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# The Faint Cepheids of the Small Magellanic Cloud: an evolutionary selection effect?

## 1 Introduction

Cepheids are variable stars located in the Color-Magnitude diagram (CM-diagram ) within the Instability Strip (IS) where pulsation phenomena take place via the $`\kappa `$mechanism. Cepheid masses approximately range between $`3`$ $`\mathrm{M}_{}`$ and $`15`$ $`\mathrm{M}_{}`$. During the past decade, microlensing experiments as MACHO111http://wwwmacho.mcmaster.ca, EROS222http://www.lal.in2p3.fr/recherche/eros, MOA333http://www.phys.vuw.ac.nz or OGLE 444http://www.astrouw.edu.pl/~ogle/ have produced a huge flow of data. As by-products of these observational programs, a large number of new variable stars, and among them, Cepheids have been detected. OGLE 2 data provide a large and high quality sample of Cepheids belonging to the Small Magellanic Cloud (SMC) which we consider in this work. This extended and homogeneous data set has already put several shortcomings of the SMC Cepheid modeling into light:

(1) the evolutionary tracks built with standard input physics and for a chemical composition $`Z_0=0.004`$ ($`Y_0=0.251`$) as usually assumed for the SMC fail to reproduce the observed Cepheid position within the CM-diagram for highest magnitudes (i.e. $`17`$ mag);

(2) the Mass-Luminosity relation ($`\mathrm{ML}^{\mathrm{puls}}`$ hereafter) derived from pulsation properties (see Beaulieu et al. 2001) and ML-relation from evolutionary tracks ($`\mathrm{ML}^{\mathrm{evol}}`$ hereafter) do not agree.

The first problem arises because theoretical “blue loops” do not cross the observed IS over the whole Cepheid mass range. Indeed an evolutionary track for a mass about 5 $`\mathrm{M}_{}`$ crosses observed IS three times, the first time (“first crossing”) is the faster one -e.g. $`0.01`$ Myr for an 5 $`\mathrm{M}_{}`$ model-, the second time (“second crossing”) is the slower -e.g. $`0.20`$ Myr- and the third time (“third crossing”) remains short, about $`0.01`$ Myr. These time scale considerations tell us that the majority of the observed objects should be in the second crossing stage. During this phase, the star burns He in its inner regions. Third and second crossing both belong to the so-called “blue loop” excursion towards the blue side of Hertzsprung Russell (HR) diagram. Consequently theoretical blue loops should cross the observed IS for the entire Cepheid mass range. As we confirm in the first part of this work, theoretical tracks with standard physics and free parameters varied in a reasonable range are not able to provide blue loops which reach the observed SMC Cepheids at low magnitude, i.e. they are not able to model the low luminosity Cepheids in the SMC case.

The second problem has been underlined -among others- by Beaulieu et al. (2001) who found a strong disagreement between the Mass-Luminosity relation $`\mathrm{ML}^{\mathrm{puls}}`$ and $`\mathrm{ML}^{\mathrm{evol}}`$ in the SMC case. They determine a $`\mathrm{ML}^{\mathrm{puls}}`$ for the LMC and SMC using pulsation calculations, independently from evolutionary calculations: for a given Cepheid the mass $`M_{}`$ and the luminosity $`L_{}`$ are found iteratively solving an equation of the type $`P_i^{\mathrm{theo}}(M_{},L_{})=P_i^{\mathrm{obs}}`$, where $`P_i^{\mathrm{obs}}`$ is the observed period ($`i=0`$ for fundamental pulsators and $`i=1`$ first overtone ones) and $`P_i^{\mathrm{theo}}`$ the theoretical one calculated with a pulsation code. The results of Beaulieu et al. (2001) are based on calculations that assume a metallicity content $`Z_0=0.004`$ which is usually assumed to represent the mean metallicity of the SMC.

We are therefore led, in the second part of this paper, to propose another possibility and show that it can reconcile both issues: the blue loops at low mass and the Mass-Luminosity relation problem. In our hypothesis no high magnitude (i.e. with a mass around $`3`$ $`\mathrm{M}_{}`$) SMC Cepheids with a metallicity as high as the mean SMC value can exist because the evolution does not bring these stars far enough on the blue side to cross the instability strip. The observed high magnitude SMC Cepheids must therefore be undermetallic (i.e. $`Z_00.001`$) with respect to the mean SMC metallicity (i.e. $`Z_00.004`$).

In Sect. 2 we recall the physical inputs used in our standard models, which are similar to what is found in the recent literature. We next compare our evolutionary tracks with OGLE 2 observed Cepheids within a $`\mathrm{CM}`$-diagram. Following a method similar to that used by Beaulieu et al. (2001), we also compare $`\mathrm{ML}^{\mathrm{evol}}`$ and $`\mathrm{ML}^{\mathrm{puls}}`$. In both cases we confirm the discrepancy.

In Sect. 3 we discuss the above issues in view of the uncertainties of the standard models and discuss the effect of non-standard physics in cases when models including such physics are available. In Sect. 4 we compare models calculated with $`Z_0=0.001`$ with observations. Sect. 5 is devoted to discussion about the possibility of the existence of SMC low luminosity Cepheids with metallicity as low as $`Z_0=0.001`$.

## 2 Standard models versus observations

### 2.1 Inputs for Standard evolutionary models

Our evolutionary models are built with the 1D Henyey type code CESAM555CESAM : Code d’Evolution Stellaire Adaptatif et Modulaire originally written by Morel (1997) in which we brought several improvements.

The equation of state is from Eggleton et al. (1973) and the external boundary condition is defined in a simplified model atmosphere involving the Eddington $`T(\tau )`$ law. The nuclear network involves 30 nuclear reactions, we have followed Schaller et al. (1992) who used the same network as in Maeder (1983) for H-burning and Maeder & Meynet (1987) He-burning network supplemented with the $`{}_{}{}^{17}\mathrm{O}(\alpha ,\mathrm{n})^{20}\mathrm{Ne}`$ reaction. Nuclear reaction rates are from Caughlan & Fowler (1988) excepted $`{}_{}{}^{12}\mathrm{C}(\alpha ,\gamma )^{16}\mathrm{O}`$, $`{}_{}{}^{17}\mathrm{O}(p,\gamma )^{18}\mathrm{F}`$ from Caughlan et al. (1985) and $`{}_{}{}^{17}\mathrm{O}(p,\alpha )^{14}\mathrm{N}`$ from Landré et al. (1990). More recent nuclear rates do exist: NACRE by Angulo et al. (1999), however adopted rate for $`{}_{}{}^{12}\mathrm{C}(\alpha ,\gamma )^{16}\mathrm{O}`$ is quite similar to NACRE one (a factor of about two higher than Caughlan & Fowler (1988) and about 80% of Caughlan & Fowler (1988) one.

The adopted mean chemical composition for the SMC is taken as $`X_0=0.745`$, $`Y_0=0.251`$ and $`Z_0=0.004`$, corresponding to a metal to helium enrichment of $`\mathrm{\Delta }Y_0/\mathrm{\Delta }Z_0=2`$ (see for instance Peimbert et al. (2000)), to a primordial helium $`Y_P=0.243`$ (Izotov et al. 1997) and to $`[\mathrm{Fe}/\mathrm{H}]=0.68`$ (Luck et al. 1998). Elemental abundances correspond to the Grevesse & Noels (1993) (GN93) mixture consistent with OPAL96 calculations.

Opacities are from Iglesias & Rogers (1996) (OPAL96) for high temperatures ($`T10,000`$ K) and Alexander & Ferguson (1994) for cooler domains. We stress that the central chemical composition during the He burning phase differs strongly from GN93 (e.g. 50 % of $`{}_{}{}^{12}\mathrm{C}`$ and 50 % of $`{}_{}{}^{16}\mathrm{O}`$). Thus we have use opacity tables allowing a variable composition in $`{}_{}{}^{12}\mathrm{C}`$ and $`{}_{}{}^{16}\mathrm{O}`$ with the aim of modeling the core as realistically as possible. These tables have been built with Magee et al. (1995) elemental opacities (Los Alamos).

The convective flux is computed according to the prescription of the Mixing Length Theory (Böhm-Vitense 1958). The mixing length value $`l_{\mathrm{MLT}}`$ -derived from solar calibration- is equal to 1.6 $`\mathrm{H}_\mathrm{p}`$. We used Schwarzschild’s criterion to decide if the energy transport is radiative or convective, and an extra mixing zone is added above the convective core (i.e. overshooting). The extension of this zone is taken to be $`l_{over}=0.2`$ $`\mathrm{H}_\mathrm{p}`$ ($`l_{over}=\alpha _{over}\mathrm{H}_\mathrm{p}`$).

For the transformation of theoretical quantities, ($`M_{\mathrm{b}ol}`$, $`T_{\mathrm{eff}}`$) into absolute magnitudes and colors, we used the Basel Stellar Library (BaSeL, version 2.2) of Lejeune et al. (1998) which provides color-calibrated theoretical flux distributions for the largest possible range of fundamental stellar parameters, $`T_{\mathrm{eff}}`$ (2000 K to 50,000 K), $`\mathrm{log}g`$ (-1.0 to 5.5), and $`[\mathrm{Fe}/\mathrm{H}]`$ (-5.0 to +1.0).

### 2.2 Comparison between models and observations: the “Blue Loop problem”

Cepheids data are from Udalski et al. (1999). We have chosen to work with $`(\mathrm{V}\mathrm{I})`$ colors for which more data are available. Fundamental and first overtone Cepheids are plotted in Fig. 1(b). A mean $`(\mathrm{V}\mathrm{I})`$ reddening is taken from Udalski (1998), $`\mathrm{E}(\mathrm{V}\mathrm{I})=0.08`$. The SMC distance modulus is fixed at $`18.94`$ from Laney & Stobie (1994) with an internal error of $`0.04\mathrm{mag}`$, this is a well accepted value, e.g. Groenewegen (2000) found $`19.11\pm 0.11`$ or $`19.04\pm 0.17`$ depending on the photometric band.

