© Copyright 2001 by the American Chemical Society VOLUME 105, NUMBER 39, OCTOBER 4, 2001

LETTERS

Novel Resonance Raman Enhancement of Local Structure around Solvated Electrons in

Water

Misao Mizuno† and Tahei Tahara*,†,‡

Institute for Molecular Science (IMS), Myodaiji, Okazaki 444-8585, Japan, and
The Institute of Physical and Chemical Research (RIKEN), 2-1 Hirosawa, Wako 351-0198, Japan
ReceiVed: May 21, 2001

Picosecond time-resolved Raman spectra of water were measured under the resonance condition with the s
f p electronic transition of the solvated electron for the first time. We found that a strong transient Raman
band appears in the frequency region 30 cm-1 lower than the OH-bend band of bulk water in accordance
with the formation of solvated electrons. The observed transient Raman band was assigned to the vibration
of the solvating water molecules that strongly interact with the solvated electron in the first solvation shell.
The mechanism of this novel resonance enhancement is discussed on the basis of the vibronic theory.

Introduction electron has a spherical s-like orbital, while the three excited
states have p-like orbitals which are mutually perpendicular.
When electrons are injected into polar solvents such as water These triple p-like excited states are nondegenerate owing to
and alcohols, electrons are solvated and form so-called solvated asymmetrical solvation cavities, which makes the s f p
electrons. This solvated electron is considered the most impor- absorption very broad.5 Ultrafast dynamics of the solvated
tant basic anionic species in solutions, and it has been electron has been studied using picosecond and femtosecond
extensively studied by variety of experimental and theoretical time-resolved visible-infrared absorption spectroscopy.8-18 The
methods.1-18 The geometrical structure of the solvated electron existence of several short-lived precursors, including “wet
in low-temperature matrices has been studied by ESR spectros- electron” , have been indicated.8-14 Time-resolved experiments
copy.2-4 In the case of water, it was concluded that the solvated using a three-pulse sequence were also carried out in order to
electron is surrounded by six equivalent water molecules that examine the relaxation process after the s f p photoexcita-
are arranged octahedrally in the first solvation shell and that tion.15-18
one of the two OH bonds of each water molecule is oriented While large number of spectroscopic studies have been carried
toward the electron.2 Concerning the electronic states, it is well- out, direct information about solvating molecules is scarce,
known that the solvated electron exhibits a broad structureless especially for the solvated electron at room temperature.
absorption band extending from the visible to near-infrared Obviously, it is very desirable to measure vibrational spectra
region. The absorption has been attributed to the strongly of the solvating molecules in order to understand the local
allowed electronic transition from the ground state to the three solvation structure around the electron. However, it is not an
lowest excited states.5-7 The ground state of the solvated easy task because the signal from the bulk solvent dominates
spectra in ordinary circumstances.
* Corresponding author. E-mail: tahara@[Link]. Fax +81-564-54- In this letter, we report transient Raman spectra of water that
2254.
† Institute for Molecular Science (IMS). were measured under the condition resonant with the s f p
‡ The Institute of Physical and Chemical Research (RIKEN). transition of the solvated electron. A transient Raman band
10.1021/jp0119173 CCC: $20.00 © 2001 American Chemical Society
Published on Web 09/07/2001
8824 J. Phys. Chem. A, Vol. 105, No. 39, 2001 Letters

appeared in accordance with the formation of solvated electrons,

and we assigned it to the resonance Raman scattering of the
water molecules that directly solvate the electron.

