J. Phys. Chem.

1996, 100, 6663-6671 6663

Computational Studies of Water Adsorption in the Zeolite H-ZSM-5

S. A. Zygmunt,† L. A. Curtiss,*,‡ L. E. Iton,‡ and M. K. Erhardt†

Department of Physics and Astronomy, Valparaiso UniVersity, Valparaiso, Indiana 46383, and
Argonne National Laboratory, Argonne, Illinois 60439
ReceiVed: October 3, 1995; In Final Form: January 26, 1996X

Ab initio molecular orbital calculations using Hartree-Fock theory and Møller-Plesset perturbation theory
have been used to study the interaction of H2O with the Brønsted acid site in the zeolite H-ZSM-5.
Aluminosilicate clusters with up to 28 T atoms (T ) Si, Al) were used as models for the zeolite framework.
Full optimization of a 3 T atom cluster at the MP2/6-31G(d) level indicates that the “ion-pair” structure,
Z-‚‚‚HOH2+, formed by proton transfer from the acid site of the zeolite (ZH) to the adsorbed H2O molecule,
is a transition state, while the “neutral” adsorption structure, ZH‚‚‚OH2, is a local energy minimum. Partial
optimization of a larger 8 T cluster at the HF/6-31G(d) level also gave results suggesting that the ion-pair
structure is a transition state. Calculations were carried out to obtain corrections for high levels of theory,
zero-point energies, and larger cluster size. The resulting energy difference between the neutral and ion-pair
structure is small (less than 5 kcal/mol and possibly close to zero). The interaction energy of ZH‚‚‚OH2 is
13-14 kcal/mol, in agreement with experiment. We find that addition of a second H2O molecule to
Z-‚‚‚HOH2+ in the 3 T atom cluster stabilizes the ion-pair structure, Z-‚‚‚H(OH2)2+, making it a local energy
minimum. Finally, calculated vibrational frequencies for a 3 T atom cluster are used to help interpret
experimental IR absorption spectra.

