Aqueous reactions of organic triplet excited states with atmospheric alkenes

Triplet excited states of organic matter are formed when colored organic matter (i.e., brown carbon) absorbs light. While these “triplets” can be important photooxidants in atmospheric drops and particles (e.g., they rapidly oxidize phenols), very little is known about their reactivity toward many classes of organic compounds in the atmosphere. Here we measure the bimolecular rate constants of the triplet excited state of benzophenone (3BP∗), a model species, with 17 water-soluble C3–C6 alkenes that have either been found in the atmosphere or are reasonable surrogates for identified species. Measured rate constants (kALK+3BP∗) vary by a factor of 30 and are in the range of (0.24–7.5)&thinsp;×109&thinsp;M−1&thinsp;s−1. Biogenic alkenes found in the atmosphere – e.g., cis-3-hexen-1-ol, cis-3-hexenyl acetate, and methyl jasmonate – react rapidly, with rate constants above 1×109&thinsp;M−1&thinsp;s−1. Rate constants depend on alkene characteristics such as the location of the double bond, stereochemistry, and alkyl substitution on the double bond. There is a reasonable correlation between kALK+3BP∗ and the calculated one-electron oxidation potential (OP) of the alkenes (R2=0.58); in contrast, rate constants are not correlated with bond dissociation enthalpies, bond dissociation free energies, or computed energy barriers for hydrogen abstraction. Using the OP relationship, we estimate aqueous rate constants for a number of unsaturated isoprene and limonene oxidation products with 3BP∗: values are in the range of (0.080–1.7)&thinsp;×109&thinsp;M−1&thinsp;s−1, with generally faster values for limonene products. Rate constants with less reactive triplets, which are probably more environmentally relevant, are likely roughly 25 times slower. Using our predicted rate constants, along with values for other reactions from the literature, we conclude that triplets are probably minor oxidants for isoprene- and limonene-related compounds in cloudy or foggy atmospheres, except in cases in which the triplets are very reactive.</p

Density Dependent Hadron Field Theory

A fully covariant approach to a density dependent hadron field theory is presented. The relation between in--medium NN interactions and field--theoretical meson--nucleon vertices is discussed. The medium dependence of nuclear interactions is described by a functional dependence of the meson--nucleon vertices on the baryon field operators. As a consequence, the Euler--Lagrange equations lead to baryon rearrangement self--energies which are not obtained when only a parametric dependence of the vertices on the density is assumed. It is shown that the approach is energy--momentum conserving and thermodynamically consistent. Solutions of the field equations are studied in the mean--field approximation. Descriptions of the medium dependence in terms of the baryon scalar and vector density are investigated. Applications to infinite nuclear matter and finite nuclei are discussed. Density dependent coupling constants obtained from Dirac--Brueckner calculations with the Bonn NN-potentials are used. Results from Hartree calculations for energy spectra, binding energies and charge density distributions of $^{16}O$, $^{40,48}Ca$ and $^{208}Pb$ are presented. Comparisons to data strongly support the importance of rearrangement in a relativistic density dependent field theory. Most striking is the simultanuous improvement of charge radii, charge densities and binding energies. The results indicate the appearance of a new "Coester line" in the nuclear matter equation of state.Comment: 48 LateX pages, 12 Figures, figures and full paper are available as postscript files by anonymous ftp at ftp://theorie.physik.uni-giessen.de/dd

Momentum-Dependent Mean Field Based Upon the Dirac-Brueckner Approach for Nuclear Matter

A momentum-dependent mean field potential, suitable for application in the transport-model description of nucleus-nucleus collisions, is derived in a microscopic way. The derivation is based upon the Bonn meson-exchange model for the nucleon-nucleon interaction and the Dirac-Brueckner approach for nuclear matter. The properties of the microscopic mean field are examined and compared with phenomenological parametrizations which are commonly used in transport-model calculations.Comment: 15 pages text (RevTex) and 4 figures (postscript in a separate uuencoded file), UI-NTH-930

