Quantum chemical semi-empirical approach to the thermodynamic characteristics of oligomers and large aggregates of alcohols at the water/air interface

Vysotsky, Yu. B.; Bryantsev, Vyacheslav S.; Fainerman, V. B.; Vollhardt, D.; Miller, R.

doi:10.1016/s0927-7757(02)00169-3

Cited by 29 publications

(111 citation statements)

References 38 publications

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“…[13][14][15][16] The surface pressure/area per one molecule (Π/A) isotherm for octadecylamine (C 18 ) at 25°C does not exhibit any critical points relevant to a transition from the liquid-expanded (LE) to liquid-condensed (LC) monolayer state. 13 At the same time, the analysis of this isotherm using the thermodynamic model proposed in refs 3 and 4 indicates that the formation of small aggregates (aggregation number [4][5][6][7][8] is probable in the LE monolayer range. The studies of eicosylamine (C 20 ) 14, 15 and docosylamine (C 22 ) 16 monolayers indicate the existence of a LE/LC phase transition point in the Π/A isotherms.…”

Section: ∆S Mmentioning

confidence: 73%

Quantum Chemical Analysis of the Thermodynamics of 2-Dimensional Cluster Formation of Alkylamines at the Air/Water Interface

et al. 2007

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The thermodynamic parameters of the formation of monomers, dimers, trimers, tetramers, and one hexamer of alkylamines with the alkyl chain length in the range of 6 to 16 carbon atoms are calculated using the semiempirical PM3 method. The dependencies of potential energy surfaces of monomers and dimers on corresponding torsion angles are analyzed to determine the most stable conformations (local and global minima) of these entities. The thermodynamic parameters of cluster formation (enthalpies, entropies, and Gibbs' energies) are calculated for the dimers, trimers, tetramers, and the hexamer. The additive approach was further developed to extend the results of the calculations of the thermodynamic properties of small associates (2-6 amine molecules) to infinite clusters. It is shown that these parameter values are stepwise-dependent on the alkyl chain length, and spontaneous cluster formation takes place for this class of compounds when the alkyl chain length becomes 18-19 carbon atoms and higher.

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Section: ∆S Mmentioning

confidence: 73%

Quantum Chemical Analysis of the Thermodynamics of 2-Dimensional Cluster Formation of Alkylamines at the Air/Water Interface

et al. 2007

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“…Also used were the AM1 [42,43] or PM3 [44,45] methods, which are semiempirical QM approaches for calculating the charge distribution of the surfactant [10] or the thermodynamic characteristics of oligomers of alcohols [9]; these routines may be used to calculate larger systems compared to DFT methods.…”

Section: Quantum Mechanical Calculationsmentioning

confidence: 99%

“…In recent years, many simulation studies on the self-assembly behavior of amphiphilic molecules in the solution or at the interface were performed by applying various computational techniques including quantum mechanics (QM) [9,10], Monte Carlo (MC) [11][12][13], molecular dynamics (MD) [14][15][16], and Mesodyn simulation [17][18][19], or dissipative particle dynamics (DPD) simulations [20][21][22]. These theoretical methods involved ab initio methods, all-atomic simulations, coarse-grain models and mesoscale simulations.…”

Section: Introductionmentioning

confidence: 99%

Surface behavior of a model surfactant: A theoretical simulation study

Yuan¹,

Yan²,

Lv³

et al. 2010

Journal of Colloid and Interface Science

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“…In the preceding paper [175], we showed that the dimerization enthalpy of alcohols in water (using the COSMO model [176]) and in the air is quite similar. Therefore, the described model has been correctly used for the calculation of the thermodynamic and structural parameters of the nonionic surfactant clusterization at the air/water interface.…”

Section: Model and Methods Descriptionmentioning

confidence: 88%

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

2015

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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 Btemperature 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.

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Quantum chemical semi-empirical approach to the thermodynamic characteristics of oligomers and large aggregates of alcohols at the water/air interface

Cited by 29 publications

References 38 publications

Quantum Chemical Analysis of the Thermodynamics of 2-Dimensional Cluster Formation of Alkylamines at the Air/Water Interface

Quantum Chemical Analysis of the Thermodynamics of 2-Dimensional Cluster Formation of Alkylamines at the Air/Water Interface

Surface behavior of a model surfactant: A theoretical simulation study

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

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