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Despite having practical applications in battery technology and serving as a model system for Fermi resonance coupling, ethylene carbonate (EC) receives little direct attention as a vibrational probe in nonlinear vibrational spectroscopy experiments. EC contains a Fermi resonance that is well-characterized in the linear spectrum, and the environmental sensitivity of its Fermi resonance peaks could make it a good molecular probe for two-dimensional infrared spectroscopy (2DIR) experiments. As a model system, we investigate the linear and 2DIR vibrational spectrum of the carbonyl stretching region of ethylene carbonate in tetrahydrofuran. The 2DIR spectrum reveals peak dynamics that evolve coherently. We characterize these dynamics in the context of Redfield theory and find evidence that EC dynamics proceed through coherent pathways, including singular coherence transfer pathways that have not been widely observed in other studies. We find that coherent contributions play a significant role in the observed dynamics of cross-peaks in the 2DIR spectrum, which must be accounted for to extract accurate measurements of early waiting time dynamics. [ABSTRACT FROM AUTHOR]

The hydration shells of phosphate ions and phosphate groups of nucleotides and phospholipid membranes display markedly different structures and hydrogen-bond strengths. Understanding phosphate hydration requires insight into the spatial arrangements of water molecules around phosphates and in thermally activated structure fluctuations on ultrafast time scales. Femtosecond two-dimensional infrared spectroscopy of phosphate vibrations, particularly asymmetric stretching vibrations between 1000 and 1200 cm−1, and ab initio molecular dynamics (AIMD) simulations are combined to map and characterize dynamic local hydration structures and phosphate–water interactions. Phosphoric acid H3PO4 and its anions H2PO4−, HPO42−, and PO43− are studied in aqueous environments of different pH value. The hydration shells of phosphates providing OH donor groups in hydrogen bonds with the first water layer undergo ultrafast structural fluctuations, which induce a pronounced spectral diffusion of vibrational excitations on a sub-300 fs time scale. With a decreasing number of phosphate OH groups, the hydration shell becomes more ordered and rigid. The 2D-IR line shapes observed with hydrated PO43− ions display a pronounced inhomogeneous broadening, reflecting a distribution of hydration geometries without fast equilibration. The AIMD simulations allow for an in-depth characterization of the hydration geometries with different numbers of water molecules in the first hydration layer and different correlation functions of the fluctuating electric field that the water environment exerts on the vibrational phosphate oscillators. [ABSTRACT FROM AUTHOR]

Dipole-bound states in anions exist when a polar neutral core binds an electron in a diffuse orbital through charge–dipole interaction. Electronically excited polar neutral cores can also bind an electron in a diffuse orbital to form Core-Excited Dipole-Bound States (CE-DBSs), which are difficult to observe because they usually lie above the electron detachment threshold, leading to very short lifetimes and, thus, unstructured transitions. We report here the photodetachment spectroscopy of cryogenically cooled acetylacetonate anion (C5H7O2−) recorded by detecting the neutral radical produced upon photodetachment and the infrared spectroscopy in He-nanodroplets. Two DBSs were identified in this anion. One of them lies close to the electron detachment threshold (∼2.74 eV) and is associated with the ground state of the radical (D0-DBS). Surprisingly, the other DBS appears as resonant transitions at 3.69 eV and is assigned to the CE-DBS associated with the first excited state of the radical (D1-DBS). It is proposed that the resonant transitions of the D1-DBS are observed ∼1 eV above the detachment threshold because its lifetime is determined by the internal conversion to the D0-DBS, after which the fast electron detachment takes place. [ABSTRACT FROM AUTHOR]

In this contribution, we investigate the formation and dissociation of boron–hydrogen (BH) pairs in crystalline silicon under thermal equilibrium conditions. Our samples span doping concentrations of nearly two orders of magnitude and are passivated with a layer stack consisting of thin aluminum oxide and hydrogen-rich silicon nitride (Al 2 O 3 /SiN x :H). This layer stack acts as a hydrogen source during a following rapid thermal annealing. We characterize the samples using low-temperature Fourier-transform infrared spectroscopy and four-point-probe resistivity measurements. Our findings show that the proportion of hydrogen atoms initially bound to boron (BH pairs) rises with increasing boron concentration. Upon isothermal dark annealing at (163 ± 2) °C, hydrogen present in molecular form, H 2 , dissociates at a rate directly proportional to the concentration of boron atoms, ∝ [ B − ], leading to the formation of BH pairs. With prolonged annealing, an unknown hydrogen complex is formed at a rate that is inversely proportional to the square of the boron concentration, ∝ 1/[B − ] 2 , resulting in the disappearance of BH pairs. Based on experimental observations, we derive a kinetic model in which we describe the formation of the unknown complex through neutral hydrogen H 0 binding to a sink. Additionally, we investigate the temperature dependence of the reaction rates and find that the H 2 dissociation process has an activation energy of (1.11 ± 0.05) eV, which is in close agreement with theoretical predictions. [ABSTRACT FROM AUTHOR]

X-ray photoelectron spectroscopy, reflection-absorption infrared spectroscopy, and temperature-programmed reaction/desorption have been employed to investigate the reaction of CH3–CHCl–C(=O)Cl on Cu (100), with the aid of density functional theory (DFT) calculations. Experimentally, CH3–CH=C=O (methylketene) is found to be the product from the dechlorination of CH3–CHCl–C(=O)Cl on Cu(100) at 120 K. The CH3–CH=C=O generated on the surface would dimerize to form 2,4-dimethylcyclobutane-1,3-dione below 180 K. In agreement with the experimental findings, our DFT molecular dynamics simulations demonstrate that the dechlorination of CH3–CHCl–C(=O)Cl, resulting in CH3–CH=C=O and two Cl atoms, occurs readily, completing within 0.6 ps at 300 K. The simulations also indicate that the cleavage of the CH–Cl bond precedes that of the C(=O)–Cl bond. The static DFT calculations suggest that the dimerization of CH3–CH=C=O primarily occurs through the coupling of two C=C bonds, which has a lower barrier of 38.08 kJ mol−1 compared to the 69.05 kJ mol−1 barrier for C=C + C=O coupling. [ABSTRACT FROM AUTHOR]

Poly(N,N-diethylacrylamide) (PdEA), one of the thermoresponsive polymers, in aqueous solutions has attracted much attention because of its characteristic properties, such as coil-to-globule (CG) transition. We performed two-dimensional infrared spectroscopy and molecular dynamics (MD) simulations to understand the hydration dynamics in the vicinity of the CG transition at the molecular level via vibrational frequency fluctuations of the carbonyl stretching modes in the side chains of PdEA. Furthermore, N,N-diethylpropionamide, a repeating monomer unit of PdEA, is also investigated for comparison. From decays of the frequency–frequency time correlation functions (FFTCFs) of the carbonyl stretching modes, we consider that inhomogeneity of the hydration environments originates from various backbone configurations of PdEA. The degree of the inhomogeneity depends on temperature. Hydration water molecules near the carbonyl groups are influenced by the confinements of the polymers. The restricted reorientation of the embedded water, the local torsions of the backbone, and the rearrangement of the whole structure contribute to the slow spectral diffusion. By performing MD simulations, we calculated the FFTCFs and dynamical quantities, such as fluctuations of the dihedral angles of the backbone and the orientation of the hydration water molecules. The simulated FFTCFs match well with the experimental results, indicating that the retarded water reorientations via the excluded volume effect play an important role in the vibrational frequency fluctuations of the carbonyl stretching mode. It is also found the embedded water molecules are influenced by the local torsions of the backbone structure within the time scales of the spectral diffusion. [ABSTRACT FROM AUTHOR]

