Visualizing the non-equilibrium dynamics of photoinduced intramolecular electron transfer with femtosecond X-ray pulses.
Ultrafast photoinduced electron transfer preceding energy equilibration still poses many experimental and conceptual challenges to the optimization of photoconversion since an atomic-scale description has so far been beyond reach. Here we combine femtosecond transient optical absorption spectroscopy with ultrafast X-ray emission spectroscopy and diffuse X-ray scattering at the SACLA facility to track the non-equilibrated electronic and structural dynamics within a bimetallic donor-acceptor complex that contains an optically dark centre. Exploiting the 100-fold increase in temporal resolution as compared with storage ring facilities, these measurements constitute the first X-ray-based visualization of a non-equilibrated intramolecular electron transfer process over large interatomic distances. Experimental and theoretical results establish that mediation through electronically excited molecular states is a key mechanistic feature. The present study demonstrates the extensive potential of femtosecond X-ray techniques as diagnostics of non-adiabatic electron transfer processes in synthetic and biological systems, and some directions for future studies, are outlined.
Department of Synchrotron Radiation Instrumentation, Lund University, PO Box 118, 22100 Lund, Sweden.
Sophie E
SE
Canton
1] Centre for Molecular Movies, Niels Bohr Institute, University of Copenhagen, DK-2100 Copenhagen, Denmark [2] Centre for Molecular Movies, Department of Physics, Technical University of Denmark, DK-2800 Lyngby, Denmark.
Kasper S
KS
Kjær
Wigner Research Centre for Physics, Hungarian Academy Sciences, PO Box 49, H-1525 Budapest, Hungary.
György
G
Vankó
Centre for Molecular Movies, Department of Physics, Technical University of Denmark, DK-2800 Lyngby, Denmark.
Tim B
TB
van Driel
High Energy Accelerator Research Organization, 1-1 Oho, Tsukuba, Ibaraki 305-0801, Japan.
Shin-ichi
S
Adachi
Wigner Research Centre for Physics, Hungarian Academy Sciences, PO Box 49, H-1525 Budapest, Hungary.
Amélie
A
Bordage
1] European XFEL, Albert-Einstein Ring 19, D-22761, Hamburg, Germany [2] The Hamburg Centre for Ultrafast Imaging, Luruper Chaussee 149, 22761 Hamburg, Germany.
Christian
C
Bressler
Department of Chemical Physics, Lund University, PO Box 124, S-22100 Lund, Sweden.
Pavel
P
Chabera
Centre for Molecular Movies, Department of Physics, Technical University of Denmark, DK-2800 Lyngby, Denmark.
Morten
M
Christensen
Department of Chemistry, Technical University of Denmark, DK-2800, Kongens Lyngby, Denmark.
Asmus O
AO
Dohn
European XFEL, Albert-Einstein Ring 19, D-22761, Hamburg, Germany.
Andreas
A
Galler
European XFEL, Albert-Einstein Ring 19, D-22761, Hamburg, Germany.
Wojciech
W
Gawelda
Center for Nanoscale Materials, Argonne National Laboratory, 9700 South Cass Avenue, Argonne, Illinois 60439, USA.
David
D
Gosztola
Centre for Molecular Movies, Department of Physics, Technical University of Denmark, DK-2800 Lyngby, Denmark.
Kristoffer
K
Haldrup
Department of Chemical Physics, Lund University, PO Box 124, S-22100 Lund, Sweden.
Tobias
T
Harlang
Department of Chemistry, Centre for Analysis and Synthesis, Lund University, S-22100 Lund, Sweden.
Yizhu
Y
Liu
Department of Chemistry, Technical University of Denmark, DK-2800, Kongens Lyngby, Denmark.
Klaus B
KB
Møller
Wigner Research Centre for Physics, Hungarian Academy Sciences, PO Box 49, H-1525 Budapest, Hungary.
Zoltán
Z
Németh
High Energy Accelerator Research Organization, 1-1 Oho, Tsukuba, Ibaraki 305-0801, Japan.
Shunsuke
S
Nozawa
Wigner Research Centre for Physics, Hungarian Academy Sciences, PO Box 49, H-1525 Budapest, Hungary.
Mátyás
M
Pápai
High Energy Accelerator Research Organization, 1-1 Oho, Tsukuba, Ibaraki 305-0801, Japan.
Tokushi
T
Sato
RIKEN SPring-8 Center, 1-1-1 Kouto, Sayo-cho, Sayo-gun, Hyogo 679-5148, Japan.
Takahiro
T
Sato
Department of Synchrotron Radiation Instrumentation, Lund University, PO Box 118, 22100 Lund, Sweden.
Karina
K
Suarez-Alcantara
Japan Synchrotron Radiation Research Institute (JASRI), 1-1-1 Kouto, Sayo-cho, Sayo-gun, Hyogo 679-5198, Japan.
Tadashi
T
Togashi
Japan Synchrotron Radiation Research Institute (JASRI), 1-1-1 Kouto, Sayo-cho, Sayo-gun, Hyogo 679-5198, Japan.
Kensuke
K
Tono
Department of Chemical Physics, Lund University, PO Box 124, S-22100 Lund, Sweden.
Jens
J
Uhlig
Department of Chemical Physics, Lund University, PO Box 124, S-22100 Lund, Sweden.
Dimali A
DA
Vithanage
Department of Chemistry, Centre for Analysis and Synthesis, Lund University, S-22100 Lund, Sweden.
Kenneth
K
Wärnmark
RIKEN SPring-8 Center, 1-1-1 Kouto, Sayo-cho, Sayo-gun, Hyogo 679-5148, Japan.
Makina
0000000224721684
M
Yabashi
Department of Chemistry, Centre for Analysis and Synthesis, Lund University, S-22100 Lund, Sweden.
Jianxin
J
Zhang
Department of Chemical Physics, Lund University, PO Box 124, S-22100 Lund, Sweden.
Villy
V
Sundström
Centre for Molecular Movies, Department of Physics, Technical University of Denmark, DK-2800 Lyngby, Denmark.
Martin M
MM
Nielsen