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Electron spectroscopy James N. O’Shea School of Physics & Astronomy Nottingham Nanoscience and Nanotechnology Centre University of Nottingham. SMALL Kick-off meeting , Madrid| Jan 2011. Outline Something to study: Dye molecules Chemical information: XPS Molecular orbitals: PES & XAS - PowerPoint PPT Presentation
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Electron spectroscopy
James N. O’SheaSchool of Physics & AstronomyNottingham Nanoscience and Nanotechnology CentreUniversity of Nottingham
SMALL Kick-off meeting , Madrid| Jan 2011
SMALL Kick-off meeting , Madrid| Jan 2011
Outline
Something to study: Dye moleculesChemical information: XPSMolecular orbitals: PES & XASAdsorption geometry: XASCharge transfer dynamics: RPES
Dye molecules on surfaces
Charge injection interface
LUMO
HOMO
How is the molecule bonded to the surface?What can we say about the electronic coupling?
A model dye-sensitised system
LUMO
HOMO
Core-level photoemission
LUMO
HOMO
Core level
hv
Vacuum level
KE
BE
L. Patthey et al, J. Chem. Phys. 110, 5913 (1999)
Chemical information with x-ray photoelectron spectroscopy (XPS)
Inte
nsity
(arb
. Uni
ts)
Chemical shift (eV)
Ethyl-trifluoroacetateK. Siegbahn et al
Although the core-level electrons are not directly involved in the formation of bonds, a change in the valence electrons (chemical state) will change the potential a core-electron feels and therefore modify the binding energy.
Core-level photoemission
LUMO
HOMO
Core level
hv
Vacuum level
KE
BE
L. C Mayor et al, J. Chem. Phys. 129, 114701 (2008)
Electron spectroscopy is surface sensitive
We all know that x-rays themselves can penetrate deep into most matter…
…but the electrons coming out can only travel through a couple of layers without banging into something along the way.
Surface sensitivity of XPS
Occupied states: valence photoelectron spectroscopy
Vacuum level
hv BE
KE
Unoccupied states: x-ray absorption spectroscopy (XAS)
Vacuum level
hv
BEres
BEcore
Molecular orientation & XAS
J. Ben Taylor et al, J. Chem. Phys. 127, 134707 (2007)
RPES: Participator decay
LUMOHOMO
N1s
hv
Vacuum level
Participator electrons leave the atom in a final state just like valence photoemission.
They track with constant binding energy.
RPES: Spectator decay
LUMOHOMO
N1s
hv
Vacuum level
Spectator electrons leave the atom in a final state just like Auger decay with an extra electron in an unoccupied state.
They track with constant kinetic energy…like Auger electrons but shifted up.
RPES: Auger decay
LUMOHOMO
N1s
hv
Vacuum level
Charge transfer of the originally excited electron leaves Auger decay as the only non-radiative core-hole decay option.
They track with constant kinetic energy.
Bi-isonicotinic acid on rutile TiO2(110)
J. Schnadt et al, Nature 418, 621 (2002)
Participator
LUMO
LUMO+1
LUMO+2
J. Schnadt et al, Nature 418, 621 (2002)
The sensitivity of RPES compared to XAS intensity is assessed for the decoupled molecule (multilayer) where no charge transfer is expected for any unoccupied state.
A state-dependent ratio that we call C is generated for the case of an isolated molecule (in this case, C=⅓).
The benchmark
J. Schnadt et al, Nature 418, 621 (2002)
XASRPES
XASRPESCT IIC
II
fs
fs
LUMO
sN
T
C
3
6
2
1
Pulling out charge transfer timescales
SMALL Kick-off meeting , Madrid| Jan 2011
Conclusions
Chemical information: XPSMolecular orbitals: PES & XASAdsorption geometry: XASCharge transfer dynamics: RPES