Measurements of positions, strengths and self-broadened widths of H2O from 2900 to 8000 cm: line strength analysis of the 2nd triad bands

High-resolution spectra of H₂O were recorded with a Fourier-transform spectrometer covering H₂O transitions from 2900 to 8000 cm⁻¹. Over 13,000 absorptions were measured to determine line positions, strengths and self-broadened half-width coefficients. The H₂ ¹⁶O line strengths of the (0 3 0)-(0 1 0), (1 1 0)-(0 1 0), (0 1 1)-(0 1 0) and (0 3 0)-(0 0 0), (1 1 0)-(0 0 0), (0 1 1)-(0 0 0) bands were fitted to a quantum mechanical model which involves the interactions between the (0 3 0), (1 1 0), and (0 1 1) vibrational states. Also fitted were experimental strengths of the hot bands; (1 2 0)-(0 1 0) and (0 2 1)-(0 1 0). The model includes 14 dipole matrix elements for B- and A-type transitions. The measured line positions were used along with hot water emission measurements (for the (0 3 0), (0 4 0), and (0 5 0) states of H₂ ¹⁶O) in an analysis to obtain high-accuracy energy level values in the (0 3 0), (1 1 0), (0 1 1), (0 4 0), (1 2 0), (0 2 1), (2 0 0), (1 0 1), (0 0 2), and (0 5 0) vibrational states of H₂ ¹⁶O and the (1 1 0) and (0 1 1) states of H₂ ¹⁷O. Also included were measurements and analysis of self-broadened half-widths for over 4700 absorptions between 4405 and 7729 cm⁻¹. The results from this investigation provide new information for the noted H₂ ¹⁷O bands and present a more accurate representation of the measured H₂ ¹⁶O bands.     

Electrochemical scanning tunneling microscopy examination of the structures of benzenethiol molecules adsorbed on Au(1 0 0) and Pt(1 0 0) electrodes

In situ electrochemical scanning tunneling microscopy (STM) has been used to examine the structures of benzenethiol adlayers on Au(1 0 0) and Pt(1 0 0) electrodes in 0.1 M HClO₄, revealing the formation of well-ordered adlattices of Au(1 0 0)-(√2 × √5) between 0.2 and 0.9 V and Pt(1 0 0)-(√2 × √2)R45° between 0 and 0.5 V (versus reversible hydrogen electrode), respectively. The coverage of Au(1 0 0)-(√2 × √5) is 0.33, which is identical to those observed for upright alkanethiol admolecules on Au(1 1 1). In comparison, the coverage of Pt(1 0 0)-(√2 × √2)R45° - benzenethiol is 0.5, much higher than those of thiol molecules on gold surfaces. This result suggests that benzenethiol admolecules on Pt(1 0 0) could stand even more upright than those on Au(1 0 0). All benzenethiol admolecules were imaged by the STM as protrusions with equal corrugation heights, suggesting identical molecular registries on Au(1 0 0) and Pt(1 0 0) electrodes, respectively. Modulation of the potential of a benzenethiol-coated Au(1 0 0) electrode resulted in irreversible desorption of admolecules at E ? 0.1 V (vs. reversible hydrogen electrode) and oxidation of admolecules at E ? 0.9 V. In contrast, benzenethiol admolecule was not desorbed from Pt(1 0 0) at potentials as negative as the onset of hydrogen evolution. Raising the potential rendered deposition of more benzenethiol molecules before oxidation of admolecules commenced at E > 0.9 V.     

Quantum chemical and RRKM calculations of reactions in the H/S/O system

Quantum chemical calculations at the MRCI/aug-cc-pV5Z level are used to describe the conversions between HSO, HOS, H + SO, S + OH and O + SH on the doublet H/S/O potential energy surface. An RRKM analysis of this multiple-well system was carried out in the temperature range 300-2000 K between 0.1 and 10 atm. At these pressures, the stabilization reaction H + SO → HSO or HOS is at the low pressure limit, and stabilization from S + OH and O + SH was not detected. The reactions S + OH → H + SO and O + SH → H + SO were found to be barrierless and very fast at room temperature (4 × 10¹⁴ and 1.5 × 10¹⁴ cm³ mol⁻¹ s⁻¹, respectively). The reaction channel O + SH → S + OH is two orders of magnitude slower than the more exothermic O + SH → H + SO reaction, although a second pathway involving direct H-abstraction (O + SH → S + OH) on the quartet surface appears as a minor channel at high temperatures.     

