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Physical Chemistry Chemical Physics Accepted Manuscript

Tripentaphenes: two-dimensional acepentalene-based nanocarbon
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allotropes
Paloma Vieira Silva,a,b Mayada Fadel,c Antonio Gomes Souza Filho, a Vincent Meunier, c

and Eduardo Costa Girãob

Tripentaphenes are 2D nanocarbon lattices conceptually obtained from the assembly of acepentalene
units. In this work, density functional theory is used to investigate their structural, electronic, and
vibrational properties. Their bonding configuration is rationalized with a resonance mechanism,
which is unique to each of the 2D assemblies. Their formation energies are found to lie within the
range of other previously synthesized carbon nanostructures and phonon calculations indicate their
dynamical stability. In addition, all studied tripentaphenes are metallic and display different features
(e.g., Dirac cone) depending on the details of the atomic structure. The resonance structure also
plays an important role in determining the electronic properties as it leads to delocalized electronic
states, further highlighting the potential of the structures in nanoelectronics.

1 Introduction
Carbon nanostructures have been considered as potential candi-
dates in the search for silicon replacement for future nanoelec-
tronic applications. While nanocarbon can take different forms in
0D 1 , 1D 2 , 2D 3 , and 3D 4,5 , graphene occupies a special place in
carbon science due to its remarkable properties 6 , ease of synthe-
sis 7 , and high potential for integration in operational devices 8 .
Several studies in materials science have been focused on physi-
cal 9–11 and chemical 12–14 modifications of graphene in order to
further tune its properties with the ultimate goal of using it in
nanodevice setups. Furthermore, much effort has also been de-
voted to the theoretical proposal and experimental search for the
synthesis of other carbon layered materials with tunable prop-
erties. In this regard, 2D configurations are the basic models in
nanocarbon science, as other 0D, 1D, and even 3D geometries can
conceptually be cast out of a one-atom-thick membrane. Origi-
nal ideas for new nanocarbon allotropes in two dimensions are
motivated by a number of arguments, including extended distri-
butions of reconstructions in graphene 15,16 , mixture of sp2 and
sp3 hybridizations so as to form lattices fully composed by pen-
tagons 17,18 , concatenation of graphitic 1D forms 19 , or the as-
sembly of molecular blocks 3,20,21 as motivated by bottom-up syn-
thesis routes 22–25 . It follows that a long list of hypothetical sp2
carbon materials have been theoretically proposed, with distinct
a
Departamento de Física, Centro de Ciências, Universidade Federal do Ceará, P.O. Box
6030, CEP 60455-900, Fortaleza, Ceará, Brazil.
b
Departamento de Física, Universidade Federal do Piauí, CEP 64049-550, Teresina,
Piauí, Brazil.
c
Department of Physics, Applied Physics, and Astronomy, Rensselaer Polytechnic Insti-
tute, Troy, NY, USA.
electronic properties ranging from metallic to semiconducting, as
well as systems with high anisotropy 3,15,20,21,26–33 .
In this report we propose to study the electronic properties
of three 2D carbon allotropes conceptually assembled by basic
molecular units consisting of three contiguous pentagons, as illus-
trated in Fig. 1(a). This basic block, which is similar to a dehydro-
genated acepentalene molecule, will be referred to as a TP unit,
and the 2D carbon allotropes as tripentaphenes (TPHs). Two sim-
ilar structures have been proposed earlier in the literature, where
the TPs are linked by dense molecular packing 26,27 , as illustrated
in Figs. 1(b)-(c). These forms are known as C65 26 and C57 27 . In
the present work, however, the TP motifs are assembled along sp2
hexagonal lattices with C6 symmetry, according to the following
hierarchies
• α case - direct links by the sides of the pentagons;
• β case - links through hexagonal rings; and
• σ case - links through 4-membered rings.
These systems are illustrated in Figs. 1(d)-(f) and result in
structures featuring pores which are much larger than the high-
est membered rings from the previously investigated C65- and
C57-TPHs. Two of these systems (α and σ cases) were first con-
ceptually conceived in Ref. 34, but their electronic structure was
not studied. Even though they are all metallic, we show that their
electronic structures differ significantly from each other, including
a system with Dirac cones similar to the case of graphene.
2 Methods
The electronic structure calculations were performed using
density functional theory (DFT) 35,36 as implemented in the

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(a) (b) (c) Born-Oppenheimer molecular dynamics (BO-MD) simulations us-

ing a 3 × 3 × 1 supercell within SIESTA. The total time involved in
the simulation was 3 ps (1.0 f s time step) at the temperature
of 400 K. We used an NVT (canonical) ensemble, and the Nosé
scheme for the thermostat.

