Vibrational Spectra Research Articles

Fine-tuning the photophysical properties of Imidazo[1,2-a]pyridine-based dyes by the change in substituent and solvent media: DFT and TD-DFT studies

In the present work, photophysical properties of the nine excited-state intramolecular proton transfer (ESIPT) active 2-(2 -hydroxyphenyl)imidazo[1,2-a]pyridine (HPIP)-based dyes A1-A9 (X= H, Me, F, Cl, OMe, OH, CN, NO2 and CF3) were investigated at PBE0/6-31++G(d,p) and M06-2X/6-31++G(d,p) levels of theory in the gas phase and solvent media. The structural parameters, relative energies, vibrational spectra, photophysical properties, potential energy curves, natural bond orbital (NBO) charges, hole and electron isosurfaces, electron density properties and reduced density gradient (RDG) spikes were computed. The H-bonding is strengthened at the S1 state by comparing infrared vibrational spectra, the relevant bond length and bond angle, electron density properties and RDG analysis. The results revealed that ESIPT in the A1-A7 and A9 in the gas phase is a barrier-less process, while there is an energy barrier for the A8 (X=NO2). In polar solvents, it is predicted that the ESIPT process only in A5 and A6 is a barrier-less process. The A2, A4 and A5 exhibited the greatest redshift in the keto fluorescence emission in tetrahydrofuran solvents. The significant Stokes shift observed in the S1-K emission of certain dyes makes these molecules highly appealing for various applications such as chemosensors, fluorescent probes, laser dyes and optoelectronic devices.

Neural canonical transformations for vibrational spectra of molecules.

The behavior of polyatomic molecules around their equilibrium positions can be regarded as that of quantum-coupled anharmonic oscillators. Solving the corresponding Schrödinger equations enables the interpretation or prediction of the experimental spectra of molecules. In this study, we developed a novel approach for solving the excited states of anharmonic vibrational systems. The normal coordinates of the molecules are transformed into new coordinates through a normalizing flow parameterized by a neural network. This facilitates the construction of a set of orthogonal many-body variational wavefunctions. This methodology has been validated on an exactly solvable 64-dimensional coupled harmonic oscillator, yielding numerical results with a relative error of 10-6. The neural canonical transformations are also applied to calculate the energy levels of two specific molecules, acetonitrile (CH3CN) and ethylene oxide (C2H4O). These molecules involve 12 and 15 vibrational modes, respectively. A key advantage of this approach is its flexibility concerning the potential energy surface, as it requires no specific form. Furthermore, this method can be readily implemented on large-scale distributed computing platforms, making it easy to extend to investigating complex vibrational structures.

Structural Characterization of Pyruvic Acid Dimers Formed inside Helium Nanodroplets by Infrared Spectroscopy and Ab Initio Study.

The structural arrangements of α-keto acid complexes hold significant interest across various fields of chemistry such as enzyme modeling, drug design, or polymer blending. Herein, we report mass-selective infrared (IR) spectra of pyruvic acid monomers and dimers in the range 1720-1820 cm-1 recorded in helium nanodroplets at 0.37 K. The monomer features IR bands at 1807.1 and 1734.5 cm-1, which are assigned to the carboxylic and ketonic C═O stretching vibrations, respectively. Furthermore, the pyruvic acid dimers generated inside the helium nanodroplets are characterized by carboxylic and ketonic C═O stretch vibrations appearing at 1799.2 and 1737.0 cm-1, respectively. This frequency shift of ±7 cm-1 for both C═O stretching bands from the monomer to the dimer demonstrates that the structural motif of the monomer is maintained upon dimer aggregation in helium nanodroplets. The structural assignments were supported by a comparison of the MP2/aug-cc-pVDZ-predicted harmonic vibrational spectra at the C═O stretching region with the experiments. The global minimum monomer structure with an intramolecular hydrogen bond and its dimer stabilized by both inter- and intramolecular hydrogen bonding interactions reproduce the experimental spectra from the monomer and dimer. This assigned dimer structure lies ca.11 kJ/mol above the corresponding global minimum and is favored in helium nanodroplets due to the long-range realignment of molecules via dipole-dipole interaction, followed by short-range stabilization upon intermolecular hydrogen bond formation. The barrier for reconfiguration of the precooled monomer conformer leading to the formation of the most stable dimer structure is around 58 kJ/mol, which is infeasible at 0.37 K.

