Lanthanide and Actinide Ion Complexes Containing Organic Ligands Investigated by Surface-Enhanced Infrared Absorption Spectroscopy.

A new technique, surface-enhanced infrared absorption (SEIRA) spectroscopy, was used for the structural investigation of lanthanide (Ln) and actinide (An) complexes containing organic ligands. We synthesized thiol derivatives of organic ligands with coordination sites similar to those of 2-[N-methyl-N-hexanethiol-amino]-2-oxoethoxy-[N',N'-diethyl]-acetamide [diglycolamide (DGA)], Cyanex-272, and N,N,N',N'-tetrakis(2-pyridinylmethyl)-1,2-ethanediamine (TPEN), which have been used for separating Ln and An through solvent extraction. These ligands were attached on a gold surface deposited on an Si prism through S-Au covalent bonds; the gold surface enhanced the IR absorption intensity of the ligands. Aqueous solutions of Ln (Eu3+, Gd3+, and Tb3+) and An (Am3+) ions were loaded onto the gold surface to form ion complexes. The IR spectra of the ion complexes were obtained using Fourier transform infrared spectroscopy in the attenuated total reflection mode. In this study, we developed a new sample preparation method for SEIRA spectroscopy that enabled us to obtain the IR spectra of the complexes with a small amount of ion solution (5 µL). This is a significant advantage for the IR measurement of radiotoxic Am3+ complexes. In the IR spectra of DGA, the band attributed to C═O stretching vibrations at ∼1630 cm-1 shifted to a lower wavenumber by ∼20 cm-1 upon complexation with Ln and An ions. Moreover, the amount of the red shift was inversely proportional to the extraction equilibrium constant reported in previous studies on solvent extraction. The coordination ability of DGA toward Ln and An ions could be assessed using the band position of the C═O band. The Cyanex-272- and TPEN-like ligands synthesized in this report also showed noticeable SEIRA signals for Ln and An complexes. This study indicates that SEIRA spectroscopy can be used for the structural investigation of ion complexes and provides a microscopic understanding of selective extraction of Ln and An.

Fast, Economical, and Reproducible Sensing from a 2D Si Wire Array: Accurate Characterization by Single Wire Spectroscopy.

Silicon (Si) is promising as a field enhancement material because of its high abundance, low toxicity, and high refractive index. The field enhancement effect intensifies light-matter interactions, which improves photocatalysis, solar cell performance, and sensor sensitivity. To manufacture field enhancement materials on a production scale, the fabrication technique must be simple, cost-effective, fast, and highly reproducible and must produce a high enhancement factor (EF). Herein, we report on an economical and efficient fabrication method for a field enhancement substrate consisting of a two-dimensional Si wire array (2D-SiWA). This substrate was demonstrated as a fluorescence sensor with high sensitivity (EF > 200) and composed of a large area (6.0 mm2). In addition, single wire spectroscopy was used to identify very high reproducibility of the sensor sensitivity in regular regions (97%) and a mixture of regular and irregular regions (87%) of the 2D-SiWA. The large-area Si fluorescence sensor fabrication was cost-effective and rapid and was 50× less expensive, 20×faster, and 60,000×larger than the typical electron beam lithography method.

Cost-Effective Ultrabright Silicon Quantum Dots and Highly Efficient LEDs from Low-Carbon Hydrogen Silsesquioxane Polymers.

Cost-effective methods of synthesizing bright colloidal silicon quantum dots (SiQDs) for use as heavy-metal-free QDs, which have applications as light sources in biomedicine and displays, are required. We report simple protocols for synthesizing ultrabright colloidal SiQDs and fabricating SiQD LEDs based on hydrogen silsesquioxane (HSQ) polymer synthesis. Red photoluminescence with a quantum yield (PLQY) of 60-80% and LEDs with an external quantum efficiency (EQE) of >10% were obtained at 1/3600th of the cost of existing methods. This was achieved by using HSiCl3 and a low-polarity solvent to prepare the HSQ polymer and by optimizing the LED hole-injection layer thickness. A stochastic analysis of 31 SiQD syntheses revealed that SiQDs with the highest PLQYs were obtained from a hard, low-carbon HSQ polymer precursor containing many Si-H groups and cage structures. Notably, simple FTIR measurements predicted whether a HSQ polymer would yield high-PLQY SiQDs and high-EQE LEDs. These straightforward, cost-effective protocols should lead to advances in SiQD synthesis and LED fabrication methods.

