71 resultados para CI CALCULATIONS


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Quasiparticle calculations are performed to investigate the electronic band structures of various polymorphs of Hf and Zr oxides. The corrections with respect to density-functional-theory results are found to depend only weakly on the crystal structure. Based on these bulk calculations as well as those for bulk Si, the effect of quasiparticle corrections is also investigated for the band offsets at the interface between these oxides and Si assuming that the lineup of the potential at the interface is reproduced correctly within density-functional theory. On the one hand, the valence-band offsets are practically unchanged with a correction of a few tenths of electron volts. On the other hand, conduction-band offsets are raised by 1.3-1.5 eV. When applied to existing calculations for the offsets at the density-functional-theory level, our quasiparticle corrections provide results in good agreement with the experiment.

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It is well known that shape corrections have to be applied to the local-density (LDA) and generalized gradient (GGA) approximations to the Kohn-Sham exchange-correlation potential in order to obtain reliable response properties in time dependent density functional theory calculations. Here we demonstrate that it is an oversimplified view that these shape corrections concern primarily the asymptotic part of the potential, and that they affect only Rydberg type transitions. The performance is assessed of two shape-corrected Kohn-Sham potentials, the gradient-regulated asymptotic connection procedure applied to the Becke-Perdew potential (BP-GRAC) and the statistical averaging of (model) orbital potentials (SAOP), versus LDA and GGA potentials, in molecular response calculations of the static average polarizability alpha, the Cauchy coefficient S-4, and the static average hyperpolarizability beta. The nature of the distortions of the LDA/GGA potentials is highlighted and it is shown that they introduce many spurious excited states at too low energy which may mix with valence excited states, resulting in wrong excited state compositions. They also lead to wrong oscillator strengths and thus to a wrong spectral structure of properties like the polarizability. LDA, Becke-Lee-Yang-Parr (BLYP), and Becke-Perdew (BP) characteristically underestimate contributions to alpha and S-4 from bound Rydberg-type states and overestimate those from the continuum. Cancellation of the errors in these contributions occasionally produces fortuitously good results. The distortions of the LDA, BLYP, and BP spectra are related to the deficiencies of the LDA/GGA potentials in both the bulk and outer molecular regions. In contrast, both SAOP and BP-GRAC potentials produce high quality polarizabilities for 21 molecules and also reliable Cauchy moments and hyperpolarizabilities for the selected molecules. The analysis for the N-2 molecule shows, that both SAOP and BP-GRAC yield reliable energies omega(i) and oscillator strengths f(i) of individual excitations, so that they reproduce well the spectral structure of alpha and S-4.(C) 2002 American Institute of Physics.

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If recurrent novae are progenitors of Type Ia supernovae, their white dwarfs must have masses close to the Chandrasekhar limit. The most reliable means of determining white dwarf masses in recurrent novae is dynamically, via radial-velocity and rotational-broadening measurements of the companion star. Such measurements require the system to be both eclipsing and to show absorption features from the secondary star. Prior to the work reported here, the only dynamical mass estimate of a recurrent nova was for U Sco, which has a white dwarf mass of 1.55 +/- 0.24 Msolar (Thoroughgood et al. 2001). We present new time-resolved, intermediate-resolution spectroscopy of the eclipsing recurrent nova CI Aquilae (CI Aql) during quiescence. We find the mass of the white dwarf to be 1.00 +/- 0.14 Msolar and the mass of the secondary star to be 2.32 +/- 0.19 Msolar. We estimate the radius of the secondary to be 2.07 +/- 0.06 Rsolar, implying that it is a slightly-evolved early A-type star. The high mass ratio of q = 2.35 +/- 0.24 and the high secondary-star mass implies that the mass transfer occurs on a thermal timescale. We suggest that CI Aql is rapidly evolving into a supersoft X-ray source, and ultimately may explode as a Type Ia supernova within 10 Myr.

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Green oil, which leads to the deactivation of the catalysts used for the selective hydrogenation of acetylene, has long been observed but its formation mechanism is not fully understood. In this work, the formation of 1,3-butadiene, known to be the precursor of green oil, on both Pd(111) and Pd(211) surfaces is examined using density functional theory calculations. The pathways containing C-2 + C-2 coupling reactions as well as the corresponding hydrogenation reactions are studied in detail. Three pathways for 1,3-butadiene production, namely coupling plus hydrogenation and further hydrogenation, hydrogenation plus coupling plus hydrogenation, and a two step hydrogenation followed by coupling, are determined. By comparing the effective barriers, we identify the favored pathway on both surfaces. A general understanding toward the deactivation process of the industrial catalysts is also provided. In addition, the effects of the formation of subsurface carbon atoms as well as the Ag alloying on the 1,3-butadiene formation on Pd-based catalysts are also investigated and compared with experimental results.

