Computational and Theoretical Chemistry 1151 (2019) 12–23

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Computational and Theoretical Chemistry

journal homepage: www.elsevier.com/locate/comptc

Electronic structure of boron and nitrogen doped isomeric graphene T

nanoflakes
⁎
Cesar Gabriel Vera de la Garza, Esau Martínez Olmedo, Serguei Fomine
Instituto de Investigaciones en Materiales, Universidad Nacional Autónoma de México, Apartado Postal 70-360, CU, Coyoacán, México, DF 04510, Mexico

A R T I C LE I N FO A B S T R A C T

Keywords: Electronic properties of nitrogen and boron doped isomeric graphene nanoflakes have been explored using
Haeckelite dispersion corrected B3LYP functional and CASSCF methods. The most thermodynamically stable isomers of
Ionization energy nitrogen and boron doped systems contain phenalene and azulene motifs substituted in positions 7 and 9, re-
Doping with boron spectively. Nitrogen doping promotes nanoflake planarity, increases singlet-triplet gap and a band gap, while
Doping with nitrogen
boron doping promotes dome shaped nanoflake geometry, polyradicalic ground state, reduces singlet-triplet gap.
Electron affinity
Isomeric nanoflakes are less sensitive to doping compared to graphene nanoflakes. Nitrogen is a weak n type
dopant for isomeric nanoflakes, while boron cannot be considered as a p type dopant. This effect is explained by
non-uniform electron density distribution in pristine isomeric nanoflakes as compared to graphene nanoflakes.

1. Introduction
Two dimensional (2D) structures have recently been recognized as
potentially very important materials for multiple applications in op-
toelectronic, chemical sensing, battery fabrication, supercapacitor and
transparent semiconductor manufacturing [1–3]. The most remarkable
and the most studied 2D material today is definitely graphene; one
atom thick carbon material discovered in 2004 [4,5]. Graphene is made
of fused benzene rings, benzene itself is a very stable molecule im-
parting to graphene extraordinary structural and mechanical stability.
Moreover, graphene shows prominent electronic and magnetic prop-
erties [6]. Among them are: very high charge carrier mobility, room
temperature Hall and ambipolar effects to name a few. Delouse et al.
explored theoretically graphene nanoribbons using the formalism of
crystalline orbitals [7]. It has been found out, that symmetry-breakings
in spin-densities for singlet states, is the consequence of an approximate
treatment of electron correlation in single-determinant approaches,
and, therefore this is a methodological artefact. Rayne and Forest [8,9]
studied graphene nanoribbons assuming a closed shell singlet ground
state. They concluded that graphene nanoribbons have closed shell
ground state with vanishing degenerated singlet and triplet states at
polymeric limit. In a recent research [10,32] a conclusion has been
reached that graphene nanoribbons, present strong multiradicalic
character [11].
The outstanding properties of graphene have stimulated intense
search for other 2D materials. Some of the 2D materials like MoS2 and
metal oxides have been discovered long before graphene [12] and
graphene discovery promoted detailed study of their properties.
Others, like 2D boron nitride (BN) have been prepared shortly after
graphene discovery [13]. These 2D layered materials demonstrate in-
teresting electronic properties including superconductivity [14,15] and
have been considered promising in battery fabrication, catalysis, as
sensors and radiation detectors [16–20].
Carbon is a unique element. The carbon chemistry is the richest
chemistry out of all elements in the Periodic Table. This is due to very
special combination of carbon atom properties; small size and large
number of valence electrons allowing formation of strong hetero and
homo nuclear bonds. As a consequence graphene is not the one and the
only possible 2D structure made of carbon atoms exclusively.
Nevertheless, the ability of carbon atoms to form different 2D allo-
tropies has been relatively overlooked. The number of studies related to
the detailed search of 2D carbon allotropies is rather limited [21–23].
The most complete study explores possible 2D carbon allotropies using
density functional tight binding approach (DFTB) calculations [21]. All
found allotropies are less stable than graphene, but the two most stable
of them called haeckelites are very interesting because of their stability
and chemical relevancy. Haeckelites are made of fused pentagons and
heptagons, producing 2D structures with azulene motif (Fig. 1).
We have demonstrated in our recent work using hybrid density
functional (DFT) methods [24] that haeckelites are structurally stable
systems representing a minimum at the potential energy surface. This
is, however, no surprise since the haeckelite structures can be found in

