A Quantum Yield Map for Synthetic Eumelanin

The quantum yield of synthetic eumelanin is known to be extremely low and it has recently been reported to be dependent on excitation wavelength. In this paper, we present quantum yield as a function of excitation wavelength between 250 and 500 nm, showing it to be a factor of 4 higher at 250 nm than at 500 nm. In addition, we present a definitive map of the steady-state fluorescence as a function of excitation and emission wavelengths, and significantly, a three-dimensional map of the specific quantum yield: the fraction of photons absorbed at each wavelength that are subsequently radiated at each emission wavelength. This map contains clear features, which we attribute to certain structural models, and shows that radiative emission and specific quantum yield are negligible at emission wavelengths outside the range of 585 and 385 nm (2.2 and 3.2 eV), regardless of excitation wavelength. This information is important in the context of understanding melanin biofunctionality, and the quantum molecular biophysics therein.Comment: 10 pages, 6 figure

Effects of Solar Active Regions on Meridional Flows

The aim of this paper is to extend our previous study of the solar-cycle variations of the meridional flows and to investigate their latitudinal and longitudinal structure in the subphotospheric layer, especially their variations in magnetic regions. Helioseismology observations indicate that mass flows around active regions are dominated by inflows into those regions. On average, those local flows are more important around leading magnetic polarities of active regions than around the following polarities, and depend on the evolutionary stage of particular active regions. We present a statistical study based on MDI/SOHO observations of 1996-2002 and show that this effect explains a significant part of the cyclic change of meridional flows in near-equatorial regions, but not at higher latitudes. A different mechanism driving solar-cycle variations of the meridional flow probably operates.Comment: 4 pages, 5 figures, accepted for publication in ApJ

Energy Conservation and Gravity Waves in Sound-proof Treatments of Stellar Interiors: Part I Anelastic Approximations

Typical flows in stellar interiors are much slower than the speed of sound. To follow the slow evolution of subsonic motions, various sound-proof equations are in wide use, particularly in stellar astrophysical fluid dynamics. These low-Mach number equations include the anelastic equations. Generally, these equations are valid in nearly adiabatically stratified regions like stellar convection zones, but may not be valid in the sub-adiabatic, stably stratified stellar radiative interiors. Understanding the coupling between the convection zone and the radiative interior is a problem of crucial interest and may have strong implications for solar and stellar dynamo theories as the interface between the two, called the tachocline in the Sun, plays a crucial role in many solar dynamo theories. Here we study the properties of gravity waves in stably-stratified atmospheres. In particular, we explore how gravity waves are handled in various sound-proof equations. We find that some anelastic treatments fail to conserve energy in stably-stratified atmospheres, instead conserving pseudo-energies that depend on the stratification, and we demonstrate this numerically. One anelastic equation set does conserve energy in all atmospheres and we provide recommendations for converting low-Mach number anelastic codes to this set of equations.Comment: Accepted for publication in ApJ. 20 pages emulateapj format, 7 figure

Electronic structure and stability of nonstoichiometric titanium monoxide TiOy with structural vacancies in one of the sublattices

The electronic structure of nonstoichiometric titanium monoxide TiOy with different compositions y, which contains structural vacancies either in the metallic sublattice or in the nonmetallic sublattice, has been investigated using the supercell method within the DFT-GGA approximation with pseudopotentials. The cases of ordered and disordered arrangements of vacancies have been considered. It has been found that the complete removal of vacancies from the sublattice is energetically unfavorable, and the ordering of oxygen vacancies according to the type of the Ti6O5□1 superstructure, as well as titanium vacancies according to the Ti5black small square1O6 type, does not lead to the stabilization of the B1 basic structure of titanium monoxide. © 2013 Pleiades Publishing, Ltd

Internal energy and parameters of the order-disorder phase transition in titanium monoxide TiO y

Quantum-mechanical ab initio calculations are used to simulate the free energy functions for titanium monoxide TiO y . The effect of the long-range order of the Ti5O5 type superstructure on the internal energy of the compound is studied by the supercell method. The dependences of the configuration entropy and free energy on the long-range order parameter are determined. It is found that the order-disorder phase transition in titanium monoxide must occur in accordance with the mechanism of the first-order phase transition with a critical value of the long-range order parameter of 0.971. The calculated parameters of the phase transition are compared with the experimental data and the results obtained using the model of point charges and by calculating the Madelung energy. It is concluded that the short-range order and the phonon entropy must be taken into account in calculating the equilibrium phase diagrams for strongly nonstoichiometric compounds. © 2013 Pleiades Publishing, Ltd

