Você está na página 1de 10

View Article Online

View Journal

Physical Chemistry Chemical Physics
Accepted Manuscript

This article can be cited before page numbers have been issued, to do this please use: K. Lambropoulos
and C. Simserides, Phys. Chem. Chem. Phys., 2017, DOI: 10.1039/C7CP05134D.

Volume 18 Number 1 7 January 2016 Pages 1–636 This is an Accepted Manuscript, which has been through the
Royal Society of Chemistry peer review process and has been
accepted for publication.
Physical Chemistry Chemical Physics Accepted Manuscripts are published online shortly after

acceptance, before technical editing, formatting and proof reading.

Using this free service, authors can make their results available
to the community, in citable form, before we publish the edited
article. We will replace this Accepted Manuscript with the edited
and formatted Advance Article as soon as it is available.

You can find more information about Accepted Manuscripts in the

author guidelines.

Please note that technical editing may introduce minor changes

to the text and/or graphics, which may alter content. The journal’s
ISSN 1463-9076 standard Terms & Conditions and the ethical guidelines, outlined
in our author and reviewer resource centre, still apply. In no
Darya Radziuk and Helmuth Möhwald
Ultrasonically treated liquid interfaces for progress in cleaning and
separation processes
event shall the Royal Society of Chemistry be held responsible
for any errors or omissions in this Accepted Manuscript or any
consequences arising from the use of any information it contains.

Published on 22 September 2017. Downloaded by Gazi Universitesi on 22/09/2017 13:04:23.
Page 1 of 9
Physical Chemistry Chemical Physics
DOI: 10.1039/C7CP05134D
View Article Online

Physical Chemistry Chemical Physics Accepted Manuscript

Physical Chemistry Chemical Physics Page 2 of 9
View Article Online
DOI: 10.1039/C7CP05134D

some of the most important recent experimental results. These matrix of the unit cell (in our case, Q1 for cumulenic carbynes
results include the metallic (semiconducting) behaviour of the and Q2 Q1 for polyynic carbynes), and then using its eigendecom-
current-voltage (I-V) characteristics for cumulenic (polyynic) car- position to obtain its powers.
bynes, the effect of weakening the coupling between the leads
To obtain physically valid numerical results from a TB ap-
and one end of the system, as well as the rectifying behaviour
proach, an appropriate set of external parameters (on-site ener-

Physical Chemistry Chemical Physics Accepted Manuscript

polyynic carbynes demonstrate when there is a mismatch be-
gies and hopping integrals) is necessary. In Ref. 39 , the authors
tween their Fermi levels and the ones of the leads.
have calculated by ab initio methods the bond lengths of atomic
The cumulenic form of carbyne, in which BLA = 0, can be in-
carbon wire structures, i.e. d = 1.282 Å for the cumulenic form of
terpreted as . . . =C=C=. . . . Hence, in a TB treatment, cumulenic
carbyne, and dℓ = 1.301 Å, ds = 1.265 Å for the polyynic form.
carbyne can be considered as a homogeneous chain with one px
Taking these values, we obtain the hopping integrals we will
electron per atom and one atom per unit cell, with on-site en-
Published on 22 September 2017. Downloaded by Gazi Universitesi on 22/09/2017 13:04:23.

use below to calculate the I-V characteristics of cumulenic and

ergy εC , and a single hopping integral, t. On the contrary, its
polyynic carbynes via the Harrison formula 40 for the π bond, i.e.
polyynic form, in which BLA 6= 0, the structure can be interpreted
t = −0.63h̄2 /(md 2 ), where h̄ is the reduced Planck constant and
as . . . ≡C-C≡. . . . Hence, in a TB treatment, polyynic carbyne can
m is the electron mass. Hence, for cumulenic carbynes, t = −2.92
be considered as a chain with one px electron per atom and two
eV, while, for polyynic carbynes tℓ = −2.84 eV and ts = −3.00 eV.
atoms per unit cell, with the same εC , and two hopping integrals,
We should mention that the inclusion of longer-range terms (sec-
ts and tℓ , for the short (s) and long (ℓ) separations, respectively.
ond, third, etc neighbours) is not expected to have a significant
An identical treatment holds for the py electrons, due to energy
effect of the energy strucutre. The Harrison formula that we em-
ployed is valid for interatomic distances of the order of the co-
The rest of the paper is organized as follows: in Sec. 2, we an-
valent bond. In the case of larger distances, other, exponentially
alytically determine the electronic structure of carbynes, in terms
decaying formulas are more accurate 41,42 . Using such an expo-
of their dispersion relations (for cyclic boundaries), eigenspectra
nential law, in the fashion done in Ref. 43 , e.g. for the bond length
(for fixed boundaries) and density of states (DOS). In Sec. 3, we
we have used for cumulenic carbynes, we find that the hopping
analytically obtain the transmission coefficient at zero bias by at-
integral for the second neighbours would be smaller by one order
taching the carbynes to semi-infinite metallic leads, and discuss
of magnitude. The on-site energy of the highest occupied molec-
the effect of the coupling strength and asymmetry to the trans-
ular orbital of the sp-hybridized carbon is set to zero. As it will
parency of the system to incident carriers. Finally, in Sec. 4, we
be shown below, altering εC does not affect the energy structure
determine the I-V characteristics of atomic carbon wires, and dis-
of the carbynes, apart from an energy shift, but, when their trans-
cuss the effect of several factors that play a significant role to their
port properties are considered, the choice of the metallic leads’
shapes. Our computational results confirm and reproduce some
on-site energy relative to that of carbon is of major significance.
of the most recent experimental findings.
For cyclic boundaries (ψ0 = ψN , ψN+1 = ψ1 ), the following dis-
2 Electronic structure of carbynes persion relations hold for carbynes
Let us suppose a carbyne chain made up of N carbon atoms. In
E = εC + 2t cos(kc ac ), cumulenic, (3a)
the nearest neighbour approximation, the TB system of equations
E = εC ± t12 + t22 + 2t1 t2 cos kp ap , polyynic, (3b)

