text:
# Topology, connectivity and electronic structure of C and B cages and the corresponding nanotubes

## I Background and outline

The continuing usefulness of models of $`\pi `$electrons in conjugated systems, for example that of Hückel Huck , testifies to the importance of geometry and connectivity in determining electronic structure. There has, indeed, been renewed interest in this area, due to the potential for technology of nanostructures nano .

Therefore, in the present study of $`C`$ and $`B`$ cages, and the corresponding nanotubes, we shall not hesitate in presenting the simplest possible approaches to electronic structure of the $`\pi `$electrons when these highlight the importance of topology and connectivity. However, it will also prove useful in the course of the discussion, to refer briefly to calculations of Hartree-Fock quality that have been carried out on a variety of B boroncl  and C carboncl  cages.

The outline of the present study is then as follows. Section II below exposes, essentially via Euler’s theorem, a one-to-one correspondence between the connectivity of $`C`$ and $`B`$ cages. For example, $`C_{60}`$naturally leads to a $`B_{32}`$ cage. Considerable similarities between the electronic level spectra of both systems are reported. Also briefly discussed is the matter of pentagonal ’defects’ and the approximate relation to curvature of originally planar graphitic fragments. This is illustrated by reference to the recent Hartree-Fock calculations on $`B`$ cages of intermediate size already mentioned.

This discussion involving planar fragments, leads into Section III which presents a study of the structure and the electronic properties of boron nanotubes obtained by folding planar sheets of boron atoms. We utilize a (quantum) model akin to Kirchoff’s laws of electrical circuits, where evidently connectivity is again an essential ingredient, $`\pi `$electrons being constrained to move along bonds (wires) joining neighbouring nuclei. The dispersion relation of the $`\pi `$bands is then utilized to calculate ($`a`$) constant energy surfaces and ($`b`$) the electronic $`DOS`$ for this two-dimensional ($`2D`$) model boron lattice. This latter quantity is compared and contrasted with the study of graphene made in the early work of Coulson Coulson . These dispersion relations are then used to obtain the one-dimensional ($`1D`$) energy bands and the electronic $`DOS`$ of boron nanotubes within the ’zone folding scheme’ nano .

In section IV the theory of the inhomogeneous electron gas Lund  is applied self-consistently to infinite nanotubes, but now in a surface charge model generalizing the ’spherical March model’ of C60 Clou ; desp ; Sir , originally designed to deal with tetrahedral (eg. $`SiH_4`$and$`GeH_4)`$ and octahedral molecules orima . It is noteworthy in the present context that central to the March model is the (obviously approximate) assumption that the $`\pi `$electrons (one per $`C`$ atom) in $`C_{60}`$are distributed spherically. Naturally this is consistent with the uniform surface charge model. However, with this assumption, if we assume the nuclei are constrained on the surface of a sphere, the lowest energy isomer structure will be determined by minimizing the Coulomb repulsion energy between the nuclei. This is a very old problem going back as far as J.J. Thomson. The history is briefly recorded by Berezin probl  together with other possible references. For general $`N`$ point charges the problem remains mathematically unsolved except for small $`N`$. In particular exact solutions are known for $`N=4,\mathrm{\hspace{0.33em}6}`$ and $`12`$, and are respectively tetrahedron, octahedron and icosahedron. For $`C_{60}`$a Monte Carlo programme written specifically for boron cages boroncl  demonstrated to numerical accuracy that the European football was extremely close to (if not lowest) the favoured isomer for this molecule, provided nuclei are constrained on the surface of the sphere.

The above discussions are then generalized in Section V to treat hetero-nanostructures, earlier work on $`BN`$ cages Zhu  being briefly summarized, followed by reference to fluorinated buckminsterfullerene fluor . The essential new feature in both examples is the electronegativity difference between the component atoms. Section VI constitutes a summary, with some proposals for future directions; the salient one being the use of the progress on quantum current network models (see especially the study of Ringwood Ring ) to investigate further topologically disordered networks, which began with the work of Dancz et al. Dancz .

## II Curvature of graphitic fragment, pentagonal defects and a one-to-one correspondence between connectivity of B and C cages

### II.1 Use of Euler’s theorem

Amovilli and March boroncl  performed Hartree-Fock calculations on $`B_n`$cages, with $`n`$ varying from $`30`$ to $`54`$, under the constraint that all $`B`$ nuclei lie on the surface of a sphere. In correspondence with the ’Aufbau principle’ all boron atoms were found to be either $`5`$\- or $`6`$-fold coordinated. They noted that as the number of boron atoms gets large, the number of triangular faces becomes dominant compared to other types of faces in the optimized geometry and the number of penta-coordinated atoms approaches $`12`$ for the largest cages, though considerable scatter around this result was found.

In fact, if one assumes all faces to be triangular, one can rigorously show that the number of penta-coordinated atoms is exactly $`12`$, as we demonstrate immediately below. If all boron faces are triangular we have the following relation between the number of boron faces $`f_B`$and the number of boron edges $`e_B`$

$$e_B=\frac{3}{2}f_B$$
(1)
Following the aufbau principle we only have $`5`$ and $`6`$fold coordinated boron atoms and so if$`n_5`$and$`n_6`$ denote the number of $`5`$\- and $`6`$-fold coordinated boron atoms respectively we have that

$$e_B=\frac{5}{2}n_5+\frac{6}{2}n_6$$
(2)
with the total number of boron atoms $`n`$ evidently given by

$$n=n_5+n_6$$
(3)
But now for any closed geometrical figure, the number of faces $`f`$, the number of edges $`e`$, and the number of vertices $`v`$ are related through Euler’s theorem

$$f+v=e+2$$

and combining this theorem, where obvioulsy the number of boron vertices $`v_B=n`$, with Eqs.(1), (2) and (3) we immediately obtain that $`n_5=12`$ i.e. the number of $`5`$-fold coordinated atoms in boron clusters is uniquely predicted to be $`12`$ if one assumes all faces to be triangular.

This is reminiscent of the situation for carbon fullerenes where, as was already noted by Euler, to form a closed figure with hexagons, one always needs exactly $`12`$ pentagons. This similarity inspired us to examine whether a correspondence (or map) between the structure of a $`B_n`$boron cage, containing only triangular faces, and the structure of a $`C_N`$ fullerene, containing only pentagons and hexagons, can be established.

As will be demonstrated below, the only constraint one needs to impose is that every $`BB`$ bond crosses exactly one $`CC`$ bond. Evidently this implies that there is only one carbon atom in every boron face and vice versa.

First of all, since every carbon atom in a $`C_N`$ cage is threefold coordinated through $`sp^2`$hybridization, the crossing of the bonds is a sufficient condition to ensure that all boron faces are triangular as is required. Secondly, as is clear from Fig. $`2.1`$, a pentagonal ’defect’ in a $`C_N`$ cage (a pentagon surrounded by $`5`$ hexagons, see Fig. $`2.1`$, the thin lines) will generate a corresponding pentagonal ’defect’ in a boron cage (a penta-coordinated atom surrounded by $`5`$ hexa-coordinated atoms, see Fig. $`2.1`$, the thick lines). On the other hand, as one can easily check, sections of the $`C_N`$ cage containing only hexagons will generate only $`6`$-fold coordinated boron atoms.

