Highly Excited Vibrational States and Chemical Reactivity

  • Alessandro Lami
Part of the Progress in Mathematics book series (NSSA)

Abstract

The movement of nuclei on the potential energy surface created by electrons has a fundamental role to play in the “becoming” of matter in the animate and inanimate world. In fact, every chemical reaction happens just because, at a given instant and due to particular circumstances, a certain nucleus (or group of nuclei) may receive sufficient energy to escape from the potential well in which it exists, vibrating around an equilibrium position. It may then leave the rest of the molecule or begin to oscillate around a new equilibrium position.

Keywords

Potential Energy Surface Vibrational State Polyatomic Molecule Transition State Theory Vibrational Relaxation 
These keywords were added by machine and not by the authors. This process is experimental and the keywords may be updated as the learning algorithm improves.

Preview

Unable to display preview. Download preview PDF.

Unable to display preview. Download preview PDF.

References

  1. 1.
    See the chapters by F. Fillaux in this book, and the references therein.Google Scholar
  2. 2.
    See e.g., S. A. Rice, Dynamics of intramolecular transfer of vibrational energy, in “Advances in Chemical Physics”, J. Joiner, R. D. Levine and S. A. Rice, eds., Vol. XLVII, 117 (1981).Google Scholar
  3. 3.
    See e.g., D. G. Truhlar, R. Steckler and M. S. Gordon, Potential energy surfaces for polyatomic reaction dynamics, in “Chemical Reviews,” 87: 217 (1987).Google Scholar
  4. 4.
    G. Herzberg, “Infrared and Raman Spectra,” Van Nostrand Reihnold Company, NY (1945); P. Gans, “Vibrating Molecules. An Introduction to the Interpretation of Infrared and Raman Spectra,” Chapman and Hall, London (1971).Google Scholar
  5. 5.
    For a review on vibrational relaxation, see: V. E. Bondybey, Relaxation and vibrational energy redistribution processes in polyatomic molecules, Ann Rev. Phys. Chem. 35: 591 (1984).Google Scholar
  6. 6.
    R. Naaman, D. M. Lubman and R. N. Zare, Vibrational energy redistribution in glyoxal following internal conversion J. Chem, Phys. 71: 4192 (1979).CrossRefGoogle Scholar
  7. 7.
    J. B. Hopkins, P. R. R. Langridge-Smith and R. E. Smalley, Ground state vibrational randomization in alkylbenzenes, J. Chem. Phys. 78: 3410 (1983).Google Scholar
  8. 8.
    P. H. Vaccaro, J. L. Kinsey, R. W. Field and H. L. Dai, Electric dipole moments of excited vibrational levels in the X1A1 state of formaldehyde by stimulated emission spectroscopy, J. Chem. Phys. 78:3659 (1983); C. E. Hamilton, J. L. Kinsey and R. W. Field, Stimulated emission pumping: new methods in spectroscopy and molecular dynamics, Ann. Rev, Phys, Chem. 37: 493 (1986).Google Scholar
  9. 9.
    T. B. Simpson, J. G. Black, I. Burak, E. Yablonovitch and N. Bloembergen, Infrared multiphoton excitation of polyatomic molecules, J. Chem, Phys. 83: 628 (1985).CrossRefGoogle Scholar
  10. 10.
    K. V. Reddy, D. F. Heller and M. J. Berry, Highly vibrational excited benzene: overtone spectroscopy and intramolecular dynamics of C6H6, C6D6 and partially deuterated or substituted benzenes, J. Chem. Phys. 76: 2814 (1982).CrossRefGoogle Scholar
  11. 11.
    For a review, see F. F. Crimm, Selective excitation studies of uni-molecular reaction dynamics, Ann. Rev. Phys. Chem. 35: 657 (1984).CrossRefGoogle Scholar
  12. 12.
    A. Lami, Enhancement of reactivity through near-resonant radiative excitation of an overtone: a model study of an isomerization by hydrogen tunneling Chem, Phys. 115:399 (1987); A. Lami and G. Villani, Control of the yield of competing unimolecular reactions through double-resonance coherent trapping, J. Phys. Chem, 92: 4348 (1988).Google Scholar
  13. 13.
    E. B. Wilson, Jr., J. C. Decius and P. R. Cross, “Molecular Vibrations. The Theory of Infrared and Raman Vibrational Spectra,” McGraw-Hill Book Company, London (1955).Google Scholar
  14. 14.
    See e.g., E. C. Kemble, “The Fundamental Principles of Quantum Mechanics,” p. 237, Dover, NY (1958).Google Scholar
  15. 15.
    E. L. Sibert III, J. T. Hynes and W. P. Reinhardt, Fermi resonance from a curvilinear perspective, J. Phys. Chem. 87: 2032 (1983).CrossRefGoogle Scholar
  16. 16.
    E. L. Sibert III, W. P. Reinhardt and J. T. Hynes, Intramolecular vibrational relaxation and spectra of CH and CD overtones in benzene and perdeuterobenzenes, J. Chem, Phys. 81:1115 (1982); Photoacoustic spectroscopy of vibrational overtones in gas-phase CH3OH and CH3OD, H. L. Fong, D. M. Meister and H. L. Swofford, J. Phys. Chem, 88: 405 (1988).Google Scholar
  17. 17.
    A. Lami and G. Villani, Excitation and decay of a C-H overtone coupled to a linear hydrocarbon chain: a simple quantum-mechanical model, J. Chem. Phys. 88:8 (1988) and unpublished results.Google Scholar

Copyright information

© Springer Science+Business Media New York 1989

Authors and Affiliations

  • Alessandro Lami
    • 1
  1. 1.Istituto di Chimica Quantistica ed Energetica MolecolarePisaItaly

Personalised recommendations