Eψn = εC ψn + tn,n+1 ψn+1 + tn,n−1 ψn−1 , (1)
where kc,p ∈ 1st Brillouin Zone, ac = d, and ap = ds + dℓ . Since
∀n = 1, 2, . . . , N, where |ψn |2 is the occupation probability at site
there is only one electron per atom, cumulenic carbynes display
n. For cumulenic carbynes, the hopping integrals are all equal
metallic behaviour (there is one half-filled band), while polyynic
(tn,n±1 = t), while, for polyynic carbynes, there are two differ-
carbynes display semiconducting behaviour (one filled and one
ent integrals t1 ,t2 , reflecting the difference in the interatomic dis-
empty band). The Fermi level is E F = εC . The transition from
tances. We define the transfer matrix of a site, Qn , as
metal to semiconductor is displayed in Fig. 1(a), where Eq.
tn,n−1 (3b) is plotted as a function of the ratio t1 /t2 . We have fixed
! ! ! !
ψn+1 ψn ψn
= tn,n+1 tn,n+1 := Qn . (2) t2 = tℓ = −2.84 eV, and let t1 gain values in the interval that cor-
ψn 1 0 ψn−1 ψn−1
responds to distances 1.20 - 1.53 Å, i.e. for bond lengths varying
Hence, for cumulenic carbynes, the global transfer matrix of the from the triple to the single bond in individual gas-phase car-
chain is QN1 , while, for polyynic carbynes, it is (Q2 Q1 )
N/2 . Taking bon molecules 44 , using the Harrison formula. We notice that
into account the spectral duality relations 35,36 and the relation for t1 = ts = −3.00 eV, i.e. for the set of parameters used below
of the elements of the (unimodular) global transfer matrix with for the calculation of the I-V characteristics [black curve in Fig.
the Chebyshev polynomials of second kind 37,38 , we can deter- 1(a)], the bandgap is Eg = 0.32 eV, in perfect accordance with
mine the electronic structure of carbynes for either cyclic or fixed the gap reported in Ref. 39 , from which the bond lengths were
boundary conditions. The occurrence of the Chebyshev polyno- taken. Hence, our treatment is in excellent agreement with the
mials is a direct result of the periodicity of the chains. Chebyshev much more time-consuming and complicated ab initio method 39 .
polynomials can be related to the elements of the global transfer Generally, as t1 /t2 increases up to 1 (i.e. the cumulenic case), the
matrix of the chains by solving the eigenproblem of the transfer width of each band linearly increases and the bandgap linearly

2| 1–8
Page 3 of 9 Physical Chemistry Chemical Physics
View Article Online
DOI: 10.1039/C7CP05134D

decreases to zero. For t1 /t2 > 1, the width of each band remains in Refs. 49,50 . The fixed boundary conditions correspond to a fi-
constant and the gap starts to increase linearly (see inset of Fig. nite carbon wire structure, the ends of which induce a length-
1(a)). dependent modulation in the BLA 7 . In our model, this would
result in an alteration of the ratio t1 /t2 . Hence, for a finite struc-
ture, the modulation of the BLA could cause a shift along the

Physical Chemistry Chemical Physics Accepted Manuscript

horizontal axis of Fig. 1(b), as N increases.
The DOS of carbynes is given by the expressions
g(E) = p , cumulenic, (5a)
π 4t − (E − εC )2

N|E − εC |
Published on 22 September 2017. Downloaded by Gazi Universitesi on 22/09/2017 13:04:23.

g(E) = q , polyynic, (5b)

π 4t1 t2 − [(E − εC )2 − t12 − t22 ]2
2 2

where the double spin and double band degeneracies are not in-
corporated. Two van Hove singularities occur in cumulenic car-
bynes exactly at the band edges, i.e. for E = εC ± 2t. In polyynic
carbynes, the singularities increase to four, again at the band
edges, i.e. for E = εC ± |t1 ± t2 |. The DOS of polyynic carbynes
is displayed in Fig. 1(c) as a function of t1 /t2 . We observe that the
singularities at the top (bottom) of the valence (conduction) band
are much less sharp that the ones at the bottom (top). These less
sharp singularities vanish as t1 /t2 reaches 1, i.e. when the transi-
tion to cumulenic carbyne occurs.