So a natural correspondence between the structure and connectivity of $`C_N`$ carbon cages and that of $`B_n`$boron cages (with only triangular faces) is exposed. To find out precisely which $`B_n`$boron cage we obtain in this way starting from a certain $`C_N`$cage we again turn to Euler’s theorem. Starting from a carbon cage $`C_N,`$we have obviously $`N`$ vertices, and hence

$$f_c=e_c+2N$$
(4)
With constant threefold coordination, it follows that the number of edges, $`e_c,`$ is equal to $`\frac{3}{2}N`$and hence, inserting this value into Eq.(4) one reaches the result for $`C_N`$cages that

$$f_c=\frac{N}{2}+2$$
(5)
Since our construction implies one boron atom in every carbon face, the number of carbon faces $`f_c`$obviously equals the number of boron vertices $`v_B`$ (=$`n`$) and we obtain the following one-to-one relation between $`N`$ and $`n`$.

$$n=\frac{N}{2}+2$$
(6)
Eq.(6) applied to buckminsterfullerene itself with $`N=60`$ yields $`n=32`$, i.e. the cage $`B_{32}`$is its analogue. Note that this correspondence is purely topological. Whether or not realistic values for the bond lengths in $`C_N`$ carbon cages and $`B_n`$boron cages allow for the mapping we propose in Fig. $`2.1`$ is not relevant. Since the faces in $`B_n`$boron cages become predominantly triangular only in the limit of large $`n`$, we expect the correspondence to become especially relevant for large $`B_n`$boron clusters.

### II.2 Electronic structure of $`\pi `$electrons in $`C_{60}`$and valence electrons in $`B_{32}`$

Having emphasized topology and connectivity above, let us first record the one-electron eigenvalues obtained by Amovilli et al. carboncl  from Hartree-Fock calculations for $`C_{60}`$. To emphasize the degeneracies plus near degeneracies , the reader may refer to Fig. $`2.2`$ As is readily verified, filling these depicted $`\pi `$-eigenvalues with two electrons per level shows that the upper state is the HOMO level.

Turning to $`B_{32},`$ a large number of eigenvalues for the valence orbitals were obtained in the Hartree-Fock study of Amovilli and March boroncl . Their degeneracies (or near degeneracies) are depicted in Fig. $`2.3`$. Filling the lowest four graphs of levels would deal with $`B_{32}`$ itself if one assumes one $`\pi `$-electron per atom, which is a chemical oversimplification however.

### II.3 Pentagonal defects and curvature

To complete the present section, we wish to add some comments on cage curvature in relation to pentagonal ’defects’ (see also ref.carboncl ). If we discuss fullerenes in particular, we first note that there will be appreciable anisotropic curvature at the equilibrium geometries. To illustrate this, a best candidate for uniform curvature is a fullerene with the pentagonal ’defects’ spread as uniformly as is feasible: i.e. to form an icosahedral-symmetry cage. For such a fullerene (which we conceive for the $`C_N`$cage in the large $`N`$ limit) the pentagons can be visualized to reside at the corners of an icosahedron-type super-structure, all the remaining rings being hexagons. Then it is helpful to consider a graphitic region corresponding to a triangular face of the above super-structure, all the remaining rings being hexagons. The area of this face as measured on the surface of a uniformly curved spherical surface of radius $`R`$ is evidently $`A_{curved}=(4\pi R^2)/20,`$ there being $`20`$ such faces. The length $`l`$ of the side of such a ’spherical triangle’ is $`\theta R;`$ here $`\theta `$ denotes the angle subtended by the edge as viewed from the center of the sphere. The area of a planar triangle with edges of the same length is $`A_{plane}=(l/2)(3/4l)^{\frac{1}{2}}.`$But $`A_{plane}`$ (corresponding to an unstrained part of graphene) is different, of course, from $`A_{curved},`$and there is a strain $`\sigma `$per $`C`$ atom given by carboncl :

$$\sigma \left\{A_{plane}/(N/20)\right\}^{\frac{1}{2}}\left\{A_{curved}/(N/20)\right\}^{\frac{1}{2}}$$
(7)
such a strain occuring for each bond in the graphitic portion of the network. Therefore, with $`3N/2`$such bonds, the total stress is

$$E_{stress}(3N/2)\frac{1}{2}k\sigma ^2$$
(8)
where $`k`$ denotes a suitable force constant appropriate for $`CC`$ aromatic bonds. Substituting Eq.(7) into Eq.(8) it follows that

$$E_{stress}15k\left(\frac{3^{\frac{1}{4}}}{2}\theta \left\{\frac{\pi }{5}\right\}^{\frac{1}{2}}\right)R^2$$
(9)
But the equilibrium R is determined well by the ’rule’ of constant surface area per atom boroncl ; carboncl  i.e. $`R^2N`$ and so from Eq.(9) stress is important. If some structure other than that of icosahedral symmetry is assumed for the arrangement of the pentagons, the geometric factor in Eq.(9) will be modified, but will remain non-zero.

The question as to the relief of such curvature strain then arises (still one is considering the large $`N`$ limit). Once more, as a prototypical example, the arrangement of icosahedral symmetry can be taken. One then visualizes the structure to deform to resemble a icosahedron super-structure, having the pentagon at its apices. Then the triangular graphitic regions already discussed can be viewed as changed from their spherically curved forms to almost planar regions with anisotropic curvature at the edges which connect each triangular region to adjacent ones. Within the planar triangular areas there is neither strain nor stress: instead it occurs at the edges of the triangles. The total amount of such edge is $`30RN^{\frac{1}{2}},`$so that the stress is reduced to $`E_{stress}^{}N^{\frac{1}{2}}.`$ The proportionality constant can again be expected to depend on the way the pentagons are dispersed, the overall conclusion being that geometric Gaussion curvature is preferably localized in the region of the pentagons, with then some anisotropic curvature (without Gaussian curvature) mediating between such adjacent parts, as noted in ref.carboncl . Computations on large non-open-shell icosahedral-symmetry fullerenes reveal the proposed polyhedralization in diagrams of the geometry optimized structures (most clearly for $`C_{240};`$the largest treated).

Having referred in some detail above to the graphitic layers, we follow this account by taking a planar ’model boron’ structure and using again topology and connectivity to discuss the $`\pi `$electronic energy band structure. As was reported in the paper by Boustani et al. Bous  preliminary experimental results for pure-boron systems seem to confirm the existence of boron sheets. We will consider here a purely planar boron configuration and apply the simplest possible theories to extract the main features of the $`DOS`$which arise from topological aspects.

## III Electronic properties of boron nanotubes.

### III.1 Structure of a single wall boron nanotube

#### III.1.1 Equilateral and Isosceles zigzag symmetry.

We start by describing the model planar boron lattice which will then be folded to obtain boron nanotubes. The structure of the boron lattice we consider can be obtained simply by considering an ordinary sheet of graphene in which we replace all carbon atoms by boron atoms and place an additional boron atom in the center of every hexagon. In this way, every boron atom has a near-neighbour coordination, say $`c`$, equal to $`6`$. The resulting lattice is shown in Fig. $`3.1`$

To describe this lattice one can use two lattice vectors, say $`𝐚_1`$ and $`𝐚_2`$, which are either $`120^{}`$apart, or $`60^{}`$apart. If one only wants to describe the $`2D`$ lattice, both choices are of course equivalent. However, if one wants to use these lattice vectors to describe the nanotubes obtained by folding the $`2D`$ sheet, then the choice where both lattice vectors are $`60^{}`$apart is the most convenient as became apparent for carbon nanotubes.

To describe a nanotube obtained by folding a sheet, one starts by defining the so-called chiral vector $`𝐂_h.`$

$$𝐂_h=n𝐚_1+m𝐚_2$$
(10)
This vector connects by definition two lattice points on the sheet which have to be connected when one folds the sheet into a tube and the specific choice for $`n`$ and $`m`$ completely determines the structure of the resulting tube. From the definition of the chiral vector $`𝐂_h`$ it is clear that its length equals the circumference $`L`$ of the resulting nanotube which is then given by

$$L=a\sqrt{n^2+m^2+nm}$$
(11)
with$`a=\left|𝐚_1\right|=\left|𝐚_2\right|.`$

Similar to carbon, all possible distinct seamless nanotubes can be obtained by choosing a set of indices ($`n,m`$) with $`n`$ any integer number and $`m`$ ranging from $`0`$ to $`n`$. However, an interesting feature then arises when one is dealing with boron. As one can easily see on Fig. $`3.1`$ both the nanotube generated by a $`𝐂_h(n,n)`$ chiral vector and that generated by the $`𝐂_h(n,0)`$ vector now have in essence zigzag symmetry. However, as is clear from Fig. $`3.1`$ in the case $`n=m`$we have isosceles triangles (two equal sides), while in the case $`m=0`$ we have equilateral triangles (three sides equal) triangles. For simplicity we will refer to these limiting cases as $`(n,n)`$ i-zigzag and $`(n,0)`$ e-zigzag symmetry respectively where ’$`i`$’ then evidently stands for isosceles and ’$`e`$’ for equilateral.

