Colour in Minerals :

Colour : The term colour is used to describe at least three subtly different aspects of reality.
1. describes the property of an object as green grass
2. characteristics of light rays green grass reflects green light absorbing light of other colors
3. class sensations the brain interpretation of the specific manner in which the eye
perceives the light selectively reflected from grass results in the perception of green
According to Dean B. Judd
Colour is that aspect of the appearance of objects and lights which depends upon the
spectral composition of the radiant energy reaching the retina of the eye and upon its temporal and
Spatial distribution thereon
Conventional Wisdom of colour attributes blue green colour- to copper, deep blue - cobalt
Red chromium.
However, chromium compounds can be red, orange, yellow, brown, green and even lilac colour
Only a detailed study using variety of tools spectroscopic techniques, chemical analysis, irradiation
and heating required to identify the cause of colour.
Mineralogy : colour is often classified according to three types :
1.
2.
3.

Idiochromatic or self coloured

Allochromatic or other coloured
Pseudochromatic or false coloured.

Colour theory :
Four distinct theories which cover the whole range of colours occurring in minerals
1. Crystal field theory : covers both idiochromatic and allochromatic colours caused by
transition elements (copper in turquoise and Cr in ruby) as well as colour centers amethyst
unpaired electrons are main cause for colour in minerals
2. Molecular Orbital Theory : applies where electrons orbit around more than one atom or ion and explains
charge transfer process colours

3. Band Gap Theory : interprets a wide series of colours ranging from metallic as in gold, sliver
copper unique semiconductor colour black (galena), red (cinnabar), orange (realgar) or yellow
(sulphur), colouless (diamond) - colour involve no impurities.

4. Physical Optical effects : group of colour effects dispersion produced fired in diamond, scattering
produced star eye effects (star ruby) or interference produced by colour in thin films diffraction
produced colours in opal, labradorite..

Twelve types of color in minerals :

Color Cause

Typical minerals

Theory

Transition metal compounds

Almandite, malachite, turquoise

Crystal field theory

Transition metal impurities

Citrine, emerald, ruby

Crystal field theory

Color centers

Amethyst, fluorite, smoky quartz

Crystal field theory

Charge transfer

Blue sapphire, crocoite, lazurite

Molecular orbital theory

Organic materials

Amber, coral, graphite

Molecular orbital theory

Conductors

Copper, iron, silver

Band theory

Semiconductors

Galena, proustite, pyrite, sulfur

Band theory

Doped semiconductors

Blue diamond, yellow diamond

Band theory

Dispersion

"Fire" in faceted gems

Physical optics

Scattering

Moonstone, "stars", "eyes"

Physical optics

Interference

Iridescent chalcopyrite

Physical optics

Diffraction

Opal

Physical optics

Idiochromatic coloration in transition metal compounds

Cerium: Parisite (yellow)
Chromium : Crocoite (orange); phoenicrocoite (red); uvarovite (green)
Cobalt : Erythrite, roselite, spherocobaltite (pink)
Copper : Azurite, chrysocolla, turquoise (blue); dioptase, malachite (green); cuprite (red)
Iron: Lazulite (blue); olivine (green); almandite, ludlockite (red); cacoxenite, goethite (yellow)
Manganese : Rhodochrosite, rhodonite (pink); spessartite (orange); ganophyllite (yellow)
Nickel: Bunsenite (green)
Uranium : Autunite, carnotite (yellow); curite, masuyite (orange)
* Charge transfer may also be present in some of these.

