Journal of Chemical Physics最新文献

Sum frequency generation vibrational spectroscopy (SFG) was applied to characterize the interfacial adhesion chemistry at several buried polymer interfaces in both model systems and blown multilayer films. Anhydride/acid modified polyolefins are used as tie layers to bond dissimilar polymers in multilayer barrier structures. In these films, the interfacial reactions between the barrier polymers, such as ethylene vinyl alcohol (EVOH) or nylon, and the grafted anhydrides/acids provide covalent linkages that enhance adhesion. However, the bonding strengths vary for different polymer-tie layer combinations. Here, using SFG, we aim to provide a systematic study on four common polymer-tie interfaces, including EVOH/polypropylene-tie, EVOH/polyethylene-tie, nylon/polypropylene-tie, and nylon/polyethylene-tie, to understand how the adhesion chemistry varies and its impact on the measured adhesion. Our SFG studies suggest that adhesion enhancement is driven by a combination of reaction kinetics and the interfacial enrichment of the anhydride/acid, resulting in stronger adhesion in the case of nylon. This observation matches well with the higher adhesion observed in the nylon/tie systems in both lap shear and peel test measurements. In addition, in the polypropylene-tie systems, grafted oligomers due to chain scission may migrate to the interface, affecting the adhesion. These by-products can react or interfere with the barrier-tie chemistry, resulting in reduced adhesion strength in the polypropylene-tie system.

Colloidal solutions of gold nanorods and silver-coated gold nanorods were prepared. The seeded growth synthesis protocols were improved by adding a flocculation purification step. The resulting populations of pure gold nanorods and Au@Ag core-shell cuboids were characterized by very low dispersion in size and shape. UV-vis-near-infrared absorption measurements were performed on several batches of well-calibrated nano-objects, supported by calculations based on the discrete dipole approximation, allowed to highlight the impact of various morphological features on the optical response. In addition to the well-known effect of the nanorod aspect ratio on the shift of the longitudinal surface plasmon resonance mode, special attention was paid to changing either the rounding of the nanorod end-caps or that of the edges of the coating silver shell. Nanorods and cuboids were modeled as superellipsoids. This approach enabled us to model precisely their complex shapes using just a few simple parameters and analyze the evolution of their extinction spectra as a function of the rounding of their tips and edges. Such nano-objects are widely used for various applications in fields such as biomedical, biosensing, or surface-enhanced Raman spectroscopy, thus making it crucial to precisely assess the impact of each morphological feature for optimizing their performance.

We investigate the phase ordering (pattern formation) of systems of two-dimensional core-shell particles using Monte Carlo (MC) computer simulations and classical density functional theory (DFT). The particles interact via a pair potential having a hard core and a repulsive square shoulder. Our simulations show that on cooling, the liquid state structure becomes increasingly characterized by long wavelength density modulations and on further cooling forms a variety of other phases, including clustered, striped, and other patterned phases. In DFT, the hard core part of the potential is treated using either fundamental measure theory or a simple local density approximation, whereas the soft shoulder is treated using the random phase approximation. The different DFTs are benchmarked using large-scale grand-canonical-MC and Gibbs-ensemble-MC simulations, demonstrating their predictive capabilities and shortcomings. We find that having the liquid state static structure factor S(k) for wavenumber k is sufficient to identify the Fourier modes governing both the liquid and solid phases. This allows us to identify from easier-to-obtain liquid state data the wavenumbers relevant to the periodic phases and to predict roughly where in the phase diagram these patterned phases arise.

The effect of cadmium ions introduced into fluorophosphate glass on the growth and photoluminescence (PL) of the CsPb1-xCdxBr3 perovskite nanocrystals (NCs) is systematically studied. The x-ray diffraction patterns have shown that cadmium ions are really incorporated into the NCs that results in a decrease in the lattice constant from 5.85 (x = 0) to 5.75 Å (x = 0.45). At the large cadmium content in the glass (x > 0.38), simultaneous formation of the perovskite CsPb1-xCdxBr3 NCs and the non-luminescent CsCdBr3 NCs in the hexagonal phase is found. It is also found that the lattice contraction leads to an increase in the bandgap energy and a noticeable shift of the PL band to the blue region of the spectrum (from 2.42 to 2.68 eV) with a drop in quantum yield from 85% for CsPbBr3 NCs down to 4% for CsPb0.55Cd0.45Br3 NCs. It is shown that the PL quantum yield decreases due to the formation of deep trap states, which manifest themselves as a PL band in the energy range of 1.6-2.5 eV at cryogenic temperatures. A simple model explaining the behavior of the PL band as a function of temperature in the range from 30 to 300 K is proposed.

We combine the use of molecular dynamics simulations and the generalized Langevin equation to study the diffusion of a fluid adsorbed within kerogen, the main organic phase of shales. As a class of microporous and amorphous materials that can exhibit significant adsorption-induced swelling, the dynamics of the kerogen's microstructure is expected to play an important role in the confined fluid dynamics. This role is investigated by conducting all-atom simulations with or without solid dynamics. Whenever the dynamics coupling between the fluid and solid is accounted for, we show that the fluid dynamics displays some qualitative differences compared to bulk fluids, which can be modulated by the amount of adsorbed fluid owing to adsorption-induced swelling. We highlight that working with the memory kernel, the central time correlation function of the generalized Langevin equation, allows the fingerprint of the dynamics of the solid to appear on that of the fluid. Interestingly, we observe that the memory kernels of fluid diffusion in kerogen qualitatively behave as those of tagged particles in supercooled liquids. We emphasize the importance of reproducing the velocity-force correlation function to validate the memory kernel numerically obtained as confinement enhances the numerical instabilities. This route is interesting as it opens the way for modeling the impact of fluid concentration on the diffusion coefficient in such ultra-confining cases.

