Photochemistry and molecular
photovoltaics make frequent use of so-called transition metal complexes which
consist of a central metal ion bonded to a group of surrounding ligands. Such
materials display a strong absorption of ultraviolet or visible light, making
them attractive as primary light absorbers in molecular solar cells and other
devices of molecular optoelectronics. Absorption of light is followed by an
extremely fast shift of electrons from the metal ion to the ligands, a
mechanism that is essential for generating an electric voltage. All
applications rely on solid state materials in which transition metal complexes
are densely packed and can interact with each other. So far, the influence of
this interaction on the very fast electron motions following the absorption of
light has remained unclear.
In the current issue of Journal
of Chemical Physics, Benjamin Freyer, Flavio Zamponi, Vincent Juve,
Johannes Stingl, Michael Woerner, Thomas Elsaesser and Majed Chergui report the
first in-situ x-ray imaging of electron and atom motions induced by such an
electron transfer excitation. For the prototype material [Fe(bpy)3]2+(PF6-)2,
they show time-dependent 'electron maps' derived from x-ray snapshots taken
with 100 fs long hard x-ray flashes. Taking x-ray snapshots at various times
during and after the optical pulse that triggers the charge transfer, creates a
molecular movie of electron and atom motions.
To the big surprise of the researchers, the time-dependent 'electron maps'
reveal a transfer of electronic charge not only from the Fe atoms to the
bipyridine units but -- so far unknown -- an even larger amount of electronic
charge from the PF6-counterions to the bipyridine units. The analysis of the
x-ray snapshots shows that the charge transfer affects approximately 30
complexes around the directly photo-excited one. This collective electron
response is caused by the electric Coulomb forces between the different ions
and minimizes the total electrostatic energy in the crystal. Such behavior is
highly favorable for charge collection and injection in optoelectronic devices.
Sticks and balls model of the transition metal complex
iron(II)-tris-bipyridine [Fe(bpy)3]2+. Iron-atoms (Fe) are brown, nitrogen (N)
blue, carbon grey, and hydrogen (H) white. The six nitrogen atoms are at the
corners of an octahedron around the Fe atom. The planes of the 3 bipyridine
subunits (N2C10H8) are mutually perpendicular.
No comments:
Post a Comment