164 J. Phys. Chem.

A 1997, 101, 164-169

Structure and Energetics of Ionized Water Clusters: (H2O)n+, n ) 2-5

R. N. Barnett and Uzi Landman*

School of Physics, Georgia Institute of Technology, Atlanta, Georgia 30332-0430
ReceiVed: September 6, 1996; In Final Form: October 23, 1996X

Energetics and geometrical structures of neutral, (H2O)n, and ionized, (H2O)n+, water clusters, with n ) 2-5,
are investigated using local-spin-density functional electronic structure calculations with exchange-correlation
gradient corrections. While the ground-state structures of the neutral clusters are hydrogen-bonded cyclic
ones, those of the molecular ions are noncyclic. The lowest energy isomers of the ionized (H2O)n+ clusters
contain a hydrazine-like fragment, (H2OOH2)+, hydrogen-bonded to the extra water molecules. Higher energy
isomers of the cluster ions are based on hydrogen bonding to a disproportionated fragment, (H3O)+OH.

1. Introduction cluster ions, (H2O)n+, have been observed (for n up to 8) using

The properties of water clusters have been the subject of a special supersonic ion beam source5 and by photoionization
increasing research activities in recent years due to the ubiquity of neutral Arm(H2O)n clusters6 (for n up to 10). However, no
of H2O as one of the most important polar solvents, as well as evidence pertaining to the structures of unprotonated ionized
the importance of water clusters in atmospheric science. These water clusters has been given in these experimental studies.
studies include investigations of neutral water clusters,1 (H2O)n, The difficulty of observing unprotonated water cluster ions
electron attachment and localization modes (surface and interior is attributed12,25 to the large configurational differences between
states) in water clusters,1b,2 (H2O)n- (see also investigations of the parent neutrals and the ionized clusters, which result in small
(H2O)n-2 in ref 3), ionized clusters,4-8 i.e., (H2O)n+, and Franck-Condon factors between the minima of the hypersur-
fragmentation processes occurring upon ionization,9-12 as well faces of the two. Consequently, the vertically ionized cluster
as studies of ion and neutral hydration systems,9,13,14 i.e., is formed in a highly vibrationally excited state, leading to
X(H2O)n and X(H2O)n(, where X is a solvated species (atom dissociation. From theoretical studies of the ionization of (H2O)2
or molecule), including protonated clusters,9,15 (H2O)nH+. Such it was concluded12 that the 2A′′ vertically ionized cation
studies provide insights into the nature of the hydrogen bonding [(H2O)2]+ (in the following square brackets surrounding the
and the rearrangement dynamics of hydrogen-bond networks, molecule denote a vertically ionized state) can undergo a fast
proton-transfer mechanisms, solvation phenomena, charging (simulated12 to be about 50 fs) barrierless “autoprotonation”
processes, and fundamental mechanisms underlying ion chem- process induced by the charge imbalance due to the localized
istry of the upper atmosphere.16 ionization hole on the proton donor, involving a significant
Mass spectra of water clusters are usually dominated by contraction of the interoxygen distance, and resulting in a
protonated cluster ions (H2O)nH+, which are produced by fast disproportionated ion (dpi), OH(H3O+), where dOO ) 2.502 Å,
intracluster reactions during the ionization process. Indeed, compared to 2.957 Å in (H2O)2 (see Figure 1 and Table 1).
protonated cluster ions have been observed as the major Excess energy in the ionized cluster may lead to dissociation
constituent in a weakly ionized gas containing at least trace of the dpi state into OH + H3O+, with a calculated endother-
amounts of water,5,18 as well as in flowing afterglows,19 in micity of ∼1 eV. (We note here12 that the energy of the
flames,20 and in Earth’s upper atmosphere.16 (The protonated vertically ionized state, [(H2O)2]+, exceeds that of the OH +
dimer ion (H2O)2H+ plays an important role in the ion chemistry H3O+ dissociation limit by 0.08 eV.) Generalization of the
of the upper atmosphere, dominating the ion composition in above sequence to larger clusters6 leads to the following scheme:
the D region in the ionosphere.21) Furthermore, charged water
vIP dpi D
species (such as the oxonium ion, H3O+, and H3O2+) occur often (H2O)n 98 [(H2O)n]+ 98 (H2O)n-2H3O+- - -OH 98
as solvated charge carriers in aqueous solutions, condensed
phases (ices), and clusters (such as the celebrated (H2O)21H+ (H2O)n-2(H3O)+ + OH
cluster,22 which may be described as (H2O)20‚H3O+, i.e., an
oxonium hydrated in a cage of 20 water molecules). Conse- where vIP, dpi, and D denote the vertical ionization, dispro-
quently, such species have been investigated extensively, portional, and dissociation processes, respectively. Therefore,
experimentally and theoretically.9,23 observation of the unprotonated ionized cluster (H2O)n+ requires
In contrast, experimental observations4-7 and theoretical that its energy be reduced sufficiently to prevent dissociation,
investigations23,24 of unprotonated (H2O)n+ cluster ions are such as via the evaporation of argon atoms in the experiments
scarce. Early photoionization studies7 of (H2O)2 have detected involving photoionization of Arm(H2O)n clusters.6 Similarly the
a low signal of (H2O)2+ near threshold and have determined an gas-phase association reaction (H2O)n + H2O+ f (H2O)n+
upper bound of the dimer adiabatic ionization potential aIP- requires effective energy transfer to the cold expanding gas, as
[(H2O)2] e 11.21 ( 0.09 eV (a lower value of 10.81-10.90 in the experiments involving injected H2O+ ions into a
eV has been recently suggested8). Later He I photoelectron supersonic water expansion.5
measurements18 determined the vertical ionization potential vIP While the dpi, (H3O)+OH, state of the ionized water dimer
{(H2O)2] ) 12.1 ( 0.1 eV. Trimer ions, (H2O)3+, have been was invoked in the above discussion, recent investigation of
observed4 (with an intensity of 1% of the H3O+(H2O) signal) pathways and dynamics of dissociation of ionized (H2O)2 have
in low-energy electron impact (15 eV) measurements, and larger revealed12 that it is not the lowest ground-state configuration
of the water dimer cation. Rather, these local-spin-density
X Abstract published in AdVance ACS Abstracts, December 15, 1996. functional (LSD) calculations (including generalized exchange-
S1089-5639(96)02761-2 CCC: $14.00 © 1997 American Chemical Society
Structure and Energetics of Ionized Water Clusters J. Phys. Chem. A, Vol. 101, No. 2, 1997 165

Dissociation of the water dimer may occur via alternative

channels:12 (i) the “oxonium channel” (O), (H2O)2 + hν f
H3O+ + OH + e-, and (ii) the “water channel” (W), (H2O)2 +
hν f H2O+ + H2O + e-. The calculated energies required
for dissociative ionization through these channels are Ed(O) )
11.67 eV (compared to 11.73 eV determined from the photoion
yield curve7), and Ed(W) ) 12.75 eV (compared to the experi-
mentally estimated25 value of 12.86 eV). We also note (see
Figure 2 in ref 12) that while the vertically ionized state,
[(H2O)2]+, may dissociate spontaneously into the O channel,
its dissociation into the W channel requires an energy of 1.01
eV.
Figure 1. Optimized configurations (calculated at the GGC level) of
If the vertically ionized dimer relaxes into the ground state
the ground-state neutral water dimer, (H2O)2, the hydrazine-like ground of the OH(H3O)+ dpi isomer, dissociation into the O channel
state of the dimer cation (H2O)2+(a) (marked “anti”) and of the (H2O)2+- requires an energy of 1.02 eV (compared to an experimentally
(g) (marked “gauche”), and disproportionated ion, (OH)(H3O)+, isomers. estimated7 lower bound of 0.6 eV), and dissociation into the W
Large and small spheres denote oxygen and hydrogen atoms, respec- channel requires 2.11 eV (compared to an experimental lower
tively. Geometrical parameters are given in Table 1. bound7 of 1.6-1.7 eV). On the other hand, the vertically
TABLE 1: Geometrical Parameters (Distances in Angstroms ionized dimer may relax into the (H2O)2+(a), ground state, or
and Angles in Degrees) of the Optimal Structures the (H2O)2+(g) isomer, in a process entailing a large configu-
(Calculated with a Plane-Wave Cutoff Energy of 158 Ry) for rational change and involving a barrier, or conversion between
the Neutral Dimer, (H2O)2, the Singly Charged Dimer the dpi and the a or g isomers may occur, involving a barrier of
Cation in the Disproportionate Ion Configuration, ∼0.2 eV (the barrier for the reverse transformation is ∼0.42
(OH)(H2O)+, the (a) Ground-State Hydrazine-like
Configuration, and the (g) Isomera eV); indeed Born-Oppenheimer (BO)-LSD-molecular dynamics
(MD) simulations of the (OH)H3O+ isomer thermalized at 150,
(H2O)2+
300, and 600 K have shown12 that at the higher temperature,
(H2O)2 (OH)(H3O)+ (a) (g) following several back-and-forth proton-transfer events, a vi-
Distances (Å) brationally excited (H2O)2+(a) state was formed. Dissociation
H11O1 0.976 1.409 0.981 0.980 of the (a) state into the W and O channels requires dissociation
H12O1 0.962 0.987 0.981 0.977 energies of 2.34 and 1.25 eV, respectively. From the above
H21O2 0.965 0.971 0.981 0.980
we conclude that the O channel is energetically favorable and
H22O2 0.965 0.971 0.981 0.977
O1O2 2.957 2.502 2.176 2.182 will dominate for cold parent dimers and low (near threshold)
H11O2 1.982 1.095 ionization energies. However, dissociation into the W channel
Angles (deg) may occur for higher excitation energies.
∠(H11O1H12) 104.2 117.3 104.5 107.9 In light of the above we focus in this paper on the energetics
∠(B1O1O2) 125.7 119.7 97.3 105.5 and structures of neutral (H2O)n and unprotonated ionized
φ1 0.0 0.0 90.0 79.8 (H2O)n+ clusters, with n e 5. The main findings of our studies
∠(H21O2H22) 104.7 112.5 104.5 107.9
are that while neutral (H2O)n clusters, with n ) 3, 4, and 5,
∠(B2O2O1) 124.0 144.1 97.3 105.5
