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Computational analysis of difference spectra between two analogous systems is a challenging issue, as reliable estimation of a tiny difference spectrum requires an extraordinary precision of the two original spectra. We have developed an alternative new method to calculate the difference spectra under background-free conditions, which greatly improved the efficiency of computation. In this paper, we report further improvement by using efficient parallel implementation and the time correlation formula based on time derivative quantities. As a consequence, the present work achieved further remarkable acceleration in the calculations of difference infrared and Raman spectra in the order of magnitude and thereby allowed us by analyzing these difference spectra at a practical cost of computation. [ABSTRACT FROM AUTHOR]

In this paper, a novel methodology is presented for the construction of ab initio effective rotation–vibration spectroscopic models from potential energy and dipole moment surfaces. Non-empirical effective Hamiltonians are obtained via the block-diagonalization of selected variationally computed eigenvector matrices. For the first time, the derivation of an effective dipole moment is carried out in a systematic way. This general approach can be implemented quite easily in most of the variational computer codes and turns out to be a clear alternative to the rather involved Van Vleck perturbation method. Symmetry is exploited at all stages to translate first-principles calculations into a set of spectroscopic parameters to be further refined on experiment. We demonstrate on H2CO, PH3, CH4, C2H4, and SF6 that the proposed effective model can provide crucial information to spectroscopists within a very short time compared to empirical spectroscopic models. This approach brings a new insight into high-resolution spectrum analysis of polyatomic molecules and will be also of great help in the modeling of hot atmospheres where completeness is important. [ABSTRACT FROM AUTHOR]

In continuation with Paper I [S. R. Reddy et al., J. Chem. Phys. 151, 054303 (2019)], the vibronic structure and dynamics of the 1 Σ u + electronic state of C15, C17, C19, and C21 chains in the coupled manifold of 1 Σ u + –1Πg–1Πu– 1 Σ g + electronic states have been investigated in this paper. The model vibronic Hamiltonian developed through extensive ab initio quantum chemistry calculations in Paper I is employed, and first principles nuclear dynamics calculations are carried out to obtain the photoabsorption band of the 1 Σ u + electronic state. Both time-independent and time-dependent quantum mechanical calculations are carried out to precisely locate the vibrational levels, assign them with the progression of vibrational modes, and elucidate the impact of both Renner-Teller and pseudo-Renner-Teller couplings on them. The nonradiative decay of the 1 Σ u + electronic state is studied, and it is found that the decay rate is comparable with the prediction made for them to be qualified as a carrier of diffuse interstellar bands in the literature. The theoretical results are found to be in good accord with the available experimental results. [ABSTRACT FROM AUTHOR]

To study the initiation and development of interfacial electrical damage in multi-layer dielectrics, an aging test of 3-layer polyimide films was conducted under pulsed voltage with a repetitive frequency of 500 Hz and a maximal amplitude of 30 kV. The variation in the damage morphology with the number of applied pulses was analyzed by a statistical method. The circuit current and partial discharge at different aging stages was measured, and the Fourier transform infrared spectrum analysis results of the aged and unaged sample regions were compared. The results demonstrate that the partial discharge in the dielectric interface gap, which is unavoidable in manufacturing, is the main cause of damage. It initiates from the interface and grows into the interior of the dielectric with the application of pulses. When there are no macroscopic defects on dielectric films, damage presents a punctiform morphology. The damage process can be divided into the following three stages: surface roughening damage, steady growth stage of damage points, and pre-breakdown stage. Differing from dielectrics without macroscopic defects, dielectrics with original void defects present transverse dendritic damage channels that initiate from the edge of the defect. [ABSTRACT FROM AUTHOR]

Mobility spectrum analysis (MSA) is a process of recovering the spectrum of carrier mobilities in an electronic material from a magnetic-field-dependent Hall measurement. This paper first presents a set of useful general properties of MSA that are true for all MSA methods. One such property is that Hall data can be classified as either "physical," with at least one spectrum of carrier mobilities that exactly fits the data, or "unphysical," where no mobility spectra exactly fit the data and the analysis must find approximate solutions. Almost all experimental Hall data collected at seven or more magnetic fields are slightly unphysical. The closest approximate solution for such unphysical data is always a set of discrete-carrier mobilities. A new method for multicarrier MSA is presented to display the likely properties of the discrete carriers as two-dimensional spectra vs both mobility and carrier density instead of one-dimensional spectra vs only mobility, as in previous methods. Measurement uncertainties are included as a fundamental part of the analysis so that the user can easily view the resultant uncertainty in the derived carrier properties. A separate method is also presented for reliably determining a smooth, high-entropy spectrum of carrier mobilities, which is constructed as the maximum-entropy linear combination of discrete-carrier solutions to the Hall data. An example using calculated Hall data corresponding to acoustic phonon scattering shows that the technique could potentially be used to measure the continuous mobility distributions that result from different scattering mechanisms. [ABSTRACT FROM AUTHOR]