3 Transmission coefficient
Suppose we interconnect the ends of a given atomic carbon wire
with two semi-infinite homogeneous leads with lattice constant
a and one electron per site, so that they are metallic. Let εmL(R)
and tmL(R) be the on-site energy and the hopping integral of the
left (right) lead, so that their energy structure is described
the dispersion relation E = εmL(R) + 2tmL(R) cos qL(R) a . Hence
εmL(R) = EmL(R) , i.e. the Fermi level of the leads, and the band-
Fig. 1 (a) Dispersion relation [(inset) width of each band and bandgap],
(b) eigenspectra for up to N = 60, (c) density of states of polyynic width is 4 tmL(R) . The coupling of the leads with the end carbon

carbynes as a function of the hopping integral ratio, t1 /t2 . "Used" atoms is described by the hopping integrals tcL(R) . If we suppose
corresponds to the ratio ts /tℓ (see text).
identical leads and, without any loss of generality, that the inci-
dent waves come from the left lead, then the transmission coef-
For fixed boundaries (ψ0 = ψN+1 = 0), the eigenenergies of car- ficient of carbynes at zero bias can be written as T (E) = 1+Λ(E)
bynes can be obtained recursively via the relations where

cumulenic, (4a)
UN (zc ) = 0, WN (E) + XN+ (E) cos(qa) XN− (E)2

Λ(E) = + , (6)
t1 4 sin2 (qa) 4
U N (z p ) = −U N −1 (z p ), polyynic, (4b)
t2 2 2
E−εC (E−εC )2 −t12 −t22 WN (E) = UN (zc )ω +UN−2 (zc )ω −1 , (7a)
where zc = Tr(Q1 /2) = 2t , z p
= Tr(Q2 Q1 /2) = and
2t1 t2 ,
Ur (z) are the Chebyshev polynomials of the second kind of de- XN± (E) = UN−1 (zc )(±χ −1 − χ), (7b)
gree r 45 . The eigenspectrum, i.e. the spectrum of eigenvalues,
as derived by Eq. (4b), for polyynic carbynes is displayed in Fig. for cumulenic, and
1(b), as a function of t1 /t2 , for up to N = 60 atoms. It is again t2
WN (E) = U N (z p )ω + U N (z p )(ω + ω −1 ) +U N −2 (z p )ω −1 , (8a)
evident that, as t1 /t2 increases above 1, an increasing gap oc- 2 t1 2 −1 2

curs. This gap vanishes when t1 /t2 = 1, i.e. when the transition
to cumulenic carbyne occurs. For t1 /t2 < 1 a bandgap starts to χ −1 χ
XN± (E) = U N −1 (z p )(E − εC )(± − ), (8b)
open again, but there is an additional eigenvalue in each band 2 t2 t1
that as N increases, reaches εC . This effect occurs straight from for polyynic. ω = ttcRm ttNcL is the coupling strength factor, and χ = ttcR

the choice of the boundary conditions. The eigenspectra of such is the coupling asymmetry factor. The zero-bias transmission coef-
systems have also been discussed, from a mathematical point of ficient of a polyynic carbyne with N = 10 is plotted as a function of
view, in Refs. 46–48 , and, from a materials physics point of view, t1 /t2 in Fig. 2, for various coupling strength and asymmetry con-

1–8 | 3
Physical Chemistry Chemical Physics Page 4 of 9
View Article Online
DOI: 10.1039/C7CP05134D

ditions. We have chosen the Fermi level of the leads, EmF (= εm ) experimental findings report currents that lie in the µA regime 28 ,
to be equal to that of the carbyne, εC . The coupling integral of as our below discussed results indicate. Quantitative differences
the leads is taken tm = −4 eV, so that their bandwidth contains all could also be attributed to the temperature effects, since the ex-
the eigenstates of the polyynic chain. As it is evident from Fig. 2, periments were carried out at room temperatures. Without spec-
the ideal and symmetric coupling condition (ω = χ = 1) leads to ifying the nature of the leads, we will choose EmL,R F = εC and

Physical Chemistry Chemical Physics Accepted Manuscript

the most enhanced transmission. When the coupling strength fac- tmL,R = 3.16 eV, a value that corresponds to the overlap of neigh-
tor deviates from the ideal case, the transmission peaks sharpen bouring atoms in a single graphitic layer plane 56 . For the carbon
and the transparency of the system is significantly reduced. If the chain, we will use t, for the cumulenic case, and t1 = ts , t2 = tℓ for
not-ideal coupling is also asymmetric, then the value of the trans- the polyynic case (see Sec. 1). As for the coupling hopping inte-
mission peaks also reduces, leading to a further decrease of the grals, we choose tcL = tcR = −2.67 eV for cumulenic carbynes, and
system’s transparency. The exact number, as well as the position tcL = −2.05 eV, tcR = −3.33 eV for polyynic carbynes, i.e. values
Published on 22 September 2017. Downloaded by Gazi Universitesi on 22/09/2017 13:04:23.

