PHOTOELECTRON

SPECTROSCOPY
 Key points
 Photoelectron spectroscopy is an experimental method used to determine
the electronic structure of atoms and molecules.
 Photoelectron spectrometers ionize samples by bombarding them with
high-energy radiation, such as UV or x-rays, and detecting the number and
kinetic energy of ejected electrons.
 The frequency and energy of incident photons can be used to calculate the
binding energy of the ejected electron using the following
equation: BE=hν−KEelectron
 The PES spectrum is a graph of electron count vs. electron binding
energy.
 The peaks in PES spectra correspond to the electrons in different subshells
of the atom. The peaks with the lowest binding energy correspond to the
valence electrons, while the peaks at the highest binding energy correspond
to the inner-shell or core electrons.
Introduction: Ionization energy

 If you look in the back of your chemistry textbook, you will most likely find a
table in the appendix that lists the various ionization energies, or ionization
potentials, for most of the elements on the periodic table. The ionization
energy is how much energy is required to remove an electron from a neutral
atom in the gaseous phase, and typically has units of kilojoules or electron
volts per mole. The first ionization energy of an element A can be written as
the following reaction:
 First I.E. + A (g)  A+ (g) + e-
 Scientists can use photoelectron spectroscopy (PES) to experimentally
determine the energy it takes to remove electrons from atoms and molecules.
The basics of photoelectron spectroscopy
 The physical phenomenon behind photoelectron spectroscopy is similar to the
photoelectric effect. From early experiments with the photoelectric effect,
physicists learned that shining high-energy radiation on metals could eject
electrons. By analyzing the kinetic energy of the ejected electrons, features about
the electronic structure of the sample material could be determined.
 Photoelectron spectroscopy applies the photoelectric effect to atoms and
molecules in the solid, gas, and liquid phase. There are 2 main types of
photoelectron spectroscopy, depending on the energy of the radiation used to
eject electrons:
Ultraviolet photoelectron spectroscopy
(UPS)
 Illuminating a sample with ultraviolet (UV) light
will typically ionize the material by ejecting
valence electrons. Valence electrons reside in the
outermost shells of an atom. Due to shielding by
the core electrons, the valence electrons feel a
reduced attraction to the nucleus. Therefore,
valence electrons require less energy to remove
compared to core electrons.
X-ray photoelectron spectroscopy (XPS)

 Because x-rays are higher in frequency and energy than UV rays, shining them on a
sample can provide enough energy to eject core electrons. Core electrons are inner-shell
electrons that are closer to the nucleus, and thus require more energy to remove
compared to valence electrons.
 Once electrons are ejected from the sample, a detector is able to calculate the kinetic
energies of the electrons, as well as the relative number of electrons with that kinetic
energy. We can use this information to calculate the minimum energy required to
remove electrons from different subshells within an atom. This is called the binding
energy of the electron, and the binding energies depend on the chemical structure and
elemental composition of a sample.
 Let's now examine the relationship between kinetic energy and binding energy in more
detail.
The relationship between binding energy
and kinetic energy of photoelectrons

 When an electron in the sample absorbs an incident photon, it

gains that photon's energy. The energy required to eject a given
electron from the atom is known as the binding energy. Core
electrons have larger binding energies than valence electrons,
because core electrons are closer to the nucleus and thus have a
stronger attraction to the nucleus. Electrons will only be ejected
from atoms if the energy of the incoming photons is greater
than the binding energy of the electrons.
Once ejected, the photoelectron is traveling with a certain velocity, and therefore has kinetic energy. By the
law of conservation of energy, the energy of the ionizing photon must be equal to the binding energy (BE),
plus the kinetic energy of the photoelectron (KEelectron). We can write this mathematically as follows:
Ephoton=BE+KEelectron
Also, recall that the energy of a photon is given by the relationship:
Ephoton=hν
where h is Planck's constant (6.626×10−34 J⋅s) and v is the frequency of the photon in Hertz
(Hz).Substituting this relationship into the equation from the conservation of energy, we get:
hν=BE+KEelectron
Since we know the frequency of radiation used in the experiment and the kinetic energy of ejected
photoelectrons, the binding energies can be calculated. We can solve the equation above for binding
energy:
BE=hν−KEelectron
The detector in the spectrometer is also able to determine the relative number of photoelectrons with a
particular kinetic energy. This number is known as the photoelectron count. From this information, the
spectrometer generates a spectrum that plots photoelectron count vs. binding energy. Let's now examine
some PES spectra for different elements.
MO diagram & Photoelectron spectrum of F2

1pg 1pu 3sg

[He] 2s22p5
1pg band shows vibrational fine structure.
Increase in n F2+-antibonding.
Same orbital energy sequence as that of O2
PES spectrum of oxygen
Let's look at an element with more electrons. This is a simulated PES
spectrum for oxygen. As we analyze the spectrum, let's keep in mind
oxygen's ground-state electron configuration 1s22s22p1

Simulated PES spectrum of oxygen

In this spectrum, we have 3 different peaks

In this spectrum, we have 3 different peaks representing electrons in 3 different subshells.
Starting with the highest binding energy peak, the peak at 52.6 MJ represents
oxygen's 2 core electrons in the 1s subshell. The next peak at 3.04MJ corresponds to
oxygen's electrons in the 2s subshell, which are valence electrons. The peak at the lowest
binding energy, 1.31MJ, corresponds to oxygen's 4 valence electrons that occupy
the 2p subshell.
Once again, this spectrum matches with the ground-state electron configuration for neutral
oxygen, which is 1s22s22p4
Notice that the sum of the electron counts for each peak in the spectrum is the total number
of electrons in a neutral oxygen atom, which is equal to the atomic number of oxygen:
# electrons in neutral O=4+2+2=8 electrons
Identifying an element based on its PES
spectrum
A sample of an unknown element was analyzed using a photoelectron
spectrometer to produce the following spectrum. What is the identity
of our mystery element?
We can start by adding up the electron counts for all the peaks in the spectrum to find the
total number of electrons in the neutral atom:
# electrons in neutral atom=1+2+6+2+2=13 electrons
Therefore, our mystery element has a total of 13 electrons. Since a neutral atom has the
same number of electrons and protons, this suggests our mystery element is aluminum
which has an atomic number of 13. Let's make sure that the peaks in the spectrum are
consistent with aluminum's electron configuration, which is:
1s2 2s2 2p6 3s2 3p1
We can start by looking at the highest binding energy peak, which corresponds to the
electrons ejected from the innermost subshell of the atom. We can see that the highest
binding energy peak at 151 MJ has an electron count of 2. The relative electron count and
binding energy of this peak match with the 2 core electrons in the 1s subshell.
The next peak occurs at a binding energy of 12.1 MJ and it has an electron count of 2. This
peak represents the 2 electrons in the 2s subshell.
Note that the binding energy of these 2electrons is more than 10 times smaller than
that of the 1s electrons. This is consistent with the electrons in the 2s subshell being
further from the nucleus than the electrons in the 1s subshell, which means they
require less energy to remove.
The next peak at 7.19 MJ has an electron count of 6. This matches the next highest-
energy subshell in aluminium, the 2p subshell, which can hold a maximum
of 6 electrons.
Lastly, the final two peaks which have the lowest binding energy represent the
valence electrons. The peak with an electron count of 2 at 1.09MJ, represents the 2
3s electrons, and the peak at 0.58 represents the 1 electron that occupies the
3p subshell. We can see that the binding energies and relative electron counts for all
the peaks in the PES spectrum match the electron configuration for aluminum.
Thankyou