Investigation of attractive and repulsive interactions associated with ketones in supercritical CO2, based on Raman spectroscopy and theoretical calculations.

Carbonyl compounds are solutes that are highly soluble in supercritical CO2 (scCO2). Their solubility governs the efficiency of chemical reactions, and is significantly increased by changing a chromophore. To effectively use scCO2 as solvent, it is crucial to understand the high solubility of carbonyl compounds, the solvation structure, and the solute-solvent intermolecular interactions. We report Raman spectroscopic data, for three prototypical ketones dissolved in scCO2, and four theoretical analyses. The vibrational Raman spectra of the C=O stretching modes of ketones (acetone, acetophenone, and benzophenone) were measured in scCO2 along the reduced temperature Tr = T∕Tc = 1.02 isotherm as a function of the reduced density ρr = ρ∕ρc in the range 0.05-1.5. The peak frequencies of the C=O stretching modes shifted toward lower energies as the fluid density increased. The density dependence was analyzed by using perturbed hard-sphere theory, and the shift was decomposed into attractive and repulsive energy components. The attractive energy between the ketones and CO2 was up to nine times higher than the repulsive energy, and its magnitude increased in the following order: acetone < acetophenone < benzophenone. The Mulliken charges of the three solutes and CO2 molecules obtained by using quantum chemistry calculations described the order of the magnitude of the attractive energy and optimized the relative configuration between each solute and CO2. According to theoretical calculations for the dispersion energy, the dipole-induced-dipole interaction energy, and the frequency shift due to their interactions, the experimentally determined attractive energy differences in the three solutes were attributed to the dispersion energies that depended on a chromophore attached to the carbonyl groups. It was found that the major intermolecular interaction with the attractive shift varied from dipole-induced dipole to dispersion depending on the chromophore in the ketones in scCO2. As the common conclusion for the Raman spectral measurements and the four theoretical calculations, solute polarizability, modified by the chromophore, was at the core of the solute-solvent interactions of the ketones in scCO2.

4D Microspectroscopy Explores Orientation and Aggregations in π-Conjugated Polymer Films Prepared by Brush Printing.

The orientation of polymers improves their mechanical, electrical, and optical properties, but aggregates alter these properties. Unfortunately, there is no definitive way to control aggregates and quantify orientations by distinguishing between polymer chains and aggregates. Herein, we show 4D microspectroscopy to examine brush-printed oriented films of π-conjugated polymers. Three-dimensional (x-y-z) and 1D (photon energy) components based on polarized-fluorescence spectra and film thickness at identical positions were measured. Stochastic analysis of 4D data for a brush-printed OLED film (30 × 30 µm2, 900 pixels) distinguished orientations of polymer chains and their aggregates with a 1 µm x-y resolution and a z-range of 20-1800 nm. Polymer chains in thin regions (t < 50 nm) were oriented parallel to the brush-printing direction, whereas aggregates were oriented perpendicularly in thicker regions (t > 1000 nm). This difference was attributed to shear stress, uneven thickness, and capillary forces. The generality of the 4D method was also examined using conventional drop casting.

Designing Efficient Si Quantum Dots and LEDs by Quantifying Ligand Effects.

The impact of colloidal silicon quantum dots (SiQDs) on next-generation light sources is promising. However, factors determining the efficiency of SiQDs, such as the photoluminescence (PL) wavelength, PL quantum yield (PLQY), and the SiQD LED performance based on the type of ligand, ligand coverage, stress, and dangling bonds, have not been quantified. Characterizing these variables would accelerate the design and implementation of SiQDs. Herein, colloidal SiQDs were synthesized by pyrolyzing hydrogen silsesquioxane and their surfaces were terminated with 1-decene by either thermal hydrosilylation (HT-SiQDs) or room-temperature hydrosilylation using PCl5 (RT-SiQD). As a result, PL, PL-excitation, and ultraviolet-visible absorption spectra were similar, but their PLQYs were significantly different: 54% (RT-SiQDs) vs 19% (HT-SiQDs). To understand their similarities and differences, surface coverages (dangling bonds, Si-H (≡Si-H1, ═Si-H2, and -Si-H3), Si-O-Si, Si-C, Si-Cl) were determined. A core stress analysis established that a single ligand terminated to a SiQD bond site stretched the Si-Si bond length by 0.3%. From the two well-defined SiQDs, the PLQY and SiQD LED efficiency were attributed to four factors: low coverage of insulator ligands, the Cl ligand effect on radiative and nonradiative rates, negligible dangling bonds, and a SiQD core with low tensile stress. The PLQY of the RT-SiQDs in toluene was 80%. In addition, the 20× electroluminescence intensity difference of the LEDs originated from a 10× difference in current density and a 2× difference in Auger recombination. The concepts demonstrated here can be applied to further improve the PLQY and LED efficiencies of SiQDs with other ligands.