Vibrational Spectra Simulations in Amino Acid-Based Imidazolium Ionic Liquids.

We present maximally localized Wannier functions and Voronoi tessellation to obtain dipole moment distributions for vibrational spectra in several important ionic liquids calculated by using ab initio molecular dynamics simulations. IR and Raman spectra of various imidazolium-based ionic liquids (ILs) paired with six amino acid anions are shown herein. For IR spectra, two approaches (Wannier and Voronoi) are in agreement with respect to the relative intensities and the overall shapes for the main peaks. Under Raman spectra, the polarizability of the covalent bonds is shown to affect the strength of the Raman scattering signal. The advantage of the Voronoi tessellation method, being that it does not have strong spikes in its time development, is demonstrated by the comparison of two theoretical methods (Wannier and Voronoi) with experimental data. We analyze the errors between theoretical and experimental spectroscopic data, with the Voronoi method shown to accurately reproduce experimental values. In addition, theoretical spectroscopy shows the ability to accurately separate components of a mixture. The combination of theoretical and experimental methods is utilized to understand the spectroscopic properties of amino acid-based imidazolium ILs.

Biogenically synthesized porous TiO2 nanostructures for advanced anti-bacterial, electrochemical, and photocatalytic applications

This study develops environmentally benign capping technique to synthesize nanoparticles of Curcuma longa-coated titanium dioxide (CR-TiO2) from titanium isopropoxide by utilizing the extract of Rosa rubiginosa flowers as reducing and chelating agent. The biogenically synthesized nanoparticles revealed excellent anti-bacterial, electrochemical, and photocatalytic properties due to the presence of porous TiO2 nanostructures. The sharp peaks by XRD pattern showed the crystallinity and phase purity of TiO2 nanoparticles. BET analysis proved mesoporous nature of the materials with specific surface area of 134 m2 g −1. The vibrational spectra suggest hydroxyl groups from flavonoids of Curcuma longa acting as functionalizing agent for TiO2 nanoporous structures with visible luminescence, which is proven in fluorescence spectra and is applicable for photocatalytic studies. The anti-bacterial studies showed good inference on TiO2 nanoparticles against Pseudomonas auruginosa and proved it to be an excellent antipseudomonal agent with the oxidative potential. The maximum degradation of phenol red dye in the presence of TiO2 under visible light conditions was observed. The supercapacitor fabricated using the biogenic TiO2 three-electrode system exhibited a specific capacitance of 128 Fg-1 (10 mV s−1), suggesting it as an excellent electrode material. The LSV curve at 50 mV s−1 scan rate showed that oxygen reduction potential (ORR) of CR-TiO2 electrodes was 121 mV. The present study is a new application of nanoparticles in sustainability consideration of the environment as well as a solution to the power crisis with fewer limitations. The well-distinguished antidiabetic and BSA denaturation potential suggests that these porous TiO2 nanostructures can be useful for drug delivery as glucose inhibitors and oral anti-inflammatory drugs with the restriction of adverse side effects.

