Capacitive deionization (CDI) is a fast-emerging technology most commonly applied to brackish water desalination. In CDI, salt ions are removed from the feedwater and stored in electric double layers (EDLs) within micropores of electrically charged porous carbon electrodes. Recent experiments have demonstrated that CDI electrodes exhibit selective ion removal based on ion size, with the smaller ion being preferentially removed in the case of equal-valence ions. However, state-of-the-art CDI theory does not capture this observed selectivity, as it assumes volume-less point ions in the micropore EDLs. We here present a theory which includes multiple couterionic species, and relaxes the point ion assumption by incorporating ion volume exclusion interactions into a description of the micropore EDLs. The developed model is a coupled set of nonlinear algebraic equations which can be solved for micropore ion concentrations and electrode Donnan potential at cell equilibrium. We demonstrate that this model captures key features of the experimentally observed size-based ion selectivity of CDI electrodes.
{"title":"Size-based ion selectivity of micropore electric double layers in capacitive deionization electrodes","authors":"M. Suss","doi":"10.1149/2.1201709jes","DOIUrl":"https://doi.org/10.1149/2.1201709jes","url":null,"abstract":"Capacitive deionization (CDI) is a fast-emerging technology most commonly applied to brackish water desalination. In CDI, salt ions are removed from the feedwater and stored in electric double layers (EDLs) within micropores of electrically charged porous carbon electrodes. Recent experiments have demonstrated that CDI electrodes exhibit selective ion removal based on ion size, with the smaller ion being preferentially removed in the case of equal-valence ions. However, state-of-the-art CDI theory does not capture this observed selectivity, as it assumes volume-less point ions in the micropore EDLs. We here present a theory which includes multiple couterionic species, and relaxes the point ion assumption by incorporating ion volume exclusion interactions into a description of the micropore EDLs. The developed model is a coupled set of nonlinear algebraic equations which can be solved for micropore ion concentrations and electrode Donnan potential at cell equilibrium. We demonstrate that this model captures key features of the experimentally observed size-based ion selectivity of CDI electrodes.","PeriodicalId":8439,"journal":{"name":"arXiv: Chemical Physics","volume":"65 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2017-04-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"89957007","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}
Pub Date : 2017-03-24DOI: 10.5339/qfarc.2018.eepp165
Zixuan Hu, G. Engel, S. Kais
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.
{"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":"14 1","pages":""},"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}
Pub Date : 2017-03-02DOI: 10.1016/bs.aiq.2017.03.004
Giuseppe M. J. Barca, Pierre‐François Loos
{"title":"Recurrence relations for four-electron integrals over Gaussian basis functions","authors":"Giuseppe M. J. Barca, Pierre‐François Loos","doi":"10.1016/bs.aiq.2017.03.004","DOIUrl":"https://doi.org/10.1016/bs.aiq.2017.03.004","url":null,"abstract":"","PeriodicalId":8439,"journal":{"name":"arXiv: Chemical Physics","volume":"35 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2017-03-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"81365419","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}
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.
{"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":"84 1","pages":""},"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}
A. Lombardi, F. Palazzetti, V. Aquilanti, G. Grossi, Alessandra F. Albernaz, P. Barreto, A. C. Cruz
The representation of the potential energy surfaces of atom molecule or molecular dimers interactions should account faithfully for the symmetry properties of the systems, preserving at the same time a compact analytical form. To this aim, the choice of a proper set of coordinates is a necessary precondition. Here we illustrate a description in terms of hyperspherical coordinates and the expansion of the intermolecular interaction energy in terms of hypersherical harmonics, as a general method for building potential energy surfaces suitable for molecular dynamics simulations of van der Waals aggregates. Examples for the prototypical case diatomic molecule diatomic molecule interactions are shown.
