Summary
Pentacoordinated molecules are thought to undergo intramolecular isomerization by the widely accepted Berry pseudorotation mechanism. Through our investigations, we have found that the actual pseudorotation for the PH4F system is more complex than that envisioned by Berry. The potential energy surface of PH4F is mapped out at the RHF/6-311G(d, p) level. According to the Berry mechanism, this system is expected to have two minima and two maxima; however, the system actually has two transition states and one global minimum. The minimum energy path from the highest transition state is followed to the second transition state, which in turn has a minimum energy path leading to the global minimum. Along the path between the two transition states there is a branching region. This portion of the potential energy surface is probed extensively.
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One of the reviewers has noted that an alternative explanation is “that the BP's, being non-symmetric, follow neither the downhillB 2 orA 1 modes per se, but must first jump over a small region of hypersurface which is higher in energy. Depending on the PIP, this may be a small or a large first step.”
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Dedicated to Prof. Klaus Ruedenberg
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Windus, T.L., Gordon, M.S. A detailed analysis of pseudorotation in PH4F. Theoret. Chim. Acta 83, 21–30 (1992). https://doi.org/10.1007/BF01113241
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DOI: https://doi.org/10.1007/BF01113241