Journal of Chemical Physics
Feedback | Help | Exit
The Journal of Chemical Physics
   
 
 
 
Previous Article
Theoretical study of one-photon and two-photon absorption properties of perylene tetracarboxylic derivatives
The geometrical structure, electronic structure, one-photon absorption (OPA) and two-photon absorption (TPA) properties of the perylene tetracarboxylic derivatives (PTCDs) were studied theoretically b...
Next Article
Energy-dependent dynamics of large-DeltaE collisions: Highly vibrationally excited azulene (E=20  390 and 38  580  cm−1) with CO2
We report the energy dependence of strong collisions of CO2 with highly vibrationally excited azulene for two initial energies, E=20  390 and 38  580  cm−1. These s...

Mixed quantum/classical investigation of the photodissociation of NH3(Ã) and a practical method for maintaining zero-point energy in classical trajectories

J. Chem. Phys. 129, 014302 (2008); doi:10.1063/1.2943213

Published 1 July 2008

You are not logged in to this journal. Log in

David Bonhommeau and Donald G. Truhlar
Department of Chemistry and Supercomputing Institute, University of Minnesota, 207 Pleasant Street S.E., Minneapolis, Minnesota 55455-0431, USA
The photodissociation dynamics of ammonia upon excitation of the out-of-plane bending mode (mode nu2 with n2=0,…,6 quanta of vibration) in the à electronic state is investigated by means of several mixed quantum/classical methods, and the calculated final-state properties are compared to experiments. Five mixed quantum/classical methods are tested: one mean-field approach (the coherent switching with decay of mixing method), two surface-hopping methods [the fewest switches with time uncertainty (FSTU) and FSTU with stochastic decay (FSTU/SD) methods], and two surface-hopping methods with zero-point energy (ZPE) maintenance [the FSTU/SD+trajectory projection onto ZPE orbit (TRAPZ) and FSTU/SD+minimal TRAPZ (mTRAPZ) methods]. We found a qualitative difference between final NH2 internal energy distributions obtained for n2=0 and n2>1, as observed in experiments. Distributions obtained for n2=1 present an intermediate behavior between distributions obtained for smaller and larger n2 values. The dynamics is found to be highly electronically nonadiabatic with all these methods. NH2 internal energy distributions may have a negative energy tail when the ZPE is not maintained throughout the dynamics. The original TRAPZ method was designed to maintain ZPE in classical trajectories, but we find that it leads to unphysically high internal vibrational energies. The mTRAPZ method, which is new in this work and provides a general method for maintaining ZPE in either single-surface or multisurface trajectories, does not lead to unphysical results and is much less time consuming. The effect of maintaining ZPE in mixed quantum/classical dynamics is discussed in terms of agreement with experimental findings. The dynamics for n2=0 and n2=6 are also analyzed to reveal details not available from experiment, in particular, the time required for quenching of electronic excitation and the adiabatic energy gap and geometry at the time of quenching. ©2008 American Institute of Physics
History: Received 28 March 2008; accepted 19 May 2008; published 1 July 2008
Permalink: http://link.aip.org/link/?JCPSA6/129/014302/1
BUY THIS ARTICLE   (US$28)
Download HTML Download Sectioned HTML Download PDF (1125 kB) View Cart

Supplemental Material

KEYWORDS and PACS

Keywords
PACS
  • 82.50.-m
    Photochemistry
  • 82.20.Kh
    Potential energy surfaces for chemical reactions
  • YEAR: 2008

