The origin of peculiar molecular bands in cool DQ white dwarfs

The DQ white dwarfs are stars whose atmosphere is enriched with carbon, which for cool stars ($T_{\rm eff}<8000\rm \, K$) is indicated by the Swan bands of $\rm C_2$ in the optical part of their spectra. With decreasing effective temperature these molecular bands undergo a significant blueshift ($\sim 100-300 \AA$). The origin of this phenomenon has been disputed over the last two decades and has remained unknown. We attempt to address this problem by investigating the impact of dense helium on the spectroscopic properties of molecular carbon under the physical conditions encountered inside helium-rich, fluid-like atmospheres of cool DQ white dwarfs. We found that the electronic transition energy $T_e$ increases monotonically with the helium density ($\Delta T_{\rm e}\rm\, (eV)\sim1.6 \, \it \rho \rm \, (g/cm^3)$). This causes the Swan absorption to occur at shorter wavelengths compared with unperturbed $\rm C_2$. On the other hand the pressure-induced increase in the vibrational frequency is insufficient to account for the observed Swan bands shifts. This is consistent with the observations and indicates that the observed Swan-like molecular bands are most likely the pressure-shifted bands of $\rm C_2$.Comment: 4 pages, 5 figures, accepted for publication in A&A letter

On the Dissociation Equilibrium of H2 in Very Cool, Helium-Rich White Dwarf Atmospheres

We investigate the dissociation equilibrium of $\rm H_2$ in very cool, helium-rich white dwarf atmospheres. We present the solution of the non-ideal chemical equilibrium for the dissociation of molecular hydrogen in a medium of dense helium. We find that at the photosphere of cool white dwarfs of $T_{\rm eff}\rm=4000 K$, the non-ideality results in an increase of the mole fraction of molecular hydrogen by up to a factor of $\sim 10$, compared to the equilibrium value for the ideal gas. This increases the $\rm H_{2}-He$ CIA opacity by an order of magnitude and will affect the determination of the abundance of hydrogen in very cool, helium-rich white dwarfs.Comment: 9 pages, 5 figures, 1 table; Accepted for publication in The Astrophysical Journa

Ab initio Stellar Astrophysics: Reliable Modeling of Cool White Dwarf Atmospheres

Over the last decade {\it ab initio} modeling of material properties has become widespread in diverse fields of research. It has proved to be a powerful tool for predicting various properties of matter under extreme conditions. We apply modern computational chemistry and materials science methods, including density functional theory (DFT), to solve lingering problems in the modeling of the dense atmospheres of cool white dwarfs ($T_{\rm eff}\rm <7000 \, K$). Our work on the revision and improvements of the absorption mechanisms in the hydrogen and helium dominated atmospheres resulted in a new set of atmosphere models. By inclusion of the Ly-$\rm \alpha$ red wing opacity we successfully fitted the entire spectral energy distributions of known cool DA stars. In the subsequent work we fitted the majority of the coolest stars with hydrogen-rich models. This finding challenges our understanding of the spectral evolution of cool white dwarfs. We discuss a few examples, including the cool companion to the pulsar PSR J0437-4715. The two problems important for the understanding of cool white dwarfs are the behavior of negative hydrogen ion and molecular carbon in a fluid-like, helium dominated medium. Using {\it ab initio} methods we investigate the stability and opacity of these two species in dense helium. Our investigation of $\rm C_2$ indicates that the absorption features observed in the ``peculiar'' DQp white dwarfs resemble the absorption of perturbed $\rm C_2$ in dense helium.Comment: 6 pages, 4 figures, submitted to proceedings of 17th European White Dwarf Workshop, Tuebingen, Germany 201

The Pseudo-continuum Bound-free Opacity of Hydrogen and its Importance in Cool White Dwarf Atmospheres

