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The role of different intermolecular interactions in the aggregation of amphiphiles in an organic solvent is studied for systems of relevance to liquid-liquid extraction (LLE), a chemical process used to selectively recover metals from complex mixtures. Of specific interest is the role, or lack thereof, of hydrogen bonding, which is often assumed to be a main driver of the organic phase structural organization that has been linked to separation efficacy. Toward that end, a series of malonamide extractants in n -dodecane have been studied in the absence of any extracted aqueous solutes, including water. The series of extractants includes N , N '-dimethyl- N , N '-dibutyltetradecylmalonamide (DMDBTDMA), two of its homologs, and N , N '-dimethyl- N , N '-dioctylhexylethoxymalonamide (DMDOHEMA). This simplified model LLE system enables systematic investigation of the role of dipole-dipole and alkyl tail steric interactions in amphiphile aggregation. Small-angle X-ray scattering (SAXS) profiles computed from molecular dynamics trajectories are in good agreement with experimental SAXS data. Molecular dynamics simulations show that malonamide aggregation results from dipole-driven self-association and lacks characteristic aggregate sizes. Mid- q correlation peaks in the SAXS profiles emerge at high concentration for each malonamide. In those densely packed solutions, the correlation peaks are observed to result from alkyl tail-induced spacing between electron-rich polar head groups, with peak positions determined by the different alkyl tail lengths present in the malonamide molecule. This explanation of the SAXS correlation peaks contrasts with the prevailing literature, which attributes mesoscale features observed in small-angle scattering to the formation of microemulsions. Instead, this work finds that these features are present in the absence of water or any reverse micellar organization of the malonamides. As such, molecular-scale malonamide self-association and packing, rather than microemulsion-based colloidal-scale descriptions, is a more appropriate framework for these LLE systems.

Redoxmers are organic molecules that carry electric charge in flow batteries. In many instances, they consist of heteroaromatic moieties modified with appended groups to prevent stacking of the planar cores and increase solubility in liquid electrolytes. This higher solubility is desired as it potentially allows achieving greater energy density in the battery. However, the present synthetic strategies often yield bulky molecules with low molarity even when they are neat and still lower molarity in liquid solutions. Fortunately, there are exceptions to this rule. Here, we examine one well-studied redoxmer, 2,1,3-benzothiadiazole, which has solubility ∼5.7 M in acetonitrile at 25 °C. We show computationally and prove experimentally that the competition between two packing motifs, face-to-face π-stacking and random N-H bond piling, introduces frustration that confounds nucleation in crowded solutions. Our findings and examples from related systems suggest a complementary strategy for the molecular design of redoxmers for high energy density redox flow cells.

Redoxmers are electrochemically active organic molecules storing charge and energy in electrolyte fluids circulating through redox flow batteries (RFBs). Such molecules typically have solvent-repelling cores and solvent-attracting pendant groups introduced to increase solubility in liquid electrolytes. These two features can facilitate nanoscale aggregation of the redoxmer molecules in crowded solutions. In some cases, this aggregation leads to the emergence of continuous networks of solute molecules in contact, and the solution becomes microscopically heterogeneous. Here, we use small-angle X-ray scattering (SAXS) and molecular dynamics modeling to demonstrate formation of such networks and examine structural factors controlling this self-assembly. We also show that salt ions become excluded from these solute aggregates into small pockets of electrolytes, where these ions strongly associate. This confinement by exclusion is also likely to occur to charged redoxmer molecules in a "sea" of neutral precursors coexisting in the same solution. Here, we demonstrate that the decay lifetime of the confined charged molecules in such solutions can increase several fold compared to dilute solutions. We attribute this behavior to a "microreactor effect" on reverse reactions of the confined species during their decomposition.

While many practically important electrolytes contain lithium ions, interactions of these ions are particularly difficult to probe experimentally because of their small X-ray and neutron scattering cross sections and large neutron absorption cross sections. Molecular dynamics (MD) is a powerful tool for understanding the properties of nonaqueous electrolyte solutions from the atomic level, but the accuracy of this computational method crucially depends on the physics built into the classical force field. Here, we demonstrate that several force fields for lithium bistriflimide (LiTFSI) in acetonitrile yield a solution structure that is consistent with the neutron scattering experiments, yet these models produce dramatically different ion dynamics in solution. Such glaring discrepancies indicate that inadequate representation of long-range interactions leads to excessive ionic association and ion-pair clustering. We show that reasonable agreement with the experimental observations can be achieved by renormalization of the ion charges using a "titration" method suggested herewith. This simple modification produces realistic concentration dependencies for ionic diffusion and conductivity in <2 M solutions, without loss in quality for simulation of the structure.

The photochemical reaction pathways of CHBr 3 in solution were unveiled using two complementary X-ray techniques, time-resolved X-ray solution scattering (TRXSS) and X-ray transient absorption spectroscopy, in a wide temporal range from 100 ps to tens of microseconds. By performing comparative measurements in protic (methanol) and aprotic (methylcyclohexane) solvents, we found that the reaction pathways depend significantly on the solvent properties. In methanol, the major photoproducts are CH 3 OCHBr 2 and HBr generated by rapid solvolysis of iso- CHBr 2 -Br, an isomer of CHBr 3 . In contrast, in methylcyclohexane, iso -CHBr 2 -Br returns to CHBr 3 without solvolysis. In both solvents, the formation of CHBr 2 and Br is a competing reaction channel. From the structural analysis of TRXSS data, we determined the structures of key intermediate species, CH 3 OCHBr 2 and iso -CHBr 2 -Br in methanol and methylcyclohexane, respectively, which are consistent with the structures from density functional theory calculations., (© 2019 Author(s).)

