Performance of Shannon-entropy compacted N-electron wave functions for configuration interaction methods

• Autores: Alcoba, Diego Ricardo; Torre, Alicia; Lain, Luis; Massaccesi, Gustavo E.; Oña, Ofelia Beatriz; Ayers, Paul W.; Van Raemdonck, Mario; Bultinck, Patrick; Van Neck, Dimitri
• Año de publicación: 2016
• Idioma: inglés
• Tipo de recurso: artículo
• Materia: Física; Entropy; Configuration interaction; Seniority; DOCI
• Institución: Universidad Nacional de La Plata

The coefficients of full configuration interaction wave functions (FCI) for N-electron systems expanded in N-electron Slater determinants depend on the orthonormal one-particle basis chosen although the total energy remains invariant. Some bases result in more compact wave functions, i.e. result in fewer determinants with significant expansion coefficients. In this work, the Shannon entropy, as a measure of information content, is evaluated for such wave functions to examine whether there is a relationship between the FCI Shannon entropy of a given basis and the performance of that basis in truncated CI approaches. The results obtained for a set of randomly picked bases are compared to those obtained using the traditional canonical molecular orbitals, natural orbitals, seniority minimising orbitals and a basis that derives from direct minimisation of the Shannon entropy. FCI calculations for selected atomic and molecular systems clearly reflect the influence of the chosen basis. However, it is found that there is no direct relationship between the entropy computed for each basis and truncated CI energies.
Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas