Struct Chem (2014) 25:1695–1710
DOI 10.1007/s11224-014-0440-4
ORIGINAL RESEARCH
A first principle study of pristine and BN-doped graphyne family
Ngangbam Bedamani Singh • Barnali Bhattacharya
Utpal Sarkar
Received: 12 November 2013 / Accepted: 5 May 2014 / Published online: 28 May 2014
Ó Springer Science+Business Media New York 2014
Abstract Based on first principle calculation using gen-
eralized gradient approximation, we report electronic
properties of graphyne and its related structures (graph-
diyne, graphyne-3, graphyne-4). Boron and nitrogen atoms
are systematically substituted into the position of carbon
atom and the corresponding changes of the properties are
reported. All the structures are found to be direct band gap
semiconductors with band gap depending on the concen-
tration and position of the doping material. Our band
structure calculation clearly shows that the band gap can be
tuned by B–N doping and the spin-polarized calculation
depicts the nonmagnetic nature of these structures. The
possibility of modulating the band gap provides flexibility
for its use in nanoelectronic devices. Projected density of
state (PDOS) analysis shed insights on the bonding nature
of these novel materials, whereas from the view point of
Crystal Orbital Hamilton Population (–COHP) analysis, the
nature of chemical bonding between neighbouring atoms
and the orbital participating in bonding and antibonding
have been explored in details.
Keywords Graphyne  Stability  Electronic band gap 
Density of states  –COHP analysis
Electronic supplementary material The online version of this
article (doi:10.1007/s11224-014-0440-4) contains supplementary
material, which is available to authorized users.
N. B. Singh  B. Bhattacharya  U. Sarkar (&)
Department of Physics, Assam University, Silchar 788011, India
e-mail: utpalchemiitkgp@yahoo.com
•
Introduction
Carbon-based nano materials have attracted great attention
due to their unique properties and wide prospect for tech-
nological applications [1–14]. Different allotropes of car-
bon such as fullerene, carbon nanotube (CNT), graphene
have already enriched the future nano-electronics [1–3]. As
a result, so many works have already been done on nano-
tube, graphene and their derivatives having different car-
bon network [10–14]. Graphene, one of the most versatile
materials of recent days, has been in the focus because of
its exciting properties and potential use in technological
applications [3–5]. For the application of graphene in nano-
electronics, the band structure near the Dirac cones has to
be suitably controlled [4]. Graphyne, a new planar allo-
trope of carbon with hexagonal rings joined together by
acetylenic linkages (–C:C–) are also shown to possess
Dirac cones [15]. The planar structure of graphyne was first
predicted by Baughman et al. [16], and the presence of
acetylenic link provides an extra flexibility in modulation
of its structure. Other members of graphyne family can be
obtained by increasing the number of –C:C– links
between two hexagonal rings. Even though, the experi-
mental fabrication of graphyne cannot achieved so far,
graphdiyne (expanded graphynes having two acetylenic
lingkages) films and graphdiyne tubes have already been
synthesized [17, 18].
Unlike graphene, graphyne and its families have non-
zero band gap which is attributed to the presence of
acetylenic linkages [19] and this non-zero band gap prop-
erty may provide a golden opportunity to use them in
electronic device. As the band gap directly depends on the
chain length and the size of hexagon, by varying the length
of chain and size of hexagon one can modulate its band
gap. That is why graphyne is more flexible than graphene
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and CNT. However, the first principle calculations [19]
have shown that graphyne and its related structures are
small band gap semiconductors which need to be widened
up in order to use in the electronic devices.
Chemical doping is one of the most common and
effective method for controlling the electronic properties of
graphene [20–22]. Hybrid boron carbon nitrogen (BNC)
structures obtained by doping B and N (BN) atoms into
carbon network and are expected to possess suitable band
gap property [23]. The doping with boron and nitrogen
affects the electronic conductivity and density of states of
graphene sheet and single-walled CNT [24]. BN doping
also changes the global and local reactivity parameters of
nanotube [25]. Nitrogen doping led to the appearance of a
true band gap in graphene electronic spectrum even for a
random distribution of the N dopants [22]. Therefore, we
can expect such widening of band gap and also interesting
changes in electronic properties due to doping on graphyne,
graphdiyne and other extended systems.
Recent investigation on the electronic and optical
properties of graphyne-like boron nitride sheet [26] reveals
their wide band gap and strong absorption behaviour in UV
region. In another theoretical investigation of boron–
nitrogen (B–N) substituted graphdiyne reveals that B–N
preferred to substitute sp-hybridized carbon at chain than
hexagon at low-doping rate, and at high-doping rate, it first
attack the hexagon before attacking chain [27].
Being influenced by these findings, and also by the
successful synthesis of BN sheet and BN-doped graphene
[28, 29]; we have carried our study considering all possi-
bility of B–N substitution on graphyne and its related
structures. For the substitution, we first consider the
structures with carbon atom at hexagonal rings linked by
BN-chains. Next, the structures with BN-rings linked by
C-chains are considered and finally, all the carbon atoms
are substituted with BN atoms. Here, our result demon-
strates the change in electronic structure by B–N substi-
tution at different sites and the associated effects. The
projected density of state (PDOS) and Crystal Orbital
Hamilton Population (–COHP) analysis have been done to
determine the orbital responsible for energy states near
Fermi level and the nature of the chemical bonding by
exploring the orbitals participating in bonding and anti-
bonding states respectively.
Computational details
The spin-polarized density functional theory calculations
[30] have been performed with GGA and Perdew–Burke–
Ernzerhof (PBE) is used to treat the exchange correlation
part of density functional. The DZP basis set has been
employed and the norm-conserving Troullier–Martins
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Struct Chem (2014) 25:1695–1710
pseudopotentials [31] are used for the core–valence inter-
actions. We have done the structure relaxations by conju-
gate-gradient method as implemented in the siesta package
[32]. Relaxation was done until the forces on the atoms are
less or equal to 0.010 eV/Å. The Brillouin zone was
sampled using 11 9 11 9 1 Monkhorst–Pack set of k
points. The mesh cut-off value was set at 300 Rydberg. To
avoid the interaction between two images, the vacuum
space of 15 Å is used along z direction. To study the sta-
bility of the various configurations, the cohesive energy is
calculated as
EðSystemÞ  ½nEðCÞ þ mEðBÞ þ lEðNÞ
Cohesive energy ¼ ;
nþmþl
where E (System), E(C), E (B) and E (N) are energies for
the whole system, carbon, boron and nitrogen atoms,
respectively, and n, m, l are the number of carbon, boron
and nitrogen atoms present in the system, respectively.
Results and discussions
The optimized geometries along with their unit cells are
presented in Fig. 1. Figure 1a represents graphyne which
contains one acytelinc linkage (–C:C–) between two
adjacent carbon hexagons of graphene. The other pristine
member of graphyne family containing more acetylenic
linkages between the nearest neighbouring carbon hexagons
is presented in Fig. 1e–g, where graphdiyne, graphyne-3 and
graphyne-4 contain two, three and four acetylenic linkages,
respectively. The BNC derivatives of graphyne, i.e.
‘graphyne with BN at linear chain’ and ‘graphyne with BN at
hexagonal ring’ are shown in Fig. 1b–c, where the former is
composed of carbon hexagonal rings linked by BN chain and
the latter is composed of BN hexagons connected by carbon
chain. Figure 1d depicts ‘graphyne-like BN sheet’ where all
the carbon atoms of pristine graphyne are replaced by
alternative arrangement of boron and nitrogen. In general,
replacement of all carbon atoms along the chain between two
carbon hexagons of pristine graphyne family by alternative
arrangement of boron and nitrogen has been termed as
‘systems with BN at linear chain,’ while substitution of all
carbon atoms of carbon hexagons of pristine graphyne
family by boron and nitrogen give rise to ‘systems with BN at
hexagonal ring’. Finally, we have replaced all the carbon
atoms of pristine graphyne family by alternative arrange-
ment of boron and nitrogen to get ‘BN sheet’.
Lattice length of all the systems in the present study is
presented in Table 1. We observed that the cell length
changes not only on replacing the carbon atom by BN
atoms but also depend on the position of the BN atoms.
The observed behaviour is because of the formation of
different types of bonds at different sites, and also different
Struct Chem (2014) 25:1695–1710 1697

