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By virtue of their motion about the nucleus, electrons possess orbital

angular momentum. The orbital angular momentum of the electron, à,
is a vector and is the vector cross product of the vectors; the linear
momentum, !, and the radius, , of the orbital motion. When
explicitly discussing vectors, the symbols for vectors will be bolded.
The angular momentum is perpendicular to the plane defined by the
linear momentum and radius vectors and has a direction defined by
the right hand rule (ș is the angle between the and ! vectors):

à = x ! = r p sin ș

Electrons also possess spin angular momentum. While it helps to

think of the spin angular momentum as you would a spinning top,
this is purely a fiction, as the electron spin angular momentum, ,
which is also a vector, is a non-classical affect that arises naturally
in the relativistic treatment of the motion of electrons in atoms.

The electron spin angular momentum can be aligned in either a

positive or negative sense along an external or laboratory defined
axis (usually designated as the z axis) giving rise to the electron spin
quantum numbers:

ms = + ½ Ĺ a ³spin up´ electron

ms = - ½ Ñ a ³spin down´ electron
Particles with integral spin are
symmetric with respect to the exchange
of these particles in a wavefunction and
are known as bosons (after Satyendra
Bose pictured on the stamp at right).
Photons with spin 1 and deuterons with
spin 0 are examples of bosons. There
is no restriction on the number of
bosons that can occupy a given state.

Particles with half integral spin are

anti-symmetric with respect to the
exchange of these particles in a
wavefunction and are known as
fermions (after Enrico Fermi
pictured on the left). Electrons have
an intrinsic spin of 1/2 and are
therefore fermions. Protons and
neutrons, also with spin 1/2, are other examples of fermions.
Because they are anti-symmetric with respect to exchange no two
fermions can occupy the same state. This restriction on fermions leads
to the Pauli Exclusion Principle (after Wolfgang Pauli shown below):

|àà
à
 

  

 
  

 


 
  
à
 

Or put another way no two electrons can have the same four quantum
numbers and hence only two electrons; one spin up with ms = +1/2
and the other spin down with ms = - 1/2, can occupy a spatial orbital,
e.g., a 1s atomic orbital, as defined by the quantum numbers; n, l, and
mà:

1s atomic orbital (n=0, l=0, mà=0) uÑ

For a given electronic configuration the electron¶s orbital and spin
angular momentum give rise to sets of microstates associated with
that electronic configuration that have different energies.

Consider a given electronic configuration, e.g., for neutral carbon, C I

(the I indicates that the C atom is unionized; a II would imply a
singly ionized carbon atom or C+):

neutral C or C I: 1s2 2s2 2p2 or [He] 2s2 2p2

Here [He] is a shorthand for 1s2 , i.e., the completed 1st period in the
periodic table.

A micro state is any arrangement of electrons consistent with a given

electronic configuration that does not violate the Pauli Exclusion
Principle.

Two microstates associated with this electronic configuration that do

not violate the Pauli Exclusion Principle and have different electronic
energies are:

2p2 ĹĻ __ __
2p2 u u


and
E 2s2 uÑ 2s2 ĹĻ

1s2 uÑ 1s2 ĹĻ

Based on this diagram is energy required to pair electrons or is it the

other way around? Give a physical explanation for your answer.
In order to identify the particular sets of microstates that give rise to
the possible electronic energies associated with a given electronic
configuration we need to develop the set of scalar values of the
electron¶s total orbital angular momentum, L, and total spin angular
momentum, S, that account for all the microstates.

First consider the contribution to L and S that come from electrons

that are paired in filled shells and sub-shells, e.g.:

[He] 2s2 or 1s2 2s2

Since each electron is in an s atomic orbital, where the orbital angular

momentum, à, is equal to zero; and hence the magnetic quantum
number, mà, is also equal to zero, each electron has:

à=0 and mà = 0 | mà | ” | à |

The sum of these individual mà gives a value for ML, the projection
of the total orbital angular momentum vector, [, on an externally
defined z axis:
ML = Ȉ mà, i = 0

Since this is the only possible value of ML for any set of filled shell
or sub-shell configurations, it is also the maximum value, which is
equal to the scalar value of L, hence:

L = 0

for any set of filled shell or sub-shell electronic configurations.

