Effect of an Electric Field on the Structure and Stability of Atmospheric Clusters.

We study the influence of an applied electric field on the structure and stability of some common bimolecular clusters that are found in the atmosphere. These clusters play an important role in new particle formation (NPF). For low values of the electric field (i.e., |E| ≤ 0.01 V Å-1), we demonstrate that the field response of the clusters can be predicted from simply calculating the dipole moment of the cluster and the dipole moments of the constituent molecules and that the influence on the association energy of the cluster is minimal (i.e., <0.5 kcal mol-1). For higher field strengths |E| > 0.2 V Å-1, there can be more dramatic effects on both structure and energetics, as the induced dipole, charge transfer, and geometric distortion play a larger role. Although such large fields are not very relevant in the atmosphere, they do exist in some situations of experimental interest, such as near interfaces and in intense laser fields.

Molecular rearrangement of bicyclic peroxy radicals is a key route to aerosol from aromatics.

The oxidation of aromatics contributes significantly to the formation of atmospheric aerosol. Using toluene as an example, we demonstrate the existence of a molecular rearrangement channel in the oxidation mechanism. Based on both flow reactor experiments and quantum chemical calculations, we show that the bicyclic peroxy radicals (BPRs) formed in OH-initiated aromatic oxidation are much less stable than previously thought, and in the case of the toluene derived ipso-BPRs, lead to aerosol-forming low-volatility products with up to 9 oxygen atoms on sub-second timescales. Similar results are predicted for ipso-BPRs formed from many other aromatic compounds. This reaction class is likely a key route for atmospheric aerosol formation, and including the molecular rearrangement of BPRs may be vital for accurate chemical modeling of the atmosphere.

Large Gas-Phase Source of Esters and Other Accretion Products in the Atmosphere.

Dimeric accretion products have been observed both in atmospheric aerosol particles and in the gas phase. With their low volatilities, they are key contributors to the formation of new aerosol particles, acting as seeds for more volatile organic vapors to partition onto. Many particle-phase accretion products have been identified as esters. Various gas- and particle-phase formation pathways have been suggested for them, yet evidence remains inconclusive. In contrast, peroxide accretion products have been shown to form via gas-phase peroxy radical (RO2) cross reactions. Here, we show that these reactions can also be a major source of esters and other types of accretion products. We studied α-pinene ozonolysis using state-of-the-art chemical ionization mass spectrometry together with different isotopic labeling approaches and quantum chemical calculations, finding strong evidence for fast radical isomerization before accretion. Specifically, this isomerization seems to happen within the intermediate complex of two alkoxy (RO) radicals, which generally determines the branching of all RO2-RO2 reactions. Accretion products are formed when the radicals in the complex recombine. We found that RO with suitable structures can undergo extremely rapid C-C ß scissions before recombination, often resulting in ester products. We also found evidence of this previously overlooked RO2-RO2 reaction pathway forming alkyl accretion products and speculate that some earlier peroxide identifications may in fact be hemiacetals or ethers. Our findings help answer several outstanding questions on the sources of accretion products in organic aerosol and bridge our knowledge of the gas phase formation and particle phase detection of accretion products. As esters are inherently more stable than peroxides, this also impacts their further reactivity in the aerosol.

Energy transfer, pre-reactive complex formation and recombination reactions during the collision of peroxy radicals.