Allochromatic coloration by transition metal impurities

Chromium : Emerald, grossularite, hiddenite, Cr-jade, Cr-tourmaline (green); alexandrite (green-red);
ruby, spinel, topaz (red)
Cobalt: Lusakite (blue)
Iron: Aquamarine, tourmaline (green); chrysoberyl, citrine, idocrase, orthoclase (yellow);
"greened amethyst" (green); jade (green-yellow-brown)
Manganese: Morganite, spodumene, tourmaline (pink); andalusite (green, yellow)
Nickel: Chrysoprase, Ni-opal, (green)
Vanadium: Apophyllite, V-emerald, "tsavorite" V-grossularite (green);
"alexandrite-colored sapphire" (green-red)

1. The crystal field Theory :

Color best explained by the crystal field theory involves predominantly ionic crystals containing ions
with unpaired electrons.
Elements with partially filled d shells such as V, Cr, Mn, Fe, Co, Ni, and Cu,
or in elements with partially filled f shells such as the actinides and lanthanides.
CFT - It is successful in describing the magnetic properties, colors, hydration enthalpies of
transition metal complexes, but it cannot provide an adequate description of bonding.
Crystal field theory was developed by the physicists Hans Bethe and John Hasbrouck van Vleck.
It was combined with molecular orbital theory to form ligand field theory, which delivers insight into the
process of chemical bonding in transition metal complexes
Pure crystal field theory assumes that the interactions between the metal ion and the ligands are purely
electrostatic (ionic). The ligands are regarded as point charges.
Shape of d orbitals important in order to get an idea of which of these orbitals will interact with the
ligands (point charges).
The bonding between a transition metal and the ligands is due to the attraction between the
positively charged metal ion and the electrons of the ligand.
Crystal field theory describes how the ligands affect the d electrons and split them in to higher and
lower (in terms of energy) groups - the energy difference between the two sets is given the symbol .

This crystal field splitting (i.e. the size of o) depends on several factors:
- the nature of the metal ion.
- the metal's oxidation state. A higher oxidation state leads to a larger splitting.
- the arrangement of the ligands around the metal ion.
-the nature of the ligands surrounding the metal ion.
The stronger the effect of the ligands then the greater the difference between the high
and low energy 3d groups.
The splitting of d orbital energies and its consequences are at the heart of crystal field theory

The most common type of complex is octahedral; here six ligands form an octahedron around the metal ion.
The ligands point directly at the metal d-orbitals and cause a large splitting.

Tetrahedral complexes are the second most common type; here four ligands form a tetrahedron around
the metal ion, and since in this case the ligands' electrons aren't oriented directly towards the d-orbitals
the energy splitting will be lower than in the octahedral case.
Transition metals form ions with partly filled d-orbitals.
There are 5 d-orbitals which each can contain two electrons.
These five d-orbitals are degenerate - they have the same energy when there are no ligands
around the metal. .

When a ligand approaches the metal ion, the electrons from the ligand will be closer to some of the
d-orbitals and farther away from others.
The electrons in the d-orbitals and the electrons in the ligand repel each other (because they're both
negatively charged), and so d-electrons closer to the ligands will have a higher energy than ones
further away because they feel more repulsion.

Thus, the d-orbitals will split in energy.

What determines the way that the orbitals split is the orientation of the ligands with respect to the metal
d orbitals.

Colour and Fluorescence of Ruby and Emerald :

1 % Cr3+ substituted for Al3+ in distorted octahedral sites of A12O3 with very strong bonding
resulting in an Al-O distance of 1.91 A

Energy levels, transitions, and color absorptions in ruby (a) to (e) and in emerald (f)

The crystal field theory is appropriate for three types of color:

- caused by transition metals either as a major ingredient or as an impurity,
- and that produced by color centers.
Idiochromatic colors caused by major transition-metal constituents
many more can be deduced with some certainty from merely knowing the chemical composition
of minerals containing essential transition-element ingredients.
Nevertheless, there are various pitfalls: some valence states need not cause color (e.g. monovalent Cu)
Allochromatic colors caused by transition-metal impurities
For this type of color are the nature of the streak - usually represents the color of the pure compound,
and the occurrence of such a mineral in various colors;
The cause of color cannot necessarily be ascribed to an impurity just because the impurity is known
to be present in a significant amount.
Other impurities at a lower concentration may be involved, or a color center may be present.
Laboratory synthesis of minerals with the controlled addition of impurities may even be needed
for unambiguous explanations of color.
same impurity can cause widely different colors, such as Cr-caused ruby red and emerald green
some emeralds which derive their color either partially or totally from vanadium

