Abstract
It is a common misconception that an ESR spectrum such as that of the naphthalene anion (Fig. 4–16) represents the spectrum that would be observed for a single radical ion. This is not true, since if the signal from a single naphthalene anion could be detected, it would consist of but one line! For example, the line occurring at the highest field in Fig. 4-16 corresponds to all eight protons having spin α (that is, M I = 1/2). Furthermore, if enough different molecules could be observed in succession, eventually all of the lines in the spectrum would be obtained. The observed ESR spectrum represents a statistical average over the ensemble of radicals. The fact that one line in the spectrum is four times as intense as another means that four times as many radicals are resonating at the field of the former line as at the field of the latter. It is tacitly assumed that all the radicals are completely independent and noninteracting. Such would be the case only at infinite dilution. This chapter is concerned with some of the effects of radicals interacting magnetically and chemically with each other and with their environment. The principal effect of these interactions is to give a finite width to the lines in the ESR spectrum. An analysis of linewidths in these spectra can give important information concerning time-dependent phenomena in solution. However, to understand the causes of line broadening one must first understand relaxation process.
This is a preview of subscription content, log in via an institution.
Buying options
Tax calculation will be finalised at checkout
Purchases are for personal use only
Learn about institutional subscriptionsPreview
Unable to display preview. Download preview PDF.
References
F. Bloch, Phys. Rev., 70: 460 (1946).
H. S. Gutowsky, D. W. McCall, and C. P. Slichter, J. Chem. Phys., 21: 279 (1953).
J. A. Pople, W. G. Schneider, and H. J. Bernstein, “High Resolution Nuclear Magnetic Resonance,” chap. 10, McGraw-Hill Book Company, New York, 1959.
H. S. Gutowsky and C. H. Holm, J. Chem. Phys., 25: 1228 (1956).
G. K. Fraenkel, J. Phys. Chem., 71: 139 (1967).
J. P. Lloyd and G. E. Pake, Phys. Rev., 94: 579 (1954).
T. A. Miller and R. N. Adams, J. Am. Chem. Soc., 88: 5713 (1966).
R. L. Ward and S. I. Weissman, J. Am. Chem. Soc., 79: 2086 (1957).
P. J. Zandstra and S. I. Weissman, J. Chem. Phys., 35: 757 (1961).
T. A. Miller and R. N. Adams, J. Am. Chem. Soc., 88: 5713 (1966).
S. I. Weissman, Z. Elektrochem., 64: 47 (1964).
F. C. Adam and S. I. Weissman, J. Am. Chem. Soc., 80: 1518 (1958).
H. Fischer, Mol. Phys., 9: 149 (1965).
G. K. Fraenkel, J. Phys. Chem., 71: 139 (1967).
N. Hirota, J. Phys. Chem., 71: 127 (1967).
J. R. Bolton and A. Carrington, Mol. Phys., 5: 161 (1962).
J. H. Freed and G. K. Fraenkel, J. Chem. Phys., 37: 1156 (1962).
P. D. Sullivan and J. R. Bolton, Advan. Mag. Resonance, 4: 39 (1970).
J. H. Freed and G. K. Fraenkel, J. Chem. Phys., 37: 1156 (1962).
C. P. Smith and A. Carrington, Mol. Phys., 12: 439 (1967).
A. Carrington, Mol. Phys., 5: 425 (1962).
P. D. Sullivan, J. Am. Chem. 89: 4294 (1967).
P. D. Sullivan and J. R. Bolton, The Alternating Line Width Effect, in J. S. Waugh (ed.), “Advances in Magnetic Resonance,” vol. 4, pp. 39 to 85. Academic Press Inc., New York, 1970.
E. L. Cochran, F. J. Adrian, and V. A. Bowers, J. Chem. Phys., 40: 213 (1963).
HR. W. Fessenden and R. H. Schuler, J. Chem. Phys., 39: 2147 (1963).
J. H. Freed and G. K. Fraenkel, J. Chem. Phys., 40: 1815 (1964).
O. H. Griffith, D. W. Cornell, and H. M. McConnell, J. Chem. Phys., 43: 2909 (1965).
E. de Boer and E. L. Mackor, J. Chem. Phys., 38: 1450 (1963).
G. K. Fraenkel, J. Phys. Chem., 71: 139 (1967).
M. R. Das and G. K. Fraenkel, J. Chem. Phys., 42: 1350 (1965).
J. R. Bolton and G.K. Fraenkel, J. Chem. Phys., 41: 944 (1964).
J. H. Freed and G. K. Fraenkel, J. Chem. Phys., 41: 699 (1964).
G. Nyberg, Mol. Phys., 12: 69 (1967).
R. Wilson and D. Kivelson, J. Chem. Phys., 44: 154 (1966).
P. W. Atkins and D. Kivelson, J. Chem. Phys., 44: 169 (1966).
J. H. Freed and G. K. Fraenkel, J. Chem. Phys., 39:326 (1963); 40: 1815 (1964).
G. K. Fraenkel, J. Phys. Chem., 71: 139 (1967).
A. Carrington and H. C. Longuet-Higgins, Mol. Phys., 5: 447 (1962).
A. G. Redfield, The Theory of Relaxation Processes, p. 1, in vol. 1 of J. S. Waugh (ed.), “Advances in Magnetic Resonance,” Academic Press Inc., New York, 1965.
K. J. Standley and R. A. Vaughan, “Electron Spin Relaxation Phenomena in Solids,” chaps. 5 to 8, Adam Hilger, Ltd., London, 1969.
J. Pescia, J. Physique, 27: 782 (1966).
A. Hudson and G.R. Luckhurst Chem. Rev. 69: 191 (1969).
R, Wilson and D. Kivelson, J. Chem. Phys., 44: 154 (1966).
Author information
Authors and Affiliations
Rights and permissions
Copyright information
© 1986 Chapman and Hall
About this chapter
Cite this chapter
Wertz, J.E., Bolton, J.R. (1986). Time-dependent Phenomena. In: Electron Spin Resonance. Springer, Dordrecht. https://doi.org/10.1007/978-94-009-4075-8_9
Download citation
DOI: https://doi.org/10.1007/978-94-009-4075-8_9
Publisher Name: Springer, Dordrecht
Print ISBN: 978-94-010-8307-2
Online ISBN: 978-94-009-4075-8
eBook Packages: Springer Book Archive