In both figures (Fig. 1(a) and Fig. 1(b)) evolutionary tracks involving standard input physics are displayed. Fig 1(a) is a HR-diagram showing $`\mathrm{log}L/L_{\mathrm{}}`$ versus $`\mathrm{log}T_{\mathrm{eff}}`$. A segment of a line shows the temperature which should be reached -according to OGLE observations- by the evolutionary tracks for a stellar mass of about 3 $`\mathrm{M}_{}`$; we will mention this mark in further discussions. An estimation of the uncertainties is also plotted in Fig. 1(b): we estimate the error on the colors to be roughly 30% of $`\mathrm{E}(\mathrm{V}\mathrm{I})`$ (which is the typical variation of reddening within the sample) and assess an error of $`0.1`$ dex on $`\mathrm{I}`$-magnitude which roughly represents the distance modulus uncertainty.

In Fig. 1(b) we have also plotted the stars from Luck et al. (1998) for information.

The general characteristics of these theoretical diagrams are similar to those shown by several groups like Geneva one, see Charbonnel et al. (1993). This is not surprising because these authors have used similar physical inputs. For instance, the effective temperature at the tip of our 3 $`\mathrm{M}_{}`$ blue loop is $`\mathrm{log}T_{\mathrm{eff}}=3.728`$ which compares well with Charbonnel et al. (1993) $`\mathrm{log}T_{\mathrm{eff}}=3.734`$. In all cases, the $`\mathrm{log}T_{\mathrm{eff}}`$ value is far from the required one of about $`3.82`$, i.e. a temperature hotter by $`1200`$ K.

The main features put in evidence in Fig 1 are:

(1) the main sequence position seems to be reasonably well reproduced by the models

(2) the position of the blue tip of the 3 $`\mathrm{M}_{}`$ blue loop is too red. For an $`\mathrm{I}`$-magnitude corresponding to a mass of about 3 $`\mathrm{M}_{}`$, we can clearly see a bulge of Cepheids. In fact 93% of fundamental pulsators and 81% of first overtone pulsators are located between $`\text{I}_{min}16.5`$ and $`\text{I}_{max}17.7`$. Such a large amount of objects -statistically significant- cannot be explained solely by $`4.0`$ $`\mathrm{M}_{}`$ first crossing models. Indeed, for a 4.0 $`\mathrm{M}_{}`$ standard model, the time spent during the first crossing is $`\tau _{first}=4.6\times 10^2`$ Myr while the time it takes for the second and third crossing is $`\tau _{\text{second crossing}}+\tau _{\text{third crossing}}=3.433`$ Myr. Hence, blue loops should cross the entire observational IS for the lowest masses. The adopted value of distance modulus $`\mu `$ does not affect this conclusion. Indeed, even if we take extreme evaluations: $`\mu _1=18.66\pm 0.16`$ from Udalski (1998) and $`\mu _2=19.05\pm 0.13`$ from Kovács (2000), the evolutionary track for $``$ 3 $`\mathrm{M}_{}`$ does not extend through the observational IS.

### 2.3 Comparison between observed and calculated Mass-Luminosity relations

#### 2.3.1 Deriving Mass-Luminosity Relations from observations

In order to derive a ML-relation from the observations, we use a method very similar to the one used by Beaulieu et al. (2001). For each object we solve iteratively the equation:

$`P_i^{\mathrm{theo}}(M_{},L_{},T_{\mathrm{eff}},Y_0,Z_0)=P_i^{\mathrm{obs}}`$ (1)
where $`P_i^{\mathrm{obs}}`$ is the observed period value ($`i=0`$ for fundamental pulsators and $`i=1`$ for first overtones) and $`P_i^{\mathrm{theo}}(M_{},L_{},T_{\mathrm{eff}},Y_0,Z_0)`$ the theoretical one, computed with the Florida LNA666Linear Non-Adiabatic pulsation code which is a Castor type code (see Castor 1971). During the iterative process, $`M_{}`$ is adjusted in order to match $`P_i^{\mathrm{obs}}`$ and $`P_i^{\mathrm{theo}}`$, for a given iteration $`M_{}`$ is fixed and we solve the following set of equations where the unknowns are $`(\mathrm{log}T_{\mathrm{eff}},\mathrm{log}R_{},\mathrm{log}L_{})`$:

$`\mathrm{log}T_{\mathrm{eff}}=\mathrm{\hspace{0.33em}3.9224}+\mathrm{\hspace{0.33em}0.0046}\mathrm{log}g+\mathrm{\hspace{0.33em}0.0012}[\mathrm{Fe}/\mathrm{H}]`$ (2)
$`\mathrm{\hspace{0.33em}0.2470}(VI(R_VR_I)E(BV))`$
$`2.5\mathrm{log}L_{}=\mu _{\mathrm{SMC}}V+R_VE(BV)+BC+4.75`$ (3)
$`L_{}=4\pi \sigma R_{}^2T_{\mathrm{eff}}^4`$ (4)
$`g=G{\displaystyle \frac{M_{}}{R_{}^2}}`$ (5)
Eq. 2 comes from Kovács (2000) Eq.2, in which we brought absorption corrections. Eq. 3 is the Beaulieu et al.’s Eq.2. Kovács (2000) who made interpolations of Castelli et al. (1997) stellar atmospheres models to convert magnitudes into bolometric and effective temperature into colors. The luminosity $`L_{}`$ is in solar units,

$`BC=0.0411+2.0727\mathrm{\Delta }T0.0274\mathrm{log}g+0.0482[\mathrm{Fe}/\mathrm{H}]`$
$`8.0634\mathrm{\Delta }T^2`$
and $`\mathrm{\Delta }T=\mathrm{log}T_{\mathrm{eff}}\mathrm{\hspace{0.33em}3.772}`$. The magnitude and color $`V`$, $`(VI)`$ are from OGLE observations, $`\mu _{\mathrm{SMC}}`$ has been taken equal to $`18.9`$ consistently with Laney & Stobie (1994). Following Udalski et al. (1999) we took $`E(BV)0.08`$, $`R_V=3.24`$ and $`R_I=1.96`$.

In order to apply this method one has to select the data. Indeed on the CCD detector, a Cepheid may be “blended” with another star, the magnitude of the object being shifted towards lower magnitudes. These “over-luminous” objects lead to wrong couples ($`\mathrm{log}M_{}`$,$`\mathrm{log}L_{}`$), therefore it is crucial to reject from the sample the stars suspected to be blended with other object(s). From OGLE data we have extracted amplitudes of pulsation in $`B`$, $`V`$ and $`I`$ bands and then derived $`\mathrm{Amplitude}\mathrm{log}P`$ relations. The criterion to suspect that an object is blended is the following: if a given object has a magnitude lower than the mean magnitude (at least 0.2 mag lower) given by the $`\mathrm{Magnitude}\mathrm{log}P`$ law and an amplitude lower than the mean amplitude given by $`\mathrm{Amplitude}\mathrm{log}P`$ relation, this object is rejected. Moreover we have also rejected some objects which appear to be suspiciously to red. Finally we retain $`1177`$ fundamental pulsators and $`709`$ first overtone pulsators and obtain similar samples of objects than Beaulieu et al. (2001).

Fig. 2 displays the resulting ML-relation derived with an assumed metallicity $`Z_0=0.004`$. We did not find significative differences with results from Beaulieu et al. (2001).

#### 2.3.2 Uncertainties in Derived ML-relations

For years the question of Magellanic Clouds distance has been a subject of debate. There were supporters for “short” distance scales -e.g. Stanek et al. (1998) with $`\mu _{\mathrm{LMC}}=18.065\pm 0.031\pm 0.09`$ mag- and for “long” distance scales -e.g. Laney & Stobie (1994) with $`\mu _{\mathrm{LMC}}=18.53\pm 0.04`$ mag- Cioni et al. (2000) derived a distance modulus for the LMC $`\mu _{\mathrm{LMC}}=18.53\pm 0.04\pm 0.08`$ mag and Mould et al. (2000) (HST Key Project Team) have adopted $`\mu _{\mathrm{LMC}}=18.50\pm 0.04\pm 0.15`$ mag. We made a test with “short” distance (i.e. $`\mu _{\mathrm{SMC}}=18.7`$ mag); this leads to differences in mass of $`\delta \mathrm{log}M/M_{}0.1`$ and in luminosity $`\delta \mathrm{log}L/L_{}0.08`$ (consistently with Eq. 3). We dismiss these “short” distance scales: (1) whatever is the technics used, recent works seem in agreement with “long” distance scales; (2) a difference in mass of $`\delta \mathrm{log}M/M_{}0.1`$ would mean that evolutionary computations would be completely wrong. We stress that Beaulieu et al. (2001) have the same point of view. Therefore we adopted a “long” distance value for the SMC distance modulus: $`\mu _{\mathrm{SMC}}=18.9\pm 0.15`$ mag; this choice is supported by the recent result of Harries et al. (2003) who found $`\mu _{\mathrm{SMC}}=18.89\pm 0.04`$ (statistical) $`\pm 0.15`$ (systematic) mag with a technics involving eclipsing binaries.

Whereas the depth of the LMC seems to be negligible (Van der Marel & Cioni 2001); the depth of the SMC has been evaluated to range between $`0.2`$ and $`0.4`$ mag (Crowl et al. 2001). Then -for extreme cases- a given object inside the SMC could have an actual distance modulus $`+0.2`$ mag larger or lower than $`\mu _{\mathrm{SMC}}=18.9`$ mag, which has to be regarded as an average value. In order to estimate either the influence of an error on $`\mu _{\mathrm{SMC}}`$ or an effect of SMC depth, we have made a test with $`\mu _{\mathrm{SMC}}=19.1`$ mag we got $`\delta \mathrm{log}M/M_{}+0.1`$ and $`\delta \mathrm{log}L/L_{}+0.08`$.

