Multiphoton ionization studies of clusters of immiscible liquids. I.

C6H6–(H2O)n, n=1,2
Albert J. Gotch and Timothy S. Zwier

Citation: J. Chem. Phys. 96, 3388 (1992); doi: 10.1063/1.461940

View online: http://dx.doi.org/10.1063/1.461940
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Published by the American Institute of Physics.

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Multiphoton ionization studies of clusters of immiscible liquids.
I. Cs Hs -(H 2 0)n, n=1,2
Albert J. Gotch and Timothy S. Zwier"l,bl
Department of Chemistry, Purdue University, West Lafayette, Indiana 47907-1393
(Received 12 July 1988; accepted 20 November 1991)
Resonant two-photon ionization (R2PI) time-of-flight mass spectroscopy is used to record
SO-SI spectra of the neutral complexes C6H6-H20, C6H6-HDO, C6H6-D20,
C6H 6-(H20)2' and C6H 6-(D 20)2' In C6H6-H20, the lack of an SO-SI origin transition
and the presence ofa splitting at 66 (which is absent in C6H 6-HDO) provide vibronic level
evidence that the water molecule is on the sixfold axis undergoing internal rotation about that
axis. Rotational band contour analysis of the 66 transitions of the isotopomers confirms this
picture and also determines a ground state center-of-mass separation between C6H6 and D 20
of 3.32 ± 0.07 A, very close to that predicted by ab initio calculations. R2PI scans of the van
der Waals structure in the isotopic series C6H6 -H20, C6H6 -HDO, and C6H6 -D2 0 provide
tentative assignments for three of the six van der Waals modes in the complex. In
C6H 6-(H 20)2' rotational band contour analysis of the origin transition provides a best-fit
structure in which the two water molecules reside on the same side of the benzene ring at a
H2 O-H20 separation close to that in the free water dimer. Qualitatively, the structure of the
1:2 cluster is thus one which maximizes the strength of the water-water hydrogen bond at the
expense of a somewhat poorer interaction of the second water molecule with the benzene ring
in an off-axis geometry. Several intriguing features of the structure are suggested by our
analysis, but are near the limit of our ability to distinguish from band contour fitting. Among
these features are (i) the on-axis water molecule is pulled slightly in toward the ring from that
in the 1:1 complex; (ii) the water dimer prefers an orientation bisecting a C-C bond in the
benzene ring; (iii) the water-water separation is -0.2 A less than that in the free water dimer;
and (iv) the water dimer axis is tilted by about 10° relative to the plane of the benzene ring.
Finally, the van der Waals structure in C6H 6-(H 20)2 and C6H 6 -(D 20)2 suggests the
possibility of large amplitude motion in these complexes as well. We postulate that this motion
involves a hindered rotation of the on-axis water molecule.

I. INTRODUCTION termed hydrophobic, the polarizable 1T electron density

The hydrophobic interaction between non-polar hydro-
carbons and water is one of the most important forces in
nature. I,2 It gives rise to the immiscibility of the bulk li-
quids, 2 plays a major role in the conformations of proteins, 3
and is central to the formation of micelles and biological
membranes. 4 Despite this importance, a molecular-scale de-
scription of the hydrophobic effect lacks a strong experimen-
tal underpinning, and models upon which much of our pres-
ent understanding are based rely on theory alone for their
support. 5- 16 At the basis of all such theories must be accu-
rate, experimentally determined two-body (and ultimately
many-body) intermolecular potentials. Such potentials have
been determined in only a very few cases. For example, in the
case of water-X interactions, the intermolecular potential is
known with spectroscopic accuracy only for the case that X
is Ar I7 (a),17(b) or CO. l7 (C)
Aromatic hydrocarbon-H 20 interactions present a spe-
cial challenge to experiment and theory due to the presence
of the conjugated 1T system. 12 C6H 6, the prototypical aro-
matic, is essentially immiscibile in water. Yet, while the in-
plane interactions of water with benzene could be readily
a) Author to whom correspondence should be addressed.
b) Alfred P. Sloan Research Fellow, 1989-1991.
should lead to hydrophilic out-of-plane interactions. Since
many of the common constituents of globular proteins (e.g.,
phenylalanine, tryptophan, and tyrosine) possess aromatic
sidechains,18 the interactions with water playa significant
role in the tertiary structure taken up by the proteins. 19 The
primary interaction of the aqueous solvent with these phenyl
rings is thought to be via hydrogen bonding with the aroma-
tic 1T cloud, a contention which recent x-ray diffraction stud-
ies have confirmed. 20
Benzene's role as the prototypical aromatic molecule
beckons detailed fundamental studies of its intermolecular
interactions with water. It is not surprising, then, that signif-
icant experimental21 -25 and theoreticaI 12- 15 ,26-30 effort has
been directed at studies of benzenelwater solutions and their
microscopic progenitors, the gas phase clusters. In an earlier
report,25 we provided vibronic level arguments constraining
the geometry of the C6H6 -H20 complex and presented a
broad-brush overview of spectra taken of the higher clusters
with two to five water molecules. Here we present a detailed
account of our investigations which extend our initial report
in several significant ways. Our focus in this paper will be on
the C6H6 -H 20 and C6H6 -( H 20) 2 complexes, while a sec-
ond paper will take up larger clusters containing up to eight
water molecules. In the case ofC6 H 6 -H20, we present and
analyze rotational band contours of the isotopic series

