title: Characterization and Quantification of Polyradical Character.
abstract: The decomposition of ⟨Ŝ(2)⟩ into atomic and diatomic contributions (local spin analysis) is used to detect and quantify the polyradical character of molecular systems. A model triradical system is studied in detail, and the local spin analysis is used to distinguish several patterns of local spin distributions and spin-spin interactions that can be found for different electronic states. How close a real molecular system is to an ideal system of k perfectly localized spin centers is utilized to define a measure of its k-radical character. The spin properties and triradical character of the lowest-lying electronic states of a number of all σ, all π, and σ-π organic triradicals are discussed in detail. The local spin contributions exhibit good correlation with experimental triradical stabilization energies.
authors.affiliation: Institut de Química Computacional i Catàlisi (IQCC) i Departament de Química, Universitat de Girona , 17071 Girona, Girona, Spain.
authors.forename: Eloy
authors.initials: E
authors.lastname: Ramos-Cordoba
authors.affiliation: Institut de Química Computacional i Catàlisi (IQCC) i Departament de Química, Universitat de Girona , 17071 Girona, Girona, Spain.
authors.forename: Pedro
authors.initials: P
authors.lastname: Salvador