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At least 685 records · Page 38
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DOE OSTI2024

Quantifying the Correlation between Coordination Chemistry, Interfacial Formation, and Electrochemical Performances for Mg Battery Electrolytes

Here, the rise of magnesium batteries as promising post-Li-ion energy storage technologies has sparked considerable attention toward understanding the fundamental aspects of coordination chemistry concerning Mg cations in multivalent electrolytes. This exploration includes investigating how coordination influences crucial electrolyte properties like solubility, electroreduction stability, and the formation of the interphase, all of which are pivotal for practical battery applications. Despite recent progress in developing a few functional electrolytes, a comprehensive understanding of the solvation structure that can facilitate efficient Mg deposition performance and the formulation of general design rules based on the solvation structure is still lacking. In our study, we endeavor to establish a connection between solvent and anion interactions with Mg 2+ , interface formation, and cycling performance through a series of organic ether solvents (tetrahydrofuran, glyme, diglyme, and triglyme) and amine solvents (dimethylamine, 3-methoxypropylamine, and dimethoxyethylamine). Our findings reveal a distinct coordination trend for solvent/Mg 2+ and (Mg-TFSI):solvent across various solvents, which dictates the extent of ion pairing for TFSI salts with increasing solvent molecule size and denticity. The solvated species in the bulk electrolyte across different solvents lead to diverse interfacial chemistries with varying decomposition components. We also explore the cycling efficiency as well as Mg deposition overpotentials for different solvents. A correlation analysis was conducted to assess the interplay between the structure and performance. Lastly, we apply the insights gained from these results to tailor the relative anion/Mg 2+ coordination structures using cosolvent systems, aiming for improved cell performance.

25 ENERGY STORAGE↗
DOE OSTI2024

Multiple Functional Bonds Integrated Interphases for Long Cycle Sodium-Ion Batteries

Sodium-ion batteries (SIBs) have garnered significant interest as one of the most promising energy suppliers for power grid energy storage. However, the poor electrode/electrolyte interfacial stability leads to continual electrolyte decomposition and transition metal dissolution, resulting in rapid performance degradation of SIBs. In this work, we propose a strategy integrating multiple functional bonds to regulate electrode/electrolyte interphase by triple-coupling of succinonitrile (SN), sodium hexafluorophosphate (NaPF 6 ) and fluorinated ethylene carbonate (FEC). Theoretical calculation and experiment results show that the solvation structure of Na + and ClO 4 – is effectively reconfigured by the solvated FEC, SN and PF 6 – in PC-based carbonate electrolyte. The newly developed electrolyte demonstrates increased Na + -FEC coordination, weakened interaction of Na + -PC and participation of SN and PF 6 – anions in solvation, resulting in the formation of a conformal interfacial layer comprising of sodium oxynitrides (NaN x O y ), sodium fluoride (NaF) and phosphorus oxide compounds (NaP x O y ). Consequently, a 3 Ah pouch full cell of hard carbon//NaNi 1/3 Fe 1/3 Mn 1/3 O 2 exhibits an excellent capacity retention of 90.4 % after 1000 cycles. Detailed postmortem analysis of interface chemistry is further illustrated by multiple characterization methods. Finally, this study provides a new avenue for developing electrolyte formulations with multiple functional bonds integrated interphases to significantly improve the long-term cycling stability of SIBs.

