Journal of Physics D: Applied Physics

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J. Phys. D : Appl. Phys., Vol. 8, 1975. Printed in Great Britain. 01975

Determination of gas temperature from unresolved bands in the

spectrum from a nitrogen discharge

D M Phillips
Australian Defence Scientific Service, Department of Defence, Weapons Research
Establishment, Salisbury, SA 5108, Australia

Received 25 June 1975

Abstract. A spectroscopic technique is described for determining the gas temperature

associated with unresolved bands in the second positive system of the emission spectrum
of molecular nitrogen. Projection operators are used in an iterative technique to estimate
gas temperature from the shape of a band. The technique is applied to temporally
resolved spectra recorded during the glow stage of spark breakdown in nitrogen. The
gas temperature is shown to rise from about room temperature at a rate that is in
agreement with the electrical power input to the glow discharge. This technique could
be of use for studying the effect of gas temperature on the performance of the nitrogen
laser.

1. Introduction

Over the last decade, spark breakdown in gases has become better understood through
the use of image converters and intensifiers and fast photomultipliers (Haydon 1967).
The measurement of fundamental discharge parameters, however, still remains difficult.
In spectroscopic studies of hydrogen sparks, Meyer (1967 and 1969) measured electron
temperatures and densities but was unable to measure gas temperatures because the
emission spectrum of molecular hydrogen is dominated by the dissociation continuum,
which has no rotational structure (private communication). Cavenor and Meyer (1969)
suggested that thermal dissociation following a rise in gas temperature was responsible
for the transition from a diffuse to a filamentary glow structure which they observed in a
hydrogen discharge. Without a knowledge of the gas temperature, however, the possible
processes of electron impact and thermal dissociation cannot readily be distinguished.
Unlike hydrogen, the intense emission spectrum of molecular nitrogen has a well
defined rotational structure. The technique described in this paper for analysing
the rotational structure to determine gas temperature was developed for studying
spark breakdown in nitrogen. The technique could also be useful for studying the
nitrogen laser, since its optical gain, and hence its efficiency, is strongly dependent on gas
temperature.
Kaslin and Petrash (1968) have shown theoretically that the optical gain of a nitrogen
laser increases significantly on cooling due to a concentration of molecules in states of
low rotational quantum number and to the narrowing of the Doppler widths of these
rotational lines. Their theory predicts a tenfold increase in gain when the temperature
is lowered from 300-100 K. Although direct measurements of gain were not carried out,

507
508 D M Phillips

this prediction was supported experimentally by three observations. The total laser
output power increased by a factor of 1.5, a sharper increase occurred in the output
power in the 0-1 band; and laser output was observed for the first time in the 1-0 band.
The fall in output power commonly observed when nitrogen lasers are operated at
high repetition rates could be partly due to a rise in gas temperature and an associated
fall in gain. In studying the performance of the nitrogen laser, therefore, it would be
useful to be able to measure the gas temperature, especially using a spectroscopic method
which would not perturb the plasma.
In molecular nitrogen, the clearest band structure for rotational analysis is the 0-0
band of the Nz' (B-X) system. It has been used by Bromer and Spieweck (1965) to
determine the gas temperature in a 50 Hz discharge and the afterglow in nitrogen at a
pressure of about 700 Pa. It has also been used by Bleekrode and van Benthem (1969)
who studied a hollow cathode discharge at a pressure of about 1 Pa.
Unfortunately, at higher pressures, the Nz+(B-X) system becomes less useful because
its intensity drops very much more rapidly with pressure than does the NZ(c-B) system.
This is because the cross section for collisional de-excitation of the Nzf B state (measured
by Johnson and Fowler 1970) is about 10 times that for the Nz c state (measured by
Nichols and Wilson 1968 and Calo and Axtmann 1971).
The intense Nz (c-B) system has been used to determine gas temperatures in high-
pressure discharges but the analysis is complicated, because it is a triplet system and
involves a transition from Hund's case (a) to case (b) at higher values of the rotational
quantum number. This system has been used by Prinzler (1961) to measure gas tempera-
tures in a steady glow discharge at a pressure of 100 kPa and by Robinson (1964) in a
hypersonic flow at 18 kPa.
In both of these examples, the discharges were steady state and high-resolution
spectra could be obtained and individual lines identified. The experimental results
described in this paper were obtained using a transient spark in nitrogen, which emitted
insufficient light for high-resolution spectra to be obtained with nanosecond time resolu-
tion. As a result, the individual lines were not resolved.
Slovetskii and Sokolov (1974) have recently described a method for determining
rotational temperatures from the shapes of unresolved bands. First, they calculated the
theoretical shapes of bands, taking into account the measured slit function and dispersion
of the spectrometer. Then, they either matched the experimental band shape to a theoreti-
cal one or compared band widths at 113 of the peak height. The technique was applied
to the emission spectrum of CO from a glow discharge in COZ.
The present study describes another technique for determining rotational tempera-
tures from the shapes of unresolved bands. This method, however, requires no detailed
knowledge of the slit function or dispersion of the spectrometer. A projection of the
whole band shape is defined to minimize the error in the temperature calculated and to
be insensitive to the width of the slit function. The projection is used in a rapidly con-
verging iterative process, which is applied to an experimental study of spark breakdown
in nitrogen.

