Fig. 1: Resonant vibrational strong-coupling can inhibit chemical reactions.
a Strong resonant (red shaded) coupling between cavity and vibrational modes can selectively inhibit a chemical reaction, i.e., preventing the appearance of products (shaded green and yellow), that is present under off-resonant (blue shaded) conditions or outside the cavity environment. b Illustration of the reaction mechanism for the deprotection of 1-phenyl-2-trimethylsilylacetylene (PTA), with tetra-n-butylammonium fluoride (TBAF) and c energetic of the reaction in b in free-space (further details see text). The successful reaction involves breaking the Si-C bond and thus overcoming a transition-state barrier of 0.35 eV. The upper (UVP) and lower (LVP) vibrational polariton splitting is comparably small to the transition-state (yellow star) enthalpy ΔH‡. d Vibrational absorption spectrum along the cavity polarization direction \({S}_{{\varepsilon }_{c}}(\omega )=2\omega \mathop{\sum }\nolimits_{j=1}^{{N}_{vib}}|{{{{{{{{\boldsymbol{\varepsilon }}}}}}}}}_{c}\cdot {{{{{{{\bf{R}}}}}}}}({\omega }_{j}){|}^{2}\delta (\omega -{\omega }_{j})\) illustrating the strong-coupling of the vibrational eigenmode at 856 cm−1 (yellow-dashed vertical line) with the cavity polarized along εc for PTAF− (magenta) and the isolated PTA complex (black). The insets show the coupled vibrational mode of PTA and the light-matter hybridization under vibrational strong-coupling. Our time-dependent calculations describe the correlated (non-adiabatic) movement of electrons, nuclei and cavity field during the reaction. The strong asymmetry between lower and upper polariton originates from the high coupling and the related interplay of electronic, nuclear and self-polarization contribution (see Supplementary Fig. 2). The cavity frequency will be changed between 43 and 1584 cm−1 in order to investigate resonant effects.
