Article
Chemistry, Physical
Tianyun Qiu, Li Yang, Yinger Xiang, Yu Ye, Guoqiang Zou, Hongshuai Hou, Xiaobo Ji
Summary: This study proposes an economic and high-yield method for preparing antimony ultrafine nanocrystals by embedding them in a porous carbon skeleton and maximizing the synergetic effect of the heterogeneous structure to overcome the rapid capacity decay issue caused by the volume effect of antimony anode materials.
Article
Chemistry, Physical
Xiaohe Lei, Annabelle Canestraight, Vojtech Vlcek
Summary: Charge injection into a molecule on a metallic interface is a critical step in photoactivated reactions. We find that the precise molecular position on the surface can significantly affect the injection energy barrier, resulting in multiple low energy barriers due to the competition between plasmonic coupling and hybridization between the molecule and the substrate.
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2023)
Article
Physics, Multidisciplinary
P. Jakob, S. Thussing
Summary: The dynamical charge transfer processes at molecule-metal interfaces, occurring on a few femtosecond timescale, can be accessed through vibrational excitations, with the characteristic timescale derived using the vibrational oscillation period as an internal clock reference.
PHYSICAL REVIEW LETTERS
(2021)
Article
Chemistry, Inorganic & Nuclear
Xiao-Lin Liu, Xiao-Yi Zhang, Hai-Xia Zhao, La-Sheng Long, Lan-Sun Zheng
Summary: This study constructed a linear Cu-3 compound with a multi-center donor-acceptor architecture using a redox-active chloranilic acid quinoid ligand and demonstrated the effectiveness of dielectric measurement in detecting charge transfer.
DALTON TRANSACTIONS
(2022)
Article
Chemistry, Multidisciplinary
Kai Braun, Otto Hauler, Dai Zhang, Xiao Wang, Thomas Chasse, Alfred J. Meixner
Summary: Surface charging effects at metal-molecule interfaces have significant impacts on the performance of organic electronics, especially with the ongoing downsizing of organic components. A spectroscopic approach based on tip-enhanced Raman spectroscopy (TERS) is utilized to study metal-molecule interfaces under applied voltage, revealing how intrinsic inductive effects in molecules can shift electron density distribution when bias voltage is applied. This experiment provides valuable insights into charged metal-molecule interfaces.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Nanoscience & Nanotechnology
Kanji Homma, Satoshi Kaneko, Kazuhito Tsukagoshi, Tomoaki Nishino
Summary: Charge transfer at metal-molecule interfaces is crucial in nanomaterials, especially for electronic applications, but its understanding at the single-molecule level is still limited. In this study, a highly conductive adsorption site was discovered in a single-molecule junction (SMJ) of naphthalenedithiol using surface-enhanced Raman scattering (SERS) and current-voltage measurements. The vibrational energy and conductance analysis revealed that the high conductivity is attributed to the adsorption site with significant charge transfer. This research demonstrates that SERS combined with transport measurements can provide insights into both the structures of SMJs and charge transfer at metal-molecule interfaces.
ACS APPLIED NANO MATERIALS
(2023)
Article
Chemistry, Physical
Enrico Gnecco, Arkadiusz Janas, Benedykt R. Jany, Antony George, Andrey Turchanin, Grzegorz Cempura, Adam Kruk, Manoj Tripathi, Frank Lee, A. B. Dalton, Franciszek Krok
Summary: The interaction between metallic nanoparticles and transition metal chalcogenides (TMDs) can lead to new functionalities in technology fields such as optoelectronics and nanoengineering. In this study, the self-assembly of triangular-shaped crystalline Au nanoislands on mechanically exfoliated or chemically vapor deposited (CVD) MoS2 flakes was investigated. The density and size of the islands were determined by substrate temperature, deposition flux, and subsurface morphology. Raman spectroscopy was used to measure the thickness of the MoS2 layers and evaluate the strain and doping distributions induced by the Au islands. Scanning electron microscopy (SEM) and high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) were used to obtain top and cross-sectional images of the Au-MoS2 interface. Sub-nanometer resolution images revealed that the MoS2 flakes followed the corrugation of the SiO2 substrate, with flattening and wrinkling effects induced by the growth of the Au islands on top.
APPLIED SURFACE SCIENCE
(2023)
Review
Chemistry, Physical
Zhouxin Luo, Guoqiang Zhao, Hongge Pan, Wenping Sun
Summary: This review provides a comprehensive overview and analysis of the formation mechanisms and surface energy minimization mechanisms of SMSI, as well as its applications in catalysts. It offers important insights for further research and design of advanced heterogeneous catalysts.
