In silico studies on the origin of selective uptake of carbon dioxide with cucurbit[7]uril amorphous material

Sahu, Debashis; Ganguly, Bishwajit

doi:10.1039/c5ra13394g

Cited by 5 publications

(4 citation statements)

References 52 publications

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“…Therefore, it is necessary to recover the adsorbed molecules from the receptor molecule. We have performed the calculations to examine the desorption (inverse of the adsorption process) of the gas molecules ,. The B3LYP–D3/6‐31G(d) calculated desorption energies per gas molecules (i. e., CH 4 and N 2 ) given in Table and .…”

Section: Resultsmentioning

confidence: 99%

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Exploiting CF Bond of Hexafluorocyclohexane and Decafluoroadamantane Systems to Capture Flue Gases: A Computational Study

Pradhan

Ganguly

2017

ChemistrySelect

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The interaction of flue gases (CO 2 , CH 4, and N 2 ) with all-cis 1,2,3,4,5,6-hexafluorocyclohexane(1) and decafluoroadamantane system have been exploited through a systematic computational study to evaluate the capturing efficacy using B3LYP-D3/6-31G(d) level of theory. The DFT results show that 1 is selective for the CO 2 . 1 can adsorb 6 CO 2 molecules with reasonable strength, i. e.,~6.0 to~10.0 kcal/mol. First report with adamantane systems (2, 3), which can adsorb twelve CO 2 molecules with reasonable adsorption energy~À5.0 to À10.0 kcal/mol. Among the three flue gases, CO 2 and CH 4 preferably bind with the polar ÀCÀF bonds whereas N 2 prefers to bind with the ÀCÀH bonds of above systems. The nature of the interaction of CO 2 with these systems has investigated using Atoms In Molecules (AIM), Molecular Electrostatic Potential Surface (MESP), and Energy Decomposition Analysis (EDA) analyses. The dispersive interaction is predominantly responsible for the binding of CO 2 molecule with the ÀCÀF bonds of 1 and AIM calculations also corroborate the noncovalent interactions. The calculated desorption energies suggest that these molecules would be kinetically active to exploit as novel materials to capture flue gases.

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Section: Resultsmentioning

confidence: 99%

“…This geometry has taken from the adsorbed CO 2 molecule with the system 1, A1 (Figure ). The EDA analysis was carried out with M06‐2X/6‐31G(d) level of theory ,. The B3LYP results, in this case, showed erroneous values for such analysis and hence the M06‐2X DFT functional has used.…”

Section: Resultsmentioning

confidence: 99%

Exploiting CF Bond of Hexafluorocyclohexane and Decafluoroadamantane Systems to Capture Flue Gases: A Computational Study

Pradhan

Ganguly

2017

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“…The energy decomposition analysis (EDA) is carried out at the BP86-D3/SDD//B3LYP-D3/TZ2P level using Amsterdam density functional program package. In EDA, the total binding energy (ΔE bind ) is decomposed into four terms, viz., Pauli repulsion (ΔE Pauli ), electrostatic (ΔE elstat ), orbital (ΔE orb ), and dispersion (ΔE disp ) terms [29]. For performing EDA analysis, the DAO guest molecule is considered as one fragment and the metal-Pillarplexes as the other fragment.…”

Section: Computational Detailsmentioning

confidence: 99%

Structure, electronic, inclusion complex formation behavior and spectral properties of pillarplex

Venkataramanan

Suvitha

2017

J Incl Phenom Macrocycl Chem

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systems. The low binding energy, and the physical adsorption of guest molecule and HOMO-LUMO spatial diagram indicates, that the Au and Ag-Pillarplex can be used as reversible host for linear alkanes Complexation of guest engenders frequency shift in the vibrational spectra. Calculated 1 H NMR reveal that guest protons which are closer to the metal sites experience larger shielding possibly due to C-H→LP* metal interaction. The 15 N signal observed for the DAO is nearly identical to that observed for the DAO@ metal-Pillarplex. NBO and AIM analysis indicate that metal centers in host, play a major role in stabilizing the guest inside the cavity than the amino group on the guest molecule.Abstract Electronic structure, vibrational and NMR spectra of metal-Pillarplex (metal = Cu, Ag and Au) and its inclusion complex with 1,8-diaminooctane (DAO) are investigated by using density functional theory. The coordinated metal atoms tune the cavity size and the height of metal-Pillarplex and form a rigid cavity thereby reducing their structural deformation. Cu-Pillarplex undergoes a large deformation both on the host and guest molecule. The calculated Gibbs free energy for the formation of inclusion complex were negative indicating their facile formation at the room temperature. Computed binding energies with various functionals and energy decomposition analysis, shows that dispersion correction is essential in these Electronic supplementary material The online version of this article (

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“…In this regard, CB[ n ]s are employed too as a possible macromolecular host for encapsulating different gas molecules. − Particularly, CB[6] (structure 1 ) was reported to encapsulate CO 2 , , CO, , noble gas atoms, , CH 4 , C 2 H 2 , and larger hydrocarbons . In fact, Kim et al showed that CB[6] adsorbs CO 2 selectively over CO and CH 4 in the solid state.…”

Section: Introductionmentioning

confidence: 99%

Selectivity in Gas Adsorption by Molecular Cucurbit[6]uril

et al. 2016

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The relative preference in adsorption among 19 common gas molecules, namely, C 2 H 2 , C 2 H 4 , C 2 H 6 , CH 4 , X 2 , HX (X = F, Cl, Br), CO 2 , CS 2 , CO, H 2 , H 2 O, H 2 S, N 2 , NO 2 , and NO within the cavity of cucurbit[6]uril (CB[6]) is investigated via density functional theory computations. Energies associated with the dissociation of gas@CB[6] producing CB[6] and gas molecules show the order of the efficacy to be encapsulated within CB[6], C 2 H 2 @CB[6] being the most viable system. However, the dissociation free energy change implies that CB[6] is most efficient in accommodating Cl 2 followed by C 2 H 2 among the considered gas molecules. In general, guest molecules having large surface contact with the host and/or high polarizability and/or having acidic hydrogen to make hydrogen bond with >CO show larger propensity to be encapsulated within CB[6] cavitand. Functionalized CB[6] are better candidates for gas adsorption than CB [6]. However, the nature of functionalization needed to improve the adsorption ability varies with the change in the guest molecule. While full −C 2 H 5 substitution improves C 2 H 2 and CO 2 adsorption ability of CB[6] the most, the −CN functionalized CB [6] is the best candidate to encapsulate C 2 H 4 and C 2 H 6 among the studied −OH, −C 2 H 5 , and −CN substituted analogues. The interaction is mostly of van der Waals type, except in the cases of C 2 H 2 , H 2 O, H 2 S, and HX (X = F, Cl, Br), in which both the electrostatic and dispersion contributions are important owing to the interaction between acidic hydrogen of these guest molecules and oxygen centers of the host moiety.

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In silico studies on the origin of selective uptake of carbon dioxide with cucurbit[7]uril amorphous material

Cited by 5 publications

References 52 publications

Exploiting CF Bond of Hexafluorocyclohexane and Decafluoroadamantane Systems to Capture Flue Gases: A Computational Study

Exploiting CF Bond of Hexafluorocyclohexane and Decafluoroadamantane Systems to Capture Flue Gases: A Computational Study

Structure, electronic, inclusion complex formation behavior and spectral properties of pillarplex

Selectivity in Gas Adsorption by Molecular Cucurbit[6]uril

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