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While new particle formation events have been observed worldwide, our fundamental understanding of the precursors remains uncertain. It has been previously shown that small alkylamines and ammonia (NH3) are key actors in sub-3 nm particle formation through reactions with acids such as sulfuric acid (H2SO4) and methanesulfonic acid (CH3S(O)(O)OH, MSA), and that water also plays a role. Because NH3 and amines co-exist in air, we carried out combined experimental and theoretical studies examining the influence of the addition of NH3 on particle formation from the reactions of MSA with methylamine (MA) and trimethylamine (TMA). Experiments were performed in a 1 m flow reactor at 1 atm and 296 K. Measurements using an ultrafine condensation particle counter (CPC) and a scanning mobility particle sizer (SMPS) show that new particle formation was systematically enhanced upon simultaneous addition of NH3 to the MSA + amine binary system, with the magnitude depending on the amine investigated. For the MSA + TMA reaction system, the addition of NH3 at ppb concentrations produced a much greater effect (i.e. order of magnitude more particles) than the addition of ∼12 000 ppm water (corresponding to ∼45-50% relative humidity). The effect of NH3 on the MSA + MA system, which is already very efficient in forming particles on its own, was present but modest. Calculations of energies, partial charges and structures of small cluster models of the multi-component particles likewise suggest synergistic effects due to NH3 in the presence of MSA and amine. The local minimum structures and the interactions involved suggest mechanisms for this effect.

Neonicotinoid (NN) pesticides have widespread use, largely replacing other pesticides such as the carbamates. Hence, there is a need to understand their environmental fates at a molecular level in various media, especially water. We report here the studies of a nitroenamine NN, nitenpyram (NPM), in aqueous solution where the absorption cross sections in the actinic region above 290 nm are observed to dramatically decrease compared to those in nonaqueous solvents. Quantum chemical calculations show that addition of a proton to the tertiary amine nitrogen in NPM breaks the conjugation in the chromophore, shifting the absorption to shorter wavelengths, consistent with experiment. However, surprisingly, adding a proton to the secondary amine nitrogen leads to its immediate transfer to the NO2 group, preserving the conjugation. This explains why the UV absorption of ranitidine (RAN), which has a similar chromophore but only secondary amine nitrogens, does not show a similar large blue shift in water. Photolysis quantum yields in aqueous NPM solutions were measured to be φ = 0.18 ± 0.07 at 254 nm, (9.4 ± 1.6) × 10-2 with broadband radiation centered at 313 nm and (5.2 ± 1.1) × 10-2 for broadband radiation centered at 350 nm (errors are 2σ). The major products in aqueous solutions are an imine that was also formed in the photolysis of the solid and a carboxylic acid derivative that is unique to the photolysis in water. Combining the larger quantum yields in water with the reduced absorption cross sections results in a calculated lifetime of NPM of only 5 min at a solar zenith angle of 35°, typical of 40°N latitude on April 1. The products do not absorb in the actinic region and hence will be long-lived with respect to photolysis.

SN2-type halide substitution and hydrolysis are two of the most ubiquitous reactions in chemistry. The interplay between these processes is fundamental in atmospheric chemistry through reactions of N2O5 and seawater. N2O5 plays a major role in regulating levels of O3, OH, NO x , and CH4. While the reactions of N2O5 and seawater are of central importance, little is known about their mechanisms. Of interest is the activation of Cl in seawater by the formation of gaseous ClNO2, which occurs despite the fact that hydrolysis (to HNO3) is energetically more favorable. We determine key features of the reaction landscape that account for this behavior in a theoretical study of the cluster N2O5/Cl-/H2O. This was carried out using ab initio molecular dynamics to determine reaction pathways, structures, and time scales. While hydrolysis of N2O5 occurs in the absence of Cl-, results here reveal that a low-lying pathway featuring halide substitution intermediates enhances hydrolysis.