⁎
Corresponding author.
E-mail address: fomine@unam.mx (S. Fomine).

https://doi.org/10.1016/j.comptc.2019.01.022
Received 16 October 2018; Received in revised form 17 January 2019; Accepted 27 January 2019
Available online 29 January 2019
2210-271X/ © 2019 Published by Elsevier B.V.
C.G. Vera de la Garza et al. Computational and Theoretical Chemistry 1151 (2019) 12–23

Fig. 1. D3bj dispersion corrected B3LYP/def2-SVP optimized ground states of H1 graphene allotropy NFs doped with boron and nitrogen. The bond lengths increase
from red to green. The shortest and the longest bond lengths are of 1.340 and 1.613 Å, respectively. (For interpretation of the references to color in this figure legend,
the reader is referred to the web version of this article.)

the real world as topological defects in graphene [23]. These defects are reduction [24]. Haeckelite nanoflakes (NFs) have a finite bandgap (Eg)
called Stone-Wales-type defects. Haeckelites are metallic [21] however, which decreases with the NF size [24]. We have discovered that unlike
their electronic properties can be modified by the dimensionality graphene, graphene NFs, and 2D haeckelites, which are plane,

13
C.G. Vera de la Garza et al.
haeckelite NFs are often not plane and planar structures are actually
transition states, not a minimum. Another important difference be-
tween graphene and haeckelite NFs is that the latter have single re-
ference ground state which facilitates their description within DFT
frame. Another approach to the properties modification apart from the
dimensionality reduction is the introduction of chemical defects either
by doping or by chemical modification. This approach has successfully
been applied to graphene, graphene nanotubes and graphene nano-
flakes [25,26]. The present work explores properties of haeckelite NFs
doped with boron and nitrogen atoms. Unlike graphene where all car-
bons are equivalent, thus reducing the number of possible structures for
doped systems, in haeckelites and especially haeckelite NFs, there are
many nonequivalent positions increasing number of possible isomers.
Therefore, this study focuses only on two variables; the distance be-
tween chemical defects and the nature of these defects. Boron and ni-
trogen atoms have been selected as a dopants since they belongs to the
same period as carbon ensuring strong electron interaction with carbon
atoms, but they differ in electronegativity and the number of valence
electrons.
2. Computational details
All geometry optimizations were carried out using TURBOMOLE 7.2
code [27]. We applied D3bj dispersion corrected B3LYP functional [28]
in combination with def2-SVP basis set for all geometry optimizations.
B3LYP functional has been shown to be a reliable tool for predicting the
geometry of conjugated polymers [29]. Although functionals with
higher fraction of Hartree-Fock exchange like BHandHLYP and M062x
predict the bond length alternation (BLA) pattern slightly better in
conjugated systems [30], the high fraction of HF exchange in these
functionals may lead to the artificial overstabilization of the high spin
states due to spin contamination. High spin contamination is a result of
the multireference character of the ground state which is not un-
common in 2D conjugated systems [11]. In some cases where the ex-
pectation values of 〈S2〉 exceed 10% of theoretical value, a complete
active space calculations (CASSCF) in combination with 6-31G* basis
set with active space consisting of 14 electrons and 14 orbitals were
performed to decrease the effect of spin contamination on the relative
energies of the different spin states. Gaussian 16 code has been used for
CASSCF calculations [31].
Triplet stability analysis calculations have been carried out for all
closed shell singlet wavefunctions. If the instability was detected, the
molecular geometry had been reoptimized using unrestricted “open
shell singlet” broken symmetry (BS) wavefunction. For Eg estimations
two different methods have been used, the first one is the HOMO-LUMO
energy difference extracted directly from DFT calculations. It has been
shown that simple B3LYP HOMO-LUMO difference reproduces sur-
prisingly well Eg of conjugated polymers [28]. The second is the time
dependent (TD) implementation of MN15 functional in combination
with def2-SVP basis set. This model has previously been tested to show
excellent results for prediction of the lowest excitation energies of na-
nocene [24].
Frequency calculations have been performed for all studied NFs to
ensure that the structures are the true minima having no imaginary
frequencies.
Two isomeric haeckelite NFs have been selected as a model for
doping, H1 and H2 (Figs. 1 and 2). They contained two dopant atoms,
which corresponds to 2.1 atomic %. Even number of dopant atoms is
