Incoherent broadband cavity-enhanced absorption spectroscopy (IBBCEAS) can achieve sensitive measurements at trace concentrations for liquid phase marine samples. The IBBCEAS system consists of a cavity-enhancement module (CEM) and a transmission hyperspectral module (THM). The CEM has cavity-enhancement factors up to 78 at 550 nm. Measurements were obtained over a wide wavelength range (420-640 nm) with a halogen lamp, and the optical cavity was formed by two concave highly reflective mirrors (R=0.99). The minimum detectable absorption coefficient αmin of 7.3×10-7cm-1 at 550 nm corresponds to a limit of detection for nutrients of 780 pM. The spectral resolution of the THM is 3 nm in the wavelength range of 400 to 750 nm. We performed the IBBCEAS measurements for biological and chemical substances, including nutrients, microalgae, and Cy5 dye. The concentrations of nutrients in a deionized water environment and artificial seawater environment were measured at nanomolar levels; the concentration of microalgae phaeocystis was detected with 3.46×104/mL, and fluorescence substances such as Cy5 dye could be measured at 0.03 mg/L. Experimental results show that the IBBCEAS system has the capability for sensitive measurements of biological and chemical substances and has strong potential forin situ ecological marine environmental monitoring function.

We analyze the nonlinear properties of social media activity(SMA) using the multifractal detrended fluctuation analysis (MF-DFA) method. Social media data related to the stock market are gathered from social media platforms. Using data on over 2000 firms in the Korean stock market for 2018-2020, we study social media activity and its differences to evaluate associated nonlinear and statistical properties. We find that the cumulative distribution function of SMA follows a stretched exponential distribution with β = 0.85 . The Hurst exponent of SMA for three datasets (2018, 2019, 2020 year) is larger than 0.9, whereas the Hurst exponents of shuffled time series have values of approximately 0.5. In particular, we find a multifractal structure in both SMA and SMA difference results irrespective of the period and degree of multifractality defined as α max - α min , which reaches a maximum value during the COVID-19 pandemic as a financial crisis.

The present study was done to evaluate chest computed tomography (CT) images of patients with 2019 novel coronavirus disease (COVID-19) by multifractal technique as a new method to find a way for comparing lung infection quantitatively and identifying progression pattern of the disease. The multifractal spectra extracted from analysis of CT images showed that these spectra were correlated with lung infection amount and disease progression so that, multifractal parameters (αmin, αmax, ∆α, f(αmin), f(αmax), ∆f(α), α(q = 0), and f(α) max) were strongly dependent on amount of lung infection. The results demonstrated that multifractality of chest CT images was increased with the increase in lung infection in patients. The interesting and promising result was that capacity dimension (D0) as a new diagnostic parameter varied linearly with progression and reduction of lung infection. A critical value was found for D0, according to which patients with D0 lower than 1.4 can be healed by treatment. Therefore, herein, a way was found for quantitative assessment of lung infection of patients with COVID-19 by analyzing chest CT images using the multifractal method. This method can be very effective for physicians in diagnosis and treatment of pneumonia caused by COVID-19 and timely identification of therapeutic effects.

A special phenomenon of resonance mode separation is observed during the study of a high sensitivity folded-cavity enhanced absorption spectroscopy for the measurement of trace gases. The phenomenon affects the measurement of gas absorption spectrum in the cavity. This resonant mode separation phenomenon of the resonant cavity is different from the resonant modes previously observed in linear-cavity enhanced absorption spectroscopy systems. To explore the mechanism of this phenomenon, a series of hypotheses are proposed. The most likely reason among these hypotheses is based on the different reflectance properties of the plane mirror at the fold of the cavity for S-polarized light and P-polarized light. Based on the matrix calculation method, the different reflectance and phase shift of the plane mirror for S-polarized light and P-polarized light are analyzed theoretically, and the results are in better agreement with the phenomena observed in the experiment. Finally, in order to eliminate the resonant mode separation phenomenon, line polarizers were added. By improving the system, the cavity enhanced absorption spectrum of residual water vapor in the cavity was successfully measured, and a minimum detectable absorption coefficient of αmin = 7.6 × 10-9 cm-1 can be obtained in a single laser scan of 10 s.