Influence of cold-rolling texture and heating rate on {1 1 0}〈0 0 1〉 development in inhibitor-free 3%Si–Fe sheets

This paper presents cold-rolling and annealing methods to obtain a high-magnetic induction in inhibitor-free 0.1-mm-thick 3% silicon–iron sheets containing 18 or 150 ppm sulfur. In case of the two-step cold-rolling, the sheets containing 150 ppm sulfur showed a strong {1 0 0} final texture at 400 °C/h, and some fraction of {1 1 0} component was observed at 25 °C/h. However, three-step cold-rolling resulted in a sharp {1 1 0}〈0 0 1〉 final texture at 25 °C/h. This is due to the difference in intensity ratio of {1 0 0}〈0 1 1〉 to {1 1 1}〈1 1 2〉 in the cold-rolling texture which influences the nucleation of {1 1 0}〈0 0 1〉 component and the selective growth kinetics of various grains. In case of 18 ppm sulfur, the final texture was mainly composed of a sharp {1 1 0}〈0 0 1〉 component even at 400 °C/h, due to the relatively low segregation concentration.     

Evaluation of image quality of DWIBS versus DWI sequences in thoracic MRI at 3 T

Purpose

To compare diffusion weighted imaging with background suppression (DWIBS) sequence with classic spectral diffusion sequence (DWI) with and without respiratory gating in mediastinal lymph node analysis at 3 T.

Materials and methods

26 patients scheduled for mediastinoscopic lymph node analysis, prospectively undergone a thoracic 3 T MRI with DWIBS (FatSat = STIR; TR/TE = 6674.1/44.7 ms; IR = 260 ms) and DWI sequences (FatSat = SPIR; TR/TE = 1291/59.6 ms) (b = 0-400-800 s/mm2) with and without (free breathing) respiratory gating.Images at b = 800 were analyzed by two radiologists. They performed qualitative analysis of fat-sat homogeneity and motion artifacts, rated from 0 to 4, and quantitative evaluation by studying signal to background (STB) of lymph nodes.

Results

Quality of fat suppression was significantly higher for DWIBS than for DWI both for free-breathing (score 3.48 ± 0.65 vs. 1.76 ± 0.96, p < 0.0001) and respiratory-gated scans (3.17 ± 0.77 vs. 1.72 ± 0.73, p = 0.0001). Similarly, artifacts were reduced with DWIBS (3.16 ± 0.47 vs. 1.76 ± 0.59, p < 0.0001; 3.0 ± 0.73 vs. 2.04 ± 0.53, p = 0.0001). Quantitative analysis showed higher STB with DWIBS (3.26 ± 1.83 vs. 0.98 ± 0.44, p < 0.0001; 3.56 ±, 2.09 vs. 0.92 ± 0.59, p < 0.0001). Gating did not improve image quality and STB on DWIBS (p > 0.05).

Conclusion

In thoracic MRI, ungated DWIBS sequence improves fat-sat homogeneity, reduces motion artifacts and increases STB of lymph nodes. Respiratory gating does not improve DWIBS image quality.     

Rate coefficients measurement for the energy-pooling collisions Cs(5D) + Cs(5D) → Cs(6S) + Cs(nl = 9D, 11S, 7F)