important to maintain formal closed shell electronic structure in doped
molecules, thus allowing a valid comparison between pristine and
doped systems. The positions of the doping centers have been selected
to explore different types of the location sites and different distances
between doping centers, thus avoiding heteroatom-heteroatom bonds
formation and edge atoms replacement. NeN and BeB bonds are no-
tably weaker compared to CeN and CeB ones [32], thus decreasing the
stability of doped NFs, while chemical environment of edge atoms is
14
Computational and Theoretical Chemistry 1151 (2019) 12–23
very different from that of the inner atoms.
Doped isomeric graphene NFs are denoted as X-Y-mnK where X
stands for the dopant type, N or B, Y – for the NF type, H1 or H2, and
mnK is the dopant position code where the first two numbers denote
the position of dopant atoms and the last letter-the distance between
them, L (large) or S (short). Graphene NFs are denoted as X-G-K, where
X stands for the dopant type, G – for graphene and K is the distance
between dopant atoms, similar to isomeric graphene NFs. Cation or
anion radicals are referred to with + and − signs, respectively.
3. Results and discussion
3.1. Relative stability and geometry
Table 1 shows the relative stability of doped haeckelite and gra-
phene NFs. As seen from Table 1 the most stable isomers are always H2
doped systems. Actually, pristine H2 NF is 43.1 kcal/mol more stable
than H1. The doped NFs continue this trend. However, the most stable
NFs have different doped positions for B- and N-doped species. As seen,
the most stable N-doped system is N-H2-11L, while the most stable B-
doped NF is B-H2-22S. Nature of the dopant atom strongly affects the
stability of the NF. While N-H2-11L is the most stable among N-doped
systems, B-H2-11L has the highest total energy out of all B-doped NFs.
The position of dopant atom also impacts the stability of a NF. Thus, the
relative energies of doped NFs of the same type, which differ only by
the position of doping atom can vary by as much as 40 kcal/mol.
Figs. 1 and 2 depicture optimized geometries of NFs where the bond
lengths are color coded; the shortest are red, the longest are green.
When comparing the relative energies of doped NFs with different do-
pant positions it is clearly seen, that the relative stability of isomers
depends not on the distance between the dopant atoms but rather on
their position within a NF. These “low energy” locations are different
for N- and B-doped systems. The lowest energy isomers for H1 and H2
N-doped NFs are 11L and 11S, respectively, while for B-doped NFs the
most stable isomers are 22L and 22S, respectively. As seen from Figs. 1
and 2, in all the most stable nitrogen doped NFs nitrogen atom replaces
carbon atoms in the position 7 of phenalene moiety of the NF, while in
the case of B-doped NFs, boron replaces position 9 of azulene motifs.
Unlike graphene, H1 and H2 NFs have strong BLA [24] which can
also be appreciated in Figs. 1 and 2. Doping causes local deformation of
the NF geometries. As seen, CeB bonds are shorter compared to the
original CeC bonds, while CeN bonds are larger. This is in line with an
increase of the bond energies from CeN to CeC and further to CeB
[32]. Doping not only causes local geometry changes, but also global
ones. Fig. 3 shows the ground state geometries of pristine H1 and H2
NFs and some of the N- and B-doped NFs.
As it has been shown earlier [24]. H1 NF is a dome shaped while H2
isomer is totally plane. Doping with N and B atoms promotes different
NF shapes. Thus, all H2 NFs doped with N are plane in their ground
state according to the frequency calculations. On the other hand, all H1
NFs doped with both N and B atoms are dome shaped. However, in the
case of B-doped H2 NFs the situation is different. While pristine H2 NF
is plane, all B-doped are dome shaped. To quantify this shape change on
doping we calculated the root mean square (RMS) deviation from plane
for each NF, and the results are shown in Table 1. The results show that
the nature and the position of dopants tune the NF shape. We could
summarize various trends inspecting Table 1.
1. Nitrogen doping promotes planarity of a NF while doping with
boron promotes non planarity. As seen, all N-doped H1 NFs have
smaller deviation from plane compared to pristine H1 NF. In case of
H2 NFs, all N-doped and pristine NF’s are plane. On the other hand,
all boron doped H1 NFs show larger deviation from plane in com-
parison with pristine H2. Moreover, all B-doped H2 NFs except for
B-H2-11L one are dome shaped unlike plane H2 NF.
2. The effect of doping on the NF shape is the most notable for closely
C.G. Vera de la Garza et al. Computational and Theoretical Chemistry 1151 (2019) 12–23

