Article

pubs.acs.org/JPCA

Benzene−Hydrogen Bond (C6H6−HX) Interactions: The Influence of

the X Nature on their Strength and Anisotropy
M. Albertí,*,† A. Aguilar,† F. Huarte-Larrañaga,† J. M. Lucas,† and F. Pirani‡
†
IQTCUB, Departament de Química Física, Universitat de Barcelona, Barcelona, Spain
‡
Dipartimento di Chimica, Università di Perugia, Perugia, Italy

ABSTRACT: The intermolecular potential energy of the

C 6 H 6 −SH 2 and C 6 H 6 −NH 3 dimers is formulated as
combination of independent electrostatic and nonelectrostatic
contributions. The relevant parameters of the nonelectrostatic
terms, derived from molecular polarizability components, have
been proved to be useful to describe in a consistent way both
size repulsion and dispersion attraction forces. The represen-
tation adopted for the electrostatic contribution asymptotically
reproduces the dipole quadrupole interaction. To test the
validity of the proposed potential formulation, the features of the most stable configurations of the systems predicted have been
compared with the available ab initio and experimental data. Moreover, the strength of the C6H6−HX interaction has been
analyzed comparing the obtained results with the corresponding ones for the C6H6−H2O and C6H6−CH4 systems, investigated
previously with the same methodology. Information on the relative orientation dependence of the partners, arising from the
anisotropy of the intermolecular interaction, evaluated at different intermolecular distances, has been also obtained. Such
information is crucial to evaluate sterodynamics effects in bimolecular collisions.

1. INTRODUCTION in proteins.8−12 Studies on XH−π systems reveal that

Noncovalent interactions, dominant at large and intermediate
intermolecular distances, affect both the static properties of
weakly interacting partners and the stereodynamics of several
phenomena. Such interactions are important in many fields of
chemistry, physics, and biology since they determine structures
and reorientation dynamics, as well as basic properties of
liquids, molecular crystals, and biological systems.1−4 Crucial
aspects to be investigated regard the nature of the
intermolecular bond, the dynamics of collisions under a variety
of conditions, the formation of weakly bound aggregates, as
well as the growth and the structure of solvation shells. Among
all intermolecular interactions, the case of hydrogen bonds has
a paradigmatic importance. They are ubiquitous in chemistry,
biology, and material science5,6 and can be grouped into three
categories (weak, moderate, and strong)7 and different
interaction components, as electrostatics, polarization and
charge transfer, combine to define their binding energies. The
relative contributions of such components vary widely among
the different categories of hydrogen bonds. Although great
attention has been focused on moderate hydrogen bonds with
binding energies between 4 and 15 kcal mol−1,8 another type of
hydrogen bond, involving aromatic π-systems, has awakened
interest, mainly due to their abundance in biological systems. In
particular, many experimental and theoretical studies reporting
details on the XH−π (X = C, O, N, S) systems can be found in
the literature. CH−π interactions are able to stabilize adducts
between aromatic residues (see for instance ref 5.) and
statistical analyses of protein databanks have shown that
OH−π, NH−π, and SH−π interactions are frequently present
molecules containing π-electrons can participate easily in the
formation of XH−π bonds, whose strength depends on the
nature of X. In particular, the OH−π and the NH−π
interactions are stronger than the CH−π ones.1 Actually, the
binding in the CH−π system lies between the weakest class of
hydrogen and van der Waals bonds.13 This feature can be
attributed to the low polar character of the CH bond in several
hydrocarbon molecules. When electrostatic effects are negli-
gible, dispersion forces provide an important contribution to
the total interaction potential energy. In the case of weak and
moderate hydrogen bond interactions, the assessment of the
relative role of the different interaction components is not
trivial. In the last years the interaction energies were often
calculated using the symmetry adapted perturbation theory
(SAPT)14−16 and SAPT(DFT)17,18 methodologies, which allow
a proper partition of the long-range potential for specific
configurations into basic components evaluated at various levels
of perturbation theory. Therefore, the detailed computational
investigation of small prototype systems, can be very instructive
and crucial for the modeling of systems at increasing
complexity.
Usually, the weak interactions as those involved in the
present systems need to be calculated using very large basis sets
(even for small systems, the full potential energy surface
depends on 3n − 6 variables, with n being the number of
Received: November 6, 2013
Revised: February 13, 2014
Published: February 13, 2014

