Journal of Chemical Physics最新文献_第4页

Single file dynamics of tethered random walkers. 拴着随机步行者的单队列动态。

IF 3.1 2区化学

Journal of Chemical Physics Pub Date : 2025-06-14 DOI: 10.1063/5.0271037

Santos Bravo Yuste, A Baumgaertner, E Abad

{"title":"Single file dynamics of tethered random walkers.","authors":"Santos Bravo Yuste, A Baumgaertner, E Abad","doi":"10.1063/5.0271037","DOIUrl":"https://doi.org/10.1063/5.0271037","url":null,"abstract":"We consider the single file dynamics of N identical random walkers moving with diffusivity D in one dimension (walkers bounce off each other when attempting to overtake). In addition, we require that the separation between neighboring walkers does not exceed a threshold value Δ and therefore call them \"tethered walkers\" (they behave as if bounded by strings that fully tighten when reaching the maximum length Δ). For a finite Δ, we study the diffusional relaxation to the equilibrium state and characterize the latter [the long-time relaxation is exponential with a characteristic time that scales as (NΔ)2/D]. In particular, our approximate approach for the N-particle probability distribution yields the one-particle distribution function of the central and edge particles (the first two positional moments are given as power expansions in Δ/4Dt). For N = 2, we find an exact solution (both in the continuum and on-lattice case) and use it to test our approximations for one-particle distributions, positional moments, and correlations. For finite Δ and arbitrary N, edge particles move with an effective long-time diffusivity D/N, in sharp contrast with the 1/ln(N)-behavior observed when Δ = ∞. Finally, we compute the probability distribution of the equilibrium system length and associated entropy. We find that the force required to change this length by a given amount is linear in this quantity; the (entropic) spring constant is 6kBT/(NΔ2). In this respect, the system behaves as an ideal polymer. The main analytical results are confirmed using Monte Carlo simulations.","PeriodicalId":15313,"journal":{"name":"Journal of Chemical Physics","volume":"162 22","pages":""},"PeriodicalIF":3.1,"publicationDate":"2025-06-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144284519","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Impact of solvent polarity on the photoinduced dynamics of a push-pull molecular motor. 溶剂极性对推挽式分子马达光致动力学的影响。

IF 3.1 2区化学

Journal of Chemical Physics Pub Date : 2025-06-14 DOI: 10.1063/5.0269998

Davide Accomasso, Dominika Makoś

{"title":"Impact of solvent polarity on the photoinduced dynamics of a push-pull molecular motor.","authors":"Davide Accomasso, Dominika Makoś","doi":"10.1063/5.0269998","DOIUrl":"https://doi.org/10.1063/5.0269998","url":null,"abstract":"Light-driven rotary molecular motors convert light energy into unidirectional rotational movement. In overcrowded alkene-based molecular motors, rotary motion is accomplished through consecutive cis-trans photoisomerization reactions and thermal helix inversion steps. To date, a complete understanding of the photoisomerization reactions of overcrowded alkene motors has not been achieved yet. In this work, we use quantum chemical calculations and quantum mechanics/molecular mechanics nonadiabatic dynamics simulations to investigate the photoinduced dynamics of a push-pull alkene-based molecular motor in two different solvents: cyclohexane and methanol. We show that, while in both solvents the main photorelaxation pathway of our investigated push-pull motor involves two different excited-state minima, in polar methanol, the photorelaxation dynamics is much faster than in nonpolar cyclohexane because of two main effects: (i) a lowering of the energy barrier between the excited-state minima and (ii) a reduction in the energy gap with the ground state at the largely twisted dark minimum, where the excited-state decay takes place. Both effects can be attributed to solvent-polarity stabilization of the charge-transfer excited state along the photorelaxation pathway. In line with the experimental findings, our simulations also indicate that, in methanol, the accelerated photoinduced dynamics goes along with a faster fluorescence decay and a large reduction in the forward photoisomerization yield of our investigated motor.","PeriodicalId":15313,"journal":{"name":"Journal of Chemical Physics","volume":"162 22","pages":""},"PeriodicalIF":3.1,"publicationDate":"2025-06-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144284517","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Variational functional in local density approximation for coulombic electrolyte correlations in the electric double layer. 双电层中库仑电解质相关的局部密度近似变分泛函。