Color centers :
The unpaired electron which produces color by light absorption into excited states do not have to be
located on a transition element ion - but - under certain circumstances it can be located on a
nontransition-element impurity ion or on a crystal defect such as a missing ion.
Both of these can be the cause of color centers.
If an electron is present at a vacancy, we have an "electron" color center; if an electron is missing
from a location where there usually is an electron pair, we have a "hole" color center.
Purple "F center" or Frenkel defect of fluorite,
one of many types - color center in fluorite.
There are several ways by which an F- ion can be
missing from its usual position:
this can occur during growth or when energetic radiation
displaces an F- ion from its usual position to another
point in the crystal;
Or on growing fluorite in the presence of excess Ca,
or by removing some F from a crystal by the application
of an electric field.
Since the crystal must remain electrically neutral,
an electron usually occupies the empty position to
produce the F-center or "electron color center"
This unpaired electron can now exist in excited states,
the energy of which is controlled by the same crystal
field factors

R. V. Karanth

Quartz structure (schematic): (A) normal, (B) containing

Al3+ substituted for Si4+ with an H+ for charge neutrality.
Radiation ejects one of a pair of electrons from an O2and leaves a "hole" color center of smoky quartz

Smoky quartz, - "hole color center."

Necessary precursor to this color center is the presence in the quartz is impurity Al3+ substituting
for Si4+ ions with some alkali (e.g. Na+) or a hydrogen ion (H+) nearby to maintain electroneutrality
Interstitial Al does not serve as a precursor to form smoky quartz.
Most natural quartz contains substitutional Al at the several hundred ppm

(a-d) : large formation energy and bleaching energy

(e) : Large formation energy but less bleaching temp required
(f) : Small formation and bleaching energy required
(PhosphorescenceSmall bleaching energy BC
-Large phosphorescence
(BC slightly deeper)
-Small phosphorescence
(BC shallower)
-If deeper BC level
would result in TL)

(Smoky Quartz)
(Maxixe type blue beryl
and Irradiated topaz)

(Photo chromatic Hackmanite, Na8Al6Si6O24(Cl2,S)

Colourless + UV = Pink/red, bleaches fast)

Amethyst - similar color center - involving Fe instead of Al.

Depending on the location and environment of the Fe the color obtained on heating amethyst is
either yellow (citrine as in most amethyst) or green (the "greened amethyst" ).
Though iron a transition element impurity involved in colouration should not be considered as
allochromatic as it is present only as a precursor for amethyst color - itself derives from a color center.
Irradiation after heating can recreate the color center and the amethyst color.
2. The molecular orbital Theory
Applied to several different types of situations where electrons are involved - are not simply located
on single atoms or ions, but must be considered to be present in multicentered orbits.
The results vary depending on whether metal-metal, metal-nonmetal, or nonmetal-nonmetal centers
The result of a molecular orbital treatment is similar to that of a crystal field treatment;
both theories result in a set of energy levels and associated transition probabilities.
Metal-metal charge transfer (Intervalence charge transfer)
Blue sapphire -corundum, Al2O3, contain both Fe and Ti impurities.
Each of the impurity ions can exist in two valence states two combinations possible.
(a) Fe2+ and Ti4+; and (b) Fe3+ and Ti3+.

The MO theory treats molecular bonds as a sharing of electrons between nuclei.

Unlike the V-B theory, which treats the electrons as localized balloons of electron density,
The MO theory says that the electrons are delocalized.
- means that they are spread out over the entire molecule
when two atoms come together, their two atomic orbitals react to form two possible molecular orbitals.
One of the molecular orbitals is lower in energy. It is called the bonding orbital and stabilizes the molecule.
The other orbital is called an anti-bonding orbital. It is higher in energy than the original atomic orbitals and
destabilizes the molecule.
Below is a picture of the molecular orbitals of two hydrogen atoms come together to form a
hydrogen molecule:

The MO Theory has five basic rules:

1.
2.
3.
4.
5.

