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

Title: Ultrafast X-ray Auger probing of photoexcited molecular dynamics

Abstract

Here, molecules can efficiently and selectively convert light energy into other degrees of freedom. Disentangling the underlying ultrafast motion of electrons and nuclei of the photoexcited molecule presents a challenge to current spectroscopic approaches. Here we explore the photoexcited dynamics of molecules by an interaction with an ultrafast X-ray pulse creating a highly localized core hole that decays via Auger emission. We discover that the Auger spectrum as a function of photoexcitation—X-ray-probe delay contains valuable information about the nuclear and electronic degrees of freedom from an element-specific point of view. For the nucleobase thymine, the oxygen Auger spectrum shifts towards high kinetic energies, resulting from a particular C–O bond stretch in the ππ* photoexcited state. A subsequent shift of the Auger spectrum towards lower kinetic energies displays the electronic relaxation of the initial photoexcited state within 200 fs. Ab-initio simulations reinforce our interpretation and indicate an electronic decay to the nπ* state.

Authors:
 [1];  [2];  [1];  [3];  [4];  [5];  [1];  [1];  [2];  [1];  [1];  [2];  [6];  [7];  [1];  [2];  [2];  [8];  [6];  [1] more »;  [6];  [2];  [1];  [9];  [2];  [1];  [2];  [2];  [2];  [1];  [1] « less
  1. SLAC National Accelerator Lab., Menlo Park, CA (United States)
  2. SLAC National Accelerator Lab., Menlo Park, CA (United States); Stanford Univ., Stanford, CA (United States)
  3. Univ. di Perugia, Perugia (Italy)
  4. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
  5. Western Michigan Univ., Kalamazoo MI (United States); Univ. of Connecticut, Storrs, CT (United States)
  6. Western Michigan Univ., Kalamazoo MI (United States)
  7. Uppsala Univ., Uppsala (Sweden); Univ. of Gothenburg, Gothenburg (Sweden)
  8. Uppsala Univ., Uppsala (Sweden)
  9. Max-Born-Institut, Berlin (Germany); UNIST, Ulsan (Republic of Korea)
Publication Date:
Research Org.:
SLAC National Accelerator Lab., Menlo Park, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC)
OSTI Identifier:
1339539
Report Number(s):
SLAC-PUB-16907
Journal ID: ISSN 2041-1723
Grant/Contract Number:  
AC02-76SF00515
Resource Type:
Accepted Manuscript
Journal Name:
Nature Communications
Additional Journal Information:
Journal Volume: 5; Journal ID: ISSN 2041-1723
Publisher:
Nature Publishing Group
Country of Publication:
United States
Language:
English
Subject:
74 ATOMIC AND MOLECULAR PHYSICS; PHYS; atomic and molecular physics; molecular dynamics

