Sample records for radiative charge transfer

  1. Radiative charge transfer in collisions of C with He+

    CERN Document Server

    Babb, James F


    Radiative charge exchange collisions between a carbon atom C(${}^3$P) and a helium ion He+, both in their ground state, are investigated theoretically. Detailed quantum chemistry calculations are carried out to obtain potential energy curves and transition dipole matrix elements for doublet and quartet molecular states of the HeC+ cation. Radiative charge transfer cross sections and rate coefficients are calculated and are found at thermal and lower energies to be large compared to those for direct charge transfer. The present results might be applicable to modelling the complex interplay of [C II] (or C+), C, and CO at the boundaries of photon dominated regions (PDRs) and in xray dominated regions (XDRs), where the abundance of He+ affects the abundance of CO.

  2. Electrodynamics of Radiating Charges

    Directory of Open Access Journals (Sweden)

    Øyvind Grøn


    Full Text Available The theory of electrodynamics of radiating charges is reviewed with special emphasis on the role of the Schott energy for the conservation of energy for a charge and its electromagnetic field. It is made clear that the existence of radiation from a charge is not invariant against a transformation between two reference frames that has an accelerated motion relative to each other. The questions whether the existence of radiation from a uniformly accelerated charge with vanishing radiation reaction force is in conflict with the principle of equivalence and whether a freely falling charge radiates are reviewed. It is shown that the resolution of an electromagnetic “perpetuum mobile paradox” associated with a charge moving geodetically along a circular path in the Schwarzschild spacetime requires the so-called tail terms in the equation of motion of a charged particle.

  3. Thermal radiation heat transfer

    CERN Document Server

    Howell, John R; Siegel, Robert


    Further expanding on the changes made to the fifth edition, Thermal Radiation Heat Transfer, 6th Edition continues to highlight the relevance of thermal radiative transfer and focus on concepts that develop the radiative transfer equation (RTE). The book explains the fundamentals of radiative transfer, introduces the energy and radiative transfer equations, covers a variety of approaches used to gauge radiative heat exchange between different surfaces and structures, and provides solution techniques for solving the RTE.

  4. Thermal radiation heat transfer. (United States)

    Siegel, R.; Howell, J. R.


    A comprehensive discussion of heat transfer by thermal radiation is presented, including the radiative behavior of materials, radiation between surfaces, and gas radiation. Among the topics considered are property prediction by electromagnetic theory, the observed properties of solid materials, radiation in the presence of other modes of energy transfer, the equations of transfer for an absorbing-emitting gas, and radiative transfer in scattering and absorbing media. Also considered are radiation exchange between black isothermal surfaces, radiation exchange in enclosures composed of diffuse gray surfaces and in enclosures having some specularly reflecting surfaces, and radiation exchange between nondiffuse nongray surfaces. The use of the Monte Carlo technique in solving radiant-exchange problems and problems of radiative transfer through absorbing-emitting media is explained.

  5. Thermal radiation heat transfer

    CERN Document Server

    Howell, John R; Mengüç, M Pinar


    Providing a comprehensive overview of the radiative behavior and properties of materials, the fifth edition of this classic textbook describes the physics of radiative heat transfer, development of relevant analysis methods, and associated mathematical and numerical techniques. Retaining the salient features and fundamental coverage that have made it popular, Thermal Radiation Heat Transfer, Fifth Edition has been carefully streamlined to omit superfluous material, yet enhanced to update information with extensive references. Includes four new chapters on Inverse Methods, Electromagnetic Theory, Scattering and Absorption by Particles, and Near-Field Radiative Transfer Keeping pace with significant developments, this book begins by addressing the radiative properties of blackbody and opaque materials, and how they are predicted using electromagnetic theory and obtained through measurements. It discusses radiative exchange in enclosures without any radiating medium between the surfaces-and where heat conduction...

  6. Intramolecular Energy Transfer, Charge Transfer & Hydrogen Bond

    Indian Academy of Sciences (India)

    Ultrafast Dynamics of Chemical Reactions in Condensed Phase: Intramolecular Energy Transfer, Charge Transfer & Hydrogen Bond · PowerPoint Presentation · Slide 3 · Slide 4 · Slide 5 · Slide 6 · Slide 7 · Slide 8 · Slide 9 · Slide 10 · Slide 11 · Slide 12 · Slide 13 · Slide 14 · Slide 15 · Slide 16 · Slide 17 · Slide 18 · Slide 19.

  7. Radiative heat transfer

    CERN Document Server

    Modest, Michael F


    The third edition of Radiative Heat Transfer describes the basic physics of radiation heat transfer. The book provides models, methodologies, and calculations essential in solving research problems in a variety of industries, including solar and nuclear energy, nanotechnology, biomedical, and environmental. Every chapter of Radiative Heat Transfer offers uncluttered nomenclature, numerous worked examples, and a large number of problems-many based on real world situations-making it ideal for classroom use as well as for self-study. The book's 24 chapters cover the four major areas in the field: surface properties; surface transport; properties of participating media; and transfer through participating media. Within each chapter, all analytical methods are developed in substantial detail, and a number of examples show how the developed relations may be applied to practical problems. It is an extensive solution manual for adopting instructors. Features: most complete text in the field of radiative heat transfer;...

  8. Radiation by moving charges

    Energy Technology Data Exchange (ETDEWEB)

    Geloni, Gianluca [European XFEL GmbH, Hamburg (Germany); Kocharyan, Vitali; Saldin, Evgeni [Deutsches Elektronen-Synchrotron (DESY), Hamburg (Germany)


    It is generally accepted that in order to describe the dynamics of relativistic particles in the laboratory (lab) frame it is sufficient to take into account the relativistic dependence of the particle momenta on the velocity. This solution of the dynamics problem in the lab frame makes no reference to Lorentz transformations. For this reason they are not discussed in particle tracking calculations in accelerator and plasma physics. It is generally believed that the electrodynamics problem can be treated within the same ''single inertial frame'' description without reference to Lorentz transformations. In particular, in order to evaluate radiation fields arising from charged particles in motion we need to know their velocities and positions as a function of the lab frame time t. The relativistic motion of a particle in the lab frame is described by Newton's second law ''corrected'' for the relativistic dependence of momentum on velocity. It is assumed in all standard derivations that one can perform identification of the trajectories in the source part of the usual Maxwell's equations with the trajectories vector x(t) measured (or calculated by using the corrected Newton's second law) in the lab frame. This way of coupling fields and particles is considered since more than a century as the relativistically correct procedure.We argue that this procedure needs to be changed, and we demonstrate the following, completely counterintuitive statement: the results of conventional theory of radiation by relativistically moving charges are not consistent with the principle of relativity. In order to find the trajectory of a particle in the lab frame consistent with the usual Maxwell's equations, one needs to solve the dynamic equation inmanifestly covariant form by using the coordinate-independent proper time τ to parameterize the particle world-line in space-time. We show that there is a difference between &apos

  9. Charge transfer in green fluorescent protein. (United States)

    van Thor, Jasper J; Sage, J Timothy


    Charge transfer reactions that contribute to the photoreactions of the wild type green fluorescent protein (GFP) do not occur in the isolated p-hydroxybenzylidene-imidazolidinone chromophore, demonstrating the role of the protein environment. The high quantum efficiency of the fluorescence photocycle that includes excited state proton transfer and the suppression of non-radiative pathways by the protein environment have been correlated with structural dynamics in the chromophore environment. A low quantum efficiency competing phototransformation reaction of GFP is accompanied by both proton and electron transfer, and closely mimics the charge redistribution that is occurring in the fluorescence photocycle. The protein response to this destabilising event has been demonstrated by cryo-trapping of early products in the reaction pathway and is found to be strong even at 100 K, including displacements of chromophore, protein, solvent and a photogenerated CO2 molecule derived from the decarboxylated Glu 222 side chain. We discuss the ramifications of the observation of strong conformational perturbations below the protein dynamical transition at approximately 200 K, in view of low temperature work on other light sensitive proteins such as myoglobin and bacteriorhodopsin. The proton and electron transfer in the phototransformation pathway mimics the proton and charge transfer which occurs during the fluorescence cycle, which leads to common structural responses in both photoreactions as shown by ultrafast spectroscopy. We review and discuss literature on light-induced and thermal charge transfer events, focusing on recent findings addressing conformational dynamics and implications for thermodynamic properties.

  10. Nonradiative charge transfer in collisions of protons with rubidium atoms (United States)

    Yan, Ling-Ling; Qu, Yi-Zhi; Liu, Chun-Hua; Zhang, Yu; Wang, Jian-Guo; Buenker, Robert J.


    The nonradiative charge-transfer cross sections for protons colliding with Rb(5s) atoms are calculated by using the quantum-mechanical molecularorbital close-coupling method in an energy range of 10-3 keV-10 keV. The total and state-selective charge-transfer cross sections are in good agreement with the experimental data in the relatively low energy region. The importance of rotational coupling for chargetransfer process is stressed. Compared with the radiative charge-transfer process, nonradiative charge transfer is a dominant mechanism at energies above 15 eV. The resonance structures of state-selective charge-transfer cross sections arising from the competition among channels are analysed in detail. The radiative and nonradiative charge-transfer rate coefficients from low to high temperature are presented.

  11. Structural transition induced by charge-transfer in RbMn[Fe(CN) sub 6]. Investigation by synchrotron-radiation X-ray powder analysis

    CERN Document Server

    Moritomo, Y; Sakata, M; Kato, K; Kuriki, A; Tokoro, H; Ohkoshi, S I; Hashimoto, K


    Temperature dependence of atomic coordinates is determined for RbMn[Fe(CN) sub 6] by means of synchrotron-radiation (SR) X-ray powder structural analysis. We observed a structural transition from the cubic (F4-bar3m; Z=4) to the tetragonal (I4-barm2; Z=2) phase at approx. =210K in the cooling run and at approx. =300K in the warming run. In the low-temperature tetragonal phase, we found Jahn-Tellar type distortion of the MnN sub 6 octahedra and compression of the averaged Fe-C bond distance. These structural data suggest that the structural transition is triggered by the inter-metallic charge-transfer from the Mn(II) site to the Fe(III) site.

  12. Utrecht Radiative Transfer Courses (United States)

    Rutten, R. J.


    The Utrecht course ``The Generation and Transport of Radiation'' teaches basic radiative transfer to second-year students. It is a much-expanded version of the first chapter of Rybicki & Lightman's ``Radiative Processes in Astrophysics''. After this course, students understand why intensity is measured per steradian, have an Eddington-Barbier feel for optically thick line formation, and know that scattering upsets LTE. The text is a computer-aided translation by Ruth Peterson of my 1992 Dutch-language course. My aim is to rewrite this course in non-computer English and make it web-available at some time. In the meantime, copies of the Peterson translation are made yearly at Uppsala -- ask them, not me. Eventually it should become a textbook. The Utrecht course ``Radiative Transfer in Stellar Atmospheres'' is a 30-hour course for third-year students. It treats NLTE line formation in plane-parallel stellar atmospheres at a level intermediate between the books by Novotny and Boehm-Vitense, and Mihalas' ``Stellar Atmospheres''. After this course, students appreciate that epsilon is small, that radiation can heat or cool, and that computers have changed the field. This course is web-available since 1995 and is regularly improved -- but remains incomplete. Eventually it should become a textbook. The three Utrecht exercise sets ``Stellar Spectra A: Basic Line Formation'', ``Stellar Spectra B: LTE Line Formation'', and ``Stellar Spectra C: NLTE Line Formation'' are IDL-based computer exercises for first-year, second-year, and third-year students, respectively. They treat spectral classification, Saha-Boltzmann population statistics, the curve of growth, the FAL-C solar atmosphere model, the role of H-minus in the solar continuum, LTE formation of Fraunhofer lines, inversion tactics, the Feautrier method, classical lambda iteration, and ALI computation. The first two sets are web-available since 1998; the third will follow. Acknowledgement. Both courses owe much to previous

  13. Charge migration and charge transfer in molecular systems

    Directory of Open Access Journals (Sweden)

    Hans Jakob Wörner


    Full Text Available The transfer of charge at the molecular level plays a fundamental role in many areas of chemistry, physics, biology and materials science. Today, more than 60 years after the seminal work of R. A. Marcus, charge transfer is still a very active field of research. An important recent impetus comes from the ability to resolve ever faster temporal events, down to the attosecond time scale. Such a high temporal resolution now offers the possibility to unravel the most elementary quantum dynamics of both electrons and nuclei that participate in the complex process of charge transfer. This review covers recent research that addresses the following questions. Can we reconstruct the migration of charge across a molecule on the atomic length and electronic time scales? Can we use strong laser fields to control charge migration? Can we temporally resolve and understand intramolecular charge transfer in dissociative ionization of small molecules, in transition-metal complexes and in conjugated polymers? Can we tailor molecular systems towards specific charge-transfer processes? What are the time scales of the elementary steps of charge transfer in liquids and nanoparticles? Important new insights into each of these topics, obtained from state-of-the-art ultrafast spectroscopy and/or theoretical methods, are summarized in this review.

  14. LRAT: Lightning Radiative Transfer (United States)

    Phanord, Dieudonne D.


    In this report, we extend to cloud physics the work done for single and multiple scattering of electromagnetic waves. We consider the scattering of light, visible or infrared, by a spherical cloud represented by a statistically homogeneous ensemble of configurations of N identical spherical water droplets whose centers are uniformly distributed in its volume V. The ensemble is specified by the average number rho of scatterers in unit volume and by rho f(R) with f(R) as the distribution function for separations R of pairs. The incident light, vector-phi(sub 0) a plane electromagnetic wave with harmonic time dependence, is from outside the cloud. The propagation parameter kappa(sub 0) and the index of refraction eta(sub 0) determine physically the medium outside the distribution of scatterers. We solve the interior problem separately to obtain the bulk parameters for the scatterer equivalent to the ensemble of spherical droplets. With the interior solution or the equivalent medium approach, the multiple scattering problem is reduced to that of an equivalent single scatterer excited from outside illumination. A dispersion relation which determines the bulk propagation parameter K and the bulk index of refraction eta of the cloud is given in terms of the vector equivalent scattering amplitude vector-G and the dyadic scattering amplitude tilde-g of the single object in isolation. Based on this transfer model we will have the ability to consider clouds composed of inhomogeneous distribution of water and/or ice particles and we will be able to take into account particle size distributions within the cloud. We will also be able to study the effects of cloud composition (i.e., particle shape, size, composition, orientation, location) on the polarization of the single or the multiple scattered waves. Finally, this study will provide a new starting point for studying the problem of lightning radiative transfer.

  15. Charge orders in organic charge-transfer salts (United States)

    Kaneko, Ryui; Tocchio, Luca F.; Valentí, Roser; Becca, Federico


    Motivated by recent experimental suggestions of charge-order-driven ferroelectricity in organic charge-transfer salts, such as κ-(BEDT-TTF)2Cu[N(CN)2]Cl, we investigate magnetic and charge-ordered phases that emerge in an extended two-orbital Hubbard model on the anisotropic triangular lattice at 3/4 filling. This model takes into account the presence of two organic BEDT-TTF molecules, which form a dimer on each site of the lattice, and includes short-range intramolecular and intermolecular interactions and hoppings. By using variational wave functions and quantum Monte Carlo techniques, we find two polar states with charge disproportionation inside the dimer, hinting to ferroelectricity. These charge-ordered insulating phases are stabilized in the strongly correlated limit and their actual charge pattern is determined by the relative strength of intradimer to interdimer couplings. Our results suggest that ferroelectricity is not driven by magnetism, since these polar phases can be stabilized also without antiferromagnetic order and provide a possible microscopic explanation of the experimental observations. In addition, a conventional dimer-Mott state (with uniform density and antiferromagnetic order) and a nonpolar charge-ordered state (with charge-rich and charge-poor dimers forming a checkerboard pattern) can be stabilized in the strong-coupling regime. Finally, when electron–electron interactions are weak, metallic states appear, with either uniform charge distribution or a peculiar 12-site periodicity that generates honeycomb-like charge order.

  16. Spectrophotometric methods based on charge transfer complexation ...

    African Journals Online (AJOL)

    The proposed methods were applied successfully for simultaneous determination of the cited drugs in their pharmaceutical formulations with good accuracy and precision and without interferences from common additives. KEY WORDS: Fluconazole, Sertaconazole nitrate, Miconazole nitrate, Charge transfer complexes, ...

  17. Essentials of radiation heat transfer

    CERN Document Server



    Essentials of Radiation Heat Transfer is a textbook presenting the essential, fundamental information required to gain an understanding of radiation heat transfer and equips the reader with enough knowledge to be able to tackle more challenging problems. All concepts are reinforced by carefully chosen and fully worked examples, and exercise problems are provided at the end of every chapter. In a significant departure from other books on this subject, this book completely dispenses with the network method to solve problems of radiation heat transfer in surfaces. It instead presents the powerful radiosity-irradiation method and shows how this technique can be used to solve problems of radiation in enclosures made of one to any number of surfaces. The network method is not easily scalable. Secondly, the book introduces atmospheric radiation, which is now being considered as a potentially important area, in which engineers can contribute to the technology of remote sensing and atmospheric sciences in general, b...

  18. spectrophotometric study of the charge transfer complexation

    African Journals Online (AJOL)

    Preferred Customer

    complex, Spectrophotometry. INTRODUCTION. Charge-transfer (CT) complexes are formed by interaction between electron donors and electron acceptors. CT complexation is important phenomenon in biochemical and bioelectrochemical energy transfer process [1]. The CT reaction has been widely studied in recent years ...

  19. Engineering calculations in radiative heat transfer

    CERN Document Server

    Gray, W A; Hopkins, D W


    Engineering Calculations in Radiative Heat Transfer is a six-chapter book that first explains the basic principles of thermal radiation and direct radiative transfer. Total exchange of radiation within an enclosure containing an absorbing or non-absorbing medium is then described. Subsequent chapters detail the radiative heat transfer applications and measurement of radiation and temperature.

  20. Metastable charge-transfer state of californium(iii) compounds. (United States)

    Liu, Guokui; Cary, Samantha K; Albrecht-Schmitt, Thomas E


    Among a series of anomalous physical and chemical properties of Cf(iii) compounds revealed by recent investigations, the present work addresses the characteristics of the optical spectra of An(HDPA)3·H2O (An = Am, Cm, and Cf), especially the broadband photoluminescence from Cf(HDPA)3·H2O induced by ligand-to-metal charge transfer (CT). As a result of strong ion-ligand interactions and the relative ease of reducing Cf(iii) to Cf(ii), a CT transition occurs at low energy (transfer state undergoes radiative and non-radiative relaxations. Broadening of the CT transition arises from strong vibronic coupling and hole-charge interactions in the valence band. The non-radiative relaxation of the metastable CT state results from a competition between phonon-relaxation and thermal tunneling that populates the excited states of Cf(iii).

  1. Radiative transfer dynamo effect. (United States)

    Munirov, Vadim R; Fisch, Nathaniel J


    Magnetic fields in rotating and radiating astrophysical plasma can be produced due to a radiative interaction between plasma layers moving relative to each other. The efficiency of current drive, and with it the associated dynamo effect, is considered in a number of limits. It is shown here, however, that predictions for these generated magnetic fields can be significantly higher when kinetic effects, previously neglected, are taken into account.

  2. Radiative transfer on discrete spaces

    CERN Document Server

    Preisendorfer, Rudolph W; Stark, M; Ulam, S


    Pure and Applied Mathematics, Volume 74: Radiative Transfer on Discrete Spaces presents the geometrical structure of natural light fields. This book describes in detail with mathematical precision the radiometric interactions of light-scattering media in terms of a few well established principles.Organized into four parts encompassing 15 chapters, this volume begins with an overview of the derivations of the practical formulas and the arrangement of formulas leading to numerical solution procedures of radiative transfer problems in plane-parallel media. This text then constructs radiative tran

  3. Medical radiation dosimetry theory of charged particle collision energy loss

    CERN Document Server

    McParland, Brian J


    Accurate radiation dosimetry is a requirement of radiation oncology, diagnostic radiology and nuclear medicine. It is necessary so as to satisfy the needs of patient safety, therapeutic and diagnostic optimisation, and retrospective epidemiological studies of the biological effects resulting from low absorbed doses of ionising radiation. The radiation absorbed dose received by the patient is the ultimate consequence of the transfer of kinetic energy through collisions between energetic charged particles and atoms of the tissue being traversed. Thus, the ability of the medical physicist to both measure and calculate accurately patient dosimetry demands a deep understanding of the physics of charged particle interactions with matter. Interestingly, the physics of charged particle energy loss has an almost exclusively theoretical basis, thus necessitating an advanced theoretical understanding of the subject in order to apply it appropriately to the clinical regime. ​ Each year, about one-third of the worl...


    African Journals Online (AJOL)


    ... thiacrown ethers in solution [19-21]. In connection with our previous studies made on the charge-transfer complexes of iodine with crown ethers and their aza derivatives in various solvents [22-28], in this work, we report the results of spectrophotometric study concerning the interaction of iodine with HT18C6 in chloroform.

  5. spectrophotometric methods based on charge transfer complexation

    African Journals Online (AJOL)

    methanol or ethanol, however, the color intensity was lower than in acetonitrile. Figure 5. Effect of solvent on the absorbance of charge transfer complex of FLU with DDQ, I2, p-CLA, and TCNQ acceptors. Effect of reaction time and temperature. Complete color development, was attained instantaneously using iodine for all ...

  6. Noncovalent Functionalization and Charge Transfer in Antimonene. (United States)

    Abellán, Gonzalo; Ares, Pablo; Wild, Stefan; Nuin, Edurne; Neiss, Christian; Miguel, David Rodriguez-San; Segovia, Pilar; Gibaja, Carlos; Michel, Enrique G; Görling, Andreas; Hauke, Frank; Gómez-Herrero, Julio; Hirsch, Andreas; Zamora, Félix


    Antimonene, a novel group 15 two-dimensional material, is functionalized with a tailormade perylene bisimide through strong van der Waals interactions. The functionalization process leads to a significant quenching of the perylene fluorescence, and surpasses that observed for either graphene or black phosphorus, thus allowing straightforward characterization of the flakes by scanning Raman microscopy. Furthermore, scanning photoelectron microscopy studies and theoretical calculations reveal a remarkable charge-transfer behavior, being twice that of black phosphorus. Moreover, the excellent stability under environmental conditions of pristine antimonene has been tackled, thus pointing towards the spontaneous formation of a sub-nanometric oxide passivation layer. DFT calculations revealed that the noncovalent functionalization of antimonene results in a charge-transfer band gap of 1.1 eV. © 2017 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.

  7. Partial charge transfer process in adsorption phenomena

    Energy Technology Data Exchange (ETDEWEB)

    Roque, R.; Pascual, R.; Diaz, C. (Centro Nacional de Investigacion Cientifica, Habana (Cuba))


    The adsorption of Fe/sup 3 +/ ions on the surface of activated charcoal was studied by Moessbauer spectroscopy. As a result of the numerical interpretation of the spectra, the existence of a chemically adsorbed state with an oxidation number larger than +3 was found. This indicates that an electron is shared between the ion and the surface and therefore, it is related with a partial charge transfer process.

  8. Radiative transfer and remote sensing (United States)

    Conrath, B. J.


    Radiative transfer, the basic theoretical tool for the quantitative interpretation of planetary infrared spectra, is discussed. The function it plays in linking the remotely sensed data to the properties of the atmosphere (composition, thermal structure, dynamics, etc.), is inferred. A brief overview of the remote sensing problem as it pertains to the interpretation of planetary spectra is presented. The presentation is tutorial rather than exhaustive.

  9. Intervalence charge transfer transition in mixed valence complexes ...

    Indian Academy of Sciences (India)

    Permanent link: Keywords. Mixed valence complexes; intervalence charge transfer; rotaxane; inclusion complex; optical electron transfer; cyclodextrin. Abstract. Intervalence charge transfer properties were studied for a set of mixed valence complexes incorporating ...

  10. Stochastic Radiative transfer and real cloudiness

    Energy Technology Data Exchange (ETDEWEB)

    Evans, F. [Univ. of Colorado, Boulder, CO (United States)


    Plane-parallel radiative transfer modeling of clouds in GCMs is thought to be an inadequate representation of the effects of real cloudiness. A promising new approach for studying the effects of cloud horizontal inhomogeneity is stochastic radiative transfer, which computes the radiative effects of ensembles of cloud structures described by probability distributions. This approach is appropriate because cloud information is inherently statistical, and it is the mean radiative effect of complex 3D cloud structure that is desired. 2 refs., 1 fig.

  11. Computational Approach to Electron Charge Transfer Reactions

    DEFF Research Database (Denmark)

    Jónsson, Elvar Örn

    -molecular mechanics scheme, and tools to analyse statistical data and generate relative free energies and free energy surfaces. The methodology is applied to several charge transfer species and reactions in chemical environments - chemical in the sense that solvent, counter ions and substrate surfaces are taken...... statistics and a simple post-sampling scheme used to generate free energy surfaces - which compare to full ab initio calculations. In the last part both the molecular dynamics and hybrid classical and quantum mechanics method are used to generate a vast data set for the accurate analysis of dynamical...... in to account - which directly influence the reactants and resulting reaction through both physical and chemical interactions. All methods are though general and can be applied to different types of chemistry. First, the basis of the various theoretical tools is presented and applied to several test systems...

  12. Flavin Charge Transfer Transitions Assist DNA Photolyase Electron Transfer (United States)

    Skourtis, Spiros S.; Prytkova, Tatiana; Beratan, David N.


