Judd-Ofelt theory (Brief Notes)

Judd–Ofelt theory is a model describing the intensity of electron transitions within the 4f shell of
rare-earth ions (RE) in solids (solutions) due to process of absorption or emission of
electromagnetic radiation. The theory was introduced independently by Brian R. Judd and George
S. Ofelt in 1962 [Judd, Ofelt]. This theory provides convenient tool to calculate a probability of
the radiation emission and absorption process using few parameters.

The different fillings of 4f shell of RE3+ ions by electrons result in formation of multiple energy
states of RE3+ ions. The energy level diagram for all lanthanides was published in [Dieke] and
known as the `Dieke diagram’. Part of the Dieke diagram in the energy range 0–23 000 cm−1 is
shown below.

.
 Energy levels of trivalent Rare-Earth ions
2𝑆𝑆+1
In the case of RE3+ ions each energy manifolds are labeled by three indexes 𝐿𝐿𝐽𝐽 , where S and
L are the spin and orbital angular momenta and J = L + S. In this notation, the orbital quantum
numbers L = 0, 1, 2, 3, 4, 5, are expressed by the capital letters S, P, D, F, G, H, I. Thus, the symbol
4
𝐹𝐹3⁄2 shows an energy level with an orbital quantum number L = 3, a spin of S =3/2, and a total
angular momentum of J = 3/2.

The Judd-Ofelt theory states that intensity of any transmission of specific ion in specific crystalline
host dependence on only combination of six parameters (U(2), U(4), U(6) and Ω(2), Ω(4), Ω(6)), where
parameters U(λ) do not depend on crystal host and calculated and tabulated for all RE ion and all
transition, while Ω𝜆𝜆 parameters are the same for all transitions of specific ion in specific crystalline
host. Most important spectroscopic parameters of radiation transitions could be expressed using
liner combination of these parameters called “line strength”:

𝑆𝑆𝐸𝐸𝐸𝐸 (𝐽𝐽; 𝐽𝐽′ ) = ∑𝜆𝜆=2,4,6 Ω𝜆𝜆 𝑈𝑈 (𝜆𝜆) = Ω2 𝑈𝑈 2 + Ω4 𝑈𝑈 4 + Ω6 𝑈𝑈 6 (eq. 6, Walsh)

In this equation the 𝑆𝑆𝐸𝐸𝐸𝐸 is line strength for transition between energy levels J and J’ due to
electric-dipole interaction. The definition for the line strength could be differ by 𝑒𝑒 2 [Kaminskii].

Using Judd–Ofelt theory, the probability of the spontaneous emission (𝐴𝐴 =

1⁄𝑇𝑇𝑟𝑟𝑟𝑟𝑟𝑟 , 𝑤𝑤ℎ𝑒𝑒𝑒𝑒𝑒𝑒 𝑇𝑇𝑟𝑟𝑟𝑟𝑟𝑟 𝑖𝑖𝑖𝑖 𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟 𝑙𝑙𝑙𝑙𝑙𝑙𝑙𝑙𝑙𝑙𝑙𝑙𝑙𝑙 ) from the upper-level J’ to the terminal level J could
be written as
2
64𝜋𝜋 4 𝑒𝑒 2 𝑛𝑛2 +2
𝐴𝐴(𝐽𝐽′ ; 𝐽𝐽) = 3ℎ(2𝐽𝐽′ +1)𝜆𝜆�3 �𝑛𝑛 � 3
� 𝑆𝑆𝐸𝐸𝐸𝐸 � (eq.33 Walsh; eq. 4.14

Kaminski; eq. 8.3.15 Powell)

Where J’-level is initial level, and λ is mean wavelength for J’→J. In SI units this expression
could be written as
2
1 64𝜋𝜋 4 𝑒𝑒 2 𝑛𝑛2 +2
𝐴𝐴(𝐽𝐽′ ; 𝐽𝐽) = 4𝜋𝜋𝜖𝜖 �3 �𝑛𝑛 � � 𝑆𝑆𝐸𝐸𝐸𝐸 � (eq. 1.5 Imbusch )
0 3ℎ(2𝐽𝐽′ +1)𝜆𝜆 3

The relation between cross-section and line strength is useful for comparison between
experimental data and theoretical calculations and could be expressed as :
 � 2
8𝜋𝜋 3 𝑒𝑒 2 𝜆𝜆 1 𝑛𝑛2 +2
∫𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚 𝜎𝜎(𝜆𝜆) 𝑑𝑑𝑑𝑑 = 3𝑐𝑐ℎ�2𝐽𝐽 +1�
�𝑛𝑛 � 3
� 𝑆𝑆𝐸𝐸𝐸𝐸 � (eq. 28 Walsh, eq. 4.15

Kaminskii, eq. 8.3.23 Powell)

