Journal of Chemical Physics
Feedback | Help | Exit
The Journal of Chemical Physics
   
 
 
 
Previous Article
Theoretical study of the effects of solvent environment on photophysical properties and electronic structure of paracyclophane chromophores
We use first-principles quantum-chemical approaches to study absorption and emission properties of recently synthesized distyrylbenzene (DSB) derivative chromophores and their dimers (two DSB molecule...
Next Article
A polarizable multistate empirical valence bond model for proton transport in aqueous solution
A multistate empirical valence bond model for proton transport in water, which explicitly includes solvent polarization, is presented. Polarization is included for each valence-bond state via induced ...

Polarizability response in polar solvents: Molecular-dynamics simulations of acetonitrile and chloroform

J. Chem. Phys. 122, 224506 (2005); doi:10.1063/1.1925275

Published 15 June 2005

You are not logged in to this journal. Log in

M. Dolores Elola and Branka M. Ladanyi
Department of Chemistry, Colorado State University, Fort Collins, Colorado 80523
The relaxation of the many-body polarizability in liquid acetonitrile and chloroform at room temperature was studied by molecular-dynamics simulations. The collective polarizability induced by intermolecular interactions was included using first- and all-orders dipole-induced-dipole models and calculated considering both molecule-centered and distributed site polarizabilities. The anisotropic response was analyzed using a separation scheme that allows a decomposition of the total response in terms of orientational and collision-induced effects. We found the method effective in approximately separating the contributions of these relaxation mechanisms, although the orientational-collision-induced interference makes a non-negligible contribution to the total response. In both liquids the main contribution to the anisotropic response is due to orientational dynamics, but intermolecular collision-induced (or translational) effects are important, especially at short times. We found that higher-order interaction-induced effects were essentially negligible for both liquids. Larger differences were found between the center-center and site-site models, with the latter showing faster polarizability relaxation and better agreement with experiment. Isotropic and anisotropic spectra were computed from the corresponding time correlation functions. The lowest-frequency contributions are largely supressed in the isotropic spectra and their overall shape is similar to the purely collision-induced contribution to the anisotropic spectra, but with an amplitude which is smaller by a factor of ~5 in acetonitrile and ~3 in chloroform. ©2005 American Institute of Physics
History: Received 3 March 2005; accepted 11 April 2005; published 15 June 2005
Permalink: http://link.aip.org/link/?JCPSA6/122/224506/1
BUY THIS ARTICLE   (US$28)
Download HTML Download Sectioned HTML Download PDF (187 kB) View Cart

KEYWORDS and PACS

Keywords
PACS
  • 31.70.Dk
    Environmental and solvent effects on electronic structure of atoms and molecules
  • 33.15.Kr
    Molecular electric and magnetic moments (and derivatives), polarizability, and magnetic susceptibility
  • 34.20.Gj
    Intermolecular and atom–molecule potentials and forces
  • YEAR: 2005

