Unusual potential energy surfaces are a theme of this blog and my book (see chapter 7). Examples might include bifurcations and valley inflection points and often lead to unusual dynamics. Tantillo has now reported a bifurcation on the PES for terpene synthesis, specifically the pathway for synthesis of abietadiene.1

Tantillo discusses two possible cation rearrangement pathways. The first is pretty ordinary, but in the second, the precursor cation 1 can rearrange through either of two transition states 2a or 2b (Scheme 1). The IRC computation from 2a connects back to 1, but in the forward direction it connects to another transition state 3. This TS (3) connects products 4 and 5. These structures are drawn in Figure 1.

Thus, the potential energy surface displays a bifurcation, and one might expect unusual dynamic effects to operate.

Scheme 1




Figure 1. B3LYP/6-31+G(d,p) optimized transition structures of 2-3.1


(1) Hong, Y. J.; Tantillo, D. J., "A potential energy surface bifurcation in terpene biosynthesis," Nature Chem. 2009, 1, 384-389 DOI: 10.1038/nchem.287.