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Molecular dynamics simulations have been performed to study the complex and heterogeneous dynamics of ions in ionic liquids. The dynamics of cations and anions in 1-ethyl-3-methyl imidazolium nitrate ...
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Isomorphic classical molecular dynamics model for an excess electron in a supercritical fluid

J. Chem. Phys. 129, 194502 (2008); doi:10.1063/1.3013357

Published 17 November 2008

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Thomas F. Miller, III
Department of Chemistry, University of California, Berkeley, California 94720, USA
Ring polymer molecular dynamics (RPMD) is used to directly simulate the dynamics of an excess electron in a supercritical fluid over a broad range of densities. The accuracy of the RPMD model is tested against numerically exact path integral statistics through the use of analytical continuation techniques. At low fluid densities, the RPMD model substantially underestimates the contribution of delocalized states to the dynamics of the excess electron. However, with increasing solvent density, the RPMD model improves, nearly satisfying analytical continuation constraints at densities approaching those of typical liquids. In the high-density regime, quantum dispersion substantially decreases the self-diffusion of the solvated electron. In this regime where the dynamics of the electron is strongly coupled to the dynamics of the atoms in the fluid, trajectories that can reveal diffusive motion of the electron are long in comparison to beta[h-bar]. ©2008 American Institute of Physics
History: Received 4 August 2008; accepted 14 October 2008; published 17 November 2008
Permalink: http://link.aip.org/link/?JCPSA6/129/194502/1
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KEYWORDS and PACS

Keywords
PACS
  • 61.20.Ja
    Computer simulation of liquid structure
  • 66.10.cg
    Mass diffusion in liquids
  • YEAR: 2008