© 2014 American Chemical Society 1651 dx.doi.org/10.1021/jp410917x | J. Phys. Chem. A 2014, 118, 1651−1662
The Journal of Physical Chemistry A
atoms) and ab initio calculations can only be performed for
selected configurations. For instance, Tsuzuki et al.1,13,19,20
investigated the C6H6−CH4 interaction energy and equilibrium
geometry using different basis sets at selected geometries.
These detailed studies demonstrated that a highly computa-
tionally demanding CCSD(T) level of calculation (using a large
basis set near saturation) is required in order to obtain a reliable
description of the system. Large basis sets have been also
exploited to investigate the origin of the attraction and the
directionality of the NH−π interaction.21 Selected geometries
have also been considered to compare the performance of
several ab initio methods in describing the C6H6−H2O dimer
binding energy curve.22 Driven by the high computational cost
of CCSD(T) level of calculation, required to obtain a good
description of the dispersion contribution, Deligkaris and
Rodriguez23 have proposed the correction of DFT interaction
energies by introducing an empirical dispersion term valid for a
defined range of intermolecular distances. Sherrill et al.24 use
large, correlation-consistent basis sets to properly describe the
potential energy curves for C6H6−SH2, C6H6−CH4, and
C6H6−C6H6 (the later accurately investigated at SAPT
level).25 In that work, the performance of several methods is
tested in the calculation of nonbonded interactions, comparing
their computational cost. High quality ab initio calculations are
indeed of fundamental importance, providing valuable
information on strength and nature of weak intermolecular
bonds. However, if such an effort is required to characterize
energy and structure of the most stable configuration, much
more difficulties are met in the characterization of the less
stable configurations. On the other hand, a good description of
the interaction cannot be limited only to the geometry and
energetic of some stable configurations. A reliable formulation
of the whole potential energy surface (PES) is absolutely
necessary in molecular dynamics (MD) simulations. In
particular, reorientation effects promoted by the interaction
anisotropy could play a crucial role on the dynamical evolution
of the approaching and removing partners. Often, in MD
simulations of a complex system, the involved PES is
constructed by considering different groups of the interaction
components, which are conveniently assembled to provide the
description of the global interaction (force field). In this case,
not only an accurate description of the system at equilibrium,
derived from accurate ab initio calculations and/or high level
experimental data,26 is needed but also the adoption of
potential energy functions able to properly describe the
energetic behavior of the system in the whole configuration
space.27
In the last years, some of us have proposed a modification of
the Lennard-Jones potential energy, the Improved Lennard-
Jones (ILJ) function,26,28 useful to describe the combination of
some effective interaction components in neutral and ionic
systems (see for instance refs 29−33). The basic parameters
involved can be anticipated by correlation formulas given in
terms of fundamental physical properties of the interacting
partners, such as the electronic polarizability α (which can be
properly decomposed for molecules in bond and/or effective
atomic components) and the charge distribution over the
molecular frame, determining total molecular charge and
permanent multipole. The ILJ function and the related
correlation formulas allow the description of systems at
increasing complexity. In particular, the formulation adopted
and the involved potential parameters allow to represent in a
suitable and compact formulation the nonelectrostatic
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component (Vnel).34 Such formulation, exploiting the balancing
of positive and negative contributions, properly includes the
combination of size repulsion, dispersion and induction
attraction, mixed terms, and damping effects. This characteristic
has been properly tested in ref 35, where a comparison with the
SAPT energy decomposition was performed. Therefore, the so
parametrized Vnel can be added to the electrostatic (Vel)
component, which can be represented under different ways.36
In the present study, we have used a point charge distribution
to maintain a compact representation of the interaction and to
make a proper comparison with other systems previously
analyzed in the same way.
In the present study, we are interested in the semiempirical
formulation of the C6H6−SH2 and C6H6−NH3 dimers. In order
to test the accuracy of the interaction model for these systems,
equilibrium geometries and energies are compared with
available ab initio data. The ultimate purpose, however,
concerns a complete investigation of the XH-C6H6 anisotropic
interaction as a function of the nature of X and the evaluation
of the energy barriers controlling the stereodynamics of
collisions under a variety of conditions. The results obtained
for C6H6−SH2 and C6H6−NH3 are also compared with those
predicted also by our model and previously published for the
C6H6−H2O37 and C6H6−CH438 systems. The paper is
structured as follows: in section 2, we outline the formulation
of the semiempirical PES, in section 3, the model predictions
for C6H6−SH2 and C6H6−NH3 are presented. In section 4, the
XH−C6H6 interaction and its anisotropy are analyzed, and
concluding remarks are given in section 5.
2. POTENTIAL ENERGY SURFACE
The total intermolecular potential energy (Vtotal) for the C6H6−
SH2 and C6H6−NH3 systems has been modeled by assuming
the separability in electrostatic, Vel, and nonelectrostatic, Vnel,
partial contributions (Vtotal = Vel + Vnel).
The electrostatic component, Vel, has been calculated by
applying the Coulomb law to any pair of point charges placed
on different molecules. The charge distribution on the SH2 and
NH3 molecules, with point charges placed on the atoms, are
compatible with the geometry and the dipole moment of the
molecules calculated at MP2FC/6-311G* level.39 In particular,
for the SH2 molecule a charge of −0.324 au has been placed on
the S atom and charges of 0.162 au have been placed on the H
atoms, while for NH3, charges of −0.996 au and 0.332 au have
been placed on the N and H atoms, respectively. On the other
hand, as in our previous studies on ion-C6H6 systems (see for
instance ref 40), a total of 18 point charges have been
distributed on the C6H6 molecule frame (six placed on the H
atoms and the remaining 12 at a fixed distances from C atoms
on both sides of the aromatic ring). Such distribution has been
chosen from the consideration that, asymptotically, Vel must