of the transmission peaks in each coupling strength and asymme- that correspond to double, single and triple bonds, respectively,
try condition can be determined by examining the degree of the between gas-phase carbon molecules 44 , according to the Haris-
terms that become dominant in Λ(E). In other words, the num- son formula (see Sec. 2). The results for the I-V characteristics
ber and position of the transmission peaks are strongly related to for cumulenic and polyynic carbynes with N = 100 for the above
the coupling strength and asymmetry, as well the ratio t1 /t2 . This mentioned parameters are shown in Fig. 3.
suggests that the peaks cannot be directly attributed to the energy
From Fig. 3 it is evident that cumulenic carbynes display a typi-
levels of the system.
cal Ohmic behaviour (linear curves), while the S-shaped curves of
4 Current-Voltage characteristics polyynic carbynes are indicative of a semiconducting behaviour.
Furthermore, the currents for cumulenic carbynes are of larger
If we assume that a constant bias is applied at the left lead, so magnitude than for polyynic carbynes, in the same bias regime,
that its dispersion relation is shifted by Vb , and a voltage drop in agreement with Ref. 27 . In the same work, the experimental I-V
within the carbyne system, then the transmission coefficient be- curves were measured at different times, as the carbyne chains
comes voltage-dependent, i.e. T (E) = T (E,Vb ). We apply a linear coupling with one of the leads becomes increasingly poorer, re-
voltage drop between the end sites of the leads, separated by a sulting to reduced currents. We interpreted this effect by calcu-
distance L, so that the on-site energy εC of the n-th carbon atom lating the I-V curves for increasing values of dcR , i.e. the distance
is shifted by Vb (n) = Vb dLn , where dn is the distance of the atom between the last carbon atom and the left lead. This results in a
from the end of the left lead. The conducting states lie in the decrease of the coupling hopping integral tcR , which is determined
intersection of the common energies between the leads and the by the Harrison formula. In Fig. 3 we show that the decrease of
bandwidth of carbyne chains. Then, the electrical current can be the carbyne coupling to the right lead results in reduced currents,
computed using the Landauer-Büttiker formalism 51–55 as in agreement with the experimental observation of Ref. 27 .
Z ∞
4e Let us now examine the influence of the leads’ properties to the
I(Vb ) = T (E,Vb )[ fL (E) − fR (E)]dE, (9)
h −∞ I-V characteristics. Suppose that there is a mismatch between the
where e is the elementary charge, and fL(R) is the Fermi-Dirac dis- Fermi level of a polyynic carbyne and that of the leads, which is
tribution at the left (right) lead. At zero temperature, i.e. the case defined as ∆ = εm − εC , and all the rest parameters are kept the
that we study here, fL (E) = θ (EmL F +V − E), f (E) = θ (E F − E),
b R
same. The calculated I-V curves and the differential conductance,
dV , for different values of ∆ are presented in Fig. 4. From the I-V
where θ denotes the Heaviside step function. The factor 4 comes
from the double spin-degeneracy of each electronic level and the curves (left panel of Fig. 4) it can be observed that increasing |∆|
double degeneracy of the bands formed by the px and py elec- from zero leads to a reduction of the gap region in the vicinity of
trons. As shown in the previous section, the coupling strength and V = 0, until |∆| exceeds 2g = 0.16 eV, in which case the gap region
asymmetry play a significant role in the transmission profile. So, around V = 0 vanishes. This happens because for ∆ > 2g (< − 2g ),
when quantitative reproduction of experimental results is consid- the Fermi level of the metal lies within the conduction (valence)
ered, explicit information about the size of the chain, electronic band of the polyynic carbyne, leading to non-vanishing currents
structure of the leads and the strength of coupling between the for small biases. The alternation of the gap region due to the
leads and the chain is necessary. In the following, we study some energetic difference between the contacts and the leads has also
of the experimental results of Ref. 27 , showing that our model can been suggested by recent ab initio calculations, where a signifi-
catch some key aspects of the experimental observations, and fo- cant difference in the I-V curves is found when the atom chain
cus on the influence of the leads’ parameters to the I-V character- is sandwiched between graphene layers and end-capped carbon
istics. Since we have no explicit information about these details, nanotubes 28 . From the right panel of Fig. 4 it can be seen that the
we will display our results for N = 100, as a representative case differential conductance has an oscillatory behaviour. Although
of relatively long atomic carbon wires (the recruitment of which for ∆ = 0, dV
is symmetric around V = 0, the increase of |∆| in-
in devices is experimentally sought) that can be treated with TB. duces an increasing asymmetry, such that dV dI dI
(∆,V ) = dV (−∆, −V ).
Our calculations show that altering N has only some quantitative Furthermore, it is evident that, for |∆| > 2g , the valley of the dif-
and not qualitative effect on the physical properties. Although ferential conductance in the vicinity V = 0 vanishes, giving rise to
the currents observed in Ref. 27 are no larger than some nA, later large conductance in the small bias regime.

4| 1–8
Page 5 of 9 Physical Chemistry Chemical Physics
View Article Online
DOI: 10.1039/C7CP05134D

Physical Chemistry Chemical Physics Accepted Manuscript

Published on 22 September 2017. Downloaded by Gazi Universitesi on 22/09/2017 13:04:23.

