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Benzene Hydrogen Bond (C6H6 HX) Interactions The Influence of The X Nature On Their Strenght and Anistropy
Benzene Hydrogen Bond (C6H6 HX) Interactions The Influence of The X Nature On Their Strenght and Anistropy
pubs.acs.org/JPCA
© 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 Article
atoms) and ab initio calculations can only be performed for component (Vnel).34 Such formulation, exploiting the balancing
selected configurations. For instance, Tsuzuki et al.1,13,19,20 of positive and negative contributions, properly includes the
investigated the C6H6−CH4 interaction energy and equilibrium combination of size repulsion, dispersion and induction
geometry using different basis sets at selected geometries. attraction, mixed terms, and damping effects. This characteristic
These detailed studies demonstrated that a highly computa- has been properly tested in ref 35, where a comparison with the
tionally demanding CCSD(T) level of calculation (using a large SAPT energy decomposition was performed. Therefore, the so
basis set near saturation) is required in order to obtain a reliable parametrized Vnel can be added to the electrostatic (Vel)
description of the system. Large basis sets have been also component, which can be represented under different ways.36
exploited to investigate the origin of the attraction and the In the present study, we have used a point charge distribution
directionality of the NH−π interaction.21 Selected geometries to maintain a compact representation of the interaction and to
have also been considered to compare the performance of make a proper comparison with other systems previously
several ab initio methods in describing the C6H6−H2O dimer analyzed in the same way.
binding energy curve.22 Driven by the high computational cost In the present study, we are interested in the semiempirical
of CCSD(T) level of calculation, required to obtain a good formulation of the C6H6−SH2 and C6H6−NH3 dimers. In order
description of the dispersion contribution, Deligkaris and to test the accuracy of the interaction model for these systems,
Rodriguez23 have proposed the correction of DFT interaction equilibrium geometries and energies are compared with
energies by introducing an empirical dispersion term valid for a available ab initio data. The ultimate purpose, however,
defined range of intermolecular distances. Sherrill et al.24 use concerns a complete investigation of the XH-C6H6 anisotropic
large, correlation-consistent basis sets to properly describe the interaction as a function of the nature of X and the evaluation
potential energy curves for C6H6−SH2, C6H6−CH4, and of the energy barriers controlling the stereodynamics of
C6H6−C6H6 (the later accurately investigated at SAPT collisions under a variety of conditions. The results obtained
level).25 In that work, the performance of several methods is for C6H6−SH2 and C6H6−NH3 are also compared with those
tested in the calculation of nonbonded interactions, comparing predicted also by our model and previously published for the
their computational cost. High quality ab initio calculations are C6H6−H2O37 and C6H6−CH438 systems. The paper is
indeed of fundamental importance, providing valuable structured as follows: in section 2, we outline the formulation
information on strength and nature of weak intermolecular of the semiempirical PES, in section 3, the model predictions
bonds. However, if such an effort is required to characterize for C6H6−SH2 and C6H6−NH3 are presented. In section 4, the
energy and structure of the most stable configuration, much XH−C6H6 interaction and its anisotropy are analyzed, and
more difficulties are met in the characterization of the less concluding remarks are given in section 5.
stable configurations. On the other hand, a good description of
the interaction cannot be limited only to the geometry and 2. POTENTIAL ENERGY SURFACE
energetic of some stable configurations. A reliable formulation The total intermolecular potential energy (Vtotal) for the C6H6−
of the whole potential energy surface (PES) is absolutely SH2 and C6H6−NH3 systems has been modeled by assuming
necessary in molecular dynamics (MD) simulations. In the separability in electrostatic, Vel, and nonelectrostatic, Vnel,
particular, reorientation effects promoted by the interaction partial contributions (Vtotal = Vel + Vnel).
