# Full Symmetry of Single- and Multi-wall Nanotubes

## I Introduction

The single-wall carbon nanotubes are quasi 1D cylindrical structures , which can be imagined as rolled up cylinders of the 2D honeycomb lattice of the single atomic layer of crystalline graphite. Frequently, several single-wall tubes are coaxially arranged, making multi-wall nanotube. Since their diameters are small (down to $`0.7\mathrm{nm}`$) in comparison to lengths (up to tens of $`\mu m`$), the theoretical model of the extended (i. e. infinite, and hence without caps at the ends) nanotube is well justified.

The symmetry of the nanotubes is relevant both for deep insight into the physical properties (quantum numbers, selection rules, optical activity, conducting properties, etc.) and to simplify calculations. As for the single-wall tubes, symmetry studies started by the classification of the graphene tubes according to fivefold, threefold or twofold axis of the related $`C_{60}`$ molecule , and gave just a part of their point group symmetry. The translational periodicity was discussed in context of the nanotube metallic properties . Finally, the helical and rotational symmetries were found : the screw axis was characterized in terms of tube parameters, as well as the order of the principle rotational axis . The first goal of this paper is to complete this task, giving the full geometric symmetry of the extended single-wall nanotubes. Due to their 1D translational periodicity, the resulting groups are the line groups ; it appears that only two line group families are relevant: the 5th for the chiral, and the 13th for the armchair and the zig-zag nanotubes.

The symmetry of the double- and multi-wall tubes has never been seriously studied, despite their importance for applications in nanodevices. Here, we present the exhaustive list of symmetries of such tubes. Depending on the single-wall constituents, and their relative arrangement, the resulting nanotube symmetry may be either line group or axial point group.

In section II, at first the necessary notions on the line groups are briefly summarized, and the relevant notation is introduced. Then, in subsection II A, the line groups of all the nanotubes are derived: the familiar symmetries of the original graphene lattice are transferred into the tubular geometry and those which remain symmetries of the rolled up lattice form the corresponding line group. Besides the rotational, translational and helical symmetries, the horizontal axes and (for zig-zag and armchair tubes) mirror- and glide-planes are also present. The symmetry groups of multi-wall nanotubes are studied in subsection II B. Note that among them there are also tubes being not translationally periodic.

Some of the possible applications of symmetry in the physics of nanotubes are discussed in the last section.

## II Symmetry of nanotubes

The line groups  contain all the symmetries of the systems periodical in one direction and usually are used in context of stereoregular polymers and quasi-1D subsystems of 3D crystals. It immediately follows that, being periodic along its axis, any extended single-wall nanotube has the symmetry described by one of the line groups.

All the line group transformations leave the tube axis ($`z`$-axis, by convention) invariant. Consequently, such a transformation $`(P|t)`$ (Koster-Seitz symbol) is some point group operation $`P`$ preserving the $`z`$-axis, followed by the translation for $`t`$ along the $`z`$-axis. Action on the point $`𝐫=(x,y,z)`$ gives $`(P|t)𝐫=(x^{},y^{},z^{})`$ with

$$x^{}=P_{xx}x+P_{xy}y,y^{}=P_{yx}x+P_{yy}y,z^{}=P_{zz}z+t.$$
(1)   
Here, $`P_{ij}`$ are elements of the $`3\times 3`$ matrix of $`P`$ in the Cartesian coordinates; those coupling $`z`$ to the other axes vanish. Such point operations are called axial, and they form seven types of the axial point groups : $`𝐂_n`$, $`𝐒_{2n}`$, $`𝐂_{nh}`$, $`𝐂_{nv}`$, $`𝐃_n`$, $`𝐃_{nd}`$, $`𝐃_{nh}`$, where $`n=1,2,\mathrm{}`$ is the order of the principle rotational axis.

There are infinitely many line groups, since there is no crystallographic restriction on the order of the principle axis, and they are classified within 13 families. Each line group is a product $`𝐋=\mathrm{𝐙𝐏}`$ of one axial point group $`𝐏`$ and one infinite cyclic group $`𝐙`$ of generalized translations (screw-axis $`𝐓_q^r`$, pure translations $`𝐓=𝐓_1^0`$, or glide plane $`𝐓_c`$, generated by the transformations $`(I|a)`$, $`(C_q^r|\frac{n}{q}a)`$ and $`(\sigma _v|\frac{a}{2})`$, respectively ). Thus, to determine the full symmetry of a nanotube, both of these factors (having only the identical transformation in common) should be found. The point factor $`𝐏`$ should be distinguished from the isogonal point group $`𝐏_I`$ of the line group : only for the symorphic groups when $`𝐙=𝐓`$, these groups are equal; otherwise $`𝐏_I`$ is not a subgroup of $`𝐋`$. Due to the convention , $`2\pi /q`$ is the minimal angle of rotation performed by the elements of the line group (if the screw axis is nontrivial it is followed by some fractional translation), as well as by its isogonal point group.

