Molecular Dynamic Simulations in Interfacial Electrochemistry

Benjamin, Ilan

doi:10.1007/0-306-46910-3_3

Cited by 31 publications

(15 citation statements)

References 183 publications

(245 reference statements)

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“…This plane forms a 60°angle relative to the surface normal. This is consistent with the tendency of water to maintain its hydrogen bonding network as observed at other water/solid interfaces 45 and it is also indicative of poor surface wetting. In contrast, the rough surfaces show broad distributions of water dipole and water O-H bonds in the 0-100°range with significant populations of O-H bonds pointing toward the surface, indicating surface wetting.…”

Section: Resultssupporting

confidence: 87%

Adsorption at the Interface between Water and Self-Assembled Monolayers: Structure and Electronic Spectra

and

Benjamin

2002

J. Phys. Chem. B

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The structure of the interface between water and self-assembled organic monolayers having different roughness and polarity is investigated by molecular dynamics computer simulations. The electronic absorption spectrum of an adsorbed chromophore at these different interfaces is computed and correlated with the structure of the interface. Several different electronic transitions characterized by different changes in the electric dipole moment are considered. We find that the effective polarity of the interface is greater than that of bulk water in contrast to the situation at several liquid/liquid interfaces, but in agreement with recent experiments at the liquid/solid interface. We show that this higher effective polarity is due to a contribution from the polar groups at the surface that is larger than the loss due to the decreased interaction with water.

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Section: Resultssupporting

confidence: 87%

Adsorption at the Interface between Water and Self-Assembled Monolayers: Structure and Electronic Spectra

and

Benjamin

2002

J. Phys. Chem. B

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“…In the original version, each charge in the liquid phase interacts with the projections of all image charges, reflected inside the electrode. This total-image method for the simulation of the polarization effects in the metal has been commonly used for water near metalic electrodes and the adsorption of liquid phases on surfaces, [5][6][7]18,19 however, some comments should be made. In the case of water near a polarizable surface, the induction effect due to a single molecule can be very large.…”

Section: Models For the Liquid Phase In Contact With The Electrodesmentioning

confidence: 99%

“…Structural factors play a major role in the processes taking place in the interfacial region determining, for example, the resultant products of electron transfer reactions. 1,2 Computer simulation techniques, namely Monte Carlo (MC) and Molecular Dynamics (MD), 3,4 have successfully been used in the study of different electrode/solution phenomena such as the molecular details concerning the structure of the liquid phase in the interfacial region [5][6][7][8][9][10][11] and the charge and field distributions in the electrical double layer (edl) in the presence of specific and non specific adsorption of ionic and organic species. [12][13][14][15][16][17][18][19] The combination of such kind of information with experimental results strongly contribute to the understanding of the behaviour of interfacial systems.…”

Section: Introductionmentioning

confidence: 99%

Monte Carlo simulation of the adsorption of phenol on gold electrodes: a simple model

Neves

Motheo

Fernandes

et al. 2004

J. Braz. Chem. Soc.

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Neste trabalho são apresentadas simulações de Monte Carlo no ensemble canônico, a 298 K, da adsorção de fenol, a partir de uma solução aquosa diluída, em eletrodos de ouro no potencial de carga zero. Os resultados sugerem que o processo de adsorção ocorre em duas etapas distintas e consecutivas. A adsorção tem início com o átomo de oxigênio da molécula de fenol apontando em direção ao eletrodo, com o anel aromático adotando um inclinação aproximadamente perpendicular em relação à superfície. Segue-se, então, a reorientação do anel, que adota a orientação paralela ao eletrodo. O efeito do solvente é analisado através do potencial da força média que atua no fenol. Apesar da simplicidade do modelo e potenciais de interação utilizados nas simulações, os resultados estão de acordo com observações experimentais, fornecendo informações sobre os detalhes microscópicos do processo de adsorção do fenol em baixas concentrações.Canonical Monte Carlo simulations, at 298 K, of the adsorption of phenol in a dilute aqueous solution on gold electrodes, at the potential of zero charge, are presented. The results suggest that the process occurs in two distinct and successive steps. Adsorption starts with the phenol oxygen atom pointing towards the gold surface and the aromatic ring in a quasi-perpendicular orientation relative to the surface. This is followed by the reorientation of the aromatic ring to a parallel configuration. The effect of the solvent is analyzed through the calculation of the potential of mean force acting on phenol. Despite the simplicity of the model and the interaction potentials used in the simulations, the results are in good agreement with experimental observations, giving insight into the microscopic details of the adsorption process of phenol at low concentrations.

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“…U w is the total water intermolecular and intramolecular potential energy surfaces, described using the flexible SPC model, 35 which has been shown to give reasonable bulk and interfacial properties. 36,37 U ν LJ and U ν Coul are the solute−water Lennard-Jones and Coulomb interaction energies, respectively, in the state ν (ν = i or f). These are explicitly given by…”

Section: A Dipolar Solute Modelmentioning

confidence: 99%

“…Thus, the potential energy surfaces of the initial and final states are .25ex2ex H i = U normalw + U i normalL normalJ + U i Coul H f = normalΔ E 0 + U normalw + U f normalL normalJ + U f Coul In eq , Δ E 0 is the vacuum energy difference between the final and initial states. U w is the total water intermolecular and intramolecular potential energy surfaces, described using the flexible SPC model, which has been shown to give reasonable bulk and interfacial properties. , U ν LJ and U ν Coul are the solute–water Lennard-Jones and Coulomb interaction energies, respectively, in the state ν (ν = i or f ). These are explicitly given by .25ex2ex U normalν normalL normalJ = 4 normalε normalν normalε normalO ∑ n = 1 N true[ true( normalσ r 1 n true) 12 − true( normalσ r 1 n true) …”

Section: A Dipolar Solute Modelmentioning

confidence: 99%

Electronic Absorption Line Shapes at the Water Liquid/Vapor Interface

Nelson

Benjamin

2012

J. Phys. Chem. B

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In order to investigate the factors that contribute to the electronic absorption line shape of a chromophore adsorbed at the water liquid/vapor interface, molecular dynamics simulations of a series of dipolar solutes undergoing various electronic transitions at various locations along the interface normal are studied. For electronic transitions that involve a change in the permanent dipole moment of the solute, the transition from the bulk water to the liquid/vapor interface involves a spectral shift consistent with the lower polarity of the interface. The change in the spectral width relative to that in the bulk is determined by several factors, which, depending on the nature of the transition and the dipole moment of the initial state, can result in a narrowing or broadening of the spectrum. These factors include the location of the interface region (which directly correlates with local polarity), the heterogeneity of the local solvation shell, and the width of the surface region. The contribution of the heterogeneity of the local solvation shell can be determined by comparing surface water with bulk methanol, whose polarity is comparable to one of the surface regions.

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Molecular Dynamic Simulations in Interfacial Electrochemistry

Cited by 31 publications

References 183 publications

Adsorption at the Interface between Water and Self-Assembled Monolayers: Structure and Electronic Spectra

Adsorption at the Interface between Water and Self-Assembled Monolayers: Structure and Electronic Spectra

Monte Carlo simulation of the adsorption of phenol on gold electrodes: a simple model

Electronic Absorption Line Shapes at the Water Liquid/Vapor Interface

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