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Effect of temperature on the formation of a boundstate of positronium with

nitrobenzene and on the related hyperfine interaction parameters


I. Billard, J. Ch. Abb, and G. Dupltre
Citation: The Journal of Chemical Physics 97, 1548 (1992); doi: 10.1063/1.463230
View online: http://dx.doi.org/10.1063/1.463230
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Effect of temperature on the formation of a bound-state of positronium


with nitrobenzene and on the related hyperfine interaction parameters
I. Billard, J. Ch. Abbe, and G. Duplatre
Centre de Recherches Nucieaires, Chimie Nucieaire, B. P. 20, 67037 Strasbourg Cedex 2, France

(Received 9 December 1991; accepted 8 April 1992)


The strong magnetic field effect on the chemical bound-state formation of positronium with
nitrobenzene in n-hexane previously studied at 294 K has been further examined as a function
of temperature, from 264 to 328 K. The model proposed before to explain the data, implying
the definition of triplet and singlet positronium bound-state, appears to be valid at all
temperatures studied. The variation with temperature of the parameters descriptive of the
bound-state are derived; the hyperfine splitting is constant at 1.06 X 10- 5 eV, while the contact
density parameter, 7]c' shows an abrupt change from 0.43 to 1.56 between 286 and 292 K.
These experiments give new insight on the structure of the bound-state formed, which may be
considered as a charge-transfer complex.

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

The chemicals, reagent grade from Aldrich, were used


as received. In a first paper, we studied the effect of the magnetic quenching on solutions of nitrobenzene in n-hexane at
294 K. 3The concentration selected for the present work was
0.025 M. The temperature (n of the sealed ampoule containing the freshly prepared solution was thermostatically
controlled within 0.1 K, from 264 to 328 K. The influence of
B on the pure solvent, already studied at 294 K, 3 was complementarily examined at 268 K. Due to the additional geometric constraints imposed by the thermostatic system, the
maximum value of the magnetic field intensity, B, was 1 T.
The experimental setup for lifetime spectroscopy (LS)
was essentially the same as that previously described. 2,3
However, two modifications were made to improve the time
resolution and counting efficiency; (i) the length of the
Plexiglas light guides was reduced from 15 to 11.5 cm; (ii)
owing to the aging of the silicon elastomer (Rhodovsil R TV2) disks inserted between the light guides and the photomultipliers to enhance light collection, these have been replaced.
In this way, the time resolution, measured as the full-width
1548

J. Chern. Phys. 97 (2), 15 July 1992

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

1992 American Institute of PhYSics

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Billard, Abbe, and Duplatre: Bound-state of positroniul')1 with nitrobenzene

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)

ta and tb for the solution at the various temperatures studied


are gi ven in Table II. The theoretical expression for R is (this
corrects a misprint in Ref. 3)
(1)

R =/(B)I/(O)

with
/(B) =

L r'h I;A;(B) exp[ , Jt

~fO IjAj(B)exp[

-Aj(B)t]dt

(2)

The experimental error on R was within 0.012.


III. THEORETICAL BASIS
A. Effects of the magnetic field

When the field is on, in the absence of any reaction with


the solute, the two magnetic substates m = 0 of Ps are
mixed, leading to an increase in the Oops (m = 0) decay rate
constant as (a similar expression holds for the poPs decay
rate constant)!!

A ~ (B)

[A; (0)

+ a 2AI (0) ]/(1 + a2 ),

= 1/AEvacuo

(4)

The measurable decay rate constants are A; (0), neglecting


the three-gamma annihilation, and
(5)
A 1 (0) = A ~ (0) + 1/As ,
where As (8 ns -I) is the intrinsic singlet decay rate constant.
As noted by Mills,9 the mathematical form ofEq. (3) is
valid if one considers a more complex e+ 1e- system than Ps,
provided that e + is bound to a set of electrons with total spin
1/2. This is the case when dealing with a bound-state of Ps
with a diamagnetic molecule, as presently. Then, specific
parameters descriptive of the Ps bound-state are to be used,

A4c (D) = [A3e(0) +b 2Ale(0)]/(l +b 2 ) ,

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

with b = [( I + .f) 1/2 - l]1y and y = 4f-lBD 1 AEme , where


AEme is the hyperfine splitting of the Ps bound-state in the
medium. Similarly to the case ofPs, AEme can be related to
the hyperfine splitting of the bound-state in vacuo, AEc'
through the following equation:

A1c(0) =1/cAse +A 3c (0) ,


(8)
where Asc is the intrinsic decay rate constant of the singlet
state of the Ps bound-state.
It may be noted that in the case of Ps alone, the only
unknown parameter expressing the field dependence is 1/, in
Eqs. (3 )-(5), while in the case of the Ps bound-state both 1/c
andAEc ' in Eqs. (6)-(8), are unknown but couldapriori be
determined through a fit of experimental data because they
appear in distinct parts of the equations.
B. Kinetic model

(3)

with a = [(1 + x 2 ) 1/2 - l]1x and x = 4f-lBB 1 AEm , where


f-l B is the Bohr magneton and AEm' the ~yperfine splitting of
Ps in the medium. The latter parameter is related to the Ps
hyperfine splitting in vacuo through a phenomenological parameter, 1/,

