Perturbation theory in the complete degenerate active space (CDAS-PT2)

Methods based on the multireference perturbation theory (MRPT) with the one-electron zeroth-order Hamiltonian are widely used for the description of excited states, for example, due to their relatively low computational cost. However, current methods have a common drawback-use of a model space with low size. In this article, we propose the MRPT method with the model space extended to the complete active space. The one-electron zeroth-order Hamiltonian suitable for this extension is formulated. The proposed method was applied to common models, such as LiF, ethylene, and trans-butadiene. It was shown to have accuracy superior to XMCQDPT2 in most cases, especially in the case of the small active space.