    This contribution describes molecular dynamics, semi-empirical and ab-initio studies of the primary photo-induced electron transfer reaction in DNA photolyase. DNA photolyases are FADH--containing proteins that repair UV-damaged DNA by photo-induced electron transfer. A DNA photolyase recognizes and binds to cyclobutatne pyrimidine dimer lesions of DNA. The protein repairs a bound lesion by transferring an electron to the lesion from FADH-, upon photo-excitation of FADH- with 350-450 nm light. We compute the lowest singlet excited states of FADH- in DNA photolyase using INDO/S configuration interaction, time-dependent density-functional, and time-dependent Hartree-Fock methods. The calculations identify the lowest singlet excited state of FADH- that is populated after photo-excitation and that acts as the electron donor. For this donor state we compute conformationally-averaged tunneling matrix elements to empty electron-acceptor states of a thymine dimer bound to photolyase. The conformational averaging involves different FADH--thymine dimer confromations obtained from molecular dynamics simulations of the solvated protein with a thymine dimer docked in its active site. The tunneling matrix element computations use INDO/S-level Green's function, energy splitting, and Generalized Mulliken-Hush methods. These calculations indicate that photo-excitation of FADH- causes a π→π* charge-transfer transition that shifts electron density to the side of the flavin isoalloxazine ring that is adjacent to the docked thymine dimer. This shift in electron density enhances the FADH--to-dimer electronic coupling, thus inducing rapid electron transfer.

  13. Probing charge transfer between molecular semiconductors and graphene. (United States)

    Matković, Aleksandar; Kratzer, Markus; Kaufmann, Benjamin; Vujin, Jasna; Gajić, Radoš; Teichert, Christian


    The unique density of states and exceptionally low electrical noise allow graphene-based field effect devices to be utilized as extremely sensitive potentiometers for probing charge transfer with adsorbed species. On the other hand, molecular level alignment at the interface with electrodes can strongly influence the performance of organic-based devices. For this reason, interfacial band engineering is crucial for potential applications of graphene/organic semiconductor heterostructures. Here, we demonstrate charge transfer between graphene and two molecular semiconductors, parahexaphenyl and buckminsterfullerene C 60 . Through in-situ measurements, we directly probe the charge transfer as the interfacial dipoles are formed. It is found that the adsorbed molecules do not affect electron scattering rates in graphene, indicating that charge transfer is the main mechanism governing the level alignment. From the amount of transferred charge and the molecular coverage of the grown films, the amount of charge transferred per adsorbed molecule is estimated, indicating very weak interaction.

  14. Radiative transfer in silylidene molecule

    Directory of Open Access Journals (Sweden)

    Sharma M.


    Full Text Available In order to search for silylidene (H2CSi in the interstellar medium, Izuha et al. (1996 recorded microwave spectrum of H2CSi in laboratory and made an unsuccessful attempt of its identification in IRC +10216, Ori KL, Sgr B2, through its 717-616 transition at 222.055 GHz. For finding out if there are other transitions of H2CSi which may help in its identification in the interstellar medium, we have considered 25 rotational levels of ortho-H2CSi connected by collisional transitions and 35 radiative transitions, and solved radiative transfer problem using the LVG approximation. We have found that the brightness temperatures of 919-818, 918-817, 101,10-919, 1019-918, 111,11-101,10, 111,10-1019 and 121,12-111,11 transition are larger than that of 717-616 transition. Thus, these transitions may help in detection of H2CSi in the interstellar medium.

  15. Charge transfer and association of Na+ with 87Rb atoms from extremely low to intermediate energies (United States)

    Yan, L. L.; Liu, L.; Wu, Y.; Qu, Y. Z.; Wang, J. G.; Buenker, R. J.


    The nonradiative charge-transfer processes in Na++87Rb(5s) collisions have been investigated by using the quantum-mechanical molecular-orbital close-coupling method and the two-center atomic-orbital close-coupling method for the energy range of 10-4-5 and 0.3-100 keV/u, respectively. The radiative charge-transfer, radiative-decay, and radiative-association processes have been investigated by using the fully quantum, optical-potential, and semiclassical methods for the energy range of 10-18-0.2 eV/u. The nonradiative charge-transfer processes dominate the collisions for energies above 0.2 eV/u and radiative-decay processes dominate in the lower-energy region. At the very low collision energies of 10-18-10-3 eV/u, the radiative-association process is more important than the radiative charge-transfer process. Most importantly, it is found that the radiative cross sections exhibit Langevin behavior as E-1/2 for energies less than 10-2 eV/u.

  16. Radiative Heat Transfer in Fractal Structures


    Nikbakht, Moladad


    The radiative properties of most structures are intimately connected to the way in which their constituents are ordered on the nano-scale. We have proposed a new representation for radiative heat transfer formalism in many-body systems. In this representation, we explain why collective effects depend on the morphology of structures, and how the arrangement of nanoparticles and their material affects the thermal properties in many-body systems. We investigated the radiative heat transfer probl...

  17. Graphene Charge Transfer, Spectroscopy, and Photochemical Reactions

    Energy Technology Data Exchange (ETDEWEB)

    Brus, Louis [Columbia Univ., New York, NY (United States)


    This project focused on the special electronic and optical properties of graphene and adsorbed molecular species. Graphene makes an excellent substrate for current collection in nanostructured photovoltaic designs. Graphene is almost transparent, and can be used as a solar cell window. It also has no surface states, and thus current is efficiently transported over long distances. Progress in graphene synthesis indicates that there will soon be practical methods for making large pieces of graphene for devices. We now need to understand exactly what happens to both ground state and electronically excited molecules and Qdots near graphene, if we are going to use them to absorb light in a nano-structured photovoltaic device using graphene to collect photocurrent. We also need to understand how to shift the graphene Fermi level, to optimize the kinetics of electron transfer to graphene. And we need to learn how to convert local graphene areas to semiconductor structure, to make useful spatially patterned graphenes. In this final report, we describe how we addressed these goals. We explored the question of possible Surface Enhanced Raman spectroscopy from molecular Charge Transfer onto Graphene substrates. We observed strong hole doping of graphene by adsorbed halogens as indicated by the shift of the graphene G Raman band. In the case of iodine adsorption, we also observed the anionic species made by hole doping. At low frequency in the Raman spectrum, we saw quite intense lines from I3- and I5- , suggesting possible SERS. We reported on Fresnel calculations on this thin film system, which did not show any net electromagnetic field enhancement.

  18. Numerical methods in multidimensional radiative transfer

    CERN Document Server

    Meinköhn, Erik


    Offers an overview of the numerical modelling of radiation fields in multidimensional geometries. This book covers advances and problems in the mathematical treatment of the radiative transfer equation, a partial integro-differential equation of high dimension that describes the propagation of the radiation in various fields.

  19. Excited state intramolecular charge transfer reaction of 4 ...

    Indian Academy of Sciences (India)


    We will use the twisted intramolecular charge transfer (TICT) model to explain the photo-induced charge transfer ..... full width at half maxima (Γ) are expressed in 103 cm–1. –ΔGr are in kJ mol–1 units. PFH: per- ..... incorrect values of thermodynamic and kinetic parameters calculated using these reaction times, leading to ...

  20. Correlation between stick-slip frictional sliding and charge transfer


    Ananthakrishna, G.; Kumar, Jagadish


    A decade ago, Budakian and Putterman (Phys. Rev. Lett., {\\bf 85}, 1000 (2000)) ascribed friction to the formation of bonds arising from contact charging when a gold tip of a surface force apparatus was dragged on polymethylmethacrylate surface. We propose a stick-slip model that captures the observed correlation between stick-slip events and charge transfer, and the lack of dependence of the scale factor connecting the force jumps and charge transfer on normal load. Here, stick-slip dynamics ...

  1. Light scattering reviews 8 radiative transfer and light scattering

    CERN Document Server

    Kokhanovsky, Alexander A


    Light scattering review (vol 8) is aimed at the presentation of recent advances in radiative transfer and light scattering optics. The topics to be covered include: scattering of light by irregularly shaped particles suspended in atmosphere (dust, ice crystals), light scattering by particles much larger as compared the wavelength of incident radiation, atmospheric radiative forcing, astrophysical radiative transfer, radiative transfer and optical imaging in biological media, radiative transfer of polarized light, numerical aspects of radiative transfer.

  2. Imaging charge transfer in iodomethane upon x-ray photoabsorption. (United States)

    Erk, Benjamin; Boll, Rebecca; Trippel, Sebastian; Anielski, Denis; Foucar, Lutz; Rudek, Benedikt; Epp, Sascha W; Coffee, Ryan; Carron, Sebastian; Schorb, Sebastian; Ferguson, Ken R; Swiggers, Michele; Bozek, John D; Simon, Marc; Marchenko, Tatiana; Küpper, Jochen; Schlichting, Ilme; Ullrich, Joachim; Bostedt, Christoph; Rolles, Daniel; Rudenko, Artem


    Studies of charge transfer are often hampered by difficulties in determining the charge localization at a given time. Here, we used ultrashort x-ray free-electron laser pulses to image charge rearrangement dynamics within gas-phase iodomethane molecules during dissociation induced by a synchronized near-infrared (NIR) laser pulse. Inner-shell photoionization creates positive charge, which is initially localized on the iodine atom. We map the electron transfer between the methyl and iodine fragments as a function of their interatomic separation set by the NIR-x-ray delay. We observe signatures of electron transfer for distances up to 20 angstroms and show that a realistic estimate of its effective spatial range can be obtained from a classical over-the-barrier model. The presented technique is applicable for spatiotemporal imaging of charge transfer dynamics in a wide range of molecular systems. Copyright © 2014, American Association for the Advancement of Science.

  3. Charge Transfer and Catalysis at the Metal Support Interface

    Energy Technology Data Exchange (ETDEWEB)

    Baker, Lawrence Robert [Univ. of California, Berkeley, CA (United States)


    Kinetic, electronic, and spectroscopic characterization of model Pt–support systems are used to demonstrate the relationship between charge transfer and catalytic activity and selectivity. The results show that charge flow controls the activity and selectivity of supported metal catalysts. This dissertation builds on extensive existing knowledge of metal–support interactions in heterogeneous catalysis. The results show the prominent role of charge transfer at catalytic interfaces to determine catalytic activity and selectivity. Further, this research demonstrates the possibility of selectively driving catalytic chemistry by controlling charge flow and presents solid-state devices and doped supports as novel methods for obtaining electronic control over catalytic reaction kinetics.

  4. Improved Charge-Transfer Fluorescent Dyes (United States)

    Meador, Michael


    Improved charge-transfer fluorescent dyes have been developed for use as molecular probes. These dyes are based on benzofuran nuclei with attached phenyl groups substituted with, variously, electron donors, electron acceptors, or combinations of donors and acceptors. Optionally, these dyes could be incorporated as parts of polymer backbones or as pendant groups or attached to certain surfaces via self-assembly-based methods. These dyes exhibit high fluorescence quantum yields -- ranging from 0.2 to 0.98, depending upon solvents and chemical structures. The wavelengths, quantum yields, intensities, and lifetimes of the fluorescence emitted by these dyes vary with (and, hence, can be used as indicators of) the polarities of solvents in which they are dissolved: In solvents of increasing polarity, fluorescence spectra shift to longer wavelengths, fluorescence quantum yields decrease, and fluorescence lifetimes increase. The wavelengths, quantum yields, intensities, and lifetimes are also expected to be sensitive to viscosities and/or glass-transition temperatures. Some chemical species -- especially amines, amino acids, and metal ions -- quench the fluorescence of these dyes, with consequent reductions in intensities, quantum yields, and lifetimes. As a result, the dyes can be used to detect these species. Another useful characteristic of these dyes is a capability for both two-photon and one-photon absorption. Typically, these dyes absorb single photons in the ultraviolet region of the spectrum (wavelengths fluorescence spectra identical to those obtained in response to excitation by single photons at half the corresponding wavelengths (300 to 400 nm). While many prior fluorescent dyes exhibit high quantum yields, solvent-polarity- dependent fluorescence behavior, susceptibility to quenching by certain chemical species, and/or two-photon fluorescence, none of them has the combination of all of these attributes. Because the present dyes do have all of these attributes

  5. A Paradox in Radiation Heat Transfer

    Indian Academy of Sciences (India)

    Home; Journals; Resonance – Journal of Science Education; Volume 12; Issue 4. A Paradox in Radiation Heat Transfer. J Srinivasan. Classroom Volume 12 Issue 4 April 2007 pp 85-91. Fulltext. Click here to view fulltext PDF. Permanent link: Keywords. Radiation ...

  6. Energy Transfer of a Shaped Charge.

    Energy Technology Data Exchange (ETDEWEB)

    Milinazzo, Jared Joseph [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)


    A cylinder of explosive with a hollow cavity on one and a detonator at the other is considered a hollow charge. When the explosive is detonated the detonation products form a localized intense force. If the hollow charge is placed near or in contact with a steel plate then the damage to the plate is greater than a solid cylinder of explosive even though there is a greater amount of explosive in the latter charge. The hollow cavity can take almost any geometrical shape with differing amounts of damage associated with each shape. This phenomenon is known in the United States as the Munroe effect.

  7. Charge transfer in time-dependent density functional theory (United States)

    Maitra, Neepa T.


    Charge transfer plays a crucial role in many processes of interest in physics, chemistry, and bio-chemistry. In many applications the size of the systems involved calls for time-dependent density functional theory (TDDFT) to be used in their computational modeling, due to its unprecedented balance between accuracy and efficiency. However, although exact in principle, in practise approximations must be made for the exchange-correlation functional in this theory, and the standard functional approximations perform poorly for excitations which have a long-range charge-transfer component. Intense progress has been made in developing more sophisticated functionals for this problem, which we review. We point out an essential difference between the properties of the exchange-correlation kernel needed for an accurate description of charge-transfer between open-shell fragments and between closed-shell fragments. We then turn to charge-transfer dynamics, which, in contrast to the excitation problem, is a highly non-equilibrium, non-perturbative, process involving a transfer of one full electron in space. This turns out to be a much more challenging problem for TDDFT functionals. We describe dynamical step and peak features in the exact functional evolving over time, that are missing in the functionals currently used. The latter underestimate the amount of charge transferred and manifest a spurious shift in the charge transfer resonance position. We discuss some explicit examples.

  8. Charge transfer reactions in nematic liquid crystals

    Energy Technology Data Exchange (ETDEWEB)

    Wiederrecht, G.P. [Argonne National Lab., IL (United States). Chemistry Div.; Wasielewski, M.R. [Argonne National Lab., IL (United States). Chemistry Div.]|[Northwestern Univ., Evanston, IL (United States). Dept. of Chemistry; Galili, T.; Levanon, H. [Hebrew Univ. of Jerusalem (Israel). Dept. of Physical Chemistry


    Ultrafast transient absorption studies of intramolecular photoinduced charge separation and thermal charge recombination were carried out on a molecule consisting of a 4-(N-pyrrolidino)naphthalene-1,8-imide donor (PNI) covalently attached to a pyromellitimide acceptor (PI) dissolved in the liquid crystal 4{prime}-(n-pentyl)-4-cyanobiphenyl (5CB). The temperature dependencies of the charge separation and recombination rates were obtained at temperatures above the nematic-isotropic phase transition of 5CB, where ordered microdomains exist and scattering of visible light by these domains is absent. The authors show that excited state charge separation is dominated by molecular reorientation of 5CB perpendicular to the director within the liquid crystal microdomains. They also show that charge recombination is adiabatic and is controlled by the comparatively slow collective reorientation of the liquid crystal microdomains relative to the orientation of PNI{sup +}-PI{sup {minus}}. They also report the results of time resolved electron paramagnetic resonance (TREPR) studies of photoinduced charge separation in a series of supramolecular compounds dissolved in oriented liquid crystal solvents. These studies permit the determination of the radical pair energy levels as the solvent reorganization energy increases from the low temperature crystalline phase, through the soft glass phase, to the nematic phase of the liquid crystal.

  9. Thermodynamic study of charge-transfer complex of iodine with ...

    African Journals Online (AJOL)

    Thermodynamic study of charge-transfer complex of iodine with HT18C6 in chloroform solution. Mahmoud Javadian Jazi, Ali Reza Firooz, Abolfazl Semnani, Hamid Reza Pouretedal, Mohammad Hossein Keshavarz ...

  10. CHARGE TRANSFER. Efficient hot-electron transfer by a plasmon-induced interfacial charge-transfer transition. (United States)

    Wu, K; Chen, J; McBride, J R; Lian, T


    Plasmon-induced hot-electron transfer from metal nanostructures is a potential new paradigm for solar energy conversion; however, the reported efficiencies of devices based on this concept are often low because of the loss of hot electrons via ultrafast electron-electron scattering. We propose a pathway, called the plasmon-induced interfacial charge-transfer transition (PICTT), that enables the decay of a plasmon by directly exciting an electron from the metal to a strongly coupled acceptor. We demonstrated this concept in cadmium selenide nanorods with gold tips, in which the gold plasmon was strongly damped by cadmium selenide through interfacial electron transfer. The quantum efficiency of the PICTT process was high (>24%), independent of excitation photon energy over a ~1-electron volt range, and dependent on the excitation polarization. Copyright © 2015, American Association for the Advancement of Science.

  11. Photoinduced intramolecular charge-transfer reactions in 4-amino-3 ...

    Indian Academy of Sciences (India)

    Photoinduced intramolecular charge-transfer reactions in 4-amino-3-methyl benzoic acid methyl ester (AMBME) have been investigated spectroscopically. AMBME, with its weak charge donor primary amino group, shows dual emission in polar solvents. Absorption and emission measurements in the condensed phase ...

  12. CNDO/SCF molecular orbital structural studies and charge transfer ...

    African Journals Online (AJOL)

    CNDO/SCF molecular orbital structural studies and charge transfer complex formation between 4,4'-dimethoxydiquinone and uracil. ... potentials and the electron affinities of the studied molecules have been calculated in addition to their charge densities giving the columbic potential energy of the donor and acceptor.

  13. CCD charge collection efficiency and the photon transfer technique (United States)

    Janesick, J.; Klaasen, K.; Elliott, T.


    The charge-coupled device (CCD) has shown unprecendented performance as a photon detector in the areas of spectral response, charge transfer, and readout noise. Recent experience indicates, however, that the full potential for the CCD's charge collection efficiency (CCE) lies well beyond that which is realized in currently available devices. A definition of CCE performance is presented and a standard test tool (the photon transfer technique) for measuring and optimizing this important CCD parameter is introduced. CCE characteristics for different types of CCDs are compared; the primary limitations in achieving high CCE performance are discussed, and the prospects for future improvement are outlined.


    Energy Technology Data Exchange (ETDEWEB)

    Edward C. Lim


    A concerted experimental and computational study of energy transfer in nucleic acid bases and charge transfer in dialkylaminobenzonitriles, and related electron donor-acceptor molecules, indicate that the ultrafast photoprocesses occur through three-state conical interactions involving an intermediate state of biradical character.

  15. Radiative heat transfer in fractal structures (United States)

    Nikbakht, M.


    The radiative properties of most structures are intimately connected to the way in which their constituents are ordered on the nanoscale. We have proposed a new representation for radiative heat transfer formalism in many-body systems. In this representation, we explain why collective effects depend on the morphology of structures, and how the arrangement of nanoparticles and their material affects the thermal properties in many-body systems. We investigated the radiative heat transfer problem in fractal (i.e., scale invariant) structures. In order to show the effect of the structure morphology on the collective properties, the radiative heat transfer and radiative cooling are studied and the results are compared for fractal and nonfractal structures. It is shown that fractal arranged nanoparticles display complex radiative behavior related to their scaling properties. We showed that, in contrast to nonfractal structures, heat flux in fractals is not of large-range character. By using the fractal dimension as a means to describe the structure morphology, we present a universal scaling behavior that quantitatively links the structure radiative cooling to the structure gyration radius.

  16. Radiative charge transfer in He{sup +}+ H{sub 2} collisions in the milli- to nano-electron-volt range: A theoretical study within state-to-state and optical potential approaches

    Energy Technology Data Exchange (ETDEWEB)

    Mrugala, Felicja [Institute of Physics, Faculty of Physics, Astronomy and Informatics, Nicolaus Copernicus University, Grudziadzka 5, PL 87-100 Torun (Poland); Kraemer, Wolfgang P. [Max-Planck-Institute of Astrophysics, Postfach 1317, D-85741 Garching (Germany)


    The paper presents a theoretical study of the low-energy dynamics of the radiative charge transfer (RCT) reaction He{sup +}({sup 2}S)+H{sub 2}(X{sup 1}{Sigma}{sub g}{sup +}){yields}He({sup 1}S)+H{sub 2}{sup +}(X{sup 2}{Sigma}{sub g}{sup +})+h{nu} extending our previous studies on radiative association of HeH{sub 2}{sup +} [F. Mrugala, V. Spirko, and W. P. Kraemer, J. Chem. Phys. 118, 10547 (2003); F. Mrugala and W. P. Kraemer, ibid. 122, 224321 (2005)]. The calculations account for the vibrational and rotational motions of the H{sub 2}/H{sub 2}{sup +} diatomics and for the atom-diatom complex formation in the reactant and the product channels of the RCT reaction. Continuum states of He{sup +}+ H{sub 2}(v= 0, j= 0) in the collision energy range {approx}10{sup -7}-18.6 meV and all quasi-bound states of the He{sup +}- H{sub 2}(para;v= 0) complex formed in this range are taken into account. Close-coupling calculations are performed to determine rates of radiative transitions from these states to the continuum and quasi-bound states of the He +H{sub 2}{sup +} system in the energy range extending up to {approx}0.16 eV above the opening of the HeH{sup +}+ H arrangement channel. From the detailed state-to-state calculated characteristics global functions of the RCT reaction, such as cross-section {sigma}(E), emission intensity I({nu}, T), and rate constant k(T) are derived, and are presented together with their counterparts for the radiative association (RA) reaction He{sup +}({sup 2}S) +H{sub 2}(X{sup 1}{Sigma}{sub g}{sup +}){yields} HeH{sub 2}{sup +}(X{sup 2}A{sup Prime })+h{nu}. The rate constant k{sup RCT} is approximately 20 times larger than k{sup RA} at the considered temperatures, 0.1 {mu}K-50 K. Formation of rotational Feshbach resonances in the reactant channel plays an important role in both reactions. Transitions mediated by these resonances contribute more than 70% to the respective rates. An extension of the one-dimensional optical potential model is

  17. Multipole charge conservation and implications on electromagnetic radiation (United States)

    Seraj, Ali


    It is shown that conserved charges associated with a specific subclass of gauge symmetries of Maxwell electrodynamics are proportional to the well known electric mul-tipole moments. The symmetries are residual gauge transformations surviving the Lorenz gauge, with nontrivial conserved charge at spatial infinity. These "Multipole charges" receive contributions both from the charged matter and electromagnetic fields. The former is nothing but the electric multipole moment of the source. In a stationary configuration, there is a novel equipartition relation between the two contributions. The multipole charge, while conserved, can freely interpolate between the source and the electromagnetic field, and therefore can be propagated with the radiation. Using the multipole charge conservation, we obtain infinite number of constraints over the radiation produced by the dynamics of charged matter.

  18. Electromagnetic radiation due to nonlinear oscillations of a charged drop (United States)

    Shiryaeva, S. O.; Grigor'ev, A. N.; Kolbneva, N. Yu.


    The nonlinear oscillations of a spherical charged drop are asymptotically analyzed under the conditions of a multimode initial deformation of its equilibrium shape. It is found that if the spectrum of initially excited modes contains two adjacent modes, the translation mode of oscillations is excited among others. In this case, the center of the drop's charge oscillates about the equilibrium position, generating a dipole electromagnetic radiation. It is shown that the intensity of this radiation is many orders of magnitude higher than the intensity of the drop's radiation, which arises in calculations of the first order of smallness and is related to the drop's charged surface oscillations.

  19. Quadrupole electromagnetic radiation of an oscillating charged droplet (United States)

    Grigor'ev, A. I.; Kolbneva, N. Yu.; Shiryaeva, S. O.


    Analytical calculations using the first order of smallness with respect to dimensionless amplitude of oscillations show that the intensity of electromagnetic radiation of a charged droplet is determined by time-dependent quadrupole moment.

  20. Molecular Arrangement and Charge Transfer in C60/Graphene Heterostructures. (United States)

    Ojeda-Aristizabal, Claudia; Santos, Elton J G; Onishi, Seita; Yan, Aiming; Rasool, Haider I; Kahn, Salman; Lv, Yinchuan; Latzke, Drew W; Velasco, Jairo; Crommie, Michael F; Sorensen, Matthew; Gotlieb, Kenneth; Lin, Chiu-Yun; Watanabe, Kenji; Taniguchi, Takashi; Lanzara, Alessandra; Zettl, Alex


    Charge transfer at the interface between dissimilar materials is at the heart of electronics and photovoltaics. Here we study the molecular orientation, electronic structure, and local charge transfer at the interface region of C60 deposited on graphene, with and without supporting substrates such as hexagonal boron nitride. We employ ab initio density functional theory with van der Waals interactions and experimentally characterize interface devices using high-resolution transmission electron microscopy and electronic transport. Charge transfer between C60 and the graphene is found to be sensitive to the nature of the underlying supporting substrate and to the crystallinity and local orientation of the C60. Even at room temperature, C60 molecules interfaced to graphene are orientationally locked into position. High electron and hole mobilities are preserved in graphene with crystalline C60 overlayers, which has ramifications for organic high-mobility field-effect devices.