Fig. 2. D3bj dispersion corrected B3LYP/def2-SVP optimized ground states of H2 graphene allotropy NFs doped with boron and nitrogen. The bond lengths increase
from red to green. The shortest and the longest bond lengths are of 1.300 and 1.585 Å, respectively. (For interpretation of the references to color in this figure legend,
the reader is referred to the web version of this article.)

located dopant atoms in both cases nitrogen and boron. As seen from
Table 1, N-doped H1 type NFs show significantly lower deviation
from plane for closely positioned nitrogen atoms compared to the
more separated locations. In the case of boron doping, closely placed
boron atoms promote non planarity in much larger extent compared
to boron doped NFs where dopant atoms are well separated.
Generally speaking, closely located dopant atoms affect the NF
shape in greater extent than separated dopant atoms.
There are two different factors of doping that could affect the NF

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C.G. Vera de la Garza et al. Computational and Theoretical Chemistry 1151 (2019) 12–23

Table 1 factor. As seen from Table 1, the deviation from plane for charged H1
Relative energies of doped isomeric graphene nanoflakes and deviations from species are very similar to that for neutral H1 and very different from
plane of these NFs. that for doped NFs, suggesting that it is the structural factor (difference
Nanoflake Erel, kcal/mol Dev, Å in the bond lengths) that tunes shapes of doped NFs. This hypothesis is
also confirmed by the analysis of the molecular shape of dications,
N-H1-11L 36.4 36.6 dianions, tetraanions and tetracations of doped NFs. Dications and
N-H1-11S 34.4 15.2
tetracations of N-doped NFs are isoelectronic to neutral pristine NFs,
N-H1-12L 55.6 31.6
N-H1-12S 56.6 9.93 and neutral B-doped NFs, respectively. Dianions and tetraanions of B-
N-H1-22L 74.5 34.8 doped NFs are isoelectronic to neutral pristine and neutral N-doped
N-H1-22S 73.0 12.0 (9.3)a (3.02)c NFs, respectively. As seen from Table 1 the deviation from plane is
B-H1-11L 95.4 62.3
defined mainly by the nature of the dopant atom and not by not by the
B-H1-11S 75.6 79.1
B-H1-12L 52.9 60.0
number of electrons.
B-H1-12S 46.9 75.0
B-H1-22L 44.7 59.3
B-H1-22S 38.8 85.5 (80.0)b (78.0)d
3.2. Electronic nature of the ground states
H1 – 43.5 (39.6)a (41.1)b
N-H2-11L 0 0.0 The doping of the NFs affects the relative energy and the nature of
N-H2-11S 2.14 0.0 the ground states. It has been shown earlier, that pristine H1 and H2
N-H2-12L 22.4 0.0
NFs have single reference singlet ground states unlike the corre-
N-H2-12S 22.2 0.0
N-H2-22L 40.9 0.0 sponding graphene NFs [11] which often show multiconfigurational
N-H2-22S 32.9 0.0 ground states. Table 2 shows the relative singlet-triplet energies
B-H2-11L 44.9 0.0 (singlet-triplet gaps) and the corresponding 〈S2〉 expectation values for
B-H2-11S 39.5 24.3 states with different multiplicity. Notable spin contamination is an in-
B-H2-12L 28.6 2.20
B-H2-12S 12.5 28.1
dicator of possible multireference character of the electronic state
B-H2-22L 5.07 5.10 which may lead to unreliable relative DFT energies of the electronic
B-H2-22S 0 31.1 states with different multiplicities [11].
H2 – 0.0 Both pristine H1 and H2 have singlet ground state, but the triplet-
N-G-L 0 0
singlet gap is much larger for H2, moreover, the closed shell singlet
N-G-S 12.6 0
B-G-L 0 0 solution is unstable for H1 and stable solution corresponds to BS wa-
B-G-S 7.79 0 vefunction. Doping with nitrogen and boron has different impacts on
G – 0 both, singlet-triplet gaps and the nature of the ground states. As seen
a
from Table 2, nitrogen doping opens up singlet triplet gap for all NF
Dicaton.
b types, while B-doping mostly decreases it. The effect of N-doping is the
Dianion.
c most notable for N-H1-11L NF where singlet-triplet gap increases from
Tetracation.
d
Tetraanion. 0.46 kcal/mol for pristine H1 to 13.2 kcal/mol for N-doped system. For
N-doped NFs of H2 series N-doping also results in an increase of the
shape, the electronic and the structural. On the one hand, carbon and singlet-triplet gap, although this effect is less important. According to
dopant atoms have different number of electrons and on the other hand, Table 2 the distance between N atoms does not affect the singlet-triplet
CeC, CeB and CeN bond lengths are also different. To distinguish gap in a systematic way.
between these 2 factors we calculated the deviation from plane for B-doping clearly affects the singlet – triplet band gap. The effect
dicationic, tetracationic, dianionic and tetraanionic species of some of depends on the distance between dopant atoms. In the majority of
the doped and pristine NFs. The results are shown in Table 1. Dication cases, well separated dopants reduce singlet triplet gap while closely
and dianion of H1 are isoelectronic to B- and N-doped species, re- positioned dopants increase it slightly. The most important finding,
spectively, but they contain no heteroatoms, thus excluding structural however, is that triplet ground states have been detected at DFT level
for 4B-doped nanoflakes B-H1-11L, B-H1-22L, B-H2-11S and B-H2-