25 ENERGY STORAGE↗
DOE OSTI2024

Prediction of Redox Potentials for U, Np, Pu, and Am in Aqueous Solution

The redox properties of the actinides in aqueous solution are important for fuel production/reprocessing and understanding the environmental impact of nuclear waste. The redox potentials for U, Np, Pu, and Am in oxidation states from 0 up to VII (as appropriate) in aqueous solutions have been predicted at the density functional theory level with the B3LYP functional, Stuttgart small core pseudopotential basis sets for the actinides, and explicit (30H 2 O molecules)/implicit treatment of the aqueous solvent using the self-consistent reaction field COSMO and SMD approaches for the implicit solvation. The predictions of the structural parameters of clusters incorporating first and second solvation shells are consistent with the available experimental data., Our results are typically within 0.2 V of the available experimental data using two explicit solvation shells with an implicit solvent model. The use of the PW91 functional substantially improved the prediction of the Pu(VI/V) redox couple. The redox couples for An(VI/IV) and An(V/IV) which involve the addition of protons and removal of the actinyl oxygens led to slightly larger differences from experiment. Here, the An(IV/0) and An(III/0) couples were reliably predicted with our approach. Predictions of the unknown An(II/I) redox potentials were negative, consistent with expectations, and predictions for unknown An(VII/VI), An(III/II), and An(II/0) redox couples improve prior estimates.

Actinides↗
DOE OSTI2025

Effect of Solvents on Lignin–Surface Interactions via Molecular Dynamics Simulations

Lignin, an essential building block of lignocellulosic biomass, is a potential abundant source of aromatic monomers for the polymer and chemical industry. Reductive catalytic fractionation (RCF) is one promising process that can produce high yields of phenolic monomers and oligomers from lignin under different catalytic conditions. An important choice in optimizing RCF is the selection of solvent; however, detailed insights into solvent effects on lignin behaviors and interactions remain limited. Here, in this work, we perform all-atom molecular dynamics simulations to study the solvation of lignin, solvent-mediated conformational changes, and the interaction of solvated lignin oligomers with model surfaces. We focus on the behavior of an oligomeric lignin model compound in methanol, ethanol, a binary mixture of ethanol and water, and water at both the RCF reaction temperature (473 K) and room temperature. Analysis of structural features of lignin suggests that these three organic solvent systems favorably solvate lignin, resulting in a more extended conformation suitable for catalytic conversion to valuable chemicals. We further introduce model palladium (Pd) and carbon (C) surfaces to understand how solvent choice impacts adsorption onto a representative catalytic surface and support, and to quantify the competition among the reactant and solvent molecules for the surface. Unbiased simulations suggest strong adsorption of lignin on both Pd and C surfaces at 473 K, with notable solvent-mediated differences in adsorption energies. Additionally, our findings indicate that lignin adsorption is promoted by the entropy change resulting from the displacement of solvent molecules from the surface. This study provides a molecular perspective of adsorption of lignin onto varying surfaces, which is a step towards understanding and optimizing the catalytic conversion of lignin into valuable chemicals.

adsorption↗
DOE OSTI2021

Localized High Concentration Electrolyte and Its Effects on Polysulfide Structure in Solution

Lithium–sulfur batteries (LiSB) are a promising next-generation lithium energy storage technology that offers a multifold improvement over the traditional lithium-ion battery. However, the LiSB still faces the unresolved issue of the polysulfide shuttle effect. This phenomenon arises from the dissolution of sulfur intermediate reduction products into the electrolyte, which then causes a cascade of issues throughout the battery. Many mitigation strategies have been proposed to counteract this effect including the use of novel electrolyte compositions. Recently, there has been increased focus on the use of hydrofluorinated ethers as a major constituent of an electrolyte for lithium batteries. Previous studies have reported that the presence of these species create localized high concentration electrolytes (LHCE) which can have many advantages resulting in improved battery performance. Here, we report on how the inclusion of a hydrofluorinated ether BTFE (bis(2,2,2-trifluoroethyl) ether) modifies the general properties of a LiSB electrolyte and the structure of dissolved polysulfide species in the electrolyte. Here, we found that the inclusion of BTFE does not modify the primary solvation structure of Li + directly but actively participates in secondary solvation shells. With a high concentration of BTFE, the LHCE formation is observed by the presence of clusters of non-BTFE molecules. The structure of polysulfide species in solution was modified by the BTFE in the same way. Much of the primary solvation structure was kept, but the presence of BTFE increased polysulfide–polysulfide clustering. These results indicate that the polysulfide solubility will be limited due to the promotion of clustering.

