22 Phys. Chem. Chem. Phys.

, 2012, 14, 2234 This journal is c the Owner Societies 2012

Cite this: Phys. Chem. Chem. Phys., 2012, 14, 2234
On the nature and signatures of the solvated electron in water
B. Abel,*
a
U. Buck,
b
A. L. Sobolewski
c
and W. Domcke
d
Received 3rd June 2011, Accepted 9th September 2011
DOI: 10.1039/c1cp21803d
The hydrated electron is one of the simplest chemical transients and has been the subject of
intense investigation and speculation since its discovery in 1962 by Hart and Boag. Although
extensive kinetic and spectroscopic research on this species has been reported for many decades,
its structure, i.e., the dominant electronwater binding motif, and its binding energy remained
uncertain. A recent milestone in the research on the hydrated electron was the determination of
its binding energy by liquid-jet photoelectron spectroscopy. It turned out that the assumption of a
single electron binding motif in liquid water is an oversimplication. In addition to dierent
isomers in cluster spectroscopy and dierent transient species of unknown structure in ultrafast
experiments, long-lived hydrated electrons near the surface of liquid water have recently been
discovered. The present article gives an account of recent work on the topic solvated electrons
from the perspectives of cluster spectroscopy, condensed-phase spectroscopy, as well as theory.
It highlights and critically discusses recent ndings and their implications for our understanding
of electron solvation in aqueous environments.
I. Introduction
The solvated electron is one of the simplest reactive species in
chemistry and biology. Electrons trapped in liquid ammonia,
water, alcohols, amines and other polar liquids have been of
interest in chemistry since a long time. The hydrated electron,
in particular, is a fundamental transient species in the radiation
chemistry of water. Initially, it has been identied as a second
reducing agent (besides the hydrogen atom) in the pulse radiolysis
of pure water, which is formed with a higher yield than the
H atom.
1
The absorption spectrum of this species, centered at
720 nm, was discovered by Hart and Boag in 1962.
2
This intense,
broad and characteristically asymmetric absorption spectrum,
3
which is shown in Fig. 1, has become the most characteristic
feature of the hydrated electron.
1
Prominent features of the hydrated electron are its nite
lifetime (of the order of microseconds in pure water), its
exceptionally high rate of diusion and its high reactivity.
1
The kinetic rate constants of numerous reactions involving the
hydrated electron have extensively been investigated and
tabulated.
4
Apart from its role in the radiation chemistry of
water (e.g., in nuclear-reactor and nuclear-waste technology
5
),
the hydrated electron is also formed by ionizing radiation in
biological tissues and has a signicant potential for the
damage of DNA.
6
From the fundamental point of view, the
hydrated electron has fascinated generations of chemical
physicists as the simplest possible model of a quantum particle
interacting with a classical thermal environment.
710
The present article is intended to give a timely account of
recent developments in the investigation of the hydrated
electron, in particular by time-resolved photoelectron emission
spectroscopy, by the spectroscopy of size-selected aqueous
clusters, as well as with computational methods. The paper
is organized as follows: after a short general introduction we
discuss theoretical models of the solvated electron in the
condensed phase. Recent insights obtained by the spectroscopy
of negatively charged water clusters, water clusters doped by
alkali metal atoms, as well as acidic water clusters are surveyed
in Section III. In Section IV, we summarize recent experiments
on the photoelectron spectroscopy of hydrated electrons in
Fig. 1 Absorption spectrum of the hydrated electron in bulk water
under ambient conditions (adapted from ref. 113).
a
Wilhelm-Ostwald-Institut fur Physikalische und Theoretische
Chemie, Universitat Leipzig, D-04103 Leipzig, Germany.
E-mail: [email protected]
b
Max Planck Institut fur Dynamik und Selbstorganisation,
D-37073 Gottingen, Germany
c
Institute of Physics, Polish Academy of Sciences, PL-02668 Warsaw,
Poland
d
Department Chemie, Technische Universitat Munchen,
D-85747 Garching, Germany
PCCP
Dynamic Article Links
www.rsc.org/pccp PERSPECTIVE
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This journal is c the Owner Societies 2012 Phys. Chem. Chem. Phys., 2012, 14, 2234 23
liquid water beams that yield reliable binding energies of the
solvated electronone of the missing links in the investigation
of the solvated electron in water. In Section V we critically
discuss what is known and what is not yet known about this
species. We close with conclusions and outlook.
II. Models of the structure and dynamics of the
hydrated electron in the liquid phase
Many decades after its discovery, the hydrated electron is still
not fully characterized in terms of structural and spectroscopic
properties. The concept of an excess electron which is trapped
in a cavity or void in the hydrogen-bonded network of liquid
water was rst proposed by Stein, Platzmann and Weiss already
in the 1950s.
79
The rst attempts towards a quantitative
description of the properties of the hydrated electron were based
on the model of a spherical charge distribution interacting with a
polarizable dielectric continuum.
10
Alternative to continuum models, so-called molecular-eld
models were proposed, where it is assumed that the excess
electron is surrounded and solvated by a xed number of
water molecules in a specic conguration, e.g. in tetrahedral
11
or octahedral
12
cages. A proposed geometrical structure of the
hydrated electron, derived from electron spin resonance data in
aqueous glasses, is shown in Fig. 2. A comprehensive review of
the early continuum and molecular-eld models of the hydrated
electron in bulk water was given by Feng and Kevan.
13
Since the 1980s, the so-called cavity model of the hydrated
electron has been elaborated in considerable detail by Rossky,
Borgis, Schwartz and coworkers, treating the excess electron
as a localized quantum particle in the environment of classical
rigid water molecules.
1418
Using partially empirical electron
water pseudopotentials, extensive numerical simulations of the
stationary and transient absorption spectra of the hydrated electron
were performed. While the position and width of the stationary
absorption spectrum could be reproduced, the simulations failed to
account for the characteristic asymmetry and the extended blue
tail of the absorption prole (see Fig. 1).
1418
Very recently, it has
been demonstrated that the blue tail can be described in simulations
with electronically polarizable water molecules.
19
On the other
hand, a recent simulation employing an improved electron
water pseudopotential suggests a model in which the excess
electron resides in a region of enhanced water density rather
than in a cavity.
20
Despite enormous progress in ab initio
quantum chemistry and in the available computer power since
the initial conception of the cavity model, a quantitative
theory of the structure and the properties of the hydrated
electron in bulk water is still elusive.
1921
While the cavity model has been the consensus picture of the
hydrated electron since six decades, alternative proposals were
sporadically made. In the 1980s, Robinson and collaborators
as well as Tuttle and Golden called the cavity model into
question and proposed that molecular solventanion complexes
or radicalanion complexes, such as hydrated H
3
OOH