2. Theoretical intensity distribution among rotational lines

The second positive system, which dominates the emission spectrum from the nitrogen
spark, arises from the c311u-B3ng transition in the nitrogen molecule. This triplet system
exhibits three sub-bands corresponding to the transitions 3110-3110, 3111-3111, and 3 b - 3 1 1 2 .
 Determinatiori of gas temperature 509

Each branch within a sub-band is split by A-type doubling in high dispersion but as the
wavelength splitting is less than about 0.004 nm it may be neglected. Even the triplet
splitting of less than about 0.08 nm is smaller than the separation of rotational lines
except near the band head. Since the present theory is intended for application when the
rotational lines remain unresolved, it is satisfactory to neglect both spin splitting and
A doubling.
The wavelength of the general rotational transition CU’J’-BU”J” may be calculated
from
5 2
A;$$,=
1
128,
p=o y=o
Y,”, ( V ’ f p [J’(J’+ l)]q- Y,”,(V”+4)qJ”(J”+Ill*
1-l

where the coefficients Too=T,, YP0, and Ypl are given by Benesch et a1 (1965) and
Yp2(=De,B e . . .) for the B state are given by Buttenbender and Herzberg (1935). The
values of YPz for the c state were deduced by fitting a cubic to the values of D~ given by
Buttenbender and Herzberg. Finally, na is the refractive index of air.
The radiant flux Fnvj of the general rotational transition (using the terminology and
notation of Schadee 1971) is
Fnvj= h vnz;jNn,v,j,Anvj, (2)
where FnvJ ( = F$$$) is the radiant flux ( W ) ,VnoJ is the frequency of the transition (Hz),
N n , v , ~isl the number of molecules in the upper general rotational state n‘v’J’, and
A n v j is the transition probability for spontaneous emission (s-1).

2. I . Transition probability of a general rotational line

The transition probability for a band is independent of the rotational quantum number
of the initial state since the electronic and vibrational motion of a molecule is essentially
independent of its rotational motion and this has been confirmed experimentally by
Johnson and Fowler (1970), therefore

If the general line strength SJ is defined so that it satisfies the normalization

given by Schadee (1971), the transition probabilities of a general rotational line and a
band are related by

in Schadee’s notation. For the C-B transition in molecular nitrogen

X = l and S = l
so that

The line strengths SJ depend on whether the transition belongs to Hund’s case (a)
or (b). The C-B transition in nitrogen changes from case (a) at small values of J to case
(b) at large values of J. The values of the line strength in this general case are given by
510 D A4 Phillips

