Vibrations Of Molecules Research Articles

Ultrastrong coupling between molecular vibrations in water and surface lattice resonances.

We investigate the vibrational ultrastrong coupling between molecular vibrations of water molecules and surface lattice resonances (SLRs) sustained by extended arrays of plasmonic microparticles. We design and fabricate an array of gold bowties, which sustain a very high field enhancement, with its SLR resonated with the OH stretching modes of water. We measure a Rabi splitting of 567 cm-1 in the strongly coupled system, whose coupling strength is 8% of the OH vibrational energy, at the onset of the ultrastrong coupling regime (10%). These results introduce metallic microparticle arrays as a platform for the investigation of ultrastrong coupling, which could be used in polaritonic chemistry to modify the dynamics of chemical reactions that require high coupling strengths.

On the study of solitary wave dynamics and interaction phenomena in the ultrasound imaging modelled by the fractional nonlinear system

This research work focuses on investigating the propagation of ultrasonic waves, which propagate mechanical vibrations of molecules or particles inside materials. Ultrasound imaging is extensively used and deeply rooted in the medical field. The key technologies that form the basis for many different uses in the area include transducers, contrast agents, pulse compression, beam shaping, tissue harmonic imaging, techniques for measuring blood flow and tissue motion, and three-dimensional imaging. The third-order non-linear β\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$\\beta$$\\end{document}-fractional Westervelt model has been used as a governing model in the imaging process for securing the different wave structures. The exact solutions of different types, including mixed, dark, singular, bright-dark, bright, complex and combined solitons are extracted. These solutions are obtained by using two newly introduced techniques, namely modified generalized Riccati equation mapping method and modified generalized exponential rational function method. Moreover, breather, lump and other waves are extracted by the assistance of logarithmic transformation and different test functions. The used methodologies are extremely effective and possess substantial computing capacity to effectively address the different solutions with a high level of accuracy in these systems. The techniques used are well-known for being effective, simple, and flexible enough to integrate multiple soliton systems into a unified framework. In addition, we provide 2D and 3D graphs that explain the behavior of the solution at various parameter values, under the influence of β\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$\\beta$$\\end{document}-fractional derivatives. The results offered in this study may improve the comprehension of the nonlinear dynamic behavior of the specific system and confirm the efficacy of the approaches used. We expect that our approaches will be beneficial for a wide range of nonlinear models and other problems in the related fields.

Dynamics of Some Perturbed Morse-Type Oscillators: Simulations and Applications

The purpose of this paper is to investigate some Morse-type oscillators. In its original form, it is a model for describing the vibrations of a diatomic molecule. The Morse potential generalizes the harmonic oscillator by introducing deviations from the classical theoretical model. In the present study, we perturbed the Morse differential equation by several periodic terms based on the cosine function and by a damping term. The frequency is driven by different coefficients. The size of the deviations is controlled by another constant. We provide two modifications w.r.t. the damping term. The Melnikov approach is applied as an indicator of the possible chaotic opportunities. We also propose a novel approach for stochastic control of the perturbations. It is based on the assumption that the coefficients of the periodic terms are the probabilities of underlying distribution. As a result, the dynamics are driven by its characteristic function. Several applications are considered. We demonstrate some specialized modules for investigating the dynamics of the proposed models, along with the synthesis of radiating antenna patterns.

Probing the Influence of Hydrophobicity of Modified Gold Nanoparticles in Modulating the Lipid Surface Behavior Using Vibrational Sum Frequency Generation Spectroscopy.