I. Introduction In this paper we report on a study of the interaction of water

Brønsted acid chemistry is a dominant feature of zeolite
catalysis in many important industrial applications. A reliable
theoretical treatment of the proton affinity of H-ZSM-5 zeolite
was obtained in previous work using high-level ab initio
calculations on large cluster models.1 Proton transfer to a strong
adsorbed base has also been studied theoretically in the
interaction of ammonia with the Brønsted acid site.2-5 The
interaction of weak bases, e.g., H2O, presents a more equivocal
situation. What kind of equilibrium structure is formed when
H2O is adsorbed at the Brønsted acid site in H-ZSM-5?
Experimental evidence in the form of 1H NMR spectroscopy
has suggested that the neutral hydrogen-bonded adsorbate and
the ion-pair structure, formed by proton transfer from the acid
site to H2O, coexist at 4 K, with the neutral complex being more
prevalent than the ion-pair structure.6,7 Studies using IR
spectroscopy have suggested that the ion-pair structure is most
stable.8-11 One ab initio theoretical study12 also gave evidence
to support this conclusion. However, more recent ab initio
studies13,14 and experimental IR studies15,16 have led to a
reinterpretation of the IR spectrum in a manner consistent with
a neutral hydrogen-bonded adsorbate. These studies suggest
that the ion-pair structure should be regarded as a transition
state and not a true equilibrium geometry. Two recent reviews
have included detailed discussions of the interpretation of the
IR spectrum.4,17 Almost all of the theoretical studies have used
small clusters to represent the acid site, and very few have
accounted for electron correlation in their optimization of
molecular geometries. In the light of the conflicting experi-
mental data on the nature of water adsorption in H-ZSM-5,
further ab initio computational studies using larger clusters and
higher levels of theory are clearly desirable.
* Author to whom correspondence should be mailed. Email:
curtiss@cmt.anl.gov.
† Valparaiso University. Email: szygmunt@exodus.valpo.edu.
‡ Argonne National Laboratory.
X Abstract published in AdVance ACS Abstracts, March 15, 1996.
0022-3654/96/20100-6663$12.00/0
with an acid site in H-ZSM-5 incorporating large cluster size,
electron correlation, and local geometry optimization in a unified
way. The calculations presented here extend our earlier study
of the adsorption of H2O on a 2 T atom (T ) Si, Al) cluster
model of H-ZSM-518 and a preliminary report of some aspects
of this work.19 In section II we describe the theoretical methods,
and in section III we present results for the geometry and
interaction energy of the neutral H2O adsorption structure, the
relative energy of the ion-pair structure resulting from proton
transfer, and the vibrational frequencies of the H2O adsorption
structure. Results for the addition of a second H2O molecule
are also presented. The calculated frequencies of these struc-
tures are used to help interpret the published experimental IR
spectra. The evidence from the 1H NMR studies is also
discussed in light of our results.
II. Theoretical Methods
The theoretical calculations presented here are based on ab
initio molecular orbital theory using Hartree-Fock (HF) theory
and Møller-Plesset (MP) perturbation theory.20,21 We used four
aluminosilicate clusters of increasing size to model the interac-
tion of H2O with the Brønsted acid site in H-ZSM-5. These
clusters include 3, 8, 18, and 28 T atoms and have a total of
14, 34, 69, and 101 atoms, respectively. Each cluster includes
one Al atom and a charge-balancing proton to maintain a neutral
zeolite framework and is terminated by H atoms at the periphery.
Their stoichiometries are H9Si2AlO2, H19Si7AlO7, H29Si17AlO22,
and H33Si27AlO40, respectively. We performed calculations on
the zeolite framework clusters as well as adsorption complexes
between these clusters and an H2O molecule. In addition, we
investigated the effect of higher H2O pressure by adding a
second H2O molecule to the 3 T cluster model. The 8, 18, and
28 T clusters have been discussed in detail in ref 1, where they
were used to assess long-range electrostatic effects of the zeolite
framework on the calculated proton affinity of the T(12)-O(24)-
T(12) site of the H-ZSM-5 zeolite framework (MFI structure).1
© 1996 American Chemical Society
6664 J. Phys. Chem., Vol. 100, No. 16, 1996
The O(24) site at the center of the 8, 18, and 28 T atom clusters
is a likely acid site in ZSM-5. Other studies have used detailed
embedding schemes to estimate the magnitude of the important
long-range effects in cluster models of adsorption in zeolites.22,23
For calculations based on the 3 T atom cluster, the geometry
was fully optimized. The 3 T atom ion-pair complex
(Z-‚‚‚HOH2+) was optimized with Cs point group symmetry,
while all other 3 T structures were optimized with C1 symmetry.
Corrections using the calculated zero-point energies for the 3
T atom clusters were used as estimates for the structures based
on the larger cluster models.
For the 8 T atom cluster, which had C1 symmetry, two
different methods were used to model the O(24) site in H-ZSM-
5. In the first method, the atoms were assumed to be fixed at
positions given by X-ray diffraction studies of H-ZSM-5,24 with
an OH distance of 0.98 Å for the acid site. Hydrogen atoms
were used to tie off the peripheral Si atoms at an Si-H distance
of 1.43 Å (a value taken from ab initio calculations on silanol).
Previous computational studies of the proton affinity of H-ZSM-
51 have questioned the ability of such a rigid cluster model to
adequately represent the zeolite framework. Its major defect
is an inability to model the structure of the SiO(H)Al bridge
that forms the Brønsted acid site, since the X-ray diffraction
data correspond to a structure very low in aluminum content.
Thus, a second approach, based on the constant-volume
relaxation (CVR) method,1 was used to account for the local
effects of atomic relaxation around the acid site in the otherwise
unperturbed H-ZSM-5 framework. The atoms of the central
O3SiOHAlO3 unit near the acid site were fully relaxed, while
atoms outside this central unit were fixed at positions determined
from X-ray diffraction data. We have found this constrained
relaxation scheme to be a useful model for the effect of an
adsorbate on the local structure of the zeolite acid site. Similar
methods were used in a semiempirical study by Redondo and
Hay25 and a density-functional study by Cook et al.26 In both
rigid and CVR cluster methods, the six intermolecular degrees
of freedom between the cluster and the adsorbate molecule were
fully optimized. In the 8 T atom calculations, the H2O and
H3O+ geometries were held fixed at the optimized geometries
of the isolated molecules.
After optimization of the 8 T atom structures with H2O and
H3O+, the effect of more distant atoms was then included by
embedding the 8 T clusters in successively larger fragments of
crystalline H-ZSM-5 to obtain first the 18 T atom and then the
28 T atom clusters. This procedure was done both for the rigid
and the CVR cluster methods. The intermolecular degrees of
freedom were not reoptimized in the 18 and 28 T atom clusters.
We tested the accuracy of this method by reoptimizing these
six coordinates in the 18 T atom complex with H3O+ at the
HF/3-21G level and comparing them to those obtained in the 8
T atom cluster (rigid cluster model). Changes in bond lengths
and angles on the order of 3-5% were noted, but the total
energy after reoptimization decreased by less than 1 kcal/mol.
Four levels of theory were used in this study. These include
HF/3-21G, HF/6-31G(d), MP2/6-31G(d), and G2(MP2,SVP).
G2(MP2,SVP) theory27,28 is a modification of G2(MP2) theory,29
in which the 6-31G(d) basis set is used instead of the
6-311G(d,p) basis set for the quadratic configuration interaction
(QCISD(T))30 calculations. Using G2(MP2,SVP) theory, the
energy of a molecule or cluster at 0 K can be written
E0 ) E(MP2/6-31G(d)) + ∆QCI + ∆BS + HLC + ∆ZPE (1)
where
∆QCI ) E(QCISD(T)/6-31G(d)) - E(MP2/6-31G(d)) (2)
Zygmunt et al.
∆BS ) E(MP2/6-311+G(3df,2p)) - E(MP2/6-31G(d)) (3)
E(MP2/6-31G(d)) is the electronic energy at the MP2/6-31G(d)
level of theory. The HLC is a higher level correction for
remaining basis set deficencies and ∆ZPE is the zero-point energy
correction. The HLC cancels out in all of the reaction energies
considered in this paper. G2(MP2,SVP) theory is based on
MP2/6-31G(d) geometries and scaled (0.893) HF/6-31G(d) zero-
point energies. G2(MP2,SVP) theory was found to have an
average absolute deviation of 1.63 kcal/mol in an assessment
of the 125 reaction energies in the G2 test set.31 This theory
was applied rigorously to the 3 T atom clusters. The basis set
(∆BS), correlation (∆QCI), and zero-point (∆ZPE) energy correc-
tions were also used as estimates for the 8 T cluster.
III. Results and Discussion
A. Reaction Energies. The reaction energies of H2O
interacting at the hydroxyl site of aluminosilicate clusters of 3,
8, 18, and 28 T atoms representing H-ZSM-5 are listed in Tables
1 and 2. The quantities calculated in this study were ∆Eion,
∆Eneut, ∆Erel, and ∆Edesorp. The ∆Eion is the complexation
energy of the “ion-pair” structure:
∆Eion ) E(Z-) + E(H3O+) - E(Z-‚‚‚HOH2+) (4)
where Z- is the unprotonated zeolitic cluster and Z-‚‚‚HOH2+
is the ion-pair structure. The ∆Eneut is the complexation energy
of the “neutral” (hydrogen-bonded) structure:
∆Eneut ) E(ZH) + E(H2O) - E(ZH‚‚‚OH2) (5)
where ZH is the protonated zeolitic cluster and ZH‚‚‚OH2 is
the neutral structure. The ∆Erel is the energy difference between
the neutral and ion-pair structures:
∆Erel ) E(ZH‚‚‚OH2) - E(Z-‚‚‚HOH2+) (6)
where a positive value would indicate that the ion-pair structure
is more stable. The ∆Edesorp is the energy required to remove
the H2O molecule from the most stable structure (ion-pair or
neutral):
∆Edesorp ) E(ZH) + E(H2O) - min[E(Z-‚‚‚HOH2+),
E(ZH‚‚‚OH2)] (7)
Note that if the neutral structure is more stable than the ion-
pair structure, then ∆Edesorp ) ∆Eneut, which is what we found
in both cases, as seen in Tables 1 and 2. The total energies of
ZH, Z-, Z-‚‚‚HOH2+, and ZH‚‚‚OH2, from which the reaction
energies in Table 2 are obtained, are listed in Table 3.
The energies in Table 1 are based on rigid zeolite cluster
calculations, while those in Table 2 are based on calculations
which include relaxation of the local region of the cluster near
the hydroxyl site, as described in the previous section. Results
for the 3 T atom cluster, for which full optimizations were
carried out, are also included in Table 2. The structures of the
ion-pair and hydrogen-bonded configurations for the 3 T cluster
are illustrated in Figure 1. At both HF/6-31G(d) and MP2/6-
31G(d) levels, the neutral structure is a local minimum on the
potential energy surface, while the ion-pair structure is a
transition state associated with proton transfer between oxygen
sites adjacent to the Al atom. The corresponding structures for
the 8, 18, and 28 T clusters are illustrated in Figure 2, where
the terminating H atoms at the periphery of the these clusters
are not shown. For the 8 T atom cluster, the HF/6-31G(d)
calculations show that the lowest energy structure is again a
Water Adsorption in the Zeolite H-ZSM-5 J. Phys. Chem., Vol. 100, No. 16, 1996 6665