Physical Chemistry Chemical Physics Accepted Manuscript

3 Results and Discussion
(d) (e) (f) 3.1 Structure and stability
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All the α-, β -, and σ -TPH structures have hexagonal lattices with
corresponding unit cells shown with the red rhombus in Fig. 2.
Their lattice constants are 7.19 Å, 8.53 Å, and 9.65 Å for α-, β -
, and σ -TPH, respectively. The number of atoms per primitive
unit cell is 14, 20, and 20 for α-, β -, and σ -TPH. The three TPHs
studied here belong to the p6mm symmetry group, like graphene
(see Fig. 2). This is different from the previously studied TPHs,
Fig. 1 (a) Basic TP structural building block; Previously studied TPH
structures: (b) C65-TPH 26 , (c) C57-TPH 27 , and systems studied here: which have their symmetries described either by the p3m1 26 or
(d) α-TPH, (e) β -TPH, and (f) σ -TPH. the p31m 27 symmetry group (also shown in Fig. 2). Detailed re-
laxed atomic positions for all the TPH structures studied in this
work are included as supplemental material.
SIESTA code 37 . Core electrons were accounted for by using
norm-conserving Troullier-Martins pseudopotentials 38 and va-
lence electronic wavefunctions expanded using a double-ζ po-
p6mm
larized (DZP) basis set. The energy shift used to define the
reach of the orbitals functions was set to 0.01 eV 37 . Exchange-
correlation functional was described by the generalized gradi-
ent approximation (GGA), as parameterized by Perdew-Burke-
Ernzerhof (PBE) 39 , and a cutoff energy of 400 Ry was employed
to represent charge on a real space grid. The layer structures
were separated from their periodic images by a vacuum region
of 30 Å in the vertical direction. A 48 × 48 × 1 (36 × 36 × 1)
Monkhorst-Pack grid was used for Brillouin zone (BZ) integration
in the case of the system with the smallest (largest) primitive cell. p3m1 p31m
Structural relaxations were carried out using a maximum force
tolerance on each atom of 10−2 eV/Å, as well as a stress tensor
tolerance of 0.1 GPa.
The phonon calculations were carried out using a finite differ-
ence scheme as developed in the Phonopy code 40 . The calcu-
lation of the force constants was performed with GPAW 41,42 , a
Python DFT-code based on the projector-augmented wave (PAW)
method and the atomic simulation environment (ASE) 43,44 . Be-
cause high numerical accuracy is needed to evaluate phonons,
the calculations of the force constants were performed by GPAW Fig. 2 (Upper Panel) Representation of the p6mm symmetry group to-
gether with the α-, β -, and σ -TPH structures corresponding to this
using a plane-wave basis set with plane-wave energy cutoff of symmetry. (Lower Panel) Representation of the p3m1 (p31m) symme-
500 eV. The exchange-correlation functional used in the calcula- try group and the C65-TPH (C57-TPH) associated to this group. In all
tions was the GGA in the PBE formulation. A Γ-centered 5 × 5 × 1 cases, the red rhombus also represent the systems’ primitive cell.
(4 × 4 × 1) Monkhorst-Pack sampling was used for α-TPH and β -
TPH (σ -TPH). Note that the electronic band structures obtained As shown in Fig. 3, α- and β -TPH are characterized by a do-
this way were identical to those obtained with SIESTA as de- decagonal hole of similar dimensions (5.47 Å × 5.63 Å and
scribed above. A symmetry check was done through Phonopy 5.66 Å × 5.70 Å, respectively). The σ -TPH system features
for each of the TPH structures to be correctly symmetrized in an larger 18-membered pore, with dimension 8.27 Å × 8.12
their symmetry group p6mm. Then, phonon calculations were Å. These three systems have a superficial atomic density ρ
carried out using a 3 × 3 × 1 supercell with displacement distance lower than that of previously studied TPHs, namely ρ ∼ 0.313
0.02 Å for each of the TPH structures. The reported phonon band atoms/Å2 (ρ ∼ 0.317 atoms/Å2 ) [ρ ∼ 0.248 atoms/Å2 ] for α-
structures were obtained after application of the acoustic sum rule TPH (β -TPH) [σ -TPH], while corresponding values for systems
as implemented in Phonopy. shown in Figs. 1(b)-(c) are ∼ 0.351 and ∼ 0.366 atoms/Å2 , re-
In order to check the thermal stability of TPHs, we performed spectively. They are also lighter than graphene, and graphane, for

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which ρ ∼ 0.376 atoms/Å2 , and ρ ∼ 0.710 atoms/Å2 (or ρ ∼ 0.355
atoms/Å2 if we do not consider the hydrogen atoms), respectively.
We also show lattice parameters and ρ values for α-graphyne,
β -graphyne, γ-graphyne, graphdiyne 45 , graphenylene 20 , and α-
naphthylene 21 in Table 1, as calculated by the same method. We
ture can be fully characterized by only three nonequivalent atoms,
labelled as 1, 2, and 3 as indicated by the red arrows in Fig 4(a).
They make three different types of interatomic bonds, namely d11 ,
d12 , and d23 , as listed below:
• d11 – bonds in between two neighbour TPs;

Physical Chemistry Chemical Physics Accepted Manuscript

note that the studied TPHs have a higher density than α-, β -
, γ-graphyne, graphdiyne, and graphenylene, except for σ -TPH
• d12 – sides of the 12-membered rings;
which is less dense than γ-graphyne and graphenylene due to the
presence of large pores. On the other hand, α-naphthylene is
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• d23 – bonds involving the TP central atom.