,
shown in Fig. 3, could be the carriers of the spectroscopic
and chemical properties of the hydrated electron.
22,23
Muguet
and Robinson emphasized the itinerant character of the H
3
O
radical in water which might explain the exceptionally high
mobility of the hydrated electron.
24
Sobolewski and Domcke
pointed out (see also Section III) that the hydrated hydronium
(H
3
O) radical is a charge-separated species in water and as such
very eectively solvated,
2527
see also ref. 28. The calculated
geometrical structures and the molecular orbitals of the unpaired
electron of H
3
O(H
2
O)
3n
, n = 0, 1, 2, clusters are shown in Fig. 4.
It is seen that the charge density of the unpaired electron detaches
from the H
3
O
+
cation with increasing cluster size. Moreover,
the ab initio calculated electronic and vibrational spectra of the
hydrated H
3
O radical exhibit striking similarities with the
spectral signatures of the hydrated electron.
25
For example,
the blue tail of the absorption spectrum is readily explained by
such molecular models of the hydrated electron.
26,27
In addition to pulse radiolysis with X-rays or electrons, the
hydrated electron can be generated by single-photon or two-
photon excitation of water,
2935
by photodetachment from
anions in aqueous solution
3640
or by photoexcitation of organic
Fig. 2 Proposed geometrical structure of the solvated electron in
aqueous glasses, derived from electron spin resonance data (adapted
from ref. 13).
Fig. 3 Intuitive structure, (H
3
OOH

), of the hydrated electron in

bulk water, postulated by Hameka, Robinson and Marsden (adapted
from ref. 22).
Fig. 4 The singly occupied highest molecular orbital of H
3
O (left),
H
3
O(H
2
O)
3
(middle) and H
3
O(H
2
O)
6
(right) clusters, calculated at the
restricted open-shell HartreeFock level.
25
The colors green/yellow
code the sign of the wavefunction. Dotted lines indicate hydrogen
bonds.
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24 Phys. Chem. Chem. Phys., 2012, 14, 2234 This journal is c the Owner Societies 2012
chromophores with acidic groups, such as indole or phenol.
4146
The resonant photodetachment of electrons from anions in
dilute salt solutions is the most convenient method of genera-
tion of hydrated electrons, since the absorption cross sections
of anions in water are large, the excitation energy is convenient
for lasers, and the quantum yields are high.
40
Despite decades
of intensive research, the mechanisms involved in photo-
ionization in aqueous solutions remain controversial. It has been
pointed out by Bradforth and coworkers that electron ejection
from neat water and photodetachment of anions in water may
be quite distinct processes.
47
The mechanisms of relaxation
towards the fully equilibrated hydrated electron are complex
and depend strongly on the excitation process. In the case of
anion photodetachment, it is assumed that charge-transfer-
to-solvent (CTTS) states are transiently populated.
40,47
In the
case of UV two-photon excitation of neat water, a number of
intermediate species (wet electrons) have been postulated
for the interpretation of transient spectra.
48
The existence of
such intermediate species and their association with structural
models remain controversial issues.
4953
The radiationless decay of the s - p excited state of the
hydrated electron has been another hotly debated issue since
several decades. The ongoing controversy concerns the mechanism
by which the electron relaxes to equilibrium after impulsive
photoexcitation. While the femtosecond pumpprobe data
obtained by several groups are similar, the controversies arise in
the interpretation. It is disputed whether the relaxation occurs by
rapid nonadiabatic radiationless decay to the electronic ground
state, followed by comparatively slow (picosecond) ground-state
cooling, or by relatively slow nonadiabatic excited-state decay,
followed by rapid equilibration in the ground state.
5457
Quantum-classical molecular simulations can explain either
scenario, depending on the electronwater pseudopotential
and the nonadiabatic surface-hopping algorithm.
16,20,5861
III. The cluster approach: models of the structure
and the dynamics of electrons in nite-size aqueous
clusters
Already very early, experiments with clusters played a crucial
role in elucidating the structure and the spectroscopic proper-
ties of the hydrated electron. Negatively charged water cluster
anions are natural nite-size models of the hydrated electron.
The size selection is no problem and once it was discovered
how to produce these clusters,
62,63
measurements of the binding
energies of the excess electron were carried out for large
64,65
and
small clusters.
66
The size dependence of the electron binding
energy followed the predicted behaviour.
67,68
Based on the
picture of spherical clusters of radius R, a plot of the measured
vertical binding energies versus 1/R (and thus n
1/3
, where n is
the cluster size) gives straight lines with negative slopes for the
cluster anions. Theoretical estimates of the slope can be derived
from dielectric continuum theory. An important issue, which is
often overlooked in using this type of diagram, is the fact that
this theory, which is based on bulk matter concepts, does not
distinguish between surface and interior states of the electron.
67
The extrapolation of the data for anionic water clusters to the
bulk value (n - N), reported by the Bowen group,
65,69,70
gives 3.3 eV. These data are shown in Fig. 5 in blue colour.
The experimental results were accompanied by calculations
which dealt with the structures and energetics of these clusters.
For large clusters in the size range n = 8128, the quantum
path-integral molecular dynamics method with a pseudo-
potential for the electronwater interaction was used.
71,72
The
calculations predicted the existence of diuse surface-bound
states as well as more compact interior states of the excess
electron. For small and intermediate sized clusters (n = 832),
the energetically favoured localisation of the excess electron is
a surface state, while for larger clusters (n = 64, 128), the
internal localisation of the electron is preferred. The calcula-
tion of the electronic absorption spectra gave good agreement
with the experimental data for the surface states.
73
Recent extensive photoelectron emission and laser-spectro-
scopic investigations of intermediate-size and large water
cluster anions by the groups of Bowen, Johnson, Zewail and
Neumark revealed a considerably more complicated picture.
69,7478
A major breakthrough in this eld was the discovery of new
classes of cluster isomers by the Neumark group when the
conditions of producing the clusters were changed.
74,79,80
The
photodetachment spectra obtained for cluster sizes n = 11200,
produced at normal pressures of 2.1 bar of the waterargon
mixture, were similar to those obtained by Coe et al.
65
When
the backing pressure was increased to 4.8 bar, however, a
much lower value of the vertical binding energy was obtained.
The complete results are plotted in Fig. 5 in red colour.
The two distinct groups of isomers are labelled I and II.
These ndings have been conrmed in an experiment with
larger photon energy (4.7 eV instead of 3.1 eV).
80
The ex-
planation of these results is as follows. In the case of expan-
sions at normal pressure (group I), the electrons are attached
to relatively warm clusters with high internal energy, which
readily leads to the lowest energy congurations by solvent
rearrangement. The expansions at high pressure (group II), on
the other hand, produce rather cold clusters with small
reorganisation energies, which carry the excess electron in a
metastable state, preferentially at the surface of the cluster.
Fig. 5 Vertical binding energies of (H
2
O)
n

clusters (blue: ref. 65;

