Equity for women and underrepresented minorities in STEM: Graduate experiences and career plans in chemistry.

Recent events prompted scientists in the United States and throughout the world to consider how systematic racism affects the scientific enterprise. This paper provides evidence of inequities related to race-ethnicity and gender in graduate school experiences and career plans of PhD students in the top 100 ranked departments in one science, technology, engineering, and math (STEM) discipline, chemistry. Mixed-model regression analyses were used to examine factors that might moderate these differences. The results show that graduate students who identified as a member of a racial/ethnic group traditionally underrepresented in chemistry (underrepresented minorities, URM) were significantly less likely than other students to report that their financial support was sufficient to meet their needs. They were also less likely to report having supportive relationships with peers and postdocs. Women, and especially URM women, were significantly less likely to report supportive relationships with advisors. Despite their more negative experiences in graduate school, students who identified as URM expressed greater commitment to finishing their degree and staying in the field. When there was at least one faculty member within their departments who also identified as URM they were also more likely than other students to aspire to a university professorship with an emphasis on research. Men were significantly more likely than women to express strong commitment to finishing the PhD and remaining in chemistry, but this difference was stronger in top-ranked departments. Men were also more likely than women to aspire to a professorship with an emphasis on research, and this difference remained when individual and departmental-level variables were controlled.

Formation and surface-stabilizing contributions to bare nanoemulsions created with negligible surface charge.

The stabilization of nanoemulsions, nanosized oil droplets dispersed in water, is commonly achieved through the addition of surfactants and polymers. However, nanoemulsions in the absence of emulsifiers have been observed to acquire a significant negative charge at their surface, which ultimately contributes to their stability. While the source of this negative charge is disputed to this day, its presence is taken as an inherent property of the aqueous-hydrophobic interface. This report provides a look at the molecular structure and bonding characteristics of bare aqueous-hydrophobic nanoemulsion interfaces. We report the creation of bare nanoemulsions with near zero surface charge, which are marginally stable for several days. The process of creating these low-charge nanoemulsions (LCNEs) required rigorous cleaning procedures and proper solvent storage conditions. Using vibrational sum-frequency scattering spectroscopy, we measure the structure and bonding of the interfacial aqueous and hydrophobic phases. The surfaces of these LCNE samples possess a measurable free OH vibration, not found in previous studies and indicative of a clean interface. Tuning the nanoemulsion charge through addition of anionic surfactants, modeling potential surface-active contaminants, we observe the free OH to disappear and a reorientation of the interfacial hydrophobic molecules at micromolar surfactant concentrations. Notably, the free OH vibration provides evidence for stronger dispersion interactions between water molecules and the hydrophobic phase at the LCNE surface compared with similar planar water-alkane interfaces. We propose the stronger bonding interactions, in addition to an ordered interfacial aqueous layer, contribute to the delayed droplet coalescence and subsequent phase separation.

Interfacial Steric and Molecular Bonding Effects Contributing to the Stability of Neutrally Charged Nanoemulsions.

In cosmetic, pharmaceutical, and food applications, many active ingredients have limited bioavailability in an aqueous environment, and in that context, nanoemulsions provide a mechanism for encapsulation, protection, and transport. These dispersed oil droplets are on the order of 100s of nanometers in diameter and owe their long-term stability to emulsifiers that are commonly charged. More recently, applications have been utilizing nonionic species as stabilizing agents due to their enhanced biosafety. DLVO (named after Derjaguin, Landau, Verwey, and Overbeek) theory has been central in the description of colloid stability, which emphasizes repulsive electrostatic forces, while extended DLVO theory also accounts for steric effects. Past studies of nanoemulsions have largely employed charged surfactants and polyelectrolytes, making it difficult to decouple electrostatic and steric effects as they relate to droplet stability. To better understand steric and molecular factors contributing to the stability of "uncharged" droplets, we have created nanoemulsions with sodium dodecyl sulfate (SDS) and poly(N-vinylacetamide) (PNVA). Though SDS is anionic, with PNVA coating the droplet surfaces, the ζ-potentials of these nanoemulsions are ∼0 mV. Despite minimizing electrostatic contributions, these nanoemulsions are stable for upward of a month with interesting dynamics. By employing dynamic light scattering, vibrational sum frequency scattering spectroscopy, and calculating interaction pair potentials using extended DLVO theory, we learn that the thickness of the PNVA layer plays a critical role in stabilizing these "uncharged" nanoemulsions. Beyond the sterics, the molecular conformation of the PNVA strands also contributes to the droplet stability. The adsorbed PNVA strands are shown to form stratified, rigid polymer networks that prevent the nanoemulsions from rapid destabilization.

