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I. INTRODUCTION
Although the possibility has been known for some
time, I it is only during the past decade that the effects of an
external magnetic field, B, on positronium (Ps) annihilation
have been used to study the physical properties of Ps in liquids,2 and also, more recently, the chemistry of PS,3,4,5 a
domain which is still poorly understood. In this context, the
strong magnetic field effect on Ps in solutions of nitrobenzene (<P-N0 2) in n-hexane, first observed by Rochanakij et
al.,6 has given new insights on the mechanism of this reaction. 3 The present paper reports on the extension of this
work to the study of the influence of temperature, in order to
assess the validity of the formerly proposed kinetic scheme
and to gain more information on the parameters descriptive
of the positron-electron hyperfine interaction within the
bound-state.
II. EXPERIMENTAL
at half-maximum of the 60Co prompt curve, has been improved to 380 ps.
Whatever the value of the field, the LS spectra should
include the contributions from several components, the two
Ps states, singlet ( p- Ps) and triplet (0- Ps), the free positron
(e +) and the bound-state of Ps with a solute molecule. As
was shown previously, 3this bound-state also presents singlet
and triplet substates. In a lifetime spectrum or when dealing
with theoretical expressions, the presence of these various
components results in an equivalent number of decay rate
constants, A, and associated intensities, I. Due to the complexity of the problem, the notations which will be used in
the following are summarized in Table I. SUbscript c will
denote parameters related to the bound-state, superscript
will denote values in the pure solvent and subscripts i = 1, 3,
4, will refer to the singlet, triplet (m = 0) and triplet
(m = 1) substates whether of Ps or of the bound-state,
respectively, while subscript 2 will be for free e+. Whether
the field is on or off will be indicated by the symbols (B) or
(0), respectively.
When the field is off, a three component analysis of the
LS spectra appears to be satisfactory, implying that the components relative to the bound-state are unresolved from the
short lived components; most probably, as shown in the following, A3c (0) is close to A 2 ( 0), and Alc (0), to Al (0).
When the field is on, due to the mixing of the spin substates as explained in the next section, additional components appear in the LS spectra. As previously,3 the LS spectra were therefore analyzed in four components, fixing the
parameters related to 0- Ps (m = 1) and the intensity of 0Ps (m = 0), in order to derive reliable values of A4 (B). Even
so, the error on lifetime 1/A4 (B) at specified T was rather
large, ranging from 0.04 ns up to 0.1 ns.
As proposed by Bisi et al.,7 however, the LS data will be
mostly expressed in terms of R, defined as the ratio of the
normalized integrals of counts in a time window (ta,t b ) of
the spectra, when the field is on and off. To focus on the
variation with B of the longest-lived components, ta was
chosen so that the contributions of free e+ and of other
short-lived components are negligible, and tb was taken at
the limit of statistically significant countings. The values of
0021-9606/92/141548-06$06.00
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1549
TABLE I. Summary of the symbols used to denote the decay rate constants
arising in the LS spectra because of the various positron states involved, in
the absence (C = 0) or in the presence (C # 0) of the solute and of the
magnetic field (B). The star points out those states whose decay rate constants are not affected by the field. The intrinsic lifetimes of the singlet states
ofPs and of the Ps bound-state with <l>N0 2, in vacuo, are A, and A"" respectively.
