Gabin Yoon, Haegyeom Kim, Inchul Park, Kisuk Kang.Journal of Electroanalytical Chemistry 2017, 804, 107-115. Effects of electrolytes on redox potentials through ion pairing. Bird, Tomokazu Iyoda, Nicholas Bonura, Jin Bakalis, Abram J. Solvents can control solute molecular identity. Physical Chemistry Chemical Physics 2019, 21 Static and dynamic scavenging of ammoniated electrons by nitromethane. Nicolás Rivas, Germán Sciaini, Ernesto Marceca.Physical Chemistry Chemical Physics 2021, 23 Ground and excited states analysis of alkali metal ethylenediamine and crown ether complexes. The Journal of Physical Chemistry A 2011, 115 General Impossibility to “Prescribe” Diffusion for a Geminate Pair in a Central Force Field and Peculiarities of Geminate Dynamics in Ionic Liquids. Simulating the Formation of Sodium:Electron Tight-Contact Pairs: Watching the Solvation of Atoms in Liquids One Molecule at a Time. The Journal of Physical Chemistry B 2013, 117 Multielement NMR Studies of the Liquid–Liquid Phase Separation and the Metal-to-Nonmetal Transition in Fluid Lithium– and Sodium–Ammonia Solutions. Rees, Neil Spencer, Kiminori Maeda, Jeffrey R. Journal of Chemical Theory and Computation 2014, 10
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Free Energies of Quantum Particles: The Coupled-Perturbed Quantum Umbrella Sampling Method. The Journal of Physical Chemistry C 2016, 120 Multiply Reduced Oligofluorenes: Their Nature and Pairing with THF-Solvated Sodium Ions.
The Role of the Solvent in the Condensed-Phase Dynamics and Identity of Chemical Bonds: The Case of the Sodium Dimer Cation in THF. The Journal of Physical Chemistry Letters 2020, 11 Nonequilibrium Solvent Effects during Photodissociation in Liquids: Dynamical Energy Surfaces, Caging, and Chemical Identity. This article is cited by 14 publications. Thus, we can explain the kinetics of Na TCP formation as being dictated by changes in the Na + solvent coordination number, and we can understand the dependence on initial conditions seen in the solvation dynamics of this system as resulting from the fact that the important solvent coordinate involves the motion of only a few molecules in the first solvation shell. Taken together, our results suggest that the Na 0/THF species with different solvent coordination numbers may be viewed as chemically distinct. Furthermore, we find that species with different solvent coordination numbers have unique absorption spectra and that interconversion between species with different solvent coordination numbers requires surmounting a free energy barrier of several k B T. On average, four THF oxygens coordinate the cation end of the TCP however, we also observe fluctuations to other solvent coordination numbers.
We find that the driving force for the displacement of sodium’s valence electron is the formation of a tight solvation shell around the partially exposed Na +. Our simulations reproduce the experimental spectroscopy of this system and clearly indicate that neutral Na atoms exist as (Na +, e −) TCPs in solution. Our interest in this particular system stems from recent pump−probe experiments in our group, which found that the rate at which this species is solvated depends on how it was created ( Science 2008, 321, 1817) in other words, the solvation dynamics of this system do not obey linear response. Thus, to shed light on the nature of alkali atoms in solution and to further our understanding of condensed-phase effects on solutes’ electronic structure, we have performed mixed quantum/classical molecular dynamics simulations of sodium atoms in liquid tetrahydrofuran (Na 0/THF). The nature of solvated alkali atoms, however, remains controversial: the consensus view is that solvated alkali atoms exist as (Na +, e −) tight-contact pairs (TCPs), species in which the alkali valence electron is significantly displaced from the alkali nucleus and confined primarily by the first solvent shell. Of the various atomic species that can be formed in solution, the quasi-one-electron alkali atoms in ether solvents have been the most widely studied experimentally, primarily due to the convenient location of their absorption spectra at visible wavelengths. With no internal vibrational or rotational degrees of freedom, atomic solutes serve as the simplest possible probe of a condensed-phase environment’s influence on solute electronic structure.
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