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Hydrogen storage capacity of Be@C115 system

Lemi Trker* and Seluk Gm Middle East Technical University, Department of Chemistry, Inonu Bulvari, 06531 Ankara, Turkey

Abstract Semiempirical quantum chemical analysis of a Be doped single-walled, semicapped, armchair type nanotube, Be@C115, was achieved at the level of PM3 (RHF) type calculations for some of its quantum chemical properties and hydrogen storage capacity. The Be@C115 system was found to be capable of storing 1-5 hydrogen molecules as endohedral dopant(s), whereas the sixth hydrogen molecule was expelled out. All the structures, (Be+nH2)@C115 were found to be stable and endothermic. Moreover, the increasing number of hydrogen molecules seemed to be stabilizing. Keywords: Nanotubes; Fullerenes; Endohedral doping; Hydrogen storage; Beryllium 1. Introduction Endohedral doping is the addition of an atom or ion into the interior hollow core of a fullerene molecule to form an endofullerene [1]. Some fullerenes having endohedrally doped atoms (including certain gases and solids) have been synthesized in the past [1]. He, Ne, La, Sc and even U doped C60 and like systems are to be mentioned. Since, the participants in these structures, namely the fullerene cage and the endohedrally doped atom(s)/ion(s) or molecules constitute a composite potential field. The resultant endohedrally doped fullerenes usually should have interesting chemical and physical properties. Some quantum chemical studies on endohedrally doped fullerenes have been reported [212]. Fullerenes depending on their sizes have a limited capacity to hold certain number of endohedral substituents. In some cases, after insertion of the dopants up to a certain number, some moderately strong interaction occurs in between the dopant(s) and the cage [12] or between different kinds of dopants (such as Li and hydrogen [8] or Be and hydrogen [7]). On the other hand, the field of carbon nanotubes is marked by the publication of Iijima on the observation of multi-walled nanotubes [13]. They are fascinating materials with nanometer

dimensions promising exciting new areas of carbon chemistry and physics. From the viewpoint of fullerene science they are also interesting because they are forms of giant fullerenes [14] known as tubular fullerenes [1]. Formally, carbon nanotubes and fullerenes have a number of common features and also many differences. The single-walled tubules are cylindrical in shape, either infinite in length or with caps at each end, such that the two caps can be joined to form a fullerene. Various forms of nanotubes are possible, such as armchair, zigzag and chiral tubules [1]. Hydrogen adsorption capacity of carbon nanotubes and alkali metal-doped carbon nanotubes were experimentally studied [1517]. In the present study, a single-walled, oneend capped (semicapped), endohedrally Be doped nanotube, Be@C115 (which is yet nonexistent) has been investigated theoretically for some of its quantum chemical properties and hydrogen storage capacity. 2. Method The geometry optimizations of all the structures leading to energy minima were achieved by using PM3 selfconsistent fields molecular orbital (SCF MO) [18,19] method at the restricted Hartree-Fock (RHF) level [20]. The optimizations were obtained by the application of MM+ molecular mechanics method then by PM3 treatment involving the steepest-descent method followed by conjugate gradient methods, Fletcher-Rieves and Polak-Ribiere, consecutively (convergence limit of 4.18x10-4 kJ/mol (0.0001 kcal/mol) and RMS gradient of 4.18x107 kJ/(mmol) (0.001 kcal/(amol))). All these computations were performed by using the Hyperchem (release 5.1) package program [21]. 3. Results and discussion In the present treatise, the initial structure of the tube C115 was constructed starting from C60 [(5,6)-fullerene-60-Ih] which was excerpted from the Hyperchem Library [21]. The halves of C60 structure were suitably used as the caps of an armchair type tube having 10 benzenoid rings as the peripheral belt. The resultant tube possesses 120 carbon atoms and both ends are closed. Then, a polar pentagon from one of the caps was removed with all its bonds which results in C115 semicapped nanotube. Finally, a Be atom was inserted as an endohedral dopant to yield Be@C115 system having 462 electrons located in 231 doubly occupied orbitals of total 464 orbitals. The removal of polar pentagon in the present treatment generated a bag-like nanotube (nanovesicle, Fig. 1) and should have some interesting properties.