The effect of water on the growth of dry nano-size acid-base particles is not yet known. In this paper, we investigate the uptake of water by nano-size particles composed of methanesulfonic acid (MSA) and methylamine (MA) using a combination of quantum chemical calculations and laboratory experiments. Calculations were performed on the (MSA-MA)4 cluster as the dry nanoparticle model, which forms a pseudo-cubic structure, to which twelve water molecules were added successively. Theoretical results show that the hydrated clusters (MSA-MA)4-(H2O)n, n = 1 to 12 are thermodynamically stable. In ab initio dynamic simulations, no loss of water or significant changes of structure are seen for at least 10 picoseconds. In all the clusters studied, most of the water molecules lie on the face of the (MSA-MA)4 initial dry unit, and water is found to be incorporated inside the initial unit for n ranging from five to twelve. Sizes of hydrated clusters exceed significantly that of the dry cluster only for n ≥ 6. These theoretical results suggest that dry MSA-MA clusters cannot dissociate in small quantities of water. Calculations of hydrated cluster distributions at steady state show that the cluster compositions studied, with up to 12 water molecules, encompass all the hydrated clusters under the experimental conditions (RH ∼ 19%, 300 K). Experiments performed in a glass flow reactor showed no changes in size or number concentration when particles formed from MSA-MA were subsequently exposed to water vapor, in contrast to increases in both size and number when water was present during particle formation. Thus, the results seem to imply for both experiment and theory that growth in size of a particle due to uptake of water requires the previous presence of some level of hydration. These results illustrate the importance for atmospheric models of understanding on a molecular basis the mechanisms of particle formation in air.

The newest NERSC supercomputer Cori is a Cray XC40 system consisting of 2,388 Intel Xeon Haswell nodes and 9,688 Intel Xeon-Phi “Knights Landing” (KNL) nodes. Compared to the Xeon-based clusters NERSC users are familiar with, optimal performance on Cori requires consideration of KNL mode settings; process, thread, and memory affinity; fine-grain parallelization; vectorization; and use of the high-bandwidth MCDRAM memory. This paper describes our efforts preparing NERSC users for KNL through the NERSC Exascale Science Application Program, Web documentation, and user training. We discuss how we configured the Cori system for usability and productivity, addressing programming concerns, batch system configurations, and default KNL cluster and memory modes. System usage data, job completion analysis, programming and running jobs issues, and a few successful user stories on KNL are presented.

High performance computing (HPC) scheduling landscape currently faces new challenges due to the changes in the workload. Previously, HPC centers were dominated by tightly coupled MPI jobs. HPC workloads increasingly include high-throughput, data-intensive, and stream-processing applications. As a consequence, workloads are becoming more diverse at both application and job levels, posing new challenges to classical HPC schedulers. There is a need to understand the current HPC workloads and their evolution to facilitate informed future scheduling research and enable efficient scheduling in future HPC systems. In this paper, we present a methodology to characterize workloads and assess their heterogeneity, at a particular time period and its evolution over time. We apply this methodology to the workloads of three systems (Hopper, Edison, and Carver) at the National Energy Research Scientific Computing Center (NERSC). We present the resulting characterization of jobs, queues, heterogeneity, and performance that includes detailed information of a year of workload (2014) and evolution through the systems’ lifetime (2010–2014).

Mechanisms of particle formation and growth in the atmosphere are of great interest due to their impacts on climate, health and visibility. However, the microscopic structures and related properties of the smallest nanoparticles are not known. In this paper we pursue computationally a microscopic description for the formation and growth of methanesulfonic acid (MSA) and methylamine (MA) particles under dry conditions. Energetic and dynamics simulations were used to assess the stabilities of proposed model structures for these particles. Density functional theory (DFT) and semi-empirical (PM3) calculations suggest that (MSA-MA)4 is a major intermediate in the growth process, with the dissociation energies, enthalpies and free energies indicating considerable stability for this cluster. Dynamics simulations show that this species is stable for at least 100 ps at temperatures up to 500 K, well above atmospheric temperatures. In order to reach experimentally detectable sizes (>1.4 nm), continuing growth is suggested to occur via clustering of (MSA-MA)4. The dimer (MSA-MA)4(MSA-MA)4 may be one of the smaller experimentally measured particles. Step by step addition of MSA to (MSA-MA)4, is also a likely potential growth mechanism when MSA is excess. In addition, an MSA-MA crystal is predicted to exist. These studies demonstrate that computations of particle structure and dynamics in the nano-size range can be useful for molecular level understanding of processes that grow clusters into detectable particles.