TABLE 1: Reaction Energies (in kcal/mol) for Clusters with Rigid Structuresa
∆Eneut ) ∆Edesorp ∆Eion ∆Erel
method/basis 3 8 18 28 3 8 18 28 3 8 18 28
HF/3-21G 31.9 35.9 35.1 147.1 151.6 153.0 -7.1 -3.2 -1.1
HF/6-31G(d) 20.1 17.9 21.2 20.0 127.1 128.6 127.7 -12.7 -10.1 -8.5 -6.9
a
All results are from rigid clusters (3, 8, 18, 28 T atoms) with only the six intermolecular coordinates optimized. For the 18 T and 28 T clusters
the 8 T optimized parameters are used. Zero-point energies not included in values.

TABLE 2: Reaction Energies (in kcal/mol) for Clusters Including Geometry Relaxationa
∆Eneut ) ∆Edesorp ∆Eion ∆Erel
method/basis 3 8 18 28 3 8 18 28 3 8 18 28
HF/3-21G 31.7 34.8 34.2 154.6 154.2 154.6 -14.1 -13.0 -10.4
HF/6-31G(d) 15.2 14.7 17.0 16.7 138.4 131.1 130.9 129.7 -14.5 -16.9 -14.7 -13.3
MP2/6-31G(d) 22.1 150.1 -6.2
a
All results are from the CVR procedure as described in text, except for the 3 T cluster, which is a full geometry optimization. The 3 T cluster
is illustrated in Figure 1; the other clusters (8, 18, 28 T atoms) are illustrated in Figure 2. For the 18 T and 28 T clusters the 8 T optimized
parameters are used. Zero-point energies not included in values.

TABLE 3: Total Energies (in hartrees) for Clusters in Table 2a

3T 8T 18 T 28 T
HF/3-21G Z- -2784.716 76 -6783.058 69 -11001.846 91
ZH -2785.240 28 -6783.574 97 -11002.360 60
ZH‚‚‚OH2 -2860.876 80 -6859.216 42 -11078.001 11
Z-‚‚‚HOH2+ -2860.854 36 -6859.195 64 -11077.984 49
HF/6-31G(d) Z- -974.338 36 -2799.554 73 -6819.126 69 -11060.226 22
ZH -974.836 32 -2800.045 63 -6819.610 18 -11060.706 12
ZH‚‚‚OH2 -1050.871 32 -2876.079 85 -6895.648 09 -11136.743 46
Z-‚‚‚HOH2+ -1050.848 21 -2876.052 97 -6895.624 60 -11136.722 21
MP2/6-31G(d) Z- -974.918 11
ZH -975.410 21
ZH‚‚‚OH2 -1051.642 24
Z-‚‚‚HOH2+ -1051.632 38
a H O: E[MP2/6-31G(d)] ) -76.196 85, E[HF/6-31G(d)] ) -76.010 75, E[HF/3-21G] ) -75.585 96. H O+: E[MP2/6-31G(d)]) -76.475 11,
2 3
E[HF/6-31G(d)] ) -76.289 34, E[HF/3-21G] ) -75.891 23.

ion-pair structures are stabilized by correlation effects as treated

Figure 1. Optimized structures of (a) ion-pair and (b) hydrogen-bonded
(neutral) configurations for H2O interacting with the hydroxyl site in
an aluminosilicate cluster with 3 T atoms. Terminating H atoms are
unlabeled.
hydrogen-bonded adsorption complex between H2O and the
zeolite framework. Although we have calculated vibrational
frequencies only for the 3 T atom cluster, the ion-pair structure
is also indicated to be a transition state in the larger clusters,
since removing the rigid structure constraint on H3O+ in the 8
T atom cluster CVR optimization at the HF/6-31G(d) level
resulted in transfer of a proton with no apparent barrier from
H3O+ to the acid site, i.e., Z-‚‚‚HOH2+ f ZH‚‚‚OH2.
The results in Tables 1 and 2 indicate that the HF/3-21G
calculations give binding energies consistently 15-25 kcal/mol
too large compared to the 6-31G(d) basis and are thus not
reliable for quantitative studies. This has also been noted in
our previous study18 using smaller clusters. At the HF/6-31G(d)
level, the rigid cluster method gives ∆Eneut, ∆Eion, and ∆Erel
values that differ from those of the CVR method by up to 7
kcal/mol. The discrepancy between the two methods is
particularly significant for ∆Erel. Finally, both the neutral and
by MP2 theory. A comparison of HF/6-31G(d) and MP2/6-
31G(d) calculations shows that these complexes are stabilized
by 5-10 kcal/mol in the 3 T atom cluster with full optimization.
There are several other factors which must be taken into
account in order to obtain accurate values of ∆Edesorp and ∆Erel
to compare with experiment and make predictions. These
include (a) electron correlation effects beyond MP2 theory; (b)
effects of larger basis sets, i.e., larger than 6-31G(d); (c) zero-
point energy effects; and (d) long-range electrostatic effects from
the zeolite framework that are not included in the cluster
calculation. We have applied G2(MP2,SVP) theory to the 3 T
atom cluster (MP2/6-31G(d) geometries), as described in section
2, to take account of the first three factors. The higher level
correlation effects are assessed by ∆QCI (eq 2); the larger basis
set effects are assessed by ∆BS (eq 3); and the zero-point energy
effects are assessed by ∆ZPE. The long-range electrostatic effect
is estimated from the dependence of the reaction energies on
cluster size using the rigid cluster results in Table 1. For the 3
T cluster this cluster size correction, ∆CS, is obtained as the
difference between the reaction energies of the 3 T cluster and
the 28 T cluster models. Our proton affinity study1 suggests
that this correction is largely due to long-range electrostatic
effects. Table 4 lists the ∆Edesorp and ∆Erel values based on 3
T cluster calculations including estimates for the four factors
discussed above.
In addition to using the 3 T atom cluster to obtain accurate
values for ∆Eneut and ∆Erel, we also used the 8 T atom CVR
cluster (HF/6-31G(d) energies in Table 2). Estimates for the
correlation effects, basis set effects, and zero-point effects
obtained from the 3 T atom cluster were applied to the 8 T
6666 J. Phys. Chem., Vol. 100, No. 16, 1996
Figure 2. Z-‚‚‚HOH2+ and ZH‚‚‚OH2 complexes for 8 T (a, b), 18 T (c, d), and 28 T (e, f) clusters. Terminating H atoms not shown.
energies. The cluster size effect, ∆CS, for the 8 T cluster is
estimated from the difference in the reaction energies of the
rigid 8 T and 28 T clusters in Table 1. The 8 T atom CVR
cluster has the advantage of being a larger cluster than the 3 T
atom cluster and should be a more realistic representation of
the local relaxation that occurs at the interaction site. However,
it has the disadvantage of not including the internal relaxation
of the H3O+ in the ion-pair transition state, which may be
significant. The 3 T cluster includes this effect since it is based
on a full optimization at the MP2/6-31G(d) level. Table 4 lists
the ∆Edesorp and ∆Erel values based on the 8 T cluster including
Zygmunt et al.
estimates for the four factors (a), (b), (c), and (d). We now
discuss the results obtained from the 3 T and 8 T clusters.
The G2(MP2,SVP) value for the desorption energy from the
3 T cluster at 0 K is 12.8 kcal/mol. Using the G2(MP2,SVP)
corrections and a correction for MP2 theory based on the 3 T
cluster, the 8 T cluster has a similar desorption energy, 12.3
kcal/mol. Correlation effects beyond the MP2 level, ∆QCI,
decrease the desorption energy by 0.9 kcal/mol in the 3 T cluster.
Correction for extension to a larger basis set, ∆BS, gives a 5.5
kcal/mol decrease in the desorption energy. The scaled HF/6-
31G(d) zero-point energy correction from the 3 T cluster, ∆ZPE,
Water Adsorption in the Zeolite H-ZSM-5 J. Phys. Chem., Vol. 100, No. 16, 1996 6667