φ2 90.0 90.0 90.0 79.8 form ground-state quasi-planar cyclic (polygonal) structures with
∠(O2O1H11) 94.5 91.1 each monomer acting as both a single donor and single acceptor,
∠(O2O1H12) 94.5 107.1 the ground-state structures of the ionized clusters are noncyclic,
∠(O1H11O2) 177.0 176.0 with chainlike structures containing a hydrazine-like fragment,
Dihedral Angles (deg) (H2O-OH2)+, being the energetically optimal ones. Molecular
B1O1B2 180.0 180.0 180.0 104.5 ion isomers containing an oxonium fragment, (H3O+)OH, are
H11O1O2H22 180.0 100.9 higher in energy (∼0.1 eV), and the cyclic (H2O)n+ structures
a Points B (or B ) are on the b (or b ) vector defined as the vector
1 2 1 2 are energetically unfavorable by a larger amount (∼0.5-0.6 eV
in the corresponding HOH plane, whose origin is on the oxygen (O1 higher in energy than the chainlike structures). Following a brief
or O2), and bisecting the corresponding ∠(HOH) angle (see Figure 1). description in section 2 of the computational method, we present
φ1 (or φ2) is the angle (see Figure 1) required in order to rotate the our results in section 3 and summarize them in section 4.
corresponding water molecule (1 or 2) about its b vector (defined
above), so that the HOH plane of the molecule coincides with the
corresponding BO1O2 plane. 2. Method
In calculations of the total energies, structural optimization,
correlation gradient corrections, GGC) predicted that an ionized and molecular dynamics simulations,12 we have used our Born-
dimer with a hydrazine-like configuration26 is lower than the Oppenheimer (BO) local-spin-density functional (LSD) molec-
dpi state by 0.22 eV (see (H2O)2+(a) in Figure 1). In this state ular dynamics (MD) method27 (BO-LSD-MD). In electronic
the dipoles of the H2O molecules are oriented antiparallel to structure calculations we have used nonlocal norm-conserving
each other, the oxygens are bonded directly with a bond length pseudopotentials28 for the valence electrons of the oxygen atoms
dOO ) 2.176 Å (compared to 2.502 Å in the dpi isomer), and (s- and p-components, with s-nonlocality) and a local pseudo-
the ionization hole is delocalized, unlike the case of (H3O+)- potential for the hydrogens. Exchange-correlation gradient
OH, where it is localized on the oxonium part. In addition to corrections (GGC; with the exchange gradient correction of
the (H2O)2+(a) ground state, a slightly higher in energy (0.02 Becke29 and the correlation gradient of Perdew30) were included
eV) isomer was found with the two water molecules of the dimer self-consistently.
cation in a “gauche” relative orientation (denoted as (H2O)2+- As discussed in detail elsewhere,27 in our method no
(g); see Figure 1). It is likely that the transformation from the supercells (i.e., periodic replicas of the ionic system) are used,
neutral dimer configuration to that of (H2O)2+(a) involves a thus allowing studies of charged and multipolar clusters in an
barrier due to the significant rearrangement of the nuclei. accurate and straightforward manner. In dynamical simulations
166 J. Phys. Chem. A, Vol. 101, No. 2, 1997 Barnett and Landman

Figure 2. Optimized configurations of the ground state of neutral (H2O)3 (a) and of the chainlike (H2O)3+(a) (b) and the (H2O)3+(dpi) isomers.
Large and small spheres denote oxygen and hydrogen atoms. Geometrical parameters are given in Table 2a.

