14. P. Oliva,J. Leonardi,J. F. Laurent, C. Delmas, J. J. Braconnier,
M. Figlarz,F. Fievet,and A. de Guibert,J. Power Sources8, 229
(1982).
15. E. S. Reid, R. P. Cooney, P. J. Hendra, and M. Fleishmann, J.
Electroanal. Chem. 80, 405 (1977).
16. R.L. Farrow, P. L. Mattern, and A. S. Nagelberg, Appl. Phys. Lett.
36, 212 (1980).
17. A. Livingstone, British Mineral. Mag. 46, 1 (1982).
18. A.F. Wells, in Structural Inorganic Chemistry (Oxford University
Press, Oxford, 1984), 5th ed., p. 631.
19. J. D. Bernal and H. D. Megaw, Proc. R. Soc. London, Ser. A, 153,
384 (1935).
20. S. Le Bihan, J. Guenot, and M. Figlarz, CR Acad. Sci., Set. C, 270,
2131 (1970).
21. H. Bode, K. Dehmelt, and J. Witte, Electrochim. Acta ll, 1079
(1966).
22. R. S. McEwen, J. Phys. Chem. 75, 1782 (1971).
23. G. Blyholder and M. C. Allen, J. Phys. Chem. 70, 352 (1966).
24. H. Bode, K. Dehmelt, and J. Witte, Z. Anorg. Allg. Chem. 366, 1
(1969).
Two-Photon-Induced Chemical Reactions in Liquids*
C. H . C H E N a n d M . P. M c C A N N t
Chemical Physics Section, Oak Ridge National Laboratory, Post Office Box 2008, Oak Ridge, Tennessee 87831-6378
The two-photon absorption process was used to obtain the first obser-
vation of particle precipitation in liquids between halogen-containing
organic compounds and silver-containing inorganic compounds. Photo-
detachment of an electron from negative ions was found to be one im-
portant mechanism that led to these chemical reactions. Similar pro-
cesses may lead to many new multiphoton-induced chemical reactions
between organic and inorganic compounds.
Index Headings: Ultraviolet; Kinetics; Chemical reactions.
INTRODUCTION
Since the invention of lasers, chemists have been trying
very h a r d to use laser b e a m s to s t u d y chemical kinetics
or to a c t u a t e chemical reactions which c a n n o t be done
b y traditional ultraviolet (UV) discharge lamps. Due to
the rapid progress in the d e v e l o p m e n t of ultrashort pulsed
lasers ( < 10 -12 s), the studies of chemical kinetics have
blossomed. 1-3 However, the d r e a m of efficient a n d highly
selective laser-induced chemical reactions still has not
b e c o m e a reality. T h e uniqueness of laser radiation is
m a i n l y due to its coherence, its high brightness per unit
wavelength, a n d the ultrahigh power of a s h o r t pulsed
laser. M o s t laser-induced chemical reactions have been
p r o d u c e d in the gas phase. A m a j o r effort in the last
decade has been to s t u d y multiple infrared p h o t o n ex-
citation of a selective vibrational mode, such as the S-F
b a n d in SFs . ~ However, the fast relaxation, dissipation
of the highly excited vibrational energy to other vibra-
tional modes, usually precludes the selective dissociation
Received 12 June 1989.
* Research sponsored by the Office of Health and Environmental Re-
search, U.S. Department of Energy under Contract DE-AC05-
840R21400 with Martin Marietta Energy Systems, Inc.
