Vacuum-Field Catalysis: Accelerated Reactions by Vibrational Ultra Strong Coupling

In conventional catalysis, the reactants interact with specific sites of the catalyst in such a way that the reaction barrier is lowered by changing the reaction path, causing the reaction rate to be accelerated. Here we take a radically different approach to catalysis by ultra-strongly coupling the vibrations of the reactants to the infrared vacuum electromagnetic field. To demonstrate the possibility of such vacuum-field catalysis (or cavity catalysis), we have studied hydrolysis reactions under the vibrational ultra strong coupling (V-USC) of the OH stretching mode of water to a Fabry-Pérot microfluidic cavity mode. This results in a giant Rabi splitting energy (92 meV), indicating the system is in the V-USC regime. We have found that V-USC water enhances the hydrolysis reaction rate of cyanate ions by 102-fold and that of ammonia borane by 104-fold. This catalytic ability is found to depend upon the coupling ratio of the vibrational light-matter interaction. Given the vital importance of water for life and human activities, we expect that our finding not only offers an unconventional way of controlling chemical reactions by vacuum-field catalysis but also brings a fresh perspective to science and technology.

Vacuum-Field Catalysis: Accelerated Reactions by Vibrational Ultra Strong Coupling

10.26434/chemrxiv.7234721 ◽

2019 ◽

Cited By ~ 1

Author(s):

Hidefumi Hiura ◽

Atef Shalabney ◽

Jino George

Keyword(s):

Strong Coupling ◽

Reaction Rate ◽

Cavity Mode ◽

Reaction Path ◽

Vacuum Field ◽

Coupling Ratio ◽

Fabry Perot ◽

Fresh Perspective ◽

In conventional catalysis, the reactants interact with specific sites of the catalyst in such a way that the reaction barrier is lowered by changing the reaction path, causing the reaction rate to be accelerated. Here we take a radically different approach to catalysis by ultra-strongly coupling the vibrations of the reactants to the infrared vacuum electromagnetic field. To demonstrate the possibility of such vacuum-field catalysis (or cavity catalysis), we have studied hydrolysis reactions under the vibrational ultra strong coupling (V-USC) of the OH stretching mode of water to a Fabry-Pérot microfluidic cavity mode. This results in a giant Rabi splitting energy (92 meV), indicating the system is in the V-USC regime. We have found that V-USC water enhances the hydrolysis reaction rate of cyanate ions by 102-fold and that of ammonia borane by 104-fold. This catalytic ability is found to depend upon the coupling ratio of the vibrational light-matter interaction. Given the vital importance of water for life and human activities, we expect that our finding not only offers an unconventional way of controlling chemical reactions by vacuum-field catalysis but also brings a fresh perspective to science and technology.

Cavity Catalysis ‒Accelerating Reactions under Vibrational Strong Coupling‒

10.26434/chemrxiv.7234721.v3 ◽

2018 ◽

Cited By ~ 8

Author(s):

Hidefumi Hiura ◽

Atef Shalabney ◽

Jino George

Keyword(s):

Electromagnetic Field ◽

Strong Coupling ◽

Chemical Reactions ◽

Reaction Rate ◽

Cavity Mode ◽

Coupling Ratio ◽

Strong Light ◽

Rabi Splitting ◽

Fabry Perot ◽

In conventional catalysis the reactants interact with specific sites of the catalyst in such a way that the reaction barrier is lowered and the reaction rate is accelerated. Here we take a radically different approach to catalysis by strongly coupling the vibrations of the reactants to the vacuum electromagnetic field of a cavity. To demonstrate the possibility of such cavity catalysis, we have studied hydrolysis reactions under strong coupling of the OH stretching mode of water to a Fabry-Pérot (FP) microfluidic cavity mode. This results in an exceptionally large Rabi splitting energy ℏΩR of 92 meV (740 cm−1), indicating the system is in vibrational ultra-strong coupling (V-USC) regime and we have found that it enhances the hydrolysis reaction rate of cyanate ions by 102 times and that of ammonia borane by 104 times. This catalytic ability is shown to depend only upon the cavity tuning and the coupling ratio. Given the vital importance of water for life and human activities, we expect our finding not only offers an unconventional way of controlling chemical reactions by ultra-strong light-matter interactions, but also changes the landscape of chemistry in a fundamental way.

