DOI: 10.1126/science.

1189588
, 65 (2010); 329 Science
et al. Ross E. Larsen
Does the Hydrated Electron Occupy a Cavity?
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Does the Hydrated Electron
Occupy a Cavity?
Ross E. Larsen,* William J. Glover, Benjamin J. Schwartz*
Since the discovery of the hydrated electron more than 40 years ago, a general consensus
has emerged that the hydrated electron occupies a quasispherical cavity in liquid water.
We simulated the electronic structure and dynamics of the hydrated electron using a rigorously
derived pseudopotential to treat the electron-water interaction, which incorporates attractive
oxygen and repulsive hydrogen features that have not been included in previous pseudopotentials.
What emerged was a hydrated electron that did not reside in a cavity but instead occupied
a ~1-nanometer-diameter region of enhanced water density. Both the calculated ground-state
absorption spectrum and the excited-state spectral dynamics after simulated photoexcitation
of this noncavity hydrated electron showed excellent agreement with experiment. The relaxation
pathway involves a rapid internal conversion followed by slow ground-state cooling, the opposite of
the mechanism implicated by simulations in which the hydrated electron occupies a cavity.
T
he nature of excess electrons in liquid wa-
ter has been of continuing interest due to
their important role in radiation chemistry
and charge-transfer reactions. Excess electrons
can be created directly by pulse radiolysis, or they
can be formed after ionization of a solute if the
detached electron resides in the liquid far from its
parent cation. When liquid water locally contains
one more electron than is needed to maintain
electrical neutrality, the metastable localized species
that is created has been termed the hydrated elec-
tron ( e

aq
). The hydrated electron has attracted
considerable theoretical interest, in part because
it poses the intriguing question of how a polar
solvent acts to localize an object whose size and
shape is determined self-consistently by interac-
tion with its surroundings. Thus, although the
hydrated electron is nominally a simple single-
electron species, the many-body nature of its inter-
actions with the surrounding water molecules has
made this a nontrivial problem in statistical me-
chanics and quantum chemistry that can directly
confront experiment.
Early continuum and semicontinuum mod-
els treated the hydrated electron as a spherical
charge distribution with a radius determined self-
consistently by polarization of the surrounding
solvent. Such models provided insight into the
mechanism by which electrons may be localized
but did not give a microscopic picture for the
structure of the solvent in the presence of the
e

aq
. Subsequent studies used molecular simu-
lations to address such structural questions; in
such simulations, the excess electron was treated
quantum-mechanically, the surrounding water
molecules were treated classically, and the electron-
water interaction was described by what is known
formally as a pseudopotential (13). Although
alternatives have been proposed (4), the consen-
sus picture that emerged from such simulations
was that a hydrated electron excludes water from
a small region, so that the e

aq
occupies a nearly
spherical void that is surrounded by water mol-
ecules whose O-H bonds point toward the cavity
(5). This picture is known as the cavity model
of the hydrated electron, and because simu-
lations in which the electron occupies a cavity
agree reasonably well with experiment, the cav-
ity model has come to dominate both experi-
mental and theoretical discussions of the e

aq
(6).
Despite this well-accepted view, important
questions still remain about the properties of the
hydrated electron. One ongoing controversy is the
mechanism by which the e

