Inelastic scattering of electrons by vibrational motion of molecules adsorbed at metal surfaces

A model for computing the inelastic scattering power of infrared active molecular vibrations for low energy electrons reflected from gas-covered metal surfaces is constructed and the results are compared to recent observations. The metallic substrate has two major effects on the inelastic intensity: (i) at or near normal incidence, reflected electrons can strongly excite vibrations perpendicular to the surface, a process which is forbidden for forward acattering (and also for excitation by normally incident infrared light); (ii) the inelastic cross section for low energy electrons is enhanced as a result of image effects. The theory also predicts that the observed inelastic intensity should be highly sensitive to the spectrometer aperture.     

Orientation dependence in the dissociative scattering of hydrogen molecules from metal surfaces

We investigate the molecular orientation dependence of the dissociation probability of neutral molecular hydrogen scattered from metal surfaces. The probability distributions are calculated in the cases when positive and negative hydrogen ions (ion pair) are formed and when two neutral hydrogen atoms are formed. On the basis of numerical results, it is found that a parallel orientation preference of probability distributions shows a tendency to be suppressed in the case when an ion pair is formed as compared with the case when two neutral hydrogen atoms are formed.     

Chemical effects on vibrational properties of adsorbed molecules on metal surfaces

Vibrational properties of chemisorbed molecules on metal surfaces are studied with a focus on the coverage (θ) dependent chemical shift of the frequencies. The electronic properties of an incomplete monolayer of adsorbates are calculated by means of the coherent potential approximation, in which the electron hopping between the adsorbates (band formation effect) and the depolarization effect due to the proximity of ionized adsorbed molecules are taken into account consideration. It is found that in a weakly chemisorbed system, such as CO/Cu, the negative shift in chemical origin amounts to the positive dipole shift at low coverage. It is also shown that the variation of the back-donated charge with θ gives rise to the coverage dependent polarizability, which in turn influences the frequency shift estimated by the previous dipole coupling theory. The coverage dependent back-donation also plays a significant role in the work function change Δϕ of the substrate. The polarity of a weakly chemisorbed CO remains unchanged compared to a free CO (⁻CO⁺) so that Δϕ exhibits the initial lowering in the presence of the positive dipoles. The increase in the back-donated charge with θ causes the decrease in the effective dipole moment towards a compensation of the positive hole due to 5σ donation. A simple explanation is offered to clarify the characteristic difference of the work function change between the strongly and weakly chemisorbed CO molecules on metal surfaces. In particular, a possible origin of the work function minimum observed for CO/Cu systems is discussed in terms of the coverage dependent back-donation.     

Dynamics of photoinduced electron transfer from adsorbed molecules into solids

Ultrafast interfacial electron transfer from the donor orbital of organic chromophores into empty electronic acceptor states of a semiconductor and of a metal was investigated by two-photon photoemission spectroscopy (2PPE). Experimental tools and procedures have been developed for carrying out wet-chemistry preparation of the molecule/solid interface. The organic chromophore perylene was investigated with several different bridge/anchor groups on TiO₂(110). One perylene compound was investigated for comparison on Ag(110). Angle and polarization dependent 2PPE measurements revealed the orientation of the perylene chromophore on the surface as controlled by the adsorption geometry of the respective anchor group on TiO₂. UPS measurements gave the position of the HOMO level of the chromophore with respect to the Fermi level of the solid. The donor level of each molecule was found high enough to fulfill the “wide band limit” of heterogeneous electron transfer dynamics. Time constants for heterogeneous electron transfer were extracted from 2PPE transients. A difference by a factor of four was found, 13 fs against 47 fs, when a conjugated bond was exchanged for a saturated bond in the otherwise identical bridge group. The two different contributions to the 2PPE transients arising firstly from the excited state of the chromophore and secondly from the injected electrons were separated by measuring the latter contribution separately in the case of instantaneous interfacial electron transfer realized with catechol as adsorbate. The time scales measured for the electron transfer step and for the subsequent electron escape process from the surface into the bulk of TiO₂ showed both good agreement with recent theoretical predictions of other groups for these systems. PACS 42.65.Ky; 79.60.BM; 78.47.+p; 73.20.-r; 79.60.Jv; 79.60.-i     

Resonance behavior of electron scattering from nitrogen molecules adsorbed on metallic surfaces

We use the coupled angular modes theory of electron scattering from molecules to identify the important role played by substrate multiple scattering in determining the lifetime of transient negative ions in adsorbed molecules. For the ²Π_g negative ion resonance in N₂, we demonstrate the phenomenon of complete resonance quenchingwhich occurs when the resonance energy is such that the probe electron is strongly reflected from the substrate. This situation may occur when the resonance energy lies in a band-gap of the unoccupied states of a metallic substrate. It is proposed that the simple resonance energy shift and lifetime reduction observed in previous experimental and theoretical studies of resonance electron scattering from adsorbates is by no means a universal phenomenon. The importance of the unoccupied metallic band structure of the substrate in determining the properties of negative ions in adsorbed molecules is discussed.     

