Conformational Preferences of Glycerol in the Gas Phase and in Water

Jeong, Keunhong; Byun, Byung Jin; Kang, Young Kee

doi:10.5012/bkcs.2012.33.3.917

Cited by 11 publications

(6 citation statements)

References 24 publications

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“…Glycerol has three flexible hydroxyl groups, and the formation of intramolecular hydrogen bonds contributes to a substantial increase in the number of isomers (e.g., 126 isomers have been reported) . Thus, over the years, several theoretical − and experimental ,,,, studies have investigated glycerol conformations. In this work, we selected 10 glycerol configurations from literature and 10 from MD simulations following the same procedure outlined in section in Theoretical Approach and Computational Details Section.…”

Section: Resultsmentioning

confidence: 99%

Glycerol Adsorption on Platinum Surfaces: A Density Functional Theory Investigation with van der Waals Corrections

2014

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Glycerol has been suggested as an additional energy source for hydrogen production for fuel cell applications, and several experimental studies have been reported on glycerol conversion on transition-metal surfaces; however, our atomistic understanding of glycerol−metal interactions is still far from satisfactory. In this work, we will report a theoretical investigation of the adsorption properties of glycerol on the Pt(110), Pt(100), and Pt(111) surfaces based on density functional theory (DFT) calculations with van der Waals (vdW) corrections to the DFT total energy. In the lowest energy configurations, which differ by millielectron volts, glycerol is almost parallel to the Pt surfaces and interacts with the Pt surfaces via one of the hydroxyl groups near the on-top Pt sites, which strongly affects the orientation of glycerol relative to the surface. Our results and analyses indicate that the adsorbate structure is among the high energy configurations of glycerol in gas phase. The vdW correction enhances the adsorption energy and hence decreases the equilibrium glycerol−metal distance; in particular, it affects mainly the adsorbate structure for glycerol on Pt(110), leading to the binding of two edge glycerol hydroxyl groups to the Pt(110) surface. Moreover, the vdW correction enhances the magnitude of the glycerol adsorption energy more on Pt(111) and less on Pt(110) surfaces; however, without changing the relative order of the adsorption energies, that is, glycerol binds more strongly on Pt(110) and more weakly on Pt(111) surface. We found large work function changes (0.7−1.0 eV) upon glycerol adsorption and negligible changes in the Bader charges of the H, C, O, and Pt atoms, and hence, polarization effects play a crucial role in the interaction mechanism.

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Section: Resultsmentioning

confidence: 99%

Glycerol Adsorption on Platinum Surfaces: A Density Functional Theory Investigation with van der Waals Corrections

2014

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“…Bastiensen [ 137 ] studied the structure by electron diffraction, and found the αα and αγ conformers as the major species. The symbols α, β, and γ refer to the heavy atom torsional positions, irrespective of the hydroxy-hydrogens positions (see [ 137 , 147 ]). He concluded that there are two intramolecular H-bonds for glycerol, which have three hydrogen-bond donor (and acceptor) OH groups.…”

Section: Conformational Equilibriamentioning

confidence: 99%

“…He concluded that there are two intramolecular H-bonds for glycerol, which have three hydrogen-bond donor (and acceptor) OH groups. Gas-phase studies by Jeong et al , [ 147 ] at the M06-2X level and by Callam et al , [ 148 ] at the G2(MP2) and CBS-QB3 levels deviate slightly regarding the conformer composition at T = 298 K. The most populated conformer is the αγ structure followed by αα or γγ. The free energies differ by less than 1.4 kJ/mol for the two most stable species by the different methods, thus the results are fairly method and basis set dependent.…”

Section: Conformational Equilibriamentioning

confidence: 99%

Competing Intramolecular vs. Intermolecular Hydrogen Bonds in Solution

Nagy

2014

IJMS

151

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A hydrogen bond for a local-minimum-energy structure can be identified according to the definition of the International Union of Pure and Applied Chemistry (IUPAC recommendation 2011) or by finding a special bond critical point on the density map of the structure in the framework of the atoms-in-molecules theory. Nonetheless, a given structural conformation may be simply favored by electrostatic interactions. The present review surveys the in-solution competition of the conformations with intramolecular vs. intermolecular hydrogen bonds for different types of small organic molecules. In their most stable gas-phase structure, an intramolecular hydrogen bond is possible. In a protic solution, the intramolecular hydrogen bond may disrupt in favor of two solute-solvent intermolecular hydrogen bonds. The balance of the increased internal energy and the stabilizing effect of the solute-solvent interactions regulates the new conformer composition in the liquid phase. The review additionally considers the solvent effects on the stability of simple dimeric systems as revealed from molecular dynamics simulations or on the basis of the calculated potential of mean force curves. Finally, studies of the solvent effects on the type of the intermolecular hydrogen bond (neutral or ionic) in acid-base complexes have been surveyed.

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“…In an implicit solvation setting, Jeong et al 42 obtained the conformational preference of glycerol at the M06-2Z/cc-pvtz level of theory in the aqueous phase. It is shown that glycerol exists as an ensemble of many feasible configurations due to weakened intramolecular hydrogen bonding.…”

Section: ■ Introductionmentioning

confidence: 99%

Elucidating Molecular Interactions in Glycerol Adsorption at the Metal–Water Interface with Density Functional Theory

Shan

Liu

2018

Langmuir

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Glycerol is an extremely versatile platform molecule for chemical and fuel production, as evidenced by successful demonstrations in electrochemical and thermochemical processes, where key catalytic chemistries occur at the solid–liquid interface. Despite the remarkable progress made in enriching the first-principles-based computational tool set to reveal and characterize solvent structures in the past decade, techniques for realistic and efficient molecular-level modeling to study aqueous-phase glycerol chemistry are still far from mature. Many aqueous-phase catalytic systems are deemed too complex for routine modeling because of their highly correlated structures at the heterogeneous solid–liquid interface. This invited feature article merges recent developments in quantum mechanical solvation models and oxygenated hydrocarbon conversion chemistry by revisiting the molecular interactions of adsorbed glycerol and its dehydrogenation intermediates at the water–metal interface. Explicit participation of water through the establishment of water–adsorbate, water–water, and water–metal interactions on Pt(111) was investigated using density functional theory. In periodic models, the adsorption favors networklike structures with adsorbates as nodal points linked by coadsorbed water molecules. We also showed that these adsorption patterns actually preserve the original bond-order-based scaling relationship framework established without the consideration of solvent. This behavior can be exploited to improve computational efficiency for future analysis of catalytic polyol conversions in the aqueous-phase environment.

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Conformational Preferences of Glycerol in the Gas Phase and in Water

Cited by 11 publications

References 24 publications

Glycerol Adsorption on Platinum Surfaces: A Density Functional Theory Investigation with van der Waals Corrections

Glycerol Adsorption on Platinum Surfaces: A Density Functional Theory Investigation with van der Waals Corrections

Competing Intramolecular vs. Intermolecular Hydrogen Bonds in Solution

Elucidating Molecular Interactions in Glycerol Adsorption at the Metal–Water Interface with Density Functional Theory

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