Why Silver Deposition is so Fast: Solving the Enigma of Metal Deposition

Pinto, Leandro Moreira de Campos; Spohr, Eckhard; Quaino, Paola; Santos, Elizabeth; Schmickler, Wolfgang

doi:10.1002/anie.201301998

Cited by 49 publications

(66 citation statements)

References 16 publications

(15 reference statements)

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“…Our first application was to the deposition of silver, which is one of the fastest electrochemical reactions. [6] From our theory we calculated the free-energy surface for silver deposition on a terrace and showed that, at zero overpotential, the energy of activation is lower than that for the subsequent incorporation of silver into a kink site, which is in accord with experimental data. [7] The high rate of the deposition was traced to two effects: 1) In aqueous solutions, small metal ions such as Ag + can get very close to the electrode surface without losing hydration energy; 2) the Ag 5s orbital interacts strongly with the silver sp band.…”

Section: Introductionsupporting

confidence: 71%

“…There is even a slight energy minimum next to the surface. As we have discussed before, [6] at these minima water forms a very effective solvation cage for such small metal ions. As water at the surface has fewer hydrogen bonds than in the bulk, it is free to orient its dipole moment in accord with the Coulomb force of the ions.…”

Section: Introductionmentioning

confidence: 95%

“…A picture of a metal ion in its solvation cage at the surface is shown in ref. [6]. We note that these metal ions behave quite differently from a halide ion, which loses a large part of its solvation energy as it approaches an electrode surface.…”

Section: Introductionmentioning

confidence: 97%

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On the Electrochemical Deposition and Dissolution of Divalent Metal Ions

Pinto¹,

Quaino²,

Santos³

et al. 2013

ChemPhysChem

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The deposition of Cu(2+) and Zn(2+) from aqueous solution has been investigated by a combination of classical molecular dynamics, density functional theory, and a theory developed by the authors. For both cases, the reaction proceeds through two one-electron steps. The monovalent ions can get close to the electrode surface without losing hydration energy, while the divalent ions, which have a stronger solvation sheath, cannot. The 4s orbital of Cu interacts strongly with the sp band and more weakly with the d band of the copper surface, while the Zn 4s orbital couples only to the sp band of Zn. At the equilibrium potential for the overall reaction, the energy of the intermediate Cu(+) ion is only a little higher than that of the divalent ion, so that the first electron transfer can occur in an outer-sphere mode. In contrast, the energy of the Zn(+) ion lies too high for a simple outer-sphere reaction to be favorable; in accord with experimental data this suggests that this step is affected by anions.

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Section: Introductionsupporting

confidence: 71%

Section: Introductionmentioning

confidence: 95%

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On the Electrochemical Deposition and Dissolution of Divalent Metal Ions

Pinto¹,

Quaino²,

Santos³

et al. 2013

ChemPhysChem

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“…Recent Density Functional Theory modeling of Ag + reduction at an electrode has shown that the ion in the double layer region exhibits an energy minimum 2.9 Å away from the electrode, sufficiently close to allow the ion to electronically interact with the electrode; the interaction between the 5 s orbital of Ag + and the sp band of the Ag electrode is therefore sufficiently strong to enable the fast deposition rate that is experimentally observed [30]. This theory, unfortunately, does not describe clearly the dynamic transition from ion to atom that Gileadi sought to understand.…”

Section: Mechanism Of Electron Transfermentioning

confidence: 99%

Electrodeposition of Alloys and Compounds in the Era of Microelectronics and Energy Conversion Technology

Zangari

2015

Coatings

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Electrochemical deposition methods are increasingly being applied to advanced technology applications, such as microelectronics and, most recently, to energy conversion. Due to the ever growing need for device miniaturization and enhanced performance, vastly improved control of the growth process is required, which in turn necessitates a better understanding of the fundamental phenomena involved. This overview describes the current status of and latest advances in electrodeposition science and technology. Electrochemical growth phenomena are discussed at the macroscopic and atomistic scale, while particular attention is devoted to alloy and compound formation, as well as surface-limited processes. Throughout, the contribution of Professor Foresti and her group to the understanding of electrochemical interfaces and electrodeposition, is highlighted.

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“…[62][63][64] Using classical molecular dynamics the authors showed that the silver cation could in fact retain a large portion of its solvation sheath quite close to the electrode. [62][63][64] Using classical molecular dynamics the authors showed that the silver cation could in fact retain a large portion of its solvation sheath quite close to the electrode.…”

Section: Watching Virtual Metal Atoms Dissolvementioning

confidence: 99%

Modeling Corrosion, Atom by Atom

Taylor¹

2014

Interface magazine

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I n the late 20 th century, computer programs emerged that could solve the fundamental quantum mechanical equations that control the interactions of atoms that give rise to bonding. These tools, first applied to molecules and bulk solid materials, then began to be applied to surfaces and, in the early 21 st century, to electrochemical environments. 1 Commercial and open-source programs are now readily available and can be used on both desktop and highperformance computing platforms to solve for the electronic structure of a given configuration of atomic centers (nuclei) and, in so doing, provide the basis for determining a whole host of properties, including electronic and vibrational spectra, electrical moments such as the system dipole, and, most importantly, the energy and forces on the atoms. 2-4 Other derived properties include the extent to which each atom is charged and bond-orders, although to compute these latter properties one of a variety of methods for dividing up and quantifying the electron density associated with each atom must be selected. 5 The physics behind these codes is complex, and, challengingly, has no rigorous analytical solution that can be obtained within a finite allotment of time. Thus, the computer programs themselves take advantage of approximations that allow for a feasible solution but, at the same time, constrain the accuracy of the result. Nonetheless, solutions can usually be reliably obtained for model systems representing materials, interfaces, or molecules that do not exceed thousands, and, more realistically, hundreds of atoms. 6 Given that system sizes of hundreds or thousands of atoms amount to no more than the smallest nanoparticle of a substance, the question arises: What can atomistic simulations teach us about corrosion?The answer to this question lies in the ability for atomistic simulation to confirm or deny key hypotheses associated with potential corrosion mechanisms. By directly simulating the structure of a molecule, its spectroscopic signatures, or the energetics of the bond-making and bond-breaking processes it engages in, much information can be gained that is useful to the interpretation of experiment and the verification of proposed theories. For instance, if a certain mechanistic step has a considerably large activation barrier (as computed from quantum mechanics), we can assume that it will not proceed unless somehow catalyzed. Furthermore, if a given atomic configuration is found to be metastable through molecular simulation, then we can predict that, over time, it will decay to a lower energy state. Furthermore, using periodic boundary conditions, it is possible to mimic the effects of semi-infinite surfaces (thus effectively going beyond the hundreds or thousands of atoms limit), albeit ensuring that careful attention is paid to address spurious results that may arise from image-image interactions.In this report we give several examples. In the first case we show how the computation of the properties of molecular systems can provide some insight as to ...

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Why Silver Deposition is so Fast: Solving the Enigma of Metal Deposition

Cited by 49 publications

References 16 publications

On the Electrochemical Deposition and Dissolution of Divalent Metal Ions

On the Electrochemical Deposition and Dissolution of Divalent Metal Ions

Electrodeposition of Alloys and Compounds in the Era of Microelectronics and Energy Conversion Technology

Modeling Corrosion, Atom by Atom

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