Quantum dynamical aspects of rotationally and vibrationally mediated photochemistry in matrices and at surfaces HCl/DCl in Ar and NH3/ND3 at Cu(111)

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Jörn Manz, Peter Saalfrank and Burkhard Schmidt


Abstract

We investigate two extensions of the concept of vibrationally mediated chemistry, from small molecules in the gas phase to small molecules in matrices and at surfaces using, as examples, the systems HCl/DCl in Ar and NH3/ND3 at Cu(111). The transition from isolated systems to the condensed phase calls for new quantum dynamical techniques and allows us to predict new phenomena. For matrix isolation, we propagate three-dimensional wavepackets representing photo-dissociated H or D atoms which penetrate from the initial cage into the lattice provided by the matrix. The cage-exit probabilities are found to depend not only on the initial vibrational, but also on the rotational states, owing to the environmental (Oh) symmetry provided by the (fcc) lattice of the matrix. As a consequence, we suggest the extension from vibrationally to rotationally, or rovibrationally mediated chemistry for matrix-isolated molecules. For molecules at surfaces, we adopt Gadzuk's jumping wavepacket plus incoherent averaging scheme, applied to an extended two-dimensional Antoniewicz-type model for the surface–molecule bond plus the vibrational coordinate which lends itself to preferential vibrational excitation (here the umbrella mode of ammonia). The desorption depends selectively on the initial vibrational state. As a consequence, we suggest the extension of traditional desorption induced by electronic transitions (DIET) to a vibrationally mediated IR–UV DIET scheme which may be used e.g. for enrichment of specific isotopomers at surfaces.