t Guest Consultant. Author to whom correspondence should be sent.
Volume 44, Number 1, 1990 00o3.7028/9o/,~101-011552.0o/o
© 1990 Society for Applied Spectroscopy
25. A. Merlin and S. J. Teichner, CR Acad. Sci. 236, 1892 (1953).
26. D. Glemser, in Handbook of Preparative Inorganic Chemistry, G.
Brauer, Ed. (Academic Press, London, 1965), Vol. 2, p. 1549.
27. D. Glemser and J. Einerhand, Z. Anorg. Allg. Chem. 261, 26 (1950).
28. D. Glemser, in Handbook of Preparative Inorganic Chemistry, G.
Brauer, Ed. (Academic Press, London, 1965), Vol. 2, p. 1551.
29. S. S. Mitra, "Vibration Spectra of Solids," in Solid State Physics,
A. Seitz and D. Turnball, Eds. (Academic Press, London, 1962),
Vol. 13, p. 1.
30. D. Krishnamurti, Proc. Indian Acad. Sci. A50, 232 (1959).
31. G. Herzberg, in Spectra of Diatomic Molecules (Van Nostrand,
Princeton, 1950), p. 560.
32. F.P. Kober, J. Electrochem. Soc., Electrochem. Sci. 114, 215 (1967).
33. W. R. Busing and H. W. Morgan, J. Chem. Phys. 28, 998 (1958).
34. C. Cabannes-Ott, Ann. Chim. 5, 905 (1960).
35. J. Desivestro, D. A. Corrigan, and M. J. Weaver, J. Phys. Chem.
90, 6408 (1986).
36. C. A. Meledres and S. Xu, J. Electrochem. Soc. 131, 2239 (1984).
of a chemical bond. T h u s , a highly selective chemical
reaction, which is not t h e r m o d y n a m i c a l l y favorable, is
e x t r e m e l y difficult to achieve. T h e p r o m o t i o n of an elec-
tron to a repulsive excited state for chemical reactions
can usually be done with a discharge U V light. Since the
cost of a laser is still m u c h higher t h a n t h a t of a discharge
l a m p a n d the excitation of an electron to a repulsive s t a t e
does not require very narrow bandwidths, the use of
lasers for chemical reactions m a y not be cost effective.
DISCUSSION
Due to the coherence property and the ultrahigh power
of a short pulsed laser, multiphoton-excitation-induced
chemical reactions are among the processes which cannot
be induced by nonlaser light sources. However, due to
the very small cross sections of multiphoton processes,
the efficiency for any chemical reaction in the gas phase
is very low. Any production of chemicals of significant
quantity by a multiphoton absorption process in the gas
phase is not likely. But a two-photon excitation process
can be efficient in a condensed phase due to the high
density of the condensed materials. Taking a typical ef-
fective cross section of a two-photon process as ~ 1 ×
10 -50 c m 4 s molecule-I, 7,8a commercially available laser
beam with very mild focusing (beam size of I m m in the
reaction region) can almost be totally absorbed in 1 c m
pathlength of absorber. Thus, the efficiency of a two-
ph0ton-induced chemical reaction in the liquid phase can
be quite high.
In this paper, we report the firstobservation of a chem-
ical reaction between an organic compound and an in-
organic compound in the condensed phase which was
induced by a two-photon absorption process.
APPLIED SPECTROSCOPY 1 15
 B e

