Atomic Term Symbols

From a spectroscopic perspective, we need to know the values for the various types of angular momenta. Term symbols provide three pieces of information 1. Total orbital angular momentum, L 2. Multiplicity of the term, 2S+1 3. Total angular momentum, J
2 S+1

LJ

Atomic Term Symbols

v L2 v L1

v L Total

Imagine then summing these vectors together. We can do it, but it is far easier to consider z-components as these add together as scalars!

Atomic Term Symbols

In terms of z-components

Ml = ml1 + ml 2 + ml3 + ....

Or in terms of magnitudes

L = l1 + l 2 + l 3 + ....
The total # or series of possible values for all orientations is given by the Clebsch-Gordon Series. For an atom with two electrons,

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

Atomic Term Symbols

L = l 1 + l 2 , l 1 + l 2 1, l 1 + l 2 2,... l 1 l 2
Maximum L corresponds to Minimum L corresponds to Quantum Number L designations are L: 0 S 1 P 2 D 3 F 4 G

l1 + l 2 l1 l 2

Atomic Term Symbols

How does this work then for an atom with an electron configuration with np2 (e.g., 1s2,2s22p2 or 1s22s22p63s23p2)?

L = l1 + l 2 , l1 + l 2 1, l1 + l 2 2,...l1 l 2
L = 2, 1, 0 Thus potential terms are D, P, S and each of these terms will differ in energy.

Atomic Term Symbols

Multiplicity Can also determine the multiplicity for the term using a Clebsch-Gordon series S=+,- = 1, 0 Multiplicity given by 2S + 1 For S =1: 2S+1 = 3 For S=0: 2S+1 = 1 Called a triplet state Called a singlet state for two electron system

Atomic Term Symbols

Total Angular Momentum Permitted values of J again, given by a Clebsch-Gordon series J = L + S, L + S - 1, L + S - 2 . |L - S|

Atomic Term Symbols

As a first example, lets consider the hydrogen atom For case with L = 1, S = term symbols are
2P 3/2

J = 1 + and 1 - and 2P1/2

Atomic Term Symbols

A portion of the hydrogen atom transition level diagram for optical spectra then, will look like
2P 3/2 2P 1/2 2D 5/2 3/2

2S 1/2

3s

3p 3p 2p 2p

2D

3d 3d

}spin-orbit
coupling

2P 3/2 2S 1/2

2s

2P 1/2

Selection rules for optical transitions

2S 1/2

1s

J = 0,1 l = 1 s = 0

Atomic Term Symbols

A portion of the hydrogen atom transition level diagram for optical spectra then, will look like
2P 3/2 2P 1/2 2D 5/2 3/2

2S 1/2

3s

3p 3p 2p 2p

2D

3d 3d

}spin-orbit
coupling

2P 3/2 2S 1/2

2s

2P 1/2

Selection rules for optical transitions

2S 1/2

1s

J = 0,1 l = 1 s = 0

Atomic Term Symbols

Lets look at some other examples. What is the term for the ground state of helium? (1s2) Here L=0 (why?) S=0 (why?) Term then is 1So.

Atomic Term Symbols

What about Ne? For 2p6 configuration, only one set of possible values. ML= m1 + m2 + m3 + m4 + m5 + m6 = 1 + 1 + 0 + 0 + (-1) + (-1) = 0 And in this case we also have S = |Ms| = ms1 + ms2 + ms3 + ms4 + ms5 + ms6 = - + - + - =0 Thus, term is 1So. We will find this to be true for ANY filled subshell. More interesting then to consider unfilled shells.

Atomic Term Symbols

What is the term symbol for helium with a 1s12s1 configuration? L = 0 (why?) S = + , - = 1, 0 Thus there are two possibilities: 3S and 1S

Atomic Term Symbols

Energy level diagram for helium then is parahelium 1S 1P 1D orthohelium 3S 3P 3D

4 3 2

4 3 2

Atomic Term Symbols

What about an atom with the configuration 1s2,2s2, 2p1,3p1 (corresponds to an excited state for carbon)

L = l1 + l 2 , l1 + l 2 1, l1 + l 2 2,...l1 l 2
L = 2, 1, 0 S can have S = 1, 0 Given these values for L and S we have
3D, 1D, 3P, 1P, 3S,

D, P, and S

and 1S

Atomic Term Symbols

Including total orbital angular momentum, we need to consider the following
3D 3, 3D 2, 3D 1, 1D 2, 3P , 3P , 3P , 1P , 3S , 2 1 0 1 1

and 1So

Question is, which of these terms corresponds to the lowest energy state?? Use Hunds Rules to determine!

Atomic Term Symbols

Hunds Rules 1. State with the largest value of S is most stable and stability decreases with decreasing S. 2. For states with same values of S, the state with the largest value of L is the most stable. 3. If states have same values of L and S then, for a subshell that is less than half filled, state with smallest J is most stable; for subshells that are more than half filled, state with largest value of J is most stable.

Atomic Term Symbols

Here we are considering the terms 3D, 3P, 3S, 1D, 1P, 1S. In terms of stability we can rank these terms as
1S 1P 1D 3S 3P 3D

Most stable

Given that the 3D states are most stable, which of these terms correspond to the most stable state?

Atomic Term Symbols

Since the two p subshells are less than half filled, we would predict that the 3D1 term corresponds to the most stable state! Simple approach for finding the ground state term symbol for any atom: 1. Find maximum value of S consistent with the Pauli Exclusion Principle S = Smax. 2. For S = Smax, find the maximum value of L consistent with the Pauli Exclusion Principle L = Lmax. 3. Apply Hunds Rules to find J for most stable state.