In this paper we study collisions between polyatomic radicals - an important process in fields ranging from biology to combustion. Energy transfer, formation of intermediate complexes and recombination reactions are treated, with applications to peroxy radicals in atmospheric chemistry. Multi-reference perturbation theory, supplemented by coupled-cluster calculations, describes the potential energy surfaces with high accuracy, including the interaction of singlet and triplet spin states during radical recombination. Our multi-reference molecular dynamics (MD) trajectories on methyl peroxy radicals confirm the reaction mechanism postulated in earlier studies. Specifically, they show that if suitable pre-reactive complexes are formed, they will rapidly lead to the formation and subsequent decomposition of tetroxide intermediates. However, generating multi-reference MD trajectories is exceedingly computationally demanding, and we cannot adequately sample the whole conformational space. To answer this challenge, we promote the use of a novel simplified semi-empirical MD methodology. It assumes the collision is governed by two states, a singlet (S0) and a triplet (T1) state. The method predicts differences between collisions on S0 and T1 surfaces, and qualitatively includes not only pre-reactive complex formation, but also recombination processes such as tetroxide formation. Finally, classical MD simulations using force-fields for non-reactive collisions are employed to generate thousands of collision trajectories, to verify that the semi-empirical method is sampling collisions adequately, and to carry out preliminary investigations of larger systems. For systems with low activation energies, the experimental rate coefficient is surprisingly well reproduced by simply multiplying the gas-kinetic collision rate by the simulated probability for long-lived complex formation.

Chemistrees: Data-Driven Identification of Reaction Pathways via Machine Learning.

We propose to analyze molecular dynamics (MD) output via a supervised machine learning (ML) algorithm, the decision tree. The approach aims to identify the predominant geometric features which correlate with trajectories that transition between two arbitrarily defined states. The data-driven algorithm aims to identify these features without the bias of human "chemical intuition". We demonstrate the method by analyzing the proton exchange reactions in formic acid solvated in small water clusters. The simulations were performed with ab initio MD combined with a method to efficiently sample the rare event, path sampling. Our ML analysis identified relevant geometric variables involved in the proton transfer reaction and how they may change as the number of solvating water molecules changes.

Ab Initio Molecular Dynamics Simulations of the Influence of Lithium Bromide Salt on the Deprotonation of Formic Acid in Aqueous Solution.

The deprotonation of formic acid is investigated using metadynamics in tandem with Born-Oppenheimer molecular dynamics simulations. We compare our findings for formic acid in pure water with previous studies before examining formic acid in aqueous solutions of lithium bromide. We carefully consider different definitions for the collective variable(s) used to drive the metadynamics, emphasizing that the variables used must include all of the possible reactive atoms in the system, in this case carboxylate oxygens and water hydrogens. This ensures that all the various possible proton exchange events can be accommodated and the collective variable(s) can distinguish the protonated and deprotonated states, even over rather long ab initio simulation runs (ca. 200-300 ps). Our findings show that the formic acid deprotonation barrier and the free energy of the deprotonated state are higher in concentrated lithium bromide, in agreement with the available experimental data for acids in salt solution. We show that the presence of Br- in proximity to the formic acid hydroxyl group effectively inhibits deprotonation. Our study extends previous work on acid deprotonation in pure water and at air-water interfaces to more complex multicomponent systems of importance in atmospheric and marine chemistry.

Ab Initio Molecular Dynamics Simulations of the Influence of Lithium Bromide on the Structure of the Aqueous Solution-Air Interface.

We present the results of ab initio molecular dynamics simulations of the solution-air interface of aqueous lithium bromide (LiBr). We find that, in agreement with the experimental data and previous simulation results with empirical polarizable force field models, Br- anions prefer to accumulate just below the first molecular water layer near the interface, whereas Li+ cations remain deeply buried several molecular layers from the interface, even at very high concentration. The separation of ions has a profound effect on the average orientation of water molecules in the vicinity of the interface. We also find that the hydration number of Li+ cations in the center of the slab Nc,Li+-H2O ≈ 4.7 ± 0.3, regardless of the salt concentration. This estimate is consistent with the recent experimental neutron scattering data, confirming that results from nonpolarizable empirical models, which consistently predict tetrahedral coordination of Li+ to four solvent molecules, are incorrect. Consequently, disruption of the hydrogen bond network caused by Li+ may be overestimated in nonpolarizable empirical models. Overall, our results suggest that empirical models, in particular nonpolarizable models, may not capture all of the properties of the solution-air interface necessary to fully understand the interfacial chemistry.

