Abstract
Calculations have been carried out on an extensive series of molecules for both the neutral species and core ionized states. Substituent effects on C1s , N1s , O1s , and F1s levels have been investigated and where available comparison has been drawn with experiment. Comparison with Koopmans' theorem has allowed a relatively detailed study of change in relaxation energies as a function of substituent effect on a given core level. Whilst for C1s levels the computed shifts in core binding energies are approximately linearly related to differences in relaxation energies for the N1s , O1s , and F1s levels, the relative electronegativity of the substituent can invert this correlation. The empirical correction of Koopmans' theorem for differences in relaxation energies at different sites has been investigated for large molecules. The results compare well with direct hole state calculations.
This is a preview of subscription content, log in via an institution to check access.
Similar content being viewed by others
References
Bagus,P.S.: Phys. Rev. A 139, 619 (1965)
Koopmans,T.A.: Physica 1, 104 (1933)
Jolly, W.L.,Hendrickson,D.N.: J. Am. Chem. Soc. 92, 1863 (1970)
Siegbahn,K.,Nordling,C., Johansson,G., Hedman, J., Heden, P.F., Hamrin, K., Gelius,U., Bergmark, T., Werme,L.O., Manne,R., Baer, Y.: ESCA applied to free molecules. Amsterdam: North Holland 1969
Ditchfield,R., Hehre,W.J., Pople,J.A.: J. Chem. Phys. 54, 724 (1971)
Clementi,E., Raimondi,D.L.: J. Chem. Phys. 38, 2686 (1963)
Stewart,R.F.: J. Chem. Phys. 50, 2485 (1969)
Hillier, I. H., Saunders,V.R.: Atlas Computer Laboratory 1973
Clementi,E., Popkie,H.: J. Am. Chem. Soc. 94, 4057 (1972)
Gelius,U., Basilier,E., Svensson,S., Bergmark,T., Siegbahn,K.: J. Electron Spectry. 2, 405 (1974)
Herzberg,G.: Molecular spectra and molecular structure. London: Van Nostrand 1966
Meyer,W.: J. Chem. Phys. 58, 1017 (1973)
Cf. Refs. [1] and [9]
Adams,D.B., Clark,D.T.: Theoret. Chim. Acta (Berl.) 31, 171 (1973)
Clark,D.T., Feast,W.J., Kilcast,D., Musgrave,W.K.R.: J. Poly. Sci. A1 11, 389 (1973)
Clark,D.T., Kilcast,D., Adams,D.B., Musgrave,W.K.R.: J. Electron Spectry. 1, 227 (1972)
Davis,D.W., Shirley,D.A., Thomas,T.D.: J. Chem. Phys. 56, 671 (1972)
Unpublished data cf. Ref. [4]
Guest,M.F., Hillier,I.H., Saunders,V.R., Wood,M.H.: Proc. Roy. Soc. (London) A 333, 201 (1973)
Gelius,U., Siegbahn,K.: Disc. Faraday Soc. Chem. Soc. 54, 257 (1972)
Perry,W.B., Jolly,W.L.: Chem. Phys. Letters 23, 529 (1973)
Clark, D. T., Lilley, D. M. J.: In preparation
Author information
Authors and Affiliations
Rights and permissions
About this article
Cite this article
Clark, D.T., Scanlan, I.W. & Muller, J. Non empirical LCAO SCF MO investigations of electronic reorganizations accompanying core ionizations. Theoret. Chim. Acta 35, 341–354 (1974). https://doi.org/10.1007/BF00548483
Received:
Published:
Issue Date:
DOI: https://doi.org/10.1007/BF00548483