Contact-passivated sensor devices allow one to measure the response of individual ultraclean single-walled carbon nanotubes to 1 ppm NO2, and show that the activation energies for desorption from nanotubes of diameters in the 1.5–3.5 nm range are of the order of 1 eV. DFT calculations based on several exchange-correlation functionals are presented and critically examined. The nature of the molecular binding is thus clarified for NO2, N2O4, and NO3, and also the dependence on the size of the nanotube. The binding strength of physisorbed NO3 is consistent with the experimental data on desorption.

1.
J.
Kong
,
N. R.
Franklin
,
C.
Zhou
,
M. G.
Chapline
,
S.
Peng
,
K.
Cho
, and
H.
Dai
,
Science
287
,
622
(
2000
).
2.
J.
Li
,
Y.
Lu
,
Q.
Ye
,
M.
Cinke
,
J.
Han
, and
M.
Meyyappan
,
Nano Lett.
3
,
929
(
2003
).
3.
D. R.
Kauffman
and
A.
Star
,
Angew. Chem.
47
,
6550
(
2008
).
4.
P.
Bondavalli
,
P.
Legagneux
, and
D.
Pribat
,
Sens. Actuators, B
140
,
304
(
2009
).
5.
J.
Kim
,
J. Nanomater.
2012
,
741647
.
6.
N.
Iqbal
,
A.
Afzal
,
N.
Cioffi
,
L.
Sabbatini
, and
L.
Torsi
,
Sens. Actuators, B
181
,
9
(
2013
).
7.
A.
Boyd
,
I.
Dube
,
G.
Fedorov
,
M.
Paranjape
, and
P.
Barbara
,
Carbon
69
,
417
(
2014
).
8.
A.
De Luca
,
M. T.
Cole
,
R. H.
Hopper
,
S.
Boual
,
J. H.
Warner
,
A. R.
Robertson
,
S. Z.
Ali
,
F.
Udrea
,
J. W.
Gardner
, and
W. I.
Milne
,
Appl. Phys. Lett.
106
,
194101
(
2015
).
9.
J.
Zhang
,
A.
Boyd
,
A.
Tselev
,
M.
Paranjape
, and
P.
Barbara
,
Appl. Phys. Lett.
88
,
123112
(
2006
).
10.
R.
Larciprete
,
L.
Petaccia
,
S.
Lizzit
, and
A.
Goldoni
,
J. Phys. Chem. C
111
,
12169
(
2007
).
11.
I.
Dube
,
D.
Jimenez
,
G.
Fedorov
,
A.
Boyd
,
I.
Gayduchenko
,
M.
Paranjape
, and
P.
Barbara
,
Carbon
87
,
330
(
2015
).
12.
L.
Valentini
,
I.
Armentano
,
J. M.
Kenny
,
C.
Cantalini
,
L.
Lozzi
, and
S.
Santucci
,
Appl. Phys. Lett.
82
,
961
(
2003
).
13.
S.
Santucci
,
S.
Picozzi
,
F.
Di Gregorio
,
L.
Lozzi
,
C.
Cantalini
,
L.
Valentini
,
J. M.
Kenny
, and
B.
Delley
,
J. Phys. Chem.
119
,
10904
(
2003
).
14.
K.
Chikkadi
,
M.
Muoth
,
V.
Maiwald
,
C.
Roman
, and
C.
Hierold
,
Appl. Phys. Lett.
103
,
223109
(
2013
).
15.
M. D.
Ellison
,
M. J.
Crotty
,
D.
Koh
,
R. L.
Spray
, and
K. E.
Tate
,
J. Phys. Chem. B
108
,
7938
(
2004
).
16.
S.
Peng
,
K.
Cho
,
P.
Qi
, and
H.
Dai
,
Chem. Phys. Lett.
387
,
271
(
2004
).
17.
J.
Dai
,
P.
Giannozzi
, and
J.
Yuan
,
Surf. Sci.
603
,
3234
(
2009
).
18.
G.
Ruiz-Soria
,
A.
Pérez Paz
,
M.
Sauer
,
D. J.
Mowbray
,
P.
Lacovig
,
M.
Dalmiglio
,
S.
Lizzit
,
K.
Yanagi
,
A.
Rubio
,
A.
Goldoni
,
P.
Ayala
, and
T.
Pichler
,
ACS Nano
8
,
1375
(
2014
).
19.
K.
Chikkadi
,
M.
Muoth
,
C.
Roman
,
M.
Haluska
, and
C.
Hierold
,
Beilstein J. Nanotechnol.
5
,
2179
(
2014
).
20.
S.
Peng
and
K.
Cho
,
Nanotechnology
11
,
57
(
2000
).
21.
H.
Chang
,
J. D.
Lee
,
S. M.
Lee
, and
Y. H.
Lee
,
Appl. Phys. Lett.
79
,
3863
(
2001
).
22.
J.
Zhao
,
A.
Buldum
,
J.
Han
, and
J. P.
Lu
,
Nanotechnology
13
,
195
(
2002
).
23.
J. P.
Perdew
,
K.
Burke
, and
M.
Ernzerhof
,
Phys. Rev. Lett.
77
,
3865
(
1996
).
24.
J. P.
Perdew
,
K.
Burke
, and
M.
Ernzerhof
,
Phys. Rev. Lett.
80
,
891
(
1998
).
25.
See supplementary material at http://dx.doi.org/10.1063/1.4940422 for details of the experimental apparatus and the computational scheme, as well as more computational results and verifications as cited in the main text.
26.

