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New six-dimensional ab initio potential energy surfaces (PESs) for the N2–CO2 complex, which involve the stretching vibration of N2 and the Q3 normal mode for the ν3 asymmetric stretching vibration of CO2, were constructed using the CCSD(T)-F12/AVTZ method with midpoint bond functions. Two vibrational averaged 4D interaction potentials were obtained by integrating over the two intramolecular coordinates. It was found that both PESs possess two equivalent T-shaped global minima as well as two in-plane and one out-of-plane saddle points. Based on these PESs, rovibrational bound states and energy levels were calculated applying the radial discrete variable representation/angular finite basis representation method and the Lanczos algorithm. The splitting of the energy levels between oN2–CO2 and pN2–CO2 for the intermolecular vibrational ground state is determined to be only 0.000 09 cm−1 due to the higher barriers. The obtained band origin shift is about +0.471 74 cm−1 in the N2–CO2 infrared spectra with CO2 at the ν3 zone, which coincides with the experimental data of +0.483 74 cm−1. The frequencies of the in-plane geared-bending for N2–CO2 at the ν3 = 0 and 1 states of CO2 turn out to be 21.6152 and 21.4522 cm−1, the latter reproduces the available experimental 21.3793 cm−1 value with CO2 at the ν3 zone. The spectral parameters fitted from the rovibrational energy levels show that this dimer is a near prolate asymmetric rotor. The computed microwave transitions as well as the infrared fundamental and combination bands for the complex agree well with the observed data. [ABSTRACT FROM AUTHOR]

Phenylpropiolic acid (C6H5C≡CCOOH, PPA) isolated in nitrogen and xenon cryogenic matrices was studied by infrared spectroscopy. The experimental studies were complemented by a series of quantum chemical calculations carried out at the density functional theory (B3LYP) and MP2 levels of theory (with different basis sets). The calculations predicted the existence of two planar PPA conformers, differing in the arrangement of the carboxylic group. The higher-energy trans-PPA conformer has a negligible population in the gas phase at room temperature and was prepared in situ in the N2 cryomatrix through vibrationally-induced rotamerization of the lower-energy cis-PPA conformer, achieved using selective narrowband infrared excitation of the OH stretching coordinate of the latter species. Broadband UV (λ > 235 nm) irradiation of matrix-isolated cis-PPA was also undertaken, leading to the observation of cis-PPA → trans-PPA isomerization. No other UV-induced photoreactions were observed. The in situ generated trans-PPA conformer was found to decay back to cis-PPA in the dark by tunneling, and its lifetimes under different experimental conditions were determined. The assignment of the infrared spectra of both conformers is presented, considerably extending the vibrational information available on this molecule. [ABSTRACT FROM AUTHOR]

The use of machine learning (ML) in chemical physics has enabled the construction of interatomic potentials having the accuracy of ab initio methods and a computational cost comparable to that of classical force fields. Training an ML model requires an efficient method for the generation of training data. Here, we apply an accurate and efficient protocol to collect training data for constructing a neural network-based ML interatomic potential for nanosilicate clusters. Initial training data are taken from normal modes and farthest point sampling. Later on, the set of training data is extended via an active learning strategy in which new data are identified by the disagreement between an ensemble of ML models. The whole process is further accelerated by parallel sampling over structures. We use the ML model to run molecular dynamics simulations of nanosilicate clusters with various sizes, from which infrared spectra with anharmonicity included can be extracted. Such spectroscopic data are needed for understanding the properties of silicate dust grains in the interstellar medium and in circumstellar environments. [ABSTRACT FROM AUTHOR]

The rise of machine learning has greatly influenced the field of computational chemistry and atomistic molecular dynamics simulations in particular. One of its most exciting prospects is the development of accurate, full-dimensional potential energy surfaces (PESs) for molecules and clusters, which, however, often require thousands to tens of thousands of ab initio data points restricting the community to medium sized molecules and/or lower levels of theory (e.g., density functional theory). Transfer learning, which improves a global PES from a lower to a higher level of theory, offers a data efficient alternative requiring only a fraction of the high-level data (on the order of 100 are found to be sufficient for malonaldehyde). This work demonstrates that even with Hartree–Fock theory and a double-zeta basis set as the lower level model, transfer learning yields coupled-cluster single double triple [CCSD(T)]-level quality for H-transfer barrier energies, harmonic frequencies, and H-transfer tunneling splittings. Most importantly, finite-temperature molecular dynamics simulations on the sub-μs time scale in the gas phase are possible and the infrared spectra determined from the transfer-learned PESs are in good agreement with the experiment. It is concluded that routine, long-time atomistic simulations on PESs fulfilling CCSD(T)-standards become possible. [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]

Carbohydrates constitute one of the four key classes of biomacromolecules but have not been studied by 2D-IR spectroscopy so far. Similarly as for proteins, a lack of native vibrational reporter groups, combined with their huge structural diversity, leads to spectrally congested infrared spectra already for single carbohydrates. Biophysical studies are further impeded by the strong overlap between water modes and carbohydrate modes. Here, we demonstrate the application of the known vibrational reporter group thiocyanate (SCN) as a label in glucose. In this first study, we are able to perform IR and 2D-IR spectroscopy of β-glucose with SCN at the C2 position in chloroform. Upon improved synthesis and the removal of all protecting groups, we successfully performed 2D-IR spectroscopy of β-glucose in H2O. All experimental results are compared to those of methyl-thiocyanate as a reference sample. Overall, we show that the concept of using site-specific vibrational reporter groups can be transferred to carbohydrates. Thus, biophysical studies with 2D-IR spectroscopy can now expand to glycoscience. [ABSTRACT FROM AUTHOR]