Biocellulose or bacterial cellulose (BC) is a biocompatible (nano) material produced with a threedimensional network structure composed of microfibrils having nanometric diameters obtained by the Gluconacetobacter xylinus bacteria. BC membranes present relatively high porosity, allowing the incorporation or synthesis in situ of inorganic nanoparticles for multifunctional applications and have been used as flexible membranes for incorporation of magnetic nanocomposite. In this work, highly stable superparamagnetic iron oxide nanoparticles (SPION), functionalized with polyethylene glycol (PEG), with an average diameter of 5 nm and a saturation magnetization of 41 emu/g at 300K were prepared. PEG-Fe2O3 hybrid was dispersed by mixing a pristine BC membrane in a stable aqueous dispersion of PEG-SPION. The PEG chains at PEG-SPION's surface provide a good permeability and strong affinity between the BC chains and SPION through hydrogen-bonding interactions. PEG-SPION also allow the incorporation of higher content of nanoparticles without compromising the mechanical properties of the nanocomposite. Structural and magnetic properties of the composite have been characterized by XRD, SEM, energy-dispersive X-ray spectroscopy (EDX), magnetization, Raman spectroscopy, and magnetic force microscopy. [ABSTRACT FROM AUTHOR]

Surfaces and interfaces play important roles in many processes and reactions and are therefore intensively studied, often with the aim of obtaining molecular-level information from just the interfacial layer. Generally, only the first few molecular layers next to the interface are relevant for the surface processes. In the past decades, 2nd-order nonlinear spectroscopies including sum-frequency generation and second harmonic generation have developed into powerful tools for obtaining molecularly specific insights into the interfacial region. These approaches have contributed substantially to our understanding of a wide range of physical phenomena. However, along with their wide-ranging applications, it has been realized that the implied surface-specificity of these approaches may not always be warranted. Specifically, the bulk quadrupole contribution beyond the electric dipole-approximation for a system with a weak nonlinear interface signal, as well as the diffuse layer contribution at charged interfaces, could mask the surface information. In this perspective paper, we discuss the surface-specificity of 2nd-order nonlinear spectroscopy, especially considering these two contributions. [ABSTRACT FROM AUTHOR]

A detailed consideration of the discrete mobility-spectrum analysis (DMSA) method and its application to transport studies in HgCdTe is given. First, a brief review of the methods of the analysis of field dependences of the Hall coefficient and conductivity in HgCdTe-based structures with a multi-carrier mobility spectrum is presented. The advantages and drawbacks of these methods, which include original mobility-spectrum analysis by Beck and Anderson, multi-carrier fitting and iterative approach by Dziuba and Górska, and the later developments of these techniques, are considered. The properties of the envelope of the mobility spectrum are analyzed, and the specifics of DMSA are presented. Analysis of some magnetic-field B dependences of conductivity tensor components σxx(B) and σxy(B) presented in the literature is performed with DMSA, and the results are compared to those obtained with other methods. [ABSTRACT FROM AUTHOR]

To further improve the remaining useful life forecasting accuracy of fuel cells using classic deep learning models, a convolutional neural network combining bidirectional long and short-term memory networks (BiLSTM) and attention mechanism (AT) is optimized with the enhanced whale optimization algorithm (EWOA). Singular spectrum analysis preprocesses the attenuation data to eliminate noise and enhance its effective information; the CNN–BiLSTM model extracts spatiotemporal features and learns historical and future information; AT further explores the spatiotemporal correlation; and EWOA optimizes its hyperparameters to reduce human intervention error. Results demonstrate that, compared with long and short-term memory, CNN–LSTM, CNN–BiLSTM, CNN–BiLSTM–AT, and CNN–BiLSTM–AT optimized with other algorithms, the CNN–BiLSTM–AT model optimized with EWOA achieves lower root mean square error, mean absolute error, mean absolute percentage error, and relative errors of 0.1951%–0.2059%, 0.1267%–0.1538%, 0.0319%–0.0366%, and 0.026%–0.036%, respectively, with different training data. Importantly, the proposed model still maintains good prediction robustness with over 40% of the missing data. [ABSTRACT FROM AUTHOR]

