Ab initio CI calculations on free‐base porphin

Abstract

AbstractAb initio configuration interaction (CI) calculations were carried out on low‐lying singlet and triplet π–π* states and ionized states of free‐base porphin. We take into account single and double excitations from σ and π electrons in the CI calculations. The composite natural orbitals were employed in order to reduce the size of orbital set to be used in the CI. The calculated excitation energies were in good agreement with experimental values. The use of split‐valence‐type basis and the inclusion of correlation effects of σ electrons were proved to be important to describe the low‐lying π–π* states, especially the Soret band.