Thermal Vibrations Research Articles

The correlation of the liquidus curves and valence electron structures of a ternary lithium halide molten-salt electrolyte for liquid metal batteries.

Liquid metal batteries have received considerable attention owing to their excellent properties. However, an electrolyte with low melting temperature is required to decrease operating temperature for the safety of liquid metal batteries and for saving energy. For revealing the mechanism of low liquefaction temperature, an empirical electron theory of solid molecules was used to study the thermal properties of pure lithium halides and their ternary-phase systems systematically. The theoretical bond lengths, melting points, liquefaction temperatures and mixed energies of pure lithium halides and their ternary phases match the experimental values well. The mechanism of liquefaction temperature for ternary lithium halides depends on their valence electron structures. The liquefaction temperature can be stabilized on a liquidus line or curve through the modulation of the constant number of covalent electrons (nc) and lattice electrons (nl). The liquefaction temperatures on various liquidus lines and curves are positively related to the linear density of valence electron pairs on the strong Li-X bond, bonding factor, and number of valence electrons in the s orbital but are negatively related to the number of valence electrons in the p orbital. With an increase in the linear density of the valence electron pair number and bonding factor, bond strength is enhanced, which increases the resistance of the strong Li-X bond against the break force induced by thermal phonon vibrations, and more thermal phonons with high vibrating energy are required for breaking the strongest Li-X bond at a higher temperature; therefore, the liquefaction temperature increases.

Resonance energy transfer in orthogonally arranged chromophores: a question of molecular representation.

Energy transfer between orthogonally arranged chromophores is typically considered impossible according to conventional Förster resonance energy transfer theory. Nevertheless, the disruption of orthogonality by nuclear vibrations can enable energy transfer, what has prompted the necessity for formal expansions of the standard theory. Here, we propose that there is no need to extend conventional Förster theory in such cases. Instead, a more accurate representation of the chromophores is required. Through calculations of the energy transfer rate using structures from a thermal ensemble, rather than relying on equilibrium geometries, we show that the standard Förster resonance energy transfer theory is still capable of describing energy transfer in orthogonally arranged systems. Our calculations explain how thermal vibrations influence the electronic properties of the states involved in energy transfer, affecting the alignment of transition dipole moments and the intensity of transitions.

One-dimensional Fe/C constructed Janus membrane enables highly-efficient and stable solar-driven interfacial evaporation

The practical use of solar-driven interfacial evaporation is hampered by high cost, low photothermal conversion efficiency, and poor stability. Herein, a one-dimensional Fe/C constructed photothermal membrane is rationally developed to replace precious metals via the combination of Fe plasmon resonance with carbon molecular thermal vibration. The membrane exhibits excellent light absorbance (95.72 ​%) and water evaporation rate (2.60 ​kg ​m−2 ​h−1) leading to photothermal conversion efficiency up to 95.65 ​% under 1 sun illumination. Janus Fe/C membrane with superhydrophobic and hydrophilic structure is further prepared by polydimethylsiloxane (PDMS) coating to improve long-term stability. The evaporation rate can be maintained at over 90 ​% after 80 ​h illumination for real seawater treatment with metal ion removal efficiency >99 ​%. It also shows high evaporation performance and stability for organic solvents such as IPA, and NMP. Thus, the 1D Fe/C constructed Janus membrane is a promising candidate for energy-saving solar-driven interfacial solvent evaporation including seawater desalination, wastewater treatment, and organic solvent purification.

A molecular descriptor of a shallow potential energy surface for the ground state to achieve narrowband thermally activated delayed fluorescence emission.

