Surface-Enhanced Hyper-Raman Spectroscopy

Abstract

Hyper-Raman scattering (HRS), first theoretically predicted by Decius and Rauch in 1959 [l] and experimentally demonstrated by Terhune et al. in 1965 [2], is a nonlinear optical process involving two incident photons (ω₀) and one emitted photon (ω). The emitted hyper- Raman photon frequencies are Raman-shifted relative to the second harmonic frequency (2ω₀) of the incident laser radiation [3–6]. The energy difference (2ω₀ – w) corresponds to one of the characteristicvibrational frequencies of the scattering medium or molecule. In Fig. 1 is given a schematic illustration of resonant and nonresonant HRS. The primary advantage of this nonlinear optical technique lies in its more relaxed selection rules compared with IR and Raman [7,8]. AlllR-active vibrational modes are hyper-Raman allowed, and those modes inactive in both IR and Raman (i.e., the “silent” modes) may be active in hyper-Raman scattering.     

Perturbative analysis of possible failures in the traditional adiabatic conditions

The breakdown of adiabatic approximation, demonstrated by Marzlin and Sanders [K.-P. Marzlin, B.C. Sanders, Phys. Rev. Lett. 93 (2004) 160408] and Tong et al. [D.M. Tong, et al., Phys. Rev. Lett. 95 (2005) 110407] for time-evolving “inverse” systems, is traced to the appearance of some nonzero terms in a perturbational treatment and is related to two time scales in the “inverse” systems' Hamiltonian. New adiabatic conditions of Ye et al. [M.-Y. Ye, et al., quant-ph/0509083] can restore the theoretical consistency.     

Phase transitions of sulfur at high pressure: Influence of temperature and pressure environment

Abstract

Phase transitions of orthorhombic sulfur were investigated above 10 GPa by Raman spectroscopy using red light excitation. Transitions into several phases that have been reported in previous studies using green light excitation, are confirmed. The phase behaviour is observed to depend strongly on the preparation method. In the presence of a pressure transmitting medium (methanol/ethanol, 4:1), a sequence of phases α-S₈ → [intermediate phase (“ip”) + S₆] → [S₆ + high pressure-low temperature phase (“hplt”)] is described and characterized. Without the use of a pressure transmitting medium, the phase sequence α-S₈ → [“ip” + “hplt”] + “hplt” is observed. In addition, contributions of amorphous sulfur are detected around 10 GPa, i.e. at pressures below the transformation of α-S₈ into the above-mentioned phases. Characteristic Raman spectra of the different phases are extracted and documented over a wide pressure range.     

On the rotation of non-epitaxy crystallites on single crystal substrate

The experimental results of Masson et al. [Surf. Sci. 27 (1971) 463] were further interpreted with regard to the rotation behavior of non-epitaxy Au crystallites on a KCl(100) substrate, which developed into primary epitaxy ([111]_Au 6 [100]_KCl; [11̄0]_Au 6 [010]_KCl), and “second” epitaxy (in fact [100]_Au 6 [100]_KCl; [010]_Au 6 [010]_KCl and [100]_Au 6 [100]_KCl; [010]_Au 6 [011]_KCl) upon annealing at 94°C. These epitaxy orders were clarified to be nonsequential events on the basis of the development of electron diffractions (220), (111) and (200) of Au. The “second” epitaxy can be attributed to the later formation of a (100)_Au|(100)_KCl contact in comparison with the preferred (111)_Au|(100)_KCl contact in the as-deposited state. The Au crystallites with irrational contact plane should have rotated and changed shape before bifurcating into (111)_Au|(100)_KCl and (100)_Au|(100)_KCl contact, upon which viscous rotation was still feasible, until the primary and “second” epitaxy were reached, respectively.     

Supersonic Turbulent Boundary Layer： DNS and RANS

We assess the performance of a few turbulence models for Reynolds averaged Navier-Stokes （RANS） simulation of supersonic boundary layers, compared to the direct numerical simulations （DNS） of supersonic flat-plate turbulent boundary layers, carried out by Gao et al. [Chin. Phys. Lett. 22（2005）1709] and Huang et al. [Sci. Chin. 48 （2005） 614], as well as some available experimental data. The assessment is made for two test cases, with incoming Mach numbers and Reynolds numbers M = 2.25, Re = 365, 000//in, and M = 4.5, Re = 1.7 × 10^7/m, respectively. It is found that in the first case the prediction of RANS models agrees well with the DNS and the experimental data, while for the second case the agreement of the DNS models with experiment is less satisfactory. The compressibility effect on the RANS models is discussed.     

