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and C. Simserides, Phys. Chem. Chem. Phys., 2017, DOI: 10.1039/C7CP05134D.

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Physical Chemistry Chemical Physics
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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-
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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-
degeneracy.
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
reads
q
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
! ! ! !
E−εC
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
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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
N
g(E) = p , cumulenic, (5a)
2
π 4t − (E − εC )2

N|E − εC |
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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
 by
the dispersion relation E = εmL(R) + 2tmL(R) cos qL(R) a . Hence
F
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)
1
,
bynes can be obtained recursively via the relations where

cumulenic, (4a)
2
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
with
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
cL

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
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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
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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,
mR
dV , for different values of ∆ are presented in Fig. 4. From the I-V
dI
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
E
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
E E
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
dI
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 ).
E
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
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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
4
1.4dcR of these changes to T (E) can quantitatively be demonstrated by
20
simply taking the average of the transmission coefficient, T̄ (E), in
I (µA)
I (µA)

2
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
-40
-6 reduced current, for the same value of bias. Finally, we can ex-
-60
-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
60


=
=
0.2 eV
0.16 eV 120 behaviour can be explained in terms of the "molecular eigenvalue
40
∆ = 0.1 eV
100
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)

0.2
V (V) V (V)
T (E)

0.3 0
0.1
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
F
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
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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
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ǫmR = ǫC - 0.2 eV bon forming in thermal decomposition of carbon monoxide


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on an iron catalyst, Russian Journal of Physical Chemistry,
tmR /tmL = 2
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I (µA)

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