The Ultrafast Dynamics of Image Potential State Electrons at the Dimethylsulfoxide/Ag(111) Interface

Strader, Matthew L.; Garrett-Roe, Sean; Szymanski, Paul; Shipman, Steven T.; Johns, James E.; Yang, Aram; Muller, Eric A.; Harris, Charles B.

doi:10.1021/jp7116664

Cited by 5 publications

(22 citation statements)

References 34 publications

(88 reference statements)

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“…In order to decouple the influence of solutes and co-adsorbates, studies have focused on the interaction and dynamics of DMSO with metal surfaces and excess electrons using surface science techniques. [23][24][25][26] Structural studies of DMSO on noble metal surfaces show that DMSO orders to the metal surface, binding in either a mono-or bi-dentate manner through the sulfur or the sulfur and oxygen lone pairs, [23][24][25] while maintaining long-range order between chains of DMSO molecules. After electron injection from a Ag(111) surface into one and two layers of DMSO, image potential states (IPS) of Ag modified by the layers of DMSO are initially formed.…”

Section: Introductionmentioning

confidence: 99%

Multistep and multiscale electron transfer and localization dynamics at a model electrolyte/metal interface

King

Broch

Demling

et al. 2018

The Journal of Chemical Physics

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The lifetime, coupling, and localization dynamics of electronic states in molecular films near metal electrodes fundamentally determine their propensity to act as precursors or reactants in chemical reactions, crucial for a detailed understanding of charge transport and degradation mechanisms in batteries. In the current study, we investigate the formation dynamics of small polarons and their role as intermediate electronic states in thin films of dimethyl sulfoxide (DMSO) on Cu(111) using time-and angle-resolved two-photon photoemission spectroscopy. Upon photoexcitation, a delocalized DMSO electronic state two monolayers from the Cu surface is initially populated, becoming a small polaron on a 200 fs timescale, consistent with localization due to vibrational dynamics of the DMSO film. The small polaron is a precursor state for an extremely long-lived and weakly-coupled multilayer electronic state, with a lifetime of several seconds, thirteen orders of magnitude longer than the small polaron. Although the small polaron in DMSO has a lifetime of 140 fs, its role as a precursor state for long-lived electronic states could make it an important intermediate in multistep battery reactivity.

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Section: Introductionmentioning

confidence: 99%

Multistep and multiscale electron transfer and localization dynamics at a model electrolyte/metal interface

King

Broch

Demling

et al. 2018

The Journal of Chemical Physics

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“…Petek and coworkers made the first 2PPE studies of electron solvation in an alcohol on a semiconductor surface rather than a metallic one by studying MeOH/TiO 2 [67]. Below, we present a summary of our most recent work on electron solvation, a study of the differential capacitance of DMSO/Ag(111) with two-photon photoemission [31].…”

Section: Ips Decay For Solvating Moleculesmentioning

confidence: 99%

“…The results for these experiments are presented in more detail in Ref. [31]. Mono-and multilayers of DMSO were successfully grown on a clean Ag(111) surface.…”

Section: Ips Decay For Solvating Moleculesmentioning

confidence: 99%

“…This method was developed and applied for studying the IPS intraband relaxation (electronic cooling) of p-xylene/Ag(111) by Garrett-Roe et al [24]. The second model we discuss is a practical model used to relate the dynamics of IPS solvation to the differential capacitance of molecules adsorbed to metal electrodes in electrochemistry, first published by Strader et al [31].…”

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confidence: 99%

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Relaxation Dynamics in Image Potential States at Solid Interfaces

Johns¹,

Muller²,

Strader³

et al. 2010

Dynamics at Solid State Surfaces and Interfaces

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The interface between metals and molecules remains an area of highly active research. The abrupt change in electronic environment between the electron gas of a metal and the covalent bonds of a molecule give rise to new surface states such as charge transfer excitons, metal-induced gap states (MIGS), and deep trap sites [1,2]. The behavior of electrons at these interfaces dominates both charge injection and charge collection in the growing number of molecular electronic devices. We have studied the dynamics and energetics of these interfacial states, specifically focusing on two particular states, the image potential state (IPS) and molecular based lowest unoccupied molecular orbitals (LUMOs).The image potential is the attractive potential that a charge feels near the surface of a conductor. An electron at the surface of metal induces a polarization in the metal, which exposes some of the underlying positive ionic cores. The actual shape of this polarization is quite complex inside the metal. Outside the metal, however, the potential is exactly that of a fictitious positive point charge placed inside the metal at a distance from the surface equal to that of the electron. This results in the classical 1/z distance-dependent form of the image potential. Quantum mechanically, this image potential can be solved analogously to a one-dimensional hydrogen atom, leading to a Rydberg-like series of bound states that converge to the vacuum level of the system.Electrons from inside the metal can be either directly or indirectly excited into these states upon exposure to ultraviolet (UV) light. For bare metal surfaces, the average distance from the surface of an electron in the first IPS (n ¼ 1, where n is the Rydberg quantum number) is on the order of 3 A . Energetically, the states are bound by 0.9-0.5 eV below the vacuum level, and decay via direct tunneling in under 50 fs. In the presence of a nonmetallic adsorbate, the IPS is partially screened by electrons in the adsorbate. The IPS can also hybridize with other molecular states at the interface, altering the energy of the state and changing the overlap of the IPS with the metal surface. In systems with strong electron-nuclear coupling such as organic molecules, the presence of an excess external charge can also lead to an induced nuclear motion that can further change the wave function and energy of the IPS. This makes

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Nonaqueous Solvent Adsorption on Transition Metal Surfaces with Density Functional Theory: Interaction of N,N-Dimethylformamide (DMF), Tetrahydrofuran (THF), and Dimethyl Sulfoxide (DMSO) with Ag, Cu, Pt, Rh, and Re Surfaces

2021

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Interfaces between solvents and transition metals play a critical role in many catalytic and electrochemical systems. In this work, we use density functional theory (DFT) to study the interactions between several common nonaqueous solvents and a number of transition metal surfaces. We investigate trends in binding energies among the metals, and the influence of specific surface sites and facets. We examine the electrostatic field dependence of the most stable binding configurations, and shed light on experimentally observed field-dependent or potential-dependent adsorption structures. We demonstrate that the reorientation of DMSO on noble metal surfaces can occur with only a relatively small change in the surface dipole moment; this result is simultaneously consistent with experimental evidence for field-dependent reorientation and measurements of surprisingly low differential capacitance of DMSO on noble metals. These results contribute to understanding competitive adsorption effects in catalysis, and also have implications for fundamental surface properties such as the surface structure, solvated work function, and potential of zero charge.

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The Ultrafast Dynamics of Image Potential State Electrons at the Dimethylsulfoxide/Ag(111) Interface

Cited by 5 publications

References 34 publications

Multistep and multiscale electron transfer and localization dynamics at a model electrolyte/metal interface

Multistep and multiscale electron transfer and localization dynamics at a model electrolyte/metal interface

Relaxation Dynamics in Image Potential States at Solid Interfaces

Nonaqueous Solvent Adsorption on Transition Metal Surfaces with Density Functional Theory: Interaction of N,N-Dimethylformamide (DMF), Tetrahydrofuran (THF), and Dimethyl Sulfoxide (DMSO) with Ag, Cu, Pt, Rh, and Re Surfaces

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