Diffusion at interfaces

From SklogWiki
Revision as of 15:09, 4 December 2007 by Dduque (talk | contribs) (more or less complete)
Jump to: navigation, search

Diffusion at the liquid-vapor interface is both interesting and controversial. The very definition of particles "at" the interface is difficult. The diffusion coefficient will in this case be a diagonal tensor; two of its elements are equal and correspond to parallel diffusion (along the interface), the third one corresponds to normal, or perpendicular diffusion (across the interface). Since the particles are continuously leaving and entering the interfacial region, it is also important to study this dynamical process by, e.g., the residence time.

Typically, slabs corresponding to the interfacial region are obtained, and diffusion processes are considered for each of them separatelly. The three Cartesian components may be mixed [1,8], or separated, as in most of the other Refs below. Sometimes diffusion is only tracked down for times shorter than the residence time [5,8]. The work by Liu et al. [10] employes a refined treatment using Smoluchowski equations. Its subtlety, combined by the application to perhaps the most interesting system, the liquid water surface, makes this reference quite important. See also Ref [17] (still unpublished) for a criticism of these techniques, and a consideration of the problem from the point of view of the intrinsic surface.


pure system Ref
ST-2 Water [2]
TIP4P/FQ Water [9], [11]
SPC/E Water [5]
Dimethyl sulfoxide [7]
Ethanol [8]
liquid metals [13]


mixture Ref
two inmiscible LJs [1], [10]
water/1,2-dichloroethane [3]
water/nitrobenzene [6]
surfactants on water [16]
ions at surfaces [12]

Confined fluids:

system Ref
water on surfaces [4]
LJ on solid [15]
water diffusion across chanels [14]


  1. M. Meyer, M. Mareschal, and M. Hayoun "Computer modeling of a liquid–liquid interface" J. Chem. Phys. 89 pp. 1067-1073 (1988)
  2. R. Michael Townsend and Stuart A. Rice "Molecular dynamics studies of the liquid–vapor interface of water" J. Chem. Phys. 94 pp. 2207-2218 (1991)
  3. Ilan Benjamin "Theoretical study of the water/1,2-dichloroethane interface: Structure, dynamics, and conformational equilibria at the liquid–liquid interface" J. Chem. Phys. 97 pp. 1432-1445 (1992)
  4. Song Hi Lee and Peter J. Rossky "A comparison of the structure and dynamics of liquid water at hydrophobic and hydrophilic surfaces—a molecular dynamics simulation study" J. Chem. Phys. 100 pp. pp. 3334-3345 (1994)
  5. R. S. Taylor, L. X. Dang, and B. C. Garrett "Molecular Dynamics Simulations of the Liquid/Vapor Interface of SPC/E Water" J. Phys. Chem. 100, 11720 (1996)
  6. Michael, D. Benjamin "Molecular dynamics simulation of the water/nitrobenzene interface", Journal of Electroanalytical Chemistry 450 p.335-345, (1998)
  7. Sanjib Senapati "A molecular dynamics simulation study of the dimethyl sulfoxide liquid–vapor interface"J. Chem. Phys. 117 pp. 1812-1816 (2002)
  8. Ramona S. Taylor and Roseanne L. Shields "Molecular-dynamics simulations of the ethanol liquid–vapor interface" J. Chem. Phys. 119 pp. 12569-12576 (2003)
  9. Pu Liu, Edward Harder, and B. J. Berne "On the Calculation of Diffusion Coefficients in Confined Fluids and Interfaces with an Application to the Liquid-Vapor Interface of Water" J. Phys. Chem. B 108 pp 6595 - 6602 (2004)
  10. Jörn B. Buhn, Philippe A. Bopp, and Manfred J. Hampe "A molecular dynamics study of a liquid–liquid interface: structure and dynamics" Fluid Phase Equilibria 224 pp. 221-230 (2004)
  11. Pu Liu, Edward Harder, and B. J. Berne "Hydrogen-Bond Dynamics in the Air-Water Interface" J. Phys. Chem. B, 109 (7) pp 2949 - 2955 (2005)
  12. Tsun-Mei Chang and Liem X. Dang "Recent Advances in Molecular Simulations of Ion Solvation at Liquid Interfaces" Chem. Rev. 106 pp 1305 - 1322 (2006)
  13. Luis E González and David J González "Ab initio study of the atomic motion in liquid metal surfaces: comparison with Lennard-Jones systems" J. Phys.: Condens. Matter 18 pp. 11021-11030 (2006)
  14. Vincent J. van Hijkoop, Anton J. Dammers, Kourosh Malek, and Marc-Olivier Coppens "Water diffusion through a membrane protein channel: A first passage time approach" J. Chem. Phys. 127 085101 (2007)
  15. J. A. Thomas and A. J. H. McGaughey "Effect of surface wettability on liquid density, structure, and diffusion near a solid surface" J. Chem. Phys. 126 034707 (2007)
  16. Javier Rodriguez and Daniel Laria "Computer simulations of catanionic surfactants adsorbed at air/water interfaces. II. Full coverage"J. Chem. Phys. 127 124704 (2007)
  17. [D. Duque, P. Tarazona, and E. Chacón To be published]