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 (59)
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. R. Schinke, Photodissociation Dynamics (Cambridge University Press, The Edinburgh Building, Cambridge CB2 2RU, UK, 1993).
  2. U. Manthe, H.-D. Meyer, and L. Cederbaum, J. Chem. Phys. 97, 3199 (1992).
  3. U. Manthe, H.-D. Meyer, and L. Cederbaum, J. Chem. Phys. 97, 9062 (1992).
  4. U. Manthe and A. Hammerich, Chem. Phys. Lett. 211, 7 (1993).
  5. G. Worth, H.-D. Meyer, and L. Cederbaum, J. Chem. Phys. 109, 3518 (1998).
  6. A. Raab, G. Worth, H.-D. Meyer, and L. Cederbaum, J. Chem. Phys. 110, 936 (1999).
  7. G. Worth, H.-D. Meyer, and L. Cederbaum, Chem. Phys. Lett. 229, 451 (1999).
  8. H. Köppel, M. Döscher, I. Baldea, H.-D. Meyer, and P. Szalay, J. Chem. Phys. 117, 2657 (2002).
  9. C. Zhu, S. Nangia, A. W. Jasper, and D. G. Truhlar, J. Chem. Phys. 121, 7658 (2004).
  10. A. W. Jasper, S. Nangia, C. Zhu, and D. G. Truhlar, Acc. Chem. Res. 39, 101 (2006).
  11. A. W. Jasper, S. N. Stechmann, and D. G. Truhlar, J. Chem. Phys. 116, 5424 (2002).
  12. A. W. Jasper, S. N. Stechmann, and D. G. Truhlar, J. Chem. Phys. 117, 10427 (2002).
  13. A. W. Jasper and D. G. Truhlar, J. Chem. Phys. 127, 194306 (2007).
  14. A. W. Jasper, C. Zhu, S. Nangia, and D. G. Truhlar, Faraday Discuss. 127, 1 (2004).
  15. C. Zhu, A. W. Jasper, and D. G. Truhlar, J. Chem. Theory Comput. 1, 527 (2005).
  16. D. G. Truhlar, in Quantum Dynamics of Complex Molecular Systems, edited by D. A. Micha and I. Burghardt (Springer, Berlin, 2007).
  17. J. C. Gray, D. G. Truhlar, L. Clemens, J. W. Duff, F. M. Chapman, Jr, G. O. Morrell, and E. F. Hayes, J. Chem. Phys. 69, 240 (1979).
  18. D. G. Truhlar and A. Kuppermann, J. Chem. Phys. 52, 3841 (1970).
  19. D. C. Chatfield, R. S. Friedman, D. G. Truhlar, and D. W. Schwenke, Faraday Discuss. Chem. Soc. 91, 289 (1991).
  20. J. M. Bowman, B. Gazdy, and Q. Sun, J. Chem. Phys. 91, 2859 (1989).
  21. W. H. Miller, W. L. Hase, and C. L. Darling, J. Chem. Phys. 91, 2863 (1989).
  22. Y. Guo, D. L. Thompson, and T. D. Sewell, J. Chem. Phys. 104, 576 (1996).
  23. K. F. Lim and D. A. McCormack, J. Chem. Phys. 102, 1705 (1995).
  24. D. A. McCormack and K. F. Lim, J. Chem. Phys. 106, 572 (1997).
  25. D. A. McCormack and K. F. Lim, Phys. Chem. Chem. Phys. 1, 1 (1999).
  26. R. Alimi, A. García-Vela, and R. B. Gerber, J. Chem. Phys. 96, 2034 (1992).
  27. Z. Xie and J. M. Bowman, J. Phys. Chem. A 110, 5446 (2006).
  28. G. Stock and M. Thoss, Phys. Rev. Lett. 78, 578 (1997).
  29. G. Stock and U. Müller, J. Chem. Phys. 111, 65 (1999).
  30. J. Biesner, L. Schnieder, G. Ahlers, X. Xie, K. H. Welge, M. N. R. Ashfold, and R. N. Dixon, J. Chem. Phys. 91, 2901 (1989).
  31. A. Bach, J. M. Hutchison, R. J. Holiday, and F. F. Crim, J. Phys. Chem. A107, 10490 (2003).
  32. M. L. Hause, Y. H. Yoon, and F. F. Crim, J. Chem. Phys. 125, 174309 (2006).