TABLE 4: Desorption and Relative Energies, ∆Edesorp and TABLE 5: Selected Geometrical Parameters and Relative
∆Erel (in kcal/mol), from 3 T and 8 T Cluster Using Energies of ZH‚‚‚OH2 and Z-‚‚‚HOH2+ for the 3 T Clustera
Corrections for Cluster Size (CS), Correlation Effects
(MP2,QCI), Basis Set (BS), and Zero-Point Energies (ZPE) HF/6-31G(d) MP2/6-31G(d)

∆Edesorp ∆Erel ion-pair structure r(OzH) 1.42 1.36

method correction 3T 8T 3T 8T
HF/6-31G(d) a 14.7 -16.9
MP2/6-31G(d)a 22.1 -6.2
∆MP2b 6.9 8.3
∆QCIc -0.9 -0.9 -1.6 -1.6
∆BSc -5.5 -5.5 0.1 0.1
∆ZPEc -2.9 -2.9 1.9 1.9
G2(MP2,SVP) 12.8 12.3d -5.8 -8.2d
∆CSe -0.1 2.1 5.8 3.2
estimatef 12.7 14.4 0.0 -5.0
a
From Table 2. HF/6-31G(d) value is from constant volume
relaxation (CVR) with rigid H2O and H3O+ structures. MP2/6-31G(d)
value is from a full optimization. b From difference in HF/6-31G(d)
and MP2/6-31G(d) results on 3 T cluster in Table 2. c From calculations
on MP2/6-31G(d) optimized geometry of 3 T cluster (see text). d This
is an approximate G2(MP2,SVP) value for 8 T based on 3 T corrections.
e Estimated correction for the effect of larger cluster size. From
difference between 8 T and 28 T clusters (HF/6-31G(d)) for 8 T and
from difference between 3 T and 28 T clusters (HF/6-31G(d)) for 3 T
(Table 1). f Estimate based on G2(MP2,SVP) energy and correction
for larger cluster size.
gives an additional 2.9 kcal/mol decrease. The final
G2(MP2,SVP) desorption energy of 12.8 kcal/mol should be
accurate to 2-3 kcal/mol for the 3 T cluster. The long-range
electrostatic effect as estimated from the rigid clusters, ∆CS, is
-0.1 kcal/mol for the 3 T cluster and 2.1 kcal/mol for the 8 T
cluster, giving final estimates of the desorption energy of 12.7
and 14.4 kcal/mol, respectively. Thermal corrections will affect
these values, but it is unclear whether the usual ideal gas
corrections used in theoretical enthalpy calculations32 are valid
in the restricted environment of the zeolite interior.
Calculation of the basis set superposition error (BSSE) in
the desorption energy for the 3 T rigid cluster by the counter-
poise method gives a BSSE of 5.5 kcal/mol at the MP2/6-31G(d)
level. This is similar to the correction obtained from using the
6-311+G(3df,2p) basis set [∆BS in Table 4] in G2(MP2, SVP)
theory. Thus, we conclude that BSSE is probably negligible at
the G2(MP2,SVP) level for these systems.
A previous theoretical estimate33 for the desorption energy
in a 2 T atom cluster was 11.2 kcal/mol, but this approach
included no correction terms besides ∆(MP2). Our earlier
study,18 using a 2 T atom cluster model including ∆MP2, ∆QCI,
and ∆BS corrections, gave a value of 10.8 kcal/mol. Both of
these results neglected the ∆ZPE correction and allowed for only
a single O‚‚‚H hydrogen bond between the ZH framework and
the H2O molecule. Another theoretical study using a 3 T atom
cluster12 resulted in a value of 14.8 kcal/mol, but it did not
account for the ∆CS, ∆QCI, and ∆BS terms calculated here. The
experimental enthalpy of adsorption, which was obtained from
a Clausius-Clapeyron analysis of p(T) data between 357 and
435 K for a coverage of less than one molecule per acid site,
was found to be 12 ( 1 kcal/mol.8 The result presented here,
in light of the uncertainties in the theoretical methods and the
neglected thermal corrections, is consistent with experiment.
The G2(MP2,SVP) value for the relative energy (∆Erel) from
the 3 T cluster at 0 K is -5.8 kcal/mol (Table 4). Using the
G2(MP2,SVP) corrections and a correction for MP2 theory
based on the 3 T cluster, the 8 T cluster has a ∆Erel of -8.2
kcal/mol (Table 4). The corrections from G2(MP2,SVP) theory
are all less than 2 kcal/mol for ∆Erel. The ∆Erel values based
on G2(MP2,SVP) corrections for both the 3 T and 8 T clusters
indicate that the neutral structure is more stable than the ionic
(Z-‚‚‚HOH2+) r(OwH) 1.05 (0.97) 1.11 (0.99)
r(OwH′) 0.95 (0.97) 0.98 (0.99)
∠HOwH 95.7(113.1) 93.6 (111.4)
∠OzAlOz 96.8 95.4
neutral structure r(OzHz) 0.97 1.02
(ZH‚‚‚OH2) r(OzH) 2.01 1.81
r(OwHz) 1.75 1.61
r(OwH) 0.96 (0.95) 0.99 (0.97)
r(OwH′) 0.95 (0.95) 0.97 (0.97)
∠HOwH′ 106.6 (105.5) 105.6 (104.1)
∠OzAlOz 98.5 97.2
∆Erel -14.5 -6.2
a
Geometrical parameters defined in Figure 1. Bond lengths in Å,
angles in degrees, and energies in kcal/mol; theoretical values for
isolated molecules in parentheses.
structure. The estimate for the long-range electrostatic effect
from the rigid clusters, ∆CS, is 5.8 kcal/mol for the 3 T cluster
and 3.2 kcal/mol for the 8 T cluster giving the final estimates
for ∆Erel of 0.0 and -5.0 kcal/mol, respectively. Thus, the long-
range electrostatic effects favor the ion-pair structure over the
neutral structure and decrease the barrier for proton transfer. If
the internal relaxation of the H3O+ were included the barrier
for the 8 T cluster would decrease further. The results for ∆Erel
suggest that the barrier is small (less than 5 kcal/mol and
possibly close to zero).
The ∆Erel cannot be directly compared to an experimental
value, but its small magnitude is consistent with the observed
ease of H-D exchange between the H-ZSM-5 acid site and gas
phase D2O at 293 K.34 Sauer et al.35 concluded in an ab initio
theoretical study using a small zeolite cluster that the proton
transfer barrier was a vanishingly small 0.1 kcal/mol, while in
the related case of CH3OH, Haase and Sauer36 calculated a
barrier of less than 1 kcal/mol. Bates and Dwyer used a density-
functional method to calculate a proton transfer barrier for
CH3OH of 1.4 kcal/mol.37
B. Structures. A comparison of the calculated geometrical
parameters for the 3 T ZH‚‚‚OH2 and Z-‚‚‚HOH2+ structures,
fully optimized at HF and MP2 levels of theory using the
6-31G(d) basis set, is shown in Table 5. As previously
mentioned, the neutral structure is a local energy minimum,
while the ion-pair structure is a transition state. In Table 5,
note particularly the significant influence of electron correlation
on the hydrogen-bond distances r(OzH) and r(OwHz) in the
neutral structure. For the 8 T atom cluster, HF/6-31G(d)
calculations also show that the lowest energy structure is a
hydrogen-bonded adsorption structure between H2O and the
zeolite framework, as shown in Figure 2b. The adsorbate is
anchored to the framework by O‚‚‚H linkages of 1.70 and 2.06
Å. These bond lengths are within 0.05 Å of the HF/6-31G(d)
results for the 3 T atom cluster shown in Table 5, and they are
nearly the same as those found in a previous study35 using a
double-zeta plus polarization (DZP) basis set at the HF level
and a 3 T atom zeolite cluster.
The influence of the adsorbed molecules on the 3 T and 8 T
atom zeolite cluster geometry in the vicinity of the acid site
can be seen in Table 6. These results show that when H2O is
adsorbed at the acid site, there is a slight lengthening of the
framework OzHz bond and a slight contraction of the SiOz and
AlOz bonds adjacent to the acid site. The SiOzAl bond angle
also contracts, consistent with a small displacement of the
bridging Oz atom toward the adsorbate. The effect of the
adsorbate is to polarize the framework OzHz bond and to donate
6668 J. Phys. Chem., Vol. 100, No. 16, 1996 Zygmunt et al.

