scholarly journals Tilting a ground-state reactivity landscape by vibrational strong coupling

Science ◽  
2019 ◽  
Vol 363 (6427) ◽  
pp. 615-619 ◽  
Author(s):  
A. Thomas ◽  
L. Lethuillier-Karl ◽  
K. Nagarajan ◽  
R. M. A. Vergauwe ◽  
J. George ◽  
...  
Keyword(s):  
Strong Coupling ◽  
Activation Barrier ◽  
Bond Cleavage ◽  
Optical Cavity ◽  
Vacuum Field ◽  
Activation Entropy ◽  
Vibrational Modes ◽  
Cleavage Sites ◽  
Chemical Methods ◽  
Site Selectivity

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.

scholarly journals Tilting a Ground State Reactivity Landscape by Vibrational Strong Coupling

2018 ◽  
Author(s):  
Anoop Thomas ◽  
Lucas Lethuillier-Karl ◽  
Kalaivanan Nagarajan ◽  
Robrecht M. A. Vergauwe ◽  
Jino George ◽  
...  
Keyword(s):  
Strong Coupling ◽  
Activation Barrier ◽  
Chemical Reactivity ◽  
Bond Cleavage ◽  
Optical Cavity ◽  
Vacuum Field ◽  
Activation Entropy ◽  
Cleavage Sites ◽  
Site Selectivity ◽  
First Time

Site-selectivity is fundamental for steering chemical reactivity towards a given product and various efficient chemical methods have been developed for this purpose. Here we explore a very different approach by using vibrational strong coupling (VSC) between a reactant and the vacuum field of a microfluidic optical cavity. For this purpose, the reactivity of a compound bearing two possible silyl bond cleavage sites, at Si-C and Si-O, was studied as a function of VSC of its various 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 significant changes to the activation entropy, confirming the modified chemical landscape under strong coupling. This study shows for the first time that VSC can impart site-selectivity for chemical reactions without the need for chemical intervention.

scholarly journals Tilting a Ground State Reactivity Landscape by Vibrational Strong Coupling

2018 ◽  
Author(s):  
Anoop Thomas ◽  
Lucas Lethuillier-Karl ◽  
Kalaivanan Nagarajan ◽  
Robrecht M. A. Vergauwe ◽  
Jino George ◽  
...  
Keyword(s):  
Strong Coupling ◽  
Activation Barrier ◽  
Chemical Reactivity ◽  
Bond Cleavage ◽  
Optical Cavity ◽  
Vacuum Field ◽  
Activation Entropy ◽  
Cleavage Sites ◽  
Site Selectivity ◽  
First Time

Site-selectivity is fundamental for steering chemical reactivity towards a given product and various efficient chemical methods have been developed for this purpose. Here we explore a very different approach by using vibrational strong coupling (VSC) between a reactant and the vacuum field of a microfluidic optical cavity. For this purpose, the reactivity of a compound bearing two possible silyl bond cleavage sites, at Si-C and Si-O, was studied as a function of VSC of its various 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 significant changes to the activation entropy, confirming the modified chemical landscape under strong coupling. This study shows for the first time that VSC can impart site-selectivity for chemical reactions without the need for chemical intervention.

scholarly journals Selective Crystallization via Vibrational Strong Coupling

2021 ◽  
Author(s):  
Kenji Hirai ◽  
Hiroto Ishikawa ◽  
Thibault Chervy ◽  
James Andell Hutchison ◽  
Hiroshi Uji-i
Keyword(s):  
Strong Coupling ◽  
Material Properties ◽  
Optical Cavity ◽  
Chemical Processes ◽  
Selective Crystallization ◽  
Vacuum Fields

The coupling of (photo)chemical processes to optical cavity vacuum fields is an emerging method for modulating molecular and material properties. Recent reports have shown that strong coupling of the vibrational...