Effects of Salt-Induced Charge Screening on AOT Adsorption to the Planar and Nanoemulsion Oil-Water Interfaces.

Nanoemulsions, nanosized droplets of oil, are easily stabilized by interfacial electric fields from the adsorption of ionic surfactants. While mean-field theories can be used to describe the impact of these interfacial fields on droplet stability, the influence of these fields on the adsorption properties of ionic surfactants is not well-understood. In this work, we study the adsorption of the surfactant sodium dioctyl sulfosuccinate (AOT) at the nanoemulsion and planar oil-water interfaces and investigate how salt-induced charge-screening affects AOT adsorption. In the absence of salt, vibrational sum-frequency scattering spectroscopy measurements reveal the ΔGads and the maximum surface density is the same for AOT at the hexadecane nanoemulsion surface as at the planar hexadecane-H2O interface. Upon the addition of NaCl, an increase in AOT surface density is detected at both interfaces, indicating that repulsive electrostatic interactions between AOT monomers are the dominant force limiting surfactant adsorption at both interfaces. The bulky alkyl chains of AOT molecules cause our observations in this study to differ from those found in previous studies investigating the adsorption of linear-chain ionic surfactants to the nanoemulsion surface. These results provide necessary information for understanding factors limiting the adsorption of ionic surfactants to nanodroplet surfaces and highlight the need for further studies into the adsorption properties of more complex macromolecules at nanoemulsion surfaces.

Playing Favorites: Preferential Adsorption of Nonionic over Anionic Surfactants at the Liquid/Liquid Interface.

While many studies have investigated synergic interactions between surfactants in mixed systems, understanding possible competitive behaviors between interfacial components of binary surfactant systems is necessary for the optimized efficacy of applications dependent on surface properties. Such is the focus of these studies in which the surface behavior of a binary surfactant mixture containing nonionic (Span-80) and anionic (AOT) components adsorbing to the oil/water interface was investigated with vibrational sum-frequency (VSF) spectroscopy and surface tensiometry experimental methods. Time-dependent spectroscopic studies reveal that while both nonionic and anionic surfactants initially adsorb to the interface, anionic surfactants desorb over time as the nonionic surfactant continues to adsorb. Concentration studies that vary the ratio of Span-80 to AOT in bulk solution show that the nonionic surfactant preferentially adsorbs to the oil/water interface over the anionic surfactant. These studies have important implications for applications in which mixed surfactant systems are used to alter interfacial properties, such as pharmaceuticals, industrial films, and environmental remediation.

Coming to Order: Adsorption and Structure of Nonionic Polymer at the Oil/Water Interface as Influenced by Cationic and Anionic Surfactants.

