arXiv - PHYS - Chemical Physics最新文献_第10页

Understanding the Optoelectronic Processes in Colloidal 2D Multi-Layered MAPbBr3 Perovskite Nanosheets: Funneling, Recombination and Self-Trapped Excitons 了解胶体二维多层 MAPbBr3 珍珠岩纳米片中的光电过程：漏斗、重组和自俘获激子

arXiv - PHYS - Chemical Physics Pub Date : 2024-08-08 DOI: arxiv-2408.04571

André Niebur, Eugen Klein, Rostyslav Lesyuk, Christian Klinke, Jannika Lauth

{"title":"Understanding the Optoelectronic Processes in Colloidal 2D Multi-Layered MAPbBr3 Perovskite Nanosheets: Funneling, Recombination and Self-Trapped Excitons","authors":"André Niebur, Eugen Klein, Rostyslav Lesyuk, Christian Klinke, Jannika Lauth","doi":"arxiv-2408.04571","DOIUrl":"https://doi.org/arxiv-2408.04571","url":null,"abstract":"Quasi two-dimensional (2D) colloidal synthesis made quantum confinement\u0000readily accessible in perovskites, generating additional momentum in perovskite\u0000LED research and lasing. Ultrathin perovskite layers exhibit high exciton\u0000binding energies and beneficial charge transport properties interesting for\u0000solar cells. In 2D perovskites, the combination of layers with different\u0000thickness helps to direct charge carriers in a targeted manner toward thicker\u0000layers with a smaller bandgap. However, detailed knowledge about the mechanisms\u0000by which excitons and charge carriers funnel and recombine in these structures\u0000is lacking. Here, we characterize colloidal 2D methylammonium lead bromide\u0000(MAPbBr3) Ruddlesden-Popper perovskites with a broad combination of layers (n =\u00003 to 10, and bulk fractions with n > 10) in one stack by femtosecond transient\u0000absorption spectroscopy and time-resolved photoluminescence, which gives\u0000comprehensive insights into the complexity of funneling and recombination\u0000processes. We find that after photoexcitation second- and third-order processes\u0000dominate in MAPbBr3 nanosheets, which indicates exciton-exciton annihilation\u0000(EEA) and Auger recombination. Long-lived excitons in thin layers (e.g., n = 5,\u0000Eb = 136 meV) funnel into high n with t = 10-50 ps, which decreases their\u0000exciton binding energy below kB T = 26 meV ( T = 300K) and leads to radiative\u0000recombination. Parallel and consecutive funneling compete with exciton trapping\u0000processes, making funneling an excellent tool to overcome exciton self-trapping\u0000when high-quality n-n interfaces are present. Free charge carriers in high n\u0000regions on the other hand facilitate radiative recombination and EEA is\u0000bypassed, which is desirable for LED and lasing applications.","PeriodicalId":501304,"journal":{"name":"arXiv - PHYS - Chemical Physics","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-08-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141935839","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Modeling the Influence of Solvation on the Electrochemical Double Layer of Salt / Solvent Mixtures 模拟溶解对盐/溶剂混合物电化学双电层的影响

arXiv - PHYS - Chemical Physics Pub Date : 2024-08-08 DOI: arxiv-2408.04314

Constantin Schwetlick, Max Schammer, Arnulf Latz, Birger Horstmann

{"title":"Modeling the Influence of Solvation on the Electrochemical Double Layer of Salt / Solvent Mixtures","authors":"Constantin Schwetlick, Max Schammer, Arnulf Latz, Birger Horstmann","doi":"arxiv-2408.04314","DOIUrl":"https://doi.org/arxiv-2408.04314","url":null,"abstract":"Modelling electrolytes accurately on both a nanoscale and cell level can\u0000contribute to improving battery chemistries.[Armand and Tarascon, Nature, 2008,\u0000451, 652-657] We previously presented a thermodynamic continuum model for\u0000electrolytes.[arXiv:2010.14915] In this paper we include solvation interactions\u0000between the ions and solvent, which alter the structure of the electochemical\u0000double layer (EDL). We are able to combine a local solvation model --\u0000permitting examination of the interplay between electric forces and the\u0000ion-solvent binding -- with a full electrolyte model. Using this, we can\u0000investigate double layer structures for a wide range of electrolytes,\u0000especially including highly concentrated solutions. We find that some of the\u0000parameters of our model significantly affect the solvent concentration at the\u0000electrode surface, and thereby the rate of solvent decomposition. Firstly, an\u0000increased salt concentration weakens the solvation shells, making it possible\u0000to strip the solvent in the EDL before the ions reach the surface. The strength\u0000of the ion-solvent interaction also affects at which potential difference the\u0000solvation shells removed. We are therefore able to qualitatively predict EDL\u0000structures for different electrolytes based on parameters like molecule size,\u0000solvent binding energy and salt concentration.","PeriodicalId":501304,"journal":{"name":"arXiv - PHYS - Chemical Physics","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-08-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141935826","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Advancing Molecular Machine (Learned) Representations with Stereoelectronics-Infused Molecular Graphs 利用注入立体电子学的分子图推进分子机器（学习）表示法