The easiest way to determine the line group $`𝐋`$ of a system is to find at first the subgroup $`𝐋^{(1)}`$, containing all the translations and the rotations around the principle axis (including the ones followed by fractional translations). Having the same screw axis ($`𝐓`$ is a special case) as $`𝐋`$, and the same order $`n`$ of the principle axis, this subgroup $`𝐋^{(1)}=𝐓_q^r𝐂_n`$ is the maximal subgroup from the first line group family. Then the symmetries complementing $`𝐋^{(1)}`$ to $`𝐋`$ should be looked for. To complete $`𝐙`$, it should be checked if there is a vertical glide plane. Also, $`𝐂_n`$ is to be complemented to $`𝐏`$ by eventual additional point group generators; at most two of them are to be chosen among the mirror planes, horizontal rotational axes of order two or rotoreflection axis (refining pure rotations that are already encountered in $`𝐂_n`$).

### A Single-wall nanotubes

Elementary cell of the hexagonal honeycomb lattice (Fig. 1) is formed by vectors $`\stackrel{}{a}_1`$ and $`\stackrel{}{a}_2`$ of the length $`a_0=2.461`$Å; within its area $`S_g=\sqrt{3}/2a_0^2`$ there are two carbon atoms at positions $`(\stackrel{}{a}_1+\stackrel{}{a}_2)/3`$ and $`2(\stackrel{}{a}_1+\stackrel{}{a}_2)/3`$. The single-wall nanotube $`(n_1,n_2)`$ is formed when the honeycomb lattice is rolled up, in such a way that the chiral vector $`\stackrel{}{c}=n_1\stackrel{}{a}_1+n_2\stackrel{}{a}_2`$ becomes the circumference of the tube (its end and origin match). The tubes $`(n_1,0)`$ and $`(n_1,n_1)`$ are called zig-zag and armchair, respectively, while the others are known as the chiral ones. The chiral angle $`\theta `$ of the nanotube is the angle between the chiral vector $`\stackrel{}{c}`$ and the zig-zag direction $`\stackrel{}{a}_1`$. When $`0\theta <\pi /3`$, all the tubes are encountered; in fact, for the zig-zag and the armchair nanotubes $`\theta `$ equals $`0`$ and $`\pi /6`$, respectively, and between these chiralities lay chiral vectors of all the chiral nanotubes with $`n_1>n_2>0`$ (the tubes $`(n_2,n_1)`$, with $`\pi /6<\theta <\pi /3`$, are their optical isomers).

There are $`n=\text{GCD}(n_1,n_2)`$ (the greatest common divisor) honeycomb lattice points laying on the chiral vector. The translations for $`s\stackrel{}{c}/n`$ in the chiral direction, on the tube appear as the rotations for $`2s\pi /n`$ ($`s=0,1,\mathrm{}`$) around the tube axis. Thus, the principal axis of order $`n`$ is a subgroup of the full symmetry of the tube $`(n_1,n_2)`$:

$$𝐂_n,n=\text{GCD}(n_1,n_2).$$
(2)   
Obviously, $`n=n_1`$ for the zig-zag $`(n_1,0)`$ and the armchair $`(n_1,n_1)`$ nanotubes.

To the primitive translation of the tube corresponds the vector $`\stackrel{}{a}=a_1\stackrel{}{a}_1+a_2\stackrel{}{a}_2`$ in the honeycomb lattice, being the minimal one among the lattice vectors orthogonal onto $`\stackrel{}{c}`$. Therefore, $`a_1`$ and $`a_2`$ are coprimes, yielding

$$\stackrel{}{a}=\frac{2n_2+n_1}{n}\stackrel{}{a}_1+\frac{2n_1+n_2}{n}\stackrel{}{a}_2,a=|\stackrel{}{a}|=\frac{\sqrt{3(n_1^2+n_2^2+n_1n_2)}}{n}a_0,$$
(3)   
with $`=3`$ if $`\frac{n_1n_2}{3n}`$ is integer and $`=1`$ otherwise. For the zig-zag and the armchair tubes $`a=\sqrt{3}a_0`$ and $`a=a_0`$, respectively. The elementary cell of the tube is the cylinder of the height $`a`$ and area $`S_t=a|\stackrel{}{c}|`$; it contains $`\frac{S_t}{S_g}=2\frac{n_1^2+n_2^2+n_1n_2}{n}`$ elementary graphene cells . So, the translational group $`𝐓`$ of the nanotube is composed of the elements $`(I|ta)`$, $`t=0,\pm 1,\mathrm{}`$

The encountered symmetries $`𝐓`$ and $`𝐂_n`$ originate from the honeycomb lattice translations: on the folded lattice the translations along the chiral vector become pure rotations, while those along $`\stackrel{}{a}`$ remain pure translations. These elements generate the whole nanotube from the sector of angle $`2\pi /n`$ of the elementary cell, with $`2\frac{n_1^2+n_2^2+n_1n_2}{n^2}`$ elementary graphene cells. This number is always greater then 1, pointing out that not all of the honeycomb lattice translations are taken into account. The missing translations are neither parallel with nor orthogonal onto $`\stackrel{}{c}`$; on the rolled up sheet they are manifested as rotations (for fraction of $`2\pi /n`$) combined with translations (for fractions of $`a`$), yielding the screw axis of the nanotube. Its generator $`(C_q^r|\frac{n}{q}a)`$ corresponds to the vector $`\stackrel{}{z}=r\frac{\stackrel{}{c}}{q}+n\frac{\stackrel{}{a}}{q}`$ of the honeycomb lattice, which, together with the encountered translations, generates the whole honeycomb lattice. Thus, $`\stackrel{}{z}`$ can be chosen to form the elementary honeycomb cell together with the minimal lattice vector $`\stackrel{}{c}/n`$ along the chiral direction. The honeycomb cell area $`S_g`$ must be the product of $`|\stackrel{}{c}|/n`$ and the length $`na/q`$ of the projection of $`\stackrel{}{z}`$ onto $`\stackrel{}{a}`$: $`a|\stackrel{}{c}|/q=\sqrt{3}a_0^2/2`$. This gives the order $`q`$ of the screw axis. Finally, $`r`$ is found  from the condition that projections of $`\stackrel{}{z}`$ on the $`\stackrel{}{a}_1`$ and $`\stackrel{}{a}_2`$ are coprimes. This completely determines the screw axis ($`\mathrm{Fr}[x]=x[x]`$ is the fractional part of the rational number $`x`$, and $`\phi (m)`$ is the Euler function, giving the number of coprimes less then $`m`$):

