arXiv: Chemical Physics最新文献_第8页

Size-based ion selectivity of micropore electric double layers in capacitive deionization electrodes 电容性去离子电极中微孔双电层基于尺寸的离子选择性

arXiv: Chemical Physics Pub Date : 2017-04-13 DOI: 10.1149/2.1201709jes

M. Suss

引用次数: 69

Accessing dark states optically through excitation-ferrying states 通过激发传递态光学地进入暗态

arXiv: Chemical Physics Pub Date : 2017-03-24 DOI: 10.5339/qfarc.2018.eepp165

Zixuan Hu, G. Engel, S. Kais

{"title":"Accessing dark states optically through excitation-ferrying states","authors":"Zixuan Hu, G. Engel, S. Kais","doi":"10.5339/qfarc.2018.eepp165","DOIUrl":"https://doi.org/10.5339/qfarc.2018.eepp165","url":null,"abstract":"The efficiency of solar energy harvesting systems is largely determined by their ability to transfer excitations from the antenna to the energy trapping center before recombination. Dark state protection, achieved by coherent coupling between subunits in the antenna structure, can significantly reduce radiative recombination and enhance the efficiency of energy trapping. Because the dark states cannot be populated by optical transitions from the ground state, they are usually accessed through phononic relaxation from the bright states. In this study, we explore a novel way of connecting the dark states and the bright states via optical transitions. In a ring-like chromophore system inspired by natural photosynthetic antennae, the single-excitation bright state can be optically connected to the lowest energy single-excitation dark state through certain double-excitation states. We call such double-excitation states the ferry states and show that they are the result of accidental degeneracy between two categories of double-excitation states. We then mathematically prove that the ferry states are only available when N, the number of subunits on the ring, satisfies N=4l+2 (l being an integer). Numerical calculations confirm that the ferry states enhance the energy transfer power of our model, showing a significant energy transfer power spike at N=6 compared with smaller N values, even without phononic relaxation. The proposed mathematical theory for the ferry states is not restricted to this one particular system or numerical model. In fact, it is potentially applicable to any coherent optical system that adopts a ring-shaped chromophore arrangement. Beyond the ideal case, the ferry state mechanism also demonstrates robustness under weak phononic dissipation, weak site energy disorder, and large coupling strength disorder.","PeriodicalId":8439,"journal":{"name":"arXiv: Chemical Physics","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2017-03-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"77038646","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

Recurrence relations for four-electron integrals over Gaussian basis functions 高斯基函数上四电子积分的递推关系

arXiv: Chemical Physics Pub Date : 2017-03-02 DOI: 10.1016/bs.aiq.2017.03.004

Giuseppe M. J. Barca, Pierre‐François Loos

引用次数: 6

Multiphase Porous Electrode Theory 多相多孔电极理论

arXiv: Chemical Physics Pub Date : 2017-02-27 DOI: 10.1149/2.0171711JES

Raymond B. Smith, M. Bazant

{"title":"Multiphase Porous Electrode Theory","authors":"Raymond B. Smith, M. Bazant","doi":"10.1149/2.0171711JES","DOIUrl":"https://doi.org/10.1149/2.0171711JES","url":null,"abstract":"Porous electrode theory, pioneered by John Newman and collaborators, provides a useful macroscopic description of battery cycling behavior, rooted in microscopic physical models rather than empirical circuit approximations. The theory relies on a separation of length scales to describe transport in the electrode coupled to intercalation within small active material particles. Typically, the active materials are described as solid solution particles with transport and surface reactions driven by concentration fields, and the thermodynamics are incorporated through fitting of the open circuit potential. This approach has fundamental limitations, however, and does not apply to phase-separating materials, for which the voltage is an emergent property of inhomogeneous concentration profiles, even in equilibrium. Here, we present a general theoretical framework for \"multiphase porous electrode theory\" implemented in an open-source software package called \"MPET\", based on electrochemical nonequilibrium thermodynamics. Cahn-Hilliard-type phase field models are used to describe the solid active materials with suitably generalized models of interfacial reaction kinetics. Classical concentrated solution theory is implemented for the electrolyte phase, and Newman's porous electrode theory is recovered in the limit of solid-solution active materials with Butler-Volmer kinetics. More general, quantum-mechanical models of Faradaic reactions are also included, such as Marcus-Hush-Chidsey kinetics for electron transfer at metal electrodes, extended for concentrated solutions. The full equations and numerical algorithms are described, and a variety of example calculations are presented to illustrate the novel features of the software compared to existing battery models.","PeriodicalId":8439,"journal":{"name":"arXiv: Chemical Physics","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2017-02-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"80825368","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: 127

