Chapter 3

Electronic spectra and magnetic

properties of the lanthanides

• Colors properties

• Electronic Spectra

• magnetic properties
 Lanthanides: SPECTRALPROPERTIES

• Electronic absorption spectra are produced when

electromagnetic radiation promotes the ions from their ground
state to excited states
4f
hν

4f

•Because of lanthanides 4f electrons, ions are largely buried in the

inner core, they are effectively shielded from their chemical
environment. As a result, the spin-orbit coupling (The interaction
between the electron's spin and its orbital motion around the
nucleus) is much larger than the crystal field (2000 cm-1 compared
to 100 cm-1) and must be considered first.
• For the lanthanides the most common of such transition
involve the excited states which are either components of the
ground term or else belong to excited states, which arise from
the same 4fn configuration as the ground term. In either case,
the transitions therefore involve only a redistribution of
electrons within the 4f orbitals (i.e. f→f transitions) and so are
orbitally forbidden
• The consequence of the relatively small effect of the crystal
field is that the energies of the electronic states are only
slightly affected by the nature of the ligands or by thermal
vibrations, and so the absorption bands are very much
sharper than those for d→d transitions. Because of this, they
provide useful means of characterizing, and quantitatively
estimating, LnIII ions.
 Lanthanides ions have distinctive colors in all oxidation states.
 The color of the compound is not affected by ligands,
which indicates that the color characteristic of ion.
 The color is due to f-f electronic transitions

4f

hν

4f

3+
Gd 3+
Lu 3+ Gd La3+
(14 –n( n

‫علي نفس العدد من االلكترونات المفردة يكون‬4f ‫االيونات التي يحتوي فيها الغليف‬
‫لها نفس اللون‬
Repeat the colors of ions from La3+ to Gd3+ and form Lu3+ to Gd3+ follow the
following rule:

(14 –n( n

Ions in which their 4f subshell has the same number of single

electrons have the same color

4f
‫لغليف‬$$‫ا ا‬$‫يه‬$$$‫حتويف‬$$‫لتيي‬$$‫اليوناتا‬$$‫ا‬
‫علي نفس العدد من االلكترونات المفردة يكون لها نفس اللون‬
 ‫االيون‬ ‫‪config‬‬ ‫اللون‬ ‫عدد االلكترونات‬ ‫‪.config‬‬ ‫االيون‬
‫المفردة‬
‫‪14‬‬ ‫‪0‬‬
‫‪+‬‬
‫‪Lu‬‬ ‫‪3‬‬ ‫‪4f‬‬ ‫عديم اللون‬ ‫‪0‬‬ ‫‪4f‬‬ ‫‪+‬‬
‫‪La3‬‬
‫‪13‬‬ ‫‪1‬‬
‫‪+‬‬
‫‪Yb‬‬ ‫‪3‬‬ ‫‪4f‬‬ ‫عديم اللون‬ ‫‪1‬‬ ‫‪4f‬‬ ‫‪+‬‬
‫‪Ce3‬‬
‫‪+‬‬
‫‪Tm‬‬ ‫‪3‬‬ ‫‪4f12‬‬ ‫اخضر‬ ‫‪2‬‬ ‫‪4f2‬‬ ‫‪+‬‬
‫‪Pr3‬‬
‫‪+‬‬
‫‪Er‬‬
‫‪3‬‬ ‫‪4f11‬‬ ‫احمر‬ ‫‪3‬‬ ‫‪4f3‬‬ ‫‪+‬‬
‫‪Nd‬‬
‫‪3‬‬

‫‪10‬‬ ‫‪4‬‬
‫‪+‬‬
‫‪Ho3‬‬ ‫‪4f‬‬ ‫وردي‬ ‫‪4‬‬ ‫‪4f‬‬ ‫‪+‬‬
‫‪Pm3‬‬
‫‪9‬‬ ‫‪5‬‬
‫‪+‬‬
‫‪Dy‬‬ ‫‪3‬‬ ‫‪4f‬‬ ‫اصفر‬ ‫‪5‬‬ ‫‪4f‬‬ ‫‪+‬‬
‫‪Sm3‬‬
‫‪+‬‬
‫‪Tb‬‬
‫‪3‬‬ ‫‪4f8‬‬ ‫وردي‬ ‫‪6‬‬ ‫‪4f6‬‬ ‫‪+‬‬
‫‪Eu‬‬
‫‪3‬‬

‫باهت‬
‫‪+‬‬
‫‪Gd‬‬
‫‪3‬‬
‫‪4f7‬‬ ‫عديم اللون‬ ‫‪7‬‬ ‫‪4f7‬‬ ‫‪+‬‬
‫‪Gd‬‬
‫‪3‬‬
 Electronic spectra and magnetic
properties of the lanthanides

• Ultraviolet is electromagnetic radiation with wavelength

from 10 nm to 400 nm,
• Shorter than that of visible light but longer than X-rays.
• UV radiation is present in sunlight, and constitutes about
10% of the total electromagnetic radiation output from the
Sun
 Luminescence of Lanthanoid Complexes

• Irradiation of some Lanthanide (III) complexes with UV

light causes them to fluoresce

• The origin of fluorescence is 4f-4f transitions.