A deep understanding of how the surface modifications of nanoparticles impact their interactions with cell membranes is vital for advancing safe and effective biomedical applications. Among the pivotal factors governing these interactions, the hydrophobicity of nanoparticles plays a crucial role, predominantly driven by the hydrophobic interactions with the cell membrane. Herein, we study the influence of the hydrophobic alkyl chain length of thiol-capped gold nanoparticles (GNPs) on lipid surfaces with the help of vibrational sum frequency generation spectroscopy. We have utilized the zwitterionic 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC) lipid monolayer as a representative model of cell membranes on the water surface. Our findings revealed that GNPs capped with the thiol ligand having a shorter alkyl chain such as heptanethiol (HT, C7) show minimal changes in the C-H stretching vibrations while interacting with the lipid monolayer. These observations could be attributed to the perturbation of the lipid chain due to hydrophobic-hydrophobic interactions between the alkyl chain of thiol-capped GNPs and the hydrophobic group of the lipid membrane or simply by the adsorption of GNPs at the interface without disrupting the monolayer structure. However, with increasing the chain length of thiol-capped GNPs from decanethiol (DDT, C10) to octadecanethiol (ODT, C18), the extent of spectral change in the C-H stretching vibration is increased. The controlled experiment performed with the deuterated lipids conforms that the changes observed in the C-H stretching vibration after adding HT (C7) GNPs are only because of their presence in the surface without altering the monolayer structure. However, in the case of DT (C10) and DDT (C12) GNPs, the strong hydrophobic interactions between the monolayer and the alkyl chain of the thiol-capped GNPs result in the increased orientational order of the monolayer. Moreover, in the case of ODT (C18) GNPs, the very long alkyl chain induces pronounced perturbations in the monolayer structure with net disordering of the monolayer. These observations are further supported by the spectral changes observed in the O-H vibration of the interfacial water molecules. Our findings reveal the crucial role of the hydrophobic nature of GNPs in influencing the interface. Understanding these effects is crucial for drug delivery applications and improving the stability and effectiveness of lipid-based systems.

Determination of Photon Mass with its Main Physical Parameters Energy, Wavelength and Velocity

The excitation, transition, vibration and rotation of nuclei, atoms and molecules leading to the emission of all photons from gamma rays to radio waves as a result of the physical mechanisms responsible for excited states. The photon energy with its corresponding frequency, wavelength and distance can be determined by the main physical parameters (mass, distance, time) of the mentioned particles (Sanad, 2024). The photon mass as a particle can be determined by its main physical parameters (energy, wavelength, velocity). The determined photon mass is 2.2X10-34 kg and it is the same value of all electromagnetic radiation from gamma rays to radio waves.

Effects of Heterogeneous Mixing of Imidazolium-Based Ionic Liquids with Alcohols on Complex Formation of Ni(II) Ion.

Understanding the complex formation of metal ions in room-temperature ionic liquids (ILs) is essential for the application of ILs in solvent extraction. Nevertheless, the research on metal complex formation in ILs lags behind other applications. The complex formation equilibria may be influenced by specific interactions among the metal ion, ligand molecule, and IL cation and anion. In the present investigation, the complex formation of Ni2+ with ethanol (EtOH) and methanol (MeOH) molecules in ILs, 1-alkyl-3-methylimidazolium bis(trifluoromethylsulfonyl)amide ([CNmim][TFSA], where N represents the alkyl chain lengths of 2 and 8) was discussed in terms of the microscopic interactions among alcohol molecules, [CNmim]+ and [TFSA]-, and the mesoscopic mixing states of alcohols in [CNmim][TFSA], with N = 2-12. The microscopic interaction of alcohol molecules with the imidazolium ring H atoms in the ILs was evaluated by using ATR-IR and 1H and 13C NMR spectroscopies. The self-hydrogen bonding of alcohol molecules was clarified from the O-H stretching vibration of alcohol molecules. MeOH molecules can be more strongly hydrogen-bonded with themselves than EtOH molecules due to the less steric hindrance and the weaker dispersion force of MeOH with the IL cation's alkyl chain. In fact, small-angle neutron scattering (SANS) experiments revealed the more heterogeneous mixing of MeOH with the ILs by the self-hydrogen bonding among MeOH molecules than EtOH. The longer the IL cation's alkyl chain, the more the MeOH clusters significantly form. In contrast, the formation of EtOH clusters becomes weaker with elongating the alkyl chain. Ultraviolet (UV)-visible spectroscopic measurements on Ni2+-[CNmim][TFSA]-alcohol solutions with N = 2 and 8 revealed that di-, tetra-, and hexa-alcohol-Ni2+ complexes are formed in both the ILs. With N = 2, the stabilities of Ni2+-EtOH and Ni2+-MeOH complexes are comparable in the IL. However, with N = 8, the complexes are more stable in the EtOH solutions than in the MeOH solutions. This is because the less heterogeneous mixing of EtOH molecules with the IL results in the larger enthalpic contribution in the complex formation, as shown by the thermodynamic parameters estimated by the van't Hoff plots on the stability constants at several temperatures.