Another source of uncertainties is the reddening; if we assume an error of $`\pm 0.03`$ mag on $`\mathrm{E}(\mathrm{B}\mathrm{V})=0.08`$ mag, in turn we get a small uncertainty on masses and luminosity: $`\delta \mathrm{log}M/M_{}\pm 0.01`$ and $`\delta \mathrm{log}L/L_{}\pm 0.05`$.

Beside this, uncertainties connected to standardization of OGLE photometry are clearly negligible; with $`\delta V=\pm 0.02`$ mag we obtained $`\delta \mathrm{log}M/M_{}\pm 0.01`$ and $`\delta \mathrm{log}L/L_{}0.01`$.

Moreover Beaulieu et al. (2001) made some additional tests: introducing turbulent convection, computing non-linear models or changing the meshes size within models does not yield to periods significantly different from those computed with LNA code. Therefore the uncertainty on distance (error on $`\mu _{\mathrm{SMC}}`$ or effect of SMC depth) remains the most important one.

#### 2.3.3 Comparison with ML-relations from evolutionary tracks

From Fig. 2, we remark a large discrepancy between the ML-relations derived from OGLE observations and from evolutionary calculations. For each evolutionary track, luminosity has been read at the “tip” of the blue loop, locus where the model spent at lot of time. The discrepancy is also found using Bono et al. (2000) mass-luminosity relation. The disagreement is getting worst when $`\mathrm{log}M/M_{}`$ decreases. We must however emphasize that for $`\mathrm{log}M/M_{}0.4`$ (i.e. $`M/M_{}2.5`$), the evolutionary track does not cross the Cepheid Instability Strip and a comparison between $`\mathrm{ML}^{\mathrm{evol}}`$ and $`\mathrm{ML}^{\mathrm{puls}}`$ for $`\mathrm{log}M/M_{}0.4`$ has no real meaning. Even an extreme value of $`\mu _{\mathrm{SMC}}`$ -i.e. $`19.1`$ mag- can not lead to a perfect agreement between all ML-relations.

## 3 Uncertainties in Standard Evolutionary Models

In this section, we review the factors affecting the blue loop extension. Before presenting any models, we briefly recall a method allowing some predictions about the blue loop extension. We follow the work of Lauterborn et al. (1971)b who have defined an “effective core potential”:

$$\mathrm{\Phi }_{\mathrm{eff}}=\frac{M_c}{R_c}\text{e}^{(\alpha \mathrm{\Delta }m\mathrm{\Delta }X)}$$
(6)
where $`M_c`$ and $`R_c`$ are respectively the mass and the radius of the $`\mathrm{H}_\mathrm{e}`$ core and $`\alpha `$ a constant. $`\mathrm{\Delta }m`$ is the width of the zone located between the $`\mathrm{H}_\mathrm{e}`$ core and the beginning of the outer chemically homogeneous region. $`\mathrm{\Delta }X`$ represents the total hydrogen mass fraction variation within $`\mathrm{\Delta }m`$. Numerical experiments done by Lauterborn et al. (1971)b have shown that a model undergoes a blue loop if this potential is lower than a critical value $`\mathrm{\Phi }_{\mathrm{eff}}^{(crit)}`$. We have to keep in mind this simple result: the lower $`\mathrm{\Phi }_{\mathrm{eff}}`$, the bluer the blue loop tip.

In the next sections, we focus on a $`3M_{}`$ track because the most severe discrepancy in the $`\mathrm{CM}`$-diagram is observed around this mass.

### 3.1 Overshooting

If we reduce the overshooting amount from $`\alpha _{\mathrm{over}}=0.2\mathrm{H}_\mathrm{p}`$ (“standard value”) to $`\alpha _{\mathrm{over}}=0.0\mathrm{H}_\mathrm{p}`$, the $`\mathrm{H}_\mathrm{e}`$ core mass $`M_c`$ decreases as a consequence of the less extended H-core on main sequence. As a consequence, loops more extended toward the blue are expected. This is confirmed in Fig. 3(b) where it clearly appears that even without any overshooting ($`\alpha _0=0.0\mathrm{H}_\mathrm{p}`$), a 3 solar masses loop still remains too short to account for the observational data.

### 3.2 Mixing Length Parameter

The Mixing Length parameter $`\alpha _{\mathrm{MLT}}=l_{\mathrm{MLT}}/\mathrm{H}_\mathrm{p}`$ has been so far set equal to 1.6 in our standard models. This value is derived from solar calibration (Lebreton et al. (1999)) and it is probably not universal: it may depend on metallicity, mass, etc … A priori, $`\alpha _{\mathrm{MLT}}`$ acts only on the convective flux ($`\alpha _{\mathrm{MLT}}`$ is involved in MLT temperature gradient calculation) and does not change the position of Schwarzschild limit, hence $`\mathrm{\Delta }X`$ in Eq. 6 should remain unchanged, more blueward loops are not expected. The tracks computed with the extreme values $`\alpha _{\mathrm{MLT}}=1.0`$ and $`\alpha _{\mathrm{MLT}}=2.0`$ are plotted in Fig. 3(a). Both tracks have been calculated with $`\alpha _{\mathrm{over}}=0.0`$ which is the most favorable situation as explained in Sect. 3.1.

As one can notice $`\alpha _{\mathrm{MLT}}`$ has a negligible influence on the blue tip position. The effective temperature of the bluest point of the loop remains approximatively equal to $`3.76`$ (in Log) which is not enough to reach the warmer edge of the observational IS, it still lacks $`850`$ K. We point out that a value of $`\alpha _{\mathrm{MLT}}=1.0`$ is very unlike because it leads to a giant branch around $`(\mathrm{V}\mathrm{I})1.5`$ where there are no stars within $`\mathrm{CM}`$-diagram.

### 3.3 Convective penetration

Similarly, although not identically as the overshooting process, turbulent eddies must penetrate to some extent downward the convective envelope into stable radiative regions. However, we do not know how far they penetrate.

Here we have carried out a calculation setting the extension of convective penetration at $`\alpha _{\mathrm{cp}}=0.7`$ $`\mathrm{H}_\mathrm{p}`$ following the Alongi et al. (1991) prescription. They found that this value is needed to reproduce the properties of red giants branch luminosity function. This amount (0.7 $`\mathrm{H}_\mathrm{p}`$) must be understood as an order of magnitude as Alongi et al. (1991)’s calculations were performed before 1992 when OPAL group published his new opacity tables.

During the giant branch (hereafter GB) episode, the convective penetration produces a deeper penetration of the external convective zone. In this way, $`\mathrm{\Delta }X`$ in Eq. 6 decreases and yields a lower $`\mathrm{\Phi }_{\mathrm{eff}}`$ and bluer loop tip. Evolutionary tracks are displayed in Fig. 3(c) for a 3 $`\mathrm{M}_{}`$ without overshooting (i.e. both with $`\alpha _{\mathrm{over}}=0.0`$ $`\mathrm{H}_\mathrm{p}`$) and show -as expected- that convective penetration slightly extends the loop but not enough to cross the entire IS. The extension difference reaches only a few $`130`$ K, remaining too cold by $`720`$ K.

### 3.4 Rotation

Maeder & Meynet (2001) present evolutionary tracks including effect of stellar rotation at low metallicity $`Z_0=0.004`$ in the mass range 9.0 to 60.0 $`\mathrm{M}_{\mathrm{}}`$. The smaller mass value remains in the Cepheid domain. In Fig.6 of Maeder & Meynet (2001) the reader can remark that the blue loop extension is substantially reduced to $`\mathrm{log}T_{\mathrm{eff}}4.12`$ to $`\mathrm{log}T_{\mathrm{eff}}3.95`$ ($`\mathrm{\Delta }\mathrm{log}T_{\mathrm{eff}}0.17`$) whereas we need $`\mathrm{\Delta }\mathrm{log}T_{\mathrm{eff}}\text{+}0.05`$. This blue loop reduction is due to the core extra-mixing added by convection equivalent to an overshooting addition.

### 3.5 Influence of the CNO-cycle energy generation rate

Although the CNO nuclear reactions cycle is rather well known, we have performed evolutionary calculations with an energy generation rate $`ϵ_{\mathrm{cno}}`$ artificially reduced by a factor two, from an arbitrary chosen post-main sequence stage (indicated by an arrow in Fig. 3,d). This magnitude of uncertainty (a factor of two) is extremely large because the consequences during the Main Sequence phase would bring unavoidable disagreements between observations and models.

One can again predict what can be expected from such a numerical experiment. A lower $`ϵ_{\mathrm{cno}}`$ leads to a lower $`M_c`$ in Eq. 6, thus to a lower $`\mathrm{\Phi }_{\mathrm{eff}}`$ and consequently to a bluer loop. Fig. 3(d) confirms this argument. Again, the loop is not extended enough and even an unrealistic uncertainty of a factor of two on the global energy generation rate $`ϵ_{\mathrm{cno}}`$ cannot explain the disagreement between observations and theory.

Enhancing by a factor two the $`3\alpha `$ reaction rate, is also found to have a negligible influence on the blue loop extension.