Fig. 3. D3bj dispersion corrected B3LYP/def2-SVP optimized ground states of pristine and some of the doped NFs.

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C.G. Vera de la Garza et al. Computational and Theoretical Chemistry 1151 (2019) 12–23

Table 2
HOMO-LUMO (EH-L), singlet-triplet (ES-T) gaps, 〈S2〉 expectation values for open shell singlet (OSS) and triplet states, ionization energies (IP) and electron affinities
(EA). Lowest singlet excitation energies (S0 → S1) of studied nanoflakes.
Nanoflake EH-L, eV ES-T, kcal/mol 〈S2〉 OSS 〈S2〉 Triplet IP, eV EA, eV S0 → S1, eV

N-H1-11L 1.21 13.2 – 2.02 5.00 2.35 1.10

N-H1-11S 1.08 10.7 – 2.03 5.07 2.57 1.03
N-H1-12L 1.04 9.80 – 2.01 4.95 2.47 0.70
N-H1-12S 1.12 11.1 – 2.12 5.09 2.54 1.00
N-H1-22L 1.05 10.0 – 2.04 4.99 2.50 0.81
N-H1-22S 1.02 9.74 – 2.03 5.07 2.62 0.94
B-H1-11L 0.67 −2.08 (28.2) 1.92 3.05 4.99 2.94 0.04
B-H1-11S 0.76 2.32 – 2.04 5.00 2.83 0.24
B-H1-12L 0.72 2.52 – 2.05 4.95 2.84 0.51
B-H1-12S 0.81 4.71 – 2.03 5.08 2.83 0.59
B-H1-22L 0.72 −0.53 (0.14) 1.04 2.05 5.14 2.98 0.59
B-H1-22S 0.88 7.51 – 2.04 5.10 2.70 0.64
H1 0.642 0.46 1.13 2.02 5.06 2.98 0.296
N-H2-11L 1.10 11.4 – 2.06 4.98 2.42 0.491
N-H2-11S 1.17 12.1 – 2.05 5.01 2.39 0.47
N-H2-12L 1.03 8.76 – 2.09 4.99 2.54 0.39
N-H2-12S 1.29 12.8 – 2.06 5.12 2.40 0.59
N-H2-22L 0.96 6.50 – 2.06 5.05 2.66 0.13
N-H2-22S 1.35 15.5 – 2.05 5.15 2.38 0.68
B-H2-11L 0.7 1.36 0.28 2.10 5.09 2.94 0.30
B-H2-11S 0.71 −0.24 (17.2)a 1.02 2.04 5.09 2.94 0.50
B-H2-12L 0.73 −0.91 (4.72)a 1.04 2.11 5.34 3.14 0.69
B-H2-12S 0.99 7.36 – 2.06 5.22 2.81 0.80
B-H2-22L 0.638 0.67 0.60 2.05 5.29 3.17 0.33
B-H2-22S 0.952 5.97 – 2.03 5.28 2.90 0.53
H2 0.95 7.66 – 2.06 5.32 2.92 0.34
N-G-L 0.56 −0.37 (−7.99)a 1.25 2.15 4.52 2.56 0.45
N-G-S 0.76 0.02 2.10 3.09 4.63 2.24 0.41
B-G-L 0.70 −0.10 (−12.39)a 1.48 2.44 5.08 2.96 0.35
B-G-S 0.98 −1.15 (9.39)a 2.00 3.32 5.26 2.93 0.35
G 1.12 −5.74 (12.62)a 2.05 3.13 4.80 2.75 1.48