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)

The reaction ofPs with nitrocompounds, leading to a Ps


bound-state, has been the subject of extensive studies in various solvents. \0.11 On the basis of an irreversible reaction and
in the absence of any magnetic field effect, the apparent reaction rate constant, k I, can be obtained from

(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

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Billard, Abbe, and Duplatre: Bound-state of positronium with nitrobenzene

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

The LS parameters of pure n-hexane at zero field and for


various temperatures are reported in Table II. Both
and
1/A. ; (0) increase smoothly with temperature, in agreement
with previous observations. 13
The experimental variations of R with B at 268 K are
shown in Fig. 1, for a time window set at fa = 6.56 ns and fb
= 9.04 ns. A best fit to the data according to Eq. (2) gives
'l/ = 0.83. Comparing with 'l/ = 0.82 found at 294 K,14,15 it
thus appears that 'l/ is temperature independent; in the various calculations to follow, a constant value of'l/ = 0.82 has
been used.

I;

The variation of R with B are shown in Figs. 2 and 3 for


all the temperatures studied; as the curve at 294 K is very
close to that reported in our first study, it is not presented.
The changes of 1/A. 4(B) with B are illustrated in Fig. 4. By
contrast with what is observed in pure solvents,2,3 it may be
seen that the curvature of the variation of R at low field is
most generally positive, as was found before for the solution

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)

FIG. 2. Variation of parameter R with magnetic field intensity. B (n. in a


0.025 M solution of nitrobenzene in n-hexane. for temperatures ranging
from 264 to 286 K. The solid lines are calculated on the basis of the model
proposed (see text). when fitting the variation of R alone.

J. Chern. Phys. Vol. 97. No.2. 15 July 1992

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Billard, Abbe, and Duplatre: Bound-state of positronium with nitrobenzene

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)

FIG. 4. Variation of 1/A4 (B) with magnetic field intensity, B( n, in a 0.025


M solution of nitrobenzene in n-hexane. The solid lines are calculated on the
basis of the model proposed (see text), when fitting the variation of 1/
A4 (B) alone.

0.8

1.0 __- - - - - - - -

A. Temperature effects on the parameters derivable at


zero field

0.9

328 K

0.8

0.5

B (T)

FIG. 3. Variation of parameter R with magnetic field intensity, B (n, in a


0.025 M solution of nitrobenzene in n-hexane, for temperatures ranging
from 292 to 328 K. For the solid lines, see Fig. 2.

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.

In all cases, u R appears to be largely insensitive to the


valueofA 3e (0), within the range 1-5 ns- I As no otherlong
lifetime than 1/A3 (0) is apparent at any temperature in the
LS spectra,A 3e (0) was fixed at 2.3 ns- I , the valueofA2( 0).
For similar reasons, Ase was fixed at 8 ns - I, the value of As'
As previously observed, the fits are sensitive to the ratio
k J k2 rather than to the absolute values of these reaction rate
constants. Therefore, the variation of kl with T was supposed to obey the Smoluchowski equation, wich has been
repeatedly used in Ps chemistry l6

kl (T)

= (2I3000)NA kB (2 + rp.lrs + rslrps) T lv,

(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

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(12)

with k; = 9x 10 ns- I and E2 = 0.37 eV.


Knowing E z, a rough approximation to the value of the
Ps affinity of nitrobenzene (PA) can be made by considering
the following: (i) the forward reaction requires little or no
activation energy as is implicit in Eq. (10); (ii) before reaction, the energy level ofPs (Eo), which is quite possibly in a
bubble within the solvent, is ~0.22 eV, as derived from the
width of the p-Ps momentum distribution. 19,2o Neglecting
the solvation terms for nitrobenzene and for the Ps complex,
this gives PA =Eo + E 2 =O.59 eV which is consistent with
the theoretically predicted value, PA = (1.11 0.81) eV. 21
7

B. Temperature effects on the hyperflne interaction


parameters

The remaining parameters to consider are Tf and b.E


which are only derivable through the variations ~f R and ~f
1/A4(B) with B, either independently or simultaneously.
Several fitting procedures were attempted.
Most generally the values for Tfc and b.Ec derived from
the variations with B of either R or 1/..1,4 (B) alone are concordant, although the uncertainty is usually higher in the
latter case.
Figure 5 shows the change with Tof Tf as derived when
fit.ting Rand 1/..1,4 (B) together. Two regions are apparent
With constant values of Tfc' above 289 K, with a mean value
at (1.56 0.05) and below, at (0.43 0.04); thevalueofTfc
at 264 K, (0.75 0.2) is not included in the latter mean
value, and possibly indicates an increase in Tfc at lower temperature. For comparison, the figure also includes Tfc
= (1.77 0.2), the average of the values previously derived at C = 0.1 and 0.05 M; this average inserts well in the
present plot.
Contrary to Tfc' b.Ec was most generally very badly defined, particularly in the temperature range between 268 and
286 K, where the variation with B of both Rand 1/A 4(B)

