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Journal of Chemical Physics / Volume 134 / Issue 1 / ARTICLES / Surfaces, Interfaces, and Materials
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J. Chem. Phys. 134, 014702 (2011); http://dx.doi.org/10.1063/1.3528980 (14 pages)

Chemical response of aldehydes to compression between (0001) surfaces of α-alumina

Sarah M. Haw and Nicholas J. Mosey

Department of Chemistry, Queen's University, Kingston, Ontario K7L 3N6, Canada

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(Received 9 August 2010; accepted 29 November 2010; published online 3 January 2011)

First-principles molecular dynamics simulations are used to investigate the chemical response of acetaldehyde molecules (MeCHO) to compression and decompression between (0001) surfaces of α-alumina (Al2O3), with pressures reaching approximately 40 GPa. The results demonstrate that the MeCHO molecules are transformed into other chemical species through a range of chemical processes involving the formation of C–O and C–C bonds between MeCHO monomers as well as proton transfer. The mechanistic details of a representative set of the observed reactions are elucidated through analysis of maximally localized Wannier functions. Analysis of the changes in structure demonstrates that the main role of compression is to reduce the distances between MeCHO molecules to facilitate the formation of C–O bonds. Additional examination of the electronic structure demonstrates that the surface plays a role in facilitating proton transfer by both rendering hydrogen atoms in adsorbed MeCHO molecules more acidic and by acting as a proton acceptor. In addition, adsorption of the MeCHO molecules on the surface renders the sp2 carbon atoms in these molecules more electrophilic, which promotes the formation of C–C and C–O bonds. It is suggested that the reaction products may be beneficial in the context of wear inhibition. Comparison of the surface structure before compression and after decompression demonstrates that the aldehydes and reaction products are capable of inhibiting irreversible changes in the structure as long as there is at least a monolayer coverage of these species. As a whole, the study sheds light on the chemical behavior of the aldehydes in response to uniaxial compression in nanoscopic contacts that likely applies to other molecules containing carbonyl groups and other metal oxide surfaces.

© 2011 American Institute of Physics

Article Outline

  1. INTRODUCTION
  2. MODELS AND METHODS
  3. RESULTS
    1. Reactions observed during compression and decompression
    2. Changes in electronic structure
    3. Changes in structure and the role of compression
    4. Role of the surface
    5. Inhibition of irreversible changes in surface structure
  4. CONCLUSIONS

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KEYWORDS and PACS

Keywords

ab initio calculations, adsorbed layers, adsorption, bonds (chemical), chemical exchanges, corundum, molecular dynamics method, organic compounds, surface states, surface structure, Wannier functions

PACS

  • 68.43.Mn

    Adsorption kinetics

  • 68.43.Bc

    Ab initio calculations of adsorbate structure and reactions

  • 82.30.Hk

    Chemical exchanges (substitution, atom transfer, abstraction, disproportionation, and group exchange)

  • 73.20.Hb

    Impurity and defect levels; energy states of adsorbed species

  • 73.20.At

    Surface states, band structure, electron density of states

  • 71.15.Pd

    Molecular dynamics calculations (Car-Parrinello) and other numerical simulations

ARTICLE DATA

Digital Object Identifier
http://dx.doi.org/10.1063/1.3528980

PUBLICATION DATA

ISSN

0021-9606 (print)  
1089-7690 (online)

Publisher

$abstract.society.value is a Member of CrossRef American Institute of Physics

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Figures (click on thumbnails to view enlargements)

FIG.1
Structure of the model system after equilibration at 300 K. Al, O, C, and H atoms are represented by large purple, medium red, medium silver, and small green spheres, respectively. The model shown represents a simulation cell that has been repeated twice along the a and b lattice vectors to better illustrate the structure.

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FIG.2
Structures observed during compression and decompression. Al, O, C, and H atoms are represented by large purple, medium red, medium silver, and small green spheres, respectively. The models shown represent simulation cells that have been repeated twice along the a and b lattice vectors to better illustrate the structure. Only MeCHO groups and other atoms related to the described processes are shown. (a) The structure of the system after compression to Δz = 8.85 Å. A hydrogen atom was transferred to a surface oxygen from the MeCHO molecule on the top layer and two MeCHO dimers were formed on the bottom surface. (b) Structure after compression to Δz = 9.40 Å. A polyether consisting of three MeCHO molecules has formed and is circled. The hydrogen atom transferred to the upper surface in (a) has been transferred to the oxygen atom in another MeCHO group on the upper surface. (c) Structure after compression to Δz = 9.80 Å. The polyether formed in (b) grows by adding a fourth MeCHO molecule within the interface, which also bonds to an MeCHO molecule adsorbed to the surface. A hydrogen atom is transferred from one of the MeCHO dimers on the bottom layer to the terminal oxygen atom of the polyether. (d) Structure during compression at Δz = 9.10 Å. The polyether has detached from the upper surface and lost one MeCHO monomer. A C–C bond has formed between sp2 carbons in two MeCHO components on the upper surface. (e) Structure during compression at Δz = 8.15 Å. An MeCHO unit is transferred between the dimers on the lower surface. (f) Structure during compression at Δz = 0.55 Å. The polyether in the interface has decomposed and a C–O bond has formed between MeCHO groups on the upper surface.