the most dense, but it has atomic density close to that of α- and
β -TPHs. Lattice parameters and ρ values for all these structures These bond lengths are 1.55 Å, 1.44 Å, and 1.42 Å values as
are summarized in Table 1. The presence of such large holes on shown in Fig. 4(a). Note that d12 and d23 are similar to the
TPHs can enable potential applications like in the selective filter- carbon-carbon bond distance in graphene (1.43 Å, as calculated
ing of chemical compounds, as proposed for a different carbon by the same methods). We attribute such a similarity with
allotrope with CO molecules, for instance 46 . In addition, all the graphene’s case to a resonance mechanism in α-TPH, as illus-
three studied systems studied show a stable planar configuration, trated in Fig. 4(b), where we drew a possible resonance structure
as illustrated in Figs. 3(d-f) where we shown the side view of the with the minimal repetition unit illustrated by the red dashed
α-, β -, and σ -TPH structures, respectively. hexagon. The resonance hybrid is composed by this canonical
structure a (from Fig. 4(b)) and other two, b and c, obtained
Table 1 Lattice parameter a (in Å) and superficial atomic density ρ (in
from the first one after ±60◦ rotations, respectively. In Fig. 14 of
atoms/Å2 ) for TPHs and other 2D carbon nanostructures. In the par-
ticular case of graphane, the value between parenthesis corresponds to ρ the Appendix, we illustrate configurations a and b as well as how
without considering the hydrogens. the double bonds change from one configuration to the other. In
the resonance hybrid, one third of all the d11 , d12 , and d23 links
System a ρ are double bonded. However, the d23 bonds are much closer to
Graphene 2.48 0.376 each other (with three such bonds sharing the central atom from
Graphane 2.55 0.710 (0.355) the TP unit), so that the resonance mechanism is stronger for
α-TPH 7.19 0.313 these bonds and they show the shortest lengths in the structure.
β -TPH 8.53 0.317 This is similar to the d12 case, as each pair of these bonds always
σ -TPH 9.65 0.248 shares an atom along the dodecagon ring. On the other hand,
C65-TPH 5.74 0.351 the d11 links are located further apart from each other than the
C57-TPH 6.16 0.366 other bond types, so that the resonance mechanism influences
α-graphyne 7.05 0.186 these connections less significantly. It follows that they show the
β -graphyne 9.58 0.227
longest bond lengths in the system.
γ-graphyne 6.95 0.287
This resonance mechanism is further supported by the exami-
Graphdiyne 9.56 0.227
nation of the charge density plots using three different isosurface
Graphenylene 6.82 0.298
values, namely 0.19 eÅ−3 , 0.23 eÅ−3 , and 0.27 eÅ−3 , as shown in
α-naphthylene 10.37 0.322
Figs. 4(c)-(e). In the first plot, we observe charge density spread-
ing over all bonds. As we increase the isosurface value to 0.23
(a) (b) (c) eÅ−3 , density is not observed in the center of the d11 links, and
for the last isosurface value we start to observe a lack of a charge
5.63 5.70
8.12 cloud in the middle of the d12 bonds. This highlights that the
8.27 bonding charge density follows ρ23 > ρ12 > ρ11 , in accordance
5.47 5.66
with the resonance mechanism and with the inverse of the bond
length trend (d23 < d12 < d11 ).
Note that this is different from what occurs for an acepental-
ene molecule, as it does not have a C3 axis symmetry and it does
α-TPH β-TPH - planar not feature any resonance. In fact, as shown in Fig. 4(f), the
(d) (e) three bonds similar to d11 are not identical, with one of them cor-
responding to a single bond and the other two being both dou-
σ-TPH β-TPH - corrugated
(f) (g) ble bonds. This is shown in the diagram depicted in Fig. 4(g).
Once acepentalene-like building blocks are assembled into α-TPH
structure, the single and double bonds rearrange over the struc-
Fig. 3 Atomic structure and dimensions (in Å) for the pores in (a) α-
,(b) β -, and (c) σ -TPH. (d-g) Side views of the α-, planar-β -, σ -, and ture through the resonance mechanism, which makes the sheet
corrugated-β -TPH layers, respectively. more stable than its 0D counterpart.
β -TPH also has a symmetry which results in only three
α-TPH is a highly symmetric system, as its entire atomic struc- nonequivalent atoms for the structure, as indicated by the red ar-

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(a) (b) length profile can also be rationalized in terms of electronic reso-
nance. Fig. 5(b) illustrates a possible β -TPH resonance structure.
As in the α case, this resonance cell coincides with the system’s
1. primitive cell. However, this resonance structure in β -TPH does
44
not feature a C2 axis symmetry, as the one from the α case. As a

Physical Chemistry Chemical Physics Accepted Manuscript

result, if we apply five successive 60◦ rotations to the form from
1.42 1.55 Fig. 5(b), we obtain the other five canonical structures forming
the resonance hybrid. In Fig. 15 of the Appendix, we illustrate
3 these a, b, c, d, e, and f configurations, as well as how bonds
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1 can move so as to go from structure a to either c or d (similar

2 transitions can lead to the other b, e, and f structures). In this
resonance hybrid, one third of all the d23 and d12 links are double
bonded, but as the d23 links are closer to each other, the resonance
(c) (d) (e) is locally stronger and this bond length shorter. In addition, when
comparing different canonical structures in the β -TPH resonance
hybrid, d23 double bonds can move not only to another d23 link,
but also to d12 links. This is different from the α- and σ -TPH cases
(as seen in the Appendix), as d23 double bonds always alternate
with another d23 link. It results that d23 is significantly shorter in
the β case when compared with the corresponding bonds in the
α and σ cases. For the d11 0 bonds, two thirds of them are double

bonded in the diagram from Fig. 5(b), but the resonance mecha-
(f) (g) nism is reduced as they are not directly connected to each other
(we always have a d11 bond in between two following d11 0 ones).
1.56 0
As a result d11 assumes a value intermediate between d23 and d12 .
1.38
.38

