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The GOME-type Total Ozone Essential Climate Variable (GTO-ECV) is a Level-3 data record, which combines individual sensor products into one single cohesive record covering the 22 year period from 1995 to 2017, generated in the frame of the European Space Agency's Climate Change Initiative Phase-II. It is based on Level-2 total ozone data produced by the GODFIT v4 algorithm as applied to the GOME/ERS-2, OMI/Aura, SCIAMACHY/Envisat and GOME-2/MetopA and /MetopB observations. In this paper we examine whether GTO-ECV meets the specific requirements set by the international climate-chemistry modelling community for decadal stability, long-term and short term accuracy. In the following, we present the validation of the 2017 release of the Climate Research Data Package Total Ozone Column (CRDP TOC), both at Level-2 and Level-3. The individual Level-2 data sets show excellent inter-sensor consistency with mean differences generally within 0.5 % at moderate latitudes (±50°), whereas the Level-3 data sets show mean differences with respect to the OMI reference data record that span between −0.2 ± 0.9 % (for GOME-2B) and 1.0 ± 1.4&htinsp;% (for SCIAMACHY). Very similar findings are reported for the Level-2 validation against independent ground-based TOC observations reported by Brewer, Dobson and SAOZ instruments; the mean bias between GODFIT v4 satellite TOC and ground instrument is well within 1.0 ± 1.0 % for all sensors, the drift per decade spans between −0.5 % to 1.0 ± 1.0 % depending on the sensor, and the peak-to-peak seasonality of the differences ranges between ~ 1 % for GOME and OMI, to ~ 2 % for SCIAMACHY. For the Level-3 validation, as a first step the aim was to show that the Level-3 CRDP produces consistent findings as the Level-2 individual sensor comparisons. We show an excellent agreement with 0.5 to 2 % peak-to-peak amplitude for the monthly mean difference time series and a negligible drift per decade in the Northern Hemisphere differences at −0.11 ± 0.10 % per decade for Dobson and +0.22 ± 0.08 % per decade for Brewer collocations. The exceptional quality of the Level-3 GTO-ECV v3 TOC record temporal stability well satisfies the requirements for the total ozone measurement decadal stability of between 1–3 % and the short term and long-term accuracy requirements of 2 % and 3 % respectively, showing an excellent inter-sensor consistency both in the Level-2 GODFIT v4 as well as in the Level-3 GTO-ECV v3 datasets and thus can be used for longer term analysis of the ozone layer, such as decadal trend studies, chemistry-climate model evaluation and data assimilation applications.

In spite of the importance of diacids and functionalised diacids for organic aerosol formation through aqueous-phase processes in droplets and aerosol water, there seems to be no reliable set of experimental values for their Henry's law constants (HLCs). We show that their estimation through the use of infinite dilution activity coefficients is also prone to error. Here we present HLC values for diacids and hydroxy polyacids determined from solubilities, water activities and vapour pressures of solids or solutions, by employing thermodynamic relationships. The vapour pressures are found to be the largest source of error, but the analysis of the obtained HLC points to inconsistencies among specific vapour pressure data sets. Although there is considerable uncertainty, the HLC defined as aqueous concentration per unit gaseous partial pressure of linear α- and ω-diacids appear to be higher than estimated by the often cited review work of Saxena and Hildemann (1996).

A new parameter model for α-pinene secondary organic aerosol (SOA) is presented, based on simulations with the detailed model BOREAM (Biogenic hydrocarbon Oxidation and Related Aerosol formation Model). The parameterisation takes into account the influence of temperature, type of oxidant, NOx-regime, photochemical ageing and water uptake, and is suitable for use in global chemistry transport models. BOREAM is validated against recent photooxidation smog chamber experiments, for which it reproduces SOA yields to within a factor of 2 in most cases. In the simple chemical mechanism of the parameter model, oxidation of α-pinene generates peroxy radicals, which, upon reaction with NO or HO2, yield products corresponding to high or low-NOx conditions, respectively. The model parameters – i.e. the temperature-dependent stoichiometric coefficients and partitioning coefficients of 10 semi-volatile products – are obtained from simulations with BOREAM, including a prescribed diurnal cycle for the radiation, oxidant and emission levels, as well as a deposition sink for the particulate and gaseous products. The effects of photooxidative ageing are implicitly included in the parameterisation, since it is based on near-equilibrium SOA concentrations, obtained through simulations of a two-week period. In order to mimic the full BOREAM model results both during SOA build-up and when SOA has reached an equilibrium concentration, the revolatilisation of condensable products due to photochemical processes is taken into account through a fitted pseudo-photolysis reaction of the lumped semi-volatile products. Modelled SOA mass yields are about ten times higher in low-NOx than in high-NOx conditions, with yields of more than 50% in the low-NOx OH-initiated oxidation of α-pinene, considerably more than in previous parameterisations based on smog chamber experiments. Sensitivity calculations indicate that discrepancies between the full model and the parameterisation due to variations in assumed oxidant levels are limited, but that changes in the radiation levels can lead to larger deviations. Photolysis of species in the particulate phase is found to strongly reduce SOA yields in the full model. Simulations of ambient conditions at 17 different sites (using oxidant, radiation and meteorological data from a global chemistry-transport model) show that overall, the parameterisation displays only little bias (2%) compared with the full model, whereas averaged relative deviations amount to about 11%. Water uptake is parameterised using fitted activity coefficients, resulting in a good agreement with the full model.

