Behavior of the Position–Spread Tensor in Diatomic Systems

• Published in: Journal of chemical theory and computation Vol. 9; no. 12; pp. 5286 - 5295
• Main Authors: Brea, Oriana, El Khatib, Muammar, Angeli, Celestino, Bendazzoli, Gian Luigi, Evangelisti, Stefano, Leininger, Thierry
• Format: Journal Article
• Language: English
• Published: United States American Chemical Society 10-12-2013
• Subjects: Chemical Sciences
• ISSN: 1549-9618; 1549-9626
• DOI: 10.1021/ct400453b

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.