Cavity Catalysis ‒Accelerating Reactions under Vibrational Strong Coupling‒

10.26434/chemrxiv.7234721.v2 ◽

2018 ◽

Cited By ~ 2

Author(s):

Hidefumi Hiura ◽

Atef Shalabney ◽

Jino George

Keyword(s):

Electromagnetic Field ◽

Strong Coupling ◽

Chemical Reactions ◽

Reaction Rate ◽

Cavity Mode ◽

Coupling Ratio ◽

Strong Light ◽

Rabi Splitting ◽

Fabry Perot ◽

In conventional catalysis the reactants interact with specific sites of the catalyst in such a way that the reaction barrier is lowered and the reaction rate is accelerated. Here we take a radically different approach to catalysis by strongly coupling the vibrations of the reactants to the vacuum electromagnetic field of a cavity. To demonstrate the possibility of such cavity catalysis, we have studied hydrolysis reactions under strong coupling of the OH stretching mode of water to a Fabry-Pérot (FP) microfluidic cavity mode. This results in an exceptionally large Rabi splitting energy ℏΩR of 92 meV (740 cm−1), indicating the system is in vibrational ultra-strong coupling (V-USC) regime and we have found that it enhances the hydrolysis reaction rate of cyanate ions by 102 times and that of ammonia borane by 104 times. This catalytic ability is shown to depend only upon the cavity tuning and the coupling ratio. Given the vital importance of water for life and human activities, we expect our finding not only offers an unconventional way of controlling chemical reactions by ultra-strong light-matter interactions, but also changes the landscape of chemistry in a fundamental way.

Cavity Catalysis ‒Accelerating Reactions under Vibrational Strong Coupling‒

10.26434/chemrxiv.7234721.v1 ◽

2018 ◽

Cited By ~ 2

Author(s):

Hidefumi Hiura ◽

Atef Shalabney ◽

Jino George

Keyword(s):

Electromagnetic Field ◽

Strong Coupling ◽

Chemical Reactions ◽

Reaction Rate ◽

Cavity Mode ◽

Coupling Ratio ◽

Strong Light ◽

Rabi Splitting ◽

Fabry Perot ◽

In conventional catalysis the reactants interact with specific sites of the catalyst in such a way that the reaction barrier is lowered and the reaction rate is accelerated. Here we take a radically different approach to catalysis by strongly coupling the vibrations of the reactants to the vacuum electromagnetic field of a cavity. To demonstrate the possibility of such cavity catalysis, we have studied hydrolysis reactions under strong coupling of the OH stretching mode of water to a Fabry-Pérot (FP) microfluidic cavity mode. This results in an exceptionally large Rabi splitting energy ℏΩR of 92 meV (740 cm−1), indicating the system is in vibrational ultra-strong coupling (V-USC) regime and we have found that it enhances the hydrolysis reaction rate of cyanate ions by 102 times and that of ammonia borane by 104 times. This catalytic ability is shown to depend only upon the cavity tuning and the coupling ratio. Given the vital importance of water for life and human activities, we expect our finding not only offers an unconventional way of controlling chemical reactions by ultra-strong light-matter interactions, but also changes the landscape of chemistry in a fundamental way.

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

10.26434/chemrxiv.14060636 ◽

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 CS2 by strong coupling to an infrared cavity photon. This is achieved by placing liquid CS2 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 CS2 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.

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

10.26434/chemrxiv.14060636.v1 ◽

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 CS2 by strong coupling to an infrared cavity photon. This is achieved by placing liquid CS2 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 CS2 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.

