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Abstract: An all-atom model for benzene is reported and tested largely in Monte Carlo simulations of pure liquid benzene,
benzene in dilute aqueous solution, and the benzene dimer in water and chloroform. Free energy profiles were obtained for
the association of the benzene dimer in liquid benzene, water, and chloroform that characterize the energetics for this prototypical
interaction between arenes in solution. In all cases a contact dimer with a ring center-ring center separation of ca. 5.5 A
is found to be energetically preferred. Face-to-face stacked structures are net repulsive. However, gas-phase optimizations
indicate that shifted, stacked structures become increasingly favorable with increasing arene size. Comparisons are made with
key experimental data, including the free energy of hydration of benzene and the association constant, K,,for the benzene
dimer in water. The agreement with the results from the new potential function provides a h i s for confidence in the accompanying
insights of relevance to molecular design.
0002-7863/90/ 15 12-4168$02.50/0
= (C..C..)'/2.
11 JJ
For benzene, there are five adjustable parameters: u and c for
carbon and hydrogen, and one charge variable since qc = -qyi
The u's and c's were required to be consistent with other values,
so the principal fitting was just for the charge. Earlier work
suggested that values of q H between 0.1 and 0.2 should be considered: The final decisions were based on fitting results of Monte
Carlo simulations for liquid benzene primarily to the observed
heat of vaporization and density," as described below. We were
also aware of the experimental C-C radial distribution function."
The resultant parameters are uc = 3.55 A, tC = 0.07kcal/mol,
U H = 2.42 A, CH = 0.03 kcal/mol, and q H = -qc = 0.1 15. For
Aromatic-Aromatic Interactions
the present study, parameters for water and chloroform were also
required so the TIP4PI4 and OPLSILcmodels were adopted. In
each case, the geometries of the monomers were based on experimental data including r(CC) = 1.40 A and r(CH) = 1.08 A
for benzene.Is
Fluid Simulations. Monte Carlo statistical mechanics simulations were carried out for liquid benzene, a single benzene
molecule in water, and the benzene dimer in water and chloroform.
All calculations were performed for systems with periodic
boundary conditions in the isothermal-isobaric (NPT)ensemble
at 25 O C and 1 atm. Standard procedures were used including
Metropolis sampling and, for the solutions, preferential sampling.11q16In addition, the ranges for translations and rotations
of the monomers were chosen to provide acceptance probabilities
of ca. 40% for new configurations.
The simulations of pure benzene involved 128 monomers in a
cubic cell ca. 27 A on a side. Lengthy equilibrationwas performed
in the course of optimizing the potential function parameters.
Averaging for the final results occurred over an additional 3.5
X lo6 configurations. The intermolecular interactions were
spherically truncated at 13 A based on the distances between ring
centers, though a correction was made to the total energy for the
Lennard-Jones interactions neglected beyong the cutoff.*
A calculation was then performed to determine the free energy
of hydration of benzene. This was done by making a single
benzene molecule disappear in TIP4P water.I7 In fact, the 12-site
model of benzene was converted to the previous 6-site model and
then to a single Lennard-Jones atom approximating methane
which had its free energy of hydration determined earlier. 265
water molecules (ca.20 x 20 x 20 A) were used in this case with
solvent-solvent and solute-solvent cutoffs of 8.5 and 9.5 A, respectively, based on the 0-0 and O-ring center distances. The
free energy changes were calculated n a series of simulations with
statistical perturbation theory (SPT)17J8and double-wide sampling.I9 Five simulations were used for both the 12-site to 6-site
and 6-site to methane mutations. Each simulation consisted of
0.5 X 106 to 1.5 X 106 configurations for equilibration, followed
by 2.0 X IO6 configuration of averaging.
The potential of mean force computations for the benzene dimer
in TIP4P water and chloroform were performed by gradually
perturbing the ring centers apart in steps of 0.2 A (each center
moved in or out by 0.1 A) with SPT. We were concerned with
possible cutoff artefacts on the asymptotic behavior, so large
systems and cutoffs were used. For the solutions, 735 water
molecules and 185 chloroform molecules were included in periodic
cells ca. 25 X 25 X 38 and 26 X 26 X 39 A, respectively. The
line between the ring centers was initially oriented along the long
axis in each simulation. In all cases, the cutoffs for the solvent-solvent and solute-solvent interactions were at 12 A with
quadratic feathering to zero over the last 0.5 A. Each simulation
involved preferential sampling, equilibration periods of 1.1 X 106
configurations, and averaging for 2 X lo6 and 4 X lo6 configurations for the chloroform and aqueous solutions. All SPT calculations were performed with the BOSSprogram on Gould 32/
8750 and Silicon Graphics 4D computers in our laboratory.
Results and Discussion
Cas-wlse Structures and Interaction Energies. The structure
of the benzene dimer in isolation has been addressed in many
experimental and theoretical ~ t u d i e s . ~ ~ Various
J Q ~ ~ alternatives
(14) Jorgensen, W. L.; Chandrasekhar, J.; Madura, J. D.; Impey, R. W.;
Klein, M. L. J . Chem. Phys. 1983, 79, 926.