KQV~C (1966)
S but the expressions are more complicated than is justified for the present
theory. The values of SJ for Hund's cases (a) and (b) are given by Bud6 (1937). Since
at small values of J case (a) applies and at large values of J the difference between the
cases (a) and (b) are negligible, the line strengths for Hund's case (a) were used for all
values of J . When the line strengths for the three branches are combined, i.e. neglecting
spin splitting, the general line strengths reduce to the following forms for the P, Q and
R branches :
P(J+ 1 ) = 6 ( J + 1)- lO/(J+ 1)
Q ( J ) = lO/J+ lO/(J+ 1)
R ( J - 1)=6J- lO/J (4)
where J = J'

2 . 2 . Populution of a general rotational state

The number of molecules in the general rotational state CU'J',which occurs in equation
(2), can be related to the number of molecules in the vibronic state by CUI

(2J'+
NCv'J' - _ -
-- W
- _1)_ - hc
exp- [_ ~ (J'+
_BvJ' ~
l)/kT]_---
Ncvt
J'=iA+P,(
(2J' + 1) exp [-he BvJ' ( J ' + l)/kT]
when thermal equilibrium applies (see Tatum 1967). When the temperature is large
compared with the energy separation of the rotational levels this expression simplifies to
IZC Bv
N W J ~= N w -( 2 J ' + 1) exp [ - hc BVJ' ( J ' + l)/kT]. (5)
kT
By combining equations (2), (3) and ( 5 ) the radiant flux from the general rotational
transition CV'J'-BV"J" of molecular nitrogen in thermal equilibrium at a temperature
Tis:
FCV'J' __
v"J" - D
SJ
+
exp [ - / I C B J ( J ' l)/kT] (6)

where the constant is given by

D =h2C Bv VELA%- Ncvtl6k.

2.3. Effect of temperature and line width on barid shape

The intensity distribution in a band is affected by the width of each rotational line. The
width of a rotational line may be due to gas processes such as Doppler or Stark broaden-
ing or it may be due to instrumental effects such as the slit width of the spectrometer.
These effects produce different line shapes which theoretically extend to infinity. For
computational simplicity the finite line shape
a - (2Ah/W)2
(7)
g ( A h ) = ~ + ( ~ - -(2Ah/W>z
2)
was used, since it is a reasonable approximation to commonly encountered line shapes.
It has a maximum of g (O)= 1, a width at half maximum of W , and the wings extend to
+
5- wa112.
 Determination of gas temperature 511

The shape of a vibrational band at a temperature T and line width W can be calculated
using equations (6) and (7). The results of several such calculations are shown in figure 1.
The top two band shapes were both calculated with a narrow line width of 0.02 nm.
It can be seen that at the higher temperature of 800K the intensity of the band head
decreases while the lines for high values of J increase in intensity. The lower two band
shapes, which were calculated for the large line width of 0.2 nm, show the same trend
even though the individual lines are no longer distinguishable. It is clear, therefore, that
the shape of a vibrational band depends on both temperature and line width.

0 00
0 101
0 051

“i,,
=0 00L
-l A ’
ZO 04,

E 0 02
.ea
200 , ,
_-

0 00 --_U

Wavelength (nm)

Figure 1. Dependence of band shape on rotational temperature and line width:

Temperatures) 300 800 300 800

Linewidth(nm) 0.02 0.02 0.2 0.2

3. Theory of determination of rotational temperature and line width

Since the shape of a vibrational band is determined by the rotational temperature and
line width, these two parameters can in principle be calculated from an observed band
shape. In practice, noise present in the observed spectra introduces errors into the
estimated values of these parameters. In order to minimize these errors, the technique
described in this section is based on three criteria. Firstly, maximum use is made of the
available data by analysing the whole band shape. Secondly, the analysis of the band
shape is designed to minimize the variance of the estimated temperature. Thirdly, the
temperature is estimated in a manner that is insentitive to the line width.
512 D M Phillips

