A first-principles alternative to empirical solvent parameters.

The use of solvents is ubiquitous in chemistry. Empirical parameters, such as the Kamlet-Taft parameters and Gutmann donor/acceptor numbers, have long been used to predict and quantify the effects solvents have on chemical phenomena. Collectively however, such parameters are unsatisfactory, since each describes ultimately the same non-covalent solute-solvent and solute-solute interactions in completely disparate ways. Here we hypothesise that empirical solvent parameters are essentially proxy measures of the electrostatic terms that dominate solvent-solute interactions. On the basis of this hypothesis, we develop a new fundamental descriptor of these interactions, , and show that it is a self-consistent, probe-free, first principles alternative to established empirical solvent parameters.

Solvent-Modulated Specific Ion Effects: Poly(N-isopropylacrylamide) Brushes in Nonaqueous Electrolytes.

Pertinent to cryopreservation as well as energy storage and batteries, nonaqueous electrolytes and their mixtures with water were investigated. In particular, specific ion-induced effects on the modulation of a poly(N-isopropylacrylamide) (PNIPAM) brush were investigated in various dimethyl sulfoxide (DMSO)-water solvent mixtures. Spectroscopic ellipsometry and neutron reflectometry were employed to probe changes in brush swelling and structure, respectively. In water-rich solvents (i.e., pure water and 6 mol % DMSO), PNIPAM undergoes a swollen to collapsed thermotransition with increasing temperature, whereby a forward Hofmeister series was noted; K+ and Li+ electrolytes composed of SCN- and I- salted-in (stabilized) PNIPAM chains, and electrolytes of Cl- and Br- salted-out (destabilized) the polymer. The cation was seen to play a lesser role than that of the anion, merely modulating the magnitude of the anion effect. In 70 mol % DMSO, a collapsed to swollen thermotransition was noted for PNIPAM. Here, concentration-dependent specific ion effects were observed; a forward series was observed in 0.2 mol % electrolytes, whereas increasing the electrolyte concentration to 0.9 mol % led to a series reversal. While no thermotransition was observed in pure DMSO, a solvent-induced specific ion series reversal was noted; SCN- destabilized the brush and Cl- stabilized the brush. Both series reversals are attributed to the delicate balance of interactions between the solvent, solute (ion), and substrate (brush). Namely, the stability of the solvent clusters was hypothesized to drive polymer solvation.

Hofmeister effects influence bulk nanostructure in a protic ionic liquid.

HYPOTHESIS: The origins and behaviour of specific ion effects have been studied in water for more than a century, and more recently in nonaqueous molecular solvents. However, the impacts of specific ion effects on more complex solvents such as nanostructured ionic liquids remains unclear. Here, we hypothesise that the influence of dissolved ions on the hydrogen bonding in the nanostructured ionic liquid propylammonium nitrate (PAN) constitutes a specific ion effect. EXPERIMENTS: We performed molecular dynamics simulations of bulk PAN and 1-50 mol% PAN-PAX (X = halide anions F-, Cl-, Br-, I-) and PAN-YNO3 (Y = alkali metal cations, Li+, Na+, K+ and Rb+) solutions to investigate how monovalent salts influence the bulk nanostructure in PAN. FINDINGS: The key structural characteristic in PAN is a well-defined hydrogen bond network formed within the polar and non-polar domains in its nanostructure. We show that dissolved alkali metal cations and halide anions have significant and unique influences on the strength of this network. Cations (Li+, Na+, K+ and Rb+) consistently promote hydrogen bonding in the PAN polar domain. Conversely, the influence of halide anions (F-, Cl-, Br-, I-) is ion specific; while F- disrupts PAN hydrogen bonding, I- promotes it. The manipulation of PAN hydrogen bonding therefore constitutes a specific ion effect - i.e. a physicochemical phenomena caused by the presence of dissolved ions, which are dependent on these ions' identity. We analyse these results using a recently proposed predictor of specific ion effects developed for molecular solvents, and show that it is also capable of rationalising specific ion effects in the more complex solvent environment of an ionic liquid.

From Hofmeister to hydrotrope: Effect of anion hydrocarbon chain length on a polymer brush.

HYPOTHESIS: Specific ion effects govern myriad biological phenomena, including protein-ligand interactions and enzyme activity. Despite recent advances, detailed understanding of the role of ion hydrophobicity in specific ion effects, and the intersection with hydrotropic effects, remains elusive. Short chain fatty acid sodium salts are simple amphiphiles which play an integral role in our gastrointestinal health. We hypothesise that increasing a fatty acid's hydrophobicity will manifest stronger salting-out behaviour. EXPERIMENTS: Here we study the effect of these amphiphiles on an exemplar thermoresponsive polymer brush system, conserving the carboxylate anion identity while varying anion hydrophobicity via the carbon chain length. Ellipsometry and quartz crystal microbalance with dissipation monitoring were used to characterise the thermoresponse and viscoelasticity of the brush, respectively, whilst neutron reflectometry was used to reveal the internal structure of the brush. Diffusion-ordered nuclear magnetic resonance spectroscopy and computational investigations provide insight into polymer-ion interactions. FINDINGS: Surface sensitive techniques unveiled a non-monotonic trend in salting-out ability with increasing anion hydrophobicity, revealing the bundle-like morphology of the ion-collapsed system. An intersection between ion-specific and hydrotropic effects was observed both experimentally and computationally; trending from good anti-hydrotrope towards hydrotropic behaviour with increasing anion hydrophobicity, accompanying a change in hydrophobic hydration.