Vibrational spectroscopy of protein structure often utilizes 13C18O-labeling of backbone carbonyls to further increase structural resolution. However, sidechains such as arginine, aspartate, and glutamate absorb within the same spectral region, complicating the analysis of isotope-labeled peaks. In this study, we report that the waiting time between pump and probe pulses in two-dimensional infrared spectroscopy can be used to suppress sidechain modes in favor of backbone amide I′ modes based on differences in vibrational lifetimes. Furthermore, differences in the lifetimes of 13C18O-amide I′ modes can aid in the assignment of secondary structure for labeled residues. Using model disordered and β-sheet peptides, it was determined that while β-sheets exhibit a longer lifetime than disordered structures, amide I′ modes in both secondary structures exhibit longer lifetimes than sidechain modes. Overall, this work demonstrates that collecting 2D IR data at delayed waiting times, based on differences in vibrational lifetime between modes, can be used to effectively suppress interfering sidechain modes and further identify secondary structures. [ABSTRACT FROM AUTHOR]

Ion pair formation is a fundamental molecular process that occurs in a wide variety of systems, including electrolytes, biological systems, and materials. In solution, the thiocyanate (SCN−) anion interacts with cations to form contact ion pairs (CIPs). Due to its ambidentate nature, thiocyanate can bind through either its sulfur or nitrogen atoms, depending on the solvent. This study focuses on the binding nature of thiocyanate with lithium ions as a function of the solvents using FTIR, 2D infrared spectroscopy (2DIR) spectroscopies, and theoretical calculations. The study reveals that the SCN− binding mode (S or N end) in CIPs can be identified through 2DIR spectroscopy but not by linear IR spectroscopy. Linear IR spectroscopy shows that the CN stretch frequencies are too close to one another to separate N- and S-bound CIPs. Moreover, the IR spectrum shows that the S–C stretch presents different frequencies for the salt in different solvents, but it is related to the anion speciation rather than to its binding mode. A similar trend is observed for the anion bend. 2DIR spectra show different dynamics for N-bound and S-bound thiocyanate. In particular, the frequency–frequency correlation function (FFCF) dynamics extracted from the 2DIR spectra have a single picosecond exponential decay for N-bound thiocyanate and a biexponential decay for S-bound thiocyanate, consistent with the binding mode of the anion. Finally, it is also observed that the binding mode also affects the line shape parameters, probably due to the different molecular mechanisms of the FFCF for N- and S-bound CIPs. [ABSTRACT FROM AUTHOR]

The supra-molecular structure of a liquid is strongly connected to its dynamics, which in turn control macroscopic properties such as viscosity. Consequently, detailed knowledge about how this structure changes with temperature is essential to understand the thermal evolution of the dynamics ranging from the liquid to the glass. Here, we combine infrared spectroscopy (IR) measurements of the hydrogen (H) bond stretching vibration of water with molecular dynamics simulations and employ a quantitative analysis to extract the inter-molecular H-bond length in a wide temperature range of the liquid. The extracted expansivity of this H-bond differs strongly from that of the average nearest neighbor distance of oxygen atoms obtained through a common conversion of mass density. However, both properties can be connected through a simple model based on a random loose packing of spheres with a variable coordination number, which demonstrates the relevance of supra-molecular arrangement. Furthermore, the exclusion of the expansivity of the inter-molecular H-bonds reveals that the most compact molecular arrangement is formed in the range of ∼ 316 − 331 K (i.e., above the density maximum) close to the temperature of several pressure-related anomalies, which indicates a characteristic point in the supra-molecular arrangement. These results confirm our earlier approach to deduce inter-molecular H-bond lengths via IR in polyalcohols [Gabriel et al. J. Chem. Phys. 154, 024503 (2021)] quantitatively and open a new alley to investigate the role of inter-molecular expansion as a precursor of molecular fluctuations on a bond-specific level. [ABSTRACT FROM AUTHOR]

Ethane ( C 2 H 6 ) is anticipated to be the most stable compound within the carbon–hydrogen system under the 100 GPa pressure range. Nevertheless, the properties of ethane under pressure are still poorly documented. Here, we present a comprehensive study of the structural and vibrational properties of C 2 H 6 in a diamond anvil cell at pressures up to 150 GPa. To obtain detailed data, ethane single-crystal was grown in a helium pressure-transmitting medium. Utilizing single-crystal x-ray diffraction, the distortion mechanism between the tetragonal and monoclinic phases, occurring over the 3.2–5.2 GPa pressure range, is disclosed. Subsequently, no phase transition is observed up to 150 GPa. The accurately measured compression curve is compared to various computational approximations. The vibrational modes measured by Raman spectroscopy and infrared absorption are well identified, and their evolution is well reproduced by ab initio calculations. In particular, an unusual anticrossing phenomenon occurs near 40 GPa between a rocking and a stretching mode, likely attributable to intermolecular interactions through hydrogen bonding. [ABSTRACT FROM AUTHOR]

Superfluid helium nanodroplets are unique nanomatrices for the isolation and study of transient molecular species, such as radicals, carbenes, and ions. In this work, isomers of C3H4+ were produced upon electron ionization of propyne and allene molecules and interrogated via infrared spectroscopy inside He nanodroplet matrices. It was found that the spectrum of C3H4+ has at least three distinct groups of bands. The relative intensities of the bands depend on the precursor employed and its pickup pressure, which indicates the presence of at least three different isomers. Two isomers were identified as allene and propyne radical cations. The third isomer, which has several new bands in the range of 3100–3200 cm−1, may be the elusive vinylmethylene H2C=CH–CH+ radical cation. The observed bands for the allene and propyne cations are in good agreement with the results of density functional theory calculations. However, there is only moderate agreement between the new bands and the theoretically calculated vinylmethylene spectrum, which indicates more work is necessary to unambiguously assign it. [ABSTRACT FROM AUTHOR]

Small molecule inhibitors (SMIs) have been gaining attention in the field of area-selective atomic layer deposition (ALD) because they can be applied in the vapor-phase. A major challenge for SMIs is that vapor-phase application leads to a disordered inhibitor layer with lower coverage as compared to self-assembled monolayers, SAMs. A lower coverage of SMIs makes achieving high selectivity for area-selective ALD more challenging. To overcome this challenge, mechanistic understanding is required for the formation of SMI layers and the resulting precursor blocking. In this study, reflection adsorption infrared spectroscopy measurements are used to investigate the performance of aniline as an SMI. Our results show that aniline undergoes catalytic surface reactions, such as hydrogenolysis, on a Ru non-growth area at substrate temperatures above 250 °C. At these temperatures, a greatly improved selectivity is observed for area-selective TaN ALD using aniline as an inhibitor. The results suggest that catalytic surface reactions of the SMI play an important role in improving precursor blocking, likely through the formation of a more carbon-rich inhibitor layer. More prominently, catalytic surface reactions can provide a new strategy for forming inhibitor layers that are otherwise very challenging or impossible to form directly through vapor-phase application. [ABSTRACT FROM AUTHOR]