anisotropy could play a crucial role on the dynamical evolution The electrostatic component, Vel, has been calculated by
of the approaching and removing partners. Often, in MD applying the Coulomb law to any pair of point charges placed
simulations of a complex system, the involved PES is on different molecules. The charge distribution on the SH2 and
constructed by considering different groups of the interaction NH3 molecules, with point charges placed on the atoms, are
components, which are conveniently assembled to provide the compatible with the geometry and the dipole moment of the
description of the global interaction (force field). In this case, molecules calculated at MP2FC/6-311G* level.39 In particular,
not only an accurate description of the system at equilibrium, for the SH2 molecule a charge of −0.324 au has been placed on
derived from accurate ab initio calculations and/or high level the S atom and charges of 0.162 au have been placed on the H
experimental data,26 is needed but also the adoption of atoms, while for NH3, charges of −0.996 au and 0.332 au have
potential energy functions able to properly describe the been placed on the N and H atoms, respectively. On the other
energetic behavior of the system in the whole configuration hand, as in our previous studies on ion-C6H6 systems (see for
space.27 instance ref 40), a total of 18 point charges have been
In the last years, some of us have proposed a modification of distributed on the C6H6 molecule frame (six placed on the H
the Lennard-Jones potential energy, the Improved Lennard- atoms and the remaining 12 at a fixed distances from C atoms
Jones (ILJ) function,26,28 useful to describe the combination of on both sides of the aromatic ring). Such distribution has been
some effective interaction components in neutral and ionic chosen from the consideration that, asymptotically, Vel must
systems (see for instance refs 29−33). The basic parameters correspond to the ion quadrupole interaction.40 This leads to a
involved can be anticipated by correlation formulas given in charge of +0.09245 au on each H atom and to two negative
terms of fundamental physical properties of the interacting charges of −0.04623 au separated by 1.905 Å on each C atom,
partners, such as the electronic polarizability α (which can be placed on opposite sides of the benzene plane.
properly decomposed for molecules in bond and/or effective Following the same procedure previously adopted to study
atomic components) and the charge distribution over the the C6H6−H2O37 and C6H6−CH438 systems, the non electro-
molecular frame, determining total molecular charge and static component of the interaction energy, Vnel, has been
permanent multipole. The ILJ function and the related decomposed into 12 molecule-bond interaction terms. The
correlation formulas allow the description of systems at intermolecular potential representation as a sum of terms, each
increasing complexity. In particular, the formulation adopted one related to the pair interaction between specific centers can
and the involved potential parameters allow to represent in a be justified at theoretical level considering distributed molecular
suitable and compact formulation the nonelectrostatic response properties36 and the decomposition of the polar-
1652 dx.doi.org/10.1021/jp410917x | J. Phys. Chem. A 2014, 118, 1651−1662
The Journal of Physical Chemistry A Article
izability in local contributions.41−43 To this end, the C6H6 Table 1. They have been obtained using the molecular and
molecular polarizability (αC6H6 = 10.32 Å3)44 has been bond polarizability components. The procedure adopted is
decomposed in bond polarizabilities (αCC and αCH),41,45 each described in detail in ref 51 (see also ref 40).
one having parallel and perpendicular components related with
the dimension and the shape (often ellipsoidal) of the Table 1. Perpendicular and Parallel Components of the Well
electronic charge distribution around the considered bond.41 Depth (ε⊥, ε∥) and of the Equilibrium Distances (r0⊥, r0∥) for
On the contrary, the polarizability of both SH2 and NH3 (αSH2= the Different Molecule-Bond Pairsa
3.98 Å3 and αNH3= 2.16 Å3),46 due to their small value in M-bond ε⊥/meV ε∥/meV r0⊥/Å r0∥/Å
comparison with that of C6H6, has not been decomposed and SH2−CC 4.981 6.868 4.139 4.404
only the corresponding average value, centered on the S and N SH2−CH 5.481 4.720 3.947 4.147
atoms, has been considered. Accordingly, the C6H6-M (where NH3−CC 4.142 5.379 3.954 4.249
M is here SH2 or NH3) interactions are expressed as a sum of NH3−CH 4.906 4.110 3.731 3.938
molecule-bond (M-CC and M-CH) terms. Thus, the overall a
1 meV = 0.02306 kcal mol−1
potential energy, Vtotal, for a C6H6-M system is expressed as
6 6 In the present study, in order to investigate the capability of
Vtotal = Vel + ∑ VM − (CC) + ∑ VM − (CH) the model to describe the C6H6−SH2 and the C6H6−NH3
i i
i=1 i=1 (1) intermolecular interactions through the molecular polarizability,
the same value of the β parameter used to study C6H6−CH4,
The VM−CC and VM−CH terms are represented by means of the equal to 8.75, has been considered.