Understanding the properties of atmospheric particles made of several components is a very challenging problem. In this paper, we perform quantum chemical calculations for small multicomponent clusters of atmospheric relevance that incorporate methanesulfonic acid (MSA), methylamine (MA), oxalic acid (OxA), and water (H2O). Potential correlations between theoretical predictions of proton transfer in the small clusters and findings of recent experiments on formation of particles of detectable sizes (>2 nm) from the same components are studied. It is proposed that proton transfer from the acid to the amine in the 1:1 clusters correlates with experiments on particle formation in systems, such as MSA-MA and MSA-MA-OxA. In the case of OxA + MA, which has been observed to give few particles, proton transfer does not occur for the 1:1 cluster but does for the 2:2 cluster. Adding H2O to OxA-MA promotes the occurrence of proton transfer, and corresponding particles are slightly enhanced. The partial charge on the MA component increases by adding OxA or H2O to MSA-MA, which is correlated with enhanced particle formation compared to MSA-MA alone. Ab initio molecular dynamics simulations show that proton transfer at room temperature (T = 298 K) and high temperature (T = 500 K) is little affected compared with the equilibrium structure (T = 0 K). These results suggest that small cluster calculations may be useful in predicting the formation of multicomponent particles in the atmosphere.

Imidacloprid (IMD) is the most widely used neonicotinoid insecticide found on environmental surfaces and in water. Analysis of surface-bound IMD photolysis products was performed using attenuated total reflectance Fourier transfer infrared (ATR-FTIR) analysis, electrospray ionization (ESI-MS), direct analysis in real time mass spectrometry (DART-MS), and transmission FTIR for gas-phase products. Photolysis quantum yields (ϕ) for loss of IMD were determined to be (1.6 ± 0.6) × 10-3 (1s) at 305 nm and (8.5 ± 2.1) × 10-3 (1s) at 254 nm. The major product is the imidacloprid urea derivative (IMD-UR, 84% yield), with smaller amounts of the desnitro-imidacloprid (DN-IMD, 16% yield) product, and gaseous nitrous oxide (N2O). Theoretical calculations show that the first step of the main mechanism is the photodissociation of NO2, which then recombines with the ground electronic state of IMD radical to form IMD-UR and N2O in a thermally driven process. The photolytic lifetime of IMD at a solar zenith angle of 35° is calculated to be 16 h, indicating the significant reaction of IMD over the course of a day. Desnitro-imidacloprid has been identified by others as having increased binding to target receptors compared to IMD, suggesting that photolysis on environmental surfaces increases toxicity.

Atmospheric particles are notorious for their effects on human health and visibility and are known to influence climate. Though sulfuric acid and ammonia/amines are recognized as main contributors to new particle formation (NPF), models and observations have indicated that other species may be involved. It has been shown that nucleation from methanesulfonic acid (MSA) and amines, which is enhanced with added water, can also contribute to NPF. While organics are ubiquitous in air and likely to be involved in NPF by stabilizing small clusters for further growth, their effects on the MSA-amine system are not known. This work investigates the effect of oxalic acid (OxA) on NPF from the reaction of MSA and methylamine (MA) at 1 atm and 294 K in the presence and absence of water vapor using an aerosol flow reactor. OxA and MA do not efficiently form particles even in the presence of water, but NPF is enhanced when adding MSA to OxA-MA with and without water. The addition of OxA to MSA-MA mixtures yields a modest NPF enhancement, whereas the addition of OxA to MSA-MA-H2O has no effect. Possible reasons for these effects are discussed.

Correction for 'New particle formation and growth from methanesulfonic acid, trimethylamine and water' by Haihan Chen et al., Phys. Chem. Chem. Phys., 2015, 17, 13699-13709.

