Solvents can control solute molecular identity

Widmer, Devon. R.; Schwartz, Benjamin J.

doi:10.1038/s41557-018-0066-z

Title: Solvents can control solute molecular identity

Journal Article · 21 May 2018 · Nature Chemistry

DOI: https://doi.org/10.1038/s41557-018-0066-z · OSTI ID:1480533

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Univ. of California, Los Angeles, CA (United States)

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 k_BT—undergoing a chemical reaction—to interconvert. In conclusion, 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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Research Organization:: Univ. of California, Los Angeles, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences, and Biosciences Division

Grant/Contract Number:: SC0017800

OSTI ID:: 1480533

Journal Information:: Nature Chemistry, Vol. 10, Issue 9; ISSN 1755-4330

Publisher:: Nature Publishing GroupCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 26 works

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