Advertisement

Excitation of infrared-inactive vibrational modes in a polyatomic molecule through hot band transitions

  • Koichiro YamakawaEmail author
Regular Article
  • 41 Downloads

Abstract

The excitation of an infrared-inactive mode (νm) in a polyatomic molecule through the electric dipole transition is discussed taking into account the high-order derivatives of the dipole moment with respect to the normal coordinates. It is revealed that this excitation requires one of the specific degenerate modes (νt) to be thermally excited in advance of infrared absorption. The third-order dipole-derivatives responsible for the hot band transition of “νm + νtνt” are identified. The author also deals with examples of hot band transitions in benzene and recommends reassignment of weak absorption features detected in previous infrared spectra of gaseous polyatomic molecules.

Graphical abstract

Keywords

Molecular Physics and Chemical Physics 

References

  1. 1.
    D. Forney, M.E. Jacox, W.E. Thompson, J. Chem. Phys. 121, 5977 (2004) ADSCrossRefGoogle Scholar
  2. 2.
    R.D. Hunt, L. Andrews, J. Chem. Phys. 86, 3781 (1987) ADSCrossRefGoogle Scholar
  3. 3.
    M.E. Jacox, W.E. Thompson, J. Chem. Phys. 119, 10824 (2003) ADSCrossRefGoogle Scholar
  4. 4.
    H.G. Hixson, M.J. Wojcik, M.S. Devlin, J.P. Devlin, V. Buch, J. Chem. Phys. 97, 753 (1992) ADSCrossRefGoogle Scholar
  5. 5.
    V. Buch, J.P. Devlin, J. Chem. Phys. 98, 4195 (1993) ADSCrossRefGoogle Scholar
  6. 6.
    D.J. Dai, G.E. Ewing, J. Chem. Phys. 98, 5050 (1993) ADSCrossRefGoogle Scholar
  7. 7.
    J. Heidberg, N. Gushanskaya, O. Schönekäs, R. Schwarte, Surf. Sci. 331, 1473 (1995) ADSCrossRefGoogle Scholar
  8. 8.
    M. Grunwald, G.E. Ewing, J. Chem. Phys. 109, 4990 (1998) ADSCrossRefGoogle Scholar
  9. 9.
    S. Briquez, S. Picaud, C. Girardet, P.N.M. Hoang, J. Heidberg, A. Voßberg, J. Chem. Phys. 109, 6435 (1998) ADSCrossRefGoogle Scholar
  10. 10.
    J. Heidberg, A. Voßberg, M. Hustedt, M. Thomas, S. Briquez, S. Picaud, C. Girardet, J. Chem. Phys. 110, 2566 (1999) ADSCrossRefGoogle Scholar
  11. 11.
    R.B. Holden, W.J. Taylor, H.L. Johnston, J. Chem. Phys. 17, 1356 (1949) ADSCrossRefGoogle Scholar
  12. 12.
    R.K. Khanna, M. Ngoh, Spectrochim. Acta A 46, 1057 (1990) ADSCrossRefGoogle Scholar
  13. 13.
    A.L.F. de Barros, V. Bordalo, E.S. Duarte, E.F. da Silveira, A. Domaracka, H. Rothard, P. Boduch, Astron. Astrophys. 531, A160 (2011) CrossRefGoogle Scholar
  14. 14.
    M.H. Moore, R.L. Hudson, Icarus 135, 518 (1998) ADSCrossRefGoogle Scholar
  15. 15.
    R. Hodyss, P.V. Johnson, J.V. Stern, J.D. Goguen, I. Kanik, Icarus 200, 338 (2009) ADSCrossRefGoogle Scholar
  16. 16.
    R. Escribano, V. Timon, O. Gálvez, B. Maté, V.J. Herrero, Phys. Chem. Chem. Phys. 16, 16694 (2014) CrossRefGoogle Scholar
  17. 17.
    O. Gálvez, B. Maté, V.J. Herrero, R. Escribano, Astrophys. J. 703, 2101 (2009) ADSCrossRefGoogle Scholar
  18. 18.
    V.J. Herrero, O. Gálvez, B. Maté, R. Escribano, Phys. Chem. Chem. Phys. 12, 3164 (2010) CrossRefGoogle Scholar
  19. 19.
    K. Yamakawa, Eur. Phys. J. D 70, 259 (2016) ADSCrossRefGoogle Scholar
  20. 20.
    E.B. Wilson Jr., J.C. Decius, P.C. Cross, Molecular Vibrations, The Theory of Infrared and Raman Vibrational Spectra (Dover Publications, 1955) Google Scholar
  21. 21.
    C.D. Lauro, Rotational Structure in Molecular Infrared Spectra (Elsevier, 2013) Google Scholar
  22. 22.
    P.F. Bernath, Spectra of Atoms and Molecules, 2nd edn. (Oxford University Press, 2005) Google Scholar
  23. 23.
    E.B. Wilson Jr., Phys. Rev. 45, 706 (1934) ADSCrossRefGoogle Scholar
  24. 24.
    J.E. Bertie, C.D. Keefe, Fresenius J. Analyt. Chem. 362, 91 (1998) CrossRefGoogle Scholar
  25. 25.
    J.E. Bertie, C.D. Keefe, J. Mol. Struct. 695–696, 39 (2004) Google Scholar
  26. 26.
    C.D. Keefe, J.E. Bertie, Spectrochim. Acta A 65, 650 (2006) ADSCrossRefGoogle Scholar
  27. 27.
    C.D. Keefe, Chem. Phys. 327, 180 (2006) CrossRefGoogle Scholar
  28. 28.
    G. Herzberg, Molecular Spectra and Molecular Structure II, Infrared and Raman Spectra of Polyatomic Molecules (Van Nostrand, 1945) Google Scholar
  29. 29.
    C.R. Bailey, J.B. Hale, C.K. Ingold, J.W. Thompson, J. Chem. Soc. 1936, 931 (1936) CrossRefGoogle Scholar

Copyright information

© EDP Sciences / Società Italiana di Fisica / Springer-Verlag GmbH Germany, part of Springer Nature 2019

Authors and Affiliations

  1. 1.Department of PhysicsGakushuin UniversityToshima-ku, TokyoJapan

Personalised recommendations