In advanced electrical grids of the future, electrochemically rechargeable fluids of high energy density will capture the power generated from intermittent sources like solar and wind. To meet this outstanding technological demand there is a need to understand the fundamental limits and interplay of electrochemical potential, stability, and solubility in low-weight redox-active molecules. By generating a combinatorial set of 1,4-dimethoxybenzene derivatives with different arrangements of substituents, we discovered a minimalistic structure that combines exceptional long-term stability in its oxidized form and a record-breaking intrinsic capacity of 161 mAh/g. The nonaqueous redox flow battery has been demonstrated that uses this molecule as a catholyte material and operated stably for 100 charge/discharge cycles. The observed stability trends are rationalized by mechanistic considerations of the reaction pathways.

Because of their extended conjugated bond network, aromatic compounds generally have higher redox stability than less saturated compounds. We conjectured that ionic liquids (ILs) consisting of aromatic heterocyclic anions (AHAs) may exhibit improved radiation and electrochemical stability. Such properties are important in applications of these ILs as diluents in radionuclide separations and electrolytes in the electric energy storage devices. In this study, we systematically examine the redox chemistry of the AHAs. Three classes of these anions have been studied: (i) simple 5-atom ring AHAs, such as the pyrazolide and triazolides, (ii) AHAs containing an adjacent benzene ring, and (iii) AHAs containing electron-withdrawing groups that were introduced to reduce their basicity and interaction with metal ions. It is shown that fragmentation in the reduced and oxidized states of these AHAs does not generally occur, and the two main products, respectively, are the H atom adduct and the imidyl radical. The latter species occurs either as an N σ-radical or as an N π-radical, depending on the length of the N-N bond, and the state that is stabilized in the solid matrix is frequently different from that having the lowest energy in the gas phase. In some instances, the formation of the sandwich π-stack dimer radical anions has been observed. For trifluoromethylated anions, H adduct formation did not occur; instead, there was facile loss of fluoride from their fluorinated groups. The latter can be problematic in nuclear separations, but beneficial in batteries. Overall, our study suggests that AHA-based ILs are viable candidates for use as radiation-exposed diluents and electrolytes.

Coordination polymers (CPs) of metal ions are central to a large variety of applications, such as catalysis and separations. These polymers frequently occur as amorphous solids that segregate from solution. The structural aspects of this segregation remain elusive due to the dearth of the spectroscopic techniques and computational approaches suitable for probing such systems. Therefore, there is a lacking of understanding of how the molecular building blocks give rise to the mesoscale architectures that characterize CP materials. In this study we revisit a CP phase formed in the extraction of trivalent lanthanide ions by diesters of the phosphoric acid, such as the bis(2-ethylhexyl)phosphoric acid (HDEHP). This is a well-known system with practical importance in strategic metals refining and nuclear fuel reprocessing. A CP phase, referred to as a "third phase", has been known to form in these systems for half a century, yet the structure of the amorphous solid is still a point of contention, illustrating the difficulties faced in characterizing such materials. In this study, we follow a deductive approach to solving the molecular structure of amorphous CP phases, using semiempirical calculations to set up an array of physically plausible models and then deploying a suite of experimental techniques, including optical, magnetic resonance, and X-ray spectroscopies, to consecutively eliminate all but one model. We demonstrate that the "third phase" consists of hexagonally packed linear chains in which the lanthanide ions are connected by three O-P-O bridges, with the modifying groups protruding outward, as in a bottlebrush. The tendency to yield linear polynuclear oligomers that is apparent in this system may also be present in other systems yielding the "third phase", demonstrating how molecular geometry directs polymeric assembly in hybrid materials. We show that the packing of bridging molecules is central to directing the structure of CP phases and that by manipulating the steric requirements of ancillary groups one can control the structure of the assembly.

In 1953, an accidental discovery by Melvin Calvin and co-workers provided the first example of a solid (the α-polymorph of choline chloride) showing hypersensitivity to ionizing radiation: under certain conditions, the radiolytic yield of decomposition approached 5 × 10(4) per 100 eV (which is 4 orders of magnitude greater than usual values), suggesting an uncommonly efficient radiation-induced chain reaction. Twenty years later, the still-accepted mechanism for this rare condition was suggested by Martyn Symons, but no validation for this mechanism has been supplied. Meanwhile, ionic liquids and deep eutectic mixtures that are based on choline, betainium, and other derivitized natural amino compounds are presently finding an increasing number of applications as diluents in nuclear separations, where the constituent ions are exposed to ionizing radiation that is emitted by decaying radionuclides. Thus, the systems that are compositionally similar to radiation hypersensitive solids are being considered for use in high radiation fields, where this property is particularly undesirable! In Part 5 of this series on organic cations, we revisit the phenomenon of radiation hypersensitivity and explore mechanistic aspects of radiation-induced reactions involving this class of task-specific, biocompatible, functionalized cations, both in ionic liquids and in reference crystalline compounds. We demonstrate that Symons' mechanism needs certain revisions and rethinking, and suggest its modification. Our reconsideration suggests that there cannot be conditions leading to hypersensitivity in ionic liquids.

Three families of "task-specific" antioxidant organic cations that include designated sites to facilitate deprotonation following electronic excitation and ionization have been introduced. The deprotonation from the excited state is reversible, leading to minimal damage of the cation, whereas the deprotonation from the oxidized cation yields persistent aroxyl and trityl radicals. This protection improves radiation stability of ionic compounds in 2.5 MeV electron beam radiolysis. Apart from the use of such cations as structural components of room temperature ionic liquid (IL) diluents for nuclear separations, their ionic compounds involving bases of superacids are well suited for use as chemically amplified acid generator resists in electron beam lithography and extreme ultraviolet photolithography.