Unusual Vibrational Coupling of the Schiff Base in the Retinal Chromophore of Sodium Ion-Pumping Rhodopsins.

A Schiff base in the retinal chromophore of microbial rhodopsin is crucial to its ion transport mechanism. Here, we discovered an unprecedented isotope effect on the C═N stretching frequency of the Schiff base in sodium ion-pumping rhodopsins, showing an unusual interaction of the Schiff base. No amino acid residue attributable to the unprecedented isotope effect was identified, suggesting that the H-O-H bending vibration of a water molecule near the Schiff base was coupled with the C═N stretching vibration. A twist in the polyene chain in the chromophore for the sodium ion-pumping rhodopsins enabled this unusual interaction of the Schiff base. The present discovery provides new insights into the interaction network of the retinal chromophore in microbial rhodopsins.

Selective excitation of vibrations in a single molecule

The capability to excite, probe, and manipulate vibrational modes is essential for understanding and controlling chemical reactions at the molecular level. Recent advancements in tip-enhanced Raman spectroscopies have enabled the probing of vibrational fingerprints in a single molecule with Ångström-scale spatial resolution. However, achieving controllable excitation of specific vibrational modes in individual molecules remains challenging. Here, we demonstrate the selective excitation and probing of vibrational modes in single deprotonated phthalocyanine molecules utilizing resonance Raman spectroscopy in a scanning tunneling microscope. Selective excitation is achieved by finely tuning the excitation wavelength of the laser to be resonant with the vibronic transitions between the molecular ground electronic state and the vibrational levels in the excited electronic state, resulting in the state-selective enhancement of the resonance Raman signal. Our approach contributes to setting the stage for steering chemical transformations in molecules on surfaces by selective excitation of molecular vibrations.

Water-mediated super-correlated proton-assisted transport mode for solid-state K−O2 batteries

A comprehensive understanding of the behavior nature of fast ions at the atomic level is essential for the development of advanced solid-state ionic conductors. The inadequate inter-ion correlation effects of current ion transport models lead to a conductivity bottleneck in designing conductors. Herein, based on water-mediated proton-assisted ion transport, a novel transport mode with simultaneous anion-cation and inter-cation coupling is designed, enabling the K-ions of the modeled solid-state ionic conductor K2Fe4O7 crystals to achieve an ultra-high conductivity of 7.6 × 10–2 S cm–1, an enhancement of two orders of magnitude. The principle of the accelerated K-ion diffusion through the rotation and vibration of water molecules around the framework oxygen atom is elaborated, and the coupling correlation between proton and K-ion transport is confirmed using in-situ impedance spectroscopy under labeled isotopes. The application of this mechanism enabled the fabricated K−O2 solid-state battery exhibit an ultra-low overpotential (0.1 V) and excellent rate performance. Further, the mechanism is also applicable for Li and Na-ion conductors, providing significant theoretical guidance for breaking existing universal design rules and for the development for faster ionic conductors.

The infrared spectrum of YI3 in the vapour phase

The vibrational spectrum of the vapour phase above YI3 was measured by infrared spectroscopy. The spectrum revealed four strong bands, three of which could be assigned to the fundamantal infrared active vibrations of the YI3 monomer molecule. The observed frequencies agree very well with quantum-chemical calculations reported in literature. The presence of dimer molecules, the fraction of which is significant in the vapour according to literature, is also discussed in the context of assigning the fourth strong band in the experimental spectrum. Although its position matches well with a strong fundamental of the dimer, its intensity suggest a dimer fraction that is far outside the range for the other rare-earth triiodides.

