Minimal Active Space for Diradicals Using Multistate Density Functional Theory.

ABSTRACT: This work explores the electronic structure as well as the reactivity of singlet diradicals, making use of multistate density functional theory (MSDFT). In particular, we show that a minimal active space of two electrons in two orbitals is adequate to treat the relative energies of the singlet and triplet adiabatic ground state as well as the first singlet excited state in many cases. This is plausible because dynamic correlation is included in the first place in the optimization of orbitals in each determinant state via block-localized Kohn-Sham density functional theory. In addition, molecular fragment, i.e., block-localized Kohn-Sham orbitals, are optimized separately for each determinant, providing a variational diabatic representation of valence bond-like states, which are subsequentl

SUBMITTER: Han J 

PROVIDER: S-EPMC9182067 | biostudies-literature | 2022 May

REPOSITORIES: biostudies-literature