Significant substitution effects in dipolar and non-dipolar supercritical fluids.

Vibrational Raman spectra of C=C stretching modes of ethylene derivates (cis-C(2)H(2)Cl(2), cis-stilbene, and trans-stilbene) were measured in supercritical fluids along an isotherm as functions of their densities. The substitution effect of the Raman shift is so significant that a difference among three solutes can be 20 times and is observed similarly in dipolar (CHF(3)) and non-dipolar (CO(2)) fluids. In particular, the shifts of trans-stilbene were enormously large among all systems for studies of vibrational spectroscopies of supercritical fluids and were equivalent to those of typical hydrogen-bonded fluids. Such large shifts arising from the significant attractive energy between solute and solvent molecules were attributed to a site-selective solvation around a phenyl group, which was driven by a dispersion force in the absence of steric hindrance. We found that the absence of steric hindrance causes the significant local density augmentation. To the best of our knowledge, Raman experiments and their theoretical analysis are the first ones quantifying how the difference of steric hindrance produces solvation structures in solution as well as supercritical solutions.

Large Field Enhancement of Nanocoral Structures on Porous Si Synthesized from Rice Husks.

Silicon (Si) is a highly abundant, environmentally benign, and durable material and is the most popular semiconductor material; and it is used for the field enhancement of dielectric materials. Porous Si (PSi) exhibits high functionality due to its specific structure. However, the field enhancement of PSi has not been clarified sufficiently. Herein, we present the field enhancement of PSi by the fluorescence intensity enhancement of a dye molecule. The raw material used for producing PSi was rice husk, a biomass material. A nanocoral structure, consisting of spheroidal structures on the surface of PSi, was observed when PSi was subjected to chemical processes and pulsed laser melting, and it demonstrated large field enhancement with an enhancement factor (EF) of up to 545. Confocal microscopy was used for EF mapping of samples before and after laser melting, and the maps were superimposed on nanoscale scanning electron microscope images to highlight the EF effect as a function of microstructure. Nanocoral Si with high EF values were also evaluated by analyzing the porosity from gas adsorption measurements. Nanocoral Si was responsible for the high EF, according to thermodynamic calculations and agreement between experimental and calculation results as determined by Mie scattering theory.

Brush Printing Creates Polarized Green Fluorescence: 3D Orientation Mapping and Stochastic Analysis of Conductive Polymer Films.

Brush printing is a unique method used to obtain uniaxially oriented films, whereby a polymer solution is brushed onto a substrate. However, there have been only a few reports on the brush-printing method. Here, we report the preparation of a uniaxially oriented film of a green light-emitting conductive polymer, poly(9,9-dioctylfluorene-alt-benzothiadiazole) (F8BT). The fluorescence polarization ratio of the oriented F8BT films was as high as 11.3, and the average orientation factor reached 0.74 ± 0.06. The orientation factor and the torsion angle of F8BT were visualized by two mappings of fluorescence and Raman spectral measurements by confocal spectromicroscopy, respectively. These two x-y mapping data with many pixels (∼750 pixels) were evaluated by x-y-z mapping of the film thickness at a single position and were used to reveal the three-dimensional (3D) orientation mechanism from a stochastic approach. Polarized green fluorescence originates from polymer chains uniaxially oriented along the brush direction. The high orientation for a film thickness < 100 nm is established by shear stress, faster capillary flow, and flow-induced chain extension for a thin solution film on a substrate. The high orientation factor was also demonstrated by a high brushing speed, whereas an optimized brushing speed existed. We found that this optimization is attributed to the property of a non-Newtonian fluid. By applying this brush-printing method to the fabrication of an optoelectrical device, polarized green electroluminescence was preliminarily demonstrated by the OLED assembled from an oriented F8BT film.

Nanogap-Rich TiO2 Film for 2000-Fold Field Enhancement with High Reproducibility.