The transition between the gas-, supercritical-, and liquid-phase behavior is a fascinating topic, which still lacks molecular-level understanding. Recent ultrafast two-dimensional infrared spectroscopy experiments suggested that the vibrational spectroscopy of N2O embedded in xenon and SF6 as solvents provides an avenue to characterize the transitions between different phases as the concentration (or density) of the solvent increases. The present work demonstrates that classical molecular dynamics (MD) simulations together with accurate interaction potentials allows us to (semi-)quantitatively describe the transition in rotational vibrational infrared spectra from the P-/R-branch line shape for the stretch vibrations of N2O at low solvent densities to the Q-branch-like line shapes at high densities. The results are interpreted within the classical theory of rigid-body rotation in more/less constraining environments at high/low solvent densities or based on phenomenological models for the orientational relaxation of rotational motion. It is concluded that classical MD simulations provide a powerful approach to characterize and interpret the ultrafast motion of solutes in low to high density solvents at a molecular level. [ABSTRACT FROM AUTHOR]

The vibrational spectrum of the alanine amino acid was computationally determined in the infrared range 1000–2000 cm−1, under various environments encompassing the gas, hydrated, and crystalline phases, by means of classical molecular dynamics trajectories, carried out with the Atomic Multipole Optimized Energetics for Biomolecular Simulation polarizable force field. An effective mode analysis was performed, in which the spectra are optimally decomposed into different absorption bands arising from well-defined internal modes. In the gas phase, this analysis allows us to unravel the significant differences between the spectra obtained for the neutral and zwitterionic forms of alanine. In condensed phases, the method provides invaluable insight into the molecular origins of the vibrational bands and further shows that peaks with similar positions can be traced to rather different molecular motions. [ABSTRACT FROM AUTHOR]

The enhancement of photo-Fenton performance in BiOBr via a synergistic approach of efficient adsorption and reduced recombination of photogenerated carriers is an innovative strategy. This research employs an in-situ precipitation process to incorporate modified TiO₂ onto the surface of BiOBr, while integrating polyethylene glycol to create an S-type heterojunction material (FT-OVs/PEG-BiOBr). The incorporation of hydroxyl groups by PEG facilitates π-π conjugation and hydrogen bonding, thereby enhancing the adsorption capacity of FT-OVs/PEG-BiOBr. The presence of oxygen vacancies extends the absorption spectrum into the infrared region, and the electron trap mechanism substantially decreases the recombination of photogenerated carriers. The developed S-type heterojunction structure efficiently directs electron transport along a specific pathway. Photoluminescence (PL) studies reveal a further reduction in the recombination of photogenerated carriers. Remarkably, there is a significant synergistic effect between adsorption and low recombination of photogenerated carriers. A profound photo-Fenton synergistic effect is observed at pH 3, leading to degradation rates of RhB and TCH of approximately 98% and 85%, respectively, within 10 min. The degradation pathway of RhB has been investigated using LC-MS analysis, and 1O₂ has been identified as the primary active species through ESR testing. This study presents a novel structural approach to significantly enhance the efficiency of catalysts in Fenton systems. [ABSTRACT FROM AUTHOR]

In this study, we have trained a deep learning (DL) potential for water using training datasets obtained from the DPLibrary (). Subsequently, we conducted classical molecular dynamics simulation (DeePMD) and path-integral MD simulation (PI-DeePMD) of liquid water based on this deep potential (DP). Using the velocity-velocity auto-correlation function (VVAF) formula, we constructed infrared (IR) spectra for the O-H stretching mode based on the DeePMD simulation trajectories. Our results showed that the DeePMD/VVAF approach accurately captured the experimental result for O-H stretching vibration, with the O-H vibrational peak located at 3400 cm−1. Additionally, the PI-DeePMD approach successfully predicted the red-shift and broadening of the O-H stretching band of water, emphasising the importance of nuclear quantum effects (NQEs). In particular, the PI-DeePMD simulation correctly reproduced the shoulder located at 3250 cm−1, which was underestimated by classical DeePMD simulation. The success of the PI-DeePMD/VVAF approach can be attributed to the following reasons: (1) the DeePMD simulation improves the accuracy of calculating atomic velocities due to the DFT-level accuracy of the DP model; (2) the PI-DeePMD simulation takes into account the contribution from nuclear quantum effects; (3) the non-Condon effect is considered in the VVAF formalism. [ABSTRACT FROM AUTHOR]

We introduce an innovative in situ infrared diffuse reflection rapid detection system, endowed with a temperature regulation function. This system is adept at conducting rapid infrared spectra scanning as well as simulating the catalytic environment of diverse reaction systems. The infrared absorption spectra of four kinds of Pt-based catalysts under vacuum conditions across a wide temperature spectrum ranging from −180 to 300 °C are obtained and analysed through IR correlation spectroscopy. A key finding is the notable variance in peak intensity within Pt/CeO2/CNT catalysts, highlighting a robust adsorption capacity for oxygen-containing groups at lower temperatures and a marked desorption at higher temperatures. By enabling rapid and accurate assessments of catalyst behavior under varying temperatures, it not only accelerates the evaluation process but also provides valuable insights that can guide the synthesis of more efficient catalysts. [ABSTRACT FROM AUTHOR]

We calculate the two-phonon contribution to the dielectric susceptibility of diamond at room and elevated temperatures, utilizing a general a b initio model that can be extended to higher n phonon processes. We calculate the second-order dipole moments using a finite displacement method to calculate the derivatives of the Born effective charge tensor. Specifically, we use results obtained from density-functional theory and density-functional perturbation theory in this finite displacement method to calculate the dipole moments of diamond in the two-phonon case. We use the calculated dipole moment to determine the contribution of two-phonon processes to the dielectric susceptibility. We then calculate the absorption curve as a function of wave-number at room or elevated temperatures. Our results indicate that the calculated absorption is in good agreement with previous calculations, and that it increases in magnitude with temperature while maintaining a consistent shape. [ABSTRACT FROM AUTHOR]

The effect of γ-radiation dose on the mechanical characteristics and structure of a polymer composite material based on PDI-3B and SKD-KTR low-molecular-mass rubbers and filled with potassium chloride has been studied. It has been shown that an increase in the radiation dose to 200 kGy does not lead to a significant change in ultimate tensile stress and strain. The radiation resistance of the synthesized polymer composite materials is also evidenced by the absence of significant changes in the structure of the irradiated composite. [ABSTRACT FROM AUTHOR]