(15) Bastiansen, 0. Acta Crysrollogr. 1957, 10, 861. Harmony, M. D.;
Laurie, V. W.; Kuczkowski, R. L.; Schwendeman, R. H.; Ramscy, D. A. J .
Phys. Chem. Ref. Dura 1979,8, 619.
(16) (a) Metropolis, N.; Roscnbluth, A. W.; Roscnbluth. M. N.; Teller,
A. H.; Teller, E. J. Chem. Phys. 1953.21, 1087. (b) Owicki, J. C. ACS Sy.
Ser. 1978, No. 86. 159.
(17) Jorgensen, W. L.; Blake, J. F.; Bucher, J. K. Chem. Phys. 1989,129,
193.
(18) Zwanzig, R. W. J . Chem. Phys. 1954, 22, 1420.
(19) Jorgensen, W. L.; Ravimohan, C. J . Chem. Phys. 1985, 83, 3050.
(20) Law, K. S.;Schaua, M.; Bernstein, E. R. J . Chem. Phys. 1984,81,
4871.
R=4.99,4
E = -2.31
R = 4.50 A
E = -2.1 1
f
R=519A
E = - 2 I5
R = 3.77
E=-1.70
85, 1726.
(22) Grover, J. R.; Walters, E. A.; Hui, E. T. J . Phys. Chem. 1987, 91,
3233.
.5
1.0
3.0
5.0
7.0
9.0
11.0
13.0
R (A)
1.5
E = -3.94
OS
O.O
R.3.11
1 i
C-H Radial Distribution Function
E = -3.80
Figure 2. Lowest energy structures optimized for benzene with chloroform and water. R is the ring center to C or 0 distance.
v,A3
C,, cal/mol.K
a
8.05 i 0.01
0.873 f 0.001
148.6 f 0.2
31.2 i 1.0
-0.90 f 0.39
A&, kcal/mol
Reference 12. Reference 23.
8.09
0.874
148.4
32.5
-0.767b
6;
1.0
3.0
5.0
7.0
9.0
11.0
13.0
R (A)
Aromatic-Aromatic Interactions
peaks and a shoulder in the 3-7 A region. By comparison, the
C-H and H-H radial distribution functions (Figure 4) have little
structure, as found previously.10
Information on the number of nearest neighbors is easier to
extract from the ring center-ring center rdf shown in Figure 5.
A well-resolved first peak with a maximum at 5.5 A is now
apparent and corresponds to the first shell of neighbors. Integration to the minimum at 7.5 A yields 12 molecules in this shell.
The same coordination number has been found experimentally
in the solid and liquidt3and from prior theoretical studies including RISM calculation^.^^^*^ The position of the first peak
is consistent with contributions from T-shaped pairs, while the
occurrence of parallel stacked dimers near their optimal separations of 3.8-4.5 A (Figure 1) must be rare since the integral of
the rdf to 4.5 A only reveals 0.1 neighbor; integration even to 5.0
A only accounts for 1 of the 12 neighbors in the first peak. It
is notable that in the analysis of structures from the Brookhaven
Protein Data Bank, Burley and Petsko obtained a distribution that
resembles Figure 5.* They plotted the normalized distribution
of phenyl ring center-phenyl rin center separations and found
a strong first maximum near 5.5 and a weak second maximum
at about 9.5 A. Singh and Thornton have also analyzed the
geometries of Phe-Phe sidechain contacts in the Protein Data
Bank.3b They found an essentially random distribution for the
angle Q between the ring planes which favors perpendicular arrangements (4 = 90) owing to the intrinsic sin Q dependence.
A similar analysis was performed here on the Monte Carlo results
for liquid benzene. For ring center-ring center separations above
5 A, sin Q behavior is basically followed. At shorter separations,
the distribution for Q peaks at progressively lower angles, which
reflects the steric constraints against larger 4s.
Dilute Aqueous Benzene. Strong motivation for going to a
12-site model of benzene with partial charges is provided by the
realization that simpler models without electrostatic interactions
are disposed to making the model benzene too hydrophobic. This
was confirmed by the conversion of the Lennard-Jones 6 4 t e
model* to methane in TIP4P water. It was previously established
that the free energy of hydration of the model methane (corresponding to transfer of the solute from the ideal gas phase into
infinitely dilute aqueous solution) is 2.27 f 0.3 kcal/mol. This
value compares well with the experimental result of 2.005
kcal/mol; in all cases, standard states with molar concentration
units are used in both phase^.".^^ The free energy of hydration
of benzene is also known to be -0,767 k c a l / m ~ l . ~Thus,
~ experimentally the free energy of hydration of methane is 2.77
kcal/mol greater than that for benzene. However, the present
SPT calculations with the 6-site model yielded a difference of only
1.06 f 0.23 kcal/mol and a net free energy of hydration for the
6-site benzene of (2.27 f 0.3) - (1.06 f 0.23) = 1.2 f 0.4
kcal/mol. The ca. 2 kcal/mol enhanced hydrophobicity for the
model benzene would clearly distort solution-phase results in many
contexts.
