Many chemical methods have been developed to favor a particular product in transformations of compounds that have two or more reactive sites. We explored a different approach to site selectivity using vibrational strong coupling (VSC) between a reactant and the vacuum field of a microfluidic optical cavity. Specifically, we studied the reactivity of a compound bearing two possible silyl bond cleavage sites—Si–C and Si–O, respectively—as a function of VSC of three distinct vibrational modes in the dark. The results show that VSC can indeed tilt the reactivity landscape to favor one product over the other. Thermodynamic parameters reveal the presence of a large activation barrier and substantial changes to the activation entropy, confirming the modified chemical landscape under strong coupling.

The ground‐state deprotection of a simple alkynylsilane is studied under vibrational strong coupling to the zero‐point fluctuations, or vacuum electromagnetic field, of a resonant IR microfluidic cavity. The reaction rate decreased by a factor of up to 5.5 when the Si−C vibrational stretching modes of the reactant were strongly coupled. The relative change in the reaction rate under strong coupling depends on the Rabi splitting energy. Product analysis by GC‐MS confirmed the kinetic results. Temperature dependence shows that the activation enthalpy and entropy change significantly, suggesting that the transition state is modified from an associative to a dissociative type. These findings show that vibrational strong coupling provides a powerful approach for modifying and controlling chemical landscapes and for understanding reaction mechanisms.

Organic semiconductors have generated considerable interest for their potential for creating inexpensive and flexible devices easily processed on a large scale [1][2][3][4][5][6][7][8][9][10][11]. However technological applications are currently limited by the low mobility of the charge carriers associated with the disorder in these materials [5][6][7][8]. Much effort over the past decades has therefore been focused on optimizing the organisation of the material or the devices to improve carrier mobility. Here we take a radically different path to solving this problem, namely by injecting carriers into states that are hybridized to the vacuum electromagnetic field. These are coherent states that can extend over as many as 10 5 molecules and should thereby favour conductivity in such materials. To test this idea, organic semiconductors were strongly coupled to the vacuum electromagnetic field on plasmonic structures to form polaritonic states with large Rabi splittings ∼ 0.7 eV. Conductivity experiments show that indeed the current does increase by an order of magnitude at resonance in the coupled state, reflecting mostly a change in field-effect mobility as revealed when the structure is gated in a transistor configuration. A theoretical quantum model is presented that confirms the delocalization of the wave-functions of the hybridized states and the consequences on the conductivity. While this is a proof-of-principle study, in practice conductivity mediated by light-matter hybridized states is easy to implement and we therefore expect that it will be used to improve organic devices. More broadly our findings illustrate the potential of engineering the vacuum electromagnetic environment to modify and to improve properties of materials.Light and matter can enter into the strong coupling regime by exchanging photons faster than any competing dissipation processes. This is normally achieved by placing the material in a confined electromagnetic environment, such as a Fabry-Perot (FP) cavity composed of two parallel mirrors that is resonant with an electronic transition in the material. Alternatively, one can use surface plasmon resonances as in this study. Strong coupling leads to the formation of two hybridized light-matter polaritonic states, P+ and P-, separated by the so-called Rabi splitting, as illustrated in Figure 1a. According to quantum electrodynamics, in the absence of dissipation, the Rabi splitting for a single molecule is given bywhere ω is the cavity resonance or transition energy ( the reduced Planck constant), 0 the vacuum permittivity, v the mode volume, d the transition dipole moment of the material and n ph the number of photons present in the system. The last term implies that, even in the dark, the Rabi splitting has a finite value which is due to the interaction with the vacuum electromagnetic field. This vacuum Rabi splitting can be further increased by coupling a large number N of oscillators to the electromagnetic mode since Ω N R ∝ √ N [12]. In this ensemble coupling, in addition to P+ an...