STKK 6742 SURFACE ANALYSIS

ASSIGNMENT 2 Title : Multiplet Splitting Phenomenon

Student Name: Madihah Ahmad (P52523) Lecturer Name: Prof. Dr. Ambar Yarmo.

Multiplet Splitting Phenomena in XPS Multiplet splitting is occurred when an atom has unpaired electrons. When a core electron vacancy is made by photoionization, there can be coupling between the unpaired electrons in the core with the unpaired electrons in the outer shell. This can create a number of final states, which will be seen in the photoelectron spectrum as a multi-peak envelope. Transition metals with unfilled p and d orbitals and rare earths with unfilled f orbitals all show multiplet splitting.

For example, Fe2O3 have 5 unpaired electrons in the 3d shell. When photoionization occur in the 3s shell, there are 2 possible final states (Figure 1).

Figure 1: Schematic of multiplet splitting following photoionization in Fe3+ .

Gupta and Sen (1975) have done the calculation of the multiplet structure of core pvalence levels of free ion state in first row transition metals and showed graphically their multiplet structure (Figure 2). These calculations are an excellent starting point for the examination of multiplet structure seen in transition metal compounds. However, there may be ligand charge transfer effects that will change the spacing and intensity of the multiplet peaks present in their spectra. These relative changes can be employed for transition metal compounds to identify those more closely approximating free ions from those in which charge transfer from the bonded neighbouring ions may have changed both the effective oxidation state and multiplet splitting of the core transition metal.

Figure 2: Calculated multiplet structure of 2p ionization created in the free ions as labeled. The zero energy is arbitrary and the intensity normalization is the same for all spectra shown. The investigation of multiplet splitting of Fe 2p XPS spectra and bonding in iron compounds by A.P Grosvenor et al. (2004) showed that the Fe3+ 2p3/2 envelopes from each of the four different compound studied (-Fe2O3,-Fe2O3,-FeOOH and -FeOOH) were fit well with Gupta and Sen multiplets (Figure 3), with a very close intensities (Figure 4). The main difference between the two sets of compounds is coordination of the Fe3+ cations. In the compounds, the crystal structure is oriented in octahedral coordinated. While in the compounds, three-quarters of the Fe3+ cations are octrahedrally coordinated whereas the other quarter of the cations are tetrahedrally coordinated. The cation vacancies also present in the crystal structure of the -compounds to balance the overall charge.

(b) Figure 3: The main peak Gupta and Sen predicted multiplets for the Fe 2p3/2 envelope. The highspin Fe3+ (a) and Fe2+ (b) compound.

(a)

Figure 4: Fe 2p3/2 spectra of (a) -Fe2O3, (b) -Fe2O3, (c) -FeOOH and (d) -FeOOH. Gupta and Sen (1975) also reported the 2p XPS spectrum of each Mn2+, Mn3+ and Mn4+ (Figure 5) in high spin states is composed of numerous peaks (multiplets) that resulted in unusually broad, of compound Mn(2p3/2) spectra. The complexity of Mn(2p) metal photo-peaks arises from coupling of angular momentum associated with partially filled core and valence shells containing unpaired electrons. They considered electrostatic, spin-orbit, and crystal field interaction to calculate the 2p multiplet splitting of 36 3d transition metal free ions that implies no electrostatic field is imposed/no associated ligands. Hence, the free ion is in high spin state.

Figure 5: XPS 2p multiplets structures for some d5,d4 and d3 free ions (high spin) calculated by Gupta and Sen.

The calculated free ion Mn2+ (2p3/2) spectrum yields four major multiplet peaks separated by approximately 1 eV contributing to the 2p3/2 line. Three of the four peaks are appear in Figure5. The fourth peak is of low intensity thus present in the flat slope on the high-binding energy side of the 2p3/2 emission. However the lower energy 2p3/2 peak of the Mn3+ free ion consists of two components that have same intensities while the third peak is located at somewhat higher binding energy and it is most intense of the multiplet peaks. A fourth peak occur as a weak shoulder with a low intensity and the fifth peak, broad, with low intensity peak occurs at greater binding energy than the most intense peak.

Rujukan A.P. Grosvenor, B.A. Kobe, M.C. Biesinger and N.S. Mclntyre. Investigation of multiplet splitting of Fe 2p XPS spectra and bonding in iron compounds. Surface and Interface Analysis. 2004; 36: 1564-1574. Gupta, RP & Sen, SK. Calculation of multiplet structure of core p vacency levels. II. Physical Review B 1975, vol. 12, no. 1, pp. 12-19. Nesbitt, H.W. & Banerjee, D. Interpretation of XPS Mn(2p) spectra on Mn oxyhydroxides and constrains on the mechanism of MnO2 precipitation. American Mineralogist,1998. Vol83, pp305-315.
http://xpsfitting.blogspot.com/2008/09/multiplet-splitting.html (atas talian) http://www.wsu.edu/~scudiero/documents/571-XPS-Lecture2_002.pdf (atas talian)