The number of molecular orbitals = the number of atomic orbitals combined

Of the two MO's, one is a bonding orbital (lower energy) and one is an anti-bonding orbital (higher energy)
Electrons enter the lowest orbital available
The maximum no. of electrons in an orbital is 2 (Pauli Exclusion Principle)
Electrons spread out before pairing up (Hund's Rule)

Below is a molecular orbital energy diagram for the hydrogen molecule.

The two AO's or atomic orbital combine to form 2 MO's - the bonding and the anti-bonding molecular orbital.
-

the five rules have been followed, the electrons having been placed in the lowest energy orbital (rule 3) and
have paired up (rule 4) and there are only two electrons in the orbitals (rule 5).

Electrons not on metal ions

Several minerals - colors are best described by molecular orbitals not involving any metal ions.
e.g. - deep blue of lazurite (lapis lazuli), (Na,Ca)8(AlSi)12O24(S2,SO4),
contains sulfur molecular units and no unpaired electrons.
The excited levels of S-3 molecular units appear to explain the color

Colors caused by molecular orbital transitions

A. Metal-metal charge transfer:

Fe2+ - Fe3+ / Fe3+ - Fe2+ : Cordierite, vivianite (blue), magnetite, etc. (black?)
Fe2+ - Ti4+ / Fe3+ - Ti3+ : Kyanite, blue sapphire (blue)
Mn2+ - Mn4+ / Mn3+ - Mn3+: Manganite, bixbyite, etc. (black?)
B. Metal-nonmetal charge transfer:
Cr6+ - 02- . Crocoite (orange)
V5+ - 02- . Vanadinite (orange)
Metal-Sulfur: Pyrite, marcasite, etc. (see band-gap semiconductors)
C. Electrons not on metal ions:
S-3: Lazurite in lapis lazuli (blue)
pi electrons: Graphite (black)
Organic pigments: amber, ivory (brown); coral (red, black); pearl (pink, green, blue black);
bitumen, lignite, etc. (brown to black)

A single electron can be caused to transfer from the Fe to the Ti by light absorption and back again.
Since state (b) has a higher energy than state (a), the transition from (a) to (b) involves the
absorption of energy, producing a broad intense absorption band at the red end of the
spectrum deep blue color.
The Fe-Ti distances are 2.65A in the c direction, along the optic axis, but 2.79A in the perpendicular
direction results in dichroism

Another charge transfer process involving only Fe,

Fe2+ + Fe3+ and Fe3+ + Fe2+ can also occur. - homonuclear metal-metal charge transfer

R. V. Karanth

The color of cordierite has also been attributed to this type of Fe2+ - Fe3+ charge transfer
black minerals containing Fe, Mn, Ti, etc., such as magnetite, ilmenite, manganite, schorl, etc.,
owe their color to some kind of charge transfer.
Charge transfer transitions usually have high transition probabilities, thus giving intense colors, and
tend to dominate crystal field transition colors when both are present, although they may also occur
in the ultraviolet part of the spectrum.
Color - hydrated iron phosphate vivianite. When fresh, this compound contains only Fe2+ - colorless.
Air-oxidation converts some of the Fe2+ to Fe3+, charge transfer becomes possible and results in the
deep blue color. iron in vivianite is present in two different sites, and one of these oxidizes
preferentially.
Tri- chroism with the deep blue color seen only with light polarized along the direction connecting the
two different Fe sites, i.e. along the Fe2+ - Fe3+ direction
e.g. PbCrO4, Wulfenite and Scheelite (WO-4 units), Lapis lazuli (electrons not on metal ions, S-3 unit)
How impure must the crystal be for it to appear colored? For sapphire, only 0.01% of titanium
and iron are needed as the electron transfers very easily
The process absorbing the photon and driving the system from the initial to the excited state is
effectively instantaneous.
It actually takes about a femtosecond or 10-15 second.
The process is instantaneous and leaves the system in an excited state

