Origins

of Color
in
Minerals
Meisam
Meisam
Ph.D.
student
of
Ph.D.
student
of
Rasouli
Rasouli
economic
economic geology
geology
Department
Department of
of Earth
Earth
Sciences,
Sciences,
Shiraz
Shiraz University
University

 crystal field theory

trap concept

Causes
of
Color

molecular orbital theory

band theory
color caused by physical optics
effects

Energies associated with electronic

transitions

The crystal field theory

ions should possess unpaired d or f shell electrons:
V, Cr, Mn, Fe, Co, Ni, and Cu, actinides, lanthanides
1s22s22p63s23p63d3 > interaction with visible
light
not interacting with visible light: Cr6+, Ce4+, Cu+
Cr6+ : energy levels:
ground state: not interacting with light
excited states
energy levels affected by:
coordination ployhedron of charges (ligand field)
> polyhedra distortions
strength of crystal field (bond strength)
4

The crystal field theory

Crystal field : Selection rules: parallel electron paths
Ruby (Corundum) Al2O3 Cr substitution for Al3+

The crystal field theory

The crystal field theory

Ruby:
Fe impurity can quench red fluorescence by siphoning
off energy from level B transition.
coincidence: red fluorescence and red transmittence

The crystal field theory

Emerald (Corundum) Al2O3 Cr substitution for Al3+
Be and Si substitution : More open structure of Be 3Al2Si6O18
compared to that of Ruby
> Crystal field of reduced strength
change in level C suppresses transmission in red and
enhances blue-green transmission.
Alexandrite (Cr3+ in Al2BeO4)
(balanced red and blue-green transmission)
(green in daylight and red in incandescent light) :
Alexandrite effect
Pleochroism: change in direction of the incident light
8

The crystal field theory

The crystal field theory

Complications:
The same ion in different crystal sites:
> complications of absorption bands
> charge transfer > molecular orbital theory
The crystal field theory describes:
idiochromatic colors: major ingredients
(some transitions may not cause color, e.g. Cu1+)
allochromatic colors: impurities
color centers

The crystal field theory

Color centers:
possibility : unpaired electron may be on a nontransition element impurity ion or on a crystal defect
such as a missing ion.
Both can be cause of color centers.
1. electron color center
2. hole color center

The crystal field theory

Color center:
F-center or Frenkel defect of fluorite (electron color
center)
growth at excess Ca, and
displacement of F- by energetic radiations
color and fluorescence can occur by the same types of
transitions governed by crystal field theory.

The crystal field theory

Frenkel defect

The crystal field theory

Color center:
Smoky quartz (hole color center):
Precursor: Al3+ substitution for Si4+ : (with some Na+ ,H+
nearby)
Irradiation with: X-rays, gamma rays, neutrons, etc.

The crystal field theory

Color center:
Smoky quartz:
hole center
electron center
Bleaching temp.
400 C

The crystal field theory

Color center:
Amethyst:
Involving Fe impurity instead of Al:
citrine (yellow), green (greened amethyst)
Heating causes transition metal colors;
even irradiation with ultraviolet light can produce band
centers that are not stable to light exposure.

The crystal field theory

Color center:
selection rule
B/E/F:
>smoky color
ground state:
> colorless
light-stable:
large A-D
large B-C
1

The crystal field theory

Color center:
bleaching during absorption:
Small B->C: Maxixe-type deep blue irradiated beryl
brown irradiated topaz
fading after days exposure to light
preservation for more than 60 years in darkness

The crystal field theory

Color center:
(f) hackmanite
elevated to D by
ultraviolet light
and bleached
by exposure to
light

The crystal field theory

Phosphorescence: very small B-C barrier energy:
enough thermal excitations at room temperature:
fluorite, calcite, diamond, etc.
Very rapid phosphorescence with low B-C barrier would
seem to be fluorescence
Thermoluminescence: deeper barrier than in
phosphorescence
greater thermal energy to surmount the barrier
Phosphorescence, Thermoluminescence and
Fluorescence are not restricted to color centers.
2

The molecular orbital theory

multi-centered orbitals
metal-metal
metal-nonmetal
nonmetal-nonmetal

The molecular orbital theory

metal-metal charge transfer
blue sapphire:

Al2O3 with Fe and Ti impurities

state a) Fe2+ + Ti4+

state b: high energy) Fe3+ +

Ti3+
absorption of the deep red results in deep blue color
dichroism: Fe-Ti distances 2.65A in the c direction and
2.79A in the perpendicular direction.
C) F2+ + Fe3+
D) Fe3+ + Fe2+
Abosoription in the infrared region of the spectrum
2

The molecular orbital theory

metal-metal charge transfer
vivianite (a hydrated iron phosphate mineral):
iron present in two different sites and one of those
oxidizes preferentially. (Fe2+ Fe3+)
deep blue color for light polarized along Fe2+-Fe3+
direction
Cordierite: Fe2+-Fe3+

The molecular orbital theory

metal-nonmetal

charge transfer
Electrons belong to the whole unit
PbCrO4: closed electron shells for Pb2+, Cr6+, and O2Charge transfer: O Cr
absorption: blue
transmittance: orange color
sheelite: O W in WO42- units

The molecular orbital theory

electrons not on metal ions:
No metals and no unpaired electrons
lazurite (lapis lazuli): (Na,Ca)8(AlSi)12O24(S2,SO4)
excited states of S3- molecular units
Graphite owes its properties to pi-electrons

The band theory

the band theory
of metals:
1023 electron per
cm3 of metal
electrons are
equivalent in
energy:
degenerate

The molecular orbital theory

band theory and semiconductors:
covalent bonding: and exactly 4 electrons per atom in
the bond
diamond, moissanite (SiC), greenockite (CdS)
valence band: exactly filled by electrons
conduction band: empty from electrons

The molecular orbital theory

The molecular orbital theory

band

theory and semiconductors:

In large band-gap semiconductors luster is not metallic.
if (band-gap energy) is small, all visible light is
absorbed resulting in black color (e.g. gallena, )
Pyrite: narrow band-gap
Heating electrons conduction band conductivity
large band-gap: minerals colorless
(e.g. pure diamond: , pure sphalerite: )

The molecular orbital theory

band

theory and semiconductors:

moderate (e.g. prousite: ) all colors are absorbed
except for red
greenockite: : blue and violet are absorbed and the
resulting color is yellow.

The molecular orbital theory

N substituting for
C in diamond
()
donor electrons
violet absorption
(Yellow color)
N:C =
1:100,000

The molecular orbital theory

B substituting for
C in diamond
acceptor levels
impurity band:
complex structure
blue color
Al / B

The molecular orbital theory

shallow

level

ambient thermal
excitation
holes in the
valence band
electricla conductivty

s
e
c
n
e
Refer

Kurt Nassau (1978) The origins of color in

minerals
Americam mineralogist, vol. 63, pp. 219-229