Several multistep strategies were developed to ensure single methylation of amines on solid support. These strategies rely on the introduction of the o-NBS protecting/activating group as a key step. We found that the state-of-the-art strategies fail for the methylation of several primary amine motifs, largely due to inefficient sulfonylation. Here we show that using the superior nucleophilic base DMAP instead of the commonly used base collidine as a sulfonylation additive is essential for the introduction of the o-NBS group to these amine motifs. DFT calculations provide an explanation by showing that the energy barrier of the DMAP intermediate is significantly lower than the one of the collidine. We demonstrate that using DMAP as a sole additive in the sulfonylation step results in an overall effective and regioselective N-methylation. The method presented herein proved highly efficient in solid-phase synthesis of a somatostatin analogue bearing three Nα-methylation sites that could not be synthesized using the previously described state-of-the-art methods.

First-principles quantum calculations for anharmonic vibrational spectroscopy of three protected dipeptides are carried out and compared with experimental data. Using hybrid HF/MP2 potentials, the Vibrational Self-Consistent Field with Second-Order Perturbation Correction (VSCF-PT2) algorithm is used to compute the spectra without any ad hoc scaling or fitting. All of the vibrational modes (135 for the largest system) are treated quantum mechanically and anharmonically using full pair-wise coupling potentials to represent the interaction between different modes. In the hybrid potential scheme the MP2 method is used for the harmonic part of the potential and a modified HF method is used for the anharmonic part. The overall agreement between computed spectra and experiment is very good and reveals different signatures for different conformers. This study shows that first-principles spectroscopic calculations of good accuracy are possible for dipeptides hence it opens possibilities for determination of dipeptide conformer structures by comparison of spectroscopic calculations with experiment.

Carbonyl oxides, or Criegee intermediates, are formed from the gas phase ozonolysis of alkenes and play a pivotal role in night-time and urban area atmospheric chemistry. Significant discrepancies exist among measurements of the strong B ̃(1)A'-X ̃(1)A' electronic transition of the simplest Criegee intermediate, CH2OO in the visible/near-UV. We report room temperature spectra of the B ̃(1)A'-X ̃(1)A' electronic absorption band of CH2OO acquired at higher resolution using both single-pass broadband absorption and cavity ring-down spectroscopy. The new absorption spectra confirm the vibrational structure on the red edge of the band that is absent from ionization depletion measurements. The absolute absorption cross sections over the 362-470 nm range are in good agreement with those reported by Ting et al. Broadband absorption spectra recorded over the temperature range of 276-357 K were identical within their mutual uncertainties, confirming that the vibrational structure is not due to hot bands.

Carbonyl oxides, or Criegee intermediates, are formed from the gas phase ozonolysis of alkenes and play a pivotal role in night-time and urban area atmospheric chemistry. Significant discrepancies exist among measurements of the strong B ̃(1)A'-X ̃(1)A' electronic transition of the simplest Criegee intermediate, CH2OO in the visible/near-UV. We report room temperature spectra of the B ̃(1)A'-X ̃(1)A' electronic absorption band of CH2OO acquired at higher resolution using both single-pass broadband absorption and cavity ring-down spectroscopy. The new absorption spectra confirm the vibrational structure on the red edge of the band that is absent from ionization depletion measurements. The absolute absorption cross sections over the 362-470 nm range are in good agreement with those reported by Ting et al. Broadband absorption spectra recorded over the temperature range of 276-357 K were identical within their mutual uncertainties, confirming that the vibrational structure is not due to hot bands.