We will now go on to define the unit cell of our boron nanotube and the corresponding Brillouin zone. Except for a few details this is identical to the carbon case and we refer the reader to the excellent book by Saito, Dresselhaus and Dresselhaus nano  for more details.

The vector perpendicular to $`𝐂_h`$going from the chosen origin to the nearest lattice point defines the translational vector of our $`1D`$ periodic nanotube and is given by.

$$𝐓=t_1𝐚_1+t_2𝐚_2$$

with the relation between $`t_1,t_2`$and $`m,n`$ unchanged as compared to the carbon system namely

$$t_1=\frac{2m+n}{d_R},t_2=\frac{2n+m}{d_R}$$
(12)
where $`d_R`$is the greatest common divisor $`(gcd)`$ of $`(2m+n)`$ and $`(2n+m).`$The rectangle generated by these two vectors $`𝐂_h`$and $`𝐓`$ is the unit cell of our boron nanotube, where the translational vector $`𝐓`$ determines the direction in which the unit cell repeats itself periodically.

#### III.1.2 Reciprocal space

The reciprocal space of the boron sheet is generated by the reciprocal lattice vectors $`𝐛_1`$and$`𝐛_2`$defined by

$$𝐛_i.𝐚_i=2\pi \delta _{ij}$$

We define the vectors in the reciprocal space of the nanotube by the relations

$`𝐂_h.𝐊_1`$ $`=`$ $`2\pi 𝐓.𝐊_1=0`$ (13)
$`𝐂_h.𝐊_2`$ $`=`$ $`0𝐓.𝐊_2=2\pi `$ (14)
which then immediately leads to the result

$$𝐊_1=\frac{1}{N}(t_2𝐛_1+t_1𝐛_2)𝐊_2=\frac{1}{N}(m𝐛_1n𝐛_2)$$
(15)
with

$$N=mt_1nt_2=\frac{\left|𝐂_h\times 𝐓\right|}{\left|𝐚_1\times 𝐚_2\right|}=\frac{2(m^2+n^2+nm)}{d_R}$$
(16)
with $`𝐛_1`$and $`𝐛_2`$the lattice vectors of the graphene Brillouin zone and $`N`$the number of atoms in the unit cell of the nanotube. Note that for the carbon sheet the number of carbon atoms in the nanotube unit cell was given by $`2N`$.

Since the boron lattice we consider can be obtained from taking only the lattice points in a graphene layer (points with identical physical environment), the Brillouin zone of the boron and the carbon sheet have identical symmetries.

#### III.1.3 Energy bands within the ’zone folding sheme’

Within the ’zone-folding sheme’ nano  one essentially assumes that the motion of the electrons in a real single wall $`3D`$ nanotube can be described by the motion of the electrons in the planar $`2D`$ strip from which that specific nanotube can be obtained by folding. In order to obtain the energy dispersion relations for the boron nanotube we first need to determine the energy dispersion relation of the boron sheet, say $`E_{2DB}(𝐤),`$ for all possible $`𝐤`$values and then restrict ourselves only to those $`𝐤`$values which are consistent with the boundary conditions for motion of the electrons on the strip which generates the boron nanotube.

Since the unit cell of the nanotube (or the infinitely long strip) defined by $`𝐓`$and $`𝐂_h`$repeats itself periodically only in one dimension (in the direction of $`𝐓)`$ the motion of the electrons along that direction is characterized in $`𝐤`$space by a quasi-continuous scalar wave-vector $`k`$ in a one-dimensional Brillouin zone of length $`\frac{2\pi }{T}`$ in the direction of $`𝐊_2.`$ The boundary conditions along the direction of the chiral vector $`𝐂_h`$ yield a discrete number (equal to $`N`$) of allowed values for the component of the wave-vector in the direction of $`𝐊_1`$ given by$`\mu \left(\frac{2\pi }{\left|𝐂_h\right|}\right)\left(\text{or equivalently }\mu \left|𝐊_1\right|\right)`$with $`\mu =0,\mathrm{}..,N1`$.

Combining this we find that the allowed $`𝐤`$values lie on a set of $`N`$ parallel lines in $`𝐤`$space directed along $`𝐊_2`$ and separated by $`𝐊_1`$. Every line represents the $`1D`$ Brillouin zone but for a different value of the component of the wave-vector along $`𝐊_1.`$The energy values for these wave-vectors are obtained by taking cross sections along these lines of the energy surface of the full $`2D`$ boron sheet. Every cross-section then gives a band in the $`1D`$ Brillouin zone of the nanotube.

We then find for the energy dispersion relations for a single wall nanotube within the ’zone folding scheme’ nano

$$E_\mu (k)=E_{2DB}\left(k\frac{𝐊_2}{\left|𝐊_2\right|}+\mu 𝐊_1\right)\left(\frac{\pi }{T}<k<\frac{\pi }{T}\right)$$
(17)
with the band index $`\mu `$ given by

$$\mu =0,\mathrm{}..,N1$$
(18)
and with $`T=\left|𝐓\right|.`$We now first turn to the determintation of the energy dispersion relation $`E_{2DB}(𝐤)`$for the planar boron sheet.

### III.2 Electronic structure of the 2D boron sheet

#### III.2.1 2D Energy dispersion bands

For the energy band of the $`2D`$ boron sheet we obtain within the Quantum Network ($`QN`$) (See Appendix A) model the relation

$$E_{2DB}^{QN}(𝐤)=\frac{q^2}{2}=\frac{1}{2}\left\{\frac{1}{a}\mathrm{cos}^1\left(\frac{1}{c}S(𝐤)\right)\right\}^2$$
(19)
The structure factor $`S(𝐤)`$appearing in Eq.(19) is defined by

$$S(𝐤)=\stackrel{c}{\underset{j=1}{}}e^{i𝐤.𝐚_j}$$
(20)
where the vectors $`𝐚_j`$ connect every lattice position $`𝐑`$to its $`c`$ nearest neighbours. On the other hand, from the tight binding ($`TB`$) method we obtain the relation (see Appendix B)

$$E_{2DB}^{TB}(𝐤)=ϵ_\pi +tS(𝐤)$$
(21)
with $`ϵ_\pi `$and $`t`$ defined in Appendix B. Since we are mainly interested in qualitative electronic properties which arise as a consequence of the periodicity and topology of the system under consideration, we have assumed in our tight binding calculations the following simple values (assumed arbitrarily in atomic units) for the parameters.

$$ϵ_\pi =0,t=1(a.u.)$$
(22)
The important point to stress here is that both expressions for the energy depend on the wave-vector $`𝐤`$ through the same structure factor $`S(𝐤)`$ for which we will derive an explicit expression immediately below.

#### III.2.2 Expression for the structure factor S(k) within a given reference frame

In particular we start by choosing the $`xy`$ coordinate system in the same direction relative to the lattice vectors $`𝐚_1`$and $`𝐚_2`$as in Fig. $`3.1`$. This then yields for the coordinates of both lattice vectors

$$𝐚_1=(\frac{\sqrt{3}}{2}a,\frac{a}{2}),𝐚_2=(\frac{\sqrt{3}}{2}a,\frac{a}{2})$$
(23)
where the lattice constant $`a`$ is now equal to the $`BB`$ bond length $`a_{BB}.`$(Note that for graphene we have the relation $`a=\sqrt{3}a_{CC}`$). We choose $`𝐚_3`$along the positive $`y`$axis which yields for the coordinates

$$𝐚_3=(0,a)$$
(24)
All near neighbour points can then be reached by the vectors $`\pm 𝐚_i(i=\mathrm{1..3}).`$We can then further evaluate the expression for the structure factor to obtain

$`S(𝐤)`$ $`=`$ $`{\displaystyle \stackrel{c}{\underset{j=1}{}}}e^{i𝐤.(𝐚_j)}`$ (25)
$`=`$ $`2{\displaystyle \stackrel{3}{\underset{i=1}{}}}\mathrm{cos}(𝐤.𝐚_i)`$
$`=`$ $`2\mathrm{cos}(ak_y)+4\mathrm{cos}\left({\displaystyle \frac{\sqrt{3}}{2}}ak_x\right)\mathrm{cos}\left({\displaystyle \frac{1}{2}}ak_y\right)`$
As mentioned above, this structure factor is common to both the $`QN`$ model and the tight binding result.