Electrokinetic flow of an aqueous electrolyte in amorphous silica nanotubes.

We study the pressure-driven flow of aqueous NaCl in amorphous silica nanotubes using nonequilibrium molecular dynamics simulations featuring both polarizable and non-polarizable molecular models. Different pressures, electrolyte concentrations and pore sizes are examined. Our results indicate a flow that deviates considerably from the predictions of Poiseuille fluid mechanics. Due to preferential adsorption of the different ionic species by surface SiO- or SiOH groups, we find that a significant electric current is generated, but with opposite polarities using polarizable vs. fixed charge models for water and ions, emphasizing the need for careful parameterization in such complex systems. We also examine the influence of partial deprotonation of the silica surface, and we find that much more current is generated in a dehydrogenated nanopore, even though the overall efficiency remains low. These findings indicate that different methods of nanopore preparation, which can produce a range of surface properties, should be examined more closely in the related experimental methods to generate electrokinetic current.

Molecular alignment in molecular fluids induced by coupling between density and thermal gradients.

We investigate, using non-equilibrium molecular dynamics simulations and theory, the response of molecular fluids confined in slit pores under the influence of a thermal gradient and/or an applied force. The applied force which has the same functional form as a gravitational force induces an inhomogeneous density in the confined fluid, which results in a net orientation of the molecules with respect to the direction of the force. The orientation is qualitatively similar to that induced by a thermal gradient. We find that the average degree of orientation is proportional to the density gradient of the fluid in the confined region and that the orientation increases with the magnitude of the force. The concurrent application of the external force and the thermal gradient allows us to disentangle the different mechanisms leading to the thermal orientation of molecular fluids. One mechanism is connected to the density variation of the fluid, while the second mechanism can be readily observed in molecular fluids consisting of molecules with mass or size asymmetry, even in the absence of a density gradient, hence it is connected to the application of the thermal gradient only.

Endometrial Ablation: Normal Imaging Appearance and Delayed Complications.

OBJECTIVE: Nonresectoscopic endometrial ablation techniques are being used as an alternative first-line management for menorrhagia. With these techniques, patients are at risk of developing delayed complications including painful obstructed menses, such as central hematometra and cornual hematometra, and postablation tubal sterilization syndrome. Pregnancy and the detection of endometrial cancer after ablation pose challenges in management. CONCLUSION: Radiologists should recognize the normal imaging findings in patients who have undergone endometrial ablation, be aware of the causes of treatment failure, and accurately identify delayed complications associated with these procedures.

Local Field Factors and Dielectric Properties of Liquid Benzene.

Local electric field factors are calculated for liquid benzene by combining molecular dynamic simulations with a subsequent force-field model based on a combined charge-transfer and point-dipole interaction model for the local field factor. The local field factor is obtained as a linear response of the local field to an external electric field, and the response is calculated at frequencies through the first absorption maximum. It is found that the largest static local field factor is around 2.4, while it is around 6.4 at the absorption frequency. The linear susceptibility, the dielectric constant, and the first absorption maximum of liquid benzene are also studied. The electronic contribution to the dielectric constant is around 2.3 at zero frequency, in good agreement with the experimental value around 2.2, while it increases to 6.3 at the absorption frequency. The π → π* excitation energy is around 6.0 eV, as compared to the gas-phase value of around 6.3 eV, while the experimental values are 6.5 and 6.9 eV for the liquid and gas phase, respectively, demonstrating that the gas-to-liquid shift is well-described.

Lithium ion-water clusters in strong electric fields: a quantum chemical study.