Shape alterations of molecular systems, induced by their (electric) charging/discharging, could facilitate useful electronic and/or mechanical functions in molecular-scale devices and machines. The present study reports structures, stabilities, charge distributions, and IR spectra for a group of complexes of a main-group metalloid (boron) atom with hydrocarbon molecules. The considered systems include the smallest species demonstrating the basic principle of operation, as well as their size-extended analogues, generalizing it to larger counterparts based on such units. The system geometries vary considerably between neutral and ionic counterparts and exhibit two–three typical conformations related to twisting by up to about 90 degrees. The predicted structures correlate with specific infrared spectra, which can enable their experimental identification and transformation tracking. The above-mentioned characteristics suggest the potential utility of such systems for intermolecular switches, with the possible spectral monitoring of their functioning. [ABSTRACT FROM AUTHOR]

Developing bio-based plastic has become an important strategy for solving environmental pollution. In this study, konjac flour (KF) and poly-vinyl alcohol (PVA) as main film-forming substances with added citric acid (CA), glutaraldehyde (GA) and glycerin, were used to prepare bio-based composite films via solution casting. How the PVA polymer amount affected the composite films including mechanical performance, structural properties and morphology was investigated. The results revealed that PVA polymer could obviously improve the mechanical property of the films, and the addition of 25% PVA based on KF mass when CA, GA and glycerin were fixed, was demonstrated as the optimal amount, maintaining an excellent tensile strength (TB) and elongation at break (EAB). Fourier transform infrared spectra (FT-IR) and X-ray diffraction (XRD) results indicated the successful cross-linking reaction between PVA and KF, and some further proofs could be confirmed from scanning electron microscopy (SEM) and thermogravimetry (TG). After modification with PVA, the cross section of the KF/PVA composite film was more dense and uniform, implying that PVA was well fused with KF system. Meanwhile, the films modified with PVA presented a good thermal resistance ability. This work provided an effective pathway for preparing KF/PVA composite films with improved mechanical properties, which may be an alternative way for using konjac flour. [ABSTRACT FROM AUTHOR]

The t‐distributed stochastic neighbour embedding algorithm or t‐SNE is a non‐linear dimension reduction method used to visualise multivariate data. It enables a high‐dimensional dataset, such as a set of infrared spectra, to be represented on a single, typically two‐dimensional graph, revealing its global and local structure. t‐SNE is very popular in the machine learning community and has been applied in many fields, generally with the aim of visualising large datasets. In vibrational spectroscopy, t‐SNE is gaining notoriety but principal component analysis (PCA) remains by far the reference method for exploratory analysis and dimension reduction. However, t‐SNE may represent a real aid in the analysis of vibrational spectroscopic datasets. It provides an at‐a‐glance global view of the dataset allowing to distinguish the main factors influencing the spectral signal and the hierarchy between these factors, and gives an indication on the possibility of performing predictive modelling. It can also provide great support in the choice of the pre‐processing, by comparing rapidly different general pre‐processing approaches according to their effect on the variable of interest. Here we propose to illustrate these advantages using different datasets. We also propose an approach based on a synergy between the t‐SNE and PCA methods, allowing respective advantages of each to be exploited. The t‐distributed stochastic neighbour embedding algorithm, or t‐SNE, is a nonlinear method enabling the visualisation of multivariate datasets in lower dimensions. In vibrational spectroscopy, t‐SNE can provide a rapid global overview of a dataset and its influencing factors, assess the potential for predictive modelling and aid with the selection of the pre‐processing workflow. These advantages are illustrated with two real vibrational spectroscopic datasets. A data exploration approach based on the synergy between t‐SNE and PCA is also proposed. [ABSTRACT FROM AUTHOR]

The prediction of the cheese yield (%CY) traits for curd, solids, and retained water and the amount of fat, protein, solids, and energy recovered from the milk into the curd (%REC) by Bayesian models, using Fourier-transform infrared spectroscopy (FTIR), can be of significant economic interest to the dairy industry and can contribute to the improvement of the cheese process efficiency. The yields give a quantitative measure of the ratio between weights of the input and output of the process, whereas the nutrient recovery allows to assess the quantitative transfer of a component from milk to cheese (expressed in % of the initial weight). The aims of this study were: (1) to investigate the feasibility of using bulk milk spectra to predict %CY and %REC traits, and (2) to quantify the effect of the dairy industry and the contribution of single-spectrum wavelengths on the prediction accuracy of these traits using vat milk samples destined to the production of Grana Padano Protected Designation of Origin cheese. Information from 72 cheesemaking days (in total, 216 vats) from 3 dairy industries were collected. For each vat, the milk was weighed and analyzed for composition (total solids [TS], lactose, protein, and fat). After 48 h from cheesemaking, each cheese was weighed, and the resulting whey was sampled for composition as well (TS, lactose, protein, and fat). Two spectra from each milk sample were collected in the range between 5,011 and 925 cm−1 and averaged before the data analysis. The calibration models were developed via a Bayesian approach by using the BGLR (Bayesian Generalized Linear Regression) package of R software. The performance of the models was assessed by the coefficient of determination (R2 VAL) and the root mean squared error (RMSE VAL) of validation. Random cross-validation (CVL) was applied [80% calibration and 20% validation set] with 10 replicates. Then, a stratified cross-validation (SCV) was performed to assess the effect of the dairy industry on prediction accuracy. The study was repeated using a selection of informative wavelengths to assess the necessity of using whole spectra to optimize prediction accuracy. Results showed the feasibility of using FTIR spectra and Bayesian models to predict cheesemaking traits. The R2 VAL values obtained with the CVL procedure were promising in particular for the %CY and %REC for protein, ranging from 0.44 to 0.66 with very low RMSE VAL (from 0.16 to 0.53). Prediction accuracy obtained with the SCV was strongly influenced by the dairy factory industry. The general low values gained with the SCV do not permit a practical application of this approach, but they highlight the importance of building calibration models with a dataset covering the largest possible sample variability. This study also demonstrated that the use of the full FTIR spectra may be redundant for the prediction of the cheesemaking traits and that a specific selection of the most informative wavelengths led to improved prediction accuracy. This could lead to the development of dedicated spectrometers using selected wavelengths with built-in calibrations for the online prediction of these innovative traits. [ABSTRACT FROM AUTHOR]