3 . I . Unbiased estimators of rotational temperature and line width

The theoretical shape of a band at a rotational temperature T and line width W is repre-
sented by a vector f ( T , W ) , in which is the light intensity at the wavelength X g .
Similarly, the light intensity in an observed band is represented by y . Both are normal-
ized so that
Cfi=1 and z y y ~ = l . (8)
i i

The observed shape is assumed to be a random departure from the theoretical shape,
hence the expected value of JI is
E(y)=f(T, w. (9)
The observed band shape is analysed by calculating the projections of y on to two
constant vectors a and b, namely
Y=u’y and Z=b’y, (10)
and similar projections off, namely
F ( T , W)=u’f(T, W ) and G ( T , W ) = b ’ f ( T ,W ) . (1 1)
Estimators and W of the rotational temperature and line width are then defined by the
simultaneous equations
F(?, @)= Y ,
G ( P , FV)=Z. (12)
The variables f and J@ so defined have the desirable property that they are unbiased
estimates of T and W , since the above equations show that
E ( F ( F , FV))=E(Y)=F(T,W )
and
E ( G ( ? , @ ) ) = E ( Z ) = G ( T ,W ) .

3.2. Estimators of minimum unriance

Use of the projection operators a and b allows the whole band shape to be taken into
account. The projector a is now defined to minimize the variance of the estimated
temperature and to be insensitive to line width, while b is defined conversely. The vari-
ance of can be related to the variance of Y through the first few terms of the Taylor
expansion
Y-F(T, W)=(T-T) &F(T, W)+(W-W) awF(T, W).
To ensure that Y - P is insensitive to line width and that its relation to F-T is simple,
the conditions
awF ( T , W )= O and aTF( T , W )= 1 (14)
are imposed. It follows that
Y - F ( T, W )= f - T (1 5 )
and hence that the variances of ?and Yare equal and given by
u p = ay2 = a’ vu (16)
 Determination of gas temperature 513

where
(17)
is the covariance matrix of y .
For the variance of to be minimum, a must satisfy the variational equations
vu - = o (18)
in which h and p are Lagrange multipliers. The solution of these equations is
a = A v-1 [ f T --fW(fT‘ V-lfw)/(fw’V-lfw)l (194
where
A = [ f T ’ v-lfT - ( f T ’ V-lfw)2I(fw’v-1fw)l-1 ( 19b)
and where f T = a T f etc. Similarly, for @’ to have minimum variance and be insensitive
to rotational temperature, the projector b is

If it is assumed that the random departures from the theoretical band shape (vi-h)
are independent and that they have the same variance u2,the covariance matrix becomes

The equations (19) and (20) then reduce to

a = [fT -fw(fT’fwifw2)1 [fT2- (fT’fw)2ifw21-1
and
b = [fw --fT(fT’fWifT2)1[fW2- (fT’fw)”T2>-1*
These equations show that U is the projection of f T orthogonal tofw and b is the reverse.
The projection operators for rotational temperature and line width, CI and b respec-
tively, are shown in figure 2 for the theoretical shape f of the 0-3 band of the NZ (c-B)
system at a gas temperature of 500 K and a line width of 0.2 nm. It can be seen that the

-0
A

Wavelength (nm)
~ 1000-
L L
CO3
5 %-lOOo-
e
e %3000.

-2 J

Figure 2. Projectors for rotational temperature and line width at 500 K and 0.2 nm.
514 D M Phillips

projector for rotational temperature is positive at wavelengths in the band tail, which
increases in intensity at high temperatures. However, near the band head, the intensity
of which reduces at high temperatures, the projector is negative. Consequently, the
projection o f f on to a (equation 11) always increases with increasing temperature.
Similarly, the projector for line width is positive at both edges of the band head and
negative at the centre. Thus, the projection off on to b (equation 1 1) always increases
with increasing line width.

