IEEE JOURNAL OF QUANTUM ELECTRONICS, VOL. 38, NO. 1, JANUARY 2002 31
Two-Photon Absorption Coefficients of Several
Liquids at 264 nm
Adrian Dragomir, John G. McInerney, Senior Member, IEEE, David N. Nikogosyan, and Albert A. Ruth
Abstract—The nonlinear absorption of water (H O), heavy
water (D O), ethanol, methanol, hexane, cyclohexane, 1,
2-dichloroethane, and chloroform at 264 nm was studied using
femtosecond laser pulses. The two-photon absorption coefficients
for these liquids were found to be between (34 3) 10 cm/W
and (95 11) 10 cm/W.
Index Terms—Femtosecond UV pulses, liquids, nonlinear trans-
mission, two-photon absorption coefficient, two-photon absorption
cross-section.
I. INTRODUCTION
L
ASER-INDUCED UV two-photon absorption in water
was first discovered in 1980 [1], [2]. With the rapid
development of high-intensity UV laser systems and their
applications in chemical and biological sciences, investigations
of two-photon absorption (TPA) in liquids have become in-
creasingly important. Over the last two decades, TPA has been
widely used for ionization and/or dissociation of neat water,
heavy water, methanol, and ethanol as well as for triggering
various photophysical processes from highly excited states,
such as electron solvation and geminate recombination [3]–[8].
However, only very few quantitative measurements of TPA
coefficients in water [9], [10] and ethanol [11] have been
performed so far.
Recently, we showed that using femtosecond pulses at
264 nm from a newly developed laser system, TPA coefficients
in fused silica and crystalline quartz can be measured with
high accuracy [12]. In the present paper, measurements of TPA
coefficients in a variety of eight liquids, i.e., water (H O),
heavy water (D O), methanol, ethanol, hexane, cyclohexane,
1, 2-dichloroethane, and chloroform, are reported.
II. EXPERIMENTAL SETUP
The experimental setup is shown schematically in Fig. 1. The
laser system
1
emitted single femtosecond pulses (about 200 fs
each) with a repetition rate of 27 Hz at 264 nm (4th harmonic
of Nd : glass laser radiation). The sample liquid was placed in
a Suprasil cuvette with an optical pathlength of 0.2 cm and a
Manuscript received July 10, 2001; revised October 1, 2001.
A. Dragomir, J. G. McInerney, and D. N. Nikogosyan are with the Department
of Physics, National University of Ireland, University College Cork, Cork, Ire-
land (e-mail: niko@physics.ucc.ie).
A. A. Ruth is with the Department of Chemistry, National University of Ire-
land, University College Cork, Cork, Ireland.
Publisher Item Identifier S 0018-9197(02)00176-8.
1
Twinkle, Light Conversion Ltd.
total thickness of 0.5 cm. A fused silica lens with a long focal
length (454 mm) was used to form a converging laser beam in
order to vary the incident intensity between 5 and 30 GW/cm ,
depending on the position of the sample in the beam. Care was
taken to keep the sample cuvette in a region between the lens and
the focal point well away from the latter, where self-focusing
is entirely negligible (see [12]). Two pyroelectric detectors in
connection with an energy meter interfaced to a computer were
used to measure the energies of the incident laser pulses and
those transmitted through the sample liquid. All measurements
were performed at room temperature.
The following liquids were used as supplied: heavy water
(Merck, 99.8%), methanol (Fluka, 99.8%), absolute ethanol
(96%), hexane (Rathburn Chemicals, 95%), cyclohexane
(Wardle, 99%), 1, 2-dichlorethane (Sigma Aldrich, 99.8%),
and chloroform (Romil Pure Chemicals, 99.8%). The doubly
distilled water was prepared in the Chemistry Department of
University College Cork.
The linear absorption of the samples at nm was mea-
sured using the spectrophotometer (HP8453). The transmittance
through the filled cuvette is determined by the expression
(1)
where is the linear absorption coefficient of the liquid, is
the optical pathlength in the liquid, is the reflectivity of the
air-fused silica interface, and is the reflectivity of the fused
silica–liquid interface. Values for and the refractive index of
the cell window material were determined from direct spec-
trophotometric measurements with an empty cell, yielding the
values of and . The reflectivity was
calculated using the Fresnel formula
(2)
where is the refractive index of the sample liquid. The
refractive indices for all liquids at nm were
extrapolated from published dispersion data [13]. In Table I,
the values for , , and the experimental linear absorption
coefficients are listed for the eight liquids investigated. The
value of either of the liquids studied is much larger than that
of Suprasil fused silica ( 0.001 cm ); therefore, the linear
absorption of the cuvette windows is not accounted for in the
evaluation procedure.
0018–9197/02$17.00 © 2002 IEEE