and K. D.

BECKER:On the Optical Absorption Edge in NiO

J. PATTANAYAK 833

phys. stat. sol. (b) 188, 833 (1995)

Subject classification: 78.40; 71.35; S10.1

Institutfir Physikalische Chemie und Elektrochemie und SFB I73 der Universitat Hannover')

On the Temperature Dependence

of the Optical Absorption Edge in Nickel Oxide
BY
J. PATTANAYAK
and K. D. BECKER')

Results are reported of a high-temperature investigation (up to lo00 "C) of the optical absorption edge
in NiO. An approximately exponential dependence of the absorption coeficient on photon energy is
observed. The absorption coeficient is found to be independent of oxygen partial pressure, i.e., of
native lattice defects. The temperature dependence of the edge gives evidence of strong exciton-phonon
coupling in NiO.
Es wird iiber Messungen des optischen Absorptionsspektrums von Nickeloxid, NiO, bei hohen
Temperaturen (bis loo0 "C) berichtet. Im Bereich der Absorptionskante wird ein naherungsweise
exponentieller Anstieg des Absorptionskoefizienten mit der Photonenenergie beobachtet. Der Absorp-
tionskoeffizient stellt sich als unabhangig vom Sauerstoffpartialdruck heraus, d. h. als unabhangig von
der Konzentration intrinsischer Gitterfehler. Die Temperaturabhangigkeit der Absorptionskante weist
auf eine starke Exciton-Phonon-Wechselwirkung in NiO hin.

1. Introduction
A feature exhibited by a large variety of solids, like insulators or semiconductors, crystalline,
disordered, glassy or amorphous, ionic or covalent solids, is an optical absorption that, in
the region of the fundamental absorption edge, increases approximately exponentially with
energy. At high temperatures, the linear absorption coefficient, a, as a function of photon
energy, E, and temperature can be described by the following empirical expression, known
as Urbach's rule [l, 21:
a(E) = a. exp [-a(Eo - E)/kT]. (1)
At sufficiently high temperatures, a. and Eo are constants which are characteristic of the
material under consideration. As a rule, the temperature dependent steepness parameter a
takes values in the order of unity at high temperatures [3]. The convergence point, Eo, of
semilogarithmic plots of the absorption coefficient at various temperatures usually takes
values near to the width of the optical band gap.
The origin of this seemingly universal behaviour has been, and continues to be,
controversial. Theoretical explanations of the Urbach edge are based on the idea that the
sharp absorption edge of the rigid band model is broadened by some mechanism. Over
the years, numerous theories have been put forward by different authors and we will mention
only few of them. Toyozawa and coworkers [4, 51 have ascribed this broadening to
exciton-phonon interactions. In their theory the origin of the Urbach rule is founded in

I) Callinstr. 3-3a, D-30167 Hannover, Federal Republic of Germany.

') Author to whom correspondence should be addressed.
834 J. PATTANAYAK
and K. D. BECKER

the momentary localization of the excitons by lattice deformations. A different approach

has been adopted by Dow and Redfield [6], who explained exponential absorption edges
by ionization of excitons induced by internal electric fields. In pure crystals the required
internal electric fields are produced by LO or TA phonons; in doped semiconductors they
may also be caused by charged impurities [7]. Recent experiments on mixed crystals, indeed,
seem to indicate the existence of different distinct causes giving rise to Urbach behaviour
[8]. An alternative explanation of Skettrup [9] considers the thermal fluctuations of the band
gap energy. Pankove [lo] and Dunstan [ll ] have invoked tails in the density of states
extending into the forbidden gap. For a compilation of pertinent results and a theoretical
discussion, see the reviews by Kurik [3] and Sumi and Sumi [12]. It is the purpose of this
work to extend the range of compounds in which this phenomenon has been studied by
presenting the first high-temperature investigation of the optical absorption edge of a
semiconducting transition metal oxide with NaCl structure. In the present paper results
are reported for NiO.

