Local Vibrational Modes Research Articles

Assessing the Partial Hessian Approximation in QM/MM-Based Vibrational Analysis.

The partial Hessian approximation is often used in vibrational analysis of quantum mechanics/molecular mechanics (QM/MM) systems because calculating the full Hessian matrix is computationally impractical. This approach aligns with the core concept of QM/MM, which focuses on the QM subsystem. Thus, using the partial Hessian approximation implies that the main interest is in the local vibrational modes of the QM subsystem. Here, we investigate the accuracy and applicability of the partial Hessian vibrational analysis (PHVA) approach as it is typically used within QM/MM, i.e., only the Hessian belonging to the QM subsystem is computed. We focus on solute-solvent systems with small, rigid solutes. To separate two of the major sources of errors, we perform two separate analyses. First, we study the effects of the partial Hessian approximation on local normal modes, harmonic frequencies, and harmonic IR and Raman intensities by comparing them to those obtained using full Hessians, where both partial and full Hessians are calculated at the QM level. Then, we quantify the errors introduced by QM/MM used with the PHVA by comparing normal modes, frequencies, and intensities obtained using partial Hessians calculated using a QM/MM-type embedding approach to those obtained using partial Hessians calculated at the QM level. Another aspect of the PHVA is the appearance of normal modes resembling the translation and rotation of the QM subsystem. These pseudotranslational and pseudorotational modes should be removed as they are collective vibrations of the atoms in the QM subsystem relative to a frozen MM subsystem and, thus, not well-described. We show that projecting out translation and rotation, usually done for systems in isolation, can adversely affect other normal modes. Instead, the pseudotranslational and pseudorotational modes can be identified and removed.

A Proof-of-Concept Study of Stability Monitoring of Implant Structure by Deep Learning of Local Vibrational Characteristics

This study develops a structural stability monitoring method for an implant structure (i.e., a single-tooth dental implant) through deep learning of local vibrational modes. Firstly, the local vibrations of the implant structure are identified from the conductance spectrum, achieved by driving the structure using a piezoelectric transducer within a pre-defined high-frequency band. Secondly, deep learning models based on a convolutional neural network (CNN) are designed to process the obtained conductance data of local vibrational modes. Thirdly, the CNN models are trained to autonomously extract optimal vibration features for structural stability assessment of the implant structure. We employ a validated predictive 3D numerical modeling approach to demonstrate the feasibility of the proposed approach. The proposed method achieved promising results for predicting material loss surrounding the implant, with the best CNN model demonstrating training and testing errors of 3.7% and 4.0%, respectively. The implementation of deep learning allows optimal feature extraction in a lower frequency band, facilitating the use of low-cost active sensing devices. This research introduces a novel approach for assessing the implant’s stability, offering promise for developing future radiation-free stability assessment tools.

Temperature‐Induced Transformation of the Atomic Configuration of the BO2* Defect in Boron‐Doped Czochralski Si

In this study, the new data concerning the electronic and vibrational properties of the BsO2i* defect in Czochralski‐grown boron‐doped silicon are reported. In silicon subjected to treatment at elevated temperatures, a new boron‐related defect is detected. An additional intracenter electronic transition for boron associated with the revealed defect is observed. The defect is identified as BsO2i due to the linear dependence of its formation efficiency on the boron content and the quadratic dependence on the oxygen concentration. The revealed complex is formed synchronously with the annealing of the previously identified BsO2i* defect. The detected complex is formed as a result of temperature transformation of the atomic configuration of the BsO2i* defect. The transformation occurs with activation energy of 2.59 eV. The local vibrational modes associated with both configurations of the BsO2i* complex are identified. The results of the study suggest that the BsO2i* defect in both configurations exists in a wide temperature interval, impacts the optical and electronic properties of the material, and must be taken into consideration when developing Si:B‐based devices.

Ligand Characterization and DNA Intercalation of Ru(II) Polypyridyl Complexes: A Local Vibrational Mode Study.

