Local work function

N.D. Lang, and A.R. Williams, Theory of local-work-function determination by photoemission from rate-gas adsorbates, Physics Review B 25(4), 2940-2942 (1982). 

The figure shows the observed variations in local work function within the three marked squares (1 is mostly on YSZ, 2 and 3 are on Pt). As shown in this figure and also in Fig. 5.47 the local work function (which increases with decreasing local brightness) follows the imposed variation in UWR. 

The ESTM experiment provides actually five measurable quantities tunnelling current, / at the applied voltage, U, and three dimensions, x, y, z. The standard STM can therefore easily be modified by recording the local l-Uy U-zy or /-z characteristics (z is vertical distance of the tip from the electrode surface). Plot of dl/dU or d//dz versus x and y brings additional information on the electronic and chemical surface properties (local work functions, density-of-states effects, etc.), since these manifest themselves primarily as l-U dependences. The mentioned plots are basis of the scanning tunnelling spectroscopy (STS). 

More than a decade ago, Hamond and Winograd used XPS for the study of UPD Ag and Cu on polycrystalline platinum electrodes [11,12]. This study revealed a clear correlation between the amount of UPD metal on the electrode surface after emersion and in the electrolyte under controlled potential before emersion. Thereby, it was demonstrated that ex situ measurements on electrode surfaces provide relevant information about the electrochemical interface, (see Section 2.7). In view of the importance of UPD for electrocatalysis and metal deposition [132,133], knowledge of the oxidation state of the adatom in terms of chemical shifts, of the influence of the adatom on local work functions and knowledge of the distribution of electronic states in the valence band is highly desirable. The results of XPS and UPS studies on UPD metal layers will be discussed in the following chapter. Finally the poisoning effect of UPD on the H2 evolution reaction will be briefly mentioned. 

Also, photoemission can be taken as the basis for microscopy. Suppose a surface is covered by separated islands of oxygen atoms and carbon monoxide, as indicated schematically in Fig. 7.23. The local work function above the O atoms will be significantly larger than that above the CO molecules, which in its turn will be higher than that of the bare surface. Hence, photoemission intensity from the O islands is weaker than that from the CO, while the metal yields the most intense photoemission. 

Figure 9.10 Up work function of alkali-promoted metals as a function of alkali coverage (see also Table 9.2). Down electrostatic potential around a single alkali atom adsorbed on jellium. The effective local work function at each position is the sum of the substrate work function and the value of the electrostatic potential in the figure (from Lang el at. [39]).

Janssens et al. [38, 40] used photoemission of adsorbed noble gases to measure the electrostatic surface potential on the potassium-promoted (111) surface of rhodium, to estimate the range that is influenced by the promoter. As explained in Chapter 3, UPS of adsorbed Xe measures the local work function, or, equivalently, the electrostatic potential of adsorption sites. The idea of using Kr and Ar in addition to Xe was that by using probe atoms of different sizes one could vary the distance between the potassium and the noble gas atom. Provided the interpretation in terms of Expression (3-13) is permitted, and this is a point the authors checked [38], one thus obtains information about the variation of the electrostatic potential around potassium promoter atoms. 

Figure 9.11 Promoter-induced binding energy shifts of Ar, Kr and Xe photoemission peaks with respect to adsorption on the clean metal as a function of the distance of the adsorption site to the nearest potassium atom on a potassium-promoted Rh( 111) surface. These curves reflect the variation of the surface potential (or local work function) around an adsorbed potassium atom. Note the strong and distance-dependent local work function at short distances and the constant local work function, which is lower than that of clean Rh( 111) at larger distances from potassium. The lowering at larger distances depends on the potassium coverage. The averaged distances between the potassium atoms are 1.61, 1.32 and 1.20 nm for coverages of 2.7, 4.1 and 5.0% respectively, vertical lines mark the half-way distances. Lines are drawn as a guide to the eye (adapted from Janssens et al. [38]).

Fig. 9.n Promoter-induced binding energy shifts of Ar, Kr and Xe photoemission peaks with respect to adsorption on the clean metal as a function of the distance of the adsorption site to the nearest potassium atom on a potassium-promoted Rh(lll) surface. These curves reflect the variation of the surface potential (or local work function) around an adsorbed potassium atom. Note the strong and distance-dependent local work function... 

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