$$𝐙=𝐓_q^r,q=2\frac{n_1^2+n_1n_2+n_2^2}{n},r=\frac{q}{n}\mathrm{Fr}\left[\frac{n}{q}(32\frac{n_1n_2}{n_1})+\frac{n}{n_1}\left(\frac{n_1n_2}{n}\right)^{\phi (\frac{n_1}{n})1}\right].$$
(4)   
Especially, for both the zig-zag $`(n,0)`$ and the armchair $`(n,n)`$ tubes, $`q=2n`$ and $`r=1`$, i. e. $`𝐙=𝐓_{2n}^1`$. Note that $`q`$ is an even multiple of $`n`$. It is equal to the number of the graphene cells in the elementary cell of the tube $`S_t/S_g`$. Therefore, $`q/n`$ is the number of the graphene cells in the sector and therefore always greater then 1; this means that all the single-wall tubes have nonsymorphic symmetry groups.

To resume, the translational symmetry of the honeycomb lattice appears as the group $`𝐋^{(1)}=𝐓_q^r𝐂_n`$ of symmetries of the nanotube, with $`q`$ and $`r`$ given by (4). Its elements $`(C_q^{rt}C_n^s|t\frac{n}{q}a)`$ ($`t=0,\pm 1,\mathrm{}`$, $`s=0,\mathrm{},n1`$) generate the whole nanotube from any adjacent pair of the nanotube atoms. The group $`𝐋^{(1)}`$ contains all the symmetries previously considered in the literature . Note that the screw axis used here is somewhat different to the previously reported ones, due to the convention . With this convention $`2\pi /q`$ is the minimal rotation (followed by some fractional translation) in the group , providing that $`q`$ is the order of the principle axis of the isogonal point group. This explains why $`q`$ is equal to the number of the graphene cells contained in the elementary cell of the tube. Note that the translational period $`a`$ and the diameter $`D`$ of the tube are determined by the symmetry parameters $`q`$ and $`n`$:

$$a=\sqrt{\frac{3q}{2n}}a_0,D=\frac{1}{\pi }\sqrt{\frac{nq}{2}}a_0.$$
(5)   
Besides the translations, there are other symmetries of the honeycomb lattice: (a) perpendicular rotational axes through the centers of the hexagons (of order six), through the carbon atoms (of order three) and through the centers of the edges of the hexagons (of order two); (b) six vertical mirror planes through the centers of the hexagons formed by the atoms (or through the atoms); (c) two types of vertical glide planes — connecting the midpoints of the adjacent edges, and the midpoints of the next to nearest neighboring edges of the hexagons.

Among the rotations, only those for $`\pi `$, leaving invariant the axis of $`\stackrel{}{a}`$, i. e. the $`z`$-axis of the tube, remain the symmetry of the rolled up lattice. Thus, two types of horizontal second order axes emerge as symmetries of any nanotube (Fig. 1): $`U`$, passing through the center of the deformed nanotube hexagons, and $`U^{}`$, passing through the midpoints of the adjacent atoms. Moreover, the first of these transformations is obtained when the second one is followed by the screw axis generator: $`U=(C_q^r|\frac{n}{q}a)U^{}`$. Thus, any of them, say $`U`$, complements the principle tube axis $`𝐂_n`$ to the dihedral point group $`𝐃_n`$. This shows that at least the line group $`𝐓_q^r𝐃_n`$ (from the 5th family) is the symmetry group of any nanotube. Note that $`U^{}`$ just permutes the two carbon atoms in the elementary honeycomb cell, meaning that all the honeycomb atoms are obtained from an arbitrary one by the translations and the rotation $`U^{}`$. Analogously, the elements of the group $`𝐓_q^r𝐃_n`$ generate the whole nanotube from any of its atoms. The action (1) of the group elements on the point $`𝐫_{000}=(\rho _0,\varphi _0,z_0)`$ (cylindrical coordinates) gives the points

$$𝐫_{tsu}=(C_q^{rt}C_n^sU^u|t\frac{n}{q}a)𝐫_{000}=(\rho _0,(1)^u\phi _0+2\pi (\frac{t}{q}+\frac{s}{n}),(1)^uz_0+t\frac{n}{q}a),$$
(6)   
($`u=0,1`$; $`s=0,\mathrm{},n1`$; $`t=0,\pm 1,\mathrm{}`$); hereafter, the $`x`$-axis is assumed to coincide with the $`U`$-axis. Using (5), it can be shown that the coordinates of the first atom (positioned at $`\frac{1}{3}(\stackrel{}{a}_1+\stackrel{}{a}_2)`$ on the honeycomb) are

$$𝐫_{000}^C=(\frac{D}{2},2\pi \frac{n_1+n_2}{nq},\frac{n_1n_2}{\sqrt{6nq}}a_0).$$
(7)   
Substituting these values in (6), the coordinates of all other atoms are obtained.

