Structural stability, magnetic and electronic properties of Co2MnSi(001)/MgO heterostructures: A density functional theory study

A computational study of the epitaxial Co2MnSi(001)/MgO(001) interface relevant to tunneling magnetoresistive (TMR) devices is presented. Employing ab initio atomistic thermodynamics, we show that the Co- or MnSi-planes of bulk-terminated Co2MnSi form stable interfaces, while pure Si or pure Mn termination requires non-equilibrium conditions. Except for the pure Mn interface, the half-metallic property of bulk Co2MnSi is disrupted by interface bands. Even so, at homogeneous Mn or Co interfaces these bands contribute little to the minority-spin conductance through an MgO barrier, and hence such terminations could perform strongly in TMR devices.Comment: 4 pages, 3 fig

The 12^{12}CO2_2 and 13^{13}CO2_2 Absorption Bands as Tracers of the Thermal History of Interstellar Icy Grain Mantles

Analyses of infrared signatures of CO$_2$ in water dominated ices in the ISM can give information on the physical state of CO$_2$ in icy grains and on the thermal history of the ices themselves. In many sources, CO$_2$ was found in the `pure' crystalline form, as signatured by the splitting in the bending mode absorption profile. To a large extent, pure CO$_2$ is likely to have formed from segregation of CO$_2$ from a CO$_2$:H$_2$O mixture during thermal processing. Previous laboratory studies quantified the temperature dependence of segregation, but no systematic measurement of the concentration dependence of segregation is available. In this study, we measured both the temperature dependence and concentration dependence of CO$_2$ segregation in CO$_2$:H$_2$O mixtures, and found that no pure crystalline CO$_2$ forms if the CO$_2$:H$_2$O ratio is less than 23%. Therefore the segregation of CO$_2$ is not always a good thermal tracer of the ice mantle. We found that the position and width of the broad component of the asymmetric stretching vibrational mode of $^{13}$CO$_2$ change linearly with the temperature of CO$_2$:H$_2$O mixtures, but are insensitive to the concentration of CO$_2$. We recommend using this mode, which will be observable towards low mass protostellar envelopes and dense clouds with the James Webb Space Telescope, to trace the thermal history of the ice mantle, especially when segregated CO$_2$ is unavailable. We used the laboratory measured $^{13}$CO$_2$ profile to analyze the ISO-SWS observations of ice mantles towards Young Stellar Objects, and the astrophysical implications are discussed.Comment: 11 pages, 12 figures, ApJ accepte

Ab initio study of element segregation and oxygen adsorption on PtPd and CoCr binary alloy surfaces

The segregation behavior of the bimetallic alloys PtPd and CoCr in the case of bare surfaces and in the presence of an oxygen ad-layer has been studied by means of first-principles modeling based on density-functional theory (DFT). For both systems, change of the d-band filling due to charge transfer between the alloy components, resulting in a shift of the d-band center of surface atoms compared to the pure components, drives the surface segregation and governs the chemical reactivity of the bimetals. In contrast to previous findings but consistent with analogous PtNi alloy systems, enrichment of Pt atoms in the surface layer and of Pd atoms in the first subsurface layer has been found in Pt-rich PtPd alloy, despite the lower surface energy of pure Pd compared to pure Pt. Similarly, Co surface and Cr subsurface segregation occurs in Co-rich CoCr alloys. However, in the presence of adsorbed oxygen, Pd and Cr occupy preferentially surface sites due to their lower electronegativity and thus stronger oxygen affinity compared to Pt and Co, respectively. In either cases, the calculated oxygen adsorption energies on the alloy surfaces are larger than on the pure components when the more noble components are present in the subsurface layers

Pure Even Harmonic Generation from Oriented CO in Linearly Polarized Laser Fields

The first high harmonic spectrum, containing only the odd orders, was observed in experiments 30 years ago (1987). However, a spectrum containing pure even harmonics has never been observed. We investigate the generation of pure even harmonics from oriented CO molecules in linearly polarized laser fields employing the time-dependent density-functional theory. We find that the even harmonics, with no odd orders, are generated with the polarization perpendicular to the laser polarization, when the molecular axis of CO is perpendicular to the laser polarization. Generation of pure even harmonics reveals a type of dipole acceleration originating from the permanent dipole moment. This phenomenon exists in all system with permanent dipole moments, including bulk crystal and polyatomic molecules

UV photodesorption of methanol in pure and CO-rich ices: desorption rates of the intact molecule and of the photofragments

Wavelength dependent photodesorption rates have been determined using synchrotron radiation, for condensed pure and mixed methanol ice in the 7 -- 14 eV range. The VUV photodesorption of intact methanol molecules from pure methanol ices is found to be of the order of 10$^{-5}$ molecules/photon, that is two orders of magnitude below what is generally used in astrochemical models. This rate gets even lower ($<$ 10$^{-6}$ molecules/photon) when the methanol is mixed with CO molecules in the ices. This is consistent with a picture in which photodissociation and recombination processes are at the origin of intact methanol desorption from pure CH$_3$OH ices. Such low rates are explained by the fact that the overall photodesorption process is dominated by the desorption of the photofragments CO, CH$_3$, OH, H$_2$CO and CH$_3$O/CH$_2$OH, whose photodesorption rates are given in this study. Our results suggest that the role of the photodesorption as a mechanism to explain the observed gas phase abundances of methanol in cold media is probably overestimated. Nevertheless, the photodesorption of radicals from methanol-rich ices may stand at the origin of the gas phase presence of radicals such as CH$_3$O, therefore opening new gas phase chemical routes for the formation of complex molecules.Comment: 13 pages, 2 figures, 1 tabl

IR Spectral Fingerprint of Carbon Monoxide in Interstellar Water Ice Models

Carbon monoxide (CO) is the second most abundant molecule in the gas-phase of the interstellar medium. In dense molecular clouds, it is also present in the solid-phase as a constituent of the mixed water-dominated ices covering dust grains. Its presence in the solid-phase is inferred from its infrared (IR) signals. In experimental observations of solid CO/water mixed samples, its IR frequency splits into two components, giving rise to a blue- and a redshifted band. However, in astronomical observations, the former has never been observed. Several attempts have been carried out to explain this peculiar behaviour, but the question still remains open. In this work, we resorted to pure quantum mechanical simulations in order to shed some light on this problem. We adopted different periodic models simulating the CO/H$_2$O ice system, such as single and multiple CO adsorption on water ice surfaces, CO entrapped into water cages and proper CO:H$_2$O mixed ices. We also simulated pure solid CO. The detailed analysis of our data revealed how the quadrupolar character of CO and the dispersive forces with water ice determine the energetic of the CO/H$_2$O ice interaction, as well as the CO spectroscopic behaviour. Our data suggest that the blueshifted peak can be assigned to CO interacting {\it via} the C atom with dangling H atoms of the water ice, while the redshifted one can actually be the result of CO involved in different reciprocal interactions with the water matrix. We also provide a possible explanation for the lack of the blueshifted peak in astronomical spectra. Our aim is not to provide a full account of the various interstellar ices, but rather to elucidate the sensitivity of the CO spectral features to different water ice environments.Comment: MNRAS, accepte