Journalof MolecularStructure (Theochem), 282 (1993) 187-191 187

0166-1280/93/$06.00 0 1993 - Elsevier Science Publishers B.V. All rights reserved

Electronic structures of the alkali-containing

buckminsterfullerenes (AX& (A = Li, Na, K, Rb, Cs)
and the halogen-containing buckminsterfullerenes
(Ha&) (H = F, Cl, Br, I)
Da-Ren Zhang”, Ji-An Wubpc, Ji-Min Yan*ld
‘Research Center for Eco-Environmental Sciences, Academia Sinica, Beijing 100085,
People’s Republic of China
‘Institute of Semiconductor, Academia Sinica, Beijing 100083, People’s Republic of China
‘Laboratory for Quantum Optics, Academia Sinica, Shanghai 201800, People’s Republic of China
‘Institute of Chemistry, Academia Sinica. Beijing 100080, People’s Republic of China

(Received 20 October 1992)

Abstract

The geometrical parameters and electronic structures of C M),(AX,) (A = Li, Na, K, Rb, Cs) and (HZ,)
(H = F, Cl, Br, I) have been calculated by the EHMO/ASED (atom superposition and electron delocalization)
method. When putting a central atom into the Cso cage, the frontier and subfrontier orbitals of (AX,) (A = Li,
Na, K, Rb, Cs) and (HdC&) (H = F, Cl) relative to those of C M) undergo little change and thus, from the
viewpoint of charge transfer, A (A = Li, Na, K, Rb, Cs) and H (H = F, Cl) are simply electron donors and
acceptors for the C, cage respectively. Br is an electron acceptor but it does influence the frontier and subfrontier
MOs for the Cso cage, and although there is no charge transfer between I and the Cm cage, the frontier and
subfrontier MOs for the Cso cage am obviously influenced by I. The stabilities AEx (AEx = (Ex+ Ecrn)- E~x~,,)
follow the sequence I < Br < None < Cl < F < Li < Na < K < Rb < Cs while the cage radii r follow the
inverse sequence. The stability order and the cage radii order have been explained by means of the (exp-6-l)
potential.

Introduction The determination of the electronic structure of

The football-like Cso molecule had been sug-
gested by chemists in the 1970s [1,2], but it stimu-
lated intense interest only after the discovery of the
compound in experiments in 1985 [3]. Besides Cso
itself, extracage complexes and intracage com-
plexes have also been discovered experimentally
[4-lo]. Cso and its complexes have very interesting
and useful properties, which have promoted many
experimental and theoretical investigations.
* Corresponding author.
the Cm molecule is a very interesting problem and
the structure has been calculated by both ab initio
and semiempirical methods [ 1 l- 161. In addition,
the electronic structures of intracage complexes
are unprecedented in chemistry, so they have a
strong attraction for chemists. The intracage com-
plex, in which an atom X is trapped inside the cage,
is written as (XdC& by means of Smalley’s
symbol [17]. In this paper, the EHMO/ASED
(atom superposition and electron delocalization)
method [18-201 was used to optimize the geome-
tries of the Cm, the alkali-containing C& (AdC6s)
188 D.-R. Zhang et al./J. Mol. Struct. (Theo&m) 282 (1993) 187-191

(A = Li, Na, K, Rb, Cs) and the halogen-contain-
ing Cm (HBC.&) (H = F, Cl, Br, I) molecules and
to calculate their electronic structures. The stabili-
ties of the complexes and the interactions between
Cso and guest atoms were investigated.
Computational method and electronic structure of
the buckminsterfullerene Cso
The semiempirical EHMO/ASED method is a
direct improvement of the EHMO method with
ASED-MO theory suggested by Anderson and
co-workers [18-201, in which the repulsive inter-
action is taken into account. The repulsive energy
acting on b for any a-b pair of atoms in a molecule
is given by
of C60,(AdC60) (A = Li, Na, K, Rb, Cs) and
(HdC@) (H = F, Cl, Br, I).
The VSIPs are taken from experimental tabula-
tions [21] and the orbital exponents, except for
those of C, which are taken from those used for
graphite and diamond [30], are taken from SCF
atomic wavefunctions [22,23]. Parameters used
here are shown in Table 1.
Css is made up of 12 five-membered C rings and
20 six-membered C rings possessing It, symmetry,
so that there are two kinds of bond lengths, long
bond lengths for five-six ring fusion and short
bond lengths for six-six ring fusion, which need
to be optimized. The optimized bond lengths and
those obtained by other calculations and experi-
ments are given in Table 2. For (ABC& and