A quantum chemical molecular dynamics repository of solvated ions.

The importance of ion-solvent interactions in predicting specific ion effects in contexts ranging from viral activity through to electrolyte viscosity cannot be underestimated. Moreover, investigations of specific ion effects in nonaqueous systems, highly relevant to battery technologies, biochemical systems and colloid science, are severely limited by data deficiency. Here, we report IonSolvR - a collection of more than 3,000 distinct nanosecond-scale ab initio molecular dynamics simulations of ions in aqueous and non-aqueous solvent environments at varying effective concentrations. Density functional tight binding (DFTB) is used to detail the solvation structure of up to 55 solutes in 28 different protic and aprotic solvents. DFTB is a fast quantum chemical method, and as such enables us to bridge the gap between efficient computational scaling and maintaining accuracy, while using an internally-consistent simulation technique. We validate the database against experimental data and provide guidance for accessing individual IonSolvR records.

Understanding specific ion effects and the Hofmeister series.

Specific ion effects (SIE), encompassing the Hofmeister Series, have been known for more than 130 years since Hofmeister and Lewith's foundational work. SIEs are ubiquitous and are observed across the medical, biological, chemical and industrial sciences. Nevertheless, no general predictive theory has yet been able to explain ion specificity across these fields; it remains impossible to predict when, how, and to what magnitude, a SIE will be observed. In part, this is due to the complexity of real systems in which ions, counterions, solvents and cosolutes all play varying roles, which give rise to anomalies and reversals in anticipated SIEs. Herein we review the historical explanations for SIE in water and the key ion properties that have been attributed to them. Systems where the Hofmeister series is perturbed or reversed are explored, as is the behaviour of ions at the liquid-vapour interface. We discuss SIEs in mixed electrolytes, nonaqueous solvents, and in highly concentrated electrolyte solutions - exciting frontiers in this field with particular relevance to biological and electrochemical applications. We conclude the perspective by summarising the challenges and opportunities facing this SIE research that highlight potential pathways towards a general predictive theory of SIE.

The electrostatic origins of specific ion effects: quantifying the Hofmeister series for anions.

Life as we know it is dependent upon water, or more specifically salty water. Without dissolved ions, the interactions between biological molecules are insufficiently complex to support life. This complexity is intimately tied to the variation in properties induced by the presence of different ions. These specific ion effects, widely known as Hofmeister effects, have been known for more than 100 years. They are ubiquitous throughout the chemical, biological and physical sciences. The origin of these effects and their relative strengths is still hotly debated. Here we reconsider the origins of specific ion effects through the lens of Coulomb interactions and establish a foundation for anion effects in aqueous and non-aqueous environments. We show that, for anions, the Hofmeister series can be explained and quantified by consideration of site-specific electrostatic interactions. This can simply be approximated by the radial charge density of the anion, which we have calculated for commonly reported ions. This broadly quantifies previously unpredictable specific ion effects, including those known to influence solution properties, virus activities and reaction rates. Furthermore, in non-aqueous solvents, the relative magnitude of the anion series is dependent on the Lewis acidity of the solvent, as measured by the Gutmann Acceptor Number. Analogous SIEs for cations bear limited correlation with their radial charge density, highlighting a fundamental asymmetry in the origins of specific ion effects for anions and cations, due to competing non-Coulombic phenomena.

Lewis Strength Determines Specific-Ion Effects in Aqueous and Nonaqueous Solvents.

An analysis of specific-ion effects in aqueous and nonaqueous solvents using energy decomposition analysis is presented. Specific-ion effects induce or influence physicochemical phenomena in a way that is determined by the identity of the ions present, and not merely by their charge or concentration. Such effects have been known since the seminal work of Hofmeister and are often categorized according to the well-known Hofmeister series. Examples of specific-ion effects are ubiquitous throughout chemistry and biology and are traditionally explained in terms of the influence ions have on the structure of water. However, this explanation is unsatisfactory because it is unable to adequately explain and predict frequently observed series reversals and anomalies. Further, recent experiments have shown that specific-ion effects are observed in nonaqueous solvents. By modeling solvated ion-N-isopropylacrylamide (NIPAM) complexes, we show here that specific-ion effects on ion-NIPAM interaction free energies are observed not only in water, but also in several nonaqueous solvents (methanol, acetonitrile, DMSO) in correspondence with the ions' Lewis Strengths. Interestingly, the same trends are observed in the absence of a solvent environment altogether. Counterion effects on ion-NIPAM interaction free energies are negligible for dissociated ion pairs but are evident in associated ion pairs because of the modulation of repulsive ion-NIPAM interactions. We propose a mechanism for explaining reversals in specific-ion effects, based on the competing strengths of the ion-solvent and ion-NIPAM interaction and their relative Lewis strengths. This extends existing theories regarding specific-ion effect reversals in aqueous solutions, as we show that solvent properties must also be taken in to account for specific-ion effects to be predicted in arbitrary solvent environments.