aq
relaxes to equilibri-
um after photoexcitation. The debate is whether
relaxation occurs by rapid internal conversion to
the ground state followed by slowreequilibration
of the surrounding water molecules (79) or by
slow internal conversion followed by rapid re-
equilibration on the ground state (10, 11). An-
other concern is that the cavity model predicts
a strong anisotropy in polarized transient hole-
burning experiments (12, 13), but this predicted
signature is not seen experimentally (14, 15).
Here, we describe the results of molecular dy-
namics simulations based on a new, rigorously
derived electron-water pseudopotential. The re-
sults of our calculations suggest that the hydrated
electron does not occupy a cavity but instead en-
compasses a region of enhanced water density in
which the electronic wavefunction overlaps ~37
water molecules. We calculated several distinct
ground- and excited-state properties of this non-
cavity electron and, in every case, have found that
our predictions are consistent with experiment. For
certain properties, our simulations offer a better
match to experiment than simulations in which
the electron resides in a cavity. Thus, we suggest
that previous claims that the hydrated electron
occupies a cavity may have been premature and
that a different physical picture of this important
species may be more appropriate.
A key element in any simulation of the hy-
drated electron is the electron-water interac-
tion specified by the pseudopotential. Although
there is a formalism for deriving pseudopoten-
tials using information from quantum chemistry
calculations (16), the challenge lies in represent-
ing such pseudopotentials in a functional form
that is convenient for molecular simulation. Thus,
most bulk hydrated electron simulations have
been based on ad hoc electron-water interactions
(6, 17) or have used pseudopotentials that were
constrained to have a simple functional form
that neglected important details in the molecular-
core region (2). Recently, however, we have
shown that it is possible to generate rigorous
molecular pseudopotentials directly from the
orbitals obtained in quantum chemistry calcula-
tions (16). Thus, we decided to reexamine the
properties of the hydrated electron using a rig-
orously derived electron-water pseudopotential
(18), a two-dimensional contour plot of which
is shown in the left panels of Fig. 1. Some of
the notable features of our pseudopotential are
the presence of deep attractive wells on each
hydrogen atom, a substantial repulsion of the
electron between the two hydrogen atoms, and
Department of Chemistry and Biochemistry, University of
California, Los Angeles, Los Angeles, CA 900951569, USA.
*To whom correspondence should be addressed. E-mail:
[email protected] (R.E.L.); [email protected] (B.J.S.)
Present address: National Renewable Energy Laboratory,
Golden, CO 804013305, USA.
Present address: Department of Chemistry, Stanford Uni-
versity, Stanford, CA 943055080, USA.
2 1 0 1 2
2
1
0
1
2
z /
y

/

2 1 0 1 2
z /
2 1 0 1 2
2
1
0
1
2
z /
x

/

2 1 0 1 2
z /
2 1 0 1 2
2
1
0
1
2
y /
x

/

2 1 0 1 2
y /
Exact, smoothed Fit
-0.2
0
0.2
-
-
-
-
- -
- - - -
- -
- - - -
-
-
Energy

(hartree)
Fig. 1. Cuts of the full smoothed electron-water
pseudopotential (left panels) and our fit to the full
smoothed pseudopotential (right panels, eq. S5, and
table S1); the energy scale is in Hartree. The water
molecule lies in the y-z plane with the dipole
pointing along the z axis. The O atom is at position
y = 0.0, z = 0.11663 , and the H atoms are at y =
T0.76001, z =0.46654. The upper panels showa
cut parallel to the molecular y-z plane with x =
0.0260 ; the middle panels show a cut perpendic-
ular to the plane of the molecule with y = 0.0260
(which is the closest plane to the principal axis of the
molecule given our finite grid sampling); the bottom
panels show a cut perpendicular to the molecular
plane through the two H atoms.
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an attractive feature near the oxygen atom op-
posite the hydrogens. Although the presence of
the latter two features has been noted in work ex-
amining water-cluster anions (3, 19), these features
have not been incorporated into the pseudopoten-
tials in previous bulke

aq
simulations (1, 2), so their
importance to the behavior of the bulk hydrated
electron has not been explored. Thus, to account
for the presence of these features, we have fitted
our potential to a sum of hydrogen- and oxygen-
centered terms, plus a sum of terms centered mid-
way between the two hydrogen atoms; the fit is
shown in the right panels of Fig. 1, and the fitting
parameters and functional form of our pseudopo-
tential are given in table S1.
Using our rigorously determined potential,
we have run extensive mixed quantum/classical
molecular dynamics (MD) simulations of hun-
dreds of water molecules confined with a single
excess electron in a cubic box. The water-water
interactions were governed by a flexible simple
point charge model (18), and the simulation time
step was 0.5 fs. The adiabatic eigenstates of the
electron were found at every time step on a 32
by 32 by 32 cubic grid that was 18.17 on a side
using the Lanczos algorithm in the manner de-
scribed in (20); we verified that the eigenstates did
not change by more than 0.03 eV when a 64
3
grid
was used. The equilibrium (ground state) results
displayed here come from 30 ps of dynamics with
499 water molecules in a box 24.64 on a side in
the microcanonical ensemble (constant number of
molecules, volume, and total energy) at an aver-
age temperature of ~300 K. The nonadiabatic,
excited-state trajectories were performed with
200 water molecules in a box the same size as the
cubic grid. A comparison of the spectroscopic and
other properties found with 200 and 499 water
molecules is given in figs. S3 and S4.
Figure 2 displays structural and electronic
properties of the e