red: ref. 74; green: ref. 81) as functions of n
1/3
. The light blue points
mark the binding energies of interior and surface electrons in the
liquid.
129
The violet triangles are based on recent calculations.
144
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This interpretation was conrmed by a very recent measure-
ment of the vertical binding energies of very cold clusters.
81
In
this experiment, heating occurred between the production and
the thermalisation of the clusters to low temperatures, so that
the clusters of class II are nearly completely suppressed and
only isomers of class I are observed. The photoelectron spectra
consist of up to three peaks, the energies of which are plotted in
Fig. 5 in green colour. Very recent DFT-based molecular
dynamics simulations for n = 32 demonstrated that in cold
clusters the electron becomes trapped in a metastable state with
comparatively low binding energy,
82
while electron attachment
to warm, liquid clusters results in an equilibrated and compara-
tively strongly bound species.
83,84
Since calculations usually
predict that internally solvated electrons are more strongly
bound than those at the surface,
71,85
the class I isomers are
assigned to internally bound electrons and class II isomers to
surface-bound electrons. We note, however, that the calculated
binding energies do not agree with the measurements, being in
both cases too large. Interestingly, the measured electronic
absorption spectra
86
are better reproduced by the surface
isomers in the computational simulations up to n = 50.
85
The experimental results were complemented by the measure-
ment of electronic relaxation time scales
75,76
and vibrational
spectroscopy of the OH stretching band.
77
In the latter case,
the spectra exhibit the double-acceptor motif for small clusters
of the isomer class I.
87
From the variety of experimental
results and the dierent data sets for the class I isomers, it is
dicult to pin down exactly the group of clusters for
which the data extrapolate correctly to the bulk values. Recent
BornOppenheimer (BO) molecular-dynamics simulations for
(H
2
O)
32

at T = 350 K, based on DFT with the PBE

functional, showed a strong correlation of the binding energy
with the degree of localisation of the electron, rather than with
the interior or surface character.
88
Extensive simulations of (H
2
O)
n

clusters of various sizes

and at various temperatures with established mixed-quantum-
classical methods did not lead to denitive structural assign-
ments.
85,8991
Ab initio molecular dynamics calculations provided
evidence that the excess electron is located at the surface of the
cluster, even if it is initially placed in the interior.
88
Although
numerous ab initio calculations with self-consistent-eld (SCF),
second-order MllerPlesset (MP2) or DFT methods have been
performed for selected structures of (H
2
O)
n

clusters, it is not
possible to explore systematically the isomers due to the huge
number of possible structures.
9296
The question of the electron
binding motif of intermediate-size water cluster anions and its
extrapolation to bulk water thus remains unsettled.
An alternative approach towards the modeling of the
hydrated electron by nite-size clusters is inspired by the
well-known beautifully blue solution of metallic sodium in
liquid ammonia.
97
In the pioneering work of Schulz, Hertel
and coworkers as well as Fuke and collaborators, the size-
dependence of the vertical ionization energy, the vertical
electronic excitation energy and the excited-state lifetime of
M(H
2
O)
n
(M = Li, Na, K) clusters were determined.
98103
The
electronic excitation energy of Na(H
2
O)
n
clusters exhibits a
signicant and non-monotonic dependence on the cluster
size.
101
The excited-state lifetimes of Na(H
2
O)
n
clusters are
systematically shorter than those of (H
2
O)
n

clusters.
103
In IR
spectra of size-selected sodium-doped water clusters, nger-
print OH vibrations have been detected which indicate a
delocalized electron at the surface of the clusters.
104,105
The results of the Hertel group for the ionization potentials
(IPs) of Na(H
2
O)
n
clusters were very surprising. Only the rst
four values of the measured IP decrease, as expected, in the
n
1/3
plot, while the IP stays constant at a value of 3.17 eV for
all larger clusters.
99,100
Very similar results were obtained for
Li(H
2
O)
n
clusters with an IP of 3.12 eV and Cs(H
2
O)
n
clusters
with an IP of 3.10 eV for n Z 4.
98,106
There were numerous
speculations on the explanation of the unexpected constant
behaviour of the IP of alkaliwater clusters. In one of the rst
experimental papers,
99
the transition from a one-center to a
two-center localization of the electron was discussed, taking
up an idea of Jortner.
68
The earliest calculation on sodium
water clusters, based on spin density functional theory, conrmed
indeed the complete separation of the electron from the Na
+
cation from n Z 4 onwards and its delocalization over the water
molecules.
107
As for the reason of the constant ionization potential,
a compensation of forces was suggested. Ab initio calculations at
the UMP2 level were also carried out for small Na and Li water
complexes.
108,109
The calculated IPs for the interior complexes are
lower than the experimental values, while the calculated IPs of the
surface complexes are higher than the measured values. In a more
recent publication, the constant IP was explained by an auto-
ionization process after a transition to high Rydberg states and
the release of considerable vibrational reorganisation energy.
110
Very recently, a second class of isomers has been observed
also for Na-doped water clusters in a special experimental
set-up which is capable of generating molecular beams with high
abundances of large clusters.
111
These results are displayed in
Fig. 6. One group with the already known IP of 3.2 eV (group I)
has been extended up to the size n = 500, and the existence of a
second group of isomers with the lower IP of 2.8 eV has been
established (group II). In the second group, the IP decreases in
the range 11 rn r15 and then stays constant, as was found for
class I. The existence of two classes of isomers in Na(H
2
O)
n
clusters calls for a comparison with the data obtained for the
water cluster anions, which are included in Fig. 6. Apart from
the dierent asymptotic behaviour, there are other remarkable
dierences. The bifurcation of the IPs into two branches occurs
for the Na-doped clusters at smaller sizes and for the same
expansion conditions. The dierence of the two extrapolated
electron binding energies is smaller for the Na(H
2
O)
n
clusters
(0.4 eV) than for the largest (H
2
O)
n

clusters (1.05 eV). For the

Na(H
2
O)
n
clusters, the lower IP and the larger critical size of
group II indicate that the charge-separation distance of the
Na
+
e

ion pair should be larger in the isomers II. This is

indeed conrmed by a simulation of the structures, using ab initio
molecular dynamics and the modelling of the ionization spectra
with the PMP2 method.
111
For n = 15, two isomers could be
distinguished with IPs of 3.1 eV and 2.6 eV, respectively, close to
the measured values. According to the simulations, the electron is
in both cases distributed over the water molecules at the surface
of the cluster. The isomers dier, however, in the Na
+
e

distance, which is 3.28 A

for the group I clusters and 4.86 A

for the group II clusters. It was concluded that one isomer

corresponds to a contact ionelectron pair and the other isomer
to a solvent-separated electronion pair.
111
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26 Phys. Chem. Chem. Phys., 2012, 14, 2234 This journal is c the Owner Societies 2012
The hydronium (oxonium) radical, H
3
O, is isoelectronic with
the sodium atom. It is thus not surprising that the H
3
O radical
dissociates into an H
3
O
+
cation and a solvated electron in water
clusters,
25,28,112
as has been found for alkaliwater clusters.
There is a fundamental dierence, however: while the spherical
alkali cations can be solvated by numerous conformations of the
hydrogen-bonded network of water, the H
3
O
+
cation is a rather
rigid trigonal pyramid which forms exceptionally strong and
directed hydrogen bonds with the rst solvation shell (the
so-called Eigen structure of protonated water). The H
3
O
+
cation thus induces, by its rigid geometry, a microcavity in the
hydrogen-bond network of water.
25
It has been argued that
the structural rigidity of the (H
3
O
+
)
aq
(e