ILJ function26,47 as
⎡ 3. RESULTS
m ⎛ r0(γ ) ⎞n(r , γ )
VILJ(r , γ ) = ε(γ )⎢ ⎜ ⎟ In this section, the potential energy model described in the
⎢⎣ n(r , γ ) − m ⎝ r ⎠ previous section is used to calculate the interaction energy
m⎤
profiles as the molecule (SH2 or NH3) and the benzene
n(r , γ ) ⎛ r0(γ ) ⎞ ⎥ approach under selected configurations. The energy minima
− ⎜ ⎟
n(r , γ ) − m ⎝ r ⎠ ⎥⎦ along these interaction curves are identified and characterized
(2) (geometries) comparing these data with ab initio and
where r corresponds to the distance from the S or N atom to experimental data available in the literature. Subsequently,
the center of a bond and γ is the angle between the r vector and this static study is complemented by performing MD
the bond axis. The m parameter is taken equal to 6, the typical simulations of both C6H6−SH2 and C6H6−NH3 systems, by
value for neutral−neutral interactions. The well depth, ε(γ), allowing SH2 and NH3 to explore the whole phase space
and the equilibrium distance, r0, for each interaction pair are around the benzene molecule.
modulated from the corresponding perpendicular (ε⊥, r0⊥) and The molecules have been kept rigid throughout this study.
parallel (ε∥, r0∥) values The geometry adopted for C6H6 has been the same used in our
previous studies (see for instance ref 38), with D6h symmetry
ε(γ ) = ε⊥ sin 2 γ + ε cos2 γ (3) 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
r0 = r0 ⊥ sin 2 γ + r0 cos2 γ (4) geometries obtained from ab initio optimizations employing a
MP2FC/6-311G* level of theory, which report for dihydrogen
which are derived by exploiting the values of αSH2 or αNH3 with sulfide a SH distance of 1.341 Å and a HSH angle of 93.437°.39
the parallel and perpendicular components of αCC and αCH.48 At the same level of accuracy, the ammonia molecule exhibits a
The angular dependence allows us to take into account the NH distance of 1.0105 Å and a HNH angle of 107.274°.39 In
variation of the well depth and the equilibrium distance for order to compare more directly our static results with the
different approaches of the molecule (SH2 or NH3), considered similar ones found in the literature, the potential energy values
as a “pseudoatom”, to a particular bond (ε(γ) and r0(γ)). The are given in kcal mol−1.
first term in eq 2 (positive) represents the size-repulsion 3.1. Energy and Geometry Predictions for C6H6−SH2.
contribution associated with each molecule-bond pair, while the In order to obtain a general idea of the shape of the PES and
second one (negative) provides the effective dispersion plus the possible equilibrium geometries we have designed seven
induction attraction. The n(r,γ) exponent, defining simulta- possible approaches between the SH2 and C6H6 molecules. In
neously the falloff of the molecule-bond repulsion and the all the cases, the relative orientation of both fragments is kept
strength of the attraction is expressed as fixed and only the distance between the S atom and the
benzene center of mass (c.m.) is varied. The charge distribution
⎛ r ⎞2 of C6H6 favors out of plane approaches, especially with SH2
n(r , γ ) = β + 4.0⎜ ⎟ situated along the C6 axis of C6H6 (axial approaches), with the
⎝ r0(γ ) ⎠ (5)
two H atoms placed at shorter distances from the aromatic ring
where β is an adjustable parameter related to the hardness of than S.
the interacting partners, which adds flexibility to the potential The potential energy curves for the selected configurations of
energy function in comparison to the Lennard-Jones one.26 In the system are shown in Figure 1 as a function of the distance
particular, the decrease of β can indirectly include stabilization from the S atom to the C6H6 c.m.
effects due to a charge transfer in the perturbative Panels a and b correspond to perpendicular approaches of
limit.27,35,49,50 All the parameters of the ILJ function describing SH2 to the aromatic plane, while panels c and d describe the on
the C6H6−SH2 and the C6H6−NH3 interactions are given in plane ones (equatorial approaches). More in detail, in panel a,
1653 dx.doi.org/10.1021/jp410917x | J. Phys. Chem. A 2014, 118, 1651−1662
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 from the literature are also included for comparison. As can be
the C2v symmetry axis of SH2 coincides with the C6 symmetry seen, the predictions of the model are in quite good agreement
axis of C6H6. In one of them, the H atoms of SH2 are aligned with available ab initio data.
