Properties of Reactive Oxygen Species by Quantum Monte Carlo

The electronic properties of the oxygen molecule, in its singlet and triplet states, and of many small oxygen-containing radicals and anions have important roles in different fields of Chemistry, Biology and Atmospheric Science. Nevertheless, the electronic structure of such species is a challenge for ab-initio computational approaches because of the difficulties to correctly describe the statical and dynamical correlation effects in presence of one or more unpaired electrons. Only the highest-level quantum chemical approaches can yield reliable characterizations of their molecular properties, such as binding energies, equilibrium structures, molecular vibrations, charge distribution and polarizabilities. In this work we use the variational Monte Carlo (VMC) and the lattice regularized Monte Carlo (LRDMC) methods to investigate the equilibrium geometries and molecular properties of oxygen and oxygen reactive species. Quantum Monte Carlo methods are used in combination with the Jastrow Antisymmetrized Geminal Power (JAGP) wave function ansatz, which has been recently shown to effectively describe the statical and dynamical correlation of different molecular systems. In particular we have studied the oxygen molecule, the superoxide anion, the nitric oxide radical and anion, the hydroxyl and hydroperoxyl radicals and their corresponding anions, and the hydrotrioxyl radical. Overall, the methodology was able to correctly describe the geometrical and electronic properties of these systems, through compact but fully-optimised basis sets and with a computational cost which scales as $N^3-N^4$, where $N$ is the number of electrons. This work is therefore opening the way to the accurate study of the energetics and of the reactivity of large and complex oxygen species by first principles

Non-Arrhenius ionic conductivities in glasses due to a distribution of activation energies

Previously observed non-Arrhenius behavior in fast ion conducting glasses [\textit{Phys.\ Rev.\ Lett.}\ \textbf{76}, 70 (1996)] occurs at temperatures near the glass transition temperature, $T_{g}$, and is attributed to changes in the ion mobility due to ion trapping mechanisms that diminish the conductivity and result in a decreasing conductivity with increasing temperature. It is intuitive that disorder in glass will also result in a distribution of the activation energies (DAE) for ion conduction, which should increase the conductivity with increasing temperature, yet this has not been identified in the literature. In this paper, a series of high precision ionic conductivity measurements are reported for $0.5{Na}_{2}{S}+0.5[x{GeS}_{2}+(1-x){PS}_{5/2}]$ glasses with compositions ranging from $0 \leq x \leq 1$. The impact of the cation site disorder on the activation energy is identified and explained using a DAE model. The absence of the non-Arrhenius behavior in other glasses is explained and it is predicted which glasses are expected to accentuate the DAE effect on the ionic conductivity.Comment: 2 figure

Quantum Mechanics helps in searching for a needle in a haystack

Quantum mechanics can speed up a range of search applications over unsorted data. For example imagine a phone directory containing N names arranged in completely random order. To find someone's phone number with a probability of 50%, any classical algorithm (whether deterministic or probabilistic) will need to access the database a minimum of O(N) times. Quantum mechanical systems can be in a superposition of states and simultaneously examine multiple names. By properly adjusting the phases of various operations, successful computations reinforce each other while others interfere randomly. As a result, the desired phone number can be obtained in only O(sqrt(N)) accesses to the database.Comment: Postscript, 4 pages. This is a modified version of the STOC paper (quant-ph/9605043) and is modified to make it more comprehensible to physicists. It appeared in Phys. Rev. Letters on July 14, 1997. (This paper was originally put out on quant-ph on June 13, 1997, the present version has some minor typographical changes

Deviations from ozone photostationary state during the International Consortium for Atmospheric Research on Transport and Transformation 2004 campaign: Use of measurements and photochemical modeling to assess potential causes

