Infrared Spectroscopy of Molecules Adsorbed on Metal Surfaces

Ryberg, R.

doi:10.1002/9780470141250.ch1

Cited by 22 publications

(11 citation statements)

References 77 publications

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“…In this configuration of near-parallel transition dipole moments aligned preferentially along the surface normal, we anticipate that the underlying cause of the blue shift of the AX peak with increasing coverage is dipole−dipole coupling. The formalism of these coupling interactions has been elaborated in detail by Persson and co-workers, − and has quantitatively described the behavior of systems such as CO/metals, whereby individual transition dipole moments are aligned parallel to the surface normal. − The fundamental aspect of their model (and of previous less sophisticated models , ) is to consider the perturbation of the oscillation modes of the surface species by the simultaneous oscillations of the surrounding dipole moments; these neighboring oscillators must include the real molecular systems, as well as the image dipoles mathematically positioned within the conductive substrate. This coupling is expressed as a sum of dipole−dipole interactions across both types of species, including the appropriate geometric factors required to define the system.…”

Section: Discussionmentioning

confidence: 99%

Fe(CO)₅ Thin Films Adsorbed on Au(111) and on Self-Assembled Organic Monolayers: I. Structure

2005

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The adsorption of Fe(CO)(5) onto Au(111)/mica and C(4), C(8), C(12), and C(16) SAMs/Au(111)/mica surfaces has been studied using infrared spectroscopy to elucidate the coverage-dependent structures of these films and the intermolecular couplings that determine the form of the spectra. For all substrates, the first layer is composed of molecules physisorbed with one axial and two equatorial carbonyl groups directed toward the substrate; subsequent layers are preferentially oriented with the C(3) molecular axis aligned perpendicular to the substrate (i.e., one axial carbonyl group directed toward the substrate). The axial vibrational band systematically shifts to higher frequencies with increasing surface coverage because of the effects of intermolecular coupling of the quasiparallel transition dipole moments. The strong effects of dipolar coupling are also witnessed by the trends of the band positions when the distance to the image plane is systematically varied using highly organized self-assembled organic substrates; no band shifts are observed when dilute Fe(CO)(5) is embedded in Xe matrixes under identical experimental conditions. The as-deposited films are structurally stable below 125 K on Au(111)/mica surfaces and below 100 K on the organic self-assembled monolayers. The instability of the films above these temperatures demonstrates that the as-adsorbed films do not form thermodynamically well-defined phases but are structurally metastable. The results presented herein and in the companion paper provide a consistent framework to interpret the spectroscopy of these systems that resolves outstanding issues concerning these films and provides a structural model that explains the dynamic properties of these films during exposure to low-energy electron beams.

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Section: Discussionmentioning

confidence: 99%

Fe(CO)₅ Thin Films Adsorbed on Au(111) and on Self-Assembled Organic Monolayers: I. Structure

2005

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“…The break in the Stark tuning rate of the carbonate peak in the electrocatalytic region can be attributed to a decrease in the local surface concentration of η 1 -CO 3 2− by negative surface charge and hydrogen adsorption. A decrease in the local surface concentration of randomly adsorbed dipoles pulls their collective vibrational frequency down because it makes their dipole-dipole coupling weaker (54).…”

Section: −mentioning

confidence: 99%

On the origin of the elusive first intermediate of CO ₂ electroreduction

Чернышова

Somasundaran

Ponnurangam

2018

Proc. Natl. Acad. Sci. U.S.A.

393

332

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We resolve the long-standing controversy about the first step of the CO electroreduction to fuels in aqueous electrolytes by providing direct spectroscopic evidence that the first intermediate of the CO conversion to formate on copper is a carboxylate anion *CO coordinated to the surface through one of its C-O bonds. We identify this intermediate and gain insight into its formation, its chemical and electronic properties, as well as its dependence on the electrode potential by taking advantage of a cutting-edge methodology that includes operando surface-enhanced Raman scattering (SERS) empowered by isotope exchange and electrochemical Stark effects, reaction kinetics (Tafel) analysis, and density functional theory (DFT) simulations. The SERS spectra are measured on an operating Cu surface. These results advance the mechanistic understanding of CO electroreduction and its selectivity to carbon monoxide and formate.

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“…Thus it can be difficult to extract accurate homogeneous line widths from IR spectra of adsorbates. Despite this, infrared line-shapes have provided useful evidence of vibrational coupling of adsorbates to phonons, EHPs and to other adsorbate vibrations [30][31][32][33][34][35]. For example, Ryberg reported intrinsic linewidths of CO on Cu(1 0 0) close to 5 cm À1 suggesting ps timescales for vibrational relaxation [30].…”

Section: Infrared Linewidthsmentioning

confidence: 99%

Energy transfer and chemical dynamics at solid surfaces: The special role of charge transfer

Wodtke

Matsiev

Auerbach

2008

Progress in Surface Science

172

161

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Molecular energy transfer processes at solid surfaces are profoundly important, influencing trapping, desorption, diffusion, and reactivity; in short, all of the elementary steps needed for surface chemistry to take place. In this paper we review recent progress in our understanding of energy transfer at surfaces with a particular emphasis on those phenomena, which are peculiar to solids with delocalized electronic structure, e.g. electronically nonadiabatic energy transfer. This area of study represents an area requiring significant extensions of our theoretical understanding, which is largely based on density functional theory. This review provides an overview of some of the experimental and theoretical tools presently being used in this field and a description of several illustrative examples of work that have helped to shape our understanding.

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Infrared Spectroscopy of Molecules Adsorbed on Metal Surfaces

Cited by 22 publications

References 77 publications

Fe(CO)₅ Thin Films Adsorbed on Au(111) and on Self-Assembled Organic Monolayers: I. Structure

Fe(CO)₅ Thin Films Adsorbed on Au(111) and on Self-Assembled Organic Monolayers: I. Structure

On the origin of the elusive first intermediate of CO ₂ electroreduction

Energy transfer and chemical dynamics at solid surfaces: The special role of charge transfer

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Infrared Spectroscopy of Molecules Adsorbed on Metal Surfaces

Cited by 22 publications

References 77 publications

Fe(CO)5 Thin Films Adsorbed on Au(111) and on Self-Assembled Organic Monolayers: I. Structure

Fe(CO)5 Thin Films Adsorbed on Au(111) and on Self-Assembled Organic Monolayers: I. Structure

On the origin of the elusive first intermediate of CO 2 electroreduction

Energy transfer and chemical dynamics at solid surfaces: The special role of charge transfer

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Fe(CO)₅ Thin Films Adsorbed on Au(111) and on Self-Assembled Organic Monolayers: I. Structure

Fe(CO)₅ Thin Films Adsorbed on Au(111) and on Self-Assembled Organic Monolayers: I. Structure

On the origin of the elusive first intermediate of CO ₂ electroreduction