ESCA Electron spectroscopy for chemical analysis

XPS x-ray photoelectron spectroscopy

 Kai Siegbahn
Karl M. G. Siegbahn

Nobel Prize in Physics (1924) Nobel Prize in Physics (1981)

 σu
UV-PES spectrum of N2

πg

σg
πu
2g
σu
1u

1u
σg
Inelastic scattering of electrons. If the electron originating from the O 1s core level undergoes an inelastic
collision on the way to the surface it will be detected with somewhat lower kinetic energy, meaning that it will
contribute to the spectrum at higher binding energy than all other O 1s electrons that make it without collisions.
In XPS all transitions except from s-orbitals exhibit
a doublet peak structure, as shown in the image
above. The origin of this phenomenon lies in the
quantum-mechanical principle of spin-orbit
coupling.

Electrons, being fermions, have an associated spin

angular momentum s=1/2. In addition to their spin
they can have an orbital angular momentum l
(lower case L) depending on the type of orbital they
are in. The orbital angular momentum can have the
values 0,1,2, and 3 corresponding to s-, p-, d-, and f-
orbitals, respectively.

When an orbital angular momentum is present

(true for all types except s) it can couple with the
electron's spin s, resulting in a total angular
momentum j. The two angular momenta can couple
in two ways, namely parallel or antiparallel, as
illustrated below for a p-orbital (l=1) electron.
There is an energy associated with the spin-orbit coupling, due to the magnetic moment that both l and
s carry. The moments are oriented in such a way that the interaction energy is higher for
parallel and lower for antiparallel coupling. For XPS this means that the photoelectron's binding
energy is affected by the spin orbit coupling and depends on the orientation of its spin s.

Consequence: The peak corresponding to the higher total angular momentum j in a doublet
structure therefore always has the lower binding energy in an XPS spectrum !

The binding energy difference observed in doublet peaks is a direct measure of the spin orbit coupling energy.
Qualitatively, the coupling energy increases with atomic number Z and decreases with orbital angular
momentum l.
Degeneracy of the Two States
The total momentum j can have different orientations in space (indexed by their magnetic quantum
number mj), all sharing the same spin orbit-coupling energy. These states are then said to be degenerate.
The ratio of degeneracy between the peaks of a doublet therefore defines their natural peak intensity
(area) ratios.
Degeneracy = (2j+1)

The above figure illustrates the allowed mj of the individual degenerate states. Keep in mind that
mj can only change by ±1. The table shows the resulting degeneracy ratios for all the orbitals.
The knowledge of the binding energy difference and the intensity ratios proves very valuable when
building a peak model for core-level XPS data, as we will see during training.
 Spin orbit splitting with Z

Ti 22 Fe 26

Zn 30
Cu 29
 Spin orbit splitting - distance from the nucleus

2p vs 3d vs 4f
Where do Binding Energy Shifts Come From?
-or How Can We Identify Elements and Compounds?

Fermi Level
Pure Element
Electron-electron Binding
Energy
repulsion
Look for changes here
Electron by observing electron
binding energies

Electron-nucleus
attraction Electron-
Nucleus
Separation

Nucleus
Elemental Shifts
Binding Energy (eV)
Element 2p3/2 3p 

Fe 707 53 654
Co 778 60 718
Ni 853 67 786
Cu 933 75 858
Zn 1022 89 933

Electron-nucleus attraction helps us identify the

elements
Elemental Shifts
2p6
Oxidation state
Oxidation state
physisorbed
 Aromatic nitrogen

285.2 eV aromatic carbon Glycine nitrogen

286.5 eV carbon bonded to nitrogen
289.0 eV carboxylic/carbonyl carbon
ITO
Initial state effect - Spin orbit coupling
Chemical shift

Final state effect: Satellite, multiplet, plasmon

Monopole excitation or ionization
Shake-up and shake-off

Photoemission process can leave the ions in

the ground state (main peak) and also
possibly in an excited sate (shake-up/shake-
off satellites), the latter makes the KE of
photoelectron less: higher BE.

- excitation of electron to bound state

shake-up satellite

- excitation of electron to unbound

(continuum) state shake-off satellite
Shake-off Shake-up Main
Multiplet splitting

Coupling of existing unpaired electrons with the unpaired electron generated upon
photoemission

Multiplet splitting can give a measurement of the bonding character of the unfilled valence shell

Multiplet splitting yields information on the nature of the 3d bonding multiplet splitting in a chemical

Compound is determined by two major factors:

(1) the extent of decoupling in the d orbital due to strong field ligand bonding
(2) the extent that the d electrons are delocalized due to the nature of the chemical bond

No multiplet splitting if the unpaired electrons are delocalized

More the covalency, more then delocalization of electron – small/no splitting

Iron Halides: F>Cl>Br

Plasmon
Photon
Plasmon peak arise when the outgoing electron excites
collective oscillations in the conduction band electrons and
thus suffers a discrete energy loss (or several losses in
multiples of the characteristic plasmon frequency, about 15
eV for aluminium).