Theory of the Half-integer Quantum Hall Effect in Graphene

The unusual quantum Hall effect (QHE) in graphene is described in terms of the composite (c-) bosons, which move with a linear dispersion relation. The “electron” (wave packet) moves easier in the direction [1 1 0 c-axis] ≡ [1 1 0] of the honeycomb lattice than perpendicular to it, while the “hole” moves easier in [0 0 1]. Since “electrons” and “holes” move in different channels, the particle densities can be high especially when the Fermi surface has “necks”. The strong QHE arises from the phonon exchange attraction in the neighborhood of the “neck” surfaces. The plateau observed for the Hall conductivity and the accompanied resistivity drop is due to the superconducting energy gap caused by the Bose-Einstein condensation of the c-bosons, each forming from a pair of one-electron–two-fluxons c-fermions by phonon-exchange attraction. The half-integer quantization rule for the Hall conductivity: (1/2)(2P?1)(4e²/h), P=1,2,..., is derived.     

Comments on “Rigorous bounds on the radiative interaction between real gases and scattering particles” by D. G. Goodwin and J. L. Ebert

Claims are made by Goodwin and Ebert that the work by Skocypec and Buckius¹ is “erroneous.” This claim is shown to be inappropriate and incorrect. The analytical technique, exact results and charted solutions as presented in Ref. [1] are correct and the claims by Goodwin and Ebert² are not legitimate. The form of the presentation of the charted solutions in Ref. [1]is misleading and results are presented in this paper to interpret these charted solutions more fairly. These results predict the interaction of gaseous emission with scattering and the bounds are in qualitative agreement with that obtained by standard spectral analysis. The spectral analysis presented in Ref. [2]has been available in the literature for some time. To be able to predict radiative heat transfer in a real gas and scattering medium (not only predict the maximum interaction), detailed real gas and scattering analyses as presented in Ref. [1] are required since total real gas effects are accurately modeled.     

Computer Retrieval of Spectral Data

Abstract

In the last few years the empirical interpretation of a spectrum and the quality of information gained from it can be sufficient for the demands of contemporary chemistry. The overall progress in computerization of chemistry and particularly the development of a new scientific discipline-chemical informatics [1]-allows one to apply a new approach of spectra explanation known as computer retrieval of spectral data. Here the usual meaning of “retrieval” is extended to the disclosure of abstract information hidden in various spectral curves.     

Anisotropy of L X-rays of Uranium and Thorium

INTRODUCTION

The theoretical calculations by Flugge et a1 [l] have shown that the Xrays originating from the states corresponding to J=1/2(K shell and L_I, L_II, M_I, M_II subshell etc.) are emitted to be isotropic and those corresponding to state J=5/2(e.g. Mv subshell) are emitted to be anisotropic in their spatial distribution. There are many studies on L X-ray intensity ratios. But there is little reported on isotropy and anisotropy of L X-rays. Kahlon et a1 [2,3] investigated isotropy and anisotropy of L X-rays. We investigated the anisotropy of L shell X-rays in Au and Hg [4] and the angular dependence of differential cross-sections of L X-rays from Hg, T1 and Pb [5].     

Influence of the inverse sheath on divertor plasma performance in tokamak edge plasma simulations

Recently, it was shown that strong electron thermionic emission from material walls could result in the formation of an “inverse sheath,” which prevents the flow of cold ions to the wall.^[1–3] Such regimes look very favourably from the point of view of plasma–material interactions at the edge of magnetic fusion devices, where the problem of the erosion of plasma-facing components under ion irradiation is one of the key issues for the development of future magnetic fusion reactors. However, it is not clear whether such regimes are compatible with edge plasma parameters and heat removal requirements in fusion reactors. To address the issue of practicality of the “inverse sheath” regime for edge tokamak plasma conditions, we perform a set of numerical simulations with 2D edge plasma transport code UEDGE^[4] for a DIII-D-like geometry and magnetic configuration. To describe both “standard” and “inverse sheath” conditions within the framework of the UEDGE code (which does not consider the sheath region per se), at the material surfaces, we apply effective boundary conditions that emulate both “standard” and “inverse sheath” regimes. We demonstrate that, for the same input parameters, spatial distributions of edge plasma parameters corresponding to detached divertor and “inverse sheath” regimes are similar, with only a few minor differences. We discuss the compatibility of “inverse sheath” regimes with core plasma parameters.     