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Monte Carlo calculations of quantum yield in PtSi/p-Si infrared detectors are carried out taking into account the presence of a spatially distributed barrier potential. In the 1-4 mu m wavelength range it is found that the spatial inhomogeneity of the barrier has no significant effect on the overall device photoresponse. However, above lambda = 4.0 mu m and particularly as the cut-off wavelength (lambda approximate to 5.5 mu m) is approached, these calculations reveal a difference between the homogeneous and inhomogeneous barrier photoresponse which becomes increasingly significant and exceeds 50% at lambda = 5.3 mu m. It is, in fact, the inhomogeneous barrier which displays an increased photoyield, a feature that is confirmed by approximate analytical calculations assuming a symmetric Gaussian spatial distribution of the barrier. Furthermore, the importance of the silicide layer thickness in optimizing device efficiency is underlined as a trade-off between maximizing light absorption in the silicide layer and optimizing the internal yield. The results presented here address important features which determine the photoyield of PtSi/Si Schottky diodes at energies below the Si absorption edge and just above the Schottky barrier height in particular.

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Using density functional theory calculations with HSE 06 functional, we obtained the structures of spin-polarized radicals on rutile TiO2(110), which is crucial to understand the photooxidation at the atomic level, and further calculate the thermodynamic stabilities of these radicals. By analyzing the results, we identify the structural features for hole trapping in the system, and reveal the mutual effects among the geometric structures, the energy levels of trapped hole states and their hole trapping capacities. Furthermore, the results from HSE 06 functional are compared to those from DFT + U and the stability trend of radicals against the number of slabs is tested. The effect of trapped holes on two important steps of the oxygen evolution reaction, i.e. water dissociation and the oxygen removal, is investigated and discussed.

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The reactivity of sp2 carbon materials is studied using the adsorption and dissociation of O2 on graphene and graphene oxide as model systems. The reactions on the basal plane, zigzag and armchair edges of graphene and graphene oxide with different oxygen-containing groups are calculated using first principles calculations. Two Brønsted-Evans- Polanyi relationships are identified and an electron delocalization model is suggested to understand the general trend of reactivity for sp2 carbon materials.

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The combination of density functional theory (DFT) calculations and kinetic analyses is a very useful approach to study surface reactions in heterogeneous catalysis. The present paper reviews some recent work applying this approach to Fischer-Tropsch (FT) synthesis. Emphasis is placed on the following fundamental issues in FT synthesis: (i) reactive sites for both hydrogenation and C-C coupling reactions; (ii) reaction mechanisms including carbene mechanism, CO-insertion mechanism and hydroxyl-carbene mechanism; (iii) selectivity with a focus on CH(4) selectivity, alpha-olefin selectivity and chain growth probability; and (iv) activity.

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By combining density functional theory calculation and microkinetic analysis, NO oxidation on the platinum group metal oxides (PtO(2), IrO(2), OsO(2)) is investigated, aiming at shedding light on the activities of metal oxides and exploring the activity variations of metal oxides compared to their corresponding metals. A microkinetic model, taking into account the possible low diffusion of surface species on metal oxide surfaces, is proposed for NO oxidation. The resultant turnover frequencies of NO oxidation show that under the typical experimental condition, T = 600 K, p(O2) = 0.1 atm, p(NO) = 3 x 10(-4) atm, p(NO2) = 1.7 x 10(-4) atm; (i) IrO(2)(110) exhibits higher activity than PtO(2)(110) and OsO(2)(110), and (ii) compared to the corresponding metallic Pt, Ir, and Os, the activity of PtO(2) to catalyze NO oxidation is lower, but interestingly IrO(2) and OsO(2) exhibit higher activities. The reasons for the activity differences between the metals and oxides are addressed. Moreover, other possible reaction pathways of NO oxidation on PtO(2)(110), involving O(2) molecule (NO + O(2) -> OONO) and lattice bridge-O(2c), are also found to give low activities. The origin of the Pt catalyst deactivation is also discussed.

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Ab initio total energy calculations have been performed for CO chemisorption on Pd(110). Local density approximation (LDA) calculations yield chemisorption energies which are significantly higher than experimental values but inclusion of the generalised gradient approximation (GGA) gives better agreement. In general, sites with higher coordination of the adsorbate to surface atoms lead to a larger degree of overbinding with LDA, and give larger corrections with GGA. The reason is discussed using a first-order perturbation approximation. It is concluded that this may be a general failure of LDA for chemisorption energy calculations. This conclusion may be extended to many surface calculations, such as potential energy surfaces for diffusion.