The equivalent equation in SI units is

2
1 8𝜋𝜋 3 𝑒𝑒 2 𝜈𝜈
� 1 𝑛𝑛2 +2
∫𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚 𝜎𝜎(𝜈𝜈) 𝑑𝑑𝑑𝑑 = 4𝜋𝜋𝜖𝜖 3𝑐𝑐ℎ�2𝐽𝐽
� �
+1� 𝑛𝑛 3
� 𝑆𝑆𝐸𝐸𝐸𝐸 � (eq. 1.4 Imbush.)
0

The expression for oscillator strength is another frequently used parameter in calculation
2
8𝜋𝜋 2 𝑚𝑚𝑚𝑚 𝑛𝑛2 +2
𝑓𝑓 = 3ℎ𝜆𝜆�(2𝐽𝐽′ +1) 𝑛𝑛 � 3
� 𝑆𝑆𝐸𝐸𝐸𝐸 (eq. 27 Walsh, eq. 8.3.11

Powell)

However, some authors use definitions of oscillator strength without local field factor.

Example
Let’s consider laser transitions of Nd3+ ion in YAG crystal as an example. In the most practical
applications, the metastable upper laser level is 4𝐹𝐹3⁄2 while low laser levels could be one of the
four manifolds ( 4𝐼𝐼9⁄2 , 4𝐼𝐼11⁄2 , 4𝐼𝐼13⁄2 , 4𝐼𝐼15⁄2 ). The omega parameters for Nd3+ ions in YAG
crystal were estimated to be : Ω(2)=0.37×10-20 cm2, Ω(4)=2.29×10-20 cm2 , Ω(6)=5.97×10-20 cm2;
and tabulated U(λ) from[Kaminski] are shown in the Table.

Transition Effective frequency U(2) U(4) U(6) SED

(wavelength) ×10-20 cm2
4
𝐹𝐹3⁄2 ↔ 4𝐼𝐼9⁄2 11530 cm-1 (~0.870 µm) 0 0.230 0.056 0.86

4
𝐹𝐹3⁄2 ↔ 4𝐼𝐼11⁄2 9520 cm-1(~1.05 µm) 0 0.142 0.407 2.75

4
𝐹𝐹3⁄2 ↔ 4𝐼𝐼13⁄2 7520 cm-1 (~1.33 µm) 0 0 0.212 1.27

4
𝐹𝐹3⁄2 ↔ 4𝐼𝐼15⁄2 5450 cm-1 (~1.83 µm) 0 0 0.028 0.17

As one can see from the Table, the estimated line strength is largest for at 4F3/2 ↔ 4I11/2. In deed,
the Nd:YAG laser with oscillation wavelength at 1064 nm is one of the commonly used solid
state laser. The laser oscillation at 1322nm in Nd:YAG gain element is also reported in the
literature, however, the line strength at this transition is approximately twice smaller. Therefore,
to design a Nd:YAG laser with oscillation at 1332 nm a special precautions should be taking to
the account to avoid parasitic lasing at 1064 nm .

Appendix A. Magnetic Dipole Interaction

Generally, a magnetic dipole interaction is more than an order of magnitude weaker than electric
dipole interaction. However, in some cases, the contributions to a transition from both interactions
should be considered. The above equations could be modified as
2
8𝜋𝜋 3 𝑒𝑒 2 �
𝜆𝜆 1 𝑛𝑛2 +2
∫𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑑𝑑 𝜎𝜎(𝜆𝜆) 𝑑𝑑𝑑𝑑 = 3𝑐𝑐ℎ�2𝐽𝐽 +1�
�𝑛𝑛 � 3
� 𝑆𝑆𝐸𝐸𝐸𝐸 + 𝑛𝑛𝑆𝑆𝑀𝑀𝑀𝑀 � (eq. 8.3.23 Powell, eq.

1-3 Rademaker)

, where 𝑆𝑆𝑀𝑀𝑀𝑀 is line strength for transition between energy levels J and J’ due to magnetic-dipole
interaction.

Using equation for relation between emission cross-section and radiative life-time as
�4
𝜆𝜆 �4
𝜆𝜆
∫ 𝜎𝜎𝑒𝑒𝑒𝑒 (𝜆𝜆) 𝑑𝑑𝑑𝑑 = 8𝜋𝜋𝑐𝑐𝑐𝑐2 𝑇𝑇 = 8𝜋𝜋𝑐𝑐𝑐𝑐2 𝐴𝐴 (eq. 234 Görller-
𝑟𝑟𝑟𝑟𝑟𝑟

Walrand)

, where 𝑔𝑔𝑒𝑒𝑒𝑒 (𝜈𝜈) is line form factor with integral ∫ 𝑔𝑔𝑒𝑒𝑒𝑒 (𝜈𝜈)𝑑𝑑𝑑𝑑 = 1, then
2
64𝜋𝜋 4 𝑒𝑒 2 𝑛𝑛2 +2
𝐴𝐴(𝐽𝐽′ ; 𝐽𝐽) = 3ℎ(2𝐽𝐽′ +1)𝜆𝜆�3 �𝑛𝑛 � 3
� 𝑆𝑆𝐸𝐸𝐸𝐸 + 𝑛𝑛3 𝑆𝑆𝑀𝑀𝑀𝑀 � (eq. 8.3.22 Powell,

page 3 Imbusch; eq.230 Görller-Walrand; eq.13 Carnall)

*) It should be noted that in the book [eq. 33 Walsh] the factor before 𝑆𝑆𝑀𝑀𝑀𝑀 is mistyped as 𝑛𝑛2 .