We report on the development of a simple, linear optical cavity-based system combining evanescent wave (EW) with high-sensitive cavity ring-down spectroscopy (CRDS) technique using a diode laser at 644 nm and a right-angled prism for evanescent field generation on prism surface. We characterized the setup in detail and achieved an optimum ring-down time of 159.4 ns and a minimum absorption coefficient of αmin = 1.67 × 10-6 cm-1. We utilized this setup to investigate the salt-induced aggregation kinetics of gold (Au) and silver (Ag) nanoparticles (NPs) at the prism interface with high-sensitivity. We evaluated the extinction rates on the surface due to Au and Ag NPs aggregation and examined the variations due to their respective concentrations. To demonstrate the applicability of the developed EW-CRDS prototype setup to different molecular systems, we investigated the urease-bound aggregation kinetics of the Au and Ag NPs which has not been explored earlier by this linear cavity geometry. We finally illustrated the aggregation dynamics through surface imaging, thus demonstrating an alternative analytical approach to monitor interfacial phenomena using EW-CRDS technique.

In this work, acoustic damping performances of double-layer in-duct perforated plates are studied at low Mach (Ma) and Helmholtz number (He) to evaluate the effects of (1) Ma, (2) the porosities (i.e., open-area ratio) σ1 and σ2 of the front and back plates, and (3) the axial distance Lc between these two plates. The orifices' damping is characterized by sound absorption coefficient α denoting the fraction of incident sound energy being absorbed. For this, a quasi-steady acoustic model is developed first and experiments are then conducted. When Ma = 0, α is experimentally found to oscillate with He, whatever the porosities of σ1 and σ2 are set. However, when Ma is increased to and above 0.037, the power absorption troughs, i.e., local αmin of the double-layer plates with σ1,2 ≤ 9% are more separated and shallower. Furthermore, when σ1= 9% or σ2 = 9%, the damping performances are quite different in terms of the local αmax peaks and their number. In addition, increasing Lc with respect to the downstream pipe length Ld gives rise to an increase of αmin and αmax by 10%. Finally, the double-layer plates are shown to involve a larger α than that of single-layer one over a broader He range.

Cavity ring-down spectroscopy (CRDS) is a well-established, highly sensitive absorption technique whose sensitivity and selectivity for trace radical sensing can be further enhanced by measuring the polarization rotation of the intracavity light by the paramagnetic samples in the presence of a magnetic field. In this paper, we highlight the use of this Faraday rotation cavity ring-down spectroscopy (FR-CRDS) for the detection of HO2 radicals. In particular, we use a cold atmospheric pressure plasma jet as a highly efficient source of HO2 radicals and show that FR-CRDS in the near-infrared spectral region (1506 nm) has the potential to be a useful tool for studying radical chemistry. By simultaneously measuring ring-down times of orthogonal linearly polarized light, measurements of Faraday effect-induced rotation angles (θ) and absorption coefficients (α) are retrieved from the same data set. The Faraday rotation measurement exhibits better long-term stability and enhanced sensitivity due to its differential nature, whereby highly correlated noise between the two channels and slow drifts cancel out. The bandwidth-normalized sensitivities are αmin=2.2×10-11 cm-1 Hz-1/2 and θmin=0.62 nrad Hz-1/2. The latter corresponds to a minimum detectable (circular) birefringence of Δnmin=5×10-16 Hz-1/2. Using the overlapping qQ3(N = 4-9) transitions of HO2, we estimate limits of detection of 3.1 × 108 cm-3 based on traditional (absorption) CRDS methods and 6.7 × 107 cm-3 using FR-CRDS detection, where each point of the spectrum was acquired during 2 s. In addition, Verdet constants for pertinent carrier (He, Ar) and bulk (N2, O2) gases were recorded in this spectral region for the first time. These show good agreement with recent measurements of air and values extrapolated from reported Verdet constants at shorter wavelengths, demonstrating the potential of FR-CRDS for measurements of very weak Faraday effects and providing a quantitative validation to the computed rotation angles.