3388 J. Chern. Phys. 96 (5), 1 March 1992 0021-9606/92/053388-14$06.00 @ 1992 American Institute of Physics

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 A. J. Gotch and T. S. Zwier: Multiphoton ionization of clusters. I
Ce.He.-H20, C6He.-HDO, and C 6H 6-D 20. These provide
the Ce. H6IH2 0 intermolecular separation and confirm that
the water molecule is internally rotating about the sixfold
axis of C 6 He,. The van der Waals structure of the isoto-
pomers provides tentative assignments of three of the six van
der Waals modes in the excited state. In C 6 H 6 -(H 20)2, the
rotational band contour is analyzed to provide the center-of-
mass positions of the three molecules, indicating that the
water molecules hydrogen bond to one another on the same
side of the benzene ring. The structure provides some insight
to the effects of the benzene molecule on the hydrogen bond-
ing in the water dimer itself.
II. EXPERIMENT
A schematic diagram of the molecular beam time-of-
flight mass spectrometer used in the present studies is shown
in Fig. 1. Ce,H6 -(H 20)n clusters are formed by expansion
of a mixture containing C6 He. and H 2 0 in helium from a
pulsed valve (General Valve) of 0.8 mm diam operating at
20-40 Hz. The first chamber is pumped by an unbaffled 10
in. diffusion pump, while the second chamber incorporates a
6 in. diffusion pump with a baffle cooled by a closed-cycle
refrigeration unit. The pulsed valve is mounted on an xyz
translation stage for alignment of the valve relative to the
skimmer (2 mm diam opening). Initial alignment is
achieved by maximization of the pressure reading in an on-
axis ion gauge located on the far side of the second chamber.
Typical operating pressures in the first and second chambers
are 8 X 10 - sand 2 X 10 - 6 Torr, respectively. The first
chamber can be isolated from the second chamber when de-
sired by a small, custom-made, sliding gate valve attached to
a linear translation stage (not shown).
The clusters formed are resonantly ionized by the unfo-
cused output of an excimer-pumped dye laser (Lambda
LPX 120iIFL3002E) doubled in a beta barium borate
(BBO) crystal. Typical per pulse energies of -0.03-1.0
mJ/pulse are used. The ions formed are accelerated to
- 2800 eV in a two-stage ion source of Wiley-McLaren de-
sign and focused by an einzel lens. Ions are detected either
with a 25 mm diam. chevron microchannel plate (MCP)
detector at the end of the linear time-of-flight (TOF) region
or after reflection in a retarding field by a 40 mm MCP detec-
tor located 76 cm below the reflectron. Typical mass resolu-
tions (ml b.m) at mass 100 are 350 in the linear configura-
tion and 600 in the reflect ron mode. Both these figures are
limited significantly by the laser pulse duration (15 ns).
Nonetheless, the additional resolution of the reflectron is
important in experiments on isotopomers where complete
rejection of ions at adjacent masses is required. Under identi-
cal operating conditions, signal sizes are typically a factor of
2-3 times less in the reflectron than in the linear modes.
TOF mass spectra are recorded on a fast digital oscillo-
scope (LeCroy 9400). R2PI scans involve integrating the
ion signal in 30-50 ns time windows about the arrival
time (s) of the masses of interest using either a 12-channel
separately gateable analog-to-digital converter, or the digital
oscilloscope.
Rotational band contour scans are recorded by angle
J. Chem. Phys., Vol. 96, No.5, 1 March 1992
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3389
Refiectron
Grids
Photomultiplier
Tube ~
Gauge
6·inch
Diffusion
10-inch
Pump
Diffusion
Pump
FIG. I. A schematic diagram of the molecular beam time-of-flight mass
spectrometer used in the present study.
tuning an intracavity etalon under computer control. In
these scans, it was particularly important to use low laser
powers « 0.05 mJ/pulse) in order to avoid saturation
broadening. This resulted in etalon scans being recorded
with signal levels of about one ion per laser shot. Laser reso-
lution in these scans after doubling is - 0.08 cm - , full width
at half-maximum (FWHM).
C6H6 and distilled water were used at commercially
available purities. Concentrations of the liquids are con-
trolled by metering flows of helium over the room tempera-
ture liquids using needle valves and mixing these flows with
the main flow of helium to achieve concentrations in the
range 0.4%-0.7% for C 6H6 and 0.01%-0.4% for H 2 0 at a
total pressure of 2-4 bar.
III. RESULTS
A. Survey R2PI scans and assignments
In these studies, extensive use is made of vibronic level
arguments to constrain the geometries of the clusters. To set
the stage for such arguments, a brief review of the So-S,
spectroscopy of C6H6 is provided here. The free C6H6 mole-
cule has an electric dipole forbidden So-S, transition which
is vibronically induced in first order by vibrations of e2g sym-
metry.3' Thus while the SO-SI origin transition is not ob-
served in C6H 6, 66 (ve. being an e2g in-plane ring deforma-
tion) is a prominent transition, as are members of the 661~
progression (VI being an a Ig ring breathing mode). Simple
symmetry considerations show that, upon complexation, the
H 20 molecule(s) can induce an origin transition in benzene
if they break its sixfold symmetry to lower than threefold
symmetric. The ratio of intensity at the origin to that at is 66
3390 A. J. Gotch and T. S. Zwier: Multiphoton ionization of clusters. I
thus a crude measure of the degree of this symmetry break-
ing in the complex.
Figures 2 (a) and 2 (b) present one-color R2PI scans of
the regions just to the blue of the origin and 6b transitions of
C6H6 monitoring the [C6H6-H20] + mass in the TOF
mass spectrum. The assignment of the transitions to a given
cluster size is complicated by the efficient fragmentation
these 1r hydrogen-bonded complexes undergo following
photoionization. 32-34 Since the details of our assignment
have been presented elsewhere/ s we present only a sum-
mary of the assignment and its experimental basis here.
The transition 50 cm -, blue shifted from C6H6 6b is
assigned to the 1:1 complex. No corresponding transition is
observed at the origin, with an upper bound on its intensity
of 0.1 % that at 6b. Transitions to other totally symmetric
vibrations (e.g., 1b) are also not observed. The 50 cm - ,
band is favored over those assigned to the 1:2 complex at low
water concentrations in the expansion. The 1: 1 complex un-
dergoes fragmentation following one-color R2PI with an ef-
ficiency of about 80% (extrapolated to the zero laser power
limit), indicating a 1r hydrogen-bonding interaction of the
H 20 molecule with the ring. 32 The rotational band contour
analysis which follows confirms the transition'S assignment
to the 1: 1 complex.
All transitions at the origin and the closely spaced set of
transitions beginning 75 cm - , blue of C6H6 6b are assigned
to the C6H 6-(H20)2 complex (i.e., 1:2) fragmenting into
the [C6H6-H20] + channel (i.e., 1:1) with 98% efficiency
following photoionization. 32,33 Careful scans monitoring
the 1:2 mass channel confirm this assignment, as does the
o
(8) 0 0
20 40 60 80 100 120 140
-1
Relative Frequency (cm )
FIG. 2. (a) Origin and (b) 6~ R2PI scans monitoring the [C.H 6 -H 2 0] +
mass channel. The frequency scale is relative to the corresponding transi-
tions of C 6 H6 •
J. Chem. Phys., Vol. 96, No.5, 1 March 1992
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analysis of the origin band's rotational contour (see Sec.
III C). The intensity of the origin transition is 14% of that
observed at 6b, indicating a strong breaking of the sixfold
symmetry of benzene by the pair of water molecules.
The twofold symmetry of the water molecule precludes
any rigid geometry for the 1: 1 complex which retains three-
fold or higher symmetry. Thus, the lack of an induced So-S,
origin in C6H6-H20 requires that the water molecule un-
dergo large-amplitude motion in such a way that on a vibra-
tional/y averaged basis, the complex retains the sixfold sym-
metry of the benzene ring. We conclude that the H 2 0
molecule must be on or near the sixfold axis ofC6 H 6 under-
going internal rotation about the sixfold axis.
Figure 3 presents further evidence of internal rotation in
C6H6 -H2 O. There the rotational band contours of the 6b
transitions of C6H 6-H 20, C6H 6-HDO, and C6H6-D20
are shown. The comparison of Fig. 3(a) with Fig. 3(b)
shows that, while the C6H6 -H20 6b transition is a doublet,
the C6H6 -HDO transition is a singlet. Both the lack of split-
ting in the C6H6 -HDO contour and the lack of an origin
transition in either C6H6-H20 or C6H6-HDO argue
against the H 20 molecule inducing a splitting by breaking
the degeneracy of the Vb vibration. Instead, the splitting
arises from transitions from internal rotor levels of different
nuclear spin symmetry (i.e., ortho- and para-H 2 0) which
are interconverted inefficiently by collisions in the expan-
sion. 17,35 The reduced symmetry of HDO allows intercon-
0.0 2.0 4.0 6.0 8.0 10.0
-1
Relative Frequency (cm )
FIG. 3. R2PI etalon scans (::::;0.08 em - 1 resolution) of the 6~ transitions of
(a) C 6 H.-H2 0; (b) C 6 H 6 -HDO; and (c) C 6 H 6 -D 2 0.
 A. J. Gotch and T. S. Zwier: Multiphoton ionization of clusters. I 3391

version ofthecorresponding levels in the C6H6-HDO com-

plex, resulting in a single 66 transition in that case. A more
thorough discussion of these points is left until the molecular z
symmetry analysis is presented.
With benefit of hindsight, the internal rotation of the
H 2 0 molecule in the C 6H6-H 2 ° complex is a physically
reasonable result. The large internal rotation constant of
H 2 0 (20 cm - I from Linse's calculations) 26 indicates that a
sixfold barrier to internal rotation of several hundred wave
y
numbers would be necessary to quench the internal rotation
°
of the H2 molecule. This would necessitate H 2 0 sensitive-
ly distinguishing between orientations along or bisecting ad- (al
(b)