Fourier transform infrared spectroscopy (FT-IR) is a widely used spectroscopic method for routine analysis of substances and compounds. Spectral interpretation of spectra is a labor-intensive process that provides important information about functional groups or bonds present in compounds and complex substances. In this paper, based on deep learning methods of convolutional neural networks, models were developed to determine the presence of 17 classes of functional groups or 72 classes of coupling oscillations in the FT-IR spectra. Using web scanning, the spectra of 14 361 FT-IR spectra of organic molecules were obtained. Several different variants of model architectures with different sizes of feature maps have been tested. Based on the Shapley additive explanations (SHAP) and gradient-weighted class activation mapping (GradCAM) methods, visualization tools have been developed for visualizing and highlighting the areas of absorption bands manifestation for corresponding functional groups or bonds in the spectrum. To determine 17 and 72 classes, the F1-weighted metric, which is the harmonic mean of the class' precision and class' recall weighted by class' fraction, reached 93 and 88%, respectively, when using data on the position of absorption maxima in the spectrum as an additional source layer. The resulting model can be used to facilitate the routine analysis of spectra for all areas such as organic chemistry, materials science, and biology, as well as to facilitate the preparation of the obtained experimental data for publication. [ABSTRACT FROM AUTHOR]

The combination of near-infrared spectroscopy imaging and virtual reality image technology brings new opportunities to the field of motion analysis. The development of related technologies can improve the accuracy and efficiency of motion analysis, and then promote the research and application in the field of motion analysis. This study aims to explore the application potential of virtual reality image technology based on near-infrared spectral imaging in motion analysis, in order to evaluate the effectiveness and feasibility of this technology in the process of capturing and analyzing human motion. The research collects the relevant experimental data, uses the virtual reality image technology to transform these data into visual moving images, and obtains the relevant information of motion analysis by analyzing the feature parameters in the moving images. Finally, statistical methods were used to verify the results. The results show that the virtual reality image technology based on near infrared spectrum imaging shows good effect in motion analysis. By using near-infrared spectroscopy imaging, it is possible to accurately capture subtle changes in human movement and convert them into visualized images. This kind of image analysis provides a deep understanding of the movement process and can be used in many aspects such as sports performance evaluation and sports injury prediction. [ABSTRACT FROM AUTHOR]

Solvent evaporation was used to create a novel organic Schiff-based optical crystal of Benzimidazolium gallate (BGA). The size of unit cells was determined using X-ray diffraction analysis. Fourier transform infra-red spectrum analysis revealed chemical bonds' vibrational behavior and their functional groups' existence. Optical transparency and optical bandgap (3.66 eV) were observed by the UV–visible-near infrared spectral analysis. Differential scanning calorimetry curves show that decomposition is exhibited at 215 °C. Dielectric experiments on the BGA crystal were performed at ambient temperature. High-resolution scanning electron microscope analysis shows the crystal's nature and surface shape. The Z-scan process explored the BGA crystal's nonlinearity, and the crystal is suitable for photonic, optoelectronic, and optical-limiting applications. [ABSTRACT FROM AUTHOR]

A new CO |$^+$| fluorescence emission model for analysing cometary spectra is presented herein. Accurate line lists are produced using the PGOPHER software for all transitions between the three electronic states (X |$^2\Sigma$|⁠ , A |$^2\Pi$|⁠ , B |$^2\Sigma$|⁠) with vibrational states up to |$v_\textrm {max} = 9, 8, 6$|⁠ , respectively, and maximum rotational states with rotational quantum numbers |$N\le 20$|⁠. As a result of improved molecular constants and theoretical transition rates, an expansion of the utilized solar spectrum into the infrared, and the substantial expansion of the included rovibronic states, the model provides an update of the fluorescence efficiencies of the CO |$^+$| cation. The dependencies on heliocentric velocity and distance are explicitly included. We report, for the first time, quantification of the fluorescence efficiencies for the ground state rovibrational transitions of CO |$^+$| and predict the positions and relative intensities of CO |$^+$| lines in windows accessible to both ground- and space-based observatories. The computed fluorescence efficiencies show excellent agreement with UV/optical observations of both C/2016 R2 (PanSTARRS) and 29P/Schwassmann-Wachmann 1. The updated fluorescence efficiencies allow for revised N |$_2$| /CO abundances for comets 1P/Halley, C/1987 P1 (Bradfield), and C/2016 R2 (PanSTARRS), which can change by up to 30 per cent when accounting for recent improvements to CO |$^+$| and N |$_2^+$| fluorescence efficiencies. The model code, input files, and fluorescence efficiencies are publicly available and distributed on permanent archives for future uses in cometary analyses. [ABSTRACT FROM AUTHOR]

The design of transparent conductive electrodes (TCEs) for optoelectronic devices requires a trade‐off between high conductivity and transmittivity, limiting their efficiency. This paper demonstrates the best ever achieved TCEs with the novel approach to fabricating TCEs that effectively alleviates this trade‐off: a monolithic high contrast grating integrated with metal (metalMHCG). The metalMHCG enables higher electrical conductivity than other TCEs, while providing transmissive and antireflective properties. It focuses on infrared spectrum TCEs, which are essential for sensing, thermal imaging, and automotive applications. However, due to elevated free carrier absorption, they are much more demanding than TCEs for the visible spectrum. It demonstrates a record 75% absolute transmittiance of unpolarized light, resulting in a record 108% transmittance relative to plain GaAs substrate. It achieves even larger absolute transmittance of polarized light, reaching 92% or 133% relative transmittance. Despite the record high transmittance, the sheet resistance of the metalMHCG is the best ever reported, several times lower than any other TCE, ranging from 0.5 to 1 Ω Sq−1. [ABSTRACT FROM AUTHOR]

