The Journal of Physical Chemistry Letters最新文献

How to fundamentally suppress charge transport is one of the essential issues in polymer dielectrics. This work reports significant charge transport suppression by glycidyl methacrylate (GMA) side group modification on polypropylene (PP). Experimental and computational investigations discover for the first time a quasi-hydrogen bond effect generated by carbonyl and epoxide of GMA in PP inter/intramolecular structure, while introducing trap energy levels within the HOMO–LUMO gap. These energy levels suppress the leakage current of GMA-modified PP thanks to the charge-trapping effect. The quasi-hydrogen bond originating from the interaction between the high-polar GMA group and flexible PP chain raises the thermostability while averaging the electron distribution between hydrogen and acceptor oxygen, which is conducive to lessening electric weak points, suppressing charge transport, and finally enhancing the electrical breakdown strength. This work provides new thinking on polymer dielectric design and charge transport regulation utilizing electron structure and weak interaction at the molecular scale.

The origin of the high-frequency shoulder (HFS) observed above the longitudinal optical (LO) peak around 230 cm^–1 in the Raman spectra of CdSe quantum dots (QDs) has been the subject of intense debate. We use state-of-the-art ab initio density functional theory applied to small CdSe QDs with various realistic surface passivations and find an intense Raman signal around 230 cm^–1, which corresponds to a stretching vibration of a defective 2-fold coordinated Se atom. We interpret this signal as being the origin of the HFS. Since the signal disappears in fully passivated and defect-free (magic size cluster) structures, it can be used as a fingerprint to distinguish defective from nondefective structures.

The rare observation of transient Rh···Rh excimer formation in a single crystal is reported. The estimated excited-state lifetime at 100 K is 2 ns, which makes it the shortest-lived small-molecule species caught experimentally using the laser-pump/X-ray-probe time-resolved Laue method. Upon excitation with 390 nm laser light, the intermolecular Rh···Rh distance decreases from 3.379(4) to 3.19(1) Å, and the metal–metal contact gains more bonding character. On the basis of the experimental results and theoretical modeling, the structural changes determined with 100 ps time resolution reflect principally the S₀ → S₁ electronic transition.

Brain-inspired electronics with synaptic functions hold significant promise for advancing artificial intelligent applications. In this study, we demonstrate the synaptic feature of quantum-dot light-emitting diodes (QLEDs), which can convert electrical pulses into synapse-like light signals (the brightness gradually increases as the electrical pulses are prolonged). These features are analogous to learning and forgetting in biological synapses. The enhancement of brightness can be attributed to the reduction of charge transfer from the quantum dots to ZnO electron transport layer and resistive switching effect. With an integrated complementary metal-oxide-semiconductor (CMOS) drive, arrayed synaptic QLEDs can simulate the visualization of brain-like learning processes, which can reduce the noise toward high image recognition rate (>95.0%) by deep neural networks. Our findings introduce a novel brain-inspired optoelectronic approach with potential applications in optical neuromorphic systems.

The measurement of thermodynamic properties for nanosystems is essential to comprehend the inherent characteristics of nanomaterials. Traditional spectroscopy measurements, such as Raman or ultraviolet–visible spectroscopies, are limited to offering insights near the Γ point in the Brillouin zone and thus cannot precisely determine the system’s thermodynamic properties, for example, heat capacity. Utilizing the intrinsic broad momentum distribution in highly confined plasmonic fields, here we take sp-hybridized carbyne as a proof-of-the-principle example to show that ultrahigh-resolution tip-enhanced Raman scattering (TERS) images have the ability to access all k-points in the phonon Brillouin zone of one-dimensional nanosystems, allowing the comprehensive determination of vibrational features and heat capacity for finite carbon chains. Comparing phonon dispersion spectra and heat capacities under different boundary conditions, i.e., linear carbon chains and cyclic carbon molecules, we find that the heat capacities of linear structures converge more rapidly than the counterparts of cyclic structures to the benchmark of ideal carbyne. We also study the effects of different terminal groups in linear structures as well as the aromaticity in cyclic structures on heat capacity. This study provides a practical method for characterizing the thermodynamic properties of nanosystems, demonstrating the potential applications of TERS imaging in nanomaterial science.

Optical tweezers use strongly focused light for trapping, characterizing, and manipulating objects in the microscopic and nanoscopic regimes. However, fully understanding optical trapping at the nanoscale remains a significant challenge. This holds importance because the nanoscale is the frontier for numerous promising advancements, ranging from enhancing single-molecule investigations in biology to developing hybrid devices for nanoelectronics and photonics and exploring fundamental quantum phenomena in opto-mechanics. We report an experimental and theoretical study of nanoparticles of various sizes, showing the advantages of the immense peak power of ultrashort laser pulses over conventional optical tweezers. We also demonstrate highly stable trapping of nanoparticles for extended durations at low average laser power using femtosecond lasers.

This study investigates the oxidation behavior of Cu₃Pt(100) in CO₂ using a combination of ambient-pressure X-ray photoelectron spectroscopy, mass spectroscopy, and density functional theory modeling. Our in situ measurements reveal the simultaneous oxidation and reduction of Cu₂O due to the opposing effects of atomic oxygen and CO generated from dissociative CO₂ adsorption, leading to a dynamic equilibrium state of simultaneously occurring redox reactions. Complementary atomistic calculations elucidate the inhibitory effects of subsurface Pt enrichment and the counteracting roles of CO₂ and CO in surface oxidation and reduction. These results provide mechanistic insights into the dissociative pathway of CO₂ molecules and dynamic evolution of surface composition and reactivity of Cu-based alloy catalysts in CO₂-rich environments, with broader implications for tuning gas–surface reactions by manipulating gas reactants or solid surface composition.

Since the proposition of the Hofmeister series, guanidinium (Gdm) salts hold a special mention in protein science owing to their contrasting effect on protein(s) depending on the counteranion(s). For example, while GdmCl is known to act as a potential protein denaturant, Gdm₂SO₄ offers minimal effect on protein structure. Despite the fact that theoretical studies reckon the formation of ion-pairing to be responsible for such behavior, experimental validation of this hypothesis is still in sparse. In this study, we combine electrochemical impedance spectroscopy (EIS) and THz spectroscopy to underline the effect of GdmCl and Gdm₂SO₄ on a model amide molecule N-methylacetamide (NMA). Molecular dynamics (MD) simulation studies predict that Gdm₂SO₄ forms heteroion pairing in water, which inhibits Gdm⁺ ions to approach NMA molecules, while in case of GdmCl, Gdm⁺ ions directly interact with NMA. The experimental findings on ion hydration, specifically the detailed analysis of the ion–water rattling mode, which appears in the THz frequency domain, unambiguously endorse this hypothesis. Our study establishes the fact that the propensity of ion-pairing in Gdm salts dictates their (de)stabilization effect on proteins.

Reaction induced by slow electrons is implicated in a large field of research and applications. Below 3-4 eV, dissociative electron attachment efficiently fragments molecules via (1) shape resonance or (2) mediated by the formation of a dipole bound anion. While the temperature dependence of process 1 is well-known, that of 2 is not clearly established. Nitromethane is the prototypical molecule for which the electron attachment leads to the formation of both a dipole bound and a covalent anion. We provide here a comprehensive study of the fragmentation of nitromethane by <1 eV electron and the unusual temperature effects attributed principally to process 2.