Endohedral Fullerene Complexes and In-Out Isomerism in Perhydrogenated Fullerenes

Dodziuk, Helena

doi:10.1007/978-94-007-0221-9_7

Cited by 6 publications

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“…In view of exciting properties and the prospects of applications, a prediction of stability and properties of endohedral fullerene complexes on the basis of computations seems to be quite important. In particular, the question of how many hydrogen molecules can be hosted by C 60 has drawn the attention of many researchers. , The published theoretical estimations vary from 1 to over 20, while only one H 2 molecule could be inserted in C 60 , and in the synthesized mixture of H 2 @C 70 and 2H 2 @C 70 , the latter complex was present as only a 4% admixture, which agrees well with the results obtained on the basis of a simplified model . An often neglected fact that endohedral fullerene complexes are objects with distinct topological properties is worth mentioning. , …”

Section: Introductionsupporting

confidence: 73%

“…It should be stressed that the calculations of endohedral fullerene complexes present a difficult task since, on the one hand, the systems under study are large and, on the other, weak dispersive interactions stabilizing the complexes with nonpolar or slightly polar guests are poorly described at low-level quantum chemical calculations tractable for such large systems. Earlier studies on endohedral fullerene complexes were summarized in two reviews. , A detailed discussion of published experimental and calculated data on endohedral fullerene complexes involving hydrogen guests has been published recently, applying symmetry-adapted perturbation theory (SAPT) , on H 2 @C 60 , 2H 2 @C 60 , and 2H 2 @C 70 . Therefore, here, only new results for these complexes and those involving complexes with other nonpolar or slightly polar guests will be briefly discussed.…”

Section: Introductionmentioning

confidence: 99%

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Small Molecules in C₆₀and C₇₀: Which Complexes Could Be Stabilized?

Korona

Dodziuk

2011

J. Chem. Theory Comput.

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The recent syntheses of complexes involving some small molecules in opened fullerenes and those of hydrogen molecule(s) in C60 and C70 are accompanied in the literature by numerous computations for endohedral fullerene complexes which cope with the problem of the stability of these complexes. In this contribution, stabilization energies of endohedral complexes of C60 and C70 with H2, N2, CO, HCN, H2O, H2S, NH3, CH4, CO2, C2H2, H2CO, and CH3OH guests have been estimated using symmetry-adapted perturbation theory, which, contrary to the standard DFT and some other approaches, correctly describes the dispersion contribution of the host-guest interactions. On the basis of these calculations, the endohedral complexes with all these guests were found stable in the larger fullerene, while the C60 cage was found too small to host the latter four molecules. Except for H2 and H2CO, a stabilization effect for most guests in the C60 cage is about 30 kJ/mol. For H2 and H2O guests, a typical supramolecular effect is observed; namely, the stabilization in the smaller cage is equal to or larger than that in the larger C70 host. Except for the water molecule where the induction interaction plays a non-negligible role, in all complexes the main stabilization effect comes from the dispersion interaction. The information on the stability of hypothetical endohedral fullerene complexes and physical factors contributing to it can be of importance in designing future experiments contributing to their applications.

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Section: Introductionsupporting

confidence: 73%

Section: Introductionmentioning

confidence: 99%

Small Molecules in C₆₀and C₇₀: Which Complexes Could Be Stabilized?

Korona

Dodziuk

2011

J. Chem. Theory Comput.

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“…In view of energy scarcity and global warming, the application of carbon nanotubes as molecular containers (in particular for H 2 and CO 2 ) has become a hot topic. As discussed in ref , in spite of various claims (see for instance, refs and ), endohedral fullerenes cannot play this role because, even if a molecule would be inserted into the hydrocarbon, one has to destroy the container cage to recover the guest (however, proposals to derivatize C 60 in order to induce the reversible formation of C–H bonds or create huge capsules with complicated openings to be used in hydrogen storage should be mentioned). On the other hand, carbon nanotubes (CNTs) opened at, at least, one end would be a natural solution to the problem of extracting the stored molecule.…”