Tip‐Enhanced Imaging and Control of Infrared Strong Light‐Matter Interaction

AbstractOptical antenna resonators enable control of light‐matter interactions on the nano‐scale via electron–photon hybrid states in strong coupling. Specifically, mid‐infrared (MIR) nano‐antennas coupled to saturable intersubband transitions in multi‐quantum‐well (MQW) semiconductor heterostructures allow for the coupling strength to be tuned through antenna resonance and field intensity. Here, tip‐enhanced nano‐scale variation of antenna‐MQW coupling across the antenna is demonstrated, with a spatially‐dependent coupling strength varying from 73 (strong coupling) to 24 (weak coupling). This behavior is modeled based on the spatially dependent local constructive and destructive interference between tip and antenna fields. Using a quantum‐mechanical density‐matrix model of the MQW system with its designed values of transition dipole moment, doping density, and population decay time, the picosecond IR pulse coupling to intersubband transitions and the associated tip induced strong‐field saturation effects are described. These results present a new regime of nonlinear IR light‐matter control based on the dynamic manipulation of quantum hybrid states on the nanoscale and in the infrared, with a perspective regarding extension to molecular vibrations.

Structural, Vibrational Spectroscopic and Theoretical (DFT) Studies of 4-Chloro- and 5-Chloro-7-azaindole-3-carbaldehydes

Molecular structures of 5-chloro-7-azaindole-3-carbaldehyde (5Cl7AICA) and 4-chloro-7-azaindole-3-carbaldehyde (4Cl7AICA) were investigated using infrared and Raman spectroscopy supported by density functional theory (DFT) calculations. Theoretical studies were carried out with three DFT methods, which include dispersion corrections: B3LYP-D3, PBE0-D3, and ωB97X-D. A single-crystal X-ray diffraction analysis was performed for 5Cl7AICA. The compound crystallizes in the monoclinic system, space group P21/c, with lattice parameters a = 3.82810(12) Å, b = 12.7330(3) Å, c = 15.9167(5) Å, and β = 94.539(3)°, with Z = 4. Within the crystal lattice, 5Cl7AICA molecules form dimers via dual and strong N1–H1⋅⋅⋅N7′ hydrogen bonds, accompanied by other intermolecular interactions. In the DFT calculations, two types of dimers of the investigated molecules were analyzed: dimer 1, which is present in the crystal structure of 5Cl7AICA, and dimer 2 displaying a 180° rotation of the aldehyde group compared to dimer 1. Computational results indicate that dimer 1 is more stable than dimer 2 for 5Cl7AICA, whereas dimer 2 is more stable than dimer 1 for 4Cl7AICA molecules. Furthermore, experimental and theoretical vibrational spectra were examined to elucidate the influence of internal rotation of the aldehyde group on spectroscopic properties.

Structural, Vibrational Spectroscopic and Theoretical (DFT) Studies of 4-Chloro- and 5-Chloro-7-azaindole-3-carbaldehydes

Molecular structures of 5-chloro-7-azaindole-3-carbaldehyde (5Cl7AICA) and 4-chloro-7-azaindole-3-carbaldehyde (4Cl7AICA) were investigated using infrared and Raman spectroscopy supported by density functional theory (DFT) calculations. Theoretical studies were carried out with three DFT methods, which include dispersion corrections: B3LYP-D3, PBE0-D3, and ωB97X-D. A single-crystal X-ray diffraction analysis was performed for 5Cl7AICA. The compound crystallizes in the monoclinic system, space group P21/c, with lattice parameters a = 3.82810(12) Å, b = 12.7330(3) Å, c = 15.9167(5) Å, and β = 94.539(3)°, with Z = 4. Within the crystal lattice, 5Cl7AICA molecules form dimers via dual and strong N1–H1⋅⋅⋅N7′ hydrogen bonds, accompanied by other intermolecular interactions. In the DFT calculations, two types of dimers of the investigated molecules were analyzed: dimer 1, which is present in the crystal structure of 5Cl7AICA, and dimer 2 displaying a 180° rotation of the aldehyde group compared to dimer 1. Computational results indicate that dimer 1 is more stable than dimer 2 for 5Cl7AICA, whereas dimer 2 is more stable than dimer 1 for 4Cl7AICA molecules. Furthermore, experimental and theoretical vibrational spectra were examined to elucidate the influence of internal rotation of the aldehyde group on spectroscopic properties.

Recent Progress in Solid-State Room Temperature Afterglow Based on Pure Organic Small Molecules.

