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Title: Femtosecond x-ray scattering study of ultrafast photoinduced structural dynamics in solvated [ Co ( terpy ) 2 ] 2 +

Journal Article · · Physical Review Letters
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  1. Technical Univ. of Denmark, Lyngby (Denmark)
  2. Technical Univ. of Denmark, Lyngby (Denmark); Lund Univ., Lund (Sweden); SLAC National Accelerator Lab., Menlo Park, CA (United States)
  3. Lund Univ., Lund (Sweden)
  4. Technical Univ. of Denmark, Lyngby (Denmark): Hungarian Academy Sciences, Budapest (Hungary)
  5. Hungarian Academy Sciences, Budapest (Hungary)
  6. SLAC National Accelerator Lab., Menlo Park, CA (United States)
  7. Tianjin Polytechnic Univ., Tianjin (China)
  8. European XFEL GmbH, Hamburg (Germany)
  9. European XFEL GmbH, Hamburg (Germany); Jan Kochanowski Univ., Kielce (Poland)
  10. SLAC National Accelerator Lab., Menlo Park, CA (United States); Paul Scherrer Inst. (PSI), Villigen (Switzerland)
  11. Max Planck Institute for Biophysical Chemistry, Goettingen (Germany); Deutsches Elektronen-Synchrotron (DESY), Hamburg (Germany)

Here, we study the structural dynamics of photoexcited [Co(terpy)2]2+ in an aqueous solution with ultrafast x-ray diffuse scattering experiments conducted at the Linac Coherent Light Source. Through direct comparisons with density functional theory calculations, our analysis shows that the photoexcitation event leads to elongation of the Co-N bonds, followed by coherent Co-N bond length oscillations arising from the impulsive excitation of a vibrational mode dominated by the symmetrical stretch of all six Co-N bonds. This mode has a period of 0.33 ps and decays on a subpicosecond time scale. We find that the equilibrium bond-elongated structure of the high spin state is established on a single-picosecond time scale and that this state has a lifetime of ~7 ps.

Research Organization:
SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
StG-259709; K29724; LP2013-59; 21302138; AC02-76SF00515; 20130504
OSTI ID:
1335954
Alternate ID(s):
OSTI ID: 1259990
Journal Information:
Physical Review Letters, Vol. 117, Issue 1; ISSN 0031-9007
Publisher:
American Physical Society (APS)Copyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 83 works
Citation information provided by
Web of Science

References (42)

Femtosecond X-ray Absorption Spectroscopy at a Hard X-ray Free Electron Laser: Application to Spin Crossover Dynamics journal January 2013
Probing the 3d Spin Momentum with X-ray Emission Spectroscopy:  The Case of Molecular-Spin Transitions journal June 2006
Pixel array detector for X-ray free electron laser experiments
  • 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 https://doi.org/10.1016/j.nima.2010.11.189
journal September 2011
Development and Testing of the OPLS All-Atom Force Field on Conformational Energetics and Properties of Organic Liquids journal January 1996
Nosé–Hoover chains: The canonical ensemble via continuous dynamics journal August 1992
Spin-crossover in cobalt(II) imine complexes journal February 2007
Dynamic response of the spin-crossover solid C o ( H 2 ( fsa ) 2 e n ) ( py ) 2 to a pulsed magnetic field journal April 2002
Charge transport properties of spin crossover systems journal January 2014
Partial molal volumes of spin-equilibrium metal complexes journal April 1986
Analysis of time-resolved X-ray scattering data from solution-state systems journal February 2010
The ORCA program system: The ORCA program system journal June 2011
Observing Solvation Dynamics with Simultaneous Femtosecond X-ray Emission Spectroscopy and X-ray Scattering journal February 2016
Density-functional exchange-energy approximation with correct asymptotic behavior journal September 1988
On the calculation of x-ray scattering signals from pairwise radial distribution functions journal November 2015
Photochemistry of HgBr2 in methanol investigated using time-resolved X-ray liquidography journal January 2010
On the interpretation of time-resolved anisotropic diffraction patterns journal November 2010
More accurate X-ray scattering data of deeply supercooled bulk liquid water journal January 2011
Disentangling detector data in XFEL studies of temporally resolved solution state chemistry journal January 2015
Sub-50-fs photoinduced spin crossover in [Fe(bpy)3]2+ journal July 2015
Insights into the Spin-State Transitions in [Fe(tpy) 2 ] 2+ : Importance of the Terpyridine Rocking Motion journal November 2015
Elements of Modern X-ray Physics book March 2011
Direct Dynamics Studies of a Binuclear Metal Complex in Solution: The Interplay Between Vibrational Relaxation, Coherence, and Solvent Effects journal June 2014
Development of an improved four-site water model for biomolecular simulations: TIP4P-Ew journal May 2004
On the spin equilibrium in bis(2,2′,2″-terpyridine) cobalt(II) salts journal January 1967
Impulsive solvent heating probed by picosecond x-ray diffraction journal March 2006
Dynamics of cobalt(II) spin-equilibrium complexes journal July 1995
Guest–Host Interactions Investigated by Time-Resolved X-ray Spectroscopies and Scattering at MHz Rates: Solvation Dynamics and Photoinduced Spin Transition in Aqueous Fe(bipy) 3 2+ journal October 2012
Detailed Characterization of a Nanosecond-Lived Excited State: X-ray and Theoretical Investigation of the Quintet State in Photoexcited [Fe(terpy) 2 ] 2+ journal March 2015
Probing the Anisotropic Distortion of Photoexcited Spin Crossover Complexes with Picosecond X-ray Absorption Spectroscopy journal February 2014
Sequential Activation of Molecular Breathing and Bending during Spin-Crossover Photoswitching Revealed by Femtosecond Optical and X-Ray Absorption Spectroscopy journal November 2014
The X-ray Pump–Probe instrument at the Linac Coherent Light Source journal April 2015
High-spin-low-spin equilibriums of cobalt(2+) in the terpyridine complexes Co(terpy)2X2.nH2O journal August 1982
Crystal structure of Bis(2,2':6',2''-terpyridyl)cobalt(II) perchlorate c. 1.3 hydrate journal January 1983
Femtosecond optical Kerr effect studies of water journal June 1994
Towards accurate estimates of the spin-state energetics of spin-crossover complexes within density functional theory: a comparative case study of cobalt(ii) complexes journal January 2013
Vibrational Coherences and Relaxation in the High-Spin State of Aqueous [Fe II (bpy) 3 ] 2+ journal September 2009
Dynamic Jahn–Teller Effect in the Metastable High-Spin State of Solvated [Fe(terpy) 2 ] 2+ journal January 2015
Spin-Transition Polymers: From Molecular Materials Toward Memory Devices journal January 1998
Electronic Relaxation Phenomena Following 57 Co(EC) 57 Fe Nuclear Decay in [Mn II (terpy) 2 ](ClO 4 ) 2 · 1 / 2 H 2 O and in the Spin Crossover Complexes [Co II (terpy) 2 ]X 2 · n H 2 O (X = Cl and ClO 4 ):  A Mössbauer Emission Spectroscopic Study journal March 2001
Spin-crossover in cobalt(II) compounds containing terpyridine and its derivatives journal September 2011
Optical investigation of spin-crossover in cobalt(II) bis-terpy complexes journal October 2007
Emerging properties and applications of spin crossover nanomaterials journal January 2014