correspond to the ion quadrupole interaction.40 This leads to a
charge of +0.09245 au on each H atom and to two negative
charges of −0.04623 au separated by 1.905 Å on each C atom,
placed on opposite sides of the benzene plane.
Following the same procedure previously adopted to study
the C6H6−H2O37 and C6H6−CH438 systems, the non electro-
static component of the interaction energy, Vnel, has been
decomposed into 12 molecule-bond interaction terms. The
intermolecular potential representation as a sum of terms, each
one related to the pair interaction between specific centers can
be justified at theoretical level considering distributed molecular
response properties36 and the decomposition of the polar-
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The Journal of Physical Chemistry A
izability in local contributions.41−43 To this end, the C6H6
molecular polarizability (αC6H6 = 10.32 Å3)44 has been
decomposed in bond polarizabilities (αCC and αCH),41,45 each
one having parallel and perpendicular components related with
the dimension and the shape (often ellipsoidal) of the
electronic charge distribution around the considered bond.41
On the contrary, the polarizability of both SH2 and NH3 (αSH2=
3.98 Å3 and αNH3= 2.16 Å3),46 due to their small value in
comparison with that of C6H6, has not been decomposed and
only the corresponding average value, centered on the S and N
atoms, has been considered. Accordingly, the C6H6-M (where
M is here SH2 or NH3) interactions are expressed as a sum of
molecule-bond (M-CC and M-CH) terms. Thus, the overall
potential energy, Vtotal, for a C6H6-M system is expressed as
6 6
Vtotal = Vel + ∑ VM − (CC) + ∑ VM − (CH)
i i
i=1 i=1 (1)
The VM−CC and VM−CH terms are represented by means of the
ILJ function26,47 as
⎡ 3. RESULTS
m ⎛ r0(γ ) ⎞n(r , γ )
VILJ(r , γ ) = ε(γ )⎢ ⎜ ⎟
⎢⎣ n(r , γ ) − m ⎝ r ⎠
m⎤
n(r , γ ) ⎛ r0(γ ) ⎞ ⎥
− ⎜ ⎟
n(r , γ ) − m ⎝ r ⎠ ⎥⎦
(2)
where r corresponds to the distance from the S or N atom to
the center of a bond and γ is the angle between the r vector and
the bond axis. The m parameter is taken equal to 6, the typical
value for neutral−neutral interactions. The well depth, ε(γ),
and the equilibrium distance, r0, for each interaction pair are
modulated from the corresponding perpendicular (ε⊥, r0⊥) and
parallel (ε∥, r0∥) values
ε(γ ) = ε⊥ sin 2 γ + ε cos2 γ (3)
r0 = r0 ⊥ sin 2 γ + r0 cos2 γ (4)
which are derived by exploiting the values of αSH2 or αNH3 with
the parallel and perpendicular components of αCC and αCH.48
The angular dependence allows us to take into account the
variation of the well depth and the equilibrium distance for
different approaches of the molecule (SH2 or NH3), considered
as a “pseudoatom”, to a particular bond (ε(γ) and r0(γ)). The
first term in eq 2 (positive) represents the size-repulsion
contribution associated with each molecule-bond pair, while the
second one (negative) provides the effective dispersion plus
induction attraction. The n(r,γ) exponent, defining simulta-
neously the falloff of the molecule-bond repulsion and the
strength of the attraction is expressed as
⎛ r ⎞2
n(r , γ ) = β + 4.0⎜ ⎟ situated along the C6 axis of C6H6 (axial approaches), with the
⎝ r0(γ ) ⎠ (5)
where β is an adjustable parameter related to the hardness of
the interacting partners, which adds flexibility to the potential
energy function in comparison to the Lennard-Jones one.26 In
particular, the decrease of β can indirectly include stabilization
effects due to a charge transfer in the perturbative
limit.27,35,49,50 All the parameters of the ILJ function describing
the C6H6−SH2 and the C6H6−NH3 interactions are given in
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Table 1. They have been obtained using the molecular and
bond polarizability components. The procedure adopted is
described in detail in ref 51 (see also ref 40).
Table 1. Perpendicular and Parallel Components of the Well
Depth (ε⊥, ε∥) and of the Equilibrium Distances (r0⊥, r0∥) for
the Different Molecule-Bond Pairsa
M-bond ε⊥/meV ε∥/meV r0⊥/Å r0∥/Å
SH2−CC 4.981 6.868 4.139 4.404
SH2−CH 5.481 4.720 3.947 4.147
NH3−CC 4.142 5.379 3.954 4.249
NH3−CH 4.906 4.110 3.731 3.938
a
1 meV = 0.02306 kcal mol−1
In the present study, in order to investigate the capability of
the model to describe the C6H6−SH2 and the C6H6−NH3
intermolecular interactions through the molecular polarizability,
the same value of the β parameter used to study C6H6−CH4,
equal to 8.75, has been considered.
In this section, the potential energy model described in the
previous section is used to calculate the interaction energy
profiles as the molecule (SH2 or NH3) and the benzene
approach under selected configurations. The energy minima
along these interaction curves are identified and characterized
(geometries) comparing these data with ab initio and
experimental data available in the literature. Subsequently,
this static study is complemented by performing MD
simulations of both C6H6−SH2 and C6H6−NH3 systems, by
allowing SH2 and NH3 to explore the whole phase space
around the benzene molecule.
The molecules have been kept rigid throughout this study.
The geometry adopted for C6H6 has been the same used in our
previous studies (see for instance ref 38), with D6h symmetry
and the CC and CH distances equal to 1.390 and 1.090 Å,
respectively. On the other hand, for SH2 and NH3 we used
geometries obtained from ab initio optimizations employing a
MP2FC/6-311G* level of theory, which report for dihydrogen
sulfide a SH distance of 1.341 Å and a HSH angle of 93.437°.39
At the same level of accuracy, the ammonia molecule exhibits a
NH distance of 1.0105 Å and a HNH angle of 107.274°.39 In
order to compare more directly our static results with the
similar ones found in the literature, the potential energy values
are given in kcal mol−1.
3.1. Energy and Geometry Predictions for C6H6−SH2.
In order to obtain a general idea of the shape of the PES and
the possible equilibrium geometries we have designed seven
possible approaches between the SH2 and C6H6 molecules. In
all the cases, the relative orientation of both fragments is kept
fixed and only the distance between the S atom and the
benzene center of mass (c.m.) is varied. The charge distribution
of C6H6 favors out of plane approaches, especially with SH2
two H atoms placed at shorter distances from the aromatic ring
than S.
The potential energy curves for the selected configurations of
the system are shown in Figure 1 as a function of the distance
from the S atom to the C6H6 c.m.
Panels a and b correspond to perpendicular approaches of
SH2 to the aromatic plane, while panels c and d describe the on
plane ones (equatorial approaches). More in detail, in panel a,
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The Journal of Physical Chemistry A Article