  1. Multiple-charge transfer and trapping in DNA dimers (United States)

    Tornow, Sabine; Bulla, Ralf; Anders, Frithjof B.; Zwicknagl, Gertrud


    We investigate the charge transfer characteristics of one and two excess charges in a DNA base-pair dimer using a model Hamiltonian approach. The electron part comprises diagonal and off-diagonal Coulomb matrix elements such a correlated hopping and the bond-bond interaction, which were recently calculated by Starikov [E. B. Starikov, Philos. Mag. Lett. 83, 699 (2003)10.1080/0950083031000151374] for different DNA dimers. The electronic degrees of freedom are coupled to an ohmic or a superohmic bath serving as dissipative environment. We employ the numerical renormalization group method in the nuclear tunneling regime and compare the results to Marcus theory for the thermal activation regime. For realistic parameters, the rate that at least one charge is transferred from the donor to the acceptor in the subspace of two excess electrons significantly exceeds the rate in the single charge sector. Moreover, the dynamics is strongly influenced by the Coulomb matrix elements. We find sequential and pair transfer as well as a regime where both charges remain self-trapped. The transfer rate reaches its maximum when the difference of the on-site and intersite Coulomb matrix element is equal to the reorganization energy which is the case in a guanine/cytosine (GC)-dimer. Charge transfer is completely suppressed for two excess electrons in adenine/thymine (AT)-dimer in an ohmic bath and replaced by damped coherent electron-pair oscillations in a superohmic bath. A finite bond-bond interaction W alters the transfer rate: it increases as function of W when the effective Coulomb repulsion exceeds the reorganization energy (inverted regime) and decreases for smaller Coulomb repulsion.

  2. Valence Topological Charge-Transfer Indices for Dipole Moments

    Directory of Open Access Journals (Sweden)

    Francisco Torrens


    Full Text Available New valence topological charge-transfer indices are applied to the calculation of dipole moments. The algebraic and vector semisum charge-transfer indices are defined. The combination of the charge-transfer indices allows the estimation of the dipole moments. The model is generalized for molecules with heteroatoms. The ability of the indices for the description of the molecular charge distribution is established by comparing them with the dipole moments of a homologous series of phenyl alcohols. Linear and non-linear correlation models are obtained. The new charge-transfer indices improve the multivariable non-linear regression equations for the dipole moment. When comparing with previous results, the variance decreases 92%. No superposition of the corresponding Gk–Jk and GkV – JkV pairs is observed. This diminishes the risk of co-linearity. Inclusion of the oxygen atom in the p-electron system is beneficial for the description of the dipole moment, owing to either the role of the additional p orbitals provided by the heteroatom or the role of steric factors in the p-electron conjugation. Linear and non-linear correlations between the fractal dimension and various descriptors point not only to a homogeneous molecular structure but also to the ability to predict and tailor drug properties.

  3. Enhancing radiative energy transfer through thermal extraction

    Directory of Open Access Journals (Sweden)

    Tan Yixuan


    Full Text Available Thermal radiation plays an increasingly important role in many emerging energy technologies, such as thermophotovoltaics, passive radiative cooling and wearable cooling clothes [1]. One of the fundamental constraints in thermal radiation is the Stefan-Boltzmann law, which limits the maximum power of far-field radiation to P0 = σT4S, where σ is the Boltzmann constant, S and T are the area and the temperature of the emitter, respectively (Fig. 1a. In order to overcome this limit, it has been shown that near-field radiations could have an energy density that is orders of magnitude greater than the Stefan-Boltzmann law [2-7]. Unfortunately, such near-field radiation transfer is spatially confined and cannot carry radiative heat to the far field. Recently, a new concept of thermal extraction was proposed [8] to enhance far-field thermal emission, which, conceptually, operates on a principle similar to oil immersion lenses and light extraction in light-emitting diodes using solid immersion lens to increase light output [62].Thermal extraction allows a blackbody to radiate more energy to the far field than the apparent limit of the Stefan-Boltzmann law without breaking the second law of thermodynamics.

  4. RRTM: A rapid radiative transfer model

    Energy Technology Data Exchange (ETDEWEB)

    Mlawer, E.J.; Taubman, S.J.; Clough, S.A. [Atmospheric and Environmental Research, Inc., Cambridge, MA (United States)


    A rapid radiative transfer model (RRTM) for the calculation of longwave clear-sky fluxes and cooling rates has been developed. The model, which uses the correlated-k method, is both accurate and computationally fast. The foundation for RRTM is the line-by-line radiative transfer model (LBLRTM) from which the relevant k-distributions are obtained. LBLRTM, which has been extensively validated against spectral observations e.g., the high-resolution sounder and the Atmospheric Emitted Radiance Interferometer, is used to validate the flux and cooling rate results from RRTM. Validations of RRTM`s results have been performed for the tropical, midlatitude summer, and midlatitude winter atmospheres, as well as for the four Intercomparison of Radiation Codes in Climate Models (ICRCCM) cases from the Spectral Radiance Experiment (SPECTRE). Details of some of these validations are presented below. RRTM has the identical atmospheric input module as LBLRTM, facilitating intercomparisons with LBLRTM and application of the model at the Atmospheric Radiation Measurement Cloud and Radiation Testbed sites.

  5. Excited state intramolecular charge transfer reaction in non-aqueous ...

    Indian Academy of Sciences (India)

    concentration dependent reaction rate constant of a. TICT reaction already measured in bulk electrolyte solutions.44–46 Here, we report such a study where photo-induced intramolecular charge transfer reaction has been investigated in AOT/heptane non-aqueous reverse micelles at different Ws values, and also in.

  6. Development of Two Charge-Transfer Complex Spectrophotometric ...

    African Journals Online (AJOL)

    Development of Two Charge-Transfer Complex. Spectrophotometric Methods for Determination of ... Purpose: To develop an easy, fast and sensible spectrophotometric method for determination of tofisopam in tablet dosage form. Methods: ..... profiles of tofisopam and diazepam. Eur J Clin. Pharmacol 1982; 22: 137-142. 2.

  7. Taking control of charge transfer : strategic design for solar cells

    NARCIS (Netherlands)

    Monti, Adriano


    The thesis is focused on the investigation of the electron transfer mechanisms leading to solar fuel production and to the identification of engineering principles that can be used to design materials able to improve charge separation. Molecular systems composed of three or more subunits arranged

  8. b-Cyclodextrin-assisted intervalence charge transfer in mixed- valent

    Indian Academy of Sciences (India)


    b-Cyclodextrin-assisted intervalence charge transfer in mixed- valent [2]rotaxane complexes having metal centres linked by interrupted p-electron systems. ATINDRA D SHUKLA, H C BAJAJ and AMITAVA DAS. Silicates and Catalysis Discipline, Central Salt and Marine Chemicals. Research Institute, Bhavnagar 364 002, ...

  9. Evaluation of intramolecular charge transfer state of 4-N, N ...

    Indian Academy of Sciences (India)

    Evaluation of intramolecular charge transfer state of. 4-N, N-dimethylamino cinnamaldehyde using time-dependent density functional theory. SURAJIT GHOSHa, K V S GIRISHb and SUBHADIP GHOSHb,∗. aDepartment of Physics and Technophysics, Vidyasagar University, Midnapore 721 102, India. bSchool of Chemical ...

  10. Kinetic and Thermodynamic Studies of Charge-Transfer Complex ...

    African Journals Online (AJOL)


    the donor in the two solvents was estimated and compared with the theoretical values. KEYWORDS. Charge-transfer complex ... drug-receptor binding mechanisms,7 in solar energy storage 8,9 and in surface chemistry10 as well as in many ..... dyes-sensitized solar cells, Renew. Energ., 2010, 35, 1724–1728. 10 S.M. ...

  11. Effects of acid concentration on intramolecular charge transfer ...

    Indian Academy of Sciences (India)

    Effects of acid concentration on excited state intramolecular charge transfer reaction of 4-(azetidinyl) benzonitrile (P4C) in aprotic (acetonitrile and ethyl acetate) and protic (ethanol) solvents have been studied by means of steady state absorption and fluorescence, and time resolved fluorescence spectroscopic techniques.

  12. Correlating electronic and vibrational motions in charge transfer systems

    Energy Technology Data Exchange (ETDEWEB)

    Khalil, Munira [Univ. of Washington, Seattle, WA (United States)


    The goal of this research program was to measure coupled electronic and nuclear motions during photoinduced charge transfer processes in transition metal complexes by developing and using novel femtosecond spectroscopies. The scientific highlights and the resulting scientific publications from the DOE supported work are outlined in the technical report.

  13. Excited state intramolecular charge transfer reaction in 4-(1 ...

    Indian Academy of Sciences (India)


    Abstract. Excited state intramolecular charge transfer reaction of 4-(1-azetidinyl) benzonitrile (P4C) in deuterated and normal methanol, ethanol and acetonitrile has been studied in order to investigate the solvent isotope effects on reaction rates and yields. These quantities (reaction rates and yields) along with several.

  14. Excited state intramolecular charge transfer reaction in 4-(1 ...

    Indian Academy of Sciences (India)

    Excited state intramolecular charge transfer reaction of 4-(1-azetidinyl) benzonitrile (P4C) in deuterated and normal methanol, ethanol and acetonitrile has been studied in order to investigate the solvent isotope effects on reaction rates and yields. These quantities (reaction rates and yields) along with several other ...

  15. Charge-Transfer Interactions in Organic Functional Materials

    Directory of Open Access Journals (Sweden)

    Bih-Yaw Jin


    Full Text Available Our goal in this review is three-fold. First, we provide an overview of a number of quantum-chemical methods that can abstract charge-transfer (CT information on the excited-state species of organic conjugated materials, which can then be exploited for the understanding and design of organic photodiodes and solar cells at the molecular level. We stress that the Composite-Molecule (CM model is useful for evaluating the electronic excited states and excitonic couplings of the organic molecules in the solid state. We start from a simple polyene dimer as an example to illustrate how interchain separation and chain size affect the intercahin interaction and the role of the charge transfer interaction in the excited state of the polyene dimers. With the basic knowledge from analysis of the polyene system, we then study more practical organic materials such as oligophenylenevinylenes (OPVn, oligothiophenes (OTn, and oligophenylenes (OPn. Finally, we apply this method to address the delocalization pathway (through-bond and/or through-space in the lowest excited state for cyclophanes by combining the charge-transfer contributions calculated on the cyclophanes and the corresponding hypothetical molecules with tethers removed. This review represents a step forward in the understanding of the nature of the charge-transfer interactions in the excited state of organic functional materials.

  16. Charge-Transfer Complexes Studied by Dynamic Force Spectroscopy

    Directory of Open Access Journals (Sweden)

    Jurriaan Huskens


    Full Text Available In this paper, the strength and kinetics of two charge-transfer complexes, naphthol-methylviologen and pyrene-methylviologen, are studied using dynamic force spectroscopy. The dissociation rates indicate an enhanced stability of the pyrene-methylviologen complex, which agrees with its higher thermodynamic stability compared to naphthol-methylviologen complex.

  17. Enhancing radiative energy transfer through thermal extraction (United States)

    Tan, Yixuan; Liu, Baoan; Shen, Sheng; Yu, Zongfu


    Thermal radiation plays an increasingly important role in many emerging energy technologies, such as thermophotovoltaics, passive radiative cooling and wearable cooling clothes [1]. One of the fundamental constraints in thermal radiation is the Stefan-Boltzmann law, which limits the maximum power of far-field radiation to P0 = σT4S, where σ is the Boltzmann constant, S and T are the area and the temperature of the emitter, respectively (Fig. 1a). In order to overcome this limit, it has been shown that near-field radiations could have an energy density that is orders of magnitude greater than the Stefan-Boltzmann law [2-7]. Unfortunately, such near-field radiation transfer is spatially confined and cannot carry radiative heat to the far field. Recently, a new concept of thermal extraction was proposed [8] to enhance far-field thermal emission, which, conceptually, operates on a principle similar to oil immersion lenses and light extraction in light-emitting diodes using solid immersion lens to increase light output [62].Thermal extraction allows a blackbody to radiate more energy to the far field than the apparent limit of the Stefan-Boltzmann law without breaking the second law of thermodynamics. Thermal extraction works by using a specially designed thermal extractor to convert and guide the near-field energy to the far field, as shown in Fig. 1b. The same blackbody as shown in Fig. 1a is placed closely below the thermal extractor with a spacing smaller than the thermal wavelength. The near-field coupling transfers radiative energy with a density greater than σT4. The thermal extractor, made from transparent and high-index or structured materials, does not emit or absorb any radiation. It transforms the near-field energy and sends it toward the far field. As a result, the total amount of far-field radiative heat dissipated by the same blackbody is greatly enhanced above SσT4, where S is the area of the emitter. This paper will review the progress in thermal

  18. Charge-transfer interactions of Cr species with DNA. (United States)

    Nowicka, Anna M; Matysiak-Brynda, Edyta; Hepel, Maria


    Interactions of Cr species with nucleic acids in living organisms depend strongly on Cr oxidation state and the environmental conditions. As the effects of these interactions range from benign to pre-mutagenic to carcinogenic, careful assessment of the hazard they pose to human health is necessary. We have investigated methods that would enable quantifying the DNA damage caused by Cr species under varying environmental conditions, including UV, O 2 , and redox potential, using simple instrumental techniques which could be in future combined into a field-deployable instrumentation. We have employed electrochemical quartz crystal nanogravimetry (EQCN), cyclic voltammetry (CV), and electrochemical impedance spectroscopy (EIS) to evaluate the extent of DNA damage expressed in terms of guanine oxidation yield (η) and changes in specific characteristics provided by these techniques. The effects of the interactions of Cr species with DNA were analyzed using a model calf thymus DNA (ctDNA) film on a gold electrode (Au@ctDNA) in different media, including: (i) Cr(VI), (ii) Cr(VI) reduced at -0.2V, (iii) Cr(III)+UV radiation+O 2 , and Cr(III), obtaining the η values: 7.4±1.4, 1.5±0.4, 1.1±0.31%, and 0%, respectively, thus quantifying the hazard posed. The EIS measurements have enabled utilizing the decrease in charge-transfer resistance (R ct ) for ferri/ferrocyanide redox probe at an Au@ctDNA electrode to assess the oxidative ctDNA damage by Cr(VI) species. In this case, circular dichroism indicates an extensive damage to the ctDNA hydrogen bonding. On the other hand, Cr(III) species have not induced any damage to ctDNA, although the EQCN measurements show an electrostatic binding to DNA. Copyright © 2017 Elsevier Inc. All rights reserved.

  19. Successive Charge Transitions of Unusually High-Valence Fe3.5+ : Charge Disproportionation and Intermetallic Charge Transfer. (United States)

    Hosaka, Yoshiteru; Denis Romero, Fabio; Ichikawa, Noriya; Saito, Takashi; Shimakawa, Yuichi


    A perovskite-structure oxide containing unusually high-valence Fe3.5+ was obtained by high-pressure synthesis. Instability of the Fe3.5+ in Ca0.5 Bi0.5 FeO3 is relieved first by charge disproportionation at 250 K and then by intermetallic charge transfer between A-site Bi and B-site Fe at 200 K. These previously unobserved successive charge transitions are due to competing intermetallic and disproportionation charge instabilities. Both transitions change magnetic and structural properties significantly, indicating strong coupling of charge, spin, and lattice in the present system. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. Charges and Electromagnetic Radiation as Topological Excitations

    Directory of Open Access Journals (Sweden)

    Manfried Faber


    Full Text Available We discuss a model with stable topological solitons in Minkowski space with only three degrees of freedom, the rotational angles of a spatial Dreibein. This model has four types of solitons differing in two topological quantum numbers which we identify with electric charge and spin. The vacuum has a two-dimensional degeneracy leading to two types of massless excitations, characterised by a topological quantum number which could have a physical equivalent in the photon number.

  1. Study of charge transfer reactions in a microbial fuel cell

    Energy Technology Data Exchange (ETDEWEB)

    Martin, E.; Savadogo, O. [Ecole Polytechnique, Montreal, PQ (Canada). Dept. de Genie Chimique; National Research Council of Canada, Montreal, PQ (Canada). Biotechnology Research Inst.; Tartakovsky, B. [National Research Council of Canada, Montreal, PQ (Canada). Biotechnology Research Inst.


    Electron transfer reactions in a microbial fuel cell (MFC) were evaluated. The MFC was inoculated with anaerobic mesophilic sludge and operated with carbon felt, carbon cloth, and platinum (Pt) coated carbon cloth. The MFC was then fed with either acetate or glucose as a source of fuel and operated at a temperature of 25 degrees C and a pH of 7. Scanning electron microscopy (SEM) micrographs demonstrated that the micro-organisms colonized the anodes. Cyclic voltammetry and polarization tests were conducted using different fractions of the anodophilic biofilm in order to determine charge transfer routes. The study characterized the electron transfer mechanisms used by the exoelectrogenic micro-organisms to produce electricity. It was concluded that further research is needed to characterize reaction transfer routes. 2 refs., 1 fig.

  2. Composite biasing in Monte Carlo radiative transfer (United States)

    Baes, Maarten; Gordon, Karl D.; Lunttila, Tuomas; Bianchi, Simone; Camps, Peter; Juvela, Mika; Kuiper, Rolf


    Biasing or importance sampling is a powerful technique in Monte Carlo radiative transfer, and can be applied in different forms to increase the accuracy and efficiency of simulations. One of the drawbacks of the use of biasing is the potential introduction of large weight factors. We discuss a general strategy, composite biasing, to suppress the appearance of large weight factors. We use this composite biasing approach for two different problems faced by current state-of-the-art Monte Carlo radiative transfer codes: the generation of photon packages from multiple components, and the penetration of radiation through high optical depth barriers. In both cases, the implementation of the relevant algorithms is trivial and does not interfere with any other optimisation techniques. Through simple test models, we demonstrate the general applicability, accuracy and efficiency of the composite biasing approach. In particular, for the penetration of high optical depths, the gain in efficiency is spectacular for the specific problems that we consider: in simulations with composite path length stretching, high accuracy results are obtained even for simulations with modest numbers of photon packages, while simulations without biasing cannot reach convergence, even with a huge number of photon packages.

  3. Why do Physicists Love Charge-Transfer Salts? (United States)

    Singleton, John


    I describe some of the phenomena encountered in charge-transfer salts that make them very attractive for condensed-matter physicists. These materials exhibit many interesting electronic properties, including reduced dimensionality, strong electron-electron and electron-phonon interactions and the proximity of antiferromagnetism, insulator states and superconductivity. A wide variety of low-temperature groundstates have been observed in the salts; frequently, one is able to move between these states by applying magnetic field, temperature, pressure or "chemical pressure". In spite of this complex behavior, the charge-transfer salts possess very simple electronic bandstructure which it is often possible to measure in great detail. Hence, one can use the salts as "model systems" in which tractable theoretical calculations for phenomena such as superconductivity are compared directly with experiment.

  4. Charge transfer in conjugated oligomers encapsulated into carbon nanotubes

    Energy Technology Data Exchange (ETDEWEB)

    Almadori, Y.; Alvarez, L.; Michel, T.; Le Parc, R.; Bantignies, J.L.; Hermet, P.; Sauvajol, J.L. [Laboratoire Charles Coulomb UMR 5521, Universite Montpellier 2, 34095 Montpellier (France); Laboratoire Charles Coulomb UMR 5521, CNRS, 34095 Montpellier (France); Arenal, R. [Laboratoire d' Etude des Microstructures, CNRS-ONERA, 92322 Chatillon (France); Laboratorio de Microscopias Avanzadas, Instituto de Nanociencia de Aragon, U. Zaragoza, 50018 Zaragoza (Spain); Babaa, R. [Laboratoire de Chimie des Surfaces et Interfaces, CEA, IRAMIS, SPCSI, 91191 Gif-sur-Yvette Cedex (France); Chemical Engineering Department, University of Technology PETRONAS, UTP, Ipoh-Perak (Malaysia); Jouselme, B.; Palacin, S. [Laboratoire de Chimie des Surfaces et Interfaces, CEA, IRAMIS, SPCSI, 91191 Gif-sur-Yvette Cedex (France)


    This study deals with a hybrid system consisting in quaterthiophene derivative encapsulated inside single-walled and multi-walled carbon nanotubes. Investigations of the encapsulation step are performed by transmission electron microscopy. Raman spectroscopy data point out different behaviors depending on the laser excitation energy with respect to the optical absorption of quaterthiophene. At low excitation energy (far from the oligomer resonance window) there is no significant modification of the Raman spectra before and after encapsulation. By contrast, at high excitation energy (close to the oligomer resonance window), Raman spectra exhibit a G-band shift together with an important RBM intensity loss, suggesting a significant charge transfer between the inserted molecule and the host nanotubes. Those results suggest a photo induced process leading to a significant charge transfer. (Copyright copyright 2011 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  5. Charge Transfer Plasmons: Optical Frequency Conductances and Tunable Infrared Resonances. (United States)

    Wen, Fangfang; Zhang, Yue; Gottheim, Samuel; King, Nicholas S; Zhang, Yu; Nordlander, Peter; Halas, Naomi J


    A charge transfer plasmon (CTP) appears when an optical-frequency conductive pathway between two metallic nanoparticles is established, enabling the transfer of charge between nanoparticles when the plasmon is excited. Here we investigate the properties of the CTP in a nanowire-bridged dimer geometry. Varying the junction geometry controls its conductance, which modifies the resonance energies and scattering intensities of the CTP while also altering the other plasmon modes of the nanostructure. Reducing the junction conductance shifts this resonance to substantially lower energies in the near- and mid-infrared regions of the spectrum. The CTP offers both a high-information probe of optical frequency conductances in nanoscale junctions and a new, unique approach to controllably engineering tunable plasmon modes at infrared wavelengths.

  6. Understanding Charge Transfer in Carbon Nanotube–Fullerene Bulk Heterojunctions

    Energy Technology Data Exchange (ETDEWEB)

    Gong, Maogang; Shastry, Tejas A.; Cui, Qiannan; Kohlmeyer, Ryan R. [National Research Council, Washington, D.C. 20001, United States; Soft; Luck, Kyle A.; Rowberg, Andrew; Marks, Tobin J.; Durstock, Michael F. [Soft; Zhao, Hui; Hersam, Mark C.; Ren, Shenqiang


    Semiconducting single-walled carbon nanotube/fullerene bulk heterojunctions exhibit unique optoelectronic properties highly suitable for flexible, efficient, and robust photovoltaics and photodetectors. We investigate charge-transfer dynamics in inverted devices featuring a polyethylenimine-coated ZnO nanowire array infiltrated with these blends and find that trap-assisted recombination dominates transport within the blend and at the active layer/nanowire interface. We find that electrode modifiers suppress this recombination, leading to high performance.

  7. Excited state charge transfer reaction in (mixed solvent + electrolyte ...

    Indian Academy of Sciences (India)

    charge transfer reaction of 4-(1-azetidinyl)benzonitrile (P4C) in two sets of mixed solvents, (1-propanol + ethyl acetate) and (propylene ...... Harun Al Rasid Gazi and Ranjit Biswas. PrOH+EA. Normalized F.I.. 0. 1. Normalized F.I.. 0. 1. -3. 0. 3. 3000. 4000. 5000. 6000. Residual. -3. 0. 3. Residual. -3. 0. 3. Time(ps). 3000. 4000.

  8. SKIRT: Hybrid parallelization of radiative transfer simulations (United States)

    Verstocken, S.; Van De Putte, D.; Camps, P.; Baes, M.


    We describe the design, implementation and performance of the new hybrid parallelization scheme in our Monte Carlo radiative transfer code SKIRT, which has been used extensively for modelling the continuum radiation of dusty astrophysical systems including late-type galaxies and dusty tori. The hybrid scheme combines distributed memory parallelization, using the standard Message Passing Interface (MPI) to communicate between processes, and shared memory parallelization, providing multiple execution threads within each process to avoid duplication of data structures. The synchronization between multiple threads is accomplished through atomic operations without high-level locking (also called lock-free programming). This improves the scaling behaviour of the code and substantially simplifies the implementation of the hybrid scheme. The result is an extremely flexible solution that adjusts to the number of available nodes, processors and memory, and consequently performs well on a wide variety of computing architectures.

  9. Accumulative electron transfer: multiple charge separation in artificial photosynthesis. (United States)

    Karlsson, Susanne; Boixel, Julien; Pellegrin, Yann; Blart, Errol; Becker, Hans-Christian; Odobel, Fabrice; Hammarström, Leif


    To achieve artificial photosynthesis it is necessary to couple the single-electron event of photoinduced charge separation with the multi-electron reactions of fuel formation and water splitting. Therefore, several rounds of light-induced charge separation are required to accumulate enough redox equivalents at the catalytic sites for the target chemistry to occur, without any sacrificial donors or acceptors other than the catalytic substrates. Herein, we discuss the challenges of such accumulative electron transfer in molecular systems. We present a series of closely related systems base on a Ru(II)-polypyridine photosensitizer with appended triaryl-amine or oligo-triaryl-amine donors, linked to nanoporous TiO2 as the acceptor. One of the systems, based on dye 4, shows efficient accumulative electron transfer in high overall yield resulting in the formation of a two-electron charge-separated state upon successive excitation by two photons. In contrast, the other systems do not show accumulative electron transfer because of different competing reactions. This illustrates the difficulties in designing successful systems for this still largely unexplored type of reaction scheme.

  10. Band Alignment and Charge Transfer in Complex Oxide Interfaces

    Directory of Open Access Journals (Sweden)

    Zhicheng Zhong


    Full Text Available The synthesis of transition metal heterostructures is currently one of the most vivid fields in the design of novel functional materials. In this paper, we propose a simple scheme to predict band alignment and charge transfer in complex oxide interfaces. For semiconductor heterostructures, band-alignment rules like the well-known Anderson or Schottky-Mott rule are based on comparison of the work function or electron affinity of the bulk components. This scheme breaks down for oxides because of the invalidity of a single work-function approximation as recently shown in [Phys. Rev. B 93, 235116 (2016PRBMDO2469-995010.1103/PhysRevB.93.235116; Adv. Funct. Mater. 26, 5471 (2016AFMDC61616-301X10.1002/adfm.201600243]. Here, we propose a new scheme that is built on a continuity condition of valence states originating in the compounds’ shared network of oxygen. It allows for the prediction of sign and relative amplitude of the intrinsic charge transfer, taking as input only information about the bulk properties of the components. We support our claims by numerical density functional theory simulations as well as (where available experimental evidence. Specific applications include (i controlled doping of SrTiO_{3} layers with the use of 4d and 5d transition metal oxides and (ii the control of magnetic ordering in manganites through tuned charge transfer.

