A Simple Chart for the Instant Structural electronic density of states symmetrically placed on

either side of the Fermi level, are closely related to the

Assignment of the Single-Walled Carbon physical structure and an important intrinsic
Nanotubes. characteristic of a given SWNT.2 These energies span
the UV, visible and near IR regions of the
electromagnetic spectrum thus leading to interesting
Ramesh Sivarajan optical properties. An equally important and
The single-walled carbon nanotubes (SWNT) unique characteristic of a given SWNT is its Raman
constitute the largest and unique family of molecules radial breathing mode which scales linearly with the
formed by a single element and closely related physical inverse tube diameter. 3 The intensity of the RBM is
properties guided by a common structural motif. The enhanced when the wavelength of the excitation source
SWNTs are formed by rolling up a graphene sheet with is in resonance with the optical transition characteristic
the roll up vector defined by a set of indices (n, m ) of a given SWNT. 4 Kataura et al 5 have reported a
indicating the diameter and helicity of the tube. detailed study of optical absorption and resonant Raman
Interesting structural, electronic and optical properties of scattering studies on SWNTs of assorted types and
the SWNT arise from the one-dimensional periodicity diameters and made correlations to the band gaps
are closely related to the diameter and chiral angle. 1 The predicted using the zone folding formalism. Smalley and
energy gap between the van Hove singularities in the colleagues recently reported fluorescence from

0.69

575. 518. 463.3 414.7 372.9 337.6

5 443 720 833
0.83

481.7
* * 441.8 402.9
356 1

367.2
522
335.4
483
307.7
425

283.4
© Ramesh Sivarajan, 2003
6
All rights reserved.
500 653 894 443 873 975
335 632 418 398 581 2 567
476 0.96

414.7 385.4 356.4 329.2 304.4 282.1 262.3 244.7

7 962 473 802 992 478 1023 1122
1
395 372 626 505 447 644 647 4 529 1.10

364.4 342.0 319.7 298.3 278.5 260.4 243.9 229.1 215.7

8 776 1041 491 952 1113 522 1172 1267
660 471 420 5 588 1.24
663 587 502 716 728 Diameter (nm)
325.3 307.6 289.9 272.8 256.6 241.6 227.8 215.1 203.6 193.1
9 496 912 1139 524 1101 1244 576 1323 1414
407 2
693 551 475 3
720 671 790 809
645 1.38

294.0 279.7 265.3 251.3 237.9 225.3 213.6 202.7 192.7 183.5 175.0
n 10 1156 529 1053 1250 571 1250 1380 629 1474 1555
537 456 734 633 530 786 756 618 868 892
705 1.51

268.4 256.6 244.7 233.0 221.7 211.1 201.0 191.6 182.9 174.8 167.2 160.3
11 1037 1263 572 1197 1372 622 1397 1525 687 1629 1702
745 3
611 4
510 792 714 590 858 6
838 676 944 969
767 1.65

247.1 237.2 227.2 217.3 207.7 198.5 189.8 181.6 174.0 166.8 160.1 153.8 147.9
12 573 1171 1376 619 1342 1496 675 1553 1657 746 1765 1848
502 797 685 565 857 795 647 921 917 736 1024 1049
829 1.79

229.1 220.6 212.1 203.6 195.4 187.4 179.8 172.6 165.9 159.5 153.4 147.8 142.5 137.5
13 1384 618 1307 1497 668 1485 1640 732 1692 1799 807 1912 1994
5
677 552 859 760 626 928 874 709 1004 997 798 1102 1128
891 1.92

213.6 206.3 198.9 191.6 184.5 177.5 170.9 164.5 158.5 152.7 147.3 142.2 137.4 132.9 128.6
14 1295 1502 665 1447 1623 722 1633 1768 790 1840 1942 869 2059 2141
6 954
859 748 608 920 842 684 999 955 770 1080 1078 861 1181 1208
202.8 196.3 189.8 183.4 177.1 170.8 164.8 159.1 153.6 148.1 143.4 138.7 134.3 130.1 126.1 122.4
15 664 1425 1622 716 1589 1752 778 1779 1907 850 1987 2086 931 2207 2287 1018
603 927 822 664 986 921 745 1064 1035 832 1156 1158 924 1259 1288


