Abstract
A matrix technique for calculating the probabilities of many-photon transitions in the framework of the full configuration interaction which corresponds to an exact solution of the finite-dimensional Schrödinger equation is suggested. The method is applied to π-electron shells of a number of typical conjugate molecules (polyenes, benzene, naphthalene, and indacene). In the case of one-photon excitations, π-electron correlation decreases the intensities of the lowest transitions by no more than an order of magnitude. For two-photon transitions, the standard Hartree-Fock scheme exaggerates the probabilities by two or three orders of magnitude, and only a transition to spin-polarized versions (unrestricted and extended Hartree-Fock methods) significantly improves the results. Therefore, a correct description of many-photon transitions requires taking account of many-particle effects.
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Translated from Zhurnal Struktumoi Khimii, Vol. 39, No. 4, pp. 563–570, July–August, 1998.
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Ivanov, V.V., Boichenko, I.V. & Luzanov, A.V. Influence of many-electron effects on the probabilities of one- and two-photon ππ*-Transitions in conjugate organic molecules. Found Phys Lett 15, 457–463 (2002). https://doi.org/10.1007/BF02701372
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DOI: https://doi.org/10.1007/BF02701372