title: Behavior of the Position-Spread Tensor in Diatomic Systems.
abstract: The behavior of the Position-Spread Tensor (Λ) in a series of light diatomic molecules (either neutral or negative ions) is investigated at a Full Configuration Interaction level. This tensor, which is the second moment cumulant of the total position operator, is invariant with respect to molecular translations, while its trace is also rotationally invariant. Moreover, the tensor is additive in the case of noninteracting subsystems and can be seen as an intrinsic property of a molecule. In the present work, it is shown that the longitudinal component of the tensor, Λ∥, which is small for internuclear distances close to the equilibrium, tends to grow if the bond is stretched. A maximum is reached in the region of the bond breaking, then Λ∥ decreases and converges toward the isolated-atom value. The degenerate transversal components, Λ⊥, on the other hand, usually have a monotonic growth toward the atomic value. The Position Spread is extremely sensitive to reorganization of the molecular wave function, and it becomes larger in the case of an increase of the electron mobility, as illustrated by the neutral-ionic avoided crossing in LiF. For these reasons, the Position Spread can be an extremely useful property that characterizes the nature of the wave function in a molecular system.
authors.affiliation: Laboratoire de Chimie et Physique Quantiques, Université de Toulouse et CNRS , 118, Route de Narbonne, F-31062 Toulouse Cedex, France.|Departamento de Química, Facultad de Ciencias, Módulo 13, Universidad Autónoma de Madrid , Cantoblanco, 28049 Madrid, Spain.
authors.forename: Oriana
authors.initials: O
authors.lastname: Brea
authors.affiliation: Laboratoire de Chimie et Physique Quantiques, Université de Toulouse et CNRS , 118, Route de Narbonne, F-31062 Toulouse Cedex, France.
authors.forename: Muammar
authors.initials: M
authors.lastname: El Khatib
authors.affiliation: Dipartimento di Scienze Chimiche e Farmaceutiche, Università di Ferrara , Via Borsari 46, I-44121 Ferrara, Italy.
authors.forename: Celestino
authors.initials: C
authors.lastname: Angeli
authors.affiliation: P.A.M. Università di Bologna , Dipartimento di Chimica Industriale "Toso Montanari", Viale Risorgimento 4, I-40136 Bologna, Italy.
authors.forename: Gian Luigi
authors.initials: GL
authors.lastname: Bendazzoli
authors.affiliation: Laboratoire de Chimie et Physique Quantiques, Université de Toulouse et CNRS , 118, Route de Narbonne, F-31062 Toulouse Cedex, France.
authors.forename: Stefano
authors.initials: S
authors.lastname: Evangelisti
authors.affiliation: Laboratoire de Chimie et Physique Quantiques, Université de Toulouse et CNRS , 118, Route de Narbonne, F-31062 Toulouse Cedex, France.
authors.forename: Thierry
authors.initials: T
authors.lastname: Leininger