JOURNAL OF CHEMICAL PHYSICS VOLUME 114, NUMBER 14 8 APRIL 2001

Adsorption of linear hydrocarbons in zeolites:

A density-functional investigation
Lubomir Benco,a) Thomas Demuth, and Jürgen Hafner
Institut für Materialphysik and Center for Computational Materials Science, Universität Wien,
Sensengasse 8, A-1090 Wien, Austria
François Hutschka
Total Raffinage Distribution, Centre Europèen de Recherche et Technique, B. P. 27,
F-76700 Harfleur, France
Herve Toulhoat
Institut Français du Pétrole, F-92852, Rueil-Malmaison Cedex, France
共Received 11 October 2000; accepted 23 January 2001兲
An extensive first-principles periodical study of adsorption properties of linear hydrocarbons in
zeolites is presented. The applicability of density-functional theory to weak interactions is inspected
within both local-density 共LDA兲 and generalized-gradient 共GGA兲 approaches for C1 to C6 linear
hydrocarbons. The LDA adsorption energies are due to the overbinding ⬃2.5 times larger than the
GGA values. A compact diagram is constructed showing the increase of the adsorption energy with
the length of the adsorbed molecule and with the concentration of acid sites in the zeolite support.
The flow of the electron density induced by the adsorption indicates that the adsorption on the acid
site is realized through the hydrogen bonding between the OH group and the CH3 group. The pattern
of the reconstructed bonding, however, is more complex than that of the simple hydrogen bond. The
regions of redistributed electron density within the adsorbed molecule are spread over the whole
CH3 group and the adjacent C–C bond. The off-centering of the reconstructed regions from atomic
positions is in good agreement with recent 13C measurements, showing only slight variation of
chemical shifts with the hydrocarbon length for both proton-free and the protonated forms of
zeolites. © 2001 American Institute of Physics. 关DOI: 10.1063/1.1355769兴

I. INTRODUCTION complex defect structures produced by the postsynthetic pro-

Zeolites are microporous materials widely used in tech-
nological processes as multipurpose materials.1 They are
very good sorbents with a high internal surface. Their
channel-like structures make the transport of molecules in-
side or outside the crystals an easy process. Because of the
high stability and numerous imperfections such as Si/Al sub-
stitutions compensated with acid protons or with extra-
framework cations, zeolites perform well as heterogeneous
catalysts.
In a series of intrazeolite processes through which reac-
tants are converted into products, the adsorption of mol-
ecules to the internal surface represents an important first
step. The strength of the interaction depends on the compo-
sition of the zeolite being the weakest for the purely siliceous
compounds and proportionally increased with the increased
concentration of the acid sites. For different structure types
different adsorption energies have been measured. In the
more compact structures 共ZSM-22, MOR兲 the contact be-
tween the framework and the adsorbed molecule is tighter
and leads to higher adsorption energies. On the contrary,
adsorption energies for the more open structures with smaller
framework densities 共Y,X兲 are smaller.2 A wide range of
a兲
Electronic mail: lubomir.benco@univie.ac.at. Permanent address: Institute
of Inorganic Chemistry, Slovak Academy of Sciences, Dubravska cesta 9,
SK-84236 Bratislava, Slovakia.
cessing of zeolites causes the interaction energy to increase
proportionally to the concentration of defects.
Hydrocarbons 共HC兲 are raw materials for many techno-
logically important products and their adsorption in zeolites
is of continuous attention to both experimentalists and theo-
reticians. The adsorption isotherms of C5 –C10 normal al-
kanes in silicalite crystals are measured by Sun et al.3 The
adsorption of C3 –C6 normal alkanes in acidic zeolites is
studied by Eder et al.,4 and Denayer et al. have recently re-
ported on the adsorption of n-alkanes at high temperatures.2
The experimental data indicate that adsorption energies of
the HC are much smaller than those of small polar molecules
such as ammonia and water. The adsorption of polar mol-
ecules is accomplished through relatively strong N–H¯O
and O–H¯O hydrogen bonds 共HB兲 with typical adsorption
energies of ⬃200 kJ/mol 共NH3 5兲 and ⬃100 kJ/mol
(CH3OH, 6 H2O7兲. The strength of the adsorption forces act-
ing on the HC is documented, e.g., by the adsorption energy
of propane. For acidic ferrierite 共Si/Al⫽45兲 the measured
value is 49 kJ/mol.4 For n-hexane Eder et al.4 deduced the
dependence of the heat of adsorption on the zeolite frame-
work density. Supposing that a similar dependence is valid
also for other n-alkanes, the estimate for the adsorption of
propane in acidic gmelinite is ⬃40 kJ/mol and a much lower
adsorption energy is expected for the purely siliceous struc-
ture.

