Shift and broadening of adsorbate vibrational modes

The shift and broadening of the vibrational frequency of the adsorbate on a metal surface are calculated on the basis of two different models. The first model is an anharmonic one which includes multiphonon processes to all order in first-order perturbation theory. We show that anharmonic damping due to multiphonon processes is substantial for CO adsorbed on a Ni(100) surface and small for H adsorbed on a W(100) surface. At room temperature multiphonon processes with n > 2 are very important even in cases when the frequency of vibration of the adsorbate lies below twice the maximum phonon frequency of the substrate (n is the order of the process). For the CNi stretching mode of top-bonded CO on Ni(100) our results are in accord with the experimental data. The second model is an electronic one which includes the electron-hole pair loss mechanism. We show that the observed shift and broadening of the CO stretching vibration mode for a CO molecule adsorbed on Cu(100) and for a H atom adsorbed on a W(100) surface can be explained on the basis of this model. Variation of the shift and broadening of the CO stretching mode with the distance from a CO molecule to Ni(111) surface are calculated.     

Benzene adsorbed at a metal surface: Which vibrational modes are observable?

The effect of a metal surface on the vibrational spectroscopic activity of an adsorbate is discussed, with benzene as example. The metal influences are classified to show that the intensity of certain adsorbate bands provides information on particular metal/adsorbate interactions.     

A methane molecule adsorbed on a graphite surface

In this paper we present a molecular dynamics study of a methane molecule adsorbed on a graphite surface. The methane is modelled using five interaction sites and the surface is an infinite hexagonal array of carbon atoms. The potential parameters are fitted using static calculations to the rotational barrier heights and using molecular dynamics to the isoteric enthalpy at zero coverage. The effective pairwise potential predicts the height of the monolayer above the surface and the vibrational frequency against the surface. We have examined the translational and rotational behaviour of a single methane molecule across the surface.     

Scattering of a diatomic molecule by a stationary surface

The CCGM [N. Cabrera, V. Celli, F.O. Goodman and R. Manson, Surface Sci. 19 (1970) 67] theory of elastic scattering (diffraction) of atoms by surfaces is generalized to the case of scattering of diatomic molecules. No extensive applications of the theory are made, but an example considered by R.M. Logan [Mol. Phys. 17 (1969) 147] of the scattering of a low-energy beam of h₂ by a cold surface is re-examined in the context of the new theory. It is concluded that, because of the uncertainties in the form of the molecule-surface interaction potential and in the values of the interaction parameters, no quantitative reliance can be placed on calculations of molecule-surface scattering probabilities at the present time. Future comparisons with experimental data should help to reduce these uncertainties.     

Role of intermolecular interactions on the electronic and geometric structure of a large pi-conjugated molecule adsorbed on a metal surface

The organic semiconductor molecule 3,4,9,10-perylene-tetracarboxylic-dianhydride (PTCDA) exhibits two adsorption states on the Ag(111) surface: one in a metastable disordered phase, prepared at low temperatures, the other in the long-range ordered monolayer phase obtained at room temperature. Notably, the two states differ substantial in their vertical bonding distances, intramolecular distortions, and electronic structures. The difference is explained by intermolecular interactions, which are particularly relevant for the long-range ordered phase, and which hence require attention.     

The change of the vibrational frequencies of a chemisorbed diatomic caused by the electrostatic interactions with the metal surface

Results of density functional calculations are used to discuss the change of the vibrational frequency of an adsorbed molecule caused by the electrostatic interaction between a chemisorbed molecule — simulated by two effective charges — and a metallic surface.     

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.     

Influence of a metal surface on the luminescence of adsorbed europium compounds

Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 62, No. 6, pp. 130–134, November–December, 1995.     

Shift and broadening of surface polaritons of sapphire upon deposition of a quasicrystalline film

The influence of a quasicrystalline Al-Pd-Re film on the shift and broadening of surface polaritons of a substrate (sapphire) has been studied. Measurements have been performed both on a sample containing only the quasicrystalline phase and on a sample which, in addition to the quasicrystalline phase, contains the crystalline (metallic) phase. The complex dielectric function of the films in the mid-IR region (650–800 cm⁻¹) has been estimated.     

On the structure of a water molecule chemisorbed on a metal surface

A model using the electrostatic image force and the harmonic restoring force has been adapted to find the equilibrium structure of a chemisorbed water molecule on a metal surface. An estimate of the maximum possible increase in the HOH interbond angle upon chemisorption due to image forces is given.     

一种获取双原子分子的转动常数的方法

本文给出了对于任何双原子分子或双原子自由基分子,由其振动常数结合RKR方程、结合从头计算,获得势能曲线及其转动常数的方法.并对CN的基态和激发态进行了计算,结果与实验值符合得非常一致.A     

非Born-Oppenheimer近似一对双原子分子振动光谱的修正

为提高Born-Oppenheimer(BO)近似的精确度,修正BO近似所得到的令人不太满意的结果,此文在电子与原子核之间引入一个位相差,并利用小参数微扰法推导出了双原子分子核振动的波函数及红外能谱的计算公式,由修正后的结果得到的双原子分子红外振动光谱线的位置应更接近于实验观测值.     

States of water molecule adsorbed on Si(111) surface

Calculated electronic energy structure of an overlayer of water molecules chemisorbed on Si(111), with a molecular plane perpendicular to the surface, reveals that 3a₁ molecular state is removed upon adsorption, and the resulting state densities cannot be reconciled with the UPS spectrum. These results, and state densities obtained from different atomic configurations are interpreted to rule out the molecular adsorption on Si(111) surface at room temperature.     

Highest rotational and vibrational excitation of swift diatomic molecules scattered by solid surface

It is shown that at nondissociative scattering of swift molecules by solid surface and inverse population of the highest rotational and some vibrational states unattainable at thermal excitation could be achieved. For single crystal surface a specific polarization and orientational effects in rotational and vibrational excitation of the scattered molecules could be observed.