The qualitative and quantitative analysis to trace gas in exhaled human breath has become a promising technique in biomedical applications such as disease diagnosis and health status monitoring. This paper describes an application of a high spectral resolution optical feedback cavity enhanced absorption spectroscopy (OF-CEAS) for ammonia detection in exhaled human breath, and the main interference of gases such as CO2 and H2O are approximately eliminated at the same time. With appropriate optical feedback, a fibered distributed feedback (DFB) diode laser emitting at 1531.6 nm is locked to the resonance of a V-shaped cavity with a free spectral range (FSR) of 300 MHz and a finesse of 14,610. A minimum detectable absorption coefficient of αmin = 2.3 × 10-9 cm-1 is achieved in a single scan within 5 s, yielding a detection limit of 17 ppb for NH3 in breath gas at low pressure, and this stable system allows the detection limit down to 4.5 ppb when the spectra to be averaged over 16 laser scans. Different from typical CEAS with a static cavity, which is limited by the FSR in frequency space, the attainable spectral resolution of our experimental setup can be up to 0.002 cm-1 owing to the simultaneous laser frequency tuning and cavity dither. Hence, the absorption line profile is more accurate, which is most suitable for low-pressure trace gas detection. This work has great potential for accurate selectivity and high sensitivity applications in human breath analysis and atmosphere sciences.

In this study, some important intrinsic dynamics have been captured after analyzing the relationships between the dynamic pressure at an outlet of centrifugal compressor and fractal characteristics, which is one of powerful descriptions in entropy to measure the disorder or complexity in the nonlinear dynamic system. In particular, the fractal dynamics of dynamic pressure of the flow is studied, as the centrifugal compressor is in surge state, resulting in the dynamic pressure of flow and becoming a serious disorder and complex. First, the dynamic pressure at outlet of a centrifugal compressor with 800 kW is tested and then obtained by controlling the opening of the anti-surge valve at the outlet, and both the stable state and surge are initially tested and analyzed. Subsequently, the fractal dynamics is introduced to study the intrinsic dynamics of dynamic pressure under various working conditions, in order to identify surge, which is one typical flow instability in centrifugal compressor. Following fractal dynamics, the Hurst exponent, autocorrelation functions, and variance in measure theories of entropy are studied to obtain the mono-fractal characteristics of the centrifugal compressor. Further, the multi-fractal spectrums are investigated in some detail, and their physical meanings are consequently explained. At last, the statistical reliability of multi-fractal spectrum by modifying the original data has been studied. The results show that a distinct relationship between the dynamic pressure and fractal characteristics exists, including mono-fractal and multi-fractal, and such fractal dynamics are intrinsic. As the centrifugal compressor is working under normal condition, its autocorrelation function curve demonstrates apparent stochastic characteristics, and its Hurst exponent and variance are lower. However, its autocorrelation function curve demonstrates an apparent heavy tail distribution, and its Hurst exponent and variance are higher, as it is working in an unstable condition, namely, surge. In addition, the results show that the multi-fractal spectrum parameters are closely related to the dynamic pressure. With the state of centrifugal compressor being changed from stable to unstable states, some multi-fractal spectrum parameters Δα, Δf(α), αmax, and f(αmin) become larger, but αmin in the multi-fractal spectrum show the opposite trend, and consistent properties are graphically shown for the randomly shuffled data. As a conclusion, the proposed method, as one measure method for entropy, can be used to feasibly identify the incipient surge of a centrifugal compressor and design its surge controller.

The objective of this study was to evaluate the effect of two photoactivation modes of dental LED light-curing unit (LCUs) (conventional and "Soft Start" mode) on surface texture parameters of two dental resin-based nanocomposites. LED LCUs were considered as standard light-curing devices in contemporary dental practice. Atomic force microscopy (AFM) was applied to investigate surface morphology on 90 × 90 μm2 scanning area through 2D multifractal detrended fluctuation analysis with computational algorithms basis. In order to compare 3D surface roughness at nanometer scale, singularity spectrum f[α] was used which characterize local scale properties of multifractal nature of samples. The results confirmed that larger spectrum width Δα (Δα = αmax - αmin) of f(α) is associated with non-uniform surface morphology. Moreover, materials whose polymerization was photoactivated by the "soft start" polymerization mode, showed better quality of the surface microstructure with lower values of AFM surface texture parameters.

Cavity-enhanced absorption spectroscopy is promising for many applications requiring a very high concentration sensitivity but often accompanied by low temporal resolution. In this Letter, we demonstrate a broadband cavity-enhanced absorption spectrometer capable of detection rates of up to 50 kHz, based on a spatially coherent supercontinuum (SC) light source and an in-house-built, high-speed near-infrared spectrograph. The SC spectrometer allows for the simultaneous quantitative detection of CO2, C2H2, and H2O within a spectral range from 1420 to 1570 nm. Using cavity mirrors with a specified reflectivity of R=98.0±0.3% a minimal spectrally averaged absorption coefficient of αmin=1·10-5 cm-1 can be detected at a repetition rate of 50 kHz.