Titanium dioxide (TiO2) is a crucial semiconductor for photocatalysts, solar cells, hydrogen evolution reactions, and antivirus agents. The properties and performances of these applications can improve significantly if the integrated TiO2 acts as a light harvester through a large field enhancement. This study investigates the electromagnetic field enhancement of a nanogap-rich TiO2 film with a large area, prepared by a facile dry process at room temperature. Herein, the loading pressure is applied to the TiO2 particles for closely packing them in the film. The field enhancement, as a function of the loading pressure, is explored from the fluorescence intensity enhancement of a dye molecule. An average enhancement factor >2000 is achieved, which is a remarkable record for semiconductors. Furthermore, the reproducibility is significant; the relative standard deviation value is small (∼4%). Calculations were performed using the finite-difference-time-domain method. A nanogap of 5 nm yields the highest EF for triangular-prism TiO2 particles.

1% defect enriches MoS2 quantum dot: catalysis and blue luminescence.

Defects in solids are typically recognized as unfavorable, leading to degradation of the structure and properties of the material. However, defects occasionally provide extraordinary benefits as the active sites of catalysts and chemical reactions, and can result in the creation of new electronic states. In particular, a low-dimensional material can become a defect-rich material due to the unique ratio of surface area to volume, giving many dangling bonds. Herein, we report the rapid (20 min) synthesis of MoS2 quantum dots (QDs) with a diameter of 4 nm at room temperature using nanosecond pulsed laser ablation in a binary solvent. The MoS2 QDs are crystalline particles composed of 3-5 layers and contain sulfur vacancies at an atomic concentration of 1% acting as a functional defect. The MoS2 QDs exhibit excellent electrocatalytic performance (Tafel slope = 49 mV dec-1) for the hydrogen evolution reaction and high quantum yield blue photoluminescence with a large Stokes shift.

Solvation structures of cis- and trans-1,2-dichloroethylene in supercritical CO2 investigated by Raman spectroscopy and attractive energy calculations.

Vibrational Raman spectra of the C horizontal lineC stretching modes of cis- and trans-1,2-dichloroethylene (C(2)H(2)Cl(2)) were measured in supercritical carbon dioxide (CO(2)). The spectra were collected at a fixed solute mole fraction by varying the fluid density by a factor of 20. As the density increased, the peak frequencies of the C horizontal lineC stretching modes shifted toward the low-energy side at isotherms of reduced temperature, T(r) = T/T(c) = 1.02, 1.06, and 1.20. By analyzing these density dependences using the perturbed hard-sphere theory, we decomposed the shifts into attractive and repulsive components. The repulsive shifts of cis-C(2)H(2)Cl(2) were almost equivalent to those of trans-C(2)H(2)Cl(2). However, the attractive shifts of nonpolar trans-C(2)H(2)Cl(2) were significantly greater than those of polar cis-C(2)H(2)Cl(2) at all densities and temperatures. To evaluate the difference in the isomers, we calculated the attractive shifts of the C horizontal lineC stretching modes of each isomer, composing of dispersion, dipole-induced-dipole, and dipole-quadrupole interactions between solute C(2)H(2)Cl(2) and solvent CO(2) molecules. These three interactions were quantified by considering molecular configurations and orientations, and solvation structures around the isomers were elucidated by 3D schematic diagrams. As a result, it was shown that the anisotropic solvation structure around trans-C(2)H(2)Cl(2) was responsible for the larger attractive shifts in the supercritical CO(2). The difference of solvation structures between the isomers was significant at T(r) = 1.02 but became minor as the temperature increased to T(r) = 1.20.

Spectrum of excess partial molar absorptivity. I. Near infrared spectroscopic study of aqueous acetonitrile and acetone.