1,1,2,2-Tetra(4-carboxylphenyl)ethylene-Based Metal-Organic Gel as Aggregation-Induced Electrochemiluminescence Emitter for the Detection of Aflatoxin B1 Based on Nanosurface Energy Transfer.

In this Letter, a sensitive DNA sensing platform was developed using an indium-ion-coordinated 1,1,2,2-tetra(4-carboxylphenyl)ethylene (TPE) metal-organic gel (In-MOG) as an aggregation-induced electrochemiluminescence (AIECL) emitter and nanosurface energy transfer (NSET) as an efficient quenching strategy for detecting aflatoxin B1 (AFB1), the most dangerous food toxin. The coordination occurred in indium ions, and carboxyl groups restricted the internal rotation and vibration of TPE molecules, forcing them to release photons via radiative transitions. The quenchers of microfluidic-produced gold nanoparticles were embedded in a long-tailed triangular DNA structure, where the quenching phenomenon aligned with the theory of ECL-NSET under the overlap of spectra and appropriate donor-acceptor spacing. The proposed analytical method showed a sensitive ECL response to AFB1 in the wide concentration range of 0.50-200.00 ng/mL with a limit of detection of 0.17 ng/mL. Experimental results confirmed that constraining luminescent molecules using coordination and bonding to trigger the AIECL phenomenon was a promising method to prepare signal labels for the trace detection of food toxins.

Disorder-dominated and scattering-dominated thermal transport in clathrate hydrates

Methane hydrate (MH) is an ice-like compound where methane molecules are encased within a lattice of water molecules. Found abundantly on ocean floors, MHs can influence future methane supplies, ocean floor stability, and climate change. In this study, a high-precision deep neural network interatomic potential for MHs is developed using ab initio molecular dynamics. Our findings reveal a transition between disorder-dominated and scattering-dominated lattice thermal transport in partially filled MHs, which are the most common form in real-world conditions. Although guest methane molecules have a minimal effect on the anharmonicity of the host lattice and the phonon band structure, they significantly increase the scattering rate of host lattice phonons by enlarging their anharmonic scattering phase space. Spectral phonon analysis further shows that methane guest molecules scatter low-frequency phonons associated with water molecule vibrations, considerably reducing the thermal conductivity of filled MHs.

Nanobody-Based Microfluidic Immunosensor Chip Using Tetraphenylethylene-Derived Covalent Organic Frameworks as Aggregation-Induced Electrochemiluminescence Emitters for the Detection of Thymic Stromal Lymphopoietin.

In this letter, a sensitive microfluidic immunosensor chip was developed using tetrakis(4-aminophenyl)ethene (TPE)-derived covalent organic frameworks (T-COF) as aggregation-induced electrochemiluminescence (AIECL) emitters and nanobodies as efficient immune recognition units for the detection of thymic stromal lymphopoietin (TSLP), a novel target of asthma. The internal rotation and vibration of TPE molecules were constrained within the framework structure, forcing nonradiative relaxation to convert into pronounced radiative transitions. A camel-derived nanobody exhibited superior specificity, higher residual activity and epitope recognition postcuring compared to monoclonal antibodies. Benefiting from the affinity between silver ions (Ag+) and cytosine (C), a double-stranded DNA (dsDNA) embedded with Ag+ was modified onto the surface of TSLP. A positive correlation was obtained between the TSLP concentration (1.00 pg/mL to 4.00 ng/mL) and ECL intensity, as Ag+ was confirmed to be an excellent accelerator of the generation of free radical species. We propose that utilizing COF to constrain luminescent molecules and trigger the AIECL phenomenon is another promising method for preparing signal tags to detect low-abundance disease-related markers.