aq
computed from these sim-
ulations. The black dashed and solid curves in
Fig. 2A display average values of the hydrated
electrons charge density and r
2
times this den-
sity, respectively, relative to the electrons aver-
age position, or center-of-mass (COM). These
curves show that the hydrated electron is clearly
not a point-particle but instead has charge dis-
tributed over a ~2.6 radius of gyration, in
good agreement with the experimental value of
~2.5 obtained from spectral moment analysis
(21). Fig. 2A also shows radial distribution func-
tions (RDFs), which give the probability of
finding either H atoms (red dashed curve) or O
atoms (solid blue curve) on the surrounding wa-
ter molecules relative to the electrons COM.
Clearly, the electrons charge density has con-
siderable overlap with regions containing a high
density of water molecules: A major fraction
of the charge density of the e

aq
is found be-
tween the first hydrogen and oxygen peaks in
the RDFs. This is seen explicitly in the snap-
shots shown in Fig. 2, B and C, which show that
many water molecules reside inside the volume
occupied by the hydrated electron.
The radial distribution functions (RDFs) in
Fig. 2A make clear that the hydrated electron
does not exclude a discrete volume about itself,
so that a description of the e

aq
as residing in a
cavity is inappropriate. Although the RDFs be-
come small at distances close to the electrons
COM, the fall-off is gradual, more akin to the
solvation structure around a soft sphere rather
than a hard excluded volume. Moreover, the
RDFs do not reach zero at the origin, indicating
that solvent fluctuations occasionally allow wa-
ter oxygen atoms to penetrate all the way to the
hydrated electrons COM. The fact that there is
a higher probability for H atoms to be close to
the electrons COM than O atoms indicates that
the electron induces a net orientational ordering
of the water molecules inside the electron (an
ordering that can also be seen in Fig. 2, B and
C), although the preference for water O-H bonds
to point toward the COM is reduced from that
seen in cavity models of the electron (2, 5, 10).
The slight maxima and minima in the RDFs
show that the electron also induces some transla-
tional structural organization of the nearby water
molecules, but even the slight minimum in the
oxygen RDF at ~3.5 A

lies above 1. Integration of

the RDF gives an average number of molecules
within 6 A

of the electron COM of ~37, whereas

only ~30 water molecules would be expected with-
in this distance if the average local density were
that of neat water. Thus, rather than pushing water
away from the region of maximum electron den-
sity, as in the cavity model, our simulations show
that the hydrated electron occupies a region of
enhanced water density extending out ~6 A

. This
result implies that the net interaction of the electron
with water is attractive, inducing an electrostric-
tion effect, in direct contrast to the overall repulsive
interaction necessary to produce a cavity. The ef-
fect that the hydrated electron has on the structure
of the nearby water molecules is summarized in
Fig. 2D, which shows water-water RDFs for water
molecules inside the electron (within 3.25 A

of the
electrons COM, middle curves) and those in pure
water at both normal (1.00 g/cm
3
, lower curves)
and higher (1.23 g/cm
3
, upper curves) densities.
Clearly, the water molecules inside the electron are
packed together more like water at high density
than like water at normal density.
Figure 3 shows various energetic and spec-
troscopic properties of the hydrated electron
calculated with our potential. As expected, the
time-dependent adiabatic energy levels shown
in Fig. 3A fluctuate in response to water mo-
tions, but the energy levels differ in two ways from
those calculated in simulations in which the elec-
0
0.5
1
1.5
2
2.5
0 2 4 6 8 10 12
e

w
a
t
e
r

g
(
r
)
r ()
Hydrogen
Oxygen
r
2
||
2
||
2
e to:
COM
B
C
0
1
2
3
4
5
6
7
8
1.5 2 2.5 3 3.5
Hydrogen-Hydrogen
Hydrogen-Oxygen
Oxygen-Oxygen
r ()

w
a
t
e
r

w
a
t
e
r

g
(
r
)
water in e
aq
1.23 g/cc water
1.00 g/cc water
A
D
Fig. 2. (A) Electron COM-to-water site radial distribution functions (colored curves). The dashed curve is
the square of the wavefunction as a function of distance from the COM, calculated as a time-average
over 12.5 ps of dynamics, and the solid curve is this quantity multiplied by r
2
(both in arbitrary units).
(B) All water molecules within 6.0 of the COM of the electron for a representative configuration. The
wire mesh outer contour encloses 90% of the electrons charge density, and the opaque inner contour
encloses 50%. (C) Expanded version of the configuration in (B), with the 50% contour represented by a
mesh. (D) Water-water radial distribution functions for pure water at density 1.00 g/cm
3
(lower curves),
1.23 g/cm
3
(upper curves), and for water molecules located within 3.25 of the electron center of mass
(middle curves). The three sets of curves have been shifted vertically for clarity.
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tron resides in a cavity. First, in our calculations
the excited states form a continuous band, unlike
cavity models that have three low-lying excited
states and then an energy gap below the higher-
lying, so-called continuum states. Second, in our
model, the solvent induces greater fluctuations in
the ground-state energy than in the excited-state
energies. In calculations with approximate pseudo-
potentials where the electron resides in a cavity,
the fluctuations of the ground- and excited-state
energies are of similar magnitude (1, 2, 10).
We calculated the optical absorption spec-
trum of the e