  11. Electromagnetic radiation from linearly and nonlinearly oscillating charge drops (United States)

    Grigor'ev, A. I.; Shiryaeva, S. O.


    It has been shown that analytic calculations of the intensity of electromagnetic radiation from an oscillating charged drop in the approximation linear in the oscillation amplitude (small parameter is on the order of 0.1) give only the quadrupole component of the total radiation. The dipole component can only be obtained in calculations using higher-order approximations. Nevertheless, the intensity of the dipole radiation turns out to be substantially higher (by 14-15 orders of magnitude). This is because the decomposition of radiation from a system of charges into multipole components (differing even in the rates of decrease in the potential with the distance) is carried out using the expansion in a substantially smaller parameter, viz., the ratio of the size of the emitting system (in our case, a drop of radius 10 μm) to the distance to the point of observation in the wave zone of the emission of radiation (emitted wavelength) of 100-1000 m. As a result, this second small parameter is on the order of 10-7 to 10-8. On the other hand, in accordance with the field theory, the ratio of intensities of quadrupole and dipole radiations is proportional to the squared ratio of the hydrodynamic velocity of the oscillating surface of a charged drop to the velocity of propagation of an electromagnetic signal in vacuum (velocity of light), which yields a ratio of 10-14 to 10-15.

  12. Efficient charge generation by relaxed charge-transfer states at organic interfaces

    KAUST Repository

    Vandewal, Koen


    Interfaces between organic electron-donating (D) and electron-accepting (A) materials have the ability to generate charge carriers on illumination. Efficient organic solar cells require a high yield for this process, combined with a minimum of energy losses. Here, we investigate the role of the lowest energy emissive interfacial charge-transfer state (CT1) in the charge generation process. We measure the quantum yield and the electric field dependence of charge generation on excitation of the charge-transfer (CT) state manifold via weakly allowed, low-energy optical transitions. For a wide range of photovoltaic devices based on polymer:fullerene, small-molecule:C60 and polymer:polymer blends, our study reveals that the internal quantum efficiency (IQE) is essentially independent of whether or not D, A or CT states with an energy higher than that of CT1 are excited. The best materials systems show an IQE higher than 90% without the need for excess electronic or vibrational energy. © 2014 Macmillan Publishers Limited.

  13. Mouse brain responses to charged particle radiation (United States)

    Nelson, Gregory; Nelson, Gregory; Chang, Polly; Favre, Cecile; Fike, John; Mao, Xiao-Wen; Obenaus, Andre; Pecaut, Michael; Vlkolinsky, Roman; Song, Sheng-Kwei; Spigelman, Igor; Stampanoni, Marco

    CHANGES IN DISEASE LATENCY AND HOMEOSTASIS: 1) APP23 transgenic mice exhibit many of the pathological features of Alzheimer's Disease, and the disease progression is continuous over several months. Electrophysiological measurements have shown that disease-related decreases in synaptic efficacy occur earlier in irradiated APP23 animals. 2) Using vascular polymer cast technology combined with micro-tomographic imaging, microvasculature changes following irradiation have been detected and are consistent with loss of vessels and an increased spacing between them. The time course of vessel changes to control and irradiated animals is being constructed. 3) In order to assess the ability of the brain to respond to external environmental shocks and restore orderly normal function (homeostasis), we apply a controlled septic shock by treating animals with lipopolysaccharide (LPS). We find that in irradiated animals, the patterns of electrophysiological changes associated with reactions to lipopolysaccharide (LPS) are complex and unlike those of either LPS or irradiation alone. They further suggest that the brain continues to remodel for up to 6 months following radiation. This is consistent with the idea that irradiation may potentiate the risks from late secondary insults.

  14. Quantum Charge Transfer Study of Triply Charged Ions in the Adiabatic Representation: the (BHe3+ System

    Directory of Open Access Journals (Sweden)

    López-Castillo A.


    Full Text Available Full quantum charge transfer study of the process B3+ + He -> B2+ + He+ has been investigated in the collision energy range 1-102 eV using an ab-initio interaction potential. A new method to solve the Schrödinger equation in an adiabatic basis was used, where the radial and rotational coupling were taken into account, and the importance of the coupling between states of different symmetry was discussed. Moreover, by using the well known Landau-Zener model, it was concluded that the two state model cannot be applied for the present system, and this might indicate that such a model should be applied carefully for other systems when a charge transfer process is considered. Finally, the quantum total cross sections were compared with the previous published work of Gargaud and co-workers and a fair agreement was achieved.

  15. Super-iron Nanoparticles with Facile Cathodic Charge Transfer

    Energy Technology Data Exchange (ETDEWEB)

    M Farmand; D Jiang; B Wang; S Ghosh; D Ramaker; S Licht


    Super-irons contain the + 6 valence state of iron. One advantage of this is that it provides a multiple electron opportunity to store additional battery charge. A decrease of particle size from the micrometer to the nanometer domain provides a higher surface area to volume ratio, and opportunity to facilitate charge transfer, and improve the power, voltage and depth of discharge of cathodes made from such salts. However, super-iron salts are fragile, readily reduced to the ferric state, with both heat and contact with water, and little is known of the resultant passivating and non-passivating ferric oxide products. A pathway to decrease the super-iron particle size to the nano-domain is introduced, which overcomes this fragility, and retains the battery capacity advantage of their Fe(VI) valence state. Time and power controlled mechanosynthesis, through less aggressive, dry ball milling, leads to facile charge transfer of super-iron nanoparticles. Ex-situ X-ray Absorption Spectroscopy is used to explore the oxidation state and structure of these iron oxides during discharge and shows the significant change in stability of the ferrate structure to lower oxidation state when the particle size is in the nano-domain.

  16. Polaron assisted charge transfer in model biological systems (United States)

    Li, Guangqi; Movaghar, Bijan


    We use a tight binding Hamiltonian to simulate the electron transfer from an initial charge-separating exciton to a final target state through a two-arm transfer model. The structure is copied from the model frequently used to describe electron harvesting in photosynthesis (photosystems I). We use this network to provide proof of principle for dynamics, in quantum system/bath networks, especially those involving interference pathways, and use these results to make predictions on artificially realizable systems. Each site is coupled to the phonon bath via several electron-phonon couplings. The assumed large energy gaps and weak tunneling integrals linking the last 3 sites give rise to"Stark Wannier like" quantum localization; electron transfer to the target cluster becomes impossible without bath coupling. As a result of the electron-phonon coupling, local electronic energies relax when the site is occupied, and transient polaronic states are formed as photo-generated electrons traverse the system. For a symmetric constructively interfering two pathway network, the population is shared equally between two sets of equivalent sites and therefore the polaron energy shift is smaller. The smaller energy shift however makes the tunnel transfer to the last site slower or blocks it altogether. Slight disorder (or thermal noise) can break the symmetry, permitting essentially a "one path", and correspondingly more efficient transfer.

  17. A stochastic formation of radiative transfer in clouds

    Energy Technology Data Exchange (ETDEWEB)

    Stephens, G.L.; Gabriel, P.M.


    The research carried out under this award dealt with issues involving deterministic radiative transfer, remote sensing, Stochastic radiative transfer, and parameterization of cloud optical properties. A number of different forms of radiative transfer models in one, two, and three dimensions were developed in an attempt to build an understanding of the radiative transfer in clouds with realistic spatial structure and to determine the key geometrical parameter that influence this transfer. The research conducted also seeks to assess the relative importance of these geometrical effects in contrast to microphysical effects of clouds. The main conclusion of the work is that geometry has a profound influence on all aspects of radiative transfer and the interpretation of this transfer. We demonstrate how this geometry can influence estimate of particle effective radius to the 30-50% level and also how geometry can significantly bias the remote sensing of cloud optical depth.

  18. Radiative Transfer on Mesoscopic Spatial Scales (United States)

    Gardner, Adam Ronald

    Accurate predictions of light transport produced by illumination of turbid media such as biological tissues, cloudy atmospheres, terrestrial surfaces, and soft matter is essential in many applications including remote sensing, functional optical imaging, realistic image synthesis, and materials characterization. The inability to model light transport on mesoscopic scales limits the spatial resolution and information content that can be extracted from optical measurements. While effective approaches exist to model light transport in singly- and diffusely-scattering regimes, modeling light propagation over the mesoscopic spatial scales remains an important challenge. Radiative transfer on these scales must account for the complete 5-dimensional spatial and angular distributions of the radiant field. Here, we present novel stochastic and analytic methods to analyze and predict light propagation in turbid media generated by collimated illumination on mesoscopic scales. We also consider coupled transport problems, resulting from illumination and detection, to facilitate measurement design and inverse problems. Specifically, we introduce a coupled Forward-Adjoint Monte Carlo (cFAMC) method that leverages generalized optical reciprocity to enable the computation of spatially-resolved distributions of light interrogation for specific source-detector pairs. cFAMC can aid the design of optical diagnostic measurements by tailoring the light field to interrogate specific sub-volumes of interest. We use cFAMC to examine the effects of angular resolution on the resulting interrogation distributions and analyze a diagnostically-relevant compact fiber probe design for the detection of epithelial precancer. While Monte Carlo simulation is considered a gold standard method to solve the equation of radiative transfer (ERT), it is computationally expensive. Thus, methods to obtain ERT solutions at lower computational cost are valuable. We introduce a general analytical framework to

  19. Charge transfer and polarization screening at organic-metal interfaces

    Energy Technology Data Exchange (ETDEWEB)

    Peisert, Heiko; Kolacyak, Daniel; Chasse, Thomas [University of Tuebingen (Germany). Institute of Physical and Theoretical Chemistry


    Core hole screening effects at organic/metal interfaces were studied using core level X-ray photoemission spectroscopy (XPS), x-ray excited Auger electron spectroscopy (XAES) and valence band ultraviolet photoemission spectroscopy (UPS). The comparison of energetic shifts in XPS and XAES enables the estimation of electronic relaxation energy (screening ability). Magnesium phthalocyanine (MgPc), zinc phthalocyanine (ZnPc) and perfluorinated zinc phthalocyanine (ZnPcF16) evaporated on single crystalline Au(100) were used as model molecules. Two different features in the metal Auger spectra can be clearly separated for (sub-)monolayer coverages while only minor changes of the shape of corresponding photoemission features are observed. In contrast, Auger spectra of fluorine in ZnPcF16 do not show different components for ultrathin films. Applying a dielectric continuum model, the major screening mechanism cannot be described sufficiently by polarization screening due to mirror charges, significant contributions by charge transfer screening have to be considered.

  20. Charge transfer and transport in polymer-fullerene solar cells

    Energy Technology Data Exchange (ETDEWEB)

    Parisi, J.; Dyakonov, V.; Pientka, M.; Riedel, I.; Deibel, C. [Faculty of Physics, Dept. of Energy and Semiconductor Research, Univ. of Oldenburg, Oldenburg (Germany); Brabec, C.J. [Faculty of Physics, Dept. of Energy and Semiconductor Research, Univ. of Oldenburg, Oldenburg (Germany); Siemens AG, CT MM1 Innovative Polymers, Erlangen (Germany); Sariciftci, N.S. [Faculty of Physics, Dept. of Energy and Semiconductor Research, Univ. of Oldenburg, Oldenburg (Germany); Inst. of Physical Chemistry and Linz Inst. of Organic Solar Cells, Univ. of Linz, Linz (Austria); Hummelen, J.C. [Faculty of Physics, Dept. of Energy and Semiconductor Research, Univ. of Oldenburg, Oldenburg (Germany); Stratingh Inst. and Materials Research Center, Univ. of Groningen, Groningen (Netherlands)


    The development of polymer-fullerene plastic solar cells has made significant progress in recent years. These devices excel by an efficient charge generation process as a consequence of a photo-induced charge transfer between the photo-excited conjugated polymer donor and acceptor-type fullerene molecules. Due to the paramagnetic nature of the radical species, the photo-induced charge transfer can be analyzed by the help of light-induced electron spin resonance spectroscopy. Upon looking at an interpenetrating donor-acceptor composite consisting of the polymer MDMO-PPV and the fullerene derivative PCBM, we disclose two well separated line groups having a strongly anisotropic structure. The line shape can be attributed to an environmental axial symmetry of the polymer cation and a lower rhombohedric symmetry of the fullerene anion. Since the signals were found to be independent of one another with different spin-lattice relaxation times, the radical species can be discriminated via separate characterization procedures. In order to study the bulk charge transport properties, we carried out admittance spectroscopy on the polymer-fullerene solar cell device including a transparent semiconductor oxide front contact (ITO/PEDOT:PSS) and a metal back contact (Al). The temperature- and frequency-dependent device capacitance clearly uncovers two different defect states, the first, having an activation energy of 9 meV, indicates a shallow trap due to a bulk impurity, the latter, having an activation energy of 177 meV, can be assigned to an interfacial defect state located between the polymer-fullerene composite and the metal back contact. (orig.)

  1. Tunable charge transfer properties in metal-phthalocyanine heterojunctions. (United States)

    Siles, P F; Hahn, T; Salvan, G; Knupfer, M; Zhu, F; Zahn, D R T; Schmidt, O G


    Organic materials such as phthalocyanine-based systems present a great potential for organic device applications due to the possibility of integrating films of different organic materials to create organic heterostructures which combine the electrical capabilities of each material. This opens the possibility to precisely engineer and tune new electrical properties. In particular, similar transition metal phthalocyanines demonstrate hybridization and charge transfer properties which could lead to interesting physical phenomena. Although, when considering device dimensions, a better understanding and control of the tuning of the transport properties still remain in the focus of research. Here, by employing conductive atomic force microscopy techniques, we provide an insight about the nanoscale electrical properties and transport mechanisms of MnPc and fluorinated phthalocyanines such as F16CuPc and F16CoPc. We report a transition from typical diode-like transport mechanisms for pure MnPc thin films to space-charge-limited current transport regime (SCLC) for Pc-based heterostructures. The controlled addition of fluorinated phthalocyanine also provides highly uniform and symmetric-polarized transport characteristics with conductance enhancements up to two orders of magnitude depending on the polarization. We present a method to spatially map the mobility of the MnPc/F16CuPc structures with a nanoscale resolution and provide theoretical calculations to support our experimental findings. This well-controlled nanoscale tuning of the electrical properties for metal transition phthalocyanine junctions stands as key step for future phthalocyanine-based electronic devices, where the low dimension charge transfer, mediated by transition metal atoms could be intrinsically linked to a transfer of magnetic moment or spin.

  2. Influence of radiation heat transfer during a severe accident

    Energy Technology Data Exchange (ETDEWEB)

    Cazares R, R. I.; Epinosa P, G.; Varela H, J. R.; Vazquez R, A. [Universidad Autonoma Metropolitana, Unidad Iztapalapa, San Rafael Atlixco No. 186, Col. Vicentina, 09340 Ciudad de Mexico (Mexico); Polo L, M. A., E-mail: [Comision Nacional de Seguridad Nuclear y Salvaguardias, Dr. Barragan No. 779, Col. Narvarte, 03020 Ciudad de Mexico (Mexico)


    The aim of this work is to determine the influence of the radiation heat transfer on an average fuel channel during a severe accident of a BWR nuclear power plant. The analysis considers the radiation heat transfer in a participating medium, where the gases inside the system participate in the radiation heat transfer. We consider the steam-water mixture as an isothermal gray gas, and the boundaries of the system as a gray diffuse isothermal surface for the clad and refractory surfaces for the rest, and consider the average fuel channel as an enclosure system. During a severe accident, generation and diffusion of hydrogen begin at high temperature range (1,273 to 2,100 K), and the fuel rod cladding oxidation, but the hydrogen generated do not participate in the radiation heat transfer because it does not have any radiation properties. The heat transfer process in the fuel assembly is considered with a reduced order model, and from this, the convection and the radiation heat transfer is introduced in the system. In this paper, a system with and without the radiation heat transfer term was calculated and analyzed in order to obtain the influence of the radiation heat transfer on the average fuel channel. We show the behavior of radiation heat transfer effects on the temporal evolution of the hydrogen concentration and temperature profiles in a fuel assembly, where a stream of steam is flowing. Finally, this study is a practical complement for more accurate modeling of a severe accident analysis. (Author)

  3. SAFARI 2000 Surface Atmospheric Radiative Transfer (SMART), Dry Season 2000 (United States)

    National Aeronautics and Space Administration — ABSTRACT: Surface-sensing Measurements for Radiative Transfer (SMART) and Chemical, Optical, and Microphysical Measurements of In-situ Troposphere (COMMIT) consist...


    Energy Technology Data Exchange (ETDEWEB)

    Blandford, R


    Accretion onto compact objects plays a central role in high energy astrophysics. In these environments, both general relativistic and plasma effects may have significant impacts upon the spectral and polarimetric properties of the accretion flow. In paper I we presented a fully general relativistic magnetoionic theory, capable of tracing rays in the geometric optics approximation through a magnetized plasma in the vicinity of a compact object. In this paper we discuss how to perform polarized radiative transfer along these rays. In addition we apply the formalism to a barotropic thick disk model, appropriate for low luminosity active galactic nuclei. We find that it is possible to generate large fractional polarizations over the innermost portions of the accretion flow, even when the emission mechanism is unpolarized. This has implications for accreting systems ranging from pulsars and X-ray binaries to AGN.

  5. Positron Annihilation in Solid Charge-Transfer Complexes

    DEFF Research Database (Denmark)

    Lévay, B.; Jansen, P.


    Positron lifetime and angular correlation measurements have been carried out on 1:1 charge-transfer complexes, on their pure donor and acceptor components and on the 1:1 M mechanical mixtures of these components. Complex formation reduced the intensity of the long-lifetime component of the donor ...... compounds nearly to the low level of the acceptors. The angular correlation curves obtained for the pure acceptor and the complex were practically identical and were substantially broadened as compared to that of the donor....

  6. Optics of Chromites and Charge-Transfer Transitions

    Directory of Open Access Journals (Sweden)

    Andrei V. Zenkov


    Full Text Available Specific features of the charge-transfer (CT states and O2p→Cr3d transitions in the octahedral (CrO69− complex are considered in the cluster approach. The reduced matrix elements of the electric-dipole transition operator are calculated on many-electron wave functions of the complex corresponding to the initial and final states of a CT transition. Modeling the optic spectrum of chromites has yielded a complicated CT band. The model spectrum is in satisfactory agreement with experimental data which demonstrates the limited validity of the generally accepted concept of a simple structure of CT spectra.

  7. Photoinduced charge accumulation by metal ion-coupled electron transfer. (United States)

    Bonn, Annabell G; Wenger, Oliver S


    An oligotriarylamine (OTA) unit, a Ru(bpy)3(2+) photosensitizer moiety (Ru), and an anthraquinone (AQ) entity were combined to a molecular dyad (Ru-OTA) and a molecular triad (AQ-Ru-OTA). Pulsed laser excitation at 532 nm led to the formation of charge-separated states of the type Ru(-)-OTA(+) and AQ(-)-Ru-OTA(+) with lifetimes of ≤10 ns and 2.4 μs, respectively, in de-aerated CH3CN at 25 °C. Upon addition of Sc(OTf)3, very long-lived photoproducts were observed. Under steady-state irradiation conditions using a flux of (6.74 ± 0.21) × 10(15) photons per second at 450 nm, the formation of twofold oxidized oligotriarylamine (OTA(2+)) was detected in aerated CH3CN containing 0.02 M Sc(3+), as demonstrated unambiguously by comparison with UV-Vis absorption spectra obtained in the course of chemical oxidation with Cu(2+). Photodriven charge accumulation on the OTA unit of Ru-OTA and AQ-Ru-OTA is possible due to the lowering of the O2 reduction potential caused by the interaction of superoxide with the strong Lewis acid Sc(3+). The presence of the anthraquinone unit in AQ-Ru-OTA accelerates the rate-determining reaction step for charge accumulation by a factor of 10 compared to the Ru-OTA dyad. This is attributed to the formation of Sc(3+)-stabilized anthraquinone radical anion intermediates in the triad. Possible mechanistic pathways leading to charge accumulation are discussed. Photodriven charge accumulation is of key importance for solar fuels because their production will have to rely on multi-electron chemistry rather than single-electron reaction steps. Our study is the first to demonstrate that metal ion-coupled electron transfer (MCET) can be exploited to accumulate charges on a given molecular unit using visible light as an energy input. The approach of using a combination of intra- and intermolecular electron transfer reactions which are enabled by MCET is conceptually novel, and the fundamental insights gained from our study are relevant in the greater

  8. Development of radiation hardened pixel sensors for charged particle detection

    CERN Document Server

    Koziel, Michal


    CMOS Pixel Sensors are being developed since a few years to equip vertex detectors for future high-energy physics experiments with the crucial advantages of a low material budget and low production costs. The features simultaneously required are a short readout time, high granularity and high tolerance to radiation. This thesis mainly focuses on the radiation tolerance studies. To achieve the targeted readout time (tens of microseconds), the sensor pixel readout was organized in parallel columns restricting in addition the readout to pixels that had collected the signal charge. The pixels became then more complex, and consequently more sensitive to radiation. Different in-pixel architectures were studied and it was concluded that the tolerance to ionizing radiation was limited to 300 krad with the 0.35- m fabrication process currently used, while the targeted value was several Mrad. Improving this situation calls for implementation of the sensors in processes with a smaller feature size which naturally imp...

  9. A Radiative Transfer Model for Climate Calculations (United States)

    Bergstrom, Robert W.; Mlawer, Eli J.; Sokolik, Irina N.; Clough, Shepard A.; Toon, Owen B.


    This paper describes a radiative transfer model developed to accurately predict the atmospheric radiant flux in both the infrared and the solar spectrum with a minimum of computational effort. We use a newly developed k-distribution model for both the thermal and solar parts of the spectrum. We employ a generalized two-stream approximation for the scattering by aerosol and clouds. To assess the accuracy of the model, the results are compared to other more detailed models for several standard cases in the solar and thermal spectrum. We perform several calculations focussing primarily on the question of absorption of solar radiation by gases and aerosols. We estimate the accuracy of the k-distribution to be approx. 1 W/sq m for the gaseous absorption in the solar spectrum. We estimate the accuracy of the two-stream method to be 3-12 W/sq m for the downward solar flux and 1-5 W/sq m for the upward solar flux at the top of atmosphere depending on the optical depth of the aerosol layer. We also show that the effect of ignoring aerosol absorption on the downward solar flux at the surface is 50 W/sq m for the TARFOX aerosol for an optical depth of 0.5 and 150 W/sq m for a highly absorbing mineral aerosol. Thus, we conclude that the uncertainty introduced by the aerosol solar radiative properties (and merely assuming some "representative" model) can be considerably larger than the error introduced by the use of a two-stream method.

  10. Scattering of Non-Relativistic Charged Particles by Electromagnetic Radiation (United States)

    Apostol, M.


    The cross-section is computed for non-relativistic charged particles (like electrons and ions) scattered by electromagnetic radiation confined to a finite region (like the focal region of optical laser beams). The cross-section exhibits maxima at scattering angles given by the energy and momentum conservation in multi-photon absorption or emission processes. For convenience, a potential scattering is included and a comparison is made with the well-known Kroll-Watson scattering formula. The scattering process addressed in this paper is distinct from the process dealt with in previous studies, where the scattering is immersed in the radiation field.

  11. Analytical Study for the Charge-Transfer Complexes of Pregabalin

    Directory of Open Access Journals (Sweden)

    Hesham Salem


    Full Text Available Studies were carried out, for the first time, to investigate the charge-transfer reactions of Pregabalin (PRE as n-electron donor with various π-acceptors: 7,7,8,8-tetracyanoquinodimethane (TCNQ, 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ, 2,5-dichloro-3,6-dihydroxy-1,4-benzoquinone (chloranilic acid, pCA, tetracyanoethylene (TCNE and 2,3,5,6-tetrachloro-1,4-benzoquinone (chloranil. Different colored charge-transfer complexes and radical anions were obtained. Different variables affecting the reactions were studied and optimized. The formations of the colored complexes were utilized in the development of simple, rapid and accurate spectrophotometric methods for the analysis of PRE in pure form as well as in its pharmaceutical preparation. Under the optimum reaction conditions, linear relationships with good correlation coefficients (0.9995-0.9999 were found between the absorbance and the concentrations of PRE in the range of 8-400 µg mL-1. The limits of assays detection ranged from 0.60 to 8.11 µg mL-1. No interference could be observed from the additives commonly present in the capsules. The methods were successfully applied to the analysis of capsules that contain PRE, with good accuracy and precision; the recovery percentages ranged from 100.19±0.83 to 100.50±0.53. The results were compared favorably with the reported method.

  12. Transfer RNA: a dancer between charging and mis-charging for protein biosynthesis. (United States)

    Zhou, Xiaolong; Wang, Enduo


    Transfer RNA plays a fundamental role in the protein biosynthesis as an adaptor molecule by functioning as a biological link between the genetic nucleotide sequence in the mRNA and the amino acid sequence in the protein. To perform its role in protein biosynthesis, it has to be accurately recognized by aminoacyl-tRNA synthetases (aaRSs) to generate aminoacyl-tRNAs (aa-tRNAs). The correct pairing between an amino acid with its cognate tRNA is crucial for translational quality control. Production and utilization of mis-charged tRNAs are usually detrimental for all the species, resulting in cellular dysfunctions. Correct aa-tRNAs formation is collectively controlled by aaRSs with distinct mechanisms and/or other trans-factors. However, in very limited instances, mis-charged tRNAs are intermediate for specific pathways or essential components for the translational machinery. Here, from the point of accuracy in tRNA charging, we review our understanding about the mechanism ensuring correct aa-tRNA generation. In addition, some unique mis-charged tRNA species necessary for the organism are also briefly described.