EB = −E(CNT + NOx) + E(CNT) + E(NOx), where the energies of both the interacting and the separate systems refer to their respective equilibrium configuration. Note that each calculation is made within the same scheme and, in particular, in the same supercell.

27.

Both NO2 and NO3 are radicals. Neglecting spin-polarization is not correct and increases the binding energy by ∼0.1–0.2 eV.25 

28.
A.
Ricca
and
C. W.
Bauschlicher
, Jr.
,
Chem. Phys.
323
,
511
(
2006
).
29.
J. W.
Lawson
,
C. W.
Bauschlicher
, Jr.
,
J.
Toulouse
,
C.
Filippi
, and
C. J.
Umrigar
,
Chem. Phys. Lett.
466
,
170
(
2008
).
30.
Y.
Kanai
,
V. R.
Khalap
,
P. G.
Collins
, and
J. C.
Grossman
,
Phys. Rev. Lett.
104
,
066401
(
2010
).
31.
J. M. H.
Kroes
,
F.
Pietrucci
,
A.
Curioni
, and
W.
Andreoni
,
J. Chem. Theory Comput.
10
,
4672
(
2014
).
32.
A. D.
Becke
,
Phys. Rev. A
38
,
3098
(
1988
).
33.
C.
Lee
,
W.
Yang
, and
R. G.
Parr
,
Phys. Rev. B
37
,
785
(
1988
).
34.
S.
Grimme
,
J. Comput. Chem.
27
,
1787
(
2006
).
35.
C.
Adamo
and
V.
Barone
,
J. Chem. Phys.
110
,
6158
(
1999
).
36.
H.-V.
Nguyen
and
G.
Galli
,
J. Chem. Phys.
132
,
044109
(
2010
).
37.
L.
Schimka
,
J.
Harl
,
A.
Stroppa
,
A.
Grneis
,
M.
Marsman
,
F.
Mittendorfer
, and
G.
Kresse
,
Nat. Mater.
9
,
741
(
2010
).
38.
V. R.
Cooper
,
Phys. Rev. B
81
,
161104
(
2010
).
39.
A.
Tkatchenko
,
R. A. J.
DiStasio
,
R.
Car
, and
M.
Scheffler
,
Phys. Rev. Lett.
108
,
236402
(
2012
).
40.
V. V.
Gobre
and
A.
Tkatchenko
,
Nat. Commun.
4
,
2341
(
2013
).
41.
K.
Berland
,
V. R.
Cooper
,
K.
Lee
,
E.
Schrder
,
T.
Thonhauser
,
P.
Hyldgaard
, and
B. I.
Lundqvist
,
Rep. Prog. Phys.
78
,
066501
(
2015
).
42.
L.
Durrer
,
J.
Greenwald
,
T.
Helbling
,
M.
Muoth
,
R.
Riek
, and
C.
Hierold
,
Nanotechnology
20
,
355601
(
2009
).
43.

We remark the assumption that the desorption rate is proportional to the change of the adsorbate density is valid only if the transconductance of the transfer characteristics around the working point of the sensor does not change with it. Therefore, caution has been taken that at the applied voltage Vg corresponding to the measurement of the signal, the slope does not change appreciably.

44.
R. E.
Huffman
and
N.
Davidson
,
J. Am. Chem. Soc.
81
,
2311
(
1959
).
45.
W.-G.
Liu
and
W. A.
Goddard
,
J. Am. Chem. Soc.
134
,
12970
(
2012
).
46.
P.
Sjövall
,
S. K.
So
,
B.
Kasemo
,
R.
Franchy
, and
W.
Ho
,
Chem. Phys. Lett.
172
,
125
(
1990
).
47.
A. A.
Savin
,
R.
Nesper
,
S.
Wengert
, and
T. F.
Fässler
,
Angew. Chem.
36
,
1808
(
1997
).
48.
R.
Bader
,
Atoms in Molecules: A Quantum Theory
(
Oxford University Press
,
Oxford
,
1994
).
49.
S. E.
Snyder
and
S. V.
Rotkin
,
JETP Lett.
84
,
348
(
2006
).
50.

For the sake of comparison, our LSDA values for EB25 are significantly lower than in Ref. 16: 0.15 eV for NO2—in excellent agreement with Ref. 13—and 0.8 eV for NO3.

51.

For CNTs, we refer to Ref. 52 (B3LYP) and to Ref. 25 for our specific case (PBE0).

52.
Y.
Matsuda
,
J.
Tahir-Kheli
, and
W. A.
Goddard
 III
,
J. Phys. Chem. Lett.
1
,
2946
(
2010
).

Supplementary Material

You do not currently have access to this content.