Rolling up deforms any plane perpendicular onto the graphene sheet, unless it is either parallel with $`\stackrel{}{c}`$ (then it becomes horizontal plane) or orthogonal onto $`\stackrel{}{c}`$ (giving vertical plane). Thus, only the tubes with the chiral vectors being parallel or orthogonal to the enumerated mirror and glide planes obtain additional symmetries of these types. The zig-zag and armchair tubes are immediately singled out by simple inspection. Precisely, only in these cases the chiral vector is in a perpendicular mirror plane; when the sheet is rolled up, this plane becomes the horizontal mirror plane $`\sigma _h`$ of the corresponding nanotubes. Enlarging the previously found point symmetry group $`𝐃_n`$ by $`\sigma _h`$, the point group $`𝐃_{nh}`$ of the zig-zag and armchair tubes is obtained. Finally, taking into account the generalized translations (4), the full symmetry groups of the single-wall nanotubes are (besides the factorized notation, the international symbol is given also):

$$𝐋_{\text{chiral}}=𝐓_q^r𝐃_n=𝐋q_p22,p=q\mathrm{Fr}\left[\frac{n}{q}\frac{(\frac{2n_2+n_1}{n})^{\phi (\frac{2n_1+n_2}{n})1}qn_2}{2n_1+n_2}\right],$$
(9)   
$$𝐋_{\text{armchair}}=𝐋_{\text{zig-zag}}=𝐓_{2n}^1𝐃_{nh}=𝐋2n_n/mcm.$$
(10)   
Their isogonal point groups  are $`𝐃_q`$ and $`𝐃_{2nh}`$.

The line group $`𝐓_{2n}^1𝐃_{nh}`$ (13th family) contains various new symmetries (Fig. 2), being combinations of the ones mentioned above. In fact, when $`\sigma _h`$ has been added to the group $`𝐓_{2n}^1𝐃_n`$, the other mirror and glide planes parallel to and orthogonal onto $`\stackrel{}{c}`$ are automatically included in the symmetry groups of the zig-zag and armchair nanotubes. These transformations can be seen as $`\sigma _h`$ followed by some of the elements from $`𝐓_{2n}^1𝐃_n`$. At first, there are $`n`$ vertical mirror planes (one of them is $`\sigma _v=\sigma _hU`$, and the others are obtained by pure rotations; by the previous convention, the $`\sigma _h`$ plane is the $`xy`$-coordinate plane). Bisecting the mirror planes, there are glide planes (e. g. the product $`(\sigma _v^{}|\frac{1}{2})=(C_{2n}|\frac{1}{2}a)\sigma _v`$), and the vertical rotoreflection axis of order $`2n`$ (generated by $`\sigma _vU^{}=C_{2n}\sigma _h^{}`$, the reflection in the $`\sigma _h^{}`$ plane, followed by the rotation for $`\pi /n`$).

The vectors obtained from $`\stackrel{}{c}`$ by the rotations from the point symmetry group $`𝐂_{6v}`$ of the honeycomb lattice, produce the nanotubes which are essentially the same one, only looked at from the rotated coordinate systems. Nevertheless, the vertical mirror plane image of $`\stackrel{}{c}`$ (e. g. in the vertical plane bisecting the angle of $`\stackrel{}{a}_1`$ and $`\stackrel{}{a}_2`$) produces the tube which can be considered as the same one only in the coordinate system with the opposite sign (the coordinate transformation involves the spatial inversion). Thus, the tubes $`(n_1,n_2)`$ and $`(n_2,n_1)`$ are the optical isomers. Only the mirror image of zig-zag and armchair tube is equivalent to the original, and these tubes have no optical isomers. Concerning the symmetry groups, if $`𝐓_q^r𝐂_n`$ corresponds to the tube $`(n_1,n_2)`$, then the group of the tube $`(n_2,n_1)`$ is $`𝐓_q^{\frac{q}{n}r}𝐂_n`$ (although isomorphic, these groups are equal only when $`q=2n`$ and $`r=1`$, i. e. only for the zig-zag and the armchair tubes).

### B Double- and multi-wall nanotubes

The symmetry of a multi-wall nanotube now can be found as intersection of the symmetry groups of its single-wall constituents. This task will be considered for double-wall tubes at first, and then the results are straightforwardly generalized to the multi-wall ones. The intersection of the line groups, $`𝐋=\mathrm{𝐙𝐏}`$ and $`𝐋^{}=𝐙^{}𝐏^{}`$ has the form $`𝐋_2=𝐙_2(𝐏𝐏^{})`$. Thus, the intersection of the point groups is looked for independently of the generalized translations.