FIG.2 Download High Resolution Image (.zip file) | Export Figure to PowerPoint

FIG.3
Key species formed during the FPMD simulation. Structure 1 is a polyether formed through C–O bond formation between five MeCHO molecules as well as proton transfer. Structure 2 is a polyether formed through C–O and C–C bond formations between three MeCHO molecules. Structure 3 is a structure formed through C–C bond formation between two adsorbed MeCHO molecules occurring along with proton transfer. Structure 4 is an ether formed through C–O bonding between two adsorbed MeCHO molecules along with proton transfer. Al, O, C, and H atoms are represented by large purple, medium red, medium silver, and small green spheres, respectively. Atomic labels are provided to help orient the reader throughout the following sections.

FIG.3 Download High Resolution Image (.zip file) | Export Figure to PowerPoint

FIG.4
Motion of MLWFs during the formation of 1. (a) A proton is transferred to a surface oxygen from the methyl group in an adsorbed MeCHO molecule. (b) C–O bonds form between three MeCHO molecules. (c) O1 abstracts a proton from an MeCHO molecule. The C3–O4 bond is formed, followed by the formation of the C4–O5 bond. Al, O, C, and H atoms are represented by large purple, medium red, medium silver, and small green spheres, respectively. Small orange spheres correspond to the MLWF centers. Atom labels correspond to those in Fig. 3.

FIG.4 Download High Resolution Image (.zip file) | Export Figure to PowerPoint

FIG.5
Motion of MLWFs during the formation of 2. (a) The C–O bond formation. (b) An oxygen atom abstracts a hydrogen atom from a methyl group. (c) The C2–C3 bond forms. Al, O, C, and H atoms are represented by large purple, medium red, medium silver, and small green spheres, respectively. Small orange spheres correspond to the MLWF centers. Atom labels correspond to those in Fig. 3.

FIG.5 Download High Resolution Image (.zip file) | Export Figure to PowerPoint

FIG.6
Motion of MLWFs during the formation of 3. A lone pair in the C1–C2 double bond attacks C3 to form a C–C bond between adsorbed species. Al, O, C, and H atoms are represented by large purple, medium red, medium silver, and small green spheres, respectively. Small orange spheres correspond to the MLWF centers. Atom labels correspond to those in Fig. 3.

FIG.6 Download High Resolution Image (.zip file) | Export Figure to PowerPoint

FIG.7
Motion of MLWFs during the formation of 4. A lone pair in a surface oxygen atom attacks H1, which prompts the attack of C1 by a lone pair on O2 to form a C–O bond. Al, O, C, and H atoms are represented by large purple, medium red, medium silver, and small green spheres, respectively. Small orange spheres correspond to the MLWF centers. Atom labels correspond to those in Fig. 3.

FIG.7 Download High Resolution Image (.zip file) | Export Figure to PowerPoint

FIG.8
Interatomic distances associated with the formation of the structures in Fig. 3 as a function of time during the FPMD simulation. The Δz values and time are equivalent during the compression phase and Δz = 22 – t during decompression: (a) Structure 1; (b) Structure 2; (c) Structure 3; (d) Structure 4. All labels, e.g., C1 and C2, correspond to those of the appropriate molecule in Fig. 3.

FIG.8 Download High Resolution Image (.zip file) | Export Figure to PowerPoint

FIG.9
CDD plots. All plots show the CDD for the species of interest as well as a small portion of the surface near this species. Al, O, C, and H atoms are represented by large purple, medium red, medium silver, and small green spheres, respectively. Isosurfaces are plotted at a value of ±0.008 a.u. Blue regions indicate increased electron density and yellow regions indicate decreased electron density. Arrows are added to highlight key regions in these species mentioned in the text. (a) CDD for an adsorbed MeCHO molecule at the start of the simulation showing a decrease in electron density around the sp2 carbon. (b) CDD for an adsorbed MeCHO molecule after compression to Δz = 6.6 Å, at which point the molecule has become oriented such that the C–C bond is nearly parallel to the surface. A decrease in electron density at one hydrogen on the methyl group is evident. (c) CDD for an adsorbed MeCHO dimer. Adsorption has significant effects on the electron density, even reducing the density around the terminal sp2 carbon, rendering that atom more electrophilic. (d) CDD for the adsorbed polyether in 1 prior to its decomposition. Only atoms near the surface are shown. Adsorption increases density along the Al–O bond, withdrawing density from the neighboring C–O bonds.

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FIG.10
Structures of the systems before compression, at maximum compression, and after decompression for models composed of two (0001)-Al2O3 surfaces separated by (a) two MeCHO molecules, (b) four MeCHO molecules, and (c) eight MeCHO molecules. Al, O, C, and H atoms are represented by large purple, medium red, medium silver, and small green spheres, respectively. The models shown represent simulation cells that have been repeated twice along the a and b lattice vectors to better illustrate the structure.

FIG.10 Download High Resolution Image (.zip file) | Export Figure to PowerPoint

FIG.11
RMS displacements of the atoms in various layers of the Al2O3 surfaces after undergoing one complete compression/decompression cycle as a function of the number of MeCHO molecules present in the interface. The inset structure shows the definitions of the layers.

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