We report on the first detailed use of broadband cavity enhanced absorption spectroscopy (BBCEAS) as a detection system for immunoassay. A vertical R ≥ 0.99 optical cavity was integrated with a motorized XY stage, which functioned as a receptacle for 96-well microtiter plates. The custom-built cavity enhanced microplate reader was used to make measurements on a commercially available osteocalcin sandwich ELISA kit. A 30-fold increase in path length was obtained with a minimum detectable change in the absorption coefficient, αmin(t), of 5.3 × 10(-5) cm(-1) Hz(-1/2). This corresponded to a 39-fold increase in the sensitivity of measurement when directly compared to measurements in a conventional microplate reader. Separate measurements of a standard STREP-HRP colorimetric reaction in microtiter plates of differing optical quality produced an increase in sensitivity of up to 115-fold compared to a conventional microplate reader. The sensitivity of the developed setup compared favorably with previous liquid-phase cavity enhanced studies and approaches the sensitivity of typical fluorometric ELISAs. It could benefit any biochemical test which uses single pass absorption as a detection method, through either the label free detection of biologically important molecules at lower concentrations or the reduction in the amount of expensive biochemicals needed for a particular test, leading to cheaper tests.

The room temperature self- and foreign-continua of water vapor have been measured near 4250 cm(-1) with a newly developed high sensitivity cavity ring down spectrometer (CRDS). The typical sensitivity of the recordings is αmin≈ 6 × 10(-10) cm(-1) which is two orders of magnitude better than previous Fourier transform spectroscopy (FTS) measurements in the spectral region. The investigated spectral interval is located in the low energy range of the important 2.1 μm atmospheric transparency window. Self-continuum cross-sections, CS, were retrieved from the quadratic dependence of the spectrum base line level measured for different water vapor pressures between 0 and 15 Torr, after subtraction of the local water monomer lines contribution calculated using HITRAN2012 line parameters. The CS values were determined with 5% accuracy for four spectral points between 4249.2 and 4257.3 cm(-1). Their values of about 3.2 × 10(-23) cm(2) molecule(-1) atm(-1) are found 20% higher than predicted by the MT_CKD V2.5 model but two times weaker than reported in the literature using FTS. The foreign-continuum was evaluated by injecting various amounts of synthetic air in the CRDS cell while keeping the initial water vapor partial pressure constant. The foreign-continuum cross-section, CF, was retrieved from a linear fit of the spectrum base line level versus the air pressure. The obtained CF values are larger by a factor of 4.5 compared to the MT_CKD values and smaller by a factor of 1.7 compared to previous FTS values. As a result, for an atmosphere at room temperature with 60% relative humidity, the foreign-continuum contribution to the water continuum near 4250 cm(-1) is found to be on the same order as the self-continuum contribution.

Automatic seizure detection technology is of great significance for long-term electroencephalogram (EEG) monitoring of epilepsy patients. The aim of this work is to develop a seizure detection system with high accuracy. The proposed system was mainly based on multifractal analysis, which describes the local singular behavior of fractal objects and characterizes the multifractal structure using a continuous spectrum. Compared with computing the single fractal dimension, multifractal analysis can provide a better description on the transient behavior of EEG fractal time series during the evolvement from interictal stage to seizures. Thus both interictal EEG and ictal EEG were analyzed by multifractal formalism and their differences in the multifractal features were used to distinguish the two class of EEG and detect seizures. In the proposed detection system, eight features (α0, α(min), α(max), Δα, f(α(min)), f(α(max)), Δf and R) were extracted from the multifractal spectrums of the preprocessed EEG to construct feature vectors. Subsequently, relevance vector machine (RVM) was applied for EEG patterns classification, and a series of post-processing operations were used to increase the accuracy and reduce false detections. Both epoch-based and event-based evaluation methods were performed to appraise the system's performance on the EEG recordings of 21 patients in the Freiburg database. The epoch-based sensitivity of 92.94% and specificity of 97.47% were achieved, and the proposed system obtained a sensitivity of 92.06% with a false detection rate of 0.34/h in event-based performance assessment.