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ISSN:
0021-9606 (print)   1089-7690 (online)
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REFERENCES (63)
View in Separate Window/Tab
  1. I. R. Craig and D. E. Manolopoulos, J. Chem. Phys. 121, 3368 (2004). [MEDLINE]
  2. B. J. Braams and D. E. Manolopoulos, J. Chem. Phys. 125, 124105 (2006). [MEDLINE]
  3. J. Cao and G. A. Voth, J. Chem. Phys. 100, 5106 (1994).
  4. S. Jang and G. A. Voth, J. Chem. Phys. 111, 2371 (1999).
  5. A. D. McLachlan, Mol. Phys. 8, 39 (1964). [ISI]
  6. H. D. Meyer and W. H. Miller, J. Chem. Phys. 72, 2272 (1980). [ChemPort]
  7. J. C. Tully, J. Chem. Phys. 93, 1061 (1990). [ChemPort]
  8. J. C. Tully, Faraday Discuss. 110, 407 (1998).
  9. S. Nielsen, R. Kapral, and G. Ciccotti, J. Chem. Phys. 115, 5805 (2001).
  10. P. V. Parandekar and J. C. Tully, J. Chem. Phys. 122, 094102 (2005). [MEDLINE]
  11. J. R. Schmidt, P. V. Parandekar, and J. C. Tully, J. Chem. Phys. 129, 044104 (2008). [MEDLINE]
  12. H. Wang, X. Sun, and W. H. Miller, J. Chem. Phys. 108, 9726 (1998).
  13. X. Sun, H. Wang, and W. H. Miller, J. Chem. Phys. 109, 7064 (1998). [ISI] [ChemPort]
  14. R. Hernandez and G. A. Voth, Chem. Phys. 233, 243 (1998).
  15. J. Shao and N. Makri, J. Phys. Chem. A 103, 7753 (1999). [ISI] [ChemPort]
  16. J. Shao and N. Makri, J. Phys. Chem. A 103, 9479 (1999). [ISI] [ChemPort]
  17. Q. Shi and E. Geva, J. Phys. Chem. A 107, 9059 (2003).
  18. J. A. Poulsen, G. Nyman, and P. J. Rossky, J. Chem. Phys. 119, 12179 (2003).
  19. J. Liu and W. H. Miller, J. Chem. Phys. 127, 114506 (2007). [ISI] [MEDLINE]
  20. J. O. Hirschfelder, C. F. Curtiss, and R. B. Bird, Molecular Theory of Gases and Liquids (Wiley, New York, 1954).
  21. N. R. Kestner, J. Jortner, M. H. Cohen, and S. A. Rice, Phys. Rev. 140, A56 (1965).
  22. D. F. Coker, B. J. Berne, and D. Thirumalai, J. Chem. Phys. 86, 5689 (1987). [ISI] [ChemPort]
  23. D. F. Coker and B. J. Berne, J. Chem. Phys. 89, 2128 (1988). [ISI] [ChemPort]
  24. B. Space and D. F. Coker, J. Chem. Phys. 94, 1976 (1991). [ISI] [ChemPort]
  25. B. Space and D. F. Coker, J. Chem. Phys. 96, 652 (1992). [ISI] [ChemPort]
  26. E. Gallicchio and B. J. Berne, J. Chem. Phys. 101, 9909 (1994). [ISI] [ChemPort]
  27. E. Gallicchio and B. J. Berne, J. Chem. Phys. 105, 7064 (1996). [ISI] [ChemPort]
  28. R. P. Feynman and A. R. Hibbs, Quantum Mechanics and Path Integrals (McGraw-Hill, New York, 1965).
  29. D. Chandler and P. G. Wolynes, J. Chem. Phys. 74, 4078 (1981).
  30. M. Parrinello and A. Rahman, J. Chem. Phys. 80, 860 (1984).
  31. B. De Raedt, M. Sprik, and M. L. Klein, J. Chem. Phys. 80, 5719 (1984). [ISI] [ChemPort]
  32. D. Chandler, in Liquids, Freezing and Glass Transition, edited by D. Levesque, J. P. Hansen, and J. Zinn-Justin (Elsevier, New York, 1990).
  33. T. F. Miller III and D. E. Manolopoulos, J. Chem. Phys. 122, 184503 (2005). [MEDLINE]
  34. T. F. Miller III and D. E. Manolopoulos, J. Chem. Phys. 123, 154504 (2005). [MEDLINE]
  35. I. R. Craig and D. E. Manolopoulos, J. Chem. Phys. 122, 084106 (2005).
  36. I. R. Craig and D. E. Manolopoulos, J. Chem. Phys. 123, 034102 (2005).
  37. M. P. Allen and D. J. Tildesley, Computer Simulation of Liquids (Oxford University Press, Oxford, 1987).
  38. Centroid molecular dynamics has also been employed with the Einstein relationship to obtain the diffusion coefficient. See, for example, J. Lobaugh and G. A. Voth, J. Chem. Phys. 106, 2400 (1997) [ISI] [ChemPort]
    39. F. Paesani, W. Zhang, D. A. Case, T. E. Cheatham III, and G. A. Voth, ibid. 125, 184507 (2006). [MEDLINE]
  39. R. Collepardo-Guevara, I. R. Craig, and D. E. Manolopoulos, J. Chem. Phys. 128, 144502 (2008). [MEDLINE]
  40. S. Jang, Y. Pak, and G. A. Voth, J. Phys. Chem. A 103, 10289 (1999). [ISI]
  41. E. Geva, Q. Shi, and G. A. Voth, J. Chem. Phys. 115, 9209 (2001).
  42. G. Baym and N. D. Mermin, J. Math. Phys. 2, 232 (1961). [ISI]
  43. J. E. Gubernatis, M. Jarrell, R. N. Silver, and D. S. Sivia, Phys. Rev. B 44, 6011 (1991). [MEDLINE]
  44. J. Skilling and S. F. Gull, SIAM-AMS Proc. 14, 167 (1984).
  45. B. Buck and V. A. Macaulay, Maximum Entropy in Action (Clarendon, Oxford, 1991).
  46. M. Jarrell and J. E. Gubernatis, Phys. Rep. 269, 133 (1996).
  47. S. Habershon, B. J. Braams, and D. E. Manolopoulos, J. Chem. Phys. 127, 174108 (2007). [MEDLINE]
  48. G. Krilov and B. J. Berne, J. Chem. Phys. 111, 9147 (1999). [ISI] [ChemPort]
  49. R. K. Bryan, Eur. Biophys. J. 18, 165 (1990). [Inspec] [ChemPort]
  50. C. L. Lawson and R. J. Hanson, Solving Least Square Problems (Prentice-Hall, Englewood Cliffs, NJ, 1974).
  51. K. Miller, SIAM J. Math. Anal. 1, 52 (1970).
  52. G. J. Martyna, M. E. Tuckerman, D. J. Tobias, and M. L. Klein, Mol. Phys. 87, 1117 (1996).
  53. D. Frenkel and B. Smit, Understanding Molecular Simulation, 2nd ed. (Academic, New York, 2002).
  54. M. E. Tuckerman, B. J. Berne, and G. J. Martyna, J. Chem. Phys. 97, 1990 (1992).
  55. P. W. Anderson, Phys. Rev. 109, 1492 (1958).
  56. D. Chandler and K. Leung, Annu. Rev. Phys. Chem. 45, 557 (1994). [ISI] [ChemPort]
  57. A. L. Nichols III and D. Chandler, J. Chem. Phys. 87, 6671 (1987). [ISI] [ChemPort]
  58. G. A. Voth and T. D. Hone, J. Chem. Phys. 122, 057102 (2005). [ISI]
  59. Estimates of the DHe obtained during the RPMD simulations of the electron (see Table I) and during the purely classical simulations of the solvated electron (not shown) agree to within 2% at each density. The small difference in these results is a finite system size effect; since the RPMD model correctly includes quantum dispersion of the electron, it is effectively larger than in the classical simulations. This small difference in the size of the electron changes the available space available to the solvent atoms and thus slightly effects the solvent self-diffusion coefficient.
  60. B. Dünweg and K. Kremer, J. Chem. Phys. 99, 6983 (1993).
  61. I. -C. Yeh and G. Hummer, J. Phys. Chem. B 108, 15873 (2004).
  62. We find another minor system size effect at the lowest fluid density of rho*=0.1. Given the very high mobility of the electron at this density, the velocity autocorrelation function of the helium atoms does not fully decay to zero on the timescale required for the electron to travel the sidelength of the periodic box. The electron can thus encounter helium atoms with which it is dynamically correlated.
  63. J. Lobaugh and G. A. Voth, J. Chem. Phys. 106, 2400 (1997). [ISI] [ChemPort]

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