Benchmarking calculations of excitonic couplings between bacteriochlorophylls

Excitonic couplings between (bacterio)chlorophyll molecules are necessary for simulating energy transport in photosynthetic complexes. Many techniques for calculating the couplings are in use, from the simple (but inaccurate) point-dipole approximation to fully quantum-chemical methods. We compared several approximations to determine their range of applicability, noting that the propagation of experimental uncertainties poses a fundamental limit on the achievable accuracy. In particular, the uncertainty in crystallographic coordinates yields an uncertainty of about 20% in the calculated couplings. Because quantum-chemical corrections are smaller than 20% in most biologically relevant cases, their considerable computational cost is rarely justified. We therefore recommend the electrostatic TrEsp method across the entire range of molecular separations and orientations because its cost is minimal and it generally agrees with quantum-chemical calculations to better than the geometric uncertainty. We also caution against computationally optimizing a crystal structure before calculating couplings, as it can lead to large, uncontrollable errors. Understanding the unavoidable uncertainties can guard against striving for unrealistic precision; at the same time, detailed benchmarks can allow important qualitative questions--which do not depend on the precise values of the simulation parameters--to be addressed with greater confidence about the conclusions

Lattice thermal expansion and anisotropic displacements in urea, bromomalonic aldehyde, pentachloropyridine and naphthalene

Anisotropic displacement parameters (ADPs) are commonly used in crystallography, chemistry and related fields to describe and quantify thermal motion of atoms. Within the very recent years, these ADPs have become predictable by lattice dynamics in combination with first-principles theory. Here, we study four very different molecular crystals, namely urea, bromomalonic aldehyde, pentachloropyridine, and naphthalene, by first-principles theory to assess the quality of ADPs calculated in the quasi-harmonic approximation. In addition, we predict both thermal expansion and thermal motion within the quasi-harmonic approximation and compare the predictions with experimental data. Very reliable ADPs are calculated within the quasi-harmonic approximation for all four cases up to at least 200 K, and they turn out to be in better agreement with experiment than the harmonic ones. In one particular case, ADPs can even reliably be predicted up to room temperature. Our results also hint at the importance of normal-mode anharmonicity in the calculation of ADPs

Mirrors for slow neutrons from holographic nanoparticle-polymer free-standing film-gratings

We report on successful tests of holographically arranged grating-structures in nanoparticle-polymer composites in the form of 100 microns thin free-standing films, i.e. without sample containers or covers that could cause unwanted absorption/incoherent scattering of very-cold neutrons. Despite their large diameter of 2 cm, the flexible materials are of high optical quality and yield mirror-like reflectivity of about 90% for neutrons of 4.1 nm wavelength

The XMM-LSS survey: the Class 1 cluster sample over the extended 11 deg2^2 and its spatial distribution

This paper presents 52 X-ray bright galaxy clusters selected within the 11 deg$^2$ XMM-LSS survey. 51 of them have spectroscopic redshifts ($0.05<z<1.06$), one is identified at $z_{\rm phot}=1.9$, and all together make the high-purity "Class 1" (C1) cluster sample of the XMM-LSS, the highest density sample of X-ray selected clusters with a monitored selection function. Their X-ray fluxes, averaged gas temperatures (median $T_X=2$ keV), luminosities (median $L_{X,500}=5\times10^{43}$ ergs/s) and total mass estimates (median $5\times10^{13} h^{-1} M_{\odot}$) are measured, adapting to the specific signal-to-noise regime of XMM-LSS observations. The redshift distribution of clusters shows a deficit of sources when compared to the cosmological expectations, regardless of whether WMAP-9 or Planck-2013 CMB parameters are assumed. This lack of sources is particularly noticeable at $0.4 \lesssim z \lesssim 0.9$. However, after quantifying uncertainties due to small number statistics and sample variance we are not able to put firm (i.e. $>3 \sigma$) constraints on the presence of a large void in the cluster distribution. We work out alternative hypotheses and demonstrate that a negative redshift evolution in the normalization of the $L_{X}-T_X$ relation (with respect to a self-similar evolution) is a plausible explanation for the observed deficit. We confirm this evolutionary trend by directly studying how C1 clusters populate the $L_{X}-T_X-z$ space, properly accounting for selection biases. We point out that a systematically evolving, unresolved, central component in clusters and groups (AGN contamination or cool core) can impact the classification as extended sources and be partly responsible for the observed redshift distribution.[abridged]Comment: 33 pages, 21 figures, 3 tables ; accepted for publication in MNRA