We investigated in this work ruthenium-ligand bonding across the RuN framework in 12 Ru(II) polypyridyl complexes in the gas phase and solution for both singlet and triplet states, in addition to their affinity for DNA binding through π-π stacking interactions with DNA nucleobases. As a tool to assess the intrinsic strength of the ruthenium-ligand bonds, we determined local vibrational force constants via our local vibrational mode analysis software. We introduced a novel local force constant that directly accounts for the intrinsic strength of the π-π stacking interaction between DNA and the intercalated Ru(II) complex. According to our findings, [Ru(phen)2(dppz)]2+ and [Ru(phen)2(11-CN-dppz)]2+ provide an intriguing trade-off between photoinduced complex excitation and the strength of the subsequent π-π stacking interaction with DNA. [Ru(phen)2(dppz)]2+ displays a small singlet-triplet splitting and a strong π-π stacking interaction in its singlet state, suggesting a favorable photoexcitation but potentially weaker interaction with DNA in the excited state. Conversely, [Ru(phen)2(11-CN-dppz)]2+ exhibits a larger singlet-triplet splitting and a stronger π-π stacking interaction with DNA in its triplet state, indicating a less favorable photoinduced transition but a stronger interaction with DNA postexcitation. We hope our study will inspire future experimental and computational work aimed at the design of novel Ru-polypyridyl drug candidates and that our new quantitative measure of π-π stacking interactions in DNA will find a general application in the field.

Theoretical and simulation study on the vibration modes of shear walls in prefabricated modular construction

Abstract As prefabricated construction advances, the enhanced informatization and the industrialized modular construction method of MIC (Modular integrated construction) shear walls have been widely applied in real projects. MIC shear walls are generally made up of prefabricated wall modules with varying strength grades, using concrete of various ages, and are combined with cast-in-place concrete. Due to the unique construction requirements of these walls, defects such as interfacial delamination and internal voids might occur, arising from factors like concrete shrinkage and creep, complex interfacial structures, inadequate compaction during vibration, and construction process issues. Since these interfacial defects cannot be visually inspected from the exterior, developing non-destructive testing (NDT) methods specifically for detecting such defects in shear walls becomes an urgent necessity. This paper utilizes a combination of theoretical analysis and numerical simulation to explore the vibration modes of MIC shear walls with hidden defects. First, a theoretical model is proposed for the local vibration modes of MIC shear wall shells with consideration of interfacial delamination defects. Then, a numerical simulation model is established based on MIC shear wall construction and defect features to simulate the vibration behavior accurately. Finally, after examining the theoretical and simulated vibration characteristics of MIC shear walls, a significant theoretical foundation is established for identifying interfacial defects in MIC shear walls.

Extraction of uranyl from spent nuclear fuel wastewater via complexation—a local vibrational mode study

ContextThe efficient extraction of uranyl from spent nuclear fuel wastewater for subsequent reprocessing and reuse is an essential effort toward minimization of long-lived radioactive waste. N-substituted amides and Schiff base ligands are propitious candidates, where extraction occurs via complexation with the uranyl moiety. In this study, we extensively probed chemical bonding in various uranyl complexes, utilizing the local vibrational modes theory alongside QTAIM and NBO analyses. We focused on (i) the assessment of the equatorial O-U and N-U bonding, including the question of chelation, and (ii) how the strength of the axial U=\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$=$$\\end{document}O bonds of the uranyl moiety changes upon complexation. Our results reveal that the strength of the equatorial uranium-ligand interactions correlates with their covalent character and with charge donation from O and N lone pairs into the vacant uranium orbitals. We also found an inverse relationship between the covalent character of the equatorial ligand bonds and the strength of the axial uranium-oxygen bond. In summary, our study provides valuable data for a strategic modulation of N-substituted amide and Schiff base ligands towards the maximization of uranyl extraction.MethodQuantum chemistry calculations were performed under the PBE0 level of theory, paired with the relativistic NESCau Hamiltonian, currently implemented in Cologne2020 (interfaced with Gaussian16). Wave functions were expanded in the cc-pwCVTZ-X2C basis set for uranium and Dunning’s cc-pVTZ for the remaining atoms. For the bonding properties, we utilized the package LModeA in the local modes analyses, AIMALL in the QTAIM calculations, and NBO 7.0 for the NBO analyses.Graphical abstract

Role of chalcogen vacancies and hydrogen in the optical and electrical properties of bulk transition-metal dichalcogenides

Like in any other semiconductor, point defects in transition-metal dichalcogenides (TMDs) are expected to strongly impact their electronic and optical properties. However, identifying defects in these layered two-dimensional materials has been quite challenging with controversial conclusions despite the extensive literature in the past decade. Using first-principles calculations, we revisit the role of chalcogen vacancies and hydrogen impurity in bulk TMDs, reporting formation energies and thermodynamic and optical transition levels. We show that the S vacancy can explain recently observed cathodoluminescence spectra of MoS2 flakes and predict similar optical levels in the other TMDs. In the case of the H impurity, we find it more stable sitting on an interstitial site in the Mo plane, acting as a shallow donor, and possibly explaining the often observed n-type conductivity in some TMDs. We also predict the frequencies of the local vibration modes for the H impurity, aiding its identification through Raman or infrared spectroscopy.

