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Charge transfer driven by ultrafast spin transition in a CoFe Prussian blue analogue

Journal Article · · Nature Chemistry
 [1];  [1];  [1];  [1];  [2];  [3];  [3];  [4];  [5];  [5];  [5];  [2];  [2];  [6];  [1]
  1. Univ. Rennes (France); Centre National de la Recherche Scientifique (CNRS), Rennes (France). Institut de Physique de Rennes (IPR)
  2. Centre National de la Recherche Scientifique (CNRS), Orsay (France). Institut de Chimie Moléculaire et des Matériaux d’Orsay; Universite Paris-Saclay, Orsay (France)
  3. Sapienza Univ. of Rome (Italy)
  4. European Synchrotron Radiation Facility (ESRF), Grenoble (France)
  5. SLAC National Accelerator Lab., Menlo Park, CA (United States). Linac Coherent Light Source (LCLS)
  6. Centre National de la Recherche Scientifique (CNRS), Pessac (France). Institut de Chimie de la Matière Condensée de Bordeaux (ICMCB); Université de Bordeaux, Pessac (France); Lebanese German University (LGU), Jounieh (Lebanon)
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Photoinduced charge-transfer is an important process in nature and technology and is responsible for the emergence of exotic functionalities, such as magnetic order for cyanide-bridged bimetallic coordination networks. Despite its broad interest and intensive developments in chemistry and material sciences, the atomic-scale description of the initial photoinduced process, which couples intermetallic charge-transfer and spin transition, has been debated for decades; it has been beyond reach due to its extreme speed. In this work we study this process in a prototype cyanide-bridged CoFe system by femtosecond X-ray and optical absorption spectroscopies, enabling the disentanglement of ultrafast electronic and structural dynamics. Our results demonstrate that it is the spin transition that occurs first on the Co site within ~50 fs, and it is this that drives the subsequent Fe-to-Co charge-transfer within ~200 fs. This study represents a step towards understanding and controlling charge-transfer-based functions using light.
Research Organization:
SLAC National Accelerator Laboratory, Menlo Park, CA (United States). Linac Coherent Light Source (LCLS)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES); Agence Nationale de la Recherché (ANR); Centre national de la recherche scientifique (CNRS); Fonds Européen de Développement Régional (FEDER); Région Bretagne; Institut Universitaire de France (IUF); European Union Horizon2020
Grant/Contract Number:
AC02-76SF00515
OSTI ID:
1768384
Journal Information:
Nature Chemistry, Journal Name: Nature Chemistry Journal Issue: 1 Vol. 13; ISSN 1755-4330
Publisher:
Nature Publishing GroupCopyright Statement
Country of Publication:
United States
Language:
English

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Lattice dynamics of photoexcited insulators from constrained density-functional perturbation theory journal October 2021

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Coordination chemistry
Materials chemistry
Photochemistry
Physical chemistry