Reply to “Comment on ‘Temperature-dependent orientational ordering on a spherical surface modeled with a lattice spin model’ ”

A reply to the comment of S. Romano, Phys. Rev. E 2015 on our previous paper is provided.

Separating the influence of projected changes in air temperature and wind on patterns of sea level change and ocean heat content

We present ocean model sensitivity experiments aimed at separating the influence of the projected changes in the “thermal” (near-surface air temperature) and “wind” (near-surface winds) forcing on the patterns of sea level and ocean heat content. In the North Atlantic, the distribution of sea level change is more due to the “thermal” forcing, whereas it is more due to the “wind” forcing in the North Pacific; in the Southern Ocean, the “thermal” and “wind” forcing have a comparable influence. In the ocean adjacent to Antarctica the “thermal” forcing leads to an inflow of warmer waters on the continental shelves, which is somewhat attenuated by the “wind” forcing. The structure of the vertically integrated heat uptake is set by different processes at low and high latitudes: at low latitudes it is dominated by the heat transport convergence, whereas at high latitudes it represents a small residual of changes in the surface flux and advection of heat. The structure of the horizontally integrated heat content tendency is set by the increase of downward heat flux by the mean circulation and comparable decrease of upward heat flux by the subgrid-scale processes; the upward eddy heat flux decreases and increases by almost the same magnitude in response to, respectively, the “thermal” and “wind” forcing. Regionally, the surface heat loss and deep convection weaken in the Labrador Sea, but intensify in the Greenland Sea in the region of sea ice retreat. The enhanced heat flux anomaly in the subpolar Atlantic is mainly caused by the “thermal” forcing.

Future changes in the Western North Pacific tropical cyclone activity projected by a multidecadal simulation with a 16-km global atmospheric GCM

How tropical cyclone (TC) activity in the northwestern Pacific might change in a future climate is assessed using multidecadal Atmospheric Model Intercomparison Project (AMIP)-style and time-slice simulations with the ECMWF Integrated Forecast System (IFS) at 16-km and 125-km global resolution. Both models reproduce many aspects of the present-day TC climatology and variability well, although the 16-km IFS is far more skillful in simulating the full intensity distribution and genesis locations, including their changes in response to El Niño–Southern Oscillation. Both IFS models project a small change in TC frequency at the end of the twenty-first century related to distinct shifts in genesis locations. In the 16-km IFS, this shift is southward and is likely driven by the southeastward penetration of the monsoon trough/subtropical high circulation system and the southward shift in activity of the synoptic-scale tropical disturbances in response to the strengthening of deep convective activity over the central equatorial Pacific in a future climate. The 16-km IFS also projects about a 50% increase in the power dissipation index, mainly due to significant increases in the frequency of the more intense storms, which is comparable to the natural variability in the model. Based on composite analysis of large samples of supertyphoons, both the development rate and the peak intensities of these storms increase in a future climate, which is consistent with their tendency to develop more to the south, within an environment that is thermodynamically more favorable for faster development and higher intensities. Coherent changes in the vertical structure of supertyphoon composites show system-scale amplification of the primary and secondary circulations with signs of contraction, a deeper warm core, and an upward shift in the outflow layer and the frequency of the most intense updrafts. Considering the large differences in the projections of TC intensity change between the 16-km and 125-km IFS, this study further emphasizes the need for high-resolution modeling in assessing potential changes in TC activity.

Testing projected wild bee distributions in agricultural habitats: predictive power depends on species traits and habitat type

Species distribution models (SDM) are increasingly used to understand the factors that regulate variation in biodiversity patterns and to help plan conservation strategies. However, these models are rarely validated with independently collected data and it is unclear whether SDM performance is maintained across distinct habitats and for species with different functional traits. Highly mobile species, such as bees, can be particularly challenging to model. Here, we use independent sets of occurrence data collected systematically in several agricultural habitats to test how the predictive performance of SDMs for wild bee species depends on species traits, habitat type, and sampling technique. We used a species distribution modeling approach parametrized for the Netherlands, with presence records from 1990 to 2010 for 193 Dutch wild bees. For each species, we built a Maxent model based on 13 climate and landscape variables. We tested the predictive performance of the SDMs with independent datasets collected from orchards and arable fields across the Netherlands from 2010 to 2013, using transect surveys or pan traps. Model predictive performance depended on species traits and habitat type. Occurrence of bee species specialized in habitat and diet was better predicted than generalist bees. Predictions of habitat suitability were also more precise for habitats that are temporally more stable (orchards) than for habitats that suffer regular alterations (arable), particularly for small, solitary bees. As a conservation tool, SDMs are best suited to modeling rarer, specialist species than more generalist and will work best in long-term stable habitats. The variability of complex, short-term habitats is difficult to capture in such models and historical land use generally has low thematic resolution. To improve SDMs’ usefulness, models require explanatory variables and collection data that include detailed landscape characteristics, for example, variability of crops and flower availability. Additionally, testing SDMs with field surveys should involve multiple collection techniques.

