We propose a new approach to determine a suitable zeroth-order wavefunction for multiconfigurational perturbation theory. The same ansatz as in complete active space (CAS) wavefunction optimization is used but it is split in two parts, a principal space (A) and a much larger extended space (B). Lwdins partitioning technique is employed to map the initial eigenvalue problem to a dimensionality equal to that of (A) only. Combined with a simplified expression for the (B) portion of the wavefunction, we are able to drastically reduce the storage and computational demands of the wavefunction optimization. This scheme is used to produce reference wavefunctions and energies for subsequent second-order perturbation theory (PT2) corrections. Releasing the constraint of computing the exact CAS energy and wavefunction prior to the PT2 treatment introduces a nonstandard paradigm for multiconfigurational methods. Based on the results of test calculations, we argue that principal parts with only few percents of the total number of CAS configurations could provide final multiconfigurational PT2 energies of the same accuracy as in the standard paradigm. In the future, algorithmic improvements for this scheme will bring into reach active spaces much beyond the present limit of CAS-based methods, therefore allowing for accurate studies of systems featuring strong correlation.
Bibliographical noteFunding Information:
Fundings from the Swiss National Science Foundation (SNSF), Grant No. 200020-120007, and the Director, Office of Basic Energy Sciences, U.S. Department of Energy under Contract no. USDOE/DE-SC002183 are gratefully acknowledged. All of us dedicate this work to the loving memory of Björn Roos, for his inspiring lessons in science and in life.