°
jacent carbon atoms on the ring, which seems unlikely. Fur-
thennore, the infrared studies of C 6H6 -Hz in a matrix 21,22
also indicated the presence oflarge amplitUde motion in the
complex, as does Linse's computed potential energy surface
for H 2 0 moving in the field of a C 6 H6 molecule. o-
Already at the vibronic level much of the important «J "'/H-
H-
structural data on the complex is detennined; namely, that
°
the H2 molecule is on the sixfold axis of C 6H6 and is un-
dergoing internal rotation about this axis. Given the partial-
(e)
ly resolved rotational band contours of Fig, 3, the band con-
tour fitting is approached with two goals in mind. First, we
wish to test whether the rotational band contours are consis- FIG. 4. (a) Reference configuration used for the molecular symmetry
tent with the vibronic level analysis of the complexes. Sec- group theoretical analysis which allows for internal rotation ofH2 0 relative
ond, we seek to detennine the most important remaining to Co Ho. The x axis (the b axis) bisects the C I -C 2 bond on the benzene
structural feature of the complex; namely, the separation ring, the + z axis (the a axis) is perpendicular to the plane of the benzene
ring pointing toward the water molecule, and the internal rotor angle p is
between the C 6H6 and H 20 centers of mass. defined as the angle between the + x axis and the projection of the O-H,
axis onto the xy plane taken in a counterclockwise direction. (b) The axis
system used to describe most conveniently the intermolecular normal
B. CsHs-H20, CsHs-HDO, and C6 H6 -D20 modes. Thez' axis is coincident with the z axis. The x' andy' axes are in and
out of the plane of the water molecule, respectively, and rotate with the
t. The G24 molecular symmetry group water molecule rather than the benzene subunit. (c) Four of the six inter-
The non rigidity of the C6H6-H20 complex (by virtue molecular normal modes are shown: the in-plane bend biP ; the torsional
of the free or nearly free internal rotation of the H2 mole- ° mode in the plane of the water molecule ¢lip; the bending mode perpendicu-
lar to the plane of the water molecule bop; and the torsion of the water mole-
cule) and the observed splitting in our spectra demands the
cule out of the plane perpendicular to the benzene ring ¢lop' The two inter-
use of pennutation-inversion groups in analyzing the spec-
molecular modes not shown are the symmetric stretch about the z axis (z')
tra. Figure 4(a) presents the reference configuration we
°
have chosen for the C 6H6 -H2 complex. Feasible permuta-
tion operations in this case are those which rotate the ben-
Sz and internal rotation about this same axis ¢lz'

°
zene and H2 tops with respect to one another about the axis
joining their centers of mass (the z axis). We consider as
nonfeasible the rotation of the benzene ring about one of its
°
own C2 axes while holding H2 fixed since this requires the
breaking and refonning of the van der Waals bond. With this
operational definition offeasibility, there are 24 allowed per-
mutation-inversion operations for the C 6H 6-H 2 0/D 2 0
system, designating the group as GZ4 '
To our knowledge, neither the class structure nor the
character table of this group have been reported previously.
As a result, we have carried out such an analysis using the
methods outlined in Bunker. 36 The results are presented in
Table 1.
Inspection of the G24 character table shows it to be iso-
morphic with D 6h • Note that the (78) operation which ex-
changes protons (deuterons) on the Hz (D z 0) molecule °
plays the role that the inversion operation does in D 6h • To
avoid confusion between the D6h point group designations
appropriate to the free benzene molecule and the G24 molec-
used + / - designations for the symmetry with respect to
the (78) operation rather than theg/u designations of D6h •
The molecular symmetry group appropriate to C 6 H 6 -
HDO is G 12 , in which all operations involving (78) are re-
moved. The G I2 character table is isomorphic with C6u and
the reduction of symmetry designations from GZ4 to G 12 can
be made trivially by dropping the + / - superscript.
2. Nuclear spin statistical weights
The intensities of transitions in the rotational band con-
tour are determined in part by the ground state nuclear spin
statistical weights. The Pauli exclusion principle places con-
straints on the allowed symmetries of the total internal wave
functions of the complex r int as indicated in Table II. The
symmetries of the ground state rotation-torsion levels are
then determined by
r int =rnucXrtorXrrot·

ular symmetry group designations ofC6 H 6 -H2 0, we have The nuclear spin symmetries ofthe C6 H6 -Hz 0 isotopomers
J. Chem. Phys., Vol. 96, No.5, 1 March 1992
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3392 A. J. Gotch and T. S. Zwier: Multiphoton ionization of clusters. I

are readily det~rmined (Table II). For symmetry consider-

-5"
-5 ations, the torsional motion can be treated as a completely
.~

~
free internal rotation of the H 20 molecule about the z axis.
bh" Then if1tor a eimp, where p is the internal rotor angle defined
I I
- 0 0 ; in Fig. 4 and m is the internal rotation quantum number. The
; dependence of the angle p on the symmetry operations is
OIl
.:
~ included in the G24 character table (Table I) and the result-
eos ing symmetries of the torsional wave functions are listed in
;" Table II.
'a
- ...... ...... ...... 0 0 - ...... ...... ...... 0 0
k' Due to the free internal rotation of the H 20 molecule in
-5" our model, the ground state rotational wave functions of
.5 C 6H6 -H 20 are those of a symmetric top IJ k ). The symme-
.~ tries of these levels and the resulting nuclear spin statistical
; weights of the rotation-torsion levels are given in Table III,
=s
where we have included rotation-torsion coupling in the
-_NN ____ MN
~.,
I I I I I I
.: m = ± 1 levels. 37
os
~....
~

~ 3. Nuclear spin symmetry and cooling In the supersonic

::s
8 expansion
-5.,
I I I I I I There are a total of 12 different symmetry types for the
"os><
N nuclear spin states in C6H6-H20/D20. Of these eight are
=S allowed by the Pauli principle. Many examples are now
~
-5
<I)
known in which little population transfer occurs between
.... states of different nuclear spin symmetry in the collisional
--- 0
.:
cooling of the expansion. This spin selectivity in the cooling
I I I I I
'1... is readily seen in C6H6 itself, where Beck et a1. 38 observed
rovibronic transition intensities in 66 characterized by a ro-
...... ...... ...... ...... N N ......
I
......
I
......
I
......
I
N
I
N
I
."
.~
os

Q:;
tational temperature of 0.5 K, but with a nuclear spin "tem-
perature" which was essentially room temperature. Levels
.~
><
...os of a given nuclear spin symmetry thus effectively have differ-
I
--00

I
____

I I
00

..
-5"
::s
ent zero point energies determined by the lowest energy state
of that nuclear spin symmetry.
.8os
., In C 6H 6-H20(D 20), the m = 0 ground state rotor-
.:
:a
os sionallevels are of antisymmetric (symmetric) nuclear spin
-00----00
~ symmetry with respect to the exchange of water's protons
C!:l.
~ (deuterons), whilem = ± 1 levels are symmetric (antisym-
::s
8 metric). Thus, cooling from m = ± 1 to m = 0 is inhibited
-S in C 6H6 -H2 0/D2 O. The observed consequence is that in
~
~ C 6H6 -H2 0/D2 0, am = 0 transitions will occur originat-
I I
NC"oI__
I I I
MN
I
N ing from both m = 0 and m = ± 1. If either the average
8"" orientation or internal rotor barrier varies slightly upon elec-
Il>< tron excitation, these two transitions will be split, resulting
q::
... ...<:i.
'bO in the observed doubling in the C6H6 -H20 spectrum of Fig.
I I I I
'3 ; 3. We assign the blue-shifted (red-shifted) peak to the m = 0
al .:
'0 .~
e (m = 1) transition. This assignment is borne out by scans
..
....0"
..<:: '8 taken with different nozzle backing pressures which show
I I I I .: ~ that the red-shifted peak (m = 1) decreases slightly in inten-
sity relative to the blue-shifted peak (m = 0) at higher back-

...... ...... ...... ...... N N ...... ...... ...... ...... N N

1 .s
os
.~ . 0
.B
....
ing pressures .
Based on nuclear spin statistics alone, transitions from
tI.:l. .. f:t::::
the m = ± 1 levels in C 6H6 -H20 should be approximately
Ul
Q:; ""'".!l
.: ~ 1::
.gos P...... g- three times the intensity of the corresponding transitions
8~P. from m = 0 (Table III). We observe an m = ± 11m = 0
-tJtt-:6
.:
~~as
....- intensity ratio of about 1.5, indicating some enhancement in
the population of m = 0 C6H6-H20 complexes in the ex-
.~ ~ §
g.~~ pansion. The most likely explanation for the low m = ± 1
~ 'R ; population is that small differences in the binding energy of
~ os ....
• ~ t"' C 6H 6-H z O(m = ± 1) complexes relative to m = 0 com-