aq
from our simulations by binning
the energy gaps weighted by the square of the
appropriate transition dipole moment for the
lowest seven transitions from configurations taken
every 10 fs (18), as shown by the red dotted curve
in Fig. 3B. The agreement with the Gaussian-
Lorentzian fit to the experimental spectrum (solid
black curve) is remarkable: The spectrum cal-
culated with our model matches the experimen-
tal spectrum more closely than calculations with
pseudopotentials that lead to a cavity-based hy-
drated electron (1, 2, 10). Moreover, shifting the
experimental spectrum 0.15 eV lower in ener-
gy (dashed black curve) shows that the shape
of the low-energy edge of the calculated spec-
trum is correct. We do not expect to reproduce
the high-energy tail of the spectrum in these
calculations, both because of the small number of
excited states we have included (calculations with
20 states on a few configurations showthat the tail
does begin to fill in) and because we have not
accounted for quantum effects in the solvent (22).
Fig. 3C shows a decomposition of the calculated
absorption spectrum of the e

aq
into sub-bands as-
sociated with transitions from the ground state to
each of the lowest seven excited states. As in the
cavity model, the bulk of the spectrumcomes from
transitions to the lowest three excited states. How-
ever, because there is no gap between the first
three excited states and the higher-lying states, our
computed spectrum does not show the unphys-
ical dip between the bright states and the high-
energy tail typically seen in spectra predicted by
cavity models (1, 2, 6, 10, 17, 22).
The three lowest excited states that contrib-
ute the most to the absorption spectrum in our
model of the e

aq
each have a positive and a neg-
ative lobe, as shown for a representative configu-
ration in fig. S1, although the lobes are typically
of different sizes. These three lowest-lying quasi-
p-like states are substantially larger than the
ground state of the hydrated electron, having
average radii of gyration of 4.6(0.3), 5.0(0.5),
and 5.4(0.6) A

, in increasing order of energy

(root-mean-squared deviations given in parenthe-
ses). These radii match well with the estimates
from excited-state scavenging experiments (23).
Perhaps more interestingly, the three low-lying
quasi-p-like states do not point in rigorously
orthogonal directions: Dot products between the
normalized transition dipoles from the ground to
the three quasi-p-like states, cos q

u
i


u
j
, are
distributed roughly as exp(cosq/0.1), as shown
in fig. S2. These deviations from strict orthogo-
nality occur because small fluctuations in the
positions of water molecules far from the electron
COM can alter the orientation of one of the ex-
cited states without greatly affecting the other
two. This is in sharp contrast to what occurs
when the electron occupies a cavity: In that case,
the cavitys shape strictly determines the relative
orientations of the transition dipoles (supporting
online text) (12, 24).
In the cavity model, the width of the elec-
trons absorption spectrum reflects fluctuations
in the shape of the cavity that change the split-
ting of three relatively well-separated sub-bands,
representing transitions to the three bright p-like
excited states (24). In contrast, our calculations
suggest that the spectrum is broadened by large
fluctuations in the ground-state energy, so the
underlying individual absorption sub-bands over-
lap substantially and are not distinct, as shown
in Fig. 3C. Each of the three bright sub-spectra
spans roughly 3/4 of the width of the entire
band, consistent with experimental estimates of
the magnitude of homogeneous broadening in
the hydrated electron spectrum (25). The fact that
the transitions to the different excited states over-
lap in energy and have transition dipoles that are
not strictly orthogonal suggests that there should
be no detectable anisotropy in polarized pump-
probe hole-burning measurements on the hydrated
electron (15). This is a very different prediction
from the strong polarized anisotropy that emerges
in simulations based on the cavity model (12, 13).
Thus, unlike the cavity model, our calculations
are consistent with the experimental observations
that polarized hole-burning experiments on the
e

aq
show no anisotropy (14, 15).
In addition to the ground-state electronic
structure, a sound model for the e

aq
should also
be able to correctly predict the relaxation dy-
namics after photoexcitation to one of the low-
lying optically accessible excited states. Thus, we
chose to compute the relaxation dynamics of a
photoexcited hydrated electron with our model
by running 20 nonadiabatic, nonequilibrium tra-
jectories in which the electron is instantane-
ously resonantly excited by light of energy 1.55 T
.01 eV (~800 nm) (18). For probe wavelengths
near the excitation wavelength, the red curve
in Fig. 4C shows that the calculated transient dy-
namics of the e