Narrowband thermally activated delayed fluorescence (TADF) molecules have extensive applications in optoelectronics, biomedicine, and energy. The full-width at half-maximum (FWHM) holds significant importance in assessing the luminescence efficiency and color purity of TADF molecules. The goal is to achieve efficient and stable TADF emissions by regulating and optimizing the FWHM. However, a bridge from the basic physical parameters (such as geometric structure and reorganization energy) to the macroscopic properties (delayed fluorescence, efficiency, and color purity) is needed and it is highly necessary and urgent to explore the internal mechanisms that influence FWHM. Herein, first-principles calculations coupled with the thermal vibration correlation function (TVCF) theory were performed to study the energy consumption processes of the excited states for the three TADF molecules (2,3-POA, 2,3-DPA, and 2,3-CZ) with different donors; inner physical parameters affecting the FWHM were detected. By analyzing the basic geometric and electronic structures as well as the transition properties and reorganization energies, three main findings in modulating FWHM were obtained, namely a large local excitation (LE) proportion in the first singlet excited state is advantageous in reducing FWHM, a donor group with weak electron-donating ability is beneficial for achieving narrowband emission, and small reorganization energies for the ground state are favorable for reducing FWHM. Thus, wise molecular design strategies to achieve efficient narrowband TADF emission are theoretically proven and proposed. We hope that these results will promote an in-depth understanding of FWHM and accelerate the development of high color purity TADF emitters.

The influence of heteroatoms on the circularly polarized luminescence performance of [7]helicene derivatives: aromatic vs. non-aromatic five-membered rings.

Helicenes are promising candidates for circularly polarized luminescence (CPL) materials, although the performance is poor due to the unsatisfactory dissymmetric factor (glum) and fluorescence quantum efficiency (ΦF). Herein, the influence of heteroatoms (C, Si, Ge, O, S and Se) on the electronic structures and chiroptical properties of [7]helicene derivatives is systematically investigated using density functional theory (DFT) and time-dependent DFT calculations combined with the thermal vibration correlation function theory. The results reveal that the non-radiative energy consumption processes for helicene systems are closely related to the variation of bond length upon electronic excitation. Moreover, by introducing five-membered rings and heteroatoms, the dipole-forbidden S1 → S0 emission of [7]helicene changes to dipole-allowed transition due to the rearrangement of occupied orbitals and lifting of the nearly degenerate orbitals, resulting in an enhancement of ΦF. As the heteroatomic radius increases, ΦF decreases while the glum increases. Compared with the derivatives containing aromatic five-membered rings ([7]H-O, [7]H-S, and [7]H-Se), the non-aromatic counterparts ([7]H-C, [7]H-Si, and [7]H-Ge) exhibit a balance in ΦF and glum values. The present study helps to clarify the relationship between structures and chiroptical properties and offers a feasible strategy for the future design of helicene-based CPL materials.

Modulation of luminescence properties of circularly polarized thermally activated delayed fluorescence molecules with axial chirality by donor engineering.

Multifunctional thermally activated delayed fluorescence (TADF) materials are currently a trending research subject for luminescence layer materials of organic light-emitting diodes (OLEDs). Among these, circularly polarized thermally activated delayed fluorescence (CP-TADF) materials have the advantage of being able to directly achieve highly efficient circularly polarized luminescence (CPL). The simultaneous integration of outstanding luminescence efficiency and excellent luminescence asymmetry factor (glum) is a major constraint for the development of CP-TADF materials. Therefore, on the basis of first-principles calculations in conjunction with the thermal vibration correlation function (TVCF) method, we study CP-TADF molecules with different donors to explore the feasibility of using the donor substitution strategy for optimizing the CPL and TADF properties. The results indicate that molecules with the phenothiazine (PTZ) unit as the donor possess small energy difference, a great spin-orbit coupling constant and a rapid reverse intersystem crossing rate, which endow them with remarkable TADF features. Meanwhile, compared with the reported molecules, the three designed molecules exhibit better CPL properties with higher glum values. Effective molecular design strategies by donor engineering to modulate the CPL and TADF properties are theoretically proposed. Our findings reveal the relationship between molecular structures and luminescence properties of CP-TADF molecules and further provide theoretical design strategies for optimizing the CPL and TADF properties.