{"title":"Spherical and hyperspherical harmonics representation of van der Waals aggregates","authors":"A. Lombardi, F. Palazzetti, V. Aquilanti, G. Grossi, Alessandra F. Albernaz, P. Barreto, A. C. Cruz","doi":"10.1063/1.4968631","DOIUrl":"https://doi.org/10.1063/1.4968631","url":null,"abstract":"The representation of the potential energy surfaces of atom molecule or molecular dimers interactions should account faithfully for the symmetry properties of the systems, preserving at the same time a compact analytical form. To this aim, the choice of a proper set of coordinates is a necessary precondition. Here we illustrate a description in terms of hyperspherical coordinates and the expansion of the intermolecular interaction energy in terms of hypersherical harmonics, as a general method for building potential energy surfaces suitable for molecular dynamics simulations of van der Waals aggregates. Examples for the prototypical case diatomic molecule diatomic molecule interactions are shown.","PeriodicalId":8439,"journal":{"name":"arXiv: Chemical Physics","volume":"124 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2016-12-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"77437621","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}
F. Palazzetti, A. Lombardi, Shiun-Jr Yang, M. Nakamura, T. Kasai, K. Lin, Dock-Chil Che, Po-Yu Tsai
Hexapole oriented 2-bromobutane is photodissociated and detected by a slice-ion-imaging technique at 234 nm. The laser wavelength corresponds to the C – Br bond breaking with emission of a Br atom fragment in two accessible fine-structure states: the ground state Br (2P3/2) and the excited state Br (2P1/2), both observable separately by resonance-enhanced multiphoton ionization (REMPI). Orientation is evaluated by time-of-flight measurements combined with slice-ion-imaging.
{"title":"Stereodirectional photodynamics: Experimental and theoretical perspectives","authors":"F. Palazzetti, A. Lombardi, Shiun-Jr Yang, M. Nakamura, T. Kasai, K. Lin, Dock-Chil Che, Po-Yu Tsai","doi":"10.1063/1.4968646","DOIUrl":"https://doi.org/10.1063/1.4968646","url":null,"abstract":"Hexapole oriented 2-bromobutane is photodissociated and detected by a slice-ion-imaging technique at 234 nm. The laser wavelength corresponds to the C – Br bond breaking with emission of a Br atom fragment in two accessible fine-structure states: the ground state Br (2P3/2) and the excited state Br (2P1/2), both observable separately by resonance-enhanced multiphoton ionization (REMPI). Orientation is evaluated by time-of-flight measurements combined with slice-ion-imaging.","PeriodicalId":8439,"journal":{"name":"arXiv: Chemical Physics","volume":"70 1","pages":"020020"},"PeriodicalIF":0.0,"publicationDate":"2016-12-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"85844415","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}
F. Palazzetti, A. Lombardi, M. Nakamura, Shiun-Jr Yang, T. Kasai, K. Lin, Po-Yu Tsai, Dock-Chil Che
Electrostatic hexapoles are revealed as a powerful tool in the rotational state-selection and alignment of molecules to be utilized in beam experiments on collisional and photoinitiated processes. In the paper, we report results on the application of the hexapolar technique on the recently studied chiral molecules propylene oxide, 2-butanol and 2-bromobutane, to be investigated in selective photodissociation and enantiomeric discrimination.
{"title":"Rotational state-selection and alignment of chiral molecules by electrostatic hexapoles","authors":"F. Palazzetti, A. Lombardi, M. Nakamura, Shiun-Jr Yang, T. Kasai, K. Lin, Po-Yu Tsai, Dock-Chil Che","doi":"10.1063/1.4968645","DOIUrl":"https://doi.org/10.1063/1.4968645","url":null,"abstract":"Electrostatic hexapoles are revealed as a powerful tool in the rotational state-selection and alignment of molecules to be utilized in beam experiments on collisional and photoinitiated processes. In the paper, we report results on the application of the hexapolar technique on the recently studied chiral molecules propylene oxide, 2-butanol and 2-bromobutane, to be investigated in selective photodissociation and enantiomeric discrimination.","PeriodicalId":8439,"journal":{"name":"arXiv: Chemical Physics","volume":"427 1","pages":"020019"},"PeriodicalIF":0.0,"publicationDate":"2016-12-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"76488014","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}
Pub Date : 2016-12-01DOI: 10.6084/m9.figshare.2007486
P. Hockett, E. Frumker
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.
