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Chemical Physics Letters 414 (2005) 483488 www.elsevier.


The atomization process of endohedrally conned hydrogen molecules

Ruben Santamara *, Jacques Soullard
Instituto de Fsica, UNAM, Theoretical Physics, Circuito de la Investigacion Cien, Ciudad Universitaria Alvaro Obreg, A.P. 20-364, Mexico DF 01000, Mexico Received 9 June 2005; in nal form 19 August 2005

Abstract We investigate the conformations and electronic structure behavior of endohedrally conned hydrogen molecules using density functional theory. An H60 cavity is used to imprison 13H2 molecules. The variation of the connement cage radius leads to dierent compression rates, with the corresponding evolution of the molecular structure, energy, electron density, Mulliken populations, HOMOLUMO gap and ionization potential. At low pressures our results compare favorably with measurements on the crystal. At moderate pressures the hydrogen molecules self-assemble into a stable cluster. In the high pressure range molecular dissociation occurs due to a high population in an antibonding orbital. Our results are of interest in the scientic challenge to achieve the metallic state of hydrogen under pressure. 2005 Elsevier B.V. All rights reserved.

1. Introduction Hydrogen is the most abundant element in the Universe and the simplest element of the periodic table. Nearly everything is known of hydrogen in the gas phase state. Still, hydrogen presents challenges under extreme conditions. For example, by exerting strong pressure, molecular hydrogen is expected to undergo a change from a non-conducting state to a metallic phase [1]. Although progress has been made in understanding the insulatormetal transition, as well as the properties of the metallic state, the investigation reveals the need for more accurate methods to calculate the metallization pressure, energy band gap and crystal structures of hydrogen under pressure. With respect to the insulatormetal transition, it is ignored if the hydrogen atoms in the high pressure range should persist paired, as molecular entities, or if the hydrogen molecules should break into atoms/ions to reach the metallic phase. Also, it is unclear if the transition is gradual or not (see review of [2]). Calculations based on density functional theory
Corresponding author. Fax: +52 5 5622 5015. E-mail addresses: (R. Santamara), soullard@ (J. Soullard). 0009-2614/$ - see front matter 2005 Elsevier B.V. All rights reserved. doi:10.1016/j.cplett.2005.08.099

within the local density approximation (LDA) showed to be insucient to solve the structural problem [3], while calculations beyond the LDA put the metallization pressure about 450 GPa [4], a value which is in agreement with the predicted experimentally [5]. The results obtained with a rst-principles path-integral molecular dynamics method show that quantum uctuations of protons are important in predicting crystal structures [6]. However, an analysis of the low-temperature phase diagram of hydrogen reveals that the structural problem of solid hydrogen remains open [7]. An interesting experimental fact is concerned with the existence of hydrogen molecules at high pressure (316 GPa) [5]. In [8], the binding of a proton pair at high pressures is found as the result of interpair interactions assisted by enhanced Friedel oscillations. In retrospective, there is not a unanimous consent on the phases and structures that hydrogen is supposedly to show. Therefore, it calls our attention to investigate the pressure dependence of the energy, electron density and geometry of hydrogen. Our approach diers from traditional crystal and slab calculations, as we work with a supermolecule model, which consists of a hydrogen cavity compressing a set of hydrogen molecules [9]. In the next section we present the characteristics of the conning cavity and discuss the number