)
aq
ion pair could be
the origin of the surprising shape stability
113
of the absorption
spectrum of the hydrated electron.
While H
3
O(H
2
O)
n
clusters are dicult to prepare directly
(through charge exchange of H
3
O
+
(H
2
O)
n
clusters with alkali
atoms
114,115
), their transient existence has been inferred indirectly
through the photodissociation of hydrogen halide (HX) molecules
in water/ice nanoparticles.
116118
The solvated H
3
O radical is
generated in these experiments through CTTS excitation of the
charge-separated H
3
O
+
X

species and is detected by the

characteristic translational energy distribution of the H-atoms
arising from the dissociation of metastable H
3
O(H
2
O)
n
clusters.
The experiments on the photodissociation of pure and doped
water clusters were carried out in the standard molecular beam
arrangement.
119
The HX(H
2
O)
n
clusters were generated by
adiabatic expansion and then dissociated by UV laser photons
at 193 nm or 243 nm. The arising H-atoms were observed by
resonance-enhanced multiphoton ionisation at 243 nm. The
H-atom fragment kinetic energy was detected in a time-of-ight
spectrometer and is the main observable in these experiments. The
photodissociation of hydrogen halides on Ar
n
clusters, in which
no ion-pair separation takes place, serves as a reference.
120,121
The
results for HClAr
n
clusters are shown in Fig. 7.
120
The narrow
peak at zero kinetic energy corresponds to the caged fragments,
while the peaks at higher energy result from the direct cage exit of
the fragments, reecting the two spinorbit states of the Br
radical. The results for the HX(H
2
O)
n
systems look completely
dierent, as shown in Fig. 8.
117,122
They exhibit only slow
fragments with energies below 0.5 eV. The dierences between
the HXAr
n
and HX(H
2
O)
n
kinetic-energy spectra can be
explained by postulating the formation of the H
3
O radical in
the HX(H
2
O)
n
clusters. The suggested mechanism is depicted
in Fig. 9.
117,118,122
It starts with the acidic dissociation of the
HX molecule in the ground state, followed by laser excitation
of the X

anion to a CTTS state. The latter relaxes by a

radiationless transition to a H
3
OX biradical.
94,122,123
The H
3
O
radical is metastable and will ultimately decay, yielding an
H
2
O molecule and the H atom which is nally detected.
Several experimental ndings support this picture.
(1) Double isotope substitution: measurements with isotopic
variants of HX and H
2
O provide strong experimental evidence
for the hypothesis that the detected H-atom originates from
the H
3
O species. Assuming hydronium radical generation
from the HX and H
2
O molecules (without H/D scrambling),
the H
3
O, H
2
DO and HD
2
O radicals would be produced in
HX(H
2
O)
n
, DX(H
2
O)
n
and HX(D
2
O)
n
clusters, respectively.
Therefore, the expected ratio of H-signals from these species
would correspond to the number of H-atoms in these radicals,
i.e., 3 : 2 : 1.
117,118
Table 1 summarizes the measured ratios of
the H-fragment signals from HX(H
2
O)
n
clusters to H-signals
from the deuterated species, HD
2
O from HX(D
2
O)
n
and
H
2
DO from DX(H
2
O)
n
, clusters, which are generally in good
Fig. 7 Kinetic-energy distribution spectra for the photolysis of
HBrAr
n
clusters with n = 100.
120
Fig. 8 Kinetic-energy distribution spectra for the photolysis of
HX(H
2
O)
n
clusters with n = 400.
117,122
Fig. 6 Ionisation potentials and vertical electron binding energies of
the dierent isomers of Na(H
2
O)
n
clusters (green)
99,111
and (H
2
O)
n

clusters (red)
74
as functions of n
1/3
. The light blue points mark the
binding energies of interior and surface electrons in the liquid.
129
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agreement with the expected values. These ratios suggest that
statistical H/D scrambling does not occur in the clusters at
least on the timescale of the present experiment (B0.65 ms).
(2) Shape of the H-atom kinetic-energy distribution: it has
been mentioned above that the dierences between the HXAr
n
and HX(H
2
O)
n
kinetic-energy spectra indicate a mechanism of
H-fragment formation in HX(H
2
O)
n
clusters which diers
from the direct photodissociation of the HX molecule. In
addition, the spectra in Fig. 8 are the same for all three HX
molecules within the experimental error bars, which is not at
all the case for the corresponding HXAr
n
clusters. The similarity
of these spectra suggests that the H-fragments originate from the
same species in all three systems, namely from the H
3
O radical,
rather than from the dierent HX molecules. The measured
shape agrees well with what is known of the energetics of the
decay H
3
O -H
2
O + H. The corresponding potential-energy
curve is shown in Fig. 10.
25
From the top of the low barrier, the
maximal energy gain is about 0.7 eV, in good agreement with the
measurements.
(3) HCl/HBr cross-section ratio: the acidic dissociation of
HCl and HBr leads to a signicant red shift of the absorption
spectrum. In fact, a new band, the CTTS band, appears. This
band can be used to detect whether HCl or HBr are acidically
dissociated under the experimental conditions. The ratio
j(HBr)/j(HCl) of the photolysis rates at the specic wave-
lengths of 191 and 243 nm is 7.4 1 for HX deposited on
water clusters. Calculations for small clusters give values around
2 for the dissociated structures and about 45 for the covalently
bonded structures.
116
This is a clear indication that the HX
molecules are acidically dissociated, preferentially forming a
contact ion pair, since otherwise we would have observed a
pronounced dilution in the isotopically substituted experiments.
This result is in agreement with other experiments using Fourier
transform IR-spectroscopy
124
and Cs
+
ion scattering
125
from
ice particles. The transition occurs at temperatures between
80 and 120 K, while the internal temperature of our clusters is
estimated to be 100120 K.
126
Alternative evidence of the formation of hydroniumhalogen
biradicals by CTTS excitation has been obtained by Castleman
and coworkers through the detection of the released iodine
atom from HI(H
2
O)
n
clusters.
127,128
Both experiments, the
detection of the released hydrogen atom and the detection of
the halogen atom, illustrate that cluster experiments can
provide information through observables which are not easily
accessible in the condensed phase, namely the kinetic-energy
distribution of the nascent products. The experimental evidence
of the central role of the H
3
O radical in the photochemistry of
acidic and salty water clusters has been supported by computa-
tional studies of excited-state potential-energy surfaces of
HX(H
2
O)
n
, X = Cl, Br and MX(H
2
O)
n
, M = Li, Na, K,
clusters.
94,123
There is thus increasing evidence that the hydrated
H
3
O radical actually exists and that it can be detected spectro-
scopicallyat least in (small and cold) water cluster environ-
ments. It is less clear whether it is actually the second reducing
species in the radiolysis and photolysis of liquid water, as has
been postulated by Robinson and coworkers long ago.
22
IV. Photoelectron spectroscopy of hydrated
electrons in liquid jets: the missing link
Very recently four research teams reported the determination
of the vertical binding energy of the solvated electron in water,
by liquid water microjet photoelectron spectroscopy.
129132
In
all these experiments, the hydrated electrons were generated by
resonant photodetachment of electrons from an anion (I