Introduction of Local Resonators to a Nonlinear Metamaterial With Topological Features

Abstract Recent work in nonlinear topological metamaterials has revealed many useful properties such as amplitude dependent localized vibration modes and nonreciprocal wave propagation. However, thus far, there have not been any studies to include the use of local resonators in these systems. This work seeks to fill that gap through investigating a nonlinear quasi-periodic metamaterial with periodic local resonator attachments. We model a one-dimensional metamaterial lattice as a spring-mass chain with coupled local resonators. Quasi-periodic modulation in the nonlinear connecting springs is utilized to achieve topological features. For comparison, a similar system without local resonators is also modeled. Both analytical and numerical methods are used to study this system. The dispersion relation of the infinite chain of the proposed system is determined analytically through the perturbation method of multiple scales. This analytical solution is compared to the finite chain response, estimated using the method of harmonic balance and solved numerically. The resulting band structures and mode shapes are used to study the effects of quasi-periodic parameters and excitation amplitude on the system behavior both with and without the presence of local resonators. Specifically, the impact of local resonators on topological features such as edge modes is established, demonstrating the appearance of a trivial bandgap and multiple localized edge states for both main cells and local resonators. These results highlight the interplay between local resonance and nonlinearity in a topological metamaterial demonstrating for the first time the presence of an amplitude invariant bandgap alongside amplitude dependent topological bandgaps.

Bond analysis in meta- and para-substituted thiophenols: overlap descriptors, local mode analysis, and QTAIM.

This study delves into the chemical nuances of thiophenols and their derivatives through a comprehensive computational analysis, moving beyond traditional energetic perspectives such as bond dissociation enthalpy and S-H dissociation dynamics. By employing the overlap model along with its topological descriptors (OP/TOP), quantum theory of atoms in molecules (QTAIM), and local vibrational mode (LVM) theories, the research provides a deeper understanding of the S-H and C-S bonding scenarios in substituted thiophenols. The investigation follows the electron-donating capacity of S-H substituent variation with the nature and positioning of other ring substituents. Energy profile analyses indicate distinct stability differences in the cis and trans conformations of meta- and para-PhSH systems, influenced by the electron-donating strength of these substituents. The study also uncovers significant variations in S-H bond distances and descriptor values, particularly in para-substituted PhSH, reflecting the influence of electron-donating or withdrawing substituents. In contrast, alterations at the meta-position show minimal effects on C-S bond descriptors, while para-substitutions markedly influence C-S bond characteristics, demonstrating a clear correlation with the electron-donating or withdrawing capabilities of the substituents. This research sheds light on the intricate bond dynamics in aromatic systems with diverse substituents, highlighting the complex interaction between electronic effects and molecular conformation. The study employs the B97X-D/Def2TZVP level of theory for molecular geometries, ensuring accurate characterization of structures as true minima via analytical harmonic frequency determination. The electronic properties of S-H and C-S bonds in variously substituted thiophenols were analyzed using OP/TOP, QTAIM, and LVM methodologies. Computational processes, including conformational scans, geometry optimizations, and vibrational frequency calculations, were conducted using Gaussian 09, with ultra-fine integration grids and tight convergence criteria for the SCF procedure. Bond descriptors were computed utilizing ChemBOS, Multiwfn, and LModeA software, providing a robust and detailed examination of bond properties.

Prediction of phonon properties of cubic boron nitride with vacancy defects and isotopic disorders by using a neural network potential

Cubic boron nitride (c-BN) is a promising ultra-wide bandgap semiconductor for high-power electronic devices. Its thermal conductivity can be substantially modified by controlling the isotope abundance and by the quality of a single crystal. Consequently, an understanding of the phonon transport in c-BN crystals, with both vacancy defects and isotopic disorders at near-ambient temperatures, is of practical importance. In the present study, a neural network potential (NNP) for c-BN has been developed, which has facilitated the investigation of phonon properties under these circumstances. As a result, the phonon dispersion and the three- and four-phonon scattering rates that were predicted with this NNP were in close agreement with those obtained from density-functional theory (DFT) calculations. The thermal conductivities of the c-BN crystals were also investigated, with boron (B) vacancies ranging from 0.0% to 0.6%, by using equilibrium molecular dynamics simulations based on the Green-Kubo formula. These simulations accurately capture vacancy-induced phonon softening, localized vibration modes, and phonon localization effects. As has previously been experimentally prepared, four isotope-modified c-BN samples were selected for analyses in the evaluation of the impact of isotopic disorders. The calculated thermal conductivities aligned well with the DFT benchmarks. In addition, the present study was extended to include a c-BN crystal with a natural abundance of B atoms, which also contained B vacancies. Reasonable thermal conductivities and vibrational characteristics, within the temperature range of 250–500 K, were then obtained.

