Binding energy of gas molecule with two pyrazine molecules as organic linker in metal–organic framework: its theoretical evaluation and understanding of determining factors

Deshmukh, Milind M.; Sakaki, Shigeyoshi

doi:10.1007/s00214-011-1025-6

Cited by 11 publications

(8 citation statements)

References 54 publications

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“…These authors reported that the electrostatic component strongly correlates with σ and r , the dispersion component correlates with a combination of r and MR and the exchange repulsion term correlates well only with r . Similarly, Deshmukh et al found a linear correlation between the z -component of polarizability and the dispersion energy for the complexes of small molecules with the pyrazine dimer system . We have also carried out similar multidimension correlation analysis for the methane complexes in our earlier work .…”

Section: Resultssupporting

confidence: 53%

C–H···π Interactions and the Nature of the Donor Carbon Atom

2014

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The influence of multiple substituents (F, CH3, NO2, CN, Cl, OH and NH2) on the C-H···π interaction in benzene-ethylene complex was investigated using the estimated CCSD(T) method and complete basis set limit. The results were compared with our earlier reported complexes of benzene-acetylene and benzene-methane, thus completing the sp, sp(2) and sp(3) series of C-H donors. The stabilization energy values for multiple fluoro-substituted benzene-ethylene complexes are found to be very close to those of the multiple fluoro-substituted benzene-methane complexes. Expectedly, the stabilization energies for the multiple methyl-substituted benzene-ethylene complexes lie between those of the multiple methyl-substituted benzene-methane and benzene-acetylene complexes. Energy decomposition analysis using the DFT-SAPT method predicts the dispersion energy to be dominant, similar to the benzene-methane complexes. For the symmetrically disubstituted complexes (-OH, -Cl, -NH2, -CN and -NO2), additional C-H···X interaction was observed, possibly due to the angular orientation of the ethylene molecule. Multidimensional correlation analysis between the electrostatic, dispersion and exchange-repulsion with the C-H···π interaction distance (r), Hammett constant (σ) and the molar refractivity (MR) revealed strong correlation between dispersion energy and the C-H···π interaction distance (r) as well as molar refractivity (MR).

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Section: Resultssupporting

confidence: 53%

C–H···π Interactions and the Nature of the Donor Carbon Atom

2014

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“…A simple linear correlation between the polarizability of gas molecules and the dispersion forces in MOFs has been found using quantum mechanics calculations. 48 In order to illustrate the nature of the problem one can assume that the adsorptive is a monoatomic gas and the adsorbent a dielectric medium. Then, the enthalpy change that occurs when a monoatomic gas is adsorbed from a vacuum medium state to a composite medium of polarizability a a and uniform density r is approximately given by 26,49 DH 0 % À 8 hr…”

Section: Discussionmentioning

confidence: 99%

Quantification of the confinement effect in microporous materials

García

Pérez-Pellitero

Jallut

et al. 2013

Phys. Chem. Chem. Phys.

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The confinement effect plays a key role in physisorption in microporous materials and many other systems. Confinement is related to the relationship between the pore geometry (pore size and topology) and the geometry of the adsorbed molecule. Geometric properties of the porous solid can be described using the concepts of Gaussian and mean curvatures. In this work we show that the Gaussian and mean curvatures are suited descriptors for mathematically quantifying the confinement of small molecules in porous solids. A method to determine these geometric parameters on microporous materials is presented. The new methodology is based on the reconstruction of the solid's accessible surface. Then, a numerical calculation of the Gaussian and mean curvatures is carried out over the reconstructed mesh. On the one hand, we show that the local curvature can be used to identify the most favourable adsorption sites. On the other hand, the global mean curvature of the solid is correlated to the heat of adsorption of CO2 and CH4 on several zeolites and MOFs. A theoretical justification for this empirical correlation is provided. In conclusion, our methodology allows for a semi-quantitative estimation of confinement, applicable to any pore geometry, independent of the chemical composition, and without the need for applying a force field.

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“…DFT was used for the low-level region, and the scaled MP2 methods SCS-MP2 and MP2.5 (the arithmetic mean of MP2 and MP3) were used for the high-level regions. The ONIOM(MP2.5:DFT)-calculated binding energy was mainly used for the discussion because the MP2.5 method presents binding energies similar to those obtained using CCSD(T), whereas the binding energy is overestimated in general by the MP2 method . In the DFT calculations, the M06-2X functional was employed because this functional was suggested to evaluate the noncovalent interaction well .…”

Section: Computational Details and Modelsmentioning

confidence: 99%

Absorption of CO₂ and CS₂ into the Hofmann-Type Porous Coordination Polymer: Electrostatic versus Dispersion Interactions

et al. 2013

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Absorption of CO2 and CS2 molecules into the Hofmann-type three-dimensional porous coordination polymer (PCP) {Fe(Pz)[Pt(CN)4]}n (Pz = pyrazine) was theoretically explored with the ONIOM(MP2.5 or SCS-MP2:DFT) method, where the M06-2X functional was employed in the DFT calculations. The binding energies of CS2 and CO2 were evaluated to be -17.3 and -5.2 kcal mol(-1), respectively, at the ONIOM(MP2.5:M06-2X) level and -16.9 and -4.4 kcal mol(-1) at the ONIOM(SCS-MP2:M06-2X) level. It is concluded that CS2 is strongly absorbed in this PCP but CO2 is only weakly absorbed. The absorption positions of these two molecules are completely different: CO2 is located between two Pt atoms, whereas one S atom of CS2 is located between two Pz ligands and the other S atom is between two Pt atoms. The optimized position of CS2 agrees with the experimentally reported X-ray structure. To elucidate the reasons for these differences, we performed an energy decomposition analysis and found that (i) both the large binding energy and the absorption position of CS2 arise from a large dispersion interaction between CS2 and the PCP, (ii) the absorption position of CO2 is mainly determined by the electrostatic interaction between CO2 and the Pt moiety, and (iii) the small binding energy of CO2 comes from the weak dispersion interaction between CO2 and the PCP. Important molecular properties relating to the dispersion and electrostatic interactions, which are useful for understanding and predicting gas absorption into PCPs, are discussed in detail.

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Binding energy of gas molecule with two pyrazine molecules as organic linker in metal–organic framework: its theoretical evaluation and understanding of determining factors

Cited by 11 publications

References 54 publications

C–H···π Interactions and the Nature of the Donor Carbon Atom

C–H···π Interactions and the Nature of the Donor Carbon Atom

Quantification of the confinement effect in microporous materials

Absorption of CO₂ and CS₂ into the Hofmann-Type Porous Coordination Polymer: Electrostatic versus Dispersion Interactions

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Binding energy of gas molecule with two pyrazine molecules as organic linker in metal–organic framework: its theoretical evaluation and understanding of determining factors

Cited by 11 publications

References 54 publications

C–H···π Interactions and the Nature of the Donor Carbon Atom

C–H···π Interactions and the Nature of the Donor Carbon Atom

Quantification of the confinement effect in microporous materials

Absorption of CO2 and CS2 into the Hofmann-Type Porous Coordination Polymer: Electrostatic versus Dispersion Interactions

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Product

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Absorption of CO₂ and CS₂ into the Hofmann-Type Porous Coordination Polymer: Electrostatic versus Dispersion Interactions