### 3.6 Effects of helium

The initial helium content adopted, $`Y_0`$ is expected to have only a minor influence on the blue loop extension, indeed:

* the central helium content $`Y_c`$ during the blue loop episode does not depend on the helium content of the initial homogeneous model $`Y_0`$. Hence $`Y_0`$ does not influence $`ϵ_{\mathrm{He}}`$ the He-burning energy production rate because within the inner regions $`Y_c=1Z_c`$ (with $`Z_c`$ the central heavy elements mass fraction) whatever the $`Y_0`$ value is.
* during the blue loop the H-burning shell moves through the “$`X`$-profile” where $`Y`$ varies between $`1`$ (boundary of He core) and $`Y=Y_0`$ (chemically homogeneous region mixed during the dredge-up episode when the model is closed to the Red Giants Branch). These Intermediate $`Y`$ values are independent of $`Y_0`$ (obviously excepted values closed to $`Y_0`$ itself)

Therefore the influence of $`Y_0`$ on the blue loop extension is expected to be very small. As a verification, models have been calculated with $`Y_0=0.23`$ and $`Y_0=0.28`$ which represent two extreme values: $`Y_0=0.23`$ is a rather low value for primordial helium and $`Y_0=0.28`$ which implies $`\mathrm{\Delta }Y_0/\mathrm{\Delta }Z_09`$ while “reasonable” values are around 2, for a review see Luridiana (2002). The tracks with $`Y_0=0.23`$ and $`Y_0=0.28`$ in (Fig. 3(e)) show that the initial helium content has no influence on the blue loop extension: the effective temperature of the tip remains equal to 3.76, i.e. $`850`$ K colder than blue edge of IS, even in the favorable scheme of zero overshooting.

### 3.7 Effects of metallicity

The high sensivity of a blue loop extension to metallicity is well known. The physical origin of this phenomenon is in the H-burning shell where material is processed through CNO cycle. For a fixed heavy elements mixture (here GN93) the lower $`Z_0`$, the lower $`X_\mathrm{C}`$, $`X_\mathrm{N}`$, $`X_\mathrm{O}`$ (respectively C, N and O mass fractions) are. These three elements play the same role of catalysts in chemical reactions, therefore a C, N, O deficiency leads to a lower energy generated. Then, $`M_c`$ in Eq. 6 remains lower for a longer time and one obtains more extended blue loops. On one hand, the H-burning shell drives the star structure on the Giant Branch, on the other hand, during the blue loop episode, the $`\mathrm{He}`$-burning core pulls the model towards the blue edge, where the $`\mathrm{He}`$ main sequence is located. The lower $`ϵ_{\mathrm{CNO}}`$, the stronger He central burning effect.

As a confirmation of this high metallicity sensivity, we have computed an evolution at 3 $`\mathrm{M}_{}`$ taking a very low value: i.e. $`Z_0=0.001`$ which corresponds to $`[\mathrm{Fe}/\mathrm{H}]1.3`$. We compare the resulting extensions in Fig. 3(f). The blue loop crosses the entire IS, the tip reaching a position bluer than the blue edge of IS.

Therefore the only way we have found to extend blue loops towards the high temperature edge of the HR diagram is to decrease the metallicity. In the next section we compare observational constraints and models built with $`Z_0=0.001`$.

## 4 Models with $`Z_0=0.001`$

### 4.1 Blue loops at $`Z_0=0.001`$

We have calculated a grid of evolutionary tracks at very low metallicity, i.e. $`Z_0=0.001`$. The results are displayed in Fig. 4 where one can remark that the whole observed Instability Strip is crossed by the theoretical tracks, even the fainter part, i.e. the lower region of the color-magnitude diagram. These results suggest that a great part of SMC Cepheids could be metal deficient compared to the mean metallicity of the Small Cloud.

One interesting point is that the shape of the Instability Strip at high magnitude is well reproduced by the decrease of the blue loop extension when going from higher to lower masses.

### 4.2 Mass-Luminosity relation at $`Z_0=0.001`$

In Fig. 5 we have displayed the Mass-Luminosity relations derived from OGLE observations assuming a metallicity of $`Z_0=0.001`$. Fig. 5b shows a better agreement between $`\mathrm{ML}^{\mathrm{evol}}`$ and $`\mathrm{ML}^{\mathrm{puls}}`$, if we assume $`\mu _{\mathrm{SMC}}=19.0`$ mag -consistently with recent determinations- the agreement for low masses is excellent. Unfortunately it remains a discrepancy for higher masses -i.e. for $`\mathrm{log}M/M_{}0.7`$, this point will be discussed within the next section.

## 5 Conclusion and discussion

Sect. 4 shows that looking for an agreement between models and SMC observations for both blue loop extensions and M-L relations for the SMC gives strong hints that high magnitude (i.e. low mass) SMC Cepheids could be metal deficient compared to the mean metallicity of the SMC; this fact could be explained by a “selection effect”: only stars with low enough metallicity could have an evolutionary track crossing Cepheids Instability Strip. Unfortunately direct spectroscopic determinations of $`[\mathrm{Fe}/\mathrm{H}]`$ for the SMC Cepheids around I-mag $`17`$ are not yet available. We discuss now a few issues in favor of the above proposition. First we consider another metal poor galaxy and then discuss the information which can be drawn from Cepheids in SMC clusters and beat Cepheids which supports the existence of SMC Cepheids as metal poor as $`[\mathrm{Fe}/\mathrm{H}]1.3`$ dex.

### 5.1 Comparison between our model and a very low metallicity Cepheid population

Udalski et al. (2001) provided a sample of Cepheids belonging to the galaxy IC1613 with a metallicity $`[\mathrm{Fe}/\mathrm{H}]1.3\pm 0.2`$ (see Lee et al. 1993). This data set offers the opportunity to check whether our evolutionary models are valid for metallicity as low as the value suspected for SMC Cepheids located below the $`\mathrm{\Delta }`$ line in a CM-diagram. Fig. 6 displays OGLE objects and our evolutionary tracks for $`Z_0=0.001`$. The distance modulus for IC1613 is taken to be $`24.2\pm 0.1`$ mag and absorption is $`\mathrm{A}_\mathrm{I}=0.05`$ (see Udalski et al. 2001); reddening is given by Schlegel et al. (1998). Fig. 6 shows that the evolutionary tracks cross the whole instability strip as defined by the observed Cepheids. For this galaxy, no problem of blue loop exists with our models indicating that the main features of our models likely capture the essential evolutionary properties at low metallicity. One can notice that even a cut-off of OGLE detector around I-mag $`22`$ can not really change our conclusion because the blue loop for 2.5 $`M_{}`$ is extended enough to model Cepheids as faint as I-mag $`22.2`$.

### 5.2 Evidences for metal poor stars within the SMC

Luck et al. (1998) have determined the chemical composition of Cepheids in SMC by means of high resolution spectroscopy. The $`[\mathrm{Fe}/\mathrm{H}]`$ values found by the authors range between $`0.84`$ and $`0.65`$ corresponding to a mass fraction $`Z_0`$ ranging between $`0.0030`$ and $`0.0045`$, these values bracket the commonly assumed metallicity mean value for SMC, i.e. $`Z_0=0.004`$. However two remarks are in order here: (1) the sample studied by Luck et al. (1998) has a quite poor statistic (6 objects) while OGLE sample contains about 2000 objects; (2) more importantly, as shown by Fig. 1(b) the stars studied by Luck et al. (1998) are objects much brighter than those around I-magn$`17`$ which are not reached by our blue loops. The reason for the choice of bright objects is that spectroscopic determinations are easier for brighter objects. Therefore any biais -concerning high magnitude SMC Cepheids metallicity- cannot be excluded.

On the other hand, one may think that it is possible to infer some indirect information about the SMC Cepheid metallicity. OGLE team has indeed discovered many stellar clusters in the SMC, (see Pietrzynski et al. 1998). Moreover Pietrzynski & Udalski (1999c) have detected 132 Cepheids belonging to these clusters. One of the main properties of stars belonging to a given cluster is to present the same chemical composition. Therefore any indications about metallicity of these SMC clusters gives an information about the metallicity of Cepheids belonging to clusters. The literature is quite poor about metallicity determinations for SMC clusters. Table 1 mainly taken from Crowl et al. (2001) gives metallicity estimations for SMC clusters. Thanks to a cross identification we have found 2 clusters belonging to the catalogue of Pietrzynski & Udalski (1999c) and having a metallicity determination in the literature: NGC 330 (`SMC0107` in OGLE catalogue) and NGC 416 (`SMC0158`). However these clusters are known to be young or intermediate-age systems; one has to check whether the ages of Cepheids are compatible with age of the cluster hosting them.

In the case of NGC 330 Chiosi et al. (1995) have found a maximum age of 48 Myr; beside this Pietrzynski & Udalski (1999b) have derived from their study $`31.6_{6.5}^{+8.2}`$ Myr. From HST observations Mighell et al. (1998b) estimate an absolute age for NGC 416 of $`6.6\pm 0.5`$ Gyr assuming that Lindsay 1 cluster is 9 Gyr old; Pietrzynski & Udalski (1999b) confirm that NGC 416 is older than 1 Gyr. We underline that neither NGC 330 nor NGC 416 are mentioned in the erratum Pietrzynski & Udalski (1999a).

For the Cepheid (`SMC_SC7 206038` in OGLE catalogue) suspected to belong to NGC 330 if we assume a metallicity $`[\mathrm{Fe}/\mathrm{H}]=0.7`$ ($`Z_0=0.004`$) and a mass about 3.5 $`M_{}`$ consistently with its position within CMD; we found an age of $`230`$ Myr; assuming $`[\mathrm{Fe}/\mathrm{H}]=1.3`$ ($`Z_0=0.001`$) and 3.0 $`M_{}`$ we obtain $`300`$ Myr. Thus the Cepheid is likely a field star and does not belong to NGC 330.

Stars suspected to be NGC 416 objects have an I-magnitude between $`15`$ and $`16`$ mag; this corresponds to a mass around 4 $`M_{}`$ for $`[\mathrm{Fe}/\mathrm{H}]=1.3`$ (metallicity consistent with cluster one). From our evolutionary calculations we get -for such mass and metallicity- an age of $`150`$ Myr.

