H2O-CH4 and H2S-CH4 complexes: a direct comparison through molecular beam experiments and ab initio calculations

New molecular beam scattering experiments have been performed to measure the total ( elastic plus inelastic) cross sections as a function of the velocity in collisions between water and hydrogen sulfide projectile molecules and the methane target. Measured data have been exploited to characterize the range and strength of the intermolecular interaction in such systems, which are of relevance as they drive the gas phase molecular dynamics and the clathrate formation. Complementary information has been obtained by rotational spectra, recorded for the hydrogen sulfide-methane complex, with a pulsed nozzle Fourier transform microwave spectrometer. Extensive ab initio calculations have been performed to rationalize all the experimental findings. The combination of experimental and theoretical information has established the ground for the understanding of the nature of the interaction and allows for its basic components to be modelled, including charge transfer, in these weakly bound systems. The intermolecular potential for H2S-CH4 is significantly less anisotropic than for H2O-CH4, although both of them have potential minima that can be characterized as `hydrogen bonded'.

Ab Initio MD Simulations of the Bronsted Acidity of Glutathione in Aqueous Solutions: Predicting pK(a) Shifts of the Cysteine Residue

The tripeptide glutathione (GSH) is one of the most abundant peptides and the major repository for nonprotein sulfur in both animal and plant cells. It plays a critical role in intracellular oxidative stress management by the reversible formation of glutathione disulfide with the thiol-disulfide pair acting as a redox buffer. The state of charge of the ionizable groups of GSH can influence the redox couple, and hence the pK(a) value of the cysteine residue of GSH is critical to its functioning. Here we report ab initio Car-Parrinello molecular dynamics simulations of glutathione solvated by 200 water molecules, all of which are considered in the simulation. We show that the free-energy landscape for the protonation-deprotonation reaction of the cysteine residue of GSH computed using metadynamics sampling provides shift in the dissociation constant values as compared with the isolated accurate estimates of the pK(a) and correctly predicts the cysteine amino acid.

Non-covalent C-Cl center dot center dot center dot pi interaction in acetylene-carbon tetrachloride adducts: Matrix isolation infrared and ab initio computational studies

Non-covalent halogen-bonding interactions between n cloud of acetylene (C2H2) and chlorine atom of carbon tetrachloride (CCl4) have been investigated using matrix isolation infrared spectroscopy and quantum chemical computations. The structure and the energies of the 1:1 C2H2-CCl4 adducts were computed at the B3LYP, MP2 and M05-2X levels of theory using 6-311++G(d,p) basis set. The computations indicated two minima for the 1:1 C2H2-CCl4 adducts; with the C-Cl center dot center dot center dot pi adduct being the global minimum, where pi cloud of C2H2 is the electron donor. The second minimum corresponded to a C-H...Cl adduct, in which C2H2 is the proton donor. The interaction energies for the adducts A and B were found to be nearly identical. Experimentally, both C-Cl center dot center dot center dot pi and C-H center dot center dot center dot Cl adducts were generated in Ar and N2 matrixes and characterized using infrared spectroscopy. This is the first report on halogen bonded adduct, stabilized through C-Cl center dot center dot center dot pi interaction being identified at low temperatures using matrix isolation infrared spectroscopy. Atoms in Molecules (AIM) and Natural Bond Orbital (NBO) analyses were performed to support the experimental results. The structures of 2:1 ((C2H2)(2)-CCl4) and 1:2 (C2H2-(CCl4)(2)) multimers and their identification in the low temperature matrixes were also discussed. (C) 2015 Elsevier B.V. All rights reserved.

Ab initio pair potentials at metal-ceramic interfaces

A systematic approach is proposed to obtain the interfacial interatomic potentials. By inverting ab initio adhesive energy curves for the metal-MgO ceramic interfaces, We derive interfacial potentials between Ag and O2-, Ag and Mg2+, Al and O2-, Al and Mg2+. The interfacial potentials, obtained from this method, demonstrate general features of bondings between metal atoms and ceramic ions.