or
Fe(CN)
6
4
).
40,133
In the rst report on solvated electrons in a
water micro-jet, Siefermann et al. additionally generated
hydrated electrons by 267 nm two-photon excitation of neat
liquid water.
129
In ref. 130 and 131, the solvated electron was
detected via photoemission after excitation with 274, 266, 260
or 213 nm laser light, while EUV radiation (32 nm) was
employed in ref. 129. Recently, Lu bcke et al. and Tang et al.
reported femtosecond time-resolved photoelectron spectra of
the hydrated electron in a liquid jet.
132,134
Instead of using UVphotoelectron detachment, Siefermann et al.
directly measured vertical binding energies of hydrated electrons in
a liquid micro jet in vacuum employing a high-harmonic light
Fig. 9 Mechanism of the photodissociation of HX(H
2
O)
n
clusters.
117,118,122
Table 1 Ratios of H-fragments from HX(H
2
O)
n
clusters to H-signals
from the deuterated species, that is, HD
2
O from HX(D
2
O)
n
and
DH
2
O from DX(H
2
O)
n
118
X Cl Br I I Expected
Wavelength, l 193 193 193 243
HX(D
2
O)
n
2.7 0.4 3.0 0.3 3.1 0.5 3.9 1.0 3.0
DX(H
2
O)
n
1.1 0.4 1.4 0.2 1.6 0.4 2.5 1.0 1.5
Fig. 10 Potential-energy function along the minimum-energy path
for H-atom detachment from the hydronium radical solvated by three
water molecules, H
3
O(H
2
O)
3
(adapted from ref. 25).
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28 Phys. Chem. Chem. Phys., 2012, 14, 2234 This journal is c the Owner Societies 2012
source driven by a femtosecond laser system.
135,136
The special
features in their novel approach are the generation of solvated
electrons by a femtosecond pump pulse and the registration
of the photoelectron spectra using a time-delayed 38.7 eV
(32 nm) probe pulse, using a multiplex photoelectron time-of-
ight spectrometer to record the entire photoemission spectrum
for a particular time step.
In the latter study, hydrated electrons in liquid water were
generated rst by 267 nm laser pulse excitation of Fe(CN)
6
4
anions in a 0.5 M aqueous solution of K
4
Fe(CN)
6
. The
(Fe(CN)
6
4
)
aq
anion complex has a strong CTTS absorption
band near 267 nm. After absorption of UV light, the released
excited electron relaxes to an equilibrated solvated electron
within approximately 0.5 ps.
37
In the experiments, the EUV
probe pulse was delayed by >100 ps relative to the CTTS
excitation in order to assure equilibration of the electron. The
intensity of the UV pump pulse was tuned to avoid
two-photon excitation of water, but was suciently high to
generate a signicant density of hydrated electrons via CTTS
excitation of Fe(CN)
6
4
anions. The EUV photoelectron probe
has a high surface sensitivity and selectivity. However, in this
particular experiment the detected solvated electrons were
generated mainly in the bulk and not at the surface, because
Fe(CN)
6
4
anions are known to be repelled from the surface.
137
The photoelectron spectrum obtained from such an experiment
is displayed in Fig. 11 (error bars are indicated). The strongly
rising photoelectron signal near 4.5 eV results from the direct
ionization of the ferrocyanide anion. The photoemission line
peaking at 3.3 eV with a linewidth of 0.8 eV is observed only in
the presence of the pump pulse. The photoelectron spectrum in
Fig. 11 is the rst direct measurement of the binding energy of a
bulk hydrated electron in liquid water.
A number of experiments by other groups using liquid-jet
technology, but employing UV light (267213 nm) instead of
EUV light for ionization, have been reported recently as well.
In these experiments, the hydrated electrons were generated
also by CTTS excitation of anions (Fe(CN)
6
4
or I

). From
experiments of Tang et al.,
130
a vertical electron binding
energy of 3.27 eV was concluded, whereas Shreve et al.
131
and Lu bcke and co-workers
132
measured 3.6 eV and 3.4 eV,
respectively. Small deviations on the order of 0.10.2 eV in the
measured binding energies of the hydrated electrons may arise
from dierent anions as electron sources, dierent salt con-
centrations, or dierent (not perfect) calibration conditions or
beam charging. However, from all available experiments an
average reference value (3.4 0.2 eV) for the ionization
potential of the hydrated electron in liquid water can be
deduced. As noted above, an additional source of error may
arise from the calibration procedures used in ref. 130132 which
are based upon gas-phase measurements rather than on liquid-
phase measurements. Shreve et al.,
131
who generated hydrated
electrons from (I

)
aq
and (Fe(CN)
6
4
)
aq
, could show that the
binding energy of (e

)
aq
is insensitive to the choice of the precursor.
The experiments by Tang et al.
130
and Lu bcke et al.
132
additionally
revealed some new information on the solvation dynamics
following CTTS excitation of I

in aqueous solution and provided

a somewhat more complete picture of the ultrafast ejection,
solvation and recombination dynamics of the hydrated electron.
In an additional experiment by Siefermann et al., liquid
water in a micro-jet was excited with two 267 nm photons,
corresponding to an excitation energy of 9.30 eV, just below
the ionization potential of liquid water.
2931
The measured
EUV photoelectron emission spectrum is displayed in Fig. 12.
Contrary to the spectrum in Fig. 11, the photoemission peaks
at 1.6 eV binding energy (with a somewhat larger width of
1.3 eV) appearas in the previous caseonly in the presence
of the 267 nm pump pulse. This spectrum, which has been
generated by two-photon excitation of water, was assigned to
a novel type of hydrated electron. Surprisingly, identical
pumpprobe photoelectron spectra were obtained when the
delay time of the EUV probe pulse was varied between 2 and
100 ps, which implies that the lifetime of this transient, which
was nally assigned to a surface-bound hydrated electron by
Siefermann et al., exceeds 100 ps.
A photoemission signal of the less strongly bound hydrated
electron (1.6 eV binding energy) could only be detected by UV
two-photon excitation of neat water and with EUV ionization.
The assignment of the transient to correspond to a surface-
bound electron is consistent with the very low probing depth
of EUV generated electrons.
138,139
The dierences to the
experiments not observing the surface-bound electron are the
precursor and the probe wavelength. With respect to the latter,
it is important to realize that the photoemitted electrons
generated by the EUV probe pulse possess kinetic energy of
about 35 eV, which is near the minimum of the electron
attenuation length (EAL) curve of about 2 mm,
138,139
making
the ultrafast probe very surface selective for short-lived species.
In the laser photoionization experiments of Tang et al.,
Fig. 11 Photoelectron signal of the interior solvated electron in the
liquid jet.
129
Fig. 12 Photoelectron signal of the surface-bound electron in the
liquid jet.
129
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Shreve et al., and Lu bcke et al., on the other hand, the
photoelectron kinetic energies are of the order of 1 eV, for
which the EAL is at least one order of magnitude larger, which
explains why the surface-bound electron could not be detected,
although Lu bcke et al. report an excellent dynamical range of
their set-up (c1000). Another reason may be the choice of the
dierent precursors, which may be an indication that this
surface species can be generated by two-photon excitation of
water, but not by laser photodetachment of solvated anions.
This conjecture is supported by the fact that another surface-
sensitive technique, second harmonic generation (SHG), also
failed to detect a surface-bound electron when applied to
hydrated electrons generated by CTTS excitation of I

anions.
140
The hydrated electrons prepared by anion photo-
detachment in salt solutions and by two-photon UV excitation
of neat water thus may be physically or chemically distinct
species. Recently, the Mafune group reported spectra of iodide
anions hydrated at the surface and in the bulk, respectively.
It was pointed out that excitation with dierent wavelengths
(and thus excitation of dierent CTTS bands) may produce
dierent transients of the hydrated electron.
141
Shedding light on the energetics and qualitative binding
motifs of the bulk hydrated electron, (e