The selection rules for magnetic dipole transitions are Δ𝑙𝑙 = 0, Δ𝑆𝑆 = 0, Δ𝐿𝐿 = 0, Δ𝐽𝐽 =
0, ±1, 𝑛𝑛𝑛𝑛 0 ↔ 0, Δ𝑀𝑀𝐽𝐽 (𝜎𝜎) = 0 , Δ𝑀𝑀𝐽𝐽 (𝜋𝜋) = ±1 [Powell, Carnall W.T(1979)]. The selection rules
on Δ𝐽𝐽 = 0, ∓1 restricts consideration to the three cases [ eq. 24.12-14 Carnall W.T(1979)].:
𝐽𝐽(𝐽𝐽+1)+𝑆𝑆(𝑆𝑆+1)−𝐿𝐿(𝐿𝐿+1)
(1) 𝐽𝐽′ = 𝐽𝐽 𝑆𝑆𝑀𝑀𝑀𝑀 = 𝑔𝑔ℏ[𝐽𝐽(𝐽𝐽 + 1)(2𝐽𝐽 + 1)]1⁄2 ,where 𝑔𝑔 = 1 +
2𝐽𝐽(𝐽𝐽+1)

(𝑆𝑆+𝐿𝐿+𝐽𝐽+1)(𝑆𝑆+𝐿𝐿+1−𝐽𝐽)(𝐽𝐽+𝑆𝑆−𝐿𝐿)(𝐽𝐽+𝐿𝐿−𝑆𝑆) 1⁄2
(2) 𝐽𝐽′ = 𝐽𝐽 − 1 𝑆𝑆𝑀𝑀𝑀𝑀 = ℏ � �
4𝐽𝐽

(𝑆𝑆+𝐿𝐿+𝐽𝐽+2)(𝑆𝑆+𝐽𝐽+1−𝐿𝐿)(𝐿𝐿+𝐽𝐽+1−𝑆𝑆)(𝑆𝑆+𝐿𝐿−𝐽𝐽) 1⁄2
(3) 𝐽𝐽′ = 𝐽𝐽 + 1 𝑆𝑆𝑀𝑀𝑀𝑀 = ℏ � �
4𝐽𝐽
Appendix B. Where U(2) and Ω(2) Parameters were tabled ?

The reduced matrix elements (U(2)) were summarized in

• The Nielson, C.W., and J.E Koster, 1963, Spectroscopic Coefficients for the pn dn and fn
configurations (MI.T. Press, Cambridge, MA).
• Carnall W.T., Crosswhite H., Crosswhite H.M. Energy Level Structure and Transition
Probabilities in the Spectra of the Trivalent Lanthanides in LaF3 Argonne National Lab.
(ANL, Argonne, IL (United States (1978)

Some reduced matrix elements and Ω parameters for laser active transmission are summarized in
[Kaminskii]. The review of the Ω parameters are presented in [Görller-Walrand]

References
Judd: Judd, B. R. (1962). "Optical Absorption Intensities of Rare-Earth Ions". Phys. Rev. 127
(3): 750.
Ofelt: Ofelt, G. S. (1962). "Intensities of Crystal Spectra of Rare-Earth Ions". J. Chem. Phys. 37
(3): 511.
Dieke: Dieke G. H. (1968), Spectra and Energy Levels of Rare Earth Ions in Crystals, John
Wiley, New York, London, Sydney and Toronto.
Walsh: Walsh, Brian M. (2015)."Chapter 21: Judd-Ofelt theory: Principles and practices". In Di
Bartolo, B.; Forte, O. (eds.). Advances in Spectroscopy for Lasers and Sensing.
Springer Netherlands. pp. 403–433.
Kaminskii: Alexander A. Kaminskii, “Laser Crystals: Their Physics and Properties”, Second
Edition, Springer-Verlag Berlin Heidelberg 1981 and 1990
Powell: Richard C. Powell, “Physics of Solid-State Laser Materials”, Springer-Verlag New York
1998
Imbusch: G. F. Imbusch and R. Kopelman “Chapter 1: Optical Spectroscopy of Electronic
Centers in Solids” in Laser Spectroscopy of Solids (Topics in Applied Physics), by W.
M. Yen and Peter M. Selzer (Editors), Second Edition, Springer-Verlag Berlin
Heidelberg 1981 and 1986
Görller-Walrand Christiane Görller-Walrand, Koen Binnemans “Chapter 167 Spectral
intensities of f-f transitions ” Handbook on the Physics and Chemistry of Rare Earths,
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94620258