MBE-CASSCF Approach for the Accurate Treatment of Large Active Spaces
arXiv:2403.17836 · doi:10.1021/acs.jctc.4c00388
Abstract
We present a novel implementation of the complete active space self-consistent field (CASSCF) method that makes use of the many-body expanded full configuration interaction (MBE-FCI) method to incrementally approximate electronic structures within large active spaces. On the basis of a hybrid first-order algorithm employing both Super-CI and quasi-Newton strategies for the optimization of molecular orbitals, we demonstrate both computational efficacy and high accuracy of the resulting MBE-CASSCF method. We assess the performance of our implementation on a set of established numerical tests before applying MBE-CASSCF in the investigation of the triplet-quintet spin gap of iron(II) porphyrin with active spaces as large as 50 electrons in 50 orbitals.
arXiv comment27+8 pages, 6 figures. SI as an ancillary file
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