Sulfuric acid (H2SO4), formed from oxidation of sulfur dioxide (SO2) emitted during fossil fuel combustion, is a major precursor of new airborne particles, which have well-documented detrimental effects on health, air quality, and climate. Another precursor is methanesulfonic acid (MSA), produced simultaneously with SO2 during the atmospheric oxidation of organosulfur compounds (OSCs), such as dimethyl sulfide. In the present work, a multidisciplinary approach is used to examine how contributions of H2SO4 and MSA to particle formation will change in a large coastal urban area as anthropogenic fossil fuel emissions of SO2 decline. The 3-dimensional University of California Irvine-California Institute of Technology airshed model is used to compare atmospheric concentrations of gas phase MSA, H2SO4, and SO2 under current emissions of fossil fuel-associated SO2 and a best-case futuristic scenario with zero fossil fuel sulfur emissions. Model additions include results from (i) quantum chemical calculations that clarify the previously uncertain gas phase mechanism of formation of MSA and (ii) a combination of published and experimental estimates of OSC emissions, such as those from marine, agricultural, and urban processes, which include pet waste and human breath. Results show that in the zero anthropogenic SO2 emissions case, particle formation potential from H2SO4 will drop by about two orders of magnitude compared with the current situation. However, particles will continue to be generated from the oxidation of natural and anthropogenic sources of OSCs, with contributions from MSA and H2SO4 of a similar order of magnitude. This could be particularly important in agricultural areas where there are significant sources of OSCs.

Nitryl chloride (ClNO2) and nitrosyl chloride (ClNO) are potential sources of highly reactive atmospheric chlorine atoms, hence of much interest, but their formation pathways are unknown. This work predicts production of these nitrogen oxychlorides from ab initio molecular dynamics (AIMD) simulations of N2O5 or an NO2 dimer on the surface of a thin film of water which is struck by gaseous HCl. Both of these heterogeneous reactions proceed at the liquid/vapor interface by an SN2 mechanism where the nucleophile is chloride ion formed from the ionization of HCl on the aqueous surface. The film of water enhances the otherwise very slow gas phase reaction to occur by (1) stabilizing and localizing the adsorbed N2O5 or NO2 dimer so it is physically accessible for reaction, (2) ionizing the impinging HCl, and (3) activating the adsorbed oxide for nucleophilic attack by chloride. Though both nitrogen oxychloride products are produced by SN2 reactions, the N2O5 mechanism is unusual in that the electrophilic N atom to be attacked oscillates between the two normally equivalent NO2 groups. Chloride ion is found to react with N2O5 less efficiently than with N2O4. The simulations provide an explanation for this. These substitution/elimination mechanisms are new for NOx/y chemistry on thin water films and cannot be derived from small cluster models.

Nitryl chloride (ClNO2) and nitrosyl chloride (ClNO) are potential sources of highly reactive atmospheric chlorine atoms, hence of much interest, but their formation pathways are unknown. This work predicts production of these nitrogen oxychlorides from ab initio molecular dynamics (AIMD) simulations of N2O5 or an NO2 dimer on the surface of a thin film of water which is struck by gaseous HCl. Both of these heterogeneous reactions proceed at the liquid/vapor interface by an SN2 mechanism where the nucleophile is chloride ion formed from the ionization of HCl on the aqueous surface. The film of water enhances the otherwise very slow gas phase reaction to occur by (1) stabilizing and localizing the adsorbed N2O5 or NO2 dimer so it is physically accessible for reaction, (2) ionizing the impinging HCl, and (3) activating the adsorbed oxide for nucleophilic attack by chloride. Though both nitrogen oxychloride products are produced by SN2 reactions, the N2O5 mechanism is unusual in that the electrophilic N atom to be attacked oscillates between the two normally equivalent NO2 groups. Chloride ion is found to react with N2O5 less efficiently than with N2O4. The simulations provide an explanation for this. These substitution/elimination mechanisms are new for NOx/y chemistry on thin water films and cannot be derived from small cluster models.

New particle formation from gas-to-particle conversion represents a dominant source of atmospheric particles and affects radiative forcing, climate and human health. The species involved in new particle formation and the underlying mechanisms remain uncertain. Although sulfuric acid is commonly recognized as driving new particle formation, increasing evidence suggests the involvement of other species. Here we study particle formation and growth from methanesulfonic acid, trimethylamine and water at reaction times from 2.3 to 32 s where particles are 2-10 nm in diameter using a newly designed and tested flow system. The flow system has multiple inlets to facilitate changing the mixing sequence of gaseous precursors. The relative humidity and precursor concentrations, as well as the mixing sequence, are varied to explore their effects on particle formation and growth in order to provide insight into the important mechanistic steps. We show that water is involved in the formation of initial clusters, greatly enhancing their formation as well as growth into detectable size ranges. A kinetics box model is developed that quantitatively reproduces the experimental data under various conditions. Although the proposed scheme is not definitive, it suggests that incorporating such mechanisms into atmospheric models may be feasible in the near future.