0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15
6.2 13.1 20.3 24.9 28.9

Figure 1. The assignment chart for single-walled carbon nanotubes based on their (n,m) index. At the left hand side of the chart is the index “n”
and at the bottom of the chart is the index “m”. The achiral zig-zag tubes with an index (n, 0) fall in the first column of the table. The diagonal row
at the extreme right, colored in blue is the family of armchair tubes with a chiral angle of 30o . Semimetals (see text for definition) marked in green
fall in diagonal fashion as well. The rest of the cells in yellow represent semiconducting tubes. The blue and red dotted lines that run across the
table divide the table into bins where SWNT of approximately same diameter and chiral angle ranges respectively could be located. For the low
diameter tubes marked with an asterisk, the predicted values do not match closely.

© Ramesh Sivarajan, 2004; All rights reserved.

www.carbonwall.com
semiconducting SWNT due to direct band gap emission
when excited with a photon of appropriate energy. 6
This observation led to the assignment of n,m indices
for individual SWNT ( structural assignment ) for a
larger library of SWNT fluorescing over a wider range
of wavelengths .7,8 Based on an accurate empirical fit to
the experimental data, Weisman and Bachilo 9 also
reported the predicted values for a wide range of
semiconducting SWNT. Smalley and colleagues also
recently reported a list of optical transition values
specifically for metallic tubes , based on resonant
Raman scattering experiments and calculations using
tight binding approximation. 10 Accordingly, a i
reasonable library of experimentally observed data and
predicted values for the spectral parameters is now
available making UV-Vis-NIR absorption/ emission
spectroscopy and resonance Raman spectroscopy as
indispensable tools in the structural assignment of
individual SWNT. However, the non-availability of all
this scattered information in a single source, convenient
format makes the ready use of this information a
difficult task. In this communication a simple, easy to
use assignment chart is presented in a tabular format
based on the (n,m ) indices of SWNT, that collates the
vast array of spectroscopic information currently
available. The table, which could be called as
“Assignment Chart for Single- Walled Carbon
Nanotubes ” is shown in figure 1. The table facilitates
the instant structural assignment of a given SWNT
based on the RBM and UV-Vis -NIR absorption and
emission characteristics .
At the left hand side of the table is the index “n”
and the bottom of the table is the index m. The achiral
zig-zag tubes with an index (n, 0) fall in the first
column of the table. The diagonal row at the extreme
right colored in blue is the family of armchair tubes
(n = m )with a chiral angle of 30o . These are metallic
tubes that display no trigonal warping 10. Tubes with an
( n,m ) index that satisfy the n-m = 3I condition
( where I is a positive integer ) are semimetals marked
in green color. The rest of the cells in yellow color
represent the semiconducting tubes. The blue dotted
lines that run across the table slice the table into bins
where SWNT of approximately the same diameter are
housed. Similarly, the red dotted lines divide the table
into zones that house tubes falling in a certain chiral
angle range. These lines serve to quickly locate SWNT
falling in a given diameter or chiral angle range. The
ranges are only approximate as the the original (n,m)
vectors for SWNT, defined on a hexagonal lattice
cannot be mapped exactly on to a square grid.
Figure.2 shows three cells each representing a (a)
semiconductor, (b) semi-metal and (c) an armchair
metallic tube respectively. The value shown on the
upper left hand side corner of each of these cells is the
Raman radial breathing mode (RB in inverse
© Ramesh Sivarajan, 2004; All rights reserved.
www.carbonwall.com
centimeters. The values are obtained using a simple
expression 7
RBM (cm-1) = [223.5/ d] +12.5 ……..(1)
where “d” is the diameter of the SWNT expressed in