Organic electronics (OE) such as organic light-emitting diodes or organic solar cells represent an important and innovative research area to achieve global goals like environmentally friendly energy production. To accelerate OE material discovery, various computational methods are employed. For the initial generation of structures, a molecular cluster approach is employed. Here, we present a semi-automated workflow for the generation of monolayers and aggregates using the GFNn-xTB methods and composite density functional theory (DFT-3c). Furthermore, we present the novel D11A8MERO dye interaction energy benchmark with high-level coupled cluster reference interaction energies for the assessment of efficient quantum chemical and force-field methods. GFN2-xTB performs similar to low-cost DFT, reaching DFT/mGGA accuracy at two orders of magnitude lower computational cost. As an example application, we investigate the influence of the dye aggregate size on the optical and electrical properties and show that at least four molecules in a cluster model are needed for a qualitatively reasonable description.

An improved global potential energy surface (PES) for the electronic ground state of the HeLiH+ system is reported. The data points are calculated at the full configuration-interaction level of theory and extrapolated to the complete basis set limit. The fitting procedure implements a combination of neural network and Aguado-Paniagua functional forms to fit the ab initio data points. The fitted surface reproduces the ab initio data points accurately in short as well as long ranges and has an overall root mean square error of 1.76 × 10-3 eV (14.21 cm-1) in energy space <10 and 9.28 × 10-4 eV (7.48 cm-1) upto 2 eV. The optimized global minimum is also accurately reproduced using the fitted surface. To establish the accuracy of the new PES, dynamics investigation of the He + LiH+(v = 0, j = 0) → LiHe+ + H reaction is performed using the Coriolis coupled quantum mechanical and quasi-classical trajectory methods. The results, such as integral cross sections and rate constants, show the effect of the opening of the collision-induced dissociation (CID) channel at low collision energy and are significantly different from the earlier study of Tacconi et al. [Phys. Chem. Chem. Phys. 14, 637-645 (2012)]. These discrepancies appear to be a result of the treatment of the CID channel in the dynamics calculations, which is excluded from the reactive channel in the current work.

Controlling composition and plasmonic response of bimetallic nanoparticles (NPs) is of great relevance to tune their catalytic activity. Herein, we demonstrate reversible composition and plasmonic response transitions from a core/shell to a bimetallic alloyed palladium/gold NP triggered by CO adsorption and sample temperature. The use of self-organized growth on alumina template film allows scrutinizing the impact of core size and shell thickness onto NP geometry and plasmonic response. Topography, molecular adsorption, and plasmonic response are addressed by scanning tunneling microscopy, vibrational sum frequency generation (SFG) spectroscopy, and surface differential reflectance spectroscopy, respectively. Modeling CO dipolar interaction and optical reflectivity corroborate the experimental findings. We demonstrate that probing CO adsorption sites by SFG is a remarkably sensitive and relevant method to investigate shell composition and follow in real-time Pd atom migration between the core and the shell. Pd-Au alloying is limited to the first two monolayers of the shell and no plasmonic response is found, while for a thicker shell, a plasmonic response is observed, concomitant with a lower Pd concentration in the shell. Above 10-4 mbar, at room temperature, CO adsorption triggers the shell restructuration, forming a Pd-Au alloy that weakens the plasmonic response via Pd migration from the core to the shell. NP annealing at 550 K, after pumping CO, leads to the desorption of remaining CO and gives enough mobility for Pd to migrate back inside the core and recover a pure gold shell with its original plasmonic response. This work demonstrates that surface stoichiometry and plasmonic response can be tuned by using CO adsorption and NP annealing.

The three-body fragmentation dynamics of benzene trications C6H63+ induced by 200 eV electron-impact produced by a photoemission cathode is investigated. All three fragment ions are detected in coincidence, and their momentum vectors are determined by employing a COLTRIMS reaction microscope. The detailed kinematical information of three deprotonation fragmentation channels of H+ + C3H2+ + C3H3+, H+ + C2H3+ + C4H2+, and H+ + C2H2+ + C4H3+ are obtained. By analyzing the momentum and energy correlation spectra among all the three fragment ions, we find that all the three channels are primarily generated by sequential fragmentation processes. Each channel has two deprotonation pathways, corresponding to proton emission in the first or second step of sequential fragmentation, respectively. These results provide insight into the mechanisms and dynamics of deprotonation and ring-breaking reactions in the three-body fragmentation processes of aromatic ring molecules.

It is challenging to simulate open quantum systems that are connected to a reservoir through multiple channels. For example, vibrations may induce fluctuations in both energy gaps and electronic couplings, which represent two independent channels of system-bath couplings. Systems of this kind are ubiquitous in the processes of excited state radiationless decay. Combined with density matrix renormalization group (DMRG) and matrix product states (MPS) methods, we develop an interaction-picture chain mapping strategy for vibrational reservoirs to simulate the dynamics of these open systems, resulting in time-dependent spatially local system-bath couplings in the chain-mapped Hamiltonian. This transformation causes the entanglement generated by the system-bath interactions to be restricted within a narrow frequency window of vibrational modes, enabling efficient DMRG/MPS dynamical simulations. We demonstrate the utility of this approach by simulating singlet fission dynamics using a generalized spin-boson Hamiltonian with both diagonal and off-diagonal system-bath couplings. This approach generalizes an earlier interaction-picture chain mapping scheme, allowing for efficient and exact simulation of systems with multi-channel system-bath couplings using matrix product states, which may further our understanding of nonlocal exciton-phonon couplings in exciton transport and the non-Condon effect in energy and electron transfer.