An IR–vacuum ultraviolet (VUV) ion-dip spectroscopy method is utilized to examine the IR spectrum of acetaldehyde oxide (CH3CHOO) in the overtone CH stretch (2νCH) spectral region. IR activation creates a depletion of the ground state population that reduces the VUV photoionization signal on the parent mass channel. IR activation of the more stable and populated syn-CH3CHOO conformer results in rapid unimolecular decay to OH + vinoxy products and makes the most significant contribution to the observed spectrum. The resultant IR–VUV ion-dip spectrum of CH3CHOO is similar to that obtained previously for syn-CH3CHOO using IR action spectroscopy with UV laser-induced fluorescence detection of OH products. The prominent IR features at 5984 and 6081 cm−1 are also observed using UV + VUV photoionization of OH products. Complementary theoretical calculations utilizing a general implementation of second-order vibrational perturbation theory provide new insights on the vibrational transitions that give rise to the experimental spectrum in the overtone CH stretch region. The introduction of physically motivated small shifts of the harmonic frequencies yields remarkably improved agreement between experiment and theory in the overtone CH stretch region. The prominent features are assigned as highly mixed states with contributions from two quanta of CH stretch and/or a combination of CH stretch with an overtone in mode 4. The generality of this approach is demonstrated by applying it to three different levels of electronic structure theory/basis sets, all of which provide spectra that are virtually indistinguishable despite showing large deviations prior to introducing the shifts to the harmonic frequencies. [ABSTRACT FROM AUTHOR]

Small anionic nickel clusters with ethanol are investigated with a combination of mass-selective infrared photodissociation spectroscopy in a molecular beam and density functional theory simulations at the BLYP/6-311g(d,p) and TPSSh/def2-TZVPP level. In this context, the O–H stretching vibration of the ethanol is analyzed to obtain information about the structural motif, the geometry of the metal core, and the spin state of the clusters. For the [Ni2(EtOH)]− and [Ni3(EtOH)]− clusters, we assign quartet states of motifs with a hydrogen bond from the ethanol to the linear nickel core. The aggregation of a further ethanol molecule, yielding the [Ni3(EtOH)2]− cluster, results in the formation of a cooperative hydrogen bond network between the nickel core and the two ethanol molecules. [ABSTRACT FROM AUTHOR]

The gas-phase rotational spectrum from 8 to 750 GHz and the high-resolution infrared (IR) spectrum of pyridazine (o-C4H4N2) have been analyzed for the ground and four lowest-energy vibrationally excited states. A combined global fit of the rotational and IR data has been obtained using a sextic, centrifugally distorted-rotor Hamiltonian with Coriolis coupling between appropriate states. Coriolis coupling has been addressed in the two lowest-energy coupled dyads (ν16, ν13 and ν24, ν9). Utilizing the Coriolis coupling between the vibrational states of each dyad and the analysis of the IR spectrum for ν16 and ν9, we have determined precise band origins for each of these fundamental states: ν16 (B1) = 361.213 292 7 (17) cm−1, ν13 (A2) = 361.284 082 4 (17) cm−1, ν24 (B2) = 618.969 096 (26) cm−1, and ν9 (A1) = 664.723 378 4 (27) cm−1. Notably, the energy separation in the ν16-ν13 Coriolis-coupled dyad is one of the smallest spectroscopically measured energy separations between vibrational states: 2122.222 (72) MHz or 0.070 789 7 (24) cm−1. Despite ν13 being IR inactive and ν24 having an impractically low-intensity IR intensity, the band origins of all four vibrational states were measured, showcasing the power of combining the data provided by millimeter-wave and high-resolution IR spectra. Additionally, the spectra of pyridazine-dx isotopologues generated for a previous semi-experimental equilibrium structure (reSE) determination allowed us to analyze the two lowest-energy vibrational states of pyridazine for all nine pyridazine-dx isotopologues. Coriolis-coupling terms have been measured for analogous vibrational states across seven isotopologues, both enabling their comparison and providing a new benchmark for computational chemistry. [ABSTRACT FROM AUTHOR]

Functionalization of perovskite nanocrystal surfaces with thiocyanate anions presents a transformative approach to enhancing stability and photoluminescence quantum yield (PLQY) through surface defect passivation. This study investigates the role of thiocyanate ligands in modifying the optoelectronic properties of CsPbBr3 nanocrystals. We employed ultrafast two-dimensional infrared spectroscopy to investigate the nature of the dynamic interaction of thiocyanate ligands with nanocrystal surfaces, providing insights into the mechanisms underlying the observed increase in PLQY and stability. Our analysis reveals that the thiocyanate ligands efficiently passivate the surface defects, thereby enhancing the PLQY and the stability of the treated nanocrystals. The spectroscopic evidence supports a model where thiocyanate binds to under-coordinated lead atoms, contributing to a stable nanocrystal surface with enhanced optoelectronic performance. This ligand-induced passivation mechanism advances our understanding of surface chemistry's role in optimizing nanomaterials for solar cell and LED applications. [ABSTRACT FROM AUTHOR]

Fluorescence-encoded infrared (FEIR) spectroscopy is a recently developed technique for solution-phase vibrational spectroscopy with detection sensitivity at the single-molecule level. While its spectroscopic information content and important criteria for its practical experimental optimization have been identified, a general understanding of the electronic and nuclear properties required for highly sensitive detection, i.e., what makes a molecule a "good FEIR chromophore," is lacking. This work explores the molecular factors that determine FEIR vibrational activity and assesses computational approaches for its prediction. We employ density functional theory (DFT) and its time-dependent version (TD-DFT) to compute vibrational and electronic transition dipole moments, their relative orientation, and the Franck–Condon factors involved in FEIR activity. We apply these methods to compute the FEIR activities of normal modes of chromophores from the coumarin family and compare these predictions with experimental FEIR cross sections. We discuss the extent to which we can use computational models to predict the FEIR activity of individual vibrations in a candidate molecule. The results discussed in this work provide the groundwork for computational strategies for choosing FEIR vibrational probes or informing the structure of designer chromophores for single-molecule spectroscopic applications. [ABSTRACT FROM AUTHOR]

β-Ga2O3 is an ultrawide bandgap semiconductor that is attracting much attention for applications in next-generation high-power, deep UV, and extreme-environment devices. Hydrogen impurities have been found to have a strong effect on the electrical properties of β-Ga2O3. This Tutorial is a survey of what has been learned about O–H centers in β-Ga2O3 from their vibrational properties. More than a dozen, O–H centers have been discovered by infrared absorption spectroscopy. Theory predicts defect structures with H trapped at split configurations of a Ga(1) vacancy that are consistent with the isotope and polarization dependence of the O–H vibrational spectra that have been measured by experiment. Furthermore, O–H centers in β-Ga2O3 have been found to evolve upon thermal annealing, giving defect reactions that modify conductivity. While much progress has been made toward understanding the microscopic properties and reactions of O–H centers in β-Ga2O3, many questions are discussed that remain unanswered. A goal of this Tutorial is to inspire future research that might solve these puzzles. [ABSTRACT FROM AUTHOR]

We describe Reflection Absorption Infrared Spectroscopy (RAIRS) and first-principles Density Functional Theory (DFT) studies of ammonia adsorption on the Cu{311} surface. Our experimental results indicate an upright chemisorbed species at low coverages, with at least one additional species accompanying this at higher coverages. Our high-coverage RAIRS data cannot be fully explained by DFT models containing only ammonia or its dissociation products, even allowing for molecular tilt and/or the formation of a bilayer. We therefore also consider urea and formamide as possible products of surface reaction with residual carbon monoxide, but these species are again not fully compatible with our observed spectra. The overlayer composition at high coverages remains mysterious. [ABSTRACT FROM AUTHOR]

