JOURNAL OF CHEMICAL PHYSICS VOLUME 114, NUMBER 12 22 MARCH 2001

Low-temperature dynamics and spectroscopy in exohedral rare-gas C60

fullerene complexes
A. Ruiz, J. Hernández-Rojas, J. Bretón, and J. M. Gomez Llorentea)
Departamento de Fı́sica Fundamental II, Universidad de La Laguna, 38205 Tenerife, Spain
共Received 14 August 2000; accepted 5 January 2001兲
The adatom dynamics in exohedral C60 fullerene complexes of rare-gas atoms are studied with a
three degrees of freedom model. The eigenvalue problem of the corresponding quantum
Hamiltonian is solved and the electric-dipole spectra for ArC60, NeC60, and HeC60 in the
low-temperature range from 5 to 40 K are simulated. The most important spectral features are
related to the degree of angular anisotropy in the adatom–C60 interaction. The ArC60 and NeC60
complexes present very simple spectra which can be assigned in terms of three-mode oscillators; the
corresponding motion takes place in the deep hexagon wells 共also in the pentagon wells for NeC60)
of the interaction potential. On the contrary, the HeC60 complex shows more complicated spectra
with important tunneling effects due to the smaller angular anisotropy of the interaction. The onset
of almost free internal rotation takes place in this complex at rather low energies, and this gives rise
to a low-frequency rotational band in the spectra at temperatures above T⬃15 K. © 2001
American Institute of Physics. 关DOI: 10.1063/1.1350918兴

I. INTRODUCTION large polarizability values are not longer observed.5 The

The discovery and synthesis of C60 and other fullerenes
has given rise to a whole class of new molecular species
known as fullerene complexes. The simplest of these systems
are formed by an atom or small molecule trapped either in-
side 共endohedral complexes, X@C60) or outside 共exohedral
complexes, XC60) the fullerene cage. Examples of X are
alkali and other metal atoms, rare-gas atoms, small diatomic
molecules such as CO, etc. While endohedral complexes are
extremely difficult to produce in macroscopic quantities, the
exohedral ones can be obtained by standard procedures and
constitute the building blocks of doped fullerites. Very inter-
esting properties and important applications have been either
found or suggested for these new materials. All this has
stimulated the experimental study of exohedral complexes in
gas phase. For instance, photoionization time-of-flight mass
spectroscopy has been used to analyze the abundance of al-
kali and alkaline-earth Xn C60 complexes 共n in the range
0–500兲;1,2 low-energy molecular-beam techniques have pro-
vided information on the interaction between C60 and Na
⫺
clusters;3 electron photo-detachment experiments on Nan C60
have given information on the electronic structure and inter-
action of these complexes.4
Recent experiments that use molecular beam deflection
techniques have even revealed information on the dynamics
of the adsorbed atom on the fullerene surface5,6. With these
methods the polarizability of KC60 has been measured as a
function of temperature in the range from 300 to 483 K; the
very high values found for such electronic property are at-
tributed to the almost free skating of the potassium atom on
the C60 surface at those temperatures. At low temperatures
the K atom is trapped in the surface potential wells and the
a兲
Electronic mail: jmgomez@ull.es
same techniques were applied to the RbC60 complex and
provided, in this case, a value of the barrier activation energy
of 20 meV for the rotational motion of the alkali metal on the
C60 surface.6
The internal rotational–vibrational dynamics are, there-
fore, interesting aspects of these molecular systems. Sup-
ported by the latter experimental results, one may imagine
the adatom having a very complicated motion with a radial
共i.e., out-of-surface兲 stretching mode, and two angular 共i.e.,
on-surface兲 modes which may be either bendings, when the
adatom is trapped in the surface potential wells, or internal
rotations when it has enough energy to cross over the surface
barriers; all these motions may further interact with the
fullerene vibrations and rotations. As is well known, molecu-
lar spectroscopy is one of the most direct experimental ways
of obtaining detailed information on this motion. To our
knowledge, no experimental spectra have been reported so
far, thus the development of reliable theoretical models to
predict them becomes of great relevance in understanding
these dynamics and in guiding future experimental work.
These are main goals of this paper.
The interaction between the fullerene molecule and the
adatom is a determining factor in the molecular dynamics.
Ab initio data on this interaction is sparse and almost inex-
istent for exohedral complexes.7 However, if we restrict the
class of complexes to those with closed-shell electronic
structure, semiempirical methods can be used to construct
reliable potential energy surfaces.8–11 This has motivated our
choice of the exohedral complexes of rare-gas atoms, for
which the interaction is of van der Waals-type. These are
also very convenient molecular systems from the experimen-
tal point of view. As a matter of fact, in the last two decades
many spectroscopic techniques have been used in the study