Diruthenium complexes with bridging diethynyl polyaromatic ligands: synthesis, spectroelectrochemistry, and theoretical calculations

This work describes syntheses and electrochemical, spectroscopic, and bonding properties in a new series of dinuclear ruthenium(II) complexes bridged by polyaromatic (biphenyl, fluorene, phenanthrene, and pyrene) alkynyl ligands. Longitudinal expansion of the π-conjugated polyaromatic core of the bridging ligands caused a reduced potential difference between the anodic steps and reinforced their bridge-localized nature, as evidenced by UV/vis/near-IR and IR spectroelectrochemical data combined with DFT and TDDFT calculations. Importantly, the intricate multiple IR ν(CC) absorption bands for the singly oxidized states imply a thermal population of a range of conformers (rotamers) with distinct electronic character. This behavior was demonstrated with more accurate DFT calculations of selected nontruncated 1e− oxidized complexes in three different conformations. The combined experimental and theoretical data reveal that thermally populated rotamers featuring various mutual orientations of the ligated metal termini and the bridging diethynyl polyaromatic moieties have a significant impact on the electronic absorption and ν(CC) wavenumbers of the singly oxidized systems.

Projected changes in tropical cyclones over Vietnam and the South China Sea using a 25 km regional climate model perturbed physics ensemble

The regional climate modelling system PRECIS, was run at 25 km horizontal resolution for 150 years (1949-2099) using global driving data from a five member perturbed physics ensemble (based on the coupled global climate model HadCM3). Output from these simulations was used to investigate projected changes in tropical cyclones (TCs) over Vietnam and the South China Sea due to global warming (under SRES scenario A1B). Thirty year climatological mean periods were used to look at projected changes in future (2069-2098) TCs compared to a 1961-1990 baseline. Present day results were compared qualitatively with IBTrACS observations and found to be reasonably realistic. Future projections show a 20-44 % decrease in TC frequency, although the spatial patterns of change differ between the ensemble members, and an increase of 27-53 % in the amount of TC associated precipitation. No statistically significant changes in TC intensity were found, however, the occurrence of more intense TCs (defined as those with a maximum 10 m wind speed > 35 m/s) was found to increase by 3-9 %. Projected increases in TC associated precipitation are likely caused by increased evaporation and availability of atmospheric water vapour, due to increased sea surface and atmospheric temperature. The mechanisms behind the projected changes in TC frequency are difficult to link explicitly; changes are most likely due to the combination of increased static stability, increased vertical wind shear and decreased upward motion, which suggest a decrease in the tropical overturning circulation.

Projected changes in medicanes in the HadGEM3 N512 high-resolution global climate model

Medicanes or “Mediterranean hurricanes” represent a rare and physically unique type of Mediterranean mesoscale cyclone. There are similarities with tropical cyclones with regard to their development (based on the thermodynamical disequilibrium between the warm sea and the overlying troposphere) and their kinematic and thermodynamical properties (medicanes are intense vortices with a warm core and even a cloud-free eye). Although medicanes are smaller and their wind speeds are lower than in tropical cyclones, the severity of their winds can cause substantial damage to islands and coastal areas. Concern about how human-induced climate change will affect extreme events is increasing. This includes the future impacts on medicanes due to the warming of the Mediterranean waters and the projected changes in regional atmospheric circulation. However, most global climate models do not have high enough spatial resolution to adequately represent small features such as medicanes. In this study, a cyclone tracking algorithm is applied to high resolution global climate model data with a horizontal grid resolution of approximately 25 km over the Mediterranean region. After a validation of the climatology of general Mediterranean mesoscale cyclones, changes in medicanes are determined using climate model experiments with present and future forcing. The magnitude of the changes in the winds, frequency and location of medicanes is assessed. While no significant changes in the total number of Mediterranean mesoscale cyclones are found, medicanes tend to decrease in number but increase in intensity. The model simulation suggests that medicanes tend to form more frequently in the Gulf of Lion–Genoa and South of Sicily.

Hydrodynamics with spin angular momentum from systematic coarse graining: a tutorial example

The derivation of time evolution equations for slow collective variables starting from a micro- scopic model system is demonstrated for the tutorial example of the classical, two-dimensional XY model. Projection operator techniques are used within a nonequilibrium thermodynamics framework together with molecular simulations in order to establish the building blocks of the hydrodynamics equations: Poisson brackets that determine the deterministic drift, the driving forces from the macroscopic free energy and the friction matrix. The approach is rather general and can be applied for deriving the equations of slow variables for a broad variety of systems.

