Journal of Chemical Physics
Feedback | Help | Exit
The Journal of Chemical Physics
   
 
 
 
Previous Article
Structure and dynamics of nonaqueous mixtures of dipolar liquids. I. Infrared and far-infrared spectroscopy
Mixtures of acetone/methanol, acetonitrile/methanol, and acetone/acetonitrile over their whole composition range were studied with infrared and far-infrared (THz) spectroscopy. Experimental spectra of...
Next Article
Analysis of water–ethanol nucleation rate data with two component nucleation theorems
We generalize the second nucleation theorem to multicomponent systems. Nucleation theorems are used to extract the molecular composition and excess internal energy of the critical cluster from experim...

Structure and dynamics of nonaqueous mixtures of dipolar liquids. II. Molecular dynamics simulations

J. Chem. Phys. 113, 3249 (2000); doi:10.1063/1.1287146

Issue Date: 22 August 2000

You are not logged in to this journal. Log in

Dean S. Venables and Charles A. Schmuttenmaer
Department of Chemistry, Yale University, 225 Prospect Street, P.O. Box 208107, New Haven, Connecticut 06520-8107
Molecular dynamics simulations have been used to study mixtures of acetone/methanol, acetonitrile/methanol, and acetone/acetonitrile over their entire composition range. Using the effective pair potentials of the neat liquids, the simulations reproduce much of the experimental spectra presented in the previous paper [D. S. Venables, A. Chiu, and C. A. Schmuttenmaer, J. Chem. Phys. 113, 3243 (2000)]. In addition to the total dipole spectra, autocorrelation functions and their corresponding spectra were calculated for the single dipole moment as well as the translational and rotational velocities of each component in the mixtures. Radial and spatial distribution functions, hydrogen bonding, and methanol chain formation in the mixtures were also analyzed. The red-shift of the high frequency librational band is attributed to methanol chains breaking up into shorter segments, and to hydrogen bonding between methanol and co-solvent molecules. Methanol molecules have a strong tendency to reside in chains, even at low methanol concentrations, and hydrogen bonding is the primary determinant of structure in the mixtures. ©2000 American Institute of Physics.
History: Received 13 March 2000; accepted 24 May 2000
Permalink: http://link.aip.org/link/?JCPSA6/113/3249/1
BUY THIS ARTICLE   (US$28)
Download HTML Download Sectioned HTML Download PDF (411 kB) View Cart

EDITORIALLY RELATED

  1. Structure and dynamics of nonaqueous mixtures of dipolar liquids. I. Infrared and far-infrared spectroscopy
    Dean S. Venables et al.
    J. Chem. Phys. 113, 3243 (2000)

KEYWORDS and PACS

Keywords
PACS
  • 61.25.Em
    Structure of solids and liquids; crystallography Studies of specific liquid structures Molecular liquids
  • 61.20.Ja
    Structure of solids and liquids; crystallography Structure of liquids Computer simulation of liquid structure
  • 64.75.+g
    Equations of state, phase equilibria, and phase transitions Solubility, segregation, and mixing; phase separation
  • 63.50.+x
    Lattice dynamics Vibrational states in disordered systems
  • YEAR: 2000

RELATED DATABASES


To view database links for this article,
you need to log in.
To view database links for this article,
you need to log in.

PUBLICATION DATA

ISSN:
0021-9606 (print)   1089-7690 (online)
Publisher:
AIP is a member of CrossRef AIP

