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Why do some reactions possess similar reaction rate in wildly different viscous media? A possible explanation via frequency-dependent friction

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Abstract

We explore herein the interconnection between the collective intermolecular solvent modes (CIM) and ultrafast reaction rate, assuming that frequency-dependent solvent friction controls the rate of such reactions. We attempt to find a possible explanation for the observed near-insensitivity of ultrafast reaction rates (for example, charge transfer reaction) to the medium viscosity. Results are presented here by employing an analytical scheme that estimates the high-frequency solvent frictional response. Representative room temperature reaction media considered here are an ionic liquid (BMIMPF6, \(\eta \sim 310\mathrm{ cP}\)), a dipolar solvent (ethanol, \(\eta \sim 1.09\mathrm{ cP}\)) and a deep eutectic solvent (Acetamide+ LiBr, \(\eta \sim 1950\mathrm{ cP}\)). It is found that the wavenumber and frequency-dependent rotational friction, \({\Gamma }_{R}(\kappa ,z)\), estimated by using the available experimental dielectric relaxation (DR) data for the ionic liquid and the deep eutectic solvent (DES), cannot predict the viscosity independence of \({\Gamma }_{R}(\kappa ,z)\) at high frequency. Missing dispersion in the DR data of the DES appears to be critical and incorporation of this missing amplitude via collective solvent intermolecular modes centered around 100 cm-1 markedly improves the high-frequency behaviour of \({\Gamma }_{R}\left(\kappa ,z\right).\) Subsequently, the calculated \({\Gamma }_{R}(\kappa ,z)\) for these solvents at high frequency exhibits near-insensitivity to medium viscosity and explain the viscosity independence of ultrafast reaction rates.

Graphical abstract

Comparison of the frequency dependent rotational friction among three different solvent systems considered – normal liquid (ethanol), deep eutectic solvent (acetamide/LiBr) and ionic liquid ([BMIM][BF6]). Note the high frequency friction values for these solvents are very similar, although their zero frequency values differ quite considerably because of widely different viscosities.

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  1. Department of Chemical, Biological and Macromolecular Sciences, S. N. Bose National Centre for Basic Sciences, JD Block, Sector-III, Salt Lake, Kolkata, 700106, India

    ATANU BAKSI & RANJIT BISWAS

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BAKSI, A., BISWAS, R. Why do some reactions possess similar reaction rate in wildly different viscous media? A possible explanation via frequency-dependent friction. J Chem Sci 134, 51 (2022). https://doi.org/10.1007/s12039-022-02045-1

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