Notable differences between oxidized diruthenium complexes bridged by four isomeric diethynyl benzodithiophene ligands

Four new diruthenium complexes [{(η5-C5Me5)Ru(dppe)}2(μ-CuC–L–CuC)] featuring different bridging isomeric diethynyl benzodithiophenes viz. L = benzo[1,2-b;4,5-b’]dithiophene (complex 1), benzo[2,1-b;4,5b’]dithiophene (complex 2), benzo[1,2-b;3,4-b’]dithiophene (complex 3) and benzo[1,2-b;4,3-b’]-dithiophene (complex 4), were synthesized and characterized by molecular spectroscopic and crystallographicmethods. The subtle changes in the molecular structure introduced by the diethynyl benzodithiophene isomers have a notable impact on the stability of the oxidized complexes and their absorption characteristics in the visible-NIR and IR spectral domains. Electronic properties of stable oxidized complexes[1]n+ and [4]n+ (n = 1, 2) were investigated by cyclic voltammetry, UV-vis-NIR and IR spectroelectrochemistry as well as DFT and TDDFT calculations. The results document the largely bridgelocalized character of the oxidation of parents 1 and 4. Cations [2]+ and [3]+ are too unstable at ambient temperature to afford their unambiguous characterization. UV-vis-NIR absorption spectral data combined with TDDFT calculations (BLYP35) reveal that the broad electronic absorption of [1]+ and [4]+ in the NIR region has a mixed intraligand π–π* and MLCT character, with similar contribution from their spin-delocalized trans and cis conformers. A spin-localized (mixed-valence) rotamer was only observed for [1]+ at ambient temperature as a minor component on the time scale of IR spectroscopy.

Least square projection: A fast high-precision multidimensional projection technique and its application to document mapping

The problem of projecting multidimensional data into lower dimensions has been pursued by many researchers due to its potential application to data analyses of various kinds. This paper presents a novel multidimensional projection technique based on least square approximations. The approximations compute the coordinates of a set of projected points based on the coordinates of a reduced number of control points with defined geometry. We name the technique Least Square Projections ( LSP). From an initial projection of the control points, LSP defines the positioning of their neighboring points through a numerical solution that aims at preserving a similarity relationship between the points given by a metric in mD. In order to perform the projection, a small number of distance calculations are necessary, and no repositioning of the points is required to obtain a final solution with satisfactory precision. The results show the capability of the technique to form groups of points by degree of similarity in 2D. We illustrate that capability through its application to mapping collections of textual documents from varied sources, a strategic yet difficult application. LSP is faster and more accurate than other existing high-quality methods, particularly where it was mostly tested, that is, for mapping text sets.

Partial spectral projected gradient method with active-set strategy for linearly constrained optimization

A method for linearly constrained optimization which modifies and generalizes recent box-constraint optimization algorithms is introduced. The new algorithm is based on a relaxed form of Spectral Projected Gradient iterations. Intercalated with these projected steps, internal iterations restricted to faces of the polytope are performed, which enhance the efficiency of the algorithm. Convergence proofs are given and numerical experiments are included and commented. Software supporting this paper is available through the Tango Project web page: http://www.ime.usp.br/similar to egbirgin/tango/.

Synthesis, mechanism of formation, and molecular orbital calculations of arylamidoximes

A simple and easy synthesis of ten arylamidoximes from arylnitriles and hydroxylamine is described. The formation of the arylamides has been observed to a much lesser extent in the present work. A new mechanism for the formation of arylamidoximes, as well as arylamides, from arylnitriles and hydroxylamine is suggested. Quantum mechanical calculations have been carried out to support this mechanism. The enthalpy of formation in conjunction with atomic charges of the reactants and intermediates helped to understand more about the generation of the products.

Extending the use of canonical and microcanonical Monte Carlo algorithms to spin models

We describe the canonical and microcanonical Monte Carlo algorithms for different systems that can be described by spin models. Sites of the lattice, chosen at random, interchange their spin values, provided they are different. The canonical ensemble is generated by performing exchanges according to the Metropolis prescription whereas in the microcanonical ensemble, exchanges are performed as long as the total energy remains constant. A systematic finite size analysis of intensive quantities and a comparison with results obtained from distinct ensembles are performed and the quality of results reveal that the present approach may be an useful tool for the study of phase transitions, specially first-order transitions. (C) 2009 Elsevier B.V. All rights reserved.

DNA alters the bilayer structure of cationic lipid diC14-amidine: A spin label study

Cationic lipids-DNA complexes (lipoplexes) have been used for delivery of nucleic acids into cells in vitro and in vivo. Despite the fact that, over the last decade, significant progress in the understanding of the cellular pathways and mechanisms involved in lipoplexes-mediated gene transfection have been achieved, a convincing relationship between the structure of lipoplexes and their in vivo and in vitro transfection activity is still missing. How does DNA affect the lipid packing and what are the consequences for transfection efficiency is the point we want to address here. We investigated the bilayer organization in cationic liposomes by electron spin resonance (ESR). Phospholipids spin labeled at the 5th and 16th carbon atoms were incorporated into the DNA/diC14-amidine complex. Our data demonstrate that electrostatic interactions involved in the formation of DNA-cationic lipid complex modify the packing of the cationic lipid membrane. DNA rigidifies the amidine fluid bilayer and fluidizes the amidine rigid bilayer just below the gel-fluid transition temperature. These effects were not observed with single nucleotides and are clearly related to the repetitive charged motif present in the DNA chain and not to a charge-charge interaction. These modifications of the initial lipid packing of the cationic lipid may reorient its cellular pathway towards different routes. A better knowledge of the cationic lipid packing before and after interaction with DNA may therefore contribute to the design of lipoplexes capable to reach specific cellular targets. (c) 2009 Elsevier B.V. All rights reserved.