Abstract
Extended X-ray absorption fine structure (EXAFS) refers to the oscillatory variation of the X-ray absorption as a function of photon energy beyond an absorption edge. The absorption, normally expressed in terms of absorption coefficient (ยต), can be determined from a measurement of the attenuation of X-rays upon their passage through a material. When the X-ray photon energy (E) is tuned to the binding energy of some core level of an atom in the material, an abrupt increase in the absorption coefficient, known as the absorption edge, occurs. For isolated atoms, the absorption coefficient decreases monotonically as a function of energy beyond the edge. For atoms either in a molecule or embedded in a condensed phase, the variation of absorption coefficient at energies above the absorption edge displays a complex fine structure called EXAFS.
This is a preview of subscription content, log in via an institution to check access.
Access this chapter
Tax calculation will be finalised at checkout
Purchases are for personal use only
Preview
Unable to display preview. Download preview PDF.
References
R. de L. Kronig, Z. Physik., 70, 317 (1931)
R. de L. Kronig, Z. Physik., 75, 191 (1932)
E. A. Stern, Phys. Rev. B, 10, 3027 (1974);
E. A. Stern, D. E. Sayers, and F. W. Lytle, Phys. Rev. B, 11, 4836 (1975), and references cited therein.
B. M. Kincaid and P. Eisenberger, Phys. Rev. Lett., 34, 1361 (1975);
H. Winick and A. Bienenstock, Ann. Rev. Nucl. Part. Sci., 28, 33 (1978);
I. Lindau and H. Winick, J. Vac. Sci. Tecnol., 15, 977 (1978);
R. E. Watson and M. L. Perlman, Science, 199, 1295 (1978);
B. W. Batterman and N. W. Ashcroft, Science, 206, 157 (1979).
The physics and biological aspects of EXAFS have been reviewed elsewhere by others, see, e.g., (a) E. A. Stern, Contemp. Phys., 19, 289 (1978);
P. Eisenberger and B. M. Kincaid, Science, 200, 1441 (1978);
R. G. Shulman, P. Eisenberger, and B. M. Kincaid, Ann. Rev. Biophys. Bioeng., 7, 559 (1978);
D. R. Sandstrom and F. W. Lytle, Ann. Rev. Phys. Chem., 30, 215 (1979);
S. P. Cramer and K. O. Hodgson, Prog. Inorg. Chem., 25, 1 (1979);
T. M. Hayes, J. Non-Cryst. Solids, 31, 57 (1978);
J. Wong in โMetallic Glassesโ, H. J. Guntherodt, Ed., Springer-Verlag, Berlin (1980);
โSynchrotron Radiation Researchโ, ed. H. Winick and S. Doniach, Plenum, N.Y. (1980);
P. A. Lee, P. H. Citrin, P. Eisenberger, and B. M. Kincaid, Rev. Mod. Phys., in press.
U. C. Srivastava and H. L. Nigam, Coord. Chem. Rev., 9, 275 (1972โ73).
R. G. Shulman, Y. Yafet, P. Eisenberger, & W. E. Blumberg, Proc. Natl. Acad. Sci. U.S.A, 73, 1384 (1976);
F. W. Lytle, P. S. P. Wei, R. B. Greegor, G. H. Via, and J. H. Sinfelt, J. Chem. Phys., 70, 4849 (1979);
L. Powers, W. E. Blumberg, B. Chance, C. H. Barlow, J. S. Leigh, Jr., J. Smith, T. Yonetani, S. Vik, and J. Peisach, Biochim. Biophy. Acta, 546, 520 (1979).