Fig. 1 Geometric structure of optimized a graphyne, b graphyne with BN at linear chain, c graphyne with BN at hexagonal ring, d graphyne-like
BN sheet, e graphdiyne, f graphyne-3, g graphyne-4

Table 1 Lattice cell (in angstrom) of graphyne, graphdiyne, graphyne-3, graphyne-4 and their BN analogues
System Number of Pristine Systems with BN Systems with BN BN sheet
acetylenic lingkages (Lattice at linear chain at hexagonal ring (Lattice
in chain cell in Å) (Lattice cell in Å) (Lattice cell in Å) cell in Å)

Graphyne and its analogues 1 6.909 6.992 6.995 7.001

Graphydiyne and its analogues 2 9.502 9.589 9.589 9.620
Graphyne-3 and its analogues 3 12.095 12.207 12.183 12.233
Graphyne-4 and its analogues 4 14.681 14.827 14.772 14.860

atomic radii of carbon, boron and nitrogen atoms. Overall,
the lattice lengths are seen to increase when B, N atoms are
introduced and the BN sheet has maximum lattice cell
length. When B, N atoms are doped at the hexagon site, it
has minimum cell length compared to BN sheet.
Detailed structures
For the sake of clarity, we denote different types of bonds
of pristine structures by assigning numbers as shown in
Fig. 2. Let us first consider the structure of graphyne,