A similar argument applies to the development of the scalar value
of the total spin angular momentum, S, for any set of filled shells or
sub-shells.

Since each electron in a filled atomic orbital with two electrons will
have one electron with a spin quantum number of + ½ and the
other of ± ½, their sum will zero, e.g.:

1s2 ĹĻ Ȉ ms, i = (+1/2) + (-1/2) = 0

Thus for any set of filled shells or sub-shells the value MS, the
projection of the total spin angular momentum vector, , on an
externally defined z axis:

MS = Ȉ m , i = 0

Since this is the only possible value of MS for any set of filled shell
or sub-shell configurations, it is also the maximum value, which is
equal to the scalar value of S, hence:

S = 0

for any set of filled shell or sub-shell electronic configurations.

Any set of filled shells of sub-shells always contributes zero to the

calculation of the scalar values of L and S and therefore all filled
shells and sub-shells can be ignored in determining L and S for
electronic configurations with a partially filled sub-shell!
Thus in determining the scalar values of L and S for any electronic
configuration involving partially filled sub-shells we only need to
focus on the partially filled subshells, e.g., for neutral carbon, C I, we
only need to consider microstates like:

2p2 u u

Since there are three possible magnetic quantum numbers for a p

atomic orbital:
__ __ __
mà = +1 0 -1

and each electron can be either spin up, Ĺ, or spin down, Ñ, in these
orbitals, there are 6 possible states for each electron and since in a p2
electronic configuration there are two electrons that can be placed in
these 6 states there are:

6 ! / [ 2 ! ( 6 ± 2 ) ! ] = 15 microstates associated with a

p2 electronic configuration
To calculate the electronic states associated with C I we first
enumerate in some systematic way the 15 possible microstates
associated with the partially filled 2p2 subshell:

mà = +1 0 -1 ML MS

1 ĹĻ 2 0
2 Ĺ Ĺ 1 1
3 Ĺ Ļ 1 0
4 Ĺ Ĺ 0 1
5 Ĺ Ļ 0 0
6 Ļ Ĺ 1 0
7 Ļ Ļ 1 -1
8 Ļ Ĺ 0 0
9 Ļ Ļ 0 -1
10 ĹĻ 0 0
11 Ĺ Ĺ -1 1
12 Ĺ Ļ -1 0
13 Ļ Ĺ -1 0
14 Ļ Ļ -1 -1
15 ĹĻ -2 0

and calculate the:

ML = Ȉ mà, i

MS = Ȉ m , I

associated with each microstate.

Ëow pick out the maximum ML from these set of micro states?

ML, max = +2

Since the ML are the projections of the electron¶s total orbital

angular momentum vector, [, on the externally defined z axis:

z
ML = +2
ML = +1 [
ML = 0
ML = -1
ML = -2

It should be clear that the scalar value of L is equal to ML, max:

L = ML, max = +2

Electronic states associated with particular scalar values of the

scalar value of the total orbital angular momentum , L ,are given
letter designations:

L = 0 1 2 3 4 5 6 7
S P D F G H I K

Thus we know that an L = 2 or D state exists for C I.

Ëow look for the maximum MS associated with ML = +2:

MS, max = 0 (for ML = +2)

Since, like ML and L, the MS are the projections of the electron¶s

total spin angular momentum vector, , on the externally defined z
axis, an:
MS, max = 0 => S = 0

The value of the total spin angular momentum vector, , is usually

encoded as the spin multiplicity:

spin multiplicity = 2 S + 1 = 2 (0) + 1 = 1 (a singlet state)

which is equal to the number of values that MS can take on where

MS can range from +S to -S, changing by integer values:

MS = +S, +S-1, « , +1, 0, -1, « -S+1, -S

The scheme for determining the electronic states that we have
described so far is known as Russell-Saunders coupling and is
applicable to the lighter elements.