arXiv - PHYS - Chemical Physics Pub Date : 2024-08-08 DOI: arxiv-2408.04520

Daniil A. Boiko, Thiago Reschützegger, Benjamin Sanchez-Lengeling, Samuel M. Blau, Gabe Gomes

{"title":"Advancing Molecular Machine (Learned) Representations with Stereoelectronics-Infused Molecular Graphs","authors":"Daniil A. Boiko, Thiago Reschützegger, Benjamin Sanchez-Lengeling, Samuel M. Blau, Gabe Gomes","doi":"arxiv-2408.04520","DOIUrl":"https://doi.org/arxiv-2408.04520","url":null,"abstract":"Molecular representation is a foundational element in our understanding of\u0000the physical world. Its importance ranges from the fundamentals of chemical\u0000reactions to the design of new therapies and materials. Previous molecular\u0000machine learning models have employed strings, fingerprints, global features,\u0000and simple molecular graphs that are inherently information-sparse\u0000representations. However, as the complexity of prediction tasks increases, the\u0000molecular representation needs to encode higher fidelity information. This work\u0000introduces a novel approach to infusing quantum-chemical-rich information into\u0000molecular graphs via stereoelectronic effects. We show that the explicit\u0000addition of stereoelectronic interactions significantly improves the\u0000performance of molecular machine learning models. Furthermore,\u0000stereoelectronics-infused representations can be learned and deployed with a\u0000tailored double graph neural network workflow, enabling its application to any\u0000downstream molecular machine learning task. Finally, we show that the learned\u0000representations allow for facile stereoelectronic evaluation of previously\u0000intractable systems, such as entire proteins, opening new avenues of molecular\u0000design.","PeriodicalId":501304,"journal":{"name":"arXiv - PHYS - Chemical Physics","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-08-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141935827","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Surface potentials of conductors in electrolyte solutions 电解质溶液中导体的表面电位

arXiv - PHYS - Chemical Physics Pub Date : 2024-08-08 DOI: arxiv-2408.04434

Olga I. Vinogradova, Elena F. Silkina, Evgeny S. Asmolov

{"title":"Surface potentials of conductors in electrolyte solutions","authors":"Olga I. Vinogradova, Elena F. Silkina, Evgeny S. Asmolov","doi":"arxiv-2408.04434","DOIUrl":"https://doi.org/arxiv-2408.04434","url":null,"abstract":"When we place conducting bodies in electrolyte solutions, their surface\u0000potential $Phi_s$ appears to be much smaller in magnitude than the intrinsic\u0000one $Phi_0$ and normally does not obey the classical electrostatic boundary\u0000condition of a constant surface potential expected for conductors. In this\u0000paper, we demonstrate that an explanation of these observations can be obtained\u0000by postulating that diffuse ions condense at the \"wall\" due to a reduced\u0000permittivity of a solvent. For small values of $Phi_0$ the surface potential responds linearly. On\u0000increasing $Phi_0$ further $Phi_s$ augments nonlinearly and then saturates to\u0000a constant value. Analytical approximations for $Phi_s$ derived for these\u0000three distinct modes show that it always adjusts to salt concentration, which\u0000is equivalent to a violation of the constant potential condition. The latter\u0000would be appropriate for highly dilute solutions, but only if $Phi_0$ is\u0000small. Surprisingly, when the plateau with high $Phi_s$ is reached, the\u0000conductor surface switches to a constant charge density condition normally\u0000expected for insulators. Our results are directly relevant for conducting\u0000electrodes, mercury drops, colloidal metallic particles and more.","PeriodicalId":501304,"journal":{"name":"arXiv - PHYS - Chemical Physics","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-08-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141935828","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