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Fig. 2 Bond types of a graphyne and its analogues, b graphdiyne and its analogues, c graphyne-3 and its analogues, d graphyne-4 and its
analogues
where the carbon atoms forming the hexagonal ring is sp2
hybridized, and these hexagons are joined by sp-hybridized
acetylenic linkages. In the present study, the C–C bond in
hexagonal rings of graphyne (bond 1) is found to be
1.427 Å. This bond between two sp2 hybridized C atoms
has (r ? big p) character as in pristine graphene sheet and
lies in between single (*1.470 Å) and double (*1.380 Å)
bonds. px, py and s orbitals contribute to r bond, and the p
bond is contributed by pz orbitals. Hence, the p conjugation
feature of graphene still remains in the hexagons. The bond
between the hexagonal ring and C-chain (bond 2 and 4) is
1.412 Å, which is shorter than single r bond (*1.470 Å),
implying the presence of p bonding between them. This
bond between sp2 and sp-hybridized C atoms is contributed
by px, py and s orbitals. The C–C bond between two sp-
hybridized C atoms (bond 3) in the chain is observed to be
1.232 Å, close to the triple bond (*1.210 Å), indicating
that a triple bond is formed in between them. These two sp-
hybridized C atoms are (r ? 2p) bonded, where px, py and
s orbitals contribute to r bond and one of the p bond, while
the other p bond is contributed by px and py orbitals. The
distance between two nearest hexagonal rings is 6.909 Å.
When BN are placed at the linear chain positions of
graphyne as presented in Fig. 1b, the bond between two C
atoms in the hexagonal ring (bond 1) increases to 1.445 Å,
and the bond between sp2 hybridized C atom and boron (or
nitrogen) is 1.516 Å (or 1.335 Å). The carbon– nitrogen
(C–N) bond is much shorter than the C–B bond due to the
different atomic radii of BN. The C–B bond is mainly
contributed by the pz orbitals of C and B atoms (and dis-
cussed in –COHP analysis below). The bond between BN
atoms, in the linear chain (bond 3) is 1.264 Å, which has a
triple bond type of character.
On putting BN atoms at the hexagonal rings, while the C
atoms remain at the linear chain positions as shown in
Fig. 1c, we observed that the B–N bond (bond 1) is
1.461 Å, which is slightly higher than the calculated values
of 1.452 Å in the pristine BN sheet [33, 34]. The bond
between C and B atom (bond 2) is 1.494 Å, while C and N
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Struct Chem (2014) 25:1695–1710
atom (bond 4) is 1.346 Å. The C–C bond in the linear chain
(bond 3) retains its triple bond characteristics with the bond
length being 1.231 Å.
Next, we consider the structure of the graphyne-like BN
sheet which consists of BN hexagons and linear BN chain
units as seen in Fig. 1d. Such system consists of mixed
type of hybridization (sp2 ? sp). The B–N bond in the
hexagons (bond 1) is found to be 1.466 Å, which is larger
than the pristine BN sheet bond length of 1.452 Å [33, 34].
The B–N bond at the middle of the linear chain (bond 3) is
1.271 Å and has triple bond characteristics. The B–N bond
between B atom at hexagon and N atom at linear chain
(bond 2) is observed to be 1.395 Å, whereas the bond
between N atom at hexagon and B atom at linear chain
(bond 4) is 1.399 Å (slightly higher than bond 2). This
slight difference in the bond lengths of bond 2 and bond 4
arises due to the different neighbouring environments of B
and N atoms. In case of bond 2, B atom is bonded with
three N atoms (two at hexagons and one at chain), whereas
in bond 4, B atom is bonded with only two N atoms (one at
linear chain and another at hexagon). An approximate
character of single and double bond alternations is
observed in the linear BN chain.
The bond lengths of graphyne and its derivatives are
represented in Fig. 3. In case of graphdiyne, the bond length
in the hexagon (bond 1) is found to be 1.432 Å, which lies in
between typical single and double C–C bonds. The bond at
the centre of the linear chain (bond 4) is found to be 1.349 Å,
which is basically the bond length for single C–C bond in
diacetylene (*1.380 Å). The bond joining the carbon atoms
at the hexagon and at the chain (bonds 2 and 6) is 1.402 Å,
shorter than the typical single C–C bond, while the bonds 3
and 5 are found to be 1.242 Å, which is nearly equal to the
triple bond length (*1.210 Å). Thus, we observed an
approximate alternation of triple and single bonds in the
linear chain of graphdiyne and also in its BN analogues (see
Fig. 3b). Similar behaviour of bond alternations is also
observed in graphyne-3 (Fig. 3c) and graphyne-4 (Fig. 3d)
and in their BN analogues. The C–C bond in the hexagon
Struct Chem (2014) 25:1695–1710
Fig. 3 Bond lengths of a graphyne and its analogues, b graphdiyne and its analogues, c graphyne-3 and its analogues, d graphyne-4 and its
analogues
(bond 1) is same (1.432 Å) for graphdiyne, graphyne-3 and
graphyne-4, which clearly signify that increasing the number
of atoms in the linear chain has negligible effects to the atoms
at the hexagons for these systems. This constant bond length
behaviour of bond 1, on increasing the number of atoms in
the chain positions, is also true when BN atoms are placed in
graphdiyne, graphyne-3 and graphyne-4 and can be seen
from Fig. 3b, c and d.
Bandstructure
We have presented the spin-resolved bandstructure of