Spherical and hyperspherical harmonics representation of van der Waals aggregates 范德华聚集体的球面和超球面谐波表示

arXiv: Chemical Physics Pub Date : 2016-12-07 DOI: 10.1063/1.4968631

A. Lombardi, F. Palazzetti, V. Aquilanti, G. Grossi, Alessandra F. Albernaz, P. Barreto, A. C. Cruz

引用次数: 12

Stereodirectional photodynamics: Experimental and theoretical perspectives 立体定向光动力学:实验和理论的观点

arXiv: Chemical Physics Pub Date : 2016-12-07 DOI: 10.1063/1.4968646

F. Palazzetti, A. Lombardi, Shiun-Jr Yang, M. Nakamura, T. Kasai, K. Lin, Dock-Chil Che, Po-Yu Tsai

引用次数: 7

Rotational state-selection and alignment of chiral molecules by electrostatic hexapoles 静电六极手性分子的旋转状态选择和排列

arXiv: Chemical Physics Pub Date : 2016-12-07 DOI: 10.1063/1.4968645

F. Palazzetti, A. Lombardi, M. Nakamura, Shiun-Jr Yang, T. Kasai, K. Lin, Po-Yu Tsai, Dock-Chil Che

引用次数: 6

Response to 'Comment on "Time delays in molecular photoionization"': Extended Discussion & Technical Notes 对“关于“分子光电离的时间延迟”的评论”的回应:扩展讨论和技术笔记

arXiv: Chemical Physics Pub Date : 2016-12-01 DOI: 10.6084/m9.figshare.2007486

P. Hockett, E. Frumker

{"title":"Response to 'Comment on \"Time delays in molecular photoionization\"': Extended Discussion & Technical Notes","authors":"P. Hockett, E. Frumker","doi":"10.6084/m9.figshare.2007486","DOIUrl":"https://doi.org/10.6084/m9.figshare.2007486","url":null,"abstract":"In a comment on our article Time delays in molecular photoionization [1], Baykusheva & W\"orner reproduce canonical scattering theory, and assert that our results are inconsistent with this well-established theory [2]. We absolutely refute this assertion and the spirit of the comment, although we do agree with Baykusheva & W\"orner that the textbook theory is correct. In a short response, Response to Comment on \"Time delays in molecular photoionization\" [3], we have already provided a clear rebuttal of the comment, but gave no technical details. In this fuller response we extend those brief comments in the spirit of completeness and clarity, and provide three clear rebuttals to Baykusheva & W\"orner based on (1) logical fallacy (category error), (2) theoretical details of the original article, (3) textural content of the original article. In particular, rebuttal (1) clearly and trivially points to the fact that there is no issue here whatsoever, with recourse to theoretical details barely required to demonstrate this, as outlined in the short version of our response. Our numerical results are correct and reproduce known physical phenomena, as discussed in the original article hence, as careful readers will recognise, the formalism used is canonical scattering theory, and cannot be anything other. In fact, there is no new fundamental physics here to dispute whatsoever, and nor was this the raison d'etre of the original article. Additionally, rebuttal (2) provides the opportunity to discuss, at length, some of these textbook aspects of photoionization theory, and we hope this discussion might be of service to new researchers entering this challenging field.","PeriodicalId":8439,"journal":{"name":"arXiv: Chemical Physics","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2016-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"72755335","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

arXiv: Chemical Physics Pub Date : 2016-11-04 DOI: 10.1063/1.4973482

D. Mourad

引用次数: 1

Predicting Solvation Free Energies and Thermodynamics in Polar Solvents and Mixtures Using a Solvation-Layer Interface Condition 用溶剂层界面条件预测极性溶剂和混合物的溶剂化自由能和热力学

arXiv: Chemical Physics Pub Date : 2016-11-03 DOI: 10.1063/1.4977037

A. Tabrizi, S. Goossens, A. Rahimi, M. Knepley, J. Bardhan

{"title":"Predicting Solvation Free Energies and Thermodynamics in Polar Solvents and Mixtures Using a Solvation-Layer Interface Condition","authors":"A. Tabrizi, S. Goossens, A. Rahimi, M. Knepley, J. Bardhan","doi":"10.1063/1.4977037","DOIUrl":"https://doi.org/10.1063/1.4977037","url":null,"abstract":"We demonstrate that with two small modifications, the popular dielectric continuum model is capable of predicting, with high accuracy, ion solvation thermodynamics in numerous polar solvents, and ion solvation free energies in water--co-solvent mixtures. The first modification involves perturbing the macroscopic dielectric-flux interface condition at the solute--solvent interface with a nonlinear function of the local electric field, giving what we have called a solvation-layer interface condition (SLIC). The second modification is a simple treatment of the microscopic interface potential (static potential). We show that the resulting model exhibits high accuracy without the need for fitting solute atom radii in a state-dependent fashion. Compared to experimental results in nine water--co-solvent mixtures, SLIC predicts transfer free energies to within 2.5 kJ/mol. The co-solvents include both protic and aprotic species, as well as biologically relevant denaturants such as urea and dimethylformamide. Furthermore, our results indicate that the interface potential is essential to reproduce entropies and heat capacities. The present work, together with previous studies of SLIC illustrating its accuracy for biomolecules in water, indicates it as a promising dielectric continuum model for accurate predictions of molecular solvation in a wide range of conditions.","PeriodicalId":8439,"journal":{"name":"arXiv: Chemical Physics","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2016-11-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"85437474","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: 12