Article
Chemistry, Physical
The Hoang Ngoc Minh, Benjamin Rotenberg, Sophie Marbach
Summary: This study examines ionic fluctuations in finite volumes using Brownian dynamics and develops an analytical framework applicable to systems with pairwise interactions. The correlations between particle number and charge exhibit diverse phenomenology over time. The hyperuniform behavior of charge fluctuations is preserved over time and even becomes proportional to the box perimeter at long times. These findings pave the way for understanding fluctuations in more complex systems.
FARADAY DISCUSSIONS
(2023)
Article
Chemistry, Physical
Vilde Braten, Dick Bedeaux, Oivind Wilhelmsen, Sondre Kvalvag Schnell
Summary: Small systems exhibit properties that may vary depending on the system's ensemble, as seen in the comparison of grand canonical and canonical systems. While analytical methods can be used to investigate ideal gas systems, simulations are required for systems with interacting particles. Clear differences between properties in open and closed systems were found, highlighting the importance of understanding these differences in small systems.
JOURNAL OF CHEMICAL PHYSICS
(2021)
Article
Thermodynamics
Xuehua Zhang, Rongguan Lv, Rong Xing, Weizhong Shi, Hongkun Zhao, Wanxin Li, Abolghasem Jouyban, William E. Acree
Summary: Equilibrium solubility and model correlations were studied for systems formed by solid solute of thiabendazole and binary aqueous blends of different solvents. The solubility was well described by two different models with low relative average deviations, and good predictions were observed using the extend Hildebrand solubility approach. The interaction parameters and solubility parameters of the solvents' blends were analyzed to understand the solubility variation, with descriptors of blended solvents playing a key role in determining solubility.
JOURNAL OF CHEMICAL THERMODYNAMICS
(2021)
Article
Chemistry, Physical
Tomislav Primorac, Martina Pozar, Franjo Sokolic, Larisa Zoranic
Summary: Kirkwood-Buff integrals (KBIs) serve as a powerful tool linking atomic scale structuring accessed by simulations with thermodynamics, bridging the gap between microscopic and macroscopic quantities. This study presents simulation research on the concentration dependence of KBIs for various binary ethanol mixtures, demonstrating that the best approach to KBI calculation varies depending on the structural complexity of the simulated system.
JOURNAL OF MOLECULAR LIQUIDS
(2021)
Article
Chemistry, Physical
Pauf Neupane, David M. Bartels, Ward H. Thompson
Summary: Using the Kirkwood-Buff approach, the partial molar volume is found to provide valuable insights into the structure of the hydrated electron. It not only indicates the size of the cavity, but also provides information about the solvation structure. This information is important for developing and evaluating models of the hydrated electron.
JOURNAL OF PHYSICAL CHEMISTRY B
(2023)
Article
Chemistry, Physical
P. Kumari, V. V. S. Pillai, D. Gobbo, P. Ballone, A. Benedetto
Summary: Molecular dynamics simulations were used to study the nanostructure in water solutions of three organic ionic liquids relevant for biological applications, revealing the formation of salt-rich or water-rich domains at different salt concentrations, and the possible formation of stoichiometric liquid ionic hydrates.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2021)
Article
Chemistry, Physical
A. O. Dohn, V. Markmann, A. Nimmrich, K. Haldrup, K. B. Moller, M. M. Nielsen
Summary: This study focuses on investigating the structure of molecules in solution using x-ray scattering methods. It introduces a correction method to eliminate simulation errors and recover the correct scattering limit. The reliability of the correction method is demonstrated through experiments with neat water and transition metal complexes solvated in various water densities.
JOURNAL OF CHEMICAL PHYSICS
(2023)
Article
Chemistry, Physical
Signe Kjelstrup, Astrid Fagertun Gunnarshaug, Oystein Gullbrekken, Sondre K. Schnell, Anders Lervik
Summary: In this study, we show how the choice of variables can determine a complete set of transport properties efficiently. Applying the entropy production invariance condition to different sets of electrolyte variables, we obtain a general set of formulas. We demonstrate the application of these formulas to a typical electrolyte for lithium-ion batteries, namely 1M lithium hexafluorophosphate in a 1:1 wt. % mixture of ethylene and diethyl carbonates. Our findings emphasize the importance of a complete set of transport coefficients for accurate modeling of complex electrochemical systems and the need for careful consideration of the choice of variables used to determine these properties.