graphyne family and observed that all the structures are
direct band gap semiconductors. No splitting of band
structure for spin up and spin down has been observed in
their band structure.
Our calculation of valence band maximum (VBM) and
conduction band minimum (CBM) of graphyne (repre-
sented in Fig. 4a) reveals that both VBM and CBM are
located at M point in the hexagonal brillouin zone and the
gap is 0.454 eV, consistent with the results of other GGA–
PBE calculation [35]. The bandstructure for graphdiyne is
presented in Fig. 4b, depicts that graphdiyne is direct band
1699
gap semiconductor with a gap of 0.485 eV. The CBM and
VBM are located at the gamma (C) point of the brillouin
zone. We see that graphdiyne has higher band gap compare
to graphyne. The bandstructure of graphyne-3 and graph-
yne-4, as shown in Fig. 4c, d, respectively, depicts that
they are also direct band gap semiconductor with band gap
of 0.566 eV located at M point and 0.542 eV located at C
point of the brillouin zone, respectively. So the band gap
location is characterized by the number of acetylenic
linkages present between two neighbouring benzene rings.
Next, we calculate the bandstructures by introducing BN
atoms at the linear chain positions, at the hexagonal posi-
tions and at linear chain, as well as in hexagonal positions
and are presented in Fig. 4e, f and g, respectively. The
bandstructure of graphyne with BN atoms at linear chain
site (Fig. 4e) indicates that both VBM and CBM are at the
M point and the band gap is 1.392 eV, which is much
greater than that of graphyne. But the placement of BN
atoms at the hexagons of graphyne increased the band gap
to 2.502 eV, with VBM and CBM at M point, as shown in
Fig. 4f. However, the bandstructure for graphyne-like BN
sheet given in Fig. 4g, reveals that VBM and CBM are
located at M point of the brillouin zone with a wide band
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Fig. 4 Bandstructure of a graphyne, b graphdiyne, c graphyne-3, d graphyne-4, e graphyne with BN at linear chain, f graphyne with BN at
hexagonal ring, g graphyne-like BN sheet
gap of 4.110 eV. The band gaps for pristine graphyne
systems (one to four acetylenic linkages along linear chain)
and BN-substituted graphyne systems (one to four BN
linkages along linear chain) are presented in Fig. 5a.
We see that the band gap for graphyne, graphydiyne,
graphyne-3 and graphyne-4 is increased when BN atoms
are placed in the system. When all the carbon atoms are
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Struct Chem (2014) 25:1695–1710
replaced by BN, i.e. BN sheet, the gap becomes very large
(4.110, 3.759, 3.609, 3.416 eV for graphyne, graphydiyne,
graphyne-3 and graphyne-4-like BN sheets, respectively).
Hence, by changing the length of the carbon atom chain
and also by introducing BN, the band gap in such systems
can be tuned. This property might be useful in electronics
and semiconductor industry.
Struct Chem (2014) 25:1695–1710
Fig. 5 a Band gaps of graphyne, graphdiyne, graphyne-3, graphyne-4 and their BN-doped structural analogues. b Cohesive energies of
graphyne, graphdiyne, graphyne-3, graphyne-4 and their BN-doped structural analogues
Cohesive energy
Since more negative cohesive energy signifies greater sta-
bility of the system, it is clear from Fig. 5b that the pristine
systems are more stable than their BN analogues. The BN
sheet has more negative cohesive energy than the systems
where BN placed at linear or hexagonal position. The
stability of the pristine systems is in the order of graph-
yne [ graphdiyne [ graphyne-3 [ graphyne-4, and the
stability on placing BN atoms is in the order of pris-
tine [ BN sheet [ BN at linear chain [ BN at hexagons,
as depicted in Fig. 5b. It is also clear from Fig. 5b that
cohesive energy tends to attain a saturation value when
number of acetylenic linkage in the linear chain increases.
Density of states
For an understanding of the contribution of each constitu-
ent, we have presented spin resolved PDOSs along with
total density of states. Our spin-polarized calculation shows
that the pristine graphyne family and their BN analogues
are nonmagnetic, and the density of states for both spin are
symmetric. For the sake of simplicity, here we have dis-
cussed the density of states for up spin only.
The density of states for pristine graphyne is depicted in
Fig. 6a, the region above -2.000 eV and below the Fermi
level (Fig. 6a (ii)) in the valence band (VB) is mainly
contributed by pz orbitals, and the region between -3.000
and -1.600 eV is dominated by px, py and pz orbitals,
though pz contribution is less than that of px and py. It is
clear from the Fig. 6a (iii) that in the valence band, the
energy levels from -1.400 eV to the Fermi energy are
equally contributed by C atoms at linear chain, as well as at
the C atoms at hexagons. But the contribution from atoms
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at linear chain becomes dominant in the range -3.500 to
-1.500 eV (Fig. 6a (iii)). In the conduction band (CB),
energy levels up to 3.300 eV above the Fermi level is
contributed more or less equally by both, C atoms in
hexagonal ring position and C atoms at linear chain posi-
tion, while above 3.300 eV, the main contribution comes
from atoms in linear chain position. The main contribution