NMR Studies of Crowded Diels–Alder Adducts of Phencyclone with N‐(2,6‐Dialkylphenyl)maleimides. Hindered Rotations and Magnetic Anisotropy

Abstract

Phencyclone, 1, reacted with N‐(2,6‐dimethylphenyl)maleimide, 2a; with N‐(2,6‐diethylphenyl)maleimide, 2b; and with N‐(2,6‐diisopropylphenyl)maleimide, 2c, respectively, to yield the corresponding Diels–Alder adducts, 3a–c. The adducts were extensively characterized by NMR (7 T) at ambient temperatures using one‐ and two‐dimensional (1D and 2D) proton and carbon‐13 techniques for assignments. Slow exchange limit (SEL) spectra were observed, demonstrating slow rotations on the NMR timescales, for the unsubstituted bridgehead phenyl groups [C(sp³)–C(aryl sp²) bond rotations] and for the 2,6‐dialkylphenyl groups [N(sp²)–C(aryl sp²) bond rotations]. Substantial magnetic anisotropic shifts were seen in the adducts. For example, in the N‐(2,6‐dialkylphenyl) moieties of the adducts, one of the alkyl groups is directed “into” the adduct cavity, toward the phenanthrenoid portion, and these “inner” alkyl proton NMR signals were shifted upfield. Thus, in CDCl₃, the “inner” methyl of adduct 3a exhibits a proton resonance at ?0.13 ppm, upfield of tetramethylsilane (TMS); the “inner” ethyl group signals from 3b appear at 0.026 ppm (CH₂, quartet), and ?0.21 ppm (CH₃, triplet); and the “inner” isopropyl group from 3c is seen at ?0.06 ppm (methine, approx. septet) and ?0.39 ppm (CH₃, doublet). Proton NMR of the crude N‐(2,6‐dialkylphenyl)maleamic acids (used as precursors of the maleimides, 2a–c) exhibited two sets of AB quartet signals, suggesting possible conformers from hindered rotation in the amide groups about the HN–C?O bonds.     

Uplifting the Iwasawa

The Iwasawa manifold is uplifted to seven‐folds of either G₂ holonomy or SU(3) structure, explicit new metrics for the same having been constructed in this work. We uplift the Iwasawa manifold to a G₂ manifold through “size” deformation (of the Iwasawa metric), via Hitchin's Flow equations, showing also the impossibility of the uplift for “shape” and “size” deformations (of the Iwasawa metric). Using results of Dall'Agata and Prezas, Phys. Rev. D 69 , 066004 (2004) [arXiv:hep‐th/0311146] [1], we also uplift the Iwasawa manifold to a 7‐fold with SU(3) structure through “size” and “shape” deformations via generalisation of Hitchin's Flow equations. For seven‐folds with SU(3)‐structure, the result could be interpreted as M5‐branes wrapping two‐cycles embedded in the seven‐fold (as in [1]) ‐ a warped product of either a special hermitian six‐fold or a balanced six‐fold with the unit interval. There can be no uplift to seven‐folds of SU(3) structure involving non‐trivial “size” and “shape” deformations (of the Iwasawa metric) retaining the “standard complex structure” ‐ the uplift generically makes one move in the space of almost complex structures such that one is neither at the standard complex structure point nor at the “edge”. Using the results of Konopelchenko and Landolfi, J. Geom. Phys. 29 , 319 (1999) [arXiv:math.DG/9804144] [2], we show that given two “shape deformation” functions, and the dilaton, one can construct a Riemann surface obtained via Weierstraß representation for the conformal immersion of a surface in R ^l, for a suitable l, with the condition of having conformal immersion being a quadric in CP ^l‐1.     

A Benzothiazole-Based Fluorescence Turn-on Sensor for Copper(II)

A new benzothiazole-based chemosensor BTN (1-((Z)-(((E)-3-methylbenzo[d]thiazol-2(3H)-ylidene)hydrazono)methyl)naphthalen-2-ol) was synthesized for the detection of Cu²⁺. BTN could detect Cu²⁺ with “off-on” fluorescent response from colorless to yellow irrespective of presence of other cations. Limit of detection for Cu²⁺ was determined to be 3.3 μM. Binding ratio of BTN and Cu²⁺ turned out to be a 1:1 with the analysis of Job plot and ESI-MS. Sensing feature of Cu²⁺ by BTN was explained with theoretical calculations, which might be owing to internal charge transfer and chelation-enhanced fluorescence processes.

     

Rietveld analysis of high pressure powder diffraction data

Abstract

X-ray and neutron powder diffraction data obtained from samples contained within high pressure cells are generally of lower quality than data collected from samples at ambient conditions. The far smaller sample size as well as possible contamination of the pattern by the pressure cell means that Rietveld refinement techniques must be adapted to extract the maximum useful information from the data. These problems become paramount as larger structures at high pressure are attempted. Techniques such as “leBail extraction”, “soft restraints” and “rigid body refinement” will be discussed with application to analysis of high pressure neutron powder diffraction data.     

