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Billard 1992

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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

View Table of Contents: http://scitation.aip.org/content/aip/journal/jcp/97/2?ver=pdfcov

Published by the AIP Publishing

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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

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

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

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)

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) =

~fO IjAj(B)exp[

-Aj(B)t]dt

(2)

III. THEORETICAL BASIS

A. Effects of the magnetic field

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)

= 1/AEvacuo

(4)

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,

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

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:

(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)

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)

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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J. of

Chern.

Phys., Vol.

97, No.2,

15 July

1992

137.112.220.85 On: Fri, 12 Dec 2014 16:47:15

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

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;

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)

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.

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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)

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 __- - - - - - - -

zero field

0.9

328 K

0.8

0.5

B (T)

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.

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)

(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)

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

parameters

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)

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.

2.0

I1c

1.5

1.0

0.5

300

T (K)

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-

137.112.220.85 On: Fri, 12 Dec 2014 16:47:15

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

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

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.

IG. Fabri, G. Poletti, and G. Randone, Phys. Rev. A 35,80 (1963).

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