We report experimental rate coefficients for the energy-pooling collisions Cs(5D) + Cs(5D) → Cs(6S) + Cs(nl = 9D, 11S, 7F). In the experiment the Cs(5D) state was populated via photodissociation of Cs₂ molecules using an argon-ion laser at wavelength 488.0 nm. We also consider the competing process 6P_1/2 + 7S → 6S + (nl = 9D, 11S, 7F) that might also populate 9D, 11S and 7F. An intermodulation technique was used to select the fluorescence contributions due only to the process 6P_1/2 + 7S → 6S + (nl = 9D, 11S, 7F). The excited atom (nl_J) density and spatial distribution were mapped by monitoring the absorption of a counterpropagating probe laser beam tuned to various transitions. The measured excited atom densities are combined with measured fluorescence ratios to yield rate coefficients for the energy-pooling collisions Cs(5D) + Cs(5D) → Cs(6S) + Cs(nl = 9D, 11S, 7F). The rate coefficients for nl = 9D, 11S, 7F are (4.1 ± 2.0) × 10⁻¹⁰ cm³ s⁻¹, (1.6 ± 0.8) × 10⁻¹⁰ cm³ s⁻¹ and (3.6 ± 1.8) × 10⁻¹⁰ cm³ s⁻¹, respectively. The contributions to the rate coefficients from other energy transfer processes are also discussed.     

Theoretical investigation on structural stability of InN thin films on 3C-SiC(0 0 1)

The structural stability of InN thin films on 3C-SiC(0 0 1) substrate is systematically investigated based on an empirical interatomic potential, which incorporates electrostatic energy due to covalent bond charges and ionic charges. The calculated energy differences among coherently grown 3C-InN(0 0 1), 3C-InN(0 0 1) with misfit dislocations (MDs), and 2H-InN(0 0 0 1) imply that the coherently grown 3C-InN(0 0 1) is stable when the film thickness is less than 7 monolayers (MLs) while 2H-InN(0 0 0 1) is stabilized for the thickness beyond 8 MLs. This is because InN layers in 2H-InN(0 0 0 1) are fully relaxed by one MD. The analysis of atomic configuration at the 3C-InN(0 0 1)/3C-SiC(0 0 1) interfaces reveals that the coordination number of interfacial atoms is quite different from that in the bulk region. Thus, 3C-InN(0 0 1) with MDs on 3C-SiC(0 0 1) is always metastable over entire range of film thickness, consistent with the successful fabrication of 2H-InN(0 0 0 1) on 3C-SiC(0 0 1) by the molecular beam epitaxy. These results suggest that the mismatch in atomic arrangements at the interface crucially affects the structural stability of InN thin films on 3C-SiC(0 0 1) substrate.     

The dissimilar twins - a comparative, site-selective in situ study of CO adsorption and desorption on Pt(3 2 2) and Pt(3 5 5)

The adsorption and desorption of CO on stepped Pt(3 2 2) = Pt(S)-[5(1 1 1) × (1 0 0)] and Pt(3 5 5) = Pt(S)-[5(1 1 1) × (1 1 1)] were investigated using in situ high-resolution X-ray photoelectron spectroscopy at BESSY II, which allows to clearly distinguish between different step and terrace adsorption sites. For the two surfaces, with the same nominal terrace width of five atomic rows, but different step orientation, significant differences are observed. While for Pt(3 5 5) CO adsorption at steps only occurs at on-top sites, on Pt(3 2 2) both step on-top and bridge sites are occupied, albeit with a significantly lower coverage (0.07 vs. 0.13 ML at 200 K). On both surfaces terrace sites are only occupied when the step sites are almost saturated confirming the enhanced binding energy at step sites. CO adsorbed at the (1 1 1) steps on Pt(3 5 5) is more strongly bound than on the (1 0 0) steps on Pt(3 2 2), which is attributed to the different electronic and geometric structure of the steps. The relative occupation of terrace and step sites at a given coverage remains the same between 120 and 290 K on Pt(3 5 5) K, but shows major changes on Pt(3 2 2), between step on-top and bridge sites as well as terrace on-top and bridge sites. On Pt(3 5 5) a smaller CO terrace coverage is found (0.36 vs. 0.40 ML on Pt(3 2 2) at 200 K), mainly due to the lower occupation of terrace bridge sites. For Pt(3 2 2), an ordered adsorbate phase is deduced from a c(4 × 2)-like LEED pattern, which indicates adsorbate order beyond the extension of a single terrace. A model for this structure is proposed.     

