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r g nsof Color
inMinerals
of Color
inMinerals
MeisamRasouli
MeisamRasouliPh.D. student ofeconomic geology
Department of EarthSciences,Shiraz University
Ph.D. student ofeconomic geology
Department of EarthSciences,Shiraz University
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crystal eld theory trap concept
molecular or!ital theory
" !and theory
# color caused !y physical opticse$ects
%auses
of%olor
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Energies associated 'ith electronictransitions
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)he crystal eld theory
ions should possess unpaired dor fshell electrons*+, %r, n, -e, %o, i, and %u, actinides, lanthanides/s22s22p0&s2&p0&d& > interaction 'ith visi!le
lightnot interacting 'ith visi!le light* %r01, %e(1, %u1
%r01* energy levels*ground state* not interacting 'ith lightecited states
energy levels a$ected !y*coordination ployhedron of charges 3ligand eld4
5 polyhedra distortionsstrength of crystal eld 3!ond strength4
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)he crystal eld theory
%rystal eld * Selection rules* parallel electron paths
7u!y 3%orundum4 8l29& %rsu!stitution for 8l&1
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)he crystal eld theory
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)he crystal eld theory
7u!y*
-e impurity can ;uench red
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)he crystal eld theory
Emerald 3%orundum4 8l29& %rsu!stitution for 8l&1
=eand Sisu!stitution * ore open structure of =e&8l2Si09/>
compared to that of 7u!y5 %rystal eld of reduced strength
change in level %suppresses transmission in red andenhances !lue?greentransmission.
8leandrite3%r&1in 8l2=e9(4
3!alanced red and !lue?green transmission43green in daylight and red in incandescent light4 *8leandrite e$ect
Pleochroism* change in direction of the incident light
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)he crystal eld theory
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)he crystal eld theory
%omplications*)he same ion in di$erent crystal sites*5 complications of a!sorption !ands5 charge transfer 5 molecular or!ital theory
)he crystal eld theorydescri!es*idiochromatic colors* maBor ingredients
3some transitions may not cause color, e.g. %u/14allochromatic colors* impurities
color centers
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)he crystal eld theory
%olor centers*possi!ility * unpaired electron may !e on a non?transition element impurity ion or on a crystal defectsuch as a missing ion.=oth can !e cause of color centers.
/. Celectron color center2. Chole color center
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)he crystal eld theory
%olor center*-?centeror -reneldefect of
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)he crystal eld theory
-reneldefect
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)he crystal eld theory
%olor center*Smoy ;uartz 3hole color center4*
Precursor* 8l&1 su!stitution for Si(1 * 3'ith some a1,F1near!y4
Grradiation'ith* H?rays, gamma rays, neutrons, etc.
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)he crystal eld theory
%olor center*Smoy ;uartz*
hole centerelectron center
=leachingtemp.(AA C
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)he crystal eld theory
%olor center*8methyst*
Gnvolving -e impurity instead of 8l*citrine 3yello'4, green 3greened amethyst4
Feating causes transition metal colorsI
even irradiation 'ith ultraviolet light can produce !andcenters that are not sta!le to light eposure.
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)he crystal eld theory
%olor center*
selection rule
=JEJ-*
5smoy colorground state* 5 colorless
light?sta!le* large 8?D large =?%
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)he crystal eld theory
%olor center*!leaching during a!sorption*Small =?5%* aie?type deep !lue irradiated !eryl!ro'n irradiated topaz
fading after days eposure to light
preservation for more than 0A years in darness
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)he crystal eld theory
%olor center*
3f4 hacmanite
elevated to D !y
ultraviolet light
and !leached!y eposure to
light
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)he crystal eld theory
Phosphorescence* very small =?% !arrier energy*enough thermal ecitations at room temperature*
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)he molecular or!ital theory
multi?centered or!italsmetal?metalmetal?nonmetalnonmetal?nonmetal
h l l !i l h
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)he molecular or!ital theory
metal?metal charge transfer
!lue sapphire* 8l29&'ith -e and )i impurities
state a4 -e211 )i(1 state !* high energy4 -e&11
)i&1
a!sorption of the deep red results in deep !lue color
dichroism* -e?)i distances 2.068 in the c direction and
2.:@8 in the perpendicular direction.
%4 -211 -e&1 D4 -e&11 -e21
8!osoription in the infrared region of the spectrum
)h l l !i l h
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)he molecular or!ital theory
metal?metal charge transfer
vivianite 3a hydrated iron phosphate mineral4*iron present in t'o di$erent sites and one of thoseoidizes preferentially. 3-e21-e&14
deep !lue color for light polarized along -e21?-e&1
direction
%ordierite* -e21?-e&1
)h l l !it l th
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)he molecular or!ital theory
metal?nonmetal charge transferElectrons !elong to the 'hole unitP!%r9(* closed electron shells for P!21, %r01, and 92?
%harge transfer* 9 %ra!sorption* !lue
transmittance* orange color
sheelite* 9 K in K9(2?units
)h l l !it l th
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)he molecular or!ital theory
electrons not on metal ions*o metals and no unpaired electronslazurite 3lapis lazuli4* 3a,%a4>38lSi4/292(3S2,S9(4
ecited states of S&?molecular units
Mraphiteo'es its properties to pi?electrons
)h ! d th
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)he !and theory
the !and theory
of metals*
/A2&electron per
cm&of metal
electrons aree;uivalent in
energy*degenerate
)h l l !it l th
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)he molecular or!ital theory
!and theory and semiconductors*covalent !onding* and eactly ( electrons per atom inthe !ond
diamond, moissanite 3Si%4, greenocite 3%dS4valence !and* eactly lled !y electrons
conduction !and* empty from electrons
)h l l !it l th
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)he molecular or!ital theory
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)h l l !it l th
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)he molecular or!ital theory
!and theory and semiconductors*moderate 3e.g. prousite* 4 all colors are a!sor!edecept for red
greenocite* * !lue and violet are a!sor!ed and the
resulting color is yello'.
)h l l !it l th
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)he molecular or!ital theory
su!stituting for% in diamond34
donor electronsviolet a!sorption3Nello' color4
*% O/*/AA,AAA
)he molecular or!ital theor
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)he molecular or!ital theory
= su!stituting for% in diamond
acceptor levels
impurity !and*comple structure!lue color
8l J =
)he molecular or!ital theory
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)he molecular or!ital theory
shallo' level
am!ient thermalecitationholes in the
valence !andelectricla conductivty
es
ces
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7eferences7eferences
urt assau 3/@:>4 )he origins of color inminerals8mericam mineralogist, vol. 0&, pp. 2/@?22@
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