14. P. Oliva,J. Leonardi,J. F. Laurent, C. Delmas, J. J. Braconnier, 25. A. Merlin and S. J. Teichner, CR Acad. Sci. 236, 1892 (1953).

M. Figlarz,F. Fievet,and A. de Guibert,J. Power Sources8, 229 26. D. Glemser, in Handbook of Preparative Inorganic Chemistry, G.
(1982). Brauer, Ed. (Academic Press, London, 1965), Vol. 2, p. 1549.
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Electroanal. Chem. 80, 405 (1977). 28. D. Glemser, in Handbook of Preparative Inorganic Chemistry, G.
16. R.L. Farrow, P. L. Mattern, and A. S. Nagelberg, Appl. Phys. Lett. Brauer, Ed. (Academic Press, London, 1965), Vol. 2, p. 1551.
36, 212 (1980). 29. S. S. Mitra, "Vibration Spectra of Solids," in Solid State Physics,
17. A. Livingstone, British Mineral. Mag. 46, 1 (1982). A. Seitz and D. Turnball, Eds. (Academic Press, London, 1962),
18. A.F. Wells, in Structural Inorganic Chemistry (Oxford University Vol. 13, p. 1.
Press, Oxford, 1984), 5th ed., p. 631. 30. D. Krishnamurti, Proc. Indian Acad. Sci. A50, 232 (1959).
19. J. D. Bernal and H. D. Megaw, Proc. R. Soc. London, Ser. A, 153, 31. G. Herzberg, in Spectra of Diatomic Molecules (Van Nostrand,
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20. S. Le Bihan, J. Guenot, and M. Figlarz, CR Acad. Sci., Set. C, 270, 32. F.P. Kober, J. Electrochem. Soc., Electrochem. Sci. 114, 215 (1967).
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(1966). 35. J. Desivestro, D. A. Corrigan, and M. J. Weaver, J. Phys. Chem.
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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- of a chemical bond. T h u s , a highly selective chemical
vation of particle precipitation in liquids between halogen-containing reaction, which is not t h e r m o d y n a m i c a l l y favorable, is
organic compounds and silver-containing inorganic compounds. Photo- 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-
detachment of an electron from negative ions was found to be one im-
tron to a repulsive excited state for chemical reactions
portant mechanism that led to these chemical reactions. Similar pro-
cesses may lead to many new multiphoton-induced chemical reactions can usually be done with a discharge U V light. Since the
between organic and inorganic compounds. cost of a laser is still m u c h higher t h a n t h a t of a discharge
Index Headings: Ultraviolet; Kinetics; Chemical reactions. 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.
INTRODUCTION
DISCUSSION
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 Due to the coherence property and the ultrahigh power
or to a c t u a t e chemical reactions which c a n n o t be done of a short pulsed laser, multiphoton-excitation-induced
b y traditional ultraviolet (UV) discharge lamps. Due to chemical reactions are among the processes which cannot
the rapid progress in the d e v e l o p m e n t of ultrashort pulsed be induced by nonlaser light sources. However, due to
lasers ( < 10 -12 s), the studies of chemical kinetics have the very small cross sections of multiphoton processes,
blossomed. 1-3 However, the d r e a m of efficient a n d highly the efficiency for any chemical reaction in the gas phase
selective laser-induced chemical reactions still has not is very low. Any production of chemicals of significant
b e c o m e a reality. T h e uniqueness of laser radiation is quantity by a multiphoton absorption process in the gas
m a i n l y due to its coherence, its high brightness per unit phase is not likely. But a two-photon excitation process
wavelength, a n d the ultrahigh power of a s h o r t pulsed can be efficient in a condensed phase due to the high
laser. M o s t laser-induced chemical reactions have been density of the condensed materials. Taking a typical ef-
p r o d u c e d in the gas phase. A m a j o r effort in the last fective cross section of a two-photon process as ~ 1 ×
decade has been to s t u d y multiple infrared p h o t o n ex- 10 -50 c m 4 s molecule-I, 7,8a commercially available laser
citation of a selective vibrational mode, such as the S-F beam with very mild focusing (beam size of I m m in the
b a n d in SFs . ~ However, the fast relaxation, dissipation reaction region) can almost be totally absorbed in 1 c m
of the highly excited vibrational energy to other vibra- pathlength of absorber. Thus, the efficiency of a two-
tional modes, usually precludes the selective dissociation ph0ton-induced chemical reaction in the liquid phase can
be quite high.
Received 12 June 1989. In this paper, we report the firstobservation of a chem-
* Research sponsored by the Office of Health and Environmental Re- ical reaction between an organic compound and an in-
search, U.S. Department of Energy under Contract DE-AC05-
840R21400 with Martin Marietta Energy Systems, Inc. organic compound in the condensed phase which was
t Guest Consultant. Author to whom correspondence should be sent. induced by a two-photon absorption process.