Hydrophobic room-temperature ionic liquids (ILs) hold promise as replacements for molecular diluents for processing of used nuclear fuel as well as for the development of alternative separations processes, provided that the solvent can be made resistant to ionizing radiation. We demonstrate that 1-benzylpyridinium cations are uniquely suited as radiation resistant cations due to the occurrence of charge delocalization in both their reduced and oxidized forms in the ILs. It is suggested that the excess electron and hole in the latter ILs are stabilized through the formation of π-electron sandwich dimers that are analogous to the well-known dimer radical cations of aromatic molecules. This charge delocalization dramatically reduces the yield of fragmentation by deprotonation and the loss of benzyl arms, thereby providing a synthetic path to radiation resistant ILs that are suitable for nuclear fuel processing.

Due to their superb structural versatility, guanidinium cations find increasing use as constituent ions in room temperature ionic liquids (ILs). This versatility allows fine-tuning of hydrophobicity, which is an important concern for the use of ILs as diluents for metal ion separations. However, the presence of six C-N bonds in such cations poses a question, whether the guanidinium based ILs can be considered as diluents for nuclear separations, given that the radiation emitted by the decaying radionuclides can break these relatively weak bonds over the use cycle of the solvent. As nothing is presently known about the radiolytic stability of the guanidinium cations, we addressed this question using 2-dialkylamino-1,3-dimethylimidazolidine based cations (R = Et, Pr, and Bu) as a representative model for the entire class of such cations, and assessed their stability in 2.5 MeV electron beam radiolysis. Electron paramagnetic resonance spectroscopy, nuclear magnetic resonance spectroscopy, and mass spectrometry have been used to establish chemical mechanisms for radiation damage in guanidinium cations. Our conclusion is that radiation stability of these cations is not significantly different from that of more familiar aliphatic and aromatic IL cations. In fact, these cations yield exceptionally stable radicals, and fragmentation occurs only in their radiolytically generated excited states. The predominant chemical pathway for the cation decomposition is the elimination of their aliphatic arms, with radiolytic yields of 0.65 to 1.06 to 1.46 per 100 eV from R = Et to R = Bu, respectively. The total loss of the parent cation was estimated as 2.62, 1.65, and 1.98 species per 100 eV. While this attrition is not negligible, it is comparable to other organic cations that have fewer fissile C-N bonds. Many of the products are either modified guanidinium ions or protonated bases that are not expected to interfere with radionuclide separations.

In order to use hydrophobic room temperature ionic liquids (ILs) as diluents in nuclear separations for advanced fuel cycles, it is desirable to reduce the breakdown of the constituent ions caused by ionizing radiation. In this series, we survey radiation stability for different classes of organic cations used to formulate ILs. While radiolysis of 1-alkyl-3-methylimidazolium cations has been extensively studied, there have not been complementary studies of 1-benzyl derivatives of these cations nor organic cations that are derived from 5-membered ring heterocycles other than imidazole, such as 1,2,4-triazole and thiazole. In part 1, we establish the fragmentation pathways for such cations and quantify product yields for 2.5 MeV electron beam radiolysis of these aromatic cations. Radiolytic reduction of 1-benzyl cations derived from imidazole and 1,2,4-triazole is shown to cause the elimination of benzyl radicals from their electron adducts, whereas this elimination does not occur in the thiazole derivatives due to stabilization of the excess electron as a dimer radical cation. No such elimination occurs in the corresponding 1-alkyl derivatives, but there is significant C-N and C-C bond fragmentation in the aliphatic arms. As such bond dissociation reactions are irreversible, there is significant loss of 1-alkyl cations during the radiolysis. For 1-benzyl derivatives, this electronic excitation causes fragmentation of the C-N bonds in the benzyl arms with the release of the corresponding base and the benzyl carbocation that can subsequently attack this base or add to another cation. Such systems exhibit more predictable fragmentation patterns and yield well-defined products; some of the systems also exhibit increased radiation resistance. The C-N bond fragmentation in the reduced cations can be further suppressed through the use of appropriate electron scavengers, including acids and aromatic imide anions. The observed trends are rationalized using density functional theory calculations, and the implications of these results for the design of IL diluents are examined.

One- and two- photon excitation of halide anions (X(-)) in polar molecular solvents results in electron detachment from the dissociative charge-transfer-to-solvent state; this reaction yields a solvated halide atom and a solvated electron. How do such photoreactions proceed in ionic liquid (IL) solvents? Matrix isolation electron paramagnetic resonance (EPR) spectroscopy has been used to answer this question for photoreactions of bromide in aliphatic (1-butyl-1-methylpyrrolidinium) and aromatic (1-alkyl-3-methyl-imidazolium) ionic liquids. In both classes of ILs, the photoreaction (both 1- and 2-photon) yields bromine atoms that promptly abstract hydrogen from the alkyl chains of the IL cation; only in concentrated bromide solutions (containing >5-10 mol % bromide) does Br2(-•) formation compete with this reaction. In two-photon excitation, the 2-imidazolyl radical generated via the charge transfer promptly eliminates the alkyl arm. These photolytic reactions can be contrasted with radiolysis of the same ILs, in which large yield of BrA(-•) radicals was observed (where A(-) is a matrix anion), suggesting that solvated Br(•) atoms do not occur in the ILs, as such a species would form three-electron σ(2)σ(*1) bonds with anions present in the IL. It is suggested that chlorine and bromine atoms abstract hydrogen faster than they form such radicals, even at cryogenic temperatures, whereas iodine mainly forms such bound radicals. These XA(-•) radicals convert to X2(•-) radicals in a reaction with the parent halide anion. Ramifications of these observations for photodegradation of ionic liquids are discussed.