0021-9606/2001/114(14)/6327/8/$18.00 6327 © 2001 American Institute of Physics

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6328 J. Chem. Phys., Vol. 114, No. 14, 8 April 2001
Theoretical ab initio works investigating a contact be-
tween the zeolitic framework and the HC include molecules
of various complexity, starting with methane8 and ending
with long linear hydrocarbon chains9 or unsaturated
branched molecules like isobutene.10 The HC to zeolite in-
teraction has been, however, inspected mostly by means of
the molecular cluster approach, which uses a fragment of the
zeolite containing the active site as a representative model of
the zeolite. The fragment is cut out from the parent structure
with the hydrogen atoms saturating terminal bonds. Two
main disadvantages of this approach are 共i兲 a relaxation of
the cluster resulting in the lost of resemblance to the envi-
ronment of the active site, and 共ii兲 omitting of long-range
electrostatic effects. Both relaxation producing the more
tight contact between the adsorbent and the adsorbate and
neglection of electrostatic repulsion lead to adsorption ener-
gies too high compared with experimental data. The former
drawback is eliminated by usage of a constrained cluster. An
influence of the long-range electrostatic interactions is taken
into account via embedding techniques11,12 based on the
combination of the quantum mechanics 共‘‘inner’’ region of
interest兲 and the molecular mechanics 共less important outer
region兲. Application of both corrections end with adsorption
energies diminished to values compared reasonably with ex-
perimental data.10
The density-functional theory 共DFT兲13 and the general-
ized gradient approximation 共GGA兲 for the exchange
functional14 have been used in numerous applications in
which DFT compares well with experiment and with the
most accurate ab initio calculations for properties such as
structure and bond energy and are now in routine use for a
number of fundamental properties of chemical and physical
systems. Despite the successes, problems remain. The GGA
considerably improves bond distances and bond energies for
strong interactions of both covalent and ionic character com-
pared to the uncorrected local density approach 共LDA兲. Ap-
plicability of GGA to weak intermolecular forces has been
tested on rare-gas diatomic molecules.15 Though GGA func-
tionals significantly improve the LDA values of bond
lengths, binding energies, and vibrational frequencies, the
agreement is still not quantitative. Interaction energy com-
prises a high percentage of dispersion energy 共more than
90% in He2 兲. Because dispersion energy scales with r ⫺6 , it
is sensitive to interatomic distances. Undervaluation of bond
lengths which often occurs in GGA, e.g., for Ar and Kr,15
then leads to too small GGA interaction energies. Investiga-
tion of alkali metal adsorption at the surface of MgO16 have
shown that application of GGA functionals decreases inter-
action energies by a factor of ⬃1.6 共PBE9617兲 and by ⬃2.7
共BLYP18兲.
We have performed an extensive study of properties of
zeolite structures aiming at increasing knowledge of in-
trazeolite chemistry. Within the periodical approach the to-
pology of the inner surface of zeolites is preserved and long-
range electrostatic effects are taken into account. Both a
model structure and a zeolite of technological importance are
under study. Gmelinite as a model structure represents, due
to its relatively high symmetry and the small number of at-
oms per cell, a framework convenient for numerical simula-
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Benco et al.
tions of chemical processes. Subsequent comparative studies
on technological zeolite are performed with mordenite. We
have compared structural properties as well as energetics of
protonation of the two structures19,20 complemented by cal-
culations of the stretching frequencies of hydroxyl groups. A
dynamical study of H2O adsorbed in Na-free gmelinite has
demonstrated the existence of the spontaneous proton trans-
fer 共PT兲 between O sites.21 A similar scenario of the PT is
found for the Na zeolite.22
The present report describes the adsorption of linear hy-
drocarbons in zeolites. The periodical approach is used to
preserve the surface structure of the zeolitic framework and
to include the long-range electrostatic effects. Two basic
DFT approaches, LDA and GGA, are used to calculate the
adsorption energies. Weak interactions between the hydro-
carbon molecules and the zeolite framework represent a
probe for the applicability of commonly used functionals to
adsorption phenomena in zeolites.
II. STRUCTURE AND MODEL OF ADSORPTION
The simulation of the adsorption of hydrocarbons in a
zeolite is modeled on the gmelinite structure. Gmelinite is a
rather rare natural zeolite with the chemical composition
Na8共AlO2兲8共SiO2 ) 16 . The primary building blocks 共SiO4 and
AlO4 tetrahedra兲 are stacked into hexagonal prisms which
are secondary building units isomorphous with those of the
technologically important faujasites.23 Parallel linkage of
hexagonal prisms leads to a hexagonal structure ( P6 3 mmc).
The set of irreducible atomic positions contains only one
tetrahedral site 共Si/Al兲 and four oxygen sites.24 The largest
aperture is a ⬃7 Å channel circumscribed by a ring of 12
SiO4 tetrahedra 共12-membered ring: 12MR兲, which runs par-
allel to the c axis. From the main channel perpendicular to
the c axis the smaller eight-membered rings 共8MR兲 lead to
the gmelinite cages which is the only type of cage in the
structure. Figure 1 presents the structure, the orientation of
12MR and 8MR, the situation of the gmelinite cage, and the
positions of irreducible O atoms. The x-ray structure refine-
ment performed on natural gmelinite with an Si/Al ratio of
approximately 2 and containing the corresponding number of
counterions and approximately 24 water molecules per cell
yields cell dimensions of a⫽13.756 Å and c⫽10.048 Å. 24
The simulations of the adsorption of n-hydrocarbons are
performed with the fixed volume and shape of the experi-
mental unit cell of the hydrated zeolite.24 The experimental
volume was shown to be only slightly larger than that ob-
tained by the optimization within the GGA approach19 共cf.
similar results for mordenite20 and chabazite25兲. Because the
adsorption in a zeolite always leads to slight expansion of the
crystal lattice, the cell volume determined on hydrated
samples reasonably compares with the optimized unit cell of
the zeolite. The hydrocarbons are placed in the 12MR. The
most probable position of the adsorbed molecules, trans-
ported into the structure by the stream of gaseous or liquid
hydrocarbons flowing along the main channels, is parallel to
the main channel. The position of the hydrocarbon molecule
is therefore chosen parallel to the c axis in which any energy
loss due to the deformation of the the linear chain of the
molecule is avoided. The acid proton is located at the O4
J. Chem. Phys., Vol. 114, No. 14, 8 April 2001
FIG. 1. Hexagonal structure of gmelinite. Top view showing large 12MR
channels 共a兲. Side view of the framework structure 共b兲 displaying the 8MR
and the gmelinite cages. Short arrows indicate the four inequivalent O sites
surrounding the tetrahedral site.
site, the OH group pointing to the center of the main
channel.19 To facilitate a maximum contact of the adsorbed
molecule with two acid sites 共AS兲, a second proton is placed
at a relatively short distance from the first one located on
another O4 atom. Two Al atoms corresponding to two AS
are placed in second-neighbor positions, obeying the Löwen-
stein rule for the distribution of the Al-sites. The fragment of
the structure, the position of the adsorbed molecule, the lo-
cation of the acid protons and of the Al atoms, respectively,
are displayed in Fig. 2.
III. COMPUTATIONAL DETAILS
Periodic first-principles calculations are performed
within the density-functional theory 共DFT兲 using the Vienna
ab initio simulation package VASP.26,27 The simulations use
both the local-density 共LDA兲 and gradient-corrected 共GGA兲
density functionals in standard versions proposed by Ceper-
ley and Alder and parametrized by Perdew and Zunger28 and
by Perdew and Wang.29 The valence-electron wave functions
are expanded in terms of plane waves,30,31 and the electron–
ion interaction is described by Blöchl’s projector augmented
wave 共PAW兲 technique32,33 applied to ultrasoft
pseudopotentials.34,35 The calculations are performed with a
plane wave cutoff energy of E pw⫽400 eV. Cutoff radii of
r s ⫽r p ⫽r d ⫽1.9 a.u. for the pseudo-wave functions are used
for aluminum and silicon, respectively. Cutoff radii of r s
⫽1.3 a.u. and r p ⫽r d ⫽1.5 a.u. are used for oxygen and car-
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Adsorption of linear hydrocarbons in zeolites 6329
FIG. 2. Fragment of the structure showing the location of the adsorbed
hydrocarbon molecule, the Al atoms, and the acid protons, respectively. Top
view 共a兲 and the side view 共b兲.
bon, and radii of r s ⫽r p ⫽1.1. a.u. are used for hydrogen.
Brillouin-zone sampling is restricted to the ⌫ point. The total
energy is converged to 10⫺5 eV; the convergence is im-
proved using a modest smearing of the eigenvalues. The op-
timization of atomic positions within the unit cell is per-
formed combining both the quasi-Newton and the conjugate-
gradient algorithms. In relaxed positions the residual
analytical Hellman–Feynman force acting on atoms is not
larger than 0.1 eV Å⫺1.
IV. RESULTS AND DISCUSSION
A. Adsorption energies
The adsorption of HC in a purely siliceous zeolite is
realized via the contact between the zeolite O sites and the
hydrogen atoms of the HC. In a protonated structure the
strongest interaction occurs between the Brønsted O–H
group of the zeolite and one carbon atom of the HC. Figure
3 schematically compares these two types of bonding to the
ordinary O–H¯O hydrogen bond and orders the bonding
contacts according to a decreasing bond strength. All of them
belong to the category of the hydrogen bonds.36 Compared to
the typical O–H¯O interaction 关Fig. 3共a兲兴 the other two
contacts, O–H¯C 关Fig. 3共b兲兴 and C–H¯O 关Fig. 3共c兲兴, are
much weaker due to much lower electronegativity of carbon
compared with oxygen. Adsorption energies are calculated
using the expression
E ads⫽E 共 zeo⫹HC兲 ⫺E 共 zeo兲 ⫺E 共 HC兲 , 共1兲
6330 J. Chem. Phys., Vol. 114, No. 14, 8 April 2001 Benco et al.