We report on a quartz-enhanced photoacoustic (QEPAS) gas sensing system for hydrogen sulphide (H₂S) detection. The system architecture is based on a custom quartz tuning fork (QTF) optoacoustic transducer with a novel geometry and a quantum cascade laser (QCL) emitting 1.1 mW at a frequency of 2.913 THz. The QTF operated on the first flexion resonance frequency of 2871 Hz, with a quality factor Q = 17,900 at 20 Torr. The tuning range of the available QCL allowed the excitation of a H₂S rotational absorption line with a line-strength as small as S = 1.13·10⁻²² cm/mol. The measured detection sensitivity is 30 ppm in 3 seconds and 13 ppm for a 30 seconds integration time, which corresponds to a minimum detectable absorption coefficient α(min) = 2.3·10⁻⁷ cm⁻¹ and a normalized noise-equivalent absorption NNEA = 4.4·10⁻¹⁰ W·cm⁻¹·Hz(-1/2), several times lower than the values previously reported for near-IR and mid-IR H₂S QEPAS sensors.

We consider degree-biased random walkers whose probability to move from a node to one of its neighbors of degree k is proportional to k(α), where α is a tuning parameter. We study both numerically and analytically three types of characteristic times, namely (i) the time the walker needs to come back to the starting node, (ii) the time it takes to visit a given node for the first time, and (iii) the time it takes to visit all the nodes of the network. We consider a large data set of real-world networks and we show that the value of α which minimizes the three characteristic times differs from the value α(min)=-1 analytically found for uncorrelated networks in the mean-field approximation. In addition to this, we found that assortative networks have preferentially a value of α(min) in the range [-1,-0.5], while disassortative networks have α(min) in the range [-0.5,0]. We derive an analytical relation between the degree correlation exponent ν and the optimal bias value α(min), which works well for real-world assortative networks. When only local information is available, degree-biased random walks can guarantee smaller characteristic times than the classical unbiased random walks by means of an appropriate tuning of the motion bias.

Cavity enhanced techniques enable high sensitivity absorption measurements in the liquid phase but are typically more complex, and much more expensive, to perform than conventional absorption methods. The latter attributes have so far prevented a wide spread use of these methods in the analytical sciences. In this study we demonstrate a novel BBCEAS instrument that is sensitive, yet simple and economical to set up and operate. We use a prism spectrometer with a low cost webcam as the detector in conjunction with an optical cavity consisting of two R = 0.99 dielectric mirrors and a white light LED source for illumination. High sensitivity liquid phase measurements were made on samples contained in 1 cm quartz cuvettes placed at normal incidence to the light beam in the optical cavity. The cavity enhancement factor (CEF) with water as the solvent was determined directly by phase shift cavity ring down spectroscopy (PS-CRDS) and also by calibration with Rhodamine 6G solutions. Both methods yielded closely matching CEF values of ~60. The minimum detectable change in absorption (αmin) was determined to be 6.5 × 10(-5) cm(-1) at 527 nm and was limited only by the 8 bit resolution of the particular webcam detector used, thus offering scope for further improvement. The instrument was used to make representative measurements on dye solutions and in the determination of nitrite concentrations in a variation of the widely used Griess Assay. Limits of detection (LOD) were ~850 pM for Rhodamine 6G and 3.7 nM for nitrite, respectively. The sensitivity of the instrument compares favourably with previous cavity based liquid phase studies whilst being achieved at a small fraction of the cost hitherto reported, thus opening the door to widespread use in the community. Further means of improving sensitivity are discussed in the paper.

A cw distributed feedback quantum cascade laser (DFB-QCL) coupled to a two-mirror linear optical cavity has been used to successfully demonstrate optical-feedback cavity-enhanced absorption spectroscopy (OF-CEAS) at 5.5 μm. The noise-equivalent absorption coefficient, α(min), was 2.4×10(-8) cm(-1) for 1 s averaging, limited by etalon-fringing. The temporal stability of the instrument allows NO detection down to 5 ppb in 2 s.