Figure 3. Same as Figure 2 but for the neutral and singly charged water tetramer. Geometrical parameters are given in Table 2b.

the Hellman-Feynman forces on the ions are evaluated between superior to that obtained by previous high-level quantum
each MD step, involving iterative solution of the LS Kohn- chemistry ab initio calculations (see comparisons and citations
Sham equations, thus ensuring that the ionic trajectories are in refs 1a, 31-34) and overall in somewhat better agreement
followed on the BO potential energy surface. In the calculations with experiments than recent gradient-corrected density func-
for neutral and charged (H2O)n clusters a plane-wave cutoff of tional calculations (see ref 35, where dOO ) 2.926, 2.789, and
96 Ry was used (for n ) 2 we quote also results from our earlier 2.683 Å is given for n ) 2, 3, and 4). The shortening of the
calculations,12 where a larger value, i.e., 158 Ry, has been used). O-O distances is associated (for n ) 4 and 5) with a decrease
A typical time step ∆t ) 0.3 fs was used in integration of the in the distances between the (donor) hydrogens (Hd) and the
ionic equations of motion. acceptor (Oa) oxygen atoms hydrogen bonds, Od-Hd‚‚‚Oa (with
average values of 1.825 and 1.795 Å for n ) 4 and 5 compared
3. Energetics and Structures of (H2O)n and (H2O)n+, for to 1.982 Å in the dimer; in the trimer two of these distances
ne5 are relatively short, i.e., 1.947 and 1.961 Å and one in longer,
(a) Neutral (H2O)n, n ) 2-5 Clusters. The optimal 2.085 Å, see Table 2a). At the same time Od-Hd bonds in the
structures for neutral (H2O)n clusters and for their cations donor molecules in these clusters tend to elongate1a compared
(H2O)n+ with n e 5 are shown in Figure 1 (for n ) 2) and to that in the dimer (0.976 Å), with average values of 0.982
Figures 2-4 (for n > 2), and their corresponding geometrical and 0.984 Å for n ) 4 and 5. Additionally, these structures
parameters are given in Table 1 (for n ) 2) and Table 2 (for n exhibit a larger degree of nonlinearity of the hydrogen bonds
> 2). The energetics of these clusters are given in Table 3. (i.e., the angle ∠(Od-Hd‚‚‚Oa)) compared to that in the dimer
In the neutral (H2O)n clusters (Figures 1, 2a, 3a, and 4a) the (177°), having average values of 152°, 170°, and 176° for n )
molecules are hydrogen-bonded and for the trimer, tetramer, 3, 4, and 5, respectively, and showing a trend of decreased
and heptamer their ground-state structures are cyclic, close to hydrogen-bond nonlinearity for larger clusters (with n > 2).
planar, polygons1a (for (H2O)4 the oxygen marked O4 in Figure The shortening of the O-O distances is also correlated with
3a is located 0.090 Å above the O1-O2-O3 plane, and for the monotonic increase with n of the binding energy (see Eb in
(H2O)5 the oxygens marked O1 and O4 in Figure 4a are located Table 3, Eb ) E((H2O)n) - nE(H2O)) and consequently an
in 1.0 and 0.8 Å, respectively, above the O2-O3-O5 plane). In increase of the hydrogen-bond energy (see EHB in Table 3; EHB
the tetrahamer all the H2O molecules are equivalent to each ) Eb/nHB, where nHB is the number of hydrogen bonds in the
other and the directions of their dipoles (being approximately cluster). The pattern of increase of EHB indicates nonadditivity
along the bisector of the intermolecular H-O-H angle) alternate effects suggesting that simple pair-potentials cannot provide
above and below the plane of the cluster, while for the odd accurate descriptions of the geometries of such small water
numbered clusters not all molecules are equivalent since such clusters.35
cyclic alternation around the polygon cannot be completed. The relative stability of the water tetramer cluster, which as
The angles formed between the oxygens in these structures aforementioned is characterized by a cyclic alternation of the
are close to the ideal polygonal ones (i.e., (n - 2) 180°/n), and molecular dipole directions, is portrayed by the relatively large
the distances between neighboring oxygens are shorter than in value of the H2O removal energy calculated for it (see ∆(H2O)
the dimer molecule (dOO ) 2.957 Å), with their average values in Table 3; ∆(H2O) ) E((H2O)n) - E((H2O)n-1 - E(H2O)) and
being 2.890, 2.798, and 2.778 Å for n ) 3, 4, and 5, respectively, the relative ease of H2O removal from the pentamer cluster.
in good agreement with experimentally determined values1a,31-34 The relatively high value of ∆(H2O) for the trimer is related to
(2.976, 2.90, 2.78, and 2.76 Å for n ) 2-5, respectively), the fact that upon removal of a water molecule from this cluster
Structure and Energetics of Ionized Water Clusters J. Phys. Chem. A, Vol. 101, No. 2, 1997 167

Figure 4. Same as Figure 2 but for the neutral and singly charged water petamer. The neutral (H2O)5 geometry is shown in part a, the geometries
of two “hydrazine-based” isomers, (H2O)5+(aI) and (H2O)5+(aII), are shown in parts b and c, and the geometries of two “disproportionated ion-
based” isomers, (H2O)5+(dpiI) and (H2O)+(dpiII), are shown in parts d and e. Geometrical parameters are given in Table 2c.

