We have formulated a polarization propagator approach which yields excitation energies, transition moments, and dynamic polarizabilities which are consistent through second order in the electronic repulsion. Certain terms are proven to be missing in our previous second order calculations of transition moments and dynamic polarizabilities and in the equation‐of‐motion calculations of the same quantities. Numerical calculations on carbon monoxide are performed. The calculations show that the major difference between the polarizability (and some transition moments) in the RPA and in the second order polarization propagator approximation is due to these terms. The total effect of all correction terms has been to improve considerably the agreement between theoretical and experimental estimates of the excitation properties for carbon monoxide.
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15 December 1980
Research Article|
December 15 1980
Transition moments and dynamic polarizabilities in a second order polarization propagator approach
Egon S. Nielsen;
Egon S. Nielsen
Department of Chemistry, Århus University, DK‐8000 Århus C., Denmark
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Poul Jo/rgensen;
Poul Jo/rgensen
Department of Chemistry, Århus University, DK‐8000 Århus C., Denmark
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Jens Oddershede
Jens Oddershede
Department of Chemistry, Odense University, Campusvej 55, DK‐5230 Odense M, Denmark
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J. Chem. Phys. 73, 6238–6246 (1980)
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Citation
Egon S. Nielsen, Poul Jo/rgensen, Jens Oddershede; Transition moments and dynamic polarizabilities in a second order polarization propagator approach. J. Chem. Phys. 15 December 1980; 73 (12): 6238–6246. https://doi.org/10.1063/1.440119
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