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# Electronic States of Atoms

## l: orbital angular momentum quantum L: orbital angular momentum quantum number

number (0,1, n-1 e.g., for 2 e-: L = l1+l2, l1+l2 -1, l1+l2 -2, ,| l1-l2 |
where 0=s, 1=p, 2=d, 3=f) 0 = S, 1 = P, 2 = D, 3 = F

ml: orbital magnetic quantum number ML: orbital magnetic quantum number (Sml)
(l, l-1, , 0, , -l ) 2L+1 possible values

## s: electron spin quantum number (1/2) S: total spin quantum number

S = s1+s2, s1+s2 -1, ,| s1-s2 |
S = 0 singlet, S = 1 doublet, S = 2 triplet

ms: spin magnetic quantum number MS: spin magnetic quantum number (Sms)
(+1/2, -1/2) 2S+1 possible values

## J: total angular quantum number

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

## Example: Ground State of Sodium 1s22s22p63s1

Consider only the one valence electron (3s1)
L = l = 0,
S = s = ,
J=L+S=
so, the term symbol is 2S
Are you getting the concept?
Write the ground state term symbol for fluorine.
Spectroscopic Description of
All Possible Electronic States Term Symbols
C 1s22s22p2
Step 1:Consider two valence p electrons
1st 2p electron has n = 2, l = 1, ml = 0, 1, ms = 6 possible sets of quantum
numbers
2nd 2p electron has 5 possible sets of quantum numbers (Pauli Exclusion
Principle)
For both electrons, (6x5)/2 = 15 possible assignments since the electrons are
indistinguishable

## Step 2: Draw all possible microstates.

Calculate ML and MS for each state.
Step 2: Draw all possible
microstates. Calculate ML
and MS for each state.
Spectroscopic Description of
All Possible Electronic States Term Symbols
C 1s22s22p2
Step 3: Count the number of microstates for each MLMS possible combination

## Step 4: Extract smaller tables representing each possible term

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
Hunds Rules