Polymer-surfactant mixtures are versatile chemical systems because of their ability to form a variety of complexes both in bulk solution and at surfaces. The adsorption and structure of polymer-surfactant complexes at the oil/water interface define their use surface chemistry applications. Previous studies have investigated the interactions between charged polyelectrolytes and surfactants; however, a similar level of insight into the interfacial behavior of nonionic polymers in mixed systems is lacking. The study herein uses vibrational sum frequency (VSF) spectroscopy to elucidate the molecular details of nonionic polyacrylamide (PAM) adsorption to the oil/water interface in the presence of surfactant. The polymer's adsorption and conformational structure at the interface is investigated as it interacts with cationic and anionic surfactants. Where the polymer will not adsorb to the interface on its own in solution, the presence of either cationic or anionic surfactant causes favorable adsorption of the polymer to the oil/water interface. VSF spectra indicate that the cationic surfactant interacts with PAM at the interface through charge-dipole interactions to induce conformational ordering of the polymer backbone. However, conformational ordering of polymer is not induced at the interface when anionic surfactant is present.

Probing the Molecular Structure of Coadsorbed Polyethylenimine and Charged Surfactants at the Nanoemulsion Droplet Surface.

Nanoemulsions, nanoscale oil droplets dispersed in an aqueous medium, can be stabilized by polymer-surfactant (PS) mixtures, making them ubiquitous in commercial, industrial, and pharmaceutical applications. It is well-known that the presence of PS layers coadsorbed at the droplet surface plays a significant role in droplet stability and functionality; however, little is understood about the molecular nature of this coadsorption. Such insights are especially important for application in drug delivery where physiological conditions can vary the environmental pH and significantly impact stabilization. Hence, the focus of this study examines the surface properties of ∼300 nm nanoemulsions stabilized by the coadsorption of polyethylenimine (PEI) and charged alkyl surfactants sodium dodecyl sulfate (SDS) and dodecyltrimethylammonium bromide (DTAB). PEI is a common charge-tunable polymer used in nanocarrier templates. This study employs vibrational sum frequency scattering spectroscopy, coupled with ζ-potential and surface pressure measurements performed as a function of varying concentrations and pH. The surface specific spectroscopic results reported herein reveal that PEI adsorption and molecular ordering is influenced by both electrostatic and hydrophobic interactions. While the degree of PEI adsorption is stronger in the presence of anionic SDS than cationic DTAB, for both surfactants, PEI is molecularly disordered in acidic conditions and adopts a persistent net ordering as the solution pH becomes more basic. Both surfactants also display degrees of interfacial conformational ordering that is altered by the presence of the coadsorbed polymer. These results demonstrate the molecular-level diversity in PEI behavior at the droplet interface and provide insight into how such behavior can be controlled to yield nanocarrier technology with specific functions and enhanced efficacy.

Diol it up: The influence of NaCl on methylglyoxal surface adsorption and hydration state at the air-water interface.

Methylglyoxal (MG)-an atmospherically important α-dicarbonyl implicated in aqueous-phase secondary organic aerosol formation-is known to be surface-active. Due to the presence of carbonyl moieties, MG can hydrate to form geminal diols in solution. Recently, it has been shown that MG exists predominantly as a monohydrate at the neat air-water interface. However, inorganic aerosol constituents have the potential to "salt-out" MG to the interface, shift its hydration equilibria, and catalyze self- and cross-oligomerization reactions. Here, we study the influence of the non-reactive salt, sodium chloride (NaCl), on the MG's surface adsorption and hydration state using vibrational sum frequency spectroscopy. The presence of NaCl is found to enhance MG's surface activity but not to the extent that water is fully excluded from the interface. Perturbations in the interfacial water structure are attributed to shifts in MG's hydration equilibrium at higher ionic strengths. Evidence of surface-active MG oligomer species is presented, but such oligomers are not thought to contribute significantly to the interfacial population. This work builds on the published studies on MG in pure water and gives insight into the interface's perturbation by NaCl, which has important implications for understanding MG's atmospheric fate.

Molecular characterization of water and surfactant AOT at nanoemulsion surfaces.