As it has been derived in (2), the tubes $`(n_1,n_2)`$ and $`(n_1^{},n_2^{})`$ are invariant under the rotations around their axes for the multiples of the angles $`2\pi /n`$ and $`2\pi /n^{}`$ ($`n=\text{GCD}(n_1,n_2)`$, $`n^{}=\text{GCD}(n_1^{},n_2^{})`$), respectively. The tube composed of these coaxially arranged components is invariant under the rotation for $`2\pi /N`$, being the minimal common rotation of the components, and its multiples. Thus, the principle axis subgroup of the double-wall nanotube is $`𝐂_N`$, with $`N=\text{GCD}(n,n^{})=\text{GCD}(n_1,n_2,n_1^{},n_2^{})`$. The horizontal second order rotational axis $`U`$ (and $`U^{}`$) is also symmetry of all single-wall nanotubes. Nevertheless, such an axis remains the symmetry of the composite tube only if it is common to all of the components, and then the point symmetry is $`𝐃_N`$. Obviously, if a nanotube contains at least one chiral component, then $`𝐃_N`$ is its maximal point symmetry. Only the tubes composed exclusively of the zig-zag and armchair single-wall components may have additional mirror and glide planes, as well as the rotoreflectional axis. Analogously to the horizontal axis, these are symmetries of the whole tube only if they are common for all of the components (the rotoreflectional axis appear only if the horizontal planes $`\sigma _h^{}`$ coincides).

After the point symmetries are thereby completely determined, the more difficult study of the generalized translational factor $`𝐙_2`$ remains. At first, note that it may be completely absent. Suppose that double-wall tube has the translational period $`A`$. If the translational periods of its constituents are $`a`$ and $`a^{}`$, then $`A`$ is obviously the minimal distance being multiple both of $`a`$ and of $`a^{}`$: $`A=\alpha a=\alpha ^{}a^{}`$, where $`\alpha `$ and $`\alpha ^{}`$ are positive coprimes (to assure minimality). Thus, the double-wall tube is translationally periodic if and only if the translational periods of its constituents are commensurate, i. e. only when $`a^{}/a`$ is rational. On the contrary, if $`a^{}/a`$ is an irrational number, the composed tube is not translationally periodic, and $`𝐙_2`$ is trivial (identical transformation only); the total symmetry reduces to the already found point group.

In the commensurate case it remains to examine if the translational group can be refined by a screw axis, common to all of the single-wall components. The task is to determine the screw axis generator $`(C_Q^R|F)`$ with maximal $`Q`$, appearing in the both groups $`𝐋=𝐓_q^r𝐂_n`$ and $`𝐋^{}=𝐓_q^{}^r^{}𝐂_n^{}`$. Thus, it is looking for the values of $`Q`$, $`R`$ and $`F`$ (in accordance with ), such that there exist integers $`t`$, $`s`$, $`t^{}`$ and $`s^{}`$ (enumerating the elements of $`𝐋`$ and $`𝐋^{}`$) satisfying

$$(C_Q^R|F)=(C_q^{rt}C_n^s|tf)=(C_q^{}^{r^{}t^{}}C_n^{}^s^{}|t^{}f^{})\text{ with }F=\frac{N}{Q}A,f=\frac{n}{q}a,f^{}=\frac{n^{}}{q^{}}a^{}.$$
(11)   
Obviously, the fractional translation $`F`$ is multiple $`F=tF^{}`$ of the minimal common fractional translation $`F^{}`$, implying $`A=\frac{Q}{N}tF^{}`$. Analogously to $`A`$, the translation $`F^{}`$ is found as the minimal distance being multiple both of $`f`$ and $`f^{}`$; thus it is given by the unique solution in the coprimes $`\varphi `$ and $`\varphi ^{}`$ of the equation $`F^{}=\varphi f=\varphi ^{}f^{}`$. Since the translational periods of the single-wall components are multiples of their fractional translations, $`A`$ is multiple of $`F^{}`$, i. e. $`A=\mathrm{\Phi }F^{}`$. With help of number theory, it can be shown  that only the tubes with the same $``$ may be commensurate; then $`\alpha =\varphi ^{}=\sqrt{\frac{q^{}/n^{}}{\text{GCD}(q/n,q^{}/n^{})}}`$, $`\alpha ^{}=\varphi =\sqrt{\frac{q/n}{\text{GCD}(q/n,q^{}/n^{})}}`$ and $`\mathrm{\Phi }=\sqrt{\frac{qq^{}}{nn^{}}}`$. Thus, $`Q=\mathrm{\Phi }N/\tau `$, and the minimal $`\tau `$ is looked for to provide the finest screw axis. The translational part of (11) immediately shows that $`t=\tau \alpha ^{}`$ and $`t^{}=\tau \alpha `$. With this values substituted, the rotational part of (11) gives the equations:

$$C_Q^R=C_q^{r\alpha ^{}\tau }C_n^s=C_q^{}^{r^{}\alpha \tau }C_n^{}^s^{}.$$
(12)   
The minimal $`\tau `$ for which the last equation is solvable in $`s`$ and $`s^{}`$ is $`\tau =\mathrm{\Phi }/\text{GCD}(r\alpha \frac{n^{}}{N}r^{}\alpha ^{}\frac{n}{N},\mathrm{\Phi })`$. Finally, $`Q=N\text{GCD}(r\alpha \frac{n^{}}{N}r^{}\alpha ^{}\frac{n}{N},\sqrt{\frac{qq^{}}{nn^{}}})`$, and $`R`$ is easily found from the first equation (12).

All these results are immediately generalized to the multi-wall tubes. Note that the generalized translations and the principle rotational axis of the multi-wall nanotube depend only on the types of their single-wall components. On the contrary, the appearance of the mirror and glide planes and the horizontal axes in the common symmetry group is additionally determined by the relative positions of these components.