The freezing winter temperatures in Northeast China hinder the breakdown speed of straw, making it challenging to implement widespread straw return in rice fields, meaning that crop remnants are not efficiently utilised. This study involved a pot experiment conducted on rice plants that were treated with varying quantities of biochar: CK (no biochar); BC1 (5 t ha−1); BC2 (10 t ha−1); and BC3 (20 t ha−1). An investigation was conducted to examine the impact of biochar on the soil organic carbon (SOC), humus (HS) composition, humic acid (HA) structure, and rice yield of paddy fields. The findings demonstrated that the use of biochar led to a substantial rise in SOC and HA-C concentrations in the soil layer between 20 and 40 cm. Additionally, biochar's application enhanced soil humification. Notably, the treatment with BC3 (20 t ha−1) had the most pronounced impact. The O/C ratio in the HA and the relative strength of the peaks at 1620 cm−1 on the infrared spectra showed a more pronounced response to the BC3 treatment compared to the other biochar treatments. However, the application of the BC1 treatment at a rate of 5 t ha−1 and the BC2 treatment at a rate of 10 t ha−1 had a minimal impact on the fluorescence intensity of humic acid (HA). The application of the BC3 treatment increased the aromatic nature of the humic acid (HA) in paddy soil, leading to the formation of an intricate and enduring HA structure. Furthermore, the use of the BC3 treatment resulted in a notable enhancement in the quantity of spikes, spike weight, and number of grains per spike. Additionally, it positively impacted the accumulation of dry matter in the spike, leading to a substantial 13.7% increase in the rice yield. Applying biochar at a rate of 20 t ha−1 is a sensible and effective approach to enhance the soil organic carbon (SOC) content, enhance the stability of the humic acid (HA)'s structure, and raise the rice yield in the rice-growing area of Northeast China. This study's findings will establish a theoretical foundation for utilising soil biochar in the rice fields located in Northeast China. [ABSTRACT FROM AUTHOR]

We here study the effect that a lowering of the pH has on the excited state processes of cytidine and a cytidine/cytidine pair in solution, by integrating time‐dependent density functional theory and CASSCF/CASPT2 calculations, and including solvent by a mixed discrete/continuum model. Our calculations reproduce the effect of protonation at N3 on the steady‐state infrared and absorption spectra of a protonated cytidine (CH+), and predict that an easily accessible non‐radiative deactivation route exists for the spectroscopic state, explaining its sub‐ps lifetime. Indeed, an extremely small energy barrier separates the minimum of the lowest energy bright state from a crossing region with the ground electronic state, reached by out‐of‐plane motion of the hydrogen substituents of the CC double bond, the so‐called ethylenic conical intersection typical of cytidine and other pyrimidine bases. This deactivation route is operative for the two bases forming an hemiprotonated cytidine base pair, [CH·C]+, the building blocks of I‐motif secondary structures, whereas interbase processes play a minor role. N3 protonation disfavors instead the nπ* transitions, associated with the long‐living components of cytidine photoactivated dynamics. [ABSTRACT FROM AUTHOR]

Background: Estimation of prognosis of oral squamous cell carcinoma (OSCC) is inaccurate prior to surgery, only being effected following subsequent pathological analysis of the primary tumour and excised lymph nodes. Consequently, a proportion of patients are overtreated, with an increase in morbidity, or undertreated, with inadequate margins and risk of recurrence. We hypothesise that it is possible to accurately characterise clinical outcomes from infrared spectra arising from diagnostic biopsies. In this first step, we correlate survival with IR spectra derived from the primary tumour. Methods: Infrared spectra were collected from tumour tissue from 29 patients with OSCC and subject to classification modelling. Results: The model had a median AUROC of 0.89 with regard to prognosis, a median specificity of 0.83, and a hazard ratio of 6.29 in univariate Cox proportional hazard modelling. Conclusion: The data suggest that FTIR spectra may be a useful early biomarker of prognosis in OSCC. [ABSTRACT FROM AUTHOR]

The objective of this study is to investigate the effects of okara and its dietary fiber (DF) on the retrogradation and rheological characteristics of potato starch. DF or okara increases the syneresis, but decrease the gel strength of potato starch with the increase of concentration. Storage modulus and loss modulus of potato starch are markedly increased with a high concentration of okara or DF during temperature sweep, especially DF. Shear‐thinning behavior and apparent viscosity of potato starch are increased with more addition of DF or okara. The X‐ray diffraction pattern demonstrates that okara or DF does not change the type of crystal structure but significantly increases the crystallinity of the starch matrix, especially DF. Fourier‐transformed infrared spectra indicate the addition of okara or DF increases hydrogen bonds in potato starch and brings in ester carbonyl from the fiber. The addition of okara and DF can alter the retrogradation and rheology characteristics of potato starch. [ABSTRACT FROM AUTHOR]

Rate coefficients, k1, for the gas‐phase OH radical reaction with the heterocyclic ether C4H4O (1,4‐epoxybuta‐1,3‐diene, furan) were measured over the temperature range 273–353 K at 760 Torr (syn. air). Experiments were performed using: (i) the photochemical smog chamber THALAMOS (thermally regulated atmospheric simulation chamber, IMT NE, Douai‐France) equipped with Fourier Transform Infrared (FTIR) and Selected Ion Flow Tube Mass Spectrometry (SIFT‐MS) detection methods and (ii) a photochemical reactor coupled with FTIR spectroscopy (PCR, University of Crete, Greece). k1(273–353 K) was measured using a relative rate (RR) method, in which the loss of furan was measured relative to the loss of reference compounds with well‐established OH reaction rate coefficients. k1(273–353 K) was found to be well represented by the Arrhenius expression (1.30 ± 0.12) × 10−11 exp[(336 ± 20)/T] cm3 molecule−1 s−1, with k1(296 K) measured to be (4.07 ± 0.32) × 10−11 cm3 molecule−1 s−1. The k1(296 K) and pre‐exponential quoted error limits are 2σ and include estimated systematic errors in the reference rate coefficients. The observed negative temperature dependence is consistent with a reaction mechanism involving the OH radical association to a furan double bond. Quantum mechanical molecular calculations show that OH addition to the α‐carbon (ΔHr(296 K) = −121.5 kJ mol−1) is thermochemically favored over the β‐carbon (ΔHr(296 K) = −52.9 kJ mol−1) addition. The OH‐furan adduct was found to be stable over the temperature range of the present measurements. Maleic anhydride (C4H2O3) was identified as a minor reaction product, 3% lower‐limit yield, demonstrating a non‐ring‐opening active reaction channel. The present results are critically compared with results from previous studies of the OH + furan reaction rate coefficient. The infrared spectrum of furan was measured as part of this study and its estimated climate metrics are reported. [ABSTRACT FROM AUTHOR]

