Volume 156, number I CHEMICAL PHYSICS LETTERS 24 March 1989

ONE- AND TWO-PHOTON OPTOGALVANIC SPECTRUM OF Ne: 610-730 nm

K. NARAYANAN, G. ULLAS and S.B. RAI

Laser and Spectroscopy Laboratory, Departmen of Physics, Banaras Hindu University. Varanasi 221005. India

Received 9 December 1988

The laser optogalvanic (LOG) spectrum of Ne in the region 6 IO-730 nm has been recorded using Nd-YAG laser pumped dye
laser and a Hamamatsu FeNe hollow cathode lamp. Forty-five lines have been observed in the LOG spectrum and have been
explained as originating from one- and two-photon transitions in Ne. The negative signal for a few lines and the observedvariation
in LOG signal with lamp voltage and laser power have been explained.

1. Introduction 2. Experimental

Optogalvanic spectroscopy is one of the noble
techniques for elucidating the structure of atoms and
molecules. Besides its experimental simplicity, the
high signal-to-noise ratio which one obtains has made
it very useful. In the present paper we present some
new results on the optogalvanic spectrum of the Ne
atom recorded in the spectral region 610-730 nm.
The Ne atomic spectrum has been extensively stud-
ied [l-40] by optogalvanic technique. The wave-
length range of 400-760 nm has been covered and
in addition to the normal one-photon spectrum, two-
and three-photon-mediated transitions have also been
observed [ 371. With a view to obtaining a calibra-
tion spectrum of Ne, we recorded the optogalvanic
spectrum of a FeNe hollow cathode lamp in the re-
gion 560-730 nm. While the optogalvanic signals
observed in the region 560-610 nm are in close
agreement with the previous studies, however, the
spectrum observed in the region 6 1O-730 nm showed
The optogalvanic spectrum of Ne was recorded us-
ing a Hamamatsu (model L233) FeNe hollow cath-
ode lamp. The experimental set up used is shown in
fig. 1. A stabilized dc voltage capable of variation
from 150 to 190 V at a constant current in the range
lo-20 mA was applied across the electrodes of the
lamp. Radiation from a Nd-YAG (Quanta Ray
DCR-2 with. 10 Hz repetition rate) pumped dye laser
(Quanta Ray PDG2) was used. Various dyes (e.g.
R590, DCM and oxazine) were excited by the sec-
ond harmonic of Nd-YAG radiation to cover the de-
sired spectral range. Focusing of radiation was found
essential for all the dyes used. A current-limiting load
I I
current I
High Volto9o

a large number of new lines which were not present

in the previous spectra. A detailed study of lines ob-
I+
I
R

I
Limiting
Rssisior
I
I

served in this region is given.

We have also studied the effect of varying the dis-
charge voltage and the laser power on the optogal-
vanic spectrum. An attempt has been made to ex-
plain these observations.

Fig. I. Experimental set up used for recording the optogalvanic

spectrum of neon.

0 009-26 14/89/$ 03.50 0 Elsevier Science Publishers B.V. 55

( North-Holland Physics Publishing Division )
Volume 156,number I CHEMICAL PHYSICS LETTERS 24 March 1989

resistor was placed in the circuit between the power dicates the variation of signal intensity with laser
supply and the hollow cathode lamp to control the power or discharge voltage. The assignment of the
current. The signal was received through a capacitor, observed lines made use of the observed energy lev-
processed by an EG&G 164 boxcar averager and fi- els of Ne as given in ref. [ 9 1. The lines observed along
nally fed to a double pen omniscribe recorder. A small with energy levels involved are shown in fig. 3.
part of the dye laser beam was fed to a 0.5 m mono-
chromator to obtain wavelength calibration.
The LOG spectra were recorded at different dis- 3. Results
charge voltages ranging from 150 to 190 V in steps
of 10 V while keeping the laser power constant. Each As mentioned earlier we recorded the LOG speo
of these studies were also repeated at different laser trum of Ne in the spectral range MO-730 nm. Since
powers. A part of the spectrum obtained under dif- our observed spectrum in the region 560-6 10 nm was
ferent conditions is shown in fig. 2 which clearly in- identical to the one reported by earlier workers [ l-
8,10-27,29-37,39,40]. We will not discuss this part
8 Lamp Voltage =18OV of our results any further.
Laser Energy =1,2niJ
The LOG spectrum of Ne observed in the region
t I
61 O-730 nm has been discussed by many workers
[ 12,13,26,37]. Smyth and coworkers [ 12,131 ob-
served twelve lines in the region 610-653 nm and
have assigned them to one-photon transitions of the
type ls,-2p,. Nester [26] recorded this spectrum
between 580 and 760 nm and reported twenty-two
lines. Bickel and Innes [ 371 made an extensive study
of LOG spectrum of Ne in the region 720-760 and
577-630 nm and observed large number of one- and
two-photon and two-colour two-photon lines.
We observed a total of forty-five lines in the wave-
length region of 6 1O-730 nm. We could not identify
Lamp Voltage =1eov seven of these lines while sixteen of these could be
Laser Energy =0.7mJ
i assigned to two-photon excitations. The remaining
04. twenty-three lines are easily assigned to one-photon
z
ci excitations involving mainly the 1s, level, though ex-
f9 citations from some other levels are also seen. The
0 -2,
I
lines observed in one-photon excitation are listed in
Lomp Voltage =15OV table 1. Two lines show matching frequency for one-
Laser Energy=0.7mJ and two-photon transitions both.
4-
The ground state of Ne atom is (2~~) ‘S,, state
while the first excited state with configuration 2~~3s
is represented as 1s, in the Paschen notation has four
components, namely, 1sg, Is,, 1~ and lsz. The cor-
responding levels in LS coupling are ‘Pz, ‘PI, ‘PO and
‘PI. Since the LS coupling approximation is reason-
ably well satisfied in the ground and the first excited
-2L , I I states of Ne, all three components of the ‘P state, i.e.
136966 136751 14053.5 I4232
levels denoted by Isg, 1s4 and 1sj in the Paschen no-
LASER FREOUENCYbm-1)
tation, behave like metastable states while the fourth
Fig. 2. Variation of optogalvanic signal with laser power and lamp ‘P, state (Is, in Paschen notation) can combine ra-
voltage. diatively with the ground state. The second excited