Vibrational Ultra Strong Coupling of Water and Ice

10.26434/chemrxiv.9808508.v1 ◽

2019 ◽

Author(s):

Hidefumi Hiura ◽

Atef Shalabney ◽

Jino George

Keyword(s):

Hydrogen Bonding ◽

Strong Coupling ◽

Vibrational Energy ◽

Molecular Structures ◽

Strong Light ◽

Rabi Splitting ◽

New Findings ◽

Fabry Perot ◽

Vibrational Energies

Water is of vital importance for life and human activities on Earth—it exhibits unique properties due to its interlinked and multipoint hydrogen bonding network. Here, we experimentally show that water can undergo vibrational ultra strong coupling (V-USC) in both the liquid and solid forms when the OH stretching mode of water or ice is resonantly coupled with an optical mode of an infrared Fabry−Pérot cavity. The light-coupled H2O under V-USC reveals the largest Rabi splitting ever reported, reaching 22% and 26% of the vibrational energy for water and ice, respectively. We confirm that the extraordinarily large Rabi splitting stems from the densely packed minuscule molecular structures, large vibrational energies, and broad and intense absorptions due to intermolecular hydrogen bonding. These new findings offer a brand-new platform in polaritonic chemistry for controlling the properties of water with an ultra strong light-matter interaction.

Cavity Catalysis by Co-operative Vibrational Strong Coupling of Reactant and Solvent Molecules

10.26434/chemrxiv.7531544.v1 ◽

2018 ◽

Author(s):

Jyoti Lather ◽

Pooja Bhatt ◽

Anoop Thomas ◽

Thomas W. Ebbesen ◽

Jino George

Keyword(s):

Strong Coupling ◽

Reaction Rate ◽

Coupling Effect ◽

Cavity Resonance ◽

New Frontier ◽

Fabry Perot ◽

Strong Coupling Effect ◽

Order Of Magnitude ◽

Solvent Molecules ◽

Exponential Relation

para-nitrophenyl acetate hydrolysis is studied under vibrational strong coupling in a Fabry-Perot cavity. By tuning the cavity resonance to the C=O vibrational stretching mode of both the reactant and solvent molecules, it is found that the reaction is accelerated by an order of magnitude. It is shown that this cavity catalysis involves a co-operative strong coupling effect between the solvent and reactant molecules. The reaction rate follows an exponential relation with respect to the solvent coupling strength. The combination of co-operative effects and cavity catalysis confirms the potential of VSC as a new frontier in chemistry.

Vibrational Ultra Strong Coupling of Water and Ice

10.26434/chemrxiv.9808508 ◽

2019 ◽

Cited By ~ 1

Author(s):

Hidefumi Hiura ◽

Atef Shalabney ◽

Jino George

Keyword(s):

Hydrogen Bonding ◽

Strong Coupling ◽

Vibrational Energy ◽

Molecular Structures ◽

Strong Light ◽

Rabi Splitting ◽

New Findings ◽

Fabry Perot ◽

Vibrational Energies

Water is of vital importance for life and human activities on Earth—it exhibits unique properties due to its interlinked and multipoint hydrogen bonding network. Here, we experimentally show that water can undergo vibrational ultra strong coupling (V-USC) in both the liquid and solid forms when the OH stretching mode of water or ice is resonantly coupled with an optical mode of an infrared Fabry−Pérot cavity. The light-coupled H2O under V-USC reveals the largest Rabi splitting ever reported, reaching 22% and 26% of the vibrational energy for water and ice, respectively. We confirm that the extraordinarily large Rabi splitting stems from the densely packed minuscule molecular structures, large vibrational energies, and broad and intense absorptions due to intermolecular hydrogen bonding. These new findings offer a brand-new platform in polaritonic chemistry for controlling the properties of water with an ultra strong light-matter interaction.