A model calculation for photo-stimulated desorption of molecules adsorbed on metal surfaces

A model calculation is presented for the photo-stimulated desorption of molecules adsorbed on a metal surface. In the model, the electronic system of the material consists of two energy bands which are described by a tight binding Hamiltonian. The total energy of the electronic system is assumed to give the potential energy for the molecular motion. The time development of the total wavefunction including one coordinate of the molecular center-of-mass and those of electrons is calculated in order to see the relation between the electronic transition by light irradiation and the transition of the state for the molecular motion explicitly. The magnitude of the photodesorption probability calculated for NO/Cu(111) is comparable to that deduced from experimental results.     

Nonadiabatic dynamics of electron injection into organic molecules

We numerically investigate the injection process of electrons from metal electrodes to one-dimensional organic molecules by combining the extended Su-Schrieffer-Heeger (SSH) model with a nonadiabatic dynamics method. It is found that a match between the Fermi level of electrodes and the highest occupied molecular orbital (HOMO) or the lowest unoccupied molecular orbital (LUMO) of organic molecules can be greatly affected by the length of the organic chains, which has a great impact on electron injection. The correlation between oligomers and electrodes is found to open more efficient channels for electron injection as compared with that in polymer/electrode structures. For oligomer/electrode structures, we show that the Schottky barrier essentially does not affect the electron injection as the electrode work function is smaller than a critical value. This means that the Schottky barrier is pinned for a small work-function electrode. For polymer/electrode structures, we find that it is possible for the Fermi level of electrodes to be pinned to the polaronic level. The condition under which the Fermi level of electrodes exceeds the polaronic level of polymers is shown to not always lead to spontaneous electron transfer from electrodes to polymers.     

Identification of adsorbed species at metal surfaces by electron energy loss spectroscopy (EELS)

Electron energy loss spectroscopy (EELS) is a surface analysis method for measuring vibrational spectra of adsorbed species on metal surfaces. This paper summarizes recent work on the study of bonding of simple adsorbates on metal surfaces, and the identification of new chemical intermediates in reactions between two or more species in the adsorbed monolayer. The spectra of atomic oxygen, di-oxygen, water and ammonia adsorbed on platinum, copper and silver are discussed with emphasis on identification of the adsorbed species and their orientations relative to the surface plane. Surface reactions between atomic oxygen and water, methanol and formic acid yield the new surface intermediates hydroxyl (OH), methoxy (CH₃O) and formate (HCOO), respectively, on copper and silver surfaces. Each species was identified by comparison of surface spectra with known infrared spectra and through the use of deuterium isotopic shifts. The ability to identify and distinguish between chemical species at surfaces with high sensitivity will allow direct correlation of low pressure UHV surface experiments with high pressure surface reactions on catalysts and liquid-solid interfaces.     

Role of electron-hole pair excitations in the dissociative adsorption of diatomic molecules on metal surfaces

We quantitatively evaluate the contribution of electron-hole pair excitations to the reactive dynamics of H2 on Cu(110) and N2 on W(110), including the six dimensionality of the process in the entire calculation. The interaction energy between molecule and surface is represented by an ab initio six-dimensional potential energy surface. Electron friction coefficients are calculated with density functional theory in a local density approximation. Contrary to previous claims, only minor differences between the adiabatic and nonadiabatic results for dissociative adsorption are found. Our calculations demonstrate the validity of the adiabatic approximation to analyze adsorption dynamics in these two representative systems.     

Vibrational dynamics of fullerene molecules adsorbed on metal surfaces studied with synchrotron infrared radiation

Infrared (IR) spectroscopy of chemisorbed C₆₀ on Ag (111), Au (110) and Cu (100) reveals that a non-IR-active mode becomes active upon adsorption, and that its frequency shifts proportionally with the charge transferred from the metal to the molecule by about 5 cm^-1 per electron. The temperature dependence of the frequency and the width of this IR feature have also been followed for C₆₀/Cu (100) and were found to agree well with a weak anharmonic coupling (dephasing) to a low-frequency mode, which we suggest to be the frustrated translational mode of the adsorbed molecules. Additionally, the adsorption is accompanied by a broadband reflectance change, which is interpreted as due to the scattering of conduction electrons of the metal surface by the adsorbate. The reflectance change allows determination of the friction coefficient of the C₆₀ molecules, which results in rather small values (∼2×10⁹ s^-1 for Ag and Au, and ∼1.6×10⁹ s^-1for Cu), consistent with a marked metallic character of the adsorbed molecules. Pre-dosing of alkali atoms onto the metal substrates drastically changes the IR spectra recorded during subsequent C₆₀ deposition: anti-absorption bands, as well as an increase of the broadband reflectance, occur and are interpreted as due to strong electron–phonon coupling with induced surface states. Received: 6 June 2001 / Accepted: 23 October 2001 / Published online: 3 April 2002     