aq
involve bleach recovery on both
fast (150 fs, 75% amplitude) and slow (1.1 ps,
25% amplitude) time scales (black curve). The
transient dynamics in this region resemble the
time traces of Barbara and co-workers (at a
~740-nm pump wavelength, to account for the
slight red shift of our calculated spectrum) (7).
At wavelengths longer than the excitation pulse,
our calculations predict an initial bleach followed
by a delayed transient absorption (blue and green
curves in Fig. 4C), also similar to the experimen-
tal data (11). We note that the magnitude of the
delayed absorption should be slightly underes-
timated by our calculations because we compute
transitions only to the lowest seven excited states.
Figure 4D shows that this means that the agree-
ment between our calculated transient absorption
spectra and experiment is at least as good as
and possibly better thanthat with the cavity
model (dotted blue curve at t = 1 ps), which
requires the calculated spectra to be red-shifted
by nearly 0.7 eV to come close to matching the
experimental data (dashed blue curve at t = 1 ps)
(2, 12).
Simulations in which the electron resides in
a cavity suggest that the transient absorption dy-
namics are governed primarily by solvation of
the excited state, with a slow internal conversion
followed by fast equilibration of the ground state
0.5 1 1.5 2 2.5 3 3.5
I
(
E
)

(
a
r
b
.

u
n
i
t
s
)
Energy (eV)
Current results
Experiment
Exp. (shifted)
0.5 1 1.5 2 2.5 3
I
(
E
)

(
a
r
b
.

u
n
i
t
s
)
Energy (eV)
Total
-6.5
-6
-5.5
-5
-4.5
-4
-3.5
-3
0 0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6
E
n
e
r
g
y

(
e
V
)
Time (ps)
A B C
Fig. 3. Equilibrium properties of the hydrated electron. (A) Time evolution
of the lowest eight adiabatic energy levels. (B) Calculated absorption
spectrum (red dotted curve) from the ground to the lowest seven excited
states, analytical fit to the experimental absorption spectrum [black solid
curve (30)], and experimental spectrum shifted by 0.15 eV (black dashed
curve). (C) Total absorption spectrum (black curve) and absorption spectra
associated with excitation to each of the lowest seven adiabatic states (col-
ored curves).
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(10, 12, 13). This adiabatic picture, however, is
not the only way to interpret the observed spectral
behavior. Early pump-probe measurements on the
e

aq
were explained in terms of a nonadiabatic
model involving rapid internal conversion followed
by slow cooling of a nonequilibrium ground state
(7, 8). Moreover, more recent experiments studying
the excitation of water cluster anions also strongly
suggest that relaxation occurs by rapid internal
conversion followed by slow ground-state cooling
(9). The experimental literature on the relaxation
of the bulk hydrated electron seems to be about
evenly divided between the adiabatic and non-
adiabatic relaxation mechanisms.
Figure 4A shows a representative excited-
state trajectory of the hydrated electron simu-
lated with our model. The salient features are
that the ground-to-occupied energy gap closes
very rapidly [an observation that is consistent
with photon echo experiments on the hydrated
electron (26)]; the electron then makes a transition
to the ground state rapidly, in ~280 fs; and after
the transition, the ground-state energy returns to
its equilibrium value slowly, in a time 1 ps.
Figure 4B shows the probability of the hydrated
electron remaining excited as a function of time
after excitation for our 20-trajectory ensemble;
the average excited-state lifetime is ~280 fs with
a root-mean-squared deviation of ~150 fs. Taken
together, our calculations predict that photoex-
cited hydrated electrons return to the ground state
much faster than suggested by calculations in
which the e

aq
resides in a cavity (10, 20).
Because the underlying relaxation mechanism
in our simulations is different, it is important to
contrast our assignment of the delayed near-IR
transient absorption to those from simulations in
which the electron resides in a cavity. In our sim-
ulations, the induced absorption results from tran-
sitions originating from a nonequilibrated ground
state of the e

aq
, produced after rapid internal con-
version. In the cavity model, the delayed absorp-
tion comes from so-called p-to-p transitions from
the occupied first excited state to higher-lying ex-
cited states; both the energy gap and the transition
dipole magnitudes of these transitions increase
over the first few hundred fs (10). Thus, although
both models appear to describe the pump-probe
data roughly equally well, provided that an em-
pirical shift of the predicted spectra is used for
the cavity model, the interpretation of the dy-
namics underlying the spectral transients in the
two models is completely different.
Finally, we note that our results also appear
consistent with resonance Raman measurements
on the hydrated electron (27), which showed that
waters near the e