Finally, d11 links are always single bonded, explaining why they
9 1

1.4
3 are the longest bonds in this membrane. For further insights into
1.4
1.4

3
1.4 the bond characteristics, the charge density for β -TPH is plotted
9
1.33

in Fig. 5(c). One observes the electron densities along the d23
9
1.3

bonds are significantly higher than those of the other bonds, with
1.3
9

1.52 1.52
Fig. 4 (a) A portion of the α-TPH sheet showing the three nonequivalent
atoms (indicated by red arrows) and all the three different bond lengths
(in Å) characterizing the structure; (b) Possible resonance structure: The
red dashed hexagon highlights the minimal repetition unit of such dia-
gram; (c-e) Charge density plots of α-TPH for iso-surface values 0.19,
0.23, and 0.27, respectively (in eÅ−3 ); (f) Atomic structure of an acepen-
talene molecule with detailed carbon-carbon bond lengths (in Å); and (g)
Single- and double- bonds configuration for an acepentalene molecule.
rows in Fig. 5(a). However, this structure presents four different
types of C −C bonds, according to the following list
• d11 – bonds shared by a 5- and a 12-ring;
0 – bonds shared by a 6- and a 12-ring;
• d11
d12 and d11 0 following close to each other, and d
11 showing the
lowest density.
σ -TPH has a structure similar to the α-TPH lattice, with the
difference that neighbouring TP units are now linked by a 4-
membered rings, resulting in the TPH with the largest lattice pa-
rameter (a = 9.65 Å). In addition, it features 18-membered pores
significantly larger than the 12-rings from α- and β -TPHs. These
different structural properties can enable applications through the
strategical choice of TPHs with a given pore radius targeting the
filtering of chemical compounds with specific sizes, for instance.
In this case, the σ system can allow the flow of larger molecules
than the α and β ones. As in the β case, σ -TPH has three
nonequivalent atoms (indicated by the red arrows in Fig. 6(a))
and it requires 4 different types of interatomic bonds for a full
structural characterization, namely:
• d11 – bonds between a 4-ring and a pentagon;

• d12 – bonds shared by a 5- and a 6-ring;
• d23 – bonds involving the TP central atom.
Fig. 5(a) shows these bond length values. Each 12-ring in β -
TPH has bond lengths alternating between d11 = 1.60 Å and
0 = 1.44 Å. The 6-rings are elongated, with two d 0 bonds alter-
d11
11
nating with pairs of d12 = 1.47 Å bonds (shared with the TP units).
The bonds involving the TP central atom are d23 = 1.34 Å and are
the shortest bonds from all the systems studied here. This bond
0 – bonds linking two pentagons from neighbour TP units;
• d11
• d12 – sides of the 18-rings belonging to the TP unit;
• d23 – bonds involving the TP central atom.
These bond lengths are d11 ≈ 1.53 Å, d11 0 ≈ 1.43 Å, and d ≈
12
0 are simi-
d23 ≈ 1.44 Å (see Fig. 6(a)). Note that d23 , d12 , and d11
lar to the carbon-carbon distance in graphene (1.43 Å). As in the
previous cases, a resonance mechanism can also account for the

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(a)
1.4 1.60
4 44
1.47
1.34
3 1.44
2 3
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1 1
(b) (c)
Fig. 5 (a) A portion of the β -TPH sheet showing the three nonequiv-
alent atoms (as indicated by the red arrows) and all the four unique
bond lengths (in Å) needed to characterize the structure; (b) Possible
resonance configuration for β -TPH. The red dashed hexagon marks the
minimal repetition unit of such diagram. (c) Charge density plot for
β -TPH. An isovalue value of 0.26 eÅ−3 was used.
bonding profile, as we illustrate through the resonance structure
depicted in Fig. 6(b). The minimal unit of this resonance diagram
is highlighted by the red dashed hexagon. As in α-TPH, the reso-
nance hybrid has 3 canonical structures, namely a (Fig. 6(b)) and
the b and c ones obtained by rotating a by ±60◦ . In Fig. 16 of the
Appendix, we illustrate configurations a and b as well as how
the double bonds change from one configuration to the other.
One third of all d12 and d23 links are double bonded and these
two connections show similar bond lengths. Two thirds of the
0 connections are double bonded, but they show a bond length
d11
only 0.01 Å shorter than d23 and d12 as d11 0 links do not connect
directly to each other (having two d12 bonds in between them),
lowering the influence of resonance. Finally, d11 are the longest
bonds as they are always single bonded in the resonance hybrid.
We further illustrate the charge profile for the bonds in σ -TPH in
Fig. 6(c).
We also investigated the possible occurrence of buckling on
these structures. Starting from the relaxed planar systems, we
applied random out-of-plane displacements and proceeded with
a new relaxation procedure. Among the three studied TPHs,
only the β case did not return to the full planar configuration.
The TP units in β -TPH undergo alternating upward and down-
ward buckling, with a total width of 2.82 Å. A lateral view of
this configuration is shown in Fig. 3(g). This buckling breaks
the resonance mechanism introduced to explain the bond length
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(a)
1.
1.43
Physical Chemistry Chemical Physics Accepted Manuscript
1.53
2
(b) (c)
Fig. 6 (a) A portion of the σ -TPH sheet showing the three nonequiv-
alent atoms (as marked by the red arrows) and all the different bond
lengths (in Å) needed to characterize the structure; (b) Possible reso-
nance structure for σ -TPH. The red dashed hexagon highlights the min-
imal repetition unit of such diagram. (c) Charge density plot for σ -TPH.
An isovalue value of 0.26 eÅ−3 was used.
distribution in the planar β -TPH structure. In fact, the three
d23 bonds in the buckled β -TPH are no longer the same, with
two of them being ∼1.43 Å , and the remaining one being
shorter (∼1.38 Å), similarly to what happens to the acepentha-
lene molecule. The other d11 , d11 0 , and d
12 bonds also assume
different values. Namely, one/two third(s) of the d11 (d11 0 ) bonds
are ∼1.49 Å/1.47 Å(∼1.43 Å/1.47 Å) long. For the d12 links, one
third is ∼1.49 Å long, one third has ∼1.46 Å bond length, and
the remaining bonds have an intermediate ∼1.45 Å value. The
specific locations of these bonds are represented in Fig. 7, where
the shorter (longer) bonds of each type are represented by the
red (black) symbols, with the intermediate case of the d12 bonds
represented in green. The buckled lattice parameter is also re-
duced to 7.73 Å, about 9.4% shorter than the planar counterpart,
so that its superficial atomic density ρ is now increased to 0.386
atoms/Å2 . This makes corrugated β -TPH heavier than the the
previously studied C65- and C57-TPH, and graphene. As a conse-
quence of the resonance breaking, the system looses the hexago-
nal character of its lattice, since the two lattice vectors now make
an angle of ∼60.8◦ . This changes the lattice to a centered rect-
angular geometry. The reduced symmetry of the structure is now
described by the cm group, as mirror reflections and glide planes
are the only symmetry operations displayed by the structure.
We will now explore tripentaphenes’ thermodynamic and en-
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The dynamical stability of all the structures considered in this