Two-dimensional infrared Raman spectroscopy is a powerful technique for studying the structure and interaction in molecular and biological systems. Here, we present a new implementation of the simulation of the two-dimensional infrared Raman signals. The implementation builds on the numerical integration of the Schrödinger equation approach. It combines the prediction of dynamics from molecular dynamics with a map-based approach for obtaining Hamiltonian trajectories and response function calculations. The new implementation is tested on the amide-I region for two proteins, where one is dominated by α-helices and the other by β-sheets. We find that the predicted spectra agree well with experimental observations. We further find that the two-dimensional infrared Raman spectra at least of the studied proteins are much less sensitive to the laser polarization used compared to conventional two-dimensional infrared experiments. The present implementation and findings pave the way for future applications for the interpretation of two-dimensional infrared Raman spectra. [ABSTRACT FROM AUTHOR]

A model of a bulk water system describing the vibrational motion of intramolecular and intermolecular modes is constructed, enabling analysis of its linear and nonlinear vibrational spectra as well as the energy transfer processes between the vibrational modes. The model is described as a system of four interacting anharmonic oscillators nonlinearly coupled to their respective heat baths. To perform a rigorous numerical investigation of the non-Markovian and nonperturbative quantum dissipative dynamics of the model, we derive discretized hierarchical equations of motion in mixed Liouville–Wigner space, with Lagrange–Hermite mesh discretization being employed in the Liouville space of the intramolecular modes and Lagrange–Hermite mesh discretization and Hermite discretization in the Wigner space of the intermolecular modes. One-dimensional infrared and Raman spectra and two-dimensional terahertz–infrared–visible and infrared–infrared–Raman spectra are computed as demonstrations of the quantum dissipative description provided by our model. [ABSTRACT FROM AUTHOR]

Structural characterization of neutral water clusters is crucial to understanding the structures and properties of water, but it has been proven to be a challenging experimental target due to the difficulty in size selection. Here, we report the size-specific infrared spectra of confinement-free neutral water nonamer (H2O)9 based on threshold photoionization, using a tunable vacuum ultraviolet free-electron laser. Distinct OH stretch vibrational fundamentals in the 3200–3350 cm−1 region are observed, providing unique spectral signatures for the formation of an unprecedented (H2O)9 structure evolved by adding a ninth water molecule onto a hydrogen bond-unbroken edge of the (H2O)8 octamer with D2d symmetry. This nonamer structure coexists with the five previously identified structures that can be viewed as derived by inserting a ninth water molecule into a hydrogen bond-broken edge of the D2d/S4 octamer. These findings provide key microscopic information for systematic understanding of the formation and growth mechanism of dynamical hydrogen-bonding networks that are responsible for the structure and properties of condensed-phase water. [ABSTRACT FROM AUTHOR]

Computational protocols for the simulation of two-dimensional infrared (2D IR) spectroscopy usually rely on vibrational exciton models which require an empirical parameterization. Here, we present an efficient quantum-chemical protocol for predicting static 2D IR spectra that does not require any empirical parameters. For the calculation of anharmonic vibrational energy levels and transition dipole moments, we employ the localized-mode vibrational self-consistent field (L-VSCF)/vibrational configuration interaction (L-VCI) approach previously established for (linear) anharmonic theoretical vibrational spectroscopy [P. T. Panek and C. R. Jacob, ChemPhysChem 15, 3365–3377 (2014)]. We demonstrate that with an efficient expansion of the potential energy surface using anharmonic one-mode potentials and harmonic two-mode potentials, 2D IR spectra of metal carbonyl complexes and dipeptides can be predicted reliably. We further show how the close connection between L-VCI and vibrational exciton models can be exploited to extract the parameters of such models from those calculations. This provides a novel route to the fully quantum-chemical parameterization of vibrational exciton models for predicting 2D IR spectra. [ABSTRACT FROM AUTHOR]

Through this paper, the authors propose using the quantum cluster equilibrium (QCE) theory to reinvestigate ammonia clusters in the liquid phase. The ammonia clusters from size monomer to hexadecamer were considered to simulate the liquid ammonia in this approach. The clusterset used to model the liquid ammonia is an ensemble of different structures of ammonia clusters. After studious research of the representative configurations of ammonia clusters through the cluster research program ABCluster, the configurations have been optimized at the MN15/6‐31++G(d,p) level of theory. These optimizations lead to geometries and frequencies as inputs for the Peacemaker code. The QCE study of this molecular system permits us to get the liquid phase populations in a temperature range of 190–260 K, covering the temperatures from the melting point to the boiling point. The results show that the population of liquid ammonia comprises mainly the ammonia hexadecamer followed by pentadecamer, tetradecamer, and tridecamer. We noted that the small‐sized ammonia clusters do not contribute to the population of liquid ammonia. In addition, the thermodynamic properties, such as heat of vaporization, heat capacity, entropy, enthalpy, and free energies, obtained by the QCE theory have been compared to the experiment given some relatively good agreements in the gas phase and show considerable discrepancies in liquid phase except the density. Finally, based on the predicted population, we calculated the infrared spectrum of liquid ammonia at 215 K temperature. It comes out that the calculated infrared spectrum qualitatively agrees with the experiment. [ABSTRACT FROM AUTHOR]

Two-dimensional infrared (2DIR) spectroscopy has become an established method for generating vibrational spectra in condensed phase samples composed of mixtures that yield heavily congested infrared and Raman spectra. These condensed phase 2DIR spectrometers can provide very high temporal resolution (<1 ps), but the spectral resolution is generally insufficient for resolving rotational peaks in gas phase spectra. Conventional (1D) rovibrational spectra of gas phase molecules are often plagued by severe spectral congestion, even when the sample is not a mixture. Spectral congestion can obscure the patterns in rovibrational spectra that are needed to assign peaks in the spectra. A method for generating high resolution 2DIR spectra of gas phase molecules has now been developed and tested using methane as the sample. The 2D rovibrational patterns that are recorded resemble an asterisk with a center position that provides the frequencies of both of the two coupled vibrational levels. The ability to generate easily recognizable 2D rovibrational patterns, regardless of temperature, should make the technique useful for a wide range of applications that are otherwise difficult or impossible when using conventional 1D rovibrational spectroscopy. [ABSTRACT FROM AUTHOR]