Organic room temperature afterglow (ORTA) can be categorized into two key mechanisms: continuous thermally activated delayed fluorescence (TADF) and room-temperature phosphorescence (RTP), both of which involve a triplet excited state. However, triplet excited states are easily quenched by non-radiative transitions due to oxygen and molecular vibrations. Solid-phase systems provide a conducive environment for triplet excitons due to constrained molecular motion and limited oxygen permeation within closely packed molecules. The stimulated triplet state tends to release energy through radiative transitions. Despite numerous reports on RTP in solid-phase systems in recent years, the complexity of these systems precludes the formulation of a universal theory to elucidate the underlying principles. Several strategies for achieving ORTA luminescence in the solid phase have been developed, encompassing crystallization, polymer host-guest doping, and small molecule host-guest doping. Many of these systems exhibit luminescent responses to various physical stimuli, including light stimulation, mechanical stimuli, and solvent vapor exposure. The appearance of these intriguing luminescent phenomena in solid-phase systems underscores their significant potential applications in areas such as light sensing, biological imaging, and information security.

Recent Progress in Solid-State Room Temperature Afterglow Based on Pure Organic Small Molecules

Organic room temperature afterglow (ORTA) can be categorized into two key mechanisms: continuous thermally activated delayed fluorescence (TADF) and room-temperature phosphorescence (RTP), both of which involve a triplet excited state. However, triplet excited states are easily quenched by non-radiative transitions due to oxygen and molecular vibrations. Solid-phase systems provide a conducive environment for triplet excitons due to constrained molecular motion and limited oxygen permeation within closely packed molecules. The stimulated triplet state tends to release energy through radiative transitions. Despite numerous reports on RTP in solid-phase systems in recent years, the complexity of these systems precludes the formulation of a universal theory to elucidate the underlying principles. Several strategies for achieving ORTA luminescence in the solid phase have been developed, encompassing crystallization, polymer host-guest doping, and small molecule host-guest doping. Many of these systems exhibit luminescent responses to various physical stimuli, including light stimulation, mechanical stimuli, and solvent vapor exposure. The appearance of these intriguing luminescent phenomena in solid-phase systems underscores their significant potential applications in areas such as light sensing, biological imaging, and information security.

A novel domain adaptive method for gearbox fault diagnosis using maximum multiple-classifier discrepancy network

Abstract Domain adaptive gearbox fault diagnosis methods have made impressive achievements for the past several years. However, most of the traditional domain adaptive methods have significant limitations under fluctuating operating conditions. The acquired acceleration signals will result in different signal vibration spectra and peak vibration amplitudes due to the different working conditions between the source and target domains. There is an obvious discrepancy between the distribution of fault samples in the source domain and the target domain, which in turn makes it difficult to classify the target domain samples with fuzzy fault category boundaries. Therefore, how to measure the discrepancy between two distributions has been an important research direction in machine learning. A good metric helps to discover better features and build better models. In this paper, a novel domain adaptive method for gearbox fault diagnosis using maximum multiple-classifier discrepancy network (MMCDN) is proposed. The sparse stack autoencoder (SSAE) is used by the MMCDN as a feature extractor for fault feature extraction, and a kind of composite distance is adopted for domain discrepancy measurement of source and target domain features for domain alignment. Then the extracted features are input into a three-classifier of the model for adversarial training. The trained model classifiers have high performance in fault classification. The combination of domain adaptation and multi-classifier discrepancy output can effectively solve the impact of working condition changes and the misclassification problem for fuzzy samples with class boundaries. Experimental validation with two planetary gearbox datasets shows that the MMCDN has more favorable diagnostic accuracy and performance than other methods.