Ionic liquids (IL) are being considered as replacements for molecular diluents in spent nuclear fuel reprocessing. This development is hampered by the dearth of constituent anions that combine high hydrophobicity, low metal cation and proton affinity, and radiation resistance. We demonstrate that polynitrile anions have the potential to meet these challenges. Unlike the great majority of organic anions, such polynitrile anions are resistant to oxidative fragmentation during radiolysis, yielding stable N- and C-centered radicals. Moreover, their radical dianions (generated by reduction of the anions) generally undergo protonation in preference to elimination of the cyanide. This is in contrast to fluorinated anions (another large class of anions with low proton affinity), for which radiation-induced release of fluoride is a common occurrence. The "weak spot" of the polynitrile anions appears to be their excited-state dissociation, but at least one of these anions, 1,1,2,3,3-pentacyanopropenide, is shown to resist fragmentation in room temperature radiolysis. We suggest beginning the exploration of ionic liquids based on such polynitrile anions.

Room-temperature hydrophobic ionic liquids (ILs) are considered for processing of spent nuclear fuel, including as possible replacements for molecular diluents in liquid-liquid extraction. This application requires radiation stability of the constituent ions. Previous research indicated that most of the anions that are currently used in the synthesis of ILs are prone to fragmentation under prolonged radiation exposure, which causes deterioration of the corresponding ILs. An exception to this general rule is phthalimide; unfortunately, this anion is too basic to be useful for extraction solvents, as these separations involve acidic conditions. The acidity of the imide can be increased by replacing the carbonyl groups by sulfonyl groups, which incidentally transform these imides into familiar artificial sweeteners such as saccharin. In the present study, we use electron paramagnetic resonance spectroscopy, nuclear magnetic resonance spectroscopy, and mass spectrometry to assess the radiation stability of ILs based on such "sweet" sulfonyl imide anions. Our results suggest that saccharinate and o-benzenedisulfonimide are remarkably stable to radiation-induced fragmentation.

Alkylamides (such as N,N'-dimethylformamide, N,N'-diethylformamide, and N,N'-dimethylacetamide) are aprotic solvents that are widely used in organic synthesis. These polar molecules have no electron affinity, and it is believed that irradiated liquid and solid amides stabilize excess electrons as cavity-type species analogous to hydrated and ammoniated electrons. In this study, we use isotope substitution and EPR spectroscopy to demonstrate that, in frozen amides, the suspected "cavity electron" is, in fact, a solvent-stabilized monomer anion. Our observations call into question other attributions of such features in the literature, both in low temperature solids and room temperature liquids. We also provide a general scheme describing amide radiolysis, as the related amides are used as metal ion extracting agents in nuclear separations., (© 2012 American Chemical Society)

N,N,N',N'-Tetraalkyldiglycolamides are extracting agents that are used for liquid-liquid extraction of trivalent metal ions in wet processing of spent nuclear fuel. This application places such agents in contact with the decaying radionuclides, causing radiolysis of the agent in the organic diluent. Recent research seeks to replace common molecular diluents (such as n-dodecane) with hydrophobic room-temperature ionic liquids (ILs), which have superior solvation properties. In alkane diluents, rapid radiolytic deterioration of diglycolamide agents can be inhibited by addition of an aromatic cosolvent that scavenges highly reactive alkane radical cations before these oxidize the extracting agent. Do aromatic ILs exhibit a similar radioprotective effect? To answer this question, we used electron paramagnetic resonance spectroscopy to study the fragmentation pathways in radiolysis of neat diglycolamides, their model compounds, and their solutions in the ILs. Our study indicates that aromatic ILs do not protect these types of solutes from extensive radiolytic damage. Previous research indicated a similar lack of protection for crown ethers, whereas the ILs readily protected di- and trialkyl phosphates (another large class of metal-extracting agents). Our analysis of these unanticipated failures suggests that new types of organic anions are required in order to formulate ILs capable of radioprotection for these classes of solutes. This study is a cautionary tale of the fallacy of analogical thinking when applied to an entirely new and insufficiently understood class of chemical materials., (© 2012 American Chemical Society)

Hydrophobic room-temperature ionic liquids (ILs) are considered as possible replacements for molecular diluents for nuclear separations, as well as the basis of new separations processes. Such applications may put the solvents both in high radiation fields and in contact with aqueous raffinate containing 1-6 M HNO(3). In this study, we address the effect of the extracted nitrate and nitric acid on the radiation chemistry of hydrophobic ILs composed of 1-alkyl-3-methylimidazolium cations (and closely related systems). We demonstrate that the nitrate anion competes with the solvent cation as an electron scavenger, with most of the primary radical species converted to NO(3)(•2-) and NO(2)(•) that initiate a complex sequence of radical reactions. In hydrophobic ILs equilibrated with 3 M HNO(3), nearly all electrons released by the ionizing radiation are converted to NO(2)(•). While the reductive pathway is strongly affected by the nitrate and there is also some N-O bond scission via direct excitation, the extent of interference with the oxidative pathway is relatively small; the cation damage is not dramatically affected by the presence of nitrate as most of the detrimental radiolytic products are generated via the oxidative pathway. These results are contrasted with the behavior of dialkylphosphoric acids (a large class of extraction agents for trivalent metal ions). We demonstrate that IL solvents protect these dialkylphosphoric acids against radiation-induced dealkylation.