R. Santamara, J. Soullard / Chemical Physics Letters 414 (2005) 483488

of hydrogen molecules to be conned. Section 3 briey presents the method. The subsequent sections are dedicated to analyze the conformation changes and the electronic structure behavior with pressure. The conclusion section summarizes our most important results. 2. A hydrogenic fullerene model The model consists of a fullerene-like cavity made of 60 hydrogen atoms. The purpose of working with an H60 cage is to produce the compression forces over a set of imprisoned hydrogen molecules. We have located 13 hydrogen molecules inside the cavity. The reason to chose 13 of them is because they properly t inside H60, allowing us to reach high compression rates before the cavity atoms start to form bonds with the conned hydrogen particles. The pressure eects are taken into consideration by changing the cavity radius or, in other words, the boundary conditions are imposed by the cavity. The enclosed hydrogen molecules are allowed to relax and achieve a minimum energy structure for each radius of the rigid cavity. The pressure is characterized as a static-cold pressure due to the fact that we do not contemplate the vibrational neither the thermal motion of the nuclei. The nite size of the model only permits to analyze local properties, without taking long-range eects into account like, for example, the lattice vibrations. Our work builds on a previous work [9], where molecular hydrogen was endohedrally conned in H20 and H60 cages. More specically, pressure eects were studied on a single hydrogen molecule inside the H20 cavity. It was also investigated the structural arrangement of 15 hydrogen molecules inside an H60 cage, though only for a single (pressure) cavity radius. The present study extends the previous work by analyzing structural changes of 13 hydrogen molecules under dierent compression rates. The cavity plus the conned molecules are considered all together as a single supermolecule. Clearly, the supermolecule approach allows to track changes in the electronic structure with pressure, at a lower computational cost than other more sophisticated methods. To our best knowledge, the supermolecule model used here is the rst of its kind to investigate pressure eects on a set of hydrogen particles. 3. The method We have recourse to the KohnSham (KS) version of density functional theory (DFT) to determine the conformations and electronic structure behavior with pressure. The KSDFT formalism is applied as for molecules. Since particles under compression show highly inhomogeneous electron clouds, gradient corrections of the Becke-88 and LeeYangParr types are included in the exchange and correlation energy functionals, respectively. The molecular orbitals are of Gaussian type and include polarization terms. We use grids capable to yield an accuracy of 106 au in the numerical integrations of the exchange and correlation potentials. The KSDFT one-electron equa-

tions are solved according to the self-consistent eld approximation with a tight convergence criteria. More details of the method are found in [9,10]. The KSDFT implementation presented here is computationally ecient, allowing repeated application of the method on a supermolecule of shrinking size. However, due to their computational cost, the thermal motions, spinorbit interactions and other eects are not contemplated in the present scheme. The energy of the conned hydrogen molecules is determined by subtracting the cage energy EH60 from the supermolecule energy E13H2 @H60 . This is, for a xed cage radius RH60 , the energy of the 13H2 system is: E13H2 E13H2 @H60 EH60 . We have computed basis set superposition errors (BSSE) according to the counter-poise method. At low densities, such errors increase E13H2 by less than 1%, and at higher densities the BSSE increase slowly. Given the computational cost and negligible contribution of the BSSE, specially for the range of densities we are interested in, we have decided not to include them in the calculations. On the other hand, if we consider that the density of the cage atoms and the density of the conned atoms equally share the space in between (they all are of the same species), then the molecular volume of the imprisoned molecules is calculated as the volume of a sphere with radius Rmol R13H2 RH60 R13H2 =2. where R13H2 is the radius of the 13H2 subsystem. Once the molecular energy and molecular volume are computed from the previous equations for a particular cage radius, the pressure is obtained as the rate of change of E13H2 with Vmol, namely: P DE13H2 =DV mol . Thus, the variation of the cage radius leads to dierent compression rates on 13H2, with corresponding changes in the geometry, molecular energy, electron density and other interesting properties which we now proceed to investigate. 4. The geometrical structure behavior with pressure Whenever the 26 hydrogen atoms were under connement, a cluster was observed to self-assemble. In order to briey analyze the geometrical features of the clusters in terms of the conning cavity radius, the radial distribution function is displayed in Fig. 1. It was computed by measuring the distances from each atom to the cavity center. For the largest connement radius, the hydrogen atoms form molecules whose mass centers (MC) are located on two coaxial rings with vefold symmetry around an axis dened by three molecules (see for example structures in Fig. 1). Alternatively, the cluster presents an icosahedral conguration with a hydrogen molecule at the center. This structure persists up to a volume of 3.53 cm3/mol (connement