Quantum geometry and the Schwarzschild singularity

In homogeneous cosmologies, quantum geometry effects lead to a resolution of the classical singularity without having to invoke special boundary conditions at the singularity or introduce ad-hoc elements such as unphysical matter. The same effects are shown to lead to a resolution of the Schwarzschild singularity. The resulting quantum extension of space-time is likely to have significant implications to the black hole evaporation process. Similarities and differences with the situation in quantum geometrodynamics are pointed out.Comment: 31 pages, 1 figur

Palladium nanoparticles by electrospinning from poly(acrylonitrile-co-acrylic acid)-PdCl2 solutions. Relations between preparation conditions, particle size, and catalytic activity

Catalytic palladium (Pd) nanoparticles on electrospun copolymers of acrylonitrile and acrylic acid (PAN-AA) mats were produced via reduction of PdCl2 with hydrazine. Fiber mats were electrospun from homogeneous solutions of PAN-AA and PdCl2 in dimethylformamide (DMF). Pd cations were reduced to Pd metals when fiber mats were treated in an aqueous hydrazine solution at room temperature. Pd atoms nucleate and form small crystallites whose sizes were estimated from the peak broadening of X-ray diffraction peaks. Two to four crystallites adhere together and form agglomerates. Agglomerate sizes and fiber diameters were determined by scanning and transmission electron microscopy. Spherical Pd nanoparticles were dispersed homogeneously on the electrospun nanofibers. The effects of copolymer composition and amount of PdCl2 on particle size were investigated. Pd particle size mainly depends on the amount of acrylic acid functional groups and PdCl2 concentration in the spinning solution. Increasing acrylic acid concentration on polymer chains leads to larger Pd nanoparticles. In addition, Pd particle size becomes larger with increasing PdCl2 concentration in the spinning solution. Hence, it is possible to tune the number density and the size of metal nanoparticles. The catalytic activity of the Pd nanoparticles in electrospun mats was determined by selective hydrogenation of dehydrolinalool (3,7-dimethyloct-6- ene-1-yne-3-ol, DHL) in toluene at 90 °C. Electrospun fibers with Pd particles have 4.5 times higher catalytic activity than the current Pd/Al2O3 catalyst

Degenerate Configurations, Singularities and the Non-Abelian Nature of Loop Quantum Gravity

Degenerate geometrical configurations in quantum gravity are important to understand if the fate of classical singularities is to be revealed. However, not all degenerate configurations arise on an equal footing, and one must take into account dynamical aspects when interpreting results: While there are many degenerate spatial metrics, not all of them are approached along the dynamical evolution of general relativity or a candidate theory for quantum gravity. For loop quantum gravity, relevant properties and steps in an analysis are summarized and evaluated critically with the currently available information, also elucidating the role of degrees of freedom captured in the sector provided by loop quantum cosmology. This allows an outlook on how singularity removal might be analyzed in a general setting and also in the full theory. The general mechanism of loop quantum cosmology will be shown to be insensitive to recently observed unbounded behavior of inverse volume in the full theory. Moreover, significant features of this unboundedness are not a consequence of inhomogeneities but of non-Abelian effects which can also be included in homogeneous models.Comment: 28 pages, 1 figure; v2: extended discussion of singularity removal and summar

The XXL Survey X: K-band luminosity - weak-lensing mass relation for groups and clusters of galaxies