Figure 1. Potential energy curves for the selected approaches of SH2 to the benzene ring indicated in the figure as a function of the distance from S
to the C6H6 c.m.

Table 2. Intermolecular Interaction Energy (Vtotal) at Equilibrium and the Corresponding Distance from S Atom to the Center
of C6H6 (RS−C6H6) for Approaches of SH2 with a HS Bond on the Rotational Axis of C6H6 (Cs Symmetry) and for Approaches in
Which the C2 Axis of SH2 and the C6 One of C6H6 Are Coincident (C2v Symmetry)
symmetry group Vtotal/kcal mol−1 RS−C6H6/Å methodology
Cs −2.71 3.693 present
C2v −2.72 3.675 present
C2v −2.64 3.80 CCSD(T)/aug-cc-pVTZ52
C2v −2.74 3.80 CCSD(T)/aug-cc-pVQZ52
C2v −2.81 − CBS CCSD(T)52
C2v −2.83 3.80 CBS CCSD(T)24
C2v −2.85 3.80 CCSD(T)/aug-cc-pVQZ//CCSD(T)/CBS53

the interaction energy is illustrated for two approaches in which
the C2v symmetry axis of SH2 coincides with the C6 symmetry
axis of C6H6. In one of them, the H atoms of SH2 are aligned
with a HCCH axis of C6H6, while in the second one the H
atoms of SH2 point toward the center of two CC parallel bonds.
Panel b in Figure 1 contains the potential energy curve
corresponding to an axial approach with one of the SH bonds
of the SH2 molecule pointing along the C6 symmetry axis of
C6H6. As regarding equatorial approaches, panel c contains the
values of the potential energy for two coplanar approaches of
SH2 to C6H6 in which the S atom of the SH2 molecule points
toward the center of a CC bond. On the contrary, in panel d,
the S atom point toward an H atom of C6H6. As it can be seen,
perpendicular approaches are energetically favored with respect
to coplanar ones. Moreover, the minimum potential energy
values associated with the different axial approaches, with one
or both H atoms pointing to the aromatic ring, are very similar
indicating that, for these approaches, the PES is very flat. In
particular, observing the two curves in Figure 1a, it is evident
that the potential energy values are nearly independent of the
relative position of the H atoms of SH2 in the bidentate
conformation, being the differences in energy of about 0.01 kcal
mol−1. This result is in agreement with the previous work of
Tauer et al.,52 which found a negligible barrier for the twisting
of SH2 above C6H6. This interaction feature allows the SH2
molecule to rotate freely around its C2v axis. Clearly, minimum
energy equilibrium geometries can be identified from the curves
shown in Figure 1, parts a and b, one with C2v symmetry (a)
and another one with Cs symmetry. The total interaction
energy, Vtotal and the internuclear distance R at equilibrium for
these adducts are given in Table 2, where some results available
from the literature are also included for comparison. As can be
seen, the predictions of the model are in quite good agreement
with available ab initio data.
The overall similarity of the plots in parts a and b of Figure 1
suggests that the minima should be connected through low
rotational barriers. In order to check this feature, we have
explored the rotation of SH2 in the yz plane being C6H6
confined in the xy plane maintaining the axial configuration and
the Bz-SH2 intermolecular distance close to the equilibrium
geometry (3.680 Å). The rotation angle ϕ has been taken as the
one formed by one SH bond and the C6 rotational axis of C6H6.
The PES values are represented in Figure 2 as a function of the
rotation showing a minimum energy of −2.804 kcal mol−1 at a
rotational angle of 17°. Identical results are obtained when SH2
rotates in the xz plane. As expected, small variations on the
potential energy are observed when ϕ varies from 0 to 90°.
These results are indicative of the flatness of the PES for axial
approaches.
Figure 2. Potential energy represented as a function of the rotation of
SH2 in the yz plane at a fixed value of RS−C6H6 = 3.680 Å. For ϕ = 0°,
one SH bond is aligned along the C6 rotational axis of C6H6.