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 (60)
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. B.J. Berne and R. Pecora, Dynamic Light Scattering with Applications to Chemistry, Biology and Physics (Dover, New York, 2000).
  2. S. Mukamel, Principles of Nonlinear Optical Spectroscopy (Oxford University Press, New York, 1995).
  3. B. M. Ladanyi and Y. Q. Liang, J. Chem. Phys. 103, 6325 (1995).
  4. M. Paolantoni and B. M. Ladanyi, J. Chem. Phys. 117, 3856 (2002).
  5. S. Saito and I. Ohmine, J. Chem. Phys. 106, 4889 (1997).
  6. B. M. Ladanyi, J. Chem. Phys. 78, 2189 (1983).
  7. L. C. Geiger and B. M. Ladanyi, J. Chem. Phys. 87, 191 (1987).
  8. L. C. Geiger and B. M. Ladanyi, J. Chem. Phys. 89, 6588 (1988).
  9. L. C. Geiger and B. M. Ladanyi, Chem. Phys. Lett. 159, 413 (1989).
  10. P. A. Madden and D. J. Tildesley, Mol. Phys. 55, 969 (1985).
  11. K. Kiyohara, K. Kamada, and K. Ohta, J. Chem. Phys. 112, 6338 (2000).
  12. T. Keyes and B. M. Ladanyi, Mol. Phys. 33, 1271 (1977).
  13. B. M. Ladanyi and T. Keyes, J. Chem. Phys. 68, 3217 (1978).
  14. J. Applequist, J. R. Carl, and K. K. Fung, J. Am. Chem. Soc. 94, 2952 (1972).
  15. B. M. Ladanyi, T. Keyes, D. J. Tildesley, and W. B. Streett, Mol. Phys. 39, 645 (1980).
  16. L. C. Geiger, B. M. Ladanyi, and M. E. Chapin, J. Chem. Phys. 93, 4533 (1990).
  17. T. Keyes, J. Chem. Phys. 104, 9349 (1996).
  18. T. Keyes, J. Chem. Phys. 106, 46 (1997).
  19. R. L. Murry, J. T. Fourkas, W. X. Li, and T. Keyes, Phys. Rev. Lett. 83, 3550 (1999).
  20. X. Ji, H. Alhborn, and B. Space, J. Chem. Phys. 112, 4186 (2000).
  21. X. Ji, H. Ahlborn, and B. Space, J. Chem. Phys. 113, 8693 (2000).
  22. S. Mossa, G. Ruocco, and M. Sampoli, J. Chem. Phys. 117, 3289 (2002).
  23. B. T. Thole, Chem. Phys. 59, 341 (1981).
  24. A. Tokmakoff, J. Chem. Phys. 105, 1 (1996).
  25. D. Frenkel and J. P. McTague, J. Chem. Phys. 72, 2801 (1980).
  26. A. De Santis and M. Sampoli, Chem. Phys. Lett. 96, 114 (1983).
  27. A. De Santis and M. Sampoli, Chem. Phys. Lett. 102, 425 (1983).
  28. V. Mazzacurati, M. A. Ricci, G. Ruocco, and M. Nardone, Mol. Phys. 50, 1083 (1983).
  29. P. Benassi, V. Mazzacurati, M. Nardone, M. A. Ricci, and G. Ruocco, Mol. Phys. 62, 1467 (1987).
  30. R. Frattini, M. Sampoli, M. A. Ricci, and G. Ruocco, Chem. Phys. Lett. 141, 297 (1987).
  31. C. J. Fecko, J. D. Eaves, and A. Tokmakoff, J. Chem. Phys. 117, 1139 (2002).
  32. M. Khalil, O. Golonzka, N. Demirdöven, C. J. Fecko, and A. Tokmakoff, Chem. Phys. Lett. 321, 231 (2000).
  33. M. Khalil, N. Demirdöven, O. Golonzka, C. J. Fecko, and A. Tokmakoff, J. Phys. Chem. A 104, 5711 (2000).
  34. P. T. van Duijnen and M. Swart, J. Phys. Chem. A 102, 2399 (1998).
  35. H. Torii, Chem. Phys. Lett. 353, 431 (2002).
  36. H. Torii, Vib. Spectrosc. 29, 205 (2002).
  37. M. S. Skaf and S. M. Vechi, J. Chem. Phys. 119, 2181 (2003).
  38. T. L. C. Jansen, J. G. Snijders, and K. Duppen, J. Chem. Phys. 114, 10910 (2001).
  39. R. L. Murry and J. T. Fourkas, J. Chem. Phys. 107, 9726 (1997).
  40. B. M. Ladanyi and T. Keyes, Mol. Phys. 33, 1063 (1977).
  41. D. McMorrow, Opt. Commun. 86, 236 (1991).
  42. M. Cho, M. Du, N. F. Scherer, and G. R. Fleming, J. Chem. Phys. 99, 2410 (1993).
  43. H. Stassen, T. Dorfmüler, and B. M. Ladanyi, J. Chem. Phys. 100, 6318 (1994).
  44. D. M. F. Edwards, P. A. Madden, and I. R. McDonald, Mol. Phys. 51, 1141 (1984).
  45. H. Kovacs, J. Kowalewski, and A. Laaksonen, J. Phys. Chem. 94, 7378 (1990).
  46. M.P. Allen and D.J. Tildesley, Computer Simulation of Liquids (Oxford University Press, New York, 1994).
  47. J. P. Ryckaert, G. Ciccotti, and H. J. C. Berendsen, J. Comput. Phys. 23, 327 (1977).
  48. A. K. Burnham, G. R. Alms, and W. H. Flygare, J. Chem. Phys. 62, 3289 (1975).
  49. B. J. Loughnane, A. Scodinu, R. A. Farrer, J. T. Fourkas, and U. Mohanty, J. Chem. Phys. 111, 2686 (1999).
  50. D. McMorrow and W. T. Lotshaw, J. Phys. Chem. 95, 10395 (1991).
  51. S. Park and N.F. Scherer (private communication).
  52. S. Park, B. N. Flanders, X. Shang, R. A. Westervelt, J. Kim, and N. F. Scherer, J. Chem. Phys. 118, 3917 (2003).
  53. Y. J. Chang and E. W. Castner, Jr., J. Phys. Chem. 100, 3330 (1996).
  54. P. P. Wiewior, H. Shirota, and E. W. Castner, Jr., J. Chem. Phys. 116, 4643 (2002).
  55. J. S. Friedman and C. Y. She, J. Chem. Phys. 99, 4960 (1993).
  56. N. A. Smith and S. R. Meech, Int. Rev. Phys. Chem. 21, 75 (2002).
  57. B. M. Ladanyi and S. Klein, J. Chem. Phys. 105, 1552 (1996).
  58. A. Ryu and R. M. Stratt, J. Phys. Chem. B 108, 6782 (2004).
  59. M. I. Aralaguppi, C. V. Jadar, and T. M. Aminabhavi, J. Chem. Eng. Data 41, 1309 (1996).
  60. A. Samoc, J. Appl. Phys. 94, 6167 (2003).

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