We present EVAPORATION (Estimation of VApour Pressure of ORganics, Accounting for Temperature, Intramolecular, and Non-additivity effects), a method to predict (subcooled) liquid pure compound vapour pressure p0 of organic molecules that requires only molecular structure as input. The method is applicable to zero-, mono- and polyfunctional molecules. A simple formula to describe log10p0(T) is employed, that takes into account both a wide temperature dependence and the non-additivity of functional groups. In order to match the recent data on functionalised diacids an empirical modification to the method was introduced. Contributions due to carbon skeleton, functional groups, and intramolecular interaction between groups are included. Molecules typically originating from oxidation of biogenic molecules are within the scope of this method: aldehydes, ketones, alcohols, ethers, esters, nitrates, acids, peroxides, hydroperoxides, peroxy acyl nitrates and peracids. Therefore the method is especially suited to describe compounds forming secondary organic aerosol (SOA).

Multicomponent organic aerosol (OA) is likely to be liquid, or partially liquid. Hence, to describe the partitioning of these components, their liquid vapour pressure is desired. Functionalised acids (e.g. diacids) can be a significant part of OA. But often measurements are available only for solid state vapour pressure, which can differ by orders of magnitude from their liquid counterparts. To convert such a sublimation pressure to a subcooled liquid vapour pressure, fusion properties (two out of these three quantities: fusion enthalpy, fusion entropy, fusion temperature) are required. Unfortunately, experimental knowledge of fusion properties is sometimes missing in part or completely, hence an estimation method is required. Several fusion data estimation methods are tested here against experimental data of functionalised acids, and a simple estimation method is developed, specifically for this family of compounds, with a significantly smaller estimation error than the literature methods.

BOREAM, a detailed model for the gas-phase oxidation of α-pinene and its subsequent formation of Secondary Organic Aerosol (SOA), is tested against a large set of SOA yield measurements obtained in dark ozonolysis experiments. For the majority of experiments, modelled SOA yields are found to agree with measured yields to within a factor 2. However, the comparisons point to a general underestimation of modelled SOA yields at high temperatures (above 30 °C), reaching an order of magnitude or more in the worst cases, whereas modelled SOA yields are often overestimated at lower temperature (by a factor of about 2). Comparisons of results obtained using four different vapour pressure prediction methods indicate a strong sensitivity to the choice of the method, although the overestimated temperature dependence of the yields is found in all cases. Accounting for non-ideality of the aerosol mixture (based on an adapted UNIFAC method) has significant effects, especially at low yields. Our simulations show that the formation of oligomers through the gas-phase reactions of Stabilised Criegee Intermediates (SCI) with other molecular organic products could increase the SOA yield significantly only at very low relative humidity (below 1%). Further tests show that the agreement between model and measurements is improved when the ozonolysis mechanism includes additional production of non-volatile compounds.

Secondary organic aerosol (SOA) is a complex mixture of water and organic molecules. Its composition is determined by the presence of semi-volatile or non-volatile compounds, their saturation vapor pressure and activity coefficient. The activity coefficient is a non-ideality effect and is a complex function of SOA composition. In a previous publication, the detailed chemical mechanism (DCM) for α-pinene oxidation and subsequent aerosol formation BOREAM was presented. In this work, we investigate with this DCM the impact of non-ideality by simulating smog chamber experiments for α-pinene degradation and aerosol formation and taking the activity coefficient into account of all molecules in the aerosol phase. Several versions of the UNIFAC method are tested for this purpose, and missing parameters for e.g. hydroperoxides and nitrates are inferred from fittings to activity coefficient data generated using the SPARC model. Alternative approaches to deal with these missing parameters are also tested, as well as an activity coefficient calculation method based on Hansen solubility parameters (HSP). It turns out that for most experiments, non-ideality has only a limited impact on the interaction between the organic molecules, and therefore on SOA yields and composition, when water uptake is ignored. The reason is that often, the activity coefficient is on average close to 1 and, specifically for high-VOC experiments, partitioning is not very sensitive on the activity coefficient because the equilibrium is shifted strongly towards condensation. Still, for ozonolysis experiments with low amounts of volatile organic carbon (low-VOC), the UNIFAC parameterization of Raatikainen et al. leads to significantly higher SOA yields (by up to a factor 1.6) compared to the ideal case and to other parameterizations. Water uptake is model dependent, in the order: ideal > UNIFAC-Raatikainen > UNIFAC-Peng > UNIFAC-Hansen ≈ UNIFAC-Magnussen ≈ UNIFAC-Ming. In the absence of salt dissolution, phase splitting from pure SOA is unlikely.