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The Journal of Physical Chemistry A
Figure 3. Potential energy curves for the selected approaches of NH3 to benzene indicated in the figure as a function of the distance from the N
atom to the C6H6 c.m.
Table 3. Interaction Energy (Vtotal) and Distance from N Atom to the Center of C6H6 (RN−Bz) for Axial Approachesa
complex Vtotal/kcal mol−1
tridentate −2.17
tridentate −1.70
monodentate −2.32
monodentate −2.37
monodentate −2.22
monodentate −2.37
monodentate −2.43
monodentate −2.47
a
Tridentate complex refers to a confirmation with both molecules symmetry axis aligned and monodentate to the configuration with one NH aligned
with the benzene C6 axis (see text).
3.2. Energy and Geometry Predictions for C6H6−NH3.
In order to characterize the C6H6−NH3 PES, we have
proceeded in an analogous way to what has just been explained
in the case of SH2, building potential energy curves for
intermolecular approaches at fixed relative configurations. The
potential energy curves for some selected configurations of the
C6H6−NH3 complex are shown in Figure 3.
Panels a and b in Figure 3 represent potential energy curves
corresponding to two axial approaches of NH3 perpendicular to
the benzene plane, while the on plane (equatorial) ones are
shown in panels c and d. Similarly to the case of dihydrogen
sulfide, axial approaches present a larger interaction energy and
more stable minima than equatorial approaches. However,
these differences are less noticeable in the case of ammonia.
The representations in panel a correspond to approaches of
NH3 in which the C3 symmetry axis of the molecule coincides
with the C6 one of C6H6 and, therefore, the three hydrogen
atoms are equidistant to the benzene plane (tridentate
configuration), while in panel b) is described an approach of
NH3 in which a NH bond coincides with the C6 symmetry axis
of C6H6 (monodentate configuration). On the other hand, in
panel c are represented the values of the potential energy for
two equatorial approaches of NH3 to C6H6, with the N atom of
NH3 pointing toward an H atom of C6H6, while in panel d, the
N atom of NH3 point toward the center of a CC bond of the
aromatic molecule. As it can be seen in Figure 3a, the potential
energy curves for the two axial configurations with NH3
differently oriented above the benzene plane are almost
identical, reflecting again the flatness of the PES with respect
to rotation of the ammonia molecule around its C3v axis. These
results are in agreement with the high-resolution optical and
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RN−C6H6/Å methodology
3.506 present
3.6 MP2/cc-pVQZ21
3.505 present
3.6 MP2/cc-pVQZ21
3.6 ECCSD(T)limit (cc-pVDZ)21
− CCSD(T)/AVTZ55
3.60 CCSD(T)/aug-cc-pVTZ53
3.60 CCSD(T)/aug-cc-pVQZ53
microwave spectra of C6H6−NH3 in the gas phase (the
appearance of two peaks suggests that the ammonia can freely
rotate in C6H6−NH3).54 Moreover, they also agree with the
high-level ab initio calculations carried out by Tsuzuki et al.21
The results of the intermolecular interaction energy Vtotal and
the intermolecular distance R corresponding to the equilibrium
structures for the tridentate and monodentate complexes
represented in panels a and b of Figure 3, respectively, are
listed in Table 3, where some results, available from the
literature, are included for comparison. Our potential energy
model predicts that the monodentate complex is slightly more
stable than the bidentate (not shown) and tridentate ones.
However, the model predicts smaller differences of the binding
energy for the different geometries of the adducts than those
obtained from ab initio methods. In particular, our potential
energy predictions at the equilibrium geometry for the mono
and tridentate complexes differ only for 0.25 kcal mol−1,
whereas this energy difference is increased to 0.67 kcal mol−1 by
MP2 calculations using a large basis set.21
Furthermore, the C6H6−NH3 PES has been investigated
more in detail exploring the rotation of NH3 around C6H6. The
rotation angle ϕ has been taken as the one formed by one NH
bond and the C6 rotational axis of C6H6. In Figure 4 the
interaction energy is represented as a function of ϕ at a fixed
distance from N to the C6H6 c.m. of 3.505 Å.
Results indicate that the most stable geometry of the C6H6−
NH3 is the one in which one of the NH bonds (the closest to
the aromatic plane) forms an angle, ϕ, of about 18° with the C6
rotational axis of C6H6, being he minimum of the potential
energy equal to −2.491 kcal mol−1.
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The Journal of Physical Chemistry A Article

Figure 4. Potential energy represented as a function of the rotation of

NH3 at a fixed value of the distance from N to the center of mass of
C6H6 (see text). ϕ = 0° corresponds to a monodentate configuration.

3.3. Molecular Dynamics Simulations. The static results

of the previous sections indicate that the most stable structures
correspond to axial configurations in which neither symmetry
axis of the molecules nor the bond are completely aligned with
the C6 rotational axis of C6H6. The preferred relative position of
both SH2 and NH3 respect to C6H6 is further investigated by
performing molecular dynamics (MD) simulations of the
C6H6−SH2 and C6H6−NH3 dimers in gas phase using the
DL−POLY program.56 Bearing in mind that at low temper-
atures, if the initial configuration of the system is not far from
equilibrium, the distribution of distances, angles and config-
uration energies, Ecfg, probed along the trajectory provides Figure 5. Relevant distributions for the C6H6−SH2 system derived
information on near-equilibrium structures, MD trajectories from MD simulations at T = 10 K. Top panel: distances from the S
have been run in the 10−50 K temperature range, analyzing the atom of SH2 to the center of mass of C6H6; middle panel: angles
corresponding statistics. Simulations have been carried out at formed by the dimer intermolecular axis and the C2 axis of SH2 and
lower panel: configuration energy values (for the definition of
constant total energy, using a time step of 0.001 ps and running
distances and angles see the top panel of Figure 8).
trajectories for 10 ns (after being equilibrated for 0.5 ns). The
statistics outcome of a MD trajectory of the SH2−C6H6 dimer
at a temperature value of 10 K is shown in Figure 5. The figure
focuses on the intermolecular (S−C6H6) distance distribution
(top panel), the angular distribution (middle panel) with α
being the angle between the intermolecular (S−C6H6) axis and
the C2v symmetry axis, and the average (potential) config-
uration energy (bottom panel). Clear maxima can be identified
in all three distributions shown in the figure at about of 3.75 Å
(top panel), 30° (middle panel) and −2.8 kcal mol−1 (lower
panel).
The C6H6−NH3 system has been studied analogously,
running MD trajectories and extracting statistical averages.
The results of this analysis are shown in Figure 6. The
distribution of the distances from N to the benzene c.m.,
RN−C6H6, evaluated along the trajectory (top panel of Figure 6)
shows a narrow peak at about 3.55 Å.
The middle panel of Figure 6 shows two well-defined peaks
in the distribution of the distances from the three H atoms of
NH3 to the center of mass of C6H6, RH−C6H6. One of them is
placed at shorter distances than RN−C6H6, while the other is
located at larger distances. These observations indicate that one
of the H atoms of NH3 tends to point toward the aromatic
plane, while the other two tend to be positioned equidistantly
at larger distances from C6H6. The interaction energy
associated with these configurations, as can be derived from
the energy distribution shown in the lower panel of Figure 6, is
of about −2.6 kcal mol−1. Figure 6. Relevant distributions for the C6H6−NH3 system derived
A better estimation of the total potential energy at from MD simulations at T = 10 K. Top panel: distances from the N
equilibrium, V(total)eq, can be obtained from a linear extrap- atom of NH3 to the center of mass of C6H6. Middle panel: distances
from the H atoms of NH3 to the center of mass of C6H6. Lower panel:
olation to T = 0 K of the mean values of Ecfg ( Ecfg ), evaluated configuration energy values (for the definition of distances and angles
along trajectories run at several (low) temperatures (see, for see the lower panel of Figure 8).