Unfortunately this value is not compatible with the estimated age for NGC416; indeed the age spread (probably around $`0.5`$ Gyr) does not allow such young objects to belong to the cluster. Nevertheless one can notice that the majority of SMC clusters in Tab. 1 are metal deficient, thus SMC stars with metallicity lower than $`Z_00.004`$ ($`[\mathrm{Fe}/\mathrm{H}]0.7`$) does exist and the hypothesis of metal deficient SMC Cepheids appears to be reasonable.

### 5.3 Information brought by SMC Beat Cepheids

OGLE Team has discovered a sample of 93 beat Cepheids in the SMC. Udalski et al. (1999) found that 23 pulsate simultaneously on the fundamental mode (hereafter F) and the first overtone (hereafter 1OT), the remaining objects have been found to pulsate simultaneously on the first and second overtones (hereafter 2OT).

In order to derive their $`\mathrm{ML}^{\mathrm{puls}}`$ Beaulieu et al. (2001) choose three quantities among the four observational ones: $`T_{\mathrm{eff}}`$, $`L`$ and the periods $`P_k`$ and $`P_{k+1}`$ ($`P_0`$ for F/1OT and $`P_1`$ for 1OT/2OT); they calculate the theoretical value of $`P_{k+1}`$ which is noted $`P_{k+1}(\mathrm{calc})`$ (the observed one being $`P_{k+1}(\mathrm{obs})`$). They next define the parameter $`ϵ=P_{k+1}(\mathrm{calc})/P_{k+1}(\mathrm{obs})`$) allowing a comparison between theory and observations. They explore the influence of different important parameters, particularly distance modulus and reddening and finally conclude that a solution (i.e. $`ϵ1`$) is found simultaneously for F/1OT pulsators and 1OT/2OT only if the metallicity is settled to $`Z_0=0.001`$ (i.e. $`[\mathrm{Fe}/\mathrm{H}]1.3`$).

In Fig. 8 we have plotted the observed beat Cepheids together with evolutionary tracks and the straight line $`\mathrm{\Delta }`$ defined in Sect. 2. This plot clearly shows that the beat Cepheids are located in the region where we suspect that objects are metal deficient (i.e. with a metallicity around $`Z_00.001`$). All 1OT/2OT pulsators are below $`\mathrm{\Delta }`$ (excepted one object) while F/1OT pulsators are scattered slightly above and below.

Thus these pulsation/evolution models of SMC beat Cepheids argue in favor of a relation between a metal deficiency (with respect to the mean value of the SMC) and the existence of SMC Cepheids at low magnitude.

### 5.4 The case of high mass Cepheid

Although it is slightly out of scope of this paper where we focus on faint SMC Cepheids, we will debate in this paragraph the case of brighter objects: i.e. $`\mathrm{log}M/M_{}0.70.8`$ corresponding to $`3.6\mathrm{log}L/L_{}4.1`$. Whatever is the assumed metallicity: $`Z_0=0.004`$ or $`Z_0=0.001`$, few objects with an evaluated mass around $`\mathrm{log}M/M_{}0.77`$ ($`M6M_{}`$) have a $`\mathrm{ML}^{\mathrm{puls}}`$ in discrepancy with the related $`\mathrm{ML}^{\mathrm{evol}}`$.

We can make some hypothesis: as shown in Sect. 2.3.2 with a larger distance modulus -i.e. $`\mu _{\mathrm{SMC}}=19.1`$ mag- we get $`\delta \mathrm{log}M/M_{}+0.1`$ and $`\delta \mathrm{log}M/M_{}+0.08`$ (compared with the situation with $`18.9`$ mag), but this extreme value is not able to bring a full agreement between $`\mathrm{ML}^{\mathrm{puls}}`$ and $`\mathrm{ML}^{\mathrm{evol}}`$ for brighter objects. On the other hand it is unlike that all these stars would be located deeper in SMC than others.

For a given mass value, a way to enhance the luminosity is to consider a larger overshooting amount. As suggested by Cordier et al. (2002), it can not be excluded that average overshooting amount for intermediate mass stars increases when metallicity decreases; they have derived -assuming $`Z_0=0.004`$ for SMC main sequence stars- $`\alpha _{\mathrm{over}}=0.40_{0.06}^{+0.12}\mathrm{H}_\mathrm{p}`$. With a LMC bump Cepheids study Keller & Wood (2002) infer an overshooting amount $`\mathrm{\Lambda }_\mathrm{c}=0.63\pm 0.03\mathrm{H}_\mathrm{p}`$ ($`0.3\mathrm{H}_\mathrm{p}`$ in our formalism).

We made a test -involving all mass values- with $`\alpha _{\mathrm{over}}=0.4\mathrm{H}_\mathrm{p}`$, as expected blue loop extensions are reduced (for low masses tracks the excursion of blue loop within IS is less deep) and luminosity is increased not enough ($`\delta \mathrm{log}L/L_{}+0.1`$) to get an agreement between $`\mathrm{ML}^{\mathrm{evol}}`$ and $`\mathrm{ML}^{\mathrm{puls}}`$ for $`\mathrm{log}M/M_{}0.77`$. Then, to increase the overshooting amount over the whole range of mass is not the solution.

Another possibility is that overshooting can depend on mass, increasing with mass; as suggested for instance by Young et al. (2001). Thus we have concentrated us on $`6M_{}`$ models, varying overshooting amount between $`0.2\mathrm{H}_\mathrm{p}`$ (our “standard” value here) up to $`0.6\mathrm{H}_\mathrm{p}`$; this for both metallicities: $`Z_0=0.001`$ and $`Z_0=0.004`$. Results are shown in Fig. 7; it is clear that beyond $`0.4\mathrm{H}_\mathrm{p}`$ one no longer gets blue loop for $`Z_0=0.004`$. In contrast with $`Z_0=0.001`$ blue loop extension decreases, but in a way where Cepheids IS is crossed by tracks. $`\mathrm{log}L/L_{}`$ increases reaching large enough value (for $`0.6\mathrm{H}_\mathrm{p}`$, see diamond symbol in Fig. 5(b)) in order to make it up $`\mathrm{ML}^{\mathrm{evol}}`$ and $`\mathrm{ML}^{\mathrm{puls}}`$ for $`\mathrm{log}M/M_{}0.77`$. We stress that Keller & Wood (2002) found their quite “high” overshooting amount using a sample of bright LMC Cepheids, this support our proposal of an higher overshooting for brighter Cepheids. One more time our work favors a solution involving low metallicity. Towards high masses, another selection effect could occur if the overshooting increases with mass and reached $`0.6\mathrm{H}_\mathrm{p}`$ for masses larger than $`6M_{}`$ at low metallicity. A detailed study is needed on this topic and is out of the main goal of this paper.

### 5.5 Summary

In this paper we have explored two main problems related to the SMC Cepheid population: (1) the blue loop extension for high magnitude stars, (2) the Mass-Luminosity relation. We have first shown that blue loop extension is extended enough only if the metallicity is substantially lower than the commonly used value for SMC objects models.

Evolutionary tracks computed with $`Z_0=0.001`$ correctly reproduce the Instability Strip shape for low masses and Mass-Luminosity relation derived from these tracks is in rather good agreement with $`\mathrm{ML}^{\mathrm{puls}}`$ deduced from observations using a technique similar to Beaulieu et al. (2001) one. The remaining discrepancy for the small population of brighter objects could be explained by a joined effect of low metallicity and rather enhanced core mixing process. Further researches are needed on this subject. We emphasize that Pietrukowicz (2002) -who estimates period change rates of SMC OGLE Cepheids- found also for brighter objects a rather bad agreement between models and observations.

Our point is that all Cepheids below $`\mathrm{\Delta }`$ are likely metal poor and stars above $`\mathrm{\Delta }`$ belong probably to a “mixed” population. Finally, the present work strongly suggests the existence of an evolutionary selection effect for fainter Cepheids belonging to SMC. High resolution spectroscopic chemical composition determinations for SMC Cepheids through the entire IS and particularly around magnitude $`17`$ are requested to bring definitive arguments in favor or against the present suggestion. This could be possible for a sample of few stars with UVES VLT spectrograph. Results would put a new light on the cosmologically important metallicity dependence of the Cepheids Period-Magnitude relation.

###### Acknowledgements.

We warmly thank the anonymous referee who contribute to the improvement of this paper with his/her remarks and suggestions. We also thank Jean-Philippe Beaulieu and J.Robert Buchler for valuable discussions; we are also grateful to the OGLE group for providing their data and to people involved in `GNU/Linux` projects. D. Cordier thanks E.N.S.C.R. for working facilities and his “Aménagement de service” during 2002$`/`$2003 Academic Year.


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# Ab initio density functional investigation of B₂₄ cluster: Rings, Tubes, Planes, and Cages

## I Introduction

Atomic clusters are of great interest due to their novel properties which can serve as building blocks for self-assembled material in order to realize miniaturized nanodevices. Due to increasing technological importance of nanoscale devices, the investigation of the structural, and the related physical and chemical properties of clusters, especially boron, carbon, silicon-based systems, is becoming an expanding research area.

The discovery of C60 carbon buckminsterfullerene molecule and its unique electronic properties has triggered an explosive growth of research in the field of cluster physics. Superconducting and magnetic fullerides, atoms trapped inside the fullerene cage, chemically bonded fullerene complexes have generated much excitement. Since then, much attention has been focused to fabricate small caged clusters of various elements like C, Si, and B. However, small clusters of silicon and carbon ($`n<15`$) do not form stable cage structures. One of the ways of stabilizing these cages is by trapping a foreign atom at the center of the cage. Recent work by Kumar et al demonstrated the feasibility of metal-encapsulation of fullerene-like caged clusters of Si.

On the similar grounds it would be interesting to look at boron cages, since boron and boron-rich compounds exhibit some of the most interesting chemistry of all elements in the periodic table. Atomic boron is the first light element of group III with one $`p`$\- valence electron. It is semiconducting in its bulk phase with low density, very high melting point, and hardness close to that of diamond. Due to $`sp^2`$ hybridization of the valence electron, large coordination number, and short covalent radius, boron prefers to form strong directional bond with various elements.