IF 3.1 2区化学

Journal of Chemical Physics Pub Date : 2025-06-14 DOI: 10.1063/5.0250135

Nils Bruch, Tobias Binninger, Jun Huang, Michael Eikerling

引用次数: 0

Repeated interaction scheme for the quantum simulation of non-Markovian electron transfer dynamics. 非马尔可夫电子转移动力学量子模拟的重复相互作用方案。

IF 3.1 2区化学

Journal of Chemical Physics Pub Date : 2025-06-14 DOI: 10.1063/5.0268071

Lea K Northcote, Matthew S Teynor, Gemma C Solomon

{"title":"Repeated interaction scheme for the quantum simulation of non-Markovian electron transfer dynamics.","authors":"Lea K Northcote, Matthew S Teynor, Gemma C Solomon","doi":"10.1063/5.0268071","DOIUrl":"https://doi.org/10.1063/5.0268071","url":null,"abstract":"Quantum algorithms have the potential to revolutionize our understanding of open quantum systems in chemistry. In this work, we demonstrate that a repeated interaction model, which could serve as the foundation for a digital quantum algorithm, can effectively reproduce non-Markovian electron transfer dynamics under four different donor-acceptor parameter regimes and for a donor-bridge-acceptor system. We systematically explore how the model scales for the regimes. Notably, our approach exhibits favorable scaling in the required repeated interaction duration as the electronic coupling, temperature, damping rate, and system size increase. Furthermore, a single Trotter step per repeated interaction leads to an acceptably small error, and high-fidelity initial states can be prepared with a short time evolution. This efficiency highlights the potential of the model for tackling increasingly complex systems. When fault-tolerant quantum hardware becomes available, algorithms based on this model could be extended to incorporate structured baths, additional energy levels, or more intricate coupling schemes, enabling the simulation of real-world open quantum systems that remain beyond the reach of classical computation.","PeriodicalId":15313,"journal":{"name":"Journal of Chemical Physics","volume":"162 22","pages":""},"PeriodicalIF":3.1,"publicationDate":"2025-06-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144284518","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Hydrogen diffusion in the confinement between graphene and Ni(111): Full-dimensional simulation of nuclear quantum effects. 氢在石墨烯和Ni之间的扩散（111）：核量子效应的全维模拟。

IF 3.1 2区化学

Journal of Chemical Physics Pub Date : 2025-06-07 DOI: 10.1063/5.0268691

J Steffen

{"title":"Hydrogen diffusion in the confinement between graphene and Ni(111): Full-dimensional simulation of nuclear quantum effects.","authors":"J Steffen","doi":"10.1063/5.0268691","DOIUrl":"https://doi.org/10.1063/5.0268691","url":null,"abstract":"The temperature-dependent diffusion of hydrogen on a Ni(111) surface and in the confinement between Ni(111) and an adsorbed graphene sheet [Gr/Ni(111)] is studied by ring polymer molecular dynamics (RPMD) simulations on neural network potentials. Static periodic density-functional theory calculations reveal weakened bonding of hydrogen and higher diffusion barriers in the confinement. Furthermore, local density of hydrogen atoms has a significant influence on their shape and properties. For a hydrogen density of 0.25 ML, the graphene sheet switches to the weaker bound van der Waals configuration, resulting in a broad confinement with similar properties as the clean metal surface. For a hydrogen density of 0.04 ML, the graphene behaves like a carpet and bends up locally around the hydrogen atom. This presses the hydrogen atom to the surface, resulting in lower intercalation energy and a higher diffusion barrier. The RPMD simulations were used to quantify the effect of temperature and nuclear quantum effects on the diffusion. For 0.25 ML hydrogen coverage, the diffusion coefficients are similar to the clean surface, with a crossover temperature to the deep-tunneling regime of ∼100 K, whereas for 0.04 ML, diffusion at low temperatures is significantly decreased. At temperatures above 200 K, on the other hand, diffusion is more similar for both hydrogen coverages due to a more flexible graphene sheet. This study reveals that two-dimensional confinements adapt to their content, and full-dimensional simulations with the inclusion of nuclear quantum effects can greatly enhance our understanding of them, needed for their targeted usage as storage media or catalysts.","PeriodicalId":15313,"journal":{"name":"Journal of Chemical Physics","volume":"162 21","pages":""},"PeriodicalIF":3.1,"publicationDate":"2025-06-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144234287","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Ion dynamics in hexagonal boron nitride ionogel electrolytes. 六方氮化硼离子凝胶电解质的离子动力学。