In a recent paper [Aschi et al., ChemPhysChem 6, 53 (2005)], we characterized, by means of theoretical-computational procedures, the electronic excitation of water along the typical liquid state isochore (55.32 mol/l) for a large range of temperature. In that paper we were able to accurately reproduce the experimental absorption maximum at room temperature and to provide a detailed description of the temperature dependence of the excitation spectrum along the isochore. In a recent experimental work by Marin et al. [J. Chem. Phys. 125, 104314 (2006)], water electronic excitation energy was carefully analyzed in a broad range of density and temperature, finding a remarkable agreement of the temperature behavior of the experimental data with our theoretical results. Here, by means of the same theoretical-computational procedures (molecular dynamics simulations and the perturbed matrix method), we investigate water electronic absorption exactly in the same density-temperature range used in the experimental work, hence, now considering also the absorption density dependence. Our results point out that, (1) for all the densities and temperatures investigated, our calculated absorption spectra are in very good agreement with the experimental ones and (2) the gradual maxima redshift observed increasing the temperature or decreasing the density has to be ascribed to a real shift of the lowest X→A electronic transition, supporting the conclusions of Marin et al. [ABSTRACT FROM AUTHOR]

There is a growing concern within the surface science community that the massive increase in the number of XPS articles over the last few decades is accompanied by a decrease in work quality including in many cases meaningless chemical bond assignment. Should this trend continue, it would have disastrous consequences for scientific research. While there are many factors responsible for this situation, the lack of insight of physical principles combined with seeming ease of XPS operation and insufficient training are certainly the major ones. To counter that, we offer a comprehensive tutorial written in the form of a step-by-step guide starting from experimental planning, through sample selection and handling, instrument setup, data acquisition, spectra analysis, and results presentation. Six application examples highlight the broad range of research questions that can be answered by XPS. The topic selection and the discussion level are intended to be accessible for novices yet challenging possible preconceptions of experienced practitioners. The analyses of thin film samples are chosen for model cases as this is from where the bulk of XPS reports presently emanate and also where the author's key expertise lies. At the same time, the majority of discussed topics is applicable to surface science in general and is, thus, of relevance for the analyses of any type of sample and material class. The tutorial contains ca. 160 original spectra and over 290 references for further reading. Particular attention is paid to the correct workflow, development of good research practices, and solid knowledge of factors that impact the quality and reliability of the obtained information. What matters in the end is that the conclusions from the analysis can be trusted. Our aspiration is that after reading this tutorial each practitioner will be able to perform error-free data analysis and draw meaningful insights from the rich well of XPS. [ABSTRACT FROM AUTHOR]

The (sub-)millimeter wave spectrum of the non-rigid CH2OH radical is investigated both experimentally and theoretically. Ab initio calculations are carried out to quantitatively characterize its potential energy surface as a function of the two large amplitude ∠H1COH and ∠H2COH dihedral angles. It is shown that the radical displays a large amplitude torsional-like motion of its CH2 group with respect to the OH group. The rotation–torsion levels computed with the help of a 4D Hamiltonian accounting for this torsional-like motion and for the overall rotation exhibit a tunneling splitting, in agreement with recent experimental investigations, and a strong rotational dependence of this tunneling splitting on the rotational quantum number Ka due to the rotation–torsion Coriolis coupling. Based on an internal axis method approach, a fitting Hamiltonian accounting for tunneling effects and for the fine and hyperfine structure is built and applied to the fitting of the new (sub)-millimeter wave transitions measured in this work along with previously available high-resolution data. 778 frequencies and wavenumbers are reproduced with a unitless standard deviation of 0.79 using 27 parameters. The N = 0 tunneling splitting, which could not be determined unambiguously in the previous high-resolution investigations, is determined based on its rotational dependence. [ABSTRACT FROM AUTHOR]

This paper is devoted to the semiclassical analysis of the spectrum of the Dirichlet–Pauli operator on an annulus. We assume that the magnetic field is strictly positive and radial. We give an explicit asymptotic expansion at the first order of the lowest eigenvalues of this operator in the semiclassical limit. In particular, we exhibit the Aharonov–Bohm effect that has been revealed, for a constant magnetic field, in a recent paper by Helffer and Sundqvist. [ABSTRACT FROM AUTHOR]

This paper determines all the 13 elastic constants Cij of monoclinic β-Ga2O3, which has never been achieved since the discovery of this crystal about 100 years ago. We used resonant ultrasound spectroscopy with laser-Doppler interferometry, where the resonant-mode identification was unambiguously made by comparing measured and calculated displacement distributions on the vibrating specimen surface. Using more than 110 resonance frequencies, we inversely determined the Cij: C11 = 242.8 ± 2.9, C22 = 343.8 ± 3.8, C33 = 347.4 ± 2.5, C44 = 47.8 ± 0.2, C55 = 88.6 ± 0.5, C66 = 104.0 ± 0.5, C12 = 128 ± 0.1, C13 = 160 ± 1.5, C23 = 70.9 ± 2.1, C15 = –1.62 ± 0.05, C25 = 0.36 ± 0.01, C35 = 0.97 ± 0.03, and C46 = 5.59 ± 0.69 GPa. We also performed a density-functional-theory calculation and found that the local density approximation yields both the lattice parameters and Cij closer to the measurements than the generalized gradient approximation. Strong elastic-stiffness anisotropy is found in the diagonal elastic constants: C11 is smaller than C22 and C33 by ∼30%, and the difference between C44 and C66 exceeds 50%. Our measurements also reveal anomalous Poisson's ratios: ν21 and ν31 exceed 0.5, and ν23 and ν32 are almost zero. We explain these unusual elastic properties with the truss-like deformation of the tetrahedra-octahedra network and confirm this view with the ab- initio calculation. [ABSTRACT FROM AUTHOR]

