The total Position Spread in mixed‐valence compounds: A study on the H4+ model system

The behavior of the Total Position Spread (TPS) tensor, which is the second moment cumulant of the total position operator, is investigated in the case of a mixed‐valence model system. The system consists of two H2 molecules placed at a distance D. If D is larger than about 4 bohr, the singly ionized system shows a mixed‐valence character. It is shown that the magnitude of the TPS has a strong peak in the region of the avoided crossing. We believe that the TPS can be a powerful tool to characterize the behavior of the electrons in realistic mixed‐valence compounds. © 2014 Wiley Periodicals, Inc.

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