Mechanism of carbon nanotubes unzipping into graphene ribbons

Norma L. Rangel, Juan C. Sotelo, and Jorge M. Seminario

Citation: The Journal of Chemical Physics 131, 031105 (2009); doi: 10.1063/1.3170926
View online: http://dx.doi.org/10.1063/1.3170926
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 THE JOURNAL OF CHEMICAL PHYSICS 131, 031105 共2009兲

Mechanism of carbon nanotubes unzipping into graphene ribbons

Norma L. Rangel,1,2 Juan C. Sotelo,2,a兲 and Jorge M. Seminario1,2,3,b兲
1
Materials Science and Engineering Graduate Program, Texas A&M University, College Station,
Texas 77843, USA
2
Department of Chemical Engineering, Texas A&M University, College Station, Texas 77843, USA
3
Department of Electrical and Computer Engineering, Texas A&M University, College Station,
Texas 77843, USA
共Received 19 May 2009; accepted 12 June 2009; published online 21 July 2009兲

The fabrication of graphene nanoribbons from carbon nanotubes 共CNTs兲 treated with potassium
permanganate in a concentrated sulfuric acid solution has been reported by Kosynkin et al. 关Nature
共London兲 458, 872 共2009兲兴. Here we report ab initio density functional theory calculations of such
unzipping process. We find that the unzipping starts with the potassium permanganate attacking one
of the internal C–C bonds of the CNT, stretching and breaking it. The created defect weakens
neighboring bonds along the length of the CNT, making them energetically prone to be attacked
too. © 2009 American Institute of Physics. 关DOI: 10.1063/1.3170926兴

I. INTRODUCTION In this paper we aim to explain the controlled oxidation

Graphene nanoribbons 共GNRs兲 are promising materials
for a wide range of applications, but their practical imple-
mentation requires edge and width controllability, low fabri-
cation costs, and large scale production. Kosynkin et al.1
reported a solution to fabricate these graphene nanoribbons
by unzipping carbon nanotubes 共CNTs兲 treated with potas-
sium permanganate in a concentrated sulfuric acid solution
共H2SO4 – KMnO4兲. Their procedure, referred to from now as
the “experiment,” allows the fabrication of uniform, narrow,
100–500 nm wide, semiconducting and metallic, straight
edges 共presumed zigzag兲, single and multilayers GNR from
multiwalled carbon nanotubes of approximately 15–20 con-
centric single wall carbon nanotubes with diameters of
40–80 nm. These nanoribbons are soluble in polar solvents.
Other fabrication methods for GNR based on longitudi-
nally cutting CNTs have also been reported recently. Jiao et
al.2 obtained narrower semiconductor ribbons by embedding
multiwalled carbon nanotubes in a polymer matrix and then
attacking the surface with argon plasma etching. Cano-
Marquez et al.,3 on the other hand, obtained GNR by treating
multiwalled carbon nanotubes with lithium and ammonia.
Oxidative cutting was used by Liu et al.4 to transversally cut
long nanotubes into smaller tubes and Li et al.5 provided
insight into the atomic-level mechanisms of oxidation in car-
bon materials.
Graphitic material such as carbon nanotubes and nanor-
ibbons can be used in a wide range of applications from
lubrication to electronics to novel mechanochemical
devices;6 therefore, controlled chemical cutting of such ma-
terials to create novel structures could be a powerful tech-
nique in the nanotechnology toolbox. However, the mecha-
nisms of how this is achieved are still far from clear.7
a兲
Permanent address: Departamento de Física, Informática y Matemáticas,
Universidad Peruana Cayetano Heredia, Lima, Perú.
b兲
Electronic mail: seminario@tamu.edu.
mechanisms of the experiment of unzipping CNT 共Ref. 1兲
using ab initio density functional theory molecular orbital
calculations.
II. METHODOLOGY
To study the fabrication of graphene nanoribbons from
carbon nanotubes, we use the armchair 共5,5兲 CNT and 共3,3兲
CNT as model systems.
Calculations for the 共5,5兲 and 共3,3兲 CNT systems are
performed at the B3PW91/ 6-31G共d兲 共Ref. 8兲 and
PBE/ 6-31G共d , p兲,9 respectively, levels of theory. All struc-
tures are tested to be local minima and all calculations are
performed with the program GAUSSIAN-03.10
III. RESULTS
A. Formation of manganate ester
The first step is the formation of manganate ester, there-
fore, we calculate the optimized structures of the permanga-
nate bonded to the 共5,5兲 CNT from B1 to B5, respectively, as
shown in Figs. 1共a兲–1共e兲.
The total and binding energies, are shown in Table I for
the 共5,5兲 CNT, the permanganate anion 共MnO4−1兲, and the
anion bonded to the B1–B5 bonds along with the unbonded
MnO4−1 interacting in the neighborhood of the 共5,5兲 CNT.
Also shown in Table I is the distance of the carbon atoms
participating in the ester formation.
FIG. 1. Optimized geometries 关共a兲–共e兲兴 of the structures obtained when
approaching the opener anion MnO4−1 to the CNT connecting initially two
of the oxygen atoms from the permanganate to the B1–B5 bonds, respec-
tively, 共vide infra兲.