J. Jaklevic, J. A. Kirby, M. P. Klein, A. S. Robertson, G. S. Brown, and P. Eisenberger, Solid State Comm., 23, 679 (1977);
F. S. Goulding, J. M. Jaklevic, and A. C. Thompson, SSRL Report No. 78/04, May 1978;
E. A. Stern and S. M. Heald, Rev. Sci. Instrum., 50, 1579 (1979);
P. H. Citrin, P. Eisenberger, and R. Hewitt, Phys. Rev. Lett., 41, 309 (1978);
J. Stohr, D. Denley, and P. Perfetti, Phys. Rev. B, 18, 4132 (1978);
M. Isaacson, J. Chem. Phys., 56, 1818 (1972);
J. I. Ritsko, S. E. Schnatterly and P. G. Gibbons, Phys. Rev. Lett., 32, 671 (1974);
R. A. Bonham in โMomentum Wave Functions-1976โ, American Institute of Physics, New York (1977);
B. M. Kincaid, A. E. Meixner, and P. M. Platzman, Phys. Rev. Lett., 40, 1296 (1978);
D. C. Joy and D. M. Maher, Science 206, 162 (1979).
C. A. Ashley and S. Doniach, Phys. Rev. B, 11, 1279 (1975).
P. A. Lee and G. Beni, Phys. Rev. B, 15, 2862 (1977);
P. A. Lee and J. B. Pendry, ibid. 11, 2795 (1975).
Though simply defined as x = (ยต - ยต o )/ยต o (where ฮผ and ยต o are the observed and โfree atomโ absorption coefficients, respectively), the determination of x (generally termed as โbackground substrationโ) is by no means straightforward since ยต o is generally not known. A general procedure is to approximate ยต o by a smooth curve (some polynomial or spline) fitted to ฮผ. In transmission experiments, generally drops off monotonically due primarily to the energy dependence of the ionization chamber efficiency and the absorption due to other atoms. In fluorescence experiments, on the other hand, the baseline rises as a function of energy owing to increasing sample penetration, increased Compton scattering, reduced absorption of the scattering, and other effects.
It should be cautioned that the Debye-Waller factor as determined by EXAFS is different from that implied by conventional crystallography in that it refers to the root-mean-square relative displacement along the bond direction and not the absolute root-mean-square displacement of individual atoms. For the first shell, the motions are significantly correlated whereas for higher shells the correlation is greatly reduced.
S. J. Cyrin, Molecular Vibrations and Mean Square Amplitudes, Elsevier, Amsterdam, 1968, p. 77.
G. Beni and P. M. Platzman, Phys. Rev. B, 14, 1514 (1976).
R. B. Greegor and F. W. Lytle, Phys. Rev. B, 20, 4902 (1979).
E. Sevillano, H. Meuth, and J. J. Rehr, Phys. Rev. B, 20, 4908 (1979).
P. Eisenberger and G. S. Brown, Solid State Commun., 29, 481 (1979) .
T. M. Hayes and J. B. Boyce, Chapter 5 of this book.
T. M. Hayes, J. B. Boyce, and J. L. Beeby, J. Phys. C, 11, 2931 (1978).
E. D. Crozier, Chapter 6 of this book.
E. D. Crozier and A. J. Seary, Can. J. Phys., 58, 1388 (1980).
J. J. Rehr, E. A. Stern, R. L. Martin, and E. R. Davidson, Phys. Rev. B, 17, 560 (1978).
E. A. Stern, B. Bunker, and S. M. Heald, Chapter 4 of this book
E. A. Stern, B. A. Bunker, and S. M. Heald, Phys. Rev. B, 21, 5521 (1980).
P. Eisenberger and B. Lengeler, to be published in Phys. Rev. B (1980).
B. K. Teo, J. Am. Chem. Soc., submitted for publication.
C. J. Powell, Surface Sci., 44, 29 (1974) .
D. R. Penn, Phys. Rev. B, 13, 5248 (1976).
M. P. Seah and W. A. Dench, Surface Inter. Anal., 1, 2 (1979).
Strictly speaking, the single-electron single-scattering theory of EXAFS already includes one particular multiple scattering correction: viz., the backscattering process involving the central atom which gives rise to the 2kr phase factor. In this paper, โmultiple scatteringโ refers to processes involving atoms other than the central atom.