Nanoemulsions and microemulsions are environments where oil and water can be solubilized in one another to provide a unique platform for many different biological and industrial applications. Nanoemulsions, unlike microemulsions, have seen little work done to characterize molecular interactions at their surfaces. This study provides a detailed investigation of the near-surface molecular structure of regular (oil in water) and reverse (water in oil) nanoemulsions stabilized with the surfactant dioctyl sodium sulfosuccinate (AOT). Vibrational sum-frequency scattering spectroscopy (VSFSS) is used to measure the vibrational spectroscopy of these AOT stabilized regular and reverse nanoemulsions. Complementary studies of AOT adsorbed at the planar oil-water interface are conducted with vibrational sum-frequency spectroscopy (VSFS). Jointly, these give comparative insights into the orientation of interfacial water and the molecular characterization of the hydrophobic and hydrophilic regions of AOT at the different oil-water interfaces. Whereas the polar region of AOT and surrounding interfacial water molecules display nearly identical behavior at both the planar and droplet interface, there is a clear difference in hydrophobic chain ordering even when possible surface concentration differences are taken into account. This chain ordering is found to be invariant as the nanodroplets grow by Ostwald ripening and also with substitution of different counterions (Na:AOT, K:AOT, and Mg:AOT) that consequently also result in different sized nanoparticles. The results paint a compelling picture of surfactant assembly at these relatively large nanoemulsion surfaces and allow for an important comparison of AOT at smaller micellar (curved) and planar oil-water interfaces.

Molecular Interactions Leading to the Coadsorption of Surfactant Dodecyltrimethylammonium Bromide and Poly(styrenesulfonate) at the Oil/Water Interface.

The strong synergistic adsorption of mixed polymer/surfactant (P/S) systems at the oil/water interface shows promise for applications such as oil remediation and emulsion stabilization, especially with respect to the formation of tunable mesoscopic multilayers. There is some evidence that a combination of dodecyltrimethylammonium bromide (DTAB) and sodium poly(styrenesulfonate) (PSS) exhibits the adsorption of a secondary P/S layer, though the structure of this layer has long eluded researchers. The focus of this study is to determine whether the DTAB-assisted adsorption of PSS at the oil/water interface occurs as a single layer or with subsequent multilayers. The study presented uses vibrational sum-frequency spectroscopy and interfacial tensiometry to determine the degree of PSS adsorption and orientation of its charged groups relative to the interface at three representative concentrations of DTAB. At low and intermediate DTAB concentrations, a single mixed DTAB/PSS monolayer adsorbs at the oil/water interface. No PSS adsorbs above the system critical micelle concentration. The interfacial charge is found to be similar to that of P/S complexes solvated in the aqueous solution. The surface adsorbate and P/S complexes in the bulk both exhibit a charge inversion at around the same DTAB concentration. This study demonstrates the importance of techniques which can differentiate between coadsorbing species and calls into question current models of P/S adsorption at an oil/water interface.

On the Rise: Experimental and Computational Vibrational Sum Frequency Spectroscopy Studies of Pyruvic Acid and Its Surface-Active Oligomer Species at the Air-Water Interface.

It is well known that atmospheric aerosol play important roles in the environment. However, there is still much to learn about the processes that form aerosols, particularly aqueous secondary organic aerosols. While pyruvic acid (PA) is often better known for its biological significance, it is also an abundant atmospheric secondary organic ketoacid. It has been shown that, in bulk aqueous environments, PA exists in equilibrium between unhydrated α-keto carboxylic acid (PYA) and singly hydrated geminal diol carboxylic acid (PYT), favoring the diol. These studies have also identified oligomer products in the bulk, including zymonic acid (ZYA) and parapyruvic acid (PPA). The surface behavior of these oligomers has not been studied, and their contributions (if any) to the interface are unknown. Here, we address this knowledge gap by examining the molecular species present at the interface of aqueous PA systems using vibrational sum frequency spectroscopy (VSFS), a surface-sensitive technique. VSFS provides information about interfacial molecular populations, orientations, and behaviors. Computational studies using classical molecular dynamics and quantum mechanical density functional theory are employed in combination to afford further insights into these systems. Our studies indicate populations of at least two intensely surface-active oligomeric species at the interface. Computational results demonstrate that, along with PYA and PYT, both PPA and ZYA are surface-active with strong VSF responses that can account for features in the experimental spectra.