We investigate the importance of the pseudo-continuum bound-free opacity from hydrogen atoms in the atmospheres of cool white dwarfs. This source of absorption, when calculated by the occupation probability formalism applied in the modeling of white dwarf atmospheres with $T_{\rm eff}\rm <17000 K$, dominates all other sources of opacity at optical wavelengths. This is unrealistic and not observed. On the other hand, a significant flux suppression in the blue part of the spectra of cool white dwarfs has been reported, and mainly interpreted as a result of the pseudo-continuum absorption from atomic hydrogen. We investigate this problem by proposing a new, more realistic approach to calculating this source of opacity. We show that this absorption is orders of magnitude smaller than that predicted by current methods. Therefore, we rule out the pseudo-continuum opacity as a source of the flux deficiency observed in the spectra of cool white dwarfs.Comment: 11 pages, 5 gigures, accepted for publication in the Astrophysical Journa

A New Generation of Cool White Dwarf Atmosphere Models Using Ab Initio Calculations

Due to their high photospheric density, cool helium-rich white dwarfs (particularly DZ, DQpec and ultracool) are often poorly described by current atmosphere models. As part of our ongoing efforts to design atmosphere models suitable for all cool white dwarfs, we investigate how the ionization ratio of heavy elements and the H$_2$-He collision-induced absorption (CIA) spectrum are altered under fluid-like densities. For the conditions encountered at the photosphere of cool helium-rich white dwarfs, our ab initio calculations show that the ionization of most metals is inhibited and that the H$_2$-He CIA spectrum is significantly distorted for densities higher than 0.1 g/cm$^3$.Comment: 4 pages, 2 figures, submitted for publication in the proceedings of the 20th European Workshop on White Dwarf

Ab initio prediction of equilibrium boron isotope fractionation between minerals and aqueous fluids at high P and T

Over the last decade experimental studies have shown a large B isotope fractionation between materials carrying boron incorporated in trigonally and tetrahedrally coordinated sites, but the mechanisms responsible for producing the observed isotopic signatures are poorly known. In order to understand the boron isotope fractionation processes and to obtain a better interpretation of the experimental data and isotopic signatures observed in natural samples, we use first principles calculations based on density functional theory in conjunction with ab initio molecular dynamics and a new pseudofrequency analysis method to investigate the B isotope fractionation between B-bearing minerals (such as tourmaline and micas) and aqueous fluids containing H_3BO_3 and H_4BO_4- species. We confirm the experimental finding that the isotope fractionation is mainly driven by the coordination of the fractionating boron atoms and have found in addition that the strength of the produced isotopic signature is strongly correlated with the B-O bond length. We also demonstrate the ability of our computational scheme to predict the isotopic signatures of fluids at extreme pressures by showing the consistency of computed pressure-dependent beta factors with the measured pressure shifts of the B-O vibrational frequencies of H_3BO_3 and H_4BO_4- in aqueous fluid. The comparison of the predicted with measured fractionation factors between boromuscovite and neutral fluid confirms the existence of the admixture of tetrahedral boron species in neutral fluid at high P and T found experimentally, which also explains the inconsistency between the various measurements on the tourmaline-mica system reported in the literature. Our investigation shows that the calculated equilibrium isotope fractionation factors have an accuracy comparable to the experiments.Comment: 19 pages, 11 figures, Accepted for publication in Geochimica et Cosmochimica Act

Pressure Distortion of the H2_2-He Collision-Induced Absorption at the Photosphere of Cool White Dwarf Stars