2. Experimental

Optical spectra have been measured using a Perkin-Elmer Lambda 9 spectrophotometer

modified to our special requirements. The quantity measured in the experiments is the
absorbance, A, of the sample, which is defined as A = lg ( I , / I ) , where I , is the intensity of
the incoming and I that of the transmitted light. According to Lambert-Beer's law, we have
A = ad + A,, where a is the (linear) absorption coefficient and d the thickness of the
absorber. A , = -21g(l - R ) represents losses due to the reflectivity, R , of the sample.
Details of the experimental set-up suitable for high-temperature optical spectroscopy may
be found in [13]. In the present work, a Xe high-pressure lamp has been used for illumination.
Most of the measurements have been done on a set of four samples with thicknesses of
120,210, and 535 nm (on S O , glass) and of 4.6 pm (on single crystalline MgO). The 4.6 pm
NiO absorber was prepared by decomposition of NiBr, of 99.99% purity [14]. Other
absorbers were prepared by reactive sputtering using 99.99% pure metal. The thicknesses
of these thin films were determined from their characteristic interference patterns. In the
calculation of the absorption coefficients of the two thickest absorbers, Fig. 2, an energy
independent reflectivity of R = 0.17 of bulk NiO [15] was taken into account.

3. Results and Discussion

High-quality optical spectra of NiO, including the region of the absorption edge, have
already been reported by Newman and Chrenko [15] for 70K and room temperature.
Our room temperature data, Fig. 1, are in good agreement with the spectrum observed by
these authors. Fig. 2 shows our results for the absorption coefficient in the region of the
absorption edge for several temperatures between room temperature and 1000 "C. However,
in comparison with other cases, e.g., alkali and silver halides [2, 3, 161, the range of the
exponential behaviour of the absorption coefficient is rather limited in NiO. This is due to
the d-d ligand-field transitions, which are the characteristic features of the optical spectra
of transition metal compounds. As can be recognized from Fig. 1, there are such transitions
at about 26000, 24000, and 22000 cm-' (at room temperature). Especially the two
high-energy transitions strongly interfere with the shape of the absorption edge at elevated
temperatures. The energy parameter Eo obtained by extrapolation to the convergence point
On the Temperature Dependence of the Optical Absorption Edge in Nickel Oxide 835

15 20 25 30
Wave number(lo3cm -9-
Fig. 1. Room temperature spectrum of NiO. Absorbance A = lg ( I o / I )as a function of photon energy;
absorber thickness d = 4.6 pm
is given by Eo = (31300 f 150) cm-' = (3.88 f 0.02) eV, which is in agreement with the
energy of the optical gap of about 4 eV reported by Newman and Chrenko [15] from their
optical study. The steepness parameter as a function of temperature is shown in Fig. 3. It
is interesting to note that the high-temperature limit of the a-parameter turns out to be
considerably smaller than that found in the isostructural alkali and silver halides, where
values usually range between 0.6 and 1.0 [3, 161.
A question of fundamental importance to be addressed in the discussion of exponential
absorption edges is whether the observed Urbach behaviour is an intrinsic or an extrinsic
property of the solid under consideration. Indeed, recent results on (GaJn, -,),Se, [8] and
Zn,Cdl -,Se [ 171 mixed crystals indicate the existence of at least two distinct contributions
giving rise to Urbach behaviour: one being related to lattice vibrations and the other resulting
from structural and compositional disorder. However, the degree of compositional disorder,
x,was considerable in these studies (0 5 x 5 0.4) [8] and 0 5 x 5 1 [17]). In other cases
[18], however, it has been shown that even small impurity concentrations of the order of
(KC1:Br) may have a marked influence on the Urbach behaviour. In our study we
used two different procedures for the preparation of the NiO thin films, which resulted in
identical behaviour of the absorption coefficient near the edge. We, therefore, conclude that
impurities clearly can be excluded from the discussion in the present case.
Transition metal oxides, like NiO, provide the unique possibility to test for a possible
influence of intrinsic, native lattice defects on the absorption edge at constant temperatures.
This is made possible by the fact that nickel oxide, Nil -aO,is a nonstoichiometric compound.
Its composition can be adjusted and varied isothermally by means of external atmospheres
of appropriate oxygen partial pressures. Oxygen is incorporated into the crystal resulting
in the formation of singly and doubly charged cation vacancies and electron holes, VLi,
Vki, and h', respectively, according to
1/2 0, s VNi + h' + 0;; (24
836 and K. D. BECKER
J. PATTANAYAK

I6
I 1 I I I I I I

.
I.