Ge/SiGe multi-quantum well heterostructures are highly sought-after for silicon-integrated optoelectronic devices operating in the broad range of the electromagnetic spectrum covering infrared to terahertz wavelengths. However, the epitaxial growth of these heterostructures at a thickness of a few micrometers has been a challenging task due to the lattice mismatch and its associated instabilities resulting from the formation of growth defects. To elucidate these limits, we outline herein a process for the strain-balanced growth on silicon of 11.1/21.5 nm Ge/Si0.18Ge0.82 superlattices (SLs) with a total thickness of 16 μm corresponding to 500 periods. Composition, thickness, and interface width are preserved across the entire SL heterostructure, which is an indication of limited Si–Ge intermixing. High crystallinity and low defect density are obtained in the Ge/Si0.18Ge0.82 layers; however, the dislocation pileup at the interface with the growth substrate induces micrometer-long cracks on the surface. This eventually leads to significant layer tilt in the strain-balanced SL and in the formation of millimeter-long, free-standing flakes. These results confirm the local uniformity of structural properties and highlight the critical importance of threading dislocations in shaping the wafer-level stability of thick multi-quantum well heterostructures required to implement effective silicon-compatible Ge/SiGe photonic devices. [ABSTRACT FROM AUTHOR]

A stochastic theory is developed to predict the spectral signature of proton-transfer processes and is applied to infrared spectra computed from ab initio molecular-dynamics simulations of a single H 5 O 2 + cation. By constraining the oxygen atoms to a fixed distance, this system serves as a tunable model for general proton-transfer processes with variable barrier height. Three spectral contributions at distinct frequencies are identified and analytically predicted: the quasi-harmonic motion around the most probable configuration, amenable to normal-mode analysis, the contribution due to transfer paths when the proton moves over the barrier, and a shoulder for low frequencies stemming from the stochastic transfer-waiting-time distribution; the latter two contributions are not captured by normal-mode analysis but exclusively reported on the proton-transfer kinetics. In accordance with reaction rate theory, the transfer-waiting-contribution frequency depends inversely exponentially on the barrier height, whereas the transfer-path-contribution frequency is rather insensitive to the barrier height. [ABSTRACT FROM AUTHOR]

We describe improvements to the quasicentroid molecular dynamics (QCMD) path-integral method, which was developed recently for computing the infrared spectra of condensed-phase systems. The main development is an improved estimator for the intermolecular torque on the quasicentroid. When applied to qTIP4P/F liquid water and ice, the new estimator is found to remove an artificial 25 cm−1 red shift from the libration bands, to increase slightly the intensity of the OH stretch band in the liquid, and to reduce small errors noted previously in the QCMD radial distribution functions. We also modify the mass-scaling used in the adiabatic QCMD algorithm, which allows the molecular dynamics timestep to be quadrupled, thus reducing the expense of a QCMD calculation to twice that of Cartesian centroid molecular dynamics for qTIP4P/F liquid water at 300 K, and eight times for ice at 150 K. [ABSTRACT FROM AUTHOR]

Experimental and theoretical studies have highlighted protonated water clusters (PWCs) as important models of the excess proton in aqueous systems. A significant focus has been characterizing the spectral signatures associated with different excess proton solvation motifs. Accurate vibrational frequency calculations are crucial for connecting the measured spectra to the structure of PWCs. In this paper, we extend and characterize a coupled local mode (CLM) approach for calculating the infrared spectra of PWCs using the H + ( H 2 O) 4 cluster as a benchmark system. The CLM method is relatively low cost and incorporates the anharmonicity and coupling of OH vibrations. Here, we demonstrate the accuracy of the technique compared to experiments. We also illustrate the dependence of calculated spectral features on the underlying electronic structure theory and basis sets used in the local mode frequency and coupling calculations. [ABSTRACT FROM AUTHOR]

A variational model for the infra-red spectrum of vanadium monoxide (VO) is presented, which aims to accurately predict the hyperfine structure within the VO X Σ − 4 electronic ground state. To give the correct electron spin splitting of the X Σ − 4 state, electron spin dipolar interaction within the ground state and the spin–orbit coupling between X Σ − 4 and two excited states, A Π 4 and 1 Σ + 2 , are calculated ab initio alongside hyperfine interaction terms. Four hyperfine coupling terms are explicitly considered: Fermi-contact interaction, electron spin-nuclear spin dipolar interaction, nuclear spin-rotation interaction, and nuclear electric quadrupole interaction. These terms are included as part of a full variational solution of the nuclear-motion Schrödinger equation performed using program Duo, which is used to generate both hyperfine-resolved energy levels and spectra. To improve the accuracy of the model, ab initio curves are subject to small shifts. The energy levels generated by this model show good agreement with the recently derived empirical term values. This and other comparisons validate both our model and the recently developed hyperfine modules in Duo. [ABSTRACT FROM AUTHOR]

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]

The two-electron scenario is proposed for the high-order harmonic generation (HHG) by an atom interacting with an intense infrared field and attosecond pulse. The two-electron dynamics involved in the proposed scenario is realized for the specific attosecond pulse, which can excite the resonance between the valence and deeper shells. Within the numerical solution of the time-dependent Kohn–Sham equations, we analyze the contribution of the single [Phys. Rev. A 98, 063433 (2018)] and two-electron scenarios of HHG by decreasing the duration of attosecond pulse having carrier frequency detuned from the atomic resonance. Favorable conditions are formulated for the realization of a two-electron scenario, which causes the enhancement of the harmonic yield in the spectral range exceeding the cutoff energy of the HHG spectrum in the infrared field. [ABSTRACT FROM AUTHOR]