Section: Introductionmentioning

confidence: 99%

Carbon Nanotube Container: Complexes of C₅₀H₁₀with Small Molecules

Dodziuk

Korona

Lomba³

et al. 2012

J. Chem. Theory Comput.

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The stability of complexes of a recently synthetized (Scott et al. J. Am. Chem. Soc.2011, 134, 107) opened nanocontainer C50H10 with several guest molecules, H2, N2, CO, HCN, H2O, CO2, CS2, H2S, C2H2, NH3, CH4, CH3CN, CH3OH, CH3CCH, 2-butyne, methyl halides, and with noble gas atoms, has been examined by means of symmetry-adapted perturbation theory of intermolecular interactions, which fully incorporates all important energy components, including a difficult dispersion term. All complexes under scrutiny have been found stable for all studied guests at 0 K, but entropic effects cause many of them to dissociate into constituent molecules under standard conditions. The estimation of temperature at which the Gibbs free energy ΔG = 0 revealed that the recently observed (Scott et al. J. Am. Chem. Soc.2011, 134, 107) complex CS2@C50H10 is the most stable at room temperature while the corresponding complexes with HCN and Xe guests should decompose at ca. 310 K and that with CO2 at room temperature (ca. 300 K). In agreement with the ΔG estimation, molecular dynamics simulations performed in vacuum for the CS2@C50H10 complex predicted that the complex is stable but decomposes at ca. 350 K. The MD simulations in CHCl3 solution showed that the presence of solvent stabilizes the CS2@C50H10 complex in comparison to vacuum. Thus, for the complexes obtained in solution the CO2 gas responsible for the greenhouse effect could be stored in the C50H10 nanotube.

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“…The electronic structure of endohedral fullerenes has been widely studied, and the potential for industrial development based on encapsulated metal or semimetal atoms in fullerenes is widely realized. − Previous studies by electronic structure methods usually focused on the ground electronic states at their equilibrium molecular structures, with less attention to global or semiglobal features of the ground or excited state potential energy surfaces. Here we consider the nature of intersecting low-energy electronic states that provide accessible mechanisms for altering charge distribution and are responsible for some unique properties of endohedral fullerenes.…”

mentioning

confidence: 99%

Atom-Cage Charge Transfer in Endohedral Metallofullerenes: Trapping Atoms Within a Sphere-Like Ridge of Avoided Crossings

Tishchenko

Truhlar

2013

J. Phys. Chem. Lett.

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Endohedral fullerences have great potential for a variety of techological applications. Here we consider B@C60 and show that the amount of charge transfer from the semimetal boron atom to the cage is a strong function of the radial distance of the atom from the center of the fullerene, and it is controlled by multistate conical intersections whose associated ridge of avoided crossings has the topology of a Euclidean sphere. The potential energy surfaces of B@C60 are characterized by two kinds of local minima: those with a boron atom located in the geometric center of the fullerene, and those with a boron atom bound to the fullerene inner wall. At the lowest-energy minimum, at the center, the boron atom is neutral, whereas the transition to the wall is accompanied by an electron transfer from boron to the fullerene cage. The two kinds of minima are separated by a ridge of avoided crossings that forms a surface with a nearly spherical shape. The properties of such systems may be altered by controlling the populations of the two kinds of minima, for example, by application of an external field. Such switchable atom-cage charge transfer may find applications in novel molecular devices.

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Endohedral Fullerene Complexes and In-Out Isomerism in Perhydrogenated Fullerenes

Cited by 6 publications

References 271 publications

Small Molecules in C₆₀and C₇₀: Which Complexes Could Be Stabilized?

Small Molecules in C₆₀and C₇₀: Which Complexes Could Be Stabilized?

Carbon Nanotube Container: Complexes of C₅₀H₁₀with Small Molecules

Atom-Cage Charge Transfer in Endohedral Metallofullerenes: Trapping Atoms Within a Sphere-Like Ridge of Avoided Crossings

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Endohedral Fullerene Complexes and In-Out Isomerism in Perhydrogenated Fullerenes

Cited by 6 publications

References 271 publications

Small Molecules in C60and C70: Which Complexes Could Be Stabilized?

Small Molecules in C60and C70: Which Complexes Could Be Stabilized?

Carbon Nanotube Container: Complexes of C50H10with Small Molecules

Atom-Cage Charge Transfer in Endohedral Metallofullerenes: Trapping Atoms Within a Sphere-Like Ridge of Avoided Crossings

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Product

Resources

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Small Molecules in C₆₀and C₇₀: Which Complexes Could Be Stabilized?

Small Molecules in C₆₀and C₇₀: Which Complexes Could Be Stabilized?

Carbon Nanotube Container: Complexes of C₅₀H₁₀with Small Molecules