Ultrafast electron dynamics at water covered alkali adatoms adsorbed on Cu(111)

Meyer, Michael; Agarwal, Ishita; Wolf, Martin; Bovensiepen, Uwe

doi:10.1039/c4cp05356g

Cited by 9 publications

(25 citation statements)

References 30 publications

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“…As shown in Figure , we found an excellent linear correlation between the experimentally measured T m and our calculated BE’s, which prompts us to linearize eq . To the first order in the Taylor expansion of logarithms, ln(1 ± ϵ) ≈ ± ϵ, we obtain where ΔT = T m ,1 – T m ,2 and ΔE d = E d,1 – E d,2 .…”

Section: Results and Discussionsupporting

confidence: 73%

“…Equation was expressed in terms of ratios for convenience because they are better suited for comparison to experiments. The experimental TDS peaks are rather broad, but the peak of maximum rate occurs roughly at T m ≈ 210, 200, and 175 K for Na, K, and Cs, respectively …”

Section: Results and Discussionmentioning

confidence: 96%

“…Here we discuss the binding energies (BE) of water on alkali adatoms adsorbed on Cu(111) in light of the TDS findings of ref .…”

Section: Results and Discussionmentioning

confidence: 99%

“…The first (theoretical) definition is preferred when one does not know the experimental saturation coverage and will be used throughout this paper. As in ref , here we also studied a low alkali coverage to avoid dissociation of water molecules by the preadsorbed alkali ions. All calculations presented here are for an alkali coverage of θ = 1/16.…”

Section: Calculation Methods and Modelsmentioning

confidence: 99%

“…Our work is further motivated by an experimental study of submonolayer alkali-covered Cu(111) surface by Meyer et al After hydrating an alkali precovered Cu(111) surface, the authors found that (1) a new peak at higher temperature develops in thermal desorption spectroscopy (TDS) experiments, and it was attributed to water molecules directly bonded to the alkali adatom preadsorbed on Cu(111). Moreover, it was found that the desorption temperature peak decreases as one goes down the alkali group (Na > K > Cs) suggesting that the interaction alkali–water becomes weaker for heavier alkali.…”

Section: Introductionmentioning

confidence: 94%

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Hydrated Alkali Atoms on Copper(111): A Density Functional Theory Study

Paz

Rubio

2021

J. Phys. Chem. C

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We present a systematic computational study of submonolayer coverage of alkali atoms (Na, K, Cs) on Cu(111) surface hydrated from 1 to 6 water molecules. Our calculations show that water molecules preferentially bind to the adsorbed alkali ion and that a gradual detachment of the alkali from the Cu(111) surface is found as the hydration increases. This decoupling of the alkali from the Cu(111) surface results in a linear decrease of the charge transfer to the substrate. The orientation of the water dipoles pointing toward the surface leads to a gradual increase of the work function of the substrate as the number of coordinated water molecules increases from 1 to 4. Beyond 5 coordinated water molecules, the alkali adatom becomes saturated, and water adsorption sets in on the Cu(111) surface with the expected decrease in the work function of the system, as measured in two-photon photoemission spectroscopy (2PPE) experiments. From the detailed analysis of the orientation of the water electric dipoles, we were able to understand the experimentally observed initial increase of work function upon hydration and its subsequent decrease after saturation of alkali sites with water molecules. From the calculated energetics, we gauge the relative strengths of the alkali–Cu(111), alkali–water, and water–Cu(111) interactions as we move across the alkaline group. We found an excellent linear correlation between experimental water desorption temperatures and our computed water–alkali binding energies on Cu(111)

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Section: Results and Discussionsupporting

confidence: 73%

Section: Results and Discussionmentioning

confidence: 96%

“…Here we discuss the binding energies (BE) of water on alkali adatoms adsorbed on Cu(111) in light of the TDS findings of ref .…”

Section: Results and Discussionmentioning

confidence: 99%

Section: Calculation Methods and Modelsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 94%

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Hydrated Alkali Atoms on Copper(111): A Density Functional Theory Study

Paz

Rubio

2021

J. Phys. Chem. C

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A simple approximate solution for the H3+ ion

Paz

2022

Int J of Quantum Chemistry

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Here I derive analytical expressions for the total energy of the H þ 3 cation in its equilateral and linear geometries. The theoretical model consists of a simple variational trial wavefunction made of the sum of three 1S Gaussian functions, each centered on each nucleus. Detailed derivations are presented and the advantages and limitations of this simple model are discussed. The correctness of the results was verified independently via Monte Carlo integration. This simple model correctly predicts and rationalizes the preference of H þ 3 for the equilateral geometry rather than the linear configuration. Despite its simplicity, the calculated H H bond length (R = 0.9088 Å) and breathing vibrational frequency (ν 1 = 3276.59 cm À1 ) for equilateral H þ 3 ion are in good agreement with high-level ab initio methods and the experiment, respectively.

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Femtosecond Electron-Transfer Dynamics across the D₂O/Cs⁺/Cu(111) Interface: The Impact of Hydrogen Bonding

Thomas,

Patwari,

Langguth

et al. 2023

J. Phys. Chem. C

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Hydrogen bonding is essential in electron-transfer processes at water−electrode interfaces. We study the impact of the H-bonding of water as a solvent molecule on real-time electron-transfer dynamics across a Cs + −Cu(111) ion−metal interface using femtosecond time-resolved two-photon photoelectron spectroscopy. We distinguish in the formed water−alkali aggregates two regimes below and above two water molecules per ion. Upon crossing the boundary of these regimes, the lifetime of the excess electron localized transiently at the Cs + ion increases from 40 to 60 fs, which indicates a reduced alkali−metal interaction. Furthermore, the energy transferred to a dynamic structural rearrangement due to hydration is reduced from 0.3 to 0.2 eV concomitantly. These effects are a consequence of H-bonding in the water−water interaction and the beginning formation of a nanoscale water network. This finding is supported by real-space imaging of the solvatomers and vibrational frequency shifts of the OH stretching and bending modes calculated for these specific interfaces.

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Ultrafast electron dynamics at water covered alkali adatoms adsorbed on Cu(111)

Cited by 9 publications

References 30 publications

Hydrated Alkali Atoms on Copper(111): A Density Functional Theory Study

Hydrated Alkali Atoms on Copper(111): A Density Functional Theory Study

A simple approximate solution for the H3+ ion

Femtosecond Electron-Transfer Dynamics across the D₂O/Cs⁺/Cu(111) Interface: The Impact of Hydrogen Bonding

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Ultrafast electron dynamics at water covered alkali adatoms adsorbed on Cu(111)

Cited by 9 publications

References 30 publications

Hydrated Alkali Atoms on Copper(111): A Density Functional Theory Study

Hydrated Alkali Atoms on Copper(111): A Density Functional Theory Study

A simple approximate solution for the H3+ ion

Femtosecond Electron-Transfer Dynamics across the D2O/Cs+/Cu(111) Interface: The Impact of Hydrogen Bonding

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Femtosecond Electron-Transfer Dynamics across the D₂O/Cs⁺/Cu(111) Interface: The Impact of Hydrogen Bonding