Boron clusters have been investigated mainly via computer simulation although some experimental results are available. La Placa et al proposed existence of B36N24 cluster with the same structure as that of the fullerene C60. However, the only heteroatomic species that were observed in the experiment were BN and B2N. In contrast, an earlier experiment had detected the existence of BnN$`{}_{}{}^{+}{}_{m}{}^{}`$ for various combination of $`n`$ and $`m`$ for $`n=217`$. Other abundant distribution and fragments of clusters of group III were also found. Rao and Jena carried out a comprehensive theoretical study of the equilibrium geometries, vertical ionization potentials, and the fragmentation patterns of B2-B6 clusters in neutral and singly charged states, as well as the stability of boron-rich clusters, B$`{}_{n}{}^{}X`$; $`n`$=1,5,12;$`X`$=Be,C. They show that the electronic bonding in boron clusters is similar to that in boron-rich solids and is characterized by a three-center bond. In spite of being trivalent element having three centered bonds, a B20 dodecahedron composed of pentagonal faces with each atom being three-fold coordinated, does not exhibit unusual stability. Ab initio investigations of small boron clusters by Boustani reveal that most of the stable structures are composed of two fundamental units: hexagonal or pentagonal pyramids. Hayami has investigated the encapsulation of impurity atoms, from H to Ne, in $`\mathrm{B}_{12}`$ icosahedron. He found that H and Li are most likely to get trapped and stabilize the cage. He also found that the highest occupied molecular orbital(HOMO)-lowest unoccupied molecular orbital(LUMO) gap is largest for C.

Boron exists in various crystalline and amorphous forms of which $`\alpha `$, $`\beta `$ rhombohedral ($`\alpha `$rh and $`\beta `$rh) and $`\alpha `$ tetragonal ($`\alpha `$tet) are well known phases. The $`\alpha `$ and $`\beta `$-rh boron solids are composed of unit cells containing $`\mathrm{B}_{12}`$ icosahedra. The $`\alpha `$-rh boron, also called low temperature or red boron, have high level of crystal purity. The $`\mathrm{B}_{12}`$ icosahedra in this form are slightly distorted which are weakly bound to each other by three-center bonds situated in alternating parallel planes. This leads to weak thermal stability and therefore $`\alpha `$rh boron on annealing at a temperature of about 1200oC transforms into $`\beta `$rh. In contrast, a hypothetical $`\alpha `$rh boron quasicrystal contains two elemental unit cells: a prolate and an oblate, stacked in a quasi-periodic manner. The prolate unit cell in the quasicrystal is slightly distorted which transforms into oblate unit cell to form the quasicrystal. Formation of such icosahedral quasicrystal is also seen in Al-Mn alloy. An interesting question concerns the transformation of the distorted prolate unit cells into oblate unit cell. Takeda et al found that the mechanism of this transition as an inter-penetrating process of the two $`\mathrm{B}_{12}`$ icosahedra lying along the short body diagonal in a prolate cell in the quasicrystal. Boustani and coworkers investigated the fusion of those two $`\mathrm{B}_{12}`$ icosahedra lying along the short body diagonal. Their calculations reveal that a stable drum-like boron cluster can be formed without removing any atoms within the two approaching icosahedra as suggested by Takeda et al. They have considered various configurations of two $`\mathrm{B}_{12}`$ icosahedra connected to each other in different orientation. The optimization and search for local minima was performed with certain symmetry restrictions. The relative stability of these geometries were not compared with the other possible isomers of the 24-atom boron cluster. This is especially important since the geometry most stable isomer of $`\mathrm{B}_{24}`$ could be completely different from the drum-like structure and could be much lower in energy.

In the present work, we address some of these questions concerning fusion of two boron icosahedra and the $`\mathrm{B}_{24}`$ cluster. It is known that the number of isomers on an energy surfaces increases exponentially with the size of the cluster. Since, $`\mathrm{B}_{24}`$ is a medium size cluster, it has a large number of isomers. An interesting aspect of medium size boron cluster is the competition between quasiplanar, tubular and closed structures. The strains in the bonds due to the curvature in the closed structures favors the quasiplanar structure, whereas, the dangling bonds in quasiplanar and convex structures favors the tube and cage isomers. We discuss the energetics, stability and bonding properties in certain representative isomers of the 24-atom boron cluster, followed by the discussion on the process of fusion of two $`\mathrm{B}_{12}`$ icosahedra. Previous reports as well as our investigation reveals that such the fusion results into a closed structure. Although, this structure is stable, it need not be the lowest energy isomer. In order to understand the relative stability of this fused structure, and hence the stability of the quasicrystal, we have investigated the various representative low-lying structure of the 24-atom boron cluster.

In section-II, we describe the numerical method used followed by a discussion of the results in section-III.

## II Theoretical Details

We employ Born-Oppenheimer molecular dynamics (BOMD) based on Kohn-Sham (KS) formulation of density functional theory using damped equation method within the pseudopotential approximation.

The electronic structure and the total energy of the isomers, have been computed using the ultrasoft pseudopotentials within the local density approximation (LDA) and the generalized gradient approximation (GGA) using the VASP package. The Ceperley-Alder exchange-correlation potential for LDA and the Perdew-Wang potential for GGA has been used. The geometries were optimized using the conjugate gradient and the steepest descent method. The size of the simulation cell was varied according to the structure studied.

| Isomer | Simulation Cell (Å) |
| --- | --- |
| Ring 1x24 | 18x18x4 |
| Ring 1x24 | 17x17x11 |
| Tube 3x8 | 14x14x13 |
| Tube 4x6 | 15x15x16 |
| Quasiplanar and Convex | 15x15x10 |
| Cages | 13x13x15 |

The structures were considered to be converged when the forces on each ion was less than 0.01eV/Åwith a convergence in the total energy of about $`10^410^6`$eV.

The fusion of two icosahedra was carried out using the inhouse package. Norm-conserving pseudopotential of Bachelet et al  in Kleinman and Bylander form with $`s`$-part treated as non-local was employed. The exchange-correlation potential by Ceperley-Alder, was used. A cubic supercell of length 40a.u. with an energy cutoff of 21.0 rydberg provided sufficient convergence in the total energy. During the dynamics, the norm of each of the states defined as, $`h\psi _iϵ_i\psi _i^2`$ (where $`ϵ_i`$ being the KS-eigenvalue corresponding to the KS-eigenstate $`\psi _i`$) was maintained at $`10^710^9`$a.u. The final structures were considered to be converged when the forces on all atoms were less than $`10^4`$ to $`10^3`$ a.u.

The nature of the bonding has been investigated using the electron localization function (ELF) along with the charge density. Such ELF have been found to been useful for elucidating the bonding characteristics of a variety of system, especially in conjunction with the charge density. For a single determinantal wavefunction built from KS orbitals $`\psi _i`$, the ELF is defined as

$$\chi _{ELF}=\left[1+\left(\frac{D}{D_h}\right)\right]^1$$

where

$$D=\frac{1}{2}\underset{i}{}\left|\varphi _i\right|^2\frac{1}{8}\frac{\left|\rho \right|^2}{\rho }$$

$$D_h=\frac{3}{10}\left(3\pi ^2\right)^{5/3}\rho ^{5/3}$$

with $`\rho =\rho (𝐫)`$ the valence-electron density. A value of $`\chi _{ELF}`$ nearly 1 represents a perfect localization of the valence electron density.

## III Results and Discussion

The present investigation can be separated into two groups. First, we present results for various isomers of a 24-atom boron cluster which can be classified into: (i) the rings, (ii) the tubes, (iii) the convex and the quasiplanar structures and, (iv) the closed structure isomers of $`\mathrm{B}_{24}`$. Since $`\mathrm{B}_{24}`$ has a large number of isomers, we restrict our study to a certain isomers of the above representative classes. First, we discuss the geometry and the bonding in these isomers computed by GGA, followed by the energetics and stability of these isomers. Finally, we discuss the fusion of two boron icosahedra.

### A Isomers of $`\mathrm{B}_{24}`$

#### 1 Rings

In this section, we present the results for two rings, viz. a monocyclic-ring and a double-ring. In fig.1, we show, the optimized geometry, the isovalued surfaces of the electron localization function, and the total charge density for the HOMO and the LUMO states for the monocyclic-ring. It turns out that this structure is the least stable, and makes an interesting contrast with the most stable structure, viz., the double-ring.

The monocyclic-ring has a diameter of 11.81Å. In spite of being the least stable isomer, the ELF plot, in fig.1b, shows a localized $`p_xp_x`$ $`\sigma `$ bond. It is interesting to examine the behavior of the HOMO state. The HOMO state in the monocyclic ring is doubly degenerate. In fig.1c, we show the charge density for the one of the HOMO state. It can be noted that the $`\pi `$-bond has six spatial nodes. The other HOMO state is similar to this state with a phase shift. As a result, an effective delocalisation of the $`\pi `$ bonds similar to that in benzene  is seen. The difference in the HOMO states of benzene and $`\mathrm{B}_{24}`$ is that in benzene the $`\pi `$ bonds is perpendicular to the plane of the carbon ring, whereas in $`\mathrm{B}_{24}`$, the HOMO is formed by the in-plane $`p_yp_y`$ orbitals. During the formation of benzene molecule, each carbon atom promotes an electron from the 2$`s^2`$ state into the empty 2$`p_z`$ orbital, whereas in boron, an electron from the 2$`s^2`$ state is promoted to the empty 2$`p_y`$ orbital. Thus, the reason for formation of in-plane $`\pi `$ bond in $`\mathrm{B}_{24}`$ is the absence of $`p_z`$ electron. The LUMO state of $`\mathrm{B}_{24}`$ , on the other hand, is out of the ring-plane $`p_zp_z`$(fig.1d).