Fig. 2 Zero-bias trasmission coefficient for a polyynic carbyne with N = 10 atoms, as a function of the ratio t1 /t2 . Identical leads have been assumed,
with εm = εC and tm = −4 eV. (Top) Ideal coupling condition. (Middle) Strong coupling condition with ω = 1/2. (Bottom) Weak coupling condition with
ω = 2. (Left column) Symmetric coupling condition. (Right column) Asymmetric coupling condition, with χ = 2, 1/2. The transmission coefficient that
corresponds to the parameters t1 = ts = −3.00 eV, t2 = tℓ = −2.84 eV, as derived by the bond distances of Ref. 39 , is noted with horizontal dashed lines
in each panel.

(a) (b) 8 it can be seen that for V = 0.50 V, the peaks become wider, their
60 dcR = 1.34 Å 6
dcR = 1.20 Å position alters, and their value is smaller. The synergetic effect
40 1.1dcR 1.1dcR
1.4dcR of these changes to T (E) can quantitatively be demonstrated by
simply taking the average of the transmission coefficient, T̄ (E), in
I (µA)
I (µA)

0 0
each case [inset of Fig. 5(a)]. By observing the inset of Fig. 5(a),
-20 -2
-4 we can expect that the increase of the leads’ bandwidth results in
-6 reduced current, for the same value of bias. Finally, we can ex-
-8 pect that the increase of the current value between 0.36 and 0.50
-0.4 -0.2 0 0.2 0.4 -0.4 -0.2 0 0.2 0.4
V (V) V (V) V will be significantly smaller for increased leads’ bandwidth, i.e.
the I-V curve in this case will have a more step-like behaviour.
Fig. 3 I-V characteristics of (a) cumulenic (b) polyynic carbynes with These observations are supported by the explicit calculation of
N = 100 carbon atoms. The effect of enlarging the distance between the
the current-voltage curves via Eq. (9), which are presented in
end of the chain and the right lead, dcR (continuous blue curves), is also
demonstrated, for 10% (red dashed curves) and 40% (green dotted Fig. 5(b). The progressive increase of the leads bandwidth leads
curves) increase. generally to reduced currents and gradually to a step-like increase
of the current with applied bias. The occurrence of this step-like

0.2 eV
0.16 eV 120 behaviour can be explained in terms of the "molecular eigenvalue
∆ = 0.1 eV
staircase" 57 . As the bias increases, more transmission peaks (res-
∆ = 0 eV
onances) are included in the broadening conductance channel,
dI/dV (µS)

∆ = -0.1 eV
20 ∆ = -0.16 eV 80
resulting in gradual jumps in the I-V curves.
I (µA)

∆ = -0.2 eV
0 60

-20 40 (a) 0.6 V = 0.36 V,tm (b) 60 tm

V = 0.36 V, 2.5tm 1.5tm
-40 20 0.5 40
V = 0.50 V, tm 2tm
-60 0 V = 0.50 V, 2.5tm 2.5tm
0.4 20
-1 -0.5 0 0.5 1 -0.5 0 0.5
I (µA)
T (E)

V (V) V (V)
T (E)

0.3 0
0.2 -20
Fig. 4 I-V characteristics (left) and differential conductance (right) of a 0
polyynic carbyne with N = 100 atoms for different values of the energy 0.1 -40
difference between the Fermi level of the carbyne and the metallic leads. 0 -60
0 0.1 0.2 0.3 0.4 0.5 -1 -0.5 0 0.5 1
E − EM (eV) V (V)

Next, we examine the effect of altering the leads bandwidth on Fig. 5 (a) Transmission coefficients of a polyynic carbyne with N = 100
the I-V curves. For a specific value of bias, the increase of leads atoms for V = 0.36 V and V = 0.50 V for different leads’ bandwidths
(tm = 3.16 eV and 2.5tm ). The average values of the transmission
bandwidth, in terms of increasing |tm |, for fixed coupling hopping
coefficient in the energy interval of the incident carriers are presented in
integrals, results in increasing ω (thus weakening the coupling), the inset. (b) I-V characteristics of the same system, for different leads’
so the transmission peaks become sharper. This is evident by com- bandwidths, as determined by tm .
paring the peaks that occur for V = 0.36 V and for V = 0.50 V in
Fig.5(a), where the T (E) is plotted in the interval of the inci- Finally, we examine how considering different contacts affects
dent carrier energies in each case. Furthermore, from Fig. 5(a) the I-V characteristic of the carbon chain. We assume that the

1–8 | 5
Physical Chemistry Chemical Physics Page 6 of 9
View Article Online
DOI: 10.1039/C7CP05134D

Fermi level of the left (right) lead is shifted 0.2 eV above (below) a difference in the electronic structure of the leads results in rec-
the Fermi level of the polyynic carbyne and that tmL = 3.16 eV tifying I-V curves. Our results reproduce some of the most recent
= 0.5tmR . The calculated I-V curve under these conditions, which experimental findings.
is presented in Fig. 6, displays a rectifying behaviour. This is
in accordance with the experimental findings of Ref. 27 , in which References

Physical Chemistry Chemical Physics Accepted Manuscript

a rectifying behaviour is observed when the carbyne chains are
lying between two different contacts. 1 H. W. Kroto, J. R. Heath, S. C. O’Brien, R. F. Curl, R. E. Smal-
ley, C60 : Buckminsterfullerene, Nature, 1985, 318, 162-163.
2 S. Iijima, Helical microtubules of graphitic carbon, Nature,
40 1991, 354, 56-58.
ǫmL = ǫC + 0.2 eV 3 L. V. Radushkevich, V. M. Lukyanovich, The structure of car-
Published on 22 September 2017. Downloaded by Gazi Universitesi on 22/09/2017 13:04:23.