,I-
E
v
u
a 5
9

2: 200 oc
3: 400 o c
4 : 600 O C
5 : 8OOOC
5 6: 1000°C

18 20 22 24 26 28 30 32
Wave nu mber(103cm-')--c
Fig.2. The optical absorption edge in NiO at different temperatures (in air). Linear absorption
coefficient as a function of photon energy

and/or
112 O2 e Vki + 2 h' + 0; .
Neutral cation vacancies have been shown to play no important role in NiO [19].
At 1000 "C,the deviation from stoichiometry, 6 = [Vx] + [Vki], of pure Nil -,O in oxygen
is about [19]. Here, the square brackets denote molar fractions. This value is reduced
by about one order of magnitude if the oxygen partial pressure, po2, of the surrounding
gas is reduced to roughly 10 Pa [19]. Hence, oxygen partial pressure constitutes an important
experimental variable in the investigation of defect-dependent properties of transition metal
oxides. The variation of po2 allows to make appreciable isothermal changes in native defect
concentrations. We believe that the present study represents the first example of this kind
in the context of the optical properties of solids in the edge region. Fig. 4 shows results of
an in-situ experiment in which defect concentrations of the sample have been changed in
this way isothermally at high temperatures. As can be seen, there is virtually no influence
of oxygen partial pressure on the absorption coefficient in the edge region. We thus conclude
that the observed Urbach behaviour represents a truely intrinsic property which is unaffected
On the Temperature Dependence of the Optical Absorption Edge in Nickel Oxide 837

Fig. 3. Steepness parameter in NiO as a function of temperature

by the concentration of the native lattice defects formed by the incorporation of oxygen,
see (2). The maximum in the AA values observed in Fig. 4 at energies around 22000 cm-'
may be due to colour centres in NiO [13].
We will discuss the results of our experiments with reference to the models proposed by
Toyozawa and coworkers [4,5]and by Dow and Redfield [6], in which exponential absorption
edges are explained by processes involving excitons. The quasi-chemical formation reaction
of the exciton in NiO can be written as

0 (h', e') . (3)

The present finding of the insensitivity of the absorption edge to oxygen partial pressure,
i.e. to native defects formed by reactions (2), is clearly compatible with Toyozawa's model
of the momentarily localized exciton [4, 51, for which no influence is expected from
defects, like vacancies or impurities. Hence, a change in defect concentration induced
by oxygen partial pressure variations is predicted, in the framework of this model, to
have no consequences. Also the concentration of excitons, [(h', according to (3), is
independent of po2 and is a function of temperature exclusively. In contrast, in models
of the Dow-Redfield type, the charged lattice defects involved in the reactions of (2)
will produce internal electric fields and thus may exert an influence on the position
and the shape of the absorption edge. However, it is not clear, whether the variation in
defect concentrations achieved in the present case, Fig. 4, would suffice to influence the
absorption edge noticeably. This situation may be different in other transition metal
monoxides as, e.g., COO and MnO, where much higher native defect concentrations can
be reached.
In the Toyozawa model [4, 51, the steepness parameter c represents the exciton-phonon
coupling, while in the Dow-Redfield model [6, 71 it is a measure of the rms amplitude of
the inner-crystalline electric fields. In both models, however, the temperature dependence
838 and K. D. BECKER
J. PATTANAYAK

t
$
0
2’o
1.5 0.050:
t
n
L
0
m

1.0 0.025

0.5 0

-
0
10 15 20 25 30
Wave number(103crn-’)-
Fig. 4. Absorption edge at different oxygen partial pressures. The spectrum measured at air (po,
= 0.213 x lo5 Pa) and in N, ( p o , zz 10 Pa) is shown as open circles and full line, respectively. Also
shown is the difference, AA, of the two absorbances; absorber thickness d = 120 nm

of this parameter is given by an expression of the form

a(T) = 00(2kT/ho)tanh (ho/2kT). (4)