‘%@b) = zb Za/Rb - Pa(r)/k
[ J
where Z, r and R are the nuclear charge of the
atom, the electron coordinate and the nuclear coor-
dinate respectively. The off-diagonal elements of
the hamiltonian are modified, so that the hamilto-
nian has the form
Hii = -(VSIP)i
Hij = l.l25(Hii + Hjj)Sijexp (-0.13R’)
where VSIP is the valence-state ionization poten-
tial, R’ is the internuclear distance and Sij is the
overlap integral. The EHMO/ASED method can
predict molecular geometry and some other prop-
erties [ 18-201. We used this method to optimize the
geometries and to calculate the electronic structure
1 (1)
(H&&) molecules, the same bond lengths are opti-
- Rbidr mized when the A (A = Li, Na, K, Rb, Cs) or H
(H = F, Cl, Br, I) atoms are kept at the center of
the cage.
From Table 2 it can be seen that the bond lengths
obtained by the EHMO/ASED method are in good
agreement with the experimental values. The sym-
metries and degeneracies of energy levels obtained
(2) by the EHMO/ASED method are consistent with
those obtained by other methods. Table 3 presents
(3) the energy levels of frontier orbitals and some other
orbitals. The shake-up spectra of the X-ray photo-
emission of Cso indicated that the lowest electronic
transition is 1.9 eV [15], which can be explained on
the basis of monopole transition. In the distribu-
tion of energy levels given here, HOMO(4HJ +
LUMO(ST,,) is symmetry forbidden, so the low-

Table 1
Orbital exponents (C) and ionization potentials (VSIP) (eV)

Li Na K Rb CS

c 0.6396 0.8358 0.8738 0.9969 1.0605

VSIP 5.392 5.139 4.341 4.180 3.890

C F Cl Br I
c 1.8174 2.5638 2.3561 2.6382 2.6807
1.7717 2.5500 2.0387 2.2570 2.3223
VSIP 16.59 37.85 24.54 23.80 20.61
11.26 17.42 12.97 11.85 10.45
D.-R. Zhang et aI.lJ. Mol. Struct. (Theochem) 282 (1993) 187-191 189

Table 2 original C,; (3) there is a long distance between

Calculated and experimental bond lengths of CW the center atoms and the C atoms on the Cm cage.
Method Bond length (A) Ref. The energy of the p atomic orbitals of Br (see Table
1) is close to that of the HOMO for Cm, so there is
Short Long a greater influence on the frontier and subfrontier
molecular orbitals of original Ca. The energy of
X-Ray 1.388 1.432 24
13C NMR 1.400 1.450 25 the p atomic orbitals of I (see Table 1) is between
STO-3G 1.376 1.465 11 those of the HOMO and LUMO for Cm, so there
DZ basis set 1.369 1.453 12 is the greatest influence on the frontier and sub-
4-31G 1.370 1.450 16
frontier molecular orbitals of original Cso.
MNDO 1.400 1.474 13
IND0/2 1.398 1.451 14 In Table 5 the stabilities AEx (AE= (Ex+
EHMO/ASED 1.389 1.457 This work EC,) - EfxBc,)), gaps and charges of the center
atoms for (AXha) (A = Li, Na, K, Rb, Cs) and
e&-lying allowed transition is HOM0(4H,) + (HaC& (H = F, Cl, Br, I) are presented. From
LUMO + 1(2T,,) and its value is 2.2eV, which is the data in Table 5, it is shown that the stability
in quite good agreement with experiment. order when an atom is put into the center of the (?,a
The results presented in Table 3 show that the cage is as follows:
EHMO/ASED method is basically feasible for Ca
A& < AEBr < AENone < AEcr < AEF
systems.
< AELi < AENa < AEK < AE,, < AEa
Calculation results and discussion From the viewpoint of charge transfer, on putting
A (A = Li, Na, K, Rb, Cs) and H (H = F, Cl, Br,
Table 4 presents the calculation results of I) into the center of the C60 cage (see Tables 4 and
(AXa) (A = Li, Na, K, Rb, Cs) and (HBC& 5), A (A = Li, Na, K, Rb, Cs) is just an electron
(H = F, Cl, Br, I) including the symmetries, ener- donor and H (H = F, Cl) is just an electron accep-
gies and occupations of the frontier and subfrontier tor for the Cm cage, Br is an electron acceptor for
orbitals. From Table 4 it can be seen that the sym- the Cti cage but it will have little influence on the
metries and energies of the frontier and subfrontier frontier and subfrontier molecular orbitals for the
molecular orbitals for original Cm are only slightly Cm cage, and for I, although there is no charge
affected when the A (A = Li, Na, K, Rb, Cs) or H transfer from I to the Cbo cage, the frontier and
(H = F, Cl, Br, I) atom, except Br and I, is put into subfrontier molecular orbitals for the Cm cage
the C6a cage. This is explained by three reasons: (1) are obviously influenced.
the symmetries of the s atomic orbitals for the center The optimized bond lengths and cage radii of
atoms do not match with the symmetries of the (AXso) (A = Li, Na, K, Rb, Cs) and (HXso)
frontier and subfrontier molecular orbitals of origi- (H = F, Cl, Br, I) are given in Table 6. Generally
nal C,; (2) the energies of the valence atomic orbi- speaking, there is only a small influence on the
tals for the center atoms are far from the energies of radius of the Cbo cage when an atom A (A = Li,
the frontier and subfrontier molecular orbitals of Na, K, Rb, Cs) or H (H = F, Cl, Br, I) is put into
Table 3
Some energy levels (eV) of valence molecular orbitals of Cm

Order HO-3 1 HO-30 .a. HO-2 HO-1 HOMO LUMO LU+I Lu+2 ...