0021-9606/2009/131共3兲/031105/4/$25.00 131, 031105-1 © 2009 American Institute of Physics

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TABLE I. Energies and binding energies for the CNT, the permanganate, unbroken from 1.45 to 1.57 Å. Moreover, the top O-atom of
and the optimized structures of CNT when MnO4−1 is bonded, unbounded, b6 moves closer to the nearest site on the CNT’s edge
on B1–B5, as shown in Fig. 1. The C–C distance corresponds to the carbons
bonded to the oxygen atoms.
共which has coordination two兲, forming an epoxylike bridge
between both sites 关Fig. 2共d兲兴. This suggests forming a
共5,5兲CNT, MnO4−1 Energy Binding energy C–C distance bridge to a site of coordination two releases more energy
structures 共hartree兲 共kcal/mol兲 共Å兲 than doing so to a site of coordination three.
If, on the other hand, the second pair binds to b2 on the
CNT ⫺3808.165,69
MnO4−1 ⫺1451.669,16
opposite side of the CNT 关Fig. 2共e兲兴, b2 breaks, leaving a
MnO4−1 on B1 ⫺5259.875 61 ⫺25.6 1.62 large hole of 3.99 Å on the CNT. The opening left by the
MnO4−1 on B2 ⫺5259.870 13 ⫺22.1 1.62 previously broken b5 widens too from 1.66 to 3.02 Å. Fi-
MnO4−1 on B3 ⫺5259.859 24 ⫺15.3 1.62 nally, if the second oxygen pair binds to b4 共in the same
MnO4−1 on B4 ⫺5259.867 86 ⫺20.7 1.71 C-ring as b5 and opposite to b5兲, the CNT unzips completely
MnO4−1 on B5 ⫺5260.084 58 ⫺156.7 1.42 yielding a flat nanoribbon 关Fig. 2共c兲兴. In summary, if the path
Nonbonded ⫺5259.856 24 ⫺13.4 of the attacking oxygen pairs consists of linearly aligned
parallel internal bonds, then the attacked bonds break, lead-
ing to the longitudinal unzipping of the CNT by the buttress-
The energies shown in Table I suggest that MnO4−1, the ing ketones in concordance with the experiment.
anion, attacks the CNTs bonds because the energy of the Two pairs of oxygen atoms do not bind to the same C–C
overall system for the bound anion 共onto B1–B5兲 is lower bond as this would yield higher coordination than allowed to
than the energy for the unbound one. The binding energy of the carbon atoms. From Table II, we conclude that once a
the unbound one, ⫺13.4 kcal/mol, is ⬃2 kcal/mol higher pair binds to b5, the largest lowering 共or stabilization兲 en-
than the weakest binding energy of a bound anion to the ergy 共⫺332 kcal/mol兲 to bind a second pair is achieved on
CNT 共onto B3兲, ⫺15.3 kcal/mol. Even though the lowest b4 关Fig. 2共c兲兴; the smallest such energy 共⫺106 kcal/mol兲 is
total energy 共singlet multiplicity兲 is attained when the per- attained when the pair binds on b6 关Fig. 2共d兲兴.
manganate anion binds to the edge bond B5, the attack
leaves the bond unbroken, the C–C distance in B5 goes from
1.24 to 1.42 Å. Whereas when the anion binds to the CNT on C. Opening of the CNT
B1–B4, the C–C distance in the bonds increases 0.2–0.3 Å, The sequential addition of oxygen pairs to the CNT
leading to their rupture and thus to the partial unzipping of weakens the adjacent bonds and facilitates the adsorption of
the nanotube. the next oxygen pair; here we use the 共5,5兲 CNT which has
an internal edge bond B1 and an external edge bond B5.
B. Oxygen adsorption Because of the large ratio of internal to edge bonds in the
CNT, the small spread in binding energies for the B2–B4
To study the interaction between oxygen pairs adsorbed bonds 共Table I兲, and the breaking of any of B2–B4 bonds
on the CNT, we have computed the energy for pairs both in under attack by an oxygen pair, we choose the middle bond
close proximity and separated 共Fig. 2兲. The C–C bonds on B3 共as an on average representative of bonds in the mid
which the oxygen pairs are adsorbed are given in Fig. 2共a兲. section of a long CNT兲 to start the unzipping process sequen-
Starting with an oxygen pair adsorbed onto b5 关Fig. 2共b兲兴, a tially adding oxygen pairs as shown in Fig. 3.
second pair is adsorbed on an internal bond either parallel to The first oxygen-pair attack starts on B3, stretching the
b5, b4 关Fig. 2共c兲兴, or oblique to it, b6 关Fig. 2共d兲兴. In either bond from 1.43 to 1.65 Å 共Table III兲. The neighboring bonds
case, the internal bond is in the same C-ring as b5. The B2 and B4 elongate by 0.03 Å, becoming weaker and vul-
second pair may adsorb too at the opposite side of the CNT nerable to the next two attacks 关Figs. 3共c兲 and 3共d兲, respec-
on b2 关Fig. 2共e兲兴. tively兴. The attack continues on the internal and external
When an oxygen-pair binds to the CNT on b5, the bond edge bonds B1 and B5 关Figs. 3共e兲 and 3共f兲, respectively兴; the
stretches from 1.45 to 1.66 Å and breaks 关Fig. 2共b兲兴. If then, bonds stretch but do not break, blocking the unzipping. How-
a second pair binds on b6, the bond connecting b5 with b6
snaps. As a result, b5 relaxes to 1.50 Å and b6 stretches