study was assessed by calculating their phonon band structure,
using the DFT method described in Section 2. The phonon disper-
sion bands shown in Fig. 8 clearly indicate the absence of com-
plex frequencies (which would conventionally show as negative

Physical Chemistry Chemical Physics Accepted Manuscript

frequencies in the graphical representation), thus demonstrating
the dynamical stability of all the TPH structures considered in
this work, including the β case in its both planar and corrugated
structural configurations. This indicates that the planar β -TPH
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configuration corresponds to a local minimum, rather than being

Fig. 7 A portion of the buckled β -TPH sheet showing all the different
0 , d , and d . The shorter, interme-
bonds which are indicated as d11 , d11
12 23
diate, and longer bonds of each type are colored in red, green and black,
respectively.
ergetic stability. In order to do so, we calculated their cohesive
energies per atom, Ecoh , using the following formula
at an inflexion point. One also notes that the planar β -TPH struc-
ture is the only one to feature phonon frequencies above 50 THz.
We found they correspond to vibrations spatially localized on the
pentagonal rings. Not surprisingly, these frequencies disappear
from the phonon band structure in the corrugated configuration
of the same structure, as the atoms are better accommodated in
this lower energy configuration.

Ecoh = (Etot − n × EC )/n, (1) 50 50

40 40

Frequency (THz)

Frequency (THz)
where Etot is the system’s total energy, EC is the energy of an 30 30
isolated carbon atom, and n is the total number of atoms. Ta- 20 20
ble 2 shows the Ecoh values and lattice parameters for TPHs, a
10 10
C60 fullerene, and other hexagonal 2D carbon structures, as cal-
0 0

culated by the same methods for reference. In this list, note that Γ Μ Κ Γ Γ Μ Κ Γ

graphene and graphdiyne 47 have been synthesized, so that the

range defined by their cohesive energies can be considered as
60 50
a good indication for experimentally relevant carbon nanostruc-
50 40
tures. From Table 2, one observes that the three studied TPHs

Frequency (THz)
Frequency (THz)

40
30
have Ecoh values intermediate between graphene and graphdiyne. 30
20
The α case is the TPH with the lowest cohesive energy, being also 20

lower than sp + sp2 -hybridized 2D carbon structures such as 10 10

α-graphyne, β -graphyne, γ-graphyne, and graphdiyne. Further- 0 0

Γ Μ Κ Γ Γ Μ Κ Γ K’ M’ Γ
more, it is slightly more (less) stable than the full-sp2 grapheny-
lene (α-naphthylene), which also features dodecagonal pores. Fig. 8 Phonon band structures of the three systems considered in this
study. The band structures for the hexagonal cells are shown along line
Our results also suggest that the β and σ -TPHs have stability sim-
connecting high-symmetry points (Γ, K and M) of the Brillouin zones.
ilar to others carbon structures previously reported in the litera- The absence of complex modes indicates dynamical stability.
ture, as show in Table 2. In addition, we observe that the buckled
version of the β -TPH is the preferable configuration for this lat-
tice, as it has lower Ec than its planar counterpart. While the absence of imaginary frequencies in the phonon band
structures indicates dynamical stability at zero temperature, we
Table 2 Cohesive energy Ec (in eV/atom) and lattice parameter (in Å)
also examined the thermal stability of TPHs above room temper-
of different 2D carbon structures.
ature using BO-MD simulations. In the case of the β structure, we
System Ec Lattice parameter considered the planar configuration as starting point. During the
α-TPH -8.94 7.19 entire simulation, no reconstruction was observed for the three
β -TPH-planar -8.72 8.53 studied TPHs. In the case of the β system, the structure assumed
β -TPH-corrugated -8.77 7.73 a corrugated configuration during the entire simulation time, but
σ -TPH -8.66 9.65 no bond breaking/formation took place in comparison to the pla-
Graphene -9.52 2.48 nar phase. This is consistent with the fact that the corrugated
Fullerene -9.13 –
form is the lowest energy configuration for β -TPH. In addition,
α-graphyne -8.46 7.05
we computed the local Lindemann index δi for every atom i from
β -graphyne -8.56 9.58
γ-graphyne -8.80 6.95 the structure by the following relation 48,49 :
Graphdiyne -8.63 9.56 q
Graphenylene -8.88 6.82 1 hdi2j i − hdi j i2
-8.96 10.37 δi = ∑ , (2)
α-naphthylenes n j6=i hdi j i