to form the dimer, the number of hydrogen bonds is reduced show a relatively small ER ≈ 0.1 eV); relaxations of the mo-
from three to one. lecular cations into cyclic structures result in higher energy
(b) Ionized (H2O)n+, n ) 2-5, Clusters. As noted already isomers than the noncyclic ones, with corresponding larger aIP
in the Introduction, we have found recently that a hydrazine- values (for example, the aIP of (H2O)3 to form a cyclic molec-
like structure ((H2O)2+(a) in Figure 1) is a stable ground state ular ion is 10.48 eV, and that for (H2O)4 is 10.28 eV, the latter
of the ionized dimer with an energy 0.2 eV lower than the value calculated at the PLSD level, that is, including exchange-
disproportionated ion, (H3O)+(OH) isomer. The main result of correlation gradient corrections, but using the wave functions
the present study is that the lowest energy isomers of the larger and geometry obtained from LSD calculations). For all cases
molecular water cations (H2O)n+, 2 < n < 5, whose neutral studied here the molecular ion clusters based on a hydrazine-
parents form cyclic ringlike structures, are noncyclic with the like component (denoted as (H2O)n+(a)) are more stable (i.e.,
lowest energy corresponding to chainlike ones containing a lower aIP values) than the ones containing a disproportionated
hydrazine-like component (see Figures 2b, 3b, and 4b,c). For ion (dpi), with an energy difference of ∼0.1 eV.
the pentamer cluster ions we show two isomers for the (a) and In the ionized clusters the distances between hydrogen-bonded
(dpi) motifs; in descending order of stability these are denoted oxygens are smaller than in the corresponding neutral ones (i.e.,
as: (aI) corresponding to (H2O)2(H2OOH2)+(H2O), where the 2.472 and 2.426 Å in the (a) and (dpi) states of (H2O)3+,
two H2O molecules on the left are hydrogen-bonded directly to compared to 2.890 Å in the neutral; 2.570 and 2.493 Å in the
one of the H2O molecules of the hydrazine fragment; (aII) (a) and (dpi) states of (H2O)4+, compared to 2.798 Å in the
corresponding to (H2O)(H2O)(H2OOH2+)(H2O), where only one neutral; and the values in the range of ∼2.5-2.65 Å in the
H2O molecule is hydrogen-bonded directly to each of the (H2O)5+ isomers compared to an average distance of 2.778 Å
molecules of the hydrazine fragment; (dpiI) corresponding to in the neutral). Additionally, in general the hydrogen bonds in
(H2O)2(H3O)+(H2O)OH, where the oxonium fragment is 3-fold the ionized clusters are closer to linear than in the neutral
hydrogen-bonded to water molecules; (dpiII) corresponding to parents. These results correlate with increased values for the
(H2O)2(H3O)+(OH)(H2O), where the oxonium fragment is water removal energies from the cluster ions (∆+(H2O) )
hydrogen-bonded directly to only two water molecules. E(H2O)n+ - E(H2O)n-1+ - E(H2O)), compared to those for
The vertical ionization potentials (vIP in Table 3) of the the corresponding neutrals (compare ∆(H2O) and ∆+(H2O) in
(H2O)n clusters show a monotonic decreasing trend with Table 3).
increasing n, and the reorganization energies (ER ) vIP(H2O)n)
- aIP((H2O)n)) upon structural relaxation of the ionized clusters 4. Summary
are rather significant (compare values in Table 3 to the single In this paper the energetics and structures of neutral, (H2O)n,
water molecule, where both measurements and calculations and singly charged (H2O)n+, water clusters, with n e 5 were
168 J. Phys. Chem. A, Vol. 101, No. 2, 1997 Barnett and Landman