FIG. 2. 共a兲 共3,3兲 armchair CNT with b2 = 1.47 Å, b4 = b5 = 1.45 Å, and

b6 = 1.46 Å, and two edge bonds, b1 = b3 = 1.28 Å 共all labeled bonds but
b6 are orthogonal to the plane of the page兲. Conformations 共b兲 after an
oxygen-pair attack to bond b5; 共c兲 after a couple of oxygen pairs attack b4 FIG. 3. 关共a兲–共f兲兴 Optimized structures obtained through the gradual unzip-
and b5; 共d兲 when an oxygen pair attacks conformation 共b兲 on b6, and 共e兲 ping of a 共5,5兲 CNT. Pairs of oxygen atoms are added sequentially. A new
when an attacking oxygen pair breaks b2 on conformation 共b兲. geometry optimization is performed after each pair addition of oxygen
atoms.
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 031105-3 Unzipping of CNTs J. Chem. Phys. 131, 031105 共2009兲

TABLE II. Total and binding energies for the 共3,3兲 CNT and attacking oxygen pair structures. Second-pair binding energy yields the binding energy of an
oxygen-pair after a successful attack of bond b5 by a first oxygen pair. Multiplicities 共m兲 of the structures are included in parenthesis.

共3,3兲 CNT– oxygen Energy All O’s binding Second-pair binding b1 b2 b3 b4 b5 b6

pair structures 共hartree兲 energy 共kcal/mol兲 energy 共kcal/mol兲 共Å兲 共Å兲 共Å兲 共Å兲 共Å兲 共Å兲

共3,3兲 CNT 共m = 3兲 ⫺1140.850 32 1.28 1.47 1.28 1.45 1.45 1.46

Figure 2共b兲 共m = 1兲 ⫺1291.065 46 ⫺65.3 1.26 1.47 1.25 1.49 1.66 1.45
Figure 2共c兲 共m = 3兲 ⫺1441.712 91 ⫺500.5 ⫺332.6 1.25 1.44 1.25 - - 1.51
Figure 2共d兲 共m = 3兲 ⫺1441.353 24 ⫺274.6 ⫺106.6 1.26 1.45 1.26 1.48 1.50 1.57
Figure 2共e兲 共m = 3兲 ⫺1441.565 98 ⫺408.7 ⫺168.1 1.26 3.99 1.26 1.44 3.02 1.49