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Energy levels and radiative rates are reported for transitions in Cl-like W LVIII. Configuration interaction (CI) has been included among 44 configurations (generating 4978 levels) over a wide energy range up to 363 Ryd, and the general-purpose relativistic atomic structure package (grasp) adopted for the calculations. Since no other results of comparable complexity are available, calculations have also been performed with the flexible atomic code (fac), which help in assessing the accuracy of our results. Energies are listed for the lowest 400 levels (with energies up to ~98 Ryd), which mainly belong to the 3s23p5, 3s3p6, 3s23p43d, 3s23p33d2, 3s3p43d2, 3s23p23d3, and 3p63d configurations, and radiative rates are provided for four types of transitions, i.e.E1, E2, M1, and M2. Our energy levels are assessed to be accurate to better than 0.5%, whereas radiative rates (and lifetimes) should be accurate to better than 20% for a majority of the strong transitions.

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Energy levels and radiative rates are reported for transitions in Br-like tungsten, W XL, calculated with the general-purpose relativistic atomic structure package (grasp). Configuration interaction (CI) has been included among 46 configurations (generating 4215 levels) over a wide energy range up to 213 Ryd. However, for conciseness results are only listed for the lowest 360 levels (with energies up to ~43 Ryd), which mainly belong to the 4s24p5,4s24p44d,4s24p44f,4s4p6,4p64d,4s4p54d,4s24p34d2, and 4s24p34d4f configurations, and provided for four types of transitions, E1, E2, M1, and M2. Comparisons are made with existing (but limited) results. However, to fully assess the accuracy of our data, analogous calculations have been performed with the flexible atomic code, including an even larger CI than in grasp. Our energy levels are estimated to be accurate to better than 0.02 Ryd, whereas results for radiative rates (and lifetimes) should be accurate to better than 20% for a majority of the strong transitions.

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We report calculations of energy levels, radiative rates, oscillator strengths and line strengths for transitions among the lowest 345 levels of Ti X. These include 146 levels of the n 3 configurations and 86 of 3s 24ℓ, 3s25ℓ and 3s3p4ℓ, plus some of the 3s26ℓ, 3p24ℓ and 3s3p5ℓ levels. The general-purpose relativistic atomic structure package and flexible atomic code are adopted for the calculations. Radiative rates, oscillator strengths and line strengths are provided for all electric dipole (E1), magnetic dipole (M1), electric quadrupole (E2) and magnetic quadrupole (M2) transitions among the 345 levels, although calculations have been performed for a much larger number of levels. Comparisons are made with existing results and the accuracy of the data is assessed. Additionally, lifetimes for all 345 levels are listed. Extensive comparisons of lifetimes are made for the lowest 40 levels, for which discrepancies with recent theoretical work are up to 30%. Discrepancies in lifetimes are even larger, up to a factor of four, for higher excited levels. Furthermore, the effect of large configuration interaction (CI) is found to be insignificant for both the energies and lifetimes for the lowest 40 levels of Ti X which belong to the 3s23p, 3s3p2, 3s23d, 3p3 and 3s3p3d configurations. However, the contribution of CI is more appreciable for the energy levels and radiative rates among higher excited levels. Our listed energy levels are estimated to be accurate to better than 1% (within 0.1 Ryd), whereas results for other parameters are probably accurate to better than 20%. © 2013 The Royal Swedish Academy of Sciences.

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The second harmonic generation (SHG) intensity spectrum of SiC, ZnO, GaN two-dimensional hexagonal crystals is calculated by using a real-time first-principles approach based on Green's function theory [Attaccalite et al., Phys. Rev. B: Condens. Matter Mater. Phys. 2013 88, 235113]. This approach allows one to go beyond the independent particle description used in standard first-principles nonlinear optics calculations by including quasiparticle corrections (by means of the GW approximation), crystal local field effects and excitonic effects. Our results show that the SHG spectra obtained using the latter approach differ significantly from their independent particle counterparts. In particular they show strong excitonic resonances at which the SHG intensity is about two times stronger than within the independent particle approximation. All the systems studied (whose stabilities have been predicted theoretically) are transparent and at the same time exhibit a remarkable SHG intensity in the range of frequencies at which Ti:sapphire and Nd:YAG lasers operate; thus they can be of interest for nanoscale nonlinear frequency conversion devices. Specifically the SHG intensity at 800 nm (1.55 eV) ranges from about 40-80 pm V(-1) in ZnO and GaN to 0.6 nm V(-1) in SiC. The latter value in particular is 1 order of magnitude larger than values in standard nonlinear crystals.