Citation Formats

McFarland, B. K., Farrell, J. P., Miyabe, S., Tarantelli, F., Aguilar, A., Berrah, N., Bostedt, C., Bozek, J. D., Bucksbaum, P. H., Castagna, J. C., Coffee, R. N., Cryan, J. P., Fang, L., Feifel, R., Gaffney, K. J., Glownia, J. M., Martinez, T. J., Mucke, M., Murphy, B., Natan, A., Osipov, T., Petrović, V. S., Schorb, S., Schultz, Th., Spector, L. S., Swiggers, M., Tenney, I., Wang, S., White, J. L., White, W., and Gühr, M. Ultrafast X-ray Auger probing of photoexcited molecular dynamics. United States: N. p., 2014. Web. doi:10.1038/ncomms5235.
McFarland, B. K., Farrell, J. P., Miyabe, S., Tarantelli, F., Aguilar, A., Berrah, N., Bostedt, C., Bozek, J. D., Bucksbaum, P. H., Castagna, J. C., Coffee, R. N., Cryan, J. P., Fang, L., Feifel, R., Gaffney, K. J., Glownia, J. M., Martinez, T. J., Mucke, M., Murphy, B., Natan, A., Osipov, T., Petrović, V. S., Schorb, S., Schultz, Th., Spector, L. S., Swiggers, M., Tenney, I., Wang, S., White, J. L., White, W., & Gühr, M. Ultrafast X-ray Auger probing of photoexcited molecular dynamics. United States. doi:10.1038/ncomms5235.
McFarland, B. K., Farrell, J. P., Miyabe, S., Tarantelli, F., Aguilar, A., Berrah, N., Bostedt, C., Bozek, J. D., Bucksbaum, P. H., Castagna, J. C., Coffee, R. N., Cryan, J. P., Fang, L., Feifel, R., Gaffney, K. J., Glownia, J. M., Martinez, T. J., Mucke, M., Murphy, B., Natan, A., Osipov, T., Petrović, V. S., Schorb, S., Schultz, Th., Spector, L. S., Swiggers, M., Tenney, I., Wang, S., White, J. L., White, W., and Gühr, M. Mon . "Ultrafast X-ray Auger probing of photoexcited molecular dynamics". United States. doi:10.1038/ncomms5235. https://www.osti.gov/servlets/purl/1339539.
@article{osti_1339539,
title = {Ultrafast X-ray Auger probing of photoexcited molecular dynamics},
author = {McFarland, B. K. and Farrell, J. P. and Miyabe, S. and Tarantelli, F. and Aguilar, A. and Berrah, N. and Bostedt, C. and Bozek, J. D. and Bucksbaum, P. H. and Castagna, J. C. and Coffee, R. N. and Cryan, J. P. and Fang, L. and Feifel, R. and Gaffney, K. J. and Glownia, J. M. and Martinez, T. J. and Mucke, M. and Murphy, B. and Natan, A. and Osipov, T. and Petrović, V. S. and Schorb, S. and Schultz, Th. and Spector, L. S. and Swiggers, M. and Tenney, I. and Wang, S. and White, J. L. and White, W. and Gühr, M.},
abstractNote = {Here, molecules can efficiently and selectively convert light energy into other degrees of freedom. Disentangling the underlying ultrafast motion of electrons and nuclei of the photoexcited molecule presents a challenge to current spectroscopic approaches. Here we explore the photoexcited dynamics of molecules by an interaction with an ultrafast X-ray pulse creating a highly localized core hole that decays via Auger emission. We discover that the Auger spectrum as a function of photoexcitation—X-ray-probe delay contains valuable information about the nuclear and electronic degrees of freedom from an element-specific point of view. For the nucleobase thymine, the oxygen Auger spectrum shifts towards high kinetic energies, resulting from a particular C–O bond stretch in the ππ* photoexcited state. A subsequent shift of the Auger spectrum towards lower kinetic energies displays the electronic relaxation of the initial photoexcited state within 200 fs. Ab-initio simulations reinforce our interpretation and indicate an electronic decay to the nπ* state.},
doi = {10.1038/ncomms5235},
journal = {Nature Communications},
number = ,
volume = 5,
place = {United States},
year = {2014},
month = {6}
}

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

Citation Metrics:
Cited by: 64 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

Zur Quantentheorie der Molekeln
journal, January 1927


Diabolical conical intersections
journal, October 1996


Isomerization Through Conical Intersections
journal, May 2007


Electronically excited states and photodynamics: a continuing challenge
journal, January 2012

  • Plasser, Felix; Barbatti, Mario; Aquino, Adélia J. A.
  • Theoretical Chemistry Accounts, Vol. 131, Issue 1
  • DOI: 10.1007/s00214-011-1073-y

Perspective: Nonadiabatic dynamics theory
journal, December 2012

  • Tully, John C.
  • The Journal of Chemical Physics, Vol. 137, Issue 22
  • DOI: 10.1063/1.4757762

Neutral-Ionic State Correlations in Strong-Field Molecular Ionization
journal, November 2012


Femtosecond Time-Resolved Photoelectron Spectroscopy
journal, April 2004

  • Stolow, Albert; Bragg, Arthur E.; Neumark, Daniel M.
  • Chemical Reviews, Vol. 104, Issue 4
  • DOI: 10.1021/cr020683w

Ultrafast X-ray Absorption Spectroscopy
journal, April 2004

  • Bressler, Christian; Chergui, Majed
  • Chemical Reviews, Vol. 104, Issue 4
  • DOI: 10.1021/cr0206667

Photo-Induced Spin-State Conversion in Solvated Transition Metal Complexes Probed via Time-Resolved Soft X-ray Spectroscopy
journal, May 2010

  • Huse, Nils; Kim, Tae Kyu; Jamula, Lindsey
  • Journal of the American Chemical Society, Vol. 132, Issue 19
  • DOI: 10.1021/ja101381a

Femtosecond and Subfemtosecond X-Ray Pulses from a Self-Amplified Spontaneous-Emission–Based Free-Electron Laser
journal, February 2004