25 ENERGY STORAGE↗
DOE OSTI2018

Electrolyte with Low Polysulfide Solubility for Li-S Batteries

Here, Li-S battery is one of the most promising next generation rechargeable battery technologies due to its high theoretical energy density and low material cost. While its success is impeded by the low energy efficiency and fast capacity fade primarily caused by the discharge intermediates, Li-polysulfides (PS), dissolution in the electrolyte. Mitigation of PS dissolution in electrolyte involves the search of new electrolyte solvent system that exhibits poor solvation to the PS while still have good solvation ability to the electrolyte salt for high ionic conductivity. Applying co-solvents with reduced solvating power but compatible with the state of art Li-S battery’s ether-based electrolyte is one of the most promising concepts. This route is also advantageous of having a low scale-up cost. With the aids of Quantum Chemical Calculation, we have identified high carbon-to-oxygen (C/O) ratio ethers as co-solvent in the new electrolytes that effectively impede PS dissolution while still maintaining high ionic conductivity. Significantly improved cycle life and cycling Coulombic efficiency are observed for Li-S cells using the new composite electrolytes. Anode analysis with different methods also demonstrate that reducing electrolyte’s PS solubility results in less sulfur total amount on the lithium anode surface and lower ratio of the longer-chain PS, which is probably a sign of suppressed side reactions between the anode and PS in the electrolyte.

25 ENERGY STORAGE↗
DOE OSTI2025

Epoxide Alcoholysis over M-BEA Zeolites: Effects of Alcohol Chain Length on Rates and Regioselectivities

The structures of nucleophilic reactants affect their coordination behavior among solvent molecules and kinetics of reactions with surface intermediates within the confines of fluidfilled pores of zeolites and other microporous materials. Consequently, rates and regioselectivities of diverse chemistries may depend sensitively on nucleophile identity in manners not observed for classic fluid phase reactions. Here, we examine the impact of varying the primary alcohol (ROH) chain length on the kinetics of 1,2-epoxybutane (C 4 H 8 O) ring-opening within Brønsted (Al-BEA) and Lewis acid (Zr-BEA) zeolites. Turnover rates increase by factors of ∼6 (Al-BEA) and 4-fold (Zr-BEA) between methanol and 1-hexanol, yet the reaction mechanisms remain comparable. Despite modest rate differences, apparent activation enthalpies calculated from rates and activities of solvated reactants decrease linearly by 12 (Al-BEA) to 33 kJ mol −1 (Zr- BEA) with increased proton affinity, which suggests bond formation energies for the nucleophile strongly influence rate increases. The molecular interpretation of these trends demonstrates, however, that the solvation of ring-opening transition states by zeolite pore structures and solvent molecules also governs rates. The impact of local solvating interactions appears most directly as changes in regioselectivities, which tend to enhance terminal alcohol formation with increasing ROH chain length. Regioselectivities largely do not vary with differences in fluid composition for a given ROH. The addition of H 2 O increases the number of hydrogen bonds among reactive species, and trends in regioselectivities imply that the decreased hydrogen bonding ability of longer chain ROH, and not the nucleophile strength or steric bulk, determines the regioselectivities of the resulting products. This work provides direct experimental evidence that nucleophilicity and hydrogen bonding influence reaction barriers and regioselectivities in zeolitecatalyzed epoxide ring-opening, offering pathways to better control reaction kinetics.

acidic zeolites↗
DOE OSTI2025

Locally Confined Polysulfide-Reactive Electrolytes for Shuttle-Free Sodium–Sulfur Batteries