Detection of apple moldy core disease by fusing vibration and Vis/NIR spectroscopy data with dual-input MLP-Transformer

Moldy core is a highly contagious internal disease of apples, and even a small number of diseased apples can trigger large-scale infections during the storage stage. In this study, a combined acoustic vibration and Vis/NIR spectroscopy method for moldy core apple identification was proposed to improve the accuracy of moldy core identification. The vibration signals and Vis/NIR spectroscopy of apples were collected using a self-designed micro-LDV detection device and Vis/NIR spectroscopy online detection device respectively for constructing multiple moldy core apple classification models. The results showed that the classification model combining vibration spectrum and Vis/NIR spectral data had significant advantages in apple moldy core identification accuracy compared to the classification model using a single vibration spectrum or Vis/NIR spectral data. Ultimately, dual-input MLP-Transformer (DMLPT) demonstrated the best recognition performance with an overall classification accuracy of 99.31% for the model, with 100%, 97.56%, 100.00% and 100% accuracy for normal, mild moldy core disease, moderate moldy core disease and severe moldy core disease apples, respectively. This study demonstrated the excellent performance and great potential of acoustic vibration and visible/near-infrared spectral data fusion for fruit internal quality detection.

Experimental and Theoretical Studies on Indigo-Dye-Modified Conjugated Polymers.

The present work reports the synthesis of indigo-dye-incorporated polyaniline (Indigo-PANI), poly(1-naphthylamine) (Indigo-PNA), poly(o-phenylenediamine) (Indigo-POPD), polypyrrole (Indigo-PPy), and polythiophene (Indigo-PTh) via an ultrasound-assisted method. The synthesized oligomers were characterized using FTIR, UV-visible spectroscopy, X-ray diffraction (XRD), scanning electron microscopy (SEM), fluorescence studies, and thermogravimetric analysis (TGA). The experimental data were theoretically compared to analyze the vibrational and electronic spectra via time-dependent density-functional theory (TD-DFT) by applying the Becke, three-parameter, and Lee-Yang-Parr (B3LYP) method with a 6-311G (d,p) basis set. The experimental, theoretical vibrational, and electronic spectra were found to be in close agreement and confirmed the successful incorporation of indigo dye in PANI, PNA, POPD, PPy, and PTh. These studies confirmed that multifunctional oligomers could be synthesized through a facile technique by incorporating dye moieties to enhance their optoelectronic properties, allowing them to be utilized as near-infrared-emitting probes for photodynamic therapy.

Fourier-transform infrared spectroscopy with undetected photons from high-gain spontaneous parametric down-conversion

Fourier-transform infrared spectroscopy (FTIR) is an indispensable analytical method that allows label-free identification of substances via fundamental molecular vibrations. However, traditional FTIR spectrometers require mid-infrared (MIR) elements, including low-efficiency MIR photodetectors. SU(1,1) interferometry has previously enabled FTIR with undetected MIR photons via spontaneous parametric down-conversion in the low-parametric-gain regime, where the number of photons per mode is much less than one and sensitive photodetectors are needed. In this work, we develop a high-parametric-gain SU(1,1) interferometer for MIR-range FTIR with undetected photons. Using our method, we demonstrate three major advantages: a high photon number at the interferometer output, a considerably lower photon number at the sample, and improved interference contrast. In addition, we broaden the spectral range of the interferometer by aperiodic poling in the gain medium. Exploiting the broadband SU(1,1) interferometer, we measure and evaluate the MIR absorption spectra of polymers in the 3-μm region.

Synthesis and structural, morphological, and chimico-optical properties of Sr2FeO4 Ruddlesden-Popper oxide

The citrate sol-gel process was used to produce Sr2FeO4 strontium ferrite powder. The method involves metallic nitrates, citric acid and distilled water as a solvent, followed by calcination. The Ruddlesden-Popper structure of the resulting compound was identified by XRD analysis. The different molecular structures and vibration bands were studied by FTIR. The morphology of the powder was analysed using SEM. Samples appear of good crystalline quality and with interesting nanostructure. We studied optical properties and determined the band gap energy to lie about 2.8 eV, Sr2FeO4 can thus absorb photons having a wavelength less than 444 nm, approximately, making this compound potentially interesting for applications.

