Beyond the Debye–Hückel limit: Toward a general theory for concentrated electrolytes DOI Creative Commons
Mohammadhasan Dinpajooh, Nadia N. Intan, Timothy T. Duignan

и другие.

The Journal of Chemical Physics, Год журнала: 2024, Номер 161(23)

Опубликована: Дек. 16, 2024

The phenomenon of underscreening in concentrated electrolyte solutions leads to a larger decay length the charge-charge correlation than prediction Debye-Hückel (DH) theory and has found resurgence both theoretical experimental interest chemical physics community. To systematically understand investigate this electrolytes requires describe correlations beyond DH theory. We review theories that can transition from limit concentrations where charge dominate, giving rise associated Kirkwood Transitions (KTs). In perspective, we provide conceptual approach formulation exploits competition between molecular-informed short-range (SR) long-range interactions. demonstrate all deviations for real be expressed through single function ΣQ determined theoretically numerically. Importantly, directly related details SR interactions and, therefore, used as tool how differences representations interaction influence collective effects. precise form inferred Gaussian field number densities. resulting is validated by experiment accurately screening bulk electrolytes. predictions lengths appear less ∼1 nm at above KTs.

Язык: Английский

Space-local memory in generalized master equations: Reaching the thermodynamic limit for the cost of a small lattice simulation DOI
Srijan Bhattacharyya, Thomas Sayer, Andrés Montoya−Castillo

и другие.

The Journal of Chemical Physics, Год журнала: 2025, Номер 162(9)

Опубликована: Март 5, 2025

The exact quantum dynamics of lattice models can be computationally intensive, especially when aiming for large system sizes and extended simulation times necessary to converge transport coefficients. By leveraging finite memory access long-time using only short-time data, generalized master equations offer a route simulating the problems efficiently. However, such simulations are limited small lattices whose exhibit finite-size artifacts that contaminate coefficient predictions. To address this problem, we introduce novel approach exploits in both time space efficiently predict many-body dissipative involving short-range interactions. This advance enables one leverage nonperturbatively exactly simulate arbitrarily systems over long times. We demonstrate strengths method by focusing on nonequilibrium polaron relaxation dispersive Holstein model, successfully two dimensions free from effects, thereby reducing computational expense multiple orders magnitude. Our is broadly applicable provides an accurate efficient means investigate with microscopic resolution mesoscopic length scales relevant experiments.

Язык: Английский

Процитировано

1
On the Stability Constants of Metal-Nitrate Complexes in Aqueous Solutions DOI Creative Commons
Mohammadhasan Dinpajooh,

Greta L. Hightower,

Richard Overstreet

и другие.

Physical Chemistry Chemical Physics, Год журнала: 2025, Номер 27(18), С. 9350 - 9368

Опубликована: Янв. 1, 2025

Stability constants of simple reactions involving addition the NO3- ion to hydrated metal complexes, [M(H2O)x]n+ are calculated with a computational workflow developed using cloud computing resources. The performs conformational searches for complexes at both low and high levels theories in conjunction continuum solvation model (CSM). low-level theory is mainly used initial searches, which complemented high-level density functional CSM framework determine coordination chemistry relevant stability constant calculations. In this regard, lowest energy conformations found obtain reaction free energies one where M represents Fe(II), Fe(III), Sr(II), Ce(III), Ce(IV), U(VI), respectively. Structural analysis hundreds optimized geometries reveals that coordinates Fe(II) Fe(III) either monodentate or bidentate manner. Interestingly, lowest-energy metal-nitrate exhibit number 6 while seven-coordinated approximately 2 kcal mol-1 higher energy. Notably, configuration more stable than six-coordinated (monodentate bidentate) by few thermal units. contrast, U(VI) ions predominantly coordinate manner, exhibiting typical numbers 7, 9, 5, accordingly linear approaches account systematic errors good agreements obtained between available experimental data.

Язык: Английский

Процитировано

0
Asymptotic Underscreening in Concentrated Electrolytes Measured by Optical Second Harmonic Scattering of Water DOI
Fabien Rondepierre, Pierre‐François Brevet, Julien Duboisset

и другие.