Baykusheva & W orner在对我们的文章《分子光电离的时间延迟》发表评论时，重现了正则散射理论，并断言我们的结果与这一已建立的理论不一致。我们绝对驳斥这种说法和评论的精神，尽管我们同意Baykusheva和W orner的观点，即教科书理论是正确的。在对“分子光电离时间延迟”评论的简短回应[3]中，我们已经对评论进行了明确的反驳，但没有提供技术细节。在这篇更完整的回复中，我们本着完整性和清晰度的精神扩展了那些简短的评论，并根据(1)逻辑谬误(类别错误)，(2)原文的理论细节，(3)原文的纹理内容，对Baykusheva & W orner提供了三个明确的反驳。特别是，反驳(1)清楚而琐碎地指出了这样一个事实，即这里无论如何都没有问题，借助于几乎不需要证明这一点的理论细节，正如我们回应的简短版本所概述的那样。我们的数值结果是正确的，并且再现了已知的物理现象，正如原文中所讨论的那样，因此，细心的读者会认识到，所使用的形式主义是正则散射理论，而不是其他任何东西。事实上，这里没有任何新的基础物理学值得争论，这也不是原文章存在的原因。此外，反驳(2)提供了详细讨论光电离理论的一些教科书方面的机会，我们希望这种讨论可能对进入这一具有挑战性的领域的新研究人员有所帮助。
{"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":"4 1","pages":""},"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}
We argue that the experimentally easily accessible optical absorption spectrum can often be used to distinguish between a random alloy phase and a stoichiometrically equivalent core/shell realization of ensembles of monodisperse colloidal semiconductor quantum dots without the need for more advanced structural characterization tools. Our proof-of-concept is performed by conceptually straightforward exact-disorder tight-binding calculations. The underlying stochastical tight-binding scheme only parametrizes bulk band structure properties and does not employ additional free parameters to calculate the optical absorption spectrum, which is an easily accessible experimental property. The method is applied to selected realizations of type-I Cd(Se,S) and type-II (Zn,Cd)(Se,S) alloyed quantum dots with an underlying zincblende crystal structure and the corresponding core/shell counterparts.
{"title":"Structure-Related Optical Fingerprints in the Absorption Spectra of Colloidal Quantum Dots: Random Alloy vs. Core/Shell Systems","authors":"D. Mourad","doi":"10.1063/1.4973482","DOIUrl":"https://doi.org/10.1063/1.4973482","url":null,"abstract":"We argue that the experimentally easily accessible optical absorption spectrum can often be used to distinguish between a random alloy phase and a stoichiometrically equivalent core/shell realization of ensembles of monodisperse colloidal semiconductor quantum dots without the need for more advanced structural characterization tools. Our proof-of-concept is performed by conceptually straightforward exact-disorder tight-binding calculations. The underlying stochastical tight-binding scheme only parametrizes bulk band structure properties and does not employ additional free parameters to calculate the optical absorption spectrum, which is an easily accessible experimental property. The method is applied to selected realizations of type-I Cd(Se,S) and type-II (Zn,Cd)(Se,S) alloyed quantum dots with an underlying zincblende crystal structure and the corresponding core/shell counterparts.","PeriodicalId":8439,"journal":{"name":"arXiv: Chemical Physics","volume":"5 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2016-11-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"73143805","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}
A. Tabrizi, S. Goossens, A. Rahimi, M. Knepley, J. Bardhan
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.
{"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":"9 1","pages":""},"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}
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