This study explores the effects of wear and shaft-shape error defects on the tribo-dynamic responses of water-lubricated bearings under nonlinear propeller disturbance using a numerical model. The model proposed in this paper is verified by comparing the results from experiments and simulations in published studies. Numerical simulation studies reveal the effects of nonlinear propeller disturbance on the dynamic behavior and lubrication performance, such as hydrodynamic force, contact force, and journal trajectory, of the water-lubricated bearings with wear and shaft-shape errors. In addition, the effects of the critical factors for wear and shaft-shape errors, including wear depth, deviation angle, magnitude, and waviness order, on the tribo-dynamic responses of water-lubricated bearings are identified. The results of numerical spectrum analyses show that the nonlinear disturbance significantly affects the dynamic behavior (shown as the fluctuation range of the journal trajectory increases), and reasonable wear parameters can improve the lubrication performance of the water-lubricated bearing. Moreover, the effects of shaft-shape errors on the transient hydrodynamic force, contact force, film thickness, pressure, and journal trajectory are greater than that of wear. [ABSTRACT FROM AUTHOR]

The Robert-Bonamy formalism has been commonly used to calculate half-widths and shifts of spectral lines for decades. This formalism is based on several approximations. Among them, two have not been fully addressed: the isolated line approximation and the neglect of coupling between the translational and internal motions. Recently, we have shown that the isolated line approximation is not necessary in developing semi-classical line shape theories. Based on this progress, we have been able to develop a new formalism that enables not only to reduce uncertainties on calculated half-widths and shifts, but also to model line mixing effects on spectra starting from the knowledge of the intermolecular potential. In our previous studies, the new formalism had been applied to linear and asymmetric-top molecules. In the present study, the method has been extended to symmetric-top molecules with inversion symmetry. As expected, the inversion splitting induces a complete failure of the isolated line approximation. We have calculated the complex relaxation matrices of selfbroadened NH3. The half-widths and shifts in the ν1 and the pure rotational bands are reported in the present paper. When compared with measurements, the calculated half-widths match the experimental data very well, since the inapplicable isolated line approximation has been removed. With respect to the shifts, only qualitative results are obtained and discussed. Calculated off-diagonal elements of the relaxation matrix and a comparison with the observed line mixing effects are reported in the companion paper (Paper II). [ABSTRACT FROM AUTHOR]

High Energy Lasers (HELs) used for defense applications require operational distances ranging from few hundred meters to several kilometers. As the distance increases, the incident beam properties and, consequently, the anticipated effect delivered to the sample become less predictable. Therefore, the direct observation of the event induced by the laser can become an asset. In this paper, we propose a novel spectroscopic method that analyses in real time the spectral components present in the flames produced during the interaction of a HEL with a metallic piece at a long distance. This method was used on aluminum and carbon steel samples placed 200m away from the laser system. It was discovered that the aluminum and iron oxides created as a by-product of the HEL reaction with the samples emitted clear fingerprint signatures that could be detected remotely using a spectroscopic receiver placed beside the HEL beam director. The real-time assessment of the laser-induced effect can be achieved by monitoring the temporal evolution of the oxide signatures, hence providing information to the operator about the reaction and the nature of the sample illuminated. [ABSTRACT FROM AUTHOR]

Liquid water's rich sub-picosecond vibrational dynamics arise from the interplay of different highand low-frequency modes evolving in a strong yet fluctuating hydrogen bond network. Recent studies of the OH stretching excitations of H2O indicate that they are delocalized over several molecules, raising questions about whether the bending vibrations are similarly delocalized. In this paper, we take advantage of an improved 50 fs time-resolution and broadband infrared (IR) spectroscopy to interrogate the 2D IR lineshape and spectral dynamics of the HOH bending vibration of liquid H2O. Indications of strong bend-stretch coupling are observed in early time 2D IR spectra through a broad excited state absorption that extends from 1500 cm-1 to beyond 1900 cm-1, which corresponds to transitions from the bend to the bend overtone and OH stretching band between 3150 and 3550 cm-1. Pump-probe measurements reveal a fast 180 fs vibrational relaxation time, which results in a hot-ground state spectrum that is the same as observed for water IR excitation at any other frequency. The fastest dynamical time scale is 80 fs for the polarization anisotropy decay, providing evidence for the delocalized or excitonic character of the bend. Normal mode analysis conducted on water clusters extracted from molecular dynamics simulations corroborate significant stretch-bend mixing and indicate delocalization of δHOH on 2-7 water molecules. [ABSTRACT FROM AUTHOR]