Investigation of carbon-related complexes in highly C-doped GaN grown by metalorganic vapor phase epitaxy

We investigated the C-related complexes in highly C-doped GaN by electron spin resonance (ESR) spectroscopy, Fourier transform IR spectroscopy (FTIR), and minority carrier transient spectroscopy (MCTS) measurements. In the ESR spectra, two resonances with g values of 2.02 and 2.04 were found to be assigned by (0/−) deep acceptor and (+/0) charge transition levels of carbon substituting for nitrogen site (CN). In the FTIR spectra, two local vibrational modes positioned at 1679 and 1718 cm−1 were confirmed to be associated with tri-carbon complexes of CN–CGa–CN (basal) and CN–CGa–CN (axial), respectively. In the MCTS spectra, we observed the hole trap level of E v + 0.25 ± 0.1 eV associated with the tri-carbon complexes, which are the dominant C-related defects, suggesting that these complexes affect the electronic properties in the highly C-doped GaN.

Multimodal seismic assessment of infrastructures retrofitted with exoskeletons: insights from the Foggia Airport case study

AbstractAddressing the seismic vulnerability of infrastructures is critical, especially for those built before the introduction of the current seismic regulations. One of the primary challenges lies in retrofitting these buildings without interrupting their functionality. In this context, the use of exoskeletons for seismic retrofitting represents an effective solution. This approach increases the seismic resistance and ensures the continuous operation of the building during retrofitting. This advantage is especially crucial for critical infrastructures, such as airports. Nevertheless, traditional seismic assessment methods based on pushover analyses might not accurately predict the seismic capacity of complex infrastructures dominated by local vibration modes. To bridge this gap, the study proposes refining the multimodal pushover analysis tailored for seismic vulnerability assessments of large infrastructures with exoskeletons characterized by low modal participation ratios. The Foggia Airport case study exemplifies these points and highlights the practical applications of the discussed advancements. The authors compared two force distributions for push-over analysis, addressing the fine-tuning of exoskeletons to maximize their seismic resistance.

An investigation of high-frequency vibration of bogie frame due to wheel/rail short-pitch irregularities and its control methodologies

High frequency impacts arising from wheel/rail short pitch irregularities have been widely reported as main casual factor of high frequency vibration of bogie frames recent years. This study aims at exploring characteristics of high frequency vibration of a metro bogie frame and its control methodologies. Firstly, the measurements obtained from a field test were employed to demonstrate the elastic vibration of bogie frame due to rail corrugation-induced impacts. Secondly, a rigid/flexible coupled dynamic model neglecting the wheel/rail contact model was established to simulate the vibration of bogie frame. Subsequently, the control methodologies were proposed to suppress the high frequency vibration of bogie frame. The results showed that the end of bogie frame is predominated by the localized bending vibration mode at 220 Hz, which is close to the passing frequency of rail corrugation at the rubber booted short sleeper track. The structural resonance serves as the main driving force of fatigue failure for the end of bogie frame. The structural improvement through installing a stiffener at end of bogie frame can effectively suppress the local bending of end of bogie frame. The piezoelectric-based actuator could serve as an alternative method to reduce the vibration level for considered frequency range.