The effects of exoskeleton use on human response to simulated overhead tasks with vibration

The use of occupational exoskeletons has grown fast in manufacturing industries in recent years. One major scenario of exoskeleton use in manufacturing is to assist overhead, power hand tool operations. This preliminary work aimed to determine the effects of arm-supporting exoskeletons on shoulder muscle activity and human-hand tool coupling in simulated overhead tasks with axially applied vibration. An electromagnetic shaker capable of producing the random vibration spectrum specified in ISO 10819 was hung overhead to deliver vibrations. Two passive, arm-supporting exoskeletons, with one (ExoVest) transferring load to both the shoulder and pelvic region while the second one (ExoStrap) transferring load primarily to the pelvic region, were used in testing. Testing was also done with the shaker placed in front of the body to better understand the posture and exoskeleton engagement effects. The results collected from 6 healthy male subjects demonstrate the dominating effects of the overhead working posture on increased shoulder muscle activities. Vibration led to higher muscle activities in both agonist and antagonist shoulder muscles to a less extent. Exoskeleton use reduced the anterior deltoid and serratus anterior activities by 27% to 43%. However, wearing the ExoStrap increased the upper trapezius activities by 23% to 38% in the overhead posture. Furthermore, an increased human-shaker handle coupling was observed in the OH posture when wearing the ExoVest, indicating a more demanding neuromuscular control.

Biosynthesis, Structural, Spectroscopic, Photoluminescence, and Antifungal Activity of Ni-doped CeO2 Nanoparticles.

Pedalium Murex leaf extract was used in this study to create Nickel-doped Cerium oxide (Ni-CeO2) nanoparticles at 3mol% and 5mol% molar concentrations. The biosynthesized process was applied for the fabrication of Ni-CeO2 NPs. The X-ray diffraction method was used to identify their crystal structure. The XRD measurements showed that the Ni-CeO2 NPs crystallized into the face-centred cubic system. Fourier transform infrared spectral study was applied to explore the molecular vibrations and chemical bonding. The surface texture and chemical ingredients of Ni-CeO2 NPs were studied using field-emission scanning electron microscopy and energy-dispersive X-ray analysis. The EDX mapping spectra illustrate the uniform dispersal of Ce, Ni, and O atoms over the sample's surface. X-ray photoelectron spectroscopy (XPS) was conducted to confirm the chemical state of the Ni-CeO2 NPs. UV-Vis spectrum study was performed to ascertain the photon absorption, bandgap, and Urbach edge of Ni-CeO2 NPs. Photoluminescence (PL) research has been used to study the light-emitting characteristic of Ni-CeO2 NPs. The emissive intensity transition corresponding to Ni-CeO2 NPs was found to increase with the dopant level. The CIE 1931 chromaticity map was plotted to find the aptness of the samples for optical uses.The antifungal ability of Ni-CeO2 NPs was evaluated against the fungi candida albicans and candida krusein with the agar well-diffusion process. The fungicidal activity of the 3mol% Ni doped CeO2 nanoparticles has shown a maximum zone of inhibition. The experimental findings illustrate the utility of Ni-CeO2 NPs for optical and antifungal applications.

Composition effects on equilibrium oxygen isotope fractionation factors between garnets and quartz/calcite/olivine: Implication from vibration frequencies of garnets at high temperatures and high pressures

