The Spin-Partitioned Total-Position Spread Tensor: An Application To Diatomic Molecules

详细信息    查看全文

• 作者：Oriana Brea ; Muammar El Khatib ; Gian Luigi Bendazzoli ; Stefano Evangelisti ; Thierry Leininger ; Celestino Angeli
• 刊名：Journal of Physical Chemistry A
• 出版年：2016
• 出版时间：July 14, 2016
• 年：2016
• 卷：120
• 期：27
• 页码：5230-5238
• 全文大小：519K
• 年卷期：0
• ISSN：1520-5215

文摘

The spin partition (SP) of the total-position spread (TPS) tensor is applied to the case of a few light diatomic molecules at full configuration interaction (FCI) level. It appears that the SP-TPS tensor gives informations that are complementary with respect to the corresponding spin-summed (SS) quantity. The spin-summed total position-spread tensor (SS-TPS, Λ) is defined as the second moment cumulant of the total position operator, and the SP-TPS is its partition in equal (Λ_αα+ββ) and different spin (Λ_αβ+βα) contributions. Then, the SS-TPS allows description of the molecule charge mobility, while the SP-TPS allows description of the spin delocalization. The most relevant Cartesian-component for both tensors (SS-TPS and SP-TPS) is the component along the chemical bond (Λ^∥), and it was found that its behavior was related to the type of interaction involved. For covalent bonds the SP-TPS has a squared growth when the bond is stretched, while for ionic bonds there exists a faster-than-linear growth after the avoided-crossing between the covalent and the ionic states. Other exotic bonds, like He₂ and Be₂, were also considered, and a particular spin delocalization was able to describe the different character of the two weakly bonded molecules, and specially the multireference character of the wave function along the dissociative potential energy curve.