3.3. Verijkation of iterative process

An iterative process using the above theory can now be defined. Let TI and W1 be the
initial estimates of the rotational temperature and line width used to commence the
iteration. The vectors a1 and bl are first evaluated at TI and "1 and then used to cal-
culate Y1 and 21 from equation (10) and F1 ( T I , W1) and GI ( T I , "1) from equation
(11). Taylor expansions about (TI, Wl),such as that used to derive equation (15), yield
new estimates of temperature and line width given by

Since the above expressions for temperature and line width are derived from the
first-order terms of a Taylor expansion, they should be reliable for small corrections.
This was checked theoretically for the 0-3 band of the N2 (c-B) system and the results
are shown in figure 3. A band shape was first theoretically simulated using the theory in

on true values.
 Determination of gas temperature 515

92 at a temperature and line width denoted in figure 3 by ‘true rotational temperature’

and ‘true line width’. Then the initial values of 500 K and 0.2 nm were used in equation
(24) to yield the ‘estimated rotational temperature’ and ‘estimated line width’ shown in
figure 3. The estimated values are read from the rectangular grid at the intersection of
the curves corresponding to the true values. For example, when the band shape sim-
ulated at the true rotational temperature of 400 K and true line width of 0.3 nm was
analysed with this technique, the result was an estimated rotational temperature of 413 K
and an estimated line width of 0.284 nm. The results in figure 3 confirm that the esti-
mated values closely approach the true ones when the correction is small, but become
inaccurate for large corrections.
By repeated application of the above process, the iteration converges to the true
values of gas temperature and line width. This was verified using theoretical band shapes
at temperatures from 200-800 K and line widths from 0.1-0.3 nm. The convergence is
rapid under these conditions-usually taking only 3 or 4 steps.
As a final test of the iteration process, an experimental band shape was simulated
by superimposing random noise with a gaussian distribution on to the theoretical
shape of the 0-3 band of the N2 (c-B) system at a temperature of 500 K and a line width
of 0.2 nm. The iteration rapidly converged to T=487 K and W=0*20nm. Figure 4
shows the simulated band shape and, on the same scale, the error between it and the
theoretical shape at the estimated temperature and line width. A good fit is indicated by
the random noise being centred on zero at all wavelengths.

A
3139 400 401 402 403 404 405 406 467
0.011 Wavelength (nm)

Figure 4. Theoretical band shape with superimposed noise. True temperature and line
width: 500 K, 0.2 nm; estimated temperature and line width: 487 K and 0.2 nm.

This test was performed 20 times with different sets of random noise superimposed
on the same theoretical band shape at 500 K and 0.2 nm. The 20 temperatures estimated
by this process had a mean of 500 K and a standard deviation of 24 K and the 20 line
widths had a mean of 0.20 nm and a standard deviation of 0.01 nm. This was considered
adequate verification of the iterative process described in this section.

4. Measured gas temperatures in a nitrogen discharge

4 . I . Apparatus
The technique described in the previous section for determining rotational temperatures
and line widths from unresolved bands was used to analyse temporally resolved emission
516 D A4 Phillips

spectra recorded with the apparatus shown in figure 5 (see also Phillips 1973). A spark
was produced in nitrogen at a pressure of 13 kPa with an overvoltage of less than 1 %.
The discharge occurred between two electrodes separated by 2.0 mm in a 50 Q coaxial
spark chamber designed and first used by Schroder (1966). The current pulse was

Attenuator Spark chamber

Figure 5. Apparatus used to record temporally resolved emission spectra from a nitrogen
spark.

att nuat d and then recorded by one channel of the sampling oscilloscope. The light
pulse was resolved spectrally, detected, and then recorded by the other channel of the
oscilloscope. By sampling the light pulse at a specified time and scanning the wavelength
range with the spectrometer, the spectrum at the specified time was traced out by the
pen recorder.