References

  1. V. S. Letokhov, Science, 1973, 180, 451.
  2. P. F. Zittel and D. D. Little, J. Chem. Phys., 1979, 71, 713 CrossRef CAS.
  3. F. F. Crim, Science, 1990, 249, 1387 CAS.
  4. R. L. Van der Wal, J. L. Scott and F. F. Crim, J. Chem. Phys., 1990, 92, 803 CrossRef CAS.
  5. S. S. Brown, H. L. Berghout, R. B. Metz and F. F. Crim, J. Chem. Phys., in the press Search PubMed.
  6. F. F. Crim, Annu. Rev. Phys. Chem., 1993, 44, 397 CrossRef CAS.
  7. F. F. Crim, J. Phys. Chem., 1996, 100, 12725 CrossRef CAS.
  8. A. Sinha, M. C. Hsiao and F. F. Crim, J. Chem. Phys., 1991, 94, 4928 CrossRef CAS.
  9. M. Shapiro and E. Segev, J. Chem. Phys., 1982, 77, 5604 CrossRef CAS.
  10. V. Engel and R. Schinke, J. Chem. Phys., 1988, 88, 6831 CrossRef CAS; V. Engel, R. Schinke and V. Staemmler, J. Chem. Phys., 1988, 88, 129 CrossRef CAS.
  11. J. Zhang and D. J. Imre, Chem. Phys. Lett., 1988, 149, 233 CrossRef CAS; D. J. Imre and J. Zhang, Chem. Phys., 1989, 139, 89 CrossRef CAS.
  12. K. Kudla and G. C. Schatz, J. Chem. Phys., 1993, 98, 4644 CrossRef and references therein.
  13. D. Wang and J. M. Bowman, J. Chem. Phys., 1992, 96, 8906 CrossRef CAS.
  14. D. H. Zhang, J. Chem. Phys., 1993, 99, 5615 CrossRef CAS.
  15. J. E. Combariza, C. Daniel, B. Just, E. Kades, E. Kolba, J. Manz, W. Malisch, G. K. Paramonov and B. Warmuth, in Isotope Effects and Gas-Phase Chemistry, ed. J. A. Kaye, ACS Symposium Series 502, American Chemical Society, Washington, DC, 1992, p. 310 Search PubMed.
  16. C. Daniel, R. de Vivie-Riedle, M.-C. Heitz, J. Manz and P. Saalfrank, Int. J. Quant. Chem., 1996, 57, 595 CrossRef CAS.
  17. C. Daniel, M.-C. Heitz, L. Lehr, J. Manz and T. Schröder, J. Phys. Chem., 1993, 97, 12485 CrossRef CAS.
  18. M. Chergui and N. Schwentner, Trends Chem. Phys., 1992, 2, 89 Search PubMed.
  19. R. Alimi, R. B. Gerber and V. A. Apkarian, J. Chem. Phys., 1990, 92, 3551 CrossRef CAS.
  20. R. Schriever, M. Chergui, H. Kunz, V. Stepanenko and N. Schwentner, J. Chem. Phys., 1989, 91, 4128 CrossRef CAS; R. Schriever, M. Chergui and N. Schwentner, J. Chem. Phys., 1990, 93, 9206 CrossRef CAS; J. Phys. Chem., 1991, 95, 6124 Search PubMed.
  21. J. Zoval and V. A. Apkarian, J. Phys. Chem., 1994, 98, 7945 CrossRef CAS.
  22. K. H. Gödderz, N. Schwentner and M. Chergui, J. Chem. Phys., 1996, 105, 451 CrossRef.
  23. R. Alimi, R. B. Gerber and V. A. Apkarian, J. Chem. Phys., 1988, 89, 174 CrossRef CAS; R. Alimi and R. B. Gerber, Chem. Phys. Lett., 1990, 173, 393 CrossRef.
  24. I. H. Gersonde and H. Gabriel, J. Chem. Phys., 1993, 98, 2094 CrossRef CAS.
  25. A. I. Krylov and R. B. Gerber, in Ultrafast Chemical and Physical Processes in Molecular Systems, ed. M. Chergui, World Scientific, Singapore, 1996, p. 628 Search PubMed; A. I. Krylov and R. B. Gerber, J. Chem. Phys., to be published Search PubMed.
  26. R. Alimi and R. B. Gerber, Phys. Rev. Lett., 1990, 64, 1453 CrossRef CAS; R. B. Gerber and R. Alimi, Chem. Phys. Lett., 1990, 173, 393 CrossRef.
  27. L. Liu and H. Guo, Chem. Phys. Lett., 1995, 237, 299 CrossRef CAS; J. Chem. Phys., 1996, 104, 528 Search PubMed.
  28. R. Alimi, A. Brokman and R. B. Gerber, J. Chem. Phys., 1989, 91, 1611 CrossRef CAS.
  29. H. Kunttu and V. A. Apkarian, Chem. Phys. Lett., 1990, 171, 4856 CrossRef CAS.
  30. A. V. Benderskii and C. A. Wight, J. Chem. Phys., 1994, 101, 292 CrossRef CAS.
  31. B. Schmidt, P. Jungwirth and R. B. Gerber, in ref. 25. p. 637.
  32. B. Schmidt, J. Chem. Phys., in preparation Search PubMed.
  33. R. C. Mowrey and D. J. Kouri, J. Chem. Phys., 1986, 84, 6466 CrossRef CAS.