Exploring Jahn-Teller distortions: a local vibrational mode perspective

The characterization of normal mode (CNM) procedure coupled with an adiabatic connection scheme (ACS) between local and normal vibrational modes, both being a part of the Local Vibrational Mode theory developed in our group, can identify spectral changes as structural fingerprints that monitor symmetry alterations, such as those caused by Jahn-Teller (JT) distortions. Employing the PBE0/Def2-TZVP level of theory, we investigated in this proof-of-concept study the hexaaquachromium cation case, [Cr(OH2)6]3+\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$[\ ext {Cr}{(\ ext {OH}_{2})}_{6}]^{3+}$$\\end{document}/[Cr(OH2)6]2+\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$[\ ext {Cr}(\ ext {OH}_{2})_{6}]^{2+}$$\\end{document}, as a commonly known example for a JT distortion, followed by the more difficult ferrous and ferric hexacyanide anion case, [Fe(CN)6]4-\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$[\ ext {Fe}{(\ ext {CN})}_{6}]^{4-}$$\\end{document}/[Fe(CN)6]3-\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$[\ ext {Fe}{(\ ext {CN})}_{6}]^{3-}$$\\end{document}. We found that in both cases CNM of the characteristic normal vibrational modes reflects delocalization consistent with high symmetry and ACS confirms symmetry breaking, as evidenced by the separation of axial and equatorial group frequencies. As underlined by the Cremer-Kraka criterion for covalent bonding, from [Cr(OH2)6]3+\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$[\ ext {Cr}{(\ ext {OH}_{2})}_{6}]^{3+}$$\\end{document} to [Cr(OH2)6]2+\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$[\ ext {Cr}{(\ ext {OH}_{2})}_{6}]^{2+}$$\\end{document} there is an increase in axial covalency whereas the equatorial bonds shift toward electrostatic character. From [Fe(CN)6]4-\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$[\ ext {Fe}{(\ ext {CN})}_{6}]^{4-}$$\\end{document} to [Fe(CN)6]3-\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$[\ ext {Fe}{(\ ext {CN})}_{6}]^{3-}$$\\end{document} we observed an increase in covalency without altering the bond nature. Distinct π\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$\\pi $$\\end{document} back-donation disparity could be confirmed by comparison with the isolated CN-\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$\ ext {CN}^{-}$$\\end{document} system. In summary, our study positions the CNM/ACS protocol as a robust tool for investigating less-explored JT distortions, paving the way for future applications.Graphical abstractThe adiabatic connection scheme relates local to normal modes, with symmetry breaking giving rise to axial and equatorial group local frequencies

Structural and optical characterization of dilute Bi-doped GaN nanostructures grown by molecular beam epitaxy

We have carried out detailed studies on the epitaxy and characterization of dilute Bi-doped GaN nanostructures. A comprehensive investigation of Bi-doped GaN nanowires and quasi-film epitaxial growth conditions has been performed. Scanning electron microscopy studies show that lowering the GaBiN growth temperature causes gradual changes in top c-plane nanowire morphology due to the incremental incorporation of foreign Bi atoms. This trend is further substantiated by the secondary ion mass spectroscopy analysis of a multi-layer Bi-doped GaN quasi-film. However, it is also found that the amount of Bi incorporation into the GaN lattice is relatively independent of the N2 flow rate variation under the growth conditions investigated. Furthermore, room-temperature micro-Raman spectra show that there are additional peaks near 530, 650, and 729 cm−1 wave numbers in the Bi-doped GaN samples, which can primarily be attributed to Bi local vibrational modes, indicative of a small amount of Bi incorporation in the GaN lattice. Moreover, phonon calculations with density functional theory indicate that Bi replacing the N sites is the likely origin of the experimentally measured Raman modes. X-ray photoelectron spectroscopy measurements have also been obtained to deduce the electronic interaction between the Bi dopant atom and the GaN nanostructure. Such one-dimensional nanowires permit the synthesis of dislocation-free highly mismatched alloys due to strain relaxation, allowing efficient light absorption and charge carrier extraction that is relevant for solar energy harvesting and artificial photosynthesis.

Chemical bonding in Uranium-based materials: A local vibrational mode case study of Cs UO Cl and UCl crystals.

The Local Vibrational Mode Analysis, initially applied to diverse molecular systems, was extended to periodic systems in 2019. This work introduces an enhanced version of the LModeA software, specifically designed for the comprehensive analysis of two and three-dimensional periodic structures. Notably, a novel interface with the Crystal package was established, enabling a seamless transition from molecules to periodic systems using a unified methodology. Two distinct sets of uranium-based systems were investigated: (i) the evolution of the Uranyl ion (UO ) traced from its molecular configurations to the solid state, exemplified by Cs UO Cl and (ii) Uranium tetrachloride (UCl ) in both its molecular and crystalline forms. The primary focus was on exploring the impact of crystal packing on key properties, including IR and Raman spectra, structural parameters, and an in-depth assessment of bond strength utilizing local mode perspectives. This work not only demonstrates the adaptability and versatility of LModeA for periodic systems but also highlights its potential for gaining insights into complex materials and aiding in the design of new materials through fine-tuning.

Unraveling the effect of aromaticity for the dynamics of excited states of single benzene fluorophores.