ǫmR = ǫC - 0.2 eV bon forming in thermal decomposition of carbon monoxide

on an iron catalyst, Russian Journal of Physical Chemistry,
tmR /tmL = 2
1952, 26, 88-95 (in Russian).
I (µA)

20 4 K. S. Novoselov, A. K. Geim, S. V. Morozov, D. Jiang, Y. Zhang,

S.V. Dubonos, I. V. Grigorieva, A. A. Firsov, Electric Field Ef-
fect in Atomically Thin Carbon Films, Science, 2004, 306, 666-
10 669.
5 D. Malko, C. Neiss, C. Viñes, A. Görling, Competition for
0 Graphene: Graphynes with Direction-Dependent Dirac Cones,
Phys. Rev. Lett., 2012, 108, 086804.
-0.6 -0.4 -0.2 0 0.2 0.4 0.6 6 F. Banhart, Chains of carbon atoms: A vision or a new nano-
material?, Beilstein J. Nanotechnol., 2015, 6, 559-569.
V (V)
7 C. S. Casari, M. Tommasini, R. R. Tykwinskic, A. Milani,
Fig. 6 I-V curve of a polyynic carbyne with N = 100 atoms, sandwiched Carbon-atom wires: 1-D systems with tunable properties,
between two different leads. Nanoscale, 2016, 8, 4414-4435.
8 O. Cretu, A. R. Botello-Mendez, I. Janowska, C. Pham-Huu,
The significant influence the contacts have on the charge trans- J.-C. Charlier, F. Banhart, Electrical Transport Measured in
port properties of carbon wires demonstrated by our results is Atomic Carbon Chains, Nano Lett., 2013, 13, 3487-3493.
in accordance with the conclusions of experimental works us- 9 W. A. Chalifoux, R. R. Tykwinski, Synthesis of polyynes to
ing the Scanning tunneling microscope break junction (STM- model the sp-carbon allotrope carbyne, Nat. Chem., 2010, 2,
BJ) technique in order to study the conductance of end-capped 967-971.
oligoynes 21,22 . 10 L. Shi, P. Rohringer, K. Suenaga, Y. Niimi, J. Kotakoski, J. C.
5 Conclusions Meyer, H. Peterlik, M. Wanko, S. Cahangirov, A. Rubio, Z. J.
Lapin, L. Novotny, P. Ayala, T. Pichler, Confined linear carbon
We employed a simple TB model in order to obtain the electronic
chains as a route to bulk carbyne, Nat. Mater., 2016, 15, 634-
structure of cumulenic and polyynic carbynes, in terms of their
dispersion relations (for cyclic boundaries), eigenspectra (fixed
11 G. Wu, J. Dong, Anomalous heat conduction in a carbon
boundaries), and DOS, obtaining a bandgap for polyynic carbynes
nanowire: Molecular dynamics calculations, Phys. Rev. B,
at 0.32 eV, in agreement with more complex ab initio calculations.
2005, 71, 115410.
We analytically determined the transmission coefficient at zero-
12 M. Wang, S. Lin, Ballistic Thermal Transport in Carbyne and
bias by attaching the carbynes to semi-infinite metallic leads, and
Cumulene with Micron-Scale Spectral Acoustic Phonon Mean
displayed the effect of the coupling strength and asymmetry to
Free Path, Sci. Rep., 2015, 5, 18122.
the transparency of the system to the incident carriers. Then,
we calculated the I-V characteristics of cumulenic and polyynic 13 X. Liu, G. Zhang, Y.-W. Zhang, Tunable Mechanical and Ther-
carbynes, which display metallic and semiconducting behaviour, mal Properties of One-dimensional Carbyne Chain: Phase
respectively. Finally, we studied the effect on the I-V curves of fac- Transition and Microscopic Dynamics, J. Phys. Chem. C, 2015,
tors such as the weakening of the coupling of the system to one of 119, 24156-24164.
the leads, the relative position of the Fermi levels of the carbyne 14 Y. Deng, S. W. Cranford, Thermal conductivity of 1D carbyne
and the leads, the leads’ bandwidth and, finally, the difference in chains, Comp. Mater. Sci., 2017, 129, 226-230.
the energy structure between the leads. Weakening the coupling 15 A. Milani, M. Tommasini, G. Zerbi, Carbynes phonons: A tight
of the system to the leads reduced currents. Altering the relative binding force field, J. Chem. Phys., 2008, 128, 064501.
position of the Fermi levels of the carbyne and the leads has an 16 M. Tommasini, A. Milani, D. Fazzi, M. Del Zoppo, C. Cas-
effect in the gap region and significantly changes the differential tiglioni, G. Zerbi, Modeling phonons of carbon nanowires,
conductance. Increasing the bandwidth reduces the currents and Physica E, 2008, 40, 2570-2576.
leads to a more step-like increase with bias. Finally, introducing 17 N. R. Agarwal, A. Lucotti, D. Fazzi, M. Tommasini, C. Cas-