Here ho is a characteristic energy of the lattice vibrational mode interacting with the exciton
and a. is the high-temperature limit of the steepness parameter. The line drawn through
the experimental data, Fig. 3, is given by (4) with ho = 0.051 eV (413 cm-I). According to
Gielisse et al. [20], the LO and TO lattice vibrations in NiO have wave numbers of 580
and 400 cm- I, respectively. The agreement of our data with the transverse optical mode
may be fortuitous, however, it is clearly of the right order of magnitude for lattice vibrations.
For the prefactor go, we have determined a value of a. = 0.21, which turns out to be rather
low when compared to the isostructural alkali and silver halides, see Table 1.
In the theory of the momentarily localized exciton [4,5,21], a. can be written as a. = s/g,
where s is a numerical factor of order unity, and where g = ELJB represents the
exciton-phonon coupling parameter. Here, EL, is the lattice relaxation energy, i.e., the energy
gained by exciton formation due to lattice polarization, and B denotes the half width of
the exciton band. If the relaxation energy exceeds a certain limit, excitons may become
localized by being trapped by the lattice distortion they have induced. In the case of
three-dimensional cubic lattices, Schreiber and Toyozawa [21] have predicted self-trapping
ofexcitons to occur for g > 0.92.Thus, based on measurements of the exponential absorption
edge, it can be predicted whether self-trapping of excitons is to be expected or not. The
On the Temperature Dependence of the Optical Absorption Edge in Nickel Oxide 839

value of the s-parameter depends on the nature of the optical transition. According to
Schreiber and Toyozawa [21] s = 1.5 holds for direct transitions. Thus, self-trapping is
expected for steepness parameters a, 6 1.64. For indirect transitions these authors derived
s = 0.85. In this case self-trapping is predicted for a, 6 0.88 [22]. In the alkali halides
exciton localization occurs as well as in AgCl, Table 1. A borderline case is provided by
AgBr (a, = l.O), where the transition is an indirect one. In agreement with the above
prediction, the exciton in AgBr, indeed, has been found to be in the free exciton state [23].
According to the above criteria, independent of the nature of the transition, the exciton in
NiO is self-trapped (ao = 0.21) and the small value of a. gives evidence of the strong
exciton-phonon interaction prevailing in this compound.
Finally, we would like to draw attention to a simple expression for the exciton-phonon
coupling parameter g. Toyozawa [24] has given the following approximate expression in
terms of the static and optical dielectric constants E, and too,
the effective reduced mass of
the exciton, p*, and the lattice constant a,:

Table 1
Dielectric constants E,, E,, lattice constants a,, experimental steepness parameters oo,
effective reduced masses of excitons p*, and masses of electrons mr and m,* of NaC1-type
crystals

NaF 5.05 1.74 4.620 0.69 0.68 0.19

NaCl 5.90 2.34 5.628 0.741 0.67 0.32') 0.348)
NaBr 6.28 2.59 5.973 0.765 0.68 0.19')
NaI 7.28 2.93 6.473 0.845 0.71 0.18')
KC1 4.84 2.19 6.293 0.745 0.56 0.32') 0.34h) 0.43') 0.92')
KBr 4.90 2.34 6.600 0.114 0.56 0.28') 0.31') 0.37') 0.70')
KI 5.10 2.62 7.065 0.830 0.56 0.23') 0.26') 0.21') 0.30') 0.32') 0.48') 0.54')
AgCl 12.3 4.0 5.547 0.82 1.05 0.37") 0.30') 0.43 ')
AgBr 13.1 4.6 5.174 1.0 1.17 0.28") 0.21') 0.29 ')
NiO 11.75 5.7 4.168 0.21 1.03

") From [29].

') From [30].
") Data for alkali and silver halides according [16] and [3], respectively; o,(NiO) is from the present
work.
d, According to (5).
') Calculated from exciton binding energies G(eV) = 13.60(p*/c2).
') G = E , - El, calculated using E , and El from [31]; E = E , from [29].
Miyata and Tomiki [32].
h, Tomiki [33].
') Tomiki et al. [34].
j) Ramamurti and Teegarden [35].
') Hodby [36].
') Jenkin et al. [37].
") G from [27]; E = E~ from [29].
840 and K. D. BECKER
J. PATTANAYAK