Given the difficulty of obtaining analytical solutions for the diffusion of interacting geminate pairs of (ion) radicals in liquids, it is common, following the original treatment of Mozumder, to "prescribe" this diffusion. A demonstration is given that such a prescription is impossible for any interaction potential other than the Coulomb potential. This demonstration suggests the inadequacy of this common approach to modeling geminate pair and spur dynamics in the largest emerging class of organic solvents: room-temperature ionic liquids.

In part 1 of this study, radiolytic degradation of constituent anions in ionic liquids (ILs) was examined. The present study continues the themes addressed in part 1 and examines the radiation chemistry of 1,3-dialkyl substituted imidazolium cations, which currently comprise the most practically important and versatile class of ionic liquid cations. For comparison, we also examined 1,3-dimethoxy- and 2-methyl-substituted imidazolium and 1-butyl-4-methylpyridinium cations. In addition to identification of radicals using electron paramagnetic resonance spectroscopy (EPR) and selective deuterium substitution, we analyzed stable radiolytic products using (1)H and (13)C nuclear magnetic resonance (NMR) and tandem electrospray ionization mass spectrometry (ESMS). Our EPR studies reveal rich chemistry initiated through "ionization of the ions": oxidation and the formation of radical dications in the aliphatic arms of the parent cations (leading to deprotonation and the formation of alkyl radicals in these arms) and reduction of the parent cation, yielding 2-imidazolyl radicals. The subsequent reactions of these radicals depend on the nature of the IL. If the cation is 2-substituted, the resulting 2-imidazolyl radical is relatively stable. If there is no substitution at C(2), the radical then either is protonated or reacts with the parent cation forming a C(2)-C(2) σσ*-bound dimer radical cation. In addition to these reactions, when methoxy or C(α)-substituted alkyl groups occupy the N(1,3) positions, their elimination is observed. The elimination of methyl groups from N(1,3) was not observed. Product analyses of imidazolium liquids irradiated in the very-high-dose regime (6.7 MGy) reveal several detrimental processes, including volatilization, acidification, and oligomerization. The latter yields a polymer with m/z of 650 ± 300 whose radiolytic yield increases with dose (~0.23 monomer units per 100 eV for 1-methyl-3-butylimidazolium trifluorosulfonate). Gradual generation of this polymer accounts for the steady increase in the viscosity of the ILs upon irradiation. Previous studies at lower dose have missed this species due to its wide mass distribution (stretching out to m/z 1600) and broad NMR lines, which make it harder to detect at lower concentrations. Among other observed changes is the formation of water immiscible fractions in hydrophilic ILs and water miscible fractions in hydrophobic ILs. The latter is due to anion fragmentation. The import of these observations for use of ILs as extraction solvents in nuclear cycle separations is discussed.

Room temperature ionic liquids (IL) find increasing use for the replacement of organic solvents in practical applications, including their use in solar cells and electrolytes for metal deposition, and as extraction solvents for the reprocessing of spent nuclear fuel. The radiation stability of ILs is an important concern for some of these applications, as previous studies suggested extensive fragmentation of the constituent ions upon irradiation. In the present study, electron paramagnetic resonance (EPR) spectroscopy has been used to identify fragmentation pathways for constituent anions in ammonium, phosphonium, and imidazolium ILs. Many of these detrimental reactions are initiated by radiation-induced redox processes involving these anions. Scission of the oxidized anions is the main fragmentation pathway for the majority of the practically important anions; (internal) proton transfer involving the aliphatic arms of these anions is a competing reaction. For perfluorinated anions, fluoride loss following dissociative electron attachment to the anion can be even more prominent than this oxidative fragmentation. Bond scission in the anion was also observed for NO(3)(-) and B(CN)(4)(-) anions and indirectly implicated for BF(4)(-) and PF(6)(-) anions. Among small anions, CF(3)SO(3)(-) and N(CN)(2)(-) are the most stable. Among larger anions, the derivatives of benzoate and imide anions were found to be relatively stable. This stability is due to suppression of the oxidative fragmentation. For benzoates, this is a consequence of the extensive sharing of unpaired electron density by the π-system in the corresponding neutral radical; for the imides, this stability could be the consequence of N-N σ(2)σ(*1) bond formation involving the parent anion. While fragmentation does not occur for these "exceptional" anions, H atom addition and electron attachment are prominent. Among the typically used constituent anions, aliphatic carboxylates were found to be the least resistant to oxidative fragmentation, followed by (di)alkyl phosphates and alkanesulfonates. The discussion of the radiation stability of ILs is continued in the second part of this study, which examines the fate of organic cations in such liquids.

Nuclear magnetic resonance (NMR) spectroscopy has been used to study hydrogen-bonding interactions between water, associated and dissociated acids (i.e., nitric and methanesulfonic acids), and the constituent ions of several water-immiscible room-temperature ionic liquids (ILs). In chloroform solutions also containing a crown ether (CE), water molecules strongly associate with the IL ions, and there is rapid proton exchange between these bound water molecules and hydronium associated with the CE. In neat ILs, the acids form clusters differing in their degree of association and ionization, and their interactions with the CEs are weak. The CE can either promote proton exchange between different clusters in IL solution when their association is weak or inhibit such exchange when the association is strong. Even strongly hydrophobic ILs are shown to readily extract nitric acid from aqueous solution, typically via the formation of a 1:1:1 {H(3)O(+)•CE}NO(3)(-) complex. In contrast, the extraction of methanesulfonic acid is less extensive and proceeds mainly by IL cation-hydronium ion exchange. The relationship of these protic equilibria to the practical application of hydrophobic ILs (e.g., in spent nuclear fuel reprocessing) is discussed.

