The MÃ¶ssbauer Effect and Its Application in Chemistry - American

10 Mössbauer Spectroscopy of Tellurium

Downloaded by UNIV OF CALIFORNIA SANTA BARBARA on June 23, 2016 | http://pubs.acs.org Publication Date: June 1, 1967 | doi: 10.1021/ba-1967-0068.ch010

C. E. VIOLET Lawrence Radiation Laboratory, University of California, Livermore, Calif.

125

The Mössbauer effect in Te can provide information on both the nuclear properties of the 35.6-k.e.v. first excited state of Te and the chemical properties of pure Te and Te compounds. Nuclear properties which have already been determined include the quadrupole moment, |Q | = 0.20 ± 0.03 barn, and the magnetic moment, µ = +0.60 ± 0.02 nm. Information on chemical bonding of Te can be obtained from the Te Mössbauer spectra of various Te compounds. The isomer shift which is related to the valence s electrons gives a measure of the ionic character while the quadrupole splitting can provide information on ionic character and hybridized covalent bonds. 125

1

1

125

g t u d i e s of the Mossbauer effect associated with the 35.6-k.e.v. transition from the first excited state

+ ^ to the ground state ^

1 2 5

1 2 5

+ ^ of

T e have provided information on the T e nucleus and the properties of pure Te and Te compounds between liquid helium and liquid nitrogen temperatures (3, 5, 7, 8, 12, 13, 15, 16, 17). The Mossbauer effect might also be observable in another isotope of tellurium, T e . However, the high transition energy, 159 k.e.v., makes the effect difficult to observe, and the associated line width is about an order of magnitude greater than that of the T e transition, resulting in a corresponding decrease in energy resolution. Since the solid-state aspects of the Mossbauer effect are independent of the nuclear transition, it is sufficient to use the more readily observable T e transition to study the properties of Te and its compounds. In this presentation we discuss experimental aspects asso ciated with measuring the resonance spectra of T e , review important experimental results, and suggest further T e Mossbauer experimenta tions which might yield useful results. 123

1 2 5

1 2 5

125

1 2 5

Library American Chemical Society Herber; The Mössbauer Effect and Its Application in Chemistry 1 4 7

Advances in Chemistry; American Chemical Society: Washington, DC, 1967.

148

THE

MÔSSBAUER

EFFECT

AND

ITS

APPLICATION

IN

CHEMISTRY

Sources 1 2 5

T e Môssbauer sources with convenient lifetimes can be made from Sb, Ι , or the 58d isomer of T e . This is evident from the level diagram shown i n Figure 1. Single line sources can be made with S b and I if these isotopes are incorporated into materials of cubic sym metry, thereby avoiding quadrupole effects. This has been done by electroplating S b or I on a copper foil and annealing (13, 16). Sources have also been made by neutron irradiation of pure Te enriched with T e (5). The 58-day T e isomer is then produced by neutron capture of T e . However, pure Te is noncubic, and a two-line source results from the associated quadrupole effect. For a source of I in C u , the recoilless fraction at 82°K. is about 20% (16). These T e sources emit 27.4-k.e.v. K and 31.1-k.e.v. Κβ x-rays of 125

1 2 δ

125

125

1 2 5


125

1 2 5

1 2 4

1 2 5

124

1 2 5

1 2 5

a

Te, as well as the 35.6-k.e.v. γ-rays, in the ratios: Κ : Κ : — 1:0.22:0.073 α

β

γ

The low γ-ray intensity relative to the Κ x-ray background therefore presents a problem of obtaining a reasonably good signal-to-background ratio. Detectors 1 2 5

Three types of detectors have been used in observing the Te Môssbauer effect: proportional counters, N a l crystals, and Li-drifted Ge crystals. Figure 2a shows the source spectrum obtained with a Xe-filled proportional counter. The Te K and Κ β rays and the γ-rays which constitute the high-energy group are barely resolvable. The escape peak for this counter is visible at lower energy. Setting the single-channel analyzer window to detect the 35.6-k.e.v. gammas results in a signal-tobackground ratio of about 6 to 1. Figure 2b shows the source spectrum as detected by a thin N a l ( T l ) crystal with a C u absorber (336 mg. per sq. cm.) and an A l absorber (137 mg. per sq. cm.) placed in front of the source. In this case the components of the high-energy group are unresolved. This problem can be circumvented by setting the singlechannel analyzer to detect the escape peak (2). Since the Κ edge of iodine is 33.16 k.e.v., the Te x-rays make no contribution to the escape peak. The signal-to-background ratio associated with this technique is about 10:1, The C u absorber enhances the intensity of the gammas relative to the Κ x-rays, and the A l absorber "stops" the 7-k.e.v. C u x-rays generated in the C u absorber. This same technique could also be used with the X e proportional counter. Using Li-drifted Ge detectors, the 35.6 k.e.v. gammas can be virtually separated from the x-ray background, a

Herber; The Mössbauer Effect and Its Application in Chemistry Advances in Chemistry; American Chemical Society: Washington, DC, 1967.

10.

