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à = x ! = r p sin ș
|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:
Here [He] is a shorthand for 1s2 , i.e., the completed 1st period in the
periodic table.
2p2 ĹĻ __ __
2p2 u u
and
E 2s2 uÑ 2s2 ĹĻ
1s2 uÑ 1s2 ĹĻ
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
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.:
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
2p2 u u
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:
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
ML = Ȉ mà, i
MS = Ȉ m , I
ML, max = +2
z
ML = +2
ML = +1 [
ML = 0
ML = -1
ML = -2
L = ML, max = +2
L = 0 1 2 3 4 5 6 7
S P D F G H I K
J = |2+0| = 2 to |2-0| = 2
or a single value of J = 2.
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
1D
2
This 1D state (for all possible values of J for this state) accounts for:
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
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
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.
1S
0
1D
2
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):
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?
à = x!
Bosons are particles with integral spin which are symmetric with
respect to the exchange of the particles.
|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.
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
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.