)
aq
, and the surface-
bound hydrated electron, (e

)
sf
, is quite important for the
understanding of how electrons can attach to molecules in
aqueous environments and break covalent bonds. A cartoon
picture of a typical bond-breaking situation for an organic
molecule is displayed in Fig. 13. On the left-hand side, the
binding energy (ruler) of the solvated electron and its photo-
emission spectrum are shown. As has been discussed in detail
in ref. 129, the energy acceptance window of organic molecules
with energetically suitable LUMOs (lowest unoccupied orbitals)
for solvated electrons is governed by the energies for vertical
electron attachment (VEA), adiabatic electron attachment
(AEA), as well as the vertical electron detachment energy (VDE)
of the target molecules. As can be seen in Fig. 13, the surface-
bound solvated electron is often approximately isoenergetic with
the electron attachment energy of many organic molecules, such
as DNA or CFCs (chlorinated and/or uorinated hydrocarbons),
for example. Thus, the measured binding energies of solvated
electrons provide reference values for important electron-transfer
processes taking place in aqueous solution, in particular resonant
dissociative electron attachment (RDEA) processes. The VBEs of
(e

)
aq
and (e

)
sf
together with the RDEA model allow us to
understand how electrons in aqueous solution can easily break
strong covalent bonds in systems like DNA or CFCs. This
qualitative picture reveals (in a semiquantitative fashion) why
(e

)
sf
as well as optically excited hydrated electrons may play an
important role in radiation-induced DNA damage and organic
molecule bond cleavage. RDEA of organic molecules like CFCs
indicates that the (e

)
sf
transient may also be involved in atmo-
spheric ozone chemistry, although the main reaction channels are
dominated by radicals rather than ionic species.
129
V. Synopsis: what do we know about the solvated
electron in clusters, at interfaces and in the bulk
The measured binding energies of the hydrated electron
prepared by laser photodetachment from anions in a liquid
jet are 3.3 eV,
129,130
3.4 eV,
132
and 3.6 eV,
131
which lead to a
not very accurate, but reliable reference value (3.4 0.2 eV)
for the ionization potential of the hydrated electron in liquid
water. A more weakly bound electron (1.6 eV binding energy),
prepared by UV two-photon excitation of neat water, could be
detected only with EUV ionization.
129
The interpretation as a
surface-bound hydrated electron is consistent with the very
low probing depth of EUV generated electrons.
129
The
existence of a long-lived (>100 ps) surface-bound electron in
liquid water with an ionization potential of 1.6 0.1 eV has
thus been established for the rst time. While surface-bound
hydrated electrons with low electron binding energies have
frequently been observed in cold anionic water clusters, this is
the rst report of a surface-type electron in water at ambient
temperatures. The observation of two signicantly dierent
ionization potentials of the solvated electron in liquid water is
a surprising and important nding in the long and entangled
history of the hydrated electron. The notion of a single
equilibrated hydrated electron species in liquid water, which
pervades all previous experimental and theoretical research in
the condensed phase, seems to be an oversimplication.
It should also be kept in mind that the two species
with B3.4 eV and 1.6 eV binding energies, respectively, were
prepared in a dierent manner. The hydrated electron with the
larger binding energy was generated by a CTTS transition in a
salt solution.
129132
In this case, the solvated excess electron is
accompanied by a positive counterion (Na
+
or K
+
in the
experiments discussed here). It is plausible that the positive
counter-ion stabilizes a rather localized electronic charge distribu-
tion in the interior of the solvent, which can explain the larger
binding energy of the bulk hydrated electron compared to the
surface-bound hydrated electron. Calculations predict that
the electronic absorption spectrum and the binding energy of
the solvated electron are essentially independent of the counter-
ion (Li
+
, Na
+
, K
+
, etc. in the case of salt solutions, or H
3
O
+
in
the case of neat water or acidic solutions).
27,142
The surface-bound electron in liquid water was generated by
excitation of neat water with two 267 nm photons.
129
The
excitation energy of 9.30 eV is below the ionization potential
of liquid water.
40
A water molecule is thus excited to a high
Rydberg state. If the excitation occurs suciently close to the
surface, the diuse Rydberg orbital is squeezed out of the
Fig. 13 Schematic view of the energy acceptance window for solvated
electrons depending upon the VEA (vertical electron attachment energy),
the VDE (vertical detachment energy), and the AEA (adiabatic electron
attachment energy).
129
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tight hydrogen-bond network of water, whereas the H
2
O
+
cation is stabilized (at least for very short times) by solvation
within the liquid. The measured binding energy of the surface-
bound electron in water
129
is consistent with the binding
energy of surface-type hydrated electrons in cold (H
2
O)
n

clusters.
7981
The bulk solvated and the surface-bound electrons
may thus be distinct (chemical) species (a (M
+
)
aq
(e

)
aq
contact
ion pair in the former case, and a separated (H
2
O
+
)
aq
(e

)
aq
pair in the latter case). This concept can explain the long
lifetime of the surface-bound electron in liquid water. Other-
wise, the existence of a substantial barrier for the incorporation
of the surface electron into the bulk has to be assumed. Such a
barrier seems unlikely in warm, liquid water.
8284
With the knowledge of denitive values of the ionization
potentials of surface and interior excess electrons in liquid
water at room temperature, we may return to the analysis of
the extrapolation of the (H
2
O)
n

and M(H
2
O)
n
cluster data
towards n = N (cf. Section III). The early data set
65
for the
group I water anions extrapolates nicely to the newly established
ionization potential of the bulk hydrated electron, see Fig. 5. The
more recent data for larger clusters, on the other hand, appear to
extrapolate to an ionization potential of 3.6 eV
74
or 4.0 eV,
81
somewhat larger than the bulk value, see Fig. 5. This nding is
surprising in view of the lack of a positive counter-ion in these
clusters. Could it be that the excess electron induces ionic
dissociation of a water molecule in large clusters, forming
(H
3
O
+
)
aq
, (e

)
aq
and (OH

)
aq
? The less eectively screened
interaction of (H
3
O
+
)
aq
and (e

)
aq
in nite-size clusters could
explain the unexpectedly high value of the ionization potential of
(e

)
aq
in (H
2
O)
n

clusters. The water cluster anions of group II

exhibit smaller electron binding energies which extrapolate nicely
to the newly determined value (1.6 eV) of the surface-bound
hydrated electron when only the cluster data for the larger sizes
are taken into account (see Fig. 5).
74
This fact strongly supports
the assignment of the group II clusters as surface-bound anions.
This interpretation implies that the binding energy of the surface-
bound electron in the liquid jet is not aected too much by the
presence of the H
2
O
+
counter-ion.
The deciphering of the electronic and molecular structures
of the multiple isomers of large water cluster anions may not
be possible without predictive theory. An important step
forward has recently been achieved by the calculation of
electron binding energies of large (H
2
O)
n

clusters with
ab initio methods for all electrons.
143,144
The results obtained
for (H
2
O)