56
Volume 156, number 1 CHEMICAL PHYSICS LETTERS 24 March 1989

i .76.

1.69.

I-62
n
51
x
T
6
t
5 1.55

5
t
”

1.48

I.41

1.34

Fig. 3. Energy level diagram for the observed neon transitions. The lines marked by * represent two-photon transitions.

state configuration in Ne is 2p53p and gives rise to
ten excited states designated as 2p,-2p10 in the
Paschen notation. In these states it is the interme-
diate JL coupling which is more appropriate and J
is the only good quantum number with a selection
rule AJ= 0, 2 1. As a result of this, the transition be-
tween the different excited states and the ground state
does not follow the same selection rules. The selec-
tion rules for transitions between the ground state
and the first excited states arc AS= 0, bL = 0, k 1 and
AJ=O, I? 1 (with J=O++J=O). On the basis of this,
one can easily explain the transitions observed in our
experiment.
Out of the twenty-three lines observed as one-pho-
ton transitions (table 1) five involve excitation from
the ~s~(~P*), six involve excitation from IQ(~P,)
three involve excitation from Is~(~P,J), two involve
excitation from Zp,, one from 2s, and the remaining
six involve excitation from 1s2 ( ‘P, ). In all the cases
except the transition from 2p, and 2s5 states the final
levels are the levels of the 2p (Paschen notation)
state. The LOG signal obtained in the first seventeen
cases are positive whereas in the last six cases they
are negative. This difference in the LOG signal can
be easily understood if we note that the initial states
in the first fourteen transitions are 1sS( “Pz ) , Is, ( ‘P, )

57
Volume 156.number I CHEMICAL PHYSICS LETTERS 24 March 1989

Table 1
One-photon transitions observed in neon

Frequency of Assignment Direction

transition (cm-’ ) of OGS

1 13789 ls,(‘P,),J=l-2p,,,J=l Pas

2 13935 1s2(‘P,),J=l-2p8,J=2 neg
3 14232 ls2(‘P,),J=l-2p,,J=l neg
4 14215 k+(3P,),J=2-2p,,, J= 1 POS
5 14464 2s,, J= 2-8p,, J= 2 Pas
6 14883 lsl(‘P,), J=l-2p,,J=l w
7 14969 ls2(‘P,),J=l-2p,,J=2 nei3
8 15028 lsl(‘Pl), J=l-2p,, J=O neg
9 15149 1s2(‘P,).J=1-Zp>,J=l neg
10 15302 ls#P,), J=O-2p,, J= I POS
II 15364 ls,(3P,),J=l-2pg,J=2 Pas
12 15615 ~s~{~P~),J=2-2p,, J=3 pas
13 15662 ls,(‘P,),J=l-2p,,J=l pas
14 15782 lss(‘Pz), J-2-2p,, J=2 POS
15 15856 ~s~(~P,),J=~-Z~~,J=~ pas
16 15953 Is~(~P~), J=O-2p,, J= 1 POS
17 16079 ~s~(~P~),J=Z-2p,, J= 1 POS
18 16116 2p,, J=2-4dS, J= 1 pas
19 16168 2p,, J=2-4dz, J= 1 pas
20 16219 &(‘P,), J=O-Zp,, J=l pas
21 16274 I.s~(~P~),J=2-2p, J=2 pas
22 16312 l&P,), J= 1-2p,, J=l pas
23 16399 ls#P,), J=l-2p, J=2 Pas