nanometers. In the case of semiconductors, there are
two values listed in the lower right hand side corner.
-1
RBM; cm
298.3 (a)
11; nm
22; nm
952
Isoradials
-
RBM; cm
(b)
227.8
11; nm
576 11; nm
557
- 160.3 (c)
RBM; cm
11; nm
767
Figure 2. Key for the contents of the assignment table shown in
figure 1 (a) yellow squares representing semiconducting tubes. The red
lettered entry in the lower right hand corner is the value of 11 in
nanometers corresponding to the E11 gap. The entry in blue below this is
the value of 22 in nanometers corresponding to the E22 gap. The red
circle in a corner of some SWNT represents isoradial pairs of identical
diameters. The pairs are matched with the number “i” inside the red
circle. (b) green squares representing semimetals. Both the entries in
red at the lower right hand corner correspond to an E11 gap. The values
are in nanometers. The upper one corresponds to the positive value
arising from a splitting due to trigonal warping (see ref.10) The lower
one corresponds to the negative value. (c) blue squares represent
armchair metallic tubes which do not exhibit trigonal warping leading
to a single value only. The values in nanometer, corresponding to the
E11 gap are printed in red in the lower right hand corner. The values in
the upper left hand side of each of the boxes corresponds to the
predicted Raman radial breathing mode in cm-1. All the entries for 11
and 22 in boldface are experimentally observed values as cited in
references 7,8 and 10
The entry marked in red color is the wavelength in
nanometers corresponding to the E11 transition. The
number in blue is the wavelength in nanometers
corresponding to the E22 transition. In the case of
semimetals both the values shown in red are for the E11
transition, but account for the positive and negative
splittings respectively that arise from trigonal
warping. 10 The armchairs tubes are metallic as well, but
exhibit no trigonal warping and hence have a single
value listed for the E11 transition.
The table consists of 110 entries covering all the tubes
from (5,0) to (15,15) This includes 77 semiconductors,
22 semimetals and 11 armchair tubes. Although
extending this table to higher diameter tubes (higher n,
m indices) is a simple exercise, it has limited value as
the present table covers the diameter range of practical
interest. Experimental observations of at least one of
the electronic transitions have been made for close to
half of the SWNTs listed in the table. These include
values reported by Bachilo et al 7 and Lebedkin et al 8
for semi -conductors and Strano et al 10 for semimetals
and metals. Wherever possible, an experimentally
observed value has been reported in the place of the
predicted value. These entries are shown in boldface in
the table. Lebedkin et al ,8 have listed assigned E11 and
E22 values for 15 different semiconductors based on
photoluminescence measurements, of which (16,2) (
E11=0.793 eV, E22 = 1.26 eV ) has not been included in
the table. Of the remaining fourteen tubes nine were
also experimentally observed by Bachilo et al7. In
those cases Bachilo, et al’ s values have been included
in the current table. Lebedkin et al’s values have been
included in the case of (13,6), (14,6), (11,9), (11, 7) and
(12,7) tubes . The table has been designed in an
expandable format to include SWNT with higher values
of n and m . The predicted values in the current table
can also be replaced with observed values as more and
more tubes get assigned experimentally.
Acknowledgements:
The author thanks late Professor Richard E. Smalley
for introducing him to the wonderful world of the single
walled carbon nanotube. This assignment table was
conceived and drafted by the author during his stay at
Rice, in the laboratory of Professor Smalley. He also
thanks Dr. R.H. Hauge, Dr, W. Wade Adams , Prof.
Bruce Weisman and Prof. W. E. Billups for their
encouragement during his stay at Rice. Erik H. Haroz
is acknowledged for his help in verifying the calculated
values for the metallic tubes.
© Ramesh Sivarajan, 2004; All rights reserved.
www.carbonwall.com
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