ADVANCED ENERGY MATERIALS
(2022)
Article
Chemistry, Analytical
Seol Baek, Donghoon Han, Seung-Ryong Kwon, Vignesh Sundaresan, Paul W. Bohn
Summary: Understanding the functional states of individual redox enzymes is vital for life. The use of zero-mode waveguides allows for studying single-enzyme reactions and has potential applications in molecular diagnostics.
ANALYTICAL CHEMISTRY
(2022)
Article
Chemistry, Physical
Yi Zhao, Yang Liu, Yuying Wang, Shulan Li, Yi Liu, Zhong Lin Wang, Peng Jiang
Summary: Solid-liquid interfaces are widely present in nature and have various applications. Electron transfer at the interface has been discovered, and a two-step theory for the formation of solid-liquid electric double layer (EDL) has been proposed. Hydroxyl radical (.OH) is generated at the interface without external interference, and its concentration increases with pH, indicating that it is generated from hydroxide ions (OH-) through electron transfer during contact electrification. The generation of reactive oxygen species (.OH and .O2-) at the interface has potential applications in pollutant degradation.
Article
Chemistry, Physical
Haihua Zhang, Jiannian Yao, Kaige Zhou, Yongan Yang, Hongbing Fu
Summary: A soluble luminescent thermometer based on thermally activated dual-emissions of Mn2+-alloyed 2D perovskite quantum wells has been reported. The temperature-dependent charge transfer efficiency allows for continuous ratiometrical modulation, making it suitable for monitoring the ultracold-chain logistics of COVID-19 vaccines.
CHEMISTRY OF MATERIALS
(2022)
Article
Electrochemistry
Dong Il Park, Sangmin Jung, Hyo Jae Yoon, Kyoungsuk Jin
Summary: This review article provides an overview of published studies on electrochemical asymmetric synthesis, aiming to offer insightful perspectives for new ideas and innovations in the field. The methodologies of electrode functionalization with chiral molecules are discussed, along with recent studies on electrochemical asymmetric synthesis using electrodes with chiral surfaces or using electrolytes containing chiral components. Furthermore, the review extensively discusses related reaction mechanisms and proposes potential research directions for designing efficient electrochemical asymmetric synthesis.
ELECTROCHIMICA ACTA
(2021)
Article
Nanoscience & Nanotechnology
Yocefu Hattori, Sol Gutierrez Alvarez, Jie Meng, Kaibo Zheng, Jacinto Sa
Summary: The recent discovery of metal nanoparticles generating hot carriers upon light excitation is considered a breakthrough in the fields of plasmonics and photonics. Efforts to suppress loss mechanisms and harness charges before relaxation are ongoing. Comparative ultrafast spectroscopy investigations have revealed the significant role of metal/semiconductor interfaces and semiconductor electronic structure in electron injection efficiency and recombination.
ACS APPLIED NANO MATERIALS
(2021)
Article
Chemistry, Analytical
S. V. Pavlov, E. O. Kozhevnikova, S. A. Kislenko
Summary: In this study, the kinetics of outer-sphere electron transfer at graphene with different number of layers in the presence and absence of metal substrates were theoretically investigated. It was found that the electrocatalytic activity of the metal substrate for few-layer graphene can be explained under the assumption of nonadiabatic electron transfer. However, electron transfer at the metal-supported single-layer graphene is likely adiabatic. The enhanced electron transfer in the presence of the metal substrate is explained by the hybridization of the metal and graphene electronic states, which provides more efficient interaction of the metal substrate with the reactant near the graphene surface.
JOURNAL OF ELECTROANALYTICAL CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Yipeng Zang, Chen Di, Zhiming Geng, Xuejun Yan, Dianxiang Ji, Ningchong Zheng, Xingyu Jiang, Hanyu Fu, Jianjun Wang, Wei Guo, Haoying Sun, Lu Han, Yunlei Zhou, Zhengbin Gu, Desheng Kong, Hugo Aramberri, Claudio Cazorla, Jorge iniguez, Riccardo Rurali, Longqing Chen, Jian Zhou, Di Wu, Minghui Lu, Yuefeng Nie, Yanfeng Chen, Xiaoqing Pan
Summary: The study reveals a significant enhancement of interfacial thermal resistance at metal/ferroelectric interfaces and highlights the crucial role of surface charges in this process. By applying uniaxial strain, the interfacial thermal resistance can vary substantially, attributed to the renormalized interfacial electron-phonon coupling caused by charge redistribution at the interface.