ever, when the edges of the CNT are passivated with hydro- So far we have assumed that either the MnO4− anion or
gen atoms, the internal bond B1 breaks with the attack and pair of O-atoms is readily available. We now present an ab
opens the tube as shown in Fig. 4共b兲. The attack of the oxy- initio model calculation showing how the unzipping might
gen pairs fails to break the external bond B5, which elon- take place when an armchair 共3,3兲 CNT reacts with potas-
gates to 1.59 Å. sium permanganate, KMnO4, in an acidic medium here rep-
This finding suggests that if oxidation takes place along resented by H2SO4 + H2O molecules 共Fig. 5兲.
a longitudinal path containing an edge bond, then complete We let the attack take place starting from the back, along
unzipping of the armchair CNT does not take place. This, the longitudinal path of the two internal bonds 共parallel to
may be due to an edge bond 关such as B5 in Fig. 3共a兲兴 being the CNT’s rims兲 at the top of the CNT in Fig. 5共a兲. As ex-
much stronger 关about 16% for the armchair CNT of Fig. pected, the bond breaks, yielding 关CNT兴共MnO2兲OH and
3共a兲兴 than the internal bonds 共B1–B4兲, thus more difficult to 关CNT兴O – K+ – SO3共OH兲− at the sides of the broken bond
break 共see Table III兲. Thus, oxidation of the armchair CNT 关Fig. 5共b兲兴. This system is further hydrated with three water
along a longitudinal cleavage path is not enough for the com- molecules and then fully reoptimized 共not shown兲. Next, we
plete unzipping to take place. place another KMnO4 group attacking the CNT on the sec-
Finally, in a zigzag 共6,0兲 CNT 共of diameter 5.3 Å兲 the ond internal bond and add one H2SO4 and H2O. What takes
cleavage path spirals along the tube in an angle about 30° place next depends on the angle of attack of the KMnO4 to
with the CNT’s axis. As indicated in Fig. 4共c兲 and 4共d兲, un- the bond. For a slanted K–Mn axis 关relative to the CNT’s
zipping of the CNT happens only when its rims are passi- axis, Fig. 5共c兲兴, so that the forward attacking O-atom is
vated with hydrogen atoms. Because of the high reactivity of aligned with the CNT’s axis, there is no bond breaking and
the rims of the zigzag CNT 共Ref. 11兲 some of their C-atoms
begin to locally cluster tightly together 共not shown兲 when
they are not passivated with H-atoms, effectively blocking
the unzipping. Specifically, in runs we have made for an
oxygen pair on the rim of an nonpassivated zigzag CNT, the
O-atom in the coordination three site moved to the nearest
unoccupied site on the zigzag border 共which has coordina-
tion two兲 forming an epoxylike bridge between the two sites.
A few small triangular C-rings formed on the zigzag rims
too. This effect was more pronounced for smaller diameter
tubes, as our 共6,0兲 CNT 共Fig. 4共c兲兲. For the latter CNT, in
contrast to the armchair CNTs we have tested, the unzipping
of the CNT may start with an oxygen-pair attacking a C–C
bond in the zigzag edge, as H-passivation effectively trans-
forms the edge C-atoms into coordination three sites. In fact,
the passivated CNT becomes more stable by oxidation and
breaking of an edge bond rather than a central bond along the
oxidation path 共not shown兲.

FIG. 5. Chemical reaction of an armchair 共3,3兲 CNT with KMnO4 on an

acidic H2SO4 environment. 共a兲 Bare armchair 共3,3兲 CNT. 共b兲 CNT attacked
on an internal bond by KMnO4 on H2SO4 − H2O. 共c兲 CNT is attacked on a
second bond parallel to the first one with the forward pointing attacking
O-atom parallel to the CNT axis on acidic medium 2H2SO4 − 5H2O. 共d兲
Final structure from the initial one in 共c兲; the attacked bond does not break
and the MnO4−1 anion goes to the edge of the CNT. 共e兲 An alternative
FIG. 4. The edges of the unopened 共5,5兲 CNT 关Fig. 3共f兲兴 are passivated with second attacking KMnO4, with the attacking O-atom pointing downward to
hydrogen atoms 共a兲 and the optimized structure 共b兲 opens on the internal the hole left by the first attack; the attacked bond and acidic medium are as
bond B1 but not on the edge bond B5. Hydrogen passivation of the 共6,0兲 in 共c兲. 共f兲 Final structure from the initial one in 共e兲; the attacked bond breaks
zigzag CNT 共c兲 followed by oxidation of the path of internal bonds slanted leading to an unzipped CNT; flattening of the ribbon is impeded by the
by 30° relative to the CNT rims leads to the unzipping of the tube 共d兲. moieties product of the reaction.
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 031105-4 Rangel, Sotelo, and Seminario J. Chem. Phys. 131, 031105 共2009兲

TABLE III. Total energies of each step in the studied unzipping process shown in Figs. 3 and 4共b兲 along with
the lengths of the carbon-carbon distance in each oxidized bond.