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The Journal of Physical Chemistry A
instance, ref 31). Under these conditions, without phase
changes of the system, Ecfg varies linearly with T. In Figure 7,
Ecfg is represented as a function of temperature for the C6H6−
SH2 and C6H6−NH3 systems in the top and lower panels,
respectively.
Figure 7. Mean configuration energy, Ecfg , of C6H6−SH2 (top panel)
and C6H6−NH3 (lower panel) as a function of temperature for very
low T values. The labeled arrow indicates the potential energy value
extrapolated at T = 0 K.
The process of running consecutive MD simulations at
decreasing lower temperatures can be regarded as a simulated
annealing minimization.57 However, given that this procedure
can run into problems whenever the thermal energy is of order
of the isomerization energy barriers, we judged better to
extrapolate to 0 K values rather than running MD trajectories
below 5 K.
The extrapolated value of Ecfg at T = 0 K, represented by
V(total)eq, is equal to −2.881 and −2.618 kcal mol−1 for the
C6H6−SH2 and the C6H6−NH3 systems, respectively. These
values are very similar to the lowest potential energy values
sampled by the MD trajectory and equal to −2.843 and −2.606
kcal mol−1, respectively. Accordingly, it can be expected that
the configurations in the MD trajectory with an interaction
potential energy equal to −2.843 kcal mol−1 for C6H6−SH2 and
equal to −2.606 kcal mol−1 for C6H6−NH3 should be similar to
the equilibrium ones. Such configurations have been extracted
from the simulations and are represented in Figure 8.
For the C6H6−SH2 dimer, the predicted values of the RS−C6H6
distance and of the angle α equal to 3.692 Å and 29.2°. Similar
values of RS−C6H6 and α are obtained at MP2/aug-cc-pVDZ level
(3.625 Å and 27°), with an interaction energy of −3.05 kcal
mol−1.58 Tauer et al.,52 applying the coupled-cluster theory
through perturbative triple substitutions, CCSD(T),59 with the
aug-cc-pVDZ basis set, estimate values of RS−C6H6= 3.8 Å and α
= 30°, with an interaction energy of −2.74 kcal mol−1
(complete basis set extrapolation yield a CCSD(T) interaction
energy of −2.81 kcal mol−1). The geometrical parameters
coming out of the MD simulations are also in agreement with
the data reported from the measured rotational spectrum
(RS−C6H6 = 3.818 Å and α = 28.5°).60 Unfortunately, while some
1657
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theoretical works addressed to characterize computationally the
SH−π interaction, can be found in the literature,24,52,53,61−67 we
have only found one experimental (rotational spectroscopy)
report providing information on the geometry of the C6H6−
SH2 system. Therefore, the model predictions of the binding
energy can be only compared with theoretical results.
For the C6H6−NH3 dimer, the predicted values of the
RN−C6H6 distance and of the angle α (formed by the vector going
from the C6H6 c.m. to N and the C3 axis of NH3) amount to
3.523 Å and 50.2°, respectively, while the value of the angle
(not shown in Figure 8) formed by the C6 axis of C6H6 and the
Figure 8. Equilibrium geometry of the C6H6−SH2 (top panel) and of
C6H6−NH3 (lower panel) systems.
C3 one of NH3 is equal to 58.8°, which is in good agreement
with that of about 60° obtained from a high-resolution optical
and microwave spectra of benzene−ammonia.54 Moreover, the
difference between the predicted value of the RN−C6H6 distance
(3.523 Å) and that derived from the experiment (equal to 3.590
Å) is less than a 2%.
The fact that the tilted structure with an H atom pointing
toward the aromatic plane is the most stable one can be
explained pointing out that the bonding between ammonia and
benzene is mostly electrostatic in origin. As has been explained
before,68 C6H6 and NH3 exhibit a charge distribution
compatible with quadrupole and dipole moments, respectively.
The asymptotic dipole−quadrupole interaction favors ap-
proaches of NH3 with the C3 axis pointing straight toward
the C6H6, while the quadrupole−quadrupole interaction favors
approaches of NH3 with the C3 axis parallel to the aromatic
plane. The observed tilt is a compromise between these two
electrostatic terms.
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The Journal of Physical Chemistry A Article