Fig. 5. Plot of the experimental steepness pa-

rameters g o , Table l, as a function of (&*/&) a;,
according to ( 5 )

where E* is the effective dielectric con-

stant, E* = &('; - &;')-', and uH is the
Bohr radius. As shown by the 0, versus
( E * / E ~ , ) ui plot of Fig. 5, (5) possesses the
remarkable property to divide the 0 ,
parameters from Table 1 into three groups,
the sodium halides, the potassium ha-
lides, and AgCl, AgBr, and NiO. Ac-
cording to (5), the slope of this plot is
proportional to p*3. Using the above
( E* / d )a%(103nm3)- s-value of 1.5, one obtains reduced exci-
ton masses of about 0.7 and 0.6 for the
sodium and potassium halides, respectively, and of around 1 for the silver halides and NiO,
see Table 1, where exciton masses derived from (5) are denoted by p*(oo). Thus, by means
of (5) at least reasonable estimates can be derived for the reduced exciton masses of a large
range of materials.
Conventionally, reduced exciton masses have been determined from optical transition
energies to exciton states En = E , - G/n2, where the binding energy G of the exciton is
given by G(eV) = 13.6O(p*/c2). Such literature data and data derived from reported
transition energies are shown in Table 1 as p*(G). As can be seen, the p*(a,) values are
considerably larger than the exciton masses deduced from binding energies. As has been
pointed out before [25,26], however, the determination of p*(G) is hampered by the difficulty
of the proper choice of the dielectric constant, E, that is to be used in the evaluation of
p*(G). As discussed by Knox and Teegarden [25] and Hodby et al. [26], instead of the
conventionally used optical dielectric constant, E = E ~ a , somewhat larger value should be
employed for E, where the upper limit of E would be represented by the static dielectric
constant E,. For the calculation of p*(G) in Table 1, we have used E , in the case of alkali
halides, while E, has been used in the case of silver halides, see [27]. In view of the likelihood
that electron holes are heavy in the alkali and also in the silver halides, it has been argued
[25, 261 that p* values should be close to the values of the effective electron masses. Hence,
p* should either be of magnitude similar to that of band masses, or to polaron masses of
electrons: p* z rn: or p* FZ mt. In the case of the potassium halides, the reduced exciton
masses derived from binding energies are fully compatible with the reported band masses,
while our data for p*(a,) are more consistent with polaron masses, see Table 1.
The obvious discrepancies between p*(a,) and p*(G) observed for AgCl and AgBr in
part may be due to problems of (5) in treating properly the polarization effects in crystals
composed of ions possessing d-electron shells. However, the comparison of p*(o,) with
p*(G) and with the various electron masses may be misleading also for other reasons. The
cited exciton and electron masses from the literature usually have been determined at low
temperatures, while our optical measurements on NiO, and also the other Urbach-type
experiments reported in Table 1, yield 6, data that are valid for much higher temperatures.
On the Temperature Dependence of the Optical Absorption Edge in Nickel Oxide 84 1

Information on a possible temperature dependence of effective electron masses are scarce.

According to Baxter et al. [28], for example, the polaronic electron mass in AgBr at low
temperatures adopts a value of 0.29 and possesses a high-temperature limiting value of 1.3,
which is in good agreement with p*(o,) = 1.17.In view of this evidence, we tend to conclude
that at least part of the discrepancies, which were also encountered in the case of alkali
halides, may be due to the mere fact that p*(ao)and p*(G) data were obtained at, and are
valid for, quite different regions of temperature. We therefore consider p*(oo) = 1.0, a
realistic estimate of the high-temperature reduced exciton mass in NiO.

4. Conclusions
This study has shown that the observed exponential absorption edge in NiO is of intrinsic
origin and, in particular, that the optical process giving rise to the Urbach behaviour is
not affected by native lattice defects. The steepness parameter a. obtained from the
temperature dependence of the absorption edge gives clear evidence of a strong exciton-
phonon coupling in NiO, which is found to be much larger than in the isostructural alkali
and silver halides. In the framework of Toyozawa’s theory of the excitonic nature of
exponential absorption edges, the exciton in NiO is found to be self-trapped. An estimate
of p* = 1.0has been derived for the effective reduced high-temperature exciton mass in NiO.

Acknowledgement
The authors would like to acknowledge financial assistance from the Fonds der Chemischen
Industrie.

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(Received December 12, 1994)