Thymine Dimerization in DNA Is an Ultrafast Photoreaction
journal, February 2007


Ultrafast Excited-State Dynamics in Nucleic Acids
journal, April 2004

  • Crespo-Hernández, Carlos E.; Cohen, Boiko; Hare, Patrick M.
  • Chemical Reviews, Vol. 104, Issue 4
  • DOI: 10.1021/cr0206770

Intrinsic Lifetimes of the Excited State of DNA and RNA Bases
journal, November 2002

  • Kang, Hyuk; Lee, Kang Taek; Jung, Boyong
  • Journal of the American Chemical Society, Vol. 124, Issue 44
  • DOI: 10.1021/ja027627x

Excited states dynamics of DNA and RNA bases: Characterization of a stepwise deactivation pathway in the gas phase
journal, February 2005

  • Canuel, Clélia; Mons, Michel; Piuzzi, François
  • The Journal of Chemical Physics, Vol. 122, Issue 7
  • DOI: 10.1063/1.1850469

Thymine relaxation after UV irradiation: the role of tautomerization and πσ* states
journal, January 2009

  • González-Vázquez, Jesús; González, Leticia; Samoylova, Elena
  • Physical Chemistry Chemical Physics, Vol. 11, Issue 20
  • DOI: 10.1039/b815602f

Electronic relaxation dynamics in DNA and RNA bases studied by time-resolved photoelectron spectroscopy
journal, January 2004

  • Ullrich, Susanne; Schultz, Thomas; Zgierski, Marek Z.
  • Physical Chemistry Chemical Physics, Vol. 6, Issue 10
  • DOI: 10.1039/b316324e

Ab Initio Molecular Dynamics and Time-Resolved Photoelectron Spectroscopy of Electronically Excited Uracil and Thymine
journal, August 2007

  • Hudock, Hanneli R.; Levine, Benjamin G.; Thompson, Alexis L.
  • The Journal of Physical Chemistry A, Vol. 111, Issue 34
  • DOI: 10.1021/jp0723665

Photodynamics Simulations of Thymine: Relaxation into the First Excited Singlet State
journal, November 2009

  • Szymczak, Jaroslaw J.; Barbatti, Mario; Soo Hoo, Jason T.
  • The Journal of Physical Chemistry A, Vol. 113, Issue 45
  • DOI: 10.1021/jp905085x

Conical Intersections in Thymine
journal, December 2006

  • Perun, Serhiy; Sobolewski, Andrzej L.; Domcke, Wolfgang
  • The Journal of Physical Chemistry A, Vol. 110, Issue 49
  • DOI: 10.1021/jp0633897

Unified Model for the Ultrafast Decay of Pyrimidine Nucleobases
journal, December 2006

  • Merchán, Manuela; González-Luque, Remedios; Climent, Teresa
  • The Journal of Physical Chemistry B, Vol. 110, Issue 51
  • DOI: 10.1021/jp066874a

Photophysics of the π,π* and n,π* States of Thymine: MS-CASPT2 Minimum-Energy Paths and CASSCF on-the-Fly Dynamics
journal, September 2009

  • Asturiol, David; Lasorne, Benjamin; Robb, Michael A.
  • The Journal of Physical Chemistry A, Vol. 113, Issue 38
  • DOI: 10.1021/jp905303g

Higher-order approximations for the particle-particle propagator
journal, October 1984

  • Schirmer, J.; Barth, A.
  • Zeitschrift f�r Physik A Atoms and Nuclei, Vol. 317, Issue 3
  • DOI: 10.1007/BF01438358

The calculation of molecular double ionization spectra by Green’s functions
journal, October 2006


Toward a systematic molecular orbital theory for excited states
journal, January 1992

  • Foresman, James B.; Head-Gordon, Martin; Pople, John A.
  • The Journal of Physical Chemistry, Vol. 96, Issue 1
  • DOI: 10.1021/j100180a030

Internal conversion to the electronic ground state occurs via two distinct pathways for pyrimidine bases in aqueous solution
journal, December 2006

  • Hare, P. M.; Crespo-Hernandez, C. E.; Kohler, B.
  • Proceedings of the National Academy of Sciences, Vol. 104, Issue 2
  • DOI: 10.1073/pnas.0608055104

Singlet Excited-State Behavior of Uracil and Thymine in Aqueous Solution:  A Combined Experimental and Computational Study of 11 Uracil Derivatives
journal, January 2006

  • Gustavsson, Thomas; Bányász, Ákos; Lazzarotto, Elodie
  • Journal of the American Chemical Society, Vol. 128, Issue 2
  • DOI: 10.1021/ja056181s

