Identification of Minerals Using Reflectance Spectroscopy

Nancy H. Thomas
University of Washington

Abstract
Reflectance spectroscopy is a valuable technique in remote sensing used to
identify minerals on Mars to characterize the planets surface geology. Electronic
processes shape the absorption features present in the visible and near-infrared
wavelengths. One of these processes, crystal field theory can be applied to
analyze the spectral features present in transition metals. In particular, we can
analyze olivine, a common mineral found on both Earth and Mars, using this
technique. Using sample spectra of olivine from Earth and Mars, I calculated a
range of crystal field stabilization energies of 0.47-0.52 eV, which fell within the
range of previous results.

Introduction and Motivation
Remote sensing is a variety of techniques
used to understand geological processes over
large and inaccessible regions without ever
touching the surface. This work combines
aspects of physics, geology and spectroscopy.
Remote sensing techniques allow us to
interpret images from spacecraft such as the
Mars Reconnaissance Orbiter (MRO) to
better understand surface properties. This
research is particularly compelling as we can
use our understanding of quantum mechanics
and reflectance spectroscopy to identify
minerals on another planet.
Orbital spectroscopy is one method for
analyzing the surface composition of Mars,
and is providing evidence for the presence of
liquid water throughout the planets history.
In order to determine surface mineralogy, we
use remotely sensed visible/near-infrared
(VNIR) (defined here as roughly 0.3 - 3 m
wavelengths) spectroscopic datasets.
Minerals have unique spectral absorptions
(colors) that allow us to make identifications
on Mars. Knowing the mineral composition
of a region allows us to infer the previous
conditions present. For example, if we
identify carbonates, we know water must
have been present during their formation.
Ultimately, we can gain a stronger and more
detailed understanding of surface
composition and aqueous processes on Mars.
Based on these processes we can then invoke
different conditions conducive for the
development of life on Mars.

Reflectance Spectroscopy
Visible and near-infrared light that is
incident on opaque materials is partly
absorbed or partly reflected by them. There
are two kinds of reflection processes: that
occurring when light is reflected from a flat
polished surface of the mineral (specular
reflectance) and that occurring when the light
is reflected from the mineral after it has been
finely powdered (diffuse reflectance). These
processes can be observed in VNIR spectral
data collected by the Compact
Reconnaissance Imaging Spectrometer for
Mars (CRISM) on board the MRO (Murchie,
2007). A vast dataset, each CRISM image
measures the surface reflectance across 438
wavelengths from 1.0 to 3.9 m.
Electrons in isolated atoms or ions have
well-defined, discrete energy states, which
(in principle) can be calculated from the
Schrdinger equation. As the ions are
brought together in a solid, the wave
functions of the outer electrons overlap and
perturb one another. The result of the
Thomas 2

perturbations is to split the energy levels, so
that the system of many atoms has a large
number of states that are closely spaced in
energy. The quantum mechanical energy
levels overlap because they have a finite
width. As a result, the system has several
wide, continuous bands in which the
electrons can exist, separated by gaps in
which no solution of the wave equation is
possible.
The wave functions of electrons in the
valence band, the highest energy band,
generally are localized in discrete ions or
atoms. The lowest energy band in which all
states are not occupied, is called the
conduction band, which may be partially
filled or completely empty. Electrons in the
conduction band are not bound to any
specific atom or ion, but are free to move
about the solid lattice, where they contribute
to both the electrical and thermal
conductivities.

Electronic Processes
Electromagnetic radiation in the near-
ultraviolet (~0.25 m) through the mid-
infrared (~3.0 m) portions of the spectrum,
particularly with energies between
approximately 4.0-0.5 eV, interacts with the
electrons in solids (or liquids or gases). These
interactions give rise to the processes of
absorption and reflection qualitatively
observed in minerals as the properties of
color and luster. The quantitative
measurement of such absorption and
reflection processes forms the basis of
electronic (optical) absorption spectroscopy.
The absorption and reflection phenomena
arise from electronic excitation processes
involving the valence electrons, excitation
processes that may be of several kinds
including:
1. Crystal-field transitions. Splitting of
the d-orbital energy levels of a transition-
metal ion by the crystal field of the
surrounding anions gives rise to the
possibility of electronic transitions between
these levels. Such d-d transitions are
responsible for the colors of many of the
transition-metal-bearing minerals and are
best treated within the formalism of crystal
field theory.
2. Charge-transfer transitions. Electrons
may be transferred between filled (or partly
filled) orbitals and empty orbitals on adjacent
anion and cation or between adjacent cations
(usually metals). Such charge transfer
transitions are best treated within the
formalism of molecular orbital theory.
3. Electronic transitions involving color
centers. The presence of interstitial
impurities, of vacancies or of other
imperfections, can introduce electrons that
may absorb electromagnetic energy in
transitions to various excited states.
4. Electron transitions involving energy
bands. In metals and in semiconductors in
which the energy gap between large numbers
of filled and vacant energy levels is small (<2
eV as in many metal oxides and sulfides),
intense absorption and reflection of light will
occur, resulting in a metallic appearance. The
absorption resulting from transitions between
such adjacent filled and vacant energy levels
is best treated within the formalism of band
theory.
The electronic process of (1) and (3) are
generally localized and give rise to color in
minerals that nevertheless remain translucent
(like carbonates). The electronic processes
also create the unique spectral absorption
patterns or fingerprints we can use to
identify minerals. The processes under (4)
commonly result in opaque minerals since
the availability of large numbers of vacant
energy levels into which the electrons may be
excited causes very strong absorptions. When
this happens, reflectance is also high because
light is re-emitted when the electrons return
to the ground state. Translucent phases may
be studied using the methods of electronic
absorption spectroscopy as follows.
Thomas 3

