Virtual Issue on Proton Transfer

Hammes‐Schiffer, Sharon

doi:10.1021/acs.jpcb.1c01929

Cited by 11 publications

(14 citation statements)

References 35 publications

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“…Proton transfer reactions are essential in many chemical and biological systems due to their key roles in energy conversion processes . The ability to control the rate of proton transfer reactions can potentially have a large impact on technological advances such as the design of fuel cells as well as electrochemical and solar energy harvesting devices.…”

Section: Introductionmentioning

confidence: 99%

“…Proton transfer reactions are essential in many chemical and biological systems due to their key roles in energy conversion processes. 1 The ability to control the rate of proton transfer reactions can potentially have a large impact on technological advances such as the design of fuel cells as well as electrochemical and solar energy harvesting devices. For instance, strong light-matter interactions created by quantum fluctuations or external pumping in optical or nanoplasmonic cavities offer a promising route to modulate reaction rates of chemical reactions in a nonintrusive way.…”

Section: ■ Introductionmentioning

confidence: 99%

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Cavity-Modulated Proton Transfer Reactions

2022

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Proton transfer is ubiquitous in many fundamental chemical and biological processes, and the ability to modulate and control the proton transfer rate would have a major impact on numerous quantum technological advances. One possibility to modulate the reaction rate of proton transfer processes is given by exploiting the strong light-matter coupling of chemical systems inside optical or nanoplasmonic cavities. In this work, we investigate the proton transfer reactions in the prototype malonaldehyde and Z-3-amino-propenal (aminopropenal) molecules using different quantum electrodynamics methods, in particular, quantum electrodynamics coupled cluster theory and quantum electrodynamical density functional theory. Depending on the cavity mode polarization direction, we show that the optical cavity can increase the reaction energy barrier by 10–20% or decrease the reaction barrier by ∼5%. By using first-principles methods, this work establishes strong light-matter coupling as a viable and practical route to alter and catalyze proton transfer reactions.

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Section: Introductionmentioning

confidence: 99%

Section: ■ Introductionmentioning

confidence: 99%

Cavity-Modulated Proton Transfer Reactions

2022

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“…Proton transfer belongs to the most important elementary reactions taking part in various chemical, biochemical, and biological processes. − To elucidate the precise mechanisms of proton-transfer reactions, i.e., possible intermediates such as contact ion pairs and rate constants of the individual steps, so-called photoacids have proven particularly powerful tools. − These photoacids are molecules that exhibit an acidity increase, i.e., a decrease in p K a , upon electronic excitation, which can trigger an excited-state proton transfer (ESPT) to a suitable proton acceptor. , Due to limited acid strengths, the use of most photoacids was restricted to the study of ESPT in water or aqueous solutions containing either an additional base or a cosolvent. − Only special photoacids, referred to as superphotoacids, are particularly strong and exhibit in water negative p K a values in the excited state, − which often also allows them to perform an ESPT in neat protic − or even aprotic solvents. − …”

Section: Introductionmentioning

confidence: 99%

Theoretical Study on the Photoacidity of Hydroxypyrene Derivatives in DMSO Using ADC(2) and CC2

Sülzner

Hättig

2022

J. Phys. Chem. A

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This work applies the thermodynamic Förster cycle to theoretically investigate the pK a *, i.e., excited-state pK a values of pyranine-derived superphotoacids developed by Jung and co-workers. The latter photoacids are strong enough to transfer a proton to the aprotic solvent dimethyl sulfoxide (DMSO). The Förster cycle provides access to pK a * via the ground-state pK a and the electronic excitation energies. We use the conductor-like screening model for real solvents (COSMO-RS) to compute the ground-state pK a and the correlated wavefunction-based methods ADC(2) and CC2 with the continuum solvation model COSMO to calculate the pK a change upon excitation. A comparison of the calculated UV/Vis absorption and fluorescence emission energies to the experimental results leads us to infer that this approach allows for a proper description of the electronic excitations. In particular, implicit solvation by means of the COSMO model appears to be sufficient for the treatment of these photoacids in DMSO. The calculations confirm the presumption that a charge redistribution from the hydroxy group to the aromatic ring and the electron-withdrawing substituents is the origin of photoacidity for these photoacids. Moreover, the calculations with the continuum solvation model predict that the pK a jump upon excitation decreases with increasing solvent polarity, as rationalized based on the Förster cycle.

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“…Proton transfer is ubiquitous in chemistry and related fields. 1 Among countless examples, its involvement in catalytic 2 and enzymatic 3 reactions or the energy storage using fuel cells 4 are perhaps most noticeable at present. Reflecting this overall high importance, much work has been invested for a long time into the investigation of protontransfer reactions in general, 5 and the determination of pK a values or their associated acid dissociation constants in particular.…”

Section: Introductionmentioning

confidence: 99%

“…Proton transfer is ubiquitous in chemistry and related fields 1 . Among countless examples, its involvement in catalytic 2 and enzymatic 3 reactions or the energy storage using fuel cells 4 are perhaps most noticeable at present.…”

Section: Introductionmentioning

confidence: 99%

Prediction of acid pK_a values in the solvent acetone based on COSMO‐RS

et al. 2022

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In this contribution we extent the use of the conductor-like screening model for realistic solvation (COSMO-RS) to the prediction of pK a values in acetone, a commonly used dipolar aprotic solvent. For this, we calculated the Gibbs free energy of dissociation of 120 organic acids (nine acrylic acids, 87 benzoic acids, nine phenols, and 15 benzenesulfonamides) using COSMO-RS at the two levels BP-TZVP and BP-

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Virtual Issue on Proton Transfer

Cited by 11 publications

References 35 publications

Cavity-Modulated Proton Transfer Reactions

Cavity-Modulated Proton Transfer Reactions

Theoretical Study on the Photoacidity of Hydroxypyrene Derivatives in DMSO Using ADC(2) and CC2

Prediction of acid pK_a values in the solvent acetone based on COSMO‐RS

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Virtual Issue on Proton Transfer

Cited by 11 publications

References 35 publications

Cavity-Modulated Proton Transfer Reactions

Cavity-Modulated Proton Transfer Reactions

Theoretical Study on the Photoacidity of Hydroxypyrene Derivatives in DMSO Using ADC(2) and CC2

Prediction of acid pKa values in the solvent acetone based on COSMO‐RS

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Product

Resources

About

Prediction of acid pK_a values in the solvent acetone based on COSMO‐RS