Theoretical study of host-guest interaction and its manifestations in the properties of model endohedral fullerenes with small covalent molecules inside the C n and C n H m cages

Чаркин, О. П.; Клименко, Н. М.; Charkin, Dmitri O.; Mebel, Alexander M.; Lin, Sheng Hsien

doi:10.1134/s0036023606130018

Cited by 18 publications

(36 citation statements)

References 45 publications

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“…Several masses are markedly depleted, but the type of dramatic etching seen with HI is not occurring. The most striking depletions occur at Al 15 Ϫ , Al 18…”

Section: Al N à ¿Himentioning

confidence: 97%

“…Theoretical predictions of superatomic salt formation 4 -7 have fueled much research in this area, and with increasing frequency, various synthetic techniques have been applied to the realization of aluminum-based cluster-assembled materials. [8][9][10] While many studies involving the doping of Al clusters with electropositive atoms have supported the conceptual basis for superatomic cluster assembly, [11][12][13][14][15][16][17] no true saltlike materials have yet been built from bare clusters mimicking atoms. The utilization of superatoms in materials synthesis will ultimately provide a third dimension to the traditional periodic table of elements, representing an entirely new generation of nanostructured materials.…”

Section: Introductionmentioning

confidence: 99%

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Formation and properties of halogenated aluminum clusters

Bergeron

Castleman

Morisato

2004

The Journal of Chemical Physics

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The fast-flow tube reaction apparatus was employed to study the halogenation of aluminum clusters. For reactions with HX (X=Cl, Br, and I), acid-etching pathways are evident, and we present findings for several reactions, whereby Al(n)X(-) generation is energetically favorable. Tandem reaction experiments allowed us to establish that for Al(n)Cl(-), Al(n)I(-), and Al(n)I(2) (-), species with n=6, 7, and 15 are particularly resistant to attack by oxygen. Further, trends in reactivity suggest that, in general, iodine incorporation leaves the aluminum clusters' electronic properties largely unperturbed. Ab initio calculations were performed to better interpret reaction mechanisms and elucidate the characteristics of the products. Lowest energy structures for Al(13)X(-) were found to feature icosahedral Al(13) units with the halogen atom located at the on-top site. The charge density of the highest occupied molecular orbital in these clusters is heavily dependent on the identity of X. The dependence of reactivity on the clusters' charge state is also discussed. In addition, we address the enhanced stability of Al(13)I(-) and Al(13)I(2) (-), arguing that the superhalogen behavior of Al(13) in these clusters can provide unique opportunities for the synthesis of novel materials with saltlike structures.

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“…Several masses are markedly depleted, but the type of dramatic etching seen with HI is not occurring. The most striking depletions occur at Al 15 Ϫ , Al 18…”

Section: Al N à ¿Himentioning

confidence: 97%

Section: Introductionmentioning

confidence: 99%

Formation and properties of halogenated aluminum clusters

Bergeron

Castleman

Morisato

2004

The Journal of Chemical Physics

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“…48 Noteworthy is that the CH 4 @C 60 is predicted to be unstable also by DFT if empirical dispersion corrections are not used. 30,31 The non-dispersive correction due to electron correlation was small and repulsive (∆E C non−disp = +1.00 kcal/mol). As expected, London dispersion is the dominant intermolecular interaction mechanism.…”

Section: Dlpno-ccsd(t)-led Repulsion Stabilizationmentioning

confidence: 99%

“…Harmonic vibrational frequencies of the endohedral CH 4 @C 60 complex have been computed at the level of GGA and hybrid DFT approximations without using dispersion corrections, 30,31 and at the Hartree-Fock level of theory. 32 Hence, those frequencies were evaluated on structures corresponding to energy minima in situation where London dispersion interactions had not been accounted for.…”

Section: Spectroscopic Properties Of the Ch 4 @C 60 In Ir And Uv-vismentioning

confidence: 99%

“…21 Substantial theoretical efforts have directed to studies of C 60 endohedral complexes and associated intermolecular interactions. Pioneering ab initio studies by Jerzy Cioslowski [22][23][24] at the Hartree-Fock (HF) level of theory were expanded by studies of Bühl et al 25,26 , Patchkovskii et al 27 , Darzynkiewicz et al, 28 and Autschbach et al 29 among others, [30][31][32][33][34][35] where density functional theory (DFT) and secondorder Møller-Plesset perturbation theory (MP2) were used. However, within the supermolecular approach with the interaction energy being the arithmetic relation of related energies (E int = E AB − (E A + E B )), DFT is essentially blind to long-range dispersion.…”

Section: Introductionmentioning

confidence: 99%

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Local Energy Decomposition Analysis and Molecular Properties of Encapsulated Methane in Fullerene (CH4@C60)

Jaworski

Hedin²

2021

Preprint

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Methane has been successfully encapsulated within cages of C60 fullerene, and it is an appropriate model system to study confinement effects. Its chemistry and physics is also relevant for theoretical model descriptions. Here we provided insights into intermolecular interactions and predicted spectroscopic responses of the CH4@C60 complex and compared with results from other methods and with literature data. Local energy decomposition analysis (LED) within the domain-based local pair natural orbital coupled cluster singles, doubles, and perturbative triples (DLPNO-CCSD(T)) framework was used, and an efficient protocol for studies of endohedral complexes of fullerenes is proposed. This approach allowed us to assess energies in relation to electronic and geometric preparation, electrostatics, exchange, and London dispersion for the CH4@C60 endohedral complex. The calculated stabilization energy of CH4 inside the C60 fullerene was −13.5 kcal/mol and its magnitude was significantly larger than the latent heat of evaporation of CH4. Evaluation of vibrational frequencies and polarizabilities of the CH4@C60 complex revealed that the infrared (IR) and Raman bands of the endohedral CH4 were essentially “silent” due to dielectric screening effect of the C60, which acted as a molecular Faraday cage. Absorption spectra in the UV-Vis domain and ionization potentials of the C60 and CH4@C60 were predicted. They were almost identical. The calculated 1H/13C NMR shifts and spin-spin coupling constants were in very good agreement with experimental data. In addition, reference DLPNO-CCSD(T) interaction energies for complexes with noble gases (Ng@C60 ; Ng = He, Ne, Ar, Kr) were calculated. The values were compared with those derived from supermolecular MP2/SCS-MP2 calculations and estimates with London-type formulas by Pyykkö and coworkers [Phys. Chem. Chem. Phys., 2010, 12, 6187-6203], and with values derived from DFT-based symmetry-adapted perturbation theory (DFT SAPT) by Hesselmann & Korona [Phys. Chem. Chem. Phys., 2011, 13, 732-743]. Selected points at the potential energy surface of the endohedral He2@C60 trimer were considered. In contrast to previous theoretical attempts with the DFT/MP2/SCS-MP2/DFT-SAPT methods, our calculations at the DLPNO-CCSD(T) level of theory predicted the He2@C60 trimer to be thermodynamically stable, which is in agreement with experimental observations.

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