ELECTRONIC SPECTROSCOPY OF ATOM

By Yusuf Wicaksono and Regi Kusumaatmadja

INTODUCTION

Electronic Spectroscopy of atom is the study of transitions

( absorption or emission ) between electronic states of an
atom.
Atoms are unique in this respect as they have only
electronic degree of freedom.
To understand electronic spectroscopy of atom, it is
require to understand spectra of atom from alkali metal,
Hydrogen, Helium, alkaline earth metal and other
polyelectronic atom.

OUTLINE

Theory of Electronic Spectroscopy of Atom

Apparatus of Electronic Spectroscopy of Atom

Application of Electronic Spectroscopy of Atom

Paper About Electronic Spectroscopy of Atom

THEORY OF ELECTRONIC SPECTROSCOPY

Atoms and Quantum Number of Atom

Angular Momentum of Electrons in Atom

Spectra of Varies Atoms

HAMILTONIAN OF POLYELECTRONIC ATOM

Recall Hamiltonian for hydrogen atom or hydrogen-like ions ( He+, Li2+,

etc. ) which is have single electron:
2

Ze2
2
H=

2
4 0 r

Meanwhile for polyelectronic atom, the Hamiltonian should be

2

Ze2
e2
2
H=
i 4 r + 4 r
2 i
i
0 i i< j
0 ij

which the third term is electron-electron repulsion interaction.

Schroedinger equation from Hamiltonian above is difficult to be solve,

Using Hartree's approximation the Hamiltonian became
2

Ze2
2
H=
i
+ V (r i)

2 i
i 4 0 r i
i

which mean the contribution to the potential energy due to electron

repulsion as a sum of contribution from individual electron

EFFECT OF ELECRON REPULSION

The effect of electron repulsion is remove degeneracy energy in

hydrogen atom.
In polyelectronic atom, the energy not only depends to quantum
number n but also quantum number l
The value of Ei for particular orbital increases with the nuclear
charge of the atom
Hydrogen atom energy level

Polyelectronic atom energy level

1s

POLYELECTRONIC ENERGY LEVEL

Feeding in electron to energy level follows two principle;

Aufbau's principle and Pauli exclusion principle
The two principles forbid electron to have same set of
quantum number n,l,ml and ms
The total electron can fill energy level for any particular of n
and l is 2(2l + 1).
In polyelectronic atom, there are term of configuration and
state, which is both of them is different

Configuration describe the way in which electrons are

distributed among various orbital

Configuration may gives rise to more than one states

MOMENTUM ANGULAR OF ELECTRON

Each electron in an atom has two possible kinds of angular

momentum; orbital angular momentum and spin angular
momentum
The magnitude of orbital angular momentum is

[l(l+1)]

1/ 2

=l

The magnitude of spin angular momentum is

[s (s +1)]1 /2 =s *

For electron having orbital and spin angular momentum there

is a quantum number j ( angular momentum total ) which is
have magnitude

[ j( j +1)]1/ 2 = j *

MAGNETIC MOMENT OF ELECTRON

Electron circulating in an orbit give arise current flow and cause

magnetic moment
Magnetic moment which is arise from orbital momentum
angular is called magnetic moment orbital (L).
Electron spinning about its own axis arise magnetic moment
called magnetic moment spin (S).
The vector between l and L also s and S opposite each other.

MOMENTUM ANGULAR COUPLING

Interaction between orbital and spin magnetic moment give arise coupling of
the angular momentum
The strength of coupling (spin-orbit coupling) depends on the atom
concerned
The possibility interaction between angular momentum is

Spin one electron with spin other electron

Spin one electron with own orbital angular momentum

Orbital one electron with orbital other electron

There are two approximation to study about interaction between angular

momentum:

Coupling between spin-spin and orbital-orbital momenta neglected, but

coupling between total momentum (j) week but appreciable

Coupling between spin-orbital has been neglected but assume coupling

between orbital-orbital is strong and between spin-spin is week but
appreciable. (Russel-Saunders coupling).