appear to be completely insensitive to this parameter. As in


the high temperature region and at 264 K a somewhat constant value was found for b.Ec at ~ 10- 5 eV, a fitting of all
the data at all temperatures was attempted with only three
parameters, Tfc above 289 K and below 289 K, and b.Ec. The
resulting values for Tfc are the same as the average values
given above, obtained when fitting the data for each temperature separately (solid line in Fig. 5), together with b.Ec
= 1.06 X 10- 5 eV. Considering the relevant changes in 0and O-A.' this last value is only meaningful within, roughly, ~
factor of2. The values of b.Emc = Tfc b.Ec = 1.65 X 10- 5 eV
(Tfc = 1.56) or 4.56x 10- 6 eV (Tfc = 0.43) for the Ps
bound-state in n-hexane are very low, compared to b.Em
= Tf b.Evacuo = 0.82 X 8.45 X 10- 4 eV = 6.93 X 10- 4 eV obtained for Ps in pure n-hexane. These give a ratio
b.Emc/ b.Em of 2.4% down to 0.6%, according to the temperature region considered for Tfc' It may be noted that theoretical calculations lead to a value of ~ 2.5%,22 which compares well with the present data. It is worth noting that the
same order of magnitUde is experimentally found for the
ratio of the hyperfine splitting energies for muonium boundstates and muonium. 23
The sharp variation in Tfc around 289 K is not understood at the moment. The implication of interactions between solvent molecules and the Ps bound-state at the level
of the N0 2 moiety cannot be excluded; the change from Tfc
= 0.43 at low T to Tfc = 1.56 at high temperature might
therefore reflect a temperature-assisted deeper penetration
ofPs into N0 2 accompanied by a stronger overlap of the e+
and e- wave functions. On this basis, whether the concept of
bubble and bubble shrinkage at the moment of the boundstate formation 17,24 or, more generally, changes in the dielectric constant and solvation shell are dominant factors has yet
to be established. Anyhow, it is clear that the proposed model is somewhat simplified in its use of parameter Tfc because
Eq. (4), and its equivalent for the Ps bound-state, Eq. (7),
are only valid as long as the wave function ofPs is spherical,
which implies values of Tf c not too far from unity, 9 In spite of
this simplification, the quantitative treatment has been successfully applied to all temperatures investigated.

C. Comparison with other models

2.0
I1c

1.5

1.0

0.5
300

T (K)

FIG. 5. Variation of parameter 17< with temperature, T(K), as derived when


fitting Rand l/il 4 (B) together (open circles), in a 0.025 M solution of
nitrobenzene in n-hexane. Filled circle = average value obtained previously
(Ref. 3) for nitrobenzene concentrations of 0.05 and 0.1 M. Solid lines
= fitting values of 17< for all data, below and above 289 K (see text).

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-

J. Chern. Phys., Vol. 97, No.2, 15 July 1992

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Billard, Abbe, and Duplatre: Bound-state of positronium with nitrobenzene

sity parameters, calculations have been performed on a 0.1


M solution of nitrobenzene in n-hexane at 294 K, with the
assumption that all Ps atoms form a bound-state. 26 With this
crude hypothesis, it is found that the interaction of the positron with only two electrons is sufficient to recover the
anomalous variation of R with B, and the values of the contact density parameters for each of the two electrons are
(Ref. 27) 1/a = 1.65 and 1/b = 0.14.
Whereas Brusa et al. 26 have considered essentially the
mathematical description of a distorted positronium .attached to a molecule to form a bound-state, our approach,
which is based on a wealth of experimental data, is of a more
phenomenological nature. However, the two explanations
are very similar. Actually, the high value of 1/0 = 1.65 as
compared to 1/b = 0.14 shows that one of the electrons involved interacts strongly with the positron, while the contribution from a second electron is only marginal; this fits in
very well with our description. Furthermore, within the errors, the value of 1/0 coincides with the average found in this
work, 1/c = (1.56 0.05). Summarizing, the bound-state
can be described as presenting a singlet and a triplet state, in
such a way that the identities of the components, <l>N02 and
Ps are, to a large extent, preserved. Chemically speaking,
this resembles a loose charge-transfer complex,28 even
though one of the partners of the association is somewhat
unusual, with <l>N02 as the electron acceptor and Ps as the
electron donor.

VI. CONCLUSION

The strong sensitivity of the solution of nitrobenzene in


n-hexane to the magnetic field appears to be dependent on
temperature. These complementary experiments have been
rewarding not only to assess the assumptions of our model,
but also to gain information on the temperature dependence
ofthe hyperfine parameters of the Ps bound-state with nitrobenzene. The absence of sensitivity of the hyperfine splitting,
AEc ' to temperature is not surprising, as this is an intrinsic
parameter. Conversely, some variation of1/c with Tmight be
expected as this parameter can be influenced by the solvent.

1553

However, the abruptness with which 1/c changes around 289


K is not yet understood.
At present, the effect of temperature and of magnetic
field have been studied extensively and it seems necessary to
consider other possible factors. In this context, examining
the influence of pressure and of the nature of the solvent
appears promising.
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