FIG. 3. Schematic illustration of different hydrogen bonds 共HBs兲 in zeolites.

Ordinary O–H¯O HB for adsorbed water 共a兲, the O–H¯C contact be-
tween the acid site and a hydrocarbon 共b兲, and the C–H¯O contact between
the purely siliceous zeolite and the hydrocarbon molecule.

where E(zeo⫹HC) is the energy of the relaxed zeolite struc-

ture containing the HC molecule adsorbed in the main chan-
nel, E(zeo) is the energy of the adsorbate-free zeolite struc-
ture, and E(HC) is the energy of the HC molecule optimized
in vacuo. Geometries of both free HC molecules and ad-
sorbed complexes are given below. No volume (p•⌬V) and
entropy (T•⌬S) terms are considered in the calculation of
adsorption energies.
Figure 4 displays the adsorption energies as a function of
the HC length for the purely siliceous structure 共a兲, for one
acid site/cell 共b兲, and for two acid sites/cell located in the
framework at the short distance of ⬃4.8 Å 共c兲. For a series of
C1 –C6 molecules adsorbed in the purely siliceous structure,
a quasilinear dependence is observed for both GGA and
LDA. The values calculated using the GGA result from a
tedious structure optimization often ending in numerous lo-
cal minima of the potential energy surface. Figure 4共a兲
shows a slight increase between C1 and C2 . The adsorption
energies for longer HC then oscillate around the value of ⫺4
kJ/mol and do not increase for longer HC. Within the LDA
the corresponding adsorption energies are much higher than
those obtained with GGA, e.g., for ethane the GGA and
LDA values are ⫺4.7 and ⫺11.2 kJ/mol, respectively. A
modest increase of the LDA adsorption energies between C1
and C2 is followed by a quasilinear increase for higher HC
with an increment of ⬃⫺4.3 kJ/mol per C atom. The quasi-
linear behavior of LDA energies agrees reasonably with the
experimental data obtained for adsorption of n-alkanes in
acid zeolites2,4 as well as with the adsorption data for
silicalite.3 The linearity is due to the homogeneous increase FIG. 4. Adsorption energies of linear alkanes. Adsorption of C1 to C6 in the
purely siliceous structure 共a兲, C3 to C6 to one acid site 共b兲, and C3 to C6 to
of the lateral interactions between adsorbed molecules and
two acid sites 共c兲.
zeolite structure with every CH2 group of the HC. Much
lower values of the GGA adsorption energies calculated for
weak interactions are in agreement with the former results.
The applications to rare-gas diatomic molecules15 and alkali nonlinear increase between C4 and C5 . The reason for the
metal adsorption at the surface of MgO16 have documented step-like dependence is another contact of the adsorbed mol-
that when GGA functionals overvalue bond lengths the long- ecule to the second acid site. While C3 and C4 molecules
range van der Waals forces otherwise making substantial make only one contact, the C5 and C6 molecules are long
contributions to the adsorption energy vanish due to too large enough to make contacts to both acid sites. The gain in ad-
interatomic distances. sorption energy through the formation of this contact is
Energies calculated for one acid site/cell 关Fig. 4共b兲兴 are ⬃⫺25 kJ/mol 共LDA兲 and ⬃⫺9 kJ/mol 共GGA兲, i.e., almost
quasilinear for GGA and LDA, both shifted to higher adsorp- the same as for the first bond to the acid site. This increase of
tion energies by an almost constant increment of about 28 the adsorption energies is expected for protonated structures
kJ/mol 共LDA兲 and 8 kJ/mol 共GGA兲 compared with corre- with high concentration of acid sites 共Si/Al⫽1兲 provided that
sponding values for the purely siliceous structures. This the geometry of the adsorbed molecules and the distribution
proves that the strength of the O–H¯C interaction 关Fig. of the acid sites allow for a simultaneous formation of two
3共b兲兴 is larger than that of the C–H¯O bond 关Fig. 3共c兲兴. unstrained bonds. No such data, however, are available to be
Figure 4共c兲 shows that on structures with two acid sites compared with our calculated adsorption energies.
the adsorption energies are further increased, displaying a Figure 5 comprehends the adsorption data as a function

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J. Chem. Phys., Vol. 114, No. 14, 8 April 2001 Adsorption of linear hydrocarbons in zeolites 6331

TABLE I. Geometry parameters of a propane molecule in vacuo 共distances

in Å, angles in deg, and deviation 共␦兲 in percent兲. Notation according
to Fig. 6.

Exp. 共Ref. 37兲 LDA ␦ GGA ␦

C–C 1.526共2兲 1.509 ⫺1.11 1.528 ⫹0.13
C2–H 1.096共2兲 1.107 ⫹1.00 1.102 ⫹0.55
C1–Hs 1.089共9兲 1.102 ⫹1.19 1.099 ⫹0.92
C1–Ha 1.094 1.105 ⫹1.01 1.101 ⫹0.64
C1–H 1.091共10兲a 1.104a ⫹1.19 1.100a ⫹0.82
C–C–C 112.4共2兲 111.9 ⫺0.44 112.7 ⫹0.27
H–C2–H 106.1共2兲 105.5 ⫺0.57 106.0 ⫺0.09
Ha–C1–Ha 107.3 107.0 ⫺0.28 107.4 ⫹0.09
Ha–C1–Hs 108.1 107.7 ⫺0.37 107.6 ⫺0.46
H–C1–H 107.7共10兲a 107.5a ⫺0.19 107.5a ⫺0.19
C2–C1–Hs 111.8共10兲 112.5 ⫹0.63 111.9 ⫹0.09
FIG. 5. Adsorption energies as a function of the hydrocarbon length and the C2–C1–Ha 110.6 110.8 ⫹0.18 111.1 ⫹0.45
concentration of acid sites. a
Average value.