Energy B1 B2 B3 B4 B5
Unzipping of CNT 共hartree兲 共Å兲 共Å兲 共Å兲 共Å兲 共Å兲

Figure 3共a兲 ⫺3808.165 693 1.43 1.42 1.43 1.44 1.24

Figure 3共b兲 ⫺3958.377 548 1.44 1.46 1.65 1.46 1.24
Figure 3共c兲 ⫺4108.705 771 1.38 2.66 2.98 1.47 1.24
Figure 3共d兲 ⫺4259.187 961 1.48 3.50 5.25 4.67 1.26
Figure 3共e兲 ⫺4409.409 991 1.55 3.11 4.95 4.62 1.26
Figure 3共f兲 ⫺4559.823 011 1.56 2.90 4.05 2.96 1.57
Figure 4共b兲 关Fig. 3共f兲 with H passivation兴 ⫺4573.135 841 1.59

thus no unzipping of the CNT 关Fig. 5共d兲兴. In contrast, if the
K–Mn axis is roughly parallel to the axis of the CNT, 关Fig.
5共e兲兴, with the forward attacking O-atom pointing downward
to the hole left by the breaking of the first bond, the second
attacked bond stretches and breaks yielding the opening of
the CNT 关Fig. 5共f兲兴.
IV. SUMMARY AND CONCLUSIONS
Pairs of oxygen atoms from the permanganate anion
bind and break the internal C–C bonds in the CNT, the
stretching of the bonds involved in the first attack weakens
the neighbor parallel bonds making them more vulnerable
for the next oxygen pair attack, which takes place longitudi-
nally along the CNT, consistent with what was found in the
experiment. However, the external bonds in the armchair
CNTs are not broken by the permanganate attack yielding
ribbons with closed endings. Furthermore, our results sug-
gest that the initial attack takes place in the middle section of
the CNT because the population of B3 bonds is higher. In
addition, bonds in the unzipping path whose ends have coor-
dination three are most likely broken as inferred from the
fact that armchair unlike zigzag edge bonds break when at-
tacked by an oxygen-pair. Also, the difference in strength of
edge bonds for H-passivated armchair and zigzag CNTs sug-
gests that bonds with an end site connected to only C-atoms
are more likely to break under the attack by oxygen pairs. On
the other hand, there is no much difference whether the an-
ionic MnO4− or the neutral KMnO4 species or even the ex-
pected HMnO4, is used in the calculations. When HMnO4
attacks, it breaks internal but not edge bonds just as in the
anionic case. These results suggest that all unzipped CNTs
end up in zigzagged edge ribbons no matter what we start
with. Nevertheless, information will be very useful from ad-
ditional experimental evidence as theory and experiment can
have complementary information about the systems being
analyzed rather than a mutual validation or exclusion. Defi-
nitely our results do not prove the mechanism in the experi-
ment leading to the unzipping of the CNTs, yet it provides
valuable clues about one of the proposed mechanisms at play
in the unzipping process; actually, no calculation can prove
such mechanisms but it simply shows that the results are
consistent with each other. We have not considered multi-
walled CNTs and we have not taken into account tempera-
ture effects in the unfolding process. In the experimental
procedure, the CNT soup is heated up at some point to either
promote or accelerate the reaction of KMnO4. This could be
done with sophisticated molecular dynamics simulations.
Hopefully this work will trigger others to do it.
In conclusion, the results are consistent with the reported
experimental results: longitudinal or spiraling unzipping is
the preferred route for the unfolding of the CNTs.
ACKNOWLEDGMENTS
We thank James Tour for discussion of our conclusions
and details of their experimental findings. We also acknowl-
edge financial support from the U.S. Defense Threat Reduc-
tion Agency 共DTRA兲 through the U.S. Army Research Office
共ARO兲 as well as from the DURIP program of the U.S. ARO.
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