Sodium-sulfur batteries promise high-energy-density and sustainable electrochemical energy storage but suffer from uncontrolled polysulfides dissolution and high sodium reactivity. These challenges fundamentally originate from poor electrolyte-electrode compatibility. Current electrolyte research inadequately addresses the trade-off between minimal polysulfides solvation and stabilizing sodium interfaces. Here, we present a locally-confined polysulfide-reactive electrolyte strategy that mediates the polysulfide dissolution dynamics and sodium stability by leveraging an electrophilic solvating species with a localized high-concentration electrolyte. This design enables shuttle-free cell operation by synergistically restricting the global solvating power of the electrolyte through intermolecular interactions and locally scavenging sparingly dissolved polysulfides via electrolyte electrophilicity. The precisely confined surface reaction facilitates a protective cathode-electrolyte interface, realizing a quasi-solid-state sulfur conversion in our liquid ether-based electrolyte, which crucially avoids crossover-induced catastrophic sodium-metal degradation. The proposed electrolyte demonstrates long-term cycling of high-mass-loading sulfur cathodes (> 3 mg S cm −2 with commercial carbon host and 70 wt% sulfur content), which afford 710 mA h g −1 over 400 cycles in coin cells and steady pouch cell operation over 180 cycles. Furthermore, this work establishes a scalable electrolyte design protocol that regulates the reaction chemistry of highly reactive electrodes, offering a pathway toward sustainable renewable energy storage.

25 ENERGY STORAGE↗
DOE OSTI2013

Cluster-continuum quantum mechanical models to guide the choice of anions for Li{sup +}-conducting ionomers

A quantum-mechanical investigation on Li poly(ethylene oxide)-based ionomers was performed in the cluster-continuum solvation model (CCM) that includes specific solvation in the first shell surrounding the cation, all surrounded by a polarizable continuum. A four-state model, including a free Li cation, Li{sup +}-anion pair, triple ion, and quadrupole was used to represent the states of Li{sup +} within the ionomer in the CCM. The relative energy of each state was calculated for Li{sup +} with various anions, with dimethyl ether representing the ether oxygen solvation. The population distribution of Li{sup +} ions among states was estimated by applying Boltzmann statistics to the CCM energies. Entropy difference estimates are needed for populations to better match the true ionomer system. The total entropy change is considered to consist of four contributions: translational, rotational, electrostatic, and solvent immobilization entropies. The population of ion states is reported as a function of Bjerrum length divided by ion-pair separation with/without entropy considered to investigate the transition between states. Predicted concentrations of Li{sup +}-conducting states (free Li{sup +} and positive triple ions) are compared among a series of anions to indicate favorable features for design of an optimal Li{sup +}-conducting ionomer; the perfluorotetraphenylborate anion maximizes the conducting positive triple ion population among the series of anions considered.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2014

Network analysis of proton transfer in liquid water

Proton transfer in macromolecular systems is a fascinating yet elusive process. In the last ten years, molecular simulations have shown to be a useful tool to unveil the atomistic mechanism. Notwithstanding, the large number of degrees of freedom involved make the accurate description of the process very hard even for the case of proton diffusion in bulk water. Here, multi-state empirical valence bond molecular dynamics simulations in conjunction with complex network analysis are applied to study proton transfer in liquid water. Making use of a transition network formalism, this approach takes into account the time evolution of several coordinates simultaneously. Our results provide evidence for a strong dependence of proton transfer on the length of the hydrogen bond solvating the Zundel complex, with proton transfer enhancement as shorter bonds are formed at the acceptor site. We identify six major states (nodes) on the network leading from the “special pair” to a more symmetric Zundel complex required for transferring the proton. Moreover, the second solvation shell specifically rearranges to promote the transfer, reiterating the idea that solvation beyond the first shell of the Zundel complex plays a crucial role in the process.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2014

