Abstract
Ab initio, spatially projected generalized valence bond [GVB(SP)] calculations are reported for the ground and (pi-electron) excited states of allyl radical. We find that the wavefunctions of the ground and first excited state correspond closely to the classical valence bond description of resonant and anti-resonant states,
. The higher states involve excitation of Rydberg orbitals, but even here the orbitals of the GVB(SP) wavefunctions are basically localized. The theoretical value obtained for the allyl resonance energy is 14 kcal in good agreement with thermochemical estimates.
This is a preview of subscription content, log in via an institution to check access.
Similar content being viewed by others
References
Levin,G., Goddard III.,W. A.: J. Am. Chem. Soc. (In press)
Levin, G.: Ph. D. Thesis, California Institute of Technology 1974
Goddard III., W. A.: Phys. Rev.151, 81 (1967)
Ladner, R.C., Goddard III., W. A.: J. Chem. Phys.51, 1073 (1967)
Ladner,R.C.: Ph. D. Thesis, California Institute of Technology 1972
Levin, G., Goddard III., W. A.: Chem. Phys.4, 409 (1974)
Huzinaga, S.: J. Chem. Phys.42, 1293 (1965)
Dunning,Jr., T.H.: J. Chem. Phys.53, 2823 (1970)
Dunning, Jr., T. H.: Private communication 1971
Golden, D.M., Benson, S.W.: Chem. Rev.69, 125 (1969)
Herzberg, G.: Molecular spectra and molecular structure Vol. III, Electronic spectra and electronic structure of polyatomic molecules. Princeton, New Jersey: Van Nostrand 1967
Peyerimhoff, S.D., Buenker, R.J.: J. Chem. Phys.51, 2528 (1969)
Hirst,D.M., Linnett,J.W.: J. Chem. Soc. 1035 (1962)
Author information
Authors and Affiliations
Additional information
Partially supported by grants (GP-15423 and GP-40783X) from the National Science Foundation.
National Science Foundation Predoctoral Fellow 1969–1972 and DuPont Summer Fellow 1973.
Contribution No. 4987.
Rights and permissions
About this article
Cite this article
Levin, G., Goddard, W.A. Spatially projected generalized valence bond description of the pi-states of allyl radical. Theoret. Chim. Acta 37, 253–267 (1975). https://doi.org/10.1007/BF01028395
Received:
Issue Date:
DOI: https://doi.org/10.1007/BF01028395