title: The best orbital and pair function for describing ionic and excited states on top of the exact ground state.
abstract: Many-body processes inevitably lead to the transition from one many-body wavefunction to another. Due to the complexity of the initial and final states many-body wavefunctions, one often wishes to try and describe such transitions using only a single-particle function. While there are numerous types of orbitals and densities which are commonly used, the question remains which one is optimal and in which sense. Here we present the optimal one and two body functions whose anti-symmetrized product with the initial state yields the maximal overlap with the final state. A definition of the above optimal condition and its rigorous proof are given. The resulting optimal functions shed additional light on the well-known Dyson orbital and reduced transition matrix, demonstrating further their physical meaning as independent functions.
authors.affiliation: Theoretische Chemie, Physikalisch-Chemisches Institut, Universität Heidelberg, Im Neuenheimer Feld 229, D-69120 Heidelberg, Germany.
authors.forename: Shachar
authors.initials: S
authors.lastname: Klaiman
authors.affiliation: Theoretische Chemie, Physikalisch-Chemisches Institut, Universität Heidelberg, Im Neuenheimer Feld 229, D-69120 Heidelberg, Germany.
authors.forename: Lorenz S
authors.initials: LS
authors.lastname: Cederbaum