a
CASSCF/6-31G*//B3LYP/def2-SVP.

Fig. 4. Superposition of active orbitals with populations close to 1 from CASSCF/6-31G* single point calculations (a) and unpaired spin density obtained from BS
B3LYP/def2-SVP calculations (b).

12L. When revising 〈S2〉 expectation values for open shell singlet states M

of these systems, one can notice strong spin contamination, while spin
contamination of triplets is much lower. This may result in an artificial
overstabilization of the triplet states. Therefore, we have performed
single point CASSCF calculations using DFT optimized geometry for all
singlet and triplet states for these 4 cases where DFT calculations in-
dicate triplet ground states to eliminate all possible artefacts. Since
CASSCF method lacks spin contamination problem, there would be no
artificial overstabilization of high spin states.
As seen from Table 2, for all four boron doped NFs CASSCF calcu-
lations confirm singlet to be ground state.
CASSCF calculation also allows us to estimate the number of ef-
fectively unpaired electrons in the molecule, using Head-Gordon for-
mula (1) [33]
Nu = ∑ n2i (2 − ni )2
i=1 (1)
where Nu is the number of effectively unpaired electrons, ni is the oc-
cupation of i-th natural orbital and M is a total number of active orbi-
tals. We have shown previously [11] that unlike graphene NFs where
the number of effectively unpaired electrons increases rapidly with size,
in case of H1 and H2 NFs the number of effectively unpaired electrons
does not change with the NF size remaining about 0.2. We have esti-
mated this number using CASSCF wavefunction for 4 boron doped NFs
showing high spin contamination of singlet states. The results were of
0.2, 2.0, 0.1, 0.1 effectively unpaired electrons for B-H1-11L, B-H1-
22L, B-H2-11S and B-H2-1-2L NFs, respectively. As seen, strong spin
contamination is not always an indication of the multireference

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C.G. Vera de la Garza et al. Computational and Theoretical Chemistry 1151 (2019) 12–23

Fig. 5. Total (TDOS) and projected (PDOS) density of states for selected doped and pristine NFs. PDOS1 and PDOS2 are the contributions from the NF and dopant
atoms, respectively.