Emerald

Green Beryl

Aquamarine

heliodor

Bixbite

Be3Al2Si6O18

Morganite

Goshenite

R. V. Karanth

Irradiation (2 Mev)

Colourless beryl

Greenish - yellow

Heating ~ 300oC

Yellow beryl

Heating ~ 400oC

Blue beryl

3. The Band Gap Theory

The crystal field and molecular orbital theories apply to electrons located on ions, at defects, and on
groups of atoms. Band theory treats electrons as belonging to the crystal as a whole and applies to
a wide range of materials - metallic conductors and semiconductors
In a crystal of a metal such as copper or an alloy such as brass, each metal atom contributes its outer
electrons, those usually involved in chemical bonding, to a joint pool. These electrons are free to move
throughout the whole crystal. Free movement of such a pool of electrons in a metal results in the
high electrical and thermal conductivities as well as in the metallic luster and metallic reflection
typical metal, there are more than 1023 electrons per cm3 all equivalent to each other
Applying quantum consideration individual energy levels broaden into bands
At each energy levels there is room for so many electrons (density of states)
The available number of electrons fill the band structure up to the Fermi Surface
Metals have one continuous bands extending to higher energies, but density of state different for
different energies..
Surface of metal can absorb light of energy, transition occurs between filled part the outer empty par
and most of the light is remitted at the surface (metallic luster)
Efficiency of this process depends on the shape of the band above the Fermi Surface
Resulting in colour difference in metals and alloys.

Colour of semiconductors
There is a large group of minerals where the bonding is predominantly covalent (electron sharing) and
where the average number of bonding electrons is exactly four per atom.
-elements of the fourth column of the periodic table such as diamond, IV-IV compounds such as
moissanite (SiC), II-VI compounds such as greenockite (CdS).
Band theory applied to such materials shows a gap between two separate bands,
lower - "valence band," filled with electrons, while the upper - "conduction band," is completely empty

wavelength

Photon/energy

wavenumber

If the band gap is smaller than the visible-light range - all light energies can be absorbed
and a dark gray or black color results, as in galena
If a narrow-band-gap semiconductor is heated to a high enough temperature so that thermal
excitation can bridge the band-gap, then the electrons excited into the conduction band will cause
the material to behave as a metal
large-band-gap semiconductors" larger than the range of visible light will not be able to absorb in the
visible and will thus be colorless, - pure diamond and sphalerite with Eg about 5.4 eV and 3.5 eV
With an intermediate band-gap of about 2eV, as in proustite, only red light is transmitted; all other
colors have energies larger than Eg and therefore are absorbed
With a band-gap of about 2.5eV, as in greenockite, only blue and violet are absorbed and the resulting
is yellow.
The overall sequence of band gap colors is thus black/red/orange/yellow/colorless.

Impurities in semiconductors
Medium- and large-band-gap semiconductors do not conduct electricity at room temperature when
pure, since the ambient excitation is insufficient to bridge the band-gap.
Presence of certain impurities can affect both the conductivity as well as the light absorption.

Consider nitrogen impurity atoms substituting for carbons in a diamond crystal (Eg about 5.4 eV).
N has one more electron than C, each nitrogen donates one extra electron above the Fermi surface
and these "donor" electrons form an impurity level within the band-gap,
The nitrogen impurity level is still 4eV below the conduction band (a "deep" donor).
It can only absorb a little violet at 3eV, thus giving a yellow color.
A typical deep-yellow diamond may contain one nitrogen atom for every 100,000 carbon atoms.
The reduction in the bandgap is insufficient to permit electrical conductivity at room temperature.