Model Behavior: Characterization of Hydroxyacetone at the Air-Water Interface Using Experimental and Computational Vibrational Sum Frequency Spectroscopy.

Small atmospheric aldehydes and ketones are known to play a significant role in the formation of secondary organic aerosols (SOA). However, many of them are difficult to experimentally isolate, as they tend to form hydration and oligomer species. Hydroxyacetone (HA) is unusual in this class as it contributes to SOA while existing predominantly in its unhydrated monomeric form. This allows HA to serve as a valuable model system for similar secondary organic carbonyls. In this paper the surface behavior of HA at the air-water interface has been investigated using vibrational sum frequency (VSF) spectroscopy and Wilhelmy plate surface tensiometry in combination with computational molecular dynamics simulations and density functional theory calculations. The experimental results demonstrate that HA has a high degree of surface activity and is ordered at the interface. Furthermore, oriented water is observed at the interface, even at high HA concentrations. Spectral features also reveal the presence of both cis and trans HA conformers at the interface, in differing orientations. Molecular dynamics results indicate conformer dependent shifts in HA orientation between the subsurface (∼5 Šdeep) and surface. Together, these results provide a picture of a highly dynamic, but statistically ordered, interface composed of multiple HA conformers with solvated water. These results have implications for HA's behavior in aqueous particles, which may affect its role in the atmosphere and SOA formation.

Interaction of SO2 with the Surface of a Water Nanodroplet.

We present a comprehensive computational study of interaction of a SO2 with water molecules in the gas phase and with the surface of various sized water nanodroplets to investigate the solvation behavior of SO2 in different atmospheric environments. Born-Oppenheimer molecular dynamics (BOMD) simulation shows that, in the gas phase and at a temperature of 300 K, the dominant interaction between SO2 and H2O is (SO2)S···O(H2O), consistent with previous density-functional theory (DFT) computation at 0 K. However, at the surface of a water nanodroplet, BOMD simulation shows that the hydrogen-bonding interaction of (SO2)O···H(H2O) becomes increasingly important with the increase of droplet size, reflecting a marked effect of the water surface on the SO2 solvation. This conclusion is in good accordance with spectroscopy evidence obtained previously (J. Am. Chem. Soc. 2005, 127, 16806; J. Am. Chem. Soc. 2006, 128, 3256). The prevailing interaction (SO2)O···H(H2O) on a large droplet is mainly due to favorable exposure of H atoms of H2O at the air-water interface. Indeed, the conversion of the dominant interaction in the gas phase (SO2)S···O(H2O) to the dominant interaction on the water nanodroplet (SO2)O···H(H2O) may incur effects on the SO2 chemistry in atmospheric aerosols because the solvation of SO2 at the water surface can affect the reactive sites and electrophilicity of SO2. Hence, the solvation of SO2 on the aerosol surface may have new implications when studying SO2 chemistry in the aerosol-containing troposphere.

Interfacial Insights into a Carbon Capture System: CO2 Uptake to an Aqueous Monoethanolamine Surface.

Monoethanolamine (MEA) is a benchmark scrubber for CO2 gas emissions reductions. Preliminary studies have indicated surface monoethanolamine could influence the greater chemistry of CO2 uptake. MEA is known to be surface active and orients at aqueous surfaces such that its nitrogen lone pair electrons are pointing toward the gas phase. This MEA orientation has the potential to facilitate CO2 surface chemistry; however, a thorough description of the chemistry at play during this important carbon capture reaction is lacking. These studies investigate the surface behavior of MEA during CO2 gas flow, monitoring product formation and species migration. A combination of experimental vibrational sum frequency spectroscopy (VSFS), surface tensiometry, molecular dynamics simulations, and density functional calculations are used to investigate this complex chemistry. CO2 is shown to react with MEA, perturbing the interface and leading to the presence of carbamic acid in the surface region. However, throughout this chemistry the surface remains largely populated by unreacted MEA. These studies provide insight into this important carbon capture reaction and provide a framework for future work examining interfacial reactions and dynamics.