FEATURES OF PHASE DIAGRAMS OF A TWO-FREQUENCY PENDULUM IN JAN-TELLER POTENTIAL AND HEAT CAPACITY OF WATER

A simulation of rotational vibrations of a water molecule was carried out using a model of a two-frequency pendulum in a simple Jahn–Teller potential (JTP), which has a minimum potential at a certain angle of deviation of the pendulum from the axis (the bending angle of the intermolecular hydrogen bond of the water molecule). It has been established that at low initial speeds for a given potential a new type of oscillations is observed - transverse oscillations of the pendulum inside the circular gutter JTP, at medium speeds - two-frequency independent oscillations (IO) along two axes, and at large ones - ellipse-like oscillations (ELO) at a single frequency. The work examines phase diagrams (PD) and mixed PD (MPD) in two coordinates for these two-dimensional oscillations. A significant difference between these diagrams in the JTP and standard PD is shown. The appearance of additional ellipses, loops and waves on the PD due to the appearance of transverse vibrations in the nuclear fuel gutter was discovered. To obtain ellipses in phase diagrams from all transverse oscillations of the pendulum, it is proposed to construct a PD versus radius (PDR) for the oscillation trajectory. It is shown that ellipses on the PDR for transverse oscillations of the pendulum are clearly observed at low initial speeds, but for medium and high speeds the transverse part of speed is not independently distinguished from the total speed. The presence of stable transverse vibrations in the JTP gutter for rotational vibrations of hydrogen atoms of water molecules around the axes of intermolecular bonds can be considered as new degrees of freedom for its new collectivized transverse vibrations in this potential. Their existence may lead to an explanation for the contribution of these types of oscillations to the anomalously large heat capacity of water in the liquid phase. However, for the presence of such new degrees of freedom for transverse vibrations of water molecules, it is necessary that their vibrations always take place in the region of “small” velocities - in the JTP gutter. To do this, it is necessary to increase this range of vibrations so that the maximum value of the potential on the axis of the intermolecular bond would be large. This should ensure the existence of transverse rotational oscillations in the JTP gutter for water molecules in all liquid phase temperatures.

A comprehensive study of experimental and theoretical characterization and in silico toxicity analysis of new molecules

In this study, for the first time in the literature, a 2-(3-methoxyphenylamino)-2-oxoethyl acrylate (3MPAEA) molecule was synthesized in two steps, and a 2-chloro-N-(3-methoxyphenyl)acetamide (m-acetamide) was obtained in the first step. Experimental results were obtained using FTIR, 1H, and 13C NMR spectroscopy methods for m-acetamide and 3MPAEA compounds created in the laboratory environment and compared with theoretical results. Band gap (BG) energy, chemical hardness, electronegativity, chemical potential, and electrophilicity index were calculated. With vibration spectroscopic analysis, atom–molecule vibrations of the theoretical and experimental peaks of the spectrum were observed. The locations of C and H atoms were determined by nuclear magnetic resonance spectroscopy. The green, blue, and red regions of the potential energy map (MEP) map were examined. Some observed that the energy thermal, heat capacity, and entropy graphs increased in direct proportion to increasing the temperature in Kelvin, which is known as thermochemistry. The changes in the rotation, translation, and vibration of the molecule as its temperature increased were examined. When the thermochemistry surface map was examined, some observed that the temperature was high in the middle binding site of the molecules. Covalent interactions were graphed using the non-covalent interactions (NCIs) calculation method. In silico toxicity studies were carried out for m-acetamide and 3MPAEA molecules: fathead minnow LC50 (96 h), Daphnia magna LC50 (48 h), Tetrahymena pyriformis IGC50 (48 h), oral rat LD50, water solubility, bioconcentration factor, developmental toxicity, mutation, normal boiling point, flash point, melting point, density, thermal conductivity, viscosity, vapor pressure, etc. parameters were investigated.

A general representation of thermodynamic properties for gaseous boron trifluoride

We present an accurate model for predicting the thermodynamic properties for boron trifluoride. Unlike conventional computational approaches that rely on numerous experimental spectroscopy or calorimetry data, this model only uses a small number of molecular constants. The values for entropy, enthalpy, specific heat and Gibbs free energy are computed within the temperature range from 100 to 6000 K and compared with the available experimental data. This representation introduces a new approach to deal with the anharmonic vibrations of polyatomic molecules in general.