in the CB up to 3.400 eV, comes from pz orbital of C
atoms; and the region between 3.400 and 5.200 eV, px, py
and pz orbitals are contributing, sometimes pz is contrib-
uting more than px and py or vice versa (Fig. 6a (ii)).
The density of states for graphdiyne, seen in Fig. 6b (ii),
depicts that near the Fermi energy (-1.100 to 1.700 eV),
the energy states are contributed by the pz orbitals. The s,
px and py orbitals do not make any substantial contributions
to the energy states around the Fermi energy. In the region
between -2.000 and -1.500 eV of the VB, the major
contribution is coming from px and py orbitals, while s-
orbital contribution is negligible. But in the CB, the region
from 2.300 to 3.000 eV, the energy states are contributed
by px, py and pz orbitals, however, pz contribution is less
than the other two orbitals. The contribution from atoms at
the linear chain is more than from that of atoms at hexa-
gons and is evident from Fig. 6b (iii). When we compare
graphyne and graphdiyne, we see that the contribution from
the linear chain atoms is more than from that of atoms at
hexagons (Fig. 6a (iii), b (iii)) and it is expected since the
number of atoms in linear chain is greater than that of
hexagons, in case of graphdyine, while they are equal for
graphyne.
The density of states for graphyne-3 and graphyne-4 is
presented in Fig. 6c, d, respectively. In the VB and CB
region of graphyne-3 and graphyne-4, we observed that s,
px, py and pz orbitals are contributing in the same fashion as
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Fig. 6 Total and partial DOS of a graphyne, b graphdiyne, c graphyne-3, d graphyne-4, e graphyne with BN at linear chain, f graphyne with BN
at hexagonal ring, g graphyne-like BN sheet
they do for graphyne and graphdiyne. The only difference
is that the contribution of px and py orbitals starts con-
tributing at energy levels closer to Fermi level compared to
that of graphyne and graphdiyne. As observed in case of
graphyne and graphdiyne, the contributions of s, px and py
orbitals near the Fermi energy (-0.800 to 1.500 eV for
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Struct Chem (2014) 25:1695–1710
graphyne-3 and -0.600 to 1.100 eV for graphyne-4) is
negligible and only pz orbital is contributing in graphyne-3
and graphyne-4.
In Fig. 6e, f and g, we represent the total and partial
density of states when graphyne is doped by BN atoms at
the linear chain site, at the hexagonal position and
Struct Chem (2014) 25:1695–1710
Fig. 6 continued
throughout the system, respectively. The contribution of
carbon, nitrogen and boron atom is presented in Figs. 6e
(ii), (iii) and (iv). From Fig. 6e (ii), it is clear that for
carbon atom the pz orbital is basically contributing in the
valance band, as well as in CB. In case of nitrogen and
boron atom, all the p-orbitals are contributing (Fig. 6e (iii)
and (iv)) in the valence and conduction band. However,
1703
p-orbitals contribution in the VB is more than that of the
CB in case of nitrogen, whereas, opposite effect has been
seen in case of boron. For all three atoms, the pz orbital first
start to contribute to the energy levels in both side of the
Fermi level compared to other orbitals.
Figure 6f (ii), (iii) and (iv) show the contribution of
individual atoms to the density of states when BN atoms
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Fig. 7 –COHP analysis of pristine a graphyne, b graphdiyne, c graphyne-3, d graphyne-4
are doped at the hexagonal positions of graphyne. We
observed that all the p orbitals of C atoms (Fig. 6f (ii))
contribute both in the valance and conduction band. This
feature was not seen when BN atoms are situated at linear
chain site of graphyne, in which only pz orbitals of C atoms
contribute mainly to both the bands (Fig. 6e (ii)). The N
atoms contribution is mainly coming from pz orbitals with a
small part coming from px and py orbitals in the VB as can
be seen from Fig. 6f (iii). For B atoms, shown in Fig. 6f
(iv), the contribution of pz orbitals is again much larger as
compared to other orbitals.
For graphyne like BN sheet, energy levels near the
Fermi level of VB come from the p-orbitals of the N atoms
(Fig. 6g (ii)) and near the Fermi level of CB come from the
p-orbitals of the B atoms (Fig. 6g (iii)). In both situations
pz orbital start contributing first and its contribution is
higher than others. Major contribution in the valence region
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Struct Chem (2014) 25:1695–1710
comes from N atoms but for conduction region, major
contribution is from B atoms. The significant contribution
of N atoms in the VB comes from those atoms which are at
the linear chain site, while atoms at the hexagons con-
tribute very less (Fig. 6g (iv)). As far as the contribution of
B atoms in the CB near the Fermi level is considered,
contributions of both the B atoms at the linear chain and
hexagon sites are nearly equal (Fig. 6g (iv)).
–COHP analysis
In order to partition the band structure energy in terms of
orbital pair contribution and have a clear vision about
chemical bonding, we have considered the –COHP analy-
ses which illustrate pair wise interaction of occupied
(bonding) and unoccupied (antibonding) band. The –COHP
analyses gives an idea about the participating orbital pair,
Struct Chem (2014) 25:1695–1710 1705