Crown ethers (CEs) are macrocyclic ionophores used for the separation of strontium-90 from acidic nuclear waste streams. Room temperature ionic liquids (ILs) are presently being considered as replacements for traditional molecular solvents employed in such separations. It is desirable that the extraction efficacy obtained with such solvents should not deteriorate in the strong radiation fields generated by decaying radionuclides. This deterioration will depend on the extent of radiation damage to both the IL solvent and the CE solute. While radiation damage to ILs has been extensively studied, the issue of the radiation stability of crown ethers, particularly in an IL matrix, has not been adequately addressed. With this in mind, we have employed electron paramagnetic resonance (EPR) spectroscopy to study the formation of CE-related radicals in the radiolysis of selected CEs in ILs incorporating aromatic (imidazolium and pyridinium) cations. The crown ethers have been found to yield primarily hydrogen loss radicals, H atoms, and the formyl radical. In the low-dose regime, the relative yield of these radicals increases linearly with the mole fraction of the solute, suggesting negligible transfer of the excitation energy from the solvent to the solute; that is, the solvent has a "radioprotective" effect. The damage to the CE in the loading region of practical interest is relatively low. Under such conditions, the main chemical pathway leading to decreased extraction performance is protonation of the macrocycle. At high radiation doses, sufficient to increase the acidity of the IL solvent significantly, such proton complexes compete with the solvent cations as electron traps. In this regime, the CEs will rapidly degrade as the result of H abstraction from the CE ring by the released H atoms. Thus, the radiation dose to which a CE/IL system is exposed must be maintained at a level sufficiently low to avoid this regime.

Radical chemistry initiated by one-electron reduction of 1-methyl-3-alkylimidazolium cations in the corresponding ionic liquids (ILs) is examined. The reaction scheme is examined in light of the recent experimental data on photo-, radiation-, and electrochemically induced degradation of the practically important hydrophobic alkylimidazolium ILs. It is suggested that the primary species leading to the formation of the oligomers and acidification of the IL is a sigmasigma* dimer radical cation that loses a proton, yielding a neutral radical whose subsequent reactions produce C(2)-C(2) linked oligomers, both neutral and charged. The neutral oligomers (up to the tetramer) account for the features observed in the NMR spectra of cathodic liquid generated in electrolytic breakdown of the IL solvent. In photolysis and radiolysis, these neutral species and/or their radical precursors are oxidized by radical (ions) derived from the counteranions, and only charged dimers are observed. The dication dimers account for the features observed in the mass spectra of irradiated ILs. The products of these ion radical and radical reactions closely resemble those generated via carbene chemistry, without the formation of the carbene via the deprotonation of the parent cation. As the loss of 2-protons increases the proticity of the irradiated IL, it interferes with the extraction of metal ions by ionophore solutes, while the formation of the oligomers modifies solvent properties. Thus, the peculiarities of radical chemistry in the alkylimidazolium ILs have significant import for their practical applications.

Room-temperature ionic liquids (ILs) are a promising class of solvents for applications ranging from photovoltaics to solvent extractions. Some of these applications involve the exposure of the ILs to ionizing radiation, which stimulates interest in their radiation and photo- chemistry. In the case of ILs consisting of 1,3-dialkylimidazolium cations and hydrophobic anions, ionization, charge transfer and redox reactions yield charge-trapped species thought to be radicals resulting from neutralization of the constituent ions. Using computational chemistry methods and the recent results on electron spin resonance (ESR) and transient absorption spectroscopy of the ionized ILs, we argue that electron localization in the imidazolium ILs yields a gauche dimer radical cation with the elongated C(2)-C(2) bond. This species is shown to absorb in the near-infrared and the visible regions and accounts for the observed ESR spectra. We suggest that the excess electron in these aromatic ILs is localized as such a dimeric ion, and consider the chemical implications of this attribution. We also suggest that three-electron N-N bonding with the formation of a dimer radical anion occurs for amide anions, such as dicyanamide, when the parent anion traps holes; steric hindrance prevents the analogous reaction for bis(triflyl)amide anion. For another anion of practical importance, bis(oxalato)borate, a pathway involving the elimination of CO(2) is suggested. Together, these results indicate the unanticipated tendency of the ILs to localize primary charges as radical ions as opposed to neutral radicals. Thus, it appears that secondary chemistry in the ionized ILs may be dominated by radical ion reactions, similarly to the previously studied conventional organic liquids, depending on the composition of the IL.

Radical intermediates generated in radiolysis and photoionization of ionic liquids (ILs) composed of ammonium, phosphonium, pyrrolidinium, and imidazolium cations and bis(triflyl)amide, dicyanamide, and bis(oxalato)borate anions have been studied using magnetic resonance spectroscopy. Large yields of terminal and penultimate C-centered radicals are observed in the aliphatic chains of the phosphonium, ammonium, and pyrrolidinium cations, but not for imidazolium cation. This pattern is indicative of efficient deprotonation of a hole trapped on the parent cation (the radical dication) that competes with rapid electron transfer from a nearby anion. This charge transfer leads to the formation of stable N- or O-centered radicals; the dissociation of parent anions is a minor pathway. Addition of 10-40 wt % of trialkyl phosphate (a common extraction agent) has relatively little effect on the fragmentation of the ILs. The yield of the alkyl radical fragment generated by dissociative electron attachment to the trialkyl phosphate is <4% of the yield of the radical fragments derived from the IL solvent. The import of these observations for radiation stability of the prospective nuclear cycle extraction systems based upon the ILs is discussed.