Assembly and molecular order of two-dimensional peptoid nanosheets through the oil-water interface.

Peptoid nanosheets are a recently discovered class of 2D nanomaterial that form from the self-assembly of a sequence-specific peptoid polymer at an air-water interface. Nanosheet formation occurs first through the assembly of a peptoid monolayer and subsequent compression into a bilayer structure. These bilayer materials span hundreds of micrometers in lateral dimensions and have the potential to be used in a variety of applications, such as in molecular sensors, artificial membranes, and as catalysts. This paper reports that the oil-water interface provides another opportunity for growth of these unique and highly ordered peptoid sheets. The monolayers formed at this interface are found through surface spectroscopic measurements to be highly ordered and electrostatic interactions between the charged moieties, namely carboxylate and ammonium residues, of the peptoid are essential in the ability of these peptoids to form ordered nanosheets at the oil-water interface. Expanding the mechanism of peptoid nanosheet formation to the oil-water interface and understanding the crucial role of electrostatic interactions between peptoid residues in nanosheet formation is essential for increasing the complexity and functionality of these nanomaterials.

A means to an interface: investigating monoethanolamine behavior at an aqueous surface.

The use of amine scrubbers to trap carbon dioxide from flue gas streams is one of the most promising avenues for atmospheric carbon dioxide reduction. However, modifications are necessary to efficiently scale these scrubbers for use in fossil fuel plants. Current advances in tailoring amines for CO2 capture involve improvements of bulk kinetic and thermodynamic parameters, with little consideration to surface chemistry and behavior. Aqueous alkanolamine solutions, such as monoethanolamine (MEA), are currently highly favored sorbents in CO2 post-combustion capture. Although numerous studies have explored MEA-CO2 chemistry at the macroscopic scale, few have investigated the role of the interface in the gas adsorption process. Additionally, as these amines become more industrially ubiquitous, their presence on and the need to understand their behavior at atmospheric and environmental surfaces will increase. This study investigates the surface behavior of monoethanolamine at the vapor/water interface, with particular focus on MEA's surface orientation and footprint. Using vibrational sum frequency spectroscopy, surface tensiometry, and computational techniques, MEA is found to adopt a constrained gauche interfacial conformation with its methylene backbone oriented toward the vapor phase and its functional groups solvated in the bulk solution. Computational and experimental analysis agree well, giving a complete picture with vibrational mode assignments and surface orientation of MEA. These findings can assist in the tailoring of amine structures or to facilitate improvements in engineering design to exploit favorable surface chemistry, as well as to serve as a starting point toward understanding aqueous amine surface behavior relevant to environmental systems.

Hydration, Orientation, and Conformation of Methylglyoxal at the Air-Water Interface.

Aqueous-phase processing of methylglyoxal (MG) has been suggested to constitute an important source of secondary organic aerosol (SOA). The uptake of MG to aqueous particles is higher than expected because its carbonyl moieties can hydrate to form geminal diols, as well as because MG and its hydration products can undergo aldol condensation reactions to form larger oligomers in solution. MG is known to be surface active, but an improved description of its surface behavior is crucial to understanding MG-SOA formation. These studies investigate MG adsorption, focusing on its hydration state at the air-water interface, using a combined experimental and theoretical approach that involves vibrational sum frequency spectroscopy, molecular dynamics simulations, and density functional theory calculations. Together, the experimental and theoretical data show that MG exists predominantly in a singly hydrated state (diol) at the interface, with a diol-tetrol ratio at the surface higher than that for the bulk. In addition to exhibiting a strong surface activity, we find that MG significantly perturbs the water structure at the interface. The results have implications for understanding the atmospheric fate of methylglyoxal.