Self-Hybridized Vibrational-Mie Polaritons in Water Droplets

We study the self-hybridization between Mie modes supported by water droplets with stretching and bending vibrations in water molecules. Droplets with radii >2.7 μm are found to be polaritonic on the onset of the ultrastrong light-matter coupling regime. Similarly, the effect is observed in larger deuterated water droplets at lower frequencies. Our results indicate that polaritonic states are ubiquitous and occur in water droplets in mists, fogs, and clouds. This finding may have implications not only for polaritonic physics but also for aerosol and atmospheric sciences. Published by the American Physical Society 2024

Decoupling excitons from high-frequency vibrations in organic molecules

The coupling of excitons in π-conjugated molecules to high-frequency vibrational modes, particularly carbon–carbon stretch modes (1,000–1,600 cm−1) has been thought to be unavoidable1,2. These high-frequency modes accelerate non-radiative losses and limit the performance of light-emitting diodes, fluorescent biomarkers and photovoltaic devices. Here, by combining broadband impulsive vibrational spectroscopy, first-principles modelling and synthetic chemistry, we explore exciton–vibration coupling in a range of π-conjugated molecules. We uncover two design rules that decouple excitons from high-frequency vibrations. First, when the exciton wavefunction has a substantial charge-transfer character with spatially disjoint electron and hole densities, we find that high-frequency modes can be localized to either the donor or acceptor moiety, so that they do not significantly perturb the exciton energy or its spatial distribution. Second, it is possible to select materials such that the participating molecular orbitals have a symmetry-imposed non-bonding character and are, thus, decoupled from the high-frequency vibrational modes that modulate the π-bond order. We exemplify both these design rules by creating a series of spin radical systems that have very efficient near-infrared emission (680–800 nm) from charge-transfer excitons. We show that these systems have substantial coupling to vibrational modes only below 250 cm−1, frequencies that are too low to allow fast non-radiative decay. This enables non-radiative decay rates to be suppressed by nearly two orders of magnitude in comparison to π-conjugated molecules with similar bandgaps. Our results show that losses due to coupling to high-frequency modes need not be a fundamental property of these systems.

The computational molecular technology for complex reaction systems: The Red Moon approach

AbstractFor dealing with complex reaction (CR) systems that show typical chemical phenomena in molecular aggregation states, the Red Moon (RM) approach is introduced based on a new efficient and systematic RM methodology. First, the theoretical background with my motivation to develop the RM approach is presented from the recent necessity to perform ‘atomistic’ molecular simulation of large‐scale and long‐term phenomena of (i) complex chemical reactions, (ii) stereospecificity, and (iii) aggregation structures. The RM methodology uses both the molecular dynamics (MD) method for molecular motions (translation, rotation, and vibration of molecules) that frequently occur on a short‐time scale and the Monte Carlo (MC) method for rare events such as chemical reactions that hardly do on that time scale. Then, under the transition rate using both the potential energy difference before and after a rare event trial and its chemical kinetic probability, it is tested and judged by the MC method whether the trial is possible (Metropolis method). Next, typical applications of the RM approach are reviewed in two main research fields, (i) polymerization and (ii) storage battery (rechargeable battery or secondary cell), with various examples of our successful studies. Finally, we conclude that the RM approach using the RM methodology should become an efficient new‐generation approach as one promising computational molecular strategy (CMT). We believe it will play an essential role in surveying, at the multilevel resolution, various specificities of CR systems in molecular aggregation states.This article is categorized under: Theoretical and Physical Chemistry > Reaction Dynamics and Kinetics Structure and Mechanism > Reaction Mechanisms and Catalysis Molecular and Statistical Mechanics > Molecular Dynamics and Monte‐Carlo Methods

Quantum model of anharmonic vibrations of a diatomic molecule with a variable force constant and a small value of the anharmonicity coefficient

Quantum model of anharmonic vibrations of a diatomic molecule with a variable force constant and a small value of the anharmonicity coefficient