Positron state
C#O
C#O
singlet Ps (p#Ps)
free positron*
triplet Ps (o-Ps, m = 1)*
triplet Ps (o-Ps, m = 0)
singlet Ps bound-state (p-C)
triplet Ps bound-state (o-C, m = I)"
triplet Ps bound-state (o-C, m = 0)
A'I(B)
A ;(0)
A; (0)
AI(B)
A2 (0)
A,(O)
A.(B)
A,c (B)
A3c (O)
A.c(B)
A~(B)
R =/(B)I/(O)
with
/(B) =
~fO IjAj(B)exp[
-Aj(B)t]dt
(2)
A ~ (B)
[A; (0)
= 1/AEvacuo
(4)
I:
l/A; (0)
l/A)(O)
(ta,tb )
(%)
(ns)
(ns)
(ns,ns)
264
268
273
279
286
292
294
300
303
313
328
40.1
40.4
40.7
40.9
41.1
41.7
41.8
42.0
42.0
42.6
43.0
3.57
3.58
3.64
3.65
3.74
3.74
3.75
3.76
3.76
3.79
3.87
2.29
2.35
2.57
2.78
2.99
3.30
3.30
3.27
3.32
3.46
3.59
4.21,
4.30,
4.71,
5.06,
5.49,
6.05,
6.15,
6.00,
6.08,
6.34,
6.57,
5.80
5.93
6.49
6.97
7.57
8.34
8.50
8.27
8.38
8.74
9.06
(3)
AEm
T
(K)
AEme = 1/cAEc .
(7)
To complete the parallel in the formal treatments for
both Ps and the bound-state, A Ie (0) in Eq. (6) is given by
A;(B)t ]dt /
TABLE II. Experimental LS data for pure n-hexane, I; and 1/A; (0), and
for the 0.025 M nitrobenzene solution, 1/A) (0), at zero field; (ta ,tb ) are the
values for the time windows defining parameter R, used for the solution.
(6)
(9)
where C is the solute concentration. However, it has been
repeatedly shown that the reaction of Ps with nitrobenzene
is, in fact, reversible,12 involving the forward (k l ) and reverse (k 2 ) reaction rate constants. In our previous study of
the magnetic field effects, it appeared that the data could be
explained on the basis of the following hypotheses 3 :
(i) Similarly as for Ps proper, one can define a singlet
(p-C) and a triplet (o-C, with substates m = 0, 1) state
for the complex. As in the case ofPs, the decay rate constants
of the two m = 0 substates of the complex [Ale (D) and
A4c (D)] are liable to magnetic field effects, while all intensities and the decay rate constant of the m = 1 substates
[A3e (0)] are unaffected. (ii) A particular (sub ) state of Ps
1550
can only lead, through the chemical reaction, to the corresponding (sub) state of the complex.
The kinetic equations are then written as follows (the
rate constants for the reversible reaction, not noted, are kl
and k 2 ):
-<; (Bl
2y
<-
p-Ps
+ <I>-N02
-< ~(Bl
2y
+-
o-Ps(m = 0)
-<le(Bl
p-C
+ <I>-N02
2y,
-+
(I)
-<'e(Bl
o-C (m = 0)
-+
2y,
(II)
-<;(0)
2y
+-
o-Ps(m
= 1) + <I>-N02
-<3e(0)
o-C (m
= 1)
-+
2y.
TABLE III. Kinetic parameters derived from the data in Table II; apparent
(k '). forward [k,; calculated from Eq. (10)], and reverse (k2) reaction rate
constants.
T
(K)
264
268
273
279
286
292
294
300
303
313
328
29.3
30.6
32.4
34.4
37.0
39.2
40.0
42.2
43.4
47.4
55.7
6.26
5.86
4.58
3.53
2.68
1.43
1.45
1.59
1.41
1.01
0.81
7.68
8.75
12.8
19.3
28.6
58.1
51.2
53.9
65.5
103
158
(III)
IV. RESULTS
A. Pure solvent
I;
1.0
R
0.9
B. Solution
Lifetime 1/A.2 (0) appears to be constant at all temperatures, at (0.43 0.03) ns, while 1/A. 3(0) increases with T
(Table II). The values of the apparent reaction rate constants, k', derived from Eq. (9), are given in Table III; it may
be noted that the value at 294 K is in fairly good agreement
with other determinations. 3,4 The continuous decrease of k '
with increased temperature is indicative of the reversibility
of the reaction; the maximum in the apparent reaction rate
constant has been reported to occur at ~ 220 K.12
1.0
ci>err.