The problem can be resolved by the 12-site model owing to the
added electrostatic interactions. SPT calculations were performed
to convert the 12-site model to the 6-site model in TIP4P water,
as described above. A free energy change of 2.1 1 f 0.10 kcal/mol
was obtained, which gives a net free energy of hydration of -0.9
f 0.4 kcal/mol for the 12-site model (Table I). This result is in
gratifying accord with the experimental value of -0.767 kcal/mol
since it was obtained after the parametrization of the model was
complete. However, the statistical uncertainty for the computed
result, 0.4 kcal/mol, is significant. It is associated with the large
perturbation involved in the complete removal of the benzene solute
from water. Nevertheless, the cumulative results on the gas-phase
dimer, pure liquid, and hydration of benzene reveal no obvious
sources of e r n for the present potential functions abilities
to describe the energetics of benzene association in solution.
Earlier simulation studies of benzene in water should be notd6.252
Both
6 groups used potential functions derived from ab initio
2.0
-2.0
i
3
I
5
11
R (A)
_______
1M
__
2M
3M
----
a.rtl
I.7tA
Figwe 10. Random configuration for the benzene dimer in water in the
vicinity of the solvent-separated minimum. Water molecules were sclected as in Figure 9.
-2.0 3
I1
R (A)
Figure 7. Evolution of the computed potential of mean force for the
benzene dimer in water. Results are shown after averaging for 1-4million configurations for each increment in R.
1.111
S.7bA
L.lll
..ltA
displays the pmf in water after 1-, 2-, 3-, and 4-million configurations of averaging and the 1.1-million configurations of
equilibration for each of the 16 simulations. The changes from
2- to rlmillion configuraltions are modest particular1 for the depths
of the free energy wells centered near 5.5 and 7.5 ,though there
is a progressive diminution of the barrier near 6.5 A. It is apparent
that the pmf is changing slowly. This means that the results are
reasonably well converged or that attainment of precise results
would require great extension of the computations. Additional
support for the former position is provided by the results below
for the association constant, K,, in water.
Figure 6 contains the key information on the energetic impact
of aryl-aryl interactions in the prototypical case. In all three
media, the optimal interaction occurs at a separation of about 5.5
A corresponding to a contact dimer. Graphical analyses of
configurations from the simulations near this separation reveal
predominantly a range of distorted T - s h a d pairs, including some
roughly parallel stacked and displaced structures that can be
regarded as part of the pathway between distorted Ts. Two
random examples, the last configurations in the simulations, are
illustrated in Figures 8 and 9 for the chloroform and aqueous
solutions. Only the nearest solvent molecules are shown. The
example in Figure 8 is a distorted T-shaped pairing that is reminiscent of the lowest energy dimer in Figure 1, while the example
in water (Figure 9) has more parallel, displaced character, though
the rings do not overlap as in the middle structure in Figure 1.
The benzenebenzene interaction energy is only -0.84 kcal/mol
for the configuration in Figure 9 versus -1.78 kcal/mol for Figure
8. Though striking solute-solvent interactions are not plentiful
Aromatic-Aromatic Interactions
6.0
1
I
4.0
3.0-
2.0
R=483d
E = -3.47
1.0-
0.0
3
1 0 1 1
(A)
Rpre 12. Computed association constants for the benzene dimer in
water and chloroform as a function of the cutoff limit, c.
c
Y
R=428d
E - - 3 I5
thalene.
1'9 exp(-w(r)/kBT) d r
R=5DId
E = 4.34
R = 3.93 d
E I -4.07
B = -27r Jm9[exp(-w(r)/kBr)
0
- 11 d r
(3)
cene.
4774
S
T
S
2.74
2.08
3.61
0.35
-0.57
0.61
-6.23
-4.85
-8.29
-3.15
-3.34
-4.07
Abstrack The electronic excited states of the gaseous ions C2H3S+and CZHpO' generated from a variety of precursor molecules
by electron impact were investigated by means of translational energy spectroscopy ( T g ) . The spectra of CzH3S+show three
%'A), (B X'A), and (A'A RIA). The observation of the
electronic transitions that can be assigned to CzH3S+
latter transition and its measured energy is the first experimental evidence that this ion has a long-lived (ca. 2 ps) electronic
excited state located at 2.7 eV above its ground state. The spectra of CzH30+offer no evidence of long-lived excited states.
However, two collisionally induced electronic transitions involving the X'A, ground state and two upper electronic excited
states are clearly evident. The relative intensities of both transitions are clearly dependent on the identity of the precursor
molecule. This dependence is attributed to the formation of different structures of the incident C2H3O' ion. This deduction
is in accord with earlier experimental data and high-level theoretical calculations.
(e
collision spectro~copy,'-~
ion cyclotron resonance$.5 photoionization$" and a b initio molecular orbital calculation^.^ Despite
(1) Paradisi, C.; Scorrano, G.; Daolio, S.; Traldi, P. Org. Mars Spctrom.
1984, 19, 198.
( 2 ) Cwks, R. G.; Mabud, Md. A.; Homing, S. R.; Yang, X.-Y.; Paradisi,
C.; Traldi, P. J. Am. Chem. Soc. 1989, 111, 859.