Tuesday, November 16, 2010

Finding the lost twin

This beautiful picture is on the cover of A Chemist's guide to Valence Bond Theory by Shaik and Hiberty. It summarises the main idea in a paper, The Twin-Excited State as a Probe for the Transition State in Concerted Unimolecular Reactions: The Semibullvalene Rearrangement.
It illustrates how the use of diabatic states (K1 and K2) based on chemical intuition can lead to adiabatic potential energy surfaces with complex structure. Furthermore, it illustrates the notion of an excited state (K1 - K2) which is a "twin state" to the ground state, K1+K2. The relevant vibrational frequency is higher in the excited state than in the ground state.
An earlier post discussed the analogous picture for benzene.

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