The unimolecular photochemistry of aldehydes has been extensively studied, both experimentally and computationally. However, less is known about the role of cross-molecular photochemical processes in the condensed-phase photolysis of aldehydes. The triplet-state photochemistry of pentanal in its pentameric (n = 5) cluster was investigated as a model for photochemical reactions of aliphatic aldehydes in atmospheric aerosols. This study employs "on the fly" dynamics simulations using a semi-empirical MRCI electronic code for the singlet and triplet states involved. Previous studies have shown that the triplet-state photochemistry of an isolated pentanal molecule is dominated by Norrish I and II reactions. The main findings for the cluster are: (1) 55% of the trajectories lead to a unimolecular or cross-molecular reaction within a timescale of 100 ps; (2) cross-molecular reactions occur in over 70% of the reactive trajectories; (3) the main cross-molecular processes involve an H-atom transfer from the CHO group of the excited pentanal to an O atom of a nearby pentanal; and (4) the unimolecular Norrish II reaction is suppressed by the cluster environment. The predictions are qualitatively supported by experimental results on the condensed-phase photolysis of an aliphatic aldehyde, undecanal. The computational approach should be useful for predicting the mechanisms of other condensed-phase organic photochemical reactions. These results demonstrate a major role of cross-molecular processes in the condensed-phase photolysis of carbonyls. The cross-molecular reactions discussed in this work are relevant to photolysis-driven processes in atmospheric organic aerosols. It is expected that the condensed-phase environment of an organic aerosol particle should support a multitude of similar cross-molecular photochemical processes.

We present an ab initio molecular dynamics study of deprotonation of sulfuric acid on wet quartz, a topic of atmospheric interest. The process is preferred, with 65% of our trajectories at 250 K showing deprotonation. The time distribution of the deprotonation events shows an exponential behavior and predicts an average deprotonation time of a few picoseconds. The process is exoergic, with most of the temperature increase being due to formation of hydrogen bonds prior to deprotonation. In agreement with existing studies of H2SO4 in water clusters, in liquid water, and at the air-water interface, the main determinant of deprotonation is the degree of solvation of H2SO4 by neighboring water molecules. However, we find that if both hydrogens of H2SO4 are simultaneously donated to water oxygens, deprotonation is disfavored. Predicted spectroscopic signatures showing the presence of solvated hydronium and bisulfate are presented. Increasing the temperature up to 330 K accelerates the process but does not change the main features of the deprotonation mechanisms or the spectroscopic signatures. The second deprotonation of H2SO4, studied only at 250 K, occurs provided there is sufficient solvation of the bisulfate by additional water molecules. In comparison to HCl deprotonation on the identical surface examined in our previous work, the first deprotonation of H2SO4 occurs more readily and releases more energy.

We present an ab initio molecular dynamics study of deprotonation of sulfuric acid on wet quartz, a topic of atmospheric interest. The process is preferred, with 65% of our trajectories at 250 K showing deprotonation. The time distribution of the deprotonation events shows an exponential behavior and predicts an average deprotonation time of a few picoseconds. The process is exoergic, with most of the temperature increase being due to formation of hydrogen bonds prior to deprotonation. In agreement with existing studies of H2SO4 in water clusters, in liquid water, and at the air-water interface, the main determinant of deprotonation is the degree of solvation of H2SO4 by neighboring water molecules. However, we find that if both hydrogens of H2SO4 are simultaneously donated to water oxygens, deprotonation is disfavored. Predicted spectroscopic signatures showing the presence of solvated hydronium and bisulfate are presented. Increasing the temperature up to 330 K accelerates the process but does not change the main features of the deprotonation mechanisms or the spectroscopic signatures. The second deprotonation of H2SO4, studied only at 250 K, occurs provided there is sufficient solvation of the bisulfate by additional water molecules. In comparison to HCl deprotonation on the identical surface examined in our previous work, the first deprotonation of H2SO4 occurs more readily and releases more energy.