#### III.2.3 Constant energy surfaces and DOS of the 2D boron sheet

The constant energy contours from the QN model are given in Fig. $`3.2`$. Similar to the carbon case, we note that also here so-called ’trigonal warping effect’ trig  occurs, whereby the constant energy contours change from the circular behaviour around the center and the $`K`$points to a triangular shape near the $`M`$ points.

The $`DOS_{2D}`$ of the $`2D`$ energy bands can then be calculated from the expression

$$DOS_{2D}(E)=\frac{2}{(2\pi )^2}\frac{ds}{\left|_𝐤E(𝐤)\right|}$$
(26)
where the line integral is along a surface of constant energy $`E`$. Returning to the constant energy surfaces in Fig. $`3.2`$, we have performed the line integration in Eq.(26) with $`E(k)`$ given for the ’model boron lattice’ by Eq.(19) with $`c=6`$, and the results are depicted in Fig. $`3.3`$. It is worthwhile to compare and contrast the form of $`N(E)`$ shown there with the $`\pi `$bands for graphite first obtained by Coulson Coulson  using the same $`QN`$ model. First, the $`\pi `$bands touched in graphite, at the point where $`N(E)=0`$, i.e. one had semimetallic behaviour (both zero gap and zero $`N(E_F))`$at the Fermi (or HOMO) level $`E_F.`$In contrast, the ’model boron lattice’, by counting the $`\pi `$electrons, is metallic (zero gap and non-zero $`N(E_F)`$at the HOMO level). A van Hove singularity ($`vHs)`$ arises near the edge of the Brillouin zone where the energy bands level off due to periodicity. Results from the tight binding method yielded similar results for all features.

### III.3 1D energy bands of (n,n) i-zigzag boron nanotubes

Within the chosen orientation for the $`xy`$ coordinate system, the chiral vector $`𝐂_h,`$ (and correspondingly also $`𝐊_1`$) is directed along the positive $`x`$-axis for the special case where $`m=n.`$Whereas for graphene this special choice for the indices leads to nanotubes exhibiting armchair symmetry, in the case of boron it leads to $`i`$-zigzag symmetry, as discussed above. Applying periodic boundary conditions along the circumferential direction then leads to the quantization

$$k_{x,j}=\frac{2\pi }{n\sqrt{3}a}j(j=1,\mathrm{}..,2n)$$
(27)
This then yields for the $`i`$zigzag structure factor $`S_j^{iz}(𝐤)`$

$`S_j^{iz}(k)`$ $`=`$ $`2\mathrm{cos}(ak)+4\mathrm{cos}\left({\displaystyle \frac{\pi j}{n}}\right)\mathrm{cos}\left({\displaystyle \frac{ak}{2}}\right)`$ (28)
$`(j`$ $`=`$ $`1,\mathrm{},2n)({\displaystyle \frac{\pi }{a}}<k<{\displaystyle \frac{\pi }{a}})`$
From this expression, one can immediately write down the corresponding expression for the $`(n,n)`$ energybands $`E_q^{iz}(k)`$, either in the tight binding approximation or from the Quantum Network model.

Fig. $`3.4(a)`$ shows the energy bands obtained from the $`QN`$ method for a boron $`(3,3)`$ $`i`$-zigzag nanotube which has from Eq.(11) a diameter $`L5.20a`$. Clearly since $`𝐊_1`$ is directed along a symmetry axes of the $`2D`$ Brillouin zone, we have energy bands symmetrical around the origin. From tight binding calculations we found a similar set of bands, with the same general form and degeneracy.

### III.4 1D energy bands of (n,0) e-zigzag boron nanotubes

We will now go on to derive an expression for the energy bands in the special case that $`m=0.`$As in the case of graphene this leads to zigzag nanotubes but as discussed above, we now need to make the extra specification that we are dealing with equilateral zigzag symmetry . In order to obtain an explicit expression for the energy bands it is helpful to consider a coordinate transformation to a more suitable reference system. Following Saito, Dresselhaus and Dresselhaus nano  we consider a passive coordinate transformation counterclockwise over $`120{}_{}{}^{}.`$This implies we now use the $`xy`$ coordinate system depicted in their Fig. $`4.3`$ $`(b)`$. This transformation leaves the expression for the structure factor (25) unchanged as one can easily check, but brings the chiral vector $`𝐂_h`$for the $`(n,0)`$ system under consideration along the (negative) $`y`$-axis. Again applying periodic boundary conditions along the circumferential direction leads to the quantization

$$k_{y,j}=\frac{2\pi }{na}j(j=1,\mathrm{}..,2n)$$
(29)
For the $`e`$-zigzag structure factor $`S_j^{ez}(k)`$one then obtains

$`S_j^{ez}(k)`$ $`=`$ $`2\mathrm{cos}({\displaystyle \frac{2\pi }{n}}j)+4\mathrm{cos}\left({\displaystyle \frac{\pi j}{n}}\right)\mathrm{cos}\left({\displaystyle \frac{\sqrt{3}}{2}}ak\right)`$ (30)
$`(j`$ $`=`$ $`1,\mathrm{},2n)({\displaystyle \frac{\pi }{\sqrt{3}a}}<k<{\displaystyle \frac{\pi }{\sqrt{3}a}})`$
from which one can again immediately obtain the corresponding $`(n,0)`$ energybands $`E_j^{ez}(k).`$The resulting energy bands from the $`QN`$ model are plotted in Fig. $`3.4(b)`$. We chose a value for $`n`$ which yields approximately a nanotube of the same radius as for the $`(3,3)`$ zigzag tube, namely $`n=5`$ which yields for the circumference $`L=5a.`$

### III.5 1D energy bands for general chiral symmetry

For a general $`(n,m)`$ system we go back to the original coordinate system (as for the armchair nanotubes). The coordinates of the lattice vectors $`𝐛_1`$and$`𝐛_2`$ in reciprocal space are then given by

$$𝐛_1=(\frac{2\pi }{\sqrt{3}a},\frac{2\pi }{a}),𝐛_2=(\frac{2\pi }{\sqrt{3}a},\frac{2\pi }{a})$$
(31)
which implies the relations

$$𝐛_1.𝐛_1=𝐛_2.𝐛_2=\frac{4}{3}\left(\frac{2\pi }{a}\right)^2\text{and}𝐛_1.𝐛_2=\frac{2}{3}\left(\frac{2\pi }{a}\right)^2$$
(32)
We then obtain for the $`x`$ and $`y`$ components of the vector $`k\frac{𝐊_2}{\left|𝐊_2\right|}+\mu 𝐊_1`$

$`k_x`$ $`=`$ $`{\displaystyle \frac{k}{\left|𝐊_2\right|}}\left[{\displaystyle \frac{mn}{N}}\right]\left({\displaystyle \frac{2\pi }{\sqrt{3}a}}\right)+\mu \left[{\displaystyle \frac{m+n}{N}}\right]\left({\displaystyle \frac{2\pi }{a}}\right)\sqrt{3}`$ (33)
$`k_y`$ $`=`$ $`{\displaystyle \frac{k}{\left|𝐊_2\right|}}\left[{\displaystyle \frac{m+n}{N}}\right]\left({\displaystyle \frac{2\pi }{a}}\right)+\mu \left[{\displaystyle \frac{nm}{N}}\right]\left({\displaystyle \frac{2\pi }{\sqrt{3}a}}\right)`$ (34)
with

$$\left|𝐊_2\right|=\sqrt{𝐊_2.𝐊_2}=\sqrt{\left[\left(\frac{m}{N}\right)^2+\left(\frac{n}{N}\right)^2\right]𝐛_1.𝐛_12\left(\frac{nm}{N}\right)𝐛_1.𝐛_2}$$
(35)
and the dependence of $`N`$ on $`m`$ and $`n`$ given by Eq.(16). For a general choice of $`n`$ and $`m`$, the number of atoms in the unit cell of the nanotube, and correspondingly the number of $`1D`$ dispersion relations gets very large compared to the simpler $`(n,n)`$ and $`(n,0)`$ cases and is less insightfull.