We study the mixing schemes or the molecular processes occurring in aqueous acetonitrile (ACN) and acetone (ACT) by near-infrared spectroscopy (NIR). Both solutions (any other aqueous solutions) are not free from strong and complex intermolecular interactions. To tackle such a many-body problem, we first use the concept of the excess molar absorptivity, epsilonE, which is a function of solute mole fraction in addition to that of wavenumber, nu. The plots of epsilonE calculated from NIR spectra for both aqueous solutions against nu showed two clearly separated bands at 5020 and 5230 cm(-1); the former showed negative and the latter positive peaks. At zero and unity mole fractions of solute, epsilonE is identically zero independent of nu. Similar to the thermodynamic excess functions, both negative and positive bands grow in size from zero to the minimum (or the maximum) and back to zero, as the mole fraction varies from 0 to 1. Since the negative band's nu-locus coincides with the NIR spectrum of ice, and the positive with that of liquid H(2)O, we suggest that on addition of solute the "ice-likeness" decreases and the "liquid-likeness" increases, reminiscent of the two-mixture model for liquid H(2)O. The modes of these variations, however, are qualitatively different between ACN-H(2)O and ACT-H(2)O. The former ACN is known to act as a hydrophobe and ACT as a hydrophile from our previous thermodynamic studies. To see the difference more clearly, we introduced and calculated the excess partial molar absorptivity of ACN and ACT, epsilon(E)(N) and epsilon(E)(T), respectively. The mole fraction dependences of epsilon(E)(N) and epsilon(E)(T) show qualitatively different behavior and are consistent with the detailed mixing schemes elucidated by our earlier differential thermodynamic studies. Furthermore, we found in the H(2)O-rich region that the effect of hydrophobic ACN is acted on the negative band at 5020 cm(-1), while that of hydrophilic ACT is on the positive high-energy band. Thus, the present method of analysis adds more detailed insight into the difference between a hydrophobe and a hydrophile in their effects on H(2)O.

Size-Selected Submicron Gold Spheres: Controlled Assembly onto Metal, Carbon, and Plastic Substrates.

Size-selected submicron spheres become very useful building blocks if the spheres could be synthesized and integrated at any desired position. In particular, spheres having a similar size to visible-light wavelength have attracted much attention. Here, we show the synthesis and assembly of size-selected submicron gold spheres using pulsed laser ablation of a gold plate in a supercritical fluid. Four findings were obtained in the study. Submicron spheres with a narrow size distribution were generated, and the polydispersity was ≈ 6%. The average diameter was controlled from 600 to 1000 nm. A thermodynamic condition for scalable synthesis was found. The assembly of spheres onto a metal, carbon, or plastic substrate was accomplished.

Difference of solute-solvent interactions of cis- and trans-1,2-dichloroethylene in supercritical CO2 investigated by raman spectroscopy.

Vibrational Raman spectra of CC stretching modes of both cis- and trans-1,2-dichloroethylene (C2H2Cl2) were measured as a function of density in supercritical carbon dioxide (CO2). Measurements were performed with solute mole fraction of 0.01 at an isotherm of T r = T/ T c = 1.02. As the density of CO2 increased, peak frequencies of the CC stretching modes shifted toward the low energy side. By analyzing these density dependences using perturbed hard-sphere theory, we decomposed the shifted amounts into attractive and repulsive components. The amounts of repulsive shifts were almost equivalent, whereas those of the attractive shifts of trans-C2H2Cl 2 were larger than those of cis-C2H2Cl2 at all densities. This means that the nonpolar solute, trans-C2H2Cl2, shows stronger solute-solvent interactions than those of the polar solute cis-C2H2Cl2. The difference of attractive interactions between these isomers is the greatest at a density where local density enhancement of supercritical CO2 reaches the maximum.

Mechano-synthesized orange TiO2 shows significant photocatalysis under visible light.

Nitrogen and carbon co-doped TiO2 particles with a brilliant yellow-orange color were produced mechanochemically by high-energy ball milling as one-pot synthesis. This facile synthesis required only grinding TiO2 with melamine at room temperature. Using monochoromatic lights with the same intensity in visible and UV, the photocatalytic activity of the TiO2 particles was accurately evaluated with respect to the degradation of an aqueous dye (methylene blue) solution. The activities under visible light (450 and 500 nm) were, respectively, 4 and 2 times higher than that of the unmilled TiO2 under UV light (377 nm), corresponding to 9 and 5 times higher than the UV under the solar light condition. The properties and structure of the co-doped TiO2 particles before and after milling were analyzed using eight experimental methods. As a result, it was found that the nitrogen replaced as an oxygen site in milled TiO2 has the highest concertation (2.3%) in the past studies and the structure of milled TiO2 is composed of a polymorphism of four different solid phases of TiO2, gives significant higher photocatalytic activity at visible light than that of UV light. A good repeatability of the photocatalyst was investigated by the number of cycles for the decomposition reaction of the aquesous dye solution.

Field enhancement of MoS2: visualization of the enhancement and effect of the number of layers.