The photophysical properties of a series of recently synthesized single benzene fluorophores were investigated using ensemble density functional theory calculations. The energetic stability of the ground and excited state species were counterposed against the aromaticity index derived from local vibrational modes. It was found that the large Stokes shift of the fluorophores (up to ca. 5800 cm ) originates from the effect of electron donating and electron withdrawing substituents rather than -delocalization and related (anti-)aromaticity. On the basis of nonadiabatic molecular dynamics simulations, the absence of fluorescence from one of the regioisomers was explained by the occurrence of easily accessible S /S conical intersections below the vertical excitation energy level. It is demonstrated in the manuscript that the analysis of local mode force constants and the related aromaticity index represent a useful tool for the characterization of -delocalization effects in -conjugated compounds.

Lattice dynamics and elastic waves scattering by surrogate atoms in quasi-one dimensional atomic assemblies

An analytical and numerical formalism is developed to study the influence of the various positions of substitution atoms B on the scattering and transmission vibration modes in quasi-1D monatomic structures A. The matching technique is employed to calculate the dynamical properties and transmittance spectra of two substituted atomic sites. The theoretical formalism gives a complete description of the lattice dynamics and the vibration-waves propagation in the presence of the impurity sites. Numerical calculations are performed for three different positions of the two substituted atoms B in the low-dimensional structure consisting of double monatomic parallel chains. First, we examine the position where the two B atoms are adjacent in the y-direction, afterwards, we place the two sites side by side in the x-direction. Lastly, the two sites are placed in oblique configuration. The obtained results show that phonons associated to the inhomogeneous structures are strongly dependent on the scattering frequency, elastic force parameters and the position of the atomic substituted sites. In the three considered positions, the presence of the B atoms gives rise to localized vibration effects. The fluctuations observed in the vibration spectra are related to resonances due to the coherent coupling between travelling phonons and the localized vibration modes in the neighborhood of the impurity sites.

Metal-ring interactions in group 2 ansa-metallocenes: assessed with the local vibrational mode theory.

Ansa-metallocenes, a vital class of organometallic compounds, have attracted significant attention due to their diverse structural motifs and their pivotal roles in catalysis and materials science. We investigated 37 distinct group 2 ansa-metallocenes at the B3LYP-D3/def2-TZVP level of theory. Utilizing local mode force constants derived from our local vibrational mode theory, including a special force constant directly targeting the metal-ring interaction, we could unveil latent structural differences between solvated and non-solvated metallocenophanes and the influence of the solvent on complex stability and structure. We could quantify the intrinsic strength of the metal-cyclopentadienyl (M-Cp) bonds and the influence of the bridging motifs on the stiffness of the Cp-M-Cp angles, another determinant of complex stability. LMA was complemented by the analysis of electronic density, utilizing the quantum theory of atoms in molecules (QTAIM), which confirmed both the impact of solvent coordination on the strength of the M-Cp bond(s) and the influence of the bridging motif on the Cp-M-Cp angles. The specific effect of the ansa-motif on the M-Cp interaction was further elucidated by a comparison with linear/bent metallocene structures. In summary, our results identify the local mode analysis as an efficient tool for unraveling the intricate molecular properties of ansa-metallocenes and their unique structural features.

Topology optimization of extruded beams modeled with the XFEM for maximizing their natural frequencies

In this paper, an efficient topology optimization approach is developed for maximizing the fundamental natural frequency of extruded beams. Mass fraction and static compliance bounds are defined using inequality-type constraints in the optimization problem. An XFEM approach, previously proposed by the authors for analyzing beam elements, is extended herein to compute the natural frequencies of the beam. The method allows for 3D modeling of beams with a significant reduction in the number of degrees of freedom and therefore also yields efficient optimization procedure. This reduction is made possible by incorporating global enrichment functions in the longitudinal direction, which enables a significant reduction in the number of elements in that direction without loss of accuracy. A nonlinear optimization problem is formulated using continuous density-based design variables that represent the material distribution in the beam’s cross-section. The optimization problem is then solved using a gradient-based approach with analytical sensitivities. The well-known Solid Isotropic Material with Penalization (SIMP) method is used to acquire discrete solutions. We study the optimal design of short and long beams. It is shown that for short beams, localized vibration modes appear within the cross-section, leading to a significant distortion deformation mode of the cross-section. The optimized design of the long beam shows global deformation modes with an increase of 15% in the fundamental frequency compared with a non-optimized design consisting of a hollow rectangular cross-section with the same mass.