Collision-induced absorption (CIA) from molecular hydrogen is a dominant opacity source in the atmosphere of cool white dwarfs. It results in a significant flux depletion in the near-IR and IR parts of their spectra. Because of the extreme conditions of helium-rich atmospheres (where the density can be as high as a few g/cm$^3$), this opacity source is expected to undergo strong pressure distortion and the currently used opacities have not been validated at such extreme conditions. To check the distortion of the CIA opacity we applied state-of-the-art ab initio methods of computational quantum chemistry to simulate the CIA opacity at high densities. The results show that the CIA profiles are significantly distorted above densities of $0.1\,{\rm g/cm}^3$ in a way that is not captured by the existing models. The roto-translational band is enhanced and shifted to higher frequencies as an effect of the decrease of the interatomic separation of the H$_2$ molecule. The vibrational band is blueward shifted and split into $Q_R$ and $Q_P$ branches, separated by a pronounced interference dip. Its intensity is also substantially reduced. The distortions result in a shift of the maximum of the absorption from $2.3\,\mu{\rm m}$ to $3-7 \mu{\rm m}$, which could potentially explain the spectra of some very cool, helium-rich white dwarfs.Comment: 12 pages, 13 figures. Accepted for publication in The Astrophysical Journa

Towards an Understanding of the Atmospheres of Cool White Dwarfs

Cool white dwarfs with Teff < 6000 K are the remnants of the oldest stars that existed in our Galaxy. Their atmospheres, when properly characterized, can provide valuable information on white dwarf evolution and ultimately star formation through the history of the Milky Way. Understanding the atmospheres of these stars requires joined observational effort and reliable atmosphere modeling. We discuss and analyze recent observations of the near-ultraviolet (UV) and near-infrared (IR) spectrum of several cool white dwarfs including DQ/DQp stars showing carbon in their spectra. We present fits to the entire spectral energy distribution (SED) of selected cool stars, showing that the current pure-hydrogen atmosphere models are quite reliable, especially in the near-UV spectral region. Recently, we also performed an analysis of the coolest known DQ/DQp stars investigating further the origin of the C2 Swan bands-like spectral features that characterize the DQp stars. We show that the carbon abundances derived for DQp stars fit the trend of carbon abundance with Teff seen in normal cool DQ stars. This further supports the recent conclusion of Kowalski A&A (2010) that DQp stars are DQ stars with pressure distorted Swan bands. However, we encounter some difficulties in reproducing the IR part of the SED of stars having a mixed He/H atmosphere. This indicates limitations in current models of the opacity in dense He/H fluids.Comment: 6 pages, 4 figures, to appear in the proceedings of the "18th European White Dwarf Workshop" in Krakow, Poland (2012

Ideal, Defective, and Gold--Promoted Rutile TiO2(110) Surfaces: Structures, Energies, Dynamics, and Thermodynamics from PBE+U

Extensive first principles calculations are carried out to investigate gold-promoted TiO2(110) surfaces in terms of structure optimizations, electronic structure analyses, ab initio thermodynamics calculations of surface phase diagrams, and ab initio molecular dynamics simulations. All computations rely on density functional theory in the generalized gradient approximation (PBE) and account for on-site Coulomb interactions via inclusion of a Hubbard correction, PBE+U, where U is computed from linear response theory. This approach is validated by investigating the interaction between TiO2(110) surfaces and typical probe species (H, H2O, CO). Relaxed structures and binding energies are compared to both data from the literature and plain PBE results. The main focus of the study is on the properties of gold-promoted titania surfaces and their interactions with CO. Both PBE+U and PBE optimized structures of Au adatoms adsorbed on stoichiometric and reduced TiO2 surfaces are computed, along with their electronic structure. The charge rearrangement induced by the adsorbates at the metal/oxide contact are also analyzed and discussed. By performing PBE+U ab initio molecular dynamics simulations, it is demonstrated that the diffusion of Au adatoms on the stoichiometric surface is highly anisotropic. The metal atoms migrate either along the top of the bridging oxygen rows, or around the area between these rows, from one bridging position to the next along the [001] direction. Approximate ab initio thermodynamics predicts that under O-rich conditions, structures obtained by substituting a Ti5c atom with an Au atom are thermodynamically stable over a wide range of temperatures and pressures.Comment: 20 pages, 12 figures, accepted for publication in Phys. Rev.