of the acid site concentration for C3 –C6 molecules. It dem-

onstrates that at all concentrations the GGA adsorption ener-
gies are approximately 2.5 times lower than those by LDA.
More pronounced LDA-calculated adsorption energies dem-
onstrate that the strength of the interaction between the HC
and the zeolite framework is approximately doubled for the
acid zeolite compared with the purely siliceous structure.
With the increase of the acid site concentration the gain in
energy is slowed down, probably due to steric constraints. In
structures with a concentration of up to one acid site per
adsorbed molecule the adsorption energy increases almost
linearly with increased length of the HC. For higher acid site
concentrations, however, a pronounced nonlinearity appears,
distinguishing between molecules according to the number
of contacts with framework acid sites 共C3 ,C4 —one contact;
C5 ,C6 —two contacts兲.
B. Structure of adsorption complexes
As a response to the interaction with the zeolite support
structural changes are induced in an extent which depends on
the interaction strength. This section reports details of the
geometries of the adsorbate sorbent complex at the example
of the propane molecule.
1. Molecule in vacuo
Geometry parameters of the propane molecule optimized
in vacuo by means of PAW-projected pseudopotentials
within both LDA and GGA are compiled in Table I together
with experimental data.37 These values indicate that for in-
teratomic distances the GGA performs slightly better than
the LDA. All the LDA distances deviate by about 1% from
the experimental value, the C–C bond length being underes-
timated and the C–H bonds overestimated by this amount.
Within the GGA all distances are slightly overestimated and
compare reasonably to experimental data. The angles calcu-
lated within both LDA and GGA are of acceptable quality.
siliceous structure does not induce any remarkable deforma-
tion of the adsorbed molecule. The distances and angles of
the Ha atoms which are in contact with the zeolite are similar
to those of the free molecule 共cf. Tables II and I兲. The
O1¯Ha distances to the framework O sites, however, are
considerably shorter within LDA. The adsorption to the acid
site gives rise to changes which are observable in both LDA
and GGA. These changes, however, are more pronounced
within LDA. The OH-to-C1 contact, which represents the
strongest interaction, keeps the adsorbed molecule at a dis-
tance shorter than that in the siliceous structure 共cf. averaged
LDA values of 2.593 and 2.623 Å, respectively兲. The inter-
action leads to a widening of the Ha–C1–Ha angle and to
the elongation of the C1–Ha bonds. On the side of the zeo-
lite the O1–H bond is elongated, giving evidence for the
formation of the O–H¯C hydrogen bond.
The adsorption of the hydrocarbon induces a deforma-
tion of the zeolite structure as well. Table II reports the angle
O1⬘ –O4–O1 characterizing the curvature of the inner sur-
face of the zeolite 共cf. Fig. 6兲. The comparison of this angle
with the values in parentheses, which correspond to the
adsorbent-free zeolite structures, shows that both the sili-
ceous and the acid zeolite are deformed in the same manner.
The uniform decrease of this angle indicates that in response
to the local adsorption, a global deformation of the frame-
work occurs producing an ellipsoidal shape of the main
channel. Different O1⬘ –O4–O1 angles observed for the acid

2. Adsorbed molecule
The geometrical arrangement of the contact site between
the zeolite support and the hydrocarbon molecule is dis-
FIG. 6. Geometry of the contact site between zeolite and the hydrocarbon
played in Fig. 6 and the geometry parameters are collected in molecule. Purely siliceous zeolite 共a兲, bonding at the acid site 共b兲. For the
Table II. The weak interaction between the molecule and the numerical values of bond-distances and angles, see Table II.

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6332 J. Chem. Phys., Vol. 114, No. 14, 8 April 2001 Benco et al.

TABLE II. Geometry parameters of the adsorbate/sorbent complex for pro-

pane adsorbed in gmelinite 共distances in Å and angles in deg兲. Notation
according to Fig. 6.