VIOLET

149

Tellurium 52 Sb

1 2 5

Te

(35.6 kev)

2.7y - V E R Y COMPLEX 13% 125m 58d Τβ' 11/2* 145 , 2 5

57d

T

'EC 100% -^35.6


3/2+I/2+Te""

Figure 1. Level diagram for

125

Te.

Half life of (J^ + ^ level is m ( ) = 1.4 Χ ΙΟ" s. Correspond ing full width at half maximum of Mossbauer line is Δν = 0.27 cm./ sec, assuming no experimental broadening 2

5

yu

125

Figure 2. I source spectra for (a) xenon proportional counter, (b) Nal (Tl) crystal, (c) Li-drifted Ge crystal


150

THE

MÔSSBAUER

E F F E C T A N D ITS A P P L I C A T I O N

IN CHEMISTRY

as shown i n Figure 2c. The preamplifier has a cooled field-effect tran sistor to reduce noise i n the input stage. The signal-to-noise ratio which we observe with this detector is about 20:1. Nuclear Properties Excited State Magnetic Moment. The magnetic moment of the T e 35.6-k.e.v. level has been measured by Shikazono (13) and Huntzicker et al. (8). Sources were prepared by diffusing S b into metallic F e foils. The T e impurities produced by the decay of S b experience a hyperfine field at the T e nucleus transferred from the ferromagnetic 1 2 5


125

1 2 5

1 2 5

1 2 5

F e host. The spins (Figure 3) of the 35.6-k.e.v. level ί ^ ) and the ground state (

) are the same as for the well-known

5 7

F e transition, and the

splitting of the two levels by the magnetic hyperfine interaction is simi lar (10). A Môssbauer spectrum for a Sb-in-Fe source and a single-line ZnTe absorber is shown i n Figure 3 ( 6 ) . The line intensities are i n the ratios 3:2:1:1:2:3, which demonstrates that the ratio of the first excitedstate to ground-state magnetic moments must be negative. [The same intensity ratios exist i n the magnetic hyperfine spectrum of F e , where the ratio of the first excited-state moment to the ground-state moment is (μι/μο) = —1.715 (10).] Using an independent determination of the T e ground-state magnetic moment, μ = —0.88715 nm. ( 9 ) , and the measured line separations i n Figure 3, Huntzicker et al. (8) determined the T e first excited-state magnetic moment: μ = +0.60 ± 0.02 nm. Electric Quadrupole Moment. A Môssbauer resonance spectrum typical of a Te-in-Te absorber, and a single line I - i n - C u source is shown i n Figure 4. The quadrupole splitting at 4.8 °K. is 0.76 ± 0.02 cm. per second or (0.90 ± 0.03) Χ 10" e.v. (16,17). The quadrupole splitting for a nonaxially symmetric field gradient 3 with spin ί = ^ i s given by (4) 125

57

1 2 5

0

1 2 5

1

125

125

6

(1) To calculate the nuclear quadrupole moment from the measured quadrupole splitting, it is necessary to know the electric field gradient, q, at the Te nucleus as well as the asymmetry parameter, η. These can be calculated i n the Townes and Dailey approximation (4) by knowing the chemical bonding i n Te. The arrangement of the atoms i n a Te crystal is shown i n Figure 5a. The atoms are arranged i n spiral chains. The bonds between adjacent atoms on the same chain are covalent whereas between chains they are


10.

VIOLET

151

Tellurium


RELATIVE

V E L O C I T Y (cm/sec)

Figure 3. Magnetic hyperfine spectrum of Te as impurity in metallic Fe 125

VELOCITY (cm/sec)

125

Figure 4. Electric quadrupole spectrum of Te in pure Te at 4.8°K. Source, I in Cu at 82°K. Total absorber thickness, 30.0 mg./sq. cm. of tellurium enriched in Te—i.e., Te/Te = 40.4%. Individual lines of this doublet have a full width at half maximum of 0.73 cm./sec. Our experimental line widths for absorbers vary from 0.67-1.01 cm./sec. 125

125

125

a weak mixture of electronic and van der Waals binding. Because of the strong binding between atoms on the same chain, the chain can be treated as a single molecule. Considering only bonding between adjacent atoms on the same chain, the principal axes of the field gradient tensor are shown i n Figure 5b.



152

THE

M Ô S S B A U E R E F F E C T A N D ITS A P P L I C A T I O N IN

CHEMISTRY

Figure 5. Arrangement of atoms in (a) crystal structure of pure Te and (b) principal axes of electric field gradient From the atomic orbitals s, p , p , and p , the following set of molecular orbitals can be constructed: x

y

z

ψ ι = ( 1 - 2 « ) * * - ( 2 « ) ^ ψ =

s +

ψ, _ ^

s

2

[I (1

-

2«)] V + | / |

+ |j.(l_

-

(Pv)

|/1 (p, )

ψ = ρ. 4

The amount of s character in the bonding orbitals, ψ and ^ is determined from a = cos Θ/(cos θ — 1), where 0 is the bonding angle. For the bonding angle of Te (θ = 102.6°) we have a = 0.179. One can now determine the number of unbalanced ρ electrons ( U ) and the asymmetry parameter 2

3

p

U, — j N + 1 N - N = a - 1 = x

y

z

-0.821 (3)

'

Ν + N„ — 22V* β

1 —α

where N , N , and are the electron populations i n the p , p , and p states. For atomic Te the contribution to q from one unbalanced ρ electron is c/atTe = 3.9 Χ 10 e.s.u. ( 1 ). Thus the contribution to the field gradient at the Te nucleus owing to bonding along the molecular chain is —3.2 X 10 e.s.u., weighted by the fractional importance of such bonding. The fractional importance of bonding along the chains can be ob tained by comparing with the situation in crystalline iodine (11). Iodine x

y

x

y

6

16


z

10.