REFERENCES (42)
View in Separate Window/Tab
For access to fully linked references, you need to log in. For access to fully linked references, you need to Log in.
  1. D. S. Venables, A. Chiu, and C. A. Schmuttenmaer, J. Chem. Phys. 113, 3243 (2000), preceding paper.
  2. E. Hawlicka, Pol. J. Chem. 70, 821 (1996).
  3. W. L. Jorgensen, J. Phys. Chem. 90, 1276 (1986).
  4. M. Haughney, M. Ferrario, and I. R. McDonald, J. Phys. Chem. 91, 4934 (1987).
  5. M. Matsumoto and K. E. Gubbins, J. Chem. Phys. 93, 1981 (1990).
  6. J. Martí, J. A. Padró, and E. Guàrdia, J. Mol. Liq. 64, 1 (1995).
  7. M. S. Skaf, T. Fonseca, and B. M. Ladanyi, J. Chem. Phys. 98, 8929 (1993).
  8. P. Jedlovszky and G. Pálinkás, Mol. Phys. 84, 217 (1995).
  9. M. Ferrario, M. Haughney, I. R. McDonald, and M. L. Klein, J. Chem. Phys. 93, 5156 (1990).
  10. W. L. Jorgensen, J. M. Briggs, and M. L. Contreras, J. Phys. Chem. 94, 1683 (1990).
  11. W. L. Jorgensen and J. M. Briggs, Mol. Phys. 63, 547 (1988).
  12. T. Ohba and S. Ikawa, Mol. Phys. 73, 999 (1991).
  13. T. Radnai and P. Jedlovszky, J. Phys. Chem. 98, 5994 (1994).
  14. A. Laaksonen and P. Stilbs, Mol. Phys. 74, 747 (1991).
  15. Y. P. Puhovski and B. M. Rode, J. Chem. Phys. 102, 2920 (1995).
  16. H. Kovacs and A. Laaksonen, J. Am. Chem. Soc. 113, 5596 (1991).
  17. D. A. Zichi and P. J. Rossky, J. Chem. Phys. 84, 2814 (1986).
  18. I. A. Borin and M. S. Skaf, Chem. Phys. Lett. 296, 125 (1998).
  19. M. S. Skaf, J. Phys. Chem. A 103, 10719 (1999).
  20. M. P. Allen and D. J. Tildesley, Computer Simulation of Liquids (Clarendon, Oxford, 1987).
  21. A. Luzar and D. Chandler, J. Chem. Phys. 98, 8160 (1993).
  22. H. Tanaka and K. E. Gubbins, J. Chem. Phys. 97, 2626 (1992).
  23. G. Pálinkás, E. Hawlicka, and K. Heinzinger, Chem. Phys. 158, 65 (1991).
  24. Y. P. Puhovski and B. M. Rode, J. Phys. Chem. 99, 1566 (1995).
  25. D. S. Venables and C. A. Schmuttenmaer, J. Chem. Phys. 108, 4935 (1998).
  26. B. M. Ladanyi and M. S. Skaf, J. Phys. Chem. 100, 1368 (1996).
  27. D. S. Venables and C. A. Schmuttenmaer (unpublished).
  28. H. Kovacs, J. Kowalewski, and A. Laaksonen, J. Phys. Chem. 94, 7378 (1990).
  29. The MolDy program was coded by K. Refson, and can be downloaded from the internet at http://www.earth.ox.ac.uk/%7Ekeith/moldy.html
  30. A. Bródka and T. W. Zerda, J. Chem. Phys. 104, 6319 (1996).
  31. D. R. Lide, Ed., CRC Handbook of Chemistry and Physics, 73rd ed. (CRC Press, Boca Raton, 1992).
  32. B. Guillot, J. Chem. Phys. 95, 1543 (1991).
  33. D. A. McQuarrie, Statistical Mechanics (Harper-Collins, New York, 1976).
  34. A. Kramers–Kronig calculation requires the high frequency index of refraction. The indices of refraction for the neat liquids at 20 °C are 1.359 (acetone), 1.344 (acetonitrile), and 1.328 (methanol) (Ref. 31). Ideal values of the indices of refraction were used for the mixtures.
  35. M. Souaille and J. C. Smith, Mol. Phys. 87, 1333 (1996).
  36. D. M. F. Edwards and P. A. Madden, Mol. Phys. 51, 1163 (1984).
  37. J. E. Bertie and S. L. Zhang, J. Chem. Phys. 101, 8364 (1994).
  38. A. Laaksonen, P. G. Kusalik, and I. M. Svishchev, J. Phys. Chem. A 101, 5910 (1997).
  39. G. Pálinkás, I. Bakó, K. Heinzinger, and P. Bopp, Mol. Phys. 73, 897 (1991).
  40. G. Eaton, A. S. Pena-Nuñez, and M. C. R. Symons, J. Chem. Soc., Faraday Trans. 1 84, 2181 (1988).
  41. G. Eaton, A. S. Pena-Nuñez, M. C. R. Symons, M. Farrario, and I. R. McDonald, Faraday Discuss. Chem. Soc. 85, 237 (1988).
  42. M. C. R. Symons and G. Eaton, J. Chem. Soc., Faraday Trans. 1 81, 1963 (1985).

CITING ARTICLES
For access to citing articles, you need to log in.
For access to citing articles, you need to Log in.


Copyright © American Institute of Physics