Dependence of the strain energies on grain orientations in HCP metal films

A thin polycrystalline film bonded tightly to a thick substrate of different thermal expansion coefficients will experience thermal strain when the temperature is changed. Calculations of the strain energies for grains having various crystallographic orientations (h k l) relative to the film surface were made for a polycrystalline film composed of the close-packed hexagonal (HCP) metal Be, Cd, Co, Hf, Mg, Re, Ru, Sc, Ti, Y, Zr and Zn, respectively. From strain energy minimization, the (0 0 1), (0 1 3), (0 4 5), (1 2 3), (2 5 8), (0 5 7), (0 3 5), (0 5 7), (0 1 0), (5 5 8), (1 4 7) and (0 0 1) textures should be favorable in Be, Cd, Co, Hf, Mg, Re, Ru, Sc, Ti, Y, Zr and Zn film, respectively.     

Atomistic simulation of point defects at low-index surfaces of noble metals

The formation energies and the migration energies of an isolated vacancy and adatom formed on low-index surfaces are calculated with MAEAM for three noble metals Cu, Ag and Au. The results indicate that the formation energies of an isolated vacancy or adatom increase with increasing atom density in the sequence (1 1 0) → (1 0 0) → (1 1 1), and it is more difficult to form an adatom than to form a vacancy at the same surface. For the mobility of an isolated vacancy, the migration energy grows in the sequence (1 0 0) → (1 1 0) → (1 1 1) for each noble metal. However, a much less migration energy is obtained for the migration of an adatom on (1 1 1) surface.     

Structures of Co and Pt nanoclusters on a thin film of Al2O3/NiAl(1 0 0) from reflection high-energy electron diffraction and scanning-tunnelling microscopy

With reflection high-energy electron diffraction (RHEED) and scanning-tunnelling microscopy (STM), we made measurements on Co and Pt nanoclusters grown by vapour deposition on a thin film of Al₂O₃/NiAl(1 0 0). The results show that the annealed Co nanoclusters (with mean diameters 2.5, 3.4, 5.8 nm and heights 0.7, 1.5, 1.5 nm, respectively) and Pt nanoclusters (with mean diameter 2.25 nm and height 0.4 nm) are highly crystalline and that their structures are significantly affected by the oxide substrate. Structural analysis based on the RHEED patterns indicates that both Co and Pt clusters have a fcc phase and grow with their (0 0 1) facets parallel to the θ-Al₂O₃(1 0 0) surfaces, and with their [1 1 0] and [−1 1 0] axes along the [0 1 0] and [0 0 1] directions of the oxide surface, respectively, so (Co(0 0 1)[1 1 0]∥Al₂O₃(1 0 0)[0 1 0] and Pt(0 0 1)[1 1 0]∥Al₂O₃(1 0 0)[0 1 0]). This growth is optimal as the Co and Pt fcc (0 0 1) facets match well with the oxygen mesh. To minimize the lattice mismatch, the lattice parameter of the Co clusters expands 4-5% relative to fcc Co bulk, whereas the lattice parameter of the Pt clusters remains near the bulk value, as the Pt fcc (0 0 1) plane has a close lattice match with the oxide surface.     

Spectroscopic interpretation for Na-induced phase transitions on Na/Si(1 1 1)3 × 1

Na adsorption at room temperature causes the Na/Si(1 1 1)3 × 1 surface with Na coverage of 1/3 monolayer (ML) to transit into the Na/Si(1 1 1)6 × 1 surface at 1/2 ML and sequentially into the Na/Si(1 1 1)3 × 1 surface at 2/3 ML. The phase transition was studied by Si 2p core-level photoemission spectroscopy. The detailed line shape analysis of the Si 2p core-level spectrum of the Na/Si(1 1 1)3 × 1 surface (2/3 ML) is presented and compared to the Na/Si(1 1 1)3 × 1 surface (1/3 ML) which is composed of Si honeycomb chain-channel structures. This suggests that as additional Na atoms form atomic chains resulting in the Na/Si(1 1 1)3 × 1 surface (2/3 ML), the inner atoms of the Si honeycomb chain-channel structure is buckled due to the additional Na atoms.     

The combined effect of hypertension and type 2 diabetes mellitus on aortic stiffness and endothelial dysfunction: An integrated study with high-resolution MRI

Purpose

The purpose of this study was to investigate the combined effect of hypertension and type 2 diabetes mellitus (DM2) on aortic stiffness and endothelial dysfunction by using an integrated MRI approach.