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J. Chem. Phys., Vol. 114, No. 12, 22 March 2001
of similar 共in principle兲 aromatic rare-gas van der Waals
complexes.12
Theoretical rotational dipole and Raman spectra have al-
ready been predicted by our group for endohedral fullerene
complexes such as Li⫹ @C60, Na⫹ @C60, CO@C60,
LiH@C60, and LiF@C60. 9,13–16 The strong confinement con-
straints existing in these molecular systems simplifies con-
siderably their numerical treatment by allowing the separa-
tion of the internal rotational motion of the guest species
from all other motions. This is not possible, in general, for
the exohedral complexes which will, therefore, require a si-
multaneous treatment of the adatom rotations and vibrations.
In this work we present electric-dipole spectra for the
exohedral complexes HeC60, NeC60, and ArC60 in the tem-
perature range from 5 to 40 K. The analysis of these spectra
will display the important effect of temperature and show
how the adatom on-surface dynamics can change from bend-
ing vibrations to almost free rotations. In Sec. II we present
the effective Hamiltonian for the rotational–vibrational mo-
tion of the adatom. Section III gives some details of the
calculations and presents the structure of the eigenvalue
spectrum for the effective Hamiltonian. Section IV presents
and analyzes the electric-dipole spectra. The main conclu-
sions are put together in Sec. V.
II. AN EFFECTIVE ROTATIONAL–VIBRATIONAL
HAMILTONIAN
The effective Hamiltonian describing the dynamics of an
atom interacting with a C60 fullerene was derived in Refs. 9
and 13 共see also Ref. 17兲. In the body fixed frame it takes the
form
1 2 p r2 l2
H rv⫽ K ⫹ ⫹ ⫹V 共 r, ␪ , ␾ 兲 , 共1兲
2I c 2␮ 2␮r2
where K⫽J⫺l is the fullerene angular momentum operator,
which is the difference between the total angular momentum
J and the atom angular momentum l: I c ⫽ 32 60M R 2 is the
fullerene moment of inertia, with R being the fullerene radius
共3.55 Å兲 and M the C atom nuclear mass; p r is the adatom
radial momentum operator and ␮ ⫽60M m/(60M ⫹m) its re-
duced mass; finally, V is the potential of the effective inter-
action between the adatom and the fullerene, which depends
on the adatom spherical coordinates r, ␪, ␾.
Three approximations were performed to derive Eq. 共1兲:
The usual Born–Oppenheimer separation of the electronic
degrees of freedom, the adiabatic separation of the C60 vibra-
tions, and the standard rigid-rotor approximation for the
fullerene molecule.
The relatively large value of the fullerene moment of
inertia I c makes a full quantal treatment of the fullerene ro-
tation a formidable task; the problem lies in the large number
of J values involved in the rotational spectra, even at the low
temperatures considered here 共J up to ⬃300兲. One must try
then a further approximation. This is the fullerene infinite-
mass approximation discussed in Ref. 9, which is based on
the large ratio between fullerene and adatom masses. The
effective Hamiltonian then becomes
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Exohedral rare-gas C60 fullerene complexes 5157
p r2 l2
H⫽ ⫹ ⫹V 共 r, ␪ , ␾ 兲 . 共2兲
2␮ 2␮r2
This approximation neglects the effects of the fullerene rota-
tion on the adatom motion. As shown in Refs. 9 and 13,
when the spectrum is dominated by radial and bending vi-
brational bands 共as will be the general case in this work兲 the
effect of the fullerene rotations is just a rotational broadening
of the spectral lines, which can be very well reproduced by
coarse-graining the spectra with an appropriate convolution
function.
The reliability of our theoretical analysis will depend
primarily on the accuracy of the C60-adatom effective inter-
action potential V. Symmetry constrains considerably the
form of V; namely, this belongs to the totally symmetric
irreducible representation of the I h point group, which is the
representation and symmetry group of the fullerene elec-
tronic and vibrational ground states used in the successive
adiabatic approximations leading to Hamiltonian in Eq. 共2兲.
We can take advantage of this symmetry by expanding the
angular dependence of the potential V in the spherical har-
monic basis Y L,M
V 共 r, ␪ , ␾ 兲 ⫽2 ␲ 1/2 兺
L,M
c L,M 共 r 兲 Y L,M 共 ␪ , ␾ 兲 . 共3兲
Then only L subspaces that contain the totally symmetric
representation of the I h group can appear; these are L⫽0, 6,
10, 12, 16, etc. As will be seen later, this expansion is very
convenient also for computational reasons.
As mentioned in the Introduction, ab initio data on the
adatom–fullerene interaction is sparse and almost inexistent
for exohedral complexes. However, in our case the total in-
teraction energy, which occurs between two closed shell sys-
tems, is dominated by dispersion-repulsion terms. In such
case, there are in the literature several semiempirical expres-
sions for V. 8,9,11 Here we will use in the potential Y LM ex-
pansion an expression of us which consists of two-body
Lennard-Jones interactions between the fullerene C atoms
and the adatom.8,9 This form has been used in numerical
studies of the classical dynamics of atoms trapped inside and
outside the C60 fullerene, and reproduces accurately enough
the available experimental and ab initio data for both en-
dohedral and exohedral complexes. We then find that a trun-
cation of the expansion in Eq. 共3兲 at L⫽16 gives very good
account of the interaction, specially of those features more
relevant in our study such as main well depths, frequencies
and barrier heights.
Figure 1 presents a view of the potential angular depen-
dence at fixed r for the three rare-gas exohedral complexes.
We observe minima at the pentagon and hexagon centers of
the C60 truncated icosahedrum, hexagon being always more
stable. Figure 2 displays the r-dependence of some of the
Y LM expansion coefficients c L,M (r), and the total interaction
along the C 3 symmetry axis. As can be seen the isotropic
(L⫽0) term dominates the interaction at intermediate-large
distances and practically determines radial equilibrium posi-
tions r e and radial vibrational frequencies. This particular
5158 J. Chem. Phys., Vol. 114, No. 12, 22 March 2001 Ruiz et al.