R. Santamara, J. Soullard / Chemical Physics Letters 414 (2005) 483488


Fig. 1. Variation of the radial distribution function of hydrogen atoms in terms of the RH60 connement radius. The structures of conned hydrogen clusters are also exhibited (but not the fullerene cages). The pressures corresponding to the given cage radii are 20, 184 and 520 GPa. Bonds appear/disappear when the distance between atoms is lower/greater than 0.74 A. Atoms at the front side appear darker than atoms at the back side.

radius of 3.40 A) and is characterized by the decrease of the bond lengths of all the molecules (refer to curves with solid squares, circles and inset of Fig. 2). If the volume is smaller than 3.53 cm3/mol, the icosahedral conguration disappears and a re-denition of pairs takes place, the cluster

Fig. 2. The variation of the inter- and intra-pair distances of the 13H2 system with the volume. The curve with open diamonds describes the average of the n(n1)/2 distances among the mass centers of the n = 13 hydrogen pairs, while the curve with solid squares and inset describe the average molecular bond length of the 13 hydrogen pairs in terms of the volume. The curve with solid circles describes the bond length of the central molecule.

can still be described as formed by a central molecule and 12 distinct pairs of hydrogen atoms, but for some pairs the distance between atoms becomes greater than that of the free molecule, 0.74 A (curve with solid squares of Fig. 2). These results are consistent with the atomization process of the hydrogen solid proposed by Wigner and Huntington [1], assumed to occur prior to the metallic transition where, presumably, the pressure brings the intermolecular distances close to the intramolecular distances. Our results are also in agreement with the variation of the intramolecular distance in the regime of molecular dissociation as proposed by Loubeyre et al. [11]. The variation of the intramolecular distance is considered the outcome of two competing eects: on the one side, the compression over the molecule progressively decreases its bond length but, on the other side, the electron density overlap together with the nuclear repulsion tend to increase it. Therefore, a minimum in the variation of the H2 molecule bond length is achieved before dissociation (inset of Fig. 2). Still, the cluster as a whole shrinks by reaccommodating its atoms (Fig. 1). In this regard, the distances among the MC of molecules decreases monotonously (curve with open diamonds of Fig. 2). When the cavity radius is further reduced, the atomization process extends in a slowly progressive manner to more hydrogen molecules and the supermolecule model is still considered as made of two parts: a rigid external spherical surface conning a set of 26 hydrogens atoms. Due to the gradual manner in which the atomization process occurs, we cannot associate a particular transition (threshold) pressure. For cavity radii equal or smaller than 2.5 A (volume of 1.55 cm3/mol) the cluster atoms start to integrate to the spherical H60 surface by forming bonds. Our supermolecule model to explore pressure eects is not expected to be valid for cavity radius lower than 2.5 A because boundary eects start to play an important role. This is the reason that in the present work we limit our analysis to cavity radii greater than 2.5 A (or pressures lower than 650 GPa). Unconned clusters of hydrogen molecules have been studied using a dierent method (the quantum path integral Monte Carlo method or QPIMC), where the eect of a low temperature (25 K) was included [12,13]. The cluster geometry that we obtain at the highest connement radius is in agreement with that using QPIMC for 13H2. In both cases, an icosahedral structure is observed and the radial distribution function presents two peaks (one relative to the central molecule and a broader one corresponding, in our case, to the two dierent groups of atoms in the cluster). As our calculation is performed taking no temperature eect into account, our structural prole does not exhibit the softness seen in [12]. Also, if the rigid H60 structure is removed once the 13H2 cluster is stabilized, the latter expands and a minimum is not found, indicating the instability of the 13H2 cluster in free space. At this point, the two calculations are dierent too. We now turn to investigate the evolution of the electronic structure with pressure.