6| 1–8
Page 7 of 9 Physical Chemistry Chemical Physics
View Article Online
DOI: 10.1039/C7CP05134D

tiglioni, W. A. Chalifoux, R. R. Tykwinski, Structure and chain byne From First Principles: Chain of C atoms, a Nanorod or a
polarization of long polyynes investigated with infrared and Nanorope, ACS Nano, 2013, 7, 10075-10082.
Raman spectroscopy, J. Raman Spectrosc., 2013, 44, 1398- 33 V. I. Artyukhov, M. Liu, B. I. Yakobson, Mechanically Induced
1410. Metal-Insulator Transition in Carbyne, Nano Lett., 2014, 8,
18 A. K. Nair, S. W. Cranford, M. J. Buehler, The minimal 4224-4229.

Physical Chemistry Chemical Physics Accepted Manuscript

nanowire: Mechanical properties of carbyne, EPL, 2011, 95, 34 A. Milani, M. Tommasini, V. Barbieri, A. Lucotti, V. Russo, F.
16002. Cataldo, C. S. Casari, Semiconductor-to-Metal Transition in
19 L. Ravagnan, P. Piseri, M. Bruzzi, S. Miglio, G. Bongiorno, A. Carbon-Atom Wires Driven by sp2 Conjugated End Groups, J.
Baserga, C. S. Casari, A. Li Bassi, C. Lenardi, Y. Yamaguchi, Phys. Chem. C, 2017, 121, 10562-10570.
T. Wakabayashi, C. E. Bottani, and P. Milani, Influence of 35 L. Molinari, Transfer matrices and tridiagonal-block Hamil-
Cumulenic Chains on the Vibrational and Electronic Proper- tonians with periodic and scattering boundary conditions, J.
Published on 22 September 2017. Downloaded by Gazi Universitesi on 22/09/2017 13:04:23.

ties of sp − sp2 Amorphous Carbon, Phys. Rev. Lett., 2007, 98, Phys. A: Math. Gen., 1997, 30, 983-997.
216103. 36 L. Molinari, Spectral duality and distribution of exponents for
20 B. Standley, W. Bao, H. Zhang, J. Bruck, C. N. Lau, and M. transfer matrices of block-tridiagonal Hamiltonians, J. Phys.
Bockrath, Graphene-Based Atomic-Scale Switches, Nano Lett., A: Math. Gen., 2003, 36, 4081-4090.
2008, 8, 3345-3349. 37 P. Yeh, A. Yariv, C. S. Hong, Electromagnetic propagation in
21 C. Wang, A. S. Batsanov, M. R. Bryce, S. Martín, R. J. periodic stratified media. I. General theory, J. Opt. Soc. Am.,
Nichols, S. J. Higgins, V. M. García-Suárez, and C. J. Lambert, 1977, 67, 423-438.
Oligoyne Single Molecule Wires, J. Am. Chem. Soc., 2009, 38 E. Maciá Barber, Aperiodic Structures in Condensed Matter,
131, 15647-15654. Fundamentals and Applications, CRC Press, Taylor and Fran-
22 P. Moreno-García, M. Gulcur, D. Z. Manrique, T. Pope, W. cis Group, LLC, 2009. ISBN-13: 978-1-4200-6827-6.
Hong, V. Kaliginedi, C. Huang, A. S. Batsanov, M. R. Bryce, C. 39 S. Cahangirov, M. Topsakal, S. Ciraci, Long-range interactions
Lambert, and Thomas Wandlowski, Single-Molecule Conduc- in carbon atomic chains, Phys. Rev. B, 2010, 82, 195444.
tance of Functionalized Oligoynes: Length Dependence and 40 W. A. Harrison, Electronic Structure and the Properties of
Junction Evolution, J. Am. Chem. Soc., 2013, 135, 12228- Solids: the Physics of the Chemical Bond. 2nd edition, Dover,
12240. New York, 1989.
23 M. Tommasini, D. Fazzi, A. Milani, M. Del Zoppo, C. Cas- 41 M. Menon and R. E. Allen, Simulations of atomic processes at
tiglioni, G. Zerbi, Effective hamiltonian for π electrons in lin- semiconductor surfaces: General method and chemisorption
ear carbon chains, Chem. Phys. Lett., 2007, 450, 86-90. on GaAs(110), Phys. Rev. B, 1988, 38, 6196.
24 A. La Magna, I. Deretzis, V. Privitera, Insulator-metal transi- 42 N. Lathiotakis and A. N. Andriotis, The applicability of scaling
tion in biased finite polyyne systems, Eur. Phys. J. B, 2009, 70, laws in tight-binding molecular-dynamics ,Solid State Comm.,
311-316. 1993, 87, 871-875.
25 Y. Zhang, Y. Su, L. Wang, E. S.-W. Kong, X. Chen, Y. Zhang, 43 L. G. D. Hawke, G. Kalosakas, and C. Simserides, Empirical
A one-dimensional extremely covalent material: monatomic LCAO parameters for π molecular orbitals in planar organic
carbon linear chain, Nanoscale Res. Lett., 2011, 6, 577. molecules, Mol. Phys., 2009, 107, 1755-1771.
26 P. N. D’yachkov, V. A. Zaluev, E. Y. Kocherga, N. R. Sadykov, 44 W. M. Haynes, (editor-in-Chief) CRC Handbook of Chemistry
Tight Binding Model of Quantum Conductance of Cumulenic and Physics, 95th Edition, 2014.
and Polyynic Carbynes, J. Phys. Chem. C, 2013, 117, 16306- 45 J. C. Mason, D. C. Handscomb, Chebyshev Polynomials. CRC
16315. Press, Taylor and Francis Group, LLC, 2003. ISBN: 0-8493-
27 A. La Torre, A. Botello-Mendez, W. Baaziz, J.-C. Charlier, F. 0355-9.
Banhart, Strain-induced metal-semiconductor transition ob- 46 M. J. C. Gover, The eigenproblem of a tridiagonal 2-Toeplitz
served in atomic carbon chains, Nat. Commun., 2015, 6, 6636. matrix, Linear Algebra Appl., 1994, 197-198, 63-78.
28 F. Ben Romdhane, J.-J. Adjizian, J.-C. Charlier, F. Banhart, 47 F. Marcellán and J. Petronilho, Eigenproblems for tridiagonal
Electrical transport through atomic carbon chains: The role 2-Toeplitz matrices and quadratic polynomial mappings, Lin-
of contacts, Carbon, 2017, 122, 92-97. ear Algebra Appl., 1997, 260, 169-208.
29 R. E. Peierls, Quantum Theory of Solids; Oxford University 48 R. Álvarez-Nodarse, J. Petronilho, N. R. Quintero, On some
Press, Oxford, 2001. tridiagonal k-Toeplitz matrices: Algebraic and analytical as-
30 A. Milani, M. Tommasini, G. Zerbi, Connection among Ra- pects. Applications, J. Comput. Appl. Math., 2005, 184, 518-
man wavenumbers, bond length alternation and energy gap 537.
in polyynes, J. Raman Spectrosc., 2009, 40, 1931-1934. 49 K. Lambropoulos, M. Chatzieleftheriou, A. Morphis, K. Kakla-
31 A. Milani, M. Tommasini, M. Del Zoppo, C. Castiglioni, G. manis, M. Theodorakou, C. Simserides, Unbiased charge os-
Zerbi, Carbon nanowires: Phonon and π-electron confine- cillations in B-DNA: Monomer polymers and dimer polymers,
ment, Phys. Rev. B, 2006, 74, 153418. Phys. Rev. E, 2015, 92, 032725.
32 M. Liu, V. I. Artyukhov, H. Lee, F. Xu, B. I. Yakobson, Car- 50 K. Lambropoulos, M. Chatzieleftheriou, A. Morphis, K. Kak-