Thermochromism and thermal crystal structure evolution of YIn0.9Mn0.1O3

YIn1-x Mn x O3 is a newly discovered inorganic blue pigment whose vivid blue color results from MnO5 trigonal bipyramidal (TBP) polyhedra. Recently, it has been reported that commercial YIn1-x Mn x O3 powders exhibit a temperature-induced color change, i.e. thermochromism. In this study, we investigate the thermochromism and temperature-induced crystal structure evolution of synthetic YIn0.9Mn0.1O3 powders. We observe that a vivid blue color at RT gradually changed to a dark blue color with increasing temperature. This thermochromism is mainly attributed to a broadening of optical absorption bands in the visible and UV regions, and can also be contributed to by an enhancement of the UV absorption. Our crystal structure analysis using powder synchrotron X-ray diffraction data not only confirms the thermal expansion and enhanced thermal vibrations of oxygen, but also reveals a temperature-induced deformation of the TBP polyhedra. Based on these results, we discuss a possible mechanism for the thermochromism of the YIn0.9Mn0.1O3 system.

Temperature-dependent work function, thermionic emission and bulk modulus of TiC: a study on the identification of free valence electrons and localized valence electrons and their roles played in carbides.

By analyzing the projected states of valence electrons (fatband structures), the localized valence electrons and the free valence electrons of TiC were identified, respectively. After defining the volumes and the magnitudes of localized valence electrons and free valence electrons, the influences of the temperature, including the thermal expansion and the atomic thermal vibration, on the localized valence electron density and the free valence electron density were investigated, respectively. Based on the metallic plasma model (MPM), the temperature-dependent work functions and the thermionic emission current densities of TiC were calculated in terms of temperature-dependent free valence electron densities. The results were in good agreement with experimental results. Furthermore, as it was observed, the linear dependence of the bulk modulus on the localized valence electron density demonstrated that the bulk modulus of TiC was determined by the localized valence electron density. The different roles played by the free valence electrons and the localized valence electrons in the work function and the bulk modulus of TiC could be attributed to their different contributions to the kinetic energy density of valence electrons. The influences of the temperature on the work function, thermionic emission and bulk modulus of TiC indicated that the transition metal carbides with lower free valence electron density, higher localized valence electron density and heavier atomic mass were desired to achieve lower work function, higher current density and higher stability.

Contact Defect Detection of Gas-Insulated Line Via Thermal–Vibration Feature Fusion and Deep Neural Network Technique

Contact Defect Detection of Gas-Insulated Line Via Thermal–Vibration Feature Fusion and Deep Neural Network Technique

Determining shunt resistances via modeling the photovoltaic performance of organic solar cells

The thermal vibration of molecules is markedly enhanced upon illumination (photoexcitation), leading to an increase in the (vibrational) free volume of photoactive layer and thereby markedly decreasing shunt resistance of device.

Identification of Kikuchi lines in electron diffraction patterns collected in small-angle geometry.

It is demonstrated that Kikuchi features become clearly visible if reflection high-energy electron diffraction (RHEED) patterns are filtered using digital image processing software. The results of such pattern transformations are shown for SrTiO3 with mixed surface termination for data collected at different azimuths of the incident electron beam. A simplified analytical approach for the theoretical description of filtered Kikuchi patterns is proposed and discussed. Some examples of raw and filtered patterns for thin films are shown. RHEED patterns may be treated as a result of coherent and incoherent scattering of electron waves. The effects of coherent scattering may be considered as those occurring due to wave diffraction by an idealized crystal and, usually, only effects of this type are analysed to obtain structural information on samples investigated with the use of RHEED. However, some incoherent scattering effects mostly caused by thermal vibrations of atoms, known as Kikuchi effects, may also be a source of valuable information on the arrangements of atoms near the surface. Typically, for the case of RHEED, Kikuchi features are hidden in the intensity background and researchers cannot easily recognize them. In this paper, it is shown that the visibility of features of this type can be substantially enhanced using computer graphics methods.

