Photoelectron Spectroscopy

Essential Knowledge 1.B.1

Presented By, Mark Langella, APSI
Chemistry 2013 , PWISTA.com
Presented By, Mark Langella, APSI
Chemistry 2013 , PWISTA.com
PES
Presented By, Mark Langella, APSI
Chemistry 2013 , PWISTA.com
Photoelectric Effect
experimentally that when light shines
on a metal surface, the surface emits
electrons
you can start a current in a circuit just
by shining a light on a metal plate
Einstein noted that careful
experiments involving the
photoelectric effect could show
whether light consists of particles or
waves
If it's waves, the energy contained in
one of those waves should depend
only on its amplitude--that is, on the
intensity of the light
frequency, should make no difference
Einstein Proved frequency was key
http://phet.colorado.edu/en/simulati
on/photoelectric

Presented By, Mark Langella, APSI
Chemistry 2013 , PWISTA.com
Coulomb's Law
That an electron in a given shell will require a
certain energy to be separated from the atom.
An electron can be said to occupy an energy
level in an atom.
Each electron must be in a shell at a particular
distance from the nucleus, and the energy
levels corresponding to these shells are
quantizedthat is, only certain discrete
energy levels should be found.

Presented By, Mark Langella, APSI
Chemistry 2013 , PWISTA.com
Shell Concept
Presented By, Mark Langella, APSI
Chemistry 2013 , PWISTA.com
PES
method that provides information on all the
occupied energy levels of an atom (that is, the
ionization energies of all electrons in the
atom) is known as photoelectron
spectroscopy; this method uses a photon (a
packet of light energy) to knock an electron
out of an atom.
Presented By, Mark Langella, APSI
Chemistry 2013 , PWISTA.com
Methodology
Electrons obtained in this way are called photoelectrons.
Very high energy photons, such as very-short-wavelength
ultraviolet radiation, or even x-rays, are used in this
experiment.
The gas phase atoms are irradiated with photons of a
particular energy.
If the energy of the photon is greater than the energy
necessary to remove an electron from the atom, an
electron is ejected with the excess energy appearing as
kinetic energy, mv
2
, where v is the velocity of the ejected
electron.
The speed of the ejected electron depends on how much
excess energy it has received.


Presented By, Mark Langella, APSI
Chemistry 2013 , PWISTA.com
Ionization Energy
IE is the ionization energy of the electron and KE is the
kinetic energy with which it leaves the atom, we have
E
photon
= IE + KE
rearranging the equation,
IE = E
photon
KE
kinetic energy of the electrons is measured in a
photoelectron spectrometer
photons of sufficient energy are used, an electron may
be ejected from any of the energy levels of an atom
every electron in each atom has an (approximately)
equal chance of being ejected
Presented By, Mark Langella, APSI
Chemistry 2013 , PWISTA.com
Spectrum
for a large group of identical atoms, the
electrons ejected will come from all possible
energy levels of the atom
because the photons used all have the same
energy, electrons ejected from a given energy
level will all have the same energy.
Only a few different energies of ejected
electrons will be obtained, corresponding to
the number of energy levels in the atom.
Presented By, Mark Langella, APSI
Chemistry 2013 , PWISTA.com
Photoelectron spectrum
plot of the number of ejected electrons (along
the vertical axis) vs. the corresponding ionization
energy for the ejected electrons (along the
horizontal axis)
the kinetic energy of the ejected electrons that is
measured by the photoelectron spectrometer
we can obtain the ionization energies of the
electrons in the atom from the kinetic energies of
the ejected electrons
a photoelectron spectrum uses the ionization
energy as the horizontal axis
Presented By, Mark Langella, APSI
Chemistry 2013 , PWISTA.com
Photoelectron Spectrum
The photoelectron spectrum is a plot of the number of electrons emitted versus their
kinetic energy. In the diagram below, the X axis is labeled high to low energies so
that you think about the XY intersect as being the nucleus.



http://www.chem.arizona.edu/chemt/Flash/photoelectron.html

Presented By, Mark Langella, APSI
Chemistry 2013 , PWISTA.com
Presented By, Mark Langella, APSI
Chemistry 2013 , PWISTA.com
Interpretations from the data:
1. There are no values on the y axis in the tables above. Using the
Periodic Table and Table 1, put numbers on the y axis.
2. Label each peak on the graphs above with s, p, d, or f to indicate
the suborbital they represent..
3. What is the total number of electrons in a neutral potassium atom?
Orbital names s, p, d,
and f stand for names
given to groups of lines
in the spectra of the
alkali metals. Early
chemists called the line
groups sharp, principal,
diffuse, and
fundamental.
Presented By, Mark Langella,
APSI Chemistry 2013 ,
PWISTA.com
PES Question
If a certain element being studied by an X-ray
PES displays an emission spectrum with 5
distinct kinetic energies. What are all the
possible elements that could produce this
spectrum?
Determine the orbitals that the spectral lines
are originating from and then determine the
elements that have electrons in only these
orbitals.
Presented By, Mark Langella, APSI
Chemistry 2013 , PWISTA.com