We analyze the accuracy of the Coulomb energy calculated using the Gaussian-and-finite-element-Coulomb (GFC) method. In this approach, the electrostatic potential associated with the molecular electronic density is obtained by solving the Poisson equation and then used to calculate matrix elements of the Coulomb operator. The molecular electrostatic potential is expanded in a mixed Gaussian-finite-element (GF) basis set consisting of Gaussian functions of s symmetry centered on the nuclei (with exponents obtained from a full optimization of the atomic potentials generated by the atomic densities from symmetry-averaged restricted open-shell Hartree-Fock theory) and shape functions defined on uniform finite elements. The quality of the GF basis is controlled by means of a small set of parameters; for a given width of the finite elements d, the highest accuracy is achieved at smallest computational cost when tricubic (n = 3) elements are used in combination with two (γ(H) = 2) and eight (γ(1st) = 8) Gaussians on hydrogen and first-row atoms, respectively, with exponents greater than a given threshold (αmin (G)=0.5). The error in the calculated Coulomb energy divided by the number of atoms in the system depends on the system type but is independent of the system size or the orbital basis set, vanishing approximately like d(4) with decreasing d. If the boundary conditions for the Poisson equation are calculated in an approximate way, the GFC method may lose its variational character when the finite elements are too small; with larger elements, it is less sensitive to inaccuracies in the boundary values. As it is possible to obtain accurate boundary conditions in linear time, the overall scaling of the GFC method for large systems is governed by another computational step-namely, the generation of the three-center overlap integrals with three Gaussian orbitals. The most unfavorable (nearly quadratic) scaling is observed for compact, truly three-dimensional systems; however, this scaling can be reduced to linear by introducing more effective techniques for recognizing significant three-center overlap distributions.

Sensitive spectroscopic techniques involving high-finesse Fabry-Perot resonators are widely used in the microwave and near-infrared spectral regimes, but hardware limitations have hindered their extension to far-infrared wavelengths. While there is no theoretical limit to the frequency region where cavity-enhanced techniques are practical, the sensitivity of these methods does depend explicitly on the availability of highly reflective optics and, in the case of cavity ringdown spectroscopy, sufficiently fast detectors. Here, we describe a novel high-finesse cavity that uses wire-grid polarizers as the reflective surfaces. Quality factors on the order of 10(5) are achieved at 250 GHz. Based on the optimized cavity design, we investigate the feasibility of extending the cavity ringdown technique to far-infrared wavelengths. With the present commercially available technology, we find spectrometer performance to be limited by both the available optics and detectors. With a 120 cm cavity and a detector response time of ~500 ns, we predict a minimum detectable absorption coefficient, αmin, on the order of 10(-7) cm(-1). Given the sensitivity and noise requirements for the ringdown measurements, faster and more sensitive detectors are needed before implementation of the spectrometer is practical or offers any significant advances to existing methods at far-infrared wavelengths.

We present here the instrument design and first experimental results from a multipass millimeter/submillimeter spectrometer designed to probe dissociative reaction dynamics. This work focuses on benchmarking the instrument performance through detection of the CH3O and H2CO products from methanol dissociation induced by a high-voltage plasma discharge. Multiple rotational lines from CH3O and H2CO were observed when this plasma discharge was applied to a sample of methanol vapor seeded in an argon supersonic expansion. The rotational temperature of the dissociation products and their abundance with respect to methanol were determined using a Boltzmann analysis. The minimum detectable absorption coefficient for this instrument was determined to be αmin ≤ 5 × 10(-9) cm(-1). We discuss these results in the context of future applications of this instrument to the study of photodissociation branching ratios for small organic molecules that are important in complex interstellar chemistry.

