Carbon Nanotube Container: Complexes of C₅₀H₁₀with Small Molecules

Abstract

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.

Perspective: Found in translation: Quantum chemical tools for grasping non-covalent interactions

“…145 Still, SAPT generally remains more costly than variational EDAs and visualization tools (vide infra). The work to improve efficiency has produced the aforementioned XSAPT 116,146 as well as linear-scaling SAPT, 147 but these approaches use modified or semiempirical dispersion expressions.…”

Chiral recognition by fullerenes: CHFClBr enantiomers in the C82cage

“…29 The present study of chiral recognition by a fullerene cage was carried out as a continuation of our calculations on endohedral fullerene complexes. [30][31][32][33] We have shown that C 60 can host only one hydrogen molecule whereas for C 70 we demonstrated the possible existence of both complexes with one or two H 2 guests, 34 the calculated energy difference between them, partly accidentally, was equal to a later determined experimental result. 35 One of the present authors (HD) postulated as early as in 2001 that for applications of endohedral fullerene complexes, efficient synthetic and purification procedures for higher fullerenes are needed.…”

“…The interaction energy was calculated either by the supermolecular (DFT, MP2) or by the perturbational approach. In previous studies, [31][32][33] eqn (1) was utilized with the three energies calculated by either DFT using the B97D or PBE + D3(BJ) functional, 66,67 MP2, or the spin-component-scaled MP2 (SCS-MP2). 68 For all supermolecular calculations, the Boys-Bernardi counterpoise scheme 69 was applied in order to reduce the basis-set superposition errors (BSSE), i.e.…”

Encapsulation of monocyclic carbon clusters into carbon nanotubes: A continuum modeling approach

“…5–9 In addition to having high structural perfection, exceptional electronic, mechanical, optical, thermal, and transport properties, the hollow spaces within the cylindrical structures could be employed for a plethora of purposes in molecular encapsulation such as gas storage and drug delivery. 10–13 The current work is motivated by recent developments in CNT research, wherein CNTs are shown to act as novel porous materials for the adsorption of gases, 14–16 as storage materials for various molecules, 17–19 as potential candidates for targeted drug delivery 20,21 and for the encapsulation of biologically important molecules such as the DNA. 22,23…”