R. Santamara, J. Soullard / Chemical Physics Letters 414 (2005) 483488

5. The electronic structure behavior with pressure The variation of the pressure with volume is exhibited in Fig. 3. The PV curve was derived from the EV curve displayed in the inset. Experimental measurements are depicted for comparison [1416]. The main deviations among the experimental data emerge in the region where the pressure starts rapidly growing. Due to the fact that the data from the experiment have been extrapolated in the high-pressure regime, it is dicult to conclude on

the data showing the correct behavior. In spite of that, our PV curve follows quite closely the measurements of Hemley et al. [14], while the EV curve compares favorably with the quantum Monte Carlo simulations of Ceperley and Alder [17]. We also include curves from [9] corresponding to a single hydrogen molecule conned in an H20 cavity, and 15H2 molecules conned in an H60 cavity. Clearly, our results are compatible with the data obtained from the larger system 15H2@H60. If we follow the indications given in [18] and take the zero-pressure reference volume V0 as 23 cm3/mol, then the elasticity parameters K0 and K 0 0 that better t our PV points are 0.00788 and 15.10986 GPa, respectively. In this regard, our parameterized PV curve is: h i 2=3 1=3 P 3K 0 V =V 0 1 V =V 0  h i 3 0 1=3 K 1 1 V =V 0 exp . 2 0 When we compare the K0 and K 0 0 parameters with those of the system H2@H20 dierences appear, because the single H2 compressed molecule in the H2@H20 system has no interaction with other compressed molecules. In spite of that, the identication of the present elasticity values with physical meaningful values at high pressures is still to be determined through experimentation. In Fig. 4, we show Mulliken populations of the hydrogen cluster under dierent pressures exerted by the H60 cavity. As it is appreciated from the Fig. 4a inset, the cluster as a whole takes charge from its environment, but the charge

Fig. 3. The variation of the pressure and energy with the volume for the 13H2 system. Points due to other theoretical and experimental measurements are depicted for comparison.

Fig. 4. Mulliken charges and density proles of compressed hydrogen. (a) The behavior of Mulliken populations with pressure for the 13H2 system and H60 cavity. (b and c) Mulliken charge of atoms of the cluster and cavity at particular pressures. The rst 60 atoms build the hydrogen cavity and atoms from 61 to 86 conform the hydrogen cluster. Gray shadows delimit regions where the Mulliken charge is equal or lower than 1 and the atom number is equal or lower than 60. (d) Density proles along an internuclear axis with pressure. The proles correspond to an arbitrarily chosen hydrogen molecule, located in one of the hydrogen cluster coaxial rings.