Purely siliceous zeolite Acid zeolite

Hydrocarbon GGA LDA GGA LDA

C–C 1.527 1.508 1.529 1.509

C2–H 1.103 1.107 1.101 1.105
C1–Hs 1.099 1.103 1.098 1.102
C1–Ha 1.101 1.106 1.107 1.115
C–C–C 112.4 112.4 113.3 112.3
H–C2–H 105.9 105.8 106.4 106.1
Ha–C1–Ha 107.2 106.9 111.7 113.1
共107.4兲a 共106.7兲a

Contact site
O4共zeo兲¯C1 3.514 3.150 3.085 2.941
O4–H 0.996 1.014
H¯C 2.090 1.927
O1¯Ha 2.908 2.604 2.781 2.669
O1⬘¯Ha 2.994 2.642 2.672 2.517
O1¯Ha 2.951b 2.623b 2.727b 2.593b

zeolite
O1⬘ –O4–O1 158.6 156.3 163.4 162.1
共159.4兲c 共158.4兲c 共164.2兲c 共163.9兲c
a
Values in parentheses refer to the contact-free methyl group.
b
Average value.
c
Sorbent-free zeolite structures.

zeolite compared to the siliceous structure are due to the

local deformation raised by the Al/Si substitution.

C. Bonding to zeolite framework

The formation of a chemical bond between the zeolite
support and the adsorbed molecule is accompanied by a re-
distribution of the electron density. The change of bonding is
displayed by the differential charge density calculated as the
difference between the electron density of the adsorbed com-
plex and that of the adsorbent-free support and of the free
nonadsorbed molecule, all systems preserving the relaxed
atomic positions of the adsorbed complex.
FIG. 7. Difference electron densities of the propane molecule adsorbed in
the purely siliceous zeolite. Spheres show atomic positions of the adsorbed
molecule and the zeolite fragment adjacent to the contact site. Light gray
regions indicate a gain and the dark regions a depletion of the electron
density. LDA 共a兲 and GGA 共b兲 approaches 共isosurfaces of ⫹10 e/Å3 and
⫺7.5 e/Å3兲.

1. Purely siliceous zeolite

Figure 7 displays the difference electron densities of the
propane molecule adsorbed in the purely siliceous structure.
Only minor changes of the electron density are induced
within both LDA 关Fig. 7共a兲兴 and GGA 关Fig. 7共b兲兴 as shown
by the low-value isosurfaces of ⫹10 and ⫺7.5 e/Å3 共cf. iso-
surfaces of the acid zeolite displayed below兲. A different
pattern of stabilizing interactions is obtained within LDA
and GGA, none of them indicating a hydrogen bonding of
the type O共zeo兲¯H–C. The GGA leads to a very small
charge redistribution not localized on atoms. The LDA func-
tional leads to a more pronounced charge flow in correspon-
dence with higher LDA adsorption energies 共Figs. 4 and 5兲
and shorter O4共zeo兲¯C1 distances 共Table II兲. The bonding
is of clear directional character localized between the O at-
oms of the zeolite and the CH3 group of the hydrocarbon
molecule 关Fig. 7共a兲兴. The changes are of comparable extent
on both the adsorbed molecule and on the zeolite framework.
The shortest contact between C1 and O4 induces a slight
increase of the electron density between the two Ha atoms
close to the C1 atom and a polarization of the framework O4
atom on which the charge density is withdrawn from the side
of the zeolite and accumulated towards the CH3 group of the
adsorbed molecule. The other end of the molecule makes
another contact between the second C1 atom and the frame-
work O3 atom of 3.343 Å. For this weaker contact Fig. 7共a兲
shows a charge redistribution of an extent comparable to that
within the shortest contact between O4 and C1. The electron
density is again accumulated on the framework O3 atom, but
depleted from the C–H bond.
2. Acidic zeolite
The charge flow induced by the interaction of the pro-
pane molecule with the zeolite acid site is displayed in Fig.
8. A distinct redistribution of the charge density is obtained
for both LDA 关Fig. 8共a兲兴 and GGA 关Fig. 8共b兲兴 functionals