Intermolecular charge transfer and solid-state solvent effect synergistically induce near-infrared thermally activated delay fluorescence in the guest-host system.

The host matrix is an important means to tune emission color and improve luminescence efficiency of near-infrared (NIR) thermally activated delay fluorescence (TADF) light-emitting diodes. However, the mechanism of NIR TADF of the guest-host systems is still unclear. Namely, there is a controversy on whether the formation of J-aggregation, solid-state solvent effect, molecular polarization or intermolecular charge transfer (CT) is responsible for the NIR TADF. Here, the morphologies, geometrical and electronic structures, and photophysical properties are explored by combining molecular dynamics simulation, density functional theory and thermal vibration correlation function theory for the guest-host (TPAAP: TPBi) films with different concentrations. It is found that the red TADF is generated largely by the solid-state solvent effect in the low 1 wt% doped film while the NIR TADF is attributed to the synergistic effect of solid-state solvent and guest-guest intermolecular CT in the high 20 wt% film. These findings provide a deeper understanding of the mechanism of NIR-TADF of the guest-host systems.

Molecular Dynamics of the Norbornyl Cation in Solution and Its Generation in Winstein-Trifan Solvolysis: The Timing of Sigma Bridging.

Molecular dynamics simulations were performed on the solvolyses of exo- and endo-norbornyl brosylate and for the "nonclassical" σ-bridged norbornyl cation in an acetic acid solution. This computational modeling of the original Winstein-Trifan experiment confirms that exo-solvolysis is accompanied by σ-bridging in the transition state, while endo-solvolysis is not; σ-bridging eventually occurs in a dynamically stepwise fashion. Simulations of the norbornyl cation in solution show typical vibrations due to zero-point and thermal vibrations but no tendency to sample localized "classical cation" geometries.

Environmentally friendly photothermal reconstruction of cement/asphalt road: Can road markings also be cleaned in such unexpected ways?

This paper innovatively proposes a new method for safe and environmentally friendly road markings removal, using nanosecond pulsed lasers to clean the standard yellow, white, red, and black cold spray markings of cement concrete road and asphalt concrete roads by dry cleaning and wet (liquid-assisted) cleaning. The optimal cleaning process for road markings was explored by changing the laser's energy density and spot overlap ratio. The markings' dry and wet dynamic stripping behavior and removal mechanism was analyzed by combining morphology characterization, EDS analysis, XRD analysis, infrared spectroscopy, infrared images, and a high-speed camera. In the complete cleaning state, markings is entirely removed without damage to the road. Dry laser cleaning can meet the cleaning needs of cement roads, and wet laser cleaning can meet the cleaning needs of asphalt roads. The dry laser cleaning mechanism for yellow and white markings is evaporation and phase explosion caused by thermal ablation, the dry laser cleaning mechanism for red markings is thermal stress vibration, and the dry laser cleaning mechanism for black markings is mainly evaporation caused by ablation. The wet laser cleaning mechanism of each color marking is that the rapid growth of steam bubbles in the superheated liquid provokes the explosive evaporation of the liquid film layer. Laser cleaning can slightly increase cement/asphalt concrete road roughness and enhance anti-slip performance.

Theoretical Study of the Photocyclization Reaction-Induced Dual Aggregation-Induced Emission Phenomenon.