ADVANCED MATERIALS
(2022)
Article
Chemistry, Physical
Henning Kirchberg, Abraham Nitzan
Summary: This study considers a molecular junction immersed in a solvent, where the electron transfer occurs through Marcus-type steps. It is found that although the charge transfer is continuous, the solvent does not reach thermal equilibrium throughout the transport. By investigating the nonequilibrium solvent dynamics, the electrical, thermal, and thermoelectric properties of the molecular junction are examined. The results show that by tuning the friction, heat dissipation into the solvent can be reduced and heat transfer between the electrodes can be enhanced.
JOURNAL OF CHEMICAL PHYSICS
(2022)
Article
Chemistry, Physical
Mohammadhasan Dinpajooh, Abraham Nitzan
Summary: This work investigates the effect of stretching on the heat conduction of molecular junctions using nonequilibrium molecular dynamics simulations. The thermal conductance of these junctions is found to depend on the nature of metal leads and the stretching behavior is similar to pure polymeric structures. These findings suggest that the thermal conductivity under stretching is an intrinsic property of the polymer chain and not significantly influenced by interfacial structures.
JOURNAL OF CHEMICAL PHYSICS
(2022)
Article
Chemistry, Physical
Tao E. Li, Abraham Nitzan, Joseph E. Subotnik
Summary: In this study, the mechanism of polariton relaxation in liquid CO2 under weak external pumping is systematically investigated using classical cavity molecular dynamics (CavMD) simulations. The results show that polariton relaxation is a combination of cavity loss through the photonic component and dephasing of the bright-mode component to vibrational dark modes mediated by intermolecular interactions. The rate of polaritonic dephasing is proportional to the product of the weight of the bright mode in the polariton wave function and the spectral overlap between the polariton and dark modes, and is sensitive to parameters such as the Rabi splitting and cavity mode detuning. The CavMD simulations yield similar parameter dependence for the upper polariton relaxation lifetime compared to Fermi's golden rule calculation based on a tight-binding harmonic model, but sometimes show modest disagreement for the lower polariton. The authors suggest that this discrepancy may be due to polariton-enhanced molecular nonlinear absorption caused by molecular anharmonicity, which is not accounted for in the analytical model. Recent progress on probing nonreactive VSC dynamics with CavMD is also summarized.
JOURNAL OF CHEMICAL PHYSICS
(2022)
Article
Chemistry, Physical
Monosij Mondal, Maicol A. Ochoa, Maxim Sukharev, Abraham Nitzan
Summary: The interaction between excited states of a molecule and excited states of a metal nanostructure leads to hybrid states with modified optical properties. The condition for strong coupling between plasmons and molecules can be easily satisfied if the only contributions to the spectral width are associated with the radiative and nonradiative relaxation of a single molecular vibronic transition. However, the observation of Rabi splitting becomes more challenging when the molecule-metal surface distance is varied due to the spectral shift associated with the same molecule-plasmon interaction.
JOURNAL OF CHEMICAL PHYSICS
(2022)
Article
Chemistry, Physical
Tao E. Li, Abraham Nitzan, Sharon Hammes-Schiffer, Joseph E. Subotnik
Summary: This study presents a quantum simulation of vibrational strong coupling in the collective regime using thermostated ring-polymer molecular dynamics. The simulation shows that including nuclear and photonic quantum effects does not change the Rabi splitting but broadens polaritonic line widths. Additionally, both quantum and classical simulations predict that the static dielectric constant of liquid water remains largely unchanged inside vs outside the cavity under thermal equilibrium. However, this disagrees with a recent experiment, suggesting potential limitations of the approach or unexplored experimental factors.
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2022)
Article
Chemistry, Physical
Bingyu Cui, Abraham Nizan
Summary: This study investigates the implications of the collective optical response of molecular ensembles in optical cavities on molecular vibronic dynamics. The results suggest that strong molecule-radiation field coupling can lead to polaron decoupled dynamics, but the observed dynamics mainly reflect the local nature of the electronic polariton.
JOURNAL OF CHEMICAL PHYSICS
(2022)
Article
Chemistry, Physical
Henning Kirchberg, Abraham Nitzan
Summary: In this study, the zero-frequency charge current noise and the thermodynamic uncertainty relation (TUR) in a metal-molecule-metal junction in a thermal environment were investigated using a classical master equation. The researchers found that the classical current noise had a similar structure to its quantum analog and determined the bound on the entropy production in an electrochemical junction in the Marcus regime. The same methodology was also applied to predict the upper bound for the efficiency of energy conversion in a prototype photovoltaic cell.