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Structural Dynamics upon Photoexcitation in a Spin Crossover Crystal Probed with Femtosecond Electron Diffraction journal May 2017
Spectroscopic, Structural, and Kinetic Investigation of the Ultrafast Spin Crossover in an Unusual Cobalt(II) Semiquinonate Radical Complex journal January 2017
Disentangling Ultrafast Electronic and Structural Dynamics with X-Ray Lasers journal September 2018
Tracking multiple components of a nuclear wavepacket in photoexcited Cu(I)-phenanthroline complex using ultrafast X-ray spectroscopy journal August 2019
Vibrational wavepacket dynamics in Fe carbene photosensitizer determined with femtosecond X-ray emission and scattering journal January 2020
Taking the plunge: chemical reaction dynamics in liquids journal January 2017
Finding intersections between electronic excited state potential energy surfaces with simultaneous ultrafast X-ray scattering and spectroscopy journal January 2019
Resolving structures of transition metal complex reaction intermediates with femtosecond EXAFS journal January 2020
Ligand manipulation of charge transfer excited state relaxation and spin crossover in [Fe(2,2′-bipyridine) 2 (CN) 2 ] journal July 2017
Perspective: Opportunities for ultrafast science at SwissFEL journal November 2017
SVD-aided non-orthogonal decomposition (SANOD) method to exploit prior knowledge of spectral components in the analysis of time-resolved data journal March 2019
Theory of ultrafast x-ray scattering by molecules in the gas phase journal November 2019
A versatile experimental system for tracking ultrafast chemical reactions with X-ray free-electron lasers journal September 2019
Simulation of ultrafast excited-state dynamics and elastic x-ray scattering by quantum wavepacket dynamics journal September 2019
Solvent-dependent complex reaction pathways of bromoform revealed by time-resolved X-ray solution scattering and X-ray transient absorption spectroscopy journal November 2019
Roadmap of ultrafast x-ray atomic and molecular physics journal January 2018
On the limits of observing motion in time-resolved X-ray scattering
  • Ware, Matthew R.; Glownia, James M.; Natan, Adi
  • Philosophical Transactions of the Royal Society A: Mathematical, Physical and Engineering Sciences, Vol. 377, Issue 2145 https://doi.org/10.1098/rsta.2017.0477
journal April 2019
Scientific instrument Femtosecond X-ray Experiments (FXE): instrumentation and baseline experimental capabilities journal August 2019
Interplay of electron-phonon nonadiabaticity and Raman scattering in the wavepacket dynamics of electron-phonon-photon systems journal June 2019
Short-wavelength free-electron laser sources and science: a review text January 2017
Initial metal-metal bond breakage detected by fs X-ray scattering in the photolysis of Ru3(CO)12 in cyclohexane at 400 nm text January 2019
Structural Dynamics upon Photoexcitation in a Spin Crossover Crystal Probed with Femtosecond Electron Diffraction journal May 2017
Vibrational wavepacket dynamics in Fe carbene photosensitizer determined with femtosecond X-ray emission and scattering text January 2020
Initial metal–metal bond breakage detected by fs X-ray scattering in the photolysis of Ru 3 (CO) 12 in cyclohexane at 400 nm journal January 2019
Tracking multiple components of a nuclear wavepacket in photoexcited Cu(I)-phenanthroline complex using ultrafast X-ray spectroscopy text January 2019
Perspective: Opportunities for ultrafast science at SwissFEL text January 2017
Short-wavelength free-electron laser sources and science: a review journal October 2017
Roadmap of ultrafast x-ray atomic and molecular physics text January 2018
Excited-State Solvation Structure of Transition Metal Complexes from Molecular Dynamics Simulations and Assessment of Partial Atomic Charge Methods text January 2018