We use density functional theory to investigate the impact that strong electric fields have on the structure and energetics of small lithium ion-water clusters, Li(+)·nH2O, with n = 4 or 6. We find that electric field strengths of ∼0.5 V/Å are sufficient to break the symmetry of the n = 4 tetrahedral energy minimum structure, which undergoes a transformation to an asymmetric cluster consisting of three water molecules bound to lithium and one additional molecule in the second solvation shell. Interestingly, this cluster remains the global minimum configuration at field strengths ≳0.15 V/Å. The 6-coordinated cluster, Li(+)·6H2O, features a similar transition to 5- and 4-coordinated clusters at field strengths of ∼0.2 and ∼0.3 V/Å, respectively, with the tetra-coordinated structure being the global minimum even in the absence of the field. Our findings are relevant to understanding the behavior of the Li(+) ion in aqueous environments under strong electric fields and in interfacial regions where field gradients are significant.

Thermo-molecular orientation effects in fluids of dipolar dumbbells.

We use molecular dynamics simulations in applied thermal gradients to study thermomolecular orientation (TMO) of size-asymmetric dipolar dumbbells with different molecular dipole moments. We find that the direction of the TMO is the same as in apolar dumbbells of the same size, i.e. the smaller atom in the dumbbell tends to orient towards the colder temperature. The ratio of the electrical polarization to the magnitude of the thermal gradient does not vary much with the magnitude of the molecular dipole moment. We also investigate a novel second order TMO that persists even in size-symmetric dipolar dumbbells where molecules have a slight tendency to orient perpendicular to the gradient except very close to the hot region, where (anti-)parallel orientations are preferred. Finally, we investigate rotational correlation functions and characteristic rotational times in these systems in an attempt to model possible spectroscopic signatures of TMO in experiments. Although we cannot detect any difference in integrated rotational times between equilibrium simulations and simulations in a thermal gradient, more careful modelling of the anisotropic rotational dynamics in the thermal gradient may be more successful.

Molecular dynamics simulations to examine structure, energetics, and evaporation/condensation dynamics in small charged clusters of water or methanol containing a single monatomic ion.

We study small clusters of water or methanol containing a single Ca(2+), Na(+), or Cl(-) ion with classical molecular dynamics simulations, using models that incorporate polarizability via the Drude oscillator framework. Evaporation and condensation of solvent from these clusters is examined in two systems, (1) for isolated clusters initially prepared at different temperatures and (2) those with a surrounding inert (Ar) gas of varying temperature. We examine these clusters over a range of sizes, from almost bare ions up to 40 solvent molecules. We report data on the evaporation and condensation of solvent from the clusters and argue that the observed temperature dependence of evaporation in the smallest clusters demonstrates that the presence of heated gas alone cannot, in most cases, solely account for bare ion production in electrospray ionization (ESI), neglecting the key contribution of the electric field. We also present our findings on the structure and energetics of the clusters as a function of size. Our data agree well with the abundant literature on hydrated ion clusters and offer some novel insight into the structure of methanol and ion clusters, especially those with a Cl(-) anion, where we observe the presence of chain-like structures of methanol molecules. Finally, we provide some data on the reparameterizations necessary to simulate ions in methanol using the separately developed Drude oscillator models for methanol and for ions in water.

Nanoscale wetting under electric field from molecular simulations.

Applying an electric field is a well-established experimental method to tune surface wettability. As accessible experimental length scales become shorter, the modification of interfacial properties of water using electric field must come to grips with novel effects existing at the nanoscale. We survey recent progress in understanding these effects on water interfacial tension and on water-mediated interactions using molecular simulations. We highlight the key role of external conditions in determining the system's response to applied electric field. We further discuss the role of appropriate boundary conditions in modeling polar fluids subject to collective polarization. The work reviewed here broadens the basic understanding of applied and internal field effects that can operate in condensed phase systems, from modulating local hydrophilicity/hydrophobicity of engineered and biological surfaces, to surface manipulation in nanofluidic devices.

How are completely desolvated ions produced in electrospray ionization: insights from molecular dynamics simulations.

We apply molecular dynamics (MD) simulations to study the final phase of electrospray ionization (ESI), where an ion loses all of its associated solvent molecules. By applying an electric field to a cluster of H(2)O molecules solvating an ion and including a surrounding gas of varying pressure, we demonstrate that collisions with the gas play a major role in removing this final layer of solvent. We make quantitative predictions of the critical velocity required for the cluster to start losing molecules via collisions with gas and propose that this should be important in real ESI experiments. Such collisions have heretofore not been explicitly considered in discussions of the ESI process.