18
C.G. Vera de la Garza et al.
Fig. 6. Electrostatic potential mapped onto total electron density for pristine and doped graphene and isomeric graphene NFs, obtained from B3LYP/def2-SVP
calculations.
character of the electronic state. However, it also can be noted, that B-
doping may lead to the polyradicalic ground state of the NFs. Fig. 4
visualises unpaired spin density obtained from BS B3LYP calculations,
and active orbitals with population close to 1 from CASSCF calcula-
tions. As seen, both methods give qualitatively similar picture of spin
distribution in biradicalic state of B-H1-22L. It is interesting to note
that although boron doping induces polyradicalic character in the NFs,
boron atoms do not have any appreciable spin density on them.
Unlike H1 and H2, NFs doping can change the multiplicity of the
ground state in graphene NFs as seen from Table 2. Spin contamination
is very strong in graphene NFs due to strong multireference character of
the singlet and even triplet states [11]. Thus, according to CASSCF
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Computational and Theoretical Chemistry 1151 (2019) 12–23
calculations the number of effectively unpaired electrons for singlet
states of G, B-G-S, B-G-L, N-G-S and N-G-L NFs are of 4.1, 4.0, 3.0, 2.1
and 3.1, respectively. Therefore DFT energies are not reliable for cor-
rect assignment of their ground states. The ground state of graphene NF
must be singlet according to Ovchinnikov’s rule [34], and this is con-
firmed by both, CASSCF and DFT calculations. Doped graphene NFs,
however, not necessarily must have singlet ground state since Ovchin-
nikov rule does not apply to them anymore. Both nitrogen and boron
dopant promote triplet ground states in graphene NFs when dopant
atoms are well separated, while graphene NFs with closely positioned
dopant atoms maintain singlet ground state of graphene NFs (Table 2).
Fig. 5 shows total (TDOS) and projected (PDOS) density of states for
C.G. Vera de la Garza et al.
Fig. 7. Spin density distribution in polaron cations and polaron anions of some N doped H1 and H2 NFs estimated at B3LYP/def2-SVP level.
pristine and the most the stable B- and N-doped NFs. TDOS of graphene
NF is also shown for comparison. Graphene is semimetal while allo-
tropies H1 and H2 systems are metallic [21]. The corresponding NFs
possess a band gap as seen from Fig. 5 in accordance with more ela-
borated TD-DFT calculations. The Fermi energy (Ef) is the lowest for H2
and the highest for H1 NF, however the difference is very small as seen
from the TDOS spectra. N-doping slightly increases Ef, while B-doping
decreases it slightly. All doped NFs show a bandgap in agreement with
TD-DFT calculations. TDOS of doped and pristine NFs are very similar,
the contribution of heteroatoms to TDOS is rather small especially near
20
Computational and Theoretical Chemistry 1151 (2019) 12–23
the Fermi level.
3.3. Ionization energies, electron affinities and the band gaps
Ionization potentials (IP), electron affinities (EA) and Eg's of NFs are
listed in Table 2. As seen, doping with nitrogen changes IPs very little,
reducing them in most of the cases. The reduction of IPs is more notable
for H2 NFs compared to H1. Nitrogen doping also reduces slightly EAs
for both NF types. It is interesting to note that IPs and EAs depend on
the distance between doping centers. Smaller distance between dopant
C.G. Vera de la Garza et al.
Fig. 8. Spin density distribution in polaron cations and polaron anions of some B-doped H1 and H2 NFs estimated at B3LYP/def2-SVP level.
centers results in smaller changes in both IPs and EAs. The difference is
not large (about 0.1 eV) but consistent for all doped NFs. The behavior
of H1 and H2 NFs on doping with nitrogen atoms resembles that of
graphene NFs as seen from Table 2. However, in the case of graphene
the results of IP and EA reduction are more notable. In all cases N
dopants belong to “graphitic” type of nitrogen [36] where nitrogen
atom shares one electron with π electron cloud of the NF, thus being n
type of dopant [15]. This effect can be appreciated in Fig. 6 where the
electrostatic potential of nitrogen and boron doped H1, H2 and gra-
phene NFs are mapped over their total electron densities. Pristine NFs
21
Computational and Theoretical Chemistry 1151 (2019) 12–23
are also shown for the comparison purpose. When comparing nitrogen
doped NFs with these of pristine ones, one can note that a part of the
electron density of nitrogen atoms is delocalized over the entire NFs. In
this particular case nitrogen doping causes similar effects in isomeric
graphene and graphene NFs, however, to a smaller extent.
In case of doping with boron atoms, IPs of doped H1 and H2 NFs
remain practically unaffected as can be seen from Table 2. EAs are also
affected very little by B-doping for H1 NF type, slightly increasing for
doped H2 NFs. This behavior differs from that of graphene NF where B-
doping causes notable increase of both IP and EA. Boron is a p dopant
C.G. Vera de la Garza et al.
atom for graphene NF [35], but as a dopant, boron atoms behaves
differently in H1 and H2 NFs. As seen from Fig. 6 showing the elec-