### III.6 Density of States of one-dimensional boron nanotubes

We now calculate the $`DOS`$ per boron atom from these $`1D`$ energy dispersion relations using the formula

$$DOS(E)=\frac{2}{\left(2\pi \right)}\frac{\left|𝐓\right|}{N}\stackrel{N}{\underset{\mu =1}{}}\delta \left(EE_\mu (k)\right)𝑑k$$
(36)
where the integration is over the $`1D`$ Brillouin zone of the nanotube. The results are shown in Fig.$`3.5(a)`$and $`(b)`$ for the $`(3,3)`$ $`i`$-zigzag tube and the $`(5,0)`$ $`e`$-zigzag tube respectively. Obviously since the first cuts in the $`2D`$ energy bands of the boron sheet are within the region where the constant energy contours are circular, irrespective of the direction of $`𝐂_h(n,m)`$we find a similar $`DOS`$ for the low energy values. On the whole we find that the $`DOS`$ looks similar, the main difference being that the two peaks which were nearly degenerate for the $`(3,3)`$ $`i`$-zigzag tube are further apart for the $`(5,0)`$ $`e`$-zigzag tube.

All of the boron nanotubes we considered were found to be metallic. Of course, we must expect also here that a Peierls distortion nano  will occur which will then possibly open a small gap in the $`DOS`$ of the first energy band but this is beyond the scope of the present study.

## IV ’The March model’ applied to nanotubes

Contrary to the density of states, we expect other quantities relating to the electrons to be only very slightly dependent on the detailed structure of the carbon or boron frame. To exemplify this point F.E. Leys et al. surface  calculated the self consistent field in which the $`2s`$ and $`2p`$ valence electrons move in an isolated carbon nanotube under the assumption that the positive charge of the $`C^{4+}`$ions can be smeared out uniformly over the surface of an infinitely long cylinder, thereby neglecting all structure and only retaining the basic cylindrical symmetry of the problem. The spirit of this assumption goes back to the early work of March orima  on tetrahedral and octahedral molecules where, for instance in $`GeH_4,`$the external field in which the electrons move was approximated by smearing out the four $`H`$ protons over the surface of a sphere of equal radius to the $`GeH`$ bond length and centered on the $`Ge`$ nucleus. The inhomogeneous electron gas created by this model external potential was then treated using the Thomas-Fermi method. In evaluating the nuclear-nuclear potential energy however the correct geometry of the nuclear framework was always retained. This method has recently experienced renewed interest. Thus the work of Clougherty and Zhu Clou  on $`C_{60}`$calculated the equilibrium cage radius for $`C_{60}`$using the method they termed ’the March-model’. Further studies include those of Despa desp , also on $`C_{60}`$, and Amovilli and March boroncl  on boron cages. (See also Siringo et al. Sir ). We will now briefly summarize the main results of the study of Leys et al. surface .

If we take $`\mathrm{\Theta }(r)`$to be minus the self-consistent potential $`V_{sc}(r)`$ we obtain for$`\mathrm{\Theta }(r)`$the differential equation

$$\frac{^2\mathrm{\Theta }}{r^2}+\frac{1}{r}\frac{\mathrm{\Theta }}{r}=c\mathrm{\Theta }^{\frac{3}{2}}c=\frac{2^{\frac{7}{2}}}{3\pi }$$
(37)
where $`r`$ denotes the distance from the axis of the tube. This equation was solved subject to the appropriate boundary conditions and in particular the surface charge $`\sigma `$ was taken into account through the boundary condition at the radius$`R_t`$of the tube

$$\left(\frac{\mathrm{\Theta }_1}{r}\right)_{R_t}=4\pi \sigma +\left(\frac{\mathrm{\Theta }_2}{r}\right)_{R_t}$$
(38)
where$`\mathrm{\Theta }_1`$denotes the solution inside the tube and $`\mathrm{\Theta }_2`$ outside the tube. The condition (50) reflects the discontinuity in the electric field across the surface charge..

Figs. 4.1 shows our results for the potential $`V_{sc}(r)`$. The data used in determining $`\sigma `$ is mentioned in the captions. Östling et al. ost  performed full Kohn-Sham calculations on the same model system and we have used their results for comparison. The electron density $`\rho (r)`$ was found to be reasonably well described by $`TF`$ theory but we especially found very good agreement for the self-consistent potential $`\mathrm{\Theta }(r),`$ both qualitatively and quantitatively. Moreover, in the same study, Östling et al. compared their results with those obtained from tight binding when the exact atomic positions were taken into account and found only very small differences from their Kohn-Sham results on the model system. This clearly indicates that we can expect also our results, following the original procedure of March, to be a good approximation to the self-consistent field. Obviously the main merit of our work is its relative simplicity allowing one to obtain analytic results in certain cases, for instance for the power law behaviour at large $`r`$ which was found to be

$$\mathrm{\Theta }(r)=\left(\frac{16}{c}\right)^2\frac{1}{r^4}\left[1+\frac{F_1}{r^c}+higherorderterms\right]withc=2\sqrt{6}4$$
(39)
and $`F_1`$ an integration constant.

## V Hetero-nanostructures

So far we have focussed attention on the homonuclear cases of $`B`$ and of $`C`$. In this penultimate section, we shall extend these considerations to two specific heteronuclear systems: (i) $`BN`$ cages and (ii) fluorinated buckminsterfullerene. We shall take these in turn below

### V.1 Boron nitride cages: effect of electronegativity difference on electronic structure

Let us commence this section on $`BN`$ with two general references to this area: ($`a`$) the work of Niedenzu and Dawson nieden  on boron-nitrogen compounds and ($`b`$) the more technologically oriented work on the synthesis and properties of boron nitride edited by Pouch and Alterovitz Pouch .

With no electronegativity difference included, Fig. $`6`$ of ref.Zhu  shows the Hückel $`\pi `$bands of the structures depicted in Fig. $`5`$ of the same reference. It is immediately clear from the uppermost and the lowest parts of their Fig. $`6`$ that the $`\pi `$bands touch, whereas for the other $`3`$ structures depicted in their Fig. $`5`$ there are energy gaps. But when electronegativity is included in the Hückel treatment (i.e. $`\alpha _B\alpha _N),`$the zero-gap cases with $`\alpha _B=\alpha _N`$also have energy gaps: the most important consequence of the electronegativity difference. Zhu et al. Zhu  also have used the so-called extended Hückel model, but although the bands change somewhat in detailed shape the salient feature of the electronegativity as introducing energy gaps where originally $`\pi `$bands touched is confirmed.