Crystal Field Theory
Crystal field transitions originate when
electrons are excited by light between
incompletely filled 3d orbital energy levels
within a transition metal ion. The principle
parameters derived from measuring the
positions of the absorption bands in crystal-
field spectra are the crystal-field spectra are
the crystal-field splitting parameter (!) and
the Racah parameters (B and C), which
provide a measure of the degree of covalent
character of the cation-anion bonds.
Since the d-electrons are situated on the
central metal ion, it is convenient to relate the
electrostatic potential of the assembly of
negative charges to a set of coordinates
centered on the transition metal ion. In the
particular case of an octahedral set of charges,
imagine the central ion as the origin of a set
of cartesian and polar coordinates. The
negative charge Ze then is at a distance a
along the x, y, and z axis and the polar angles
" and # measured from the +z axis and +x
axis.
To expand the field potential for an
octahedral set of charges, we start with the
basic potential

V
1
= + Ze
2
/ d

where d is the distance from charge 1 to P.
By incorporating the other charges as
outlined in Dunn et al., we can solve for the
total potential of the crystal field system:

V =
!!"
!!
!
$
1/2
r
4
[Y
4
0
+ (5/14)
1/2
(Y
4
4
+ Y
4
-4
)]

as expressed in terms of the spherical
harmonics Y
l
m
.
Assignment of the features in a crystal
field spectrum is normally undertaken using
an energy level diagram. Here, the possible
d-electron excited-state configurations are
calculated in an octahedral field of increasing
strength, using the formalisms of crystal field
theory. The intensity of an absorption band is,
in fact, related to the probability of the
transition that is proportional to the transition
moment (Q) where:

Q ! ! !
!
!!
!!
! !
!
!" !
!


and %
g
and %
E
are the wave functions of the
ground and excited states, is the electric
dipole moment operator, and d& is the volume
element. A transition is forbidden when Q=0.
The transition moment can be further broken
into its special and spin components unless
(%
g
)
spin
= (%
E
)
spin
, then the spin component is
zero and the transition is spin forbidden.
Spin-forbidden transitions are still
observed as weak features. This is because of
the interaction between the electron spin
magnetic moment and the magnetic moment
due to the orbital motion of the electron
(spin-orbit coupling).
For an ion such as Cr
3+
in an octahedral
site (as in garnet, olivine, and corundum) the
lowest-energy spin allowed transition gives
an absorption band with frequency '
1
that is
equivalent to the crystal-field splitting
parameter !
o
. The second spin allowed
transition gives rise to an absorption band '
2

the energy of which is given by:

'
2
= ( (15B + 30!) ( ((15B 10 !)
2

+ 12B!)
1/2


from which the B Racah parameter can be
calculated using the equation:

B = ((2'
1
'
2
)('
2
'
1
)/(27'
1
- 15'
2
)

Calculation
Using a laboratory spectrum of an olivine
(Mg, Fe)
2
SiO
4
collected by Brown
University and a spectrum of olivine
collected by CRISM, we can quantitatively
calculate the crystal field stabilization energy.
As shown in Figure 1, the spectrum of olivine
has an absorption maximum between 0.8 and
1.3 m. There is also an intense band
Thomas 4

between 1.04 and 1.08 m. Variations in the
position of the absorption maxima show
compositional variations and shift to longer
wavelengths with increasing iron content.


Figure 1: Reflectance spectra of olivine
from Brown University samples and
CRISM FRT00009DB4 from Valles
Marineris, Mars.

The crystal structure of olivine is shown
in Figure 2. It consists of independent SiO
4

tetrahedra linked by divalent cations in six-
fold coordination. The two points designated
as M1 and M2 represent the two six
coordinate positions in the structure where
there is distortion from octahedral symmetry.


Figure 2: The crystal structure of olivine
projected along the axis out of the page.
The isolated tetrahedral are linked by Mg
and Fe in octahedral coordination. Two
distinct M-sites are recognized as M
1
and
M
2
.