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 Page 7 of 13 Physical Chemistry Chemical Physics
where di j is the distance between atoms i and j, the averages are
calculated over the simulation time, and the sum over j is made
through all the n atoms within a given cutoff radius rL from the
equilibrium position of atom i, except i itself. The system-average
index δ is computed using
1
δ=
N ∑ δi , (3)
i
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where N is the number of atoms in the supercell. The system-
average index, as well as the minimum and maximum values of
δi , are plotted as a function of the radius rL for the three studied
TPHs in Fig. 9. As a reference for comparison, we consider the
δNT =0.03 value related to carbon nanotubes 50 . We note that the
Lindemann index is below 0.02 for the three TPHs (except for a
slightly larger value for the α and β structures when rL is below
4.5 Å), thereby indicating that TPHs should maintain structural
integrity at room temperature.
δ δi (min) δi (max)
0.02
0.01
Lindemann index
0
0.02
0.01
0
0.02
0.01
0 Fermi level. An isovalue of 0.00006 eÅ−3 was used here. Fermi level EF
4 6 8 10 12 14 16 18 20
Cuttof radius rL (Å)
Fig. 9 Lindeman index for the three studied TPHs as a function of
the cutoff radius rL . The system-average index is represented by the
black curves, while minimum and maximum values of local index δi are
represented by green and red lines, respectively.
3.2 Electronic Properties
We now turn our attention to electronic properties. The electronic
band structure and density of states (DOS) of α-TPH are shown in
Fig. 10(a) and Fig. 10(b), respectively. This is a metallic system,
with two bands crossing the Fermi level along the Γ − M path,
one along the Γ − K line, and one in the vicinity of the K point.
These bands are marked as I (higher one) and II (lower one),
and they are plotted over the entire Brillouin zone in Figs. 10(c)-
(d), respectively, by a surface and a colormap plots. Note that
the highest of these branches crosses EF along an intricate curve
similar to a six-tip star (as seen from its top view in Fig. 10(c).
In addition, the lower band crosses EF along a path similar to an
hexagon around the Γ point, as can be seen from a top view of
this surface (see Fig. 10(d)). These features indicate that if rolled
up onto a nanotube geometry, α-TPH is likely to result in metal-
View Article Online
DOI: 10.1039/D0CP02574G
lic nanotubes, independently on the chirality. This can be antic-
ipated from a zone folding point of view, as the k-space curves
corresponding to E = EF form closed paths around the Γ point,
as in fullerene based nanotubes reported in the literature 51 .
(a) (b)
Physical Chemistry Chemical Physics Accepted Manuscript
3
2
1 I
E-EF (eV)
0
II
-1
-2
-3
Γ Μ Κ Γ DOS (a.u.)
(c) I E max
(e)
(d) II
E min
Fig. 10 (a) Electronic band structure for α-TPH and (b) corresponding
density states (DOS). (c-d) Frontier bands over the entire Brillouin zone
(surface and color plots). EF is represented by the yellow hexagon. (e)
Local density of states (LDOS) for a 0.1 eV energy interval around the
has been set at E = 0.
In the DOS plotted in Fig. 10(b) we observe a broad range of
energy values around the Fermi level with no forbidden regions,
thus indicating that this system can potentially act as a good elec-
tron injector. Additional calculations are necessary to fully eluci-
date transport properties. We note a set of van Hove singularities
around the Fermi level, specially those at -0.61 eV and 0.42 eV,
which are the closest ones to EF . The system presents a large
density of delocalized states, as shown by the plot of the local
DOS (LDOS), at the Fermi energy value in Fig. 10(e). We note
that these frontier states feature significant overlap involving pz
orbitals from different 12-rings, both through the d11 bonds and
the three-tip-stars of three d23 bonds, leading to the formation of
a π-conjugated framework. The interplay between delocalization
of p electrons and metallic behaviour has also been observed in
carbon-phosphorous systems 52,53 . In these hybrid structures, for
instance, it is shown that hydrogenation changes carbon’s (phos-
phorous) hybridization into sp3 (sp3 d), breaking electron delocal-
ization and turning the systems into semiconductors.
Figs. 11(a)-(b) show the electronic band structure and DOS for
β -TPH in its planar configuration, respectively. One notes that
the valence and conduction energy bands meet at the Fermi level
at the corners of the BZ. Conversely, we observe a zero DOS ex-
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 Physical Chemistry Chemical Physics
actly at the Fermi level in the DOS plot of Fig. 11(b), so that β -
TPH is a zero gap semiconductor similar to graphene. In fact, the
bands form a Dirac cone at EF , as further illustrated in Fig. 11(c),
where we plot the valence and conduction bands over the entire
BZ. These Dirac cones are located at the K points, analogously
to graphene and α-graphyne 54,55 . Note that β -TPH has both in-
version and time reversal symmetries, which are the same sym-
metries protecting the Dirac cones in graphene 56 . However, com-
pared to graphene and α-graphyne, β -TPH’s Fermi velocity (vF ) is
Published on 10 September 2020. Downloaded by Cornell University Library on 9/11/2020 7:24:45 PM.
significantly smaller with vF ∼ 3.93·10−7 m/s, which was obtained
by the vF = h̄−1 ∂ E(k)/∂ k relation applied at the K point (Dirac
point). This value is about 76% and 48% of the α-graphyne and
graphene’s Fermi velocities at their K points, respectively, as cal-
culated by the same approach. The structure also features two
van Hove singularities around EF at −0.61 eV and 0.34 eV. In
order to gain further insight on the characteristics of the states
close to the vertex of the Dirac cone, we plot the LDOS for a
0.1 eV energy range around the Fermi level in Fig. 11(d). These
electronic states are highly delocalized, with the corresponding
partial charge densities from different 12-pores being strongly
connected to each other by the atoms forming the d23 bonds,
resulting in a π-conjugated network. It is also known that an
hybrid HSE06 functional for exchange-correlation describes band
gap values with higher accuracy for many systems 57,58 . In or-
der to have an additional verification of the zero-gap behaviour
for planar β -TPH, we calculated its electronic structure using the
HSE06 functional within GPAW and the results confirm the PBE-
based results. The DOS for the planar β -TPH according to the
HSE06 calculation is shown in Fig. 11(e), where we note that the
DOS is zero exactly at EF . On the other hand, the Fermi velocity
is about 77% higher for the HSE06 functional compared with the
corresponding PBE value as calculated in GPAW.
Note it is expected that if they were prepared in tubular geome-
try, these electronic properties are likely to result in corresponding
β -TPH nanotubes with electronic properties closely related to the
system’s chirality, as in the graphene case 59 . From a zone fold-
ing method, nanotubes with armchair chirality are expected to
be metallic, while the zigzag type nanotube should exhibit semi-
conductor character with band gap depending on the size of the
tube, in an analogous way as to conventional carbon nanotubes
and α-graphyne nanotubes 60,61 .
When we consider the corrugated β -TPH structure, the system
is no longer a zero-gap semiconductor, but a metallic system. The
electronic band structure, along selected paths of the BZ, is plot-
ted in Fig. 12(a), together with its DOS. Note that the BZ is no
longer a regular hexagon an we expanded the k-path in compar-
ison to the planar β -TPH. While the system becomes metallic,
the Dirac cones are still present. However, their energy is 0.40
eV above EF and the k-point where they occur is also moved to
be along the Γ − K 0 direction, as indicated by the green circle in
Fig. 12(a). Note that these cones keep being protected by both
inversion and time-reversal symmetries, as in the planar case, in
analogy to graphene’s case. The cones can be more easily identi-
fied in Fig. 12(b), where we plot the frontier bands (marked by
I and II) over the entire BZ (The Fermi level is represented by
the horizontal hexagon). Looking at the states at the EF , we plot
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View Article Online
DOI: 10.1039/D0CP02574G
(a) (b)
3
2
1
E-EF (eV)
Physical Chemistry Chemical Physics Accepted Manuscript
0
-1
-2
-3
Γ Μ Κ Γ DOS (a.u.)
(c) (d) (e)
HSE06
DOS (arb. units)
-3 -2 -1 0 1 2 3
E-EF (eV)
Fig. 11 (a) Electronic band structure for planar β -TPH, and (b) corre-
sponding density states (DOS); (c) Valence and conduction bands over
the entire BZ (EF is represented by the yellow hexagon); (d) Local den-
sity of states (LDOS) for a 0.1 eV interval around the Fermi level. An
isovalue of 0.00004 eÅ−3 was used. (e) DOS as calculated by the HSE06
functional. Fermi level EF has been set at E = 0.
their corresponding LDOS in Fig. 12(c) and we note that are still
delocalized over the structure, but with larger contributions due
to the pentagons involving the two longer d23 bonds from each
TP.
Finally, we turn to the electronic properties of the σ case. This
sheet is also a metallic system, as shown by its band structure
plotted along high symmetry lines of the BZ in Fig. 13(a), to-
gether with its DOS (Fig. 13(b)). We observe a total of three
bands crossing the Fermi energy, two of them around the Γ and
the other in the vicinity of the K points in the Brillouin zone.
These three branches of the electronic structure are marked as I
(higher one), II (middle one), and III (lower one), and they are
plotted over the entire Brillouin zone in Figs. 13(c)-(e), respec-
tively, both by surface and colormap plots. The LDOS for states
around the Fermi level is plotted in Fig. 13(f). These states are
delocalized over all σ -TPH atoms, but show a stronger contribu-
tion from the 4-membered rings. As in α-TPH, we expect that any
σ -TPH-based nanotubes should be metallic, as their 2D counter-
parts, since the E = EF states of two frontier bands lie in a k-space
closed path around the Γ point (see Figs. 13(c)-(d). In addition,
a careful inspection of the band structure shows a Dirac cone at
the K points, but with a vertex located at ∼ 0.35 eV above EF . On
the other hand, σ -TPH also has a forbidden energy region below
EF , between -1.33 eV and -0.54 eV, a gap which can play an im-
portant role in electronic transport setups due to its proximity to
the Fermi level.
In the DOS plot (Fig. 13(b)) we observe a smooth curve with
nonzero DOS values around the Fermi energy, as observed in the
 Page 9 of 13 Physical Chemistry Chemical Physics
View Article Online
DOI: 10.1039/D0CP02574G

