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Solvents can control solute molecular identity

Nature Chemistry volume 10, pages 910–916 (2018)Cite this article

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Abstract

For solution-phase chemical reactions, the solvent is often considered simply as a medium to allow the reactants to encounter each other by diffusion. Although examples of direct solvent effects on molecular solutes exist, such as the compression of solute bonding electrons due to Pauli repulsion interactions, the solvent is not usually considered a part of the chemical species of interest. We show, using quantum simulations of Na2, that when there are local specific interactions between a solute and solvent that are energetically on the same order as a hydrogen bond, the solvent controls not only the bond dynamics but also the chemical identity of the solute. In tetrahydrofuran, dative bonding interactions between the solvent and Na atoms lead to unique coordination states that must cross a free energy barrier of ~8 kBT—undergoing a chemical reaction—to interconvert. Each coordination state has its own dynamics and spectroscopic signatures, highlighting the importance of considering the solvent in the identity of condensed-phase chemical systems.

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Fig. 1: Representative simulation snapshots of Na2 reveal deformation of the bonding electronic density in the condensed phase.
Fig. 2: Pair distribution function g(r), showing chelation of the Na+ cores in Na2 by THF, leading to the formation of metal–oxygen dative bonds.
Fig. 3: The stable coordination states of Na2 in liquid THF behave as distinct molecules.
Fig. 4: Different potentials of mean force for the Na2 molecule with different local solvent coordination in liquid THF.
Fig. 5: Different Na2 coordination states are spectroscopically distinct.

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Acknowledgements

Early portions of this work were supported by the National Science Foundation (grant CHE-1565434). Beginning in September 2017, this work was supported by the US Department of Energy Condensed Phase and Interfacial Molecular Science programme (grant 0000228903). The authors acknowledge the Institute for Digital Research and Education (IDRE) at UCLA for use of the hoffman2 computing cluster, B. Taggart for assistance setting up the simulations, and W. Glover and C.-C. Zhou for discussions.

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  1. Department of Chemistry & Biochemistry, University of California, Los Angeles, Los Angeles, CA, USA

    Devon. R. Widmer & Benjamin J. Schwartz

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The work described in this text was completed by D.R.W. under the supervision of B.J.S.

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Correspondence to Devon. R. Widmer or Benjamin J. Schwartz.

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Widmer, D.R., Schwartz, B.J. Solvents can control solute molecular identity. Nature Chem 10, 910–916 (2018). https://doi.org/10.1038/s41557-018-0066-z

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