JOURNAL OF CHEMICAL PHYSICS
(2023)
Article
Chemistry, Physical
Yani Zhao, Swaminath Bharadwaj, Nico F. A. van der Vegt
Summary: This study investigates the combined effect of weakly hydrated and strongly hydrated ions on the lower critical solution temperature (LCST) of poly(N-isopropylacrylamide)(PNIPAM) using atomistic molecular dynamics simulations. The results show that the nonadditive ion effects on the coil-to-globule transitions of PNIPAM arise from the interplay between the depletion of strongly hydrated sulfate ions and the preferential accumulation of iodide ions on the polymer surface, leading to favorable PNIPAM-I- interactions. The depletion of sulfate ions and the binding of iodide ions are coupled through the role of cations, resulting in a mutual enhancement of both effects.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2022)
Article
Chemistry, Multidisciplinary
Quy Ong, Ting Mao, Neda Iranpour Anaraki, Carla Malinverni, Xufeng Xu, Francesca Olgiati, Paulo Henrique Jacob Silva, Anna Murello, Antonia Neels, Davide Demurtas, Seishi Shimizu, Francesco Stellacci
Summary: A method is presented to extract thermodynamic quantities for nanoparticle dispersions in solvents using cryogenic electron tomography, with gold nanoparticles as a demonstration. The approach allows for the calculation of thermodynamic quantities without assumptions and the evaluation of key dispersion properties.
MATERIALS HORIZONS
(2022)
Article
Chemistry, Physical
Pauf Neupane, David M. Bartels, Ward H. Thompson
Summary: Mixed quantum-classical molecular dynamics simulations are important tools for studying the hydrated electron. They generally use a one-electron pseudopotential to describe the interactions with water molecules. However, there has been debate about the accuracy of these pseudopotentials in describing the properties of the hydrated electron. In this paper, the authors present an alternative approach where the pseudopotential parameters are optimized to reproduce key experimental properties, resulting in improved predictions of various properties.
JOURNAL OF PHYSICAL CHEMISTRY B
(2023)
Article
Thermodynamics
Chenghong Li, Qianqian Xu, Xianlang Chen, Rongrong Li
Summary: The study experimentally investigated the saturated solubility of bezafibrate in various solvents and aqueous co-solvent mixtures, and mathematically described the mole fraction solubility using different models. The preferential solvation of bezafibrate by different solvents in alcohol-rich and water-rich compositions was quantitatively analyzed. The main factors related to solvent effect were identified through linear solvation energy relationships.
JOURNAL OF CHEMICAL THERMODYNAMICS
(2021)
Article
Chemistry, Physical
Jas Kalayan, Richard H. Henchman
Summary: This study simulated five pure liquids of differing polarity to analyze solvation shells. The findings indicate that locally defined solvation shells should not be directly comparable to solute-centric shells or distance.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2021)
Article
Chemistry, Physical
Madhusmita Tripathy, Swaminath Bharadwaj, Nico F. A. van der Vegt
Summary: This study investigates the effect of urea and methanol on the density fluctuations and thermodynamic properties in the solvation shell of an extended hydrophobic solute. The results show that the mode of action of urea and methanol is strongly coupled to their hydration behavior, with urea preferential accumulation quenching density fluctuations and methanol accumulation enhancing density fluctuations.
JOURNAL OF CHEMICAL PHYSICS
(2022)
Article
Chemistry, Medicinal
Vilde Braten, Oivind Wilhelmsen, Sondre Kvalvag Schnell
Summary: The new method calculates chemical potential differences by sampling fluctuations in small systems, allowing for the extraction of chemical potential differences in the thermodynamic limit and demonstrating the size dependence of particle distributions in small systems.
JOURNAL OF CHEMICAL INFORMATION AND MODELING
(2021)
Article
Chemistry, Physical
Thijs J. H. Vlugt
Summary: In this manuscript, a method is presented to compute the partial molar properties of fluid mixtures from single Molecular Dynamics simulations. The method uses post-processing techniques involving least squares linear regression and the Small System Method. The results show that the method is applicable to systems with any number of components and any type of intermolecular interactions.