Splitter
a m
I I / Q u a r t z Cell
~L~-~ Harm°nic
Cenerat°r[ ILaserl ~

Fie. 1. Schematic diagram of the experimental arrangement. (Note

that the dye laser can be moved in and out of the experiment.)
~'f': :': :'i.:':! ::..:.:.:>:':::'.:.::'.'::
•
, ' . ' . L

. . . .
-

.
"

.
•

.
"

.
•

.
. .

.
. . • ,
\>
/
Laser
Beam

Particles / • . . . .

forming /
The following chemical reactions were pursued by laser in Solution ___..__Solution
excitation: (slowly falling)

(1) AgN03 + CCI4 (7) AgN02 + CeHsBr

(2) AgNO3 + CH2C12 (8) AgN02 + C6HsI
(3) AgN03 + C6HsBr (9) Ag2CO3 + CC14
(4) AgN03 + CoHsI (10) Ag2C03 + CH2C12
(5) AgN02 + CC14 (11) Ag2CO3 + CsHsBr
(6) AgN02 + CH2CI2 (12) Ag2C03 + CsHsI.
The concentrations of AgN03, AgN02, and Ag2CO3 in
water are 1 M, 0.I M, and 0.05 M, respectively. A slight
amount of H2S04 was added to the aqueous Ag2CO3 so-
lution to increase the solubility of Ag2COs. Since carbon
tetrachloride (CC14), dichloromethane (CH2C10, bro-
mobenzene (C6HsBr), and iodobenzene (CeHsI) are not
water soluble, these reagents were dissolved in methanol
(10% solute in methanol). All chemicals used in this work
were research grade, without further purification or dis-
tillation.
An experimental schematic is shown in Fig. 1. Laser-
induced chemical reactions were carried out in mixtures
of inorganic solutions containing silver compounds with
organic solutions containing halogen compounds. In gen-
eral, the mixing volume ratio between reagents A (silver-
containing compound) and reagents B (halogen-contain-
ing compound) is 1 to 10. No precipitates were observed
before the laser beam irradiated the cell. A frequency-
doubled Nd:YAG laser beam at 532 nm wavelength was
Fro. 2. Diagram of particles formed in the cell by laser.
precipitates was about linearly proportional to the laser
energy. However, a Nd:YAG laser beam at 1.064/zm with
500 mJ/pulse, which was used to irradiate the reaction
cell, produced no observable precipitates. A X e lamp was
used to shine on the samples, and the reaction products
were observed. When a cutoff filter with cutoff wave-
length at 340 nm was used, no precipitates were observed.
The chemical reactions obtained were confirmed to be
due to a photon excitation process instead of a thermal-
induced chemical reaction process. Similar experiments
were done without utilizing methanol, by mixing a silver
solution with an organic solvent containing halogen com-
pounds. Silver halide particles were produced at the in-
terface between the layers of organic and inorganic com-
pounds upon exposure to the laser light. If either layer
was exclusively exposed to the laser beam, no precipitates
were produced.
Two possible mechanisms are introduced to account
for the production of silver halides. Mechanism A in-
volves a two-photon induced dissociation process of a
halogen-containing compound as an initiating step. The
mechanism speculated is as the follows:
2 h v

used for two-photon excitation. The laser energy is 100
millijoule per pulse with 5 nanosecond duration. For all
of the experiments listed above, silver halide precipitates
were produced immediately after laser excitation. To our
knowledge, this is the first observation of particle for-
mation in a condensed phase, which has been recently
referred to as "laser snow" in gas-phase experiments. 9 A
diagram of this laser-induced particle precipitation is
shown in Fig. 2. The precipitates were separated from
the solution by a centrifuge method. The elemental anal-
ysis of the precipitates by x-ray fluorescence confirmed
that the components of the precipitate were silver halide
(AgX). The quantity of precipitates was estimated to be
approximately proportional to the square of the laser
energy. Since there are no one-photon absorptions at 532
nm for any of the reagent compounds, only multiphoton-
absorption-induced chemical reactions are possible. Sim-
ilar experiments were done with a 355-nm (40 mJ/pulse)
laser beam which was produced by third harmonic gen-
eration of a Nd:YAG laser beam. The production effi-
ciency of silver halide precipitates was higher than that
RX-. R+X
X+H20~X- + H + + OH
X - + Ag + -~ AgXI.
If the above mechanism is correct, the acidity of the
solution will increase after the irradiation by the laser
beam. We measured the pH values of the solution before
and after the laser excitation. The pH values for all of
the reactions listed above showed significant reduction.
The results indicate that dissociation of halogen-con-
taining compounds by a two-photon process can at least
account for part of the production of silver halide pre-
cipitates when the wavelength of the laser is short enough
for the dissociation.
There is another possible mechanism that could ac-
count for the silver halide precipitates produced. Mech-
anism B involves electron photodetachment by a two-
photon process as an initiating step.
2 h v

obtained by the 532-nm laser excitation. The chemical N0~- -~ N03 + e -

reactions induced by the 355-nm laser beam were also
through a two-photon excitation process. A 266-nm (10 e- + R X - ~ R + X -
mJ/pulse) laser beam was also used to produce chemical
reactions for lower AgNO3 concentration; the yield of the X - + Ag + -~ AgXl.