  13. Effects of radiation on charge-coupled devices (United States)

    Carnes, J. E.; Cope, A. D.; Rockett, L. R.; Schlesier, K. M.


    The effects of 1 MeV electron irradiation upon the performance of two phase, polysilicon aluminum gate CCDs are reported. Both n- and p-surface channel and n-buried channel devices are investigated using 64- and 128-stage line arrays. Characteristics measured as a function of radiation dose include: Transfer inefficiency, threshold voltage, field effect mobility, interface state density, full well signal level and dark current. Surface channel devices are found to degrade considerably at less than 10 to the 5th power rads (Si) due to the large increase in fast interface state density caused by radiation. Buried channel devices maintain efficient operation to the highest dose levels used.

  14. Comparing the Effect of Radiative Transfer Schemes on Convection Simulations


    Tanner, Joel D.; Basu, Sarbani; Demarque, Pierre


    We examine the effect of different radiative transfer schemes on the properties of 3D simulations of near-surface stellar convection in the superadiabatic layer, where energy transport transitions from fully convective to fully radiative. We employ two radiative transfer schemes that fundamentally differ in the way they cover the 3D domain. The first solver approximates domain coverage with moments, while the second solver samples the 3D domain with ray integrations. By comparing simulations ...

  15. Study on radiation transfer in human skin for cosmetics (United States)

    Yamada, Jun; Kawamura, Ayumu; Miura, Yoshimasa; Takata, Sadaki; Ogawa, Katsuki


    In order to design cosmetics producing the optical properties that are required for a beautiful skin, the radiation transfer in the skin has been numerically investigated by the Monte Carlo method and the effects of skin texture and cosmetics on the radiation transfer have been empirically investigated using an artificial skin. The numerical analysis showed that the total internal reflection suppresses large portion of radiation going out through the skin surface Additionally, the experimental study revealed that skin texture and cosmetics not only diffusely reflect the incoming radiation, but also lead the internally reflected radiation to the outside of the skin.

  16. 21 CFR 892.5050 - Medical charged-particle radiation therapy system. (United States)


    ... 21 Food and Drugs 8 2010-04-01 2010-04-01 false Medical charged-particle radiation therapy system...-particle radiation therapy system. (a) Identification. A medical charged-particle radiation therapy system...) intended for use in radiation therapy. This generic type of device may include signal analysis and display...

  17. Free convection effects and radiative heat transfer in MHD Stokes ...

    Indian Academy of Sciences (India)

    which controls the gasification rate of the energetic material for estimating heat transfer. Radiation effect on flow and heat transfer is important in the context of space technology and processes involving high temperature. In recent years, the problems of free convective and heat transfer flows through a porous medium under ...

  18. Impact of charge-transfer excitons in regioregular polythiophene on the charge separation at polythiophene-fullerene heterojunctions (United States)

    Polkehn, M.; Tamura, H.; Burghardt, I.


    This study addresses the mechanism of ultrafast charge separation in regioregular oligothiophene-fullerene assemblies representative of poly-3-hexylthiophene (P3HT)-[6,6]-phenyl-C61 butyric acid methyl ester (PCBM) heterojunctions, with special emphasis on the inclusion of charge transfer excitons in the oligothiophene phase. The formation of polaronic inter-chain charge separated species in highly ordered oligothiophene has been demonstrated in recent experiments and could have a significant impact on the net charge transfer to the fullerene acceptor. The present approach combines a first-principles parametrized multi-site Hamiltonian, based on time-dependent density functional theory calculations, with accurate quantum dynamics simulations using the multi-layer multi-configuration time-dependent Hartree method. Quantum dynamical studies are carried out for up to 182 electronic states and 112 phonon modes. The present analysis follows up on our previous study of (Huix-Rotllant et al 2015 J. Phys. Chem. Lett. 6 1702) and significantly expands the scope of this analysis by including the dynamical role of charge transfer excitons. Our investigation highlights the pronounced mixing of photogenerated Frenkel excitons with charge transfer excitons in the oligothiophene domain, and the opening of new transfer channels due the creation of such charge-separated species. As a result, it turns out that the interfacial donor/acceptor charge transfer state can be largely circumvented due to the presence of charge transfer excitons. However, the latter states in turn act as a trap, such that the free carrier yield observed on ultrafast time scales is tangibly reduced. The present analysis underscores the complexity of the transfer pathways at P3HT-PCBM type junctions.

  19. Positron annihilation studies of some charge transfer molecular complexes

    CERN Document Server

    El-Sayed, A; Boraei, A A A


    Positron annihilation lifetimes were measured for some solid charge transfer (CT) molecular complexes of quinoline compounds (2,6-dimethylquinoline, 6-methoxyquinoline, quinoline, 6-methylquinoline, 3-bromoquinoline and 2-chloro-4-methylquinoline) as electron donor and picric acid as an electron acceptor. The infrared spectra (IR) of the solid complexes clearly indicated the formation of the hydrogen-bonding CT-complexes. The annihilation spectra were analyzed into two lifetime components using PATFIT program. The values of the average and bulk lifetimes divide the complexes into two groups according to the non-bonding ionization potential of the donor (electron donating power) and the molecular weight of the complexes. Also, it is found that the ionization potential of the donors and molecular weight of the complexes have a conspicuous effect on the average and bulk lifetime values. The bulk lifetime values of the complexes are consistent with the formation of stable hydrogen-bonding CT-complexes as inferred...

  20. Self-interaction effects on charge-transfer collisions

    CERN Document Server

    Quashie, Edwin E; Andrade, Xavier; Correa, Alfredo A


    In this article, we investigate the role of the self-interaction error in the simulation of collisions using time-dependent density functional theory (TDDFT) and Ehrenfest dynamics. We compare many different approximations of the exchange and correlation potential, using as a test system the collision of $\\mathrm{H^+ + CH_4}$ at $30~\\mathrm{eV}$. We find that semi-local approximations, like PBE, and even hybrid functionals, like B3LYP, produce qualitatively incorrect predictions for the scattering of the proton. This discrepancy appears because the self-interaction error allows the electrons to jump too easily to the proton, leading to radically different forces with respect to the non-self-interacting case. From our results, we conclude that using a functional that is self-interaction free is essential to properly describe charge-transfer collisions between ions and molecules in TDDFT.

  1. Octahedral engineering of orbital polarizations in charge transfer oxides (United States)

    Cammarata, Antonio; Rondinelli, James M.


    Negative charge transfer ABO3 oxides may undergo electronic metal-insulator transitions (MIT) concomitant with a dilation and contraction of nearly rigid octahedra. On both sides of the MIT are in-phase or out-of-phase (or both) rotations of adjacent octahedra that buckle the B-O-B bond angle away from 180∘. Using density functional theory with the PBEsol +U approach, we describe an octahedral engineering avenue to control the B 3d and O 2p orbital polarization through enhancement of the BO6 rotation “sense” rather than solely through conventional changes to the B-O bond lengths, i.e., crystal field distortions. Using CaFeO3 as a prototypical material, we show the flavor of the octahedral rotation pattern when combined with strain-rotation coupling and thin film engineering strategies offers a promising avenue to fine tune orbital polarizations near electronic phase boundaries.

  2. Electromagnetic radiation of charged particles in stochastic motion (United States)

    Harko, Tiberiu; Mocanu, Gabriela


    The study of the Brownian motion of a charged particle in electric and magnetic fields has many important applications in plasma and heavy ions physics, as well as in astrophysics. In the present paper we consider the electromagnetic radiation properties of a charged non-relativistic particle in the presence of electric and magnetic fields, of an exterior non-electromagnetic potential, and of a friction and stochastic force, respectively. We describe the motion of the charged particle by a Langevin and generalized Langevin type stochastic differential equation. We investigate in detail the cases of the Brownian motion with or without memory in a constant electric field, in the presence of an external harmonic potential, and of a constant magnetic field. In all cases the corresponding Langevin equations are solved numerically, and a full description of the spectrum of the emitted radiation and of the physical properties of the motion is obtained. The power spectral density of the emitted power is also obtained for each case, and, for all considered oscillating systems, it shows the presence of peaks, corresponding to certain intervals of the frequency.

  3. Excitation of Terahertz Charge Transfer Plasmons in Metallic Fractal Structures (United States)

    Ahmadivand, Arash; Gerislioglu, Burak; Sinha, Raju; Vabbina, Phani Kiran; Karabiyik, Mustafa; Pala, Nezih


    There have been extensive researches on terahertz (THz) plasmonic structures supporting resonant modes to demonstrate nano and microscale devices with high efficiency and responsivity as well as frequency selectivity. Here, using antisymmetric plasmonic fractal Y-shaped (FYS) structures as building blocks, we introduce a highly tunable four-member fractal assembly to support charge transfer plasmons (CTPs) and classical dipolar resonant modes with significant absorption cross section in the THz domain. We first present that the unique geometrical nature of the FYS system and corresponding spectral response allow for supporting intensified dipolar plasmonic modes under polarised light exposure in a standalone structure. In addition to classical dipolar mode, for the very first time, we demonstrated CTPs in the THz domain due to the direct shuttling of the charges across the metallic fractal microantenna which led to sharp resonant absorption peaks. Using both numerical and experimental studies, we have investigated and confirmed the excitation of the CTP modes and highly tunable spectral response of the proposed plasmonic fractal structure. This understanding opens new and promising horizons for tightly integrated THz devices with high efficiency and functionality.

  4. Delocalization and dielectric screening of charge transfer states in organic photovoltaic cells

    National Research Council Canada - National Science Library

    Bernardo, B; Cheyns, D; Verreet, B; Schaller, R D; Rand, B P; Giebink, N C


    Charge transfer (CT) states at a donor-acceptor heterojunction have a key role in the charge photogeneration process of organic solar cells, however, the mechanism by which these states dissociate efficiently into free...

  5. Femtosecond insights into direct electron injection in dye anchored ZnO QDs following charge transfer excitation. (United States)

    Kumar, Pushpendra; Kumar, Sunil; Ghosh, Subrata; Pal, Suman Kalyan


    The role of the charge transfer (CT) state in interfacial electron transfer in dye-sensitized semiconductor nanocrystals is still poorly understood. To address this problem, femtosecond transient absorption (TA) spectroscopy is used as a probe to investigate the electron injection across a newly synthesized coumarin dye (8-hydroxy-2-oxo-4-phenyl-2 benzo[h]chromene-3-carbonitrile, coded BC5) and ZnO quantum dots (QDs). Steady state and time-resolved spectroscopic measurements reveal that BC5 dye interacts strongly with ZnO QDs in the ground state forming a CT complex. The BC5-ZnO QD complex absorbs more towards red compared to only the dye and QDs, and emits fluorescence due to radiative recombination of photogenerated charges. The formation of charges following the excitation of the CT complex has been demonstrated by observing the signature of dye radical cations and electrons in the conduction band (CB) of the QDs in the TA spectra. The TA signals of these charges grow sharply as a result of ultrafast direct electron injection into the QD. We have monitored the complete dynamics of photogenerated charges by measuring the TA signals of the charges up to a couple of nanoseconds. The injected electrons that are free or shallowly trapped recombine with a time constant of 625 fs, whereas deeply trapped electrons disappear slowly (526 ps) via radiative recombination. Furthermore, theoretical studies based on ab initio calculations have been carried out to complement the experimental findings.

  6. Investigations of Planet Formation with Combined Hydrodynamics and Radiative Transfer (United States)

    Jang-Condell, Hannah; Kloster, D.


    Our aim is to investigate how the dynamics of protoplanetary disks are affected by environmental factors such as the presence of a planetary-mass object orbiting at the midplane and the radiation produced by the disk's host star. To accomplish this task we utilize the finite-volume numerical code PLUTO (Mignone, et al. 2007) to compute the evolution of the disk as a magnetohydrodynamics (MHD) simulation in 3D spherical coordinates, combined with a radiative transfer code (Jang-Condell 2008). At each iteration of the PLUTO simulation we will apply the radiative transfer code to the disk profile to model both processes simultaneously. The combined MHD and radiative transfer simulation will provide us with a much more accurate description of protoplanetary disk evolution than either isolated disk MHD or static disk radiative transfer models could individually.

  7. Energy and Charge Transfer in Open Plasmonic Systems (United States)

    Thakkar, Niket

    Coherent and collective charge oscillations in metal nanoparticles (MNPs), known as localized surface plasmons, offer unprecedented control and enhancement of optical processes on the nanoscale. Since their discovery in the 1950's, plasmons have played an important role in understanding fundamental properties of solid state matter and have been used for a variety of applications, from single molecule spectroscopy to directed radiation therapy for cancer treatment. More recently, experiments have demonstrated quantum interference between optically excited plasmonic materials, opening the door for plasmonic applications in quantum information and making the study of the basic quantum mechanical properties of plasmonic structures an important research topic. This text describes a quantitatively accurate, versatile model of MNP optics that incorporates MNP geometry, local environment, and effects due to the quantum properties of conduction electrons and radiation. We build the theory from first principles, starting with a silver sphere in isolation and working our way up to complex, interacting plasmonic systems with multiple MNPs and other optical resonators. We use mathematical methods from statistical physics and quantum optics in collaboration with experimentalists to reconcile long-standing discrepancies amongst experiments probing plasmons in the quantum size regime, to develop and model a novel single-particle absorption spectroscopy, to predict radiative interference effects in entangled plasmonic aggregates, and to demonstrate the existence of plasmons in photo-doped semiconductor nanocrystals. These examples show more broadly that the theory presented is easily integrated with numerical simulations of electromagnetic scattering and that plasmonics is an interesting test-bed for approximate methods associated with multiscale systems.

  8. Doping graphene films via chemically mediated charge transfer

    Directory of Open Access Journals (Sweden)

    Ishikawa Ryousuke


    Full Text Available Abstract Transparent conductive films (TCFs are critical components of a myriad of technologies including flat panel displays, light-emitting diodes, and solar cells. Graphene-based TCFs have attracted a lot of attention because of their high electrical conductivity, transparency, and low cost. Carrier doping of graphene would potentially improve the properties of graphene-based TCFs for practical industrial applications. However, controlling the carrier type and concentration of dopants in graphene films is challenging, especially for the synthesis of p-type films. In this article, a new method for doping graphene using the conjugated organic molecule, tetracyanoquinodimethane (TCNQ, is described. Notably, TCNQ is well known as a powerful electron accepter and is expected to favor electron transfer from graphene into TCNQ molecules, thereby leading to p-type doping of graphene films. Small amounts of TCNQ drastically improved the resistivity without degradation of optical transparency. Our carrier doping method based on charge transfer has a huge potential for graphene-based TCFs.

  9. GLERL Radiation Transfer Through Freshwater Ice (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — Radiation transmittance (ratio of transmitted to incident radiation) through clear ice, refrozen slush ice and brash ice, from ice surface to ice-water interface in...

  10. Radiative transfer in atmosphere-sea ice-ocean system

    Energy Technology Data Exchange (ETDEWEB)

    Jin, Z.; Stamnes, K.; Weeks, W.F. [Univ. of Alaska, Fairbanks, AK (United States); Tsay, S.C. [NASA Goddard Space Flight Center, Greenbelt, MD (United States)


    Radiative energy is critical in controlling the heat and mass balance of sea ice, which significantly affects the polar climate. In the polar oceans, light transmission through the atmosphere and sea ice is essential to the growth of plankton and algae and, consequently, to the microbial community both in the ice and in the ocean. Therefore, the study of radiative transfer in the polar atmosphere, sea ice, and ocean system is of particular importance. Lacking a properly coupled radiative transfer model for the atmosphere-sea ice-ocean system, a consistent study of the radiative transfer in the polar atmosphere, snow, sea ice, and ocean system has not been undertaken before. The radiative transfer processes in the atmosphere and in the ice and ocean have been treated separately. Because the radiation processes in the atmosphere, sea ice, and ocean depend on each other, this separate treatment is inconsistent. To study the radiative interaction between the atmosphere, clouds, snow, sea ice, and ocean, a radiative transfer model with consistent treatment of radiation in the coupled system is needed and is under development.

  11. Charge Transfer and Support Effects in Heterogeneous Catalysis

    Energy Technology Data Exchange (ETDEWEB)

    Hervier, Antoine [Univ. of California, Berkeley, CA (United States)


    The kinetic, electronic and spectroscopic properties of two-dimensional oxide-supported catalysts were investigated in order to understand the role of charge transfer in catalysis. Pt/TiO2 nanodiodes were fabricated and used as catalysts for hydrogen oxidation. During the reaction, the current through the diode, as well as its I-V curve, were monitored, while gas chromatography was used to measure the reaction rate. The current and the turnover rate were found to have the same temperature dependence, indicating that hydrogen oxidation leads to the non-adiabatic excitation of electrons in Pt. A fraction of these electrons have enough energy to ballistically transport through Pt and overcome the Schottky barrier at the interface with TiO2. The yield for this phenomenon is on the order of 10-4 electrons per product molecule formed, similar to what has been observed for CO oxidation and for the adsorption of many different molecules. The same Pt/TiO2 system was used to compare currents in hydrogen oxidation and deuterium oxidation. The current through the diode under deuterium oxidation was found to be greater than under hydrogen oxidation by a factor of three. Weighted by the difference in turnover frequencies for the two isotopes, this would imply a chemicurrent yield 5 times greater for D2 compared to H2, contrary to what is expected given the higher mass of D2. Reversible changes in the rectification factor of the diode are observed when switching between D2 and H2. These changes are a likely cause for the differences in current between the two isotopes. In the nanodiode experiments, surface chemistry leads to charge flow, suggesting the possibility of creating charge flow to tune surface chemistry. This was done first by exposing a Pt/Si diode to visible light while using it as a catalyst for H2 oxidation. Absorption of the light in the Si, combined with

  12. Oxidation and metal-insertion in molybdenite surfaces: evaluation of charge-transfer mechanisms and dynamics

    National Research Council Canada - National Science Library

    Ramana, CV; Becker, U; Shutthanandan, V; Julien, CM


    .... In addition, understanding the insertion of metals into molybdenite and evaluation of charge-transfer mechanism and dynamics is important to utilize these minerals in technological applications...

  13. Effect of Molecular Packing and Charge Delocalization on the Nonradiative Recombination of Charge-Transfer States in Organic Solar Cells

    KAUST Repository

    Chen, Xian Kai


    In organic solar cells, a major source of energy loss is attributed to nonradiative recombination from the interfacial charge transfer states to the ground state. By taking pentacene–C60 complexes as model donor–acceptor systems, a comprehensive theoretical understanding of how molecular packing and charge delocalization impact these nonradiative recombination rates at donor–acceptor interfaces is provided.

  14. Optical diffraction radiation for position monitoring of charged particle beams (United States)

    Kieffer, R.; Bravin, E.; Lefevre, T.; Mazzoni, S.; Bergamaschi, M.; Karataev, P.; Kruchinin, K.; Billing, M.; Conway, J.; Shanks, J.; Terunuma, N.; Bobb, L.


    In the framework of the future linear collider collaboration (CLIC, ILC), non-intercepting beam monitoring instruments are under development for very low emittance and high charge density beams. Optical diffraction radiation (ODR) was studied and developed during the last years focussing on beam size measurements. We propose in the paper to consider the use of diffraction radiation for ultra relativistic beams as position monitors with applications for the centering of scrapers, collimators and targets with high resolution. We present the experimental results obtained using small aperture slits on the ATF2 extraction beam line at KEK and on the Cornell Electron Storage Ring with 1.2 GeV and 2.1 GeV electrons respectively.

  15. Investigation of radiative heat transfer in fixed bed biomass furnaces

    Energy Technology Data Exchange (ETDEWEB)

    T. Klason; X.S. Bai; M. Bahador; T.K. Nilsson; B. Sunden [Lund Institute of Technology, Lund (Sweden). Division of Fluid Mechanics


    This paper presents an investigation of the radiative heat transfer process in two fixed bed furnaces firing biomass fuels and the performance of several widely used models for calculation of radiative heat transfer in the free-room of fixed bed furnaces. The effective mean grey gas absorption coefficients are calculated using an optimised version of the exponential wide band model (EWBM) based on an optical mean beam length. Fly-ash and char particles are taken into account using Mie scattering. In the investigated updraft small-scale fixed bed furnace radiative transfer carries heat from the bed to the free-room, whereas in the cross-current bed large-scale industry furnace, radiative transfer brings heat from the hot zones in the free-room to the drying zone of the bed. Not all the investigated models can predict these heat transfer trends, and the sensitivity of results to model parameters is fairly different in the two furnaces. In the small-scale furnace, the gas absorption coefficient predicted by using different optical lengths has great impact on the predicted temperature field. In the large-scale furnaces, the predicted temperature field is less sensitive to the optical length. In both furnaces, with the same radiative properties, the low-computational-cost P1 model predicts a temperature field in the free-room similar to that by the more time consuming SLW model. In general, the radiative heat transfer rates to the fuel bed are not very sensitive to the radiative properties, but they are sensitive to the different radiative heat transfer models. For a realistic prediction of the radiative heat transfer rate to the fuel bed or to the walls, more computationally demanding models such as the FGG or SLW models should be used. 37 refs., 7 figs., 2 tabs.

  16. Charge-Transfer in Time-Dependent Density Functional Theory: Insights from the Asymmetric Hubbard Dimer

    CERN Document Server

    Fuks, J I


    We show that an asymmetric two-fermion two-site Hubbard model illustrates the essential features of long-range charge-transfer dynamics in a real-space molecule. We apply a resonant field that transfers one fermion from one site to the other. Via constrained search we find the exact ground-state exchange-correlation functional, and use it to propagate the Kohn-Sham system, giving the first "adiabatically-exact" calculation of time-resolved charge-transfer. This propagation fails to properly transfer charge. We analyze why by comparing the exact and adiabatically-exact potentials and discuss the role of the derivative discontinuity. The implication for real-space molecules is that even the best possible adiabatic approximation, despite capturing non-local step features relevant to dissociation and charge-transfer excitations, cannot capture fully time-resolved charge-transfer dynamics.

  17. Light scattering reviews 9 light scattering and radiative transfer

    CERN Document Server

    Kokhanovsky, Alexander A


    This book details modern methods of the radiative transfer theory. It presents recent advances in light scattering (measurements and theory) and highlights the newest developments in remote sensing of aerosol and cloud properties.

  18. Near-field radiative heat transfer between metasurfaces

    DEFF Research Database (Denmark)

    Dai, Jin; Dyakov, Sergey A.; Bozhevolnyi, Sergey I.


    Metamaterials possess artificial bulk and surface electromagnetic states. Tamed dispersion properties of surface waves allow one to achieve a controllable super-Planckian radiative heat transfer (RHT) process between two closely spaced objects. We numerically demonstrate enhanced RHT between two...

  19. SAFARI 2000 Surface Atmospheric Radiative Transfer (SMART), Dry Season 2000 (United States)

    National Aeronautics and Space Administration — Surface-sensing Measurements for Radiative Transfer (SMART) and Chemical, Optical, and Microphysical Measurements of In-situ Troposphere (COMMIT) consist of a suite...

  20. Modeling of Radiative Heat Transfer in an Electric Arc Furnace (United States)

    Opitz, Florian; Treffinger, Peter; Wöllenstein, Jürgen


    Radiation is an important means of heat transfer inside an electric arc furnace (EAF). To gain insight into the complex processes of heat transfer inside the EAF vessel, not only radiation from the surfaces but also emission and absorption of the gas phase and the dust cloud need to be considered. Furthermore, the radiative heat exchange depends on the geometrical configuration which is continuously changing throughout the process. The present paper introduces a system model of the EAF which takes into account the radiative heat transfer between the surfaces and the participating medium. This is attained by the development of a simplified geometrical model, the use of a weighted-sum-of-gray-gases model, and a simplified consideration of dust radiation. The simulation results were compared with the data of real EAF plants available in literature.

  1. Radiative Transfer Effects during Photoheating of the Intergalactic Medium


    Abel, Tom; Haehnelt, Martin G.


    The thermal history of the intergalactic medium (IGM) after reionization is to a large extent determined by photoheating. Here we demonstrate that calculations of the photoheating rate which neglect radiative transfer effects substantially underestimate the energy input during and after reionization. The neglect of radiative transfer effects results in temperatures of the IGM which are too low by a factor of two after HeII reionization. We briefly discuss implications for the absorption prope...

  2. Dynamic measurement of near-field radiative heat transfer


    Lang, S.; G. Sharma; Molesky, S.; Kränzien, P. U.; Jalas, T.; Z. Jacob; Petrov, A. Yu.; Eich, M.


    Super-Planckian near-field radiative heat transfer allows effective heat transfer between a hot and a cold body to increase beyond the limits long known for black bodies. Until present, experimental techniques to measure the radiative heat flow relied on steady-state systems. Here, we present a dynamic measurement approach based on the transient plane source technique, which extracts thermal properties from a temperature transient caused by a step input power function. Using this versatile me...

  3. Electron transfer mechanism and photochemistry of ferrioxalate induced by excitation in the charge transfer band. (United States)

    Chen, Jie; Zhang, Hua; Tomov, Ivan V; Rentzepis, Peter M


    The photoredox reaction of ferrioxalate after 266/267 nm excitation in the charge transfer band has been studied by means of ultrafast extended X-ray absorption fine structure (EXAFS) analysis, optical transient spectroscopy, and quantum chemistry calculations. The Fe-O bond length changes combined with the transient spectra and kinetics have been measured and in combination with ultrahigh frequency density functional theory (UHF/DFT) calculations are used to determine the photochemical mechanism for the Fe(III) to Fe(II) redox reaction. The present data and the results obtained with 266/267 nm excitations strongly suggest that the primary reaction is the dissociation of the Fe-O bond before intramolecular electron transfer occurs. Low quantum yield electron photodetachment from ferrioxalate has also been observed.

