Intramolecular orbital alignment can be controlled by conformational tuning of the initial wavepacket location on the two-dimensional potential-energy surfaces of thiophenol (see picture; CI=conical intersection). Chemical substitution induces conformational preference, leading to a dramatic change of the branching ratio between X̃ and à states of the phenylthiyl radical.
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Lim et al. (2008) studied this question.
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