Fig. 1 shows the presently considered (Be+nH2)@C115 systems (n: 0, 1, 5 and 6). Actually the sixth hydrogen molecule cannot be accommodated endohedrally. Although, initially it was placed inside the tube, during the geometry optimization process it was expelled out. Note the position of the Be atom in that case which is nearby the capped side of the tubular cavity. The position of hydrogen molecule in each case is almost along the tubular axis. The Be@C115 system constitutes a positive electrostatic potential field more dense on the outer surface (Fig. 2) whereas at the orifice a peculiar shaped negative potential field is generated which has more protuberant inner zone in the case of n: 6. At the base of this hump-like zone, sixth hydrogen molecule resides. At the first sight, this sixth hydrogen, which is outside the tube, could be considered as free from the cage system. However, the three-dimensional electrostatic field maps (Fig. 2) as well as energetic of the system reveal that it is coupled to the cage system. Table 1 shows some calculated energies of the systems presently considered. The data in the table show that all these systems are thermodynamically stable (the total and binding energies) but endothermic (the heat of formation values) in character. The interesting point is that as the number of hydrogens increases the composite system gets more and more stable and less endothermic. Normally, one anticipates the pronouncing effect of repulsive energies as the hydrogens crowd in the tubular cavity. However, this is not the case. The reason for it is due to shift of position of Be atom towards the interior surface of the cage due to hydrogen population (see Fig. 2). When it is viewed in the direction of tubular axis, Be atom seems to be almost at the center of the pentagon in the case n: 0 and 1 whereas it is shifted to a side for n: 5 and 6. There might be some sort of interaction between the cage and Be atom such that the overall effect totally stabilizing as n increases. Fig. 3 displays the HOMOs of the systems. As seen there, (n: 5 and 6 cases) carbon atoms mainly at the Be side contribute to the HOMO but atoms at the opposite side contribute nil or little. It is also an indication of the presence of some interaction between the cage and the dopant(s). Table presently considered. Whereas the Fig. 4 stands for the LUMOs of the species 2 displays the HOMO and LUMO molecular orbital energy spectra are shown in Fig. 5. The range of molecular orbital energies of the systems. energies are shown in Table 3. The variation of the frontier molecular orbital energies with the number of hydrogens do not exhibit any regular trend. Note that the present treatments consider these systems in vacuum conditions. Probably exertion of a certain pressure enables one to

accommodate more hydrogen molecules in the tubular cavity and release of the external pressure then should cause rapid evolution of hydrogen gas from these nanovesicles. 4. Conclusion Hydrogen is a new clean energy source but the storage and safety problems are the main disadvantages because of its easier burning. The discovery of new type materials having nanometer and subnanometer size opened new horizons so that excellent hydrogen storage media compared to the traditional hydrogen storage systems could be obtained. The present treatment puts some light to these yet nonexistent systems to explore their hydrogen storage capacities as well as some quantum chemical properties.

FIGURE CAPTIONS Figure 1: The geometry optimized structures of the systems of present concern. Figure 2: Three-dimensional electrostatic field maps of the structures. Figure 3: The HOMOs of the structures. Figure 4: The LUMOs of the structures. Figure 5: The molecular orbital energy spectra of the structures.

References

[1] M.S. Dresselhause, G. Dresselhaus, P.C. Eklund, Science of Fullerenes and Carbon Nanotubes, Academic Press, New York, 1996. [2] L. Trker, J. Mol. Struct. (Theochem) 668 (2004) 225. [3] L. Trker, J. Mol. Struct. (Theochem) 680 (2004) 165. [4] L. Trker, S. Gm, J. Mol. Struct. (Theochem) 681 (2004) 21. [5] L. Trker, . Erko, J. Mol. Struct. (Theochem) 638 (2003) 37. [6] L. Trker, Int. J. Hydrogen Energy 28 (2003) 1115. [7] L. Trker, J. Mol. Struct. (Theochem) 577 (2002) 205. [8] L. Trker, Int. J. Hydrogen Energy 28 (2003) 223. [9] L. Trker, J. Mol. Struct. (Theochem) 624 (2003) 233. [10] L. Trker, J. Mol. Struct. (Theochem) 588 (2002) 127. [11] L. Trker, S. Gm, J. Mol. Struct. (Theochem) 674 (2004) 15. [12] L. Trker, J. Mol. Struct. (Theochem) 619 (2002) 135. [13] S. Iijima, Nature (London) 354 (1991) 56. [14] H.W. Kroto, J.R. Heath, S.C. OBrien, R.F. Curl, R.E. Smalley, Nature 318 (1985) 162. [15] P. Chen, X. Wu, J. Lin, K.L. Tan, Science 285 (2) (1999) 91. [16] X.B. Wu, P. Chen, J. Lin, K.L. Tan, Int. J. Hydrogen Energy 25 (3) (2000) 261. [17] C. Liu, Y.Y. Fan, M. Liu, H.T. Cong, H.M. Cheng, M.S. Dresselhause, Science 286 (5) (1999) 1127. [18] J.J.P. Stewart, J. Comput. Chem. 10 (1989) 209. [19] J.J.P. Stewart, J. Comput. Chem. 10 (1989) 221. [20] A.R. Leach, Molecular Modelling, Longman, Essex, 1997. [21] Hyperchem, Hypercube Inc., Gainesville, FL.

Tables

Table 1 Some calculated energies of the species considered (Energies in kJ/mol, n, number of hydrogen molecules).

Table 2 The HOMO and LUMO energies of the presently considered structures (Energies in 10-19 J. Symmetries in parenthesis).

Table 3 The range of molecular orbital energies (Energies in 10-19 J. LOMO, the lowest occupied molecular orbital; HUMO, the highest unoccupied molecular orbital).

Figures

Figure 1

Figure 2

Figure 3

Figure 4

Figure 5