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


Operation of a free-electron laser from the extreme ultraviolet to the water window
journal, June 2007


A compact X-ray free-electron laser emitting in the sub-ångström region
journal, June 2012


X-ray–optical cross-correlator for gas-phase experiments at the Linac Coherent Light Source free-electron laser
journal, March 2012

  • Schorb, S.; Gorkhover, T.; Cryan, J. P.
  • Applied Physics Letters, Vol. 100, Issue 12
  • DOI: 10.1063/1.3695163

Ultraintense X-Ray Induced Ionization, Dissociation, and Frustrated Absorption in Molecular Nitrogen
journal, June 2010


Auger Electron Angular Distribution of Double Core-Hole States in the Molecular Reference Frame
journal, August 2010


Double Core-Hole Production in N 2 : Beating the Auger Clock
journal, August 2010


Femtosecond electronic response of atoms to ultra-intense X-rays
journal, July 2010


Nonlinear Atomic Response to Intense Ultrashort X Rays
journal, February 2011


Dynamics of Hollow Atom Formation in Intense X-Ray Pulses Probed by Partial Covariance Mapping
journal, August 2013


The High Resolution L 2,3 MM and M 4,5 NN Auger Spectra from Krypton and M 4,5 NN and N 4,5 OO Auger Spectra from Xenon
journal, August 1972


    Works referencing / citing this record:

    Time-resolved inner-shell photoelectron spectroscopy: From a bound molecule to an isolated atom
    journal, April 2018


    Photophysics of indole upon X-ray absorption
    journal, January 2018

    • Kierspel, Thomas; Bomme, Cédric; Di Fraia, Michele
    • Physical Chemistry Chemical Physics, Vol. 20, Issue 30
    • DOI: 10.1039/c8cp00936h

    Pulse Duration of Seeded Free-Electron Lasers
    journal, June 2017


    Probing ultrafast ππ*/nπ* internal conversion in organic chromophores via K-edge resonant absorption
    journal, June 2017


    Photophysics of indole upon X-ray absorption
    journal, January 2018

    • Kierspel, Thomas; Bomme, Cédric; Di Fraia, Michele
    • Physical Chemistry Chemical Physics, Vol. 20, Issue 30
    • DOI: 10.1039/c8cp00936h

    Time-resolved inner-shell photoelectron spectroscopy: From a bound molecule to an isolated atom
    journal, April 2018


    Pulse Duration of Seeded Free-Electron Lasers
    journal, June 2017


    Diffractive imaging of a rotational wavepacket in nitrogen molecules with femtosecond megaelectronvolt electron pulses
    journal, April 2016

    • Yang, Jie; Guehr, Markus; Vecchione, Theodore
    • Nature Communications, Vol. 7, Issue 1
    • DOI: 10.1038/ncomms11232

    Ultrafast intersystem crossing dynamics in uracil unravelled by ab initio molecular dynamics
    journal, January 2014

    • Richter, Martin; Mai, Sebastian; Marquetand, Philipp
    • Phys. Chem. Chem. Phys., Vol. 16, Issue 44
    • DOI: 10.1039/c4cp04158e

    UV-induced long-lived decays in solvated pyrimidine nucleosides resolved at the MS-CASPT2/MM level
    journal, January 2018

    • Pepino, Ana Julieta; Segarra-Martí, Javier; Nenov, Artur
    • Physical Chemistry Chemical Physics, Vol. 20, Issue 10
    • DOI: 10.1039/c7cp08235e

    Multistate hybrid time-dependent density functional theory with surface hopping accurately captures ultrafast thymine photodeactivation
    journal, January 2019

    • Parker, Shane M.; Roy, Saswata; Furche, Filipp
    • Physical Chemistry Chemical Physics, Vol. 21, Issue 35
    • DOI: 10.1039/c9cp03127h

    Modeling multidimensional spectral lineshapes from first principles: application to water-solvated adenine
    journal, January 2020

    • Segarra-Martí, Javier; Segatta, Francesco; Mackenzie, Tristan A.
    • Faraday Discussions
    • DOI: 10.1039/c9fd00072k

    Stochastic stimulated electronic x-ray Raman spectroscopy
    journal, February 2016

    • Kimberg, Victor; Rohringer, Nina
    • Structural Dynamics, Vol. 3, Issue 3
    • DOI: 10.1063/1.4940916

    Photoelectron spectra of 2-thiouracil, 4-thiouracil, and 2,4-dithiouracil
    journal, February 2016

