JCP Nameplate
  • Volume/Page
  • Keyword
  • DOI
  • Citation
  • Advanced
   
 
 
 

You Tube Flickr Twitter UniPHY Group iResearch App Facebook

Journal of Chemical Physics / Volume 136 / Issue 6 / ARTICLES / Condensed Phase Dynamics, Structure, and Thermodynamics: Spectroscopy, Reactions, and Relaxation

J. Chem. Phys. 136, 064510 (2012); http://dx.doi.org/10.1063/1.3683436 (9 pages)

Mechanism of OH radical hydration: A comparative computational study of liquid and supercritical solvent

Dorota Swiatla-Wojcik and Joanna Szala-Bilnik

Institute of Applied Radiation Chemistry, Technical University of Lodz, Zeromskiego 116, 90-924 Lodz, Poland

View MapView Map

(Received 15 November 2011; accepted 21 January 2012; published online 10 February 2012)

Flexible models of the radical and water molecules including short-range interaction of hydrogen atoms have been employed in molecular dynamic simulation to understand mechanism of •OH hydration in aqueous systems of technological importance. A key role of H-bond connectivity patterns of water molecules has been identified. The behavior of •OHaq strongly depends on water density and correlates with topological changes in the hydrogen-bonded structure of water driven by thermodynamic conditions. Liquid and supercritical water above the critical density exhibit the radical localization in cavities existing in the solvent structure. A change of mechanism has been found at supercritical conditions below the critical density. Instead of cavity localization, we have identified accumulation of water molecules around •OH associated with the formation of a strong H-donor bond and diminution of non-homogeneity in the solvent structure. For all the systems investigated, the computed hydration number and the internal energy of hydration ΔhU showed approximately linear decrease with decreasing density of the solvent but a degree of radical-water hydrogen bonding exhibited non-monotonic dependence on density. The increase in the number of radical-water H-acceptor bonds is associated with diminution of extended nets of four-bonded water molecules in compressed solution at ∼473 K. Up to 473 K, the isobaric heat of hydration in compressed liquid water remains constant and equal to −40 ± 1 kJ mol−1.

© 2012 American Institute of Physics

Article Outline

  1. INTRODUCTION
  2. SIMULATION METHOD
  3. RESULTS AND DISCUSSION
    1. Structural properties
    2. Radical-water hydrogen bonding
    3. Water-water hydrogen bonding
    4. Energetic properties of • OH
  4. CONCLUSION

RELATED DATABASES

To view database links for this article, you need to log in.

KEYWORDS and PACS

Keywords

free radicals, hydrogen bonds, molecular dynamics method, solvation, water

PACS

  • 82.30.Rs

    Hydrogen bonding, hydrophilic effects

  • 82.30.Nr

    Association, addition, insertion, cluster formation

ARTICLE DATA

Digital Object Identifier
http://dx.doi.org/10.1063/1.3683436

PUBLICATION DATA

ISSN

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

Publisher

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

For access to fully linked references, you need to log in.
    D. Swiatla-Wojcik and J. Szala-Bilnik, J. Chem. Phys. 134, 054121 (2011)JCPSA6000134000005054121000001.

    R. Car and M. Parrinello, Phys. Rev. Lett. 55, 2471 (1985).

    T. D. Kuhne, M. Krack, F. Mohamed, and M. Parrinello, Phys. Rev. Lett. 98, 066401 (2007).

    G. Raabe and R. J. Sadus, J. Chem. Phys. 134, 234501 (2011)JCPSA6000134000023234501000001.

    M. G. Campo and J. R. Grigera, J. Chem. Phys. 123, 084507 (2005)JCPSA6000123000008084507000001.

    B. Guillot and Y. Guissani, J. Chem. Phys. 108, 10162 (1998)JCPSA6000108000024010162000001.

    N. Matubayasi, C. Wakai, and M. Nakahara, J. Chem. Phys. 107, 9133 (1997)JCPSA6000107000021009133000001.


Figures (13) Tables (2)

Access to article objects (figures, tables, multimedia) requires a subscription; log in to view available files.
(Access to supplementary files, where available, is free for this journal.)

Access to article objects (figures, tables, multimedia) requires a subscription; log in to view available files.
(Access to supplementary files, where available, is free for this journal.)


Close

Google Calendar

ADVERTISEMENT

Your Recent History Recent History Help

Recently Viewed

  1. Mechanism of OH radical hydration: A comparative computational study of liquid and supercritical solvent
  2. Time-resolved simultaneous polarized and depolarized light scattering system with high sensitivity to optical anisotropy: Application to phase separation of an optically isotropic liquid mixture
  3. Dynamics and efficiency of a self-propelled, diffusiophoretic swimmer
  4. First principles analysis of the initial oxidation of Si(001) and Si(111) surfaces terminated with H and CH3
  5. Elucidation of spin echo small angle neutron scattering correlation functions through model studies
Go to AIP Home
Copyright © American Institute of Physics
close