Elasticity, stability, and ideal strength of beta-SiC in plane-wave-based ab initio calculations

On the basis of the pseudopotential plane-wave method and the local-density-functional theory, this paper studies energetics, stress-strain relation, stability, and ideal strength of beta-SiC under various loading modes, where uniform uniaxial extension and tension and biaxial proportional extension are considered along directions [001] and [111]. The lattice constant, elastic constants, and moduli of equilibrium state are calculated and the results agree well with the experimental data. As the four SI-C bonds along directions [111], [(1) over bar 11], [11(1) over bar] and [111] are not the same under the loading along [111], internal relaxation and the corresponding internal displacements must be considered. We find that, at the beginning of loading, the effect of internal displacement through the shuffle and glide plane diminishes the difference among the four Si-C bonds lengths, but will increase the difference at the subsequent loading, which will result in a crack nucleated on the {111} shuffle plane and a subsequently cleavage fracture. Thus the corresponding theoretical strength is 50.8 GPa, which agrees well with the recent experiment value, 53.4 GPa. However, with the loading along [001], internal relaxation is not important for tetragonal symmetry. Elastic constants during the uniaxial tension along [001] are calculated. Based on the stability analysis with stiffness coefficients, we find that the spinodal and Born instabilities are triggered almost at the same strain, which agrees with the previous molecular-dynamics simulation. During biaxial proportional extension, stress and strength vary proportionally with the biaxial loading ratio at the same longitudinal strain.

Ab initio investigation of the elasticity and stability of aluminium

On the basis of the pseudopotential plane-wave (PP-PW) method in combination with the local density functional theory (LDFT), complete stress-strain curves for the uniaxial loading and uniaxial deformation along the [001] and [111] directions, and the biaxial proportional extension along [010] and [001] for aluminium are obtained. During the uniaxial loading, certain general behaviours of the energy versus the stretch and the load versus the stretch are confirmed; in each case, there exist three special unstressed structures: f.c.c., b.c.c., and f.c.t. for [001]; f.c.c., s.c., and b.c.c. for [111]. Using stability criteria, we find that all of these states are unstable, and always occur together with shear instability, except the natural f.c.c. structure. A Pain transformation from the stable f.c.c. structure to the stable b.c.c. configuration cannot be obtained by uniaxial compression along any equivalent [001] and [111] direction. The tensile strengths are similar for the two directions. For the higher energy barrier of the [111] direction, the compressive strength is greater than that for the [001] direction. With increase in the ratio of the biaxial proportional extension, the stress and tensile strength increase; however, the critical strain does not change significantly. Our results add to the existing ab initio database for use in fitting and testing interatomic potentials.

MoS2 eta WS2 monogeruzen egitura elektroniko eta magnetikoaren ab-initio kalkuloak

