Toward Highlighting the Ultrafast Electron Transfer Dynamics at the Optically Dark Sites of Photocatalysts

Forskningsoutput: TidskriftsbidragArtikel i vetenskaplig tidskrift

Abstract

Building a detailed understanding of the structure function relationship is a crucial step in the optimization of molecular photocatalysts employed in water splitting schemes. The optically dark nature of their active sites usually prevents a complete mapping of the photoinduced dynamics. In this work, transient X-ray absorption spectroscopy highlights the electronic and geometric changes that affect such a center in a bimetallic model complex. Upon selective excitation of the ruthenium chromophore, the cobalt moiety is reduced through intramolecular electron transfer and undergoes a spin flip accompanied by an average bond elongation of 0.20 +/- 0.03 angstrom. The analysis is supported by simulations based on density functional theory structures (B3LYP*/TZVP) and FEFF 9.0 multiple scattering calculations. More generally, these results exemplify the large potential of the technique for tracking elusive intermediates that impart unique functionalities in photochemical devices.

Detaljer

Författare
  • Sophie Canton
  • Xiaoyi Zhang
  • Jianxin Zhang
  • Tim B. van Driel
  • Kasper S. Kjaer
  • Kristoffer Haldrup
  • Tobias Harlang
  • Karina Suarez Alcantara
  • Yizhu Liu
  • Jorge Perez Tuero
  • Amelie Bordage
  • Matyas Papai
  • Gyoergy Vanko
  • Guy Jennings
  • Charles A. Kurtz
  • Mauro Rovezzi
  • Pieter Glatzel
  • Grigory Smolentsev
  • Asmus O. Dohn
  • Morten Christensen
  • Andreas Galler
  • Wojciech Gawelda
  • Christian Bressler
  • Henrik T. Lemke
  • Klaus B. Moller
  • Martin M. Nielsen
  • Reiner Lomoth
Enheter & grupper
Forskningsområden

Ämnesklassifikation (UKÄ) – OBLIGATORISK

  • Naturvetenskap
  • Fysik
  • Atom- och molekylfysik och optik
  • Kemi
Originalspråkengelska
Sidor (från-till)1972-1976
TidskriftThe Journal of Physical Chemistry Letters
Volym4
Utgåva nummer11
StatusPublished - 2013
PublikationskategoriForskning
Peer review utfördJa