  4. Thermal radiation heat transfer (3rd revised and enlarged edition) (United States)

    Siegel, Robert; Howell, John R.

    This book first reviews the overall aspects and background information related to thermal radiation heat transfer and incorporates new general information, advances in analytical and computational techniques, and new reference material. Coverage focuses on radiation from opaque surfaces, radiation interchange between various types of surfaces enclosing a vacuum or transparent medium, and radiation including the effects of partially transmitting media, such as combustion gases, soot, or windows. Boundary conditions and multiple layers are discussed with information on radiation in materials with nonunity refractive indices.

  5. The thermodynamics of charge transfer in DNA photolyase: using thermodynamic integration calculations to analyse the kinetics of electron transfer reactions. (United States)

    Krapf, Sebastian; Koslowski, Thorsten; Steinbrecher, Thomas


    DNA Photolyases are light sensitive oxidoreductases present in many organisms that participate in the repair of photodamaged DNA. They are capable of electron transfer between a bound cofactor and a chain of tryptophan amino acid residues. Due to their unique mechanism and important function, photolyases have been subject to intense study in recent times, with both experimental and computational efforts. In this work, we present a novel application of classical molecular dynamics based free energy calculations, combined with quantum mechanical computations, to biomolecular charge transfer. Our approach allows for the determination of all reaction parameters in Marcus' theory of charge transport. We were able to calculate the free energy profile for the movement of a positive charge along protein sidechains involved in the biomolecule's function as well as charge-transfer rates that are in good agreement with experimental results. Our approach to simulate charge-transfer reactions explicitly includes the influence of protein flexibility and solvent dynamics on charge-transfer energetics. As applied here to a biomolecular system of considerable scientific interest, we believe the method to be easily adaptable to the study of charge-transfer phenomena in biochemistry and other fields.

  6. Versatile charge transfer through anthraquinone films for electrochemical sensing applications

    Energy Technology Data Exchange (ETDEWEB)

    Venarusso, Luna B. [Department of Chemistry, Universidade Federal de Mato Grosso do Sul, Caixa Postal 549, Campo Grande, MS 79070-900 (Brazil); Tammeveski, Kaido [Institute of Chemistry, University of Tartu, Ravila 14a, 50411 Tartu (Estonia); Maia, Gilberto, E-mail: [Department of Chemistry, Universidade Federal de Mato Grosso do Sul, Caixa Postal 549, Campo Grande, MS 79070-900 (Brazil)


    Cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) were employed to study the effect of anthraquinone (AQ) films on the charge transfer rate of {beta}-nicotinamide adenine dinucleotide (NAD{sup +}), dopamine (DA), and ferricyanide on glassy carbon (GC) electrodes in solutions of different pH. Maximum blocking action on the Fe(CN){sub 6}{sup 3-} redox probe was observed at pH 7 and open-circuit potential (OCP). However, maximum electron hopping effect was observed at pH 9 at both -0.58 V and -0.85 V for Fe(CN){sub 6}{sup 3-}, pH 7 at -0.58 V for NAD{sup +}, and pH 9 at -0.58 V for DA, suggesting that electron hopping in AQ films on a GC surface is dependent on both pH and electrode potential. These findings lend support for the application of these films in the detection of soluble redox probes such as NAD{sup +} and DA at biological pH values (from 7 to 9).

  7. Intramolecular charge transfer effects on 3-aminobenzoic acid

    Energy Technology Data Exchange (ETDEWEB)

    Stalin, T. [Department of Chemistry, Annamalai University, Annamalainagar, Chidambaram 608 002, Tamil Nadu (India); Rajendiran, N. [Department of Chemistry, Annamalai University, Annamalainagar, Chidambaram 608 002, Tamil Nadu (India)], E-mail:


    Effect of solvents, buffer solutions of different pH and {beta}-cyclodextrin on the absorption and fluorescence spectra of 3-aminobenzoic acid (3ABA) have been investigated. The solid inclusion complex of 3ABA with {beta}-CD is discussed by UV-Vis, fluorimetry, semiempirical quantum calculations (AM1), FT-IR, {sup 1}H NMR and Scanning Electron Microscope (SEM). The thermodynamic parameters ({delta}H, {delta}G and {delta}S) of the inclusion process are also determined. The experimental results indicated that the inclusion processes is an exothermic and spontaneous. The large Stokes shift emission in solvents with 3ABA are correlated with different solvent polarity scales suggest that, 3ABA molecule is more polar in the S{sub 1} state. Solvent, {beta}-CD studies and excited state dipole moment values confirms that the presence of intramolecular charge transfer (ICT) in 3ABA. Acidity constants for different prototropic equilibria of 3ABA in the S{sub 0} and S{sub 1} states are calculated. {beta}-Cyclodextrin studies shows that 3ABA forms a 1:1 inclusion complex with {beta}-CD. {beta}-CD studies suggest COOH group present in non-polar part and amino group present in hydrophilic part of the {beta}-CD cavity. A mechanism is proposed to explain the inclusion process.

  8. Mechanism of Charge Transfer from Plasmonic Nanostructures to Chemically Attached Materials. (United States)

    Boerigter, Calvin; Aslam, Umar; Linic, Suljo


    Plasmonic metal nanoparticles can efficiently convert the energy of visible photons into the energy of hot charge carriers within the nanoparticles. These energetic charge carriers can transfer to molecules or semiconductors, chemically attached to the nanoparticles, where they can induce photochemical transformations. Classical models of photoinduced charge excitation and transfer in metals suggest that the majority of the energetic charge carriers rapidly decay within the metal nanostructure before they are transferred into the neighboring molecule or semiconductor, and therefore, the efficiency of charge transfer is low. Herein, we present experimental evidence that calls into question this conventional picture. We demonstrate a system where the presence of a molecule, adsorbed on the surface of a plasmonic nanoparticle, significantly changes the flow of charge within the excited plasmonic system. The nanoparticle-adsorbate system experiences high rates of direct, resonant flow of charge from the nanoparticle to the molecule, bypassing the conventional charge excitation and thermalization process taking place in the nanoparticle. This picture of charge transfer suggests that the yield of extracted hot electrons (or holes) from plasmonic nanoparticles can be significantly higher than the yields expected based on conventional models. We discuss a conceptual physical framework that allows us to explain our experimental observations. This analysis points us in a direction toward molecular control of the charge transfer process using interface and local field engineering strategies.

  9. Magnetically coupled resonance wireless charging technology principles and transfer mechanisms (United States)

    Zhou, Jiehua; Wan, Jian; Ma, Yinping


    With the tenure of Electric-Vehicle rising around the world, the charging methods have been paid more and more attention, the current charging mode mainly has the charging posts and battery swapping station. The construction of the charging pile or battery swapping station not only require lots of manpower, material costs but the bare conductor is also easy to generate electric spark hidden safety problems, still occupies large space. Compared with the wired charging, wireless charging mode is flexible, unlimited space and location factors and charging for vehicle safety and quickly. It complements the traditional charging methods in adaptability and the independent charge deficiencies. So the researching the wireless charging system have an important practical significance and application value. In this paper, wireless charging system designed is divided into three parts: the primary side, secondary side and resonant coupling. The main function of the primary side is to generate high-frequency alternating current, so selecting CLASS-E amplifier inverter structure through the research on full bridge, half-bridge and power amplification circuit. Addition, the wireless charging system is susceptible to outside interference, frequency drift phenomenon. Combined with the wireless energy transmission characteristics, resonant parts adopt resonant coupling energy transmission scheme and the Series-Series coupling compensation structure. For the electric vehicle charging power and voltage requirements, the main circuit is a full bridge inverter and Boost circuit used as the secondary side.

  10. A study of Monte Carlo radiative transfer through fractal clouds

    Energy Technology Data Exchange (ETDEWEB)

    Gautier, C.; Lavallec, D.; O`Hirok, W.; Ricchiazzi, P. [Univ. of California, Santa Barbara, CA (United States)] [and others


    An understanding of radiation transport (RT) through clouds is fundamental to studies of the earth`s radiation budget and climate dynamics. The transmission through horizontally homogeneous clouds has been studied thoroughly using accurate, discreet ordinates radiative transfer models. However, the applicability of these results to general problems of global radiation budget is limited by the plane parallel assumption and the fact that real clouds fields show variability, both vertically and horizontally, on all size scales. To understand how radiation interacts with realistic clouds, we have used a Monte Carlo radiative transfer model to compute the details of the photon-cloud interaction on synthetic cloud fields. Synthetic cloud fields, generated by a cascade model, reproduce the scaling behavior, as well as the cloud variability observed and estimated from cloud satellite data.

  11. Radiative Transfer Reconsidered as a Quantum Kinetic Theory ...

    Indian Academy of Sciences (India)

    electromagnetic radiation energy (Chandrasekhar 1960; Pomraning 1973; Mihalas. 1978; Oxenius 1986; Milonni ... transfer equation can be inaccurate if the radiation has a narrow spectral band k, sufficiently so that the ... (Wigner) distribution, which can take negative values on phase space volumes of typical extent h3.


    Energy Technology Data Exchange (ETDEWEB)

    Fleming, Graham; Ahn, Tae Kyu; Avenson, Thomas J.; Ballottari, Matteo; Cheng, Yuan-Chung; Niyogi, Krishna K.; Bassi, Roberto; Fleming, Graham R.


    Energy-dependent quenching of excess absorbed light energy (qE) is a vital mechanism for regulating photosynthetic light harvesting in higher plants. All of the physiological characteristics of qE have been positively correlated with charge-transfer between coupled chlorophyll and zeaxanthin molecules in the light-harvesting antenna of photosystem II (PSII). In this work, we present evidence for charge-transfer quenching in all three of the individual minor antenna complexes of PSII (CP29, CP26, and CP24), and we conclude that charge-transfer quenching in CP29 involves a de-localized state of an excitonically coupled chlorophyll dimer. We propose that reversible conformational changes in CP29 can `tune? the electronic coupling between the chlorophylls in this dimer, thereby modulating the energy of the chlorophylls-zeaxanthin charge-transfer state and switching on and off the charge-transfer quenching during qE.

  13. Crystal growth of new charge-transfer salts based on π-conjugated donor molecules

    Energy Technology Data Exchange (ETDEWEB)

    Morherr, Antonia, E-mail: [Physikalisches Institut, Goethe-Universität Frankfurt am Main, 60438 Frankfurt am Main (Germany); Witt, Sebastian [Physikalisches Institut, Goethe-Universität Frankfurt am Main, 60438 Frankfurt am Main (Germany); Chernenkaya, Alisa [Graduate School Materials Science in Mainz, 55128 Mainz (Germany); Institut für Physik, Johannes Gutenberg-Universität, 55099 Mainz (Germany); Bäcker, Jan-Peter [Physikalisches Institut, Goethe-Universität Frankfurt am Main, 60438 Frankfurt am Main (Germany); Schönhense, Gerd [Institut für Physik, Johannes Gutenberg-Universität, 55099 Mainz (Germany); Bolte, Michael [Institut für anorganische Chemie, Goethe-Universität Frankfurt am Main, 60438 Frankfurt am Main (Germany); Krellner, Cornelius [Physikalisches Institut, Goethe-Universität Frankfurt am Main, 60438 Frankfurt am Main (Germany)


    New charge transfer crystals of π-conjugated, aromatic molecules (phenanthrene and picene) as donors were obtained by physical vapor transport. The melting behavior, optimization of crystal growth and the crystal structure are reported for charge transfer salts with (fluorinated) tetracyanoquinodimethane (TCNQ-F{sub x}, x=0, 2, 4), which was used as acceptor material. The crystal structures were determined by single-crystal X-ray diffraction. Growth conditions for different vapor pressures in closed ampules were applied and the effect of these starting conditions for crystal size and quality is reported. The process of charge transfer was investigated by geometrical analysis of the crystal structure and by infrared spectroscopy on single crystals. With these three different acceptor strengths and the two sets of donor materials, it is possible to investigate the distribution of the charge transfer systematically. This helps to understand the charge transfer process in this class of materials with π-conjugated donor molecules.

  14. EV Charging Through Wireless Power Transfer: Analysis of Efficiency Optimization and Technology Trends

    Energy Technology Data Exchange (ETDEWEB)

    Miller, John M [ORNL; Rakouth, Heri [Delphi Automotive Systems, USA; Suh, In-Soo [Korea Advanced Institute of Science and Technology


    This paper is aimed at reviewing the technology trends for wireless power transfer (WPT) for electric vehicles (EV). It also analyzes the factors affecting its efficiency and describes the techniques currently used for its optimization. The review of the technology trends encompasses both stationary and moving vehicle charging systems. The study of the stationary vehicle charging technology is based on current implementations and on-going developments at WiTricity and Oak Ridge National Lab (ORNL). The moving vehicle charging technology is primarily described through the results achieved by the Korean Advanced Institute of Technology (KAIST) along with on-going efforts at Stanford University. The factors affecting the efficiency are determined through the analysis of the equivalent circuit of magnetic resonant coupling. The air gap between both transmitting and receiving coils along with the magnetic field distribution and the relative impedance mismatch between the related circuits are the primary factors affecting the WPT efficiency. Currently the industry is looking at an air gap of 25 cm or below. To control the magnetic field distribution, Kaist has recently developed the Shaped Magnetic Field In Resonance (SMFIR) technology that uses conveniently shaped ferrite material to provide low reluctance path. The efficiency can be further increased by means of impedance matching. As a result, Delphi's implementation of the WiTricity's technology exhibits a WPT efficiency above 90% for stationary charging while KAIST has demonstrated a maximum efficiency of 83% for moving vehicle with its On Line Vehicle (OLEV) project. This study is restricted to near-field applications (short and mid-range) and does not address long-range technology such as microwave power transfer that has low efficiency as it is based on radiating electromagnetic waves. This paper exemplifies Delphi's work in powertrain electrification as part of its innovation for the real world

  15. HO-CHUNK: Radiation Transfer code (United States)

    Whitney, Barbara A.; Wood, Kenneth; Bjorkman, J. E.; Cohen, Martin; Wolff, Michael J.


    HO-CHUNK calculates radiative equilibrium temperature solution, thermal and PAH/vsg emission, scattering and polarization in protostellar geometries. It is useful for computing spectral energy distributions (SEDs), polarization spectra, and images.

  16. Dynamic measurement of near-field radiative heat transfer. (United States)

    Lang, S; Sharma, G; Molesky, S; Kränzien, P U; Jalas, T; Jacob, Z; Petrov, A Yu; Eich, M


    Super-Planckian near-field radiative heat transfer allows effective heat transfer between a hot and a cold body to increase beyond the limits long known for black bodies. Until present, experimental techniques to measure the radiative heat flow relied on steady-state systems. Here, we present a dynamic measurement approach based on the transient plane source technique, which extracts thermal properties from a temperature transient caused by a step input power function. Using this versatile method, that requires only single sided contact, we measure enhanced radiative conduction up to 16 times higher than the blackbody limit on centimeter sized glass samples without any specialized sample preparation or nanofabrication.

  17. Radiative heat transfer estimation in pipes with various wall emissivities (United States)

    Robin, Langebach; Christoph, Haberstroh


    Radiative heat transfer is usually of substantial importance in cryogenics when systems are designed and thermal budgeting is carried out. However, the contribution of pipes is commonly assumed to be comparably low since the warm and cold ends as well as their cross section are fairly small. Nevertheless, for a first assessment of each pipe rough estimates are always appreciated. In order to estimate the radiative heat transfer with traditional “paper and pencil“ methods there is only one analytical case available in literature - the case of plane-parallel plates. This case can only be used to calculate the theoretical lower and the upper asymptotic values of the radiative heat transfer, since pipe wall radiation properties are not taken into account. For this paper we investigated the radiative heat transfer estimation in pipes with various wall emissivities with the help of numerical simulations. Out of a number of calculation series we could gain an empirical extension for the used approach of plane-parallel plates. The model equation can be used to carry out enhanced paper and pencil estimations for the radiative heat transfer through pipes without demanding numerical simulations.

  18. Efficient Hot Electron Transfer by Plasmon Induced Interfacial Charge Transfer Transition (United States)

    Lian, Tianquan

    Surface plasmon resonance in metal nanostructures has been widely used to enhance the efficiency of semiconductors and/or molecular chromophore based solar energy conversion devices by increasing the absorption or energy transfer rate through the enhanced local field strength. In more recent years, it has been shown that excitation of plasmons in metal nanostructures can lead to the injection of hot electrons into semiconductors and enhanced photochemistry. This novel mechanism suggests that plasmonic nanostructures can potentially function as a new class of widely tunable and robust light harvesting materials for solar energy conversion. However, plasmon-induced hot electron injections from metal to semiconductor or molecules are still inefficient because of the competing ultrafast hot electron relaxation processes within the metallic domain. In this paper we discuss a recent study on the plasmon-exciton interaction mechanisms in colloidal quantum-confined semiconductor-gold nanorod heterostructures. In CdSe NRs with Au tips, the distinct plasmon band of the Au nanoparticles was completely damped due to strong interaction with the CdSe domain. Using transient absorption spectroscopy, we show that optical excitation of plasmons in the Au tip leads to efficient hot electron injection into the semiconductor nanorod. In the presence of sacrificial electron donors, this plasmon induced hot electron transfer process can be utilized to drive photoreduction reactions under continuous illumination. We propose that the strong metal/semiconductor coupling in CdSe/Au hetersostructures leads to a new pathway for this surprising efficient hot electron transfer. In this plasmon induced interfacial charge transfer transition (PICTT) the a plasmon decay by direct excitation of an electron from the metal to semiconductor, bypassing the competition with hot electron transfer in metal. Ongoing studies are examining the generality of this mechanism and exploring possible approaches

  19. Role of the charge transfer state in organic donor-acceptor solar cells

    Energy Technology Data Exchange (ETDEWEB)

    Deibel, Carsten; Strobel, Thomas [Experimental Physics VI, Julius-Maximilians-University of Wuerzburg (Germany); Dyakonov, Vladimir [Experimental Physics VI, Julius-Maximilians-University of Wuerzburg (Germany); Bavarian Centre for Applied, Energy Research (ZAE Bayern), Wuerzburg (Germany)


    Charge transfer complexes are interfacial charge pairs residing at the donor-acceptor heterointerface in organic solar cell. Experimental evidence shows that it is crucial for the photovoltaic performance, as both photocurrent and open circuit voltage directly depend on it. For charge photogeneration, charge transfer complexes represent the intermediate but essential step between exciton dissociation and charge extraction. Recombination of free charges to the ground state is via the bound charge transfer state before being lost to the ground state. In terms of the open circuit voltage, its maximum achievable value is determined by the energy of the charge transfer state. An important question is whether or not maximum photocurrent and maximum open circuit voltage can be achieved simultaneously. The impact of increasing the CT energy - in order to raise the open circuit voltage, but lowering the kinetic excess energy of the CT complexes at the same time - on the charge photogeneration will accordingly be discussed. Clearly, the fundamental understanding of the processes involving the charge transfer state is essential for an optimisation of the performance of organic solar cells. (Abstract Copyright [2010], Wiley Periodicals, Inc.)

  20. Radiative heat transfer in low-dimensional systems -- microscopic mode (United States)

    Woods, Lilia; Phan, Anh; Drosdoff, David


    Radiative heat transfer between objects can increase dramatically at sub-wavelength scales. Exploring ways to modulate such transport between nano-systems is a key issue from fundamental and applied points of view. We advance the theoretical understanding of radiative heat transfer between nano-objects by introducing a microscopic model, which takes into account the individual atoms and their atomic polarizabilities. This approach is especially useful to investigate nano-objects with various geometries and give a detailed description of the heat transfer distribution. We employ this model to study the heat exchange in graphene nanoribbon/substrate systems. Our results for the distance separations, substrates, and presence of extended or localized defects enable making predictions for tailoring the radiative heat transfer at the nanoscale. Financial support from the Department of Energy under Contract No. DE-FG02-06ER46297 is acknowledged.

  1. Heat radiation and transfer for point particles in arbitrary geometries (United States)

    Asheichyk, Kiryl; Müller, Boris; Krüger, Matthias


    We study heat radiation and heat transfer for pointlike particles in a system of other objects. Starting from exact many-body expressions found from scattering theory and fluctuational electrodynamics, we find that transfer and radiation for point particles are given in terms of the Green's function of the system in the absence of the point particles. These general expressions contain no approximation for the surrounding objects. As an application, we compute the heat transfer between two point particles in the presence of a sphere of arbitrary size and show that the transfer is enhanced by several orders of magnitude through the presence of the sphere, depending on the materials. Furthermore, we compute the heat emission of a point particle in front of a planar mirror. Finally, we show that a particle placed inside a spherical mirror cavity does not radiate energy.

  2. Atmospheric Radiative Transfer for Satellite Remote Sensing: Validation and Uncertainty (United States)

    Marshak, Alexander


    My presentation will begin with the discussion of the Intercomparison of three-dimensional (3D) Radiative Codes (13RC) project that has been started in 1997. I will highlight the question of how well the atmospheric science community can solve the 3D radiative transfer equation. Initially I3RC was focused only on algorithm intercomparison; now it has acquired a broader identity providing new insights and creating new community resources for 3D radiative transfer calculations. Then I will switch to satellite remote sensing. Almost all radiative transfer calculations for satellite remote sensing are one-dimensional (1D) assuming (i) no variability inside a satellite pixel and (ii) no radiative interactions between pixels. The assumptions behind the 1D approach will be checked using cloud and aerosol data measured by the MODerate Resolution Imaging Spectroradiometer (MODIS) on board of two NASA satellites TERRA and AQUA. In the discussion, I will use both analysis technique: statistical analysis over large areas and time intervals, and single scene analysis to validate how well the 1D radiative transfer equation describes radiative regime in cloudy atmospheres.

  3. Self-interaction and charge transfer in organic semiconductors

    Energy Technology Data Exchange (ETDEWEB)

    Koerzdoerfer, Thomas


    This work concentrates on the problem of self-interaction, which is one of the most serious problems of commonly used approximative density functionals. As a major result of this work, it is demonstrated that self-interaction plays a decisive role for the performance of different approximative functionals in predicting accurate electronic properties of organic molecular semiconductors. In search for a solution to the self-interaction problem, a new concept for correcting commonly used density functionals for self-interaction is introduced and applied to a variety of systems, spanning small molecules, extended molecular chains, and organic molecular semiconductors. It is further shown that the performance of functionals that are not free from self-interaction can vary strongly for different systems and observables of interest, thus entailing the danger of misinterpretation of the results obtained from those functionals. The underlying reasons for the varying performance of commonly used density functionals are discussed thoroughly in this work. Finally, this thesis provides strategies that allow to analyze the reliability of commonly used approximations to the exchange-correlation functional for particular systems of interest. This cumulative dissertation is divided into three parts. Part I gives a short introduction into DFT and its time-dependent extension (TDDFT). Part II provides further insights into the self-interaction problem, presents a newly developed concept for the correction of self-interaction, gives an introduction into the publications, and discusses their basic results. Finally, the four publications on self-interaction and charge-transfer in extended molecular systems and organic molecular semiconductors are collected in Part III. (orig.)

  4. Hidden charged dark matter and chiral dark radiation (United States)

    Ko, P.; Nagata, Natsumi; Tang, Yong


    In the light of recent possible tensions in the Hubble constant H0 and the structure growth rate σ8 between the Planck and other measurements, we investigate a hidden-charged dark matter (DM) model where DM interacts with hidden chiral fermions, which are charged under the hidden SU(N) and U(1) gauge interactions. The symmetries in this model assure these fermions to be massless. The DM in this model, which is a Dirac fermion and singlet under the hidden SU(N), is also assumed to be charged under the U(1) gauge symmetry, through which it can interact with the chiral fermions. Below the confinement scale of SU(N), the hidden quark condensate spontaneously breaks the U(1) gauge symmetry such that there remains a discrete symmetry, which accounts for the stability of DM. This condensate also breaks a flavor symmetry in this model and Nambu-Goldstone bosons associated with this flavor symmetry appear below the confinement scale. The hidden U(1) gauge boson and hidden quarks/Nambu-Goldstone bosons are components of dark radiation (DR) above/below the confinement scale. These light fields increase the effective number of neutrinos by δNeff ≃ 0.59 above the confinement scale for N = 2, resolving the tension in the measurements of the Hubble constant by Planck and Hubble Space Telescope if the confinement scale is ≲1 eV. DM and DR continuously scatter with each other via the hidden U(1) gauge interaction, which suppresses the matter power spectrum and results in a smaller structure growth rate. The DM sector couples to the Standard Model sector through the exchange of a real singlet scalar mixing with the Higgs boson, which makes it possible to probe our model in DM direct detection experiments. Variants of this model are also discussed, which may offer alternative ways to investigate this scenario.

  5. Hawking radiation of five-dimensional charged black holes with scalar fields

    Directory of Open Access Journals (Sweden)

    Yan-Gang Miao


    Full Text Available We investigate the Hawking radiation cascade from the five-dimensional charged black hole with a scalar field coupled to higher-order Euler densities in a conformally invariant manner. We give the semi-analytic calculation of greybody factors for the Hawking radiation. Our analysis shows that the Hawking radiation cascade from this five-dimensional black hole is extremely sparse. The charge enhances the sparsity of the Hawking radiation, while the conformally coupled scalar field reduces this sparsity.

  6. Internal Charging Design Environments for the Earths Radiation Belts (United States)

    Minow, Joseph I.; Edwards, David L.


    Relativistic electrons in the Earth's radiation belts are a widely recognized threat to spacecraft because they penetrate lightly shielded vehicle hulls and deep into insulating materials where they accumulate to sufficient levels to produce electrostatic discharges. Strategies for evaluating the magnitude of the relativistic electron flux environment and its potential for producing ESD events are varied. Simple "rule of thumb" estimates such as the widely used 10(exp 10) e-/sq cm fluence within 10 hour threshold for the onset of pulsing in dielectric materials provide a quick estimate of when to expect charging issues. More sophisticated strategies based on models of the trapped electron flux within the Earth s magnetic field provide time dependent estimates of electron flux along spacecraft orbits and orbit integrate electron flux. Finally, measurements of electron flux can be used to demonstrate mean and extreme relativistic electron environments. This presentation will evaluate strategies used to specify energetic electron flux and fluence environments along spacecraft trajectories in the Earth s radiation belts.