IF 3.1 2区化学

Journal of Chemical Physics Pub Date : 2025-06-07 DOI: 10.1063/5.0271227

Giselle de Araujo Lima E Souza, Moises Acero, Emilia Pelegano-Titmuss, Phillip Stallworth, Cory M Thomas, Mark C Hersam, Pedro José Oliveira Sebastião, Steven Greenbaum

{"title":"Ion dynamics in hexagonal boron nitride ionogel electrolytes.","authors":"Giselle de Araujo Lima E Souza, Moises Acero, Emilia Pelegano-Titmuss, Phillip Stallworth, Cory M Thomas, Mark C Hersam, Pedro José Oliveira Sebastião, Steven Greenbaum","doi":"10.1063/5.0271227","DOIUrl":"https://doi.org/10.1063/5.0271227","url":null,"abstract":"Ionogel electrolytes incorporating exfoliated hexagonal boron nitride (hBN) nanoplatelets are promising materials for next-generation energy storage systems. However, detailed understanding of their ion transport properties at the molecular level remains limited. This study employs diffusion and relaxation nuclear magnetic resonance (NMR) techniques, including fast-field cycling (FFC) NMR, to investigate the dynamics of ionic species in hBN-ionogels. By spanning a broad frequency range from 30 kHz using FFC NMR to high-field NMR (500-800 MHz), we reveal distinct relaxation mechanisms governing ion dynamics in ionogels with and without lithium salts. Our results highlight the role of hBN in modulating molecular rotation and translational motion, significantly affecting 1H and 19F relaxation profiles. The presence of Li+ alters the dynamic behavior in ionogels, enhancing anion mobility at the interface. Notably, 7Li relaxation reveals strong interactions with the hBN surface that cannot be detected by diffusion NMR. These findings underscore the importance of spanning a broad frequency range in NMR studies of ionogels and provide critical insights into optimizing their design as novel electrolytes.","PeriodicalId":15313,"journal":{"name":"Journal of Chemical Physics","volume":"162 21","pages":""},"PeriodicalIF":3.1,"publicationDate":"2025-06-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144234288","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Erratum: "Photoelectron spectrum of isothiocyanic acid, HNCS: Theory and experiment" [J. Chem. Phys. 162, 164310 (2025)]. 勘误：“异硫氰酸光电子能谱，HNCS：理论与实验”[J]。化学。物理学报，2016,33(5):1158 - 1158。

IF 3.1 2区化学

Journal of Chemical Physics Pub Date : 2025-06-07 DOI: 10.1063/5.0279802

Dorothee Schaffner, Ayad Bellili, Marius Gerlach, Emil Karaev, Muneerah Mogren Al Mogren, John Bozek, Ingo Fischer, Majdi Hochlaf

引用次数: 0

Chirped-pulse Fourier transform microwave spectrum of the HCl-DCl heterodimer. 盐酸- dcl异二聚体的啁啾脉冲傅立叶变换微波谱。

IF 3.1 2区化学

Journal of Chemical Physics Pub Date : 2025-06-07 DOI: 10.1063/5.0273758

Muhammad Qasim Ali, Arun Bhujel, Salma Akter, Fan Xie, Melanie Schnell, G Barratt Park

引用次数: 0

Low-frequency Raman spectra of amyloid fibrils. 淀粉样蛋白原纤维的低频拉曼光谱。