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4 - Quasielastic light scattering and diffusion

Published online by Cambridge University Press:  05 August 2012

George D. J. Phillies
George D. J. Phillies
Affiliation:
Worcester Polytechnic Institute, Massachusetts
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Summary

Introduction

For the most part, this volume does not discuss experimental methods. Other works provide sound descriptions of techniques and theoretical principles. How-ever, light scattering spectroscopy gave the earliest phenomenological findings that led me to writing this book. Also, the method was the basis of my career's experimental work. Here we consider optical techniques, and the correlation functions and diffusion coefficients that they determine. The emphasis is on understanding the physical quantities that are measured by light scattering spectrometers and related instruments. Actual measurements on complex fiuids appear in later chapters.

Quasielastic light scattering spectroscopy (QELSS) is an optical technique for observing transient local fiuctuations in the concentration and orientation of molecules in a liquid(1). Inelastic neutron scattering is sensitive to the same fluctuations. The wavelengths and time scales to which light and neutron scattering are sensitive are quite different, but a single theoretical picture describes the physical quantities observed by the two methods. Related optical techniques, notably Fluorescence RecoveryAfter Photobleaching (FRAP), Forced Rayleigh Scattering (FRS), Fluorescence Correlation Spectroscopy (FCS), and Depolarized Dynamic Light Scattering (DDLS) each give somewhat different information about molecularmotions. QELSS is also called Dynamic Light Scattering, “dynamic” in contrast to the “static” of “Static Light Scattering,” in which the experimenter determines the average intensity of the scattered light.

We first consider howlight scattering spectra are related to positions and motions of the dissolved scattering centers. We then present a nomenclature for diffusion coefficients. At least three paths have been used to calculate light scattering spectra of macromolecule solutions; each is described below.

Type
Chapter
Information
Phenomenology of Polymer Solution Dynamics , pp. 69 - 93
Publisher: Cambridge University Press
Print publication year: 2011