(a) (b) (a) (b)

3 3

2 2

1 1
E-EF (eV)

E-EF (eV)

Physical Chemistry Chemical Physics Accepted Manuscript

I II II
0 0

-1 -1 III
Published on 10 September 2020. Downloaded by Cornell University Library on 9/11/2020 7:24:45 PM.

-2 -2

-3 -3
Γ Μ Κ Γ Κ' Μ' Γ DOS (a.u.) Γ Μ Κ Γ DOS (a.u.)

(c) Κ'
Μ'
Κ
(e) (c) I (f)
Γ Μ
Emax

(d) I (d) II

II (e) III
Fig. 12 (a) Electronic band structure for buckled β -TPH and (b) corre-
Emin
sponding density states (DOS). (c) Illustration of the Brillouin zone and
high-symmetry points. (d) Frontier bands (marked by I and II) over the
entire Brillouin zone (EF is represented by the horizontal hexagon). (e)
Local density of states (LDOS) for a 0.1 eV energy interval around the
Fermi level. An isovalue of 0.0008 eÅ−3 was used here. Fermi level EF Fig. 13 (a) Electronic band structure for σ -TPH and (b) corresponding
has been set at E = 0. density states (DOS); (c-e) Frontier bands over the entire Brillouin zone
(surface and color plots); EF is represented by the yellow hexagon. (f)
Local density of states (LDOS) for a 0.1 eV energy interval around the
Fermi level. An isovalue of 0.0003 eÅ−3 was used here. Fermi level EF
band structure. We also note intense peaks consistent with two has been set at E = 0.
almost flat bands around -2.65 eV and 1.25 eV.

