Short Notes Kl59

phys. s t a t . sol. (b) 89, K159 (1978)

Subject classification: 13; 21.5
Institute of Physical Metallurgy, Czechoslovak Academy of Sciences I Brno (a)
and Institute of Experimental Physics, Bierut University, W r o d a w (b)
Positron Annihilation in Some Uranium a d Thorium Compounds
BY
A. CigEK ( a ) , M. SOB (a), E. DqBaWSKA (b), and B. ROZENFELD (b)

In /1/ it has been shown that the mean ionic radius ( F ) of a compound determines
the standard deviation ( 6 )of the Gaussian component of the ADAP (the angular dis-
tribution of annihilation photons) curve in positron annihilation investigations. Both
quantities are namely related by the simple relation

Fd = k (1)

as shown by F e r r e l l /2/. The value of the constant k depends on the electronic type
of the most complex atom in the chemical unit of a substance studied. The knowledge
of the number of electrons of this atom is only necessary f o r estimation of the
electronic type. The s-type occurs if the number of electrons lies in the interval 1
t o 4 , the p-type has 5 t o 20 electrons, 2 1 t o 56 electrons give the d-type, and the
f-type comes into consideration if the number of electrons is a t least 57.
In /1/ and especially in /3/ a large number of compounds was investigated -
from simple binary inorganic oxides to v e r y complicated organic aminoacids as
well a s polymers. However, only one case was given as an example f o r the most
complex f-type. And just h e r e the verification i s v e r y fruitful because of generali-
zation of the relation (1) t o the d- and f-electrons; F e r r e l l supposed the validity
solely f o r the s - and p-electrons.
In /4, 5/ eight compounds of uranium and thorium have been investigated by the
positron annihilation method. The uranium and thorium atoms are evidently of the
f-type. Therefore, their compounds are very suitable f o r the verification mentioned
above.
The measurements f r o m /4, 5/ were used for the calculation of F . The measured
data were fitted on the ZPA 600 computer by the least-squares method to a Gaussian,
The substances investigated a r e divided into three groups according t o the anion used
a s can be seen in Table 1 which summarizes all results.
1 2 physica (b)
K160 physica status solidi (b) 89

Table 1

The mean ionic radii of some uranium and thorium compounds

I I ionic 6
substance %

state (mrad)

up2
u6+P;- 168 163 4.03 2 0.02
6+ 3-
UAsz U As2 175 178 3.68 + 0.02
6+ 3-
USb2 U Sb2 3.61 +_ 0.02
4+ 3-
Th3As4 Th3 A s 3.90 0.04
4
4+ 3-
U3As4

UA sS
U3 A s

U As S
4
5+ 3- 2-
165 167
------I
3.99

3.93
+ 0.03

+_ 0.02
5+ 3- 2-
UAsSe

UAsTe
U

U
5+
A s Se

As
3-
Te
2- 170
177
I 173
3.86 +- 0.02
3.80+0.03 1

The mean ionic radius was calculated f o r the f-type; the corresponding constant
k in (1)has then the value of 656, if the ionic radius is measured in pm and d is ex-
3-
pressed in mrad. The Pauling ionic radii were taKen a s P : 212, As3-: 222, Sb3-:
4+ 4+ 5+
245, S2-: 184, Se2-: 198, Te2-: 221, Th : 102, U : 97, U : 89 (this value i s not
6+
listed a s Pauling radius, but it i s cited in /6/), and U : 80 pm / 6 / . The values of F
for the ionic states a r e given in Table 1. It is seen that the results are in good agree-
ment with the calculated ones in all three groups.
5+
Also the value of 89 pm for U yields a go$ result. Therefore it can be taken as
the Pauling radius of U
5+
.
It is also seen that the s i z e of the radii i s reproduced in the groups: If d is de-
creasing, the anion radius i s increasing.
Our approach does not take into account the metallic character of the compounds
considered. In our model, we take them formally as ionic ones.
 S h o r t Notes Kl61

Finally, on c a n point out that t h e generalization of t h e Ferrell relation (1) ap-

p e a r s t o be justified. It holds f o r the most electronic f-type as it is d e m o n s t r a t e d
in t h i s s h o r t note. N o case i s yet known which would disprove the validity of t h i s
generalization.

References
/1/ A . e & E K and I .YA. DEKHTYAR, t o b e published.
/2/ R.A. F E R R E L L , Rev. mod. P h y s . 2% 308 (1956).
/3/ A. C f 2 E K , M. SOB, and I.YA. DEKHTYAR, t o be published.
/4/ B. ROZENFELD and E . DgBoWSKA, Solid State C h e m . 5, 1 0 1 (1976).
/5/ B. ROZENFELD and E. DI$BOWSKA, Acta P h y s . Polon. &I, 97 (1977).
/6/ G.V. SAMSONOV, Svoistva elementov, Vol. 1 , Metalburgiya, Moscow 1976
(in R u s s i a n ) .

(Received J u n e 28, 1978)