High-level quantum chemical calculations reported here predict the existence and remarkable stability, of chemically-bound xenon atoms in fibrous silica. The results may support the suggestion of Sanloup and coworkers that chemically-bound xenon and silica account for the problem of "missing xenon" (by a factor of 20!) from the atmospheres of Earth and Mars. So far, the host silica was assumed to be quartz, which is in contradiction with theory. The xenon-fibrous silica molecule is computed to be stable well beyond room temperature. The calculated Raman spectra of the species agree well with the main features of the experiments by Sanloup et al. The results predict computationally the existence of a new family of noble-gas containing materials. The fibrous silica species are finite molecules, their laboratory preparation should be feasible, and potential applications are possible.

The interaction of water, 1,4 dioxane, and gaseous nitrogen dioxide, has been studied as a function of distance measured through the liquid-vapour interface by Raman spectroscopy with a narrow (

We study the environmental effect on molecules embedded in noble-gas (Ng) matrices. The experimental data on HXeCl and HKrCl in Ng matrices is enriched. As a result, the H-Xe stretching bands of HXeCl are now known in four Ng matrices (Ne, Ar, Kr, and Xe), and HKrCl is now known in Ar and Kr matrices. The order of the H-Xe stretching frequencies of HXeCl in different matrices is ν(Ne) < ν(Xe) < ν(Kr) < ν(Ar), which is a non-monotonous function of the dielectric constant, in contrast to the "classical" order observed for HCl: ν(Xe) < ν(Kr) < ν(Ar) < ν(Ne). The order of the H-Kr stretching frequencies of HKrCl is consistently ν(Kr) < ν(Ar). These matrix effects are analyzed theoretically by using a number of quantum chemical methods. The calculations on these molecules (HCl, HXeCl, and HKrCl) embedded in single Ng(') layer cages lead to very satisfactory results with respect to the relative matrix shifts in the case of the MP4(SDQ) method whereas the B3LYP-D and MP2 methods fail to fully reproduce these experimental results. The obtained order of frequencies is discussed in terms of the size available for the Ng hydrides in the cages, probably leading to different stresses on the embedded molecule. Taking into account vibrational anharmonicity produces a good agreement of the MP4(SDQ) frequencies of HCl and HXeCl with the experimental values in different matrices. This work also highlights a number of open questions in the field.

The reaction of (NO(+))(NO3(-)) with water is modelled in ONONO2·(H2O)4 clusters. Molecular Dynamics simulations using second-order Møller-Plesset perturbation (MP2) theory support the feasibility of the reaction of a charge-separated species to produce HONO and nitric acid.

The reaction of (NO(+))(NO3(-)) with water is modelled in ONONO2·(H2O)4 clusters. Molecular Dynamics simulations using second-order Møller-Plesset perturbation (MP2) theory support the feasibility of the reaction of a charge-separated species to produce HONO and nitric acid.

Investigations of reaction pathways between a proton and cellobiose (CB), a glucose disaccharide of importance, were carried out in cis and trans CB using Ab Initio Molecular Dynamics (AIMD) simulations starting from optimized configurations where the proton is initially placed near groups with affinity for it. Near and above 300 K, protonated CB (H(+)CB) undergoes several transient reactions including charge transfer to the sugar backbone, water formation and dehydration, ring breaking and glycosidic bond breaking events as well as mutarotation and ring puckering events, all on a 10 ps timescale. cis H(+)CB is energetically favoured over trans H(+)CB in vacuo, with an energy gap larger than for the neutral CB.

HNgY molecules are chemically-bound compounds of a noble-gas atom (Ng) with a hydrogen and with an electronegative group Y. There is considerable current interest in the stability of these species in different types of media. The kinetic stability of several compounds, HXeOH, HXeOXeH, HXeBr and HXeCCH, in water clusters is explored by ab initio calculations. It is found that the kinetic stability of the compounds is reduced by the water environment, generally falling off with the number of H2O molecules. For a relatively modest number of water molecules, the compounds decompose spontaneously. Implications of the results for storage of HNgY in molecular media are discussed.