4 Conclusions
In summary, we proposed and studied three two-dimensional
structures (coined tripentaphenes) obtained from the assembly
of acepentalene-like motifs. These structures show an intri-
cate resonance mechanism which accounts for the distribution
of bond lengths over the entire unit cells. DFT predicts that
tripentaphenes are stable structures with formation energies ly-
ing within the corresponding range of values for some existing 2D
carbon nanostructures. In addition, phonons calculations show
that tripentaphenes are dynamically stable. All the studied tripen-
taphenes are shown to be metallic, including a system with Dirac
cones at the corners of the Brillouin zone at the Fermi level. This
metallic behaviour and the strong delocalization of the frontier
states due to double bonds resonance indicate that these systems
can behave as good electron conductors, and, in turn as potential
materials for future nanoelectronics.
Conflicts of interest
There are no conflicts to declare.
Acknowledgements
P.V.S. acknowledges CAPES for scholarship support. E.C.G. ac-
knowledges support from CNPq (Process No. 307927/2017-2
and Process No. 429785/2018-6). P.V.S., A.G.S.F. and E.C.G ac-
knowledge support from PROCAD 2013/CAPES program. The
authors thank the Laboratório de Simulação Computacional Ca-
juína (LSCC) at Universidade Federal do Piauí for computational
support. Work at R.P.I. was supported by the NY State Empire
State Development’s Division of Science, Technology and Innova-
tion (NYSTAR) through Focus Center-NY–RPI Contract C150117.
Appendix: Resonance Mechanisms
In the following we illustrate the resonance structures composing
the resonant hybrids of α-, β -, and σ -TPHs. Starting with the α
case, Fig. 14 illustrates a configuration a (left hand side) and a
second one b (right hand side) obtained from a after a counter-
clockwise rotation of 60◦ around an axis passing by the center of
the pore. There is still a third canonical structure c (not shown)
obtained from a after a clockwise rotation of 60◦ . Clockwise and
counterclockwise rotations of 120◦ applied to a result in config-
urations identical to the b and c structures, respectively, while a
180◦ rotation applied to a is identical to a itself. We enumerate
the double bond in resonant structure a from 1 to 7. In b, we use
arrows to show how these bonds can migrate so as to move from
a to b structure.

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DOI: 10.1039/D0CP02574G

0o 60o For β -TPH we have six different resonant structures forming

the hybrid. In Fig. 15 we illustrate the configuration a (upper left
hand side) together with the b, c, d, e, and f structures obtained
3
1
6
from a after counterclockwise rotations of 60◦ , 120◦ , 180◦ , 240◦ ,
1
7 2
7 and 300◦ , respectively, around an axis passing by the center of the
a b 2

Physical Chemistry Chemical Physics Accepted Manuscript

3
6
3
6 5
pore. We enumerate the double bond in resonant structure a from
5 4 7 1 to 10. In c, we use arrows to show how these bonds migrate so
3 4
1
6
as to move from a to c. The same is done when comparing d to a.
1
Similar transformations can lead to configurations b, e, and f .
Published on 10 September 2020. Downloaded by Cornell University Library on 9/11/2020 7:24:45 PM.

In Fig. 16 we illustrate a resonance structure a (left hand side)

Fig. 14 Resonance structure a (left hand side) for α-TPH with all the for σ -TPH, as well as a second one b (right hand side) obtained
double bonds inside a unit cell enumerated from 1 to 7. Second resonance from a after a counterclockwise rotation of 60◦ around an axis
structure b (right hand side) obtained from a after a counterclockwise passing by the center of the pore. As in α-TPH, there is still a
rotation of 60◦ around an axis passing by the pore center. The arrows in
third canonical structure c (not shown) obtained from a after a
b represent the dislocation of double bonds from the structure a to result
in configuration b. clockwise rotation of 60◦ . Clockwise and counterclockwise rota-
tions of 120◦ applied to a result in configurations identical to the
b and c structures, respectively, while a 180◦ rotation applied to a
0o 60o is identical to a itself. We enumerate the double bond in resonant
structure a from 1 to 10. In b, we use arrows to show how these
5 7 bonds migrate so as to move from a to b.
6
4 8

3
a 9
b 0o 60o
2 1 10

5 7 6

3 4 4 1
3
2 5 5

o o a 2
b 6

120 180 1

10 7
6
1
10
7

8
9 8 6 9
5 7 1
6 7 3
4 6 8
4 8

c 10 2

3
2
9
5

3
d 9
10
1 1
5 2
5 7
7 clockwise rotation of 60◦ around an axis passing by the pore center. The
240o 300o
e f
7
Fig. 15 Resonance structure a (upper left hand side) for β -TPH with all
the double bonds inside a unit cell enumerated from 1 to 10, together
with the b, c, d, e, and f structures obtained from a by counterclockwise
rotations of 60◦ , 120◦ , 180◦ , 240◦ , and 300◦ around an axis passing by
the pore center, respectively. The arrows in c and d represent the dis-
location of double bonds from the structure a to result in the rotated
configurations.
Fig. 16 Resonance structure a (left hand side) for σ -TPH with all the
double bonds inside a unit cell enumerated from 1 to 10. Second res-
10 onance structure b (right hand side) obtained from a after a counter-
arrows in b represent the dislocation of double bonds from the structure
a to result in configuration b.
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Physical Chemistry Chemical Physics Accepted Manuscript

Published on 10 September 2020. Downloaded by Cornell University Library on 9/11/2020 7:24:45 PM.

In this work, three 2D nanocarbon allotropes containing large pores are proposed and have their electronic structure
studied by using DFT methods.