FIG. 1. The adatom–fullerene interaction V(r, ␪ , ␾ ) as a function of the

polar angle ␪ for ␾ ⫽0 and r⫽r e . One of the C 5 symmetry axis has been
chosen along the z axis of the reference frame, and one of the neighbor C 2
symmetry axis lies on the zx plane. For ␪ ⫽0 the atom is on the pentagon
center; the deep wells occur on the hexagon centers, and maximum values
appear on the C atoms. Equilibrium positions r e are given in Table I.

behavior of the fullerene–atom interaction will simplify con- FIG. 2. Radial dependence 共narrow lines兲 of some of the coefficients
siderably the calculation of the spectrum, as will be seen c L,M (r) in the potential expansion 关Eq. 共3兲兴. The reference frame axes have
next. been chosen as in Fig. 1. Labels are 共L, M兲. The 共0, 0兲 coefficient is the
spherically isotropic contribution to the potential. The thick line gives the
values of the total interaction along the C3 symmetry axis and calculated
III. THE CALCULATION OF EIGENVALUES AND from the potential expansion truncated at L⫽16.
EIGENFUNCTIONS
Led by the differences in radial and angular frequencies
at the potential minima we will write the effective Hamil- The coupling term in Eq. 共4兲 has, consequently, the fol-
tonian in Eq. 共2兲 as the sum lowing expression:
H⫽H vib⫹H rot⫹H coup ,
where H vib and H rot are, respectively, pure radial and angular
共4兲
H coup⫽ 冉
l2 1 1
⫺
2 ␮ r 2 r 2e 冊
⫹V coup共 r, ␪ , ␾ 兲 , 共9兲
Hamiltonians given by
where
p r2
H vib⫽ ⫹V vib共 r 兲 , 共5兲
2␮ V coup共 r, ␪ , ␾ 兲 ⫽2 ␲ 1/2 兺 ⬘ 关 c LM 共 r 兲 ⫺c LM 共 r e 兲兴 Y LM 共 ␪ , ␾ 兲
L,M
with