In this study, first-principles calculations were used to investigate in detail the structural, electronic, optical, and photocatalytic properties of PtS2/GeC heterostructures. The calculations demonstrate that the PtS2/GeC heterostructure has favorable stability with an inherent type-II (staggered) band alignment and a much smaller indirect bandgap of 0.83 eV than those of 2.59 and 2.80 eV for constructional PtS2 and GeC monolayers, respectively. The GeC layer transfers 0.11 ‖e‖ to the PtS2 layer and leads to a 1.3 eV potential drop, both resulting in a built-in electric field Ein from the GeC side to the PtS2 side. Both the Ein and band edge bending make the direct Z-scheme PtS2/GeC heterostructure a promising photocatalyst with the oxidation and reduction reactions achieved respectively on the PtS2 and GeC layers with high catalytic activity. The PtS2/GeC heterostructure has a higher solar-to-hydrogen (STH) energy conversion efficiency of 56.69% than that of a few previously reported photocatalytic materials. The PtS2/GeC heterostructure's ability to absorb solar light in the visible and infrared spectrum can be significantly enhanced by tensile strain. Therefore, the newly designed direct Z-scheme PtS2/GeC heterostructure is a promising photocatalyst with high STH efficiency for overall water splitting under acidic, alkaline, and neutral conditions and in large-strain regions. [ABSTRACT FROM AUTHOR]

In this paper we report an improved method of coherent sensing through the use of a generalized phase-stepping algorithm to extract magnitude and phase information from interferometric fringes acquired by laser feedback interferometry (LFI). Our approach allows for significantly reduced optical sampling and acquisition times whilst also avoiding the need for fitting to complex models of lasers under optical feedback in post-processing. We investigate theoretically the applicability of this method under different levels of optical feedback, different laser parameters, and for different sampling conditions. We furthermore validate its use experimentally for LFI-based sensing using a terahertz (THz)-frequency laser in both far-field and near-field sensing configurations. Finally we demonstrate our approach for two-dimensional nanoscale imaging of the out-of-plane field supported by individual micro-resonators at THz frequencies. Our results show that fully coherent sensing can be achieved reliably with as little as 4 sampling points per imaging pixel, opening up opportunities for fast coherent sensing not only at THz frequencies but across the visible and infra-red spectrum. [ABSTRACT FROM AUTHOR]

The key features of the interaction between peridotites of the continental lithospheric mantle and reduced hydrocarbon-rich fluids have been studied in experiments conducted at 5.5 GPa and 1200 °C. Under this interaction, the original harzburgite undergoes recrystallization while the composition of the fluid changes from CH4-H2O to H2O-rich with a small amount of CO2. The oxygen fugacity in the experiments varied from the iron-wustite (IW) to enstatite-magnesite-olivine-graphite/diamond (EMOG) buffers. Olivines recrystallized in the interaction between harzburgite and a fluid generated by the decomposition of stearic acid contain inclusions composed of graphite and methane with traces of ethane and hydrogen. The water content of such olivines slightly exceeds that of the original harzburgite. Redox metasomatism, which involves the oxidation of hydrocarbons in the fluid by reaction with magnesite-bearing peridotite, leads to the appearance of additional OH absorption bands in the infrared spectra of olivines. The water content of olivine in this case increases by approximately two times, reaching 160–180 wt. ppm. When hydrocarbons are oxidized by interaction with hematite-bearing peridotite, olivine captures Ca-Mg-Fe carbonates, which are products of carbonate melt quenching. This oxidative metasomatism is characterized by the appearance of specific OH absorption bands and a significant increase in the total water content in olivine of up to 500–600 wt. ppm. These findings contribute to the development of criteria for reconstructing metasomatic transformations in mantle rocks based on the infrared spectra and water content of olivines. [ABSTRACT FROM AUTHOR]

Silver nanoparticles (NPs) have gathered extensive attention due to their properties – chemical stability, good conductivity, catalytic activity, and antimicrobial activity. This makes NPs suitable for potential applications in the development of new technologies in the field of photonics, electronics, medicine, biochemical sensing, and imaging. Nanoprisms have local surface plasmon resonance starting from visible to near infra-red spectrum, broadening the possibilities of their applications. Ag NPs typically are synthesized in aqueous solution but the handling of NPs often requires their dispersion into nonpolar solvents and their mixing with organic compounds. Thus, nanoparticle transfer to organic media is essential for application in the field of emission enhancement due to NPs – organic semiconductor interaction. A shell changing method for NP tranfer was successfully used with a high transfer rate, but rather low stability. The previously proposed sonochemical method for NP transfer from aqueous to organic polymeric media is extended to different organic solvents. The ultrasonic method is suitable to obtain stable NPs in both organic solvent and organic solvent/organic compound solutions, and it can be stored at ambient conditions for at least several months. Transfer efficiency is suficient and NPs remain stable in an organic solvent like chlorobenzene, anisole, dichloromethane. The method has potential in NPs containing thin film preparation because sonication prevents the agglomeration of clusters. [ABSTRACT FROM AUTHOR]

Poly(aryl ether ketone) (PAEK) films with different crystallinities were obtained by controlling the cooling rate, which were subjected to the absorption and desorption of methylene chloride (CH2Cl2). We employed attenuated total reflection Fourier transform infrared (ATR-FTIR) spectroscopy analyses to investigate the diffusion behavior of CH2Cl2 in PAEK films with different crystallinities. According to the Fickian diffusion model, the calculated diffusion coefficients of CH2Cl2 in PAEK films were observed to decrease with increasing crystallinity. The effect of CH2Cl2 absorption and desorption on the mechanical properties of PAEK films with different crystallinity was further analyzed using tensile tests. The tensile tests exhibited that CH2Cl2 has two concurrent effects: plasticization and solvent-induced crystallization. Differential scanning calorimetry (DSC) and wide-angle X-ray diffraction (WXRD) techniques further confirmed solvent-induced crystallization behavior. The results would be beneficial to understand the solvent resistance of PAEK materials and consequently provide the practical application conditions of PAEK with a theoretical basis. [ABSTRACT FROM AUTHOR]