Much attention has been paid to the role of vortices in the magnetic response properties of superconductors, but less so for molecular systems. Here we present a theoretical analysis on nanographenes subject to a strong homogeneous magnetic field. The analysis is based on the simple Huckel-London model, for which we derive the topological definition of vorticity. The results are confirmed by a more elaborate model that includes nonnearest neighbor interaction, the explicit presence of nuclei and all terms due to the magnetic field. We find that due to frontier orbital intersections, large changes in magnetic dipole moments occur. Orbital energy minima and maxima can be related to change of vortex patterns with flux. ispartof: Journal of Physical Chemistry B vol:110 issue:39 pages:19340-19351 ispartof: location:United States status: published

A qualitative molecular-orbital treatment and group-theoretical analysis reveals the nature of the frontier orbitals of (3,6) and (4,6) polyhedral cages, consisting of a hexagonal network with triangular and square defects, respectively. Leapfrog (3,6) cages have two nonbonding filled orbitals. Leapfrog (4,6) cages have a high HOMO-LUMO gap, while nonleapfrog (4,6) cages with octahedral symmetry have a very small HOMO-LUMO gap. The symmetry of the frontier orbitals is determined.

We applied and compared seven vapor pressure estimation methods to the condensable compounds generated in the oxidation of α-pinene, as described by the state-of-the-art mechanism of the BOREAM model (Capouet et al., 2008). Several of these methods had to be extended in order to treat functional groups such as hydroperoxides and peroxy acyl nitrates. Large differences in the estimated vapor pressures are reported, which will inevitably lead to large differences in aerosol formation simulations. Cautioning remarks are given for some vapor pressure estimation methods.

Carbon nanotubes (CNTs) are a promising candidate to replace copper interconnects. An ab initio study is presented on the conductance of a closed-packed bundle of very narrow metallic (4,0) CNTs, which is vertically placed on a Cu (100) surface. The intertube interactions have no significant impact on the conductance. The conductance is highly dependent on the exact geometry of the interface, which is varying between 0.6 and 1.8 conductance quanta, while the theoretical maximum of the CNT is three conductance quanta. The wave-function interference can lead to conductance suppression when the packing is too high. Both features are explained by using an orbital picture. ispartof: Physical Review B, Condensed Matter and Materials Physics vol:77 issue:19 status: published

[1] We present BOREAM (Biogenic hydrocarbon Oxidation and Related Aerosol formation Model), a detailed model for the oxidation of α-pinene and the resulting formation of secondary organic aerosol (SOA). It is based on a quasi-explicit gas phase mechanism for the formation of primary products, developed on objective grounds using advanced theoretical methods, and on a simplified representation for the further oxidation of the products. The partitioning of the products follows a kinetic representation with coefficients estimated from vapor pressures calculated using a dedicated group contribution method. Particle phase and heterogeneous reactions are generally neglected, but the impact of peroxyhemiacetal formation in the aerosol is tested on the basis of laboratory estimates of the reaction rates. The model is evaluated against 28 laboratory experiments from 6 studies of α-pinene photo-oxidation covering a wide range of photochemical conditions. In contrast with previous modeling studies, the modeled and measured SOA yields agree to within a factor of 2 in most cases. The SOA yields are underestimated for the ozonolysis experiments of Presto et al. (2005a) when the standard version of the ozonolysis mechanism is used, presumably because of the lack of credible pathways for the formation of pinic and hydroxy pinonic acid. The underestimation is drastically reduced when the mechanism is modified to account for the formation of these compounds. Accounting for peroxyhemiacetal formation in the particle phase is found to further increase the SOA yields by about one third in high VOC ozonolysis experiments and to have a much smaller impact in all other cases. The model calculates that ozonolysis contributes about twice more to SOA formation than oxidation by OH, whereas NO3-initiated oxidation is negligible. In agreement with previous studies, low NOx conditions and low temperatures are calculated to favor aerosol formation, but the estimated temperature dependence is stronger than found in recent laboratory experiments.