The influence of molecular-scale roughness on the surface spreading of an aqueous nanodrop.

We examine the effect of nanoscale roughness on spreading and surface mobility of water nanodroplets. Using molecular dynamics, we consider model surfaces with sub-nanoscale asperities at varied surface coverage and with different distribution patterns. We test materials that are hydrophobic, and those that are hydrophilic in the absence of surface corrugations. Interestingly, on both types of surfaces, the introduction of surface asperities gives rise to a sharp increase in the apparent contact angle. The Cassie-Baxter equation is obeyed approximately on hydrophobic substrates, however, the increase in the contact angle on a hydrophilic surface differs qualitatively from the behavior on macroscopically rough surfaces described by the Wenzel equation. On the hydrophobic substrate, the superhydrophobic state with the maximal contact angle of 180 degrees is reached when the asperity coverage falls below 25%, suggesting that superhydrophobicity can also be achieved by the nanoscale roughness of a macroscopically smooth material. We further examine the effect of surface roughness on droplet mobility on the substrate. The apparent diffusion constant shows a dramatic slow down of the nanodroplet translation even for asperity coverage in the range of 1% for a hydrophilic surface, while droplets on corrugated hydrophobic surfaces retain the ability to flow around the asperities. In contrast, for smooth surfaces we find that the drop mobility on the hydrophilic surface exceeds that on the hydrophobic one.

Structure of aqueous solutions of monosodium glutamate.

We studied monosodium glutamate (MSG) in aqueous solution using molecular dynamics simulations and compared the results with recent neutron diffraction with isotope contrast variation/empirical potential structure refinement (EPSR) data obtained on the same system (McLain et al. J. Phys. Chem. B 2006, 110, 21251-21258). We used classical simulations with empirical force fields to study both dilute and more concentrated (1.40 M) solutions. To gauge the importance of polarization and other quantum effects, we carried out first-principles molecular dynamics in the dilute case. The glutamate structure was well reproduced by the OPLS/AA and SPC/E force fields: we found a reasonable agreement between the simulations and the experimental data with respect to the hydration numbers for glutamate carboxylate and amine groups and the observation of significant sodium ion-carboxylate binding. However, none of our simulations could reproduce the dramatic reduction in water-water correlations observed experimentally. Simulations showed a large amount of carboxylate-amine binding, as well as segregation of water and glutamate, at moderately high concentrations of MSG. We attribute this result to the breakdown of currently available classical force fields when applied to concentrated ionic solutions, especially large polyatomic ions. We also did not observe the sharing of a water proton by two carboxylate oxygens simultaneously, and we argue against this interpretation of EPSR data on a variety of physical grounds. We offer several suggestions to resolve these discrepancies between simulation and the current interpretation of neutron diffraction data, which should advance the understanding of aqueous ionic solutions in general.

Water-mediated ordering of nanoparticles in an electric field.

Interfacial polar molecules feature a strongly anisotropic response to applied electric field, favoring dipole orientations parallel to the interface. In water, in particular, this effect combines with generic orientational preferences induced by spatial asymmetry of water hydrogen bonding under confined geometry, which may give rise to a Janus interface. The two effects manifest themselves in considerable dependence of water polarization on both the field direction relative to the interface and the polarity (sign) of the field. Using molecular simulations, we demonstrate strong field-induced orientational forces acting on apolar surfaces through water mediation. At a field strength comparable to electric fields around a DNA polyion, the torques we predict to act on an adjacent nanoparticle are sufficient to overcome thermal fluctuations. These torques can align a particle with surface as small as 1 nm2. The mechanism can support electrically controlled ordering of suspended nanoparticles as a means of tuning their properties and can find application in electro-nanomechanical devices.