### V.2 Fluorinated buckminsterfullerene

A highly fluorinated fullerene, a $`D_3`$ isomer of $`C_{60}F_{48}`$, has recently been investigated by $`X`$-ray fluorescence spectroscopy fluor . The results of such study have been interpreted by quantum mechanical calculations. In particular, it has been confirmed that the contribution to the electron density of frontier orbitals, namely the occupied orbitals with the highest energy, comes from six localized $`CC`$ double bonds. Evidently, the higher electronegativity of fluorine causes, in this case, a localization of the $`\pi `$ cloud of fullerene in the $`CF`$ bond regions, which are in fact essentially orthogonal to the carbon cage surface. The twelve carbon atoms which are not bonded to fluorine thus determine six isolated $`CC`$ double bonds. Within a very simple Hückel-like formalism the situation can be simulated by substituting $`48`$ of the $`60`$ $`p`$ functions of fullerene by the same number of $`\sigma `$ $`CF`$ bond functions and also, by reducing the connectivity, namely the bond order, between all neighbour pair of functions in which one of them is a $`CF`$ bond orbital. Furthermore, the energy of $`CF`$ bond functions must be shifted to lower energies with respect to the $`p`$ carbon atomic orbitals. The resulting molecular orbitals are then split essentially in to three bands. The lowest energy band is built from $`48`$ occupied orbitals, which represent the $`48`$ $`CF\sigma `$ electron cloud, the intermediate band being constructed from $`6`$ occupied orbitals, representing the $`6`$ isolated $`\pi `$ $`CC`$ double bonds, and, finally, the highest energy band which includes the $`6`$ empty $`\pi `$ $`CC`$ antibonding orbitals.

## VI Summary and Future directions

We have stressed the way pentagonal ’defects’, present say in a $`C_{60}`$cage, can be connected with the curvature introduced into an originally planar graphitic strip. Using Euler’s theorem, a one-to-one correspondence between the geometry of $`B`$ cages and $`C`$ cage structures has been proposed. This has led us to embed topology and connectivity into a quantum current network approach to a ’model boron’ two-dimensional lattice. The electronic band dispersion relation $`E(𝐤)`$ for this lattice has been employed to obtain (i) constant energy $`E`$ surfaces in the $`𝐤=(k_x,k_y)`$plane and (ii) the density of states of the $`\pi `$electrons. The results are compared and contrasted with the earlier results of Coulson on a graphite layer. This ’model boron’ layer was then wrapped into a ’model boron nanotube’. After a discussion concerning chirality and symmetry of these tubes, the electronic properties were discussed within the zone folding scheme. As to future directions, generalizations which may prove feasible of earlier work by Dancz et al. Dancz . on a topologically disordered network are proposed.

###### Acknowledgement 1

N.H.M. wishes to thank Prof M.P. Tosi and the SNS for much hospitality during a visit to Pisa in 2002. N.H.M. is grateful to the Francqui foundation and in particular to Prof. Dr. Eyckmans for support and motivation. C.A. wishes to acknowledge financial support from Fondi di Atenes 2002 (University of Pisa). F.E.L. wishes to thank especially Prof. V. Popov and Dr. D. Lamoen for helpful and stimulating discussions.

## Appendix A The Quantum Network model.

### A.1 Introduction and general formalism

The idea behind the quantum network ($`QN`$) model is extremely simple. One joins each atom to its nearest neighbours, and then treats electrons (though quantum mechanically, of course) as though they flowed through $`1D`$ wires as in an electrical circuit obeying Kirchoff’s Laws at every node. This was first introduced by Pauling pol  and important later contributions include those of Ruedenberg and Scherr rue  who applied the method systematically to a large group of molecules, Coulson Coulson  who was the first to apply the method to periodic systems (namely graphene) and Montroll Montroll  who studied a class of model potentials along the bonds which allow for analytical solutions for the wave functions and the density of states. In particular, these methods have been applied to conjugated systems where one assumes that the $`\sigma `$-electrons form the framework, and the delocalized $`\pi `$electrons move along this network.

If$`\varphi [j]`$ denotes the value of the $`1D`$ wave function at the $`j`$th node (assuming one has made a suitable numbering of all nodes or atoms) the system of equations one has to solve is given by Montroll

$$F(q,\eta )\varphi [j]=\stackrel{c}{\underset{i=1}{}}\varphi [j_i]$$
(40)
where $`F(q,\eta )`$ is a general form factor which contains information about the (possibly parametrized via$`\eta )`$ potential along the bonds and $`j_i`$ ($`i=1..c`$) denote the index of the $`c`$ near neigbour nodes (or atoms)

For free electrons along the network (i.e. no potential along the bonds), one has that

$$F(q,\eta )=c\mathrm{cos}(qa)$$
(41)
where $`a`$ is the bond length (assumed there is only one) and the energy $`E`$ is given of course by

$$E=\frac{\mathrm{}^2q^2}{2m}$$
(42)
For certain specific choices of the potential acting along the bonds, analytic formulae for the structure factor $`F(q,\eta ),`$ the wave functions along the wires and the resulting DOS can be derived as was shown for instance in the work by Montroll Montroll .

For large molecules it is convenient to use the matrix formulation of the problem as was proposed by Ruedenberg and Scherr rue  (to which we refer the interested reader for more details). If we define for a molecule containing $`N`$ atoms or units the vector

$$\varphi =\left[\begin{array}{c}\varphi (1)\\ \varphi (2)\\ \mathrm{}\\ \mathrm{}\\ \varphi (N)\end{array}\right]$$
(43)
we can write Eq.(40) in the form

$$𝐅\varphi =\mathrm{𝟎}$$
(44)
where $`𝐅`$ is the so-called ’connectivity matrix’. It is an $`N\times N`$matrix, the structure of which can most easily be explained by writing it down for a simple molecule, for instance benzene. If we number all $`C`$ atoms in a chosen direction from $`1`$ to $`6`$, we obtain for $`𝐅`$ the matrix

$$𝐅=\left(\begin{array}{cccccc}F(q,\eta )& 1& & & & 1\\ 1& F(q,\eta )& 1& & & \\ & 1& F(q,\eta )& 1& & \\ & & 1& F(q,\eta )& 1& \\ & & & 1& F(q,\eta )& 1\\ 1& & & & 1& F(q,\eta )\end{array}\right)$$
(45)
where the omitted elements are all zero. The eigenvalues of this matrix, say $`F_n,`$then follow from the secular equation

$$\left|𝐅\right|=0$$
(46)
combined with Eqs.(41) and (42) in the case of free electrons or from a generalization of Eq.(41) in the case of a potential along the bonds.

### A.2 Periodic systems

For periodic systems equations (40) or (44) can be considerably simplified. If the vectors $`𝐚_i(i=1..c)`$connect every lattice point to its $`c`$ nearest neighbours, Bloch’s theorem implies that

$$\varphi [j_i]=\varphi [j]e^{i𝐤.𝐚_i}.$$
(47)
Then, assuming there is only one atom in the Brillouin zone Eq.(40) immediately reduces to

$$F(q,\eta )=S(𝐤)$$
(48)
with the structure factor $`S(𝐤)`$ given by

$$S(𝐤)=\stackrel{c}{\underset{i=1}{}}e^{i𝐤.𝐚_i}$$

and $`𝐤`$ a wave vector of the first Brillouin zone of the periodic structure. For free electrons along the network one immediately obtains for the energy bands $`E^{QN}(𝐤)`$

$$E^{QN}(𝐤)=\frac{q^2}{2}=\frac{1}{2}\left\{\frac{1}{a}\mathrm{cos}^1\left(\frac{1}{c}S(𝐤)\right)\right\}^2$$
(49)
where atomic units have been used. For a more detailed discussion on the use of the Quantum Network model to periodic systems we refer the interested reader to the study of Hoerni Ho .

### A.3 More recent related theories: Use of Feynman Propagators

Let us suppose that at time $`t=0`$ (i.e. canonical density matrix analogue, $`\beta =it`$where $`\beta =(k_BT)^1,`$with $`k_B`$denoting Boltzmann’s constant and $`T`$ the absolute temperature) the electron can be located at a particular point, say $`O`$, on one of the line segments of the tree. The electron wave function on this line segment for $`t>0`$ is the free-particle propagator

$$\frac{1}{\sqrt{4\pi it}}e^{i\frac{y^2}{4t}}$$
(50)
where the distance $`y`$ is to be measured from the initial point $`O`$. The electron then diffuses outward from $`O`$. As usual in the network model, the wave function is required to vary continuously, but the current divides equally down the remaining $`c1`$ branches, where $`c`$ denotes the number of nearest neighbours. The wave function $`\psi `$and $`\frac{1}{c1}\frac{\psi }{x}`$evaluated at the node serve as initial conditions for the wave function itself in the next $`c1`$ segments. These boundary conditions go back to Griffiths Griff . But, as Ringwood stresses, in this situation of an infinite tree the network is simply connected. The same procedure is to be adopted at the next node and so on.

