| Autor: |
Trinquier G; Laboratoire de chimie et physique quantiques, IRSAMC-CNRS-UMR 5626, Université Paul-Sabatier (Toulouse III), Toulouse 31062, Cedex 4, France., David G; Institut des sciences chimiques de rennes, ISCR-CNRS-UMR 6226, Université de Rennes, Rennes 35000, France., Veillon E; Laboratoire de chimie et physique quantiques, IRSAMC-CNRS-UMR 5626, Université Paul-Sabatier (Toulouse III), Toulouse 31062, Cedex 4, France., Malrieu JP; Laboratoire de chimie et physique quantiques, IRSAMC-CNRS-UMR 5626, Université Paul-Sabatier (Toulouse III), Toulouse 31062, Cedex 4, France. |
| Abstrakt: |
This work addresses a class of conjugated hydrocarbons that are expected to be singlet diradicals according to the topological Hückel Hamiltonian while possibly satisfying full on-bond electron pairing. These systems possess two degenerate singly occupied molecular orbitals (SOMOs), but aromaticity brought by properly positioned six-membered rings does prevent Jahn-Teller distortions. Density functional theory (DFT) calculations performed on two emblematic examples confirm the strong bond-length alternation in the closed-shell solutions and the clear spatial symmetry in the open-shell spin-unrestricted determinants, the latter solution always being found to have significantly lower energy. Since the SOMOs are here of different symmetry, the wave function is free from ionic valence-bond component, and spin decontamination of the unrestricted DFT solutions and wave function calculations at the CASSCF-plus-second-order-perturbation level confirm the expected pure diradical character of such molecules. In contrast to disjoint diradicals, the SOMOs of present systems have large amplitudes on neighbor atoms, and we propose to name them entangled pure diradicals, further providing some prescription rules for their design. Additional calculations point out the qualitative contrast between these molecules and the related diradicaloids. |