Bi dimentsiotako materialetan presente diren propietate elektroniko bereziek betidanik piztu izan dute komunitate zientifikoaren interesa. Idealki atomo bakarreko lodierako materialak diren hauek hasiera batean joku teoriko huts zirela uste bazen ere, A.K. Geim eta K.S. Novoselov-ek kontrakoa frogatu zuten lehenengo aldiz grafenoa sintetizatuz[1]. Grafitoa osatzen duen geruzetako bakoitza den grafenoak guztiz anomaloak diren pro- pietate elektronikoak dauzka, Dirac-en motako sei puntuz besterik ez osatutako Fermi gainazala duelarik. Honen ondorioz, eroapen elektroiak masa gabekoak balira bezala higitzen dira mobilitate elektronikoa areagotuz. Propietate berezi hauetaz baliatuko liratekeen aplikazio teknologiko posibleek[2] material honekiko interesa egun arlo zienti- fikotik at ere hedatzea eragin du. Grafenoaren sintesiaren errekonozimendu gisa Geim eta Novoselov-ek 2010ean fisikaren Nobel saria lortu zuten. Hala ere, grafenoa ez da sintetiza daitekeen material bidimentsional bakarra. Grafenoa lortzeko teknika bera erabiliz (banantze mikromekanikoa), Geim eta Novoselov-ek zu- zendutako taldeak M oS2 eta N bSe2 sintetizatzea lortu zuen[3]. Konkretuki, M oS2 mo- nogeruza erdieroalea izanik transistoreak minimizatzeko prozesuan silizioaren ordezkari gisa jarduteko hautagaia da. Hala ere, hau egin ahal izateko bere propietate elektro- nikoak sakonkiago aztertzea komeni da. Gradu amaierako lan honetan material honen egitura elektronikoaren eta magnetikoaren karakterizazio teorikoan aurrerapauso txiki bat egitea izan dugu helburu. Horrez gain, W S2 materiala ere era berean landu da, tungsteno atomoa pisutsuagoa izatean, spin-orbita elkarrekintzaren eragina nabariagoa izatea espero baita. Modu honetan, lan hau hiru atal nagusitan banatzen da. Lehenengoa teoriari dago- kio, DF T (Dentsitatearen Funtzionalaren Teoria) inplementatzeko oinarri teorikoa lan- du delarik. Magnetizazioa aztertzeko ezinbestekoa den espina inplementatzeko modua ere aztertu da, eta baita egin beharreko hurbilketen eta pseudopotentzialen metodoaren azalpen bat eman ere. Bigarren atalean QuantumEspresso kodea erabiliz burututako ab-initio kalkuluen deskripzio eta emaitzak aurkeztu dira, azkenei dagokien interpreta- zioa eginez. Bertan M oS2 -n bolumenetiketik monogeruzara pasatzeak egitura elektroni- koan duen eragina aztertu da, ondoren M oS2 eta W S2 monogeruzen banda egitura eta magnetizazioan analisi sakonagoa eginez. Azkenengo atalean ateratako ondorioak idatzi dira, etorkizunerako lanetarako ateak zabalduz.

Ab Initio Study Of Zno-Based Gas-Sensing Mechanisms: Surface Reconstruction And Charge Transfer

Density functional theory (DFT) calculations were employed to explore the gas-sensing mechanisms of zinc oxide (ZnO) with surface reconstruction taken into consideration. Mix-terminated (10 (1) over bar0) ZnO surfaces were examined. By simulating the adsorption process of various gases, i.e., H-2, NH3, CO, and ethanol (C2H5OH) gases, on the ZnO (10 (1) over bar0) surface, the changes of configuration and electronic structure were compared. Based on these calculations, two gas-sensing mechanisms were proposed and revealed that both surface reconstruction and charge transfer result in a change of electronic conductance of ZnO. Also, the calculations were compared with existing experiments.

Band Engineering in Thermoelectric Materials Using Optical, Electronic, and Ab-Initio Computed Properties

Thermoelectric materials have demanded a significant amount of attention for their ability to convert waste heat directly to electricity with no moving parts. A resurgence in thermoelectrics research has led to significant enhancements in the thermoelectric figure of merit, zT, even for materials that were already well studied. This thesis approaches thermoelectric zT optimization by developing a detailed understanding of the electronic structure using a combination of electronic/thermoelectric properties, optical properties, and ab-initio computed electronic band structures. This is accomplished by applying these techniques to three important classes of thermoelectric materials: IV-VI materials (the lead chalcogenides), Half-Heusler’s (XNiSn where X=Zr, Ti, Hf), and CoSb₃ skutterudites.

In the IV-VI materials (PbTe, PbSe, PbS) I present a shifting temperature-dependent optical absorption edge which correlates well to the computed ab-initio molecular dynamics result. Contrary to prior literature that suggests convergence of the primary and secondary bands at 400 K, I suggest a higher convergence temperature of 700, 900, and 1000 K for PbTe, PbSe, and PbS, respectively. This finding can help guide electronic properties modelling by providing a concrete value for the band gap and valence band offset as a function of temperature.

