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Theoretica chimica acta

, Volume 32, Issue 3, pp 203–216 | Cite as

Selection of configurations for SCF-CI calculations of spectral properties and comparison with TDHF calculations

I. Convergence to CCI results in PPP calculations on S0Sx transitions in 6π-electron systems
  • John W. Downing
  • Josef Michl
  • Poul Jørgensen
  • Erik W. Thulstrup
Commentationes

Abstract

Comparison is presented of energies, oscillator strengths, and polarization directions calculated using the dipole length and dipole velocity formulas for the lowest 4–7ππ* transitions in eight 6π-electron molecules of Cs symmetry using various amounts of CI, from singly excited configurations only (SCI) to complete CI (CCI), and also using the time-dependent Hartree-Fock (TDHF) method. The standard simple PPP approximation was used. For the strongest transitions, SCI and especially TDHF give results in fairly good agreement with CCI. For weaker transitions both SCI and TDHF give similar results, quite different from the CCI solutions. Rational methods for selecting a small number of configurations needed to reproduce correct order of excited states (SECI-1) or a somewhat larger number reproducing correct order, energies, oscillator strengths and polarization directions of transitions (SECI-2) are presented. Both, and particularly the latter, give similar results from both dipole length or dipole velocity formulas when Linderberg's relation is used for matrix elements of the linear momentum operator and in this respect resemble the TDHF and CCI methods for which both formulas necessarily give identical results.

Key words

Transition moment and gradient directions Selection of configurations Timedependent Hartree-Fock 

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Copyright information

© Springer-Verlag 1974

Authors and Affiliations

  • John W. Downing
    • 1
  • Josef Michl
    • 1
  • Poul Jørgensen
    • 2
  • Erik W. Thulstrup
    • 2
  1. 1.Department of ChemistryUniversity of UtahSalt Lake CityUSA
  2. 2.Department of ChemistryAarhus UniversityAarhus C.Denmark

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