104
are included in Fig. 5 as violet triangles. The
explicit values of the binding energies of (H
2
O)

104
are 2.05 eV for
the compact (interior) structure and 1.28 eV for the diuse
(surface) structure.
144
The agreement with the experimental
data is very satisfactory. Interestingly, the calculation predicts
also a compact surface state with a binding energy of 1.84 eV,
which does not fall into either group I or group II and which
has not been detected yet. According to these calculations, the
binding energy is less correlated with the location of the excess
electron on the surface or in the interior but with the compactness
of the electron density distribution. Large binding energies
correspond to compact and small binding energies to diuse
electron distributions. This correlation has been suggested
previously by calculations for smaller cluster sizes of n = 32
as well.
88
In addition, the same authors found that the process
of electron attachment to a neutral water system and subse-
quent localization is quite dierent for ambient and cryogenic
conditions.
82,84
In the former system, the cluster quickly reaches
an equilibrated structure, which corresponds to a well localized
and strongly bound solvated electron. In contrast, in a cold
system the electron gets trapped in a metastable cushion like
state at the periphery of the cluster, which is more weakly
bound. This rationalizes the observation of several isomers in
dierent cluster environments. It is plausible that anionic
clusters with a diuse electron distribution extrapolate to the
weakly bound diuse state of the liquid (surface state), while
the clusters with a compact electron distribution correlate with
the compact distribution in the liquid (interior state). We note
that despite of the fact that the clusters are solid-like and the
liquid is uid, this extrapolation is justied, since the properties
of the solvated electron are dominated by the dierent shapes of
the electron density and not so much by the solid/liquid phase
of the aqueous environment.
A common feature of the solvated electrons prepared by
laser photodetachment of salt anions (X

) in bulk water and

by dissolution of alkali atoms (M) in nite-size water clusters
is the presence of a positive counter-ion. The neutral X

, which
is generated by the photodetachment of X

, interacts weakly
with the electron and the solvent and apparently does not
aect the electronic spectra and the electron binding energy. If
the escape length of the electron is large enough and if it does
not recombine via geminate recombination with the precursor,
we may regard it (and its binding energy) to be unperturbed by
the counter ion.
It is nevertheless interesting to compare the electron binding
energies of neutral M(H
2
O)
n
clusters with the electron binding
energy of the bulk solvated electron in the liquid jet. They
should only be equal if the electron in the former case is
suciently far away or unperturbed from the cation, i.e., in
suciently large water clusters. The extrapolation of the
ionization potential of the most prominent group I of
sodiumwater clusters yields 3.2 eV (see Fig. 6), in good
agreement with the ionization potential of the hydrated
electron photodetached from Fe(CN)
6
4
anions in the liquid
jet (3.3 eV). Simulations of the electronic structure of
M(H
2
O)
n
clusters indicate that the electron distribution is
localized and corresponds to an electronion contact pair
conguration.
111
The ionization potentials of the group II of
Na(H
2
O)
n
clusters extrapolate towards 2.8 eV, see Fig. 6. A
corresponding species in the bulk has not been detected so far.
A comprehensive review of the properties of the solvated
electron in other solvents than water is beyond the scope of
this perspective. However, a brief comparison of the extra-
polation of the aqueous cluster ionization potential towards
the bulk limit with the corresponding data for two other
representative solvents, ammonia and methanol, is illuminating.
The data available for (NH
3
)
n

clusters and Na(NH

3
)
n
clusters
are shown in Fig. 14.
145
The ionization potentials of Na(NH
3
)
n
clusters decrease approximately linearly with n
1/3
, while the
electron detachment energies of the (NH
3
)
n

anions increase
linearly with n
1/3
. We note that the curves in these plots
reproduce the measured points very well. They are calculated
based on the continuum theory. Here it is crucial that the static
and the optical dielectric constants of the solid material are
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used, in accordance with the probable thermodynamic state of
the clusters under the specic production conditions. How-
ever, neither extrapolation seems to lead to the ionization
potential of the solvated electron in bulk ammonia, see
Fig. 14.
146,147
The deviations can be explained by the presence
of the counter-ion in Na(NH
3
)
n
clusters or the distance
between them and the solvated electron which is larger in
the liquid than in the solid clusters.
The results for methanol are similar, with the exception that
the ionization potentials of Na-doped clusters are constant for
large n. The ionization potential of the solvated electron in
liquid methanol has very recently been determined in a liquid
jet by laser photoionization of a NaI solution.
148
Data for
Na(CH
3
OH)
n
clusters
149
and (CH
3
OH)
n

clusters
150
also have
been reported recently. The scaling of the ionization potentials
of the clusters with n
1/3
and the value of the bulk ionization
potential (3.1 0.1 eV) are displayed in Fig. 14. Two groups
(I, II) of cluster anions with large and small electron detach-
ment energies, respectively, have been observed. In both cases,
the electron detachment energies scale linearly with n
1/3
, see
Fig. 14. As in the case of ammonia, the measured points are
reproduced by calculations with the exception of the constant
part of the ionization potentials of Na(CH
3
OH)
n
clusters
which show a behavior which is reminiscent of water. After
an initial decrease of up to n = 6, the ionization potential
remains constant and extrapolates towards 3.2 eV, in good
agreement with the measured bulk value, see Fig. 14. The
electron detachment energies of the anions, on the other hand,
extrapolate to electron binding energies which are signicantly
lower than the binding energy of the bulk solvated electron. As
observed in ammonia, a stabilizing interaction with the Na
+
counter-ion exists in the limit n -N. The solvated electrons
with and without positive counter-ions are thus dierent
species in methanol as well as in ammonia. We note that
problems with the extrapolation of excess electron properties
of amorphous solid clusters to the liquid bulk have been
predicted earlier.
82,84
In the comparison of the three solvents water, ammonia and
methanol illustrated in Fig. 5, 6 and 14, the data for water are
clearly exceptional and special. The ionization potentials of
the group-I cluster anions extrapolate towards the ionization
potential of the bulk solvated electron. The ionization poten-
tials of the group-I Na(H
2
O)
n
clusters seem to extrapolate to
the same value within the accuracy of the measurements, see
Fig. 6. The ionization potential of an excess electron in large
water clusters is thus not aected by the presence of a positive
counter-ion, in contrast to ammonia and methanol clusters.
The surface-bound electron in large (H
2
O)
n

