Confinement of (HF)2 in C  (n= 60, 70, 80, 90) cages

Khatua, Munmun; Pan, Sudip; Chattaraj, Pratim Kumar

doi:10.1016/j.cplett.2014.10.025

Cited by 13 publications

(9 citation statements)

References 35 publications

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“…The effect of confinement on the weak non-covalent type interactions present in different chemical and biological systems may affect the stability, properties, and dynamics of these systems. 26 Ng dimers (Ng 2 ) confined in the C 60 cage [27][28][29] show a shorter Ng-Ng distance than that in the free dimer. In fact, Krapp and Frenking 27 showed the formation of a 'genuine' Ng-Ng chemical bond for Ng = Ar-Xe inside the C 60 cavity, whereas in the cases of He and Ne there are only very weak interactions between them.…”

Section: Introductionmentioning

confidence: 97%

Noble gas encapsulated B₄₀cage

Pan

Ghara

Kar

et al. 2018

Phys. Chem. Chem. Phys.

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The efficacy of B borospherene to act as a host for noble gas atoms is explored via density functional theory based computations. Although the Ng@B complexes are thermochemically unstable with respect to dissociation into free Ng and B, it does not rule out their viability as all the systems possess a high activation free energy barrier (84.7-206.3 kcal mol). Therefore, once they are formed, it is hard to take out the Ng atom. Two Ng atoms can also be incorporated within B for the lighter Ng atoms (He and Ne). In fact, the destabilization offered by the encapsulation of one and two He atoms and one Ne atom inside B is significantly less than that in experimentally synthesized He@CH, highlighting their greater possibility for synthesis. Although Ar and Kr encapsulated B systems are very much destabilized by the repulsive interaction between Ng and B, an inspection of the bonding situation reveals that the confinement can even induce some degree of covalent interaction between two otherwise non-bonded Ng atoms. Ng atoms transfer electrons towards B which is smaller for lighter Ng atoms and gradually increases along He to Rn. Even if the electrostatic interaction between Ng and B is the most predominant term in these systems, the extent of the orbital interaction is also considerable. However, the very large Pauli repulsion counterbalances the attractive interaction, eventually turning the interaction repulsive in nature. Ng@B also shows dynamical behaviour involving continuous exchange between hexagonal and heptagonal holes, similar to the host cage, as understood from the very little variation in the activation barrier because of the Ng encapsulation. Furthermore, sandwich complexes like [(η-CMe)Fe(η-B)] and [(η-CMe)Fe(η-B)] are noted to be viable with the latter being slightly more stable than the former. The encapsulation of Xe slightly improves the dissociation energy associated with the decomposition into Xe@B and [Fe(η-CMe)] compared to that in the bare one.

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Section: Introductionmentioning

confidence: 97%

Noble gas encapsulated B₄₀cage

Pan

Ghara

Kar

et al. 2018

Phys. Chem. Chem. Phys.

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“…There does not seem to be any concrete experimental evidence for the displacement of the guest atom from the centre of the cage, orientation of a molecule within the cage and the interaction energy. However, different computational methods have been used to study the effect of confinement on the electronic structure of the atom/ion/molecule/cluster and the interaction energy of such endohedral complexes [23–32] . Ramachandran and Sathyamurthy reported the stability of water clusters and the breaking of hydrogen bonds between them in a confined, non‐polar environment [33] .…”

Section: Introductionmentioning

confidence: 99%

Improved Estimates of Host‐Guest Interaction Energies for Endohedral Fullerenes Containing Rare Gas Atoms, Small Molecules, and Cations

Saroj

Ramanathan

Mishra³

et al. 2022

ChemPhysChem

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Endohedral fullerenes have evinced much interest from the fundamental and applications points of view. However, given the nature of the weak interaction between the guest species and the host cage in these confined systems, the interaction energy values obtained using various theoretical methods, and different basis sets vary over a wide range. For example, the reported interaction energy for the HF@C 60 system ranges from À 2.5 kcal/mol to À 14.9 kcal/mol. In the present manuscript, we report reliable interaction energy values for different endohedral fullerenes (He

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“…The influence of encapsulation on the hydrogen bond strength in (HF) 2 within the fullerene cages is studied using DFT and ab initio MD (Khatua et al, 2014b). The optimized geometries of (HF) 2 @C n (n 60, 70, 80, 90) complexes wB97X-D/6-31G are depicted in Figure 15.…”

Section: (Hf) 2 Confinement In Fullerene Cagesmentioning

confidence: 99%

“…It brings out interesting changes in the energy levels of the confined systems, their bonding, reactivity, and properties (Grochala et al, 2007;Schettino and Bini, 2007;Sabin and Brandas, 2009;Gubbins et al, 2011;Chakraborty and Chattaraj, 2019;Pal and Chattaraj, 2021). Khatua et al (2014b) have performed a theoretical investigation on the entrapment of (HF) 2 in C n (n 60, 70, 80, 90) cages. Although CO and N 2 are isoelectric species, the latter is known to be pretty inert owing to its high ionization potential, low electron affinity, and high frontier orbital energy gap (ΔE HOMO-LUMO ).…”

Section: Introductionmentioning

confidence: 99%

Atomic Clusters: Structure, Reactivity, Bonding, and Dynamics

2021

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Atomic clusters lie somewhere in between isolated atoms and extended solids with distinctly different reactivity patterns. They are known to be useful as catalysts facilitating several reactions of industrial importance. Various machine learning based techniques have been adopted in generating their global minimum energy structures. Bond-stretch isomerism, aromatic stabilization, Rener-Teller effect, improved superhalogen/superalkali properties, and electride characteristics are some of the hallmarks of these clusters. Different all-metal and nonmetal clusters exhibit a variety of aromatic characteristics. Some of these clusters are dynamically stable as exemplified through their fluxional behavior. Several of these cluster cavitands are found to be agents for effective confinement. The confined media cause drastic changes in bonding, reactivity, and other properties, for example, bonding between two noble gas atoms, and remarkable acceleration in the rate of a chemical reaction under confinement. They have potential to be good hydrogen storage materials and also to activate small molecules for various purposes. Many atomic clusters show exceptional opto-electronic, magnetic, and nonlinear optical properties. In this Review article, we intend to highlight all these aspects.

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Confinement of (HF)2 in C (n= 60, 70, 80, 90) cages

Cited by 13 publications

References 35 publications

Noble gas encapsulated B₄₀cage

Noble gas encapsulated B₄₀cage

Improved Estimates of Host‐Guest Interaction Energies for Endohedral Fullerenes Containing Rare Gas Atoms, Small Molecules, and Cations

Atomic Clusters: Structure, Reactivity, Bonding, and Dynamics

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Confinement of (HF)2 in C (n= 60, 70, 80, 90) cages

Cited by 13 publications

References 35 publications

Noble gas encapsulated B40cage

Noble gas encapsulated B40cage

Improved Estimates of Host‐Guest Interaction Energies for Endohedral Fullerenes Containing Rare Gas Atoms, Small Molecules, and Cations

Atomic Clusters: Structure, Reactivity, Bonding, and Dynamics

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Noble gas encapsulated B₄₀cage

Noble gas encapsulated B₄₀cage