Table 2 Nature of chemical bonding in pristine graphyne, graphdiyne, graphyne-3, graphyne-4

System 1st Energy state Nature of 1st Energy state Nature of Participating Difference between
at valence band chemical at conduction chemical orbital first energy states
(near EF)) bonding band (near EF) bonding at VB and CB

Graphyne -0.256 Bonding 0.266 Bonding pz–pz 0.522

Graphdiyne -0.352 Bonding 0.352 Bonding pz–pz 0.704
Graphyne-3 -0.293 Bonding 0.274 Bonding pz–pz 0.567
Graphyne-4 -0.263 Bonding 0.264 Bonding pz–pz 0.527

Fig. 8 –COHP analysis of a B–N interaction in graphyne with BN at chain, b B–C interaction in graphyne with BN at chain, c C–C interaction
in graphyne with BN at chain, d C–N interaction in graphyne with BN at chain

where the positive value represents the bonding state and
negative value, the antibonding states.
The –COHP analysis for pristine graphyne, graphdiyne,
graphyne-3, graphyne-4 are demonstrated in Fig. 7a, b, c
and d, respectively. The states below the Fermi level (VB)
and above the Fermi level (CB) contain bonding (occupied)
states close to Fermi energy due to the contribution of
p-orbital (Fig. 7a (i)). More specifically the pz orbital of
carbon gives the clear insight (Fig. 7a (ii)) about the strong
p-bond hybridization. In the case of pristine graphyne, we
consider the carbon–carbon (C–C) interaction in chain
(Fig. 7a (i)), and found that the first bonding states appears
at -0.256 eV below and 0.266 eV above the Fermi level.
Similar result was found when a carbon atom in ring

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1706 Struct Chem (2014) 25:1695–1710

interacts with a neighbouring carbon atom in chain or with
the carbon atoms in the ring. Figure 7a (ii) states that pz has
dominant bonding contribution near the Fermi level, on
both side, and the other orbital pairs contribute in bonding
at much lower energy (see Fig. S1a in the supplementary
material). Hence pz orbital is responsible for strong p-bond
hybridization; strongly bind at the energy -0.256 and
0.266 eV (Fig. 7a (ii) inset). Similar type of bonding
interaction has been observed in pristine graphdiyne,
graphyne-3 and graphyne-4 and is depicted in Fig. 7b, c
and d. Only difference is that when the chain size increases
the bonding contribution of the px–px, py–py s–s orbital
pairs appear near the Fermi energy than graphyne (see Fig.
S1 in the supplementary material). Table 2 represents the
relative position of the bonding states.
Then, we report –COHP analysis by putting B–N at
chain and observed that four considerable interaction lies
between boron–nitrogen (B–N), boron–carbon (B–C),
carbon–carbon (C–C) and carbon–nitrogen (C–N). In B–N
interaction of graphyne, the most notable feature is the
bonding states near the Fermi level appears at -0.623 eV
due to the contribution of pz orbital of boron and nitrogen,
whereas the antibonding states are found at 0.82412 eV,
contributed by the pz orbital pair of both boron and nitrogen
(Fig. 8a). For B–C, N–C interaction, the antibonding state
appears at -0.623 eV (Fig. 8a, b), while the bonding states
appears at 0.824 eV (Fig. 8a, b). The C–C interaction is
always contributed by bonding states near the Fermi level.
Table 3 tabulates the nature of chemical bonding for
graphdiyne, graphyne-3 and graphyne-4 with BN at chain.
It has been observed that the presence of BN atoms in chain
sweeps the energy states (bonding and antibonding) away
from Fermi level as we go from graphyne to graphyne-4
which results an increasing trend for difference between
first energy states at VB and CB with order graph-
yne \ graphdiyne \ graphyne-3 \ graphyne-4.
The –COHP analysis of graphyne family with B–N at
ring has a remarkable feature that the difference between
first energy states at VB and CB (band gap) shows a
decreasing trend with increase in chain size. Another
important observation for graphyne is that the presence of
B–N at ring shifts the bonding and antibonding states away
from the Fermi level (in both CB and VB) than graphyne
with B–N at chain site and increase the band gap. In case of
graphdiyne with B–N at ring site, the first energy state
moves away in VB and comes nearer in CB than graph-
diyne with B–N at chain site which results negligible
increase in band gap. However, for graphyne-3 and
graphyne-4, the energy state is more close to Fermi level
(in both CB and VB) in comparison to B–N at chain site
showing the opposite trend for bandgap which are in good
agreement with the result depicted in Fig. 5a.
In case of B–N (Fig. 9a), B–C (Fig. 9b), and C–N
(Fig. 9c) interaction of graphyne, the first bonding (occu-
pied) state appears at -1.538, 0.954 and 0.954 eV,
respectively, whereas the antibonding (unoccupied) states