Doubly resonant sum frequency generation (DR-SFG) serves as a potent characteristic technique for probing the electronic spectra and vibronic coupling of molecules on surfaces. In this study, we successfully developed a novel infrared (IR)–white light (WL) DR-SFG spectroscopy based on narrowband IR and tunable broadband WL. This novel method was employed to explore the excitation spectrum and vibronic couplings of sub-monolayer Rhodamine 6G molecules. Our findings elucidate that the xanthene skeleton vibrational modes exhibit strong coupling with the S0–S1 electronic transition. Notably, we observed not only the 0–0 transition of the S0–S1 electronic continuum but also the 0–1 transition, a first time observation in the realm of DR-SFG spectroscopy. This advanced DR-SFG spectroscopy methodology facilitates a more sensitive examination of electronic spectra and the coupling between electronic transitions and vibrational modes, heralding a significant advancement in the understanding of molecular interactions on surfaces. [ABSTRACT FROM AUTHOR]

The α-hydroxyethyl radical (CH3·CHOH, 2A) is a key intermediate in ethanol biochemistry, combustion, atmospheric chemistry, radiation chemistry, and astrochemistry. Experimental data on the vibrational spectrum of this radical are crucially important for reliable detection and understanding of the chemical dynamics of this species. This study represents the first detailed experimental report on the infrared absorption bands of the α-hydroxyethyl radical complemented by ab initio computations. The radical was generated in solid para-H2 and Xe matrices via the reactions of hydrogen atoms with matrix-isolated ethanol molecules and radiolysis of isolated ethanol molecules with x rays. The absorption bands with maxima at 3654.6, 3052.1, 1425.7, 1247.9, 1195.6 (1177.4), and 1048.4 cm−1, observed in para-H2 matrices appearing upon the H· atom reaction, were attributed to the OHstr, α-CHstr, CCstr, COstr + CCObend, COstr, and CCstr + CCObend vibrational modes of the CH3·CHOH radical, respectively. The absorption bands with the positions slightly red-shifted from those observed in para-H2 were detected in both the irradiated and post-irradiation annealed Xe matrices containing C2H5OH. The results of the experiments with the isotopically substituted ethanol molecules (CH3CD2OH and CD3CD2OH) and the quantum-chemical computations at the UCCSD(T)/L2a_3 level support the assignment. The photolysis with ultraviolet light (240–300 nm) results in the decay of the α-hydroxyethyl radical, yielding acetaldehyde and its isomer, vinyl alcohol. A comparison of the experimental and theoretical results suggests that the radical adopts the thermodynamically more stable anti-conformation in both matrices. [ABSTRACT FROM AUTHOR]

Developing fluorescence-encoded infrared (FEIR) vibrational spectroscopy for single-molecule applications requires a detailed understanding of how the molecular response and external experimental parameters manifest in the detected signals. In Paper I [L. Whaley-Mayda, A. Guha, and A. Tokmakoff, J. Chem. Phys. 159, 194201 (2023)] we introduced a nonlinear response function theory to describe vibrational dynamics, vibronic coupling, and transition dipole orientation in FEIR experiments with ultrashort pulses. In this second paper, we apply the theory to investigate the role of intermode vibrational coherence, the orientation of vibrational and electronic transition dipoles, and the effects of finite pulse durations in experimental measurements. We focus on measurements at early encoding delays—where signal sizes are largest and therefore of most value for single-molecule experiments, but where many of these phenomena are most pronounced and can complicate the appearance of data. We compare experiments on coumarin dyes with finite-pulse response function simulations to explain the time-dependent behavior of FEIR spectra. The role of the orientational response is explored by analyzing polarization-dependent experiments and their ability to resolve relative dipole angles in the molecular frame. This work serves to demonstrate the molecular information content of FEIR experiments, and develop insight and guidelines for their interpretation. [ABSTRACT FROM AUTHOR]

Fluorescence-encoded infrared (FEIR) spectroscopy is an emerging technique for performing vibrational spectroscopy in solution with detection sensitivity down to single molecules. FEIR experiments use ultrashort pulses to excite a fluorescent molecule's vibrational and electronic transitions in a sequential, time-resolved manner, and are therefore sensitive to intervening vibrational dynamics on the ground state, vibronic coupling, and the relative orientation of vibrational and electronic transition dipole moments. This series of papers presents a theoretical treatment of FEIR spectroscopy that describes these phenomena and examines their manifestation in experimental data. This first paper develops a nonlinear response function description of Fourier-transform FEIR experiments for a two-level electronic system coupled to multiple vibrations, which is then applied to interpret experimental measurements in the second paper [L. Whaley-Mayda et al., J. Chem. Phys. 159, 194202 (2023)]. Vibrational coherence between pairs of modes produce oscillatory features that interfere with the vibrations' population response in a manner dependent on the relative signs of their respective Franck–Condon wavefunction overlaps, leading to time-dependent distortions in FEIR spectra. The orientational response of population and coherence contributions are analyzed and the ability of polarization-dependent experiments to extract relative transition dipole angles is discussed. Overall, this work presents a framework for understanding the full spectroscopic information content of FEIR measurements to aid data interpretation and inform optimal experimental design. [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]

We present an IR-PD study of tantalum cluster adsorbate complexes [Tan(N2)m]+, abbreviated (n,m), n = 5–8. We utilize infrared spectroscopy of isolated and size selected clusters as prepared and characterized by a cryogenic tandem ion trap setup, and we augment our experiments with quantum chemical simulations at the level of density functional theory. The cluster adsorbate complexes (n,m) reveal vibrational bands above 2000 cm−1, which indicate end-on coordinated μ1-N2 oscillators, and bands below 2000 cm−1, which indicate side-on μ2-κN:κN,N coordinated ones. We observe a general increase in spectral complexity and an inhomogeneous broadening, mainly towards the red, at certain points of N2 loading m, which originates from an increasingly higher amount of double and triple N2 coordination at Ta sites, eventually at all of them. Other than the small tantalum clusters Tan+, n = 2–4, the IR-PD spectra of the initial N2 adsorbate species (n,1), n = 5–8, provide strong evidence for a lack of spontaneous N2 cleavage. Spontaneous N2 cleavage by Tan+, n = 5–8, seems suppressed. Therefore, the ability of a small Ta cluster to cleave dinitrogen disappears with one more tantalum core atom. The study of stepwise N2 adsorption on size selected Tan+, n = 5–8 clusters revealed adsorption limits m(max) of [Tan(N2)m]+ that are independent of cluster size within this size range. Cryo-adsorption kinetics at 26 K allowed for kinetic fits to consecutive N2 adsorption steps, and the fits revealed significant N2 desorption rates upon higher N2 loads, and the cluster adsorbate complexes eventually reached equilibrium. Some enhanced N2 desorption rates point towards likely adsorbate shell reorganization, and there is also some evidence for the coexistence of isomeric cluster adsorbate complexes. [ABSTRACT FROM AUTHOR]