negative charge to the framework (see Table 6). This is TABLE 6: Influence of H2O and H3O+ Adsorption on
consistent with the downward shift in OzHz stretching frequency Selected Geometrical Parameters of 3 T and 8 T ZH
upon adsorption, and its enhanced IR absorption intensity (see Clustersa
section III C) is similar to other hydrogen-bonded complexes.38 ZH ZH‚‚‚OH2 Z-‚‚‚HOH2+
In the transition state, the effect of the H3O+ adsorbate on 3T b
8T c
3T b
8T c
3 Tb 8 Tc
the zeolite cluster geometry is similar to that of H2O but r(OzHz) 0.98 0.95 1.02 0.98
stronger. The SiOz and AlOz bonds contract by 0.04 Å or more, r(SiOz) 1.72 1.65 1.71 1.64 1.68 1.57
and the negative charge on the framework Oz atom increases, r(AlOz) 2.01 1.83 1.95 1.81 1.87 1.72
as shown in Table 6. One qualitative difference between the ∠SiOzAl 128.1 131.5 126.9 130.0 129.8 133.4
q(Oz) -0.95 -0.90 -1.02 -0.97 -1.06 -0.95
two cases is that H3O+ adsorption causes the SiOzAl bond angle q(Hz) 0.53 0.55 0.59 0.62
to increase by about 1.5-2.0°, while H2O causes it to decrease q(Si) 0.93 1.69 0.94 1.69 0.95 1.67
by about the same amount. q(Al) 0.91 1.35 0.90 1.36 0.91 1.36
C. Vibrational Frequency Analysis. Since much of the q(ads)d 0.04 0.04 0.74 0.82
disputed evidence about the nature of the adsorbed H2O structure a
Bond lengths in Å, bond angles in degrees, and atomic charges in
has come from IR spectroscopy, we calculated vibrational units of e. Charges from Mulliken population analysis. b MP2/6-31G(d)
frequencies for the 3 T atom clusters to compare with those level of theory with full optimization. See Figure 1 for labels. c HF/
observed in experimental spectra. While assigning the peaks 6-31G(d) level of theory with CVR optimization. See Figure 2 for
labels. d Sum of Mulliken charges of adsorbate atoms.
in the experimental IR spectra has been a matter of some
controversy, the main spectral features are clear.10 In H-ZSM-
MP2/6-31G(d) frequencies of 3612 and 3269 cm-1 (scaled41
5, sharp peaks occur at 3610 and 3726 cm-1 which have been
by 0.9427) which correspond to the two OH stretching frequen-
identified as νOH stretching modes associated respectively with
cies of the adsorbed H2O. These compare reasonably well to
the SiO(H)Al acid site and the terminal SiOH groups which
the experimental values shown in Table 7. In addition, the MP2/
are present to some degree in all zeolites. Below about 2000
6-31G(d) acidic νOH stretching mode has a greatly enhanced
cm-1 lie additional peaks associated with the zeolite lattice
intensity (1350 km/mol in ZH‚‚‚OH2 compared to 203 km/mol
modes, which overlap the in-plane bending mode (δOH) and the
in ZH) and is strongly downshifted to 2784 cm-1 (from 3480
out-of-plane bending mode (γOH) of the acid site hydroxyl
cm-1 in ZH). This is close to the first overtone of the calculated
groups, making them difficult to study with IR spectroscopy,
δOH in-plane bending mode (2 × 1325 cm-1 ) 2650 cm-1)
although they can be resolved using inelastic neutron scattering
and suggests that a strong Fermi resonance between the two
techniques. Upon adsorption of H2O, the peak at 3610 cm-1 is
modes might be expected to produce a broad, double-peaked
sharply reduced in intensity (but not totally eliminated), while
structure in the IR spectrum. This is in good agreement with
the peak at 3726 cm-1 is also reduced, although less sharply.
the two experimental peaks at 2885 and 2457 cm-1, since the
This shows that although H2O adsorbs at both types of OH sites, minimum between the two peaks is predicted by Fermi
adsorption at the Brønsted acid site predominates. resonance theory to occur at the overtone frequency (2650 cm-1)
Upon adsorption, six distinctly new features appear in IR and is observed at roughly 2675 cm-1. This interpretation of
difference spectra:10,15 weak peaks at 3695 and 3543 cm-1; a these two peaks is in qualitative agreement with previous
weak shoulder near 3380 cm-1; two broad peaks, centered at work.4,13 The third peak at 1630 cm-1 cannot be explained
2885 and 2457 cm-1; and a somewhat sharper peak at 1630 from our calculations in terms of a Fermi resonance shift. The
cm-1. These peak positions depend slightly on H2O pressure MP2/6-31G(d) γOH out-of-plane frequency is at 1045 cm-1. Both
and Si/Al ratio, which explains minor differences in published the overtone (2γ ) 2090 cm-1) and the combination modes (δ
experimental studies. It seems clear that the features in the + γ ) 2370 cm-1) lie at least 400 cm-1 below the calculated
3400-3700 cm-1 range arise from the weakly perturbed OH νOH stretching frequency, thus making the Fermi resonance
stretching modes presumably associated with the adsorbate explanation for the origin of the experimental IR peak at 1630
molecule, so the main interpretive task lies in assigning the three cm-1 seem dubious. It should be noted that Sauer’s calculation
lower frequency peaks. Some workers, in support of an ion- for the adsorption structure with CH3OH at a similar level of
pair adsorption structure, have claimed that the 2885 (A) and theory (MP2/DZP) gave a scaled νOH frequency of 2548 cm-1,
2457 cm-1 (B) peaks correspond to symmetric and asymmetric making the Fermi resonance interpretation of the C peak in the
OH stretching modes of an adsorbed H3O+, while the 1630 cm-1 IR spectrum seem more plausible for adsorbed CH3OH. We
(C) feature represents the associated HOH bending mode.10,11 have included Sauer’s4,36 calculated frequencies for the CH3OH
Others, who favor the hydrogen-bonded adsorption structure, adsorption structure in Table 7.
believe that these three peaks arise due to Fermi resonances The difference between the case of hydrogen bonding in this
between the broad, downshifted νOH stretching mode of the acid study and in the systems which exhibit the A,B,C triplet peaks
site hydroxyl and overtones of the in-plane δOH and out-of- seems to be that the resonant interaction between νOH and the
plane γOH bending modes of the hydroxyl groups (2δ, 2γ)4,13,16 overtone 2γOH is much weaker for the ZH‚‚‚OH2 structure. This
which are shifted to higher frequencies upon adsorption, or an behavior is analogous to some hydrogen-bonded systems which
overtone and combination of these modes (2δ, δ + γ).17 They exhibit distinct A and B features in their IR spectra, but no
interpret these three peaks as the A,B,C triplet well-known in clear C peak.39 A detailed theoretical analysis of the vibrational
other hydrogen-bonded systems.39 The IR spectrum of CH3OH spectrum of the hydrogen-bonded crystal CsHSeO4 suggests that
and CH3CN adsorbed in H-ZSM-5 also shows these three peaks the C peak in some hydrogen-bonded solids is due to a very
and they too have been interpreted in terms of Fermi reso- weak Fermi resonance between νOH and the combination band
nances.4,36,40 γOH + νTO, where νTO is a lattice mode of the solid with the
The calculated vibrational frequencies of the ZH‚‚‚OH2 proper symmetry.42 The combination frequency γOH + νTO is
structure (3 T atom cluster) shown in Table 7 support a modified very close to the observed C peak position because the resonance