In fig.2, we show, the optimized geometry, the isovalued surfaces of the electron localization function, and the total charge density for the HOMO and LUMO states for a double-ring. The double ring of diameter of 6.22Å, is composed two ring of 12-atoms each, 1.45Å apart, arranged in a staggered configuration. Each ring is rotated by an angle of $`\pi /12`$ with respect to the other ring in order to form the staggered configuration. It is known that boron, boron-rich compounds and boron clusters exhibit $`sp^2`$ hybridization. Such a staggered double-ring formation, facilitates such an hybridization, thereby making it the most stable structure.

The ELF plot (fig.2b) shows a polarized $`\sigma `$ bond between the atoms in the same ring, the polarization caused by the atoms in the neighboring ring. This is a signature of three-centered boron bond which is a precursor to the bonding in solid state boron. The total charge density (not shown) is also localized in the region between the two rings. The charge-density for the HOMO (fig.2c) and the LUMO (fig.2d) represents a strongly localized $`\pi `$-bond between two atoms. While the HOMO state is a $`\pi `$ bond between an atom of each ring, the LUMO state shows a lateral $`pp`$ overlap between the atoms of both the rings. Similar to the monocyclic ring, the HOMO state in this case is also doubly degenerate, giving rise to an effective delocalization.

It is instructive to analyze the total $`p`$-character in the orbitals as a function of orbital number. In fig.3a and 3b, we show such a plot for the monocyclic and the double-ring, respectively. The character in the orbitals is calculated by projecting the orbitals onto spherical harmonics centered at each ionic sites within a sphere of a specified radius around each ion. The radius of the sphere is usually taken to be half of the distance of the ion from the nearest ion. It can be noted that a monotonic decrease in the amount of $`s`$-character in a monocyclic-ring is seen, whereas, it is oscillatory for the double-ring in the central occupied orbitals. A substantial amount of $`p`$-character in the lower occupied states in the double-ring is seen. This indicates a higher degree of $`sp`$-hybridization. For both the structures, a double degeneracy is seen in most of the occupied states. These states represents resonant structures.

#### 2 Tubes

We discuss three tubes composed of: (a) three planar rings of eight atoms, (b) four planar rings of six atoms, and (c) four rings, each ring consisting of six atoms arranged in a staggered configuration.

In fig.4, we show, the optimized geometry of the tubular drum shaped boron cluster along with the HOMO state, and the ELF. This structure is composed of three rings of eight boron atoms each, with the height of the drum alternating between 2.92Å and 3.01Å. The surface of the drum is made up of an elongated rhombus with the atoms in the central rings coming closer to each other, thereby pushing apart the atoms on the outer rings. This structure has a distorted D4h symmetry. Energetically, this structure is nearly degenerate to the double ring. It has a very small HOMO-LUMO gap (0.3eV as compared to 1.28eV in the double-ring), due to Jahn-Teller distortions. The HOMO state is doubly degenerate, which on distortion gives rise to this small gap. The isovalued plot of the HOMO (fig.4b), shows a bond between an atom of the outermost rings with the two nearest atoms in the central ring along the bonding region, unlike the ring isomers where a $`\pi `$ bond is formed. The peculiar alternating height is due to the characteristic bonding in this structure. The ELF (fig.4c), shows a strong localized bond between the central atoms of the rhombus. The bonds amongst the outer-ring atoms are similar to that of the double-ring, i.e. polarized by the atoms in the central ring.

A four-ring tube with six boron atoms each, is shown in fig.5a. This tube with a small diameter of about 3.0Åis the initial structure. On geometry optimization, the open tubular structure distorts thereby closing both the ends. The optimized geometry is shown in fig.5b. It is seen that the alternate atoms in the outermost rings on either side, approach the center of the ring closing the ends. This structure can also be viewed as a distorted cage, as shown in fig.7b, without the icosahedral closing. It is interesting to note that, despite of $`sp^2`$ hybridization, there is a possibility of getting a 3-d closed structure.

We have also carried out a geometry optimization of a $`\mathrm{B}_{24}`$-D3d open structure. The geometry of this structure is depicted in fig.5c. This structure too undergoes a similar structural transformation into a close D3d boron cage (fig.7b), due to higher bond strains and a large curvature at the open ends. This result is contradictory to that reported by Boustani and coworkers. According to them, the stability of the closed tubular form $`\mathrm{B}_{24}`$-D3d increases when the closed tubular ends rearrange to form an additional ring of 6-atoms, as found within an open tubular structure of $`\mathrm{B}_{24}`$-D6d. This difference is mainly due to the differences in the theoretical approaches. We have done unrestricted geometry optimization, whereas, they have imposed certain symmetry restriction for the minimization. Moreover, we have used density functional method within plane-wave pseudopotential and GGA approximations, whereas, Boustani et al have done an all electron calculations using Hartree-Fock and local spin density functional theory.

#### 3 Quasiplanar and Convex Structures

We present the results for a couple of open structures viz. the quasiplanar and the convex stable isomers of $`\mathrm{B}_{24}`$. According to the Aufbau principle proposed by Boustani, we construct a quasiplanar and a convex structure from the basic unit of a hexagonal pyramid B7. Upon optimization, we find that the LDA computed geometry of the quasiplanar structure is nearly planar. The quasi-planarity comes from the GGA calculations. The GGA-optimized geometry of the quasiplanar structure is shown in fig.6a. Some atoms are raised above the plane while some atoms are shifted below the plane leading to a staggered-like configuration. Thus, even in the open structures, the staggering is preferred. The convex structure, on the other hand, gets distorted by both LDA as well as GGA, although the convexity is maintained. This distorted structure is depicted in fig.6d. It can be noted that both these isomers, the quasiplanar and the convex have nearly similar structure. However, the HOMO state of these structures differ drastically. In fig.6b, we show, the isovalued plot of the HOMO state of the quasiplanar structure at 1/10th of its maximum value. The HOMO state is delocalized within the plane along the bonding region. An excess electron cloud outside the cluster is also seen. This behavior in the HOMO state of the quasiplanar structure can be contrasted with that of the convex structure. In fig.6e, we show, the plot of the HOMO state for the convex structure at 1/6th of the maximum value. It is clear from this plot that the HOMO state is more localized. It represents a $`\pi `$ bond between atoms of the outermost layer, the $`\pi `$ bond being formed on the two sides of the plane of the structure.

In fig.6c and 6f, we plot, the ELF for these two structures, respectively. The nature of the ELF in both the structures is nearly similar. A polarization of the bond between the peripheral atoms is seen in both the cases. A higher degree of polarization in the quasiplanar structure is seen. Moreover, a 3-centered bond is seen in interior atoms in the quasiplanar structure.

#### 4 Closed Structures

In this class we have studied three structures. The geometry of these structures are shown in fig.7a(i), 7b(i) and fig.7c(i). We will refer these closed structures as cage-I, cage-II and cage-III respectively. It is seen that upon formation of closed structure the stability of the boron isomers decreases as compared to that of the most stable isomer. Cage-I (7a(i)) represents two interacting $`\mathrm{B}_{12}`$. It has D3h symmetry. These two icosahedra, on fusion, transforms into a closed tubular form viz. cage-II, shown in fig.7b(i). The fusion process will be discussed later. This structure has the symmetry D3d. In case of cage-II, it is seen that the atoms moves towards the fusion region, thereby decreasing the bond strains in the icosahedral units. This structure is the most stable cage isomer of $`\mathrm{B}_{24}`$. Cage-III shows a different behavior than the other two structures. The first two cages show an icosahedral unit, whereas, cage-III can be visualized as double ring of eight atoms, placed side by side. Each side of this ring is capped by 4 atoms which forms a quinted roof or bend rhombus-like structure. This cage turns out to be the least stable closed isomer of $`\mathrm{B}_{24}`$.

The bonding in the cage-I and II is similar to that of the $`\mathrm{B}_{12}`$ icosahedra except at the fusion region. In fig.7a(ii), fig.7b(ii), fig.7c(ii), we plot the ELF for cage-I through cage-III. It can be seen that in case of cage-I and cage-II, the ELF shows a high localization of the charge in the fusion region of the two icosahedra. A slight delocalization at the tube ends, as compared to the central fusion region, is seen. This shows an affinity of the boron icosahedra to get bonded to each other. On the other hand, the ELF for the cage-III, depicted in fig.7c, shows a three-centered bond between an atom of the quinted roof and two atoms from the octagonal ring. It is interesting to note that such bonding is seen in solid state boron. Thus, in spite of a three-centered bond, the boron clusters does not show enhanced stability.

#### 5 Energetics and Stability

The energetics and the stability of isomers of $`\mathrm{B}_{24}`$ can be explained via the binding energy, content of $`p`$-character in the total density, and the HOMO-LUMO gap. In fig.8a, we plot, the the binding energy per atom for all the isomers studied, computed by LDA and GGA. The binding energy is calculated as $`E_b=E_{atom}E_{B_{24}}/24`$. The trend in the binding energy by both methods is remarkably similar. The GGA gives lower binding energy for all isomers, the shift being nearly identical. The double-ring is the most stable isomer. With the exception of the monocyclic-ring and the cage-III, all the isomers are nearly degenerate to the double-ring. The stability of the isomers can be associated to the amount of $`p`$-character in the total charge density. In fig.8c, we plot, the content of $`p`$-character in the total charge density computed by GGA. The $`p`$-character is calculated by the method discussed above. The amount of $`p`$-character in the total charge density is the sum of all the projection over all the ionic sites. Interestingly, the $`p`$-character plot, nearly follows a similar trend to the binding energy. The least stable structure, viz. the monocyclic-ring, has the least $`p`$-character in the total charge density. Thus, the binding energy is largely influenced by the amount of $`p`$-character contained in the total charge density. It can be noted that due to similar structure, the convex and quasiplanar structures have nearly same binding energy, and the amount of $`p`$-character in the total density. The lower binding energy of the monocyclic-ring is not only a result of lower content of $`p`$-character but also the coordination number. The coordination number for the monocyclic-ring is 2, whereas, it is 4 for the double-ring. Among the closed structure studied, cage-II, is the most stable structure, due to larger content of $`p`$-character. In fig.8d, we plot, the minimum interatomic distances for various isomers. An increase in the interatomic distances in the double-ring is seen over the monocyclic-ring. This is due to increases the coordination number in the double-ring. The strains in the bonds also influences the interatomic distances. In the cage-I and cage-III, due to larger bond strains, the boron atoms moves away from each other, leading to a larger bond distance. As a result their binding energies is lowered.