Auger electron spectroscopy of adsorbed metal monolayers: Lead on low-index and stepped copper surfaces

Lead was deposited onto single crystals of copper (orientations (110), (100), (711) and (511) in ultrahigh vacuum. For all substrate orientations there form dense monolayers characteristic of the Stranski-Krastanov growth mode. During growth of the monolayer (at constant vapour flux) the Auger signals of the adsorbate and the substrate do not vary with exact linearity as a function of deposition time. The signal-versus-time plots show changes of slope that are associated with changes in the adsorbed layer structures as observed by LEED. More gradual variations occur near the completion of the dense monolayer. All these changes are ascribed to variations in the sticking probability. Adsorbed layers on the stepped surfaces tend to be disordered, possibly due to high mobility. The results are discussed in terms of the possibilities and difficulties for quantitative Auger electron spectroscopy.     

Normal modes of CO adsorbed on metal surfaces

A normal mode analysis of experimental data from helium atom scattering (HAS) and electron energy loss spectroscopy (EELS) for vibrations of CO molecules adsorbed in on-top and bridge sites on Ni(100) is presented, using a refined force-constant analysis. The similar case of CO adsorbed on Pt(111) is reinvestigated, revealing a misassignment of normal modes in previous work. Finally, available experimental data for CO on Pt(111) is used to construct a trial potential energy surface.     

Luminescence of molecules adsorbed on surfaces of wide gap materials

We report on the photoluminescence spectra of thin films of chain-like π-conjugated molecules on well-defined surfaces of wide gap inorganic materials. The aim is to study the energy transfer processes across the organic/substrate interface which limit the luminescence of molecules in close contact to substrate surfaces. We discuss quaterthiophene (4 T) adsorbed on the c(2×2)-ZnSe(0 0 1) surface and tetracene (Tc) on the surface of a thin epitaxial Al₂O₃ film on Ni₃Al(1 1 1). For thin films vapor-deposited at low substrate temperatures, we observe no luminescence signal for both systems, which indicates the presence of fast luminescence quenching processes at the organic/inorganic interface. After annealing, luminescence spectra corresponding to those of the bulk crystals are obtained. This can be explained by the formation of 3D-crystallites, which effectively separate most molecules from the organic/inorganic interface.     

Electronic structure of semiconducting nanotubes adsorbed on metal surfaces

A total-energy electronic-structure calculation is performed to explore energetics and electronic structures of nanotubes adsorbed on metal surfaces. We find that the charge transfer from metal surfaces to the nanotubes takes place depending on both the electronic structures of the adsorbed nanotubes and the work functions of the metal surfaces. In addition, we also find a substantial hybridization between the electron states of metal atoms and those of the nanotubes, which results in the metal-induced inhomogeneous charge distribution in the nanotubes.     

The influence of atomic impurities on the orientational transitions in localized monolayer films of diatomic molecules adsorbed on crystalline surfaces

The orientational ordering in localized films consisting of a mixture of diatomic and mono-atomic particles and formed on the (100) face of a cubic crystal is considered. It is demonstrated that the presence of atomic impurities influence the formation of orientationally ordered states. In particular, it is shown that even a simple mean-field theory leads to a qualitatively correct picture of changes in orientational properties in the film when the molar ratio of spherically symmetric particles increases.     

Alkali-metal-affected adsorption of molecules on metal surfaces

The study of coadsorption of alkali metals and simple molecules on transition metal surfaces has been a favored topic of research ever since the pioneering work by Langmuir in 1923. The main reasons for this continued interest are both of fundamental and applied nature. There are a number of interesting physical effects, such as work function changes, charge transfer, two-dimensional ordering, bond energy and molecule orientational changes, and altered surface reactive properties, which have been investigated by a large number of different surface analytical techniques. From an applied point of view, alkali metal covered surfaces are important in the areas of electron and ion emission and heterogenous catalysis, for example.In this paper we will give a short review of the adsorption of alkali metals on well-defined transition metal surfaces. The interaction of these adsorbed alkali metals with subsequently adsorbed atomic or molecular species will be treated more extensively. The emphasis will be on recent experiments dealing with well-characterized surfaces. In particular we will consider questions of adsorption energetics and kinetics, but also review in detail the vibrational, electronic, structural and reactive properties of the coadsorbed complex. Based on a wealth of experimental data, several models of the coadsorbed alkali metal-molecule complex will be introduced and discussed.