Volume 44, Number 1, 1990 00o3.7028/9o/,~101-011552.0o/o APPLIED SPECTROSCOPY 1 15

© 1990 Society for Applied Spectroscopy
 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 Fro. 2. Diagram of particles formed in the cell by laser.
(3) AgN03 + C6HsBr (9) Ag2CO3 + CC14
(4) AgN03 + CoHsI (10) Ag2C03 + CH2C12 precipitates was about linearly proportional to the laser
(5) AgN02 + CC14 (11) Ag2CO3 + CsHsBr energy. However, a Nd:YAG laser beam at 1.064/zm with
(6) AgN02 + CH2CI2 (12) Ag2C03 + CsHsI. 500 mJ/pulse, which was used to irradiate the reaction
cell, produced no observable precipitates. A X e lamp was
The concentrations of AgN03, AgN02, and Ag2CO3 in used to shine on the samples, and the reaction products
water are 1 M, 0.I M, and 0.05 M, respectively. A slight were observed. When a cutoff filter with cutoff wave-
amount of H2S04 was added to the aqueous Ag2CO3 so- length at 340 nm was used, no precipitates were observed.
lution to increase the solubility of Ag2COs. Since carbon The chemical reactions obtained were confirmed to be
tetrachloride (CC14), dichloromethane (CH2C10, bro- due to a photon excitation process instead of a thermal-
mobenzene (C6HsBr), and iodobenzene (CeHsI) are not induced chemical reaction process. Similar experiments
water soluble, these reagents were dissolved in methanol were done without utilizing methanol, by mixing a silver
(10% solute in methanol). All chemicals used in this work solution with an organic solvent containing halogen com-
were research grade, without further purification or dis- pounds. Silver halide particles were produced at the in-
tillation. terface between the layers of organic and inorganic com-
An experimental schematic is shown in Fig. 1. Laser- pounds upon exposure to the laser light. If either layer
induced chemical reactions were carried out in mixtures was exclusively exposed to the laser beam, no precipitates
of inorganic solutions containing silver compounds with were produced.
organic solutions containing halogen compounds. In gen- Two possible mechanisms are introduced to account
eral, the mixing volume ratio between reagents A (silver- for the production of silver halides. Mechanism A in-
containing compound) and reagents B (halogen-contain- volves a two-photon induced dissociation process of a
ing compound) is 1 to 10. No precipitates were observed halogen-containing compound as an initiating step. The
before the laser beam irradiated the cell. A frequency- mechanism speculated is as the follows:
doubled Nd:YAG laser beam at 532 nm wavelength was 2 h v

