Intrinsic structure and dynamics of the water/nitrobenzene interface

Miguel Jorge, M. Natalia D. S. Cordeiro

Research output: Contribution to journalArticle

87 Citations (Scopus)

Abstract

In this paper we present results of a detailed and systematic molecular dynamics study of the water/nitrobenzene interface. Using a simple procedure to eliminate fluctuations of the interface position, we are able to obtain true intrinsic profiles for several properties (density, hydrogen bonds, molecular orientation, etc.) in the direction perpendicular to the interfacial plane. Our results show that both water and organic inter-facial molecules form a tightly packed layer oriented parallel to the interface, with reduced mobility in the perpendicular direction. Beyond this layer, water quickly restores its bulk structure, while nitrobenzene exhibits structural anisotropies that extend further into the bulk region: Water molecules that protrude farthest into the organic phase point one hydrogen atom in the direction perpendicular to the interface, forming a hydrogen bond with a nitrobenzene oxygen. By fitting both the global and the intrinsic density profiles, we obtain estimates for the total and intrinsic interface widths, respectively. These are combined with capillary wave theory to produce a self-consistent method for the calculation of the inter-facial tension. Values calculated using this method are in very good agreement with direct calculations from the components of the pressure tensor.

LanguageEnglish
Pages17612-17626
Number of pages15
JournalJournal of Physical Chemistry C
Volume111
Issue number47
Early online date7 Nov 2007
DOIs
Publication statusPublished - 29 Nov 2007

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Nitrobenzene
nitrobenzenes
Water
water
Hydrogen bonds
Molecules
Molecular orientation
hydrogen bonds
capillary waves
Tensors
Molecular dynamics
Hydrogen
profiles
Anisotropy
Oxygen
molecules
hydrogen atoms
Atoms
nitrobenzene
tensors

Keywords

  • intrinsic structure
  • dynamics
  • water/nitrobenzene interface

Cite this

Jorge, Miguel ; Cordeiro, M. Natalia D. S. / Intrinsic structure and dynamics of the water/nitrobenzene interface. In: Journal of Physical Chemistry C. 2007 ; Vol. 111, No. 47. pp. 17612-17626.
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Intrinsic structure and dynamics of the water/nitrobenzene interface. / Jorge, Miguel; Cordeiro, M. Natalia D. S.

In: Journal of Physical Chemistry C, Vol. 111, No. 47, 29.11.2007, p. 17612-17626.

Research output: Contribution to journalArticle

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