Fluorescence spectra excited by laser pointers have been the subject of several papers in TPT. These papers all describe a fluorescence phenomenon in which the reflected laser light undergoes a change in color: this color change results from the combination of some partially reflected laser light and additional colors generated by fluorescent emission. Here we examine the fluorescence spectra of highlighter inks using green and violet laser pointers. We use an RSpec Explorer spectrometer to obtain spectra and compare the emission spectra of blue, green, yellow, orange, pink, and purple highlighters. The website Compound Interest details the chemical composition of highlighter inks; in addition, the site discusses how some base dye colors can be combined to produce the variety commercially available colors. Spectra obtained in this study were qualitatively consistent with the Compound Interest site. We discuss similarities and differences between various highlighter colors and conclude with the relevance of such studies to physics students. [ABSTRACT FROM AUTHOR]

Time-resolved spectroscopy that uses more than one incoherent excitation, and thus has multiple periods of time evolution, is becoming more common. A recent example is multiple population-period transient spectroscopy (MUPPETS), which is implemented as a high-order transient grating. In this paper, a formalism is developed to treat these types of incoherent spectroscopy in a manner that parallels the Liouville-pathway formalism used to treat multidimensional coherent spectroscopy. A Hilbert space of incoherent (population) states is defined and general expressions for transition and time-evolution operators acting on these states are derived from the corresponding quantum operators. This formalism describes incoherent experiments that involve an arbitrary number of temporal dimensions in terms of pathways through the Hilbert space. Each pathway is associated with a multiple-time rate-correlation function. Previous work has shown that these multiple-time correlation functions can measure heterogeneity in electronic-relaxation rates. Thus, they are an analog of coherent “echo” experiments, which measure heterogeneity in frequencies. We show that similar “MUPPETS echo” experiments can be done on any incoherent variable. For a dilute molecular solute, the Hilbert-space method leads to a systematic treatment of multidimensional transient gratings. The extension of irreducible-tensor methods to the incoherent Hilbert space results in a classification of orientational gratings of arbitrary order. The general methods developed in this paper are applied more specifically to single-photon, dipole transitions in the following paper. [ABSTRACT FROM AUTHOR]

For coherent Raman spectroscopies, common femtosecond pulses often lie in an intermediate regime: their bandwidth is too wide for measurements in the frequency domain, but their temporal width is too broad for homodyne measurements in the time domain. A recent paper [S. Nath et al., Phys. Rev. Lett. 97, 267401 (2006)] showed that complete Raman spectra can be recovered from intermediate length pulses by using simultaneous time and frequency detection (TFD). Heterodyne detection and a phase-stable local oscillator at the anti-Stokes frequency are not needed with TFD. This paper examines the theory of TFD Raman in more detail; a companion paper tests the results on experimental data. Model calculations illustrate how information on the Raman spectrum is transferred from the frequency domain to the time domain as the pulse width shortens. When data are collected in both dimensions, the Raman spectrum is completely determined to high resolution, regardless of the probe pulse width. The loss of resolution in many femtosecond coherent Raman experiments is due to the restriction to one-dimensional data collection, rather than due to a fundamental restriction based on the pulse width. [ABSTRACT FROM AUTHOR]

The preceding paper showed that, in principle, a high-resolution coherent Raman spectrum can be recovered using femtosecond probe pulses by combined detection in both time and frequency. This measurement is possible even when the pulses are too broad in frequency for conventional frequency-domain spectroscopy and too broad in time for conventional time-domain spectroscopy. In this paper, the method is tested on experimental coherent anti-stokes Raman spectroscopy data from acetonitrile. Compared to theoretical models, experimental data are complicated by noise and incomplete knowledge of the pulse structure. Despite these complications, most of the information in the Raman spectrum is recovered from the data: weak transitions are detected and natural-linewidth resolution is achieved across an 800 cm-1 spectral range. However, circumstances in which experimental limitations result in missed features or ambiguities in the recovered spectrum are also identified. These results suggest where improvements in measurement and data analysis can be made. [ABSTRACT FROM AUTHOR]

The tissue equivalent proportional counter (TEPC) is often used in the measurement of ionizing radiation. However, there are many factors that can cause the micro-dose spectrum's distortion and affect the accuracy of the measurement. In the TEPC design process, several factors can be analyzed through simulation methods. The simulation capabilities of the TEPC physical process are established and verified in this paper. The wall material, tissue equivalent gas, and electrode are selected as the main objects, and the corresponding design choices are given. The wall material has a great impact on the spectrum, and y ¯ F and y ¯ D show that A-150 plastic is closer to the human tissue in the TEPC physical process simulation. Both the two tissue equivalent gases have good simulation accuracy. After further analysis, propane-based equivalent gas is the better choice. Among the three electrode sizes, the size of 0.006 35 cm is the most suitable one for TEPC. The analysis results and analysis methods can provide references for the important elements design of TEPC. [ABSTRACT FROM AUTHOR]