B. K. Teo and P. A. Lee, J. Am. Chem. Soc., 101, 2815 (1979).
P. H. Citrin, P. Eisenberger, and B. M. Kincaid, Phys. Rev. Lett., 36, 1346 (1976);
B. K. Teo, P. A. Lee, A. L. Simons, P. Eisenberger, and B. M. Kincaid, J. Am. Chem. Soc., 99, 3854 (1977);
P. A. Lee, B. K. Teo, and A. L. Simons, J. Am. Chem. Soc., 99, 3856 (1977).
S. P. Cramer, T. K. Eccles, F. Kutzler, K. O. Hodgson, and S. Doniach, J. Am. Chem. Soc., 98, 8059 (1976).
R. G. Shulman, P. Eisenberger, W. E. Blumberg, N. A. Stombaugh, .Proc Nat. Acad. Sci. U.S.A., 72, 4002 (1975).
G. Martens, P. Rabe, N. Schwentner, and A. Werner, Phys. Rev. Lett., 39, 1411 (1977).
P. A. Lee, Chapter 2 of this book.
A. Bienenstock, Chapter 14 of this book.
B. W. Batterman, Chapter 15 of this book.
J. B. Hastings, Chapter 16 of this book.
P. J. Mallozzi, R. E. Schwerzel, H. M. Epstein, and B. E. Campbell, Science, 206, 353 (1979).
G. S. Knapp, H. Chen, T. E. Klippert, Rev. Sci. Instrum., 49, 1658 (1978).
For more detailed discussions on S/N of various EXAFS techniques, see Ref. 41.
J. B. Hastings, P. Eisenberger, B. Lengeler, and M. L. Perlman, Phys. Rev. Lett., 43, 1807 (1979).
M. Marcus, L. S. Powers, A. R. Storm, B. M. Kincaid, and B. Chance, Rev. Sci. Instrum., 51, 1023 (1980).
See Chapters 17โ21 of this book.
R. D. Leapman and V. E. Cosslet, J. Phys. D, 9, 25 (1976) .
P. E. Batson and A. J. Craven, Phys. Rev. Lett., 42, 893 (1979).
For an excellent review, see R. H. Holm, Acc. Chem. Res., 10, 427 (1977).
R. G. Shulman, P. Eisenberger, B. K. Teo, B. M. Kincaid, and G. S. Brown, J. Mol. Biol., 124, 305 (1978), and references cited therein.
B. K. Teo, R. G. Shulman, G. S. Brown, and A. E. Meixner, J. Am. Chem. Soc., 101, 5624 (1979) .
K. D. Watenbaugh, L. C. Sieker, J. R. Herriot, and L. H. Jensen, Acta Crystallogr. B, 29, 943 (1973).
B. Bunker and E. A. Stern, Biophys. J., 19, 253 (1977);
D. E. Sayers, E. A. Stern, and J. R. Herriott, J. Chem. Phys., 64, 427 (1976).
P. Eisenberger, R. G. Shulman, G. S. Brown, and S. Ogawa, Proc. Natl. Acad. Sci., U.S.A., 73, 491 (1976); (b) P. Eisenberger, R. G. Shulman, B. M. Kincaid, G. S. Brown, and S. Ogawa, Nature (London), 274, 30 (1978).
P. Eisenberger, R. G. Shulman, B. M. Kincaid, G. S. Brown, and S. Ogawa, Nature (London), 274, 30 (1978).
J. L. Hoard, Science, 174, 1295 (1971);
M. F. Perutz, Nature (London), 228, 726 (1970).
G. S. Brown, G. Navon, and R. G. Shulman, . Proc Natl. Acad. Sci., U.S.A., 74, 1794 (1977).
S. M. Heald, E. A. Stern, B. Bunker, E. M. Holt, and S. L. Holt, J. Am. Chem. Soc., 101, 67 (1979).
J. M. Brown, L. Powers, B. Kincaid, J. A. Larrabee, and T. G. Spiro, J. Am. Chem. Soc. 102, 4210 (1980) .
T. E. Wolff, J. M. Berg, C. Warrick, K. O. Hodgson, R. H. Holm, and R. B. Frankel, J. Am. Chem. Soc., 100, 4630 (1978);
S. P. Cramer, K. O. Hodgson, W. O. Gillum, and L. E. Mortenson, J. Am. Chem. Soc., 100, 3398 (1978);
S. P. Cramer, W. O. Gillum, K. O. Hodgson, L. E. Mortenson, E. I. Stiefel, J. R. Chisnell, W. J. Brill, and V. K. Shah, J. Am. Chem. Soc., 100, 3814 (1978).