116 Volume 44, Number 1, 1990

In order to s t u d y mechanism B, a tunable dye laser beam
obtained from pumping with a frequency-doubled Nd:
YAG laser was used for a two-photon-induced chemical
reaction. A dye laser beam at 608 n m was used to produce
a chemical reaction for AgN03 aqueous solution with
CC14 in methanol. A precipitate of AgC1 was observed.
A piezoelectric transducer (EDO 6166) was used to ob-
tain absorption spectra of N O c and CC14 by an optoac-
coustic method. An aqueous solution of K N 0 3 was used
for the sample N03-. T h e linear absorption thresholds
of CC14 and N O c were measured as 290 and 332 nm,
respectively. T h e q u a n t u m yield for AgN03 solution with
CC14 with the 355-nm laser beam at 15 mJ/pulse was
estimated as being close to 50%. Since CC14 does not
absorb laser wavelengths t h a t are longer t h a n 300 nm,
the photodissociation of CC14 to produce C1 atoms cannot
be achieved by a 608-nm laser beam, even through a two-
p h o t o n absorption process. On the other hand, the elec-
tron d e t a c h m e n t of NO3- is feasible by the two-photon
absorption of a 608-nm laser beam. Thus, the electron
d e t a c h m e n t process from negative ions by a two-photon
absorption is confirmed as an i m p o r t a n t mechanism for
the observed reactions. However, when the wavelength
of a laser is shorter t h a n 580 nm, mechanism A proposed
above can become a competitive process.
In conclusion, chemical reactions between organic and
inorganic compounds in liquid phase were d e m o n s t r a t e d
through a two-photon absorption process either by an
electron d e t a c h m e n t or by a dissociation process. We
take advantage of the silver halide precipitates formed
in this work for easy observation of the progression of
the reaction. However, m a n y other chemical reactions
which proceed by an electron d e t a c h m e n t process m a y
also occur concurrently without producing any precipi-
tates. Since radicals such as NO3, NO2, I, C1, and Mn04
can be produced in liquid phase by an electron detach-
m e n t process, these radicals will lead to chemical reac-
tions with other compounds in solution due to their very
reactive properties. This mechanism m a y lead to a series
Component Selection for Fiber-Optic Fluorometry
RICHARD B. THOMPSON,* MICHAEL
Bio/Molecular Engineering Branch, Code 6190, Naval Research Laboratory, Washington, D.C. 20375-5000 (R.B.T., M.L.); and
Geo-Centers Inc., Newton Center, Massachusetts 02159 (L.K.)
A wide variety of fiber-optic sensors based on fluorescence have been
developed for important applications in the last few years. Unfortunately,
no systematic study describing an optimized design has appeared. A
fiber-optic fluorescence sensor testbed was constructed, and different
optical designs and components were compared for sensitivity in de-
tecting fluorescence. Different beamsplitters, launching objectives, fil-
ters, detectors, and configurations were evaluated on the basis of their
measured signal-to-noise ratio in detecting 100 picomolar fluorescein.
Received 3 April 1989; revision received 1 June 1989.
* Author to whom correspondence should be sent.
Volume 44, Number 1, 1990 06o3-7028/90/4401.011752.0o/0
© 1990 Society for Applied Spectroscopy
of new photo-induced chemical reactions between or-
ganic and inorganic compounds in the liquid phase. T h e
absorption regions of several negative ions such as SO4 ~,
Cl-, and F - lie in the vacuum ultraviolet (VUV) re-
gion. 1°,~I It is still very difficult to produce high-power
tunable VUV laser beams. Electron-transfer-induced
chemical reactions can be done only by two-photon ab-
sorption, if at all. Since the absorption of photons for
chemical reactions by a two-photon process can be very
efficient ( q u a n t u m yield can, in principle, reach 50%),
electron d e t a c h m e n t s by a two-photon process can pos-
sibly be a unique way for producing a series of new chem-
ical reactions in the future.
ACKNOWLEDGMENTS
We would like to thank M. G. Payne, W. R. Garrett, P. C. Ho, C. Y.
Ma, and J. P. Judish for useful discussions. The technical help from
S. L. Allman and R. C. Phillips is acknowledged.We also acknowledge
Doris Crowell for help in preparation of the manuscript. Research was
sponsored by the Officeof Health and Environmental Research, U.S.
Department of Energy, under Contract DE-AC05-840R21400 with
Martin Marietta Energy Systems, Inc. M. P. McCann is a guest con-
sultant.
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LEVINE, and LYNNE KONDRACKI
Sources of noise and background were identified, and generally appli-
cable means for minimizing them are described.
Index Headings: Fiber-optic sensors; Fluorescence; Optical components.
INTRODUCTION
T h e use of fiber optics in conjunction with fluorometry
is growing in fields as diverse as biophysics, r e m o t e sens-
ing, immunodiagnostics, and chemical process monitor-
ing. 1~ Fluorescence is a well developed, powerful, and
APPLIED SPECTROSCOPY 1 17