Nitric oxide (NO) and nitrogen dioxide (NO2) were monitored at the University of New Hampshire Atmospheric Observing Station at Thompson Farm (TF) during the ICARTT campaign of summer 2004. Simultaneous measurement of ozone (O3), temperature, and the photolysis rate of NO2 (jNO2) allow for assessment of the O3 photostationary state (Leighton ratio, Φ). Leighton ratios that are significantly greater than unity indicate that peroxy radicals (PO2), halogen monoxides, nitrate radicals, or some unidentified species convert NO to NO2 in excess of the reaction between NO and O3. Deviations from photostationary state occurred regularly at TF (1.0 ≤ Φ ≤ 5.9), particularly during times of low NOx (NOx = NO + NO2). Such deviations were not controlled by dynamics, as indicated by regressions between Φ and several meteorological parameters. Correlation with jNO2 was moderate, indicating that sunlight probably controls nonlinear processes that affect Φ values. Formation of PO2 likely is dominated by oxidation of biogenic hydrocarbons, particularly isoprene, the emission of which is driven by photosynthetically active radiation. Halogen atoms are believed to form via photolysis of halogenated methane compounds. Nitrate radicals are believed to be insignificant. Higher Φ values are associated with lower mixing ratios of isoprene and chloroiodomethane and lower ratios of NOx to total active nitrogen, indicating that photochemical aging may very well lead to increased Φ values. PO2 levels calculated using a zero‐dimensional model constrained by measurements from TF can account for 71% of the observed deviations on average. The remainder is assumed to be associated with halogen atoms, most likely iodine, with necessary mixing ratios up to 0.6 or 1.2 pptv, for chlorine and iodine, respectively

Biofuels and their By-Products: Global Economic and Environmental Implications

The biofuel industry has been rapidly growing around the world in recent years. Several papers have used general equilibrium models and addressed the economy-wide and environmental consequences of producing biofuels at a large scale. They mainly argue that since biofuels are mostly produced from agricultural sources, their effects are largely felt in agricultural markets with major land use and environmental consequences. In this paper, we argue that virtually all of these studies have overstated the impact of liquid biofuels on agricultural markets due to the fact that they have ignored the role of by-products resulting from the production of biofuels. Feed by-products of the biofuel industry, such as Dried Distillers Grains with Solubles (DDGS) and biodiesel by-products (BDBP) such as soy and rapeseed meals, can be used in the livestock industry as substitutes for grains and oilseed meals used in this industry. Hence, their presence mitigates the price impacts of biofuel production on the livestock and food industries. The importance of incorporating by-products of biofuel production in economic models is well recognized by some partial equilibrium analyses of biofuel production. However, to date, this issue has not been tackled by those conducting CGE analysis of biofuels programs. Accordingly, this paper explicitly introduces DDGS and BDBP, the major by-products of grain based ethanol and biodiesel production processes, into a worldwide CGE model and analyzes the economic and environmental impacts of regional and international mandate policies designed to stimulate bioenergy production and use. We first explicitly introduce by-products of biofuel production into the GTAP-BIO database, originally developed by Taheripour et al. (2007). Then we explicitly bring in DDGS and BDBP into the Energy-Environmental version of the Global Trade Analysis Project (GTAP-E) model, originally developed by Burniaux and Truong (2002), and recently modified by McDougall and Golub (2007) and Birur, Hertel, and Tyner (2008). The structure of the GTAP-E model is redesigned to handle the production and consumption of biofuels and their by-products, in particular DDGS, across the world. Unlike many CGE models which are characterized by single product sectors, here grain based ethanol and DDGS jointly are produced by an industry, named EthanolC. The biodiesel industry also produces two products of biodiesel and BDBP jointly. This paper divides the world economy into 22 commodities, 20 industries, and 18 regions and then examines global impacts of the US Energy Independence and Security Act of 2007 and the European Union mandates for promoting biofuel production in the presence of by-products. We show that models with and without by-products demonstrate different portraits from the economic impacts of international biofuel mandates for the world economy in 2015. While both models demonstrate significant changes in the agricultural production pattern across the world, the model with by-products shows smaller changes in the production of cereal grains and larger changes for oilseeds products in the US and EU, and the reverse for Brazil. For example, the US production of cereal grains increases by 10.8% and 16.4% with and without by-products, respectively. The difference between these two numbers corresponds to 646 million bushels of corn. In the presence of by-products, prices change less due to the mandate policies. For example, the model with no by-products predicts that the price of cereal grains grows 22.7% in the US during the time period of 2006 to 2015. The corresponding number for the model with by-products is 14%. The model with no by-products predicts that the price of oilseeds increases by 62.5% in the EU during 2006-2015. In the presence of by-products, this price grows 56.4%. Finally, we show that incorporating DDGS into the model significantly changes the land use consequences of the biofuel mandate polices.Resource /Energy Economics and Policy, Environmental Economics and Policy,

An Empirical Relation Between The Large-Scale Magnetic Field And The Dynamical Mass In Galaxies