4 . 2 . Electrical and spectroscopic measurements

The current through the discharge rose in two steps as shown in figure 6(a). This resem-
bles the development of hydrogen sparks in the same coaxial chamber studied by Doran
and Meyer (1967) and by Cavenor and Meyer (1969). Therefore, the first current step
can be identified as corresponding to a glow discharge, while the second is associated
with the establishment of an arc.
The axial voltage distribution was determined from current oscillograms recorded at
different gap lengths using the static breakdown method employed by Cavenor and
Meyer. The axial electric field in the plasma deduced from these records is shown as a
function of time in figure 6(b). The power input to the plasma, calculated from the current
and axial electric field, is shown in figure 6(c). It can be seen that energy transfer to the
plasma occurs primarily during the glow stage of breakdown and that during this stage
the stored energy increases almost linearly.
The spectrum emitted by the nitrogen spark is dominated by the second positive
system, with a weaker contribution from the first negative system. The 0-3 band has
the advantage for analysis that it is well separated from other bands. The shapes of this
land, recorded at the times 10, 100 and 400 ns after the initial rise of current, are repro-
duced in figure 7. Comparison with the theoretical band shapes in figure 2 indicates that
the rotational temperature rises steadily during the glow stage of breakdown.
 Determination of gas temperature 517

2 Power(kW)

0 500 IO00
Time (ns)
Figure 6. Electrical parameters during spark breakdown,

0.001 '
399 401 403 405 407
Wavelength (nm)
Figure 7. Observed shapes of 0-3 band at different times during spark breakdown at :
( U ) 10 ns; (b) 100 ns and (c) 400 ns.

4 . 3 . Thernial equilibrium considerations

The gas temperature is linked to the rotational temperature through the relaxation
process of inelastic collisions between molecules. Several measurements have been made
of the relaxation number, which is the average number of collisions required for the
exchange of rotational and translational energy. Measurements, at about 300 K using
ultrasonic techniques by Kistemaker et aZ(l970) and Greenspan (1959) and from 300-
400 K using shock waves by Andersen and Hornig (1959), have yielded values in the
range 4-6. According to an approximate theory by Brout (1954) the relaxation number
should be essentially independent of temperature. Since the mean collision time in
nitrogen at 13 kPa and 300 K is 1.0 ns, the rotational relaxation time is about 5 ns.

40
518 D M Phillips
This is two orders of magnitude shorter than the duration of the glow stage of the ob-
served sparks. Hence, for practical purposes in this experiment the gas temperature and
the rotational temperature are equal.

4.4, Results arid discussion

The observed shapes of several bands recorded at different times during the glow stage
of breakdown were analysed by the iterative technique described in the previous section
to yield estimates of gas temperature and line width. As an indication of the accuracy
of these parameters, the difference between each experimental band shape and the
theoretical shape at the estimated temperature and line width was calculated and plotted
on the same scale as the band shape. Two examples of such plots are given in figure 8.

0.01, Wavelength (nm)

314 376 378 380 382

0 005, Wavelength (nm)

-0a05~
Figure 8. Observed band shapes at 100 ns during spark breakdown: (a) 0-3 band at
501 K and line width=0.24 nm; (b)0-2 band at 634 K and line width 0.47 nm.

It can be seen that a good fit to the observed 0-3 band has been achieved, since the error
is small compared with the band intensity and is not markedly dependent on wavelength.
On the other hand, the fit to the 0-2 band is poor and the error depends on wavelength,
which shows that the assumption in equation (21) is not satisfied. Furthermore, the
line width estimated for the 0-3 band is compatible with the instrumental value of about
0.2 nm determined by the slit width and the time constant of the recording system. The
line width estimated for the 0-2 band is clearly too large.
The observed band shapes that are unlike any theoretical shape, such as the 0-2 band
at 100 ns, are thought to be affected by self absorption for the following reasons. Firstly,
good fits were obtained to all observed band shapes at early times, when the population
of the N Z Bl-Ig
~ state would be too small to cause absorption. The population of this
state steadily increases at later times, due to its relatively long lifetime of about 4 ps
(Johnson and Fowler 1970). Secondly, the worst fits resulted from the strong 0-2 and
 Determination of gas temperature 519