TABLE 2: Geometrical Parameters (Distances in Angstroms and Angles in Degrees) of the Optimal Structures of Neutral and
Singly Charged Isomers of Water Clustersa
a
(H2O)3 (H2O)3+(a) (H2O)3+(dpi) (H2O)3 (H2O)3+(a) (H2O)3+(dpi)
Distances (Å)
H11O1 0.974 1.055 1.075 H21O3 1.961
H12O1 0.958 0.971 1.070 H11O3 1.425
H13O1 0.963 H12O3 1.361
H11O2 1.947 1.562 O1O2 2.848 2.153 2.570
H21O2 0.973 0.973 0.979 O2O3 2.842
H31O3 0.971 0.961 0.961 O3O1 2.981 2.472 2.426
Angles (deg)
∠(O1H11O2) 153 ∠(H21O2H22) 106.6 105.3
∠(O2H21O3) 149 ∠(H31O3H32) 105.9 108.7 109.7
∠(O3H31O1) 153 ∠(H11O2H21) 116.4
∠(O3H12O1) 109.7 ∠(O1O2O3) 63.2
∠(O1H11O3) 170.3 ∠(O2O3O1) 58.5
∠(H11O1H12) 105.9 106.4 111.5 ∠(O3O1O2) 58.3 107.6 102.7
b
(H2O)4 (H2O)4 (a)
+
(H2O)4 (dpi)
+
(H2O)4 (H2O)4+(a) (H2O)4+(dpi)
Distances (Å)
H11O1 0.982 1.022 1.00 H12O3 1.473
H12O1 0.960 0.970 1.026 H13O4 1.472
H13O1 1.026 O1O2 2.798 2.214 2.614
H11O2 1.825 1.614 O1O3 2.570 2.493
H31O3 0.960 0.963 0.960 O1O4 2.493
H11O3 1.565
Angles (deg)
∠(O1H11O2) 170.5 178.4 ∠(H12O1H13) 109.9
∠(O1H11O3) 166.3 ∠(O1O2O3) 89.9
∠(O1H12O3) 172.6 ∠(O2O1O3) 111.8 120.6
∠(H11O1H12) 104.4 106.7 115.9 ∠(O3O1O4) 103.2
∠(H31O3H32) 104.4 106.9 108.2
c
(H2O)5+- (H2O)5+- (H2O)5+- (H2O)5+-
(H2O)5 (H2O)5+(aI) (H2O)5+(aII) (dpiI) (dpiII) (H2O)5 (H2O)5+(aI) (H2O)5+(aII) (dpiI) (dpiII)
Distances (Å)
H11O1 0.986 1.006 1.058 1.028 1.011 H12O5 1.661
H12O1 0.959 1.006 0.968 1.028 1.011 H31O5 1.688
H13O1 1.007 1.010 H11O5 1.783 1.557
H21O1 1.772 H21O5 1.661
H21O2 0.985 1.006 1.011 0.975 1.011 O1O2 2.756 2.182 2.219 2.634
H11O2 1.630 O1O3 2.723 2.481 2.617 2.626
H31O2 1.804 O1O4 2.617 2.651
H31O3 0.984 0.959 0.990 0.959 O1O5 2.767 2.665 2.584
H41O3 1.812 O2O3 2.786
H11O3 1.726 1.441 O2O4 2.714 2.648
H12O3 1.631 O2O5 2.845 2.655
H41O4 0.982 0.959 0.962 0.959 0.959 O3O4 2.794
H21O4 1.721 1.647 O3O5 2.664
H13O4 1.616 1.647 O4O5 2.789
H51O5 0.984 0.960
Angles (deg)
∠(O1H21O2) 176.7 ∠(O2H51O5) 179.9
∠(O1H11O2) 167.6 ∠(O3H41O4) 176.9
∠(O1H12O3) 171.7 171.9 ∠(O3H31O5) 168.1
∠(O1H11O3) 170.6 166.0 ∠(O4H51O5) 176.5
∠(O1H13O4) 171.7 171.7 ∠(O1O2O3) 110.6
∠(O1H11O5) 175.8 176.9 ∠(O2O3O4) 104.1
∠(O1H12O5) 171.9 ∠(O3O4O5) 107.7
∠(O2H31O3) 175.5 ∠(O4O5O1) 106.2
∠(O2H21O4) 168.3 169.5 ∠(O5O1O2) 104.8
∠(O2H21O5) 166.9
a Results for the trimer, tetramer, and pentamer cluster are given in parts a, b, and c, respectively. For the pentamer cluster, results are given for

two isomers of the “hydrazine-based” (aI and aII) and “disproportionated ion-based” (dpiI and dpiII) cations (see Figure 4). Identification of the
atoms is as given in Figures 2-4.
investigated using LSD calculations with self-consist inclusion periments.1a,31-34 The calculated shortening of the O-O bond
of exchange-correlation gradient corrections. The main results distances for increasing water cluster sizes, which has also been
of our study may be summarized as follows. observed experimentally,1a is found to be correlated with a
(i) Neutral (H2O)n, n e 5, clusters form ground-state quasi- decrease in the distances between the (donor) hydrogens (Hd)
planar cyclic (polygonal) structures, in agreement with ex- and the acceptor (Oa) oxygen atoms involved in hydrogen bonds,
Structure and Energetics of Ionized Water Clusters J. Phys. Chem. A, Vol. 101, No. 2, 1997 169