trostatic potential mapped over the total electron densities for boron
doped H1, H2 and graphene NFs, there is a notable difference between
boron-doped graphene NFs from the one side, and H1, H2 NFs from the
other. The electrostatic potential maps are very similar for H1 and H2
NFs. It is clearly seen that in the case of graphene NFs, boron is a p
dopant, receiving electron density from the rest of π-electron cloud as
an electron deficient atom. In the case of H1 and H2 NFs, however,
there is no significant change in the electrostatic potential of the NFs on
doping. These results demonstrate that nitrogen atoms act as n dopant
in H1 and H2 NFs although the doping effect is weaker compared to
that of graphene NF. On the other hand, boron cannot be considered as
a p type dopant for H1 and H2 contrary to graphene NFs. The reason
why isomeric graphene NFs are less sensible to doping compared to
graphene NFs can be understood revising Figs. 6–8. Figs. 6 and 7 vi-
sualize spin density delocalization pattern in polaron cations and po-
laron anions of isomeric NFs corresponding to the largest and the lowest
IPs and EAs. As seen from the figures, the doping centers do not par-
ticipate in stabilization neither polaron cations nor polaron anions.
In case of graphene NFs the situation is quite different, boron and
nitrogen atoms do participate in stabilization of polaron cations and
polaron anions, respectively [11,36]. Another point is related with
“internal” doping existing in isomeric graphene H1 and H2 systems. As
seen from Fig. 6, graphene NF shows a uniform electron density dis-
tribution across the NF. Contrary to that, H1 and H2 NFs show highly
non uniform electron density distribution where some of carbon atoms
are electron deficient and another are electron enriched due to none-
quivalent chemical environments. This can be considered as “internal”
doping and new external doping center causes smaller impact on the
electronic structure of the H1 and H2 compared to graphene NFs, since
H1 and H2 are already “doped”. When it comes down to charges, both
doping centers nitrogen and boron bear small negative charges, ac-
cording to Mulliken population analysis, boron (−0.3) being slightly
more negative than nitrogen (−0.1). Charges are rather similar for all
positions and all NF types. More negative charges of boron atoms make
sense since boron accepts π electron density from carbon atoms which
is in total agreement with the electrostatic potential map.
Unlike IPs and EAs of the NFs, the doping impacts notably both,
Eg’s, calculated as HOMO-LUMO gap and as the lowest excitation en-
ergy using TD DFT framework. N-doping increases Eg from a fraction of
eV to more than 1 eV and the results are consistent for all methods used
for the calculation of Eg. This increase of Eg is more notable for doped
H1 NFs compared to doped H2 ones. As seen from Table 2 there is no
visible correlation between separation distance for nitrogen dopants
and Eg. The effect of B-doping on the Eg is much less and more erratic.
The Eǵs evolution of H1 and H2 on doping differs from that of graphene
NFs (Table 2). As seen both, boron and nitrogen doping reduce Eg's of
graphene NFs. This behavior is similar for all methods used for Eg
calculation.
4. Conclusions
The relative stability of doped isomeric graphene NFs depends
greatly on both the dopant nature and the position. The difference in
the relative energies can be as high as 40 kcal/mol. The most stable N-
and B-doped NFs have common substitution patterns: nitrogen doped
NFs have a phenalene fragment substituted in position 7 and boron
doped NFs – azulene moiety with boron atom in position 9.
Unlike graphene NFs, the doping of isomeric graphene NFs with
boron or nitrogen noticeably affect their shape. Boron doping promotes
dome shaped geometry, while nitrogen doping favors planar geometry.
This effect depends on the distance between dopant atoms. Closely lo-
cated dopant atoms have stronger effect on the NF shape compared to
separated dopant atoms.
Boron and nitrogen doping produce different effects on the
22
Computational and Theoretical Chemistry 1151 (2019) 12–23
electronic structure of H1 and H2 NFs. Nitrogen atoms promote single
reference singlet ground state, they increase singlet – triplet gap, and
Eg, boron decreases singlet – triplet energy gap and in some cases
promotes polyradicalic ground states.
IP and EA of H1 and H2 NFs are less affected by doping compared to
graphene NF. Nitrogen can still be considered as n dopant for H1 and
H2 NFs, while boron cannot be considered as p type of dopant for
isomeric graphene NFs. The probable reason for this behavior is an
“internal” doping of isomeric graphene NFs; non uniform density dis-
tribution in these NF decreases the effect of heteroatom doping on the
electronic properties.
Acknowledgments
We acknowledge the financial support from CONACyT (Grant
251684) and from supercomputing facilities of National Autonomous
University of Mexico.
Appendix A. Supplementary material
Supplementary data to this article can be found online at https://
doi.org/10.1016/j.comptc.2019.01.022.
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