Desorption induced by multiple

Some recent advances in stimulated desorption were made with the use of femtosecond lasers. For example, it was shown by using a femtosecond laser to initiate the desorption of CO from Cu while probing the surface with SHG, that the entire process is completed in less than 325 fs [90]. The mechanism for this kind of laser-induced desorption has been temied desorption induced by multiple electronic transitions (DIMET) [91]. Note that the mechanism must involve a multiphoton process, as a single photon at the laser frequency has insufScient energy to directly induce desorption. DIMET is a modification of the MGR mechanism in which each photon excites the adsorbate to a higher vibrational level, until a suflBcient amount of vibrational energy has been amassed so that the particle can escape the surface. 

Misewich J A, Heinz T F and Newns D M 1992 Desorption induced by multiple electronic transitions Phys. Rev. Lett. 68 3737... 

Thus, in this review we present the desorption phenomena focused on the rotational and translational motions of desorbed molecules. That is, we describe the DIET process stimulated by ultraviolet (UV) and visible nanosecond pulsed lasers for adsorbed diatomic molecules of NO and CO from surfaces. Non-thermal laser-induced desorption of NO and CO from metal surfaces occurs via two schemes of DIET and DIMET (desorption induced by multiple electronic transitions). DIET is induced by nanosecond-pulsed lasers and has been observed in the following systems NO from Pt(0 0 1) [4, 5],... 

Pt(l 11) [6-8], Cu(l 1 1) [9] and Ag(l 1 1) [9], and CO fromPt(00 1) [10] andPt(l 1 1) [11,12]. On the other hand, these molecules are not desorbed from Ni and Pd metal surfaces in spite of the isoelectronic character of the metals Ni, Pd and Pt [13,14]. Desorption induced by subpicosecond-pulsed laser takes place via multiple correlated (and partially coherent) electronic transitions DIMET. DIMET is a very different mechanism from DIET [15-17] and in DIMET the vibrational excitation during the multiple electronic transitions leads to the desorption. Desorption via multiple vibrational transitions has also been observed using an infrared laser [18]. However, these topics are not described in this review. 

Knotek and Feibelman [94] examined the modification to a surface when exposed to ionising radiation and assesed the damage that can be produced. They addressed the stability of ionically bonded surfaces, where the KF mechanism applies, and concluded that Auger induced decomposition only occurs when the cation in the solid is ionised to relatively deep core levels. In the case of non-maximal oxides as with NiO, Freund s group [95] showed that whilst desorption of neutral NO and CO from NiO(lOO) and (111) surfaces has thresholds at the C Is, N Is and O Is core levels, it proceeds mainly on the basis of the MGR model, involving an excited state of the adsorbate. An overview of electronic desorption presented by Feibelman in 1983 [96] examined particularly the stability of the multiple-hole final state configuration leading to desorption. The presence of multiple holes, and associated hole-hole correlation... 

ESD induced by electrons extracted at the tip of a scanning tunnelling microscope (STM) has recently applied to the study of the H-Si and Cl-GaAs(l 10) systems by Shen and Avouris [98]. A feature of the STM is the capability to provide an intense electron density (lO A/cm ) of atomic dimensions directly at the surface atoms. Under these conditions, desorption can also proceed with multiple-vibrational excitation. A combination of ESD and STM holds promise as a tool for atomistic DIET, also as a means to asses the influence of electron irradiation at surfaces [99]. In ESDIAD an interesting aspect is the determination of the trajectory of the ion on leaving the surface, which will be discussed later in relation to the TiOa surface. 

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