HNgY molecules are chemically-bound compounds of a noble-gas atom (Ng) with a hydrogen and with an electronegative group Y. There is considerable current interest in the stability of these species in different types of media. The kinetic stability of several compounds, HXeOH, HXeOXeH, HXeBr and HXeCCH, in water clusters is explored by ab initio calculations. It is found that the kinetic stability of the compounds is reduced by the water environment, generally falling off with the number of H2O molecules. For a relatively modest number of water molecules, the compounds decompose spontaneously. Implications of the results for storage of HNgY in molecular media are discussed.

Ionization of N(2)O(4) in and on thin water films on surfaces is believed to be a key step in the hydrolysis of NO(2) which generates HONO, a significant precursor to the OH free radical in the lower atmosphere. Molecular dynamics simulations using "on the fly" high-level MP2 potentials are carried out for ONONO(2) x (H(2)O)(n) clusters, n < or = 8, used to mimic the surface reaction, in order to investigate the ionization process and determine its time-scale and mechanism around room temperature. The results are (i) the isolated molecule does not convert to the NO(+)NO(3)(-) ion pair, even for long times; (ii) for ONONO(2) x (H(2)O)(n) with n = 1 and 2, ionization takes place in several picoseconds; (iii) for n > or = 3, ionization is essentially immediate, implying that the neutral species does not have sufficient lifetime to be considered a significant intermediate in the reaction; and (iv) even at ice temperatures, T < or = 250 K, ionization for n > or = 3 is immediate. The implications for hydrolysis of oxides of nitrogen on surfaces in the atmosphere are discussed.

Calculations were performed to determine the structures, energetics, and spectroscopy of the atmospherically relevant complexes (HNO(3)).(NO(2)), (HNO(3)).(N(2)O(4)), (NO(3)(-)).(NO(2)), and (NO(3)(-)).(N(2)O(4)). The binding energies indicate that three of the four complexes are quite stable, with the most stable (NO(3)(-)).(N(2)O(4)) possessing binding energy of almost -14 kcal mol(-1). Vibrational frequencies were calculated for use in detecting the complexes by infrared and Raman spectroscopy. An ATR-FTIR experiment showed features at 1632 and 1602 cm(-1) that are attributed to NO(2) complexed to NO(3)(-) and HNO(3), respectively. The electronic states of (HNO(3)).(N(2)O(4)) and (NO(3)(-)).(N(2)O(4)) were investigated using an excited state method and it was determined that both complexes possess one low-lying excited state that is accessible through absorption of visible radiation. Evidence for the existence of (NO(3)(-)).(N(2)O(4)) was obtained from UV/vis absorption spectra of N(2)O(4) in concentrated HNO(3), which show a band at 320 nm that is blue shifted by 20 nm relative to what is observed for N(2)O(4) dissolved in organic solvents. Finally, hydrogen transfer reactions within the (HNO(3)).(NO(2)) and (HNO(3)).(N(2)O(4)) complexes leading to the formation of HONO, were investigated. In both systems the calculated potential profiles rule out a thermal mechanism, but indicate the reaction could take place following the absorption of visible radiation. We propose that these complexes are potentially important in the thermal and photochemical production of HONO observed in previous laboratory and field studies.

SciDAC has had a major impact on computational beam dynamics and the design of particle accelerators. Particle accelerators -- which account for half of the facilities in the DOE Office of Science Facilities for the Future of Science 20 Year Outlook -- are crucial for US scientific, industrial, and economic competitiveness. Thanks to SciDAC, accelerator design calculations that were once thought impossible are now carried routinely, and new challenging and important calculations are within reach. SciDAC accelerator modeling codes are being used to get the most science out of existing facilities, to produce optimal designs for future facilities, and to explore advanced accelerator concepts that may hold the key to qualitatively new ways of accelerating charged particle beams. In this poster we present highlights from the SciDAC Accelerator Science and Technology (AST) project Beam Dynamics focus area in regard to algorithm development, software development, and applications.