with a HCCH axis of C6H6, while in the second one the H The overall similarity of the plots in parts a and b of Figure 1
atoms of SH2 point toward the center of two CC parallel bonds. suggests that the minima should be connected through low
Panel b in Figure 1 contains the potential energy curve rotational barriers. In order to check this feature, we have
corresponding to an axial approach with one of the SH bonds explored the rotation of SH2 in the yz plane being C6H6
of the SH2 molecule pointing along the C6 symmetry axis of confined in the xy plane maintaining the axial configuration and
C6H6. As regarding equatorial approaches, panel c contains the the Bz-SH2 intermolecular distance close to the equilibrium
values of the potential energy for two coplanar approaches of geometry (3.680 Å). The rotation angle ϕ has been taken as the
SH2 to C6H6 in which the S atom of the SH2 molecule points one formed by one SH bond and the C6 rotational axis of C6H6.
toward the center of a CC bond. On the contrary, in panel d, The PES values are represented in Figure 2 as a function of the
the S atom point toward an H atom of C6H6. As it can be seen, rotation showing a minimum energy of −2.804 kcal mol−1 at a
perpendicular approaches are energetically favored with respect rotational angle of 17°. Identical results are obtained when SH2
to coplanar ones. Moreover, the minimum potential energy rotates in the xz plane. As expected, small variations on the
values associated with the different axial approaches, with one potential energy are observed when ϕ varies from 0 to 90°.
or both H atoms pointing to the aromatic ring, are very similar These results are indicative of the flatness of the PES for axial
indicating that, for these approaches, the PES is very flat. In approaches.
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 Figure 2. Potential energy represented as a function of the rotation of
energy, Vtotal and the internuclear distance R at equilibrium for SH2 in the yz plane at a fixed value of RS−C6H6 = 3.680 Å. For ϕ = 0°,
these adducts are given in Table 2, where some results available one SH bond is aligned along the C6 rotational axis of C6H6.
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 RN−C6H6/Å methodology
tridentate −2.17 3.506 present
tridentate −1.70 3.6 MP2/cc-pVQZ21
monodentate −2.32 3.505 present
monodentate −2.37 3.6 MP2/cc-pVQZ21
monodentate −2.22 3.6 ECCSD(T)limit (cc-pVDZ)21
monodentate −2.37 − CCSD(T)/AVTZ55
monodentate −2.43 3.60 CCSD(T)/aug-cc-pVTZ53
monodentate −2.47 3.60 CCSD(T)/aug-cc-pVQZ53
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. microwave spectra of C6H6−NH3 in the gas phase (the
In order to characterize the C6H6−NH3 PES, we have appearance of two peaks suggests that the ammonia can freely
proceeded in an analogous way to what has just been explained rotate in C6H6−NH3).54 Moreover, they also agree with the
in the case of SH2, building potential energy curves for high-level ab initio calculations carried out by Tsuzuki et al.21
intermolecular approaches at fixed relative configurations. The The results of the intermolecular interaction energy Vtotal and
potential energy curves for some selected configurations of the the intermolecular distance R corresponding to the equilibrium
C6H6−NH3 complex are shown in Figure 3. structures for the tridentate and monodentate complexes
Panels a and b in Figure 3 represent potential energy curves represented in panels a and b of Figure 3, respectively, are
corresponding to two axial approaches of NH3 perpendicular to listed in Table 3, where some results, available from the
the benzene plane, while the on plane (equatorial) ones are literature, are included for comparison. Our potential energy
shown in panels c and d. Similarly to the case of dihydrogen model predicts that the monodentate complex is slightly more
sulfide, axial approaches present a larger interaction energy and stable than the bidentate (not shown) and tridentate ones.
more stable minima than equatorial approaches. However, However, the model predicts smaller differences of the binding
these differences are less noticeable in the case of ammonia.
energy for the different geometries of the adducts than those
The representations in panel a correspond to approaches of
obtained from ab initio methods. In particular, our potential
NH3 in which the C3 symmetry axis of the molecule coincides
energy predictions at the equilibrium geometry for the mono
with the C6 one of C6H6 and, therefore, the three hydrogen
atoms are equidistant to the benzene plane (tridentate and tridentate complexes differ only for 0.25 kcal mol−1,
configuration), while in panel b) is described an approach of whereas this energy difference is increased to 0.67 kcal mol−1 by
NH3 in which a NH bond coincides with the C6 symmetry axis MP2 calculations using a large basis set.21
of C6H6 (monodentate configuration). On the other hand, in Furthermore, the C6H6−NH3 PES has been investigated
panel c are represented the values of the potential energy for more in detail exploring the rotation of NH3 around C6H6. The
two equatorial approaches of NH3 to C6H6, with the N atom of rotation angle ϕ has been taken as the one formed by one NH
NH3 pointing toward an H atom of C6H6, while in panel d, the bond and the C6 rotational axis of C6H6. In Figure 4 the
N atom of NH3 point toward the center of a CC bond of the interaction energy is represented as a function of ϕ at a fixed
aromatic molecule. As it can be seen in Figure 3a, the potential distance from N to the C6H6 c.m. of 3.505 Å.