Adiabatic mixed quantum/classical (MQC) molecular dynamics (MD) simulations were used to generate snapshots of the hydrated electron in liquid water at 300 K. Water cluster anions that include two complete solvation shells centered on the hydrated electron were extracted from the MQC MD simulations and embedded in a roughly 18 Ax18 Ax18 A matrix of fractional point charges designed to represent the rest of the solvent. Density functional theory (DFT) with the Becke-Lee-Yang-Parr functional and single-excitation configuration interaction (CIS) methods were then applied to these embedded clusters. The salient feature of these hybrid DFT(CIS)/MQC MD calculations is significant transfer (approximately 18%) of the excess electron's charge density into the 2p orbitals of oxygen atoms in OH groups forming the solvation cavity. We used the results of these calculations to examine the structure of the singly occupied and the lower unoccupied molecular orbitals, the density of states, the absorption spectra in the visible and ultraviolet, the hyperfine coupling (hfcc) tensors, and the infrared (IR) and Raman spectra of these embedded water cluster anions. The calculated hfcc tensors were used to compute electron paramagnetic resonance (EPR) and electron spin echo envelope modulation (ESEEM) spectra for the hydrated electron that compared favorably to the experimental spectra of trapped electrons in alkaline ice. The calculated vibrational spectra of the hydrated electron are consistent with the red-shifted bending and stretching frequencies observed in resonance Raman experiments. In addition to reproducing the visible/near IR absorption spectrum, the hybrid DFT model also accounts for the hydrated electron's 190-nm absorption band in the ultraviolet. Thus, our study suggests that to explain several important experimentally observed properties of the hydrated electron, many-electron effects must be accounted for: one-electron models that do not allow for mixing of the excess electron density with the frontier orbitals of the first-shell solvent molecules cannot explain the observed magnetic, vibrational, and electronic properties of this species. Despite the need for multielectron effects to explain these important properties, the ensemble-averaged radial wavefunctions and energetics of the highest occupied and three lowest unoccupied orbitals of the hydrated electrons in our hybrid model are close to the s- and p-like states obtained in one-electron models. Thus, one-electron models can provide a remarkably good approximation to the multielectron picture of the hydrated electron for many applications; indeed, the two approaches appear to be complementary.

Density functional theory is used to rationalize magnetic parameters of hydrated electron trapped in alkaline glasses as observed using electron paramagnetic resonance (EPR) and electron spin echo envelope modulation (ESEEM) spectroscopies. To this end, model water cluster anions (n=4-8 and n=20, 24) that localize the electron internally are examined. It is shown that hyperfine coupling tensors of H/D nuclei in the water molecules are defined mainly by the cavity size and the coordination number of the electron; the water molecules in the second solvation shell play a relatively minor role. An idealized model of the hydrated electron (that is usually attributed to L. Kevan) in which six hydroxyl groups arranged in an octahedral pattern point toward the common center is shown to provide the closest match to the experimental parameters, such as isotropic and anisotropic hyperfine coupling constants for the protons (estimated from ESEEM), the second moment of the EPR spectra, and the radius of gyration. The salient feature is the significant transfer (10-20%) of spin density into the frontal O 2p orbitals of water molecules. Spin bond polarization involving these oxygen orbitals accounts for small, negative hyperfine coupling constants for protons in hydroxyl groups that form the electron-trapping cavity. In Part 2, these results are generalized for more realistic geometries of core anions obtained using a dynamic one-electron mixed quantum/classical molecular dynamics model.

Photostimulated electron detachment from aqueous inorganic anions is the simplest example of solvent-mediated electron transfer reaction. As such, this photoreaction became the subject of many ultrafast studies. Most of these studied focused on the behavior of halide anions, in particular, iodide, that is readily accessible in the UV. In this study, we contrast the behavior of these halide anions with that of small polyatomic anions, such as pseudohalide anions (e.g., HS(-)) and common polyvalent anions (e.g., SO(3)(2-)). Geminate recombination dynamics of hydrated electrons generated by 200 nm photoexcitation of aqueous anions (I(-), Br(-), OH(-), HS(-), CNS(-), CO(3)(2-), SO(3)(2-), and Fe(CN)(6)(4-)) have been studied. Prompt quantum yields for the formation of solvated, thermalized electrons and quantum yields for free electrons were determined. Pump-probe kinetics for 200 nm photoexcitation were compared with kinetics obtained at lower photoexcitation energy (225 or 242 nm) for the same anions, where possible. Free diffusion and mean force potential models of geminate recombination dynamics were used to analyze these kinetics. These analyses suggest that for polyatomic anions (including all polyvalent anions studied) the initial electron distribution has a broad component, even at relatively low photoexcitation energy. There seems to be no well-defined threshold energy below which the broadening of this electron distribution does not occur, as is the case for halide anions. The constancy of (near-unity) prompt quantum yields vs the excitation energy as the latter is scanned across the lowest charge-transfer-to-solvent band of the anion is observed for halide anions but not for other anions: the prompt quantum yields are considerably less than unity and depend strongly on the excitation energy. Our study suggests that halide anions are in the class of their own; electron photodetachment from polyatomic, especially polyvalent, anions exhibits qualitatively different behavior.

