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Journal of Chemical Physics / Volume 132 / Issue 13 / ARTICLES / Condensed Phase Dynamics, Structure, and Thermodynamics: Spectroscopy, Reactions, and Relaxation

J. Chem. Phys. 132, 134513 (2010); http://dx.doi.org/10.1063/1.3374410 (12 pages)

Compression-induced transformation of aldehydes into polyethers: A first-principles molecular dynamics study

Nicholas J. Mosey

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

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(Received 2 December 2009; accepted 9 March 2010; published online 7 April 2010)

First-principles molecular dynamics simulations are used to investigate the behavior of bulk acetaldehyde (MeCHO) under conditions of increasing pressure. The results demonstrate that increasing pressure causes the aldehydes to polymerize, yielding polyethers through a process involving the rapid formation of CO bonds between multiple neighboring MeCHO molecules. Attempts to induce polyether formation at different densities through the application of geometric constraints show that polymerization occurs only once a critical density of ∼ 1.7 g/cm3 has been reached. The results of simulations performed at several different temperatures are also consistent with a process that is induced by reaching a critical density. The origins of this effect are rationalized in terms of the structural requirements for the formation of CO bonds between multiple MeCHO molecules in rapid succession. Specifically, the collective formation of CO bonds requires the typical distance between the sp2 carbon atoms and oxygen atoms in neighboring MeCHO molecules to reach a value of approximately 2.5 Å. Radial distribution functions calculated at different densities show that this structural requirement is reached when the density is near the observed threshold. The observed reaction may be useful in the context of lubrication, with polyethers being effective lubricants and the extreme conditions experienced in sliding contacts providing the ability to reach the high densities needed to induce the reaction. In this context, the calculations indicate that polyether formation is associated with significant energy dissipation, while energy dissipation is minimal once the polyethers are formed. Furthermore, the polyethers are stable with respect to multiple compression/decompression cycles and pressures of at least 60 GPa.

© 2010 American Institute of Physics

Article Outline

  1. INTRODUCTION
  2. METHODS
    1. General details
    2. Compression/decompression of aldehydes
    3. FPMD simulations with geometric constraints
  3. RESULTS
    1. Compression-induced transformation of MeCHO molecules into polyethers
    2. Constrained FPMD simulations
    3. Effect of pressure of the electronic and atomic structures
    4. Dependence on conditions
    5. Equation of state, hysteresis, and energy dissipation
  4. DISCUSSION
  5. CONCLUSIONS

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KEYWORDS and PACS

Keywords

ab initio calculations, bonds (chemical), electronic density of states, energy gap, high-pressure effects, lubricants, molecular dynamics method, polymerisation, polymers

PACS

  • 62.50.-p

    High-pressure effects in solids and liquids

  • 71.20.Rv

    Polymers and organic compounds

  • 81.40.Vw

    Pressure treatment

  • 82.35.-x

    Polymers: properties; reactions; polymerization

  • 71.15.Pd

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

ARTICLE DATA

Digital Object Identifier
http://dx.doi.org/10.1063/1.3374410

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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