JOURNAL OF CHEMICAL PHYSICS
(2022)
Article
Chemistry, Physical
Monosij Mondal, Alexander Semenov, Maicol A. Ochoa, Abraham Nitzan
Summary: Controlling molecular spectroscopy and chemical behavior in a cavity environment is a hot topic. Plasmonic cavities can have strong radiation-matter coupling, even at the level of single molecules. This study presents a method for estimating the radiation-matter coupling and applies it to the calculation of infrared cavities.
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2022)
Article
Chemistry, Physical
Maxim Sukharev, Joseph Subotnik, Abraham Nitzan
Summary: This study examines the photodissociation dynamics of an ensemble of diatomic molecules resonantly coupled to a resonant optical cavity under strong coupling conditions at normal incidence. The coupled Maxwell-Schrodinger equations are numerically integrated to account for the molecular ro-vibrational degrees of freedom. It is shown that driving the system at its polaritonic frequencies significantly affects and slows down the dissociation, with no classical analog. An intuitive explanation for the dissociation slowdown at polaritonic frequencies is proposed.
JOURNAL OF CHEMICAL PHYSICS
(2023)
Article
Chemistry, Physical
Natalya A. A. Zimbovskaya, Abraham Nitzan
Summary: In this study, the effect of chain configuration on phonon heat transport in a single polymer chain is analyzed theoretically based on recent molecular dynamic simulations. It is found that when the chain is strongly compressed and tangled, multiple random bends act as scattering centers for vibrational phonon modes, resulting in diffusive heat transport. As the chain straightens up, the number of scatterers decreases and the heat transport becomes more ballistic. A model of a long atomic chain is introduced to simulate the changes in chain configuration, and the phonon thermal conductance exhibits a threshold-like transition from diffusive to ballistic transport as the scatterers are gradually removed.
JOURNAL OF CHEMICAL PHYSICS
(2023)
Article
Chemistry, Physical
Galen T. Craven, Abraham Nitzan
Summary: Theoretical investigation on the thermal transport properties resulting from electron transfer in a molecular conduction junction reveals that the properties can significantly vary based on the characteristics of the molecular bridge and its environment. The system's thermal conductance commonly deviates from Fourier's law, and in properly engineered systems, the electron hopping thermal conductance is similar to that measured in single-molecule devices.
JOURNAL OF CHEMICAL PHYSICS
(2023)
Article
Chemistry, Physical
Bingyu Cui, Maxim Sukharev, Abraham Nitzan
Summary: This work investigates the quantum mechanical description of the interaction between photons and molecules. Approximation schemes, such as perturbation theory and mean-field Hartree approximation, are commonly used. The truncated 1-exciton model is found to be suitable for strong coupling approximation, and its results agree well with semiclassical mean-field calculations in several prototype problems.
JOURNAL OF CHEMICAL PHYSICS
(2023)
Article
Chemistry, Physical
Bingyu Cui, Maxim Sukharev, Abraham Nitzan
Summary: Similar to a free particle, a broad wavepacket on an ordered lattice initially grows slowly and eventually spreads linearly with time. However, on a disordered lattice, the growth is inhibited for a long time due to Anderson localization. Through numerical simulations and analytical studies, we demonstrate that the short-term growth of particle distribution is faster on a disordered lattice than on an ordered one. This faster spread may have relevance to exciton motion in disordered systems.
JOURNAL OF CHEMICAL PHYSICS
(2023)
Article
Chemistry, Physical
Renai Chen, Mohammadhasan Dinpajooh, Abraham Nitzan
Summary: This study presents an atomistic simulation methodology for molecular heat conduction that incorporates quantum statistics and a modified Langevin equation to consider quantum effects. The results show that this quasi-classical method is suitable for the full temperature range and can simulate the effects of anharmonicity and high-frequency modes on heat conduction.
JOURNAL OF CHEMICAL PHYSICS
(2023)
Article
Chemistry, Physical
Annabelle Oz, Abraham Nitzan, Oded Hod, Juan E. Peralta
Summary: This study introduces a first-principles approach to describe electron dynamics in open quantum systems. By using time-dependent density functional theory on finite model systems and imposing open boundary conditions via the driven Liouville-von Neumann methodology, the analysis of non-equilibrium dynamics is achieved.
JOURNAL OF CHEMICAL THEORY AND COMPUTATION
(2023)