Spin-adaptation and redundancy in state-specific multireference perturbation theory.

J Chem Phys

Laboratory of Theoretical Chemistry, Loránd Eötvös University, H-1518 Budapest, POB 32, Hungary.

Published: March 2013

Spin-adaptation of virtual functions in state-specific multireference perturbation theory is examined. Redundancy occurring among virtual functions generated by unitary group based excitation operators on a model-space function is handled by canonical orthogonalization. The treatment is found to remove non-physical kinks observed earlier on potential energy surfaces. Sensitivity analysis of the new approach confirms the elimination of the drastic increase in singular values of sensitivity matrices, reported earlier.

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http://dx.doi.org/10.1063/1.4795436DOI Listing

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