used for two-photon excitation. The laser energy is 100 RX-. R+X
millijoule per pulse with 5 nanosecond duration. For all
of the experiments listed above, silver halide precipitates X+H20~X- + H + + OH
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 X - + Ag + -~ AgXI.
referred to as "laser snow" in gas-phase experiments. 9 A If the above mechanism is correct, the acidity of the
diagram of this laser-induced particle precipitation is solution will increase after the irradiation by the laser
shown in Fig. 2. The precipitates were separated from beam. We measured the pH values of the solution before
the solution by a centrifuge method. The elemental anal- and after the laser excitation. The pH values for all of
ysis of the precipitates by x-ray fluorescence confirmed the reactions listed above showed significant reduction.
that the components of the precipitate were silver halide The results indicate that dissociation of halogen-con-
(AgX). The quantity of precipitates was estimated to be taining compounds by a two-photon process can at least
approximately proportional to the square of the laser account for part of the production of silver halide pre-
energy. Since there are no one-photon absorptions at 532 cipitates when the wavelength of the laser is short enough
nm for any of the reagent compounds, only multiphoton- for the dissociation.
absorption-induced chemical reactions are possible. Sim- There is another possible mechanism that could ac-
ilar experiments were done with a 355-nm (40 mJ/pulse) count for the silver halide precipitates produced. Mech-
laser beam which was produced by third harmonic gen- anism B involves electron photodetachment by a two-
eration of a Nd:YAG laser beam. The production effi- photon process as an initiating step.
ciency of silver halide precipitates was higher than that 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 of new photo-induced chemical reactions between or-
obtained from pumping with a frequency-doubled Nd: ganic and inorganic compounds in the liquid phase. T h e
YAG laser was used for a two-photon-induced chemical absorption regions of several negative ions such as SO4 ~,
reaction. A dye laser beam at 608 n m was used to produce Cl-, and F - lie in the vacuum ultraviolet (VUV) re-
a chemical reaction for AgN03 aqueous solution with gion. 1°,~I It is still very difficult to produce high-power
CC14 in methanol. A precipitate of AgC1 was observed. tunable VUV laser beams. Electron-transfer-induced
A piezoelectric transducer (EDO 6166) was used to ob- chemical reactions can be done only by two-photon ab-
tain absorption spectra of N O c and CC14 by an optoac- sorption, if at all. Since the absorption of photons for
coustic method. An aqueous solution of K N 0 3 was used chemical reactions by a two-photon process can be very
for the sample N03-. T h e linear absorption thresholds efficient ( q u a n t u m yield can, in principle, reach 50%),
of CC14 and N O c were measured as 290 and 332 nm, electron d e t a c h m e n t s by a two-photon process can pos-
respectively. T h e q u a n t u m yield for AgN03 solution with sibly be a unique way for producing a series of new chem-
CC14 with the 355-nm laser beam at 15 mJ/pulse was ical reactions in the future.
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 ACKNOWLEDGMENTS
be achieved by a 608-nm laser beam, even through a two- We would like to thank M. G. Payne, W. R. Garrett, P. C. Ho, C. Y.
p h o t o n absorption process. On the other hand, the elec- Ma, and J. P. Judish for useful discussions. The technical help from
tron d e t a c h m e n t of NO3- is feasible by the two-photon S. L. Allman and R. C. Phillips is acknowledged.We also acknowledge
absorption of a 608-nm laser beam. Thus, the electron Doris Crowell for help in preparation of the manuscript. Research was
sponsored by the Officeof Health and Environmental Research, U.S.
d e t a c h m e n t process from negative ions by a two-photon Department of Energy, under Contract DE-AC05-840R21400 with
absorption is confirmed as an i m p o r t a n t mechanism for Martin Marietta Energy Systems, Inc. M. P. McCann is a guest con-
the observed reactions. However, when the wavelength sultant.
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 1. L. R. Khundkar, L. Knee, and A. H. Zewail,J. Chem. Phys. 87, 77
inorganic compounds in liquid phase were d e m o n s t r a t e d (1987).
2. N. F. Scherer and A. H. Zewail, J. Chem. Phys. 87, 97 (1987).
through a two-photon absorption process either by an 3. T. S. Rose, W. L. Wilson, G. W~ickerle,and M. D. Fayer, J. Chem.
electron d e t a c h m e n t or by a dissociation process. We Phys. 86, 5370 (1987).
take advantage of the silver halide precipitates formed 4. Y. T. Lee and R. Shen, Phys. Today, November, 1 (1980).
in this work for easy observation of the progression of 5. P. A. Schuly, Aa. S. Sudbo, D. J. Kranjnovich, H. S. Kwok, Y. R.
the reaction. However, m a n y other chemical reactions Shen, and Y. T. Lee, Am. Rev. Phys. Chem. 30, 379 (1979).
6. J. G. Black, E. Yablonvitch, N. Bloembergen, and S. Mukamel,
which proceed by an electron d e t a c h m e n t process m a y Phys. Rev. Lett. 40, 115 (1978).
also occur concurrently without producing any precipi- 7. A. Tam, G. Moe, and W. Happer, Phys. Rev. Lett. 35, 1630 (1975).
tates. Since radicals such as NO3, NO2, I, C1, and Mn04 8. W. R. Ferrell, C. H. Chen, M. G. Payne, and R. D. Willis, Chem.
can be produced in liquid phase by an electron detach- Phys. Lett. 97, 460 (1983).
9. R. M. Hochstrasser, G. R. Meredith, and H. P. Trommsdorff, J.
m e n t process, these radicals will lead to chemical reac- Chem. Phys. 73, 1009 (1980).
tions with other compounds in solution due to their very 10. E. Rabinowitch, Rev. Mod. Phys. 14, 112 (1942).
reactive properties. This mechanism m a y lead to a series 11. P. Delahay, Acct. Chem. Res. 15, 40 (1982).

Component Selection for Fiber-Optic Fluorometry

RICHARD B. THOMPSON,* MICHAEL LEVINE, and LYNNE KONDRACKI
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 Sources of noise and background were identified, and generally appli-
developed for important applications in the last few years. Unfortunately, cable means for minimizing them are described.
no systematic study describing an optimized design has appeared. A Index Headings: Fiber-optic sensors; Fluorescence; Optical components.
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
INTRODUCTION
measured signal-to-noise ratio in detecting 100 picomolar fluorescein. 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-
Received 3 April 1989; revision received 1 June 1989. ing, immunodiagnostics, and chemical process monitor-
* Author to whom correspondence should be sent. ing. 1~ Fluorescence is a well developed, powerful, and

Volume 44, Number 1, 1990 06o3-7028/90/4401.011752.0o/0 APPLIED SPECTROSCOPY 1 17

© 1990 Society for Applied Spectroscopy