MOLECULAR SIMULATION
(2023)
Article
Thermodynamics
H. Mert Polat, Frederick de Meyer, Celine Houriez, Christophe Coquelet, Othonas A. Moultos, Thijs J. H. Vlugt
Summary: In this study, we investigated the effect of temperature and monoethanolamine (MEA) concentration on the self-diffusivity of acid gases, CO2 and H2S, in aqueous MEA solutions. The results showed that the self-diffusivity of both acid gases depends significantly on the temperature and MEA concentration in the solution. This study is important for the development of more efficient acid gas treatment processes.
FLUID PHASE EQUILIBRIA
(2023)
Article
Physics, Applied
Tianshun Xie, Kazuki Fukuda, Mengnan Ke, Peter Krueger, Keiji Ueno, Gil-Ho Kim, Nobuyuki Aoki
Summary: This study presents a simple and controllable heavy doping method for 2H-MoTe2 crystal via high-density laser irradiation. The polarity of the doping can be controlled by changing the irradiation environment. Good performance with enhanced contact properties was achieved for MoTe2-nFET using the contact doping method via laser irradiation in a vacuum environment.
JAPANESE JOURNAL OF APPLIED PHYSICS
(2023)
Article
Chemistry, Physical
Signe Kjelstrup, Kim R. R. Kristiansen, Astrid F. F. Gunnarshaug, Dick Bedeaux
Summary: Thermogalvanic cells can convert waste heat into electricity directly, but they are not fully utilized. This article discusses theoretical tools, such as nonequilibrium thermodynamics, that can help us understand and improve the performance of these cells. It recommends using this theory with operationally defined, independent variables for well-defined experiments.
JOURNAL OF CHEMICAL PHYSICS
(2023)
Review
Engineering, Chemical
Mahinder Ramdin, Othonas A. Moultos, Leo J. P. van den Broeke, Prasad Gonugunta, Peyman Taheri, Thijs J. H. Vlugt
Summary: Electrochemical reduction of carbon dioxide (CO2) to useful products with renewable electricity is a promising concept. However, carbonation, the formation of (bi)carbonate, is a major challenge in scaling up the process. It leads to various issues including low carbon utilization efficiencies and additional costs. In this review, the causes, consequences, and potential solutions for carbonation effect in CO2 electrolyzers are discussed, aiming to provide guidance for research in low-temperature CO2 electrolysis in alkaline media.
INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH
(2023)
Article
Chemistry, Physical
H. Mert Polat, Frederick de Meyer, Celine Houriez, Othonas A. Moultos, Thijs J. H. Vlugt
Summary: We developed an open-source chemical reaction equilibrium solver in Python (CASpy) to compute the concentration of species in any reactive liquid-phase absorption system. The computed CO2 absorption isotherms and speciations showed excellent agreement with experimental data, demonstrating the accuracy and precision of our solver. However, the computed CO2 pressures were significantly underestimated due to the sensitivity of the simulations to the point charges used.
JOURNAL OF CHEMICAL THEORY AND COMPUTATION
(2023)
Article
Chemistry, Physical
Oystein Gullbrekken, Ingeborg Treu Roe, Sverre Magnus Selbach, Sondre Kvalvag Schnell
Summary: In this study, ionic conductivity and transport numbers in electrolyte systems are calculated using Molecular Dynamics (MD) simulations and compared with experimental results. The significance of the frame of reference is discussed when determining and comparing transport numbers. Two methods of computing ionic conductivity from equilibrium simulations are presented: the Nernst-Einstein approximation or the Onsager coefficients. The main features and differences between equilibrium and nonequilibrium simulations are discussed, and potential anomalies and critical pitfalls of using nonequilibrium molecular dynamics to determine transport properties are highlighted.
JOURNAL OF PHYSICAL CHEMISTRY B
(2023)
Article
Chemistry, Physical
Shrinjay Sharma, Marcello S. S. Rigutto, Richard Baur, Umang Agarwal, Erik Zuidema, Salvador R. G. Balestra, Sofia Calero, David Dubbeldam, Thijs J. H. Vlugt
Summary: Ideal Adsorbed Solution Theory (IAST) is a common method for modeling mixture adsorption isotherms, while the segregated version (SIAST) provides improved adsorbed loadings. We have adopted the concept of SIAST and developed the Segregated Explicit Isotherm (SEI) model which considers both size-effects of co-adsorbed molecules and surface heterogeneities. Compared to IAST and SIAST, SEI does not require an iterative scheme, resulting in faster simulations with excellent agreement with experimental data.