In order to investigate the technological potential ascribed to semiconductor nanowires, it is paramount to include quantum effects into the models used to simulate carrier trans-port as well as optical and excitonic features of various nanowire layouts.

We report quantum chemistry investigations of the magnetic response of large polycyclic hydrocarbons to a high magnetic field. In strong fields the magnetisation vs. field of nanosize molecules becomes strongly non-monotonic. For nanographenes containing thousands of atoms this effect develops at ca. 10(1)-10(2) T. It is related to the motion of vortices in the frontier molecular orbitals and transformations of ring current patterns. The described phenomenon is general, in principle observable in all conjugated planar nanosize molecules. (c) 2006 Elsevier B.V. All rights reserved. ispartof: Chemical Physics Letters vol:428 issue:1 pages:119-124 status: published

Accurate geometries of carbon nanocones of different sizes with a triangle, square or pentagon at the apex have been determined for the first time using a quantum chemical optimization method. The structure close to the apex is distorted from an ideal conical surface. The charging effect of the central defect is quite different from that predicted by tight-binding calculations. The symmetry behavior of the frontier orbitals and the size of the highest occupied molecular orbital-lowest unoccupied molecular orbital gap versus cone type and size is explained. The density of states quickly converges towards that of graphite when the size of the cone increases. In comparison to previous results in the literature it is found that the local densities of states of cones, that are locally different but belong to the same topo-combinatoric class, share common features. (C) 2004 American Institute of Physics. ispartof: Journal of Chemical Physics vol:121 issue:5 pages:2326-2336 ispartof: location:United States status: published

The icosahedral multipoles that break the spherical symmetry in C20, C60 and C80 are identified as the L=6, 10, and 12 components respectively. In all these cages the dominant structural feature of the valence shell is the influence of the pentagonal defects.

The transmission through side-contacted single-wall carbon nanotubes is investigated within the Landauer-Butikker formalism for arbitrary tubes, geometries of contacts, and energies of transmission (E) for the case of monoatomic contacts. An efficient method to calculate transmission within the tight-binding approach including curvature effects is devised allowing, in particular, for an analytical treatment of zigzag, armchair, and some chiral tubes. The transmission function is described as a superposition of the contributions from one-dimensional bands of all nanotube lines, each of them oscillating or/and decaying with the distance between the leads. We find five different types of antiresonances. Two of them arise from a destructive interference of the contributions from different nanotube lines when E is in the gap of semiconducting nanotubes and either are due to symmetry reasons or are accidental. A further two can show up at energies of Van Hove singularities originating from isolated singular points in 1D bands of nanotubes and can lead either to split or completely missing transmission peaks. The fifth one is related to the flat band in zigzag nanotubes at the energy of Van Hove singularity in graphene and results in zero transmission between carbon atoms belonging to different translational units in these tubes. A strong anisotropy of transmission in two opposite directions along the tube's axis is found in the middle of the energy gap of semiconducting nanotubes, which reaches several orders of magnitude in zigzag tubes. The transmission at Van Hove singularities (when nonzero) is of the order of unity and decays at a large axial distance R between the leads as R-2, similarly to monoatomic chains. The transmission in the band region of nanotubes shows two types of behavior depending on the divisibility by three of the difference between corresponding reduced nanotube indices n(')-m('). Close to the Fermi level the amplitude of the transmission function is independent from the chiral angle of the nanotubes and scales as an inverse square of their diameter. ispartof: Physical Review B, Condensed matter and materials physics vol:68 issue:12 status: published

An infinite series of (3, 6) cages is defined by trivalent carbon polyhedra composed of hexagonal and four triangular rings. A zone-folding construction is applied to the graphene band structure to yield explicit expressions for the pi-molecular orbitals, energies, and symmetries of the cages that depend only on four indices m, n, p, and q. Leapfrog members of the series (m-n=0 mod 3 and p-q=0 mod 3) have closed shells in a neutral form with two filled nonbonding orbitals; all others have closed shells as dications. Quantum chemical calculations on C-12,C-48, and C-52(2+) confirm this result. Embedding relationships are proved for the spectra of (3, 6) cages related by inflation transformations corresponding to stretching and rotation of the polyhedral net. ispartof: Physical Review B, Condensed matter and materials physics vol:65 issue:11 status: published

In this work we relate the irreducible representations of the nanotubes to the zone-folding description of the first Brillouin zone. The complete set of symmetry elements for the armchair nanotube and their representations are given. Electronic π wavefunctions, with the appropriate symmetries are constructed and the irreducible representations, classified according to their symmetries, are assigned in the special points of the first Brillouin zone of an armchair nanotube.