V vib共 r 兲 ⫽2 ␲ 1/2 兺 c LM 共 r 兲 Y LM 共 ␪ 0 , ␾ 0 兲 共6兲

⫺2 ␲ 1/2 兺 ⬘ c LM 共 r 兲 Y LM 共 ␪ 0 , ␾ 0 兲 .
L,M
共10兲
L,M
We have produced a convenient basis set 兵 兩 n,l,m 典 其 for
and
the diagonalization of the effective Hamiltonian H, by direct
l2 product of the two eigenstate basis sets corresponding to the
H rot⫽ ⫹V rot共 ␪ , ␾ 兲 , 共7兲 reference Hamiltonians H vib( 兵 兩 n 典 其 ) and H rot( 兵 兩 l,m 典 其 ). This
2 ␮ r 2e
basis is then truncated so as to include all eigenstates of
with H vib⫹H rot with eigenenergies E vib⫹E rot⭐E cut , where E cut is
an energy cutoff which is chosen high enough to ensure con-
V rot共 ␪ , ␾ 兲 ⫽2 ␲ 1/2 兺 ⬘ c LM 共 r e 兲 Y LM 共 ␪ , ␾ 兲 .
L,M
共8兲 vergence of our low-temperature spectra. The angular mo-
mentum states 兩l, m典 were used in the diagonalization of H rot
In these equations ␪ 0 and ␾ 0 define a reference orientation, and the one-dimensional Hamiltonian H vib was diagonalized
which we have chosen along a C 3 symmetry axis 共going using a standard Numerov method. Then all the angular in-
through an hexagon center兲, and r e is the equilibrium radial tegrals required in the calculation of matrix elements were
position along such orientation; in the C 3 case, r e is the analytically obtained in terms of the 3 j symbols, and the
global-equilibrium distance of the potential surface. In Eq. radial ones were evaluated numerically. Symmetry is used to
⬘ excludes the L⫽0 constant term.
共8兲 the sum 兺 L,M separate the H rot and full H diagonalizations in blocks be-

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J. Chem. Phys., Vol. 114, No. 12, 22 March 2001 Exohedral rare-gas C60 fullerene complexes 5159

TABLE I. Some details of the calculations. Values of r e give the adatom-fullerene equilibrium distances along
the C 3 symmetry axis; they correspond to global minima of the interaction potential. The number of l values
included in the diagonalization of H rot is denoted n l 共all m values are included for each l兲. E cut gives a cut-off
energy; all calculated eigenstates of H rot⫹H vib with energies E rot⫹E vib⭐E cut are included in the diagonalization
of the effective Hamiltonian H 共this cut-off restriction was not used for the A symmetry blocks兲. The total
number of these states is denoted n t ; the number of states in each symmetry representation are given in
parentheses.

r e 共Å兲 nl E cut 共cm⫺1兲 n t (A g ⫹T g ⫹G g ⫹H g ⫹A u ⫹T u ⫹G u ⫹H u )

Ar 6.67 112 ⫺220 13 776(1098⫹1659⫹1620⫹2675⫹828⫹1959⫹1592⫹2345)

Ne 6.39 90 ⫺40 6966(574⫹792⫹816⫹1365⫹399⫹1044⫹816⫹1160)
He 6.21 72 100 3768(224⫹432⫹480⫹780⫹140⫹603⫹464⫹645)

