Multireference perturbation theory for large restricted and selected active space reference wave functions

A multireference second-order perturbation theory (MRPT2) has been developed which allows the use of reference wave functions with large active spaces and arbitrary configuration selection. Internally contracted configurations are used as a basis for all configuration subspaces of the first-order wave function for which the overlap matrix depends only on the second-order density matrix of the reference function. Some other subspaces which would require the third- or fourth-order density matrices are left uncontracted. This removes bottlenecks of the complete active space second order pertubation theory (CASPT2) caused by the need to construct and diagonalize large overlap matrices. Preliminary applications of the new method for 1,2-dihydronaphthalene (DHN) and free base porphin are presented in which the effect of applying occupancy restrictions in the reference wave function (restricted active space second-order perturbation theory, RASPT2) and reference configuration selection (general MRPT2) on electro...

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