Diffusional motion of redox centers in carbonate electrolytes

Ferrocene (Fc) and N-(ferrocenylmethyl)-N,N-dimethyl-N-ethylammonium bistrifluoromethyl-sulfonimide (Fc1N112-TFSI) were dissolved in carbonate solvents and self-diffusion coefficients (D) of solutes and solvents were measured by {sup 1}H and {sup 19}F pulsed field gradient nuclear magnetic resonance (NMR) spectroscopy. The organic solvents were propylene carbonate (PC), ethyl methyl carbonate (EMC), and a ternary mixture that also includes ethylene carbonate (EC). Results from NMR studies over the temperature range of 0–50 °C and for various concentrations (0.25–1.7 M) of Fc1N112-TFSI are compared to values of D simulated with classical molecular dynamics (MD). The measured self-diffusion coefficients gradually decreased as the Fc1N112-TFSI concentration increased in all solvents. Since TFSI{sup −} has fluoromethyl groups (CF{sub 3}), D{sub TFSI} could be measured separately and the values found are larger than those for D{sub Fc1N112} in all samples measured. The EC, PC, and EMC have the same D in the neat solvent mixture and when Fc is dissolved in EC/PC/EMC at a concentration of 0.2 M, probably due to the interactions between common carbonyl structures within EC, PC, and EMC. A difference in D (D{sub PC} < D{sub EC} < D{sub EMC}), and both a higher E{sub a} for translational motion and higher effective viscosity for PC in the mixture containing Fc1N112-TFSI reflect the interaction between PC and Fc1N112{sup +}, which is a relatively stronger interaction than that between Fc1N112{sup +} and other solvent species. In the EC/PC/EMC solution that is saturated with Fc1N112-TFSI, we find that D{sub PC} = D{sub EC} = D{sub EMC} and Fc1N112{sup +} and all components of the EC/PC/EMC solution have the same E{sub a} for translational motion, while the ratio D{sub EC/PC/EMC}/D{sub Fc1N112} is approximately 3. These results reflect the lack of available free volume for independent diffusion in the saturated solution. The Fc1N112{sup +} transference numbers lie around 0.4 and increase slightly as the temperature is increased in the PC and EMC solvents. The trends observed for D from simulations are in good agreement with experimental results and provide molecular level understanding of the solvation structure of Fc1N112-TFSI dissolved in EC/PC/EMC.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2014

QM/MM investigation of the concentration effects on the second-order nonlinear optical responses of solutions

A multiscale approach combining quantum mechanics (QM) and molecular mechanics methods has been employed to investigate the effects of solute-solute interactions and therefore of concentration on the first hyperpolarizability of solutions of nitrobenzene in benzene. First, spatial distributions of solute and solvent molecules are generated using Monte Carlo simulations where the intermolecular interactions are described using the Lennard-Jones potentials and Coulomb terms. Then, a reduced number of statistically-uncorrelated configurations are sampled and submitted to time-dependent Hartree-Fock calculations of the first hyperpolarizability. When only one molecule is described quantum-mechanically and is embedded in the electrostatic polarization field of the solution described by point charges, β{sub HRS} and β{sub //} as well as the depolarization ratio increase in parallel with the concentration in nitrobenzene. This effect is attributed to the increase of the polarization field associated with the presence of polar nitrobenzene molecules in the surrounding. Then, the first solvation shell is considered explicitly in the QM calculation to address solute-solute interactions effects. When the number of nitrobenzenes in the first solvation shell increases, β{sub HRS} and β{sub //} normalized to the number of nitrobenzene molecules decrease and this decrease attains roughly 50% when there are 3 nitrobenzene molecules in the first solvation shell. These drastic reductions of the first hyperpolarizability result from (partial) centro-symmetric arrangements between the nitrobenzene molecules, as supported by the relationship between β and the angle between the nitrobenzene charge transfer axes. Moreover, these β decreases originate mostly from the reduction of the dipolar β component, whereas the octupolar one is rather constant as a function of the nitrobenzene concentration.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

Effects of the surroundings and conformerisation of n-dodecane molecules on evaporation/condensation processes