longing to the different I h irreducible representations, so that
the larger matrix found in our calculation has dimensions
2675⫻2675. Table I presents more details of the computa-
tion.
Figures 3–5 display the low-energy eigenvalue spectrum
of the effective Hamiltonian for each one of our three
fullerene complexes. The Ar complex shows the simplest
spectrum with lower-energy levels grouped in sets of 20 and
40 almost degenerate states; thus we have either one or two
states from each set for each one of the 20 hexagon wells of
the interaction potential. From this level structure and the
shape of the wave functions 共see an example in Fig. 6兲 we
conclude that at these lower energies the atom can get
trapped in one of those hexagon wells; since the splitting
between the levels in a set, which is due to quantum tunnel-
ing, is so small, such trapping occurs in fact for quite long
times. In each well the motion corresponds to a three dimen-
sional oscillator with a C 3 symmetry; the possible degenera-
cies in this symmetry group are one and two, in accordance
with the numbers given previously. The high-frequency
mode of this oscillator corresponds basically to the radial
vibration, while the other two, more strongly coupled, are
associated to the bending motion on the fullerene surface.
The pentagon potential wells occur at higher energies, so that
possible states influenced by them do not appear in Fig. 3
neither will they contribute in the low temperature spectra.
The He complex has a completely different and more
complicated structure. The analogues of the level sets in
ArC60 have split completely in HeC60, which indicates im-
portant tunneling effects at low energies and the possibility
of nearly free internal rotational motion at higher energies.
All these features are a consequence of the much lower ro-
tational barriers in the interaction potential and the small He
mass. Moreover, hexagon and pentagon potential wells are
very close in energy 共see Fig. 1兲, and both participate then in
the level structure. For instance, the lowest 20 states that
appear grouped in three sets in Fig. 5 correspond to states
whose wave functions are localized on the hexagon wells,
while the next two sets contain together 12 levels with wave
functions localized on pentagon wells of the interaction po-
tential surface 共the number of these wells is 12兲. The wave
functions for higher levels present either localization on both
wells or a more delocalized structure, which is another indi-
cation of more or less hindered internal rotational motion.
The NeC60 system represents a situation intermediate be-
tween that of the other two complexes. Most energy levels

FIG. 3. Low-energy eigenvalue spectrum for the ArC60 complex. Labels on

the right indicate the number of states contained in each energy level. The n
value on the left gives the vibrational excitation of the radial motion and FIG. 4. Low-energy eigenvalue spectrum for the NeC60 complex. Notation
labels the lowest energy state in which such an excitation appears. is as in Fig. 3.