  7. High-Order Thermal Radiative Transfer

    Energy Technology Data Exchange (ETDEWEB)

    Woods, Douglas Nelson [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Cleveland, Mathew Allen [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Wollaeger, Ryan Thomas [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Warsa, James S. [Los Alamos National Lab. (LANL), Los Alamos, NM (United States)


    The objective of this research is to asses the sensitivity of the linearized thermal radiation transport equations to finite element order on unstructured meshes and to investigate the sensitivity of the nonlinear TRT equations due to evaluating the opacities and heat capacity at nodal temperatures in 2-D using high-order finite elements.

  8. Super-Planckian far-field radiative heat transfer (United States)

    Fernández-Hurtado, V.; Fernández-Domínguez, A. I.; Feist, J.; García-Vidal, F. J.; Cuevas, J. C.


    We present here a theoretical analysis that demonstrates that the far-field radiative heat transfer between objects with dimensions smaller than the thermal wavelength can overcome the Planckian limit by orders of magnitude. To guide the search for super-Planckian far-field radiative heat transfer, we make use of the theory of fluctuational electrodynamics and derive a relation between the far-field radiative heat transfer and the directional absorption efficiency of the objects involved. Guided by this relation, and making use of state-of-the-art numerical simulations, we show that the far-field radiative heat transfer between highly anisotropic objects can largely overcome the black-body limit when some of their dimensions are smaller than the thermal wavelength. In particular, we illustrate this phenomenon in the case of suspended pads made of polar dielectrics like SiN or SiO2. These structures are widely used to measure the thermal transport through nanowires and low-dimensional systems and can be employed to test our predictions. Our work illustrates the dramatic failure of the classical theory to predict the far-field radiative heat transfer between micro- and nanodevices.

  9. Intervalence charge transfer transition in mixed valence complexes ...

    Indian Academy of Sciences (India)


    inclusion complex; optical electron transfer; cyclodextrin. 1. Introduction. Experimental and theoretical study of intervalence electron transfer between two metal centres linked by a spacer group, through which electron transfer can takes place, is an area of contemporary research interest. The consequence of this process ...

  10. Radiation Heat Transfer Procedures for Space-Related Applications (United States)

    Chai, John C.


    Over the last contract year, a numerical procedure for combined conduction-radiation heat transfer using unstructured grids has been developed. As a result of this research, one paper has been published in the Numerical Heat Transfer Journal. One paper has been accepted for presentation at the International Center for Heat and Mass Transfer's International Symposium on Computational Heat Transfer to be held in Australia next year. A journal paper is under review by my NASA's contact. A conference paper for the ASME National Heat Transfer conference is under preparation. In summary, a total of four (4) papers (two journal and two conference) have been published, accepted or are under preparation. There are two (2) to three (3) more papers to be written for the project. In addition to the above publications, one book chapter, one journal paper and six conference papers have been published as a result of this project. Over the last contract year, the research project resulted in one Ph.D. thesis and partially supported another Ph.D. student. My NASA contact and myself have formulated radiation heat transfer procedures for materials with different indices of refraction and for combined conduction-radiation heat transfer. We are trying to find other applications for the procedures developed under this grant.

  11. Fullerenes - how 25 years of charge transfer chemistry have shaped our understanding of (interfacial) interactions. (United States)

    Zieleniewska, A; Lodermeyer, F; Roth, A; Guldi, D M


    In this review article, we highlight over 25 years of fullerene research in charge transfer chemistry. The major thrust of this work is to illustrate interfacial interactions between fullerenes and porphyrins in electron donor-acceptor conjugates as well as self-assembled associates and co-crystallites all the way to organic photovoltaics. Hereby, the analysis of the fundamental proceses, namely, energy transfer, charge shift, charge separation as well as charge recombination stand at the forefront. Our examples, illustrate on how fine-tuning the structure leads to substantial alteration of interfacial interactions.

  12. Reptation Quantum Monte Carlo Calculation of Charge Transfer in The Na-Cl Dimer (United States)

    Yao, Yi; Kanai, Yosuke


    Reptation Quantum Monte Carlo (QMC) calculations are performed to describe the charge transfer behavior in a NaCl dimer. Influence of fixed node approximation on the charge transfer was examined by obtaining electron density via reputation QMC. We employ Slater-Jastrow wavefunction as the trial wavefunction, and the fermion nodes are obtained from single particle orbitals of Hartree-Fock and Density Functional Theory (DFT) with several exchange-correlation approximations. We will discuss our QMC results together with DFT calculations to give insights into observed dependence of the charge transfer behavior on the fixed-node approximation.

  13. Radiative heat transfer by the Monte Carlo method

    CERN Document Server

    Hartnett †, James P; Cho, Young I; Greene, George A; Taniguchi, Hiroshi; Yang, Wen-Jei; Kudo, Kazuhiko


    This book presents the basic principles and applications of radiative heat transfer used in energy, space, and geo-environmental engineering, and can serve as a reference book for engineers and scientists in researchand development. A PC disk containing software for numerical analyses by the Monte Carlo method is included to provide hands-on practice in analyzing actual radiative heat transfer problems.Advances in Heat Transfer is designed to fill the information gap between regularly scheduled journals and university level textbooks by providing in-depth review articles over a broader scope than journals or texts usually allow.Key Features* Offers solution methods for integro-differential formulation to help avoid difficulties* Includes a computer disk for numerical analyses by PC* Discusses energy absorption by gas and scattering effects by particles* Treats non-gray radiative gases* Provides example problems for direct applications in energy, space, and geo-environmental engineering

  14. Heat transfer in Rockwool modelling and method of measurement. Modelling radiative heat transfer in fibrous materials

    Energy Technology Data Exchange (ETDEWEB)

    Dyrboel, Susanne


    Fibrous materials are some of the most widely used materials for thermal insulation. In this project the focus of interest has been on fibrous materials for building application. Interest in improving the thermal properties of insulation materials is increasing as legislation is being tightened to reduce the overall energy consumption. A knowledge of the individual heat transfer mechanisms - whereby heat is transferred within a particular material is an essential tool to improve continuously the thermal properties of the material. Heat is transferred in fibrous materials by four different transfer mechanisms: conduction through air, conduction through fibres, thermal radiation and convection. In a particular temperature range the conduction through air can be regarded as a constant, and conduction through fibres is an insignificant part of the total heat transfer. Radiation, however, constitutes 25-40% of the total heat transfer in light fibrous materials. In Denmark and a number of other countries convection in fibrous materials is considered as non-existent when calculating heat transmission as well as when designing building structures. Two heat transfer mechanisms have been the focus of the current project: radiation heat transfer and convection. The radiation analysis serves to develop a model that can be used in further work to gain a wider knowledge of the way in which the morphology of the fibrous material, i.e. fibre diameter distribution, fibre orientation distribution etc., influences the radiation heat transfer under different conditions. The convection investigation serves to examine whether considering convection as non-existent is a fair assumption to use in present and future building structures. The assumption applied in practically is that convection makes a notable difference only in very thick insulation, at external temperatures below -20 deg. C, and at very low densities. For lager thickness dimensions the resulting heat transfer through the

  15. Radiative Heat Transfer Between Core-Shell Nanoparticles


    Nikbakht, Moladad


    Radiative heat transfer in systems with core-shell nanoparticles may exhibit not only a combination of disparate physical properties of its components but also further enhanced properties that arise from the synergistic properties of the core and shell components. We study the thermal conductance between two core-shell nanoparticles (CSNPs). We predict that the radiative heat transfer in a dimer of Au@SiO$_2$ CSNPs (i.e., silica-coated gold nanoparticles) could be enhanced several order of ma...

  16. Charge transfer in ultracold gases via Feshbach resonances (United States)

    Gacesa, Marko; Côté, Robin


    We investigate the prospects of using magnetic Feshbach resonance to control charge exchange in ultracold collisions of heteroisotopic combinations of atoms and ions of the same element. The proposed treatment, readily applicable to alkali or alkaline-earth metals, is illustrated on cold collisions of +9Be and 10Be. Feshbach resonances are characterized by quantum scattering calculations in a coupled-channel formalism that includes non-Born-Oppenheimer terms originating from the nuclear kinetic operator. Near a resonance predicted at 322 G, we find the charge exchange rate coefficient to rise from practically zero to values greater than 10-12cm3 /s. Our results suggest controllable charge exchange processes between different isotopes of suitable atom-ion pairs, with potential applications to quantum systems engineered to study charge diffusion in trapped cold atom-ion mixtures and emulate many-body physics.

  17. Ultrafast spin exchange-coupling torque via photo-excited charge-transfer processes

    National Research Council Canada - National Science Library

    Ma, X; Fang, F; Li, Q; Zhu, J; Yang, Y; Wu, Y Z; Zhao, H B; Lüpke, G


    .... Recently developed optical approaches such as ultrafast demagnetization, spin-transfer and spin-orbit torques open new pathways to manipulate spin through its interaction with photon, orbit, charge or phonon...

  18. Quantum-trajectory analysis for charge transfer in solid materials induced by strong laser fields (United States)

    Jiang, Shicheng; Yu, Chao; Yuan, Guanglu; Wu, Tong; Wang, Ziwen; Lu, Ruifeng


    We investigate the dependence of charge transfer on the intensity of driving laser field when SiO2 crystal is irradiated by an 800 nm laser. It is surprising that the direction of charge transfer undergoes a sudden reversal when the driving laser intensity exceeds critical values with different carrier-envelope phases. By applying quantum-trajectory analysis, we find that the Bloch oscillation plays an important role in charge transfer in solids. Also, we study the interaction of a strong laser with gallium nitride (GaN), which is widely used in optoelectronics. A pump-probe scheme is applied to control the quantum trajectories of the electrons in the conduction band. The signal of charge transfer is controlled successfully by means of a theoretically proposed approach.

  19. The Mechanism of the Interfacial Charge and Mass Transfer during Intercalation of Alkali Metal Cations. (United States)

    Ventosa, Edgar; Paulitsch, Bianca; Marzak, Philipp; Yun, Jeongsik; Schiegg, Florian; Quast, Thomas; Bandarenka, Aliaksandr S


    Intercalation of alkali metal cations, like Li+ or Na+, follows the same three-stage mechanism of the interfacial charge and mass transfer irrespective of the nature of the electrolyte, electrolyte composition or electrode material.

  20. Charge-transfer stabilization of molecular bicimers: ion pair formation in diarylmethanes

    Energy Technology Data Exchange (ETDEWEB)

    Locke, R.J.; Modiano, S.H.; Lim, E.C.


    The authors demonstrate here that the bicimer of aromatic hydrocarbons is stabilized largely by charge-transfer interactions. The bicimer is a dimeric species formed by the association of two identical, electronically excited molecules.

  1. Fractional integration and radiative transfer in a multifractal atmosphere

    Energy Technology Data Exchange (ETDEWEB)

    Naud, C.; Schertzer, D. [Universite Pierre et Marie Curie, Paris (France); Lovejoy, S. [McGill Univ., Montreal (Canada)


    Recently, Cess et al. (1995) and Ramathan et al. (1995) cited observations which exhibit an anomalous absorption of cloudy skies in comparison with the value predicted by usual models and which thus introduce large uncertainties for climatic change assessments. These observation raise questions concerning the way general circulation models have been tuned for decades, relying on classical methods, of both radiative transfer and dynamical modeling. The observations also tend to demonstrate that homogeneous models are simply not relevant in relating the highly variable properties of clouds and radiation fields. However smoothed, the intensity of cloud`s multi-scattered radiation fields reflect this extreme variability.

  2. A modular radiative transfer program for gas filter correlation radiometry (United States)

    Casas, J. C.; Campbell, S. A.


    The fundamentals of a computer program, simulated monochromatic atmospheric radiative transfer (SMART), which calculates atmospheric path transmission, solar radiation, and thermal radiation in the 4.6 micrometer spectral region, are described. A brief outline of atmospheric absorption properties and line by line transmission calculations is explained in conjunction with an outline of the SMART computational procedures. Program flexibility is demonstrated by simulating the response of a gas filter correlation radiometer as one example of an atmospheric infrared sensor. Program limitations, input data requirements, program listing, and comparison of SMART transmission calculations are presented.

  3. Computational Challenges of 3D Radiative Transfer in Atmospheric Models (United States)

    Jakub, Fabian; Bernhard, Mayer


    The computation of radiative heating and cooling rates is one of the most expensive components in todays atmospheric models. The high computational cost stems not only from the laborious integration over a wide range of the electromagnetic spectrum but also from the fact that solving the integro-differential radiative transfer equation for monochromatic light is already rather involved. This lead to the advent of numerous approximations and parameterizations to reduce the cost of the solver. One of the most prominent one is the so called independent pixel approximations (IPA) where horizontal energy transfer is neglected whatsoever and radiation may only propagate in the vertical direction (1D). Recent studies implicate that the IPA introduces significant errors in high resolution simulations and affects the evolution and development of convective systems. However, using fully 3D solvers such as for example MonteCarlo methods is not even on state of the art supercomputers feasible. The parallelization of atmospheric models is often realized by a horizontal domain decomposition, and hence, horizontal transfer of energy necessitates communication. E.g. a cloud's shadow at a low zenith angle will cast a long shadow and potentially needs to communication through a multitude of processors. Especially light in the solar spectral range may travel long distances through the atmosphere. Concerning highly parallel simulations, it is vital that 3D radiative transfer solvers put a special emphasis on parallel scalability. We will present an introduction to intricacies computing 3D radiative heating and cooling rates as well as report on the parallel performance of the TenStream solver. The TenStream is a 3D radiative transfer solver using the PETSc framework to iteratively solve a set of partial differential equation. We investigate two matrix preconditioners, (a) geometric algebraic multigrid preconditioning(MG+GAMG) and (b) block Jacobi incomplete LU (ILU) factorization. The

  4. Positronium Inhibition and Quenching by Organic Electron Acceptors and Charge Transfer Complexes

    DEFF Research Database (Denmark)

    Jansen, P.; Eldrup, Morten Mostgaard; Jensen, Bror Skytte


    Positron lifetime measurements were performed on a series of organic electron acceptors and charge-transfer complexes in solution. The acceptors cause both positronium (Ps) inhibition (with maybe one exception) and quenching, but when an acceptor takes part in a charge-transfer complex...... in terms of the spur reaction model of Ps formation. Correlation was also made to gas phase reaction between electron acceptors and free electron, as well as to pulse radiolysis data....

  5. Extended Holstein small polaron model for charge transfer in dry DNA. (United States)

    Wang, Yi; Fu, Liang; Wang, Ke-Lin


    In this paper, the charge transfer problem in dry DNA was investigated by employing an extended Holstein small polaron model with external potential traps being involved in consideration. The ground state energy and the probability amplitude of polaron in various DNA chains with different external trap potentials were obtained by variational method with the trial function being taken in coherent state form. The stability of transfered charges in various circumstances was discussed accordingly.

  6. Femtosecond Charge Transfer Dynamics of a Modified DNA Base: 2-Aminopurine in Complexes with Nucleotides


    Fiebig, Torsten; Wan, Chaozhi; Zewail, Ahmed H.


    As a fluorescent isomer of adenine, 2-aminopurine (Ap) is a powerful probe of DNA dynamics and DNA-mediated charge transfer processes. Here, we report studies with femtosecond resolution of the excited-state dynamics of Ap in various solvents and in bimolecular complexes with nucleotides. Using time-resolved transient absorption and fluorescence up-conversion methods we identify charge transfer as the origin for the quenching of the Ap fluorescence by all four DNA nucleotides. The direction o...

  7. Charge Transfer Interaction and Hydrogen Bonding between Vitamine K1 and Dihydrovitamine K1 (United States)

    Nagahira, Yukio; Matsuki, Kazunori; Fukutome, Hideo


    We studied visible and infrared spectra, in particular their temperature dependence, of Vitamine K1 oil dissolving dihydrovitamine K1. Vitamine K1 and dihydrovitamine K1 were found to form charge transfer complexes and hydrogen bonds in the mixture. A co-crystal of Dihydrovitamine K1 and Vitamine K1 with charge transfer interaction and hydrogen bonding was shown to grow in a narrow temperature range near -20°C.

  8. Theoretical Study of the Charge-Transfer State Separation within Marcus Theory

    DEFF Research Database (Denmark)

    Volpi, Riccardo; Nassau, Racine; Nørby, Morten Steen


    We study, within Marcus theory, the possibility of the charge-transfer (CT) state splitting at organic interfaces and a subsequent transport of the free charge carriers to the electrodes. As a case study we analyze model anthracene-C60 interfaces. Kinetic Monte Carlo (KMC) simulations on the cold...

  9. Radiative transfer simulations for the MADRAS imager of Megha ...

    Indian Academy of Sciences (India)

    These simulations have been performed by employing an in-house polarized radiative transfer code for raining systems ranging from depression and tropical ... with a parametric study of the effect of four hydrometeors (cloud liquid water, cloud ice, precipitating water and precipitating ice) on the brightness temperatures.

  10. Radiative transfer code: Application to the calculation of PAR

    Indian Academy of Sciences (India)

    Radiative transfer code: Application to the calculation of PAR. DEVRED EMMANUEL, DUBUISSON .... water vapor from Leckner (1978), with absorption coefficients for these gases taken from Gregg and. Carder (1990). ... law for the size distribution. The particle size ranges from 0.01 "m to 50 "m. 3. Validation of the code.

  11. An artificial neural network based fast radiative transfer model for ...

    Indian Academy of Sciences (India)

    In the present study, a fast radiative transfer model using neural networks is proposed to simulate radiances corresponding to the wavenumbers of INSAT-3D. Realistic atmospheric temperature and humidity profiles have been used for training the network. Spectral response functions of GOES-13, a satellite similar in ...

  12. An artificial neural network based fast radiative transfer model for ...

    Indian Academy of Sciences (India)

    the present study, a fast radiative transfer model using neural networks is proposed to simulate radiances corresponding to the wavenumbers of ... in construction, purpose and design and already in use are used. The fast RT model is able to ... porates measurements from various instruments in comparison with other ...

  13. Heat transfer with thermal radiation on MHD particle–fluid ...

    Indian Academy of Sciences (India)


    Sep 12, 2017 ... In this article, effects of heat transfer on particle–fluid suspension induced by metachronal wave have been examined. The influence of magnetohydrodynamics (MHD) and thermal radiation are also taken into account with the help of Ohm's law and Roseland's approximation. The governing flow problem for ...

  14. Thermosolutal MHD flow and radiative heat transfer with viscous ...

    African Journals Online (AJOL)

    This paper investigates double diffusive convection MHD flow past a vertical porous plate in a chemically active fluid with radiative heat transfer in the presence of viscous work and heat source. The resulting nonlinear dimensionless equations are solved by asymptotic analysis technique giving approximate analytic ...

  15. Free convection effects and radiative heat transfer in MHD Stokes ...

    Indian Academy of Sciences (India)

    The present note deals with the effects of radiative heat transfer and free convection in MHD for a flow of an electrically conducting, incompressible, dusty viscous fluid past an impulsively started vertical non-conducting plate, under the influence of transversely applied magnetic field. The heat due to viscous dissipation and ...

  16. Thermosolutal MHD flow and radiative heat transfer with viscous ...

    African Journals Online (AJOL)

    porous plate in a chemically active fluid with radiative heat transfer in the presence of viscous work and heat source. The resulting nonlinear dimensionless equations are solved by asymptotic analysis technique giving approximate analytic solutions for the steady velocity, temperature and concentration. The parameters ...

  17. Application of Stochastic Radiative Transfer Theory to the ARM Cloud-Radiative Parameterization Problem

    Energy Technology Data Exchange (ETDEWEB)

    Dana E. Veron


    This project had two primary goals: (1) development of stochastic radiative transfer as a parameterization that could be employed in an AGCM environment, and (2) exploration of the stochastic approach as a means for representing shortwave radiative transfer through mixed-phase layer clouds. To achieve these goals, climatology of cloud properties was developed at the ARM CART sites, an analysis of the performance of the stochastic approach was performed, a simple stochastic cloud-radiation parameterization for an AGCM was developed and tested, a statistical description of Arctic mixed phase clouds was developed and the appropriateness of stochastic approach for representing radiative transfer through mixed-phase clouds was assessed. Significant progress has been made in all of these areas and is detailed in the final report.

  18. Radiative transfer in a polluted urban planetary boundary layer (United States)

    Viskanta, R.; Johnson, R. O.; Bergstrom, R. W.


    Radiative transfer in a polluted urban atmosphere is studied using a dynamic model. The diurnal nature of radiative transfer for summer conditions is simulated for an urban area 40 km in extent and the effects of various parameters arising in the problem are investigated. The results of numerical computations show that air pollution has the potential of playing a major role in the radiative regime of the urban area. Absorption of solar energy by aerosols in realistic models of urban atmosphere are of the same order of magnitude as that due to water vapor. The predicted effect of the air pollution aerosol in the city is to warm the earth-atmosphere system, and the net effect of gaseous pollutant is to warm the surface and cool the planetary boundary layer, particularly near the top.

  19. Charge density analysis of two proton transfer complexes ...

    Indian Academy of Sciences (India)


    asparaginium ion and the picrate in the other complex. We have additionally performed theoretical calcu- lations at the density functional theory (DFT) level to understand the origin of enhancement of the dipole moments in the two systems. Keywords. X-ray diffraction; experimental charge density; hydrogen bonding; dipole ...

  20. Electronic Energies for Neon Dimer Dication Radiative Charge Transfer (United States)


    The Journal of Chemical Physics , 90, 1018 (1989). . James S. Cohen, and Barry...Schneider, The Journal of Chemical Physics , 61, #8, 3230-3239 (1974). s Friedrich Grein, Sigrid D. Peyerimhoff, and Robert J. Buenker, The Journal of Chemical Physics , 82...1, 353-363 (1985). 7 F. Grein and S. D. Peyerimhoff, The Journal of Chemical Physics , 87 #8, 4684-4692 (1987). s D.

  1. Communication: Charge transfer dominates over proton transfer in the reaction of nitric acid with gas-phase hydrated electrons (United States)

    Lengyel, Jozef; Med, Jakub; Slavíček, Petr; Beyer, Martin K.


    The reaction of HNO3 with hydrated electrons (H2O)n- (n = 35-65) in the gas phase was studied using Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometry and ab initio molecular dynamics simulations. Kinetic analysis of the experimental data shows that OH-(H2O)m is formed primarily via a reaction of the hydrated electron with HNO3 inside the cluster, while proton transfer is not observed and NO3-(H2O)m is just a secondary product. The reaction enthalpy was determined using nanocalorimetry, revealing a quite exothermic charge transfer with -241 ± 69 kJ mol-1. Ab initio molecular dynamics simulations indicate that proton transfer is an allowed reaction pathway, but the overall thermochemistry favors charge transfer.

  2. Femtosecond charge transfer dynamics of a modified DNA base: 2-aminopurine in complexes with nucleotides. (United States)

    Fiebig, Torsten; Wan, Chaozhi; Zewail, Ahmed H


    As a fluorescent isomer of adenine, 2-aminopurine (Ap) is a powerful probe of DNA dynamics and DNA-mediated charge transfer processes. Here, we report studies with femtosecond resolution of the excited-state dynamics of Ap in various solvents and in bimolecular complexes with nucleotides. Using time-resolved transient absorption and fluorescence up-conversion methods we identify charge transfer as the origin for the quenching of the Ap fluorescence by all four DNA nucleotides. The direction of the redox process is, however, dependent on the base, and from the rates we deduce the nature of the transfer, hole versus electron transfer. The pH and the kinetic isotope effects of these charge transfer reactions revealed no evidence for proton transfer involvement in the rate-determining step. From the measured rates and using electron transfer theory we estimate the driving force for charge transfer between all four nucleobases and Ap. The results are important for the studies of dynamics using Ap in DNA assemblies.

  3. Integer Charge Transfer and Hybridization at an Organic Semiconductor/Conductive Oxide Interface

    KAUST Repository

    Gruenewald, Marco


    We investigate the prototypical hybrid interface formed between PTCDA and conductive n-doped ZnO films by means of complementary optical and electronic spectroscopic techniques. We demonstrate that shallow donors in the vicinity of the ZnO surface cause an integer charge transfer to PTCDA, which is clearly restricted to the first monolayer. By means of DFT calculations, we show that the experimental signatures of the anionic PTCDA species can be understood in terms of strong hybridization with localized states (the shallow donors) in the substrate and charge back-donation, resulting in an effectively integer charge transfer across the interface. Charge transfer is thus not merely a question of locating the Fermi level above the PTCDA electron-transport level but requires rather an atomistic understanding of the interfacial interactions. The study reveals that defect sites and dopants can have a significant influence on the specifics of interfacial coupling and thus on carrier injection or extraction.