The evaporation/condensation coefficient (β) and the evaporation rate (γ) for n-dodecane vs. temperature, gas pressure, gas and liquid density, and solvation effects at a droplet surface are analysed using quantum chemical density functional theory calculations of several ensembles of conformers of n-dodecane molecules in the gas phase (hybrid functional ωB97X-D with the cc-pVTZ and cc-pVDZ basis sets) and in liquid phase (solvation method: SMD/ωB97X-D). It is shown that β depends more strongly on a number of neighbouring molecules interacting with an evaporating molecule at a droplet surface (this number is estimated through changes in the surface Gibbs free energy of solvation) than on pressure in the gas phase or conformerisation and cross-conformerisation of molecules in both phases. Thus, temperature and the surrounding effects at droplet surfaces are the dominant factors affecting the values of β for n-dodecane molecules. These values are shown to be similar (at reduced temperatures T/T{sub c} < 0.8) or slightly larger (at T/T{sub c} > 0.8) than the values of β calculated by the molecular dynamics force fields (MD FF) methods. This endorses the reliability of the previously developed classical approach to estimation of β by the MD FF methods, except at temperatures close to the critical temperature.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

A versatile, pulsed anion source utilizing plasma-entrainment: Characterization and applications

A novel pulsed anion source has been developed, using plasma entrainment into a supersonic expansion. A pulsed discharge source perpendicular to the main gas expansion greatly reduces unwanted “heating” of the main expansion, a major setback in many pulsed anion sources in use today. The design principles and construction information are described and several examples demonstrate the range of applicability of this anion source. Large OH{sup −}(Ar){sub n} clusters can be generated, with over 40 Ar solvating OH{sup −}. The solvation energy of OH{sup −}(Ar){sub n}, where n = 1-3, 7, 12, and 18, is derived from photoelectron spectroscopy and shows that by n = 12-18, each Ar is bound by about 10 meV. In addition, cis– and trans– HOCO{sup −} are generated through rational anion synthesis (OH{sup −} + CO + M → HOCO{sup −} + M) and the photoelectron spectra compared with previous results. These results, along with several further proof-of-principle experiments on solvation and transient anion synthesis, demonstrate the ability of this source to efficiently produce cold anions. With modifications to two standard General Valve assemblies and very little maintenance, this anion source provides a versatile and straightforward addition to a wide array of experiments.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

Molecular dynamics simulations of the structure and single-particle dynamics of mixtures of divalent salts and ionic liquids

We report a molecular dynamics study of the structure and single-particle dynamics of mixtures of a protic (ethylammonium nitrate) and an aprotic (1-butyl-3-methylimidazolium hexaflurophosphate [BMIM][PF{sub 6}]) room-temperature ionic liquids doped with magnesium and calcium salts with a common anion at 298.15 K and 1 atm. The solvation of these divalent cations in dense ionic environments is analyzed by means of apparent molar volumes of the mixtures, radial distribution functions, and coordination numbers. For the protic mixtures, the effect of salt concentration on the network of hydrogen bonds is also considered. Moreover, single-particle dynamics of the salt cations is studied by means of their velocity autocorrelation functions and vibrational densities of states, explicitly analyzing the influence of salt concentration, and cation charge and mass on these magnitudes. The effect of the valency of the salt cation on these properties is considered comparing the results with those for the corresponding mixtures with lithium salts. We found that the main structural and dynamic features of the local solvation of divalent cations in ionic liquids are similar to those of monovalent salts, with cations being localized in the polar nanoregions of the bulk mixture coordinated in monodentate and bidentate coordination modes by the [NO{sub 3}]{sup −} and [PF{sub 6}]{sup −} anions. However, stronger electrostatic correlations of these polar nanoregions than in mixtures with salts with monovalent cations are found. The vibrational modes of the ionic liquid (IL) are seen to be scarcely affected by the addition of the salt, and the effect of mass and charge on the vibrational densities of states of the dissolved cations is reported. Cation mass is seen to exert a deeper influence than charge on the low-frequency vibrational spectra, giving a red shift of the vibrational modes and a virtual suppression of the higher energy vibrational modes for the heavier Ca{sup 2+} cations. No qualitative difference with monovalent cations was found in what solvation is concerned, which suggests that no enhanced reduction of the mobility of these cations and their complexes in ILs respective to those of monovalent cations is to be expected.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