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 A. J. Gotch and T. S. Zwier: Multiphoton ionization of clusters. I 3393

C.H.-H 2O C.H.-D2 O C.H.-HDO

B I- orB 2- B tor B 2+ BI or B2
39A I+ + 13A I- +3A,+ 78A t + 39A 1- + 6A ,+ 78A I + 6A 2+
A 2- +21Bt +7B I- 3A 2- + 42B t + 21B 1- 18B I + 42B,+
9B,+3B,- +27Et 18B,+ + 9B,- + 54Et 54E I + 66E2
9E 1- + 33E,+ + lIE 2- 27E 1- + 66E,+ + 33E,-
rio<
m=O A+
I
A+
I Al
m= ± 1 E-I
E-I El
m= ±2 E+
2 E+ , E2
m= ±3 B I- +B,- B I- +B 2- BI +B2

plexes lead to preferential formation of C 6H6 -H2 0 (m = 0)
in binary displacement reactions of the type3S •39
C 6 H 6 -H 20(m = ± 1) + H 20(Ooo)
-+C6 H 6-H 20(m = 0) + H 20(lOl)
in the expansion. In C 6 H6 -D2 0, the m = ± 1 contribution
is only weakly observed in the spectrum, largely because the
m = ± 11m = 0 intensity ratio is six times less in
C 6H 6-D 20 than it is in C 6H6-H20 (Table II). In C6H 6-
HDO, no nuclear spin symmetry restrictions are placed on
the cooling of m = ± 1 to m = 0, effectively removing the
transitions due to m = ± 1 levels from the spectrum so that
only a low-intensity shoulder remains.
In C 6 H 6-H 20, the presence of the doublet complicates
and congests the rotational band contour and hinders its
fitting significantly. However, the C6H6-D20 contour ex-
hibits considerable structure and only minor interference
from m = ± 1, suggesting that our primary efforts in band
contour fitting be focused on the C 6H6 -D2 0 contour.
4. Rotational band contour analysis
a. C6H6-D]O. The rotational band contours of Fig. 3
are 6~ transitions of the isotopomers. By virtue of the degen-
eracy of Vc> (which is not broken by a freely internally rotat-
ing D2 0), the excited state levels populated possess vibra-
tional angular momentum. As a result, our analysis must
take into account three sources of angular momentum about
the top axis due to vibration (5), internal rotation (m), and
overall rotation (k). In the free internal rotor limit, the ener-
gy level expression is simply
E Jkm =BJ(J+ 1) + (Af-B)k 2 + (Af +A t )m 2
- 2Af mk - 2skAf + 2smAf'
where the last three terms couple the three types of angular
momenta. 37 In the expression, Af is the benzene frame rota-
tional constant about the a axis (thez axis), At is the top
rotational constant (which is essentially that of the internal-
ly rotating D 20 molecule), and S is the effective Coriolis
coupling parameter for 61• We further assume that (i) the
transition moment of the 66 transition remains in the plane
of the benzene ring as it is in the free benzene molecule; (ii)
the D 2 0 and C6H6 molecules are not deformed upon com-
plexation; (iii) C6H6 undergoes the same change in geome-
try upon electronic excitation as it does in the free molecule;
and (iv) the nuclear spin temperature within a given m in-
ternal rotor level is TsPin = 300 K. We apply selection rules
appropriate to a perpendicular transition of a symmetric top
with a free internal rotor AJ = 0, ± 1; AK = ± 1; = O. am
Since in the C 6H6 -D2 0 spectrum the m = ± 1 contour ap-
pears only weakly, much of our fitting has been done using
only the m = 0 contour with the m = ± 1 contour playing a
role only in the final stages of fitting. For the m = 0 contour

TABLE III. Nuclear spin statistical weights for the C. H. -H 20, C. H. -D2 0, and C. H. -HDO complexes.

Statistical weights m= ± I"

m=O H2O/D,°
Rotational
wave function r rot b H2O D 20 HDO Positive Negative

k = O,Jeven A I
+ 10 60 60 33 33
k =O,Jodd A,+ 10 60 60 33 33
k=6q±1 E+I 22 132 132 60 54
k=6q±2 E,+ 18 108 108 66 84
k=6q±3 Bj'" +Bt 28 168 168 54 54
k=6q±6 At +A,+ 20 120 120 66 66

"These levelsoccurin degenerate pairs based on the sign ofk *m; positive = 1+ k, + m) ± 1- k, - m), nega-
tive = I + k, - m) ± 1- k, + m).
bIn C bH 6-HDO, the G I2 symmetry designations are obtained by removing the ( + ) superscript.
J. Chern. Phys., Vol. 96, No.5, 1 March 1992

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3394 A. J. Gotch and T. S. Zwier: Multiphoton ionization of clusters. I

(al Expt.

-4.0 -3.0 -2.0 -1.0 0.0 1.0 _~.O 3.0 4.0

Relative Frequency (cm ) (bl Calc.

FIG. 5. (a) Experimental rotational band contour of the 6b transition of
C.H.-D 2 0. (b) The best fit contour calculated using the model described
in the text. The calculated fit corresponds to a center-of-mass separation
distance of3.32 ± 0.07 A in the ground state and 3.23 ± 0.04 A in the excit-
ed state. The Coriolis coupling parameter is - 0.56 ± 0.05. The fit param-
eters are summarized in Table IV.
within this model, the only adjustable parameters are B ", B "
5, and Trot and the spectrum is that of a perpendicular transi-
tion of a rigid symmetric top.
Figure 5 presents our best fit of the C 6 H6 -D2 0 spec-
trum within this model. Note the high quality of the fit both
in terms of positions and in its reproduction of the intensity
alternations present in the experimental contour. The best fit
parameters are given in Table IV. Not unexpectedly, 5 is, to
within our error bars, the same as that for the 66 transition of
free benzene. All essential features are reproduced admira-
bly with only the m = 0 contour. In the best fit presented in
the figure, we have included a small contribution from the
m = ± 1 contour which gives a better fit to the red tail in the
experimental contour for aA, = - 2.2 cm -1.
This fit lends considerable support to our vibronic level
arguments for a C 6H6 -D2 0 geometry in which D 20 is on
the sixfold axis, freely internally rotating about that axis. It
also provides us with a measure of the separation of masses
of C6 H6 and D 2 0 in the ground and first excited singlet
states, yielding a ground state intermolecular separation of
3.32 ± 0.07 A and excited state separation of 3.23 ± 0.04 A.
b. C6H6-HDO. The reduction in symmetry in going
-2.0 -1.0 0.0 1.0
-1
Relative Frequency (cm )
FIG. 6. (a) Experimental rotational band contour of the 6b transition of
C.H 6-HOO. (b) Best fit contour calculated using the model described in
the text. The calculated fit corresponds to a center-of-mass separation dis-
tance of 3.4 ± 0.2 A in the ground state and 3.2 ± 0.05 A in the excited
state. The Coriolis coupling parameter is - 0.05 ± 0.05. The fit parameters
are summarized in Table IV. See the text for further discussion.
from D z 0 to HDO has one major consequence in the present
context-it allows cooling from m = ± 1 to m = 0 internal
rotor levels in the complex. We noted earlier that even on a
qualitative level, the rotational band contour of the 66 transi-
tion of C 6 H6 -HDO confirms our model of an internally ro-
tating water molecule by virtue of its being a single band
(from m = 0) rather than the doublet observed for the 66
contour of C 6H6 -H2 O. It is nevertheless puzzling that the
shape of the contour is so different from that in C 6H6 -H20
and C 6H6 -D2 0 in having a strong Q branch present. In fact,
the m = 0 rotational band contours of C 6 H6 -D2 0 and
C 6 H6 -HDO would be expected to be nearly identical to one
another.
Given the sparsity of structure in the spectrum, we can
only hope to address qualitatively the source of the differ-
ence in rotational band contours. Within our model, the only
adjustable parameter which is capable of qualitatively
changing the shape of the rotational band contour in a physi-

TABLE IV. Summary of the best-fit parameters in the rotational band contour analysis.