It remains to give the summary of the symmetry groups of the multi-wall tubes. If at least one of the single-wall constituents is chiral, then in the commensurate case there are two possibilities: $`𝐓_Q^R𝐂_N`$, corresponding to the general mutual position, and $`𝐓_Q^R𝐃_N`$ in the special mutual positions with common $`U`$-axis. Analogously, the tube built of the incommensurate components have the symmetry described by the point groups $`𝐂_N`$ or $`𝐃_N`$. If the nanotube is built of the zig-zag and armchair single-wall tubes $`(n,0)`$ (or $`(n,n)`$), $`(n^{},0)`$ (or $`(n^{},n^{})`$),…, the order of the principle rotational axis is $`N=\text{GCD}(n,n^{},\mathrm{})`$. If the tube contains at least one single-wall tube of both types, no translational periodicity appears and its symmetry is described by a point group (Tab. I). On the other hand, for the tube composed of the components of the same type (either zig-zag or armchair), the translation period is equal to that of the components. Two different situations may occur: if all the integers $`n/N`$, $`n^{}/N`$…are odd (”odd” case), the translations are refined by the screw axis $`𝐓_{2N}^1`$; otherwise, if at least one of these integers is even (”even” case), no screw axis emerges. The analysis of the special arrangements of the constituents with common horizontal axes, mirror or glide planes, increasing the symmetry of the total system is summarized in the table I. Note that according to the various arrangements of the components, any of the line and axial point groups may be the resulting symmetry for the commensurate and incommensurate components, respectively.

Here we give some realistic examples (interlayer distance  of approximately $`3.4\text{Å}`$, and with diameters of the single-wall components from $`0.7\mathrm{nm}`$ to $`3\mathrm{nm}`$) of the double-wall nanotubes, with their symmetry groups in general positions. With the trivial isogonal point group there are the commensurate tubes (line group is $`\mathrm{𝐓𝐂}_1`$) $`(6,6)\text{}(11,11)`$, $`(7,7)\text{}(12,12)`$, $`(11,2)\text{}(12,12)`$, $`(22,4)\text{}(26,11)`$, $`(10,0)\text{}(19,0)`$, $`(11,0)\text{}(20,0)`$, $`(7,3)\text{}(14,6)`$, $`(21,9)\text{}(28,12)`$, $`(14,6)\text{}(21,9)`$, and the incommensurate pairs (the total symmetry group is trivial $`𝐂_\mathrm{𝟏}`$) $`(9,0)\text{}(10,10)`$, $`(15,0)\text{}(14,14)`$, $`(11,2)\text{}(21,0)`$, $`(13,4)\text{}(14,14)`$, $`(10,4)\text{}(19,4)`$, $`(6,4)\text{}(17,1)`$, $`(9,2)\text{}(19,0)`$, $`(10,0)\text{}(17,3)`$, $`(5,5)\text{}(17,0)`$, $`(6,6)\text{}(19,0)`$, $`(8,8)\text{}(23,0)`$, $`(24,9)\text{}(35,6)`$, $`(25,7)\text{}(38,0)`$, $`(27,0)\text{}(31,8)`$, $`(17,17)\text{}(30,13)`$, $`(10,0)\text{}(11,11)`$, $`(14,0)\text{}(13,13)`$, $`(17,0)\text{}(15,15)`$, $`(6,4)\text{}(13,7)`$, $`(8,6)\text{}(21,0)`$, $`(10,0)\text{}(15,6)`$, $`(16,2)\text{}(15,15)`$. The commensurate tubes $`(9,0)\text{}(17,0)`$, $`(9,6)\text{}(15,10)`$, $`(13,0)\text{}(21,0)`$, $`(5,5)\text{}(9,9)`$, $`(7,7)\text{}(11,11)`$, $`(11,0)\text{}(19,0)`$, have the line group $`𝐓_2^1𝐂_1`$, while $`\mathrm{𝐓𝐂}_2`$ is the symmetry of $`(12,8)\text{}(18,12)`$ and CC $`(6,4)\text{}(12,8)`$. The incommensurate tubes with the symmetry $`𝐂_2`$ are: $`(8,8)\text{}(22,0)`$, $`(12,6)\text{}(18,10)`$, $`(8,14)\text{}(28,0)`$, $`(6,6)\text{}(12,10)`$, $`(16,0)\text{}(14,14)`$, $`(22,12)\text{}(28,16)`$, $`(16,8)\text{}(30,0)`$, $`(14,0)\text{}(16,10)`$, $`(10,8)\text{}(16,12)`$, $`(10,2)\text{}(20,0)`$, $`(26,0)\text{}(30,8)`$, $`(22,4)\text{}(22,16)`$, $`(8,2)\text{}(18,0)`$ and $`(8,8)\text{}(16,10)`$. Finally, the examples for the higher order principle axis are commensurate tubes $`(5,5)\text{}(10,10)`$ (with line group $`𝐓_4^0𝐂_5`$), $`(8,8)\text{}(12,12)`$ ($`𝐓_4^0𝐂_4`$), $`(9,0)\text{}(18,0)`$, ($`𝐓_9^0𝐂_9`$), $`(12,0)\text{}(21,0)`$, ($`𝐓_1^0𝐂_3`$), $`(14,0)\text{}(22,0)`$ ($`𝐓_4^1𝐂_2`$), and incommensurate ones: $`(9,9)\text{}(24,0)`$, $`(18,0)\text{}(15,15)`$, $`(9,3)\text{}(18,3)`$, $`(12,9)\text{}(27,0)`$, $`(15,0)\text{}(18,9)`$, $`(24,6)\text{}(21,21)`$ (all with symmetry $`𝐂_3`$), $`(24,0)\text{}(28,8)`$, $`(20,12)\text{}(32,8)`$, $`(28,0)\text{}(32,8)`$ ($`𝐂_4`$), $`(15,15)\text{}(35,0)`$ ($`𝐂_5`$), $`(7,7)\text{}(21,0)`$ ($`𝐂_7`$), $`(11,0)\text{}(11,11)`$ ($`𝐂_11`$), $`(12,0)\text{}(12,12)`$ ($`𝐂_12`$) and $`(13,0)\text{}(13,13)`$ ($`𝐂_13`$).

