Low-lying excited states of linear all-trans polyenes: the σ–π electron correlation and the description of ionic states

Abstract

In this work, the electronic spectra of all-trans polyenes, from hexatriene to dodecahexaene are investigated. Special attention is given to the challenging description of the ionic 1¹B⁺_u state. A comprehensive wavefunction analysis of both singlet (2¹A⁻_g, 1¹B⁺_u, and 2¹B⁻_u) and triplet excited states (1³A⁻_g and 1³B⁻_u) is performed using a range of multireference correlated methods, including multireference configuration interaction with singles and doubles (MR-CISD) including a posteriori size-extensivity Pople correction (+P), and the multireference averaged quadratic coupled-cluster (MR-AQCC) method. While covalent states are well described by multi-configurational self-consistent field (MCSCF) theory, accurately describing the ionic state requires addressing size-extensivity errors, basis set effects, and, most importantly, σ–π electron correlation. Taking these factors into account, MR-CISD+P and MR-AQCC results mutually corroborate that the ionic 1¹B⁺_u state is the first vertically excited state in hexatriene and octatetraene. In decapentaene, extrapolated MR-CISD+P results indicate that the 2¹A⁻_g and 1¹B⁺_u states are nearly degenerate, while MR-AQCC suggests that the ionic state lies approximately 0.2 eV below the covalent state. From a wavefunction perspective, the ionic state is consistently well-represented by a single HOMO–LUMO excitation, whereas the contribution of doubly excited configurations increases with chain length for both covalent states.