Table 3 Nature of chemical bonding in graphyne, graphdiyne, graphyne-3 and graphyne-4 with BN at linear chain
Interaction System 1st Energy state Nature of 1st Energy state Nature of Participating orbital Difference between
at valence band chemical at conduction chemical first energy states
(near EF)) bonding band (near EF) bonding at VB and CB

B–C Graphyne -0.623 Antibonding 0.824 Bonding pz–pz 1.447

Graphdiyne -0.953 Bonding 1.127 Bonding pz–pz 2.080
Graphyne-3 -1.207 Bonding 1.145 Bonding pz–pz 2.352
Graphyne-4 -1.264 Bonding 1.267 Bonding pz–pz 2.531
B–N Graphyne -0.623 Bonding 0.824 Antibonding pz–pz 1.447
Graphdiyne -0.952 Bonding 1.127 Bonding pz–pz 2.080
Graphyne-3 -1.114 Antibonding 1.177 Bonding pz–pz 2.290
Graphyne-4 -1.174 Bonding 1.238 Bonding px–px,py–py in 2.410
valence
band and pz–pz
in conduction band.
C–C Graphyne -0.623 Bonding 0.824 Bonding pz–pz 1.447
Graphdiyne -0.953 Bonding 1.127 Bonding pz–pz 2.080
Graphyne-3 -1.207 Bonding 1.145 Bonding pz–pz 2.351
Graphyne-4 -1.264 Bonding 1.267 Bonding pz–pz 2.531
N–C Graphyne -0.623 Antibonding 0.824 Antibonding pz–pz 1.447
Graphdiyne -0.952 Bonding 1.1274 Bonding pz–pz 2.080
Graphyne-3 -1.145 Antibonding 1.207 Antibonding pz–pz 2.351
Graphyne-4 -1.264 Antibonding 1.267 Antibonding pz–pz 2.531

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Fig. 9 –COHP analysis of a B–N interaction in graphyne with BN at hexagonal ring, b B–C interaction in graphyne with BN at hexagonal ring,
c N–C interaction in graphyne with BN at hexagonal ring, d C–C interaction in graphyne with BN at hexagonal ring
are found at 0.954, -1.538 and -1.538 eV (Fig. 9c), near
the Fermi level. But in C–C (Fig. 9d) interaction, both VB
and CB comprises bonding state near the Fermi level at
-1.538 and 1.040 eV. Table 4 shows the nature of bonding
and the responsible orbital of graphdiyne, graphyne-3 and
graphyne-4.
Figure 10 depicts that all these three interaction contains
the bonding state far away from Fermi level at -2.753 and
at 1.378 eV thus results a high increase in band gap. Same
type of observation has been seen (see Figs. S2, S3 and S4
in the supplementary material) in case of graphdiyne,
graphyne-3 and graphyne-4-like BN sheet containing
bonding states at VB and CB, except for graphyne-4-like
BN sheet in the CB of B–N interaction where it shows
antibonding state near the Fermi level, and is depicted in
Table S1(in the supplementary data). Only exception is that
the px and py orbitals are also participating in bonding
along with pz orbital near the Fermi level for graphdiyne,
graphyne-3 and graphyne-4-like BN sheet which is absent
in case of graphyne-like BN sheet. It is important to note
that the difference between first energy states at VB and
1707
CB shows similar decreasing trend with increase in chain
size (presented in Table S1 in the supplementary data), as
obtained in graphyne family with BN at ring site, which is
in good agreement with the result obtained in band struc-
ture analysis.
From the above analysis of the orbital participating to
the bonding and antibonding in graphyne and graphyne
with B–N, it is clear that all the bonding and antibonding
states near the Fermi level are arises due to the dominant
contribution of pz–pz pair of the neighbouring atoms. The
states contributed by other orbital pair px–px, py–py, s–s, are
negligible near Fermi energy and arise at much lower or
much higher energy, far away from the Fermi level. When
we go from graphyne to graphyne-4, with the increasing
chain size, the bonding contribution of the px–px, py–py,
s–s orbital pair appears near the Fermi energy seen (see
Fig. S1 in the supplementary material). The –COHP ana-
lysis clearly manifest that doping with B–N shifts the
energy states away from the Fermi level. This is due to the
enhancement of bonding discrepancy between B and N
atom.
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1708 Struct Chem (2014) 25:1695–1710