The Journal of Physical Chemistry Letters, Год журнала: 2025, Номер unknown, С. 2690 - 2694

Опубликована: Март 6, 2025

We show that with optical second harmonic scattering, one can measure the screening length in bulk phase of aqueous electrolytes. The methodology is based on analysis coherent contribution describing water-water orientation correlation function present polarization-resolved scattering intensity. Measurements were performed up to highly concentrated NaCl and LiCl electrolyte solutions, enabling development a theoretical framework valid over whole salt concentration range. At low concentrations, experimental findings adhere standard Debye-Hückel theory. However, at high observed deviates from Debye reaches an asymptotic value dependent ion size. This effectively demonstrates underscreening, but no anomalous increase concentrations observed.

Язык: Английский

Процитировано

0
Effect of variable relative permittivity on the thermodynamics of asymmetric valency aqueous salts DOI Creative Commons
Abdiel Rivera, Zareen Abbas, C.W. Outhwaite

и другие.

Condensed Matter Physics, Год журнала: 2025, Номер 28(1), С. 13802 - 13802

Опубликована: Март 28, 2025

Experimentally determined empirical formulae for the concentration dependent relative permittivity of aqueous solutions MgCl2 and NiCl2 are utilized to calculate osmotic coefficient mean activity these salts a range concentrations. The systems modelled using primitive model electrolytes analyzed symmetric Poisson-Boltzmann theory, modified spherical approximation, Monte Carlo simulations. Generally, approximation theory reproduce benchmark simulation data well up ∼1.6 mol/dm3 or more in many instances, while results show discrepancies starting from ∼0.25 mol/dm3. Both simulations theories tend deviate corresponding experimental beyond ∼1 mol/kg.

Язык: Английский

Процитировано

0
Resolving the Solvation Structure and Transport Properties of Aqueous Zinc Electrolytes from Salt-in-Water to Water-in-Salt Using Neural Network Potential DOI Creative Commons
Chuntian Cao,

A. Kingan,

Ryan C. Hill

и другие.

PRX Energy, Год журнала: 2025, Номер 4(2)

Опубликована: Апрель 11, 2025

ZnCl2 solutions are promising electrolytes for aqueous zinc-ion batteries. Here, we report a joint computational and experimental study of the structural dynamic properties ZnCl2 with concentrations ranging from salt-in-water to water-in-salt (WIS). By developing neural network potential (NNP) model, perform molecular dynamics (MD) simulations accuracy but at much larger lengths longer timescales. The NNP predicted structures validated by structure factors measured X-ray total scattering experiments. MD trajectories provide comprehensive quantitative picture Zn2+ solvation shell structures. Additionally, find that O−H covalent bonds in water strengthened increasing salt concentration, thus expanding electrochemical stability window electrolytes. In terms properties, calculated experimentally conductivities good agreement. Through analysis cation transference number, propose three-stage charge carrier transport mechanism concentration: independent ion transport, strongly correlated small positive diffusion through negatively charged polymeric clusters. Our provides fundamental atomic scale insights into ZnCl2 electrolyte can aid optimization development WIS Published American Physical Society 2025

Язык: Английский

Процитировано

0
Beyond the Debye–Hückel limit: Toward a general theory for concentrated electrolytes DOI Creative Commons
Mohammadhasan Dinpajooh, Nadia N. Intan, Timothy T. Duignan

и другие.

The Journal of Chemical Physics, Год журнала: 2024, Номер 161(23)

Опубликована: Дек. 16, 2024

The phenomenon of underscreening in concentrated electrolyte solutions leads to a larger decay length the charge-charge correlation than prediction Debye-Hückel (DH) theory and has found resurgence both theoretical experimental interest chemical physics community. To systematically understand investigate this electrolytes requires describe correlations beyond DH theory. We review theories that can transition from limit concentrations where charge dominate, giving rise associated Kirkwood Transitions (KTs). In perspective, we provide conceptual approach formulation exploits competition between molecular-informed short-range (SR) long-range interactions. demonstrate all deviations for real be expressed through single function ΣQ determined theoretically numerically. Importantly, directly related details SR interactions and, therefore, used as tool how differences representations interaction influence collective effects. precise form inferred Gaussian field number densities. resulting is validated by experiment accurately screening bulk electrolytes. predictions lengths appear less ∼1 nm at above KTs.

Язык: Английский

Процитировано

2