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5160 J. Chem. Phys., Vol. 114, No. 12, 22 March 2001
FIG. 5. Low-energy eigenvalue spectrum for the HeC60 complex. The well
type in which wave functions are localized are given on the right for the two
lowest set of levels; higher states show localization in both hexagon and
pentagon wells in each wave function. Labels on the left give the symmetry
of the states in those two level sets.
can be closely grouped in sets of 20 and 40 states on one
hand, and 12 and 24 states on the other; the former corre-
spond, as in ArC60, to trapping in the hexagon wells, and the
latter to trapping in the pentagon wells; the two well types
are here, as in HeC60, close in energy 共see Fig. 1兲. Tunneling
effects are unimportant at the lower energies included in Fig.
4 and more important at higher energies. In Fig. 6 we present
two of the low-energy wave functions for this complex, one
localized on the hexagon potential wells and the other on the
pentagon wells.
IV. THE ELECTRIC-DIPOLE SPECTRA
For the calculation of the low-temperature dipole spectra
we have used the usual expression for the absorption coeffi-
cient as a function of the angular frequency ␻
␣ 共 ␻ 兲 ⫽CS 共 ␻ 兲 , 共11兲
where
S 共 ␻ 兲 ⫽ប ␻ 关 1⫺exp共 ␤ ប ␻ 兲兴 I 共 ␻ 兲 , 共12兲
FIG. 6. Stereographic projections of the angular dependence of the wave
functions for three A g states; the one in ArC60 shows localization on the
hexagon potential wells; the other two for NeC60 present localization on
either hexagon or pentagon wells. The change in sign of the wave functions
is indicated using different line types.
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Ruiz et al.
FIG. 7. Electric dipole spectra of ArC60 at different temperatures. These
have been coarse grained with a temperature-dependent convolution func-
tion to simulate the broadening effect due to the overall fullerene complex
rotation. The first peak/band at ⬃13 cm⫺1 corresponds to transitions with
one-quantum excitation of the bending motion in the hexagon potential
wells. At higher temperatures such transitions can take place not only from
the ground level but also from excited ones; then mode-coupling and anhar-
monicities in the bending motion make the narrow low-temperature peak
evolve into a broader band. The peak at ⬃37 cm⫺1 corresponds to transi-
tions with one-quantum excitation of the radial motion. Some low-intensity
harmonics are also observed.
and
1
I共 ␻ 兲⫽
Z 兺
i, j
exp关 ⫺ ␤ E j 兴 兩 di j 兩 2 ␦ 关共 E i ⫺E j 兲 /ប⫺ ␻ 兴 . 共13兲
In these equations C is a constant which depends on the
density of molecules, molecule parameters, and electromag-
netic constants;9 Z is the partition function, E i the eigenval-
ues of Hamiltonian in Eq. 共4兲, di j are matrix elements of the
effective electric dipole moment operator d⫽r, with r being
the atom position vector operator per unit charge with re-
spect to the fullerene center. We are assuming a linear de-
pendence of the dipole moment on the position vector opera-
tor.
For temperatures in the range from 0 to 40 K our spectra
are well converged. Figures 7–9 display these spectra coarse
grained, as discussed in Sec. II, with a temperature-
dependent convolution function representing the fullerene
rotational broadening. Here again the ArC60 complex pre-
sents the simplest spectrum 共Fig. 7兲. It is a vibrational spec-
trum whose lines can be assigned to transitions between the
stretching and bending states in each well. At the lowest
temperature the relevant transitions originate from the
ground level set. When temperature increases transitions
from excited levels also appear; their frequencies change
slightly due to potential anharmonicity, which gives rise to
broader vibrational bands.
The NeC60 共Fig. 8兲 complex show similar spectra, with
vibrational transitions. However, both pentagon and hexagon
potential wells contribute in this case, although the transi-
tions from the latter turn out to be more intense. At higher
temperatures, states closer to the potential barriers, where
anharmonicity is larger, contribute; mode-coupling and tun-
J. Chem. Phys., Vol. 114, No. 12, 22 March 2001
FIG. 8. Electric dipole spectra for NeC60 at different temperatures, and
coarse grained as in Fig. 7. The main peak at ⬃12 cm⫺1 in the spectrum at
T⫽5 K corresponds to a transition with one-quantum excitation of the bend-
ing motion in the hexagon potential wells, from the ground level set; its left
satellite peaks have similar origin but from excited bending states. At higher
temperatures mode-coupling, anharmonicities and tunneling effects make
these peak evolve into a broad bending vibrational band, to which one-
quantum excitations of the bending motion in the pentagon potential wells
now also contribute. The intense peak at ⬃35 cm⫺1 corresponds to transi-
tions with one-quantum excitation of the radial motion in the hexagon well;
its small satellite corresponds to the analog transition in the pentagon well.
neling effects are also noticeable in this energy region, and
all this makes the vibrational bands broaden considerably.
The most complicated spectra are shown by the HeC60
complex 共Fig. 9兲. Tunneling effects are already important at
the lowest temperatures so that the vibrational transitions