In Russell-Saunders coupling or LS the orbital angular momentum

vectors of each electron, ài, couple to form the total angular
momentum vector, [; and the spin angular momentum vector of
each electron, i, also couple to form the total spin angular
momentum vector, . These [ and  vectors in turn couple to form
the total angular momentum vector,  (not to be confused with the
rotational quantum number).

The allowed values of J are given by:

J = |L+S|, |L+S|-1, « , +1, 0, -1, « |L-S|+1, |L-S|

For the singlet D state, that we have identified as one of the

electronic states associated with the ground electronic configuration
of C I, [He] 2s2 2p2, we have the following possible values of J:

J = |2+0| = 2 to |2-0| = 2

or a single value of J = 2.

When either L or S is 0, how many values of J will there be?

For heavy atoms angular momenta couple according to JJ coupling.

In JJ coupling the individual electron orbital, i, and spin, i, angular

momenta vectors first couple to give a individual electron total
angular momentum, i:
i = i + i,

which in turn add vectorially to give total angular momentum for the
atomic species:
 = Ȉ i
An electronic term symbol describing an atomic electronic state has
the general form:
2S+1L
J

where 2S+1 is the spin multiplicity and L is the appropriate letter

designation for the total orbital angular momentum.

The electronic term symbol describing the particular electronic

state associated with the ground electronic configuration of C I,
[He] 2s2 2p2 that we have just developed is a singlet ³D two´ state:

1D
2

This 1D state (for all possible values of J for this state) accounts for:

(2S+1) (2L+1) = (2(0)+1) (2(2)+1) = 5

of the 15 microstates associated with C I, [He] 2s2 2p2 (notice that

the 1st term in the above calculation is just the spin multiplicity).
Ëow associate the 1D term (without regard to J) with 5 of the
microstates consistent with this term (these states must range from
ML = +2 to ML = -2 by integer values and must all have MS = 0):

mà = +1 0 -1 ML MS

1 ĹĻ 2 0 1D

2 Ĺ Ĺ 1 1
3 Ĺ Ļ 1 0 1D

4 Ĺ Ĺ 0 1
5 Ĺ Ļ 0 0 1D

6 Ļ Ĺ 1 0
7 Ļ Ļ 1 -1
8 Ļ Ĺ 0 0
9 Ļ Ļ 0 -1
10 ĹĻ 0 0
11 Ĺ Ĺ -1 1
12 Ĺ Ļ -1 0 1D

13 Ļ Ĺ -1 0
14 Ļ Ļ -1 -1
15 ĹĻ -2 0 1D

There may be multiple valid choice for 1D and it doesn¶t matter

which valid choice you make, as long as you assign exactly 5
microstates to 1D.
To determine the term symbols associated with the remaining
electronic states of C I, [He] 2s2 2p2 we repeat this process
(beginning from page 9 of this presentation) for any unassigned
microstates continuing in this fashion until all the microstates have
been assigned.

What is the largest unassigned value of ML?

What scalar value of L does this imply must be present?

What is the largest MS associated with the ML you have just

identified?

What scalar value of S is associated with this MS?

What is the spin multiplicity associated with this state?

What are the allowed values of J for this state?

What are the electronic term symbols in this case?

How many microstates of C I, [He] 2s2 2p2 does this electronic state
account for?
Ëow associate the 3P term with 9 of the microstates consistent with
this term (these states must range from ML = +1 to ML = -1 by integer
values and each of these ML must have an MS that ranges from
MS = +1 to MS = -1, also by integer values):

mà = +1 0 -1 ML MS

1 ĹĻ 2 0 1D

2 Ĺ Ĺ 1 1 3P

3 Ĺ Ļ 1 0 1D

4 Ĺ Ĺ 0 1 3P

5 Ĺ Ļ 0 0 1D

6 Ļ Ĺ 1 0 3P

7 Ļ Ļ 1 -1 3P

8 Ļ Ĺ 0 0 3P

9 Ļ Ļ 0 -1 3P

10 ĹĻ 0 0
11 Ĺ Ĺ -1 1 3P

12 Ĺ Ļ -1 0 1D

13 Ļ Ĺ -1 0 3P

14 Ļ Ļ -1 -1 3P

15 ĹĻ -2 0 1D

What is the final electronic term symbol associated with the single
remaining unassigned microstate of C I, [He] 2s2 2p2 ?
The complete set of electronic states, each with a different energy,
associated with ground state electronic configuration of neutral
carbon, C I, [He] 2s2 2p2 , are:

1D , 3 P2 , 3 P1 , 3 P0 , 1 S0
2

The relative ordering of these states can be

determined by applying Hund¶s rules (see
photo at left), which are applicable where
Russell-Saunders coupling is valid.