NON EQUIVALENT ELECTRON RUSSELSAUNDERS COUPLING APPROXIMATION

Non-equivalent electrons = those that have different value of either n

or l. ( example: 3p1 3d1 or 3p1 4p1).
[ ll coupling ] : Consider two electron, n1l1 (electron 1) and n2l2
(electron 2) have ll coupling. The total orbital angular momentum is

L=l 1 +l 2, l 1 +l 2 1,.... ,|l 1l 2|

with magnitude
1/ 2

[ L(L+1)] =L

Example : The two electron = 2p13d1, Total angular momentum (L) =

3,2 or 1 and the magnitude is 121/2, 61/2 or 21/2 hbar.

NON EQUIVALENT ELECTRON RUSSELSAUNDERS COUPLING APPROXIMATION (2)

The term of the atom are labelled S, P, D, F, G, .

corresponding to L = 0, 1, 2, 3, 4, .
Example : configuration two electron = 2p13d1; L = 1,2 or 3; term
= P D F.
For filled sub-shell, L = 0. It is because ML = L, L-1, . , -L,
where ML = i(ml)i = 0.
Example : we have atom Carbon in exited configuration = 1s2
2s2 2p1 3d1. In 1s1 and 2s2, L = 0 and 2p1 3d1, L = 3,2 or 1 arises
term F D P.

NON EQUIVALENT ELECTRON RUSSELSAUNDERS COUPLING APPROXIMATION (3)

[ ss coupling ] : Consider two electron with s = , the magnitude is

(3/2)1/2. The total spin angular momentum (S) is

S =s 1 +s 2, s1 + s2 1,.... ,|s1 s 2|
for two electron the value of S will be 1 or 0. And the magnitude of S
is

[S (S+1)]1 /2 =S *
and the value of magnitude of S will be only 0 or 21/2 hbar.

Total spin angular momentum indicate total states in term S, P, D, F,

. where total states can be represented by 2S+1. ( example: S = 0,
total states = 1 (singlet). If S = 1, total states = 3 (singlet) )

NON EQUIVALENT ELECTRON RUSSELSAUNDERS COUPLING APPROXIMATION (4)

The label of total states write as pre-superscript to the S, P, D, F, .

or we can write 2S+1(S, P, D, F, .)
For two electron, S = 0 because MS = S, S-1, ., -S where i(ms)i = 0
so MS = i(ms)i = 0.
For all occupied orbital are filled, the terms will be arise only 1S.
So if we have Carbon atom with configuration 1s2 2s2 2p1 3d1 the term
will be have is 1P 1D 1F for singlet and 3P 3D 3F for triplet.

NON EQUIVALENT ELECTRON RUSSELSAUNDERS COUPLING APPROXIMATION (5)

To know what states is possible in one term, it will be using total

angular momentum (J), where J is

J =L+S , L+S 1,.... ,|LS|

and the magnitude is
1 /2

[J (J +1)] =J

The states of term is express by 2S+1LJ

In example if we have Carbon atom with configuration 1s2 2s2 2p1 3d1,
the possibility states is
1

P1 3P0 3P1 3P2 1D2 3D1 3D2 3D3 1F3 3F2 3F3 3F4

EQUIVALENT ELECTRON RUSSELSAUNDERS COUPLING APPROXIMATION

Equivalent electron = those that have same n and l

example : Carbon ( ground configuration ) = 1s2 2s2 2p2

In equivalent electron we must consider to not violent Pauli

exclusion principle; pair of quantum number (ms) and (ml)
cannot simultaneously have same value for different
electron.
Electron is indistinguishable

EQUIVALENT ELECTRON RUSSELSAUNDERS COUPLING APPROXIMATION (2)

Consider Carbon with configuration 1s2 2s2 2p2. The term arising from
2 equivalent p electron is

EQUIVALENT ELECTRON RUSSELSAUNDERS COUPLING APPROXIMATION (3)

Comparing between non-equivalent term Carbon which is 1S 3S 1P 3P

1D 3D (first excitation configuration) and equivalent term of Carbon
which is 1S 3P 1D show that Pauli exclusion rule forbid 3S 1P 3D.
Another comparison show below:

EQUIVALENT ELECTRON RUSSELSAUNDERS COUPLING APPROXIMATION (4)

HUND RULES = Determine which of the term arising from equivalent

electron lies lowest in energy
HUND RULES :
1) Of the term arising from equivalent electron those with the highest
multiplicity lie lowest energy.
2) Of these, the lowest is that with the highest value of L
example : ground configuration Carbon has term 1S 3P 1D. The term with
highest multiplicity = 3P. So the ground state

Consider there is splitting of term by LS coupling, which is propotional with

J

E J EJ 1=A J
If A > 0 multiplet normal and if A < 0 multiplet inverted

So there is additional rules for ground terms which tell us whether a

multiplet arising from equivalent electron is normal or inverted

EQUIVALENT ELECTRON RUSSELSAUNDERS COUPLING APPROXIMATION (5)

Normal multiplets arise from equivalent electron when a partially

filled orbital is less than half full
example : Carbon ground configuration = 1s2 2s2 2p2

Equivalent and less than half-full = normal multiplet

The lowest term is 3P with states 3P2 3P1 3P0

The ground states is 3P0

Inverted multiplets arise from equivalent electrons when a partially

filled orbital is more than half-full
example : Oxygen ground configuration = 1s 2 2s2 2p4

Equivalent and more than half-full = inverted multiplet

The lowest term is 3P with states 3P2 3P1 3P0

The ground states is 3P2

THE FINE STRUCTURE OF HYDROGEN

ATOM SPECTRUM

The selection rule for hydrogen atom is

n = anything, l = 1 only

There is selection rule for j, which is

j = 0, 1

THE SPECTRUM OF LITHIUM AND OTHER

HYDROGEN-LIKE SPECIES

The selection rule for hydrogen lithium and other hydrogen-like is like
hydrogen which is
n = anything, l = 1 only

There is selection rule for j is like hydrogen too, which is

j = 0, 1

THE SPECTRUM OF HELIUM AND THE

ALKALINE EARTHS

The relevant selection rules for many-electron systems are:

S = 0, L = 1, J = 0, 1

Note that, with J = 0 cannot make a transition to another J = 0 states.

APPARATUS OF ELECTRONIC SPECTROSCOPY OF

ATOM

Photoelectron Spectroscopy Theory

Experimental Method

Source of Monochromatic Ionizing Radiation

Electron velocity analysers

Electron detector

Ionization process and Koopmans' theorem

Photoelectron spectra and their interpretation

UV photoelectron spectra of atom

X-ray photoelectron spectra of atom

PHOTOELECTRON SPECTROSCOPY (THEORY)

Spectroscopy will be use for electronic spectroscopy of atom is

photoelectron spectroscopy
Photoelectron spectroscopy involves the ejection of electron from atoms
following bombardment by photon
Electron will be ejected if threshold frequency is reached, because the
energy from photon equal to work function of the sample.
ht =

If frequency of photon higher than threshold frequency, electron will have

kinetic energy when ejected
ht = + mev2

For samples in the gas phase equation above will be

ht = I + mev2

PHOTOELECTRON SPECTROSCOPY (THEORY) [2]

Photoelectron spectroscopy have many type, but the most essential

methods for atom is Ultraviolet Photoelectron, X-ray Photoelectron

Process in XPS and UPS is ejection of photoelectron following interaction of

the atom which is ionized to produced singly charged A+
M + h M+ + e

EXPERIMENTAL METHOD

In UV or X-ray photoelectron spectrometer, sample in the target chamber is

bombarded with photons and then photoelectron are ejected in all direction
Electron energy analyser will be separates the electrons according to their
kinetic energy
After that spectrum will be recorded by electrons detector in the number of
electron per unit time as a function of binding energy or ionization energy

EXPERIMENTAL METHOD MONOCHROMATIC SOURCE

[ ULTRAVIOLET ]

Ultraviolet Photoelectron Spectroscopy :

Source providing 20 eV 50 eV the energy

required to ionized electron from lowest energy
ionization ( around 10 eV ) and higher-energy
ionization

Source produced by a discharge in He or Ne gas

resulting in emission of far-UV radiation from the
atom or positive ion

Helium I radiation : Helium discharged produce

21.22 eV radiation due to the 21P1(1s1 2p1)
11S0(1s2)
Helium II radiation : Helium is ionized
predominantly to He+. The radiation is due
mainly from n = 2 to n = 1 with energy 40.81 eV.
Neon radiation : Neon discharged produce 16.67
eV and 16.85 eV.