• The excited state produced decays to the ground state

with emission of energy.

• Some examples are Eu3+ (red) and Tb3+ (green)

• They can be used as phosphors in television sets and

fluorescent lighting.

• These applications are specific to lanthanoid ions because of

the sharp transitions observed.
 Electronic spectra of 4f ions

• Electrons in lanthanide atoms and complexes may be excited from their

ground states by absorption of energy

• Majority of transitions in Ln3+ ions occur from the ground state to excited
4f levels (f-f transitions)

• Orbitally-forbidden by the Laporte Selection Rule

Electronic Spectra of transition metal Complexes
For Ce3+ and Tb3+ ions, More intense electronic absorption bands in the UV,

because it is not f-f transitions but [Xe]4fn  [Xe]4fn-15d1 promotions ie

not orbitally forbidden

occur because 4fn-1 for Ce3+ = 0 (empty sub-shell): Tb3+ = 7 (half-filled)

 ‫ت‪$$$‬ظه‪$‬ر ح‪$‬زم‪ $‬ا‪$$‬لطيفعليهيئة ح‪$‬زم‪ $‬ا‪$‬متصاصية ح‪$‬ادة ب‪$$$‬سببب‪$$$‬ع‪$‬د مدارا‪$‬ت عن ‪4f 1-‬‬
‫‪.‬آ‪$‬ثر مجا‪$$‬لا‪$$‬لليجاند‬
‫‪$‬عيفوفقق‪$$‬انونا‪$$‬النتق‪$‬ا‪$$‬ل‪2-‬‬
‫ا‪$$‬النتق‪$‬ا‪$$‬لمن ض‪f-f$‬‬

‫‪[f-f transitions, orbitally-forbidden by the Laporte Selection‬‬

‫]‪Rule‬‬
‫يكون امتصاص االشعة عالي في االنتقاالت التي تكون فيها‬
‫‪l =  1‬‬

‫‪S2‬‬ ‫‪ S1P1‬‬

‫‪3+‬‬
‫‪d-d‬‬
‫ا‪$‬قلك‪$‬ثافة منا‪$$‬لعناصر ا‪$$‬النتقا‪$$‬لية ‪1-‬‬ ‫نثانية‬
‫‪Ln‬‬ ‫ا‪$$‬لوا‪$‬نا‪$‬يوناتا‪$$‬لعناصر ا‪$$‬لال‬
‫ا‪$$‬لعناصر ا‪$$‬النتقا‪$$‬لية ت‪$$$‬ظه‪$‬ر ح‪$‬زم‪ $‬ا‪$$‬لطيفع‪$‬ريضة و ذا‪$‬تك‪$‬ثافة ع‪$‬ا‪$$‬لية ب‪$$$‬سببا‪$$‬لتدا‪$‬خلمع‪ $‬ا‪$$‬لليجاند ‪2-‬‬
‫‪3+‬‬
‫‪(4f‬يا‪$,‬متصاصذا ك‪$‬ثافة ع‪$‬ا‪$$‬لية ب‪$$$‬سببا‪$$‬النتقا‪$$‬ل‪3-‬‬
‫‪), Tb‬ت‪$$$‬عط‬
‫‪8‬‬
‫‪), Ce3+‬و‪(4f1‬‬ ‫مركبات‬
‫ا‪$$‬ال‪$‬لكترونيمنا‪$$‬لنوع ا‪$$‬لمسموح ب‪$$$‬ه‪ $‬مداريا‬

‫‪4fn‬‬ ‫‪ 4fn d1‬‬

Term symbol of Pr3+ ground state is 3H4
Contracted 4f orbitals do not interact strongly with the surrounding
ligands
This has three major effects on Ln3+ absorption spectra:

1. The colours of of Ln3+ compounds are usually less intense (pale) than those
associated with d-d transitions in d-block complexes.

2. The f-f absorption bands are very sharp (fingerprinting of Ln3+). [d-d
transitions in transition metal compounds are also orbitally forbidden, but
gain intensity from and are broadened by the effects of molecular vibrations
in distorting the crystal field].

3. Optical spectra are virtually independent of environment and similar spectra

in are obtained in the gas/solution/solid phases (sharp lines like typical gas
atom spectra
Luminescence of Ln3+ centres

Many Ln3+ complexes fluoresce after UV excitation - f-f transitions

difficult to generate this luminescence by direct excitation of the lanthanide
ion because of the ions' poor ability to absorb light
Organic chromophores do a better job at absorbing light
The UV light promotes an electron to an excited ligand (antenna) singlet state
non-radiative intersystem crossing (ISC) to an excited ligand triplet state
further ISC to an excited state of the Ln3+ ion
Relaxation to the ground state by f-f fluorescence
Applications, including

• In lasers

• The use of lanthanides in lighting

• TV tubes