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Investigation of attractive and repulsive interactions associated with ketones in supercritical CO2, based on Raman spectroscopy and theoretical calculations
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10.1063/1.4817190
/content/aip/journal/jcp/139/5/10.1063/1.4817190
http://aip.metastore.ingenta.com/content/aip/journal/jcp/139/5/10.1063/1.4817190

Figures

Image of FIG. 1.
FIG. 1.

Molecular structures of ketones used as solute molecules.

Image of FIG. 2.
FIG. 2.

Typical examples of Raman spectra of C=O stretching modes of (a) acetone, (b) acetophenone, and (c) benzophenone in scCO at = 1.02. denotes the reduced temperature as = / . denotes the reduced density and is given by = / , where is the critical density. Solid lines are fits using Lorentzian functions. Arrows and dotted lines are visual guides to show the low-frequency shift due to the increase in fluid density.

Image of FIG. 3.
FIG. 3.

Density dependences of the Δ shifts of the Raman bands of the C=O stretching modes of acetone, acetophenone, and benzophenone in scCO at = 1.02. denotes the reduced temperature as = / . denotes the reduced density and is expresses as = / . Solid lines are visual guides obtained from fitting polynomial functions to the experimental data.

Image of FIG. 4.
FIG. 4.

Attractive (red), repulsive (green), and net (blue) shifts of (a) acetone, (b) acetophenone, and (c) benzophenone in scCO at = 1.02. denotes the reduced temperature as = / . denotes the reduced density and is expressed as = / .

Image of FIG. 5.
FIG. 5.

Optimized relative configurations of (a) acetone–CO, (b) acetophenone–CO, and (c) benzophenone–CO calculated with the B3LYP level using the 6-311+G(2d,p) basis set. Red, green, and gray spheres represent oxygen, carbon, and hydrogen atoms, respectively. Dashed lines are visual guides to show the interactions between the oxygen atom of the carbonyl group and the carbon atom of the CO molecule. Dotted lines are visual guides to show the interaction between the oxygen atom of the CO molecule and the hydrogen atom of the solute molecule.

Image of FIG. 6.
FIG. 6.

Mulliken charges of the oxygen atoms of acetone, acetophenone, and benzophenone at the isolated condition. The calculated values are listed in Table III .

Image of FIG. 7.
FIG. 7.

Optimized relative configurations of acetone–CO, acetophenone–CO, and benzophenone–CO calculated with the Hartree–Fock theory, Møller–Plesset theory, and density functional theory. Red, gray, and white spheres represent oxygen, carbon, and hydrogen atoms, respectively. The values in figure represent the Mulliken charges of oxygen atom in each solute molecule.

Image of FIG. 8.
FIG. 8.

Density dependences of attractive shifts of acetone (●), acetophenone (○), and benzophenone (■) in scCO at = 1.02. denotes the reduced temperature as = / . denotes the reduced density and is expressed as = / . The solid lines act as visual guides and are obtained by fitting polynomial functions to the experimental data.

Image of FIG. 9.
FIG. 9.

Attractive energies of (a) dis and (b) DID interactions between solute and solvent molecules for each system, calculated using Eqs. (3) and (4) , respectively. Attractive shifts of C=O stretching modes due to (c) dis and (d) DID interactions using in each system, calculated using Eqs. (5) and (6) , respectively, which represent the shifts from = 0 to = 1. (e) The ratio of dis interaction in Fig. 9(c) and DID interaction in Fig. 9(d) .

Tables

Generic image for table
Table I.

Molecular parameters for calculating the repulsive shifts.

Generic image for table
Table II.

Mulliken charges of atoms in Fig. 5 obtained from quantum chemistry calculations using the Gaussian 09 package at the B3LYP level and the 6-311+G(2d,p) basis set.

Generic image for table
Table III.

Mulliken charges of oxygen atoms obtained with the quantum chemistry calculations using the Gaussian 2009 package with several methods and basis sets.

Generic image for table
Table IV.

Molecular parameters of solute molecules for energy calculations of dis and DID interactions.

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/content/aip/journal/jcp/139/5/10.1063/1.4817190
2013-08-07
2014-04-21
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752b84549af89a08dbdd7fdb8b9568b5 journal.articlezxybnytfddd
Scitation: Investigation of attractive and repulsive interactions associated with ketones in supercritical CO2, based on Raman spectroscopy and theoretical calculations
http://aip.metastore.ingenta.com/content/aip/journal/jcp/139/5/10.1063/1.4817190
10.1063/1.4817190
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