EXPERIMENTAL METHOD MONOCHROMATIC

SOURCE [ X-RAY ]

X-ray Photoelectron Spectroscopy

Source used of X-ray radiation are MgK and AlK ( K mean that an
electron has been ejected from the K shell and the vacancy will fill by
electron in L shell.

The MgK produce energy primarily 1253.7 eV and 1253.4 eV; the AlK
produce energy primarily 1486.7 eV and 1486.3 eV.

EXPERIMENTAL METHOD MONOCHROMATIC

SOURCE [ BREMSSTRAHLUNG ]

In addition there are is a weak bremsstrahlung radiation and also several

satellites lines accompanying both doublets

Bremsstrahlung radiation is results from collisions between the electron

of the beam and the atoms of the target material which is make the
electron decelerated and a photon X-ray energy is produced.

The both of them can be remove by monochromator

EXPERIMENTAL METHOD MONOCHROMATIC

SOURCE [ X-RAY MONOCHROMATOR ]

Component and arrangement of monochromator is :

Q is Quartz crystal which is bent to form a concave X-ray diffraction

grating. ( Quartz used to get narrow band )
X-Ray source and Target Chamber placed in position on the
Rowland circle

Monochromator is useful too for narrowing the otherwise broad lines.

EXPERIMENTAL METHOD MONOCHROMATIC

SOURCE [ SYNCHROTRON RADIATION SOURCE ]

An important source of both far-UV and X-ray radiation is synchrotron

radiation source (SRC).

EXPERIMENTAL METHOD - ELECTRON VELOCITY

ANALYSER

Measurement of the kinetic energy of the photoelectron involves

measurement of their velocity
Measurement of the velocity of photoelectron has been achieved by various
type of analysers, two basic types of electron analyzers are encoutered:

Retarding field analyser

Slotted grid analayser

The spherical grid analyser

Dispersion analyser

The Cylindrical analayser

The Hemispherical analysers

EXPERIMENTAL METHOD - ELECTRON VELOCITY

ANALYSER [ SLOTTED GRID ANALYSER ]

Component of analyser:

The slotted grid

The retarding grid

Collector

How the analyser work is:

The photoelectron are generated along the axis

of cylindrical electron collector.

A retarding potential, applied to the cylindrical

retarding grid

An increasing potential difference applied across

the grids to retard the electron flowing from the
source to the collector

At a high enough potential difference, electrons of

energy E2 will be retarded and the collector signal
will be decrease

EXPERIMENTAL METHOD - ELECTRON VELOCITY

ANALYSER [ SPHERICAL GRID ANALYSER ]

The spherical grid analyser has the advantage of

collecting all the photoelectrons generated at the
center, in whatever direction they are travelling
There are two spherical retarding grid in this
design
The uses of two grid is same in slotted grid
analyser
Slotted grid analyser and spherical grid analyser
useful mainly for gaseous sample
Retarding-field instruments are relatively simple
and efficient but do not have the high resolution of
dispersion system

EXPERIMENTAL METHOD - ELECTRON VELOCITY

ANALYSER [ CYLINDRICAL ANALYSIS ]

Cylindrical analyser used to gaseous sample

and solid sample.
The process of the analyser is:

In this analyser electron beam is deflected by

an electrostatic field in such a way that the
electron travel in a curved path.