Eleven very weak electric quadrupole transitions Q(2), Q(1), S(0)-S(8) of the first overtone band of D(2) have been measured by very high sensitivity CW-cavity ring down spectroscopy (CRDS) between 5850 and 6720 cm(-1). The noise equivalent absorption of the recordings is on the order of α(min) ≈ 3 × 10(-11) cm(-1). By averaging a high number of spectra, the noise level was lowered to α(min) ≈ 4 × 10(-12) cm(-1) in order to detect the S(8) transition which is among the weakest transitions ever detected in laboratory experiments (line intensity on the order of 1.8 × 10(-31) cm/molecule at 296 K). A Galatry profile was used to reproduce the measured line shape and derive the line strengths. The pressure shift and position at zero pressure limit were determined from recordings with pressures ranging between 10 and 750 Torr. A highly accurate theoretical line list was constructed for pure D(2) at 296 K. The intensity threshold was fixed to a value of 1 × 10(-34) cm/molecule at 296 K. The obtained line list is provided as supplementary material. It extends up to 24,000 cm(-1) and includes 201 transitions belonging to ten v-0 cold bands (v = 0-9) and three v-1 hot bands (v = 1-3). The energy levels include the relativistic and quantum electrodynamic corrections as well as the effects of the finite nuclear mass. The quadrupole transition moments are calculated using highly accurate adiabatic wave functions. The CRDS line positions and intensities of the first overtone band are compared to the corresponding calculated values and to previous measurements of the S(0)-S(3) lines. The agreement between the CRDS and theoretical results is found within the claimed experimental uncertainties (on the order of 1 × 10(-3) cm(-1) and 2% for the positions and intensities, respectively) while the previous S(0)-S(3) measurements showed important deviations for the line intensities.

Five very weak transitions-O(2), O(3), O(4), O(5) and Q(5)-of the first overtone band of H(2) are measured by very high sensitivity CW-Cavity Ring Down Spectroscopy (CRDS) between 6900 and 7920 cm(-1). The noise equivalent absorption of the recordings is on the order of α(min)≈ 5 × 10(-11) cm(-1) allowing for the detection of the O(5) transition with an intensity of 1.1 × 10(-30) cm per molecule, the smallest intensity value measured so far for an H(2) absorption line. A Galatry profile was used to reproduce the measured line shape and derive the line strengths. The pressure shift of the O(2) and O(3) lines was accurately determined from a series of recordings with pressure ranging between 10 and 700 Torr. From an exhaustive review of the literature data, the list of H(2) absorption lines detected so far has been constructed. It includes a total of 39 transitions ranging from the S(0) pure rotational line near 354 cm(-1) up to the S(1) transition of the (5-0) band near 18,908 cm(-1). These experimental values are compared to a highly accurate theoretical line list constructed for pure H(2) at 296 K (0-35,000 cm(-1), intensity cut off of 1 × 10(-34) cm per molecule). The energy levels and transition moments were computed from high level quantum mechanics calculations. The overall agreement between the theoretical and experimental values is found to be very good for the line positions. Some deviations for the intensities of the high overtone bands (V > 2) are discussed in relation with possible pressure effects affecting the retrieved intensity values. We conclude that the hydrogen molecule is probably a unique case in rovibrational spectroscopy for which first principles theory can provide accurate spectroscopic parameters at the level of the performances of the state of the art experimental techniques.

Broadband cavity-enhanced absorption spectroscopy has been used to record, in real time, the absorption spectrum of microlitre volume aqueous phase droplets within a microfluidic chip assembly. Using supercontinuum radiation and broadband coated external mirrors, the full visible spectrum (430 nm < λ < 700 nm) of each passing droplet is acquired in situ at high repetition rates (273 Hz/3.66 ms acquisition time) and high sensitivity (α(min) < 10(-2) cm(-1)). The possibilities for further improvements in sensitivity and acquisition rate using custom designed chips are discussed.

In crustaceans with compound eyes, the corneal lens of each facet is part of the exoskeleton and thus shed during molting. Here we used an optomotor assay to evaluate the impact of molting on visual acuity (as measured by the minimum resolvable angle, α(min)) in the female blue crab, Callinectes sapidus. We found that visual acuity decreases substantially in the days prior to molting and is gradually recovered after molting. Four days prior to molting, α(min) was 1.8 deg (N=5), a value approximating the best possible acuity in this species. In the 24 h before ecdysis occurred, α(min) increased to 15.0 deg (N=12), corresponding to an eightfold drop in visual acuity. Within 6 days after molting, α(min) returned to the pre-molting value. Micrographs of C. sapidus eyes showed that a gap between the corneal lens and the crystalline cone first appeared approximately 5 days prior to shedding and increased in width as the process progressed. This separation was likely responsible for the loss of visual acuity observed in behavioral tests. In blue crabs, mating is limited to the period of the female's pubertal molt, and a reduction in acuity during this time may have an effect on the sensory cues used in female mate choice. The results described here may be broadly applicable to all arthropods that molt and have particular importance for crustaceans that molt multiple times in their lifetime or have mating cycles that are paired with molting.