aq
have both their bend and
stretch frequencies red-shifted relative to those in
pure water. Our model suggests that the water
molecules that are strongly coupled to the electron
are at an effectively higher density than water
molecules in the bulk. It is well known that the
Raman spectrum of high-density water under pres-
sure shows down-shifts of both the bending and
stretching modes, a result of the fact that O-H
bonds are weakened when protons can be more
equally shared between the O atoms of water
molecules that are closer together (28). Thus, part
of the major features seen in the Raman spectros-
copy of the hydrated electron may result from the
change in local water density and structure induced
by the presence of the electron. In addition, the
strong overlap of the electronic charge density with
antibonding molecular orbitals on multiple water
molecules also likely plays a role in weakening
the OH bonds (25). The slight orientational order-
ing of the water molecules inside the electron is
also consistent with the Raman spectroscopy,
which shows that the two O-H bonds of the water
molecules coupled to the electron experience dif-
ferent average environments (27).
How should recent ab initio simulations of
the e

aq
be viewed in light of our new model?
Boero et al. have performed a DFT-based Car-
Parrinello (CP) study of an excess electron amidst
32 water molecules, which predicted that the hy-
drated electron occupied a cavity (29), albeit one
smaller than those seen in previous cavity-model
calculations (1, 2, 10). The cavity in this CP sim-
ulation was transient, however, with a very short
lifetime (29). We found that simulations with
our model using smaller numbers of water mol-
ecules gave larger fluctuations in properties such
as the electrons radius of gyration (supporting
online text), so it is possible that with only 32 wa-
ter molecules, the transient cavities Boero et al.
observed were due to such fluctuations. Thus, we
do not see any inconsistencies between our re-
sults and the CP simulations.
References and Notes
1. J. Schnitker, P. J. Rossky, J. Chem. Phys. 86, 3462 (1987).
2. L. Turi, D. Borgis, J. Chem. Phys. 117, 6186 (2002).
-5
-4.5
-4
-3.5
-3
-2.5
-2
0 0.2 0.4 0.6 0.8 1.0 1.2 1.4
E
n
e
r
g
y

(
e
V
)
Time (ps)
Occupied state
0
0.2
0.4
0.6
0.8
1
0 100 200 300 400 500 600
E
x
c
i
t
e
d
-
s
t
a
t
e

p
r
o
b
a
b
i
l
i
t
y
Time (fs)
-0.5 0 0.5 1.0 1.5 2.0 2.5
Time (ps)
800 nm 880 nm
1240 nm
400 600 800 1000 1200
O
D

(
a
r
b
.

u
n
i
t
s
)
O
D

(
a
r
b
.

u
n
i
t
s
)
Probe Wavelength (nm)
0 ps
1 ps
2.5 ps
0
0
0
0
0
0
0
800-nm fit
A
B
C D
This Work
Experiment
0.5 ps
Cavity Model
(shifted by 0.7 eV)
Fig. 4. Nonadiabatic excited-state relaxation dynamics of the hydrated electron. (A) Adiabatic energy
levels (colored curves) as a function of time after excitation by 1.55 eV, with the heavy black curve
indicating the occupied state. (B) The probability for the electron to remain in an excited state as a
function of time after excitation for our 20 trajectories. (C) Calculated transient absorption dynamics at
130-fs time resolution for the wavelengths indicated; the curves have been offset vertically for clarity. The
black curve shows a fit of our predicted results to a double-exponential decay with time scales of 150 fs
and 1100 fs with a ~3:1 amplitude ratio, respectively, in excellent agreement with experimental data (7).
(D) Simulated transient absorption spectra (solid curves) for the indicated times after excitation, with the
curves offset vertically for clarity. Error bars are T1 SD of the mean. The dashed blue curve shows the
experimental transient spectrum at 1 ps (11). The dotted blue curve shows the cavity models simulated
transient spectrum at 1 ps, shifted by 0.68 eV to aid comparison to the experiment (13).
2 JULY 2010 VOL 329 SCIENCE www.sciencemag.org 68
REPORTS