  33. J. Biesner, L. Schneider, J. Schmeer, G. Ahlers, X. X. Xie, K. H. Welge, M. N. R. Ashfold, and R. N. Dixon, J. Chem. Phys. 88, 3607 (1988).
  34. A. Nakajima, K. Fuke, K. Tsukamoto, Y. Yoshida, and K. Kaya, J. Phys. C 95, 571 (1991).
  35. R. N. Dixon, Acc. Chem. Res. 24, 16 (1991).
  36. E. L. Woodbridge, M. N. R. Ashfold, and S. R. Leone, J. Chem. Phys. 94, 4195 (1991).
  37. S. A. Henck, M. A. Mason, W. B. Yan, K. K. Lehmann, and S. L. Coy, J. Chem. Phys. 102, 4783 (1995).
  38. D. Edvardsson, P. Baltzer, L. Karlsson, B. Wannberg, D. M. P. Holland, D. A. Shaw, and E. E. Rennie, J. Phys. B 32, 2583 (1999).
  39. R. A. Loomis, J. P. Reid, and S. R. Leone, J. Chem. Phys. 112, 658 (2000).
  40. A. Bach, J. M. Hutchison, R. J. Holiday, and F. F. Crim, J. Chem. Phys. 116, 4955 (2002).
  41. A. Bach, J. M. Hutchison, R. J. Holiday, and F. F. Crim, J. Chem. Phys. 116, 9315 (2002).
  42. H. Akagi, K. Yokoyama, and A. Yokoyama, J. Chem. Phys. 118, 3600 (2003).
  43. A. Bach, J. M. Hutchison, R. J. Holiday, and F. F. Crim, J. Chem. Phys. 118, 7144 (2003).
  44. D. R. Yarkony, J. Chem. Phys. 121, 628 (2004).
  45. Z. H. Li, R. Valero, and D. G. Truhlar, Theor. Chem. Acc. 118, 9 (2007).
  46. M. D. Hack, A. W. Jasper, Y. L. Volobuev, D. W. Schwenke, and D. G. Truhlar, J. Phys. Chem. A 103, 6309 (1999).
  47. J. C. Tully, J. Chem. Phys. 93, 1061 (1990).
  48. A. W. Jasper and D. G. Truhlar, J. Chem. Phys. 123, 064103 (2005).
  49. A. W. Jasper and D. G. Truhlar, Chem. Phys. Lett. 369, 60 (2003).
  50. W. H. Miller, N. C. Handy, and J. E. Adams, J. Chem. Phys. 72, 99 (1980).
  51. D. G. Truhlar, A. D. Isaacson, and B. C. Garrett, in Theory of Chemical Reaction Dynamics, edited by M. Baer (CRC, Boca Raton, FL, 1985), Vol. 4, pp. 65–137.
  52. R. L. Murry, J. T. Fourkas, W.-X. Li, and T. Keyes, J. Chem. Phys. 110, 10423 (1999).
  53. D. G. Truhlar and N. C. Blais, J. Chem. Phys. 67, 1532 (1977).
  54. ANT08 (Adiabatic and nonadiabatic trajectories): Z. H. Li, A. W. Jasper, D. Bonhommeau, R. Valero, and D. G. Truhlar, a code to study photochemical and thermochemical reactions, University of Minnesota, Minneapolis, 2008.
  55. See EPAPS Document No. E-JCPSA6-129-618825 for details about direct trajectories, average energy gaps, theoretical NH2 internal energy distributions, and time distributions at the last downward hop. For more information on EPAPS, see http://www.aip.org/pubservs/epaps.html [EPAPS]
  56. M. D. Hack, A. W. Jasper, Y. L. Volobuev, D. W. Schwenke, and D. G. Truhlar, J. Phys. Chem. A 104, 217 (2000).
  57. A. W. Jasper, M. D. Hack, and D. G. Truhlar, J. Chem. Phys. 115, 1804 (2001).
  58. A. W. Jasper and D. G. Truhlar, J. Chem. Phys. 122, 044101 (2005).
  59. R. Valero and D. G. Truhlar, J. Phys. Chem. A 112, 5756 (2008).

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