Counterintuitive electron localisation from density-functional theory with polarisable solvent models

Exploration of the solvated electron phenomena using density-functional theory (DFT) generally results in prediction of a localised electron within an induced solvent cavity. However, it is well known that DFT favours highly delocalised charges, rendering the localisation of a solvated electron unexpected. We explore the origins of this counterintuitive behaviour using a model Kevan-structure system. When a polarisable-continuum solvent model is included, it forces electron localisation by introducing a strong energetic bias that favours integer charges. This results in the formation of a large energetic barrier for charge-hopping and can cause the self-consistent field to become trapped in local minima thus converging to stable solutions that are higher in energy than the ground electronic state. Finally, since the bias towards integer charges is caused by the polarisable continuum, these findings will also apply to other classical polarisation corrections, as in combined quantum mechanics and molecular mechanics (QM/MM) methods. The implications for systems beyond the solvated electron, including cationic DNA bases, are discussed.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

Ion-Stockmayer clusters: Minima, classical thermodynamics, and variational ground state estimates of Li{sup +}(CH{sub 3}NO{sub 2}){sub n} (n = 1–20)

Structural optimizations, classical NVT ensemble, and variational Monte Carlo simulations of ion Stockmayer clusters parameterized to approximate the Li{sup +}(CH{sub 3}NO{sub 2}){sub n} (n = 1–20) systems are performed. The Metropolis algorithm enhanced by the parallel tempering strategy is used to measure internal energies and heat capacities, and a parallel version of the genetic algorithm is employed to obtain the most important minima. The first solvation sheath is octahedral and this feature remains the dominant theme in the structure of clusters with n ≥ 6. The first “magic number” is identified using the adiabatic solvent dissociation energy, and it marks the completion of the second solvation layer for the lithium ion-nitromethane clusters. It corresponds to the n = 18 system, a solvated ion with the first sheath having octahedral symmetry, weakly bound to an eight-membered and a four-membered ring crowning a vertex of the octahedron. Variational Monte Carlo estimates of the adiabatic solvent dissociation energy reveal that quantum effects further enhance the stability of the n = 18 system relative to its neighbors.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2016

Charge-transfer-to-solvent reactions from I{sup −} to water, methanol, and ethanol studied by time-resolved photoelectron spectroscopy of liquids

The charge-transfer-to-solvent (CTTS) reactions from iodide (I{sup −}) to H{sub 2}O, D{sub 2}O, methanol, and ethanol were studied by time-resolved photoelectron spectroscopy of liquid microjets using a magnetic bottle time-of-flight spectrometer with variable pass energy. Photoexcited iodide dissociates into a weak complex (a contact pair) of a solvated electron and an iodine atom in similar reaction times, 0.3 ps in H{sub 2}O and D{sub 2}O and 0.5 ps in methanol and ethanol, which are much shorter than their dielectric relaxation times. The results indicate that solvated electrons are formed with minimal solvent reorganization in the long-range solvent polarization field created for I{sup −}. The photoelectron spectra for CTTS in H{sub 2}O and D{sub 2}O—measured with higher accuracy than in our previous study [Y. I. Suzuki et al., Chem. Sci. 2, 1094 (2011)]—indicate that internal conversion yields from the photoexcited I{sup −*} (CTTS) state are less than 10%, while alcohols provide 2–3 times greater yields of internal conversion from I{sup −*}. The overall geminate recombination yields are found to be in the order of H{sub 2}O > D{sub 2}O > methanol > ethanol, which is opposite to the order of the mutual diffusion rates of an iodine atom and a solvated electron. This result is consistent with the transition state theory for an adiabatic outer-sphere electron transfer process, which predicts that the recombination reaction rate has a pre-exponential factor inversely proportional to a longitudinal solvent relaxation time.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