Materials and Methods

A total of 31 non-hypertensive DM2 patients and 31 hypertensive DM2 patients underwent 3.0-T MRI. Aortic distensibility (AD), pulse wave velocity (PWV) and brachial artery flow-mediated dilation (FMD) were assessed. Student's t-test, Mann–Whitney U test, chi-squared test, Pearson correlation analysis, and univariable and multiple linear regression analyses were used for statistical analyses.

Results

The hypertensive patients showed lower AD at multiple levels (ascending aorta [AA]: 2.07 ± 0.98 × 10^− 3 mm Hg^− 1 vs. 3.21 ± 1.70 × 10^− 3 mm Hg^− 1, p < 0.01; proximal thoracic descending aorta [PDA]: 2.58 ± 0.72 × 10^− 3 mm Hg^− 1 vs. 3.58 ± 1.47 × 10^− 3 mm Hg^− 1, p < 0.01; distal descending aorta [DDA]: 3.11 ± 1.84 × 10^− 3 mm Hg^− 1 vs. 4.27 ± 1.75 × 10^− 3 mm Hg^− 1, p < 0.01); faster PWV (7.46 ± 2.28 m/s vs. 5.82 ± 1.12 m/s, p < 0.05) and lower FMD (12.67% ± 6.49% vs. 20.66% ± 9.7%; p < 0.01). Systolic blood pressure was an independent predictor of PWV, AA-AD, DDA-AD and FMD. FMD was statistically significantly associated with PWV (r = − 0.37, p < 0.01) and AD (p < 0.01).

Conclusions

Hypertension has a contributive effect on aortic stiffness and endothelial dysfunction in DM2 patients.     

The comparative study of two dimensional condensation of Xe and Kr physisorbed on Ag(1 1 1) and Ag(1 0 0)

Adsorption isobars of Xe and Kr on Ag(1 1 1) and Ag(1 0 0) were observed simultaneously by an extremely-low-current low energy electron diffraction and an ellipsometry in the temperature range between 60 K and 90 K and in the equilibrium pressure range between 8 × 10⁻⁶ Pa and 2 × 10⁻⁴ Pa. Two dimensional condensation of the first layer of Xe on Ag(1 1 1) occurred at the temperature 0.3 ± 0.1 K higher than that on Ag(1 0 0). In the case of Kr on Ag(1 1 1) and Ag(1 0 0), the temperature difference was 0.2 ± 0.1 K. This temperature difference was discussed on the assumption that it is caused by the repulsive interaction between the dipoles induced in rare gas atoms. We estimated the difference of the induced dipole moment μ: μ of Xe atom on Ag(1 0 0) is 6% larger than that on Ag(1 1 1) and μ of Kr atom on Ag(1 0 0) is 14% larger than that on Ag(1 1 1).     

Secondary electron yield enhancement by MgO capping layers

The yield of secondary electrons emitted from an epitaxial three monolayer (3 ML) NiO(1 0 0)/Ag(1 0 0) film excited by soft X-ray linearly polarized synchrotron radiation at the Ni L_2,3 absorption threshold has been measured for different values of the thickness of a MgO(1 0 0) capping layer. Compared with the as grown 3 ML NiO(1 0 0)/Ag(1 0 0) film, we observe a significant enhancement by about a factor 1.2 of the secondary electron emission for the capped 8 ML MgO(1 0 0)/3 ML NiO(1 0 0)/Ag(1 0 0) sample. A further substantial yield enhancement by a factor 1.6 with respect to the uncapped NiO sample is observed after deposition of an additional 8 ML MgO(1 0 0) film, for a total capping layer thickness of 16 ML. The observed secondary electron yield enhancement is discussed in terms of modified electronic structure, surface work function changes, and characteristic electron propagation lengths.     

