Development of a small X-ray source using an ultraviolet laser and pyroelectric crystal

We investigate a miniaturized X-ray source using an ultraviolet (UV) laser and a pyroelectric crystal and discuss potential applications in medicine. The UV laser is the fourth harmonic of a Nd:YAG laser with a wavelength of 266 nm, repetition rate of 10 Hz, and pulse energy of 40 mJ. The pyroelectric crystal is a LiNbO₃ cylinder of diameter 10 mm and length 6 mm. The prototype X-ray source we fabricated is an aluminum parallelepiped of dimensions 3 × 3 × 5 cm. The X-ray count rate of the X-ray source is maximized at approximately 1,400 cps for UV laser irradiation of approximately 5 min. After 30 min of irradiation by the UV laser, the temperature of the pyroelectric crystal rose from 295 K to 312 K. The principles of X-ray generation ensure that X-ray sources using UV lasers and pyroelectric crystals offer ample opportunity for miniaturization. We believe the X-ray source developed in this work is suitable for medical applications, although further study is needed to address points such as increasing the X-ray count rate and adjusting the temperature of the pyroelectric crystal.     

Controlled dynamics at an avoided crossing interpreted in terms of dynamically fluctuating potential energy curves

The nonadiabatic nuclear wavepacket dynamics on the coupled two lowest (1)Σ(+) states of the LiF molecule under the action of a control pulse is investigated. The control is achieved by a modulation of the characteristics of the potential energy curves using an infrared field with a cycle duration comparable to the time scale of nuclear dynamics. The transition of population between the states is interpreted on the basis of the coupled nuclear wavepacket dynamics on the effective potential curves, which are transformed from the adiabatic potential curves with use of a diabatic representation that diagonalizes the dipole-moment matrix of the relevant electronic states. The basic feature of the transition dynamics is characterized in terms of the notion of the collision between the dynamical crossing point and nuclear wavepackets running on such modulated potential curves, and the transition amplitude is mainly dominated by the off-diagonal matrix element of the time-independent electronic Hamiltonian in the present diabatic representation. The importance of the geometry dependence of the intrinsic dipole moments as well as of the diabatic coupling potential is illustrated both theoretically and numerically.     

Quantification of end groups in polystyrenes by pyrolysis–gas chromatography

The determination of end groups in polystyrenes (PSts) polymerized anionically with n-butyllithium as the initiator was carried out by pyrolysis-gas chromatography (Py-GC). The relative proportions of the end groups decrease with increasing molecular weight (MW). Consequently, the peaks which reflect the structure of the end groups can be distinguished by comparing pyrograms of samples with different MW. By comparing the intensities of these peaks relative to total intensities of all the peaks in the pyrogram, the numberaverage molecular weight (M_n) of the polymer can be estimated. The observed M_n values of PSts estimated by this method are compared with those determined by size exclusion chromatography (SEC). By this method it was possible to make direct determination of M_n values of PSts with MWs between 1000 and ca. 1 million. Furthermore, the calibration curve produced by the relative intensity of one of the most characteristic peaks (2-phenyl-1-heptene; C₄H₉? CH₂C (Ph) = CH₂) for the end group to total intensity of all the peaks in the pyrogram, gave rapid and highly reproducible M_n values. © 1994 John Wiley & Sons, Inc.     

Microwave and millimeter-wave spectroscopy of the open-shell van der Waals complex Ar-HO2

Pure rotational transitions of a rare gas atom-reactive open-shell triatom van der Waals complex Ar-HO2 have been observed by Fourier transform microwave spectroscopy. The transitions observed are of a type with K(a) = 0 and 1. Furthermore, by monitoring the change of the free induction decay signal of the a-type transitions, b-type transitions have been observed by a double resonance technique in the region 18-49 GHz. All these transitions provide us precise molecular constants. The r0 structure of Ar-HO2 has been determined by fixing the structure of the HO2 monomer. The determined structure is planar and almost T shaped, where the argon atom is slightly shifted to the hydrogen atom of HO2. The experimental data supplemented by high-level ab initio calculations indicate that the van der Waals bond of Ar-HO2 is relatively rigid. On the other hand, effects on the unpaired electron distribution by the complex formation are found to be fairly small, since the fine and hyperfine constants of Ar-HO2 are well explained by those of the HO2 monomer.     