4. STRENGTH AND ANISOTROPY OF THE XH−C6H6

INTERACTION
The present results for SH2 and NH3 can be used to
complement previous studies on CH4 and H2O and analyze
the strength of the XH-C6H6 interaction. The results for the
three first clusters X (C, N, O) provide information on the
evolution of the interaction nature for some first-row hydrides,
while by comparing H2O−C6H6 and SH2−C6H6, we analyze
the interaction between benzene and two hydrides of the same
column of the periodic table. One one hand, the first-row
hydrides are characterized by an increase of the dipole moment, Figure 9. CH4−C6H6, NH3−C6H6, and H2O−C6H6 intermolecular
μ going from CH4, without permanent dipole moment, to NH3 interaction potential energy curves varying the intermolecular distance
and H2O with experimental values of μ equal to 1.47 and 1.85 maintaining an axial configuration.
D, respectively.69 On the contrary, the molecular polarizability,
α decreases in going from CH4 to H2O (αCH4 > αNH3 > αH2O). model, the authors of ref 21 indicate that the electrostatic
On the other hand, the polarizability of SH2 is higher than that contribution is mainly responsible for the magnitude of the
of CH4 and much higher than that of H2O, while the SH2 total interaction.
dipole moment is approximately a half of that of H2O. On the other hand, SH2, with a permanent dipole moment of
Accordingly, differences can be expected in both the XH-C6H6 0.97 D and a molecular polarizability higher than that of NH3
electrostatic and non electrostatic contributions, depending on and H2O, forms SH2−C6H6 complexes stabilized again by the
the nature of the central atom X. combination of both dispersion and electrostatic forces.
In previous studies, using the same potential model described However, while the electrostatic energy contribution accounts
in section 2, some of us predicted interaction energies for the for about a 55% of the total interaction in the SH2−C6H6
equilibrium configurations of H2O−C6H637 and CH4−C6H638 dimer, it contributes a 76% in the H2O−C6H6 case. However,
equal to −2.975 and −1.420 kcal mol−1, respectively. due to the larger polarizability, dispersion forces provide a
Accordingly, the relative order of the binding energies is higher contribution in SH2−C6H6 than in H2O−C6H6. The
H2O−C6H6 > SH2−C6H6 > NH3−C6H6 > CH4−C6H6. These H2O−C6H6 and SH2−C6H6 interaction energies, for the cut of
results are in agreement with the ab initio data of Cheney et al. the PES corresponding to the most favorable approach, are
on some hydrogen-bond complexes involving benzene as an H compared in Figure 10, where noticeable differences can be
acceptor.70 The mentioned study concludes that, although the seen in the repulsive zone of the PES.
magnitude of the binding energy varies using different basis sets
and including electronic correlation, the qualitative trends for
the series of systems remains essentially unchanged. This trend
on the binding energies emphasized above is also consistent
with the electronegativity order of the proton-donating atoms
(C < N < O). This suggests that the increase of the strength of
the XH−π interaction from X = C to X = O is mainly due to
electrostatic effects (see also ref 21). However, when the
electrostatic component in the XH-C6H6 system is weak or
null, the interaction is dominated by dispersion attraction,
although this effect may be hidden when electrostatic
components are dominant. For instance, the CH4 molecule,
Figure 10. H2O−C6H6 and SH2−C6H6 intermolecular interaction
without permanent dipole and quadrupole moments (having potential energy curves varying the intermolecular distance maintain-
only an octupole moment), at large and intermediate distances ing an axial configuration.
basically interacts with C6H6 through dispersion forces.38 As a
matter of fact, experimental77 and theoretical1,71−76 evidence on The equilibrium distance values, RX−C6H6, predicted by our
the dominance of the dispersion on the CH−π interaction can
be found in the literature. The NH3−C6H6 and the H2O−C6H6 model equal to 3.391 and 3.692 Å for H2O−C6H6 and SH2−
systems, due to the permanent dipole moments of NH3 and C6H6, respectively, are in agreement with the distances reported
H2O, are bound by both dispersion (weaker than for CH4− by ab initio calculations, equal to 3.35 and 3.80 Å for H2O−
C6H6) and electrostatic forces. This originates an extra stability C6H6 and SH2−C6H6, respectively.53
in the NH3−C6H6 and the H2O−C6H6 clusters with respect to For the CH4−C6H6, NH3−C6H6, H2O−C6H6, and SH2−
that of CH4−C6H6. The CH4−C6H6, NH3−C6H6 and H2O− C6H6 series, the relevant interaction energy values are given in
C6H6 interaction energies are compared in Figure 9: for a Table 4, where the predicted data are compared with the
intermolecular distance scan in the axial configuration. converged results of the CCSD(T) interaction energies toward
The obtained results are very similar to those of Tsuzuki et
al.,21 which argue that the different size of the van der Waals Table 4. Interaction Energies at Equilibrium
radii of the proton-donating atoms (C, 1.75 Å; N, 1.55 Å; O,
CH4−C6H6 NH3−C6H6 SH2−C6H6 H2O−C6H6 methodology
1.40 Å), which scales approximately as the cubic square of the
molecular polarizability, would be one of the main causes of the −1.420 −2.618 −2.881 −2.975 present
different intermolecular distances at the minimum of the −1.39 −2.47 −2.79 −3.09 aug-cc-pVQZ53
potential energy. Moreover, confirming the prediction of our −1.41 −2.50 −2.85 −3.16 CBS53