Effects of electronic confinement and substrate on the low-temperature growth of Pb islands on Si(1 0 0)-2 × 1 surfaces

The growth of Pb films on the Si(1 0 0)-2 × 1 surface has been investigated at low temperature using scanning tunneling microscopy. Although the orientation of the substrate is (1 0 0), flat-top Pb islands with (1 1 1) surface can be observed. The island thickness is confined within four to nine atomic layers at low coverage. Among these islands, those with a thickness of six layers are most abundant. Quantum-well states in Pb(1 1 1) islands of different thickness are acquired by scanning tunneling spectroscopy. They are found to be identical to those taken on the Pb(1 1 1) islands grown on the Si(1 1 1)7 × 7 surface. Besides Pb(1 1 1) islands, two additional types of Pb islands are formed: rectangular flat-top Pb(1 0 0) islands and rectangular three-dimensional (3D) Pb islands, and both their orientations rotate by 90° from a terrace to the adjacent one. This phenomenon implies that the structures of Pb(1 0 0) and 3D islands are influenced by the Si(1 0 0)-2 × 1 substrate.     

Annealing effect on CdS/SnO2 films grown by chemical bath deposition

The extensive investigation of the annealing effect in nitrogen atmosphere on the structural optical and electrical properties of chemically deposited CdS films on SnO₂ has been performed. The as-deposited film shows 2.45 eV band gap (E_g) and decreases with increasing annealing temperature. The film annealed at 623 K having pure hexagonal phase (a = 4.14 Å, c = 6.71 Å for [1 0 0] plane) and E_g = 2.36 eV shows 10 times higher conductivity for all temperature range, and shows two different activation energies E_a = 0.114 eV and E_a = 0.033 eV for the temperature range 395 K ≤ T ≤ 515 K and 515 K ≤ T ≤ 585 K, respectively. The structural parameters such as dislocation density, strain and optical parameters such as absorption and extinction coefficient are calculated and compared for all the films.     

Texture of molybdenum thin films on SrTiO3(1 0 0): A RHEED study

The structure of ultrathin Mo films on SrTiO₃(1 0 0) was studied by in situ reflection high-energy electron diffraction (RHEED). A different structure was observed for films less than 20 Å thick than for thicker films. These films were epitaxial and had a metastable structure. Thicker films had the dimensions of equilibrium bcc Mo(1 1 0). Relaxation processes transformed the metastable Mo into bcc Mo, resulting in the following orientation relationships between Mo and SrTiO₃: (1 1 0)[0 0 1]_bcc Mo ∥ (1 0 0)[0 0 1]_SrTiO3 and (1 1 0)[1 1 1]_bcc Mo ∥ (1 0 0)[0 1 1]_SrTiO3. The formation of such specific orientations is related to transformations via the Bain and Needle Path, respectively.     

High resolution Fourier transform spectrum of HDO in the 7500-8200 cm region: revisited

The HDO absorption FT spectrum is recorded and analyzed in the 7500-8200 cm⁻¹ spectral region. The high accuracy ab initio calculation of Schwenke and Partridge was successfully applied for spectrum assignment that resulted in derivation of 508 precise rovibrational energy levels for the (3 0 0), (0 3 1), (1 1 1), (0 6 0), (2 2 0), and (0 0 2) states, with 295 of them being reported for the first time. In particular, eight new energy levels, including the band center at 7914.3170 cm⁻¹, were derived for the highly excited bending (0 6 0) state from transitions borrowing their intensities through local high-order resonance coupling with the (3 0 0) and (0 3 1) states.     

Influence of crystal orientation on copper oxidation failure

The influences of crystal orientation on copper oxidation were investigated. The results indicated that crystal orientation of copper substrate has a great effect on the growth rate, the morphology of oxide film and the extent of oxidation failure. Shear test showed the adhesion strength between Cu(1 1 0) and its oxide film was the highest, whereas, the adhesion strength between Cu(3 1 1) and its oxide film was the lowest. SEM observations revealed that the oxide film grown on Cu(3 1 1) delaminated from substrate seriously, while the oxide film grown on Cu(1 0 0) and Cu(1 1 0) did not reveal such a phenomenon. Cu(1 0 0) and Cu(1 1 0) exhibited thinner oxide thickness compared to those on Cu(3 1 1) and Cu(1 1 1). The activation energy for oxide growth on Cu(1 0 0) and Cu(1 1 0) was calculated to be the highest while that on Cu(3 1 1) was the lowest.