Photochromic molecules with aggregation-induced emission (AIE) effects are of great value and prospective in various practical applications. To explore its inherent mechanism, the open isomer ap-BBTE and the closed isomer c-BBTE were chosen to perform the theoretical calculation using the quantum mechanics/molecular mechanics model combined with thermal vibration correlation function formalism. The calculations show that the photocyclization (PC) reaction from ap-BBTE to c-BBTE facilitates an improvement in the AIE effect. It is found that the fluorescence quantum yield (ΦF) enhancement of ap-BBTE is attributed to the restriction of the low-frequency rotational motion of the benzothiophene moiety and the high-frequency stretching vibrations of the C-C bond between the benzothiophene and benzylbis(thiadiazole) vinyl groups after aggregation. For c-BBTE, the increase in ΦF upon aggregation is mainly due to the suppression of the high-frequency stretching vibration of the C-C bond between the benzothiophene and the benzobis(thiadiazole) vinyl groups. In addition, the AIE effect was also enhanced from ap-BBTE to c-BBTE, which is consistent with the experimental phenomenon. The corresponding emission spectrum red-shifted from ap-BBTE to c-BBTE in both dilute solution and the crystalline state due to the improved intramolecular conjugation of c-BBTE. Moreover, the PC reaction from ap-BBTE to c-BBTE easily occurs in an excited state with a low energy barrier transition state by forming a C-C bond between benzothiophene groups effectively in dilute solution. Our calculations provide theoretical guidance for the further rational design of efficient AIE luminogens.

Solar Desalination with Monolithic Foams Containing a Combination of Graphite and SnSe Featured with a Hierarchical Structure and Bimodal Pores for Spontaneous Salt Rejection

The increasing interest in solar water evaporation technology is due to its potential to replace conventional desalination systems. In this study, we suggest a new solar desalination system that has a hierarchical photothermal structure and is structurally monolithic. The overall membrane is made up of a macroscale porous melamine foam frame that acts as a porous insulator and a mass transfer layer. The mass transfer layer is designed with a bimodal porous structure of melamine foam, with large pores coated with a composite of graphite and SnSe (G-SnSe) and small pores. This simple structure provides many benefits. First, it combines two photothermal mechanisms, thermal vibration in graphite and non-radiative relaxation in SnSe, to achieve synergies in the conversion of light to heat energy. Second, compared to the single materials, graphite or SnSe alone, the nanocomposite of G-SnSe has a higher effective surface area, resulting in increased solar absorption. Finally, the melamine foam structure with bimodal pores enhances seawater wicking and has a high salt rejection capacity due to its volumetric porosity bimodal configuration of up to 35%. The monolithic melamine foam with a hierarchical photothermal structure minimizes interference with water transport due to the resistance-free presence of a continuous interfacial layer.The monolithic structure evaporaters (MSE) achieved a high evaporation rate of 1.303 kg m-2h-1 under 1 sun condition due to increased capillarity by the small-scale pores in the photothermal layer. Furthermore, spontaneous salt rejection was observed during solar desalination, attributed to the presence of intrinsic large-scale pores in melamine foam for draining the concentrated salt water from the surface. The feasibility of outdoor solar desalination was established, with a high evaporation rate of 1.259 kg m-2h-1. The mechanical stability of MSE was achieved by incorporating a small amount of binder (less than 3% of total photothermal materials), maintaining efficient performance for up to 30 days without degradation. The proposed strategy in the simple monolithic structure with bimodal porosity provides a general toolkit for designing high-performance solar desalination devices due to high evaporation rate and spontaneous salt rejection capability.In summary, the solar water evaporation technology is becoming increasingly popular as a possible replacement for traditional desalination systems. We propose a novel monolithic solar desalination system with a hierarchical photothermal structure, which is composed of a macroscale porous melamine foam as a skeleton which has both roles : an insulator and a mass transfer layer. The bimodal porous structure of melamine foam with large pores coated with a composite of graphite and SnSe provides many benefits, including increased solar absorption and a high salt rejection capacity. The MSE structure achieves a high evaporation rate and spontaneous salt rejection, making it a feasible option for outdoor solar desalination. The proposed strategy provides a general toolkit for designing high-performance solar desalination devices.

Analysis of Atomic Thermal Vibration of CrN Based on Rietveld Refinement Method

The crystal structure of chromium nitride (CrN) is studied by X‐Ray diffraction from 25 to 600 °C. Based on the RIETAN‐2000 program of Rietveld refinement method, the experimental results are analyzed, and the crystal structure parameters of CrN powder crystals at different temperatures are refined. Atomic thermal vibration isotropic temperature factor B is directly obtained by the Rietveld refinement method. Using the maximum entropy method analytical procedure, the 3D and planar isoheight nuclear density distribution characteristics of CrN are derived, realizing the visualization of nuclear density distribution. It can help to calculate the thermal diffuse scattering.