T. E. Wolff, J. M. Berg, C. Warrick, K. O. Hodgson, and R. H. Holm, J. Am. C. S., 100, 4630 (1978);
T. E. Wolff, J. M. Berg, K. O. Hodgson, R. B. Frankel, and R. H. Holm, J. Am. C. S., 101, 4140 (1979);
G. Christou, C. D. Garner, F. E. Mabbs and T. J. King, J. C. S. Chem. Commun., 740 (1978);
G. Christou, C. D. Garner, F. E. Mabbs, and M. G. B. Drew, ibid., 91 (1979);
S. R. Acott, G. Christou, C. D. Garner, T. J. King, F. E. Mabbs, and R. M. Miller, Inorg. Chim. Acta., 35, L337 (1979);
T. E. Wolff, J. M. Berg, P. P. Power, K. O. Hodgson, R. H. Holm, and R. B. Frankel, J. C. S. Chem. Commun., 101, 5454 (1979);
D. Coucouvanis, N. C. Baenziger, E. D. Simhon, P. Stremple, D. Swenson, A. Simopoulos, A. Kostikas, V. Petrouleas, and V. Papaefthymiou, J. Am. Chem. Soc., 102, 1732 (1980).
B. K. Teo and B. A. Averill, Biochem. Biophys. Res. Commun., 88, 1454 (1979);
R. H. Tieckelmann, H. C. Silvis, T. A. Kent, B. H. Huynh, J. V. Waszczak, B. K. Teo, and B. A. Averill, J. Am. Chem. Soc., 102, 5550 (1980);
C. D. Stout, D. Ghosh, V. Pattabhi, and A. Robbins, J. Biol. Chem., 255, 1797 (1980);
Fujian Institute of Research on the Structure of Matter (PRC), private communication.
L. Powers, P. Eisenberger, and J. Stamatoff, Ann. N.Y. Acad. Sci., 307, 113 (1978).
S. P. Cramer, J. H. Dawson, K. O. Hodgson, and L. P. Hager, J. Am. Chem. Soc., 100, 7282 (1978).
V. W. Hu, S. I. Chan, and G. S. Brown,. Proc Natl. Acad. Sci. U.S.A., 74, 3821 (1977).
T. Tullius, P. Frank, and K. O. Hodgson. Proc Natl. Acad. Sci. U.S.A., 75, 4069 (1978).
For example, SSRL Publication List; SSRL Reports 78/10, 79/03, 79/10, 80/01, etc.
B. K. Teo, K. Kijima, and R. Bau. J. Am. Chem. Soc., 100, 621 (1978)
B. K. Teo, P. Eisenberger, J. Reed, J. K. Barton, S. J. Lippard, J. Am. Chem. Soc., 100, 3225 (1978), and references cited therein.