In fact the simplest procedure analytically is to employ the Green function, to be calculated, between two points, say $`O`$ and $`P`$, distanced respectively $`x`$ and $`x`$ from a node. In the initial line segment the Green function takes the form Ring

$$\frac{1}{2}\frac{1}{\sqrt{E}}e^{\sqrt{E}\left|y\right|}$$
(51)
where the energy is taken to be negative, positive energies being obtained by analytic continuation. Putting $`\omega =\sqrt{E},`$ the Green function between the two points $`O`$ and $`P`$ then follows as ($`T`$ denotes Tree)

$$G_T(P,O;E)=(e^{\omega x^{}},e^{\omega x^{}})Z(b_{N1})Z(b_{N2})\mathrm{}.Z(b_1)Z(x)\left(\genfrac{}{}{0pt}{}{\frac{\omega }{2}}{0}\right)^1$$
(52)
where $`b_i`$is the length of a segment and $`Z(b)`$ denotes the matrix

$$\frac{1}{2}(q1)^1\left(\begin{array}{cc}qe^{\omega b}\hfill & (q2)e^{\omega b}\hfill \\ (q2)e^{\omega b}\hfill & qe^{\omega b}\hfill \end{array}\right)$$
(53)
The Green function $`G_L`$on the lattice $`(L`$) is then obtained by a sum over suitable restricted walks $`(\gamma )`$ Ring  as

$$G_L(x,x^{};E)=\underset{\gamma }{}e^{i\alpha (\gamma )}G_T(\gamma x,x^{};E)$$
(54)
where $`\alpha (\gamma )`$enters the phase of the wave function through

$$\psi (\gamma x)=e^{i\alpha (\gamma )}\psi (x)$$
(55)
Ringwood Ring  uses the above results to recover the (more directly calculated) density of states in a graphitic layer given by Coulson Coulson .

## Appendix B Tight binding result for the model boron lattice and relation to the QN model.

For the model boron lattice considered above, we have only 1 atom per unit cell which is assumed to contribute only 1 $`\pi `$electron. There is thus only one band in the first Brillouin zone. The Bloch orbital corresponding to the translational eigenstate $`𝐤`$ generated by this atom is given by

$$\varphi _\pi =\frac{1}{\sqrt{N}}\stackrel{N}{\underset{i=1}{}}e^{i𝐤.𝐑_j}\phi _\pi (𝐫𝐑_i)$$
(56)
where $`\phi _\pi `$ denotes the atomic $`\pi `$orbital centered on lattice position $`𝐑_i`$and $`N`$ the number of atoms in the crystal. The energy $`E(𝐤)`$ is then given by the secular equation

$$\left|HES\right|=0$$
(57)
where the matrices $`H`$ and $`S`$ are now $`1`$dimensional. If we denote the crystal hamiltonian (which is assumed to depend only on $`𝐫`$) by $`\widehat{H}`$ the only matrix element of $`H,`$ say $`H`$, is given by

$$H=\frac{1}{N}\stackrel{N}{\underset{i,j=1}{}}e^{ik.(𝐑_i𝐑_j)}\phi _\pi (𝐫𝐑_j)\left|\widehat{H}\right|\phi _\pi (𝐫𝐑_i)$$
(58)
If we now only take into account nearest neighbour interactions this can be rewritten as

$`H`$ $`=`$ $`{\displaystyle \frac{1}{N}}{\displaystyle \stackrel{N}{\underset{i=j=1}{}}}ϵ_\pi +{\displaystyle \frac{1}{N}}{\displaystyle \stackrel{N}{\underset{i=j=1}{}}}e^{ik.(𝐑_i𝐑_j)}\phi _\pi (𝐫𝐑_j)\left|\widehat{H}\right|\phi _\pi (𝐫𝐑_i)`$ (59)
$`=`$ $`ϵ_\pi +{\displaystyle \frac{1}{N}}{\displaystyle \stackrel{N}{\underset{i=1}{}}}{\displaystyle \stackrel{c}{\underset{j=1}{}}}e^{ik.(𝐚_j)}\phi _\pi (𝐫(𝐑_i+𝐚_j)|\widehat{H}|\phi _\pi (𝐫𝐑_i)`$ (60)
$`=`$ $`ϵ_\pi +{\displaystyle \stackrel{c}{\underset{j=1}{}}}e^{ik.(𝐚_j)}\phi _\pi (𝐫(𝐑_i+𝐚_j)|\widehat{H}|\phi _\pi (𝐫𝐑_i)`$ (61)
where the vectors $`𝐚_j`$ connect every lattice position $`𝐑_i`$to its $`c`$ nearest neighbours and

$$ϵ_\pi =\phi _\pi (𝐫)\left|\widehat{H}\right|\phi _\pi (𝐫)$$

For the model boron lattice considered here we then obtain for the energy

$`E^{TB}`$ $`=`$ $`ϵ_\pi +\left\{\left[e^{ik.(𝐚_1)}+e^{ik.(𝐚_1)}\right]t_1+\left[e^{ik.(𝐚_2)}+e^{ik.(𝐚_2)}\right]t_2+\left[e^{ik.(𝐚_3)}+e^{ik.(𝐚_3)}\right]t_3\right\}`$
$`=`$ $`ϵ_\pi +tS(𝐤)`$
with

$$t_i=t=\phi _\pi (𝐫𝐚_i)\left|\widehat{H}\right|\phi _\pi (𝐫)i=\mathrm{1..3}$$
(62)
since the $`\pi `$orbitals are symmetric with respect to rotations in the plane and all near-neighbour atoms are at equal distance, and

$$S(𝐤)=\stackrel{c}{\underset{j=1}{}}e^{i𝐤.(𝐚_j)}$$

On the other hand from the $`QN`$ model we obtained (in a.u.)

$$E^{QN}(𝐤)=\frac{q^2}{2}=\frac{1}{2}\left\{\mathrm{cos}^1\left(\frac{1}{6}S(𝐤)\right)\right\}^2$$
(63)
The function

$$f(x)=\frac{1}{2}\left\{\mathrm{cos}^1(x)\right\}^2$$
(64)
is plotted over its domain $`[1,1[`$in Fig. $`B1`$. To obtain correspondence with the tight binding calculation this function should be a linear function with a negative slope. Except very close to the lower boundary, we indeed find a linear behaviour for $`f(x)`$ with a slope of about $`1.2`$ which yields for $`t`$ the value $`\frac{1.2}{c},`$where $`c`$ is the near-neighbour coordination number, here equal to $`6`$. The curve has an intersection at about $`1.2`$, which then corresponds to $`ϵ_\pi .`$ Clearly, apart from a topological similarity, both methods also exhibit analytical similarities.

## Appendix C boron-nitride systems:

### C.1 Isolated benzene and borazole levels

The building block of graphene is benzene (without its $`H`$ atoms: i.e. a hexagon of $`C`$ atoms) while for a boron nitride layer it is a hexagon on which $`B`$ and $`N`$ atoms alternate. It is natural enough therefore to appeal to a simple treatment of bonding in these two molecules an then to extend the discussion to graphene and a $`BN`$ layer. Following the survey of one of us low  we treat in this Appendix benzene and borazole by a common approach to their $`\pi `$electron level spectrum, following Roothaan and Mulliken root . We note that one of the objectives of their study was to treat the ultraviolet spectra of benzene and borazole by the semi empirical molecular orbital method.