## III Concluding remarks

All the geometrical symmetries of the nanotubes are found. In addition to the rotations, translations and screw-axes, observed previously, the single-wall tubes always possess horizontal rotational axes; the zig-zag and armchair tubes have mirror and glide planes in addition. Thus, the full symmetry group is $`𝐓_q^r𝐃_n`$ for single-wall chiral tubes and $`𝐓_2^1𝐃_{nh}`$ for zig-zag and armchair ones. The parameters $`q`$ and $`r`$ of the helical group are found in the simple and closed form. Since $`2\pi /q`$ is the angle of the minimal rotation (combined with fractional translation) performed by the symmetry group, the order of the principle axis of the isogonal group is $`q`$ and it is always even. Moreover, $`2q`$ is the number of the carbon atoms in the elementary translational cell of the tube. Let us only mention here that the different tubes cannot have the same symmetry parameters $`q`$, $`r`$, $`n`$ and $`a`$. This profound property means that the line group is sufficient to reconstruct the tube (as it is demonstrated by (6)), i. e. that the symmetry completely determines the geometry and all consequent characteristics of nanotube. The symmetries of the multi-wall tubes are quite diverse: depending on types of the single-wall components and their arrangements, all the line and axial-point groups emerge: armchair and zig-zag tubes can be combined to make a prototype for any line or axial symmetry group. This immediately shows that the properties of the nanotubes may vary greatly, depending not only on the single-wall constituents, but also on their mutual positions.

There are many physical properties based on symmetry, and the presented classification of the nanotubes according to their symmetry can be widely exploited. The most familiar consequence of symmetry, the special forms of the tensors related to the characteristics of the system, depends on the isogonal group.

Further, the symmetry can be used to find good quantum numbers. To begin with the single-wall nanotubes. The translational periodicity is reflected in the conserved quasi-momentum $`k`$, taking the values from the 1D Brillouine zone $`(\pi ,\pi ]`$, or its irreducible domain  $`[0,\pi ]`$. Also, the $`z`$-component of the quasi-angular momentum $`m`$ is the quantum number caused by the symmetry of the principle rotational axis; it takes on the integer values from the interval $`(\frac{n}{2},\frac{n}{2}]`$, and characterizes the nanotube quantum states. The parity with respect to reversal of the $`z`$-axis, induced by the horizontal rotational axis $`U`$, is the last quantum number common to all the single-wall tubes. The even and the odd states with respect to this parity are conventionally denoted by $`+`$ and $``$. For the zig-zag and the armchair tubes there is additional vertical mirror plane parity, introducing the quantum numbers $`A`$ and $`B`$, to distinguish between the even and the odd states (the parity with respect to the horizontal mirror plane is dependent on the above discussed $`U`$ and $`\sigma _v`$ parities, $`\pm `$ and $`A/B`$). Concerning the multi-wall tubes, $`m`$ is quantum number again. Again, $`z`$-reversal and vertical mirror parities may appear, depending on the concrete symmetry of the nanotube. Nevertheless, the tubes with incommensurate components are not periodic, and in such cases the quasi-momentum $`k`$ is not an appropriate quantum number; it may be interesting experimental question whether the approach of modulated systems can be applied to restore this quantity. The simple criterion of commensurability of the single-wall tubes is derived: they have same $``$ and $`\sqrt{\frac{qq^{}}{nn^{}}}`$ is an integer. The involved symmetry parameters $`q`$ and $`n`$ are discrete, allowing exact experimental check of commensurability.

The enumerated quantum numbers may be used to discuss and predict many characteristics of the nanotubes, but the most sophisticated approach to classification and properties of different quantum states is based on the irreducible representations of the corresponding line  and point groups. Let us remind that these representations are labeled by the derived quantum numbers. The most exhaustive possible information on selection rules, comprising the conservation of quantum numbers, for the processes in the nanotubes has become available  after the full line (or point) group symmetry has been established.

The dimension of an irreducible representation equals degeneracy of the corresponding energy level. For the periodic tubes, the degeneracy of the energy bands is at most fourfold; nevertheless, if the time reversal symmetry of the (spin-independent) Hamiltonian is encountered, the maximal degeneracy is eight-fold . Further, the possible degeneracies are only two-, four- and eight-fold. As for the multi-wall nanotubes with incommensurate components, the dimensions of the irreducible representations of the axial point groups are one, two and (if the time reversal symmetry is included) four, showing the possible degeneracies of the energy levels. Note that the maximal of the enumerated degeneracies (eight- and four-fold) is not possible for the tubes containing at least one chiral single-wall component. Moreover, the degeneracy of the multi-wall tube in the general position of its component is at most two-fold, which is caused by the time reversal symmetry exclusively.