This study seeks an answer to the following question: Is it possible to design a supramolecular cage that would "solvate" the excess electron in the same fashion in which several solvent molecules do that cooperatively in polar liquids? Two general strategies are outlined for this "electron encapsulation", viz. electron localization using polar groups arranged on the (i) inside of the cage or (ii) outside of the cage. The second approach is more convenient from the synthetic standpoint, but it is limited to polynitriles. We demonstrate, experimentally and theoretically, that this second approach faces a problem: the electron attaches to the nitrile groups, forming molecular anions with bent C-C-N fragments. Because the energy cost of this bending is high, for dinitrile anions in n-hexane, the binding energies for the electron are low and, for mononitriles, these binding energies are lower still, and the entropy of electron attachment is anomalously small. Density functional theory modeling of electron trapping by mononitriles in n-hexane suggests that the solute molecules substitute for the solvent molecules at the electron cavity, "solvating" the electron by their methyl groups. We argue that such species would be more correctly viewed as multimer radical anions in which the electron density is shared (mainly) between C 2p orbitals in the solute/solvent molecules, rather than cavity electrons. The way in which the excess electron density is shared by such molecules is similar to the way in which this sharing occurs in large di- and polynitrile anions, such as 1,2,4,5,7,8,10,11-octacyanocyclododecane(-). Only in this sense is the electron encapsulation possible. The work thus reveals limitations of the concept of "solvated electron" for organic liquids: it is impossible to draw a clear line between such species and a certain class of radical anions.

The excess electron in liquid ammonia ("ammoniated electron") is commonly viewed as a cavity electron in which the s-type wave function fills the interstitial void between 6 and 9 ammonia molecules. Here we examine an alternative model in which the ammoniated electron is regarded as a solvent stabilized multimer radical anion in which most of the excess electron density resides in the frontier orbitals of N atoms in the ammonia molecules forming the solvation cavity. The cavity is formed due to the repulsion between negatively charged solvent molecules. Using density functional theory calculations, we demonstrate that such core anions would semiquantitatively account for the observed pattern of Knight shifts for 1H and 14N nuclei observed by NMR spectroscopy and the downshifted stretching and bending modes observed by infrared spectroscopy. We speculate that the excess electrons in other aprotic solvents might be, in this respect, analogous to the ammoniated electron, with substantial transfer of the spin density into the frontier N and C orbitals of methyl, amino, and amide groups.

Experimental observations are presented on condensed-phase analogues of gas-phase dipole-bound anions and negatively charged clusters of polar molecules. Both monomers and small clusters of such molecules can reversibly trap conduction band electrons in dilute alkane solutions. The dynamics and energetics of this trapping have been studied using pulse radiolysis-transient absorption spectroscopy and time-resolved photoconductivity. Binding energies, thermal detrapping rates, and absorption spectra of excess electrons attached to monomer and multimer solute traps are obtained, and possible structures for these species are discussed. "Dipole coagulation" (stepwise growth of the solute cluster around the cavity electron) predicted by Mozumder in 1972 is observed. The acetonitrile monomer is shown to solvate the electron by its methyl group, just as the alkane solvent does. The electron is dipole-bound to the CN group; the latter points away from the cavity. The resulting negatively charged species has a binding energy of 0.4 eV and absorbs in the infrared. Molecules of straight-chain aliphatic alcohols solvate the excess electron by their OH groups; at equilibrium, the predominant electron trap is a trimer or a tetramer, and the binding energy of this solute trap is ca. 0.8 eV. Trapping by smaller clusters is opposed by the entropy that drives the equilibrium toward the electron in a solvent trap. For alcohol monomers, the trapping does not occur; a slow proton-transfer reaction occurs instead. For the acetonitrile monomer, the trapping is favored energetically, but the thermal detachment is rapid (ca. 1 ns). Our study suggests that a composite cluster anion consisting of a few polar molecules imbedded in an alkane "matrix" might be the closest gas-phase analogue to the core of solvated electron in a neat polar liquid.

Temporal evolution of transient absorption (TA) spectra of electrons generated by above-the-gap (12.4 eV total energy) two-photon ionization of liquid H2O and D2O has been studied on femto- and picosecond time scales. The spectra were obtained at intervals of 50 nm between 0.5 and 1.7 mum. Two distinct regimes of the spectral evolution were observed: t < 1 ps and t > 1 ps. In both of these regimes, the spectral profile changes considerably with the delay time of the probe pulse. The "continuous blue shift" and the "temperature jump" models, in which the spectral profile does not change as it progressively shifts, as a whole, to the blue, are not supported by our data. Furthermore, no p-state electron, postulated by several authors to be a short-lived intermediate of the photoionization process, was observed by the end of the 300 fs, 200 nm pump pulse. For t < 1 ps, two new TA features (the 1.15 microm peak and 1.4 mum shoulder) were observed for the electron in the spectral region where O-H overtones appear in the spectra of light water. These two features were not observed for the electron in D2O. The 1.4 mum peak observed in D2O may be the isotope-shift analogue of the 1.15 microm feature in H2O. Vibronic coupling to the modes of water molecules lining the solvation cavity is a possible origin of these features. On the sub-picosecond time scale, the absorption band of solvated electron progressively shifts to the blue. At later delay times (t > 1 ps), the position of the band maximum is "locked", but the spectral profile continues to change by narrowing on the red side and broadening on the blue side; the oscillator strength is constant within 10%. The time constant of this narrowing is ca. 0.56 ps for H2O and 0.64 ps for D2O. Vibrational relaxation and time-dependent decrease in the size and sphericity of the solvation cavity are suggested as possible causes for the observed spectral transformations in both of these regimes.