We present an IR-PD study of tantalum cluster adsorbate complexes [Tan(N2)m]+, abbreviated (n,m), n = 5–8. We utilize infrared spectroscopy of isolated and size selected clusters as prepared and characterized by a cryogenic tandem ion trap setup, and we augment our experiments with quantum chemical simulations at the level of density functional theory. The cluster adsorbate complexes (n,m) reveal vibrational bands above 2000 cm−1, which indicate end-on coordinated μ1-N2 oscillators, and bands below 2000 cm−1, which indicate side-on μ2-κN:κN,N coordinated ones. We observe a general increase in spectral complexity and an inhomogeneous broadening, mainly towards the red, at certain points of N2 loading m, which originates from an increasingly higher amount of double and triple N2 coordination at Ta sites, eventually at all of them. Other than the small tantalum clusters Tan+, n = 2–4, the IR-PD spectra of the initial N2 adsorbate species (n,1), n = 5–8, provide strong evidence for a lack of spontaneous N2 cleavage. Spontaneous N2 cleavage by Tan+, n = 5–8, seems suppressed. Therefore, the ability of a small Ta cluster to cleave dinitrogen disappears with one more tantalum core atom. The study of stepwise N2 adsorption on size selected Tan+, n = 5–8 clusters revealed adsorption limits m(max) of [Tan(N2)m]+ that are independent of cluster size within this size range. Cryo-adsorption kinetics at 26 K allowed for kinetic fits to consecutive N2 adsorption steps, and the fits revealed significant N2 desorption rates upon higher N2 loads, and the cluster adsorbate complexes eventually reached equilibrium. Some enhanced N2 desorption rates point towards likely adsorbate shell reorganization, and there is also some evidence for the coexistence of isomeric cluster adsorbate complexes. [ABSTRACT FROM AUTHOR]

The structure and dynamics of water on solid surfaces critically affect the chemistry of materials in ambient and aqueous environments. Here, we investigate the hydrogen bonding network of water adsorbed on the majority (101) surface of anatase TiO2, a widely used photocatalyst, using polarization- and azimuth-resolved infrared spectroscopy combined with neural network potential molecular dynamics simulations. Our results show that one monolayer of water saturates the undercoordinated titanium (Ti5c) sites, forming one-dimensional chains of molecule hydrogen bonded to surface undercoordinated bridging oxygen (O2c) atoms. As the coverage increases, water adsorption on O2c sites leads to significant restructuring of the water monolayer and the formation of a two-dimensional hydrogen bond network characterized by tightly bound pairs of water molecules on adjacent Ti5c and O2c sites. This structural motif likely persists at ambient conditions, influencing the reactions occurring there. The results reported here provide critical details of the structure of the water–anatase (101) interface that were previously hypothesized but unconfirmed experimentally. [ABSTRACT FROM AUTHOR]

As a prototype adsorption reaction of gas Brønsted acid on oxides, we study the adsorption of formic acid on anatase. We perform infrared spectroscopy measurements of adsorbed HCOOH and HCOOD on TiO2 nanopowders, from 13 K up to room temperature in an ultra‐high vacuum chamber. We assign the IR signals via computed spectra from nuclear quantum dynamics simulations using our divide‐and‐conquer semiclassical ab initio molecular dynamics method. The acid proton forms an extraordinarily short and strong hydrogen bond with the surface oxygen. The strength of this hydrogen bond, that compares to H bonds in ice at high pressures, is at the root of a substantial redshift with respect to the typical free OH stretching frequency, which eludes its straightforward detection. [ABSTRACT FROM AUTHOR]

Two sets of glasses were prepared by rapid melt quench method in the glass system (Eu2O3)x (Na2O)0.1 (B2O3)0.6 (SLS)0.3-x and (Eu2O3)0.01 (Na2O)0.1 (B2O3)0.6 (SLS)0.29-y (MgSO4)y with x and y = 0, 0.005, 0.01, 0.03, and 0.05 mol% to check the effect of MgSO4 inclusion on the glass properties. XRF analysis confirmed the chemical composition of the SLS glass to be 70.81wt% SiO2. The addition of MgSO4 to NaSBEu glasses lowered the sample's density due to the lower density of Mg (1.738 g/cm3), whereas Eu has a density of 5.25 g/cm3. Adding MgSO4 to NaSBEu glasses raised the band gap values from 3.85 to 3.90 eV and the indirect band gap from 3.22 to 3.23 eV for NaSBEu0.005. The absorption peaks result from the trigonal BO3 bond's relaxation, which causes asymmetric vibrational stretching of the borate. The primary basis for the network structure of these glass samples is the arrangement of BO3 and BO4 units in various structural groupings. The sharpness of the IR absorption peaks increases with the addition of MgSO4. [ABSTRACT FROM AUTHOR]

This study investigates the synthesis of zinc-based metal–organic frameworks (MOFs) using tetrahydrofuran (THF) as a solvent, focusing on forming distinct phases as models for potential battery applications. Contrary to expectations, the synthesis produced three unique phases: alpha, beta, and Zn-MOF-74a, instead of the anticipated Zn-MOF-74 structure. Comprehensive structural analysis using X-ray diffraction, infrared spectroscopy, and thermogravimetric analysis (TGA) revealed distinct crystallographic features for each phase, particularly the novel Zn-MOF-74a phase, which exhibits a heart-shaped pore structure and differs from the classic hexagonal MOF-74. The study also includes the first structural determination of the dry H4DOBDC precursor, providing crucial insights for future research. The results demonstrate the significant impact of solvent choice, temperature, and pH on MOF phase formation and offer potential applications in energy storage and catalysis, especially for larger molecules. Further investigation is required to fully understand the electrochemical properties and phase stability of the newly identified Zn-MOF-74a and beta phases. [ABSTRACT FROM AUTHOR]

We conducted a retrospective study of 1055 patients with urinary stones who attended our single center from September 2017 to June 2024. Clinical data and laboratory indicators of patients were evaluated and compared with stone components. The most common type in our study was calcium oxalate (CaOx) stones (76.6%), followed by infection stones (13.2%) and uric acid (UA) stones (7.8%). Among the 1055 specimens, 899 (85.2%) cases were mixed component stones, of which calcium oxalate monohydrate (COM) and calcium oxalate dihydrate (COD) mixture were the most frequent (34.8%). There were only 156 cases (14.8%) of pure-component stones, of which anhydrous UA was the most frequent (7.0%). There were 738 males and 317 females, with a male-to-female ratio of 2.33:1. Male dominance was evident in CaOx stones (79.0 vs. 71.0%, P = 0.005). Female dominance was noted in infection stones (21.1 vs. 9.8%, P < 0.001). The multivariate analysis showed that higher serum albumin level was a risk factor for CaOx stone formation (OR = 2.959; 95% CI 1.470–5.953, P = 0.002). Women were more likely to develop infection stones than men (OR = 1.796; 95% CI 1.150–2.803, P = 0.010). As the urine pH increased, the risk of infection stones formation increased (OR = 2.521; 95% CI 1.809–3.513, P < 0.001). Moreover, a history of hypertension (OR = 2.339; 95% CI 1.409–3.881, P = 0.001), low urine pH (OR = 0.242; 95% CI 0.147–0.399, P < 0.001), and low serum albumin level (OR = 0.351; 95% CI 0.125–0.988, P = 0.047) were risk factors for the formation of UA stones. [ABSTRACT FROM AUTHOR]