    • Ruckenbauer, Matthias; Mai, Sebastian; Marquetand, Philipp
    • The Journal of Chemical Physics, Vol. 144, Issue 7
    • DOI: 10.1063/1.4941948

    Perspective: Opportunities for ultrafast science at SwissFEL
    journal, November 2017

    • Abela, Rafael; Beaud, Paul; van Bokhoven, Jeroen A.
    • Structural Dynamics, Vol. 4, Issue 6
    • DOI: 10.1063/1.4997222

    Time-resolved electron spectroscopy for chemical analysis of photodissociation: Photoelectron spectra of Fe(CO) 5 , Fe(CO) 4 , and Fe(CO) 3
    journal, July 2018

    • Leitner, T.; Josefsson, I.; Mazza, T.
    • The Journal of Chemical Physics, Vol. 149, Issue 4
    • DOI: 10.1063/1.5035149

    An efficient approximate algorithm for nonadiabatic molecular dynamics
    journal, December 2018

    • Hanasaki, Kota; Kanno, Manabu; Niehaus, Thomas A.
    • The Journal of Chemical Physics, Vol. 149, Issue 24
    • DOI: 10.1063/1.5046757

    Brighter and faster: The promise and challenge of the x-ray free-electron laser
    journal, July 2015

    • Bucksbaum, Philip H.; Berrah, Nora
    • Physics Today, Vol. 68, Issue 7
    • DOI: 10.1063/pt.3.2845

    Roadmap of ultrafast x-ray atomic and molecular physics
    journal, January 2018

    • Young, Linda; Ueda, Kiyoshi; Gühr, Markus
    • Journal of Physics B: Atomic, Molecular and Optical Physics, Vol. 51, Issue 3
    • DOI: 10.1088/1361-6455/aa9735

    A pump–probe scheme with a single chirped pulse to image electron and nuclear dynamics in molecules
    journal, December 2018

    • Jelovina, Denis; Feist, Johannes; Martín, Fernando
    • New Journal of Physics, Vol. 20, Issue 12
    • DOI: 10.1088/1367-2630/aaf196

    Photochemical pathways in nucleobases measured with an X-ray FEL
    journal, April 2019

    • Wolf, Thomas J. A.; Gühr, Markus
    • Philosophical Transactions of the Royal Society A: Mathematical, Physical and Engineering Sciences, Vol. 377, Issue 2145
    • DOI: 10.1098/rsta.2017.0473

    Development of ultrafast capabilities for X-ray free-electron lasers at the linac coherent light source
    journal, April 2019

    • Coffee, Ryan N.; Cryan, James P.; Duris, Joseph
    • Philosophical Transactions of the Royal Society A: Mathematical, Physical and Engineering Sciences, Vol. 377, Issue 2145
    • DOI: 10.1098/rsta.2018.0386

    Nonlinear resonant Auger spectroscopy in CO using an x-ray pump-control scheme
    journal, December 2016


    Laser control over the ultrafast Coulomb explosion of N 2 2 + after Auger decay: A quantum-dynamics investigation
    journal, April 2017


    Catching Conical Intersections in the Act: Monitoring Transient Electronic Coherences by Attosecond Stimulated X-Ray Raman Signals
    journal, November 2015


    Observation of Quantum Interferences via Light-Induced Conical Intersections in Diatomic Molecules
    journal, April 2016


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


    Linac Coherent Light Source: The first five years
    journal, March 2016


    SNP hot-spots in the clam parasite QPX
    journal, June 2018


    Short-wavelength free-electron laser sources and science: a review
    text, January 2017

    • Seddon, E. A.; Clarke, J. A.; Dunning, D. J.
    • Deutsches Elektronen-Synchrotron, DESY, Hamburg
    • DOI: 10.3204/pubdb-2018-00596

    The LAMP instrument at the Linac Coherent Light Source free-electron laser
    text, January 2018

    • Osipov, Timur; Bostedt, Christoph; Castagna, J. -C.
    • Deutsches Elektronen-Synchrotron, DESY, Hamburg
    • DOI: 10.3204/pubdb-2019-00069

    Probing Dynamics in Colloidal Crystals with Pump-Probe Experiments at LCLS: Methodology and Analysis
    journal, May 2017

    • Mukharamova, Nastasia; Lazarev, Sergey; Meijer, Janne-Mieke
    • Applied Sciences, Vol. 7, Issue 5
    • DOI: 10.3390/app7050519