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, 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 kT-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.
When a solute molecule is placed in solution, is it acceptable to presume that its electronic structure is essentially the same as that in the gas phase? In this paper, we address this question from a simulation perspective for the case of the sodium dimer cation (Na2 +) molecule in both liquid Ar and liquid tetrahydrofuran (THF). In previous work, we showed that, when local specific interactions between a solute and solvent are energetically on the order of a hydrogen bond, the solvent can become part of the chemical identity of the solute. Here, using mixed quantum/classical molecular dynamics simulations, we see that, for the Na2 + molecule, solute–solvent interactions lead to two stable, chemically distinct coordination states (Na(THF)4–Na(THF)5 + and Na(THF)5–Na(THF)5 +) that are not only stable themselves as gas-phase molecules but that also have a completely new electronic structure with important implications for the excited-state photodissociation of this molecule in the condensed phase. Furthermore, we show through a set of comparative classical simulations that treating the solute’s bonding electron explicitly quantum mechanically is necessary to understand both the ground-state dynamics and chemical identity of this simple diatomic molecule; even use of the quantum-derived potential of mean force is insufficient to describe the behavior of the molecule classically. Finally, we calculate the results of a proposed transient hole-burning experiment that could be used to spectroscopically disentangle the presence of the different coordination states.
In the gas phase, potential energy surfaces can be used to provide insight into the details of photochemical reaction dynamics. In solution, however, it is unclear what potential energy surfaces, if any, can be used to describe even simple chemical reactions such as the photodissociation of a diatomic solute. In this paper, we use mixed quantum/classical (MQC) molecular dynamics (MD) to study the photodissociation of Na 2 + in both liquid Ar and liquid tetrahydrofuran (THF). We examine both the gas-phase potential surfaces and potentials of mean force (PMF), which assume that the solvent remains at equilibrium with the solute throughout the photodissociation process and show that neither resemble a nonequilibrium dynamical energy surface that is generated by taking the time integral of work. For the photodissociation of Na 2 + in liquid Ar, the dynamical energy surface shows clear signatures of solvent caging, and the degree of caging is directly related to the mass of the solvent atoms. For Na 2 + in liquid THF, local specific interactions between the solute and solvent lead to changes in chemical identity that create a kinetic trap that effectively prevents the molecule from dissociating. The results show that nonequilibrium effects play an important role even in simple solution-phase reactions, requiring the use of dynamical energy surface to understand such chemical events.
In solution-phase chemistry, the solvent is often considered to be merely a medium that allows reacting solutes to encounter each other. In this work, however, we show that moderate locally specific solute–solvent interactions can affect not only the nature of the solute but also the types of reactive chemistry. We use quantum simulation methods to explore how solvent participation in solute chemical identity alters reactions involving the breaking of chemical bonds. In particular, we explore the photoexcitation dynamics of Na2 + dissolved in liquid tetrahydrofuran. In the gas phase, excitation of Na2 + directly leads to dissociation, but in solution, photoexcitation leads to an isomerization reaction involving rearrangement of the first-shell solvent molecules; this isomerization must go to completion before the solute can dissociate. Despite the complexity, the solution-phase reaction dynamics can be captured by a two-dimensional energy surface where one dimension involves only the isomerization of the first-shell solvent molecules.
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