clusters extra-
polates linearly in n
1/3
towards the surface-bound Rydberg
state observed in the liquid jet. Again, the electron binding
energy is not aected by the presence of a H
2
O
+
counter ion in
the case of neat water. Ammonia, methanol, and water are all
hydrogen bonded systems. For water and methanol the bind-
ing energy of the hydrogen bond is signicantly larger than for
ammonia. The structure of water is dominated by a four-fold
coordination, while methanol is arranged in linear long chains.
This leads to strong short-ranged interactions in water relative
to which counterions play a minor role. Another exceptional
feature of water is its incipient ionic dissociation in very large
clusters and in the bulk. As a result, excess electrons may
induce H
3
O
+
counter-ions in neat water, an eect which blurs
the distinction between clusters with and without positive
counter-ions.
An open question which has found relatively little attention
in the literature is the origin of the nite lifetime of the
equilibrated solvated electron, which is believed to be of the
order of microseconds in neat liquid water.
1
In photoexcita-
tion of HX(H
2
O)
n
clusters, clear evidence for the formation of
metastable H
3
O(H
2
O)
n
clusters has been found, but the
lifetime of these species was too short to be measured in these
experiments.
117,122,127
By extension of the time delay in liquid-
jet photoionization measurements beyond nanoseconds, it
may be possible to measure the lifetime of the hydrated
electron in the electronic ground state under well-controlled
conditions.
VI. Conclusions and outlook
We have surveyed the currently available knowledge on the
binding energies of solvated electrons in various size-selected
aqueous clusters as well as in the liquid water jet. In liquid
water, the existence of two solvated electron species with
binding energies of B3.4 eV and B1.6 eV has been established
so far. The species with 3.4 eV binding energy is tentatively
identied as the equilibrated solvated electron in water under
ambient conditions with a compact electron distribution. This
assignment is tentative insofar as the optical absorption
spectrum of this species, which is the dening property of
the hydrated electron, has not yet been measured. The species
with the lower binding energy (1.6 eV), which could be
detected only with EUV ionization and with two-photon
excitation of water as a precursor, has tentatively been
assigned as a surface-bound hydrated electron in liquid water.
The lower binding energy indicates a more extended electron-
density distribution of this species. Since the interior electron
and the surface-bound electron have been prepared in dierent
Fig. 14 Ionization potentials and vertical electron detachment
energies for ammonia
145
and methanol
149,150
as a function of the cluster
size. Blue points: ionization potentials of neutral Na-doped clusters.
Red points: detachment energies of negatively charged clusters. Green
points: measured electron binding energies of the liquid.
146148
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32 Phys. Chem. Chem. Phys., 2012, 14, 2234 This journal is c the Owner Societies 2012
manners (by CTTS excitation of a salt solution and by
two-photon UV excitation of neat water, respectively), they
could be chemically distinct species. The interior electron
prepared in salt solutions may be associated with an alkali
counter-ion, while the equilibrated surface-bound electron
prepared in neat water presumably is separated from its
original H
2
O
+
counter-ion.
We have summarized and discussed the large amount of
electron binding-energy data which are available for (H
2
O)
n

and Na(H
2
O)
n
clusters of various sizes and temperatures. In
the plot of these electron binding energies vs. n
1/3
, certain
groups of isomers can readily be identied. The binding
energies of two of these groups seem to extrapolate towards
the two binding energies measured in the liquid jet. The data
are consistent insofar as the binding energies of a group of
clusters with an internally solvated electron mainly extrapolate
towards the binding energy of the internally solvated electron
in the liquid (3.4 eV), while the binding energies of a group of
clusters carrying a relatively weakly bound surface-type
electron extrapolate towards the binding energy of the surface-
bound electron in the liquid (1.6 eV). In addition, they also agree
in the type of the electron distribution, that is, compact for the
internally bound electron and dispersed for the surface bound
electron. We note, however, that there exist isomers of (H
2
O)
n

as well as of Na(H
2
O)
n
clusters which do not have an analogue in
the liquid, e.g., a group of (H
2
O)
n

clusters with rather large

binding energies, which seem to extrapolate towards 4.0 eV, or a
group of Na(H
2
O)
n
clusters with a size-independent binding
energy of B2.8 eV (see Fig. 5 and 6).
The comparison of the electron binding energies of anionic
or alkali-doped clusters of water, ammonia and methanol
clearly reveals the anomalous solvation properties of water.
For ammonia and methanol, the extrapolated binding energies
of clusters carrying an excess electron are signicantly lower
than the corresponding binding energies of alkali-doped
clusters, revealing the stabilizing eect of the positive counter-
ion in the alkali-doped clusters, see Fig. 14. With the exception
of alkali-doped methanol clusters, the extrapolated binding
energies of these clusters dier from the corresponding binding
energy of the liquid. In the case of water, on the other hand,
there exist clusters with internally bound electrons as well as
with surface-bound electrons with ionization potentials which
extrapolate towards the corresponding ionization potentials of
the liquid, see Fig. 5 and 6. The electron binding energies of
aqueous clusters seem to be determined by specic and
relatively short-ranged hydrogen bonding interactions, rather
than long-range dielectric screening eects. An alternative
explanation of the anomalous solvation phenomena in large
water clusters as well as in liquid water could be the unique
tendency of water towards ionic dissociation. An excess electron
in water may thus generate its own H
3
O
+
counter-ion, resulting
in an overall neutral (H
3
O
+
)
aq
(e

)
aq
solvated ion pair and an
(OH

)
aq
anion.
The experiments on the photodissociation of hydrogen-
halide doped water clusters, HX(H
2
O)
n
, have provided strong
evidence of the existence of the hydronium radical, H
3
O, in the
radiation chemistry of aqueous clusters. The HX molecules are
acidically dissociated at the surface of water clusters (as well as
in the liquid). When photoexcited to a CTTS state, they relax
to an XH
3
O(H
2
O)
n1
biradical. Both the H
3
O radical as well
as the X radical have denitively been detected in cluster
experiments, the former through its decay to H
2
O + H and
the characteristic kinetic-energy distribution of the released
H atoms. For the liquid phase, such a direct proof of the
relevance of the H
3
O radical is lacking. Calculations indicate,
however, that the H
3
O radical is eectively solvated as a
(H
3
O
+
)
aq
(e

)
aq
ion pair and that this ion pair carries the
characteristic spectroscopic properties of the bulk hydrated
electron.
25,28
The hydronium cation, H
3
O
+
, may thus be the
counter-ion of the bulk hydrated electron under certain
circumstances.
The recent successful preparation and time-resolved
detection of the hydrated electron in liquid water jets via photo-
emission spectroscopyespecially with extreme UV radiation
opens up new opportunities and avenues for the investigation of
the structure and the dynamics of this elusive species, in particular
at the interface of water due to the surface selectivity of EUV
photoelectron spectroscopy. Nevertheless, even more than
50 years after the discovery of the hydrated electron, its dynamics,
binding motifs and energetics are still not as well known as is
desirable for the simplest of all chemical species in aqueous
solution. Fundamental questions which remain to be answered
are: (i) Can the interior hydrated electron be generated in the
liquid jet by two-photon UV excitation of neat water? (ii) What
happens when the excitation/generation wavelength is tuned over
an extended range? (iii) Can we obtain insight into RDEA
processes with hydrated electrons as intermediates with time-
resolved experiments?
As demonstrated in ref. 129132, the relaxation dynamics of
the nascent hydrated electron towards the equilibrated
hydrated electron can now be followed by time-resolved
photoelectron spectroscopy, which certainly will provide novel
information on the structure and relaxation kinetics of the
transient species in electron solvation (the incompletely
solvated or wet electrons
48,49
). Polarization-resolved photo-
emission spectroscopy is expected to emerge soon and will
have the potential to provide novel information on the
electron density distribution at the interface and in the bulk.
Work along these lines is presently underway in our laboratories.
Clearly, theory is needed to help us in the development of the
complete picture of the structure and dynamics of the hydrated
electron.
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