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References

[1] G. B., Benedek. Thermal fluctuations and the scattering of light. In Statistical Physics, Phase Transitions and Superfluidity, Volume II. Eds. M., Chretien, E., Gross, and S., Deser, (New York, NY: Gordon and Breach, 1968) 1–98.Google Scholar
[2] G. D. J., Phillies. On the temporal resolution of multitau digital correlators. Rev. Sci. Instruments, 67 (1996), 3423–3427.Google Scholar
[3] G. D. J., Phillies. Suppression of multiple scattering effects in quasi-elastic light scattering by homodyne cross-correlation techniques. J. Chem. Phys., 74 (1981), 260–262.Google Scholar
[4] G. D. J., Phillies. Experimental demonstration of multiple-scattering suppression in quasi-elastic-light-scattering by homodyne coincidence techniques. Phys. Rev. A, 24 (1981), 1939–1943.Google Scholar
[5] G. D., Patterson and P. J., Carroll. Depolarized Rayleigh spectroscopy of small alkanes with picosecond relaxation times. J. Chem. Phys., 76 (1982), 4356–4360.Google Scholar
[6] G. D., Patterson and P. J., Carroll. Light scattering spectroscopy of pure fluids. J. Phys. Chem., 89 (1985), 1344–1354.Google Scholar
[7] P. A., Madden. The depolarized Rayleigh scattering from fluids of spherical molecules. Molecular Physics, 36 (1978), 365–388.Google Scholar
[8] B., Crosignani, P., DiPorto, and M., Bertoleotti. Statistical Properties of Scattered Light, (New York, NY: Academic Press, 1975).Google Scholar
[9] G. D. J., Phillies. Effects of intermacromolecular interactions on diffusion. I. Two-component solutions. J. Chem. Phys., 60 (1974), 976–982.Google Scholar
[10] G. D. J., Phillies. Effects of intermacromolecular interactions on diffusion. II. Three-component solutions. J. Chem. Phys., 60 (1974), 983–989.Google Scholar
[11] G. D. J., Phillies. Fluorescence correlation spectroscopy and non-ideal solutions. Biopolymers, 14 (1975), 499–508.Google Scholar
[12] B. A., Scalettar, J. E., Hearst, and M. P., Klein. FRAP and FCS studies of self-diffusion and mutual diffusion in entangled DNA solutions. Macromolecules, 22 (1989), 4550–4559.Google Scholar
[13] H. Z., Cummins, N., Knable, and Y., Yeh. Observation of diffusion broadening of Rayleigh scattered light. Phys. Rev. Lett., 12 (1964), 150–153.Google Scholar
[14] S. B., Dubin, J. H., Lunacek, and G. B., Benedek. Observation of the spectrum of light scattered by solutions of biological macromolecules. Proc. Natl. Acad. Sci. USA, 57 (1967), 1164–1171.Google Scholar
[15] M. J., Stephen. Doppler shifts in light scattering from macroions in solution. J. Chem. Phys., 61 (1974), 1598–1599.Google Scholar
[16] G. D. J., Phillies. Light scattering measurements of diffusion in concentrated protein solutions. Unpublished D.Sc. thesis, MIT (1973).
[17] P., Doherty and G. B., Benedek. Effect of electric charge on diffusion of macromolecules. J. Chem. Phys., 61 (1974), 5426–5434.Google Scholar
[18] W., Brown and R. M., Johnsen. Diffusion coefficients in semidilute solutions evaluated from dynamic light scattering and concentration gradient measurements as a function of solvent quality. 1. Intermediate molecular weights. Macromolecules, 18 (1984), 379–387.Google Scholar
[19] W., Brown. Dynamical properties of high molecular weight polystyrene in tetrahydrofuran in the dilute–semidilute transition region. Macromolecules, 18 (1985), 1713–1719.Google Scholar
[20] L., Onsager. Reciprocal relations in irreversible processes. I.Phys. Rev., 37 (1931), 405–426.Google Scholar
[21] L., Onsager. Reciprocal relations in irreversible processes. II.Phys. Rev., 38 (1932), 2265–2279.Google Scholar
[22] B. J., Berne and R., Pecora. Dynamic Light Scattering: With Applications in Chemistry, Biology and Physics, (New York: Wiley, 1976).Google Scholar
[23] J. L., Doob. The Brownian movement and stochastic equations. Ann. Math., 43 (1942), 351–369.Google Scholar
[24] G. D. J., Phillies. Interpretation of light scattering spectra in terms of particle displacements. J. Chem. Phys., 122 (2005), 224905 1–8.Google Scholar
[25] J. M., Carter and G. D. J., Phillies. Second-order concentration correction to the mutual diffusion coefficient of a suspension of hard Brownian spheres. J. Phys. Chem., 89 (1985), 5118–5124.Google Scholar
[26] G. D. J., Phillies. Hidden correlations and the behavior of the dynamic structure factor at short times. J. Chem. Phys., 80 (1984), 6234–6239.Google Scholar
[27] G. D. J., Phillies. Dynamics of Brownian probes in the presence of mobile or static obstacles. J. Phys. Chem., 99 (1995), 4265–4272.Google Scholar
[28] C. W. J., Beenakker and P., Mazur. Diffusion of spheres in a concentrated suspension - resummation of many-body hydrodynamic interactions. Physics Letters A, 98 (1983), 22–24.Google Scholar
[29] C. W. J., Beenakker and P., Mazur. Diffusion of spheres in a concentrated suspension. 2. Physica A, 126 (1983), 349–370.Google Scholar
[30] M., Tokuyama and I., Oppenheim. On the theory of concentrated hard-sphere suspensions. Physica A, 216 (1995), 85–119.Google Scholar
[31] M., Tokuyama. Self-diffusion in multi-component glass-forming systems. Physica A, 388 (2009), 3083–3092.Google Scholar
[32] G. J., Kynch. The slow motion of two or more spheres through a viscous fluid. J. Fluid Mech., 5 (1959), 193–208.Google Scholar
[33] R. M., Mazo. On the theory of the concentration dependence of the self-diffusion coefficient of micelles. J. Chem. Phys., 43 (1965), 2873–2877.Google Scholar
[34] G. D. J., Phillies. Contribution of nonhydrodynamic interactions to the concentration dependence of the friction factor of the mutual diffusion coefficient. J. Chem. Phys., 74 (1981), 2436–2440.Google Scholar
[35] G. D. J., Phillies. Nonhydrodynamic contribution to the concentration dependence of the self-diffusion of interacting Brownian macroparticles. Chem. Phys., 74 (1983), 197–203.Google Scholar
[36] G. D. J., Phillies. On the contribution of nonhydrodynamic interactions to the concentration dependence of the drag coefficient of rigid macromolecules. J. Chem. Phys., 67 (1977), 4690–4695.Google Scholar
[37] G. D. J., Phillies. On the contribution of direct intermacromolecular interactions to the viscosity of a suspension of hard spheres. J. Chem. Phys., 71 (1979), 1492–1494.Google Scholar
[38] G. D. J., Phillies. Observations upon the dynamic structure factor of interacting spherical polyelectrolytes. J. Chem. Phys., 79 (1983), 2325–2332.Google Scholar
[39] A., Wada, N. C., Ford, and F. E., Karasz. Rotational diffusion of tobacco mosaic virus. J. Chem. Phys., 55 (1971), 1798–1802.Google Scholar
[40] D. R., Bauer, J. I., Brauman, and R., Pecora. Depolarized Rayleigh spectroscopy studies of relaxation processes of polystyrenes in solution. Macromolecules, 8 (1975), 443–451.Google Scholar
[41] D. E., Koppel. Analysis of macromolecular polydispersity in intensity correlation spectroscopy: the method of cumulants. J. Chem. Phys., 57 (1972), 4814–4820.Google Scholar
[42] B. J., Frisken. Revisiting the method of cumulants for the analysis of dynamic light-scattering data. Applied Optics, 40 (2001), 4087–4091.Google Scholar
[43] G. D. J., Phillies. Upon the application of cumulant analysis to the interpretation of quasielastic light scattering spectra. J. Chem. Phys., 89 (1988), 91–99.Google Scholar

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