Experimental Section
The experimental setup for picosecond time-resolved Raman
measurements has been already described elsewhere.19,20 Briefly,
a picosecond mode-locked Ti:sapphire laser (Spectra-Physics,
Tsunami) pumped by an Ar+ laser (Spectra-Physics, Beam-Lok
2060-10SA) was used as the light source of the apparatus. The
output of this oscillator laser was amplified by a regenerative
amplifier (Spectra-Physics, Spitfire) with a cw Q-switched Nd:
YLF laser (Spectra-Physics, Merlin) and then used for the
experiment. The wavelength, pulse width, energy, and repetition
rate of the amplified pulse were 800 nm, 2 ps, 600 µJ, and 1
kHz, respectively. The second harmonic of the amplified pulse
was generated by a 5 mm LBO crystal, and then the third
harmonic was created by a 5 mm BBO crystal. The obtained
third harmonic (267 nm, 25 µJ) was used for photoexcitation
to generate solvated electrons in water. The residual fundamental
pulse (10 µJ) was used for probing Raman scattering under the
resonance condition with the s f p transition of the solvated
electron. The pump and probe pulses were focused with a quartz
lens (f ) 50 mm) onto a thin film-like jet stream of the sample Figure 1. Time-resolved absorption trace monitored at 800 nm (a)
solution. Typical cross correlation time between the pump and and picosecond time-resolved resonance Raman spectra (b) of water
probe pulses was about 5 ps (fwhm). The Raman scattering was in the presence of indole (1.7 × 10-3 mol dm-3; pump laser, 267 nm;
collected and introduced into a spectrometer (Jobin-Yvon, probe laser, 800 nm). The luminescence background has been subtracted
HR320) by a camera lens, after Rayleigh scattering was from each time-resolved Raman spectrum.
eliminated by a holographic notch filter (Kaiser Optical Systems,
water was observed. After photoexcitation, however, a strong
Inc.). A liquid nitrogen cooled CCD camera (Princeton Instru-
transient Raman band appeared in the frequency region about
ments, LN/CCD-1100PB) was used for the detection of Raman
30 cm-1 lower than the Raman band of bulk water (indicated
scattering. Time-resolved absorption was measured by monitor-
by arrows in the figure). The observed spectra showed that a
ing the intensity of the probe pulse passing through the sample.
transient species of water was created with the generation of
Indole (special grade) was purchased from Tokyo Chemical
the solvated electron.
Industry Co., Ltd. and sublimated in vacuo. Water was distilled
We also measured picosecond time-resolved Raman spectra
and deionized before use. Acetonitrile (special or HPLC grade)
of neat water as well as a potassium iodide aqueous solution
was purchased from Wako Pure Chemical Industries and used
under the same experimental condition. The same transient
as received.
Raman band was observed as the case of the indole aqueous
solution. In addition, we found that the intensity of the transient
Results and Discussion
Raman band coincided with the intensity of transient absorption
Figure 1a shows the time-resolved absorption trace of an signal. For example, both of the transient Raman and transient
indole aqueous solution monitored at 800 nm. The indole absorption signals were significantly weak in neat water
molecule was added in water for efficient generation of the compared with those in the indole aqueous solution. This weak
solvated electron, since indole injects electrons much more easily transient signal in neat water is ascribable to the low yield of
than neat water owing to its low ionization potential (indole, the solvated electron in the absence of the electron seed
4.35 eV;21 water, 8.8 eV8). As clearly seen in this figure, a molecule. These experimental results assured that the observed
transient absorption signal appeared immediately after photo- transient Raman signal is not due to the cation radical of the
excitation. The intensity maximum of the s f p transition of seed molecule but certainly attributable to the water transient
the solvated electron is located around 720 nm in water1 so that appears along with the solvated electron.
that the observed transient absorption is attributable to the The intensity of the observed transient Raman band was
solvated electron. Although the cation radical of indole is also obviously enhanced under the probing condition resonant with
generated with photoexcitation, it does not contribute to the the s f p transition of the solvated electron. In addition, the
signal at 800 nm since its absorption is located around 580 nm.12 OH-bending frequency of the transient is 30 cm-1 lower than
The lifetime of the solvated electron in water is as long as a that of bulk water, which implies that the structure of the
few hundreds nanoseconds in the absence of the electron relevant water transient is somewhat different from that of the
scavenger.22 Therefore, the decay of the transient absorption ordinary water molecule. These facts strongly indicate that the
was not recognized in the time range of the present measure- water molecule giving rise to the transient Raman band directly
ment. The absorption change due to the early solvation process interacts with the solvated electron.
of electrons was not observed in the present experiment because For solvated electron trapped in low-temperature glass
it is finished in the subpicosecond time region.8-11,15-18 matrices, ESR spectroscopy revealed that six water molecules
Figure 1b shows picosecond time-resolved Raman spectra solvate the electron in the first solvation shell. The distance
measured under the same condition as that of the transient between the center of the electron and the closest hydrogen atom
absorption measurement. Before the pump pulse irradiation, only was evaluated to be 0.21 nm2. A molecular dynamics simulation,
a weak Raman band due to the OH-bending vibration of bulk on the other hand, indicated that the orbital radius of the s-like
Letters J. Phys. Chem. A, Vol. 105, No. 39, 2001 8825

Figure 3. Sketch of the vibronic states of the local solvation structure

around the solvated electron.

