Theoretical description of 2D-cluster formation of nonionic surfactants at the air/water interface

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• 作者：Yu. B. Vysotsky ; E. S. Kartashynska ; D. Vollhardt
• 关键词：Amphiphilic monolayer ; Quantum chemical simulation ; Clusterization ; Nonionic surfactant ; Thermodynamic parameters
• 刊名：Colloid & Polymer Science
• 出版年：2015
• 出版时间：November 2015
• 年：2015
• 卷：293
• 期：11
• 页码：3065-3089
• 全文大小：1,506 KB
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• 作者单位：Yu. B. Vysotsky (1)
  E. S. Kartashynska (1)
  D. Vollhardt (2)
  
  1. Donetsk National Technical University, 58 Artema Str., 83000, Donetsk, Ukraine
  2. Max Planck Institute of Colloids and Interfaces, 14424, Potsdam/Golm, Germany
  
• 刊物类别：Chemistry and Materials Science
• 刊物主题：Chemistry
  Polymer Sciences
  Physical Chemistry
  Soft Matter and Complex Fluids
  Characterization and Evaluation Materials
  Food Science
  
• 出版者：Springer Berlin / Heidelberg
• ISSN：1435-1536

文摘

Recent progress in modeling of the surfactant behavior from atomistic to continuous at the air/water interface across different space-time scales is reviewed. Advantages and disadvantages of modern quantum mechanical, molecular dynamical, and mesoscale methods are discussed for description of interactions between amphiphilic molecules leading to formation of 2D films. The use of nonempirical and semiempirical methods for assessment of the thermodynamic and structural parameters of large van der Waals complexes is of particular interest. An approach for calculation of the thermodynamic and structural parameters of clusterization for nonionic surfactants at the air/water interface is proposed on the basis of the quantum chemical semiempirical PM3 method. This approach implicitly takes into account the influence of the interface on the surfactant molecules via stretching and orienting effect. The calculations are carried out in the supermolecule approximation for a limited number of small amphiphilic aggregates with different alkyl chain. The correlation analysis of the calculated data array provides the increments contributing by the intermolecular CH · · · HC interactions and interactions between hydrophilic parts into the thermodynamic parameters of formation and clusterization. Obtained increments are further used for constructing the dependencies of the thermodynamic clusterization parameters per one monomer on the alkyl chain length for large clusters up to 2D films. In the framework of the proposed theoretical approach, the next parameters are calculated as follows: enthalpy, entropy, and Gibbs’ energy of clusterization for 11 homologous series of nonionic surfactants, threshold chain length enabling the process of monolayer formation at standard conditions, the “temperature effect” of clusterization, and the structural parameters of the monolayer unit cell (particularly the tilt angle) depending on the size of the hydrophilic headgroup of the amphiphilic compound.