Physical Chemistry Chemical Physics最新文献

Active control of chirality in plasmonic metamaterials is of great importance due to their potential for diverse applications in imaging, communication and spectroscopy. Recently, inspired by the concept of bound states in the continuum (BIC), strong chiroptical responses are constructed in metamaterials by introducing structural asymmetries. However, most of these chiral metamaterials are static and cannot be modulated. Herein, we theoretically demonstrate a novel approach for manipulating chiroptical responses with enhanced circular dichroism (CD) and large modulation depths in a graphene–metal hybridized metamaterial. By introducing a structured graphene and adjusting the Fermi energy (E_F), the conversion between BIC and quasi-BIC states is achieved successfully. The proposed device demonstrates a tuneable CD in the range of 0.693–0.008 when E_F is adjusted from 0.01 eV to 1.0 eV, which can be further improved by optimizing its geometry. The proposed graphene–metal hybridized metamaterial paves a new way for manipulating polarization states at terahertz frequencies and is of great potential for practical applications such as dynamic display and optoelectronic modulation.

Vibrational circular dichroism (VCD) spectroscopy has become an important part of the (stereo-)chemists’ toolbox as a reliable method for the determination of absolute configurations. Being the chiroptical version of infrared spectroscopy, it has also been recognized as being very sensitive to conformational changes and intermolecular interactions. This sensitivity originates from the fact that the VCD spectra of individual conformers are often more different than their IR spectra, so that changes in conformational distributions or band positions and intensities become more pronounced. What is an advantage for studies focussing on intermolecular interactions can, however, quickly turn into a major obstacle during AC determinations: solute–solvent interactions can have a strong influence on spectral signatures and they must be accurately treated when simulating VCD and IR spectra. In this perspective, we showcase selected examples which exhibit particularly pronounced solvent effects. It is demonstrated that it is typically sufficient to model solute–solvent interactions by placing single solvent molecules near hydrogen bonding sites of the solute and subsequently use the optimized structures for spectra simulations. This micro-solvation approach works reasonably well for medium-sized, not too conformationally flexible molecules. We thus also discuss its limitations and outline the next steps that method development needs to take in order to further improve the workflows for VCD spectra predictions.

The heat transport properties of van der Waals layered structures are crucial for ensuring the reliability and longevity of high-performance optoelectronic equipment. Owing to the two-dimensional nature of atomic layers, the presence of bubbles is commonly observed within these structures. Nevertheless, the effect of bubbles on the interfacial thermal conductance remains unclear. Based on the elastic membrane theory and the improved van der Waals gas state equation, we develop an analytical formula to describe the influence of bubble shape on the interfacial thermal conductance. It shows that the presence of bubbles has a considerable impact on reducing the interfacial thermal conductance across graphene/graphene interfaces. More specifically, the presence of nanobubbles can result in a reduction of up to 53% in the interfacial thermal conductance. The validity of the analytical predictions is confirmed through molecular dynamic simulations. These results offer valuable insights into the thermal management of van der Waals layered structures in the application of next-generation electronic nanodevices.

An impressive collection of accurate two-body interaction energies for small complexes has been assembled into benchmark databases and used to improve the performance of multiple density functional, semiempirical, and machine learning methods. Similar benchmark data on nonadditive three-body energies in molecular trimers are comparatively scarce, and the existing ones are practically limited to homotrimers. In this work, we present a benchmark dataset of 20 equilibrium noncovalent interaction energies for a small but diverse selection of 10 heteromolecular trimers. The new 3BHET dataset presents complexes that combine different interactions including π–π, anion–π, cation–π, and various motifs of hydrogen and halogen bonding in each trimer. A detailed symmetry-adapted perturbation theory (SAPT)-based energy decomposition of the two- and three-body interaction energies shows that 3BHET consists of electrostatics- and dispersion-dominated complexes. The nonadditive three-body contribution is dominated by induction, but its influence on the overall bonding type in the complex (as exemplified by its position on the ternary diagram) is quite small. We also tested the extended SAPT (XSAPT) approach which is capable of including some nonadditive interactions in clusters of any size. The resulting three-body dispersion term (obtained from the many-body dispersion formalism) is mostly in good agreement with the supermolecular CCSD(T)–MP2 values and the nonadditive induction term is similar to the three-body SAPT(DFT) data, but the overall three-body XSAPT energies are not very accurate as they are missing the first-order exchange terms.