A' AH B' BH C' C" t a

••• b
C.H 6-0 2 O 0.0906 0.0948 0.0652 0.0636 " .b -0.56
0.0676 ... b ••• b
CoH6-HOO 0.0906 0.0948 0.0635 -0.05
C6H 6-(H 2 O)2 0.0762 0.0784 0.0511 0.0520 0.0461e 0.0467e ••• d

• Coriolis coupling constant in the 6b bands of the I: I complex. See the text for details.
b The 1: 1 complex is fit as a perpendicular transition of a symmetric top.
e The 1:2 complex is fit as a rigid asymmetric top.
d The rotational contour of the 1:2 complex was taken at the origin which lacks vibrational angular momentum.

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 A. J. Gotch and T. S. Zwier: Multiphoton ionization of clusters. I
cally reasonable way is the Coriolis coupling parameter 5.
Figure 6 presents a best fit of the C 6H6 -HDO contour in
which 5<ff has been reduced from - 0.56 down to
- 0.05 ± 0.05, whileB 'andB" are not changed from that in
C 6 H 6-D20. The calculated contour now reproduces the
overall shape of the experimental contour.
In vibrational levels containing one unit of vibrational
angular momentum, 5 can vary between the limits of - 1
and + I, depending on the type of vibrational motion and
the effectiveness of its coupling with rotation. Typically,
coupling is more efficient for vibrations which involve mo-
tion of heavy off-axis atoms (e.g., the carbon atoms in ben-
zene). Based on the present data, we can only conjecture as
to the reason for the observed change in 5. The ab initio
calculations of Linse z6 predict significant changes in the vi-
brationally averaged eqUilibrium geometry of C 6H6 -HDO
by comparison to C6H6-HzO/D20. Zero point consider-
ations lead to a preference for the deuterium atom pointing
toward the ring in HDO. Accompanying this reorientation
of HDO is a sliding of HDO off the sixfold axis by 0.15 A
(though it is still able to freely internally rotate about the
sixfold axis of C 6H6 ). It is possible, then, that the reorienta-
tion of HDO and its movement off the sixfold axis of C 6H6
changes the effective Coriolis coupling parameter of V 6 ,
leading to the observed change in rotational band contour.
However, higher resolution spectra are clearly needed to test
this hypothesis more carefully.
c. C6H6-H20. The rotational band contour of
C II H6 -H 2 0 is complicated by the overlapping bands present
in the spectrum. The overall contour is dominated by what is
likely the m = ± 1 contour in the red portion of the con-
tour. Unfortunately, unlike the m = 0 contour which is in-
dependent of the magnitude of the barrier to internal rota-
tion, the m = ± 1 band contour is sensitive to this barrier
through the internal rotation/overall rotation coupling
term. 40 In Fig. 7, we present m = 0 and m = ± I band con-
tours for C 6H6 -H2 0 at the best-fit geometry of C 6H6 -D z 0
in the limit of completely free internal rotation for the H 2 0
molecule. The spacing of the structure that is present in the
experimental spectrum is qualitatively consistent with the
calculated contours. However, we are unable to fit the over-
all contour to the same level of satisfaction as in C6H6 -D2 O.
To our consolation, in the high resolution SI contour of
C 6 H6 -N2 ,41 where internal rotation is also present, - 30%
of the observed lines were unassigned and suggested to be
due to the m = ± 1 contour in that complex.
Part of the reason for this less than satisfactory fit ap-
pears to be our assumption of completely free internal rota-
tion. As the barrier to internal rotation is raised, the splitting
and appearance of the two bandheads in the m = ± 1 con-
tour changes significantly.40 In addition, it is possible that
the observed band contour is actually a composite of three
rather than two bands. In fact, the calculations of Linse pre-
dict a near degeneracy of the m = ± 1 level with the inter-
molecular bending mode in the plane of the water molecule.
This level is of a)- symmetry and thus cannot cool to the
m = 0 level, just as the m = ± 1 level cannot. By contrast,
in C 6 Ho -D2 0, the m = ± 1 state has dropped well below
the bending mode so that no such interference should exist.
J. Chem. Phys., Vol. 96, No.5, 1 March 1992
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3395
Expt.
I
-3.0 -1.0 1.0 3.0 5.0
-1
Relative Frequency (cm )
FIG. 7. -is the experimental rotational band contour ofthe 66 transition of
Co Ho -H2 0; ... is the calculated m = 0 and m = ± 1 internal rotor con-
tours at the same geometry as in Co Ho -D2 0 with rotational constants and
statistical weights adjusted for H 20. As in the case of Co Ho-D2 0, the
m = ± 1 contour is less intense than predicted based purely on nuclear spin
statistics. See the text for further discussion.
We have in fact obtained a satisfactory fit to the C 6H6 -H 20
transition by including contributions from all three bands,
but cannot claim uniqueness given the large number of ad-
justable parameters such a fit allows. As with C 6 H 6-HDO,
higher resolution spectra are needed before a full account of
the observed rotational band contour in C 6 H6 -Hz 0 can be
given.
5. van der Waals structure in C6 H6 -H2 0, C6 H6 -HDO,
and C6 H6 -D2 0
In recording spectra of the van der Waals structure of
the complexes, we are motivated by the insight such spectra
can give to the form of the potential energy surface govern-
ing the interactions of C 6H6 and H2 O. Six intermolecular
modes are formed upon complexation ofH2 0 to C 6H 6. Due
to the internal rotation of the H2 0 molecule about the z axis,
the descriptions and symmetries of the intermolecular
modes are best defined in terms of an axis system which
rotates with the water molecule [Fig. 4(b)] rather than one
which is fixed on benzene [Fig. 4(a)] as is done in our refer-
ence configuration. We define this axis system so that the z
and z' axes coincide, the x' axis is placed in the plane of the
water molecule along H 7 , and the y' axis is perpendicular to
this plane. Three of the intermolecular modes will be corre-
lated asymptotically with translations of the water molecule:
(i) a stretch along the z (z') axis Sz'; (ii) a bending mode in
the plane of the water molecule along x', bip ; and (iii) a
bending mode out of the plane of the water molecule alongy',
bop. The other three modes are correlated with rotations of
water: (iv) internalrotationaboutz; (v) torsion of the water
molecule in its plane about the y' axis, tPip, and (vi) torsion of
the water molecule "out of plane" about the x' axis, tPo p •
These modes are illustrated in Fig. 4(c) and their symme-
tries in G24 and G12 are collected in Table V.
The facile formation of the 1:2 complex, coupled with its
extremely efficient fragmentation into the 1:1 channel fol-
3396 A. J. Gotch and T. S. Zwier: Multiphoton ionization of clusters. I