energy curves for the two axial configurations with NH3 Results indicate that the most stable geometry of the C6H6−
differently oriented above the benzene plane are almost NH3 is the one in which one of the NH bonds (the closest to
identical, reflecting again the flatness of the PES with respect the aromatic plane) forms an angle, ϕ, of about 18° with the C6
to rotation of the ammonia molecule around its C3v axis. These rotational axis of C6H6, being he minimum of the potential
results are in agreement with the high-resolution optical and energy equal to −2.491 kcal mol−1.
1655 dx.doi.org/10.1021/jp410917x | J. Phys. Chem. A 2014, 118, 1651−1662
The Journal of Physical Chemistry A Article
instance, ref 31). Under these conditions, without phase theoretical works addressed to characterize computationally the
changes of the system, Ecfg varies linearly with T. In Figure 7, SH−π interaction, can be found in the literature,24,52,53,61−67 we
have only found one experimental (rotational spectroscopy)
Ecfg is represented as a function of temperature for the C6H6−
report providing information on the geometry of the C6H6−
SH2 and C6H6−NH3 systems in the top and lower panels, SH2 system. Therefore, the model predictions of the binding
respectively. 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
The extension of this formulation to aggregates formed by Potential of Carbon Dioxide Dimer from Symmetry-Adapted
C6H6 and two or more molecules containing XH bonds is not Perturbation theory. J. Chem. Phys. 1999, 110, 3785−3803.
only possible but is also useful to investigate both the stability (17) Misquitta, A. J.; Szalewicz, K. Intermolecular Forces from
and other basic features of the solvation shells of clusters Asymptotically Corrected Density Functional Description of Mono-
mers. Chem. Phys. Lett. 2002, 357, 301−306.
formed by hydrogenated molecules around benzene.
■
(18) Misquitta, A. J.; Jeziorski, B.; Szalewicz, K. Dispersion Energy
from Density-Functional Theory Description of Monomers. Phys. Rev.
AUTHOR INFORMATION Lett. 2003, 91, 033201(1)−033201(4).
Corresponding Author (19) Shibasaki, K.; Fujii, A.; Mikami, N.; Tsuzuki, S. Magnitude and
*(M.A.) E-mail: m.alberti@ub.edu. Nature of Interactions in Benzene-X (X = Ethylene and Acetylene) in
the Gas Phase: Significantly Different CH/π Interaction of Acetylene
Notes
as Compared with those of Ethylene and Methane. J. Phys. Chem. A
The authors declare no competing financial interest.
■
2007, 111, 753−758.
(20) Fujii, A.; Shibasaki, K.; Kazama, T.; Itaya, R.; Mikami, N.;
ACKNOWLEDGMENTS Tsuzuki, S. Experimental and Theoretical Determination of the
M.A., A.A. and F.H.-L. acknowledge financial support from the Accurate Interaction Energies in Benzene-Halomethane: the Unique
Ministerio de Educación y Ciencia (Spain, Project CTQ2010- Nature of the Activated CH/π Interaction of Haloalkanes. Phys. Chem.
16709) and the Generalitat de Catalunya (2009SGR-17). Also Chem. Phys. 2008, 10, 2836−2843.
(21) Tsuzuki, S.; Honda, K.; Uchimaru, T.; Mikami, M.; Tanabe, K.
thanks are due to the Center de Supercomputació de Catalunya Origin of the Attraction and Directionality of the NH/π Interaction:
CESCA-C4 and Fundació Catalana per a la Recerca for the Comparison with OH/π and VH/π Interactions. J. Am. Chem. Soc.
allocated supercomputing time. F.P. acknowledges financial 2000, 122, 11450−11458.
support from the Italian Ministry of University and Research (22) Ma, J.; Alfè, D.; Michaelides, A.; Wang, E. The Water-Benzene
(MIUR) for PRIN Contracts. Interaction: Insight from Electronic Structure theories. J. Chem. Phys.
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