Murad Spectroscopy

7/21/2019 Murad Spectroscopy

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57Fe Mssbauer Spectroscopy

Enver Murad

Marktredwitz, Germany

Enver Murad

Marktredwitz, Germany

:

a Too !or t"e #emote $"aracterization o! %"yosiicates&


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'asic principes o!

Mssbauer spectroscopy


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E m i s s i o n ( b s o r p t i o n

# e c o i

Free emittin)and absorbin)atoms

Ener)y o! recoi

*+ray ener)y

Mass o! atom


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E m i s s i o n ( b s o r p t i o n

o r e c o i

Emittin)and absorbin)atoms !i-ed in a attice

Mass o! partice

Mssbauer spectroscopy is t"e recoi+!ree emission

and absorption o! )amma rays


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(ppearance o! Mssbauer spectra

.ependin) on t"e oca environments o! t"e Fe atoms and t"e

ma)netic properties, Mssbauer spectra o! iron o-ides can consist o! a

sin)et, a doubet, or a se-tet/

Symmetric c"ar)eo ma)netic !ied

(symmetric c"ar)eo ma)netic !ied

Symmetric or asymmetric c"ar)eMa)netic !ied 0interna or e-terna1

2 '"!34somers"i!t

5uadrupoe

spittin)

Ma)netic"y

per!ine!ied


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Fe6

+ 8 + 9 : 9 8

; e o c i t y 0 m m < s 1

#

e

a

tiv

e

T

ra

n

s

m

is

s

io

n

Fe9

+ 8 + 9 : 9 8

; e o c i t y 0 m m < s 1


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+ = : + 5 : 5 = :

; e o c i t y 0 m m < s 1

T

ra

n

s

m

is

s

io

n

+ = : + 5 : 5 = :

> = : / : : m m < s ?

= : / 8 = m m < s


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@se o! Mssbauer spectroscopy as a

A!in)erprintin)B tec"niCue

4somer s"i!ts and

Cuadrupoe spittin)s

o! Fe+bearin) p"ases

vary systematicay

as a !unction o! Fe

o-idation, Fe spin

states, and Fe

coordination/

Dnowed)e o! t"e

Mssbauer

parameters can

t"ere!ore be used to

A!in)erprintB an

unknown p"ase/


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yper!ine parameters o! Fe6o-ides

Minerarderin)

temperature 0D1Ma)netic "yper!ine !ieds

RT: '"!0T1 4.2 K: '"!0T1 2 0mm


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4ron in p"yosiicates


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=:= p"yosiicates

9:= p"yosiicates

Fe2+, Fe3+

Fe2+, Fe3+

O H , O

S i

A l

O

S i

S i

O H

A l

O

O

Fe6

Fe6


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$assi!ication o! cay+sized p"yosiicates

0cay mineras sensu stricto1

Oayer typecta"edraoccupancy

cta"edra

c"ar)e1$entracation0s1

Group $ommon species

= : = .i2 ( Daoin Daoinite, "aoysite

= : = Tri3 M) Serpentine Oizardite, c"rysotie

9 : = .i R /9 ( %yrop"yite %yrop"yite

9 : = Tri R /9 M) Tac Tac, minnesotaite

9 : = .i < Tri /9 N /I (, M), Fe Smectite Montmorionite, nontronite

9 : = .i < Tri /I N / (, M), Fe ;ermicuite ;ermicuite

9 : = .i < Tri / (, M), Fe Mica 4ite, )auconite

9 : = 0: =1 .i < Tri (, M), Fe $"orite $inoc"ore, c"amosite

1%er !ormua unit >=019?, 2/3.iocta"edra


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Mssbauer spectra o! seected

AsimpeB 0pure1 cay mineras


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T"e AsimpestB cay minera:

kaoinite >(9Si95018?

Daoin < ari U 95D

O H , O

S i

A l

O

+ 5 : 5+ 7 / 5 + 9 / 5 9 / 5 7 / 5

; e o c i t y 0 m m < s 1

G H

G H / 5

G G

G G / 5

= : :

T

ra

ns

m

is

s

io

n

0V

1


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+ = : + 5 : 5 = :; e o c i t y 0 m m < s 1

G 7

G H

G G

= : :

T

ra

n

s

m

is

s

io

n

0V

1

Daoin < ari U 8/9D


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Mssbauer parameters o! cay mineras

Minera Temp4somer s"i!t03


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4ite: 0D,61-y0(9+-M-10Si8+y(y1=019

4ite E$. Q5

+ I + 6 : 6 I

G 5

G I

G 7

G H

G G

= : :

G 7

G H

G G

= : :

T

ra

n

s

m

is

s

io

n

0V

1

Fe6: 92

G 7

G H

G G

= : :

G 7

G H

G G

= : :

+ I + 6 : 6 I

G 5

G I

G 7

G H

G G

= : :

G 5

G I

G 7

G H

G G

= : :

Tr

a

n

s

m

is

s

io

n

0V

1

G 7

G H

G G

= : :

G 7

G H

G G

= : :

+ I + 6 : 6 I

G 5

G I

G 7

G H

G G

= : :

G 5

G I

G 7

G H

G G

= : :

: : / 9 5 : / 5 : / 7 5 = = / 9 5 = / 5 = / 7 5 9 9 / 9 5

0 m m < s 1

:

8

H

= 9

= I

Tr

a

n

s

m

is

s

io

n

0V

1

%

0V

1

Fe6

: %021


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ontronite: M-Fe9 0Si8+-Fe-1=0196

7 :

H :

G :

= : :

T

ra

n

s

m

is

s

io

n

0V

1

+ = : + 5 : 5 = :

; e o c i t y 0 m m < s 1

#T

ontronite (%4 66a

96/8I V Fe

=/88 V FedX 9/6 V Gt

From (se-tX =/8 V Gt

77D

7 :

H :

G :

= : :

T

ra

n

s

m

is

s

io

n

0V

1

+ = : + 5 : 5 = :

; e o c i t y 0 m m < s 1

H 5

G :

G 5

= : :

+ = : + 5 : 5 = :

H 5

G :

G 5

= : :

+ = : + 5 : 5 = :

H 5

G :

G 5

= : :


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ontronite: M-Fe9 0Si8+-Fe-1=0196

ontronite (%4 66a

+ 8 + 9 : 9 8

; e o c i t y 0 m m < s 1

G I

G H

= : :

T

ra

n

s

m

iss

io

n

0V

1

G I

G H

= : :

T

ra

n

s

m

iss

io

n

0V

1

+ 8 + 9 : 9 8

; e o c i t y 0 m m < s 1

G 9

G 8

G I

G H

= : :

+ 8 + 9 : 9 8

G 9

G 8

G I

G H

= : :

Fe9


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$ompe- natura cays:

AT"e rea wordB


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%"ysics Today 610H1%"yosiicate wit" intercaated interayer

a

$89

ote: Fe+containin) interayer must be!rozen to s"ow Mssbauer E!!ect%"yosiicate wit" intercaated interayer:AatureZs tras"canB

Fe9

Fe6


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G G / I

G G / H

= : : / :

T

ra

n

s

m

is

s

io

n

0V

1

+ = : + 5 : 5 = :

; e o c i t y 0 m m < s 1

G G / I

G G / H

= : : / :

+ = : + 5 : 5 = :

G G / I

G G / H

= : : / :

Daoin A[o!kaB U 8/9D

.$'+treated \/==V )oet"ite

G G / I

G G / H

= : : / :

T

ra

n

s

m

is

s

io

n

0V

1

+ = : + 5 : 5 = :

; e o c i t y 0 m m < s 1

G G / I

G G / H

= : : / :


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'au-ite

G I

G H

= : :

+ = : + 5 : 5 = :

; e o c i t y 0 m m < s 1

G I

G H

= : :

T

ra

n

s

m

is

s

ion

0V

1

G I

G H

= : :

' ] +

G I

G H

= : :

G I

G H

= : :

G I

G H

= : :

+ = : + 5 : 5 = :

; e o c i t y 0 m m < s 1

G H

G G

= : :

T

ra

n

s

m

itta

n

c

e

0V

1

G H

G G

= : :

G H

G G

= : :

G H

G G

= : :

' ] +

6 - . $ ' 9 G 5 D

= : :


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#ed soi

G 9

G 8

G I

G H

= : :

T

ra

n

s

m

is

s

io

n

0V

1

+ = : + 5 : 5 = :

; e o c i t y 0 m m < s 1+ = : + 5 : 5 = :+ = : + 5 : 5 = :

9 G 5 D

G I

G H

= : := 9 : D

G I

G H

= : :7 7 D

G I

G H

= : : 8 / 9 D


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E-traterrestria Mssbauer

spectroscopy

Ounar sampesIn situMssbauer spectroscopy on Mars

Ounar AsoiB =H8


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S/S/ a!ner, =75: AT"e data s"oud not /// be interpreted

in an isoated !orm, but /// correated wit" t"e resuts o!

ot"er tec"niCues ///B/

F e 9 i n ) a s sF e 9 i n p y r o - e n e

F e 9 i n i m e n i t eF e 9 i n o i v i n e

M e t a i c i r o n a n o p " a s e i r o n

#

e

s

o

n

a

n

t

a

b

s

o

rp

tio

n

+ 5 : 5; e o c i t y 0 m m < s 1

[ a n ) e t a / , = G G 5

Ounar AsoiB =H8

For unar sampes, t"is is possibe ^


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AT"e data s"oud not /// be interpreted in an isoated !orm,

but /// correated wit" t"e resuts o! ot"er tec"niCues ///B

0S/S/ a!ner =751

A_ we assi)n t"e broad doubet present in Mssbauer

spectra o! >Mars? sois to be due to Fe9su!ates rat"er

t"an oivine _ B 0'is"op et a/ 981

Fe2su!ate&

(S(


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Summary

St t" d k ! 57F


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Stren)t"s and weaknesses o! 57FeMssbauer spectroscopy

` Sensitive ony to 57Fe0no matri- e!!ects1

` Sensitive to o-idation state

` (ows distinction o!ma)netic p"ases

` ;ery sensitive towardsma)netic p"ases

` on+destructive` #esoution imited by

uncertainty principe

` Sensitive ony to 57Fe0AseesB ony 57Fe1

` $oordination & to

` %arama)netic p"ase datao!ten ambi)uous

` .iama)netic eementsubstitution rea-ation

` Sow` 4! possibe, use ot"er

tec"niCues as we

Stren)t"s [eaknesses

!ten a combination o! Mssbauer spectroscopy wit"ot"er tec"niCues can "ep sove probems t"at cannotb d i M b t

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