The HOMO-LUMO gap shows a different behavior. In fig.8b, we plot, the HOMO-LUMO gap for these isomers, computed by LDA and GGA. Unlike the the binding energy, both methods gives nearly same value for the gap, with the exceptions of the double-ring and the isomer shown in fig.5b, where the gap is lowered as expected, and the cage-III, where the gap is increased. The increase in the gap for the cage-III is due to the degenerate HOMO state. Moreover, a wide variation in the gap for various isomers is seen. The drum-shaped isomer (fig.4a), in spite of being nearly degenerate to the most stable structure, the double-ring, exhibits a very small gap due to Jahn-Teller distortion. A similar behavior is also seen for cage-III. The quasiplanar and the convex isomer exhibits nearly same HOMO-LUMO gap.

### B Fusion of Two Boron Icosahedra

As mentioned earlier, an unit cell of $`\alpha `$-rh boron hypothetical quasicrystal consists of a prolate unit cell and an oblate unit cell, stacked in a quasi-periodic manner. The prolate unit cell is slightly distorted which transforms into oblate unit cell. The mechanism of this transformation has been studied by Takeda et al  and Boustani et al . Takeda et al suggests that in order to undergo this transformation, the two icosahedra lying along the short body diagonal in the prolate unit cell should inter-penetrate. Their model also suggests the removal of three interfacing atoms. On the other hand, Boustani et al has shown that there is no need of removing any such atoms. Their investigation reveals that a much stable closed tubular structure is formed upon fusion of the two icosahedra. To get a better insite of the fusion process, as the two icosahedra approaches towards each other, we simulate the process by the following method. Two icosahedra were kept at various distances starting from 5.0a.u. to 8.5a.u., and a linear search for an equivalent local minima was carried out. This distance is defined as the distance between the icosahedral centers. It is assumed that the composite $`\mathrm{B}_{12}`$-$`\mathrm{B}_{12}`$ will take the structures corresponding to these local minima as they approach towards each other. Local geometry minimization was carried out for nine different distances in the above mentioned range. The corresponding total energies, in hartrees, of the equilibrium structures as a function of the distances are plotted in fig.9a. This plot shows a barrier of 5.31eV at a critical distance of 6.5a.u., which the icosahedra has to cross in order to get fused. The composite structure of the two icosahedra sees a local minima just before the barrier. The structure corresponding to this minima is shown in fig.7a(i). It can be seen that the icosahedra are bonded to each other by three bonds. Each black atom of the left icosahedra is bonded to the nearest white atom of the right icosahedra. As the icosahedra moves further towards each other, these six atoms forms a staggered ring-like structure. Such staggering, as discussed earlier, facilitates $`sp^2`$ hybridization, thereby increasing the stability. At the barrier, an intermediate structure during the transition is seen. The geometry of this structure is depicted in fig.9b. Due to strained staggered ring, this structure is unstable. As the icosahedra moves further towards each other, the strains in the ring is reduced finally giving a closed D3d structure, shown in fig.7b(i). A slight rearrangement is seen during the formation of this closed tubular structure. The atoms moves towards the fusion region, consequently reducing the strains in the icosahedral units. This structure is the most stable cage isomer of $`\mathrm{B}_{24}`$ cluster. It is also nearly degenerate to the most stable isomer i.e. the double ring. This structure (cage-II) is about 1.91eV lower than the structure corresponding to the local minima (cage-I) just before the barrier. Thus, the effective barrier as seen by the fused structure is about 7.22eV. As a result, the oblate unit cell becomes much more stable than the prolate unit cell. Hence, the transformation of the prolate unit cell to oblate unit cell enhances the stability of the quasicrystal significantly.

## IV Conclusion

In the present work, we have reported the geometries and the systematics of bonding in various isomers of a 24-atom boron cluster and the fusion of two boron icosahedra using BOMD method within the framework of density functional theory. We find that the monocyclic-ring is the least stable structure. A staggered double-ring formation facilitates the $`sp^2`$ hybridization, thereby making it the most stable structure. Our calculations reveal that a 24-atom boron cluster does form a closed 3-d structures. The bonding analysis shows that a polarization of the bonds between the peripheral atoms is seen in the ring and the planar isomers. The binding energy of all isomers is largely influenced by the amount of $`p`$-character in the total charge density. An interesting observation common to all structures is the staggered arrangement of nearest neighbor atoms. In the rings, the staggering obtained by rotating the alternate rings, while in the open structures it is obtained by moving the atoms out of the plane as well as within the plane. The fusion occurs when the distance between the two icosahedra is less than a critical distance of about 6.5a.u. In order to get fused, the icosahedra has to then cross a barrier of 5.31eV. Such fusion enhances the stability of the quasicrystal significantly.

## V Acknowledgement

We gratefully acknowledge the partial financial assistance from Indo-French Center for Promotion of Advance Research (New Delhi)/Center Franco-Indian Pour la Promotion de la Recherche Advancee. IB gratefully acknowledges the financial support of the Deutsche Forschungsgemeinschaft and the Fonds der Chemischen Industrie. SC gratefully acknowledges the financial support of CSIR (New Delhi) and the local hospitality at the Universität Würzburg Germany.

List of figures

1. (a) The optimized geometry of the monocyclic-ring of 24-boron atoms. (b) The isovalued surface of the ELF at the value 0.75. (c) The isovalued charge density surface of the HOMO state at the value 0.0059$`electron/\AA ^3`$, (d) The isovalued charge density surface of the LUMO state at the value 0.0052$`electron/\AA ^3`$.
2. (a) The optimized geometry of the double-ring of 24-boron atoms. (b) The isovalued surface of the ELF at the value 0.75. (c) The isovalued charge density surface of the HOMO state of the double-ring at the value 0.0075$`electron/\AA ^3`$. (d) The isovalued charge density surface of the LUMO state of the double-ring at the value 0.0091$`electron/\AA ^3`$.
3. The amount of $`s`$ (continuous line) and $`p`$-character (dotted line), in arbitrary units, in various occupied states and the LUMO state as a function of orbital number for, (a) the monocyclic-ring and, (b) the double-ring.
4. (a) The optimized geometry of the drum shaped boron $`\mathrm{B}_{24}`$ cluster composed of three rings of eight boron atoms each. (b) The isovalued charge density surface of the HOMO state at the value 0.0036$`electron/\AA ^3`$. (c) The isovalued surface of the ELF at the value 0.75.
5. (a) The initial geometry of the four-ring tube, each ring formed by 6-boron atoms. (b) The optimized structure. (c) The open tube with D3d symmetry composed of 4-rings of staggered B6.
6. (a) The optimized geometry of the quasiplanar structure. The black circles represents atoms below the plane while the white circles represents atoms above the plane, giving the quasiplanar nature. (b) The isovalued charge density surface of the HOMO state of the quasiplanar structure at the value 0.0017$`electron/\AA ^3`$. This value is 1/10th of the maximum. (c) The isovalued surface of the ELF at the value 0.75. (d) The optimized geometry of the convex structure. The black circles represents atoms above the plane giving the convex nature. Remaining atoms are nearly planar. (e) The isovalued charge density surface of the HOMO state of the convex structure at the value 0.0031$`electron/\AA ^3`$. This value is 1/6th of the maximum. (f) The isovalued surface of the ELF at the value 0.75.
7. The geometries of closed structures: a(i) Cage-I representing two icosahedra interacting by three bond, each bond formed by atoms represented by black and white dots. a(ii) ELF plots for Cage-I at the value 0.75, b(i) Cage-II, the resultant structure of the fusion of two $`\mathrm{B}_{12}`$ icosahedra. A staggered-ring of six atoms (3 white and 3 black) is seen. b(ii) ELF plots for Cage-II at the value 0.75, c(i) Cage-III, composed of two rings of eight atoms each placed side by side, and capped by four atoms on both sides. The four atoms forms a quinted roof-like structure. c(ii) ELF plots for Cage-III at the value 0.75.
8. (a) Binding energy in eV per atom of the various $`\mathrm{B}_{24}`$ isomer computed by LDA and GGA. The dotted line represents the LDA binding energy while the continuous line represents the GGA binding energy. (b) The amount of $`p`$-character in the total density for various isomers computed by GGA. (c) The minimum interatomic distances in various isomers computed by GGA. (d) HOMO-LUMO gap, in eV, of the various $`\mathrm{B}_{24}`$ isomer computed by LDA and GGA. The dotted line represents the LDA gap while the continuous line represents the GGA gap.
9. (a) The total energy (in hartrees) of the clusters composed of two $`\mathrm{B}_{12}`$ icosahedra as they approach towards each other as a function of the inter-icosahedral distance. The arrows marked with (I) and (II) corresponds to the cage-I and cage-II. respectively, while the arrow marked with (T) corresponds to the transition structure (cage-T) depicted in fig.9b. (d) Cage-T, the intermediate structure between cage-I (fig.7a(i)) and cage-II (fig.7b(i)), representing the transition state during the fusion of two icosahedra. It shows an intermediate stage of formation of completely relaxed staggered-ring of six atoms (3 white and 3 black).