The graphene-water interface is acidic 石墨烯-水界面呈酸性

arXiv - PHYS - Chemical Physics Pub Date : 2024-08-08 DOI: arxiv-2408.04487

Xavier R. Advincula, Kara D. Fong, Angelos Michaelides, Christoph Schran

{"title":"The graphene-water interface is acidic","authors":"Xavier R. Advincula, Kara D. Fong, Angelos Michaelides, Christoph Schran","doi":"arxiv-2408.04487","DOIUrl":"https://doi.org/arxiv-2408.04487","url":null,"abstract":"Water's ability to autoionize into hydroxide and hydronium ions profoundly\u0000influences surface properties, rendering interfaces either basic or acidic.\u0000While it is well-established that the water-air interface is acidic, a critical\u0000knowledge gap exists in technologically relevant surfaces like the\u0000graphene-water interface. Here we use machine learning-based simulations with\u0000first-principles accuracy to unravel the behavior of the hydroxide and\u0000hydronium ions at the graphene-water interface. Our findings reveal that the\u0000graphene-water interface is acidic, with the hydronium ion predominantly\u0000residing in the first contact layer of water. In contrast, the hydroxide ion\u0000exhibits a bimodal distribution, found both near the surface and towards the\u0000interior layers. Analysis of the underlying electronic structure reveals strong\u0000polarization effects, resulting in counterintuitive charge rearrangement.\u0000Proton propensity to the graphene-water interface challenges the interpretation\u0000of surface experiments and is expected to have far-reaching consequences for\u0000ion conductivity, interfacial reactivity, and proton-mediated processes.","PeriodicalId":501304,"journal":{"name":"arXiv - PHYS - Chemical Physics","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-08-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141935824","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Stability Mechanisms of Unconventional Stoichiometric Crystals Exampled by Two-Dimensional Na2Cl on Graphene under Ambient Conditions 环境条件下石墨烯上的二维氯化钠所体现的非常规化学计量晶体的稳定机制

arXiv - PHYS - Chemical Physics Pub Date : 2024-08-08 DOI: arxiv-2408.04286

Liuhua Mu, Xuchang Su, Haiping Fang, Lei Zhang

{"title":"Stability Mechanisms of Unconventional Stoichiometric Crystals Exampled by Two-Dimensional Na2Cl on Graphene under Ambient Conditions","authors":"Liuhua Mu, Xuchang Su, Haiping Fang, Lei Zhang","doi":"arxiv-2408.04286","DOIUrl":"https://doi.org/arxiv-2408.04286","url":null,"abstract":"Compounds harboring active valence electrons, such as unconventional\u0000stoichiometric compounds of main group elements including sodium, chlorine, and\u0000carbon, have conventionally been perceived as unstable under ambient\u0000conditions, requiring extreme conditions including extra-high pressure\u0000environments for stability. Recent discoveries challenge this notion,\u0000showcasing the ambient stability of two-dimensional Na2Cl and other\u0000unconventional stoichiometric compounds on reduced graphene oxide (rGO)\u0000membranes. Focusing on the Na2Cl crystal as a case study, we reveal a mechanism\u0000wherein electron delocalization on the aromatic rings of graphene effectively\u0000mitigates the reactivity of Na2Cl, notably countering oxygen-induced\u0000oxidation--a phenomenon termed the Surface Delocalization-Induced Electron Trap\u0000(SDIET) mechanism. Theoretical calculations also show a substantial activation\u0000energy barrier emerges, impeding oxygen infiltration into and reaction with\u0000Na2Cl. The remarkable stability was further demonstrated by the experiment that\u0000Na2Cl crystals on rGO membranes remain almost intact even after prolonged\u0000exposure to a pure oxygen atmosphere for 9 days. The discovered SDIET mechanism\u0000presents a significant leap in stabilizing chemically active substances\u0000harboring active valence electrons under ambient conditions. Its implications\u0000transcend unconventional stoichiometric compounds, encompassing main group and\u0000transition element compounds, potentially influencing various scientific\u0000disciplines.","PeriodicalId":501304,"journal":{"name":"arXiv - PHYS - Chemical Physics","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-08-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141935845","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Electronic structure and optical properties of halide double perovskites from a Wannier-localized optimally-tuned screened range-separated hybrid functional 从万尼尔定位优化调谐筛选范围分离混合函数看卤化物双包晶的电子结构和光学特性

arXiv - PHYS - Chemical Physics Pub Date : 2024-08-07 DOI: arxiv-2408.04115

Francisca Sagredo, Stephen E. Gant, Guy Ohad, Jonah B. Haber, Marina R. Filip, Leeor Kronik, Jeffrey B. Neaton