1–8 | 7
Physical Chemistry Chemical Physics Page 8 of 9
View Article Online
DOI: 10.1039/C7CP05134D

lamanis, R. Lopp, M. Theodorakou, M. Tassi, C. Sim- 54 G. C. Liang, A. W. Ghosh, M. Paulsson, S. Datta, Electrostatic
serides, Electronic structure and carrier transfer in B-DNA potential profiles of molecular conductors, Phys. Rev. B, 2004,
monomer polymers and dimer polymers: Stationary and time- 69, 115302.
dependent aspects of wire model vs. extended ladder model, 55 S. Datta, Electronic Transport in Mesoscopic Systems, Cam-
Phys. Rev. E, 2016, 94, 062403. bridge University Press, Cambridge, 1995.

Physical Chemistry Chemical Physics Accepted Manuscript

51 R. Landauer, Spatial Variation of Currents and Fields Due to 56 M. S. Dresselhaus and G. Dresselhaus, Intercalation com-
Localized Scatterers in Metallic Conduction, IBM J. Res. Dev., pounds of graphite, Adv. Phys., 2002, 51, 1-186.
1957, 1, 223-231. 57 V. Mujica, M. Kemp, A. Roitberg, and M. Ratner, Current-
52 M. Büttiker, Y. Imry, R. Landauer, S. Pinhas, Generalized voltage characteristics of molecular wires: Eigenvalue stair-
many-channel conductance formula with application to small case, Coulomb blockade, and rectification, J. Chem. Phys.,
rings, Phys. Rev. B, 1985, 31, 6207. 1996, 104, 7296.
Published on 22 September 2017. Downloaded by Gazi Universitesi on 22/09/2017 13:04:23.

53 M. Büttiker, Symmetry of electrical conduction, IBM J. Res.

Dev., 1988, 32, 317-334.

8| 1–8
Published on 22 September 2017. Downloaded by Gazi Universitesi on 22/09/2017 13:04:23.
Page 9 of 9

76x39mm (300 x 300 DPI)

Physical Chemistry Chemical Physics
DOI: 10.1039/C7CP05134D
View Article Online

Physical Chemistry Chemical Physics Accepted Manuscript