scholarly journals Origin and Prediction of Highly Specific Bond Cleavage Sites in the Thermal Activation of Intact Protein Ions

2018 ◽  
Vol 25 (3) ◽  
pp. 823-834 ◽  
Author(s):  
Huixin Wang ◽  
Michael G. Leeming ◽  
Junming Ho ◽  
William A. Donald
Keyword(s):  
Thermal Activation ◽  
Bond Cleavage ◽  
Intact Protein ◽  
Cleavage Sites ◽  
Protein Ions

scholarly journals Boosting Self-interaction of Molecular Vibrations under Ultra-strong Coupling Condition

2021 ◽  
Author(s):  
Akhila Kadyan ◽  
Anil Shaji ◽  
Jino George
Keyword(s):  
Oscillator Strength ◽  
Strong Coupling ◽  
Cavity Mode ◽  
Linear Increase ◽  
Vacuum Field ◽  
New Paradigm ◽  
Coupling Condition ◽  
Field Coupling ◽  
Fabry Perot ◽  
Set Up

In this letter, we investigated the modification of oscillator strength of an asymmetric stretching band of CS<sub>2</sub> by strong coupling to an infrared cavity photon. This is achieved by placing liquid CS<sub>2</sub> in a Fabry-Perot resonator and tune the cavity mode position to match with the molecular vibrational transition. Ultra-strong coupling improves the self-interaction of transition dipoles of asymmetric stretching band of CS<sub>2</sub> that resulted in an increase of its own oscillator strength. We experimentally proved this by taking the area ratio of asymmetric stretching and combination band by selectively coupling the former one. A non-linear increase in the oscillator strength of the asymmetric stretching band is observed upon varying the coupling strength. This is explained by a quantum mechanical model that predicts quadratic behavior under ultra-strong coupling condition. These findings will set up a new paradigm for understanding chemical reaction modification by vacuum field coupling.

Opaque atoms turn transparent in the vacuum field of an optical cavity

Physics Today ◽  
2011 ◽  
Vol 64 (11) ◽  
pp. 14-16 ◽  
Author(s):  
R. Mark Wilson
Keyword(s):  
Optical Cavity ◽  
Vacuum Field

Phase-sensitive reflection of squeezed vacuum field in optical cavity

2012 ◽  
Vol 10 (9) ◽  
pp. 091901-91904
Author(s):  
Ke Di Ke Di ◽  
Xudong Yu Xudong Yu ◽  
Fengyu Cheng Fengyu Cheng ◽  
Jing Zhang Jing Zhang
Keyword(s):  
Optical Cavity ◽  
Vacuum Field ◽  
Squeezed Vacuum ◽  
Phase Sensitive

Free-radical anti-Markovnikov hydroalkylation of unactivated alkenes with simple alkanes

2018 ◽  
Vol 20 (15) ◽  
pp. 3432-3435 ◽  
Author(s):  
Yunfei Tian ◽  
Anbo Ling ◽  
Ren Fang ◽  
Ren Xiang Tan ◽  
Zhong-Quan Liu
Keyword(s):  
Free Radical ◽  
Functional Group ◽  
Bond Cleavage ◽  
Site Selectivity ◽  
High Site

A Cu(ii)-mediated radical anti-Markovnikov hydroalkylation of unactivated alkenes with simple alkanes via selective C(sp3)–H bond cleavage was achieved. This reaction features high site-selectivity, diverse functional group tolerance, and scalability.

scholarly journals Strong coupling between chlorosomes of photosynthetic bacteria and a confined optical cavity mode

2014 ◽  
Vol 5 (1) ◽  
Author(s):  
David M. Coles ◽  
Yanshen Yang ◽  
Yaya Wang ◽  
Richard T. Grant ◽  
Robert A. Taylor ◽  
...  
Keyword(s):  
Strong Coupling ◽  
Photosynthetic Bacteria ◽  
Cavity Mode ◽  
Optical Cavity
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