The values of ! are estimated based off
the point where the curvature changed on the
longer wavelength side of the main
absorption feature in my spectra I found
this to be 1.12 m for the laboratory
spectrum and 1.24 m for the CRISM
spectrum based on my plot shown in Figure 1.
Since the sixth 3d electron of Fe
2+
will
occupy the most stable orbit, the crystal field
stabilization energies of the Fe
2+
in the two
sites are:

Lab spectra: 0.52 eV
CRISM spectra: 0.47 eV

This calculation is further detailed in the
Appendix. This crystal field stabilization
energy represents the stability that results
from placing a transition metal ion in the
crystal field generated by a set of ligands.
Therefore, from my laboratory and
corresponding spectra from Mars, I find that
the values for the crystal field splitting
energy of iron vary from about 0.47-0.52 eV.
This is very close to published values of
0.52-0.55 eV CFSE for the olivines fayalite
and forsterite described by Burns.

Conclusions
The differential reflection and scattering
of light as a function of wavelength form the
basis of the science of reflectance
spectroscopy. As I have described, there are a
variety of quantum mechanical processes of
absorption of electromagnetic radiation by
solids and liquids. Quantitatively
understanding these processes is essential for
interpreting spectral data of minerals.
Previous identifications of minerals in
remote sensing have relied on qualitative
comparison techniques. By understanding the
spectral features predicted by crystal field
theory, we can better predict and interpret
data from instruments like CRISM.


0
0.05
0.1
0.15
0.2
0.25
0.3
0.35
0.4
0 0.5 1 1.5 2 2.5 3
R
e
f
l
e
c
t
a
n
c
e

(
u
n
i
t
l
e
s
s
)
Wavelength (m)
Laboratory Olivine
CRISM FRT 9DB4
Thomas 5

References:
Berry, Frank J, and David J.
Vaughan. Chemical Bonding and
Spectroscopy in Mineral Chemistry.
London: Chapman and Hall, 1985. Print.
Burns, Roger G. Mineralogical Applications
of Crystal Field Theory. London:
Cambridge U.P, 1970. Print.
Dunn, Thomas M, Donald S. McClure, and
Ralph G. Pearson. Some Aspects of
Crystal Field Theory. New York: Harper
& Row, 1965. Print.
Hapke, Bruce. Theory of Reflectance and
Emittance Spectroscopy. Cambridge:
Cambridge University Press, 2012.
Internet resource.
Hawthorne, Frank C. Spectroscopic Methods
in Mineralogy and Geology. Washington,
D.C: Mineralogical Society of America,
1988. Print.
Murchie S. L. et al. JGR, 112, E05S03, 2007.
Tossell, John A, and David J.
Vaughan. Theoretical Geochemistry:
Applications of Quantum Mechanics in
the Earth and Mineral Sciences. Oxford:
Oxford University Press, 1991. Print.
Figure 2 courtesy of University of Melbourne
teaching resources.


















Appendix:
To calculate the values I listed for the
crystal field stabilization energies (CFSEs), I
first calculated !. Measurements of
absorption spectra of transition metal
compounds and minerals are used to obtain
this value which can help us derive the CFSE
of the ions. The magnitude of ! depends on
(i) the valence of the ion (for example, values
of M
3+
ion being higher than those for M
2+
ions), (ii) the nature and type of ligand
coordinated to the ion, (iii) the interatomic
distance, R, between the metal and the ligand,
and (iv) the symmetry of coordinated ligands.
Based on this knowledge, I looked for the
point where the curvature first changed on
my spectra. I calculated for my spectra of
olivine ! = 0.89 m for the laboratory curve
and ! = 0.80 m for the CRISM spectra. This
is the start location of the absorption band in
the spectra where the energy required to
excite an electron from one orbital to another
of higher energy corresponds to the radiation
in the visible and infrared regions.
I was then able to calculate the CFSE for
my olivine spectra using the equation
outlined in Burns for the most stable orbital:

CFSE = (2/5 ! + 620) (units of cm
-1
)

This formula for the crystal field energy
make sense if the resolved 3d orbital energy
levels obey center of gravity rules about
the t
2g
and e
g
baricenters. For an octahedral
field, the orbitals are stabilized relative to the
barycenter by 2/5 ! and the e
g
orbitals are
destabilized by 3/5 !.
To apply these equations, we can first
convert the values for ! I found from m to
cm
-1
using the equation (wavenumbers in
cm
-1
) = 10000/m. This gives me values of
8940 cm
-1
for the lab spectrum and 8050 cm
-1
.
Plugging these values into my equation for
the CFSE point, I find:

Lab CFSE = (2/5 ! + 620) = 4196 cm
-1

Thomas 6

CRISM CFSE = (2/5 ! + 620) = 3840
cm
-1


I can then convert these units to Joules by
knowing the relationship for the energy of a
photon:

E = hc*(wavenumber)

Then, finally, I have derived that the
CFSE values are:

Lab = 0.52 eV
CRISM = 0.47 eV