TABLE 3: Energetics (in eV) of Neutral and Singly neutral dimer). Therefore, measurement of ν(OO) may serve
Charged Water Clusters (for Identification of the Various to identify and distinguish between these ionized dimer isomers.
Species See Figures 1-4)a
(H2O) (H2O)2 (H2O)3 (H2O)4 (H2O)5 Acknowledgment. Research was supported by the U.S. DOE
Eb 0.163 0.561 1.053 1.344 (Grant No. DE-FG05-86ER-4234). Computations were per-
[0.163]b formed on Cray computers at the National Energy Research
EHB 0.163 0.187 0.263 0.269 Supercomputer Center at Livermore and the Georgia Institute
∆(H2O) 0.163 0.397 0.492 0.291 of Technology Center for Computational Materials Science.
vIP 12.75 11.80 11.03 10.38 9.90
[12.69]b [11.74]b
aIP 12.66 (a)[10.42]b (a)9.86 (a)9.54 (aI)9.23 References and Notes
[12.59]b (dpi)[10.64]b (dpi)9.97 (dpi)9.63 (aII)9.29 (1) For recent reviews see: (a) Liu, K.; Cuzan, J. D.; Saykally, R. J.
(dpiI)9.34 Science 1996, 271, 877. (b) Castleman, A. W., Jr.; Bowen, K. H., Jr. J.
(dpiII)9.35 Phys. Chem. 1996, 100, 12911. (c) Buck, U. In Clusters of Atoms and
∆+(H2O) (a)2.34 (a)0.958 (a)0.816 (aI)0.604 Molecules; Haberland, H., Ed.; Springer Series in Chemical Physics 52;
(dpi)2.11 (dpi)1.069 (dpi)0.835 (aII)0.544 Springer: Berlin, 1994; p 396.
(dpiII)0.571 (2) (a) Haberland, H.; Bowen, K. H. In Clusters of Atoms and
Molecules; Haberland, H., Ed.; Springer Series in Chemical Physics 56;
a
The binding energy of (H2O)n is defined as the total energy Springer: Berlin, 1994; p 134. (b) Barnett, R. N.; Cleveland, C. L.;
difference Eb ) E((H2O)n) - nE(H2O); EHB ) Eb/nHB, where nHB is Landman, U.; Jortner, J. J. Chem. Phys. 1988, 88, 4421, 4429.
the number of hydrogen bonds in the cluster. ∆(H2O) and ∆+(H2O) (3) Kaukonen, H.-P.; Barnett, R. N.; Landman, U. J. Chem. Phys. 1992,
97, 1365.
are the water-molecule removal energies for the neutral and ionized
(4) Klots, C. E.; Compton, R. N. J. Chem. Phys.1978, 69, 1644.
clusters, respectively. vIP and aIP are the vertical and adiabatic (5) Haberland, H.; Langosch, H. Z. Phys. D. 1986, 2, 243.
ionization potentials of the (H2O)n clusters; for the aIP ionization results (6) Shinohara, H.; Nishi, N.; Washida, N. J. Chem. Phys. 1986, 84,
are given for various final-state charged isomers; for a given cluster 5561.
size an isomer with a lower aIP value is more stable and the difference (7) Ng, C. Y.; Trevor, D. J.; Tiedemann, P. W.; Ceyer, S. T.;
between the aIPs of two isomers of a given cluster is the difference Kronebusch, P. L.; Mahan, B. H.; Lee, Y. T. J. Chem. Phys. 1977, 67,
between their total energies; for example (H2O)2+(a) is more stable 4235.
than (H2O)2+(dpi) by 0.22 eV. Results for the water monomer and (8) deVisser, S. P.; deKoning, L. J.; Nibbering, N. M. H. J. Phys. Chem.
dimer marked by a superscript b correspond to calculations12 with a 1995, 99, 15444.
(9) (a) See review by Mark, T. D.; Echt, O.; in ref 2a, p 154. (b)
plane-wave cutoff energy of 158 Ry. b Calculated with Ecut ) 158 Ry. Castleman, A. W., Jr. in ref 2a, p 77. (c) Crofton, M. W.; Price, J. M.;
Lee, Y. T.; in ref 2a, p 44.
(10) Stace, A. J. Phys. ReV. Lett. 1988, 61, 306; Chem. Phys. Lett. 1990,
Od-Hd‚‚‚Oa, accompanied by elongation of the Od-Hd bonds1a 174, 103.
(11) Buck, U.; Winter, M. Z. Phys. D. 1994, 31, 291.
in the donor molecules (for n ) 4 and 5). The hydrogen bonds (12) Barnett, R. N.; Landman, U. J. Phys. Chem. 1995, 99, 17305.
for the trimer are highly nonlinear (i.e., average ∠(Od-Hd‚‚‚Oa) (13) See: Schulz, C. P.; Hertel, J. V.; in ref 2a, p 7.
value of 152°), implying a high degree of strain, and they tend (14) Barnett, R. N.; Landman, U. Phys. ReV. Lett. 1993, 70, 1775, and
references therein.
