Solvent Dependence on Cooperative Vibrational Strong Coupling and Cavity Catalysis**

Singh, Jaibir; Lather, Jyoti; George, Jino

doi:10.1002/cphc.202300016

Cited by 11 publications

(21 citation statements)

References 64 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Such a trend in temperature sensitivity has been widely observed in experiments. 14,15,18 At the catalyzing frequency ω c = 461 cm −1 , on the other hand, there is almost no change in enthalpy, but there is a noticeable change in entropy, suggesting that the mechanism dominating here is not related to the experiments which typically showed a clear change in enthalpy. It is important to emphasize that utilization of the Eyring equation is especially problematic in this domain as a further increase in reaction speed implies that the trajectory will spend less time around the reactant well.…”

Section: ■ Results and Discussionmentioning

confidence: 83%

“…The latter is essential for investigating potential modification of solvation dynamics induced by strong coupling. 18,88,90 Polaritonic chemistry remains an equally fascinating and puzzling domain of research. While major questions are yet to be answered, [2][3][4]6 especially the connection between local chemistry and collective coupling as well as the interplay with solvation, the continuous growth of theoretical methodology and additional experiments draw an optimistic picture for the future of polaritonics.…”

Section: ■ Conclusionmentioning

confidence: 99%

See 1 more Smart Citation

Machine Learning for Polaritonic Chemistry: Accessing Chemical Kinetics

Schäfer,

Fojt,

Lindgren

et al. 2024

J. Am. Chem. Soc.

View full text Add to dashboard Cite

Altering chemical reactivity and material structure in confined optical environments is on the rise, and yet, a conclusive understanding of the microscopic mechanisms remains elusive. This originates mostly from the fact that accurately predicting vibrational and reactive dynamics for soluted ensembles of realistic molecules is no small endeavor, and adding (collective) strong light−matter interaction does not simplify matters. Here, we establish a framework based on a combination of machine learning (ML) models, trained using density-functional theory calculations and molecular dynamics to accelerate such simulations. We then apply this approach to evaluate strong coupling, changes in reaction rate constant, and their influence on enthalpy and entropy for the deprotection reaction of 1-phenyl-2trimethylsilylacetylene, which has been studied previously both experimentally and using ab initio simulations. While we find qualitative agreement with critical experimental observations, especially with regard to the changes in kinetics, we also find differences in comparison with previous theoretical predictions. The features for which the ML-accelerated and ab initio simulations agree show the experimentally estimated kinetic behavior. Conflicting features indicate that a contribution of dynamic electronic polarization to the reaction process is more relevant than currently believed. Our work demonstrates the practical use of ML for polaritonic chemistry, discusses limitations of common approximations, and paves the way for a more holistic description of polaritonic chemistry.

show abstract

Section: ■ Results and Discussionmentioning

confidence: 83%

Section: ■ Conclusionmentioning

confidence: 99%

Machine Learning for Polaritonic Chemistry: Accessing Chemical Kinetics

Schäfer,

Fojt,

Lindgren

et al. 2024

J. Am. Chem. Soc.

View full text Add to dashboard Cite

show abstract

“…For example, their spectral absorption and emission can be altered by their interplay with the solvent (solvatochromic) or by the close proximity to identical molecules (concentration-dependent). Experiments under strong coupling often use organic molecules that are sensitive to their surroundings, show intense excitations, or even form aggregates. − ,− The chemical environment can then play an active role and exert significant influence, as emphasized by several vibrational strong coupling (VSC) experiments showing modification of assembly − and reactivity. ,, For a clear chemical understanding of polaritonic processes, we must then investigate the coexisting roles of the molecule, the solvent (chemical environment), and the cavity (optical environment). To this end, ab initio quantum electrodynamics (QED) merges the knowledge of quantum optics and quantum chemistry to explore single-molecule effects retaining the chemical complexity. − Even if collective states can show larger contributions from selected molecules, , local changes tend to reduce as a result of collective delocalization and an increasing number of quasi-dark states .…”

mentioning

confidence: 99%

Collective Strong Coupling Modifies Aggregation and Solvation

Castagnola,

Haugland,

Ronca

et al. 2024

J. Phys. Chem. Lett.

View full text Add to dashboard Cite

Intermolecular (Coulombic) interactions are pivotal for aggregation, solvation, and crystallization. We demonstrate that the collective strong coupling of several molecules to a single optical mode results in notable changes in the molecular excitations around a single perturbed molecule, thus representing an impurity in an otherwise ordered system. A competition between short-range coulombic and long-range photonic correlations inverts the local transition density in a polaritonic state, suggesting notable changes in the polarizability of the solvation shell. Our results provide an alternative perspective on recent work in polaritonic chemistry and pave the way for the rigorous treatment of cooperative effects in aggregation, solvation, and crystallization.

show abstract

“…One of the systems shows isokinetic behavior at room temperature, confirming the role of solvation effect modification under strong coupling. 33 Cavity catalysis is observed in many of the ester solvolysis experiments and is further correlated using kinetic and thermodynamic data.…”

Section: ■ Cooperative Vsc and Cavity Catalysismentioning

confidence: 94%