Visualizing the non-equilibrium dynamics of photoinduced intramolecular electron transfer with femtosecond X-ray pulses
Open Access
- 2 March 2015
- journal article
- research article
- Published by Springer Science and Business Media LLC in Nature Communications
- Vol. 6 (1), 6359
- https://doi.org/10.1038/ncomms7359
Abstract
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.Keywords
This publication has 69 references indexed in Scilit:
- Introducing a standard method for experimental determination of the solvent response in laser pump, X-ray probe time-resolved wide-angle X-ray scattering experiments on systems in solutionPhysical Chemistry Chemical Physics, 2013
- 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)32+The Journal of Physical Chemistry A, 2012
- A molecular ruthenium catalyst with water-oxidation activity comparable to that of photosystem IINature Chemistry, 2012
- Origin of electronic absorption spectra of MLCT-excited and one-electron reduced 2,2′-bipyridine and 1,10-phenanthroline complexesInorganica Chimica Acta, 2011
- Photochemical Fate: The First Step Determines Efficiency of H2 Formation with a Supramolecular PhotocatalystAngewandte Chemie-International Edition, 2010
- Evolution of charge and spin state of transition metals in the LaMn1−xCoxO3 perovskite seriesJournal of Applied Physics, 2008
- Low Quantum Yields of Relaxed Electron Transfer Products of Moderately Coupled Ruthenium(II)−Cobalt(III) Compounds on the Subpicosecond Laser ExcitationThe Journal of Physical Chemistry A, 2004
- Excited-state interconversion between emissive MLCT levels in a dinuclear Ru(ii) complex containing a bridging ligand with an extended π systemChemical Communications, 2000
- Direct femtosecond mapping of trajectories in a chemical reactionNature, 1990
- Femtosecond Clocking of the Chemical BondScience, 1988