We present the K-band luminosity-halo mass relation, $L_{K,500}-M_{500,WL}$, for a subsample of 20 of the 100 brightest clusters in the XXL Survey observed with WIRCam at the Canada-France-Hawaii Telescope (CFHT). For the first time, we have measured this relation via weak-lensing analysis down to $M_{500,WL} =3.5 \times 10^{13}\,M_\odot$. This allows us to investigate whether the slope of the $L_K-M$ relation is different for groups and clusters, as seen in other works. The clusters in our sample span a wide range in mass, $M_{500,WL} =0.35-12.10 \times 10^{14}\,M_\odot$, at $0<z<0.6$. The K-band luminosity scales as $\log_{10}(L_{K,500}/10^{12}L_\odot) \propto \beta log_{10}(M_{500,WL}/10^{14}M_\odot)$ with $\beta = 0.85^{+0.35}_{-0.27}$ and an intrinsic scatter of $\sigma_{lnL_K|M} =0.37^{+0.19}_{-0.17}$. Combining our sample with some clusters in the Local Cluster Substructure Survey (LoCuSS) present in the literature, we obtain a slope of $1.05^{+0.16}_{-0.14}$ and an intrinsic scatter of $0.14^{+0.09}_{-0.07}$. The flattening in the $L_K-M$ seen in previous works is not seen here and might be a result of a bias in the mass measurement due to assumptions on the dynamical state of the systems. We also study the richness-mass relation and find that group-sized halos have more galaxies per unit halo mass than massive clusters. However, the brightest cluster galaxy (BCG) in low-mass systems contributes a greater fraction to the total cluster light than BCGs do in massive clusters; the luminosity gap between the two brightest galaxies is more prominent for group-sized halos. This result is a natural outcome of the hierarchical growth of structures, where massive galaxies form and gain mass within low-mass groups and are ultimately accreted into more massive clusters to become either part of the BCG or one of the brighter galaxies. [Abridged]Comment: A&A, in pres

Measurement of Angular Distributions of Drell-Yan Dimuons in p+pp + p Interactions at 800 GeV/c

We report a measurement of the angular distributions of Drell-Yan dimuons produced using an 800 GeV/c proton beam on a hydrogen target. The polar and azimuthal angular distribution parameters have been extracted over the kinematic range $4.5 < m_{\mu \mu} < 15$ GeV/c$^2$ (excluding the $\Upsilon$ resonance region), $0 < p_T < 4$ GeV/c, and $0 < x_F < 0.8$. The $p+p$ angular distributions are similar to those of $p+d$, and both data sets are compared with models which attribute the $\cos 2 \phi$ distribution either to the presence of the transverse-momentum-dependent Boer-Mulders structure function $h_1^\perp$ or to QCD effects. The data indicate the presence of both mechanisms. The validity of the Lam-Tung relation in $p+p$ Drell-Yan is also tested.Comment: 4 pages, 3 figure

Structural characteristics of positionally-disordered lattices: relation to the first sharp diffraction peak in glasses

Positional disorder has been introduced into the atomic structure of certain crystalline lattices, and the orientationally-averaged structure factor S(k) and pair-correlation function g(r) of these disordered lattices have been studied. Analytical expressions for S(k) and g(r) for Gaussian positional disorder in 2D and 3D are confirmed with precise numerical simulations. These analytic results also have a bearing on the unsolved Gauss circle problem in mathematics. As the positional disorder increases, high-k peaks in S(k) are destroyed first, eventually leaving a single peak, that with the lowest-k value. The pair-correlation function for lattices with such high levels of positional disorder exhibits damped oscillations, with a period equal to the separation between the furthest-separated (lowest-k) lattice planes. The last surviving peak in S(k) is, for example for silicon and silica, at a wavevector nearly identical to that of the experimentally-observed first sharp diffraction peak (FSDP) in the amorphous phases of those materials. Thus, for these amorphous materials at least, the FSDP can be regarded as arising from scattering from atomic configurations equivalent to the single family of positionally-disordered local Bragg planes having the furthest separation.Comment: v2: changes in response to referees' comments: Figure 2 made more readable, improved discussion of height of peaks in S(k), other minor changes 4 pages, 3 figures, submitted to Physical Review