The radius of curvature is dependent upon the

kinetic energy energy of the electron and the
magnitude of the field

By varying the field, electron of various kinetic

energies can be focused on the detector

The relationship between the plate voltage V1

and V2 and the energy of the electron Ek is
given by
V 2V 1=2 E k R log (

R1
)
R2

EXPERIMENTAL METHOD - ELECTRON VELOCITY

ANALYSER [ HEMISPHERICAL ANALYSER ]

The work same as cylindrical analyser but has the advantage of collecting
more photoelectron.
Consisting of two concentric plates which are parts of hemispheres, socalled spherical sector plates
This analyser often used in a spectrometer which operates for both UPS and
XPS

EXPERIMENTAL METHOD ELECTRON DETECTOR

Detector may be a simple electrometer when using a cylindrical or spherical

grid analyser
Other type analyser need electron multiplier to increase sensitivity.
Electron multiplier consists of a number of dynodes, each of which produces
more electron than it receives.
Alternatively, multichannel electron multiplier in the focal plane of the
analyser can be used to collect simultaneously electron with a range of
energies

EXPERIMENTAL METHOD RESOLUTION

XPS is usually limited by the line width of the ionizing radiation

Resolution in UPS depends on such factor as

The efficiency of shielding of the spectrometer from stray magnetic field

The cleanliness of the analyser surface

Resolution of UPS decrease when the kinetic energy of photoelectron is

below about 5 eV; The highest resolution obtained is about 4 meV

IONIZATION PROCESS AND KOOPMANS' THEOREM

Ionization process in XPS and UPS as before can be write as:

M + h M+ + e

When M is an atom the total change in angular momentum for process above
must obey selection rule l = 1

Meanwhile the photoelectron can take away any amount of momentum

Example:

Electron removed from d orbital of M which is l = 2, so the photoelectron carries away l

= 1 or 3 depend on l = -1 or +1.
So the wavefunction of of a free electron has just p and f character

The energy required to eject an electron from an orbital is a direct measure

of the orbital energy.
Koopmans theorem : for a closed-shell atom the ionization energy of an
electron in a particular orbital approximately equal to the negative of the
orbital energy calculated by a self-consistency field method

IONIZATION PROCESS AND KOOPMANS' THEOREM [2]

In equation Koopmans' theorem can be write as

SCF

I i i

The negative sign is due to the convention that orbital energies i are
negative

In the level of simple valence theory this theorem is strong, but with more
accurate theory this theorem no longer strong
The three most important factor that may contribute to Koopmans' theorem
relate to the main deficiencies in SCF calculations :

Electron reorganization. The orbital in M+ are not quite the same as in M because
there is one electron fewer.
SCF

Electron correlation

Relativistic effect

SCF

(M )i

(M )

PHOTOELECTRON SPECTRA AND THEIR

INTERPRETATION

The most important information derived from photoelectron spectra is the

ionization energies for valence and core electrons
Before the development of photoelectron spectroscopy very few of these
ware known
For core electrons ionization energies were previously unobtainable and
illustrate the extent to which core orbitals differ from the pure atomic orbital
pictured in simple valence theory
Using Koopmans' theorem for closed-shell atom ionization, we shall see UV
photoelectron spectra and X-ray photoelectron spectra

PHOTOELECTRON SPECTRA AND THEIR

INTERPRETATION [ UV PHOTOELECTRON SPECTRA ]

The atom will be use for example is Ar with UV

source is He I (21.22 eV)
He I give removal of electron at 3p orbital
Ar(KL 3s2 3p6) Ar+(KL 3s2 3p5)

State arising from Ar = 1S0 and state arising from

Ar+ = 2P1/2 and 2P3/2 with 2P3/2 is ground state. There
are splitting by 0.178 eV because spin-orbit
coupling
The Ionization process Ar+(2P3/2) Ar(1S0) is
approximately twice as intense as Ar+(2P1/2)
Ar(1S0) because of degeneracy

PHOTOELECTRON SPECTRA AND THEIR

INTERPRETATION [ X-RAY PHOTOELECTRON SPECTRA ]

If ionization is done by more energetic X-ray sources, more peak are

observe in the spectra of Argon
The horizontl scale gives the binding energy which is the energy required to
remove the electron to form a particular state of the ion and is calculated by
subtracting the photoelectron energy from the photon energy

TERIMA KASIH