8b10241

    Observation of Structural Wavepacket Motion: The Umbrella Mode in Rydberg-Excited N -Methyl Morpholine
    journal, July 2017

    • Zhang, Yao; Deb, Sanghamitra; Jónsson, Hannes
    • The Journal of Physical Chemistry Letters, Vol. 8, Issue 16
    • DOI: 10.1021/acs.jpclett.7b01274

    Determining Orientations of Optical Transition Dipole Moments Using Ultrafast X-ray Scattering
    journal, October 2018

    • Yong, Haiwang; Zotev, Nikola; Stankus, Brian
    • The Journal of Physical Chemistry Letters, Vol. 9, Issue 22
    • DOI: 10.1021/acs.jpclett.8b02773

    SHARC: ab Initio Molecular Dynamics with Surface Hopping in the Adiabatic Representation Including Arbitrary Couplings
    journal, March 2011

    • Richter, Martin; Marquetand, Philipp; González-Vázquez, Jesús
    • Journal of Chemical Theory and Computation, Vol. 7, Issue 5
    • DOI: 10.1021/ct1007394

    Ab Initio Calculation of Molecular Diffraction
    journal, October 2014

    • Northey, Thomas; Zotev, Nikola; Kirrander, Adam
    • Journal of Chemical Theory and Computation, Vol. 10, Issue 11
    • DOI: 10.1021/ct500096r

    Clocking transient chemical changes by ultrafast electron diffraction
    journal, March 1997

    • Williamson, J. Charles; Cao, Jianming; Ihee, Hyotcherl
    • Nature, Vol. 386, Issue 6621
    • DOI: 10.1038/386159a0

    First lasing and operation of an ångstrom-wavelength free-electron laser
    journal, August 2010


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

    • Minitti, Michael P.; Budarz, James M.; Kirrander, Adam
    • Faraday Discuss., Vol. 171
    • DOI: 10.1039/c4fd00030g

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

    • Moreno Carrascosa, Andrés; Northey, Thomas; Kirrander, Adam
    • Physical Chemistry Chemical Physics, Vol. 19, Issue 11
    • DOI: 10.1039/c6cp06793j

    Coherence in nonradiative transitions: internal conversion in Rydberg-excited N-methyl and N-ethyl morpholine
    journal, January 2017

    • Zhang, Yao; Jónsson, Hannes; Weber, Peter M.
    • Phys. Chem. Chem. Phys., Vol. 19, Issue 38
    • DOI: 10.1039/c7cp05244h

    Symmetry controlled excited state dynamics
    journal, January 2019

    • Waters, Max D. J.; Skov, Anders B.; Larsen, Martin A. B.
    • Physical Chemistry Chemical Physics, Vol. 21, Issue 5
    • DOI: 10.1039/c8cp05950k

    Quantum beats and dephasing in isolated large molecules cooled by supersonic jet expansion and excited by picosecond pulses: Anthracene
    journal, December 1981

    • Lambert, Wm. R.; Felker, P. M.; Zewail, A. H.
    • The Journal of Chemical Physics, Vol. 75, Issue 12
    • DOI: 10.1063/1.442052

    Spectral encoding method for measuring the relative arrival time between x-ray/optical pulses
    journal, August 2014

    • Bionta, M. R.; Hartmann, N.; Weaver, M.
    • Review of Scientific Instruments, Vol. 85, Issue 8
    • DOI: 10.1063/1.4893657

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

    • Northey, Thomas; Moreno Carrascosa, Andrés; Schäfer, Steffen
    • The Journal of Chemical Physics, Vol. 145, Issue 15
    • DOI: 10.1063/1.4962256

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

    • Budarz, J. M.; Minitti, M. P.; Cofer-Shabica, D. V.
    • Journal of Physics B: Atomic, Molecular and Optical Physics, Vol. 49, Issue 3
    • DOI: 10.1088/0953-4075/49/3/034001

    On the interpretation of time-resolved anisotropic diffraction patterns
    journal, November 2010


    Optimal control of quantum-mechanical systems: Existence, numerical approximation, and applications
    journal, June 1988

    • Peirce, Anthony P.; Dahleh, Mohammed A.; Rabitz, Herschel
    • Physical Review A, Vol. 37, Issue 12, p. 4950-4964
    • DOI: 10.1103/physreva.37.4950

    Electronically Driven Structure Changes of Si Captured by Femtosecond Electron Diffraction
    journal, April 2008


    X-Ray Diffraction from Isolated and Strongly Aligned Gas-Phase Molecules with a Free-Electron Laser
    journal, February 2014


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


    Diffractive Imaging of Coherent Nuclear Motion in Isolated Molecules
    journal, October 2016


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


    Bound-State Eigenfunctions of Classically Chaotic Hamiltonian Systems: Scars of Periodic Orbits
    journal, October 1984


    The Coherent X-ray Imaging instrument at the Linac Coherent Light Source
    journal, April 2015

    • Liang, Mengning; Williams, Garth J.; Messerschmidt, Marc
    • Journal of Synchrotron Radiation, Vol. 22, Issue 3
    • DOI: 10.1107/s160057751500449x

    Imaging CF 3 I conical intersection and photodissociation dynamics with ultrafast electron diffraction
    journal, July 2018


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


    4d Ultrafast Electron Diffraction, Crystallography, and Microscopy
    journal, May 2006