Table 4 Nature of chemical bonding in graphyne, graphdiyne, graphyne-3 and graphyne-4 with BN at hexagonal ring
Interaction System 1st Energy Nature of 1st Energy state Nature of Participating Difference between
state at valence chemical at conduction chemical orbital first energy states
band (near EF)) bonding band (near EF) bonding at VB and CB

B–C Graphyne -1.538 Antibonding 0.954 Bonding pz–pz 2.492

Graphdiyne -1.386 Bonding 0.753 Bonding pz–pz 2.139
Graphyne-3 -0.866 Antibonding 0.882 Bonding pz–pz 1.748
Graphyne-4 -0.857 Antibonding 0.650 Bonding pz–pz 1.507
B–N Graphyne -1.538 Bonding 0.954 Antibonding pz–pz 2.492
Graphdiyne -1.386 Bonding 0.750 Bonding pz–pz 2.136
Graphyne-3 -0.866 Bonding 0.882 Antibonding pz–pz 1.748
Graphyne-4 -0.947 Bonding 0.650 Bonding pz–pz 1.597
C–C Graphyne -1.538 Bonding 0.954 Bonding pz–pz 2.492
Graphdiyne -1.386 Bonding 0.753 Bonding pz–pz 2.139
Graphyne-3 -0.866 Bonding 0.882 Bonding pz–pz 1.748
Graphyne-4 -0.947 Bonding 0.650 Bonding pz–pz 1.597
N–C Graphyne -1.538 Antibonding 0.954 Bonding pz–pz 2.492
Graphdiyne -1.386 Bonding 0.753 Bonding pz–pz 2.139
Graphyne-3 -0.866 Antibonding 0.882 Bonding pz–pz 1.748
Graphyne-4 -0.917 Antibonding 0.650 Bonding pz–pz 1.567

Fig. 10 –COHP analysis of a B–N interaction in graphyne-like BN sheet, b B–B interaction in graphyne-like BN sheet, c N–N interaction in
graphyne-like BN sheet

Conclusions beautiful bond alternation behaviour in the linear chain for

Using density functional theory, we have studied the geo-
metric structure and electronic properties of graphyne,
graphdiyne, graphyne-3 and graphyne-4 by systematically
doping boron and nitrogen atoms. Our spin-polarized cal-
culation reveals that all the structures are nonmagnetic in
nature. The stability of these systems is in the order of
graphyne [ graphdiyne [ graphyne-3 [ graphyne-4 for
pristine systems and on substituting BN atoms on these
systems, it becomes pristine system [ BN sheet [ BN at
linear chain [ BN at hexagons. We have obtained
all these systems. All the structures are found to be direct
band gap semiconductors with band gap depending on the
position and concentration of the doping material. In
pristine systems, the contribution to the energy levels near
the Fermi energy from the linear chain atoms is more than
that of atoms at hexagons except for graphyne where the
atoms at linear chain sites and hexagonal rings contribute
equally. Most of the contribution for these systems comes
from the pz orbitals. However, the contribution of px and py
orbitals of graphyne-3 and graphyne-4 starts at energy
levels closer to Fermi level compared to that of graphyne

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and graphdiyne. When BN atoms are substituted, the
nitrogen atom p-orbitals contribution in the VB is more
than that of the CB where as opposite effect has been seen
in case of boron. The contribution of N atoms in the VB is
more for those atoms which are placed at the linear chain
site compared to the atoms placed at the hexagonal ring.
The –COHP analysis confirms the presence of p bond
hybridization in the pristine systems due to pz orbitals. In
most of the cases, except graphdiyne-like BN sheet,
graphyne-3-like BN sheet and graphyne-4-like BN sheet,
all the bonding and antibonding states near the Fermi level
are arises due to the pair wise contribution of pz orbital of
neighbouring atoms. But the increasing chain length (when
we move from graphyne to graphyne-4) activates the
contribution of s, px, py orbitals near the the Fermi level.
The doping with BN sweeps the energy states (bonding and
antibonding) away from Fermi level. The difference
between first energy states at VB and CB increases with the
chain size when BN atoms are at chain, but opposite trend
have been observed for BN at ring or BN-like sheets.
Acknowledgments Dr U. Sarkar would like to acknowledge the
support from Prof Paul W Ayers, Department of Chemistry,
McMaster University, Canada, in various ways and SHARCNET
Canada for providing computational facilities for this research work.
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