B. K. Teo, P. Eisenberger, and B. M. Kincaid, J. Am. Chem. Soc., 100, 1735 (1978).
A. Michalowicz, J. J. Girerd, and J. Goulon, Inorg. Chem., 18, 3004 (1979).
M. Verdaguer, A. Michalowicz, J. J. Girerd, N. Alberding, and O. Kahn, Inorg. Chem., 19, 3271 (1980).
G. Martens, P. Rabe, N. Schwentner, and A. Werner, Phys. Rev. B, 17, 1481 (1978).
H. S. Chen, B. K. Teo, and R. Wang, Abst. 4th Inter. Conf. Liq. Amor. Metals, Grenoble, France, July 7โ11, 1980;
J. Wong, F. W. Lytle, R. B. Greegor, H. H. Liebermann, J. L. Walter, and F. E. Luborsky, Proc. 3rd Inter. Conf. Rapid. Quench. Metals, Sessex University, Vol. II, 1978, p. 345;
T. M. Hayes, J. W. Allen, J. Tauc, B. C. Giessen, and J. J. Hauser, Phys. Rev. Lett., 40, 1282 (1978);
E. A. Stern, S. Rinaldi, E. Callen, S. Heald, and B. Bunker, J. Mag. Mater., 7, 188 (1978).
G. S. Brown, L. R. Testardi, J. H. Wernick, A. B. Hallak, and T. H. Geballe, Solid State Commun., 23, 875 (1977).
J. B. Boyce and T. M. Hayes in Chapter 2 of Physics of Superionic Conductors, ed. M. B. Salamon, Vol. 15 of Topics in Current Physics, Springer-Verlag, Berlin (1979).
S. H. Hunter, A. Bienenstock, and T. M. Hayes, in The Structure of NonCrystalline Materials, ed. P. H. Gaskell, Taylor and Francis, London, 1977, p. 73;
S. H. Hunter, A. Bienenstock, and T. M. Hayes, in Amorphous and Liquid Semiconductors, ed. W. E. Spear, Univ. Edinburgh, Edinburgh, 1977, p. 78.
P. Eisenberger and B. M. Kincaid, Chem. Phys. Lett., 36, 134 (1975);
D. R. Sandstrom, H. W. Dodgen and F. W. Lytle, J. Chem. Phys., 67, 473 (1977);
D. R. Sandstrom, J. Chem. Phys., 71, 2381 (1979).
E. D. Grozier, F. W. Lytle, D. E. Sayers, and E. A. Stern, Can J. Chem., 55, 1968 (1977);
J. Wong and F. W. Lytle, J. Non-Cryst. Solid., 37, 273 (1980).
E. D. Crozier and A. J. Seary, Can. J. Phys., 58, 1388 (1980).
See Chapters 7 to 12 of this book.
J. Reed, P. Eisenberger, B. K. Teo, and B. M. Kincaid, J. Am. Chem. Soc., 100, 2375 (1978);
J. Reed, P. Eisenberger, B. K. Teo, and B. M. Kincaid, J. Am. Chem. Soc., 99, 5217 (1977).
J. H. Sinfelt, G. H. Via, and F. W. Lytle, J. Chem. Phys., 68, 2009 (1978);
F. W. Lytle, NBS Spec. Publ. U.S.A., 475, 34 (1977);
I. Bassi, F. W. Lytle, and G. Parravano, J. Catal., 42, 139 (1976);
G. H. Via, J. H. Sinfelt, F. W. Lytle, J. Chem. Phys., 71, 690 (1979);
J. H. Sinfelt, G. H. Via, and F. W. Lytle, J. Chem. Phys., 72, 4832 (1980);
Ref 6c.
G. H. Via, J. H. Sinfelt, and F. W. Lytle, Chapter 10 of this book.
S. M. Heald and E. A. Stern, Phys. Rev. B, 16, 5549 (1977);
L. I. Johansson and J. Stohr, Phys. Rev. Lett., 43, 1882 (1979).
Author information
Authors and Affiliations
Editor information
Editors and Affiliations
Rights and permissions
Copyright information
ยฉ 1981 Springer Science+Business Media New York
About this chapter
Cite this chapter
Teo, BK. (1981). Extended X-Ray Absorption Fine Structure (EXAFS) Spectroscopy: Techniques and Applications. In: Teo, B.K., Joy, D.C. (eds) EXAFS Spectroscopy. Springer, Boston, MA. https://doi.org/10.1007/978-1-4757-1238-4_3
Download citation
DOI: https://doi.org/10.1007/978-1-4757-1238-4_3
Publisher Name: Springer, Boston, MA
Print ISBN: 978-1-4757-1240-7
Online ISBN: 978-1-4757-1238-4
eBook Packages: Springer Book Archive