VIOLET

153

Tellurium


exists as a molecular crystal (bond length 2.70 A . ) but has next nearest neighbors at 3.54 A . compared with 4.30 A . for the sum of the van der Waals radii. In tellurium (bond length 2.86 A . ) the next nearest neigh bors on adjacent chains are at 3.45 A . compared with 4.40 A . for the sum of the van der Waals radii. Thus the importance of bonding along the chains i n tellurium should be comparable with that for nearestneighbor bonding i n crystalline iodine—namely, about 89% (11). A c cordingly, we take the fractional importance of this bonding to be u

/ — -

5 y

-0.08

The choice of wave functions to describe bonding between chains is considerably more difficult than for bonding along the chains. Most of the bond angles for next-nearest-neighbor bonding are considerably less than 90° (60° and 8 0 ° ) so that "bent" bonds are required. This i n itself is evidence of the relative unimportance of such bonding. Nonetheless, if various bonding schemes are tried, one finds a distribution of positive and negative q's with a mean value which is nearly zero. F r o m this analysis we take the field gradient owing to bonding between chains to be q' = (0.0 ± 0.8) X 10 e.s.u. From these considerations the field gradient can be determined from q = fU q vr + (1 — f)q' = 16

p

&

e

( —2.8 Zto*4 ) X 10 e.s.u. Some d-hybridization may also be involved, but d orbitals make a negligible contribution to the field gradient (4). The correction for the Sternheimer effect is also negligible i n the Townes 3 and Dailey approximation (4). F o r spin γ , the magnitude but not the 16

sign of the quadrupole coupling can be determined from the quadrupole data alone (4). F r o m these considerations and Equation 1, the magni tude of the electric quadrupole moment of the T e first excited state becomes: |Çi| = 0.20 =b 0.03 barn. 1 2 5

Chemical Properties Chemical Bonding. F r o m the above calculations, it is clear that information on chemical bonding of Te compounds can be inferred from the associated quadrupole splitting data. W e have neglected the ionic character of the Te bonds i n tellurium. However, this parameter may need to be included i n bonding calculations of Te compounds as is done, for example, i n the Townes and Dailey approximation. The isomer shift associated with Môssbauer resonance spectra also provides information on chemical bonding. The isomer shift is given by 2

2

2

δ = const [\φ (0) I - |ψ. (0) I ] [ - < V > ] α

e


(4)

154

THE

MÔSSBAUER

EFFECT

A N D ITS A P P L I C A T I O N

IN

CHEMISTRY

where 2

\ψα,8 (0) 1 = electron densities at the nucleus for absorber and source 2

2

and = mean square charge radius of the excited state and ground state


gr

The only appreciable contributions to the electron densities at the nucleus are from s electrons. Usually only valence s electrons are con sidered because the inner s electrons are much less affected by chemical bonding. Therefore, the isomer shift "gives a unique measure of the role of s electrons in chemical bonds and thus provides a physical foundation for the chemical concept of ionic character" (14). The compound N a T e 0 is an exceptional case i n which the chemical bonding can be understood i n terms of simple concepts. Accordingly, Buyrn and Grodzins (3) have stated that the electron density at the Te nucleus in N a T e 0 is less than in Te. This, combined with their mea sured isomer shift in N a T e 0 , led to the conclusion that the charge radius 2

2

4

4

2

Table I.

4

Isomer Shifts and Quadrupole Splittings at Liquid Nitrogen Temperature

Quadrupole Isomer Shift," Splitting, Symmetry Cm./Sec. Cm./Sec. fee

-0.04 (1)

MnTe

Hex

-0.03 (2)

0.3 (1)

FeTe

Tetr

0.00 (2)

0.3 (1)

Hex

+0.05 (5)

0.37 (5)

Hex Hex

+0.08 (5) +0.04 (5)

0.25 (5) 0.32 (5)

fee Rhomb

0.00 (5) -0.015 (5)

2

3

NiTe CoTe PbTe Bi Te 2

3

Te 2

2

3

2

4

4

4

Tetr. ? Cubic ?

? Cubic

+0.03 -0.01 -0.15 -0.01 +0.05 -0.05

323

Antiferromagnetic Antiferromagnetic Antiferromagnetic

63

?

? Ferro magnetic

? -Ί273

The MÃ¶ssbauer Effect and Its Application in Chemistry - American

Recommend Documents