o
n

O
c
t
o
b
e
r

2
9
,

2
0
1
2
w
w
w
.
s
c
i
e
n
c
e
m
a
g
.
o
r
g
D
o
w
n
l
o
a
d
e
d

f
r
o
m

3. L. D. Jacobson, C. F. Williams, J. M. Herbert, J. Chem.
Phys. 130, 124115 (2009).
4. A. L. Sobolewski, W. Domcke, Phys. Chem. Chem. Phys. 4,
4 (2002).
5. L. Kevan, Acc. Chem. Res. 14, 138 (1981).
6. J. Schnitker, P. J. Rossky, J. Chem. Phys. 131, 037102
(2009).
7. Y. Kimura, J. C. Alfano, P. K. Walhout, P. F. Barbara,
J. Phys. Chem. 98, 3450 (1994).
8. M. S. Pshenichnikov, A. Baltuska, D. A. Wiersma,
Chem. Phys. Lett. 389, 171 (2004).
9. A. E. Bragg, J. R. R. Verlet, A. Kammrath, O. Cheshnovsky,
D. M. Neumark, Science 306, 669 (2004).
10. B. J. Schwartz, P. J. Rossky, J. Chem. Phys. 101, 6902
(1994).
11. K. Yokoyama, C. Silva, D. H. Son, P. K. Walhout,
P. F. Barbara, J. Phys. Chem. A 102, 6957 (1998).
12. B. J. Schwartz, P. J. Rossky, Phys. Rev. Lett. 72, 3282
(1994).
13. B. J. Schwartz, P. J. Rossky, J. Chem. Phys. 101, 6917 (1994).
14. A. Baltuska, M. F. Emde, M. Pshenichnikov, D. A. Wiersma,
J. Phys. Chem. A 103, 10065 (1999).
15. M. C. Cavanagh, I. Martini, B. J. Schwartz, Chem. Phys.
Lett. 396, 359 (2004).
16. C. J. Smallwood, R. E. Larsen, W. J. Glover, B. J. Schwartz,
J. Chem. Phys. 125, 074102 (2006).
17. R. E. Larsen, W. J. Glover, B. J. Schwartz, J. Chem. Phys.
131, 037101, author reply 037102 (2009).
18. Materials and methods are available as supporting
material on Science Online.
19. T. Sommerfeld, A. DeFusco, K. D. Jordan, J. Phys. Chem. A
112, 11021 (2008).
20. R. E. Larsen, M. J. Bedard-Hearn, B. J. Schwartz, J. Phys.
Chem. B 110, 20055 (2006).
21. D. M. Bartels, K. Takahashi, J. A. Cline, T. W. Marin,
C. D. Jonah, J. Phys. Chem. A 109, 1299 (2005).
22. L. Turi, G. Hantal, P. J. Rossky, D. Borgis, J. Chem. Phys.
131, 024119 (2009).
23. T. W. Kee, D. H. Son, P. Kambhampati, P. F. Barbara,
J. Phys. Chem. A 105, 8434 (2001).
24. J. Schnitker, K. Motakabbir, P. J. Rossky, R. A. Friesner,
Phys. Rev. Lett. 60, 456 (1988).
25. M. J. Tauber, R. A. Mathies, J. Phys. Chem. A 105, 10952
(2001).
26. S. J. Rosenthal, B. J. Schwartz, P. J. Rossky, Chem. Phys.
Lett. 229, 443 (1994).
27. M. J. Tauber, R. A. Mathies, J. Am. Chem. Soc. 125, 1394
(2003).
28. G. E. Walrafen, J. Soln. Chem. 2, 159 (1973).
29. M. Boero, M. Parrinello, K. Terakura, T. Ikeshoji, C. C. Liew,
Phys. Rev. Lett. 90, 226403 (2003).
30. F.-Y. Jou, G. R. Freeman, J. Phys. Chem. 83, 2383
(1979).
31. This research was funded by NSF under grant
CHE-0908548. We thank M. C. Larsen and A. E. Bragg for
helpful discussions, C. N. Mejia for performing the
preliminary Hartree-Fock calculations that we used to
generate the new electron-water pseudopotential,
and K. D. Jordan for a critical reading of
the manuscript.
Supporting Online Material
www.sciencemag.org/cgi/content/full/329/5987/65/DC1
Materials and Methods
SOM Text
Figs. S1 to S4
Table S1
References
15 March 2010; accepted 14 May 2010
10.1126/science.1189588
Experimental Results for H
2
Formation from H

and H and
Implications for First Star Formation
H. Kreckel,
1
* H. Bruhns,
1
M. ek,
2
S. C. O. Glover,
3
K. A. Miller,
1
X. Urbain,
4
D. W. Savin
1
During the epoch of first star formation, molecular hydrogen (H
2
) generated via associative detachment
(AD) of H