Ignoring interactions between neighbouring ring atoms, one has for the secular equations for the $`6`$ molecular orbitals derivable from linear combinations of $`2p_\pi `$atomic orbitals of the ring atoms.

$$\left|\begin{array}{cccccc}A& 1& & & & 1\\ 1& A& 1& & & \\ & 1& A& 1& & \\ & & 1& A& 1& \\ & & & 1& A& 1\\ 1& & & & 1& A\end{array}\right|=0\text{(benzene)}$$
(65)
where all the omitted elements vanish. Note that this equation is idential to the secular equation obtained from the $`QN`$ model and so obviously the structure of the energyspectrum predicted by both methods will be similar.

For borazole we have similarly

$$\left|\begin{array}{cccccc}A^{}& 1& & & & 1\\ 1& A^{\prime \prime }& 1& & & \\ & 1& A^{}& 1& & \\ & & 1& A^{\prime \prime }& 1& \\ & & & 1& A^{}& 1\\ 1& & & & 1& A^{\prime \prime }\end{array}\right|=0\text{(borazole)}$$
(66)
For benzene, for example, $`A`$involves not only the desired energy $`E`$ but also Coulomb and resonance integrals, and the overlap $`S`$ between adjacent $`C`$ atoms (appropriate generalization for borazole involves evidently both $`B`$ and $`N`$ atomic orbitals).

These secular equations can be reduced (by suitable similarity transformations) to the form

$$\left|\begin{array}{cccccc}A^{}& 2& & & & \\ 2& A^{\prime \prime }& 1& & & \\ & 1& A^{}& 1& & \\ & & 1& A^{\prime \prime }& 1& \\ & & & 1& A^{}& 1\\ & & & & 1& A^{\prime \prime }\end{array}\right|=0\text{(borazole)}$$
(67)
where, to pass from the borazole result to benzene, one has to set $`A^{}=A^{\prime \prime }=A.`$

The MO’s corresponding to the roots $`A=2`$ and $`A=1`$ (twice) in benzene, or the corresponding orbitals in borazole, are each doubly occupied in the ground state.

Without going into further details, let us simply state the above in a form such that one can describe the effect of the $`\pi `$electron eigenvalues of bringing molecules together into a larger compound, the molecular levels then clearly being broadend into bands. To describe this broadening we follow Coulson and Taylor coulor  and rewrite the above formulae in an explicit manner for borazole

$$(\alpha _BE)(\alpha _NE)g^2(\beta ES)^2=0$$
(68)
where the Coulomb integrals are denoted by $`\alpha _B`$and $`\alpha _N`$ on boron and nitrogen atoms, respectively, while $`\beta `$ denotes the so-called resonance integral.

By way of example, to obtain results for benzene, we merely set $`\alpha _B=`$ $`\alpha _N=\alpha _c`$and then we find discrete allowed values of $`g^2`$(corresponding to discrete values of $`A`$ above) as $`g^2=1`$(twice) and $`g=4`$. It is to be stressed that the electronegativity difference between $`B`$ and $`N`$ will be reflected in the difference between $`\alpha _B`$and $`\alpha _N`$. The fact that boron is more electronegative than nitrogen is reflected in the inequality $`\alpha _B>\alpha _c>`$ $`\alpha _N.`$We have already emphasized in the body of the text that this is a crucial point in highlighting an essential difference between the electronic structure of graphene and of a layer of boron nitride.

### C.2 Broadening of $`\pi `$electron energy levels into bands.

For details of the tight-binding calculation of graphite,the interested reader must consult the study of Coulson and Taylor coulor . However, the point to be reiterated is that the molecular energy levels, corresponding to discrete values of$`g^2`$quoted above, will be broadend into bands. The detailed nature of the structure of graphene merely gives a spread of values of $`g^2`$that is found to embrace the range $`0`$ to $`9`$ after considerable calculation. Defining sums and differences of Coulomb integrals as

$$E_0=\frac{1}{2}(\alpha _B+\alpha _N)$$
(69)
and

$$\delta =\frac{1}{2}(\alpha _B\alpha _N)$$
(70)
and introducing also $`Z=EE_0,`$which merely shift the zero of energy, and $`\gamma =\beta E_0S`$, then one obtains

$$Z=\frac{2\gamma g^2S\pm \left[4\gamma ^2g^4S^2+4\left(\delta ^2+g^2\gamma ^2\right)\left(1g^2S^2\right)\right]}{2\left(1g^2S^2\right)}$$
(71)
Denoting the result of adopting the plus sign in Eq.(71) by $`Z_+(g),`$then by allowing $`g^2`$to embrace the range $`0`$ to $`9`$ already quoted, it is a straightforward matter to demonstrate that $`Z_+(g)`$has its lowest value equal to $`\delta ,`$having a range which is continuous up to a maximum value while, $`Z_{}(g)`$ decreases to its minimum from the value $`\delta .`$Thus, for the layer of boron nitride, the $`\pi `$levels are separated into $`2`$ sub-bands, with an energy gap $`2\delta `$which can be associated directly from the above discussion with the electronegativity difference between $`B`$ and $`N`$. In contrast, for graphene, one must put $`\alpha _B=`$ $`\alpha _N=\alpha _c`$ and $`\delta `$ tends to zero. Hence, instead of the (substantial) energy gap ($`4eV)`$in the $`BN`$ layer, in graphene the $`\pi `$bands touch since $`\delta 0.`$

$`\mathrm{𝐅𝐢𝐠𝐮𝐫𝐞𝐂𝐚𝐩𝐭𝐢𝐨𝐧𝐬}:`$

Fig. $`2.1`$: Unfolded section of a hypothetical $`C_N`$carbon cage (thin lines) with the corresponding $`B_n`$boron cage on top of it (thick lines). Boron cage is constructed by imposing the constraint that every $`BB`$ bond crosses exactly one $`CC`$ bond. The number of boron atoms is then given by $`n=\frac{N}{2}+2.`$

Fig. $`2.2`$: Hartree-Fock values of the $`\pi `$electron level spectrum of $`C_{60}`$. The degeneracies are in good agreement with predictions from Hückel theory.

Fig. $`2.3`$: Hartree-Fock values for the valence electron level spectrum of $`B_{32}.`$

Fig. $`3.1`$: Model boron lattice. Translational vector $`𝐓`$ and chiral vector $`𝐂_h`$defining the unit cell of the nanotube are shown. Special choices for the chiral vector $`𝐂_h(n,n)`$and $`𝐂_h(n,0)`$ are shown to lead to isosceles zigzag symmetry and equilateral zigzag symmetry respectively.

Fig. $`3.2`$: Brillouin zone of the boron lattice. Constant energy contours (with values in atomic units) for the quantum network model are shown. Trigonal warping effect causes deviation from spherical behaviour near the center and $`K`$ points towards triangular behaviour near the $`M`$ points.

Fig. $`3.3`$: Density of states (including spin degeneracy) for the $`2D`$ boron sheet. Outstanding feature is the van Hove singularity near the edge of the first Brillouin zone.

Fig. $`3.4(a)`$:$`\mathrm{\hspace{0.33em}1}D`$energy dispersion relations from the $`QN`$ model for a boron $`(3,3)`$ $`i`$zigzag nanotube

Fig. $`3.4(b)`$:$`\mathrm{\hspace{0.33em}1}D`$energy dispersion relations from the $`QN`$ model for a boron $`(5,0)`$ $`e`$zigzag nanotube.

Fig. $`3.5(a)`$:$`DOS`$ from the $`QN`$ model for a boron $`(3,3)`$ $`i`$zigzag nanotube.

Fig. $`3.5(b)`$:$`DOS`$ from the $`QN`$ model for a boron $`(5,0)`$ $`e`$zigzag nanotube.

Fig. $`4.1`$: Self consistent field for an isolated single wall nanotube from the March model. In calculating the surface charge, the $`CC`$ bond length was taken to be 2.68 a.u..

Fig. $`B.1`$: Plot of the function $`f(x)=\frac{1}{2}\left\{\mathrm{cos}^1(x)\right\}^2`$. To obtain analytic correspondence with the tight binding result we must have a linear relation and this is found to be true over most of the domain of $`f(x)`$.