The high sensitivity absorption spectra of methane at room temperature and 80 K were recorded by CW-Cavity Ring Down Spectroscopy in the 1.28 μm transparency window (7541-7919 cm(-1)). The empirical line parameters of 7690 and 5794 transitions were retrieved at room temperature and at 80 K, respectively. The achieved sensitivity (α(min)≈ 10(-10) cm(-1)) allowed detecting transitions with intensities as small as 5 × 10(-30) cm per molecule. In order to facilitate identification of the CH(3)D transitions present in the CRDS spectrum of methane in "natural" isotopic abundance, the spectrum of a highly enriched CH(3)D sample was recorded by differential absorption spectroscopy at room temperature and at 80 K. The CH(3)D relative contribution in the considered transparency window is found to be significant only at 80 K (up to 15%) but more limited than in the 1.58 μm transparency window.The low energy values of the transitions observed at both room temperature and 80 K were derived from the variation of their line intensities. Empirical lower states and J values have been obtained for 2821 CH(4) transitions representing 94.1 and 98.5% of the absorbance in the region at room temperature and 80 K, respectively. The good quality of these derived energy values is demonstrated by the marked propensity of the corresponding CH(4) lower state J values to be close to integers. The constructed line lists extend to higher energies the WKC (Wang-Kassi-Campargue) line lists of methane in the near infrared (1.71-1.26 μm). They allow one accounting for the temperature dependence of methane absorption between 80 K and 300 K and are of importance for the analysis of the near infrared spectrum of several planetary bodies like Titan, Uranus and Neptune. The centers of the 3ν(2) + ν(3) and 6ν(4) bands responsible of the absorption in the studied region are discussed in relation with recent theoretical calculations.

A proof of principle experiment was performed by recording the cavity enhanced absorption spectrum of the weak b-X transition of molecular oxygen in the atmosphere using a Ti:Sa femtosecond laser as an absorption source and a high resolution continuous scan Fourier transform interferometer. The cavity was mode matched and either continuously scanned or stabilized at the so-called magic point. An optimal rms noise equivalent absorption of 3x10(-7) cm(-1) Hz(-1/2) was reached in the latter case, corresponding to alpha(min)=3x10(-7) cm(-1).

A periodically poled LiNbO3 (PPLN) crystal waveguide has been used to produce up to 200 microW of mid-infrared light around 3081 cm(-1) with a wide tunability range of approximately 35 cm(-1). Two commercial near-infrared diode lasers at 1.064 microm (pump) and 1.583 microm (signal) are mixed in a nonlinear optical crystal to achieve difference frequency generation. The 48 mm long directly-bonded quasi-phase-matched (QPM) PPLN waveguide shows a conversion efficiency of 12.3% W(-1). Applications in trace gas detection have been demonstrated for ethene, using multipass absorption coupled with wavelength modulation spectroscopy, and cavity enhanced absorption spectroscopy with a lock-in detection scheme: bandwidth reduced sensitivities of alpha(min)=8 x 10(-9) and 1.6 x 10(-8) cm(-1) Hz(-1/2)(2sigma), respectively, have been achieved.

Sensitive liquid-phase measurements have been made in a 20 cm cell using broadband cavity enhanced absorption spectroscopy (BBCEAS). The cavity was formed by two high reflectivity mirrors which were in direct contact with the liquid-phase analytes. Careful choice of solvent was required to minimise the effect of background solvent absorptions. Measurements were made on the broad absorber Sudan black, dissolved in acetonitrile, using a white LED light source and R > or = 0.99 cavity mirrors, leading to a cavity enhancement factor (CEF) of 82 at 584 nm. The sensitivity as measured by the minimum detectable change in the absorption coefficient (alpha(min)) was 3.4 x 10(-7) cm(-1). Further measurements were made on the strong absorber methylene blue dissolved in acetonitrile at 655 nm. A white LED was used with the R > or = 0.99 cavity mirrors, leading to a CEF of 78 and alpha(min) = 4.4 x 10(-7) cm(-1). The use of a more intense red LED also allowed measurements with higher reflectivity R > or = 0.999 cavity mirrors, leading to a CEF of 429 and alpha(min) = 2.8 x 10(-7) cm(-1). The sensitivity was limited by dark noise from the detector but nevertheless appears to represent the most sensitive liquid-phase absorption measurement to date.