Tilting a ground-state reactivity landscape by vibrational strong coupling

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 Strong coupling of vibrational modes to an optical cavity shifts site-selectivity in competing silyl substitution reactions. 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.

[1]  H. Hiura,et al.  Cavity Catalysis ‒Accelerating Reactions under Vibrational Strong Coupling‒ , 2018 .

[2]  K. Stranius,et al.  Selective manipulation of electronically excited states through strong light–matter interactions , 2018, Nature Communications.

[3]  T. Schwartz,et al.  Long-Range Transport of Organic Exciton-Polaritons Revealed by Ultrafast Microscopy , 2018, 2018 Conference on Lasers and Electro-Optics (CLEO).

[4]  J. Sparks,et al.  Photon-mediated hybridization of molecular vibrational states. , 2018, Physical chemistry chemical physics : PCCP.

[5]  H. Appel,et al.  Ab Initio Optimized Effective Potentials for Real Molecules in Optical Cavities: Photon Contributions to the Molecular Ground State , 2017, ACS photonics.

[6]  T. Ebbesen,et al.  Voltage‐Controlled Switching of Strong Light–Matter Interactions using Liquid Crystals , 2017, Chemistry.

[7]  D. Baranov,et al.  Novel Nanostructures and Materials for Strong Light–Matter Interactions , 2017 .

[8]  Adam D. Dunkelberger,et al.  Vibrational Strong Coupling Controlled by Spatial Distribution of Molecules within the Optical Cavity , 2017 .

[9]  Y. Tischler,et al.  Vibrational Strong Light-Matter Coupling Using a Wavelength Tunable Mid-Infrared Open Microcavity , 2017 .

[10]  T. Ebbesen,et al.  Energy Transfer between Spatially Separated Entangled Molecules , 2017, Angewandte Chemie.

[11]  R. Ribeiro,et al.  Can ultrastrong coupling change ground state chemical reactions , 2017, 1705.10655.

[12]  F. García-Vidal,et al.  Many-Molecule Reaction Triggered by a Single Photon in Polaritonic Chemistry. , 2017, Physical review letters.

[13]  T. Ebbesen.  Hybrid Light-Matter States in a Molecular and Material Science Perspective. , 2016, Accounts of chemical research.

[14]  T. Ebbesen,et al.  Quantum Strong Coupling with Protein Vibrational Modes. , 2016, The journal of physical chemistry letters.

[15]  T. Ebbesen,et al.  Multiple Rabi Splittings under Ultrastrong Vibrational Coupling. , 2016, Physical review letters.

[16]  Thomas W. Ebbesen,et al.  Ground‐State Chemical Reactivity under Vibrational Coupling to the Vacuum Electromagnetic Field , 2016, Angewandte Chemie.

[17]  F. García-Vidal,et al.  Suppressing photochemical reactions with quantized light fields , 2016, Nature Communications.

[18]  Kopin Liu.  Vibrational Control of Bimolecular Reactions with Methane by Mode, Bond, and Stereo Selectivity. , 2016, Annual review of physical chemistry.

[19]  F. Spano,et al.  Cavity-Controlled Chemistry in Molecular Ensembles. , 2015, Physical review letters.

[20]  F. García-Vidal,et al.  Harvesting excitons through plasmonic strong coupling , 2015, 1502.04905.

[21]  J. Long,et al.  Coherent Coupling between a Molecular Vibration and Fabry–Perot Optical Cavity to Give Hybridized States in the Strong Coupling Limit , 2015 .

[22]  T. Ebbesen,et al.  Conductivity in organic semiconductors hybridized with the vacuum field. , 2014, Nature materials.

[23]  T. Ebbesen,et al.  Coherent coupling of molecular resonators with a microcavity mode , 2014, Nature Communications.

[24]  Michael Towrie,et al.  Toward control of electron transfer in donor-acceptor molecules by bond-specific infrared excitation , 2014, Science.

[25]  G. Lerario,et al.  Exploring Light–Matter Interaction Phenomena under Ultrastrong Coupling Regime , 2014 .

[26]  T. Ebbesen,et al.  Quantum Yield of Polariton Emission from Hybrid Light-Matter States. , 2014, The journal of physical chemistry letters.

[27]  T. Ebbesen,et al.  Modifying chemical landscapes by coupling to vacuum fields. , 2012, Angewandte Chemie.

[28]  S. T. Phillips,et al.  Use of catalytic fluoride under neutral conditions for cleaving silicon-oxygen bonds. , 2011, The Journal of organic chemistry.

[29]  Xiaohua Jiang,et al.  A fragment-based in situ combinatorial approach to identify high-affinity ligands for unknown binding sites. , 2010, Angewandte Chemie.

[30]  H. Kawamata,et al.  CH Stretching Excitation in the Early Barrier F + CHD3 Reaction Inhibits CH Bond Cleavage , 2009, Science.

[31]  J. Shaw,et al.  Zinc-catalyzed silylation of terminal alkynes. , 2008, The Journal of organic chemistry.

[32]  A. L. Utz,et al.  Bond-Selective Control of a Heterogeneously Catalyzed Reaction , 2008, Science.

[33]  X. Yue,et al.  Do Vibrational Excitations of CHD3 Preferentially Promote Reactivity Toward the Chlorine Atom? , 2007, Science.

[34]  A. Grill,et al.  Structure of low dielectric constant to extreme low dielectric constant SiCOH films: Fourier transform infrared spectroscopy characterization , 2003 .

[35]  F. Crim.  VIBRATIONAL STATE CONTROL OF BIMOLECULAR REACTIONS : DISCOVERING AND DIRECTING THE CHEMISTRY , 1999 .

[36]  A. Bassindale,et al.  Reaction Mechanisms of Nucleophilic Attack at Silicon , 1999 .

[37]  M. Majewski,et al.  Optical properties of metallic films for vertical-cavity optoelectronic devices. , 1998, Applied optics.

[38]  Zare,et al.  Laser control of chemical reactions , 1998, Science.

[39]  J. Wijnberg,et al.  Long-Range Effects of Through-Bond Orbital Interactions on the Desilylation Rate of Silyl Ethers. , 1995 .

[40]  R A Mathies,et al.  Vibrationally coherent photochemistry in the femtosecond primary event of vision. , 1994, Science.

[41]  A. Sinha,et al.  Controlling bimolecular reactions: Mode and bond selected reaction of water with hydrogen atoms , 1991 .

[42]  G. Schatz,et al.  A quasiclassical trajectory study of the state-to-state dynamics of atomic hydrogen + water .fwdarw. hydroxyl + molecular hydrogen , 1984 .

[43]  H. Frei,et al.  Vibrational excitation of ozone and molecular fluorine reactions in cryogenic matrices , 1981 .

[44]  J. Polanyi.  Concepts in reaction dynamics , 1972 .

[45]  R. T. Hall,et al.  Isomerization of Nitrous Acid: An Infrared Photochemical Reaction , 1963 .