TABLE V. Symmetry and assigned frequencies of the van der Waals modes terference from the 1:2 complexes is negligible. Table VI lists
in C.H.-H 20, C.H.-HDO, and C.H.-D 20. the observed transition frequencies (relative to the 6b transi-
tion of the corresponding complex) and their intensities.
Symmetry Assignment (cm - I)
In approaching an assignment of these features, several
vdWmode G24 G12 H 2O HDO D 20 comments should be made. First, we are guided in our as-
signments by the ab initio calculations of the ground state
b ip a l- al 43 43 43 C6 ~ -H2 OIHDOID2 0 intermolecular modes by Linse. 26
al- aI 94 77 66
Since the R2PI spectra determine excited state frequencies,
"'iP
s. at al 60 61 59
a2-
the comparison can be only semiquantitative; nevertheless,
bop a2
a2- a2
the small intensity of the van der Waals transitions suggests
"'op
Internal rotation' only modest changes in the vibrational frequencies upon
"'. electronic excitation. Second, isotopic substitution will pro-
'The symmetries of the internal rotor levels are given in Table II. duce only slight changes in the stretching and bending mode
frequencies (which involve motion of the water molecule as
a whole), while the frequencies of the torsional modes will be
lowing photoionization, makes it difficult to view the van der quite sensitive to isotopic substitution. Third, as Table V
Waals structure of the 1:1 complex free from interference indicates, the reduced symmetry of the C6H6-HDO com-
from the 1:2 complex. Nevertheless, careful control of water plex results in the bip and tPip fundamentals becoming al-
concentrations in the expansion (down to concentrations of lowed (a l in G I2 ), even though they are forbidden in
0.01 % H 20 in helium) allow the recording ofR2PI spectra C 6H6-H20 and C 6H 6-D 20 (a l- in G24 ). Fourth, Linse's
largely free from such interference, albeit at low signal-to- calculations26 predict that significant state mixing between
noise ratios. A series of such scans taken at different H 20 the intermolecular modes will be more the rule than the ex-
concentrations readily identifies the transitions due to the ception. This is suggested already in a cursory inspection of
1: 1 complex. Figure 8 shows the scans of C 6H6 -H20, C 6H6 the spectra which reveals little in the way of harmonic pro-
-HDO, and C 6H 6-D20 taken under conditions where in- gressions which can aid the assignment. Such mixing can
significantly change intensities and positions from their un-
coupled values and can render the assignment of the transi-
tion in terms of uncoupled normal modes approximate at
best.42 We thus present here a consistent set of assignments
which must await future calculations and/or dispersed flu-
orescence data as further tests of their reliability.
Of the six van der Waals modes present in the complex,
bipG>iP
only the stretching mode fundamental (sz ) will be allowed in
I (a' CsHs- H20 C 6H 6-H 20ID 20. Even overtones and totally symmetric
combination bands of the bends and torsions may also be
present. In C 6H6 -HDO, the in-plane bend and torsion will
also have allowed fundamentals (Table V). Only two bands
of significant intensity appear in the spectra of all three isoto-
pomers with little change in frequency; namely, those 60 and
86 cm - I blue of their respective 6b transitions. One of these
is almost certainly the stretch Sz, while the other is likely an

TABLE VI. Observed van der Waals transitions built on the 6~ transitions
ofC.H.-H 20, C.H.-HDO, and C.H.-D 20.

H 20 HDO D 20
o 100 200
-1 Relative Relative Relative Relative Relative Relative
Relative Frequency (cm ) frequency' intensity frequency' intensity frequency' intensity
(cm- I ) (cm- I ) . (cm- I )

FIG. 8. R2PI scans taken under conditions in which the van der Waals 0 1.00 0 1.00 0 1.00
structure built on 6~ transition is observed clearly in the I: I mass channel. 60 0.22 43 0.33 59 0.30
(a) C.H.-H 20; (b) C.H.-HDO; and (c) C.H.-D 20. The frequency 86 0.18 61 0.18 85 0.23
scale given is relative to the 66 transition of the complex at 38 658, 38 665, 110 0.12 77 0.30 91 0.18
and 38 659 cm - I, respectively. The water concentration for each scan was 141 0.18 86 0.17 113 0.23
kept at 0.0 1%-0.02 % to minimize interference from the 1:2 complex frag- 124 0.25 124 0.12
menting into the 1: 1 mass channel as noted in the figure. The feature at 170
cm - I in the C. H. -HDO scan is not due to C. H. -HDO. See the text for a "The absolute frequencies of the 66 transitions of C.H.-H 20, C.H.-
discussion of the proposed assignments. HDO, and C. H. -D2 0 are 38 658, 38 665, and 38 659 cm - I, respectively.