1-3 bands which would exhibit the strongest absorption and the best fits were obtained
from the weak 0-3 and 2-4 bands. The former bands have larger transition probabilities
than the 0-3 band and the v " = 2 and 3 levels are more heavily populated than the v"=4
level. Thirdly, compared with the theoretical shapes, which always show a pronounced
peak at the band head (see figure l), the poorly fitted observed shapes all have reduced
intensity at the band head, where absorption would be greatest. The most reliable
results, therefore, are expected from all bands at early times and from the weak 0-3
and 2-4 bands at late times.
I200

1000

2 800
2
&

$ 600
n
E
4

YI 400
W

200

0 200 400 600

Time (ns)
Figure 9. Gas temperature during spark breakdown: 0 0-3 band; 0 0-2; 0 1-3;
2-4.

The gas temperatures calculated from several observed bands at different times during
the glow stage of spark breakdown in nitrogen are shown in figure 9. The curve shows
the gas temperature calculated from the equation
U = p VCV(T- To),
where U is the electrical energy dissipated in the plasma from figure 6(c), p is the density
of nitrogen at the operating pressure, CVis the specific heat and the volume of the spark is
V= rd2 L/4,
where d is the observed diameter of 6 mm. The initial temperature TOwas assumed to be
340 K, a little above room temperature, in order to fit the spectroscopically determined
temperatures at early times. The best agreement at later times is with the temperatures
calculated from the 0-3 and 2-4 bands, which confirms the reliability of temperature
measurement expected of these bands. The scatter in the temperatures calculated from the
0-2 and 1-3 bands is attributable to the effects of self absorption, as mentioned before.
The agreement between the best spectroscopic measurements and the curve in figure 9
confirms that most of the electrical energy dissipated in the plasma produces gas heating.

5. Conclusion
A technique has been described for determining rotational temperature from the shape
of an unresolved band in the second positive system of the emission spectrum of molecular
520 D M Phillips

nitrogen. Tests with simulated band shapes show that the iterative process converges
rapidly to the correct temperature both in the absence and presence of noise. When it
was applied to temporally resolved emission spectra recorded during the glow stage of
spark breakdown in nitrogen, the calculated rise in gas temperature was in agreement with
the electrical power input to the discharge, although some observed band shapes,
distorted probably by self absorption, yielded spurious estimated temperatures.
In principle, the technique is quite general. With appropriate data it could be used
to deduce rotational temperatures from unresolved band shapes in the emission spectrum
of many molecules. The temperatures obtained with this method are potentially more
accurate than those deduced by measuring the band width at 1/3 peak height because all
the information in the whole band shape is utilized in the present technique.
Experimental band shapes can be matched to the theoretical ones in many ways but
the method described in this paper has definite advantages. It is a rapidly converging
process which requires no manual intervention. The estimate of temperature is both
unbiased and has minimum variance. The accuracy of the calculated temperatures can
be estimated, if the covariance matrix applicable to the data is known, although this has
not been developed in this paper.
The greatest limitation of this and all other methods of determining rotational
temperature from the shape of an unresolved band is the problem of self absorption.
In principle, self absorption could be included in the present theory as another parameter
that influences the shape of a band. It should then be possible to determine gas tempera-
tures even in the presence of self absorption-although this has not been attempted.
An area in which this spectroscopic technique could have particular application is
in the study of the effect of gas temperature on the performance and gain characteristics
of the nitrogen laser.

Acknowledgments

The experimental measurements described in this paper were made at the University
of New England. The equipment was provided by the Australian Institute of Nuclear
Science and Engineering and by the Electrical Research Board of Australia. The author
is indebted to Professor G A Woolsey for many helpful discussions.

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