Ultrafast Charge Transfer Times of Chemisorbed Species from Auger Resonant Raman Studies

Keller, C.; Stichler, M.; Comelli, Giovanni; Esch, F.; Lizzit, Silvano; Würth, W.; Menzel, D.

doi:10.1103/physrevlett.80.1774

Cited by 90 publications

(57 citation statements)

References 29 publications

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“…7,8 For C 6 H 6 /Cu(110) a stronger photon energy dependence was observed, most likely due to the weaker coupling of the aromatic C 6 H 6 which preserves the localized, molecular nature of the adsorbate. 7,9 This is in line with the present understanding of the femtosecond dynamics of the adsorbate/substrate charge transfer in the intermediate core excited state, achieved in resonant inelastic-scattering studies with Auger electrons [10][11][12] where a direct correspondence between coupling strength and chargetransfer probability was found.…”

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confidence: 85%

Electronic structure and screening dynamics of ethene on single-domain Si(001) from resonant inelastic x-ray scattering

et al. 2004

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We present a resonant inelastic x-ray scattering ͑RIXS͒ study of a strongly bound adsorbate on a semiconductor surface, C 2 H 4 /Si(001). The valence electronic structure as well as the photon energy dependence in RIXS can be studied without the dominating effect of dynamic metallic screening. We demonstrate that for this strongly coupled system the RIXS spectrum resulting from a selective excitation into the unoccupied CSi * resonance can be interpreted with the help of density-functional calculations. In addition, we show how excitation into different resonances leads to a significant photon energy dependence of the RIXS spectral features, not seen in strongly coupled adsorbate systems on metals. DOI: 10.1103/PhysRevB.69.153408 PACS number͑s͒: 73.20.Hb, 78.70.En The investigation of resonant inelastic scattering in the soft x-ray spectral range using third-generation synchrotron radiation sources has recently attracted great interest as a powerful method for detailed electronic structure determination.1 The inelastic-scattering process can be described as a transition from the electronic ground state of a system via an intermediate resonant core-excited state into a final state which is electronically and/or vibrationally excited. This event can be studied by either detecting scattered photons or secondary Auger electrons. The former case involving photons in the incoming as well as the outgoing channel has the advantage of being almost independent of the sample environment, thus enabling even electronic structure studies of complex interfaces and liquids. Resonant inelastic x-ray scattering ͑RIXS͒ is governed by the dipole operator, and therefore has a well-defined polarization dependence and anisotropy, which provides insight into spatial orientation and symmetry properties of the systems studied.2 Furthermore, due to the element specificity of the resonant excitation process, one is able to probe the electronic structure of complex heteronuclear systems for selected states. 1,3 In crystalline solids, momentum conservation in RIXS can be used to access the k-resolved band structure. 4 In adsorption systems, RIXS effectively suppresses contributions from the much larger number of substrate atoms and thus permits to access the atom-specific valence electronic structure of the adsorbate, 2,3,5 allowing significantly improved understanding of the surface chemical bond. 3,5 In free molecules, RIXS depends strongly on the energy of the incoming photon as a result of the interference of degenerate or near-degenerate intermediate states in the scattering process. 6 Furthermore, excitation to different resonances leads to significant differences in the spectral shape of the scattering spectra because of strong symmetry selection rules. 6 For adsorbed molecules, this situation changes because coupling to the substrate, which modifies the dynamic response of the core-hole RIXS intermediate state, has to be taken into account. To date only adsorbates on metallic substrates have been investigated with RIXS. For these...

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Electronic structure and screening dynamics of ethene on single-domain Si(001) from resonant inelastic x-ray scattering

et al. 2004

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“…the radiative decay of the coreexcited state to the ground state of the molecule, which has been observed in gas phase [48]. This decay channel is strongly suppressed for strongly interacting chemisorbed molecules due to ultrafast charge transfer out of the resonance into the metal substrate [49]. The presence of the decay channel and its increase as a function of pump-probe delay provide further support for the conclusion of laser-induced population of a more weakly bound state prior to desorption.…”

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confidence: 52%

Optical laser-induced CO desorption from Ru(0001) monitored with a free-electron X-ray laser: DFT prediction and X-ray confirmation of a precursor state

et al. 2015

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We present density functional theory modeling of time-resolved optical pump/x-ray spectroscopic probe data of CO desorption from Ru(0001). The BEEF van der Waals functional predicts a weakly bound state as precursor to desorption. The optical pump leads to a near-instantaneous (<100 fs) increase of the electronic temperature to nearly 7000 K. The temperature evolution and energy transfer between electrons, substrate phonons and adsorbate is described by the two-temperature model and found to equilibrate on a timescale of a few picoseconds to an elevated local temperature of ~2000 K. Estimating the free energy based on the computed potential of mean force along the desorption path, we find an entropic barrier to desorption (and by time-reversal also to adsorption). This entropic barrier separates the chemisorbed and precursor state, and becomes significant at the elevated temperature of the experiment (~1.4 eV at 2000 K).Experimental pump-probe x-ray absorption/x-ray emission spectroscopy indicate population of a precursor state to desorption upon laser-excitation of the system

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“…1-3 However, many fundamental phenomena including dynamical electronic screening, 4,5 electron transfer from chemisorbates, 6,7 and atomic-scale motion of electrons in or near surfaces 8 proceed on an attosecond timescale, which cannot be resolved even if interferometric two-photon photoelectron spectroscopy with wellcharacterized femtosecond laser pulses are employed. [9][10][11] Alternatively, the attosecond transient recorder (ATR) is a newly established technique that provides direct timeresolved access to these processes.…”

Section: Introductionmentioning

confidence: 99%

A flexible apparatus for attosecond photoelectron spectroscopy of solids and surfaces

Magerl

Neppl

Cavalieri

et al. 2011

Review of Scientific Instruments

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We describe an apparatus for attosecond photoelectron spectroscopy of solids and surfaces, which combines the generation of isolated attosecond extreme-ultraviolet (XUV) laser pulses by high harmonic generation in gases with time-resolved photoelectron detection and surface science techniques in an ultrahigh vacuum environment. This versatile setup provides isolated attosecond pulses with photon energies of up to 140 eV and few-cycle near infrared pulses for studying ultrafast electron dynamics in a large variety of surfaces and interfaces. The samples can be prepared and characterized on an atomic scale in a dedicated flexible surface science end station. The extensive possibilities offered by this apparatus are demonstrated by applying attosecond XUV pulses with a central photon energy of ∼125 eV in an attosecond streaking experiment of a xenon multilayer grown on a Re(0001) substrate

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Ultrafast Charge Transfer Times of Chemisorbed Species from Auger Resonant Raman Studies

Cited by 90 publications

References 29 publications

Electronic structure and screening dynamics of ethene on single-domain Si(001) from resonant inelastic x-ray scattering

Electronic structure and screening dynamics of ethene on single-domain Si(001) from resonant inelastic x-ray scattering

Optical laser-induced CO desorption from Ru(0001) monitored with a free-electron X-ray laser: DFT prediction and X-ray confirmation of a precursor state

A flexible apparatus for attosecond photoelectron spectroscopy of solids and surfaces

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