The general idea I have is, when we have photo ionised a molecule, vacancy will be created at the core and this vacancy could be filled by the electron in the outer shell (usually transition elements, which have unpaired electron), so we would have multiplet splitting. But why is this not considered Auger?
1. Is this not the same principle that happens during Auger spectroscopy?
2. It is reported in multiple papers that transition metals show multiplet. eg, NiO is reported to show multiplet, but one of the multiplet also overlaps with Ni3+. Is there a way to exactly differentiate it?
Multiplet splitting arises when an atom contains unpaired electrons (e.g. Cr(III), 3p63d3). When a core electron vacancy is created by photoionization, there can be coupling between the unpaired electron 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".
(c) http://www.xpsfitting.com/2008/09/multiplet-splitting.html
[1] J.F. Moulder, W.F. Stickle, P.E. Sobol, K.D. Bomben, Handbook of X-ray Photoelectron Spectroscopy, Perkin-Elmer Corp, Eden Prairie, MN, 1992. [2] R.P. Gupta, S.K. Sen, Phys. Rev. B 12 (1975) 15. [3] A.P. Grosvenor, M.C. Biesinger, R.St.C. Smart, N.S. McIntrye, Surf. Sci. 600 (2006) 1771. [4] N.S. McIntyre, D.G. Zetaruk, Anal. Chem. 49 (1977) 1521. [5] M.C. Biesinger, C. Brown, J.R. Mycroft, R.D. Davidson, N.S. McIntyre, Surf. Interface Anal. 36 (2004) 1550. [6] A.P. Grosvenor, B.A. Kobe, M.C. Biesinger, N.S. McIntyre, Surf. Interface Anal. 36 (2004) 1564. [7] M.C. Biesinger, L.W.M. Lau, A.R. Gerson, R.St.C. Smart, Physical Chemistry Chemical Physics, 14 (2012) 2434. [8] F. de Groot, A. Kotani, Core Level Spectroscopy of Solids, CRC Press, Boca Raton, 2008. [9] M.C. Biesinger, L.W.M. Lau, A.R. Gerson, R.St.C. Smart, Appl. Surf. Sci. 257 (2010) 887. [10] M.C. Biesinger, B.P. Payne, A.P. Grosvenor, L.W.M. Lau, A.R. Gerson, R.St.C. Smart, Appl. Surf. Sci. 257 (2011) 2717. [11] M.C. Biesinger, B.P. Payne, L.W.M. Lau, A.R. Gerson, R.St.C. Smart, Surf. Interface Anal. 41 (2009) 324.
Multiplet splitting arises when an atom contains unpaired electrons (e.g. Cr(III), 3p63d3). When a core electron vacancy is created by photoionization, there can be coupling between the unpaired electron 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".
(c) http://www.xpsfitting.com/2008/09/multiplet-splitting.html
[1] J.F. Moulder, W.F. Stickle, P.E. Sobol, K.D. Bomben, Handbook of X-ray Photoelectron Spectroscopy, Perkin-Elmer Corp, Eden Prairie, MN, 1992. [2] R.P. Gupta, S.K. Sen, Phys. Rev. B 12 (1975) 15. [3] A.P. Grosvenor, M.C. Biesinger, R.St.C. Smart, N.S. McIntrye, Surf. Sci. 600 (2006) 1771. [4] N.S. McIntyre, D.G. Zetaruk, Anal. Chem. 49 (1977) 1521. [5] M.C. Biesinger, C. Brown, J.R. Mycroft, R.D. Davidson, N.S. McIntyre, Surf. Interface Anal. 36 (2004) 1550. [6] A.P. Grosvenor, B.A. Kobe, M.C. Biesinger, N.S. McIntyre, Surf. Interface Anal. 36 (2004) 1564. [7] M.C. Biesinger, L.W.M. Lau, A.R. Gerson, R.St.C. Smart, Physical Chemistry Chemical Physics, 14 (2012) 2434. [8] F. de Groot, A. Kotani, Core Level Spectroscopy of Solids, CRC Press, Boca Raton, 2008. [9] M.C. Biesinger, L.W.M. Lau, A.R. Gerson, R.St.C. Smart, Appl. Surf. Sci. 257 (2010) 887. [10] M.C. Biesinger, B.P. Payne, A.P. Grosvenor, L.W.M. Lau, A.R. Gerson, R.St.C. Smart, Appl. Surf. Sci. 257 (2011) 2717. [11] M.C. Biesinger, B.P. Payne, L.W.M. Lau, A.R. Gerson, R.St.C. Smart, Surf. Interface Anal. 41 (2009) 324.
Multiplet splitting occurs if there are unfilled shells with lone pairs. Transition metals with partially filled p and d shells and rare earths with f orbitals all show multiplet splitting.
+Dimitry A. Zatsepin Thanks, thats right, and I have mentioned this in my question too. To be even more specific, wont we have angular momentum coupling even when we have Auger effect??
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