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Impact of ligands on adsorption in metal-organic frameworks: First principles study of the interaction of with functionalized benzenes. I. Inductive effects on the aromatic ring
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10.1063/1.3120909
/content/aip/journal/jcp/130/19/10.1063/1.3120909
http://aip.metastore.ingenta.com/content/aip/journal/jcp/130/19/10.1063/1.3120909

Figures

Image of FIG. 1.
FIG. 1.

DFT-optimized most stable configuration of the molecular complex .

Image of FIG. 2.
FIG. 2.

The three stable conformations, obtained by DFT optimization, of the molecular complex .

Image of FIG. 3.
FIG. 3.

DFT-optimized stable configurations of the molecular complex . In dimer C the reported distance of 3.427 Å refers to .

Image of FIG. 4.
FIG. 4.

DFT-optimized stable configurations of the complex .

Image of FIG. 5.
FIG. 5.

DFT-optimized stable configurations of the complex .

Image of FIG. 6.
FIG. 6.

DFT-optimized stable configurations of the complex .

Image of FIG. 7.
FIG. 7.

Electrostatic potential map around the molecular complex (dimer B). The color legend illustrates values of the electrostatic field. (Color code: blue—negative potential; yellow and red—positive potential).

Image of FIG. 8.
FIG. 8.

DFT-optimized stable configurations of the complex .

Image of FIG. 9.
FIG. 9.

DFT-optimized stable configurations of the complex .

Image of FIG. 10.
FIG. 10.

(a) Delocalized charge on the aromatic carbon atoms , plotted as a function of the substituent groups. (b) Effect of the number of substituent groups on the stability of the aromatic ring, considering only the ring top configurations of these complexes. (Electron-donating groups shown in black; electron-withdrawing in blue.)

Image of FIG. 11.
FIG. 11.

Features of the interaction in the lowest energy configurations of molecular complexes with of , , and . (a) Plot of the distance as function of the variation of ESP charge on the oxygens of molecule . (b) plot of the BE as function of the distance; (c) plot of the BE as function of the angle.

Image of FIG. 12.
FIG. 12.

(a) BE vs distance and (b) angle for the lowest energy configurations of the molecular complexes of methyl-substituted benzenes with .

Image of FIG. 13.
FIG. 13.

(a) Plot of the molecular dipoles of the different ligands vs the induced dipole on for complexes of the halogen and methyl-substituted benzenes. (b) Plot of BE vs induced dipole on for complexes of the halogen and methyl-substituted benzenes.

Image of FIG. 14.
FIG. 14.

Scatter plot of the BE landscape for the nonsubstituted benzene ring (left-hand data point) and the two classes of benzene derivatives (halogen and methyl-substituted benzenes) interacting with .

Tables

Generic image for table
Table I.

ESP fitted charges of the delocalized electron density on benzene and substituted benzene rings. In the case of benzene and halogen-substituted benzenes, the total delocalized charge is given by , while for the methyl-substituted benzenes the total delocalized charge is given by .

Generic image for table
Table II.

Properties related to the lowest energy minimum configurations for molecular complexes with of halogen and methyl-substituted benzenes. CT is the charge transfer, which is evaluated as , with denoting the ESP partial charge on the atom of the molecule.

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/content/aip/journal/jcp/130/19/10.1063/1.3120909
2009-05-18
2014-04-16
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752b84549af89a08dbdd7fdb8b9568b5 journal.articlezxybnytfddd
Scitation: Impact of ligands on CO2 adsorption in metal-organic frameworks: First principles study of the interaction of CO2 with functionalized benzenes. I. Inductive effects on the aromatic ring
http://aip.metastore.ingenta.com/content/aip/journal/jcp/130/19/10.1063/1.3120909
10.1063/1.3120909
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