Another important thermoelectric material, ZrNiSn (half-Heusler), is analyzed for both its optical and electronic properties; transport properties indicate a largely different band gap depending on whether the material is doped n-type or p-type. By measuring and reporting the optical band gap value of 0.13 eV, I resolve the discrepancy in the gap calculated from electronic properties (maximum Seebeck and resistivity) by correlating these estimates to the electron-to-hole weighted mobility ratio, A, in narrow gap materials (A is found to be approximately 5.0 in ZrNiSn).

I also show that CoSb₃ contains multiple conduction bands that contribute to the thermoelectric properties. These bands are also observed to shift towards each other with temperature, eventually reaching effective convergence for T>500 K. This implies that the electronic structure in CoSb₃ is critically important (and possibly engineerable) with regards to its high thermoelectric figure of merit.

Ab initio study of anharmonicity in high pressure Cmca-4 metallic hydrogen

Hydrogen is the only atom for which the Schr odinger equation is solvable. Consisting only of a proton and an electron, hydrogen is the lightest element and, nevertheless, is far from being simple. Under ambient conditions, it forms diatomic molecules H2 in gas phase, but di erent temperature and pressures lead to a complex phase diagram, which is not completely known yet. Solid hydrogen was rst documented in 1899 [1] and was found to be isolating. At higher pressures, however, hydrogen can be metallized. In 1935 Wigner and Huntington predicted that the metallization pressure would be 25 GPa [2], where molecules would disociate to form a monoatomic metal, as alkali metals that lie below hydrogen in the periodic table. The prediction of the metallization pressure turned out to be wrong: metallic hydrogen has not been found yet, even under a pressure as high as 320 GPa. Nevertheless, extrapolations based on optical measurements suggest that a metallic phase may be attained at 450 GPa [3]. The interest of material scientist in metallic hydrogen can be attributed, at least to a great extent, to Ashcroft, who in 1968 suggested that such a system could be a hightemperature superconductor [4]. The temperature at which this material would exhibit a transition from a superconducting to a non-superconducting state (Tc) was estimated to be around room temperature. The implications of such a statement are very interesting in the eld of astrophysics: in planets that contain a big quantity of hydrogen and whose temperature is below Tc, superconducting hydrogen may be found, specially at the center, where the gravitational pressure is high. This might be the case of Jupiter, whose proportion of hydrogen is about 90%. There are also speculations suggesting that the high magnetic eld of Jupiter is due to persistent currents related to the superconducting phase [5]. Metallization and superconductivity of hydrogen has puzzled scientists for decades, and the community is trying to answer several questions. For instance, what is the structure of hydrogen at very high pressures? Or a more general one: what is the maximum Tc a phonon-mediated superconductor can have [6]? A great experimental e ort has been carried out pursuing metallic hydrogen and trying to answer the questions above; however, the characterization of solid phases of hydrogen is a hard task. Achieving the high pressures needed to get the sought phases requires advanced technologies. Diamond anvil cells (DAC) are commonly used devices. These devices consist of two diamonds with a tip of small area; for this reason, when a force is applied, the pressure exerted is very big. This pressure is uniaxial, but it can be turned into hydrostatic pressure using transmitting media. Nowadays, this method makes it possible to reach pressures higher than 300 GPa, but even at this pressure hydrogen does not show metallic properties. A recently developed technique that is an improvement of DAC can reach pressures as high as 600 GPa [7], so it is a promising step forward in high pressure physics. Another drawback is that the electronic density of the structures is so low that X-ray di raction patterns have low resolution. For these reasons, ab initio studies are an important source of knowledge in this eld, within their limitations. When treating hydrogen, there are many subtleties in the calculations: as the atoms are so light, the ions forming the crystalline lattice have signi cant displacements even when temperatures are very low, and even at T=0 K, due to Heisenberg's uncertainty principle. Thus, the energy corresponding to this zero-point (ZP) motion is signi cant and has to be included in an accurate determination of the most stable phase. This has been done including ZP vibrational energies within the harmonic approximation for a range of pressures and at T=0 K, giving rise to a series of structures that are stable in their respective pressure ranges [8]. Very recently, a treatment of the phases of hydrogen that includes anharmonicity in ZP energies has suggested that relative stability of the phases may change with respect to the calculations within the harmonic approximation [9]. Many of the proposed structures for solid hydrogen have been investigated. Particularly, the Cmca-4 structure, which was found to be the stable one from 385-490 GPa [8], is metallic. Calculations for this structure, within the harmonic approximation for the ionic motion, predict a Tc up to 242 K at 450 GPa [10]. Nonetheless, due to the big ionic displacements, the harmonic approximation may not su ce to describe correctly the system. The aim of this work is to apply a recently developed method to treat anharmonicity, the stochastic self-consistent harmonic approximation (SSCHA) [11], to Cmca-4 metallic hydrogen. This way, we will be able to study the e ects of anharmonicity in the phonon spectrum and to try to understand the changes it may provoque in the value of Tc. The work is structured as follows. First we present the theoretical basis of the calculations: Density Functional Theory (DFT) for the electronic calculations, phonons in the harmonic approximation and the SSCHA. Then we apply these methods to Cmca-4 hydrogen and we discuss the results obtained. In the last chapter we draw some conclusions and propose possible future work.