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J. Chem. Phys., Vol. 114, No. 14, 8 April 2001
FIG. 8. Difference electron densities of the propane molecule adsorbed to
the acid site. LDA 共a兲 and GGA 共b兲 approaches 共isosurfaces of ⫹40 e/Å3
and ⫺30 e/Å3兲.
which is slightly more pronounced for LDA. Both function-
als provide the same pattern of bonding restricted to the OH
group on one side and to the terminal CH3 group on the other
side. A rather complex charge redistribution occurs in the
hydroxyl group, showing features typical of hydrogen-
bonded OH groups.38 The area of the acid H atom is depleted
of electron density which is transferred towards both the
O–H bond and the CH3 group. A rather symmetrical redis-
tribution on the O atom indicates a nonisotropic polarization
directed along the OH group, leaving the two covalent O–Si
and O–Al bonds unaffected by the hydrogen bonding. On
the side of the hydrocarbon changes occur only in that part of
the molecule which is involved in the contact with the zeo-
lite. In contrast to the typical O–H¯O hydrogen bond where
the contact is realized through a single O atom, the hydro-
carbon molecule makes contact through the entire CH3
group. Figure 8 shows that the increase of the electron den-
sity here is not centered on a single atom, but reflects a
polarization of the whole methyl group. The most pro-
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Adsorption of linear hydrocarbons in zeolites 6333
nounced feature of the hydrogen-bonded hydrocarbon mol-
ecule is the large region of increased electron density be-
tween the two Ha atoms elongated towards the zeolite acid
site. An increase of similar extent and shape is found for a
benzene molecule adsorbed in acid mordenite, as well.39 This
accumulation of the electron density weakens the C–H
bonds and leads to an increased Ha–C1–Ha angle 共cf. Table
II兲. The off-centered position of the two depleted regions
indicates that the transferred electron density comes from
nonbonding regions of the Ha atom 共Fig. 8, left兲 and of the
Hs atom. The third depleted region is localized directly on
the C–H bond. The depletion of the electron density within
the CH3 group polarizes the C–C bond whose electron den-
sity is shifted towards the CH3 group.
Figures 7 and 8 show that regions of substantial differ-
ence electron densities within hydrocarbons adsorbed in both
purely siliceous and acid zeolites are typically not localized
on atoms. Recently, adsorption properties of linear alkanes in
ZK-5 zeolites were investigated by means of 13C NMR
measurements.40 The NMR chemical shifts, which are very
sensitive to the change of bonding on the measured atomic
center, show only slight variation for hydrocarbons of differ-
ent length in both the proton-free and protonated form of the
zeolite. This agrees well with our results displaying the
change of bonding within the terminal CH3 group which is
localized close to the H atoms or within the C–C and C–H
bonds but leaves the electron density around the carbon at-
oms unchanged.
V. CONCLUSIONS
A first-principles DFT study of the adsorption properties
of linear hydrocarbons in zeolites is presented. The weak
adsorbate–sorbent interaction energies are calculated within
both LDA and GGA approaches. The LDA adsorption ener-
gies are ⬃2.5 times larger compared to the GGA values,
which is in agreement with other applications of the DFT to
weak interactions. There are no direct experimental data for
the adsorption of the hydrocarbons in gmelinite. Adsorption
experiments performed on different structures of zeolites
共mordenite, ZSM-5, ferrierite兲 show that adsorption energies
are similar to the LDA interaction energies. Experiments,
however, are performed on real crystals containing attractive
centers for the adsorption like framework defects and nano-
particles of extra framework aluminum oxides. Our calcu-
lated GGA interaction energies indicate that much lower ad-
sorption energies are expected for ideal crystal structures of
zeolites.
In the relaxed structures of adsorbed molecules obtained
by GGA, the contact between the molecule and the support is
looser compared with corresponding structures calculated us-
ing LDA. Proportionally to the decreased strength of the in-
teraction, the adsorbed molecules are in the GGA much less
deformed relative to geometries of the noninteracting mol-
ecules. The GGA adsorption energies are much smaller than
the corresponding LDA energies due to longer interatomic
distances and underestimation of long-range van der Waals
forces in the GGA. For the adsorption on the acid sites the
LDA/GGA ratio is ⬃2.6 and much larger differences are
6334 J. Chem. Phys., Vol. 114, No. 14, 8 April 2001 Benco et al.

10
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