Isotope shifts in Sm II and changes in mean-square nuclear charge radii of the stable even Sm isotopes

Isotope shifts have been measured in Sm II from which the shifts between pure configurations 4f ⁶ s and 4f ⁶5d can be determined. The specific mass shift for such a “transition” was estimated to be (?1±2)mK for a change of two neutrons. The values derived for the change in the nuclear charge distribution,δ〈r ²〉, are in good agreement with the results obtained from isotope shift measurements in Sm I (H. Brand et al.: J. Phys. B11, L99, 1978). The weighted mean values representing the best information onδ〈r ²〉 presently available are in fm²: [144, 148] 0.488(23); [148, 150] 0.285(14); [150, 152] 0.400(19); [152, 154] 0.217(11).     

Reply to “A comment on “A test of general relativity using the LARES and LAGEOS satellites and a GRACE Earth gravity model,by I. Ciufolini et al.””

In 2016, we published “A test of general relativity using the LARES and LAGEOS satellites and a GRACE Earth’s gravity model. Measurement of Earth’s dragging of inertial frames [1]”, a measurement of frame-dragging, a fundamental prediction of Einstein’s theory of General Relativity, using the laser-ranged satellites LARES, LAGEOS and LAGEOS 2. The formal error, or precision, of our test was about 0.2% of frame-dragging, whereas the systematic error was estimated to be about 5%. In the 2017 paper “A comment on “A test of general relativity using the LARES and LAGEOS satellites and a GRACE Earth’s gravity model by I. Ciufolini et al.”” by L. Iorio [2] (called I2017 in the following), it was incorrectly claimed that, when comparing different Earth’s gravity field models, the systematic error in our test due to the Earth’s even zonal harmonics of degree 6, 8, 10 could be as large as 15%, 6% and 36%, respectively. Furthermore, I2017 contains other, also incorrect, claims about the number of necessary significant decimal digits of the coefficients used in our test (claimed to be nine), in order to eliminate the largest uncertainties in the even zonals of degree 2 and 4, and about the non-repeatability of our test. Here we analyze and rebut those claims in I2017.     

Determination of the phonon spectrum from coherent neutron scattering by polycrystals

As proposed by Bredovet al. [2, 3] the phonon spectrum can be obtained approximately from coherent neutron scattering by polycrystals if suitable averages over scattering angles are considered. The accuracy of this method is estimated by comparison with analytical results for simple lattice models (discussed here in particular for Aluminium). The errors are about 5% for low order moments and about 50% near van Hove singularities for “cold” neutrons (wavelength of the order of the nearest-neighbour-distance).     

Technical Reports: Scaling Laws in High-temperature Superconductors as Revealed Through Infrared Spectroscopy

Superconductivity refers to a fascinating state of matter where the electrical resistivity is precisely zero. Originally discovered in elemental metals such as mercury and tin in the early part of the last century, the mechanism of superconductivity was elusive and nearly 50 years passed before a comprehensive theory for superconductivity in metals was proposed by Bardeen, Cooper and Schrieffer [1] (the “BCS” theory). In a normal metal, the resistivity is determined by the elastic scattering of carriers. However, when a metal becomes a superconductor, the charge carriers are no longer single electrons, but rather pairs of electrons (“Cooper pairs”), which are bound together by a phonon interaction (phonons are the vibrations of the atomic lattice), and flow without resistance.     

On the anomalon interpretation of40Ar + Cu collisions at 0.9 and 1.8 A GeV

The paper of Dersch et al. [1], concerning the results of inelastic⁴⁰Ar + Cu collisions at 1.8 and 0.9 GeV per nucleon, is discussed. The authors have explained their experimental results on the basis of the concept of anomalons of a lifetime of ～2·10^?10 s and/or as “inconsistency with known nuclear physics”. It is shown that such conclusions are untenable, and the data presented in the cited paper can be explained within the frame of known physics.     

Application of ICP-AES to Analysis of Solutions

Introduction

One of the key responsibilities of modern analytical scientists is “solving problems,” or “troubleshooting.” As a matter of fact, this is the most attractive reason for us to enter this field. “Problems” can arise in research, development, production, technical services, regulatory requirements (such as EPA or FDA), litigation, and many other areas [l]. The role of the analytical chemist in industry, quality assurance, methods and technique development, troubleshooting (also called “firefighting”), research or science resource, and miscellaneous analytical roles is described in an extremely interesting report entitled “Analytical Chemistry in Industry” [2].