Fe-doped vanadium tungsten titanium (V–W–Ti) catalysts were fabricated via an impregnation method. Furthermore, the catalysts were systematically investigated through SEM, BET, XPS, XRD, H2-TPR, NH3-TPD and in situ infrared spectroscopy. On this basis, the catalytic performance of the Fe-doped V–W–Ti catalyst for the simultaneous removal of NOx and toluene was investigated. Test results confirmed that the V–W–Ti catalyst exhibited excellent low-temperature performance with the assistance of a large specific surface area TiO2 carrier and Fe dopant. XPS results confirmed that the doping of Fe increased adsorbed oxygen and high valence vanadium, promoting the activation and adsorption of reactants and thus resulting in a conversion rate of NOx as high as 99.1% at 200 °C. In situ FTIR proved that toluene gas reduced low-temperature NH3-SCR performance via competitive adsorption with SCR gases. At the same time, enhanced oxygen mobility caused by the introduction of Fe promoted the complete oxidation of toluene, increasing the toluene removal rate by 10–20% in the synergistic denitrification and toluene removal process at 200 °C. This work provides a certain research and experimental basis for the investigation of the synergistic removal of NOx and toluene in low-temperature industrial flue gas. [ABSTRACT FROM AUTHOR]

In this study, Felodipine-loaded nanoparticles were prepared using the nanoprecipitation method, with quince seed mucilage serving as the polymer matrix and Tween 80 utilized as a stabilizing agent. The nanoparticles were thoroughly characterized using a range of analytical techniques, including dynamic light scattering (DLS), zeta potential measurement, Fourier-transform infrared spectroscopy (FTIR), thermal analysis, X-ray diffraction (XRD), and scanning electron microscopy (SEM). The Felodipine nanoparticles displayed an amorphous structure, with formulation FEL 4 achieving the highest entrapment efficiency of 67.68%. This formulation also had an average particle size of 675 ± 2.04 nm and a zeta potential of − 31.7 ± 1.34 mV. Saturation solubility tests revealed a significant enhancement in water solubility for the nanoparticles compared to pure Felodipine. Additionally, in vitro drug release studies demonstrated a sustained release profile over 24 h in phosphate buffer. Acute oral toxicity evaluations confirmed that the Felodipine nanoparticles did not exhibit any signs of toxicity. Overall, this study showed the successful fabrication of quince seed mucilage-based Felodipine-loaded nanoparticles as a promising approach to enhance solubility and achieve sustained drug release, with no evident toxicity. [ABSTRACT FROM AUTHOR]

Vibrational spectroscopy can be said to have started with the seminal work of Coblentz in the 1900s, who recorded the first recognisable infrared spectra. Today, vibrational spectroscopy is ubiquitous and there are many ways to measure a vibrational spectrum. But this is usually only the first step, almost always there is a need to assign the resulting spectra: “what property of the system results in a feature at this energy”? How this question has been answered has changed over the last century, as our understanding of the fundamental physics of matter has evolved. In this Perspective, I will present my view of how the analysis of vibrational spectra has evolved over time. The article is divided into three sections: past, present and future. The “past” section consists of a very brief history of vibrational spectroscopy. The “present” is centered around ab initio studies, particularly with density functional theory (DFT) and I will describe how this has become almost routine. For the “future”, I will extrapolate current trends and also speculate as to what might come next. [ABSTRACT FROM AUTHOR]

Electrocatalytic reduction of CO2 into C2 products of high economic value provides a promising strategy to realize resourceful CO2 utilization. Rational design and construct dual sites to realize the CO protonation and C−C coupling to unravel their structure‐performance correlation is of great significance in catalysing electrochemical CO2 reduction reactions. Herein, Cu−Cu dual sites with different site distance coordinated by halogen at the first‐shell are constructed and shows a higher intramolecular electron redispersion and coordination symmetry configurations. The long‐range Cu−Cu (Cu−I−Cu) dual sites show an enhanced Faraday efficiency of C2 products, up to 74.1 %, and excellent stability. In addition, the linear relationships that the long‐range Cu−Cu dual sites are accelerated to C2H4 generation and short‐range Cu−Cu (Cu−Cl−Cu) dual sites are beneficial for C2H5OH formation are disclosed. In situ electrochemical attenuated total reflection surface enhanced infrared absorption spectroscopy, in situ Raman and theoretical calculations manifest that long‐range Cu−Cu dual sites can weaken reaction energy barriers of CO hydrogenation and C−C coupling, as well as accelerating deoxygenation of *CH2CHO. This study uncovers the exploitation of site‐distance‐dependent electrochemical properties to steer the CO2 reduction pathway, as well as a potential generic tactic to target C2 synthesis by constructing the desired Cu−Cu dual sites. [ABSTRACT FROM AUTHOR]

The request for novel hyphenated instruments and techniques, capable of affording exhaustive information and results, is a focus continuously watched out. In this context, the present work aimed at the development of an integrated system combining gas chromatographic (GC) separation with mass spectrometry (MS) and (solid deposition) Fourier transform infrared spectroscopy (FTIR) detection. An external transfer line was designed in the lab for the parallel coupling of the two detectors, in such a way to obtain complementary analytical information consisting of an MS spectrum, an IR spectrum and linear retention indices (LRI), within a single analysis. The instrument performance was demonstrated for the analysis of a commercial mixture consisting of 139 hydrocarbons, comprising linear, branched, unsaturated and aromatic compounds. A 100-m poly(dimethylsiloxane) column was employed for the separation, and the outlet flow was split 95:5 between the IR and MS detectors using two uncoated capillaries. The IR spectra were acquired from solid deposits on a zinc selenide disc (−90 °C), over a spot (detector area) of about 0.1 mm2, in the range of 4000–700 cm−1 and at a resolution of 4 cm−1. Final identification of the separated compounds by a library search was achieved by excluding incorrect results, sequentially using a three-filter approach (85% similarity against reference MS and IR library spectra and ±10 LRI unit tolerance). Based on these preliminary results, the GC-MS/sd-FTIR system is a promising tool for the characterization of complex matrix constituents, for which identification is cumbersome, by using only one detection technique. [ABSTRACT FROM AUTHOR]

In this study, we delved into innovative strategies to make neat E‐glass fabrics (NGFs) more impact‐ and tensile‐resistant by using shear‐thickening fluids (STFs). To achieve this goal, the polyethylene glycol (PEG) in STFs has been modified. Subsequently, the STF‐impregnated fabric composites were prepared from unmodified PEG and functionally modified PEGs using malonic and tartaric acids, V/S/GF, M/S/GF, and T/S/GF composites, respectively. Fourier‐transform infrared spectroscopy (FTIR) analysis was conducted to confirm the chemical modification of PEGs. The rheological tests showed a significant improvement in the peak viscosity of modified STFs compared with virgin STF. Dynamic rheological analysis also studied media‐particle interaction, revealing improved media‐particle interaction in STFs due to abundant H‐bonding. In addition, a series of experimental tests, namely compressive impact resistance and strip tensile strength tests, have been conducted to investigate the effect of STF modification on the NGF. The results revealed notable improvements in tensile strength and energy dissipation in the T/S/GF and M/S/GF composites compared with V/S/GF and NGF. Importantly, this improvement extended to the impact performance of single, triple, and quintuple layers. Notably, we found that the peak load of 5 T/S/GF was 37.71%, 18.57%, and 11.87% lower than that of 5NGF, 5 V/S/GF, and 5 M/S/GF, respectively. The idea that made these improvements possible came from PEG functionalization, which helps hydrogen bonds form between the dispersed phase and the dispersion medium, leading to higher viscosity. This, in turn, increases inter‐yarn friction, effectively enhancing the spring‐like properties of T/S/GF and M/S/GF compared with V/S/GF. A two‐step artificial intelligence regression analysis underpinned these findings, elucidating the interplay of molecular mechanisms in high‐performance fabric composites. [ABSTRACT FROM AUTHOR]