Article
Chemistry, Physical
Shrinjay Sharma, Salvador R. G. Balestra, Richard Baur, Umang Agarwal, Erik Zuidema, Marcello S. Rigutto, Sofia Calero, Thijs J. H. Vlugt, David Dubbeldam
Summary: The RUPTURA code is introduced as a free and open-source software package for gas adsorption simulation, mixture prediction, and isotherm model fitting. It can be combined with the RASPA software to compute breakthrough curves directly from adsorption simulations. The code supports a variety of isotherm models and provides an easy way to obtain the model parameters through the fitting module.
MOLECULAR SIMULATION
(2023)
Article
Chemistry, Analytical
Tomoya Minezaki, Peter Kruger, Fatima Ezahra Annanouch, Juan Casanova-Chafer, Aanchal Alagh, Ignacio J. J. Villar-Garcia, Virginia Perez-Dieste, Eduard Llobet, Carla Bittencourt
Summary: This study investigates the hydrogen sensing mechanism of a nanostructured WS2 layer using NAP-XPS and DFT. The results suggest that hydrogen physisorbs on the WS2 active surface at room temperature and chemisorbs on tungsten atoms at higher temperatures. DFT calculations show that hydrogen adsorbs physically on the defect-free WS2 monolayer, but forms chemical bonds with tungsten atoms on sulfur defects. The hydrogen adsorption causes charge transfer and reduces the intensity of in-gap states, leading to an increase in the gas sensor resistance.
Article
Multidisciplinary Sciences
Peter Kruger
Summary: Recently, we have proposed a simple method to calculate the parameters of a ligand field multiplet model for L-edge spectra calculations using density functional theory. In this study, we extend the method to systems with arbitrary point symmetry at the metal site. The ligand field-induced splitting of the metal d-level is represented as a hermitian matrix with cross-terms between different d orbitals. The anisotropy of covalency is taken into account, leading to rescaling of electron-electron interaction and oscillator strength in an orbital-dependent manner. We apply the method to polarization-dependent V L-edge spectra of vanadium pentoxide and achieve excellent agreement with experimental results.
Article
Energy & Fuels
Bin Fang, Othonas A. Moultos, Tao Lu, Jiaxin Sun, Zhichao Liu, Fulong Ning, Thijs J. H. Vlugt
Summary: Hydrate dissociation is often accompanied by the formation of nanobubbles. Knowledge of the effects of nanobubbles on hydrate dissociation is essential for understanding the dynamic behavior of the hydrate phase change and improving the gas production efficiency.
Article
Chemistry, Physical
Signe Kjelstrup, Astrid Fagertun Gunnarshaug, Oystein Gullbrekken, Sondre K. Schnell, Anders Lervik
Summary: In this study, we show how the choice of variables can determine a complete set of transport properties efficiently. Applying the entropy production invariance condition to different sets of electrolyte variables, we obtain a general set of formulas. We demonstrate the application of these formulas to a typical electrolyte for lithium-ion batteries, namely 1M lithium hexafluorophosphate in a 1:1 wt. % mixture of ethylene and diethyl carbonates. Our findings emphasize the importance of a complete set of transport coefficients for accurate modeling of complex electrochemical systems and the need for careful consideration of the choice of variables used to determine these properties.
JOURNAL OF CHEMICAL PHYSICS
(2023)
Article
Materials Science, Multidisciplinary
Ryunosuke Sagehashi, Wei Chuang Lee, Fupin Liu, Alexey A. Popov, Matthias Muntwiler, Bernard Delley, Peter Krueger, Thomas Greber
Summary: This study experimentally determined the Dy-N axis by X-ray absorption spectroscopy (XAS) and found that the orientation of DySc2N@C80 molecules on a Pt(111) surface undergoes reversible changes with temperature. The results showed that the endohedral unit is randomly oriented at room temperature but tends to be parallel to the surface at low temperatures.
PHYSICAL REVIEW MATERIALS
(2023)
Article
Polymer Science
Caroline Einen, Sebastian E. N. Price, Kim Ulvik, Magnus Aa. Gjennestad, Rune Hansen, Signe Kjelstrup, Catharina de Lange Davies
Summary: The study found that pulsed focused ultrasound alone cannot explain the enhanced penetration of nanoparticles. However, it can be used as a tool to enhance the diffusion of particles in the tumor extracellular matrix.
