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CH2101
Al:
Spectroscopic Description of
Atomic Electronic States Term Symbols
Multiplicity (2S +1) describes the number of possible orientations of total
spin angular momentum where S is the resultant spin quantum
number (1/2 x # unpaired electrons)
Resultant Angular Momentum (L) describes the coupling of the orbital
angular momenta of each electron (add the mL values for each
electron)
Total Angular Momentum (J) combines orbital angular momentum and
intrinsic angular momentum (i.e., spin).
To Assign J Value:
if less than half of the subshell is occupied, take the minimum value J
=|LS|;
if more than half-filled, take the maximum value J = L + S;
if the subshell is half-filled, L = 0 and then J = S.
5) Hunds Rules
Hunds rules allow to establish, which of the several atomic states is the one of the lowest energy.
Consider C [He]2s22p2 as an example
Following states are possible: 1D2, 1S0, 3P2, 3P1 and 3P0
1st Hunds rule. The ground state term is that of the highest multiplicity: 3P
D2 state
2px
2pz
2py
2px
2pz
2py
P state
2nd Hunds rule. Among terms of the same multiplicity the term with the highest L value
corresponds to the most stable atomic state.
3rd Hunds rule. The lowest energy state is that of lowest J value if the subshell is less than halffilled and of highest J value in the opposite case.
3P is the most stable atomic state
0
Any atom can exist in several electronic states of different energy (atomic states). The atomic states differ
one from another by the way available a- and/or b-electrons are distributed among atomic orbitals.
Examples of atomic states:
a) H atom in 1s1 (2S1/2), 2p1 (2P3/2 or 2P1/2) or 3s1 configuration (2S1/2 state).
b) C atom in the [He]2s22p2 configuration:
1
L=0
S=0
J=0
ml
2pz
2py
-1
L=2
S=0
J=2
ml
2px
2pz
2py
-1
L=1
S=1
ml
2px
2pz
2py
-1
Each atomic state is characterized by: (a) the electronic configuration, (b) by spin S, (c) the orbital angular
momentum L, (d) the total electron angular momentum J. The state of the lowest energy is called the
ground state.
The total spin S and the total orbital angular momentum L for light elements can be obtained as a vector
sum: S = Ssi and L = Sli (LS- or Russell-Saunders coupling).
The total electron angular momentum J is also defined as a vector sum J = L + S, which holds true in the
absence of significant spin-orbit coupling (LS-coupling). Possible values of J are L+S, L+S-1, |L-S|.
To distinguish between atomic states, besides electronic configuration, each of them is assigned an atomic
term symbol which looks like 2S+1LJ. You have to put here numerical values of the spin multiplicity 2S+1
and the total angular momentum J. Symbols S, P, D, F, G, H etc. are used for orbital angular
momentum L = 0, 1, 2, 3, 4, 5 respectively.
Spectroscopic Description of
All Possible Electronic States Term Symbols
C 1s22s22p2
Step 5: Use Hunds Rules to determine the relative energies of all
possible states.
1. The highest multiplicity term within a configuration is of lowest
energy.
2. For terms of the same multiplicity, the highest L value has the
lowest energy (D < P < S).
3. For subshells that are less than half-filled, the minimum J-value
state is of lower energy than higher J-value states.
4. For subshells that are more than half-filled, the state of maximum
J-value is the lowest energy.
Based on these rules, the ground electronic configuration for carbon has
the following energy order: 3P0 < 3P1 < 3P2 < 1D2 < 1S0
Spectroscopic Description of
Excited States Term Symbols
Write term symbols in analogous manner except consider the
orbital to which an electron is promoted.
Any atom with completely-filled shells or subshells has the total spin S=0, multiplicity
2S+1=1, L=0, J=0 and can exist in the 1S0 atomic state only (He 1s2, Be [He]2s2 etc.).
Atoms with not completely filled subshells can exist in several atomic states. Hunds rules
define the lowest energy atomic state for each given electronic configuration.
3s
S1/2
2p
P3/2 656.3 nm
2
P1/2 656.2 nm
Spectroscopic Description of
Ground Electronic States Term Symbols
Term Symbol Form:
2S+1{L}
J
2S+1 multiplicity
L resultant angular momentum quantum number
J total angular momentum quantum number
Ground state has maximal S and L values.