Carbon nanotubes and their composite thermoelectric (TE) materials have significant advantages in supplying power to flexible electronics due to their high electrical conductivity, excellent flexibility, and facile preparation technology. In this work, stable n-type silver ammonia-polyethyleneimine/single-walled carbon nanotube ([Ag(NH₃)₂]⁺-PEI/SWCNT) composite films were facilely prepared by solution blending and vacuum-filtration methods. The results demonstrate that light silver ammonia doping optimizes the carrier concentration and carrier mobility of the composite film, and a maximum power factor (PF) of [Ag(NH₃)₂]⁺-PEI/SWCNT of 91.9 μW m⁻¹ K⁻² was obtained, which is higher than that of PEI/SWCNT (70.0 μW m⁻¹ K⁻²). Furthermore, when the composite films were reduced by the NaBH₄ solution, the Seebeck coefficient and the PF value were further increased to −45.5 μV K⁻¹ and 115.8 μW m⁻¹ K⁻², respectively. For demonstration, a maximum output voltage of 13.8 mV and output power of 492 nW were achieved using a three p–n junction-based TE device constructed by [Ag(NH₃)₂]⁺-PEI/SWCNT at a temperature difference of 50 K. Thus, this study provides a metal complex ion doping strategy to improve thermoelectrical properties and air stability of the PEI/SWCNT composite films, which have potential applications in flexible electronics.

In recent years, two-dimensional materials have aroused enormous interest owing to their superior electrochemical performance, abundant exposed active sites, high specific surfaces and so on. Unlike many stable allotropes, honeycomb hexagonal borophene is kinetically unstable. In this study, we introduce transition metal atoms (Cr, Fe and Co) to stabilize honeycomb hexagonal borophene, forming stable graphene-like TMB₆ (TM = Cr, Fe and Co) monolayers. Moreover, we explored the possibility of superconductivity and the anchoring materials of lithium–sulfur batteries using the first-principles density functional theory (DFT) calculation. Our results show that CoB₆ exhibited the best superconductivity with a superconducting transition temperature of 33.3 K. Furthermore, CoB₆ and FeB₆ are promising anchoring materials because of the suppression of lithium polysulfides shuttling in lithium–sulfur batteries because they can accelerate sulfur reduction reaction kinetics.

Discovery of a halogen-bonded ternary cocrystal of 1,3,5-trifluoro-2,4,6-triiodobenzene with pyrazine and triphenylphosphine sulfide has revealed a complex landscape of multicomponent phases, all achievable by mechanochemical interconversion. The observed solid-state reaction pathways were explained by periodic density-functional calculations and comprehensive intermolecular interaction analysis, supported by dissolution calorimetry measurements.

Heteroleptic coordination cages allow the design of different host structures that can bind guest molecules within their cavities. In a previous work, the energetics of organophosphate encapsulation in palladium(II)-based heteroleptic coordination cages that differ in terms of their ability to form hydrogen bonds have been investigated [Platzek et al., Endohedrally Functionalized Heteroleptic Coordination Cages for Phosphate Ester Binding, Angew. Chem., Int. Ed. 2022, 61, e2022093]. The present work focuses on the dynamics of this system. Dynamic information is obtained through the application of a Markov state model (MSM) to unbiased multi-microsecond atomistic molecular dynamics simulations of guest binding and release. The MSM reveals that both the bound state and the binding/unbinding pathways are highly dynamic, with different types of interactions mediating the binding of the diphenylphosphate guest. Thus, the simulations highlight the dynamic nature of the nanoconfinement in the host–guest systems, with possible implications for the use of such coordination cages as catalysts.

Near-infrared (NIR) phosphors with high thermal stability are significant for NIR light-emitting diodes (LEDs). For a decade, Debye temperature has been a successful indicator of structural rigidity and thermal stability for phosphors, but some exceptions exist due to its dependence on atomic mass. Inspired by the Debye temperature model that relates the elastic properties of solids, our density functional theory calculations revealed that the Vickers hardness of Cr³⁺-doped NIR phosphors was negatively correlated with Stokes shifts (Pearson's R = −0.81) and positively correlated with thermal stabilities (Pearson's R = 0.85) within a set of 13 distinct material types. Highlighting the predictive power of Vickers hardness, two new NIR phosphors were investigated: KMg(PO₃)₃:Cr³⁺ showed low thermal stability, correlating with its lower Vickers hardness, in contrast to the high thermal stability and correspondingly higher Vickers hardness of La₂MgSnO₆:Cr³⁺. Vickers hardness can be used to screen potential hosts for Cr³⁺-doped NIR phosphors with high thermal stabilities, due to the advantages of the predictable feature by density functional theory calculation and low independence on atomic mass.

We show that variations in enantiomer nuclei size and activation energy during the nucleation stage of crystallization are responsible for the chiral symmetry breaking resulting in excess of one of the possible enantiomers with respect to the other. By understanding the crystallisation process as a non-equilibrium self-assembly process, we quantify the enantiomeric excess through the probability distribution of the nuclei size and activation energy variations which are obtained from the free energy involved in the nucleation stage of crystallisation. We validate our theory by comparing it to Kondepudi et al. previous experimental work on sodium chlorate crystallisation. The results demonstrate that the self-assembly of enantiomeric crystals provides an explanation for chiral symmetry breaking. These findings could have practical applications for improving the production of enantiopure drugs in the pharmaceutical industry, as well as for enhancing our understanding of the origins of life since enantiomeric amino acids and monosaccharides are the building blocks of life.