Rule 1: Electronic states with the largest total

spin angular momentum, , lie lowest in
energy:

1D , 1 S0
2
E
3P , 3 P1 , 3 P0
2

Rule 2: For electronic states with the same total spin angular
momentum, , states with the largest total orbital angular
momentum, [, lie lowest in energy:

1S
0

E 1D
2

3P , 3 P1 , 3 P0
2
Rule 3: For electronic states with the same total spin angular
momentum, , and the same total orbital angular momentum, [,

* that are less than half filled, states with the smallest total
angular momentum, , lie lowest in energy;

* that are more than half filled, states with the largest total
angular momentum, , lie lowest in energy.

Complete the relative ordering in energy of electronic states, each

with a different energy, associated with ground state electronic
configuration of neutral carbon, C I, [He] 2s2 2p2 :

1S
0

1D
2

The procedures that have illustrated for determining the electronic

states associated with a given electronic configuration apply not only
to neutral atoms in their ground state, but also to atomic exited states
and atomic ions.

For atomic systems with greater than half-filled shells, the ³holes´ in
these shells, i.e., the absence of electrons can be treated just they
were the only electrons present. For example, except for Hund¶s
Rule #3, the results for O I, [He] 2s2 2p4 are the same as
C I, [He] 2s2 2p2 .
The actual energy differences are measured relative to the electronic
ground state and are generally determined by experiment (and
sometimes by calculation):

Which state of C I, [He] 2s2 2p2 is the ground electronic state?

These experimental differences in energy between atomic electronic

states are tabulated for both ground and excited state electronic
configurations of neutral atoms and ions in which is accessible
through the ËIST Chemistry Webbook under:

š Data at other public ËIST sites:

ËIST Atomic Spectra Database - Lines Holdings (on
physics web site)

Compare the relative ordering of the electronic states of that you

determined for C I, [He] 2s2 2p2 with that found in the ËIST
Chemistry Webbook
Grotrian diagrams are a way of visualizing the relative energies and
allowed states associated with a particular element and the allowed
or observed electronic transitions between those states.

In a Grotrian diagram energy is plotted on the vertical axis and the

electronic states are plotted as short horizontal lines at the
appropriate energy and are grouped and ordered by listing states
with highest spin multiplicity on the left, followed by states with
with lowest total orbital angular momentum, L, and finally by
states with highest total angular momentum, J.

The Grotrian diagram for the electronic states of Ëa I is:

The ËIST Chemistry Webbook under the ËIST Atomic Spectra

database and further under the link ³Lines´ has the ability to create
Grotrian diagrams.
The emission transitions shown in bold red below from the excited
electronic configuration [Ëe] 3p1 to an ground state electronic
configuration [Ëe] 3s1 of Ëa I:

2P (Ëa I [Ëe] 3p1) È 2S1/2 (Ëa I [Ëe] 3s1)

3/2

2P (Ëa I [Ëe] 3p1) È 2S1/2 (Ëa I [Ëe] 3s1)

1/2

Ëa I [Ëe] 3p1

Ëa I [Ëe] 3s1
are the famous Ëa doublet, responsible for the dominant yellow
color seen in flames where sodium is present.
The image at right, showing this sodium emission
doublet from an electric pickle resolved by a
spectrograph, was obtained by Benoit Minster of
Grenoble, France. Although it is the Ëa+ ion or
Ëa II that is present in the pickle, in the applied
electric field electronic configurations associated
with neutral Ëa I are also present and are
responsible for the spectrum.
What electronic term symbol is associated with ground electronic
configuration of neutral Zn I, [Ar] 4s2 3d10?