and H is believed to have been the main coolant of primordial gas for temperatures below
10
4
kelvin. The uncertainty in the cross section for this reaction has limited our understanding of
protogalaxy formation during this epoch and of the characteristic masses and cooling times for the first
stars. We report precise energy-resolved measurements of the AD reaction, made with the use of a
specially constructed merged-beams apparatus. Our results agreed well with the most recent theoretically
calculated cross section, which we then used in cosmological simulations to demonstrate how the reduced
AD uncertainty improves constraints of the predicted masses for Population III stars.
M
ore than 40 years ago, Saslaw and
Zipoy (1) proposed that the formation
of neutral molecular hydrogen played a
central role in the cooling of primordial gas. Col-
lisions of atomic H with molecular H
2
transfer
kinetic energy from the H into internal energy of
the H
2
through ro-vibrational excitation of the
molecule. Subsequently, the molecule can radia-
tively relax and the emitted photon may escape
from the cloud, thereby cooling the gas. Recent
numerical models for the formation of the first
(Population III) stars have demonstrated the im-
portance of primordial H
2
as a coolant (24).
During the epoch of first star formation, H
2
was formed primarily via the associative detach-
ment (AD) reaction (3),
H

H H

2
H
2
e

1
Although this is the simplest anion-neutral chem-
ical reaction, theory and experiment have failed
to reach consensus for both the magnitude and
energy dependence of the rate coefficient (5).
This uncertainty severely limits our ability to
model protogalaxies and metal-free stars forming
from initially ionized gas, such as in H II regions
created by earlier Population III stars (5, 6). For
example, it limits our ability to predict whether a
given protogalactic halo can cool and condense
on a sufficiently short time scale before it is
gravitationally disrupted through a collision with
another protogalactic halo (5). Additionally, the
cosmological simulations we have performed for
this work show that for gas in free fall, the re-
sulting spread in the minimumgas temperature
and in the gas density at which this minimum is
reachedleads to a factor of >20 difference in
the Jeans mass. Finally, for shocked gas under-
going isobaric collapse, the time required to reach
the cosmic microwave background tempera-
ture can differ by up to a factor of 3. This affects
the likelihood that such gas will cool and col-
lapse to form a star before undergoing another
shock (6).
The three most recent theoretical calculations
for Eq. 1 have not converged, although they all
used the same potential for the intermediate H
2

anion. The results of Sakimoto (7) and ek et al.

(8) are in good agreement with one another but
not with the calculations of Launay et al. (9). The
room-temperature flowing afterglow results of
(1012), however, are discrepant with the cal-
culations of Sakimoto and ek et al. but are in
reasonable agreement with those of Launay et al.
See (13) for a brief review. Unfortunately, the
existing experimental work provides no con-
straint on the temperature dependence for Eq. 1,
which limits the ability of these measurements to
benchmark theory. Considering all these issues,
we have designed and built a dedicated merged-
beams apparatus in order to perform energy-
resolved AD measurements spanning the entire
relevant collision energy range.
An overview of the experiment is shown in
Fig. 1; a detailed description is given in (14). In
the first leg of the apparatus, we extract an H

beam from a negatively biased ion source to

achieve a beam energy eU
s
of ~10 keV. We col-
limate it via standard ion beam technology. The
atomic Hbeam is generated in the central portion
of the second leg of the apparatus, where ~7.4%
of the H

is neutralized by photodetachment
(PD) with a laser diode array at 975 nm with
continuous-wave power of 1.4 kW. At the photon
energy (1.25 eV) and power density used, the PD
process produces exclusively ground-state H
atoms. The PD occurs in the center of a drift tube,
1.2 min length, used to control the relative energy
between the H

and Hbeams. When a voltage U

f
is applied to the tube, the H

ions are decelerated

as they enter the tube and are then accelerated
1
Columbia Astrophysics Laboratory, Columbia University,
New York, NY 10027, USA.
2
Charles University Prague,
Faculty of Mathematics and Physics, Institute of Theoretical
Physics, 180 00 Praha 8, Czech Republic.
3
Zentrum fr As-
tronomie der Universitt Heidelberg, Institut fr Theoretische
Astrophysik, 69120 Heidelberg, Germany.
4
Institute of Con-
densed Matter and Nanosciences, Universit Catholique de
Louvain, Louvain-la-Neuve B-1348, Belgium.
*Present address: Department of Chemistry, University of
Illinois, Urbana, IL 61801, USA.
To whom correspondence should be addressed. E-mail:
[email protected]
Present address: INFICON GmbH, D-50968 Cologne, Germany.
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