Tilting a ground-state reactivity landscape by vibrational strong coupling

• DOI: 10.1126/science.aau7742
• Publication Date: 2019-02-08T00:09:23Z
• Authors: A. Thomas; L. Lethuillier-Karl; K. Nagarajan; R. M. A. Vergauwe; J. George; T. Chervy; A. Shalabney; E. Devaux; C. Genet; J. Moran; T. W. Ebbesen
• Keywords: [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry; [CHIM.THEO] Chemical Sciences/Theoretical and/or physical chemistry; [CHIM] Chemical Sciences; [CHIM]Chemical Sciences; 01 natural sciences; 0104 chemical sciences

Shaking up reaction-site selectivity

It seems intuitive that putting vibrational energy into a chemical bond ought to promote selective cleavage of that bond. In fact, the relation of vibrational excitation to reactivity has generally proven subtler and more complex. Thomas et al. studied how strong coupling of specific vibrational modes to an optical cavity might influence a molecule with two competing reactive sites. The molecule had two silicon centers that could react with fluoride by respective cleavage of a Si–C or Si–O bond. Exciting the vibrations at either center slowed down the overall reaction while favoring otherwise disfavored Si–O cleavage.

Science , this issue p. 615