Self‐assembling peptides (SAPs) are versatile building blocks in the creation of hierarchical nanostructures. Although SAPs promise precise control over assembled morphology and dimensions, experimental validation is still crucial. In this sense, recent efforts have focused on nanospiral structures, which mimic natural architectures and hold potential for biomedical and nanotechnological applications. Here, it is demonstrated that SARS‐CoV‐2 fusion peptides are able to form specific spiral‐like structures using interfacial assembly as a fabrication methodology, along with fine‐tuning of the spiral ensembles through an imposed interfacial flow due to the uniaxial compression in a Langmuir–Blodgett trough. Molecular characterization by atomic force microscopy, neutron reflectometry, interfacial shear rheology, and infrared spectroscopy, highlighted how variations in fusion peptide sequences influence assembly, highlighting the importance of molecular design. These spiral structures are subsequently modified to serve as templates for metallic replicas, expanding the potential of peptide‐guided self‐assembly in fabricating tailored nanostructured surfaces with sub‐10 nm dimensions over cm2 areas. [ABSTRACT FROM AUTHOR]

ABSTRACT ZnO nanoparticle surface‐modified by diisooctyl phosphate (P204) was prepared by liquid‐phase in situ surface modification technique with zinc acetate as the raw material, P204 as the modifier and anhydrous ethanol as the solvent. The morphology and microstructure of the P204‐ZnO nanoparticle were characterised by transmission electron microscopy, X‐ray diffraction and Fourier transform infrared spectrometry. Its thermal stability was evaluated by thermogravimetric analysis; and its tribological properties as the additive in alkylnaphthalene were evaluated with an SRV‐5 friction and wear tester in reciprocal sliding mode. The results show that the as‐prepared P204‐ZnO nanoparticle has an average particle size of about 4 nm and a P204 content of about 42% (mass fraction); and the surface modifier is grafted onto the surface of ZnO nanoparticle by physical adsorption. With a mass fraction of 0.5% in alkylnaphthalene base oil, P204‐ZnO nano‐additive can mildly reduce the friction coefficient and drastically reduce the wear rate of the steel–steel sliding pair. This is due to the formation of the composite tribofilm via the adsorption and deposition of the nano‐additive on rubbed steel surfaces as well as the tribochemical reactions of the modifier P204 yielding phosphate and of steel substrate yielding iron oxides. The as‐formed composite tribofilm with a thickness of about 20 nm, consisting of phosphate and iron oxides as the binder as well as deposited ZnO nanoparticle as the filling phase, is responsible for the excellent friction‐reducing and antiwear abilities of P204‐ZnO nano‐additive for the steel sliding contact. [ABSTRACT FROM AUTHOR]

Infrared (IR) spectroscopy stands as a workhorse for exploring bond vibrations, offering a wealth of chemical insights across diverse frontiers. With increasing focus on the regime of single molecules, obtaining IR‐sensitive information from individual molecules at room temperature would provide essential information about unknown molecular properties. Here, we leverage bond‐selective fluorescence microscopy, facilitated by narrowband picosecond mid‐IR and near‐IR double‐resonance excitation, for high‐throughput mid‐IR structural probing of single molecules. We robustly capture single‐molecule images and analyze the combined polarization dependence, vibrational peaks, linewidths, and lifetimes of probe molecules with representative scaffolds. From bulk to single molecules, we find that vibrational lifetimes remain consistent, while linewidths are narrowed by approximately twofold and anisotropy becomes more pronounced. Additionally, unexpected peak shifts from single molecules were observed, attributed to the generation of new modes due to previously unexplored dimerization, supported by quantum chemistry calculations. These findings underscore the importance of infrared analysis on individual single molecules in ambient environments, offering molecular information crucial for functional imaging and the investigation of the fundamental properties and utilities of luminescent molecules. [ABSTRACT FROM AUTHOR]

Epoxy asphalt, a thermosetting polymer, is characterized by stable, irreversible internal chemical bonds that prevent recovery and spontaneous micro‐crack healing, unlike conventional asphalt. This study introduces a renewable nano‐modifier synthesized via esterification of carboxyl‐functionalized carbon nanotubes (CNTs‐COOH) and furfuryl alcohol (FA), termed CNTs‐FA. The successful synthesis of CNTs‐FA was confirmed through various microscopic techniques. Integrating CNTs‐FA into epoxy asphalt materials, the optimal dosage was identified as 0.05% of the total epoxy asphalt mass using tensile tests and fluorescence microscopy. Thermal reversible effects and mechanisms were further analyzed through multiple regeneration cycles using tensile properties, fluorescence microscopy, and infrared spectroscopy. The study elucidates that the thermal reversibility in epoxy asphalt is facilitated by the Diels‐Alder (DA) reaction between the conjugated diene structure in FA and the curing agent oleylamine. This research provides an effective solution to the non‐recoverability and unrepairable micro‐cracks of traditional epoxy asphalt mixtures. Highlights: CNTs‐FA was successfully prepared by esterification reaction.Using nano modification methods, introduce DA reaction into curing system.Renewable function of epoxy asphalt by DA reversible reaction. [ABSTRACT FROM AUTHOR]

Previously studied complexes with protonic and hydridic hydrogen bonds exhibit significant similarities. The present study provides a detailed investigation of the structure, stabilization, electronic properties, and spectral characteristics of protonic and hydridic hydrogen bonds using low-temperature infrared (IR) spectroscopy and computational methods. Complexes of pentafluorobenzene with ammonia (C₆F₅H⋯NH₃) and triethylgermane with trifluoroiodomethane (Et₃GeH⋯ICF₃) were analyzed using both experimental and computational tools. Additionally, 30 complexes with protonic hydrogen bonds and 30 complexes with hydridic hydrogen bonds were studied computationally. Our findings reveal that, despite the opposite atomic charges on the hydrogens in these hydrogen bonds, and consequently the opposite directions of electron transfer in protonic and hydridic hydrogen bonds, their spectral manifestations - specifically, the red shifts in the X–H stretching frequency and the increase in intensity - are remarkably similar. The study also discusses the limitations of the current IUPAC definition of hydrogen bonding in covering both types of H-bonds and suggests a way to overcome these limitations. Understanding hydrogen-bonding is essential for many fields of natural science. Here, the authors investigate protonic and hydridic hydrogen bonds using low-temperature infrared spectroscopy and computational methods, finding that despite opposite atomic charges on the hydrogens in these hydrogen bonds their spectral manifestations are remarkably similar. [ABSTRACT FROM AUTHOR]

This study is aimed at determining how gamma irradiation (5, 10, and 15 kGy) of sorghum flour affects the physicochemical, functional, pasting, and thermal characteristics of sorghum starch. The pattern of Fourier‐transform infrared spectroscopy (FTIR) spectra and X‐ray diffraction (XRD) intensity confirmed that starch structure and granules integrality were mostly preserved. Both native and irradiated starches revealed an A‐type XRD pattern, with the irradiated starches showing lower crystallinity. However, scanning electron microscopy showed that the irradiation dose enhances the development of fissures and surface cracking on elliptical, irregular, and spherical starch granules. Starch impurities such as protein and fat decreased with increasing irradiation dose. Furthermore, the increased dosages were associated with increased solubility and syneresis. The flour also showed a remarkable improvement in the absorption of water (1.19 to 1.52 g/g) and oil (1.24 to 1.58 g/g) as the doses increased. Gamma irradiation–induced depolymerization and reduced crystallinity in sorghum starch also resulted in significant reductions in viscosity and changes in gelatinization temperatures, reflecting altered pasting properties and thermal characteristics. Overall, gamma irradiation at higher doses transformed the functional and structural properties of sorghum starch, suggesting potential applications in food and industrial sectors, where reduced retrogradation or viscosity is beneficial. [ABSTRACT FROM AUTHOR]