{"title":"Electronic structure and optical properties of halide double perovskites from a Wannier-localized optimally-tuned screened range-separated hybrid functional","authors":"Francisca Sagredo, Stephen E. Gant, Guy Ohad, Jonah B. Haber, Marina R. Filip, Leeor Kronik, Jeffrey B. Neaton","doi":"arxiv-2408.04115","DOIUrl":"https://doi.org/arxiv-2408.04115","url":null,"abstract":"Halide double perovskites are a chemically-diverse and growing class of\u0000compound semiconductors that are promising for optoelectronic applications.\u0000However, the prediction of their fundamental gaps and optical properties with\u0000density functional theory (DFT) and {it ab initio} many-body perturbation\u0000theory has been a significant challenge. Recently, a nonempirical\u0000Wannier-localized optimally-tuned screened range-separated hybrid (WOT-SRSH)\u0000functional has been shown to accurately produce the fundamental band gaps of a\u0000wide set of semiconductors and insulators, including lead halide perovskites.\u0000Here we apply the WOT-SRSH functional to five halide double perovskites, and\u0000compare the results with those obtained from other known functionals and\u0000previous $GW$ calculations. We also use the approach as a starting point for\u0000$GW$ calculations and we compute the band structures and optical absorption\u0000spectrum for Cstextsubscript{2}Ag{Bi}Brtextsubscript{6}, using both\u0000time-dependent DFT and the $GW$-Bethe-Salpeter equation approach. We show that\u0000the WOT-SRSH functional leads to accurate fundamental and optical band gaps, as\u0000well as optical absorption spectra, consistent with spectroscopic measurements,\u0000thereby establishing WOT-SRSH as a viable method for the accurate prediction of\u0000optoelectronic properties of halide double perovskites.","PeriodicalId":501304,"journal":{"name":"arXiv - PHYS - Chemical Physics","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-08-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141935829","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Accurate QM/MM Molecular Dynamics for Periodic Systems in textsc{GPU4PySCF} with Applications to Enzyme Catalysis 周期系统的精确 QM/MM 分子动力学（textsc{GPU4PySCF}）及其在酶催化中的应用

arXiv - PHYS - Chemical Physics Pub Date : 2024-08-06 DOI: arxiv-2408.03273

Chenghan Li, Garnet Kin-Lic Chan

引用次数: 0

Path-integral calculation of the third dielectric virial coefficient of helium based on ab initio three-body polarizability and dipole surfaces 基于三体极化性和偶极面的氦第三介电常数的路径积分计算

arXiv - PHYS - Chemical Physics Pub Date : 2024-08-06 DOI: arxiv-2408.03176

Giovanni Garberoglio, Allan H. Harvey, Jakub Lang, Michal Przybytek, Michal Lesiuk, Bogumil Jeziorski

{"title":"Path-integral calculation of the third dielectric virial coefficient of helium based on ab initio three-body polarizability and dipole surfaces","authors":"Giovanni Garberoglio, Allan H. Harvey, Jakub Lang, Michal Przybytek, Michal Lesiuk, Bogumil Jeziorski","doi":"arxiv-2408.03176","DOIUrl":"https://doi.org/arxiv-2408.03176","url":null,"abstract":"We develop a surface for the electric dipole moment of three interacting\u0000helium atoms and use it, together with state-of-the-art potential and\u0000polarizability surfaces, to compute the third dielectric virial coefficient,\u0000$C_varepsilon$, for both $^4$He and $^3$He isotopes. Our results agree with\u0000previously published data computed using an approximated form for the\u0000three-body polarizability, and are extended to the low-temperature regime by\u0000including exchange effects. Additionally, the uncertainty of $C_varepsilon$ is\u0000rigorously determined for the first time by propagating the uncertainties of\u0000the potential and polarizability surfaces; this uncertainty is much larger than\u0000the contribution from the dipole-moment surface to $C_varepsilon$. Our results\u0000compare reasonably well with the limited experimental data. The\u0000first-principles values of $C_epsilon$ computed in this work will enhance the\u0000accuracy of primary temperature and pressure metrology based on measurements of\u0000the dielectric constant of helium.","PeriodicalId":501304,"journal":{"name":"arXiv - PHYS - Chemical Physics","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-08-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141935838","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

On Ambient-light-induced intermolecular Coulombic decay in unbound pyridine monomers 非结合吡啶单体分子间库仑衰减的环境光诱导效应

arXiv - PHYS - Chemical Physics Pub Date : 2024-08-06 DOI: arxiv-2408.02981

Shaivi Kesari, Amol Tagad, G. Naresh Patwari

引用次数: 0