In this paper, we present new insight in the degradation and subsequent recovery of charge carrier lifetime upon light soaking at 75 °C observed in float-zone silicon wafers. Variations of doping type, dielectric passivation schemes and thermal treatments after layer deposition were performed. The degradation was only observed for p-type float-zone silicon wafers passivated with passivation schemes involving silicon nitride layers. An influence of thermal treatments after deposition was found. N-type wafers did not degrade independent of their passivation scheme. Room temperature re-passivation experiments showed the degradation to affect the wafer bulk, and photoluminescence studies demonstrated fine lateral striations of effective lifetime. We conclude that the degradation is caused by bulk defects that might be related to hydrogen complexes. [ABSTRACT FROM AUTHOR]

It has been extensively demonstrated through first principles quantum mechanics calculations that water exhibits strong hydrogen bond cooperativity. Equations of state developed from statistical mechanics typically assume pairwise additivity, meaning they cannot account for these 3-body and higher cooperative effects. In this paper, we extend a second order thermodynamic perturbation theory to correct for hydrogen bond cooperativity in 4 site water. We demonstrate that the theory predicts hydrogen bonding structure consistent spectroscopy, neutron diffraction, and molecular simulation data. Finally, we implement the approach into a general equation of state for water. [ABSTRACT FROM AUTHOR]

In this paper, we focus on the relaxation dynamics of Sierpinski hexagon fractal polymer. The relaxation dynamics of this fractal polymer is investigated in the framework of the generalized Gaussian structure model using both Rouse and Zimm approaches. In the Rouse-type approach, by performing real-space renormalization transformations, we determine analytically the complete eigenvalue spectrum of the connectivity matrix. Based on the eigenvalues obtained through iterative algebraic relations we calculate the averaged monomer displacement and the mechanical relaxation moduli (storage modulus and loss modulus). The evaluation of the dynamical properties in the Rousetype approach reveals that they obey scaling in the intermediate time/frequency domain. In the Zimm-type approach, which includes the hydrodynamic interactions, the relaxation quantities do not show scaling. The theoretical findings with respect to scaling in the intermediate domain of the relaxation quantities are well supported by experimental results. [ABSTRACT FROM AUTHOR]

A novel material, ZrScW2PO12, with negative thermal expansion (NTE) behavior, at least from 138 to 1300 K, and intense photoluminescence (PL) property is first reported in this paper. Temperature dependent Raman and PL spectral studies indicate that the material holds an orthorhombic structure down to about 74K and exhibits NTE property in the temperature range. The intense PL covering nearly the whole visible region was observed and can be deconvoluted into four bands, which present different shifts with elevation of temperature. The abundant optical property may be attributed to n- and p-type like co-doping effect and the specific structure with the abnormal thermal expansion property of the material. The integrated properties might suggest potential applications of this material in light emitting diodes and other light emitting devices. [ABSTRACT FROM AUTHOR]

Resonance-enhanced multiphoton ionization (REMPI) is a widely used technique for studying molecular photoionization and producing molecular cations for spectroscopy and dynamics studies. Here, we present a model for describing hyperfine-structure effects in the REMPI process and for predicting hyperfine populations in molecular ions produced by this method. This model is a generalization of our model for fine- and hyperfine-structure effects in one-photon ionization of molecules presented in Paper I [M. Germann and S. Willitsch, J. Chem. Phys. 145, 044314 (2016)]. This generalization is achieved by covering two main aspects: (1) treatment of the neutral bound-bound transition including the hyperfine structure that makes up the first step of the REMPI process and (2) modification of our ionization model to account for anisotropic populations resulting from this first excitation step. Our findings may be used for analyzing results from experiments with molecular ions produced by REMPI and may serve as a theoretical background for hyperfine-selective ionization experiments. [ABSTRACT FROM AUTHOR]