larger than that of the Raman band of bulk water. On the other
hand, the transient absorption intensity (∆A) measured under
the same condition was 0.073, which means that the concentra-
tion of solvated electron in water is ∼1.7 × 10-4 mol dm-3.
(The extinction coefficient of the solvated electron in water is
∼1.5 × 104 mol-1 dm3 cm-1 at 800 nm,22 and the optical path
length of the jet stream of the sample solution is ∼300 µm.)
Figure 2. Time-resolved absorption trace monitored at 800 nm (a) Since we can consider that six water molecules directly solvate
and picosecond time-resolved resonance Raman spectra (b) of a water- the electron also in solution at room temperature (by referring
acetonitrile mixture (4:1) in the presence of indole (1.7 × 10-3 mol to the study in low-temperature matrices2), the concentration
dm-3; pump laser, 267 nm; probe laser, 800 nm). Raman intensity at
of the water molecule that solvates the electron is estimated to
each delay time has been normalized by using the solvent band intensity.
The luminescence background has been subtracted from each time- be 1.0 × 10-3 mol dm-3. It implies that the number of the water
resolved Raman spectrum. molecules giving rise to the strong transient Raman band is just
2.3 × 10-5 of the number of the water molecule in the bulk
(44 mol dm-3). Consequently, on the basis of the concentration
ground-state electron is ∼0.2 nm while that of p-like excited and the Raman intensity between the solvating water and the
state is ∼0.3 nm.5 Since the radius of the orbital of the solvated bulk water, we estimate the factor of the resonance Raman
electron is almost the same as the distance to the water enhancement is as large as 2 × 105.
molecules in the first solvation shell, the interaction between Although the resonance enhancement of the Raman band due
the electron and the molecules in the first solvation shell should to the solvating water molecule was unexpected, we now
be much stronger than that with molecules in the outer shell. consider that this phenomenon is explainable in the framework
Therefore, we assigned the observed water transient, which of the vibronic theory.23 Since the water molecules in the first
strongly interacts with the solvated electron, to the water solvation shell strongly interacts with the electron at the center,
molecules that solvate the electron in the first solvation shell. it is highly likely that the vibrational states of the surrounding
Since it was a little surprising to us that the water molecule water molecules are affected with the change of the electronic
gains high resonance Raman enhancement through the electronic state of the solvated electron. In other words, a significant
transition of the electron, we evaluated the magnitude of this structural change of solvating water molecules is expected to
novel resonance enhancement. The time-resolved Raman spectra occur with the s f p electronic transition of the solvated
in Figure 1b, however, are not very suitable for quantitative electron. It is well-known that those vibrational modes along
discussion about the intensity because the Raman intensity which the structural change occurs with the electronic transition
measured at the positive delay time is affected by the self- give rise to strong Raman bands in resonance Raman spectra
absorption effect due to the transient absorption. Therefore, we (the A-term mechanism). Therefore, if we consider the local
carried out picosecond time-resolved Raman measurements for solvation structure as a whole, it is natural to expect that the
a water-acetonitrile mixture. It is known that the solvated Raman band of the solvating water molecules gains high-
electron is not formed in acetonitrile.12 Thus, in the experiment intensity enhancement under the probe condition resonant with
for the mixed solvent, the Raman intensity of acetonitrile is the s f p transition of the solvated electron. The present result
expected not to change with the generation of the solvated suggests that we need to theoretically treat the vibronic states
electron so that the intensity of the Raman bands of acetonitrile of the local solvation structure as a “supermolecule” or a
can be used as the internal intensity standard for time-resolved “cluster” (Figure 3).
Raman spectra. Obviously, it is highly desirable to examine the OH-stretch
Figure 2 shows the time-resolved absorption trace and time- region of water under the same experimental condition. With
resolved resonance Raman spectra of a water-acetonitrile the probe at 800 nm, the Raman scattering due to the OH
mixture (4:1) in the presence of indole. With photoexcitation, stretching vibration appears around 1100 nm. Since our detector
the same spectral change, i.e., the appearance of the transient (CCD) has no sensitivity for this wavelength region, we could
Raman band in the OH-bend region, was observed also for the not perform any measurements at the present moment. We are
mixed solvent. By comparing the time-resolved spectrum at 50 now planning picosecond time-resolved Raman measurements
ps with the spectrum taken with only probe irradiation, we with use of an InGaAs array detector that has sensitivity for
evaluated the intensity of transient Raman band is about 4 times near-infrared region.
8826 J. Phys. Chem. A, Vol. 105, No. 39, 2001 Letters

Acknowledgment. This work was partly supported by a (11) Shi, X.; Long, F. H.; Lu, H.; Eisenthal, K. B. J. Phys. Chem. 1995,
Grant-in-Aid for Scientific Research (B) (No. 13440183) from 99, 6917.
the Japan Society for Promotion of Science (JSPS) and a Grant- (12) Hirata, Y.; Murata, N.; Tanioka, Y.; Mataga, N. J. Phys. Chem.
1989, 93, 4527.
in-Aid for Scientific Research on Priority Area (A) (No. (13) Hirata, Y.; Mataga, N. J. Phys. Chem. 1990, 94, 8503.
12042283) from the Ministry of Education, Culture, Sports, (14) Hirata, Y.; Mataga, N. J. Phys. Chem. 1991, 95, 9067.
Science and Technology. (15) Kimura, Y.; Alfano, J. C.; Walhout, P. K.; Barbara, P. F. J. Phys.
Chem. 1994, 98, 3450.
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