Ordered polyelectrolyte assembly at the oil-water interface.

Polyelectrolytes (PEs) are widely used in applications such as water purification, wastewater treatment, and mineral recovery. Although much has been learned in past decades about the behavior of PEs in bulk aqueous solutions, their molecular behavior at a surface, and particularly an oil-water interface where many of their applications are most relevant, is largely unknown. From these surface spectroscopic and thermodynamics studies we report the unique molecular characteristics that several common polyelectrolytes, poly(acrylic acid) and poly(methylacrylic acid), exhibit when they adsorb at a fluid interface between water and a simple insoluble organic oil. These PEs are found to adsorb to the interface from aqueous solution in a multistepped process with a very thin initial layer of oriented polymer followed by multiple layers of randomly oriented polymer. This additional layering is thwarted when the PE conformation is constrained. The adsorption/desorption process is highly pH dependent and distinctly different than what might be expected from bulk aqueous phase behavior.

Twist and turn: effect of stereoconfiguration on the interfacial assembly of polyelectrolytes.

Understanding the conditions that promote the adsorption, assembly, and accumulation of charged macromolecules at the interface between aqueous and hydrophobic liquids is important to a multitude of biological, environmental, and industrial processes. Here, the oil-water interfacial behavior of stereoisomers of polymethacrylic acid (PMA), a model system for both naturally occurring and synthetic polyelectrolytes, is investigated with a combination of vibrational sum-frequency (VSF) spectroscopy, surface tension, and computations. Syndiotactic and isotactic isomers both show rapid adsorption to the oil-water interface with a net orientation indicative of a high degree of ordering. The stereoconfiguration is found to affect whether only a single layer or multiple layers assemble at the interface. Surface tension measurements show additional adsorption for syndiotactic PMA over time. The additional layers do not contribute to the VSF spectrum indicating disorder in all but the initial layer. The isotactic isomer shows no evidence of accumulation at the interface beyond the single ordered layer. Molecular dynamics calculations show marked differences between the two isomers in the orientation of their substituent groups at the interface. The hydrophilic and hydrophobic moieties in the isotactic isomer are easily partitioned to the water and oil phases, respectively, whereas a fair portion of hydrophobic groups remain in the water phase for the syndiotactic PMA. The available hydrophobic contacts in the water phase at the interface are credited with allowing further adsorption.

Doubling down: delving into the details of diacid adsorption at aqueous surfaces.

The behavior of complex interfacial systems is central to an ever-increasing number of applications. Vibrational sum frequency (VSF) spectroscopy is a powerful technique for obtaining surface specific structural information. The coherent nature of VSF that provides surface specificity, however, also creates difficulty in spectral interpretation especially as the system complexity increases. Computations of VSF spectra shed light on the molecular level source of the experimental VSF signal, allowing for the analysis of more complicated systems. Unfortunately, the majority of calculations of VSF spectra look at the response of the solvent or of rigid molecules and therefore often poorly reflect the experimental environment of most VSF spectroscopic measurements. In this work, flexible solute molecules at interfaces are investigated by doubling down, obtaining and comparing experimental and theoretical spectra, to determine a more accurate computational treatment. The surface behavior and VSF spectra of glutaric acid and adipic acid at the air/water interface are determined experimentally and calculated using a combination of classical molecular dynamics and density functional theory. Both diacids are found to be surface active. At high concentrations, glutaric acid forms dimers altering its VSF response and acidic properties. Calculated VSF spectra are found to be sensitive to vibrational mode frequencies, with ordering and spacing affecting relative intensities, as well as molecular conformation. A proper description requires consideration of multiple conformers and anharmonic effects on the molecular vibrational energies.