Kinetics of isothermal and non-isothermal precipitation in an Al-6at%Si alloy

A novel theory which describes the progress of a thermally activated reaction under isothermal and linear heating conditions is presented. It incorporates nucleation, growth and impingement and takes account of temperaturedependent solubility. The model generally fits very well to isothermal calorimetry and differential scanning calorimetry data on precipitation in an Al-6 at.% Si alloy. Analysis of the data shows that two processes occur in this precipitation reaction: growth of large Si particles and growth of pre-existing small nuclei. Determination of the sizes of Si precipitates by transmission electron microscopy indicates that interfacial energy contributions are small and have a negligible influence on solubilit

Meson-induced correlations of nucleons in nuclear Compton scattering

The non-resonant (seagull) contribution to the nuclear Compton amplitude at low energies is strongly influenced by nucleon correlations arising from meson exchange. We study this problem in a modified Fermi gas model, where nuclear correlation functions are obtained with the help of perturbation theory. The dependence of the mesonic seagull amplitude on the nuclear radius is investigated and the influence of a realistic nuclear density on this amplitude is dicussed. We found that different form factors appear for the static part (proportional to the enhancement constant $\kappa$) of the mesonic seagull amplitude and for the parts, which contain the contribution from electromagnetic polarizabilities.Comment: 15 pages, Latex, epsf.sty, 9 eps figures

Hartree Fock Calculations in the Density Matrix Expansion Approach

The density matrix expansion is used to derive a local energy density functional for finite range interactions with a realistic meson exchange structure. Exchange contributions are treated in a local momentum approximation. A generalized Slater approximation is used for the density matrix where an effective local Fermi momentum is chosen such that the next to leading order off-diagonal term is canceled. Hartree-Fock equations are derived incorporating the momentum structure of the underlying finite range interaction. For applications a density dependent effective interaction is determined from a G-matrix which is renormalized such that the saturation properties of symmetric nuclear matter are reproduced. Intending applications to systems far off stability special attention is paid to the low density regime and asymmetric nuclear matter. Results are compared to predictions obtained from Skyrme interactions. The ground state properties of stable nuclei are well reproduced without further adjustments of parameters. The potential of the approach is further exemplified in calculations for A=100...140 tin isotopes. Rather extended neutron skins are found beyond 130Sn corresponding to solid layers of neutron matter surrounding a core of normal composition.Comment: Revtex, 29 pages including 14 eps figures, using epsfig.st

Renormalization of the P- and T-odd nuclear potentials by the strong interaction and enhancement of P-odd effective field

Approximate analytical formulas for the self-consistent renormalization of P,T-odd and P-odd weak nuclear potentials by the residual nucleon-nucleon strong interaction are derived. The contact spin-flip nucleon-nucleon interaction reduces the constant of the P,T-odd potential 1.5 times for the proton and 1.8 times for the neutron. Renormalization of the P-odd potential is caused by the velocity dependent spin-flip component of the strong interaction. In the standard variant of $\pi + \rho$-exchange, the conventional strength values lead to anomalous enhancement of the P-odd potential. Moreover, the $\pi$-meson exchange contribution seems to be large enough to generate an instability (pole) in the nuclear response to a weak potential.Comment: 5 pages, Revtex3, no figure

Relativistic Brueckner-Hartree-Fock calculations with explicit intermediate negative energy states

In a relativistic Brueckner-Hartree-Fock calculation we include explicit negative-energy states in the two-body propagator. This is achieved by using the Gross spectator-equation, modified by medium effects. Qualitatively our results compare well with other RBHF calculations. In some details significant differences occur, e.g, our equation of state is stiffer and the momentum dependence of the self-energy components is stronger than found in a reference calculation without intermediate negative energy states.Comment: 13 pages Revtex, 5 figures included seperatel

High‐resolution rock magnetic cyclostratigraphy in an Eocene flysch, Spanish Pyrenees

Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/95346/1/ggge1746.pd

Relativistic Contributions to Deuteron Photodisintegration in the Bethe-Salpeter Formalism

In plane wave one-body approximation the reaction of deuteron photodisintegration is considered in the framework of the Bethe-Salpeter formalism for two-nucleon system. Results are obtained for deuteron vertex function, which is the solution of the homogeneous Bethe-Salpeter equation with a multi-rank separable interaction kernel, with a given analytical form. A comparison is presented with predictions of non-relativistic, quasipotential approaches and the equal time approximation. It is shown that important contributions come from the boost in the arguments of the initial state vertex function and the boost on the relative energy in the one-particle propagator due to recoil.Comment: 29 pages, 6 figure