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 A. J. Gotch and T. S. Zwier: Multiphoton ionization of clusters. I
even overtone of one of the bends which would also show
little sensitivity to isotopic substitution. Since reasonable ar-
guments can be given for either band being the symmetric
stretch, we use the C6H 6-HDO spectrum of Fig. 8(b) to
guide our choice. Two new transitions at 43 and 77 cm - 1 are
observed in the C6H6-HDO spectrum with good intensity.
Their absence in the G24 isotopomers suggests an assignment
of the features as the in-plane bend and torsion fundamentals
which become allowed in C6H6-HDO. Linse's26 calcula-
tions in the ground state place the in-plane bend and torsion
at 20 and 50 cm - I, respectively. As a result, we tentatively
assign the 43 cm - 1 peak as b ;Ip 0 and the 77 cm - 1 transition
as tPjlpO' Then the 86 cm - I transition in the three isoto-
r
pomers is assigned as b p 0' relegating the stretch fundamen-
tal to the transition at 60 cm - I.
Finally, we tentatively assign the peaks at 141, 124, and
113 cm - 1 in C6H6 -H2 0/HDO/D20 as the totally sym-
metric b jlpotPlp 0 combination band. Based on the assign-
ments of tP;p and bip in C6 H6 -HDO, the combination band is
predicted at 120 cm - I. Corrections of tPip for changes in the
reduced mass of the torsion accompanying isotopic substitu-
tion predict the combination bands to Heat 137,120, and 109
cm - I in the isotopic series, close to that observed.
C. CsHs-(H20)2 and Ce Hs -(D 20)2
We indicated earlier that, unlike the single water mole-
cule in C6H6-H20, the pair of water molecules in
C 6H6 -( H 20) 2 induce an origin intensity which is about
14% that at 66. One may conclude on this basis that the
water molecules bind to benzene in such a way as to reduce
the symmetry of the benzene 1T cloud to lower than threefold
symmetric.
By the same token, the degeneracy of the 66 transition is
observed (Fig. 2) to be split by 5.4cm - I in C6H 6-(H20h.
The case ofC6Hs D (whose 66 transition is split by 3.2 cm - 1
even though its origin transition is not observed43 ) suggests
that mass effects, rather than electronic effects are of pri-
mary importance in determining the 66 splitting. In
C6HI> -( H 20) 2' the observed 66 splitting thus suggests that
the water molecules are aligned preferentially along a given
axis of the benzene ring, so that more mass is effectively
moved when the benzene ring deforms along one axis than
along the other. Both these vibronic level arguments are con-
sistent only with a distinctly asymmetric structure for
C6H6 -( H 20) 2' even on a vibrationally averaged basis.
1. Rotational band contour analysiS
Figure 9 (a) shows the rotational band contour of the
origin transition ofC6 H 6 -(H 20)2' Unlike the C6H6-H20
contour, the spectrum shows no evidence of tunneling split-
tings at our resolution, though such may be present at higher
resolution. As a result, we have carried out a rotational band
contour analysis of this transition treating the
C6 Ho -( H 20) 2 complex as a rigid asymmetric top. We have
been guided in our fitting by Monte Carlo searches for the
lowest energy structures for C6H 6 -(H 2 0)2 using the se-
miempirical intermolecular potential of Severance and Jor-
J. Chern. Phys., Vol. 96, No.5, 1 March 1992
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3397
(al Expt.
(b) Calc.
-1.5 1.5
-1.0 -0.5 0.0 0.5 -1 1.0
Relative Frequency (cm )
FIG. 9. (a) The experimental rotational band contour of the So-S, origin
transition in C 6 H 6 -(H 2 0)2' (b) The best fit contour using a rigid asym-
metric top model.
genson. 14 Figure 9(b) presents our best-fit contour which
reproduces nicely both the positions and intensities of the
partially resolved structure in the experimental contour.
The strong Q branch observed in the contour is charac-
teristic of a mixed contour containing components of the
transition moment along both A and B axes of the cluster.
Roughly speaking, the A axis of the complex follows the line
joining the benzene center of mass to the water dimer center
of mass. If the direction of the transition moment remains in
the plane of the benzene ring in C6H 6-(H 2 0)2' moving the
water molecules off the sixfold axis increases the percent A
character in the contour, thereby increasing the Q-branch
intensity as observed.
The rotational constants obtained from the fit are sum-
marized in Table IV. At the present experimental resolution,
the rotational band contour is sensitive only to the positions
of the centers of mass of the two water molecules and not to
the position of their hydrogen atoms. The water center-of-
mass positions are shown in Fig. 10, together with pictures of
two possible structures in which the hydrogen atoms have
been placed in chemically intuitive positions.
Several features of the structure ofC6 H 6-(H20)2 de-
serve highlighting.
(a) The best-fit structure places the water molecules on
the same side of the benzene ring at a water-water separation
of 2.75 ± 0.10 A.. This distance is close to, but slightly less
than that in the free water dimer (2.98 A.).
(b) As indicated in Fig. lOeb), the band contouris best
fit by a structure in which the on-axis water molecule is
pulled in by -0.3 A. from that in the C6H6-H20 complex.
(c) The water dimer intermolecular axis is tilted down
slightly (by about 10°) toward the benzene ring from a ge-
ometry parallel to the benzene ring.
ed) The mixed A / B character ofthe band contour iden-
3398 A. J. Gotch and T. S. Zwier: Multiphoton ionization of clusters. I
~
0
1
........ H
-0
/
H
/. ........ H_rI H
H HH
4.0
1 :1
+
1:2,
3.0 x :
I
I 1 :2
x
1.0
H C
o.0 ;,...,...,.,...p.".....-r!H,..,.,..........,.,..~Lr,L..-rII...,...,...,....,.
-3.0 -2.0 -1.0 0.0 1.0 2.0
Ax (A)
FIG. 10. (a) Best fit center-of-mass positions of the water molecule(s) in
the C. H. -H20 and C6 H6 -(H20) 2 complexes. The center-of-mass separa-
tion distances between the subunits are benzene-water#1 = 2.97 A,
fJ 1 = 97"; benzene-water#2 = 3.39 A, fJ2 = 46°; water#l-water#2 = 2.75
A. Errors in distances are ± 0.10 A, in angles ± 2°. Two plausible geome-
tries are given at the top of the figure since the hydrogen positions are com-
pletely undetermined at our resolution. The complex may be able to tunnel
between these structures. See the text for further discussion.
tifies unambiguously the water dimer orientation relative to
the benzene ring. The IB2U .... IAlg transition in C6H6 re-
duces to a lA' .... IA ' transition in Cs «(Td)' This places the
allowed transition moment in the (Td plane (i.e., bisecting a
C-C bond in the ring), resulting in a mixed A /B band con-
tour, as observed. By contrast, if the water dimer orientation
is rotated to be along a C-H bond [i.e., Cs «(Tv)], the
SI (A ") .... So (A ') transition is allowed only for a transition
moment perpendicular to the (Tv plane, resulting in a Cband
contour, at odds with that observed. Thus, the orientation of
the water dimer relative to benzene is that shown in the top
of Fig. 10. The preference of the water dimer for a single
orientation confirms the vibronic level arguments (based on
the induced origin intensity and the splitting of 6 1 ) which do
not allow for internal rotation of the water dimer about the
sixfold axis. While this may at first seem at odds with the
result of free internal rotation in C6H6 -H 2 0, it follows nat-
urally from the much reduced internal rotation constant of
the water dimer ( - 0.4 em - I) which requires only a small
barrier to localize its orientation with respect to the benzene
ring.
The major conclusion of our fitting is obvious-the
strong hydrogen bonding between the two water molecules
results in a geometry for the C6 H 6 -(H20)2 cluster in which
both molecules reside on the same side ofthe ring in a slightly
modified water dimer geometry. In some sense, the cluster
has taken the first step along the way toward immiscibility.
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(al
3.0 o 20 40 60 80
Relative Frequency (cm )
-1
FIG. 11. R2PI scans highlighting the van der Waals structure built on the
origin transitions of (a) the C6 H 6 -(H 20)2 and (b) the C.H 6 -(D 20)2
complexes. The frequency scale given is relative to the <Po transition of the
complex at 38 167 and 38 166 cm -I, respectively. Note the absence of a
transition near 5.5 cm - I in C6 H 6 -(D 2 0)2' These scans are recorded moni-
toring the 1:1 mass channel in R2PI due to the efficient fragmentation of
these complexes by loss of a single water molecule following photoioniza-
tion.
Given the choice between bonding to the first water mole-
cule or solvating the other side of the benzene ring, the sec-
ond water molecule has chosen its primary bonding to be
with the other water molecule. This is no surprise from an
energetic stand point. The water dimer binding energy is
known to be significantly greater (De = 5.4 ± 0.2 kcall
mol)44 than that calculated for the C 6H 6 /H 2 0 bond [De
:::::3.4 kcallmol (Table VII!)]. Thus, in forming
C6 H 6-(H2 0h, the geometry is dictated foremost by the
strong water-water hydrogen bond at the expense of a some-
what poorer interaction of the second water molecule with
the benzene ring.
The more subtle features of the geometry (points a-c
above) are near the limit of our ability to distinguish in our
band contour fitting, but appear to be real. The role, if any,
played by three-body interactions45 in influencing these fea-
tures is an intriguing, unexplored area. It is notable that the
water dimer separation in C 6 H 6 -(H 2 0)2 is nearly that
found in bulk ice. The structure thus may reflect on a molec-
ular scale the first stages of the increased order of the
aqueous phase which is proposed to occur at a
hydrocarbon/H2 0 interface. 12,13
2. van der Waals structure in C 6 H 6 -(H2 0)2 and
C6 H6 -(D2 0)2
Figure 11 presents R2PI scans of the origin regions of
C 6 H 6 -(H 2 0)2 and C 6 H 6 -(D2 0)2 monitoring the corre-
 A. J. Gotch and T. S. Zwier: Multiphoton ionization of clusters. I
TABLE VII. Observed van der Waals transitions built on the SO-S, origins
ofC6 H 6 -(H 2 0)2 and C6 H 6 -(D2 0)2'
C6 H 6 -(H 2 O)2 C6 H 6 -(D2 O)2
Relative Relative
frequency· Relative frequency" Relative
(em-I) intensity (em-') intensity
0 1.00 0 1.00
5 0.33
16 0.15 9 0.17
22 0.08 18 0.13
36 0.12 35 0.12
73 0.10 70 0.27
"The absolute frequencies of the <fa transitions of C.H.-(H 20)2 and
C6 H 6 -(D20h are 38167 and 38166 em -I, respectively.
sponding 1: 1 mass channel. The analogous scans of clusters
containing HOO were not recorded due to interference
caused by the fragmentation of several isotopomers [e.g.,
C 6 H 6 -(HOO)z, C 6 H 6 -(HOO)(H zO), and C 6H 6 -
HDO(DzO)] into the possible 1:1 mass channels. The fre-
quencies and intensities of the main features in the
C 6 H 6 -(H zO)2 and C 6 H 6 -(D20)2 spectra are summar-
ized in Table VII. Given the limited data set and the large
number (12) of intermolecular modes in the cluster, defini-
tive assignments will need to await dispersed fluorescence or
stimulated emission pumping experiments and/or calcula-
tions of the intermolecular frequencies in C 6 H 6 -(H2 0)2'
Nevertheless, a few comments can be made. First, of the
12 intermolecular modes of the cluster, we can roughly cate-
gorize six as being associated with motion within the water
dimer, three with translation of the water dimer relative to
benzene (two bends and a stretch), and the other three with
torsional modes of a water dimer subunit relative to benzene.
The sparse set of observed transitions are due to the small
subset of totally symmetric levels of the cluster which have
nonzero Franck-Condon factors from the ground state. By
that virtue, the observed levels will involve motions which
are sensitive to the electronic excitation in benzene. Our ex-
perience in the C 6 H6 -H 20 complex suggests that the in-
plane bend and stretch of the water dimer against benzene
are possible candidates, while comparatively little torsional
activity is to be expected. Motions within the water dimer
would also seem not to be likely candidates for significant
Franck-Condon activity. Given the nominally Cs structure
of the 1:2 complex, the in-plane bend and stretch fundamen-
tals will be totally symmetric and allowed.
A comparison of the spectra ofC6H 6 -(H 20)2 to that
ofC6 H 6 -(Dz O)2 shows two bands (at 36 and 73 cm- I )
which have clear counterparts in the deuterated species with
little frequency shift following isotopic substitution (at 35
and 70 cm - I, respectively). These could be assigned reason-
ably as the fundamental and overtone of the in-plane bend.
However, given the weakness of the fundamental band, one
would expect negligible intensity in the overtone. It seems
likely then that the 70 cm - I band contains a significant con-
tribution from the benzene-water dimer stretch and we ten-
tatively assign it as such.
J. Chern. Phys., Vol. 96, No.5, 1 March 1992
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3399
Lower frequency bands show large frequency changes
upon isotopic substitution, indicating that significant H/D
motion is involved. The most intriguing of these is the satel-
lite band of only 5.4 cm - I built on both the origin and 16
cm- I transitions in C 6 H 6 -(Hz O)2' Given the comparati-
vely light masses of the water molecules, it seems highly
unlikely that this transition is a fundamental of a vibration.
A corresponding band is not readily observed in
C 6 H 6 -(Dz O)z. However, a careful look at the origin in
C 6 H 6 -(D20)2 suggests that the 5.4 cm -I splitting in
C 6 H 6 -(H20)2 has been reduced so that the origin band is
actually a composite of two transitions in C6H6 -( O 2O>z.
This anomalous frequency change suggests a tunneling split-
ting as its source. Given the 3:1 ratio in C 6 H 6 -(H z O)z, it
seems likely that the two bands reflect a hindered internal
rotation of one of the water molecules. Then, in a manner
analogous to the C 6H6 -H20 complex, cooling would be
prohibited between the two lowest internal rotor levels in the
ground state, giving rise to a splitting in transitions to the
corresponding levels in the excited state due to a change in
the barrier to internal rotation. One might suspect that the
on-axis Hz 0 molecule could most easily undergo this mo-
tion since this motion does not involve breaking and reform-
ing the water-water hydrogen bond as the hindered rotation
of the other water molecule would. Once again, fully rota-
tionally resolved spectra of the bands of interest are needed
to confirm or deny these arguments.
IV. DISCUSSION AND CONCLUSION
Table VIII collects the various theoretical predictions
for the global and local minima in the C6H6-H20 intermo-
lecular potential energy surface. All calculations agree that
the lowest energy structure for the complex places the water
molecule on the sixfold axis in a 1T hydrogen-bonded config-
uration. A structure which places the water molecule in the
plane of the benzene ring has at most about 60% as strong
binding. 28 The ab initio calculations26-29 predict a benzene-
H 20 center-of-mass separation in the range 3.21-3.33 A,
while semiempirical calculations are ~0.2 A smaller. 14,23
Calculated binding energies for the complex are in the range
of 3.0-4.0 kcallmol. In terms of the more subtle features of
the water orientation relative to benzene, all but one calcula-
tion predict that the water molecule lies in a plane perpendic-
ular to the benzene plane. However, there is more variation
in the predicted orientation of water within this plane, i.e.,
whether water is 1T hydrogen bonded to benzene via one or
two hydrogen atoms. The semiempirical potential of Sever-
ance and Jorgenson l4 favor a single hydrogen atom down,
while others show large-amplitude bending motion in which
both hydrogens sample the benzene ring equally already at
the zero point level. 23,26-29
The major results of our work are in substantial agree-
ment with the calculational results, especially the ab initio
calculations. The experimental structure places the water
molecule's center of mass on or very near the sixfold axis.
The center-of-mass separation is 3.32 ± 0.07 A, very much
in keeping with the calculations. At the present resolution,
we cannot determine the vibrationally averaged orientation
3400 A. J. Gotch and T. S. Zwier: Multiphoton ionization of clusters. I