form of the latter interpretation. We do not consider the ion- is weak. Pelmenschikov et al.43 recognized this possibility in
pair adsorption structure since our calculations show it to be a their study of CD3CN adsorption in H-ZSM-5, and it may also
transition state. The hydrogen-bonded neutral complex has play a role in H2O adsorption.
Water Adsorption in the Zeolite H-ZSM-5
TABLE 7: Vibrational Frequencies (cm-1) for ZH‚‚‚OH2/CH3OH from IR Spectroscopy and ab Initio Calculations
this worka
assignment (ZH‚‚‚OH2)
asym OH stretch (H2O) 3612 (112)
sym OH stretch (H2O) 3269 (596)
HOH bend (H2O) 1636 (46)
νOH (ZH) 2784 (1350)
δOH (ZH) 1325 (224)
γOH (ZH) 1045 (22)
a Obtained from MP2/6-31G(d) results using scale factor of 0.9427; intensities (km/mol) in parentheses. b References 4 and 36. Obtained from
MP2/DZP results using scale factor of 0.954 . cReference 8. d Reference 15. e A broad shoulder was found in this region but no peak frequency was
reported. f We assign these peaks to Fermi resonance between νOH fundamental and 2δOH overtone modes.
A more likely explanation for the 1630 cm-1 feature in the
H2O structure is provided by the MP2/6-31G(d) HOH bending
mode of the adsorbed H2O at 1636 cm-1 (see Table 6). The
experimental peak at 1630 cm-1 is narrower than the two peaks
at 2885 and 2457 cm-1, which indicates that the effect of Fermi
resonance, if any, is slight. In addition, the experimental
difference spectra at very low H2O pressure (10-4-10-5 mbar)
show the presence of the 1630 cm-1 feature eVen before the
peaks at 2885 and 2457 cm-1 become apparent.10 Thus, this
feature may be an IR-active mode associated with the H2O
molecule which is only weakly perturbed upon adsorption,
consistent with the behavior of the MP2/6-31G(d) HOH bending
mode, which is shifted by less than 1 cm-1 compared to the
same mode for a free H2O molecule.
Additional support for this interpretation is provided by the
results of a very thorough IR spectroscopic study by Parker et
al.15 of H2O and D2O adsorption on H-ZSM-5 and D-ZSM-5.
The peak in question, measured at 1620 cm-1 for H2O adsorbed
on H-ZSM-5, persisted with decreased intensity for H2O
adsorbed on D-ZSM-5, was barely noticeable for D2O adsorbed
on H-ZSM-5, and was completely absent for D2O adsorbed on
D-ZSM-5. Thus, the peak intensity decreased as the deuteration
of the framework and adsorbate increased. The authors of this
study also noted the appearance of a peak at 1426 cm-1 as
deuteration caused the peak at 1620 cm-1 to weaken and pointed
out that these values are close to the experimental values for
the HOH (1611 cm-1) and DOH (1398 cm-1) deformation
modes determined in an IR study of matrix-isolated water
dimers.44 The behavior of these two peaks is evidence for our
assignment of this mode. In addition, the factor of 30 difference
between our calculated intensities for the 1636 and 2784 cm-1
vibrations (see Table 7) is qualitatively consistent with the IR
spectra presented in ref 15.
While the MP2/6-31G(d) vibrational frequencies of the
ZH‚‚‚OH2 structure are consistent with IR difference spectra
measured at low H2O pressures, the variable-pressure IR study
of ref 10 showed dramatic changes in the IR difference spectra
for H2O equilibrium pressures above 10-2 mbar. In order to
investigate the effect of increased pressure on the equilibrium
structure of the H2O adsorption complex, we added a second
H2O molecule to the 3 T Z-‚‚‚HOH2+ structure and performed
a full geometry optimization. While the Z-‚‚‚HOH2+ ion-pair
structure is a transition state, our calculations at both HF/6-
31G(d) and MP2/6-31G(d) levels of theory show that the
Z-‚‚‚H(OH2)2+ structure, shown in Figure 3, is a local minimum.
The presence of a second H2O molecule apparently stabilizes
the ion-pair structure in which a proton has been transferred
from the acid site to the adsorbate. This is consistent with the
fact that the water dimer has an HF/6-31G(d) proton affinity at
0 K of 194.8 kcal/mol, significantly greater than the value of
167.1 kcal/mol for the isolated water molecule. Thus, for
J. Phys. Chem., Vol. 100, No. 16, 1996 6669
Sauerb expt.c expt.d
(ZH..CH3OH) (ZH‚‚‚OH2) (ZH‚‚‚OH2)
3695 3700
3543 ∼3600
3380 e
1630 1620
2548
2885f 2900f
1353
2457f 2470f
1015
Figure 3. Z-‚‚‚H(OH2)2+ complex for 3 T cluster. Hydrogen bond
distances at MP2/6-31G(d) level of theory are shown.
coverages greater than one molecule per acid site, this result
suggests that Z-‚‚‚H(OH2)2+, or larger Z-‚‚‚H(H2O)n+ ion-pair
complexes, may be more likely to form.
The results of vibrational frequency calculations for the
Z-‚‚‚H(OH2)2+ structure help to explain the observed changes
in the IR difference spectrum of H-ZSM-5 as H2O pressure
increases.10 As the pressure increases from 10-2 to 1 mbar,
the Fermi resonance peaks at 2885 and 2457 cm-1 disappear,
and a very broad and intense peak appears near 3208 cm-1 (with
shoulders near 3300 and 3000 cm-1), along with a peak at 1700
cm-1. These spectral changes reflect a significant structural
change in the H2O adsorption complex. The calculation for
the Z-‚‚‚H(OH2)2+ structure gives scaled MP2/6-31G(d) fre-
quencies of 1734 and 2913 cm-1 but provided no evidence
supporting Fermi resonance in the region 2400-2900 cm-1. The
2913 cm-1 frequency has a large absorption intensity. The 1734
cm-1 frequency is associated with an HOH bending mode of
the H3O fragment of the H(OH2)2+ ion, while the 2913 cm-1
frequency corresponds to a perturbed OH stretching mode on
the same fragment. The calculation also yielded two frequencies
at 2305 and 2562 cm-1, corresponding to asymmetric and
symmetric OH stretching modes, respectively, on the H3O
fragment of the adsorbed H(OH2)2+ ion. These modes involve
the protons hydrogen bonded to the zeolite and have large
absorption intensities but did not appear as peaks in the
experimental spectra of ref 10. One possible explanation for
this discrepancy is that larger (n > 2) Z-‚‚‚H(OH2)n+ ion-pair
complexes, which we have not investigated, may predominate
in H-ZSM-5 at 1 mbar of H2O pressure. This possibility has
also been mentioned by Jentys et al.10 If correct, this could
also explain the difference between the calculated frequency of
2913 cm-1 and the experimental peak at 3208 cm-1. Another
possible explanation for the discrepancies between the theoreti-
6670 J. Phys. Chem., Vol. 100, No. 16, 1996
cal and experimental frequencies at higher pressures is that the
3 T cluster may not be large enough for an adsorbate as large
as H(OH2)2+. Evidence for this is that the hydrogen attached
to the Al in the 3 T cluster is only 1.84 Å away from one of the
terminal hydrogens of H(OH2)2+, suggesting that it may be
triply-anchored to the zeolite framework if the hydrogen were
replaced by an oxygen. In future studies we will examine
Z-‚‚‚H(OH2)2+ as well as the corresponding neutral structure
ZH‚‚‚(OH2)2 in larger clusters.
The 1H wide-line NMR spectra measured at 4 K have been
used by Batamack et al. to discriminate the species existing in
zeolite H-ZSM-5 and other solid acids upon water adsorption.6,7
For H-ZSM-5, at loadings up to one H2O per hydroxyl bridge,