and Is~(~P~), all of which are metastable with re-
spect to the radiative decay to the ground state. Un-
der low current density conditions, an excitation of
Ne atoms from ls5,4,3 levels to the higher twenty lev-
els depopulates the metastable state and decreases
the ionization rate of Ne atoms. This causes an in-
crease in the discharge impedance and because the
current is constant leads to a voltage increase, i.e. a
positive signal. An excitation from the lsZ ( ‘P, ) level
to one of the 2p levels on the other hand leads to an
increase in the population of the metastable states,
on rapid decay of the 2p levels. This therefore will
give a negative optogalvanic signal for the corre-
sponding transitions. There is however one possi-
bility which has to be borne in mind. If the discharge
conditions are modified so that the equilibrium pop-
ulation (before the laser light irradiation) in the four
1s levels is reduced as compared to the 2p levels the
sign of the corresponding OG signal may change. Two
other lines involving 2p, as the lower state and one
line from 2s5 have also been observed. They have
been explained exactly in the same way.
4. Two-photon LOG spectrum
As mentioned earlier, we have observed sixteen
lines caused by simultaneous absorption of two pho-
tons in the region 6 1O-730 nm. These lines along with
their assignments are listed in table 2. Some of these
lines were already observed by Nestor [26] in one-
colour two-photon absorption and by Bickel and
Innes [ 37 ] in two-colour two-photon absorption. All
the two-photon signals observed here are positive and
the selection rules hJ= 0, f 1, + 2 are followed. The
two-photon nature of these lines was verified by
studying the variation of the signal as a function of
the laser power. Out of these sixteen lines, fifteen lines
arise from the transitions involving excitation of Ne
from one of the three ‘P( ls5, ls,, 1~~) metastable
levels and the positive sign of the signal is easily
understood.
The sixteenth line observed at 14969 cm-’ coin-
cides with a transition 1s2-3~ in two-photon ab-
sorption and with ls,-2p, transitions in one-photon
absorption. At low laser powers we find that the op-

58
Volume 156, number 1 CHEMICALPHYSICS LETTERS 24 March 1989

Table 2
Two-photon transition observed in neon

Frequency of Assignment Direction

transition (cm-‘) of OGS

I 13733 1s5, J=2-3d6, J=O pas

2 13741 1s5,J=2-3d,, J= I pas
3 13774 Is,, J=2-384, .I=4 POS
4 13782 1s5, J= 2-3d,, J= 2 pas
5 13795 Is,, J=O-3s”” J=2 pas
6 13829 Is~, J=2-3;; ,‘J= 3 Qos
7 13974 IS4, J= 1-3~,,,,-~=2
I 2 POS
8 13980 Is4rJ=l-3s” I, J=2 PO3
9 13988 IS,,J=l-3s,,J=l QOS
10 14183 1s5,J-2-3s””
- J= 1 PC’S
11 14197 1s5,J=2-3s(, >= 1 Qos
12 14969 Is*,J= l-3&, J=2 QOS
13 15893 lsS,J=2-3si, 5~2 QOS
14 15935 1~5, J=2-3s,, J= 1 POS
15 16098 1S&J- l-3$, J- 1 Q”S
16 16307 Is,, J=2-3s,, 5~2 Q’=

togalvanic signal is negative and shows a positive
magnitude as the laser power is increased. It appears
that at low laser power the dominant contribution to
the absorption is due to the one-photon transition
which gives a negative signal as pointed out earlier.
In the two-photon transition the excited 3ss level can
no longer populate any of the metastable levels and
hence the cause of the negative signal is no longer
present.
5. Variation of signal
We have also studied the variation of the LOG sig-
nal with the discharge voltage ( 1SO- 190 V) and with
the laser power 0.7 to 1.2 mJ (see fig. 2). As the dis-
charge voltage is increased keeping the laser power
fixed it is found that the intensities of various pos-
itive signals decrease whereas the negative signals
become more negative irrespective of whether the
signal is due to a one-photon or a two-photon ab-
sorption. However, when only the laser power is in-
creased at a fixed discharge voltage, there is a general
increase in the magnitude of the LOG signals. These
observations may be explained in the following
manner.
The increase of the discharge voltage increases the
overall current density and associated electron tem-
perature in the tube. This causes a comparatively
larger increase in the probability of ionization when
the Ne atoms are in the higher excited states as com-
pared to the situation before irradiation. Thus laser
irradiation under these conditions contributes a de-
crease of the impedance and this will reduce the in-
tensity of the positive signals and will increase the
intensity of the negative signals. At discharge voltage
of 190 V some of the positive signal was reduced to
a very small magnitude and one hopes a further in-
crease in discharge voltage would reverse their sign.
An increase in the laser power causes more atoms
to be excited from the different initial states of Ne.
This will increase the depopulation of the metastable
levels Is~.~,~.for transitions involving these levels as
the lower state and add to their population for tran-
sition involving 1s2as the lower state. Thus, in both
cases the magnitude of the signal will increase. Of
course, if we increase the laser power still further,
saturation may set in.
6. Conclusion
The laser optogalvanic spectrum of the Ne atom
has been studied in the spectral region 6 1O-730 nm.
Twenty-three lines from absorption of one photon
and sixteen from absorption of two photons have

59
Volume 156, number 1 CHEMICAL
been observed and assigned. The sign of the signals
and their variation with laser power and discharge
voltage have been explained satisfactorily.
Acknowledgement
The authors are grateful to Professor D.K. Rai for
suggestions on the manuscript. This work is linan-
cially supported by Indo-US Project on Chemical
Dynamics and High Resolution Laser Spectroscopy.
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