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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

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