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The Journal of Physical Chemistry A
the complete basis set limit obtained by Crittenden et al.53 The
agreement, more than acceptable, could be even improved by a
fine-tuning of the value of the non transferable β parameter
(here maintained fixed), but this is outside the purpose of the
present work.
The strength of the XH−π interaction in the first row
hydrides benzene compounds follows the electronegativity
order of the proton-donating atoms (C < N < O). This
indicates that the increase of the strength of the XH−π
interaction going from X = C to X = O is mainly due to
electrostatic forces.21 However, aspects other than the electro-
negativity, such as the molecular structure and polarizability,
need to be involved. For instance, the electronegativity of S and
C is very similar but the C6H6−SH2 interaction energy is
different than the C6H6−CH4 one.24 Actually, the strength of
the C6H6−SH2 and the C6H6−H2O interactions is very similar,
with total interaction energies equal to 2.85 and 3.16 kcal mol−1
respectively,53 while lower values are reported for C6H6−CH4.
From the previous results, it seems that when X is N, O or S,
the interaction is dominated by an electrostatic contribution,
while when X is C, the interaction has a more dispersive
character. The small relevance of the electrostatic contribution
in the interaction between CH4 (highly symmetric) and C6H6 is
maintained even when polar groups are introduced in the
benzene core, giving support to the small relevance of
electrostatic effects in alkyl−benzene interactions.78
One of the main advantages of the proposed formulation of
the interaction energy is the possibility to explore the PES for
energetically less favorable approaches of the partners,
analyzing anisotropic effects. In particular, the axial approaches
in which SH2, NH3, H2O, and CH4 are rotated (in a plane
perpendicular to the aromatic ring) about 180° with respect to
the geometry of the most stable structures have been
investigated. Results indicate that the molecular rotation
generates a general increase of the intermolecular distance
and an inverse order of the adducts stability (see Figure 11).
Figure 11. H2O−C6H6, SH2−C6H6, NH3−C6H6, and CH4−C6H6
intermolecular interaction potentials for the represented molecular
approaches.
The previous results suggest lower orientational effects for
C6H6−CH4 in comparison with those present in the remaining
systems. In particular, these effects have been investigated in
detail at long-range for the two systems having similar
symmetry: H2O−C6H6 and SH2−C6H6. The corresponding
results are presented in Figure 12, where the value of ϕ = 0
corresponds to a XH bond placed along the y > 0 axis. Figure
12 shows some barriers on the PES’s and their dependence on
the intermolecular distance. These anisotropy effects in the
long-range region of the interaction can induce orientational
effects in the colliding partners, depending on the temperature
1659
Article
Figure 12. Rotational energy barriers for SH2−C6H6 (top panel) and
H2O−C6H6 (lower panel) calculated at 5 Å, 7 Å and at the equilibrium
intermolecular distance.
and energy, specially when the barrier high becomes
comparable with the rotational energy of the partners.
5. CONCLUDING REMARKS
A potential model based on the decomposition of molecular
polarizabilities has been exploited to formulate the PES for the
NH3−C6H6 and SH2−C6H6 systems and to investigate the role
of the XH−π interaction along the CH4−C6H6, NH3−C6H6,
H2O−C6H6 and SH2−C6H6 series of adducts. The non-
electrostatic component of the total interaction for each system
has been constructed by summing 12 molecule-bond (CC and
CH) components expressed by means of the ILJ function. The
relevant parameters of the ILJ functions, having a physical
meaning, have been derived from the average molecular
polarizability of NH3 and SH2 and from the polarizability
associated with the CC and CH bonds of C6H6. On another
hand, the electrostatic component has been represented by
applying the Coulomb law to 18 point charges placed in the
C6H6 frame and 4 and 3 point charges compatible with the
dipole moments of the NH3 and SH2 molecules, respectively. It
has been found that the present formulation gives binding
energies associated with specific configurations of the systems
in agreement with high quality ab initio results. It has also been
found that the lowest binding energy is that of CH4−C6H6,
arising almost exclusively by dispersion forces. By increasing the
number of electrons on the hydrides, the number of XH bonds
decrease but the interaction becomes stronger. Accordingly, the
NH−π interaction is weaker and stronger than the OH−π and
the CH−π ones, respectively. On the other hand, the
comparison of the OH−π and the SH−π interactions reveals
the influence of both, the nonelectrostatic (depending on the
molecular polarizability) and the electrostatic (depending on
the dipole and quadrupole moments) interaction components.
Reorientation effects induced by the anisotropy of intermo-
lecular noncovalent forces in these prototype systems have
been also investigated. Therefore, the obtained PES’s can be
used to define the stereodynamics of molecular collisions under
a variety of conditions by performing molecular dynamics
simulations out molecular dynamic simulations.
dx.doi.org/10.1021/jp410917x | J. Phys. Chem. A 2014, 118, 1651−1662
The Journal of Physical Chemistry A
The extension of this formulation to aggregates formed by
C6H6 and two or more molecules containing XH bonds is not
only possible but is also useful to investigate both the stability
and other basic features of the solvation shells of clusters
formed by hydrogenated molecules around benzene.
■
AUTHOR INFORMATION
Corresponding Author
*(M.A.) E-mail: m.alberti@ub.edu.
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
M.A., A.A. and F.H.-L. acknowledge financial support from the
Ministerio de Educación y Ciencia (Spain, Project CTQ2010-
16709) and the Generalitat de Catalunya (2009SGR-17). Also
thanks are due to the Center de Supercomputació de Catalunya
CESCA-C4 and Fundació Catalana per a la Recerca for the
allocated supercomputing time. F.P. acknowledges financial
support from the Italian Ministry of University and Research
(MIUR) for PRIN Contracts.
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