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Title: Solvents can control solute molecular identity

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 Na 2, 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.

Authors:
ORCiD logo [1]; ORCiD logo [1]
  1. Univ. of California, Los Angeles, CA (United States)
Publication Date:
Research Org.:
Univ. of California, Los Angeles, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Chemical Sciences, Geosciences & Biosciences Division
OSTI Identifier:
1480533
Grant/Contract Number:  
[SC0017800]
Resource Type:
Accepted Manuscript
Journal Name:
Nature Chemistry
Additional Journal Information:
[ Journal Volume: 10; Journal Issue: 9]; Journal ID: ISSN 1755-4330
Publisher:
Nature Publishing Group
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Quantum MD Simulation; Solvent Effects on Chemical Reactivity

Citation Formats

Widmer, Devon. R., and Schwartz, Benjamin J. Solvents can control solute molecular identity. United States: N. p., 2018. Web. doi:10.1038/s41557-018-0066-z.
Widmer, Devon. R., & Schwartz, Benjamin J. Solvents can control solute molecular identity. United States. doi:10.1038/s41557-018-0066-z.
Widmer, Devon. R., and Schwartz, Benjamin J. Mon . "Solvents can control solute molecular identity". United States. doi:10.1038/s41557-018-0066-z. https://www.osti.gov/servlets/purl/1480533.
@article{osti_1480533,
title = {Solvents can control solute molecular identity},
author = {Widmer, Devon. R. and Schwartz, Benjamin J.},
abstractNote = {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. 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.},
doi = {10.1038/s41557-018-0066-z},
journal = {Nature Chemistry},
number = [9],
volume = [10],
place = {United States},
year = {2018},
month = {5}
}

Journal Article:
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Cited by: 6 works
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Figures / Tables:

Table 1 Table 1: Average bond length (re), vibrational frequency (ωe), and instantaneous dipole moment (µ) for Na2 in the gas phase and in various solution environments. re and ωe values for our work were obtained from Harmonic fits to the well bottom of the potential energy surface (gas phase) or potentialmore » of mean force (solution phase); cf. Fig. 4, below. The post-Hartree-Fock gas phase fixed-point calculations were performed using coupled-cluster with singles, doubles and perturbative (linearized) triples [CCSD(T)] with the 6-311+G(d,p) basis set using GAUSSIAN 09. The gas-phase values calculated with our plane-wave-based CISD method give good agreement with theory at a similar level using more standard basis sets. The quoted errors are the standard deviations calculated from the non-linear least-squares fit.« less

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