Abstract
Since most of the important features of the Rydberg spectroscopy of small molecules have been discussed in detail in the recent literature by Robin (1) and Sandorfy (2) we will concentrate on the theoretical aspects of their photochemical behavior. We have reviewed this subject in some detail (3) so that here we will concentrate on the construction of orbital and singlet state correlation diagrams containing Rydberg components which will permit the reader to rationalize either the photochemical behavior of some simple molecules such as water, ammonia and methane or the results of theoretical calculations on other photofragmentation reactions. The single most important feature of this article will be to show the reader how to add Rydberg orbitale and states to correlation diagrams. It will also permit predicting which reaction surfaces can be correlatively treated at the SCF level, or if configuration interaction (CI) is correlatively required, what will be the major configurational composition of the CI wave function.
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
Robin, M. B.: 1974, 1975, “Higher Excited States in Polyatomic Molecules, Academic Press, N. Y.” Volumes 1 and 2.
Sandorfy, C.: 1979, “Topics in Current Chemistry, Springer-Verlag, Berlin”, 86, pp. 91–138.
Evleth, E.M., and Kassab, E.: 1980, “Quantum Theory of Chemical Activity, Daudel, R., Pullman, A., Salem, L., and Veillard, A., Ed., Reidel, Dordrecht, Holland”, Volume 2.
McMurchie, L.E., and Davidson, E.R.: 1977, J. Chem. Phys. 67, pp. 5613.
Merer, A.J., and Mulliken, R.S.: 1969, Chem. Rev. 69, pp. 639.
Mulliken, R.S.: 1976, Accts. Chem. Res. 9, pp. 7.
Mulliken, R.S.: 1977, Chem. Phys. Lett. 46, pp. 198.
Wadt, W.A., and Goddard, W.A., III: 1976, Chem. Phys. 18, pp. 1.
Horsley, J.A., and Flouquet, F.: 1970, Chem. Phys. Lett. 5, pp. 165.
Runau, R., Peyerimhoff, S.D., and Buenker, R.J.: 1977, J. Mol. Spectrosc. 68, pp. 253.
Müller, J., and Canuto, S.: 1980, Chem. Phys. Lett. 70, pp. 236.
Kassab, E., and Evleth, E.M.: to be published.
Herzberg, G.: 1950, “Molecular Spectra and Molecular Structure, Van Nostrand, N.Y.” 1, pp. 328–329.
Herzberg, G.: 1966, “Molecular Spectra and Molecular Structure, Van Nostrand, N.Y.” 3, Chapt. 3.
Longuet-Higgins, H.C., and Abrahamson, E.W.: 1965, J. Am. Chem. Soc. 87, pp. 2045.
Hoffmann, R., and Woodward, R.B.: 1965, J. Am. Chem. Soc. 87, pp. 2046, see acknowledgement in ref. 2.
Woodward, R.B., and Hoffmann, R.: 1965, J. Am. Chem. Soc. 87, pp. 395.
Woodward, R.B., and Hoffmann, R.: 1970, “The Conservation of Orbital Symmetry, Verlag Chemie, Weinheim” see pp. 176-177.
Dauben, W.G., Salem, L., and Turro, N.J.: 1975, Accts. Chem. Res. 8, pp. 41.
Bigot, B., Roux, D., Sevin, A., and Devaquet, A.: 1979, J. Am. Chem. Soc. 101, pp. 2560.
Salem, L. Leforestier, C., Segal, G., and Whetmore, R.: 1975, J. Am. Chem. Soc. 97, pp. 479.
Evleth, E.M., Gleghorn, J.F., and Kassab, E.: submitted to Chem. Phys. Lett.
Evleth, E.M., and Kassab, E.: 1978, J. Am. Chem. Soc. 100, pp. 7859.
ref. 11, pp. 515-516.
Koda, S., and Back, R.A.: 1977, Can. J. Chem. 55, pp. 1384.
Donnelly, V.M., Baronavski, A.P., and McDonald, J.R.: 1979, Chem. Phys. 43, pp. 271.
Douglas, A.E.: 1963, Disc. Faraday Soc. 35, pp. 158.
Levy, B., and Berthier, G.: 1968, Int. J. Quant. Chem. 2, pp. 307.
Peyerimhoff, S.D., and Buenker, R.J.: 1979, Can. J. Chem. 57, pp. 3182.
Halpern, A.M., and Gartman, Th.: 1974, J. Am. Chem. Soc. 96, pp. 1393.
Kassab, E., Evleth, E.M., and Gleghorn, J.T.: in preparation.
Miller, K.J., Mielczarek, R.S., and Krauss, M.: 1969, J. Chem. Phys. 51, pp. 26.
Gordon, M.S.: 1977, Chem. Phys. Lett. 52, pp. 161.
Sinanoglu, O.: 1974, “Chemical Spectroscopy and Photochemistry in the Vaccum Ultraviolet, Sandorfy, C., Ausloos, P. J., and Robin, M.B., Ed. Reidel, Dordrecht” pp. 376-378.
Author information
Authors and Affiliations
Editor information
Editors and Affiliations
Rights and permissions
Copyright information
© 1981 D. Reidel Publishing Company, Dordrecht, Holland
About this paper
Cite this paper
Evleth, E.M., Kassab, E. (1981). Theoretical Aspects of Small Molecule Rydberg Photochemistry. In: Csizmadia, I.G., Daudel, R. (eds) Computational Theoretical Organic Chemistry. NATO Advanced Study Institutes Series, vol 67. Springer, Dordrecht. https://doi.org/10.1007/978-94-009-8472-1_16
Download citation
DOI: https://doi.org/10.1007/978-94-009-8472-1_16
Publisher Name: Springer, Dordrecht
Print ISBN: 978-94-009-8474-5
Online ISBN: 978-94-009-8472-1
eBook Packages: Springer Book Archive