Energy level -24.08 -23.73 . .. -12.47 -12.45 -11.81 -10.21 -9.60 -8.39 ...
Symmetry 17’1, . .. 4% 8Hs .‘.
‘As 4% 7Hi? 5T1, 27’1,
190 D.-R. Zhang et al/J. Mol. Strut. (Theochem) 282 (1993) 187-191

Table 4
Symmetries, energies and occupations of the frontier and subfrontier orbitalsa

Center atom HOMO- 1 HOMO LUMO LUMO + 1

S E 0 s E 0 s E 0 s E 0

None 7Hs -12.446 10 4H, -11.806 10 5T1, -10.213 0 2Tls -9.597 0

Li 7Hs -12.448 10 4H, -11.798 10 5T1, -10.225 1 2T1, -9.605 0
Na 7Hs -12.450 10 4H, -11.794 10 5T1, -10.226 1 2T1, -9.603 0
K 7Hs -12.456 10 4H, -11.794 10 5T1, -10.206 1 2T1, -9.575 0
Rb 7Hs -12.460 10 4H, -11.792 10 5T1, -10.194 1 2T1s -9.558 0
cs 7Hs -12.461 10 4H, -11.793 10 5T1, -10.192 1 2T1, -9.554 0
F 7Hs -12.446 10 4H, -11.803 9 6Tlu -10.219 0 2T1s -9.602 0
Cl 7Hs -12.446 10 4H, -11.805 9 6Tlu -10.218 0 2T1, -9.602 0
Br 5T1, -11.820 6 4H, -11.804 9 6Tl” -10.220 0 2T1s -9.605 0
I 4Hu -11.796 10 5T1, -10.383 5 6Tl” -10.242 0 2T1, -9.629 0
-
a S = symmetry; E = energy; 0 = occupation; HOMO and LUMO given here denote original ones of C,.

the center of its cage, but it is interesting to see that on the Cm cage, and then the short bond length, the
the cage radius r’ exhibit an inverse order with their long bond length and the radius will reach new
stabilities: optimum values on a new minimum balance
point. The distance between the center atom and
the C on the Cm cage is nearly the sum of their van
der Waals radii, so the interaction between them
For the original C& without a center atom, the can be described with the (expd-1) formula [26,27],
short bond length, the long bond length and the in which the exp( - r) term means the repulsion
radius have their optimum values on a minimum interaction owing to the overlap of the electron
balance point. When an atom A (A = Li, Na, K, cloud, the rm6 term means the dispersion interac-
Rb, Cs) or H (H = F, Cl, Br, I) is put into the tion and the r-l term means the coulomb interac-
center of the C6s cage, a new interaction takes tion. The coulomb interaction is attractive in the
place betwen the A (or H) atom and the C atoms case considered here. A new minimum
balance point is the result of a balance among all
Table 5 the bond interactions of the 60 C atoms on the Cso
Stabilities, gaps and charges of center atoms for (A@C,) cage and between the (exp-6-l) interactions of the
and (W&O)
60 C atoms on the Cso cage and the center atom.
Center atom Stabilitya Gap Charge The larger the radius of the center atom, the larger
(ev) (ev) (lel) the overlap repulsion and the dispersion attraction
between the C on the C6e cage and the center atom,
None 1.5935
Li 8.0773 0.6192 1 while their coulomb interaction is always the same,
Na 9.2486 0.6227 1 except for I. For I, there is no coulomb interaction
K 15.8200 0.6306 1 between the center atom and the C atoms on the
Rb 19.8097 0.6366 1
Cso cage because of its neutro-electricity. When the
cs 26.2554 0.5976 1
F 5.6078 1.5847 -1 coulomb attraction plus the dispersion attraction is
Cl 1.0488 1.5869 -1 larger than the overlap repulsion,
Br -0.1458 1.5835 -1
I -0.4013 0.1405 0
r6 and rfI < r&,,,
(A = Li, Na, K, Rb, Cs; H = F, Cl)
a AEx = (Ex + Ecm) - E(XGJC,)
D.-R. Zhang et al./J. Mol. Struct. (Theochem) 282 (1993) 187-191 191

Table 6 2 E. Osawa, Kagaku Tokyo, 25 (1970) 854.

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5 F.D. Weiss, J.L. Elkind, S.C. O’Brien, R.F. Curl and
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Na 1.3897 1.4498 3.5390 Phys., 87 (1987) 4236.
K 1.3851 1.4463 3.5294 7 P.J. Benning, J.L. Martins, J.H. Weaver, L.P.F. Chi-
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10 S.P. Kelty, C. Chen and CM. Lieber, Nature, 352
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11 L.D. Raymond and M.S. Jerome, Chem. Phys. Lett.,
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Natural Science Foundation of China and we
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