Vibrational spectroscopy is a widely used technique for chemical characterizations across various analytical sciences. Its applications are increasingly extending to the analysis of complex samples such as biofluids, providing high‐throughput molecular profiling. While powerful, the technique suffers from an inherent limitation: The overlap of absorption information across different spectral domains hinders the capacity to identify individual molecular substances contributing to measured signals. Despite the awareness of this challenge, the difficulty of analyzing multi‐molecular spectra is often underestimated, leading to unsubstantiated molecular interpretations. Here, we examine the prevalent overreliance on spectral band assignment and illuminate the pitfalls of correlating spectral signals to discrete molecular entities or physiological states without rigorous validation. Focusing on blood‐based infrared spectroscopy, we provide examples illustrating how peak overlap among different substances, relative substance concentrations, and preprocessing steps can lead to erroneous interpretations. We advocate for a viewpoint shift towards a more careful understanding of complex spectra, which shall lead to either accepting their fingerprinting nature and leveraging machine learning analysis – or involving additional measurement modalities for robust molecular interpretations. Aiming to help translate and improve analytical practices within the field, we highlight the limitations of molecular interpretations and feature their viable applications. [ABSTRACT FROM AUTHOR]

Herein, we present a quick and cost-effective electrodeposition method to synthesize binder-free cobalt oxide (Co3O4) nanostructures. The structural crystallinity of the prepared electrodes was examined using X-ray diffraction (XRD), while Fourier-transform infrared spectroscopy (FTIR) was used to study the stretching and bending vibrations of metal–oxygen bonds. Scanning electron microscopy (SEM) revealed that as the concentration increased from 1 mM, nanoparticles transitioned from agglomeration to sheet formation. The supercapacitor properties of these Co3O4 nanostructure electrodes were investigated in a 6 M KOH solution. Among the electrodes, Co3O4@FNF-1 exhibited the highest capacitance of 1444 F g−1 at a current density of 0.5 A g−1. Additionally, the optimized Co3O4@FNF-1 electrode demonstrated 96% stability after 8000 cycles and showed excellent glucose sensing capabilities. These findings suggest that the binder-free Co3O4 electrode is a promising candidate for high-performance supercapacitor and biosensing applications. [ABSTRACT FROM AUTHOR]

Three-dimensional mesoporous graphitic carbon nitride (Au/3Dom CN) decorated with a gold nanoparticle composite was successfully prepared via a template-assisted method using Au–SiO2 nanospheres as sacrificial agents. Combined characterization through X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM), Fourier-transform infrared spectroscopy (FT-IR) and X-ray photoelectron spectroscopy (XPS) verified the successful fabrication of the Au/3Dom CN composite. Noteworthily, Au/3Dom CN displayed good sensing performance for the electrochemical detection of dopamine (DA) with a high selectivity of 15.23 μA mM−1 and a relatively low detection limit of 0.02 μM (S/N = 3). Besides, the Au/3Dom CN composite exhibited an excellent anti-interference performance. These results reveal that the combined advantages of Au NPs and mesoporous g-C3N4 were conducive to the composite's sensing performance. Simultaneously, a mechanism was proposed to illustrate the good selectivity of the Au/3Dom CN composite for DA. This work presents a new avenue for dopamine detection using a mesoporous g-C3N4-based composite. [ABSTRACT FROM AUTHOR]

As a high heat flux linear plasma device designed for studying divertor materials in future fusion reactors, HIT-PSI(Plasma Surface Interaction device at Harbin Institute of Technology) has been successfully constructed and has maintained stable operation since its completion. The characteristics of He plasma beams in HIT-PSI are investigated by emission spectroscopy and an infrared camera, with preliminary irradiation experiments conducted by bombarding tungsten with the beam. For relatively conservative discharge parameters, HIT-PSI achieved a steady-state heat flux capacity of ∼40 MW/m2 using infrared measurements, with the full width at half maximum (FWHM) of the heat flux beam reaching 4 mm. These characteristics make HIT-PSI an advanced platform for testing divertor materials and plasma-facing components, providing essential experimental supports for research and development of high-performance divertor materials. [ABSTRACT FROM AUTHOR]

Sialic acids are monosaccharide residues involved in several biological processes. Controlling the stereoselectivity of sialylation reactions is challenging and mechanistic studies on the structure of its intermediate, the sialyl cation, are scarce. Here it is shown that a sialyl cation can be generated and isolated from an ionized sialic acid precursor. This short‐lived species is structurally characterized for the first time using cryogenic infrared spectroscopy. In combination with quantum chemical calculations, the results reveal that the positive charge at the anomeric carbon of the sialyl cation is stabilized by remote participation of the C5‐NHAc group leading to the formation of a bridged structure. In this structure, the β‐side is shielded from nucleophilic attack, potentially explaining the α‐selectivity of this building block in SN1‐type sialylation reactions. Other modes of participation are energetically unfavored and cannot be observed experimentally. [ABSTRACT FROM AUTHOR]

Malathion is one of the commonly used pesticides in India which is toxic as per the World Health Organization. Its residue has been found in industrial effluent, water streams, and agricultural products. Various analytical methods such as gas chromatography, infrared spectroscopy, and thin‐layer chromatography were used for identifying the concentration of pesticides in aqueous phase. Though gas chromatography is one of the best available techniques in pesticide analysis, it involves higher cost. In this study, simple spectrophotometric methods for identifying the malathion in aqueous phase are experimented and compared using UV visible double beam spectrophotometer. Comparing these two methods will help us to select the most suitable method for specific analytical needs, considering factors such as accuracy, sensitivity, ease of use, and safety. This comparative analysis aids in choosing the best method for reliable and efficient determination of malathion. A regression analysis of Beers–Lambert plots showed a good correlation in the concentration range of 0.5–15 mg/L for the abovementioned two spectrophotometrical methods. The results showed that potassium bromate exhibits rapid, stable color complex and linearity in absorbance versus concentration study when compared with ammonium meta vanadate. [ABSTRACT FROM AUTHOR]

Plastics make up a great portion of solid waste that constitutes an emerging threat to the natural environment. Among plastics, polyethylene is the most widely used in the world. In this research, polyethylene materials with different densities designed for packaging applications are the subject of a degradation study. The materials were exposed to simulated solar exposure and were characterized by a combination of analytical techniques to compare both chemical and physical changes, including attenuated total reflection‐Fourier transform infrared spectroscopy (ATR‐FTIR), water contact angle measurements, Raman spectroscopy, grazing incidence X‐ray Diffraction (GIXRD) and nanoindentation tests. The experimental data were systematically analyzed using statistic methods. It was found that the extent of the increase of polar groups, hydrophilicity, crystallinity, and elastic modulus depends on both the density of polyethylene and the duration of UV aging. These changes result from photooxidation and the subsequent structure reorganization occurring in amorphous chains. The implementation of various analytical techniques and statistical analysis provides a holistic understanding of polyethylene degradation behaviors. The knowledge of increased hydrophilicity/polarity in polyethylene is crucial for understanding the fate of plastics in the environment because such polyethylene changes also facilitate the environmental biodegradation on initially non‐polar polyethylene. [ABSTRACT FROM AUTHOR]