  34. C. J. Bradley and A. P. Cracknell, The Mathematical Theory of Symmetry in Solids, Clarendon, Oxford, 1972 Search PubMed.
  35. J. M. Hutson, J. Phys. Chem., 1992, 96, 4237 CrossRef CAS.
  36. D. M. Hirst and M. F. Guest, Mol. Phys., 1980, 41, 1483 CAS.
  37. K. T. Tang and J. P. Toennies, Chem. Phys., 1991, 156, 413 CrossRef.
  38. R. Kosloff, J. Phys. Chem., 1988, 92, 2087 CrossRef CAS.
  39. B. Schmidt and P. Jungwirth, Chem. Phys. Lett., 1996, 259, 62 CrossRef CAS.
  40. H. E. Hallam, in Vibrational Spectroscopy of Trapped Species, ed. H. E. Hallam, Wiley, London, 1973, p. 67 Search PubMed.
  41. J. W. Gadzuk and C. W. Clark, J. Chem. Phys., 1989, 91, 3174 CrossRef CAS; J. W. Gadzuk, L. J. Richter, S. A. Buntin, D. S. King and R. R. Cavanagh, Surf. Sci., 1990, 235, 317 CrossRef CAS; J. W. Gadzuk, Phys. Rev. B, 1991, 44, 13 CrossRef; J. W. Gadzuk, Surf. Sci., 1995, 342, 345 CrossRef CAS.
  42. P. Guyot-Sionnest, P. Dumas, Y. J. Chabal and G. Higashi, Phys. Rev. Lett., 1990, 64, 2156 CrossRef CAS; Y. J. Chabal, J. Mol. Struct., 1993, 292, 65 CrossRef CAS.
  43. See Desorption Induced by Electronic Transitions Workshops Proceedings, Springer, Berlin Search PubMed.
  44. T. Hertel, M. Wolf and G. Ertl, J. Chem. Phys., 1995, 102, 3414 CrossRef CAS.
  45. W. Nessler, K.-H. Bornscheuer, T. Hertel and E. Hasselbrink, Chem. Phys., 1995, 205, 205 CrossRef CAS.
  46. D. Menzel and R. Gomer, J. Chem. Phys., 1964, 41, 3311 CrossRef CAS; P. A. Redhead, Can. J. Phys., 1964, 42, 886 CAS.
  47. P. R. Antoniewicz, Phys. Rev. B, 1980, 21, 3811 CrossRef CAS.
  48. P. Saalfrank, R. Baer and R. Kosloff, Chem. Phys. Lett., 1994, 230, 463 CrossRef CAS; P. Saalfrank and R. Kosloff, J. Chem. Phys., 1996, 105, 2441 CrossRef.
  49. G. Lindblad, Commun. Math. Phys., 1976, 48, 119; V. Gorini and A. Kossakowski, J. Math. Phys., 1976, 17, 821 CrossRef.
  50. P. Saalfrank, Chem. Phys., 1996, 211, 265 CrossRef CAS.
  51. P. Saalfrank, S. Holloway and G. R. Darling, J. Chem. Phys., 1995, 103, 6720 CrossRef CAS.
  52. E. Hasselbrink, M. Wolf, S. Holloway and P. Saalfrank, Surf. Sci., 1996, 363, 179 CrossRef CAS.
  53. K.-H. Bornscheuer, M. Binetti, W. Nessler, E. Hasselbrink and P. Saalfrank, Phys. Rev. Lett., in the press Search PubMed.
  54. G. K. Paramonov and P. Saalfrank, J. Chem. Phys., submitted Search PubMed.
  55. H. Guo, Chem. Phys. Lett., 1995, 240, 393 CrossRef CAS; H. Guo and T. Seideman, J. Chem. Phys., 1995, 103, 9062 CrossRef CAS.
  56. A. R. Burns, D. R. Jennison, E. B. Stechel and Y. S. Li, Phys. Rev. Lett., 1992, 68, 3359 CrossRef; A. R. Burns, E. B. Stechel, D. R. Jennison and Y. S. Li, J. Chem. Phys., 1994, 101, 6318 CrossRef CAS.
  57. X.-Y. Zhu and J. M. White, Phys. Rev. Lett., 1992, 68, 3359 CrossRef; X.-Y. Zhu, M. Wolf, T. Huett and J. M. White, J. Chem. Phys., 1992, 97, 5868 CrossRef CAS; X.-Y. Zhu, J. Chem. Phys., 1993, 98, 3410 CrossRef CAS.
  58. I. Hussla and T. J. Chuang, Ber. Bunsen-Ges. Phys. Chem., 1985, 89, 294 Search PubMed.
  59. G. K. Paramonov and P. Saalfrank, in preparation.
  60. M. D. Feit, J. Fleck Jr. and A. Steiger, J. Comput. Phys., 1982, 47, 412 CrossRef CAS.
  61. Ph. Avouris, R. E. Walkup, A. R. Rossi, H. C. Akpati, P. Nordlander, T.-C. Shen, G. C. Abeln and J. W. Lyding, Surf. Sci., 1996, 363, 368 CrossRef CAS.
  62. J. A. Misewich, T. F. Heinz and D. M. Newns, Phys. Rev. Lett., 1992, 68, 3737 CrossRef CAS.
  63. G. G. Balint-Kurti, F. Göttgas, St. Mort, A. R. Offer, A. Laganá and O. Gervasi, J. Chem. Phys., 1993, 99, 9567 CrossRef CAS.
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