Adsorbate-induced surface stress, surface strain and surface reconstruction: CH3S on Cu(100) and Cu(111)

Bradley, M. K.; Woodruff, D.P.; Robinson, J.; Sheppard, Daniel Crispin; Hentz, A.

doi:10.1016/j.susc.2014.12.003

Cited by 4 publications

(11 citation statements)

References 28 publications

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“…3 The surface stress has been studied theoretically for a number of systems in which the guest atoms are chemisorbed on the surface. [146][147][148][149] When adsorbed atoms are chemically bound to the solid surface, the change in surface free energy is dominated by the enthalpy, and the surface stresses can therefore be readily calculated from the electronic structure density functional theory (eDFT) on the static atomic configurations. The first calculation was performed by Feibelman 146 for the effect of H and O adsorption on the stress of the Pt (111) surface, which showed significant reduction of tensile stresses, comparable with experimentally observed data.…”

Section: Coupling Between Thermodynamic and Elastic Aspects Of Adsmentioning

confidence: 99%

Adsorption-induced deformation of nanoporous materials—A review

Gor

Huber

Bernstein

2017

Applied Physics Reviews

222

214

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When a solid surface accommodates guest molecules, they induce noticeable stresses to the surface and cause its strain. Nanoporous materials have high surface area and, therefore, are very sensitive to this effect called adsorption-induced deformation. In recent years, there has been significant progress in both experimental and theoretical studies of this phenomenon, driven by the development of new materials as well as advanced experimental and modeling techniques. Also, adsorption-induced deformation has been found to manifest in numerous natural and engineering processes, e.g., drying of concrete, water-actuated movement of non-living plant tissues, change of permeation of zeolite membranes, swelling of coal and shale, etc. In this review, we summarize the most recent experimental and theoretical findings on adsorption-induced deformation and present the state-of-the-art picture of thermodynamic and mechanical aspects of this phenomenon. We also reflect on the existing challenges related both to the fundamental understanding of this phenomenon and to selected applications, e.g., in sensing and actuation, and in natural gas recovery and geological CO2 sequestration.

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Section: Coupling Between Thermodynamic and Elastic Aspects Of Adsmentioning

confidence: 99%

Adsorption-induced deformation of nanoporous materials—A review

Gor

Huber

Bernstein

2017

Applied Physics Reviews

222

214

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“…Currently, the exact structure of the c(2x6) phase remains under scrutiny. 9,18,21,31,47 The c(2x6) phase has a rectangular unit cell, while the other phases have a square unit cell.…”

Section: Atomic Modelsmentioning

confidence: 99%

“…18,46,47 The buckled c(2x2) description of the c(2x6) phase has been shown to be unstable. 31 The remaining two structures are included in Figure 2. To understand the stability of the different phases, we calculated the energies required to form the adatom-rich structure from the faulted-row structure by moving Cu atoms from the bulk to the surface, as in the following reaction:…”

Section: Atomic Modelsmentioning

confidence: 99%

“…This is different for to Cu[111], where much larger distortions are induced. 31 To better understand the changes in the BDEtot of the alkane thiolates as a function of the surface coverage and chain length (Figure 5), we quantify the intermolecular and adsorbate-substrate interactions, which play a role in SAM formation. For this purpose, we use the following definitions.…”

Section: Intermolecular and Substrate-adsorbate Interactionsmentioning

confidence: 99%

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Structural Phases of Alkanethiolate Self-Assembled Monolayers (C_1–12) on Cu[100] by Density Functional Theory

et al. 2020

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The structure and as such the properties of alkanethiolate self-assembled monolayers (SAMs) on metal surfaces depend on the surface structure, thiolate coverage and chain length. The chain length dependence of alkanethiolate phases on Au surfaces is extensively documented. Much less insight exists for alkanethiolate SAMs on Cu surfaces, despite the relevance for area-selective deposition (ASD) applications. This work therefore studies the phase behavior of alkanethiolates on Cu through density functional theory (DFT) modelling. Short chain thiolates (C1,2) display no phase behavior and their saturation coverage is determined by steric hindrance. Longer thiolates (C6,12)show distinct lying-down and standing-up phases. The substrate-adsorbate interactions become weaker with increasing thiolate content, but still dominate in the standing-up phase at the saturation content of 5.1•10 14 thiolates•cm -2 . This is in contrast to Au [100] surfaces, where intermolecular interactions dominate at the saturation content, which is slightly higher than that on Cu[100]. The saturation coverage seems to be determined primarily by steric hindrance, which in turn will depend on the lattice parameter of the surface. We conclude that insights for alkanethiolate SAMs on Au cannot necessarily be transferred to Cu.

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“…The change of the surface stress due to adsorption has been studied theoretically for a number of systems in which the guest atoms are chemisorbed on the surface. − When adsorbed atoms are chemically bound to the solid surface, the change in surface free energy is dominated by the enthalpy, and the surface stresses can therefore be readily calculated from density functional theory (DFT) on static atomic configuration. The first such calculation was performed by Feibelman for the effect of H and O adsorption on the stress of the Pt (111) surface, which showed significant reduction of tensile stresses, comparable with experimentally observed data.…”

Section: Introductionmentioning

confidence: 99%

Adsorption-Induced Surface Stresses of the Water/Quartz Interface: Ab Initio Molecular Dynamics Study

Gor

Bernstein

2016

Langmuir

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Adsorption-induced deformation is expansion or contraction of a solid due to adsorption on its surface. This phenomenon is important for a wide range of applications, from chemomechanical sensors to methane recovery from geological formations. The strain of the solid is driven by the change of the surface stress due to adsorption. Using ab initio molecular dynamics, we calculate the surface stresses for the dry α-quartz surfaces, and investigate how these stresses change when the surfaces are exposed to water. We find that the nonhydroxylated surface shows small and approximately isotropic changes in stress, while the hydroxylated surface, which interacts more strongly with the polar water molecules, shows larger and qualitatively anisotropic (opposite sign in xx and yy) surface stress changes. All of these changes are several times larger than the surface tension of water itself. The anisotropy and possibility of positive surface stress change can explain experimentally observed surface area contraction due to adsorption.

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Adsorbate-induced surface stress, surface strain and surface reconstruction: CH3S on Cu(100) and Cu(111)

Cited by 4 publications

References 28 publications

Adsorption-induced deformation of nanoporous materials—A review

Adsorption-induced deformation of nanoporous materials—A review

Structural Phases of Alkanethiolate Self-Assembled Monolayers (C_1–12) on Cu[100] by Density Functional Theory

Adsorption-Induced Surface Stresses of the Water/Quartz Interface: Ab Initio Molecular Dynamics Study

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Adsorbate-induced surface stress, surface strain and surface reconstruction: CH3S on Cu(100) and Cu(111)

Cited by 4 publications

References 28 publications

Adsorption-induced deformation of nanoporous materials—A review

Adsorption-induced deformation of nanoporous materials—A review

Structural Phases of Alkanethiolate Self-Assembled Monolayers (C1–12) on Cu[100] by Density Functional Theory

Adsorption-Induced Surface Stresses of the Water/Quartz Interface: Ab Initio Molecular Dynamics Study

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Structural Phases of Alkanethiolate Self-Assembled Monolayers (C_1–12) on Cu[100] by Density Functional Theory