With the Hamiltonian derived in the preceding paper and the ab initio potentials of T. Bürgi, S. Graf, S. Leutwyler, and W. Klopper [J. Chem. Phys. 103, 1077 (1995)] and of J. G. C. M. van Duijneveldt-van de Rijdt and F. B. van Duijneveldt [Chem. Phys. Lett. 237, 560 (1995)], we calculate the pseudo-rotation tunneling levels in a rotating water trimer. The internal motions are treated by a three-dimensional discrete variable representation and the Coriolis coupling with the overall rotation is included. Also the effects of donor tunneling are included, by introducing semi-empirical coupling matrix elements. New experimental data are presented for the c-type band at 87.1 cm-1 in (H2O)3, which show that specific levels in the donor tunneling quartets of this band are further split into doublets. With the results of our quantitative calculations and the model of the preceding paper we can understand the mechanisms of all the splittings observed in the earlier high-resolution spectra of (H2O)3 and (D2O)3, as well as these new splittings, in terms of pseudo-rotation tunneling, donor tunneling and Coriolis coupling. An unambiguous assignment is given of all the bands observed and analyzed. The ab initio potential of the Van Duijneveldts yields accurate energies of the lower pseudo-rotation levels, the potential of Bürgi et al. performs better for the higher levels. With our analysis we can deduce from the spectra that donor tunneling involves inversion of the trimer. © 1996 American Institute of Physics. [ABSTRACT FROM AUTHOR]

Thermal stability of optical near field transducers is an important issue for heat-assisted magnetic recording (HAMR), which affects HAMR system lifetime. In this paper, dark-field scattering spectroscopy was used to study the stability of nanometer-scaled Au lollipop transducers that were subjected to thermal annealing. Variation in relative peak intensity and red-shifting in peak position can be observed in scattering spectra for transducer after annealing. Based on the optical characterizations on Au thin films and calculations of Mie scattering by finite-difference time domain simulations, the measured changes in transducer scattering properties can reflect annealing-induced variations in optical properties and dimensional feature size for the Au lollipop transducer. Dark-field scattering spectroscopy can be a promising method to examine HAMR near field transducer thermal stability. [ABSTRACT FROM AUTHOR]

Destructive quantum interference in single molecule electronics is an intriguing phenomenon; however, distinguishing quantum interference effects from generically low transmission is not trivial. In this paper, we discuss how quantum interference effects in the transmission lead to either low current or a particular line shape in current-voltage curves, depending on the position of the interference feature. Second, we consider how inelastic electron tunneling spectroscopy can be used to probe the presence of an interference feature by identifying vibrational modes that are selectively suppressed when quantum interference effects dominate. That is, we expand the understanding of propensity rules in inelastic electron tunneling spectroscopy to molecules with destructive quantum interference. [ABSTRACT FROM AUTHOR]

Due to the divergence characteristics of vortex microwaves, it is difficult to determine orbital angular momentum (OAM) orders through far fields, while the spiral spectrum analysis method based on the area integral of antenna near fields is complicated. In this paper, combined with near-field approximation processing, a spiral spectrum analysis method based on loop integration is proposed. According to the Laguerre–Gaussian vortex beam model, the key parameter estimation formulas suitable for low-order OAM microwave beams are derived, including the position of the reliable observation plane and the size of the annulus area. On this basis, the radius of the integral loop used for the spiral spectrum calculation is provided. Since only field data on the loop are collected in this method, the calculation amount is reduced and the analysis efficiency of the spiral spectrum is greatly improved. Due to the combination of near-field and far-field considerations, this method can fully reflect the spiral spectrum characteristics of antenna vortex waves. [ABSTRACT FROM AUTHOR]

In this paper, the results of the modeling calculations carried out for predicting the interference effects expected in the sum frequency generation (SFG) spectra of a specific thin-layer system, described in the accompanying paper, are tested by comparing them with the experimental spectra obtained for a real thin-layer film comprising an organic monolayer/variable thickness dielectric layer/gold substrate. In this system, two contributions to the SFG spectra arise, a resonant contribution from the organic film and a nonresonant contribution from the gold substrate. The modeling calculations are in excellent agreement with the experimental spectra over a wide range of thicknesses and for different polarization combinations. The introduction of another resonant monolayer adjacent to the gold substrate and with the molecules having a reverse orientation has a significant affect on the spectral shapes which is predicted. If a dielectric substrate such as CaF2 is used instead of a gold substrate, only the spectral intensities vary with the film thickness but not the spectral shapes. The counterpropagating beam geometry will change both the thickness dependent spectral shapes and the intensity of different vibrational modes in comparison with a copropagating geometry. The influences of these experimental factors, i.e., the molecular orientational structure in the thin film, the nature of the substrate, and the selected incident beam geometry, on the experimental SFG spectra are quantitatively predicted by the calculations. The thickness effects on the signals from a SFG active monolayer contained in a thin liquid-layer cell of the type frequently used for in situ electrochemical measurements is also discussed. The modeling calculation is also valid for application to other thin-film systems comprising more than two resonant SFG active interfaces by appropriate choice of optical geometries and relevant optical properties. [ABSTRACT FROM AUTHOR]