seen in the two previous cases split now in many lines. When
temperature increases, two main features characterize the
FIG. 9. Electric dipole spectra for HeC60 spectra at different temperatures,
and coarse grained as in Fig. 7. At the two lowest temperatures, bending
transitions split in many peaks due to strong tunneling between different
hexagon and pentagon wells. Above T⫽15 K, a low-frequency internal ro-
tational band appears; this assignment is confirmed by the inset figures,
which give the pure rotational spectrum for a He atom moving as a free
rigid-rotor on the C60 fullerene surface. The peak at ⬃16 cm⫺1 is assigned to
a two-quanta excitation of a bending mode orthogonal to an internal rota-
tional motion that connects the five hexagon wells around each pentagon.
The peak at ⬃53 cm⫺1 is a combination of the previous frequency and the
frequency of the radial vibrational motion.
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Exohedral rare-gas C60 fullerene complexes 5161
FIG. 10. Stereographic projections of the angular dependence of the wave
functions corresponding to the two most relevant state pairs involved in the
bending transition peak observed in the HeC60 complex at ⬃16 cm⫺1 共see
Fig. 9兲. Top figures are for final states in the G g quadruplet. Bottom figures
give the corresponding initial approximate eigenstates obtained as described
in the Appendix. The change in sign of the wave functions is indicated using
different line types. As we see the transition can be assigned to a two-quanta
excitation of a bending mode orthogonal to the internal rotational motion
that connects the five hexagon wells around each pentagon. This transition
brings the adatom very close to the top of the hexagon–pentagon potential
barriers, where it couples with the motion in the pentagon wells.
spectra. One is what looks like a pure rotational band in the
lowest frequency range. Its origin is in the internal rotational
motion that takes place above the surface potential barriers.
A confirmation of this interpretation is given by the similar-
ity between this band and the rotational spectrum of a true
free rotor with a rotational constant calculated at the mini-
mum of the spherical potential term c 00(r) 共see the insets in
Fig. 9兲.
The other relevant feature of the HeC60 spectra at higher
temperatures is the sharp peak around ⬃16 cm⫺1 which can
be assigned dominantly to a set of transitions from 10 states,
very close in energy, to the same G g quadruplet. The wave-
functions corresponding to these initial states present local-
ization on the hexagon wells, while those corresponding to
the final G g states are localized on both pentagon and hexa-
gon wells. By choosing proper linear combinations of the
initial states, as performed in the Appendix, we were able to
reduce all these transitions to only four carrying all the in-
tensity. The new states obtained in this way, which can be,
therefore, taken as approximate eigenstates, present a par-
ticular localization structure, which is displayed in Fig. 10,
together with that of the G g final states. The localization on
the five hexagon wells around a pentagon which we can ob-
serve in this Fig. 10 is indicating that the motion involved in
the sharp spectral feature can be represented as a precession
共strongly mediated by quantum tunneling兲 of the atom posi-
tion vector r around the C 5 symmetry axis. This precession
can be accompanied by the oscillation of the r-C 5 angle, and
it is the excitation of this bending motion which gives rise to
the narrow peak observed in the spectra. From the nodal
5162 J. Chem. Phys., Vol. 114, No. 12, 22 March 2001
structure of the final G g states we deduce that this transition
takes place with interchange of two quanta of the bending
motion. Since this analysis has been applied to the compo-
nent of the dipole moment operator on the C 5 symmetry
axis, it corresponds then to the linear response of the system
to an oscillating electric field along that axis direction. The
analyses for the other two orthogonal components of dipole
moment operator are somewhat more involved. However, as
discussed in the Appendix, one can demonstrate using sym-
metry arguments the equivalence of all three components.
The higher-frequency peaks appearing in the HeC60 spectra
at ⬃53 cm⫺1 and ⬃69 cm⫺1 have the same bending origin,
but in these cases one and two quantum excitations of the
radial vibrational motion also take place, respectively.
V. CONCLUSIONS
Recent gas-phase experiments on exohedral fullerene
complexes are providing interesting data on the interaction
between the adatom and the C60 fullerene. This interaction
determines the adatom dynamics, which take place on the
C60 spherical microsurface. Rotational–vibrational spectra
are a primary experimental source of information on such
dynamics. Since these are not yet available, we have proceed
in this work to their theoretical evaluation and study for the
complexes of rare-gas atoms. Existing experimental tech-
niques to obtain the spectra of similar aromatic rare-gas van
der Waals complexes could be in principle applied to the
fullerene complexes, thus making our choice of particular
interest.
By adiabatic separation of the C60 vibrational motion