Also, the lattice dynamics can be studied. As it has been mentioned above, the whole single-wall tube can be obtained from its arbitrary atom by the action of the elements of its symmetry group (1); in group theoretical language, this means that the whole nanotube is a single orbit of this group , and this is the orbit $`a_1`$ for the chiral, $`b_1`$ for the zig-zag, and $`d_1`$ for the armchair tubes . Thus, the normal modes (phonons), are already classified . The dynamical representation of the chiral tube is decomposed onto the following irreducible components (the summation over $`k`$ is over the interval $`(0,\pi )`$; in the primed sum $`m`$ takes integer values from $`(0,\frac{n}{2})`$, otherwise from $`(\frac{n}{2},\frac{n}{2}]`$; the components with $`m=n/2`$ appear only for $`n`$ even):

$$D_{\mathrm{chiral}}^{\mathrm{dyn}}=3({}_{o}{}^{}A_{o}^{+}+{}_{o}{}^{}A_{o}^{}+{}_{\pi }{}^{}A_{o}^{+}+{}_{\pi }{}^{}A_{o}^{}+{}_{o}{}^{}A_{n/2}^{+}+{}_{o}{}^{}A_{n/2}^{}+{}_{\pi }{}^{}A_{n/2}^{+}+{}_{\pi }{}^{}A_{n/2}^{})+6\underset{m}{}^{}({}_{\pi }{}^{}E_{m}^{}+{}_{o}{}^{}E_{m}^{})+6\underset{k,m}{}{}_{k}{}^{}E_{m}^{}.$$

It can be seen that all of the $`6n`$ vibrational bands are double degenerate, as it has been anticipated. As for the zig-zag and armchair tubes the corresponding decompositions are (summation in $`m`$ is over integers from $`(0,n)`$, and in the primed sums from $`(0,\frac{n}{2})`$):

$$D_{\mathrm{zig}\mathrm{zag}}^{\mathrm{dyn}}=2({}_{o}{}^{}A_{o}^{+}+{}_{o}{}^{}A_{o}^{}+{}_{o}{}^{}A_{n}^{+}+{}_{o}{}^{}A_{n}^{}+{}_{\pi }{}^{}E_{B}^{})+{}_{o}{}^{}B_{o}^{+}+{}_{o}{}^{}B_{o}^{}+{}_{o}{}^{}B_{n}^{+}+{}_{o}{}^{}B_{n}^{}+4{}_{\pi }{}^{}E_{A}^{}+$$

$$3\underset{m}{}({}_{o}{}^{}E_{m}^{+}+{}_{o}{}^{}E_{m}^{})+2\underset{k}{}[{}_{k}{}^{}E_{B_o}^{}+{}_{k}{}^{}E_{B_n}^{}+2({}_{k}{}^{}E_{A_o}^{}+{}_{k}{}^{}E_{A_n}^{})]+6\underset{m}{}^{}{}_{\pi }{}^{}G_{m}^{}+6\underset{k,m}{}{}_{k}{}^{}G_{m}^{}+3({}_{\pi }{}^{}E_{n/2}^{+}+{}_{\pi }{}^{}E_{n/2}^{}),$$

$$D_{\mathrm{armchair}}^{\mathrm{dyn}}=2({}_{o}{}^{}A_{o}^{+}+{}_{o}{}^{}B_{o}^{+}+{}_{o}{}^{}A_{n}^{+}+{}_{o}{}^{}B_{n}^{+})+{}_{o}{}^{}A_{o}^{}+{}_{o}{}^{}B_{o}^{}+{}_{o}{}^{}A_{n}^{}+{}_{o}{}^{}B_{n}^{}+3({}_{\pi }{}^{}E_{A}^{}+{}_{\pi }{}^{}E_{B}^{})+6\underset{k,m}{}{}_{k}{}^{}G_{m}^{}$$

$$+3\underset{k}{}({}_{k}{}^{}E_{A_o}^{}+{}_{k}{}^{}E_{B_o}^{}+{}_{k}{}^{}E_{A_n}^{}+{}_{k}{}^{}E_{B_n}^{})+\underset{m}{}(4{}_{o}{}^{}E_{m}^{+}+2{}_{o}{}^{}E_{m}^{})+6\underset{m}{}^{}{}_{\pi }{}^{}G_{m}^{}+3({}_{\pi }{}^{}E_{n/2}^{+}+{}_{\pi }{}^{}E_{n/2}^{}).$$

Analogous data can be directly found for each nanotube. This classification can be used to simplify calculation of the vibrational bands ; the obtained bands are automatically labelled by the symmetry based quantum numbers, meaning that Raman and IC spectra can be directly extracted by the selection rules. Note in this context, that the Jahn-Teller theorem is proved both for the point and for the line groups .

Božović (OXXEL GmbH, Bremen) and dr G. Biczó (Central Research Institute for Chemistry, Budapest), who paid our attention to this subject. Also, we thank to dr R. Kostić (Institute of Physics, Beograd) for some remarks.