toward linearity for the tetramer and heptamer. The shortening (15) Barnett, R. N.; Cheng, H.-P.; Hakkinen, H.; Landman, U. J. Phys.
of the O-O bonds with increasing cluster size is portrayed in Chem. 1995, 99, 1995, and references therein.
a monotonic increase of the hydrogen bond energy in these (16) See refs 3-12 cited in ref 12.
clusters. The vertical and adiabatic ionoization potentials for (17) Good, A.; Durden, D. A.; Kebrale, P. J. J. Chem. Phys. 1970, 52,
212, 222.
clusters with n g 2 are significantly smaller than those of the (18) Tomoda, S.; Achiba, Y.; Kimura, K. Chem. Phys. Lett. 1982, 187,
water molecule, and the aIPs decrease monotoncally (see Table 197.
3). (19) Fehsenfeld, F. C.; Mosesmann, M.; Ferguson, E. F. J. Chem. Phys.
1971, 55, 2115.
(ii) For the ionized dimer, (H2O)2+, the ground state is found12 (20) Kerbrale, P.; Godhole, E. W. J. Chem. Phys. 1963, 39, 1131.
to be of a hydrazine-like (H2O-OH2)+ structure (see Figure 1 (21) Bailey, A. D.; Narcisi, R. S. J. Geophys. Res. 1965, 70, 3687.
marked “anti”), with an energy 0.2 eV lower than that of the (22) Wei, S.; Shi, Z.; Castleman, A. W., Jr. J. Chem. Phys. 1991, 94,
disproportionated ion, (H3O)+(OH), isomer (see Figure 1). 3266.
(23) See ref 12 and citations to earlier work therein.
For larger (H2O)n+ n ) 3, 4, and 5, clusters the low-energy (24) Gill, P. M. W.; Radom, L. J. Am. Chem. Soc. 1988, 110, 4931.
ground-state isomers are predicted to be noncyclic, with the (25) Tomoda, S.; Kimura, K. Chem. Phys. 1983, 82, 215.
lowest ones forming chainlike structures and containing a (26) In ref 24 the hydrazine-like (H2O)2+(a) isomer was found, using
high-level quantum chemistry calculations, to be less stable than the
hydrazine-like component (see Figures 2b, 3b, and 4b,c), rather disproportionated ion by 37 kJ mol-1, with an isomerization barrier of 33
than the disproportionated ion (dpi) isomers (see Figures 2c, kJ mol-1.
3c, and 4d,e). The distances between hydrogen-bonded oxygens (27) Barnett, R. N.; Landman, U. Phys. ReV. B 1993, 70, 1775.
(28) Troullier, N.; Martins, J. L. Phys. ReV. B 1991, 43, 1993.
in the ionized clusters are contracted in comparison with their (29) Becke, A. D. Phys. ReV. A 1988, 38, 3098; J. Chem. Phys. 1992,
values for the corresponding neutral parents. Additionally, the 96, 2155.
hydrogen bonds in the ionized clusters are more linear than in (30) Perdew, J. P.; Wang, Y. Phys. ReV. B 1991, 44, 13298; 1991, 43,
the neutral ones. These trends correlate with higher values for 8911; 1992, 49, 13244.
(31) For the dimer see: Dyke, T. R.; Mack, K. M.; Muenter, J. S. J.
the energy required to remove a water molecule from the ionized Chem. Phys. 1977, 66, 498; Ibid. 1977, 66, 492. Pugliano, N.; Cruzan, J.
cluster as compared to the value for this process calculated for D.; Loeser, J. G.; Saykally, R. J. J. Chem. Phys. 1993, 98, 6600.
the corresponding neutral parent (compare ∆+(H2O) with (32) For the trimer see: Pugliano, N.; Saykally, R. J. Science 1992,
257, 1937; Liu K.; et al. J. Am. Chem. Soc. 1994, 116, 3507. Liu, K.; et
∆(H2O), in Table 3). al. Faraday Discuss. 1994, 97, 35.
Finally, we remark that for the ionized water dimer we (33) For the tetramer see: Cruzan, J. D.; Braly, J. B.; Kun, L.; Brown,
estimate from BO-LSD-MD simulations that the interoxygen M. G.; Loeser, J. D.; Saykally, R. J. Science 1996, 271, 59.
vibrational frequency ν(OO) is ∼750 cm-1 for the lowest energy (34) For the pentamer see: Liu, K.; Brown, M. G.; Cruzan, J. D.;
Saykally, R. J. Science 1996, 271, 62.
isomer (H2O)2+(a), while for the disproportionated ion isomer, (35) Laasonen, K.; Parrinello, M.; Car, R.; Lee, C.; Vanderbilt, K. Chem.
(H3O)+(OH), ν(OO) ∼375 cm-1 (compare to 225 cm-1 in the Phys. Lett. 1993, 207, 208.