and freezing its slow rotations, we were able to reduce the
low-energy dynamics to a problem with three degrees of
freedom, two angular ones representing the on-surface mo-
tion of the adatom on the C60 fullerene surface, and a radial
one giving the out-of-surface vibration. The interaction po-
tential between the rare-gas atom and the fullerene is
strongly constrained by the molecular symmetry; this to-
gether with its van der Waals nature make quite reliable its
estimation by semiempirical arguments. The eigenvalue
problem for the effective Hamiltonian has been solved by
expanding the angular dependence of the wave function in
spherical harmonics and the radial one using a Numerov
method. The eigenfunctions and eigenvectors obtained are
accurate enough to produce converged electric-dipole spectra
in the low-temperature range from 0 to 40 K.
The ArC60 complex presents very simple spectra that can
be assigned in terms of a three-dimensional oscillator with
C 3 symmetry; the corresponding motion takes place in the
deep hexagon wells of the interaction potential; tunneling
between these wells is negligible at these low temperatures.
NeC60 has similar spectra; however, since the pentagon wells
are now deep enough, trapping is also possible there at our
lowest temperatures; excitation of the vibrational motion that
takes place in these pentagon wells gives rise to new lines in
the spectra, although much less intense. At higher tempera-
ture these spectra reflect the increase of anharmonicity, mode
coupling and tunneling effects. Finally, the HeC60 complex
shows quite complicated spectra which reflect the important
tunneling effects. The onset of almost free internal rotation
Downloaded 24 Jul 2009 to 62.76.169.62. Redistribution subject to AIP license or copyright; see http://jcp.aip.org/jcp/copyright.jsp
Ruiz et al.
takes place now at rather low energies, and this gives rise to
a low-frequency internal rotational band in the spectra at
temperatures above T⬃15 K. An intense bending peak also
appears; if the laser field is chosen along the C 5 symmetry
axis, this peak can be easily assigned to a two-quanta exci-
tation of a bending mode orthogonal to the internal rotational
motion that connects the five hexagon wells around each
pentagon.
Concluding, our results demonstrate that low-
temperature dipole spectra of rare-gas exohedral fullerenes
complexes are a source of very detailed and relevant infor-
mation on the adatom dynamics and on its interaction with
the C60 fullerene.
ACKNOWLEDGMENTS
This work has been supported by a grant from the Span-
ish ‘‘Dirección General de Enseñanza Superior’’ 共Grant No.
PB97-1479-C02-01兲. A. R. thanks ‘‘Consejerı́a de Educa-
ción, Cultura y Deportes del Gobierno de Canarias’’ for a
fellowship. We thank Dr. O. Roncero for providing us with
the code for the resolution of the radial Schrödinger equa-
tion.
APPENDIX
The most intense bending peak in the HeC60 spectrum
was assigned to a group of transitions from a set of ten close-
in-energy states (2T u ⫹G u ) to a G g quadruply degenerate
state. In order to establish the dynamical origin of such peak
we have proceed to find four approximate eigenstates by lin-
ear combinations of the original ten initial states, so that the
transitions from these new initial states will carry all the
intensity of the spectral peak.
Let us denote with ␹ i each one of the four G g final states
and with ␾ i each one of the ten initial states. For each com-
ponent d ␣ ( ␣ ⫽x,y,z) of the dipole moment operator we de-
fine the four approximate eigenvalues as the linear combina-
tions
10
1
兩␺ j典⫽ 兺 兩 ␾ 典 c 共 j⫽1,4兲 ,
N j i⫽1 i i j
共A1兲
where
c i j ⫽ 具 ␾ i兩 d ␣兩 ␹ j 典 , 共A2兲
and 1/N j is the normalization constant with
冋兺 册
10 1/2
N j⫽ 兩 c i j兩 2 . 共A3兲
i⫽1
The dipole-moment matrix elements between these four
new initial states and the ␹ i final states can be written then in
the following form:
具 ␺ k 兩 d ␣ 兩 ␹ l 典 ⫽ 具 ␹ k 兩 D̂ ␣ 兩 ␹ l 典 共 k,l⫽1,4兲 , 共A4兲
where the operator D̂ ␣ is
10
D̂ ␣ ⫽ 兺 d ␣兩 ␾ i 典具 ␾ i兩 d ␣ .
i⫽1
共A5兲
J. Chem. Phys., Vol. 114, No. 12, 22 March 2001
Since the four final ␹ i states are degenerate, we can al-
ways fix them so that D̂ ␣ is diagonal in this set. In this way
each new initial state ␺ i will be connected by the dipole
moment operator to just one final state ␹ i . The overall line
intensity of the four transition coincides then with that of the
original transitions, i.e.,
4 10 4 Phys. Lett. 222, 88 共1994兲; S. Iglesias-Groth, J. Bretón, and C. Girardet,
兺 兩 具 ␺ j 兩 d ␣兩 ␹ j 典 兩 ⫽ i⫽1
j⫽1
2
兺 j⫽1
兺 兩 具 ␾ i兩 d ␣兩 ␹ j 典 兩 2. 共A6兲
The three components of the dipole moment operator
belong to the same I h group representation (T u ). Besides,
one can go from one component to the other using the rota-
tion operators R x , R y , R z , which, since they belong to the
T g representation, do not mix initial with final states. Then,
one can easily demonstrate that the analysis performed for
one of the d ␣ components may be conveniently transformed
to analyze completely the other two. In this way, one can
show, for instance, that each one of the three components
gives exactly the same contribution to the spectrum.
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