0.9
0.8
o
FIG. 1. Variation of parameter R with magnetic field intensity. B (n. in
pure n-hexane at 268 K. The solid line is calculated with 'TJ = 0.83.
0.5
B(T)
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1551
1.0
1/.\.0 (ns)
<p err.
3.0
R
0.9
2.5
2.5
0.8
2.0
1/.\.0 (ns)
264 K
1/.\.o(ns)
2.0
1.0
2.0
0.9
1.5
err.
o
0.5
0.5
B (T)
0.8
1.0 __- - - - - - - -
0.9
328 K
0.8
0.5
B (T)
at 294 K.3 At all temperatures, there is a very abrupt decrease of I/A 4 (B) at low field, as was the case at 294 K.3
V. DISCUSSION
On the basis of the model previously proposed, 3 thepresent data which combine the variation of R and of 1/
A4(B) with Tand B, can be fitted using the various parameters descriptive of the Ps bound-state with nitrobenzene
[7]c>AEc.A.sc,A3c (0)] and of its reversible formation (k l
and k 2 ). Note that the parameters characteristic of Ps [7]
and A; (0) ] are fully determined from the study of the pure
solvent.
For a specified temperature, due to the complexity of
the problem resulting in strong correlation between the parameters, several sets of the latter can lead to equally satisfactory fits. The quality of the fits can be assessed by considering the standard deviations, UA and U R , accordingly,
which should be close to the experimental errors in favorable
cases.
In the following, the conclusions drawn from the various attempts made to fit the data are presented concerning
the temperature dependence of (i) those parameters which
can be studied at zero field, essentially the kinetic parameters; (ii) the parameters descriptive of the Ps complex with
nitrobenzene, 7]c and AEc> which are derived by examining
the magnetic field effects.
kl (T)
(10)
with
(11)
where vis the viscosity of the solvent l2 with activation energy Ev = 0.045 eV and preexponential factor Vo = 0.054 cp,
NA is the Avogadro number, kB is the Boltzmann constant,
and rps = 0.053 nm and rs = 0.3 nm are the radii of the
reactive species, Ps and nitrobenzene, respectively. The value of rs is only a crude estimate; however, it is consistent
with rs = 0.23 nm implicit in the fitting parameters derived
to recover the variation of k with T for nitrobenzene in toluene. 17 Furthermore, the absolute value of kl calculated
from Eqs. (10) and (11) are in agreement with the experimental values of k at temperatures around and below 200
K,18 when the reverse reaction (k 2 ) is negligible, even
though the slope of the k vs Tvariation appears somewhat
higher than for k I'
On this basis, the value of k2 can be determined at each
temperature from the value of I/A3(0), through the relevant kinetic equation (not reported here)Y Table III collects the calculated values for kl together with those for k 2
Excepting T = 292 K, for which 1/A3 (0) appears somewhat too high, (see Table II), the latter values give a very
good Arrhenius plot, showing that k2 can be written as
I
J. Chern.
Phys.,
Vol.is97,
No.2,to
15the
July
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(12)
2.0
I1c
1.5
1.0
0.5
300
T (K)
The non-Arrhenius behavior of the reaction rate constant of Ps with nitrobenzene in n-hexane and in other solvents is now a well-established fact, which has been examined and explained on kinetic grounds.II,IS As concerns the
magnetic field effects, two alternative approaches have been
proposed, besides the treatment described in this paper.
One of these models involves various spur reactions and
does not allow to fit the various data, as a function of either
B, Cor T, with a limited number of parameters. 15 With the
present model, any of these variations can be recovered by
simply considering, besides the kinetic constants kl and k2'
the parameters descriptive of the hyperfine interaction of the
Ps bound-state with nitrobenzene.
The other model is based on the idea that e+ in Ps, when
bound to nitrobenzene, interacts with more than one ele25 26 D escn'b'mg th
.
t ron.'
ese'mteractlOns
through contact den-
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VI. CONCLUSION
1553
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