Boron - one electron less than carbon, acts in a similar way to produce "acceptor levels" in the
band-gap.
These are "hole" levels which can accept electrons from the valence band and are located only 0.4eV
above the top of the valence band.
The impurity band is not just a single level, but has a complex structure. resulting in a blue color.
Since the boron acceptor level is "shallow," ambient thermal excitation can raise electrons from the
valence band into the acceptor level, and the resulting holes in the valence band can then conduct
electricity.
Type IIB blue conducting diamonds such as the "Hope" contain typically one boron atom per million
carbon atoms.
Blue irradiated diamonds do not conduct electricity, thus providing distinction between the boron
acceptor and the irradiation-produced blue color center in diamond.

Diamonds can contain many elements present as substitutional (i.e., replacing carbon atoms
in the lattice) impurities: nitrogen, boron, hydrogen, oxygen, sulfur, nickel, cobalt, and iron have all
been detected.

Diamond Types
Diamonds can

be

scientifically

classified

into

types,

known

as

type

1a,

1b,

2a,

and

2b.

Diamonds are made of carbon, and are extremely pure, but in almost all diamonds there are tiny proportions of other
elements, interspersed within the carbon as part of their crystal structure. These "impurities" are not what are known as
inclusions, and are so small as to be invisible even under a very powerful microscope.
Type 1 Diamonds
Type 1 diamonds contain nitrogen. About 98% of all diamonds are type 1a
Type 1a
If the nitrogen atoms are clustered together within the carbon lattice, then the diamond is said to be a Type 1a diamond.
Because these diamonds absorb blue light, they can have a pale yellow or brown color. 98% of diamonds are Type 1a.
Type 1b
If the nitrogen atoms are evenly spread out throughout the carbon lattice, then the diamond is said to be a Type 1b
diamond. These diamonds absorb green light as well as blue light, and have a darker color than type 1a diamonds.
Depending on the precise concentration and spread of the nitrogen atoms, these diamonds can appear deep yellow
("canary"), orange, brown or greenish. Less then 0.1% of diamonds belong to Type 1b.
Type 2
Type 2 are diamonds that absorbed no, or very few, nitrogen atoms.
Type 2a
These diamonds can be considered as the "purest of the pure" - they contain no, or minuscule amounts of impurities and
are usually colorless. Unless, that is, the carbon tetrahedrons that make up the diamond were twisted and bent out of
shape while the diamond rose to the surface of the earth.
An imperfect carbon lattice will make the diamond absorb some light, which will give it a yellow, brown or even pink or red
color. 1-2% of diamonds belong to Type 2a.
Type 2b
These diamonds contain no nitrogen - but they do contain boron, which absorbs red, orange and yellow light. These
diamonds therefore usually appear to be blue, although they can also be grey or nearly colorless. All naturally blue
diamonds belong to Type 2b, which makes up 0.1% of all diamonds.

Pseudochromatic colors caused by physical optics effects

1. Color Based on Dispersion:
"Fire" in high dispersion gem-stones such as diamond, zircon, ruble, and strontium titanate.
2. Color Based on Scattering:
Chatoyancy as in cat's eyes, tiger's-eye.
Asterism as in star corundum, garnet, quartz.
Luster as in pearl, foliated talc, brucite, apophyllite, fibrous asbestos, gypum (satin spar), etc.
Aventurescence as in sunstone, aventurine albite, aventurine quartz, schiller spar,
silver-sheen obsidian.
Adularescence as in moonstone (bluish), milky opal.
3. Color Based on Interference:
Interference effects in thin films such as the tarnish film on chalcopyrite, columbite, and
bornite and within the cracks of iris quartz.
4. Color Based on Diffraction:
Diffraction grating produced by periodic spacings as in opal, labradorite, and iris agate

Asterism
Chatoyancy
(Cats eye)

Adularescence

Infrared spectrum of Type IaB diamond. (1) region of nitrogen impurities absorption, (2) B2 peak,
(3) self absorption of diamond lattice, (4) hydrogen peaks