Garnet-group minerals, with their wide range of compositions, play a significant role in Earth's crust and upper mantle, participating in various petrological and geochemical processes. Oxygen isotope fractionation factors between garnets and other minerals hold crucial implications in these contexts. In this work, vibration frequencies were measured via Raman spectra on five garnet mineral samples in the pyrope-almandine-spessartine ternary system and four synthetic pyrope-grossular solid solutions at temperatures up to 1000 °C and pressures up to 17 GPa. Isobaric (γiP) and isothermal (γiT) mode Grüneisen, as well as anharmonic (ai) parameters, were determined for the observed modes. Our study shows that the vibration bands tend to shift to lower frequencies with increasing temperature and to higher frequencies with increasing pressure. Moreover, the anharmonic correction has been found to contribute positively to equilibrium oxygen isotope fractionation β factors in garnets, typically within 0.5 ‰ above 1000 K. The 103∙lnβ(T) factors calculated from vibration spectra (considering Г points only) align closely with those from theoretical calculations (including all frequencies in the Brillouin zone). Contributions from phonon dispersion (including none-Г points) are typically smaller than the uncertainties propagated from frequency measurements. Additionally, the pressure effect on the oxygen isotope fractionation in garnet, evaluated from the isothermal Grüneisen parameters, is found to be insignificant under crustal and upper mantle conditions, consistent with thermodynamic expectations. Using published oxygen isotope fractionation β factors for quartz and calcite, the equilibrium oxygen isotope fractionation factors (103∙lnα) are calculated between garnets of diverse compositions and any of these phases as functions of temperature, pressure and fraction of garnet endmembers. Considering composition effects helps to reduce the discrepancies among experimental and empirical calibrations of oxygen isotope fractionation factors between garnet and quartz. As an example application, oxygen isotope fractionation factors 103∙lnα(P, T) between garnets and forsterite were calculated under upper mantle conditions. Our findings suggest that these fractionation factors are predominantly dependent on temperature and garnet compositions, with minor influence from pressure. Compared with our calculated fractionation factors between garnet and olivine, the oxygen isotope exchange equilibrium may have been reached in some in kimberlite and mantle xenolith samples between garnet and olivine. However, in other samples, the fractionation factors cannot be explained solely by the composition effect, likely due to metasomatism. Our results underscore the importance of considering garnet compositions when interpreting their oxygen isotope compositions.

Investigating quantum coherence of N-methylpyrrole through vibrational spectroscopy and potential energy: A theoretical study

Quantum chemical calculations are utilized to analyze the potential causes of N-methylpyrrole oscillations, focusing on vibration spectra and potential energy curves. Optimization of the ground state, ionic state and 3s state structure reveal mostly sp2 hybridization. An analysis of the 3s state vibration spectrum and adiabatic binding energy indicate that changes in dihedral angles D2,3,4,1 and plane angle A3,2,1 are potential factors contributing to molecular oscillations. The role of vertical binding energy and adiabatic binding energy in the oscillation process are also discussed, shedding light on the possible dynamic processes of N-methylpyrrole

Ab initio molecular dynamics study of hydroxyl positioning in butanediol and its impact on deep eutectic solvent structure

Electrolytes play a crucial role in enhancing the performance of energy storage devices, including batteries and supercapacitors. However, traditional electrolytes, such as aqueous solutions, organic solvents, and ionic liquids, exhibit inherent limitations and challenges. Deep eutectic solvents have recently emerged as promising alternatives due to their environmentally friendly nature and favorable properties. Despite their widespread applications in various domains, their potential as electrolytes remains relatively underexplored. This study investigates three distinct types of deep eutectic solvents derived from different isomers of butanediols combined with choline chloride. Ab initio molecular dynamics simulations are employed to analyze the microstructure of these deep eutectic solvents, focusing on non-covalent electrostatic interactions, hydrogen bonding patterns, and vibrational spectra. The results reveal significant differences in the structural configuration of hydrogen bond acceptors and hydrogen bond donors and their interactions within the deep eutectic solvents. Specifically, the positioning of functional groups in hydrogen bond donors significantly impacts the hydrogen bonding network and the interaction with monoatomic ions. Moreover, the vibrational spectra analysis highlights the existence of hydrogen bonds involving stretching modes of the OH group, as evidenced by redshift deviations. Overall, this study provides valuable insights into the unique features of deep eutectic solvents as potential electrolytes for energy storage applications. The comprehensive analysis of their microstructure and vibrational properties enhances our understanding of deep eutectic solvent utilization and opens avenues for further research in sustainable energy storage.