Multiconfigurational perturbation theory

University dissertation from Lund

Abstract: The aim of the thesis is to analyze a method which describes the electron correlation in atoms and molecules. The method is based on Rayleigh-Schrödinger perturbation theory with a partitioning of the Hamiltonian into a fairly simple zeroth-order operator and a perturbation operator. The zeroth-order Hamiltonian is founded on a one-electron Fock-type operator and two different operators have been tested. The zeroth-order wave function is constructed from a complete active space self-consistent field (CASSCF) calculation. This means that the zeroth-order wave function for open-shell systems and systems with strong configurational mixing (near degeneracy) can be obtained on an equal level as closed-shell (single determinant) states. The theory is formulated in such a way that the Möller-Plesset perturbation theory is obtained for the closed-shell (single determinant) state. The flexibility of the CASSCF method makes it possible, in principle, to construct the zeroth-order wave function (and the zeroth-order Hamiltonian) to any desired accuracy. The perturbation expansion of the energy is therefore expected to converge fast and only up to the second-order contribution has been implemented leading to fairly fast and accurate calculations. The aim of the computer implementation is to describe the electron correlation in small and medium-sized molecules (up to 20 atoms) accurately. The application of the perturbation method to a number of problems in chemistry is demonstrated in the thesis: (1) the calculation of electronic properties and harmonic vibrational frequencies of the ozone molecule; (2) the calculation of electric dipole polarizabilities of excited valence states of several first- and second-row atoms; (3) the calculation of excited states of the nickel atom, the benzene molecule, and the azabenzenes pyridine, pyrazine, pyridazine, and s-triazine

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