TABLE VIII. Geometry and binding energy of benzene-H 2O. A comparison of our experimental data with
theoretical predictions for the 1: I complex.

;~p ;~ R c .m . E bind .
Source (degree) (degree) (A) (kcaVmoi)

0 0 3.21 3.04
0 -5 3.21 3.15

b
• 4.76 1.90
0 0 3.28 3.01
28 0 3.28 3.07
0 0 3.32 3.4
0 0 3.33 3.81
52 0 3.33 3.56
-49 0 3.04 3.80
0 -60 3.1 1.44
This work Hbondingh 3.32 ±O.OT 1.63<D:; <2.7Si

• Reference 28.
b Reference 26.
cReference 29(a).
d Reference 27 .
• Reference 14.
fReference 23.
'Water molecule coplanar with the benzene ring with the water oxygen atom pointing towards the benzene
hydrogen atom.
h The precise minimum-energy orientation is not determinable at the present experimental resolution. Indirect
measures are used to surmise that the H 20 molecule is hydrogen bonded to benzene's 1T cloud (see the text).
iThe R c.m . is given for C6H6-D20.
j Bounds on the binding energy are determined from dispersed fluorescence spectra. Note that these are Do
rather than the D. values of the calculations. Details will be published elsewhere.
k The in-plane torsional angle is defined so that r:t corresponds to the C 2 axis of H 20 aligning along the C 6 axis of
benzene with the water hydrogens pointing down. See Fig. 4(b).
I The out-of-plane torsional angle is defined so that r:t corresponds to the plane of the water molecule lying
perpendicular to the plane of the benzene ring. See Fig. 4(b).

of the water molecule relative to benzene. Nevertheless, the
doubling in the C 6H6 -H20 spectrum, its disappearance in
the spectrum of C 6H 6-HDO, and the calculated fit to the
band positions and intensities using the G24 nuclear spin sta-
tistics provide strong arguments that the exchange of hydro-
gens on water is feasible, independent of the precise orienta-
tion of the water molecule. As pointed out earlier, this is not
surprising given the large internal rotation constant ofH2 0
which would require a very large V6 barrier to quench inter-
nal rotation in the complex.
There are several obvious features of the intermolecular
interactions which have not been addressed adequately by
this study. Among these are an experimental determination
of the ground state intermolecular vibrations (which would
allow direct comparison with Linse's calculations) ,26 more
accurate measures of the binding energy of the complex, and
fully rotationally resolved scans in both the ground and ex-
cited states. We are presently pursuing experiments aimed at
the first two deficiencies.
The present study has also provided the major features
of the structure of the 1:2 complex. This structure is best
described as a water dimer in which one of the water mole-
cules is hydrogen bonded to benzene's 1T cloud. Both the
rotational band contour and vibronic level arguments are
consistent with a vibrationally averaged structure in which
internal rotation about the sixfold axis of benzene is no long-
er feasible. The direction of the transition moment points to
a preference of the off-axis water molecule for a position
which bisects a C-C bond in the ring. There are also several
features of the structure which are near the limit of our reso-
lution and which by that fact deserve closer attention both
experimentally and computationally. Most notable among
these are the benzene-water intermolecular separation
(which is reduced relative to C 6 H 6-H 20), the water-water
separation [which is reduced relative to (H 20)2], and the
tilting of the water dimer axis relative to the benzene plane.
On the experimental front it will be important (i) to deter-
mine ground state frequencies and assignments of the inter-
molecular modes; (ii) to record and analyze high resolution
scans capable of resolving tunneling splittings in the com-
plex, and (iii) to determine accurate C6H6-H20 and
H2 0-H2 0 binding energies in the cluster.
From the computational viewpoint, the Monte Carlo
simulations using the intermolecular potential of Severance
and Jorgenson 14 has already proven successful in reproduc-
ing the gross features of the C 6H 6-(H 20)2 structure. How-
ever, to the author's knowledge, there are no ab initio calcu-
lations on benzene-(H 2 0)2' Ab initio predictions of the
geometry of C 6H 6-(H 2 0)2 and its vibration-libration
structure would be highly desirable.
ACKNOWLEDGMENTS
The authors gratefully acknowledge Dan Severance for
carrying out Monte Carlo simulations on the 1:2 cluster.
Acknowledgment is also made to the Donors of the Petrole-

J. Chern. Phys., Vol. 96, No.5, 1 March 1992

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 A. J. Gotch and T. S. Zwier: Multiphoton ionization of clusters. I
urn Research Fund, administered by the American Chemi-
cal Society, and to the National Science Foundation (Grant
No. CHE-9108376) for their support of this research.
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