Abstract
Chapter 2 dealt with the analysis of high resolution electronic spectra of diatomic molecules where the electronic transition also involved simultaneous changes in vibrational and rotational quantum numbers. For an N-atomic molecule there are up to three degrees of rotational freedom and (3N – 6) vibrational modes (3N – 5 if the molecule is linear). Although some of these may be degenerate if the molecular symmetry is high enough, the overall appearance of the spectrum is as a result generally very complex indeed. For example, in the analysis of the 455 nm absorption band of the asymmetric molecule glyoxal many hundreds of individual rotational transitions are observed in each of the vibrational progressions. The analysis of such spectra is a complex task and the adventurous reader is directed to the book by Herzberg [4.1] and for a modem review to Innes [4.2] . Molecular geometry parameters associated with the molecule in ground and excited electronic states constitute one of the end products and these results have been used to test qualitative and quantitative theories of bonding and molecular structure. In particular the simple molecular orbital scheme developed by Walsh [4.3] some years ago, and often called Walsh’s rules, have proven very useful in this respect for small molecules.
This is a preview of subscription content, log in via an institution to check access.
Access this chapter
Tax calculation will be finalised at checkout
Purchases are for personal use only
Preview
Unable to display preview. Download preview PDF.
References
4.1 Herzberg, G., Electronic Spectra of Polyatomic Molecules, Van Nostrand, Princeton (1966).
4.2 Innes, K., in: Molecular Spectroscopy; Modern Research (ed. Rao, K.N. and Mathews, C.W.), Academic Press, London (1972).
4.3 Walsh A.D., J. Chem. Soc., 2260 (1953), and following papers.
4.4 Snow, R.L. and Bills, J.L., J. Chem. Ed., 52, 585 (1974).
4.5 Mulliken, R.S., Phys. Rev., 43, 279 (1933).
4.6 Fleming, I. and Williams, D.H., Spectroscopic Methods in Organic Chemistry, McGraw-Hill, London (1966).
4.7 Scott, A.I., Interpretation of the Ultraviolet Spectra of Natural Products, Pergamon, Oxford (1964).
4.8 Murrell, LN., The Theory of the Electronic Spectra of Organic Molecules, Methuen, London (1963).
4.9 Schonland, D., Molecular Symmetry, Van Nostrand, London (1965).
4.10 Streitwieser, A., Molecular Orbital Theory for Organic Chemists, Wiley, London (1961).
4.11 Orgel, L.E., An Introduction to Transition Metal Chemistry; Ligand F Field Theory, Methuen, London (1966).
4.12 Kettle, S.F.A., Coordination Compounds, Methuen, London (1969).
4.13 Murrell, LN., Kettle, S.F.A. and Tedder, I.M., Valence Theory, Wiley, New York (1965).
4.14 Jφrgensen, C.K., Absorption Spectra and Chemical Bonding in Complexes, Pergamon, Oxford (1962).
4.15 Mulliken, R.S., J. Amer. Chem. Soc., 74, 811 (1952).
4.16 Hoskins, W.D., Trans. Faraday Soc., 30, 221 (1934).
4.17 Thrush, B.A., Chem. Brit., 2, 287 (1966).
4.18 Jacox, E. and Milligan, D.E., J. Chem. Phys., 46, 184 (1967).
4.19 Norrish, R.G.W. and Porter, G., Nature, 164, 685 (1950); Porter, G., Proc. Roy. Soc., A, 200, 284 (1950).
4.20 Ramsay, D.A., J. Chem. Phys., 21, 960 (1953).
4.21 Atkinson, G.H., Laufer, A.H. and Kurylo, M.J., J. Chem. Phys., 59, 350 (1973)
4.22 Norrish, R.G.W., Disc. Faraday Soc., 14, 16 (1953).
4.23 Kelly, I.M., Hermann, H. and Koerner von Gustorf, E.A., Chem. Comm., 105 (1973).
4.24 Mason, S.F., Chem. Brit., 1, 245 (1965).
Author information
Authors and Affiliations
Editor information
Editors and Affiliations
Rights and permissions
Copyright information
© 1976 Chapman and Hall Ltd
About this chapter
Cite this chapter
Straughan, B.P., Walker, S. (1976). Electronic Spectra of Polyatomic Molecules. In: Straughan, B.P., Walker, S. (eds) Spectroscopy. Springer, Dordrecht. https://doi.org/10.1007/978-94-009-5741-1_4
Download citation
DOI: https://doi.org/10.1007/978-94-009-5741-1_4
Publisher Name: Springer, Dordrecht
Print ISBN: 978-0-412-13390-9
Online ISBN: 978-94-009-5741-1
eBook Packages: Springer Book Archive