Dynamics of Confined Molecular Systems

MAY 01, 1990

By modeling restricted geometries with well‐characterized porous silica glasses, experimenters can determine a single geometric parameter that relates finite‐size effects to observed dynamic and thermodynamic behavior.

DOI: 10.1063/1.881244

J. M. Drake

J. Klafter

The dynamic and thermodynamic properties of molecular systems are known to be modified by confinement in very small spaces. However, making explicit and unambiguous connections between the geometry of the confining space and the molecular behavior has proven to be difficult, and the connections, when made, are frequently controversial. Nonetheless studies show that within a family of similarly prepared porous materials, the effect of finite size on the behavior of confined liquids and gases scales with a single geometric property of the pore space.

References

1. J. W. Cahn, J. Chem. Phys. 42, 93 (1964). https://doi.org/JCPSA6
B. C. Bunker, D. R. Tallant, T. J. Headly, G. L. Turner, R. J. Kirkpatrick, Phys. Chem. Glasses 29, 106 (1988).https://doi.org/PCGLA6
2. M. W. Shafer, D. D. Awschalom, J. Warnock, G. Ruben, J. Appl. Phys. 61, 5438 (1987).https://doi.org/JAPIAU
3. S. J. Gregg, K. S. W. Sing, Adsorption, Surface Area and Porosity, Academic P., New York (1982).
R. Sh. Mikhail, E. Robens, Microstructure and Thermal Analysis of Solid Surfaces, Wiley, New York (1983).
4. P. Levitz, G. Ehret, S. K. Sinha, J. M. Drake, to be published.
5. H. Braumberger, P. Debye, J. Phys. Chem. 61, 1623 (1957). https://doi.org/JPCHAX
P. Debye, H. R. AndersonJr, H. Brumberger, J. Appl. Phys. 28, 679 (1957). https://doi.org/JAPIAU
A. Guinier, G. Fournet, Small Angle Scattering of X‐rays, Wiley, New York (1955).
6. S. K. Sinha, Physica D (Utrecht) 38, 310 (1989).
7. J. M. Drake, P. Levitz, S. K. Sinha, in Better Ceramics Through Chemistry, C. J. Brinker, D. E. Clark, D. R. Ulrich, eds., Materials Research Society, Pittsburgh (1986), p. 305
8. P. W. Schmidt, A. Höhr, H.‐B. Neumann, H. Kaiser, D. Avnir, J. R. Lin, J. Chem. Phys. 90, 5016 (1989).https://doi.org/JCPSA6
9. J. Warnock, D. D. Awschalom, M. W. Shafer, Phys. Rev. 57, 1753 (1986).
10. J. Klafter, J. M. Drake, eds., Molecular Dynamics in Restricted Geometries, Wiley, New York (1989).
11. J. Warnock, D. D. Awschalom, M. W. Shafer, Phys. Rev. B 34, 475 (1986).https://doi.org/PRBMDO
12. P. Debye, L. Cleland, J. Appl. Phys. 30, 843 (1985).https://doi.org/JAPIAU
13. J. Klafter, A. Blumen, J. Chem. Phys. 80, 879 (1984).https://doi.org/JCPSA6
14. P. Levitz, J. M. Drake, J. Klafter, J. Chem. Phys. 89, 5224 (1988).https://doi.org/JCPSA6
15. E. L. Cussler, Diffusion: Mass Transfer in Fluid Systems, Cambridge U.P., New York (1984).
16. J. M. Drake, P. Levitz, J. Klafter, N. J. Turro, K. S. Nitsche, K. F. Cassidy, Phys. Rev. Lett. 61, 865 (1988).https://doi.org/PRLTAO
17. R. Kopelman, Science 241, 1620 (1988).https://doi.org/SCIEAS
18. P.‐G. de Gennes, C. R. Acad. Sci. Ser. B 295, 1061 (1982).
19. F. Rondelez, H. Hervet, W. Urbach, Chem. Phys. Lett. 53, 138 (1983).https://doi.org/CHPLBC
20. J. Karger, J. Lenzner, H. Pfeifer, H. Schwabe, W. Heyer, F. Yankowski, F. Wolf, S. F. Zdanov, J. Am. Ceram. Soc. 65, 69 (1983). https://doi.org/JACTAW
F. D’Orazio, S. Bhattacharja, W. P. Halperin, R. Gerhardt, Phys. Rev. Lett. 63, 43 (1989).https://doi.org/PRLTAO
21. M. T. Bishop, K. H. Langley, F. E. Karasz, Phys. Rev. Lett. 56, 197 (1986).https://doi.org/PRLTAO
22. W. D. Dozier, J. M. Drake, J. Klafter, Phys. Rev. Lett. 56, 197 (1986).https://doi.org/PRLTAO
23. R. E. Baltus, J. L. Anderson, Chem. Eng. Sci. 38, 1959 (1983).https://doi.org/CESCAC

More about the Authors

J. M. Drake. Exxon Research and Engineering Company, Annandale, New Jersey.

J. Klafter. School of Chemistry, Tel Aviv University.