The fundamental of the generation and propagation of the atmospheric pressure nonequilibrium plasma jets has recently attracted significant interests. In this paper, investigations on the effects of the parameters of the pulsed dc voltages on the optical emission intensity of the plasma jet and the bullet propagation behavior are carried out based on the temporal-spatial resolved optical emission spectroscopy measurements and the high-speed photography. It is found that, with the increase in the applied voltage, the bullet propagates out from the nozzle earlier and accelerates to higher peak-velocities. The increase in the pulse frequency exerts no significant influences on the optical emission of the plasma jet and the bullet propagation velocity. But it can induce the bullet propagates out from the nozzle earlier. Besides, it is interesting to notice that, with the increase in the pulse width in the beginning, the bullet propagates out from the nozzle with longer delay time. However, when the pulse width is increased to be more than 100 μs, the delay time of the bullet propagating out from the nozzle becomes much shorter. On the other hand, with the increase in the pulse width, the optical emission intensity of the plasma jet drops and the maximum bullet velocity decreases too. Detailed analysis shows that it may be due to the accumulation of the charges and radicals, which can shorten the prebreakdown of the discharge inside the syringe and result in the bullet propagating out earlier from the nozzle. [ABSTRACT FROM AUTHOR]

The peak-sorting capabilities of high resolution coherent two-dimensional (2D) spectroscopy provide a new way of dealing with severe rotational congestion. This paper describes the application of this technique to the polyatomic molecule, NO2. NO2 is a primary component of photochemical smog and has a notoriously complex and congested spectrum that extends from the infrared to the ultraviolet regions. This spectrum is infamous for having an unusually high density of peaks and very few regular patterns. However, the coherent 2D spectrum of NO2 shows a network consisting of numerous X-shaped patterns that mark the locations of vibronic origins. This paper describes how peak sorting leads to the formation of such patterns and how peak coupling can be used to conduct a rotational analysis of congested areas in the visible spectrum of NO2. [ABSTRACT FROM AUTHOR]

The calculation of rovibrational transition energies and intensities is often hampered by the fact that vibrational states are strongly coupled by Coriolis terms. Because it invalidates the use of perturbation theory for the purpose of decoupling these states, the coupling makes it difficult to analyze spectra and to extract information from them. One either ignores the problem and hopes that the effect of the coupling is minimal or one is forced to diagonalize effective rovibrational matrices (rather than diagonalizing effective rotational matrices). In this paper we apply a procedure, based on a quantum mechanical canonical transformation for deriving decoupled effective rotational Hamiltonians. In previous papers we have used this technique to compute energy levels. In this paper we show that it can also be applied to determine intensities. The ideas are applied to the ethylene molecule. © 2005 American Institute of Physics. [ABSTRACT FROM AUTHOR]

In this paper, we extend and elaborate upon a wavelet method first presented in a previous publication [B. Poirier, J. Theo. Comput. Chem. 2, 65 (2003)]. In particular, we focus on construction and optimization of the wavelet functions, from theoretical and numerical viewpoints, and also examine their localization properties. The wavelets used are modified Wilson-Daubechies wavelets, which in conjunction with a simple phase space truncation scheme, enable one to solve the multidimensional Schrödinger equation. This approach is ideally suited to rovibrational spectroscopy applications, but can be used in any context where differential equations are involved. © 2004 American Institute of Physics. [ABSTRACT FROM AUTHOR]

Femtosecond primary events in bacteriorhodopsin BR and its retinal modified analogs are discussed. Ultrafast time resolved electronic spectra of the primary intermediates induced in the BR photocycle are discussed along with spectral and kinetic inconsistencies of the previous models proposed in the literature. The theoretical model proposed in this paper based on vibrational coupling between the electronic transition of the chromophore and intramolecular vibrational modes allows us to calculate the equilibrium electronic absorption band shape and the hole burning profiles. The model is able to rationalize the complex pattern of behavior for the primary events in BR and explain the origin of the apparent inconsistencies between the experiment and the previous theoretical models. The model presented in the paper is based on the anharmonic coupling assumption in the adiabatic approximation using the canonical transformation method for diagonalization of the vibrational Hamiltonian instead of the commonly used perturbation theory. The electronic transition occurs between the Born—Oppenheimer potential energy surfaces with the electron involved in the transition being coupled to the intramolecular vibrational modes of the molecule (chromophore). The relaxation of the excited state occurs by indirect damping (dephasing) mechanisms. The indirect dephasing is governed by the time evolution of the anharmonic coupling constant driven by the resonance energy exchange between the intramolecular vibrational mode and the bath. The coupling with the intramolecular vibrational modes results in the Franck—Condon progression of bands that are broadened due to the vibrational dephasing mechanisms. The electronic absorption line shape has been calculated based on the linear response theory whereas the third order nonlinear response functions have been used to analyze the hole burning profiles obtained from the pump—probe time-resolved measurements. The theoretical treatment proposed in this paper provides a basis for a substantial revision of the commonly accepted interpretation of the primary events in the BR photocycle that exists in the literature. [ABSTRACT FROM AUTHOR]