For the ground electronic state of Ë I, [He] 2s2 2p3:

a. determine the term symbols of all electronic states

associated with this electronic configuration;

b. order these electronic states in terms of their relative

energy;

c. Compare your relative ordering with that found on the

ËIST Atomic Spectra Database determine the term
symbols of all electronic states associated with this
electronic configuration.

For the excited electronic state of Mg I, [Ëe] 3s1 3p1:

a. determine the term symbols of all electronic states

associated with this electronic configuration (note the 3s1
and 3p1 electrons must remain in their respective atomic
orbitals);

b. order these electronic states in terms of their relative

energy;

c. Compare your relative ordering with that found on the

ËIST Atomic Spectra Database determine the term
symbols of all electronic states associated with this
electronic configuration.
For the ground electronic configuration of the ion Cl+;
Cl II, [Ëe] 3s2 3p4:

a. determine the term symbols of all electronic states

associated with this electronic configuration;

b. order these electronic states in terms of their relative energy;

c. compare your relative ordering with that found on the ËIST

Atomic Spectra Database determine the term symbols of all
electronic states associated with this electronic
configuration.

For the ground electronic state configuration of Ëb I, [Kr] 5s1 4d4:

a. calculate the number of microstates;

b. determine the term symbol of the ground electronic state.

 ˜|

The orbital angular momentum of the electron, à, is a vector and is

the vector cross product of the vectors; the linear momentum, !, and
the radius, , of the orbital motion.

à = x!

the electron spin angular momentum, , which is also a vector, is a

non-classical affect that arises naturally in the relativistic treatment of
the motion of electrons in atoms that results in two electron spin
quantum numbers:

ms = + ½ Ĺ a ³spin up´ electron

ms = - ½ Ļ a ³spin down´ electron

Bosons are particles with integral spin which are symmetric with
respect to the exchange of the particles.

Fermions are particles with half-integral spin which are anti-

symmetric with respect to the exchange of the particles.

The Pauli Exclusion Principle states that :

|àà
à
 

   
 
 


  

 
  
à
 

and dictates that only two electrons; one spin up with ms = +1/2 and
the other spin down with ms = - 1/2, can occupy a spatial orbital.
For a given electronic configuration the electron¶s orbital and spin
angular momentum give rise to sets of microstates associated with
that electronic configuration that have different energies.

A micro state is any arrangement of electrons consistent with a given

electronic configuration that does not violate the Pauli Exclusion
Principle.

Any set of filled shells of sub-shells always contributes zero to the

calculation of the scalar values of L and S and therefore all filled
shells and sub-shells can be ignored in determining L and S for
electronic configurations with a partially filled sub-shell!

In Russell-Saunders coupling, which is applicable to the lighter

elements, the orbital angular momentum vectors of each electron, ài,
couple to form the total angular momentum vector, [; and the spin
angular momentum vector of each electron, i, also couple to form
the total spin angular momentum vector, . These [ and  vectors in
turn couple to form the total angular momentum vector, 

Electronic states associated with particular scalar values of the

scalar value of the total orbital angular momentum , L ,are given
letter designations:

L = 0 1 2 3 4 5 6 7
S P D F G H I K
An electronic term symbol describing an atomic electronic state has
the general form:
2S+1L
J

where 2S+1 is the spin multiplicity and L is the appropriate letter

designation for the total orbital angular momentum.

The relative ordering of electronic states under Russell-Saunders

coupling) can be determined by applying Hund¶s rules:

Rule 1: Electronic states with the largest total spin angular

momentum, , lie lowest in energy.

Rule 2: For electronic states with the same total spin angular
momentum, , states with the largest total orbital angular
momentum, [, lie lowest in energy.

Rule 3: For electronic states with the same total spin angular
momentum, , and the same total orbital angular momentum, [,

* that are less than half filled, states with the smallest
total angular momentum, , lie lowest in energy;

* that are more than half filled, states with the largest
total angular momentum, , lie lowest in energy.

For atomic systems with greater than half-filled shells, the ³holes´ in
these shells, i.e., the absence of electrons can be treated just they
were the only electrons present.