As2Te3-ren isolatzaile topologikorako presiopeko trantsizioaren ab-initio azterketa

Materia kondentsatuko sikan erronka nagusietako bat naturako materialen izaera eza- gutu eta ezaugarritzea da. Orain dela urte batzuk arte ezagutzen genituen material guztiak, eroale, erdieroale edo isolatzaileak ziren, materialeko balentzia elektroien izae- raren arabera. Azken urteotan sikako arlo honetan burututako lanek eman dute bere fruitua, materiaren egoera berri bat aurkitu baita naturan [1]: isolatzaile topologikoa. Isolatzaile topologikoak material isolatzaileak dira baina ertza eroalea dute. Egoera eroale hauek dira material berri honen berezkotasuna. Egoerok sistemaren topologia dela eta existitzen dira eta sistemaren simetriaren bidez babestuta daudenez, deusez- taezinak dira. Hall isolatzaile kuantikoa izan zen isolatzaile topologikoen gaia teorikoki garatzen hasteko inspirazio iturria eta esperimentalki beranduago aurkitu ziren [2]. Lan ugari egiten ari da materiaren egoera berri honen teoria osatu eta era honetako material berriak aurkitzeko. Gaur egun isolatzaile topologiko ezagunenetarikoak kalogenuro fami- liakoak dira. Talde honetakoa da 2008.urtean estrainekoz aurkitu zen hiru dimentsiotako isolatzaile topologikoa: Bi1

Spin-orbita elkarrekintza eta trukatze-korrelazio eremu eskalar eta bektorialaren ab-initio kalkuluak LAPW metodoaren bidez: Bismutoaren adibidea

Gradu amaierako lan honetan, LAPW metodoa aztertu da solidoen propietate elektronikoak era teorikoan ikertzeko eta efektu erlatibistek hauengan duten eragina zenbatesteko tresna teoriko bezala. Konkretuki spin-orbita elkarrekintzan zentratu gara, eta hau konputazionalki inplementatzeko bigarren bariazionalaren metodoa aztertu da. Bestalde, Spin-DFT teoriaren barruan spin-orbita kodifikatzen duen trukatze-korrelazio eremu bektorialaren azterketa labur bat egin da, ekarpen erlatibista beste ikuspuntu batetik aztertu eta informazio osagarria lortzeko asmoz.