they concluded that the neutral hydrogen-bonded structure for
the adsorbed water is the minimum energy state, in accord with
the results obtained in our calculations. However, they also
deduced that there was a coexisting population (20%) of species
with the ionic structure and that the concentrations of the
different species were virtually independent of temperature. The
latter result implies that the energy difference between the ion-
pair and neutral species is extremely small. This is consistent
with our estimate based on the 3 T cluster showing essential
degeneracy of the ion-pair and neutral species, but the 5.0 kcal/
mol energy difference estimate based on the larger 8 T cluster
would be too large to accommodate this interpretation of the
NMR results. We consider the 5.0 kcal/mol to be an upper
limit on ∆Erel and allow that the value could be very small.
The calculations do show, however, that the ion-pair structure
is a transition state and not a local minimum. We can suggest
two alternative rationalizations for the NMR observations.
First, we note that Batamack et al.6 also found that the relative
fraction of the ion-pair species increased with increasing water
loading for their H-ZSM-5 sample with the fewest defects. It is
possible that the species identified as the ion-pair species in
the 1H wide-line NMR spectra measured at 4 K is actually the
Z-‚‚‚H(OH2)2+ species stabilized by two water molecules as
found in our calculations (or even the higher complexes for more
highly hydrated systems). This also implies that dual hydration,
i.e., two waters per acid site, is occurring at loadings below
one H2O per bridging hydroxyl group in the experiments,
although the reason for this is not clear at this time. In future
work we will investigate the energy of the interaction of the
acid site and a water dimer and compare it to the ion-pair state
in clusters larger than 3 T to provide insight into this matter.
The alternative explanation relies on the recognition that there
can be inequivalent Brønsted acid sites in the zeolite. The
calculations were performed specifically for protonation at the
T(12)-O(24)-T(12) site of the ZSM-5 zeolite framework (MFI
structure). We have previously demonstrated that the proton
affinity is site-dependent, so the energy difference between the
ionic and neutral structures for the adsorbed water is expected
to be site-dependent also. It is therefore possible that at a
crystallographically inequivalent Brønsted acid site the relative
stability of the neutral and ionic structures is reversed. The
fraction of these sites manifested in the NMR spectra could then
reflect their fractional population (occupancy) in the zeolite
sample and would in fact be temperature invariant.
The argument presented in the previous paragraph is one of
heterogeneity in the Brønsted acid sites. This could be a sample-
dependent property, and we note that the reported species
distribution as a function of water loading differed for H-ZSM-5
samples with different defect concentrations. Although we
cannot address this result directly in the context of our
calculations, it is clear that defects present an additional basis
Zygmunt et al.
for heterogeneity in the Brønsted acid sites beyond the intrinsic
heterogeneity presented by crystallographic site inequivalence.
IV. Conclusions
Using aluminosilicate cluster models of up to 100 atoms, we
have carried out an ab initio molecular orbital study of the
adsorption of H2O at an acid site in the H-ZSM-5 zeolite. The
following conclusions can be drawn from this study:
1. The ion-pair structure is a transition state and the neutral
structure is a local minimum from calculations on the 3 T atom
cluster at the MP2/6-31G(d) level. The energy difference
represents the barrier for proton transfer between oxygen sites.
Calculations on a larger 8 T atom cluster representing the O(24)
site, with local geometry relaxation included, also suggest that
it is a transition state, although these calculations were done at
the HF/6-31G(d) level and did not include internal relaxation
of the H3O+.
2. Calculations including effects of larger cluster size, larger
basis sets, zero-point energies, and higher level of electron
correlation were used to obtain more accurate values for the
water desorption energy and the barrier. The calculations give
a water desorption energy for the O(24) site of 13-14 kcal/
mol. This is in agreement with the published experimental value
for water desorption in ZSM-5. The calculations give a small
proton transfer barrier (less than 5 kcal/mol and possibly close
to zero). This is consistent with the observed ease of H/D
exchange between the acid site and adsorbed D2O.
3. In calculating the desorption energy and the barrier, the
correlation effect is found to be very important (7-8 kcal/mol),
and most of it is accounted for by the MP2 theory which differs
by less than 1 kcal/mol from the more sophisticated QCISD(T)
technique.
4. The calculated vibrational frequencies of the H2O adsorp-
tion structure in the 3 T atom cluster are able to account for the
main features of the experimental IR spectrum and provide
evidence for a slightly different interpretation of the spectrum
than previously proposed.
5. While the the ion-pair structure is a transition state when
only one H2O molecule interacts with the Brønsted acid site in
the 3 T cluster, the addition of a second H2O molecule to the
first H2O molecule stabilizes the ion-pair structure, making it a
local minimum. Calculated vibrational frequencies of the
resulting equilibrium ion-pair structure, Z-‚‚‚H(OH2)2+, show
significant changes from those of the ZH‚‚‚OH2 structure that
are consistent with experimental IR spectra at pressures above
10-2 mbar. This Z-‚‚‚H(OH2)2+ species is also invoked in one
possible reinterpretation of published low-temperature 1H wide-
line NMR spectra. An alternative interpretation based on
heterogeneity of the Brønsted acid sites is also presented.
Note Added in Proof. After the manuscript was submitted
for publication, experimental results were published (Smith, A.
K. C.; et al. 1996, 271, 799) which give crystallographic
evidence for the coexistence of H2O and H3O+ adsorbates in
H-SAPO-34. Their result is consistent with our alternative
interpretation of the 1H-NMR data presented in section III.C,
although we reiterate that since proton affinities may vary among
crystallographically distinct Bronsted acid sites in a particular
structure, there is no a priori reason for the H2O binding
distribution to be the same in a zeolite and a SAPO material.
Acknowledgment. This work was supported by the U.S.
Department of Energy, Office of Basic Energy Sciences,
Division of Materials Sciences, under Contract No. W-31-109-
ENG-38. We acknowledge a grant of computer time at the
Water Adsorption in the Zeolite H-ZSM-5
National Energy Research Supercomputer Center. Acknowl-
edgment is also made to the donors of the Petroleum Research
Fund, adminstered by the American Chemical Society, for partial
support of this research (S.A.Z. and M.K.E).
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