The origin and evolution of cosmic magnetic fields as well as the influence of the magnetic fields on the evolution of galaxies are unknown. Though not without challenges, the dynamo theory can explain the large-scale coherent magnetic fields which govern galaxies, but observational evidence for the theory is so far very scarce. Putting together the available data of non-interacting, non-cluster galaxies with known large-scale magnetic fields, we find a tight correlation between the integrated polarized flux density, S(PI), and the rotation speed, v(rot), of galaxies. This leads to an almost linear correlation between the large-scale magnetic field B and v(rot), assuming that the number of cosmic ray electrons is proportional to the star formation rate, and a super-linear correlation assuming equipartition between magnetic fields and cosmic rays. This correlation cannot be attributed to an active linear alpha-Omega dynamo, as no correlation holds with global shear or angular speed. It indicates instead a coupling between the large-scale magnetic field and the dynamical mass of the galaxies, B ~ M^(0.25-0.4). Hence, faster rotating and/or more massive galaxies have stronger large-scale magnetic fields. The observed B-v(rot) correlation shows that the anisotropic turbulent magnetic field dominates B in fast rotating galaxies as the turbulent magnetic field, coupled with gas, is enhanced and ordered due to the strong gas compression and/or local shear in these systems. This study supports an stationary condition for the large-scale magnetic field as long as the dynamical mass of galaxies is constant.Comment: 23 pages, 4 figures, accepted for publication in the Astrophysical Journal Letter

Ideal barriers to polarization reversal and domain-wall motion in strained ferroelectric thin films

The ideal intrinsic barriers to domain switching in c-phase PbTiO_3 (PTO), PbZrO_3 (PZO), and PbZr_{1-x}Ti_xO_3 (PZT) are investigated via first-principles computational methods. The effects of epitaxial strain on the atomic structure, ferroelectric response, barrier to coherent domain reversal, domain-wall energy, and barrier to domain-wall translation are studied. It is found that PTO has a larger polarization, but smaller energy barrier to domain reversal, than PZO. Consequentially the idealized coercive field is over two times smaller in PTO than PZO. The Ti--O bond length is more sensitive to strain than the other bonds in the crystals. This results in the polarization and domain-wall energy in PTO having greater sensitivity to strain than in PZO. Two ordered phases of PZT are considered, the rock-salt structure and a (100) PTO/PZO superlattice. In these simple structures we find that the ferroelectric properties do not obey Vergard's law, but instead can be approximated as an average over individual 5-atom unit cells.Comment: 9 pages, 13 figure

Characterization of aerosol associated with enhanced small particle number concentrations in a suburban forested environment

Two elevated particle number/mass growth events associated with Aitken‐mode particles were observed during a sampling campaign (13–29 September 2004) at the Duke University Free‐Air CO2 Enrichment facility, a forested field site located in suburban central North Carolina. Aerosol growth rates between 1.2 and 4.9 nm hr−1 were observed, resulting in net increases in geometric mean diameter of 21 and 37 nm during events. Growth was dominated by addition of oxidized organic compounds. Campaign‐average aerosol mass concentrations measured by an Aerodyne quadrupole aerosol mass spectrometer (Q‐AMS) were 1.9 ± 1.6 (σ), 1.6 ± 1.9, 0.1 ± 0.1, and 0.4 ± 0.4 μg m−3 for organic mass (OM), sulfate, nitrate, and ammonium, respectively. These values represent 47%, 40%, 3%, and 10%, respectively, of the measured submicron aerosol mass. Based on Q‐AMS spectra, OM was apportioned to hydrocarbon‐like organic aerosol (HOA, likely representing primary organic aerosol) and two types of oxidized organic aerosol (OOA‐1 and OOA‐2), which constituted on average 6%, 58%, and 36%, respectively, of the apportioned OM. OOA‐1 probably represents aged, regional secondary organic aerosol (SOA), while OOA‐2 likely reflects less aged SOA. Organic aerosol characteristics associated with the events are compared to the campaign averages. Particularly in one event, the contribution of OOA‐2 to overall OM levels was enhanced, indicating the likelihood of less aged SOA formation. Statistical analyses investigate the relationships between HOA, OOA‐1, OOA‐2, other aerosol components, gas‐phase species, and meteorological data during the campaign and individual events. No single variable clearly controls the occurrence of a particle growth event