Ice Lens Formation, Frost Heave, Thin Films, and the Importance of the Polar H2O Reservoir at High Obliquity

Several lines of evidence indicate that the volume of shallow ground ice in the martian high latitudes exceeds the pore volume of the host regolith. Boynton et al. found an optimal fit to the Mars Odyssey Gamma Ray Spectrometer (GRS) data at the Phoenix landing site by modeling a buried layer of 50-75% ice by mass (up to 90% ice by volume). Thermal and optical observations of recent impact craters in the northern hemisphere have revealed nearly pure ice. Ice deposits containing only 1-2% soil by volume were excavaged by Phoenix. One hypothesis for the origin of this excess ice is that it developed in situ by a mechanism analogous to the formation of terrestrial ice lenses and needle ice. Problematically, terrestrial soil-ice segregation is driven by freeze/thaw cycling and the movement of bulk water, neither of which are expected to have occurred in the geologically recent past on Mars. If however ice lens formation is possible at temperatures less than 273 K, there are possible implications for the habitability of Mars permafrost, since the same thin films of unfrozen water that lead to ice segregation are used by terrestrial psychrophiles to metaboluze and grow down to temperatures of at least 258 K

Towards Structure-Property-Function Relationships for Eumelanin

We discuss recent progress towards the establishment of important structure-property-function relationships in eumelanins - key functional bio-macromolecular systems responsible for photo-protection and immune response in humans, and implicated in the development of melanoma skin cancer. We focus on the link between eumelanin's secondary structure and optical properties such as broad band UV-visible absorption and strong non-radiative relaxation; both key features of the photo-protective function. We emphasise the insights gained through a holistic approach combining optical spectroscopy with first principles quantum chemical calculations, and advance the hypothesis that the robust functionality characteristic of eumelanin is related to extreme chemical and structural disorder at the secondary level. This inherent disorder is a low cost natural resource, and it is interesting to speculate as to whether it may play a role in other functional bio-macromolecular systems.Comment: 19 pages, 8 figures, Invited highlight article for Soft Matte

Character of Mg(ClO4)2 Brines Under Mars Regolith Conditions

Elsewhere, we report on our investigation of the initiation and growth of ice lenses under Mars like conditions. In that work, we assume that the soil-water-ice system is gas and solute free. We conclude that initiation of lens initiation - the unloading of particle-particle contacts by thermomolecular forces at a given soil horizon - may be a common process in the shallow Martian regolith, and that the dominant property controlling the rate of lens growth is the freezing point depression (Delta-T(sub f)) associated with the interfacial forces of the soil. Lens growth is thus favored in clay-sized soils over silt soils due to the greater Delta-T(sub f), but segregated ice was observed at the Phoenix site, where soils were predominantly siltsized.. Perchlorate salts were also observed at the Phoenix site, and will strongly affect some of the properties associated with potential ice lens growth, over and above increases to Delta-T(sub f),. Here, we investigate the nature of Mg(ClO4)2 brines under Mars-like conditions, with particular emphasis on those aspects that might influence the in situ segregation of residual liquids during phase change, potentially leading to the formation of subsurface excess ice. We also discuss cyclic variations in the water activity (a(sub w)) that might affect the habitability of solutions in the shallow regolith

Solar vortex tubes : vortex dynamics in the solar atmosphere

In this work, a state-of-the-art vortex detection method, Instantaneous Vorticity Deviation, is applied to locate three-dimensional vortex tube boundaries in numerical simulations of solar photospheric magnetoconvection performed by the MURaM code. We detected three-dimensional vortices distributed along intergranular regions and displaying coned shapes that extend from the photosphere to the low chromosphere. Based on a well-defined vortex center and boundary, we were able to determine averaged radial profiles and thereby investigate the dynamics across the vortical flows at different height levels. The solar vortex tubes present nonuniform angular rotational velocity, and, at all height levels, there are eddy viscosity effects within the vortices, which slow down the plasma as it moves toward the center. The vortices impact the magnetic field as they help to intensify the magnetic field at the sinking points, and in turn, the magnetic field ends up playing an essential role in the vortex dynamics. The magnetic field was found to be especially important to the vorticity evolution. On the other hand, it is shown that, in general, kinematic vortices do not give rise to magnetic vortices unless their tangential velocities at different height levels are high enough to overcome the magnetic tension