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Atomic Spectroscopy: Emission, Absorption & Fluorescence. Powerpoint Templates. Term Symbols. L = 0, 1, 2, ... S, P, D. J = L + S. L = | l 1 + l 2 |, | l 1 + l 2 - 1 |, ..., | l 1 - l 2 |. S = | s 1 + s 2 |, | s 1 + s 2 - 1 |, ..., | s 1 - s 2 |. J = L + S

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Presentation Transcript
slide1

Atomic Spectroscopy:

Emission, Absorption & Fluorescence

Powerpoint Templates

slide2

Term Symbols

L = 0, 1, 2, ...

S, P, D

J = L + S

slide3

L = | l1 + l2|, | l1 + l2 - 1|, ..., | l1 - l2|

S = | s1 + s2|, | s1 + s2 - 1|, ..., | s1 - s2|

slide4

J = L + S

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

Russell-Saunders Coupling

jj – Coupling

ji = li + si

| j1 + j2|, | j1 + j2 - 1|, ..., | j1 - j2|

slide5

Hund’s Rules

  • The lowest energy term is that which has the greatest spin multiplicity.
  • For terms that have the same spin multiplicity, the term with the highest orbital angular momentum lies lowest in energy.
  • spin-orbit coupling (more pronounced for heavier nuclei) splits terms intolevels.
  • { If the unfilled subshell is exactly or more than half full, the level with the highest J value has the lowest energy.
  • { If the unfilled subshell is less than half full, the level with the lowest J value has the lowest energy.
slide7

Selection Rules

Helicity of a photon σ = ± 1

(Physically analogous to the angular momentum along the axis of propagation)

Upon absorption or emission of a photon the atom must change the momentum along the zz axis (considered collinear with the axis of propagation) in ± 1

ΔJ = 0; ± 1 (but J ≠ 0 if ΔJ = 0)

ΔMJ= 0; ± 1 (but ΔMJ≠ 0 if J = 0)

slide8

Electric dipole Transition moment

Spin wave functions are differentially zero (αβ) or one (αα).

ΔS = 0 allowed

ΔS ≠ 0 forbidden