Two-dimensional transition metal dichalcogenides (2D TMDCs) are layered semiconductor materials with unique electronic and optical properties. In the family of 2D TMDCs, molybdenum disulphide (MoS2) is a promising material for next-generation optoelectrical devices due to its high mobility and characteristic properties. The properties of 2D TMDCs, as well as device performances, can be further improved by a field enhancement effect. However, field enhancement has not been reported to date in the 2D TMDC family. Here, we show the field enhancement of MoS2 and its dependence on the number of layers (5-850 layers). Measurements of the fluorescence intensity of a dye solution, crystal violet, were used to visualize the enhancement factor (EF) for a MoS2 flake as a map. The EFs on the map were independently confirmed by x-y-z size measurements of the same MoS2 flake with an atomic force microscope. Furthermore, the obtained x-y-z sizes of the MoS2 flake were used for the finite-difference time-domain (FDTD) calculations to evaluate field enhancement. As a result, the MoS2 flake with a specific thickness (ca. 80 layers) gave the highest enhancement with EF = 100. Theoretical calculations based on the Mie scattering theory also confirmed the experimental EF mapping results, the dependence on the number of layers, and the component analysis of field enhancement. As another crucial point, large and small enhancement effects were attributed to the electric field and charge transfer effects, respectively, both of which depend on the number of layers. A transition region of these effects was indicated at around 300-400 layers.

Si nanocrystal solution with stability for one year.

Colloidal silicon nanocrystals (SiNCs) are a promising material for next-generation nanostructured devices. High-stability SiNC solutions are required for practical use as well as studies on the properties of SiNC. Here, we show a solution of SiNCs that was stable for one year without aggregation. The stable solution was synthesized by a facile process, i.e., pulsed laser ablation of a Si wafer in isopropyl alcohol (IPA). The long-term stability was due to a large ζ-potential of -50 mV from a SiNC passivation layer composed of oxygen, hydrogen, and alkane groups, according to the results of eight experiments and theoretical calculations. This passivation layer also resulted in good performance as an additive for a conductive polymer film. Namely, a 5-fold enhancement in carrier density was established by the addition of SiNCs into an organic conductive polymer, poly(3-dodecylthiophene), which is useful for solar cells. Furthermore, it was found that fresh (<1 day) and aged (4 months) SiNCs give the same enhancement. The long-term stability was attributed to a great repulsive energy in IPA, whose value was quantified as a function the distance between SiNCs.

Uniaxial orientation of P3HT film prepared by soft friction transfer method.

The realization of room-temperature processes is an important factor in the development of flexible electronic devices composed of organic materials. In addition, a simple and cost-effective process is essential to produce stable working devices and to enhance the performance of a smart material for flexible, wearable, or stretchable-skin devices. Here, we present a soft friction transfer method for producing aligned polymer films; a glass substrate was mechanically brushed with a velvet fabric and poly(3-hexylthiophene) (P3HT) solution was then spin-coated on the substrate. A P3HT film with a uniaxial orientation was obtained in air at room temperature. The orientation factor was 17 times higher than that of a film prepared using a conventional friction transfer technique at a high temperature of 120 °C. In addition, an oriented film with a thickness of 40 nm was easily picked up and transferred to another substrate. The mechanism for orientation of the film was investigated using six experimental methods and theoretical calculation, and was thereby attributed to a chemical process, i.e., cellulose molecules attach to the substrate and act as a template for molecular alignment.

Solvation of Esters and Ketones in Supercritical CO2.

Vibrational Raman spectra for the C═O stretching modes of three esters with different functional groups (methyl, a single phenyl, and two phenyl groups) were measured in supercritical carbon dioxide (scCO2). The results were compared with Raman spectra for three ketones involving the same functional groups, measured at the same thermodynamic states in scCO2. The peak frequencies of the Raman spectra of these six solute molecules were analyzed by decomposition into the attractive and repulsive energy components, based on the perturbed hard-sphere theory. For all solute molecules, the attractive energy is greater than the repulsive energy. In particular, a significant difference in the attractive energies of the ester-CO2 and ketone-CO2 systems was observed when the methyl group is attached to the ester or ketone. This difference was significantly reduced in the solute systems with a single phenyl group and was completely absent in those with two phenyl groups. The optimized structures among the solutes and CO2 molecules based on quantum chemical calculations indicate that greater attractive energy is obtained for a system where the oxygen atom of the ester is solvated by CO2 molecules.