Theoretical perspective for hydrostatic pressure responsive mechanism of room temperature phosphorescence molecules

Stimulus-responsive organic room temperature phosphorescence (RTP) materials are a class of materials that show emission property changes when subjected to diverse environmental stimuli. The change of molecular stacking modes and intermolecular interactions can result in mechanical stimulus-induced emission switching behaviour. The underlying mechanism of mechanoresponsive luminescent material is still unclear. Herein, based on density functional theory and time-dependent density functional theory calculations, the photophysical properties with response to hydrostatic pressure of RTP molecules in crystal are theoretically studied. Excited state dynamic processes are investigated by using quantum mechanics and molecular mechanics method coupled with thermal vibration correlation function method. Results show that the increase of pressure can blue-shift the RTP emissions which is mainly caused by the change of molecular conformation and the increase of bending vibration frequency. Under 2 Gpa, large spin–orbit coupling effect is determined, remarkable radiative and non-radiative decay processes are achieved. At 0.6 Gpa, a small non-radiative decay rate from T 1 to S 0 is obtained, high efficiency and long lifetime (more than 10 times the other pressures) are realised. Through further analysing the staking modes, reorganisation energies and SOC constants, relationships between molecular structures and RTP properties are determined, hydrostatic pressure responsive mechanism is revealed.

Ultrastrong Infrared Emission at 1460 nm from Lanthanide-Doped Nanoparticles with Interfacial Sensitization.

Fluorescent imaging in the second near-infrared window (NIR-II; 1000-1700 nm) has recently received tremendous attention due to its excellent tissue probing depths and high resolution. Under NIR pumping, lanthanide-doped nanoparticles can emit infrared light covering a wide range of 800-3000 nm which has good potential for NIR-II imaging and detection. However, the low efficiency hinders their application. Here, we report intense infrared emission at 1460 nm from lanthanide-doped core/shell nanoparticles with efficient interfacial sensitization. The emitter Tm3+ ion and the sensitizer Yb3+ and Nd3+ ions are spatially separated in core and shells so that the efficient interfacial energy transfer is established between Tm3+ and Yb3+/Nd3+ ions, while thermal vibration spread of high concentration of Yb3+ ions and cross-relaxation among Tm3+, Yb3+, and Nd3+ ions are suppressed. As a result, the ultrastrong NIR-II emission at 1460 nm is achieved, which is more than 100-times that in classic core/shell nanoparticles doped with Tm3+ (NaYF4:20%Yb,0.5%Tm@ NaYF4).

Selection of the Utility Function of the Historic Building, Taking into Account Energy Efficiency

The energy efficiency of the building should be understood as the degree of preparation of the building to ensure the comfort of its use in accordance with its intended use with the lowest possible energy consumption of the building. The article presents an in-depth analysis of the possibility of changing the utility function of a historic building in such a way that ensures all aspects of comfort while meeting energy efficiency conditions. Combinatorics methods were used for this purpose. Four possible utility functions were proposed, including the reference state, i.e., the existing state. Five aspects of comfort were considered: thermal comfort, carbon footprint, energy efficiency, noise and vibration. For these five aspects of comfort, boundary conditions were adopted depending on the adopted building class. The selected utility function is therefore the result of comfort, energy efficiency and economic aspects. The purpose of the study was to verify whether the developed methodology for the selection of the utility function for historic buildings, based on combinatorial analyses, would allow the selection of the optimal function from the point of view of energy efficiency, user comfort and environmental impact. The methodology was tested on a historic building located in southern Poland. The new utility function for the analyzed building is to use the historic villa (or some part of it) as an Art Gallery.