R. Santamara, J. Soullard / Chemical Physics Letters 414 (2005) 483488


uptake is not increased monotonically with the pressure. By analyzing individual atomic populations (Fig. 4b,c plots), it is conrmed that cluster atoms take charge from the cavity atoms (because the average population of any cavity atom is lower than 1). In the low pressure range the charge distribution of the cluster atoms is highly homogeneous and, as the pressure increases, the charge distribution becomes highly inhomogeneous. However, in the high pressure regime, the atoms of the cavity form bonds with the cluster. This explains the decreasing charge uptake of the cluster, the charge inhomogeneity of the atoms of the cluster and cavity, and conrms, from the electronic behavior point of view, that our analysis should be restricted to pressures below 650 GPa. In the Fig. 4d inset we plot electron density proles with pressure. They provide detailed information of the electron spatial redistribution pointed by the Mulliken analysis. We conrm the overall increase of charge by a hydrogen molecule as the pressure increases. Two density cusps are resolved due to a greater charge migration towards nuclear centers than to the binding region. The nature of the charge distribution suggests a high population in the antibonding orbital. As a consequence, an unstable electronic conguration similar to the observed in vacuo like (rg1s) r 1s or u (rg1s) r 1s can develop, leading to the breaking of the u molecule as, in vacuo, the molecular states 1Ru and 3Ru corresponding to the above electronic congurations are dissociative, the 3Ru state dissociates into a pair of hydrogen atoms, while the 1Ru state dissociates into a hydride ion and a proton [19,20]. We have also investigated the dependence of the HOMOLUMO energy gap with the pressure. As the pressure increases a slowly closing gap is observed, for instance at 100 GPa the energy gap is 1.14 eV, while at 520 GPa it is only 0.76 eV. We observe an almost linear variation of the HOMOLUMO energy gap with the density. The equation describing such a behavior is DHOMOLUMO [eV] = 1.55429q [mol/cm3] 1.65721 [eV]. The linear behavior is in agreement with calculations relative to the hydrogen crystal [3,4]. By extrapolating our results a completely closed gap is predicted when q = 1.0662 mol/cm3. On the other hand, the extrapolation of experimental data for the hydrogen crystal indicates a closing of the direct electronic band gap at 0.71 mol/cm3 ([5]). Although our prediction is relevant for the cluster, and not for the crystal [21], our HOMOLUMO gap value should be taken carefully, as it is known that gradient-corrected functionals do not provide the proper asymptotic decay of the electronic potential, thus aecting the gap value. To further investigate this assertion, we have performed calculations on selected cage radii using a hybrid exchange functional, namely, the B3 in conjunction with the LYP correlation functional. The B3 exchange functional has a partial contribution of the exact exchange functional and it was designed to give the proper asymptotic behavior. By using the B3LYP level of DFT theory a closed gap is found at q = 1.8315 mol/cm3, which is substantially dierent to the value obtained at the B88LYP level of

theory. Nevertheless, we should say that the linear behavior of the energy gap is preserved and total energies and geometries remain essentially the same when they are compared in both schemes. In the case of the crystal, the closing of the energy band gap may be associated to the metallic state of hydrogen but, in the case of the cluster, the ionization potential may be a more signicative quantity to explore the metallic state. In this regard, we have computed the ionization potential (IP) at three dierent pressures, in the form IP E13H2 @H60 E 2 @H60 , where the + sign refers to the 13H charged state of the system. At 20, 320 and 520 GPa, the corresponding ionization potentials are 8.36, 7.18 and 6.71 eV. When we compare these values with our computed IP of H2 in vacuo 15.46 eV (the experiment gives 15.37 eV), we conclude that the reduction of the ionization potential as the pressure increases certainly shows the feasibility to achieve the metallic state. 6. Conclusions The investigation of hydrogen under pressure represents an important topic from the fundamental and technological perspectives. In this regard, we have investigated the behavior of 13 imprisoned hydrogen molecules by working with a supermolecule model. The hydrogen molecules selfassemble into a cluster, which becomes stable at pressures dierent from zero. As the pressure increases, several geometrical conformations are adopted by the cluster, from coaxial rings to icosahedral congurations. In the high pressure range we observe the splitting of hydrogen molecules, namely, an atomization process consistent with that predicted by Wigner and Huntington. The electronic structure behavior with pressure was also investigated. Our PV and EV plots show satisfactory agreement with experimental data and more sophisticated computations. A Mulliken population analysis indicates a charge uptake by the hydrogen cluster with the pressure. Electron density proles conrm the charge uptake and point out a greater charge migration towards the nuclear centers than to the binding region. Also, as the pressure increases, a slowly closing HOMOLUMO energy gap and a reducing ionization potential were elucidated. We are not aware of any other molecular simulation where an atomization process has been observed. Finally, the investigation of the unusual electronic behavior of hydrogen under pressure becomes important to rationalize on the early formation of the Universe and for the better understanding of planet formation [22]. Acknowledgements This work is dedicated Dr. Bijan Rao, a pioneer in the investigation of atomic clusters, an excellent researcher and a wonderful friend. We acknowledge helpful discussions with Dr. Salvador Cruz, and allotment of CPU time in the ultra-f PC cluster of IFUNAM.


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