Enhancement of the Catalytic Activity of Chiral H8‐BINOL Titanium Complexes by Introduction of Sterically Demanding Groups at the 3‐Position

The activity of chiral titanium catalysts derived from H₈‐BINOL ligands in the enantioselective arylation of an aldehyde with PhTi(OiPr)₃ is significantly enhanced by an increase of the size of the substituent at the 3‐position. High enantioselectivity (> 90 % ee) can be obtained even at a substrate/catalyst ratio (S/C) of 800 for DTBP‐H₈‐BINOL (DTBP=3,5‐di‐tert‐butylphenyl) and DAP‐H₈‐BINOL (DAP=3,5‐di(9‐anthraceny)phenyl). These titanium catalysts are successfully applied to the enantioselective arylation and heteroarylation of aldehydes at a S/C ratio of 400 by using organotitanium reagents generated in situ from bromide precursors. The remarkable weakening of the intramolecular aggregation of the two ?Ti(OiPr)₃ units in a DPP‐H₈‐BINOL (DPP=3,5‐diphenylpheny)‐derived bis‐titanium complex is revealed by X‐ray and variable‐temperature (VT)‐NMR studies. Based on these observations, a catalytic cycle, involving the rate‐limiting aryl group transfer followed by aldehyde complexation and enantioselective arylation, is proposed to account for the high activity of the 3‐substituted H₈‐BINOL catalyst system.     

Rotational spectrum and hydrogen bonding of the H2O-HO radical complex

The first spectroscopic identification of the H2O-HO radical complex in the gas phase has been conducted by utilizing pulsed-discharge nozzle Fourier transform microwave spectroscopy. R-branch transitions in the Ka = 0 manifold appeared as in Hund's case (b), but extraordinarily large spin doubling implies a strong spin-orbit coupling between the electronic ground and low-lying excited states that correlate to the degenerate 2Pi state in free OH. The geometry of the complex is of C2v symmetry as a zero-point vibrational average, in which the OH radical acts as a proton donor to water. Precisely determined hyperfine coupling constants associated with hydrogen nuclei indicate a substantial rearrangement in unpaired electron distribution: there exists small but nonzero spin density on the H atoms in water.     

Microwave spectra of deuterated ethanes: Internal rotation potential function and rz structure

The microwave spectra of CH₃CHD₂ in the first excited torsional state and of CH₃CH₂D and CD₃CH₂D in the ground states have been observed by a source-modulation spectrometer and analyzed to determine the two potential constants, V₃ and V₆, simultaneously and also to assess the isotopic effects on the potential function. The results obtained for C₂H₆ are V₃ = 2.882 ± 0.010 and V₆ = 0.020 ± 0.010 kcal/mole. The staggered conformation in ethane was established by observing microwave spectra of gauche CH₂DCH₂D. The r_z structure of ethane was recalculated by adding precise rotational constants obtained in this work to previous microwave and infrared data.     

Dual-plane stereoscopic particle image velocimetry: system set-up and its application on a lobed jet mixing flow

 The technical basis and system set-up of a dual-plane stereoscopic particle image velocimetry (PIV) system, which can obtain the flow velocity (all three components) fields at two spatially separated planes simultaneously, is summarized. The simultaneous measurements were achieved by using two sets of double-pulsed Nd:Yag lasers with additional optics to illuminate the objective fluid flow with two orthogonally linearly polarized laser sheets at two spatially separated planes, as proposed by Kaehler and Kompenhans in 1999. The light scattered by the tracer particles illuminated by laser sheets with orthogonal linear polarization were separated by using polarizing beam-splitter cubes, then recorded by high-resolution CCD cameras. A three-dimensional in-situ calibration procedure was used to determine the relationships between the 2-D image planes and three-dimensional object fields for both position mapping and velocity three-component reconstruction. Unlike conventional two-component PIV systems or single-plane stereoscopic PIV systems, which can only get one-component of vorticity vectors, the present dual-plane stereoscopic PIV system can provide all the three components of the vorticity vectors and various auto-correlation and cross-correlation coefficients of flow variables instantaneously and simultaneously. The present dual-plane stereoscopic PIV system was applied to measure an air jet mixing flow exhausted from a lobed nozzle. Various vortex structures in the lobed jet mixing flow were revealed quantitatively and instantaneously. In order to evaluate the measurement accuracy of the present dual-plane stereoscopic PIV system, the measurement results were compared with the simultaneous measurement results of a laser Doppler velocimetry (LDV) system. It was found that both the instantaneous data and ensemble-averaged values of the stereoscopic PIV measurement results and the LDV measurement results agree well. For the ensemble-averaged values of the out-of-plane velocity component at comparison points, the differences between the stereoscopic PIV and LDV measurement results were found to be less than 2%. Received: 18 April 2000/Accepted: 2 February 2001