  4. Stochastic radiative transfer model for mixture of discontinuous vegetation canopies

    Energy Technology Data Exchange (ETDEWEB)

    Shabanov, Nikolay V. [Department of Geography, Boston University, 675 Commonwealth Avenue, Boston, MA 02215 (United States)]. E-mail:; Huang, D. [Brookhaven National Laboratory, Environmental Sciences Department, P.O. Box 5000, Upton, NY 11973 (United States); Knjazikhin, Y. [Department of Geography, Boston University, 675 Commonwealth Avenue, Boston, MA 02215 (United States); Dickinson, R.E. [School of Earth and Atmospheric Sciences, Georgia Institute of Technology, Atlanta, GA 30332 (United States); Myneni, Ranga B. [Department of Geography, Boston University, 675 Commonwealth Avenue, Boston, MA 02215 (United States)


    Modeling of the radiation regime of a mixture of vegetation species is a fundamental problem of the Earth's land remote sensing and climate applications. The major existing approaches, including the linear mixture model and the turbid medium (TM) mixture radiative transfer model, provide only an approximate solution to this problem. In this study, we developed the stochastic mixture radiative transfer (SMRT) model, a mathematically exact tool to evaluate radiation regime in a natural canopy with spatially varying optical properties, that is, canopy, which exhibits a structured mixture of vegetation species and gaps. The model solves for the radiation quantities, direct input to the remote sensing/climate applications: mean radiation fluxes over whole mixture and over individual species. The canopy structure is parameterized in the SMRT model in terms of two stochastic moments: the probability of finding species and the conditional pair-correlation of species. The second moment is responsible for the 3D radiation effects, namely, radiation streaming through gaps without interaction with vegetation and variation of the radiation fluxes between different species. We performed analytical and numerical analysis of the radiation effects, simulated with the SMRT model for the three cases of canopy structure: (a) non-ordered mixture of species and gaps (TM); (b) ordered mixture of species without gaps; and (c) ordered mixture of species with gaps. The analysis indicates that the variation of radiation fluxes between different species is proportional to the variation of species optical properties (leaf albedo, density of foliage, etc.) Gaps introduce significant disturbance to the radiation regime in the canopy as their optical properties constitute major contrast to those of any vegetation species. The SMRT model resolves deficiencies of the major existing mixture models: ignorance of species radiation coupling via multiple scattering of photons (the linear mixture

  5. Single and double charge transfer of He(2+) ions with molecules at near-thermal energies (United States)

    Tosh, R. E.; Johnsen, R.


    Rate coefficients were measured for charge-transfer reactions of He(2+) ions with H2, N2, O2, CO, CO2, and H2O. The experiments were carried out using a selected-ion drift-tube mass spectrometer. Total rate coefficients are found to be very large and are generally close to the limiting Langevin capture rate coefficients or the corresponding ADO-model (Su and Bowers, 1973) coefficients. The product-ion spectra indicate that both single and double charge transfer and possibly transfer ionization occur in these reactions.

  6. Design of horizontal fin array for radiative heat transfer (United States)

    Ali, Mutari Hajara; Shuaibu, Bilyaminu


    This paper presents the analytical and simulation results of optimizing the radiative heat transfer performance of horizontal rectangular fin array heat sink. The fin thickness and inter-fin spacing need to be properly designed to eliminate surface area changes accompanying the creation of fin structures. Analytical expression for this change in area is developed in this work and used in identifying the optimum number of fins and their corresponding inter-fin spacing for a given rectangular space of a radiative heat sink. COMSOL Multiphysics software is used to simulate the structures considered in the above analysis. The performances of the simulated structures as radiative heat sinks are compared with the ones suggested by the developed empirical equation. The results from the two methods agreed with each successfully in the sense that the structures with large numerical radiative power from the simulations are found to also be the optimum structures suggested by the analytical formula derived in this work.

  7. An anisotropic diffusion approximation to thermal radiative transfer

    Energy Technology Data Exchange (ETDEWEB)

    Johnson, Seth R.; Larsen, Edward W., E-mail:, E-mail: [Department of Nuclear Engineering and Radiological Sciences, University of Michigan, Ann Arbor, MI (United States)


    This paper describes an anisotropic diffusion (AD) method that uses transport-calculated AD coefficients to efficiently and accurately solve the thermal radiative transfer (TRT) equations. By assuming weak gradients and angular moments in the radiation intensity, we derive an expression for the radiation energy density that depends on a non-local function of the opacity. This nonlocal function is the solution of a transport equation that can be solved with a single steady-state transport sweep once per time step, and the function's second angular moment is the anisotropic diffusion tensor. To demonstrate the AD method's efficacy, we model radiation flow down a channel in 'flatland' geometry. (author)

  8. Space charge dosimeters for extremely low power measurements of radiation in shipping containers (United States)

    Britton, Jr; Charles, L [Alcoa, TN; Buckner, Mark A [Oak Ridge, TN; Hanson, Gregory R [Clinton, TN; Bryan, William L [Knoxville, TN


    Methods and apparatus are described for space charge dosimeters for extremely low power measurements of radiation in shipping containers. A method includes in situ polling a suite of passive integrating ionizing radiation sensors including reading-out dosimetric data from a first passive integrating ionizing radiation sensor and a second passive integrating ionizing radiation sensor, where the first passive integrating ionizing radiation sensor and the second passive integrating ionizing radiation sensor remain situated where the dosimetric data was integrated while reading-out. Another method includes arranging a plurality of ionizing radiation sensors in a spatially dispersed array; determining a relative position of each of the plurality of ionizing radiation sensors to define a volume of interest; collecting ionizing radiation data from at least a subset of the plurality of ionizing radiation sensors; and triggering an alarm condition when a dose level of an ionizing radiation source is calculated to exceed a threshold.

  9. SGPGET: AN SBDART Module for Aerosol Radiative Transfer

    Energy Technology Data Exchange (ETDEWEB)

    McComiskey, A.; Ricchiazzi, P.; Ogren, J.A.; Dutton, E.


    Quantification of the aerosol direct effect and climate sensitivity requires accurate estimates of optical properties as inputs to a radiative transfer model. Long-term measurements of aerosol properties at the Southern Great Plains (SGP) site can be used as an improvement over a best guess or global average for optical properties (e.g., asymmetry factor of 0.7) used in Atmospheric Radiation Measurement (ARM) products such as the Broadband Heating Rate Profile VAP. To make this information readily available to the ARM community and others, an add-on module for a commonly used radiative transfer model, SBDART (Ricchiazzi et al. 1998), is being developed. A look up table and algorithm will provide aerosol related model inputs including aerosol optical and atmospheric state properties at high temporal resolution. These inputs can be used in conjunction with any mode of operation and with any other information, for example, cloud properties, in SBDART or any other radiative transfer model. Aerosol properties measured at three visible wavelengths are extrapolated so that flux calculations can be made in any desired wavelength across the shortwave spectrum. Several sources of uncertainty contribute to degraded accuracy of the aerosol property estimation. The effect of these uncertainties is shown through error analysis and comparisons of modeled and observed surface irradiance. A module is also being developed for the North Slope of Alaska site.

  10. Properties of an ultrarelativistic charged particle radiation in a constant homogeneous crossed electromagnetic field

    Energy Technology Data Exchange (ETDEWEB)

    Bogdanov, O.V., E-mail: [Physics Faculty, Tomsk State University, Tomsk, 634050 (Russian Federation); Department of Higher Mathematics and Mathematical Physics, Tomsk Polytechnic University, Tomsk, 634050 (Russian Federation); Kazinski, P.O., E-mail: [Physics Faculty, Tomsk State University, Tomsk, 634050 (Russian Federation); Department of Higher Mathematics and Mathematical Physics, Tomsk Polytechnic University, Tomsk, 634050 (Russian Federation); Lazarenko, G.Yu., E-mail: [Physics Faculty, Tomsk State University, Tomsk, 634050 (Russian Federation)


    The properties of radiation created by a classical ultrarelativistic scalar charged particle in a constant homogeneous crossed electromagnetic field are described both analytically and numerically with radiation reaction taken into account in the form of the Landau–Lifshitz equation. The total radiation naturally falls into two parts: the radiation formed at the entrance point of a particle into the crossed field (the synchrotron entrance radiation), and the radiation coming from the late-time asymptotics of a particle motion (the de-excited radiation). The synchrotron entrance radiation resembles, although does not coincide with, the ultrarelativistic limit of the synchrotron radiation: its distribution over energies and angles possesses almost the same properties. The de-excited radiation is soft, not concentrated in the plane of motion of a charged particle, and almost completely circularly polarized. The photon energy delivering the maximum to its spectral angular distribution decreases with increasing the initial energy of a charged particle, while the maximum value of this distribution remains the same at the fixed photon observation angle and entrance angle of a charged particle. The ultraviolet and infrared asymptotics of the total radiation are also described. - Highlights: • Properties of an electron radiation in a crossed electromagnetic field are studied. • Spectral angular distribution of the synchrotron entrance radiation is described. • Spectral angular distribution of the de-excited radiation is described. • De-excited radiation is almost completely circularly polarized. • Photon energy at the maximum of the de-excited radiation decreases with increasing the initial energy of an electron.

  11. Charge-transfer spectra of ferrocene in halocarbon solvents under ...

    Indian Academy of Sciences (India)


    synthesized metallocene) has wide application in various technological fields 1. The important electrochemical, photochemical and photophysical properties of the material have been recognized 2–5. This material has been used (i) efficiently as mediators in various electron transfer processes 2, (ii) in the development of ...

  12. Preliminary results of a three-dimensional radiative transfer model

    Energy Technology Data Exchange (ETDEWEB)

    O`Hirok, W. [Univ. of California, Santa Barbara, CA (United States)


    Clouds act as the primary modulator of the Earth`s radiation at the top of the atmosphere, within the atmospheric column, and at the Earth`s surface. They interact with both shortwave and longwave radiation, but it is primarily in the case of shortwave where most of the uncertainty lies because of the difficulties in treating scattered solar radiation. To understand cloud-radiative interactions, radiative transfer models portray clouds as plane-parallel homogeneous entities to ease the computational physics. Unfortunately, clouds are far from being homogeneous, and large differences between measurement and theory point to a stronger need to understand and model cloud macrophysical properties. In an attempt to better comprehend the role of cloud morphology on the 3-dimensional radiation field, a Monte Carlo model has been developed. This model can simulate broadband shortwave radiation fluxes while incorporating all of the major atmospheric constituents. The model is used to investigate the cloud absorption anomaly where cloud absorption measurements exceed theoretical estimates and to examine the efficacy of ERBE measurements and cloud field experiments. 3 figs.

  13. Critical ingredients of Type Ia supernova radiative-transfer modelling (United States)

    Dessart, Luc; Hillier, D. John; Blondin, Stéphane; Khokhlov, Alexei


    We explore the physics of Type Ia supernova (SN Ia) light curves and spectra using the 1D non-local thermodynamic equilibrium (non-LTE) time-dependent radiative-transfer code CMFGEN. Rather than adjusting ejecta properties to match observations, we select as input one `standard' 1D Chandrasekhar-mass delayed-detonation hydrodynamical model, and then explore the sensitivity of radiation and gas properties of the ejecta on radiative-transfer modelling assumptions. The correct computation of SN Ia radiation is not exclusively a solution to an `opacity problem', characterized by the treatment of a large number of lines. We demonstrate that the key is to identify and treat important atomic processes consistently. This is not limited to treating line blanketing in non-LTE. We show that including forbidden-line transitions of metals, and in particular Co, is increasingly important for the temperature and ionization of the gas beyond maximum light. Non-thermal ionization and excitation are also critical since they affect the colour evolution and the ΔM15 decline rate of our model. While impacting little the bolometric luminosity, a more complete treatment of decay routes leads to enhanced line blanketing, e.g. associated with 48Ti in the U and B bands. Overall, we find that SN Ia radiation properties are influenced in a complicated way by the atomic data we employ, so that obtaining converged results is a real challenge. Nonetheless, with our fully fledged CMFGEN model, we obtain good agreement with the golden standard Type Ia SN 2005cf in the optical and near-IR, from 5 to 60 d after explosion, suggesting that assuming spherical symmetry is not detrimental to SN Ia radiative-transfer modelling at these times. Multi-D effects no doubt matter, but they are perhaps less important than accurately treating the non-LTE processes that are crucial to obtain reliable temperature and ionization structures.

  14. Fire Intensity Data for Validation of the Radiative Transfer Equation

    Energy Technology Data Exchange (ETDEWEB)

    Blanchat, Thomas K. [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States); Jernigan, Dann A. [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)


    A set of experiments and test data are outlined in this report that provides radiation intensity data for the validation of models for the radiative transfer equation. The experiments were performed with lightly-sooting liquid hydrocarbon fuels that yielded fully turbulent fires 2 m diameter). In addition, supplemental measurements of air flow and temperature, fuel temperature and burn rate, and flame surface emissive power, wall heat, and flame height and width provide a complete set of boundary condition data needed for validation of models used in fire simulations.

  15. Advanced Computational Methods for Thermal Radiative Heat Transfer

    Energy Technology Data Exchange (ETDEWEB)

    Tencer, John; Carlberg, Kevin Thomas; Larsen, Marvin E.; Hogan, Roy E.,


    Participating media radiation (PMR) in weapon safety calculations for abnormal thermal environments are too costly to do routinely. This cost may be s ubstantially reduced by applying reduced order modeling (ROM) techniques. The application of ROM to PMR is a new and unique approach for this class of problems. This approach was investigated by the authors and shown to provide significant reductions in the computational expense associated with typical PMR simulations. Once this technology is migrated into production heat transfer analysis codes this capability will enable the routine use of PMR heat transfer in higher - fidelity simulations of weapon resp onse in fire environments.

  16. Light scattering reviews 7 radiative transfer and optical properties of atmosphere and underlying surface

    CERN Document Server

    Kokhanovsky, Alexander A


    This book describes modern advances in radiative transfer and light scattering. Coverage includes fast radiative transfer techniques, use of polarization in remote sensing and recent developments in remote sensing of snow properties from space observations.

  17. Dynamical correlations in one-dimensional charge-transfer insulators


    Penc, Karlo; Stephan, Walter


    The single-particle spectral function and the density response of a two band Emery model for CuO chains is calculated for large on-site Cu repulsion U and large on-site energy difference \\Delta. For U>>U-\\Delta>>t the eigenfunctions are products of charge and spin parts, which allows analytical calculation of spectral functions in that limit. For other parameters numerical diagonalization is used. The low energy hole carriers are shown to be the one-dimensional analogs of the Zhang-Rice singl...

  18. Fullerene-Based Photoactive Layers for Heterojunction Solar Cells: Structure, Absorption Spectra and Charge Transfer Process

    Directory of Open Access Journals (Sweden)

    Yuanzuo Li


    Full Text Available The electronic structure and optical absorption spectra of polymer APFO3, [70]PCBM/APFO3 and [60]PCBM/APFO3, were studied with density functional theory (DFT, and the vertical excitation energies were calculated within the framework of the time-dependent DFT (TD-DFT. Visualized charge difference density analysis can be used to label the charge density redistribution for individual fullerene and fullerene/polymer complexes. The results of current work indicate that there is a difference between [60]PCBM and [70]PCBM, and a new charge transfer process is observed. Meanwhile, for the fullerene/polymer complex, all calculations of the twenty excited states were analyzed to reveal all possible charge transfer processes in depth. We also estimated the electronic coupling matrix, reorganization and Gibbs free energy to further calculate the rates of the charge transfer and the recombination. Our results give a clear picture of the structure, absorption spectra, charge transfer (CT process and its influencing factors, and provide a theoretical guideline for designing further photoactive layers of solar cells.


    Energy Technology Data Exchange (ETDEWEB)

    Davis, Shane W. [Canadian Institute for Theoretical Astrophysics, Toronto, ON M5S 3H4 (Canada); Stone, James M.; Jiang Yanfei [Department of Astrophysical Sciences, Princeton University, Princeton, NJ 08544 (United States)


    We describe the implementation of a module for the Athena magnetohydrodynamics (MHD) code that solves the time-independent, multi-frequency radiative transfer (RT) equation on multidimensional Cartesian simulation domains, including scattering and non-local thermodynamic equilibrium (LTE) effects. The module is based on well known and well tested algorithms developed for modeling stellar atmospheres, including the method of short characteristics to solve the RT equation, accelerated Lambda iteration to handle scattering and non-LTE effects, and parallelization via domain decomposition. The module serves several purposes: it can be used to generate spectra and images, to compute a variable Eddington tensor (VET) for full radiation MHD simulations, and to calculate the heating and cooling source terms in the MHD equations in flows where radiation pressure is small compared with gas pressure. For the latter case, the module is combined with the standard MHD integrators using operator splitting: we describe this approach in detail, including a new constraint on the time step for stability due to radiation diffusion modes. Implementation of the VET method for radiation pressure dominated flows is described in a companion paper. We present results from a suite of test problems for both the RT solver itself and for dynamical problems that include radiative heating and cooling. These tests demonstrate that the radiative transfer solution is accurate and confirm that the operator split method is stable, convergent, and efficient for problems of interest. We demonstrate there is no need to adopt ad hoc assumptions of questionable accuracy to solve RT problems in concert with MHD: the computational cost for our general-purpose module for simple (e.g., LTE gray) problems can be comparable to or less than a single time step of Athena's MHD integrators, and only few times more expensive than that for more general (non-LTE) problems.

  20. Charge Transfer Properties Through Graphene Layers in Gas Detectors

    CERN Document Server

    Thuiner, P.; Jackman, R.B.; Müller, H.; Nguyen, T.T.; Oliveri, E.; Pfeiffer, D.; Resnati, F.; Ropelewski, L.; Smith, J.A.; van Stenis, M.; Veenhof, R.


    Graphene is a single layer of carbon atoms arranged in a honeycomb lattice with remarkable mechanical, electrical and optical properties. For the first time graphene layers suspended on copper meshes were installed into a gas detector equipped with a gaseous electron multiplier. Measurements of low energy electron and ion transfer through graphene were conducted. In this paper we describe the sample preparation for suspended graphene layers, the testing procedures and we discuss the preliminary results followed by a prospect of further applications.

  1. Non-Markovian reduced dynamics of ultrafast charge transfer at an oligothiophene–fullerene heterojunction

    Energy Technology Data Exchange (ETDEWEB)

    Hughes, Keith H., E-mail: [School of Chemistry, Bangor University, Bangor, Gwynedd LL57 2UW (United Kingdom); Cahier, Benjamin [School of Chemistry, Bangor University, Bangor, Gwynedd LL57 2UW (United Kingdom); Martinazzo, Rocco [Dipartimento di Chimica Università degli Studi di Milano, v. Golgi 19, 20133 Milano (Italy); Tamura, Hiroyuki [WPI-Advanced Institute for Material Research, Tohoku University, 2-1-1 Katahira, Aoba-ku, Sendai 980-8577 (Japan); Burghardt, Irene [Institute of Physical and Theoretical Chemistry, Goethe University Frankfurt, Max-von-Laue-Str. 7, 60438 Frankfurt/Main (Germany)


    Highlights: • Quantum dynamical study of exciton dissociation at a heterojunction interface. • The non-Markovian quantum dynamics involves a highly structured spectral density. • Spectral density is reconstructed from an effective mode transformation of the Hamiltonian. • The dynamics is studied using the hierarchical equations of motion approach. • It was found that the temperature has little effect on the charge transfer. - Abstract: We extend our recent quantum dynamical study of the exciton dissociation and charge transfer at an oligothiophene–fullerene heterojunction interface (Tamura et al., 2012) [6] by investigating the process using the non-perturbative hierarchical equations of motion (HEOM) approach. Based upon an effective mode reconstruction of the spectral density the effect of temperature on the charge transfer is studied using reduced density matrices. It was found that the temperature had little effect on the charge transfer and a coherent dynamics persists over the first few tens of femtoseconds, indicating that the primary charge transfer step proceeds by an activationless pathway.

  2. Ultrafast holography and transient absorption spectroscopy in charge-transfer polymers

    Energy Technology Data Exchange (ETDEWEB)

    McBranch, D.W.; Maniloff, E.S. [Los Alamos National Lab., NM (United States); Vacar, D.; Heeger, A.J. [Univ. of California, Santa Barbara, CA (United States). Institute for Polymers and Organic Solids


    Charge-transfer polymers are a new class of nonlinear optical materials which can be used for generating femtosecond holographic gratings. Using semiconducting polymers sensitized with varying concentrations of C{sub 60}, holographic gratings were recorded by individual ultrafast laser pulses; the diffraction efficiency and time decay of the gratings were measured using non-degenerate four-wave mixing. Using a figure of merit for dynamic data processing, the temporal diffraction efficiency, this new class of materials exhibits between two and 12 orders of magnitude higher response than previous reports. The charge transfer range at polymer/C{sub 60} interfaces was further studied using transient absorption spectroscopy. The fact that charge-transfer occurs in the picosecond-time scale in bilayer structures (thickness 200 {angstrom}) implies that diffusion of localized excitations to the interface is not the dominant mechanism; the charge transfer range is a significant fraction of the film thickness. From analysis of the excited state decay curves, we estimate the charge transfer range to be 80 {angstrom} and interpret that range as resulting from quantum delocalization of the photoexcitations.

  3. Photochemistry and electron-transfer mechanism of transition metal oxalato complexes excited in the charge transfer band. (United States)

    Chen, Jie; Zhang, Hua; Tomov, Ivan V; Ding, Xunliang; Rentzepis, Peter M


    The photoredox reaction of trisoxalato cobaltate (III) has been studied by means of ultrafast extended x-ray absorption fine structure and optical transient spectroscopy after excitation in the charge-transfer band with 267-nm femtosecond pulses. The Co-O transient bond length changes and the optical spectra and kinetics have been measured and compared with those of ferrioxalate. Data presented here strongly suggest that both of these metal oxalato complexes operate under similar photoredox reaction mechanisms where the primary reaction involves the dissociation of a metal-oxygen bond. These results also indicate that excitation in the charge-transfer band is not a sufficient condition for the intramolecular electron transfer to be the dominant photochemistry reaction mechanism.

  4. Modeling Radiative Heat Transfer and Turbulence-Radiation Interactions in Engines

    Energy Technology Data Exchange (ETDEWEB)

    Paul, Chandan [Pennsylvania State Univ., University Park, PA (United States); Sircar, Arpan [Pennsylvania State Univ., University Park, PA (United States); Ferreyro-Fernandez, Sebastian [Pennsylvania State Univ., University Park, PA (United States); Imren, Abdurrahman [Pennsylvania State Univ., University Park, PA (United States); Haworth, Daniel C [Pennsylvania State Univ., University Park, PA (United States); Roy, Somesh P [Marquette University (United States); Ge, Wenjun [University of California Merced (United States); Modest, Michael F [University of California Merced (United States)


    Detailed radiation modelling in piston engines has received relatively little attention to date. Recently, it is being revisited in light of current trends towards higher operating pressures and higher levels of exhaust-gas recirculation, both of which enhance molecular gas radiation. Advanced high-efficiency engines also are expected to function closer to the limits of stable operation, where even small perturbations to the energy balance can have a large influence on system behavior. Here several different spectral radiation property models and radiative transfer equation (RTE) solvers have been implemented in an OpenFOAM-based engine CFD code, and simulations have been performed for a full-load (peak pressure ~200 bar) heavy-duty diesel engine. Differences in computed temperature fields, NO and soot levels, and wall heat transfer rates are shown for different combinations of spectral models and RTE solvers. The relative importance of molecular gas radiation versus soot radiation is examined. And the influence of turbulence-radiation interactions is determined by comparing results obtained using local mean values of composition and temperature to compute radiative emission and absorption with those obtained using a particle-based transported probability density function method.

  5. Asymmetric radiation transfer based on linear light-matter interaction (United States)

    Jia, Zi-xun; Shuai, Yong; Zhang, Jia-hui; Tan, He-ping


    In this paper, asymmetric radiation transfer based on linear light-matter interaction has been proposed. Two naturally different numerical methods, finite difference time domain (FDTD) and rigorous coupled wave analysis (RCWA), are utilized to verify that asymmetric radiation transfer can exist for linear plasmonic meta-material. The overall asymmetry has been introduced to evaluate bifacial transmission. Physics for the asymmetric optical responses have been understood via electromagnetic field distributions. Dispersion relation for surface plasmon polariton (SPP) and temporal coupled mode theory (TCMT) have been employed to verify the physics discussed in the paper. Geometric effects and the disappearing of asymmetric transmission have also been investigated. The results gained herein broaden the cognition of linear optical system, facilitate the design of novel energy harvesting device.

  6. Charge Transfer across Quantum Dot-Oxide Interfaces for High-Efficiency Photovoltaics (United States)

    Bonn, Mischa

    Metal oxides constitute robust and relatively cheap semiconductor materials that are finding increasing applications in opto-electronics, but their band gaps are typically prohibitively wide for the generation of free charges through the absorption of visible light. Several approaches have been developed to circumvent this drawback. Specifically, the sensitization of mesoporous oxides by semiconductor quantum dot (QD) nanocrystals represents a promising route for the development of low-cost photovoltaics in QD sensitized solar cells. In addition to their tuneable band gap, QDs have the ability to generate multiple charge carriers from single photons by a process called carrier multiplication (CM), which potentially provides a means towards high-efficiency photovoltaics. Although CM has been widely interrogated in colloidal QDs in solution, the collection of those multiple charge carriers at oxide electrodes has not been clearly elucidated. The contribution of CM towards the overall device performance is ultimately determined by a competition between transfer to the electrode material and charge recombination within the QDs. We report interfacial electron transfer dynamics from quantum dots grown directly onto mesoporous oxide films. Such systems are well-suited for achieving efficient multiple charge transfer by CM, as electron transfer from QD-to-oxide is substantially faster than charge recombination. However, despite CM occurring in the QD, only one electron is transferred to the oxide. This seemingly counterintuitive result can be understood by noting that efficient hot electron transfer at the QD-oxide interface can compete with CM within the QDs. Hot electron transfer is observed to occur on sub-100 fs timescales, nulling the CM efficiency. Implications of these results for solar energy conversion are discussed.

  7. SMRT: A new, modular snow microwave radiative transfer model (United States)

    Picard, Ghislain; Sandells, Melody; Löwe, Henning; Dumont, Marie; Essery, Richard; Floury, Nicolas; Kontu, Anna; Lemmetyinen, Juha; Maslanka, William; Mätzler, Christian; Morin, Samuel; Wiesmann, Andreas


    Forward models of radiative transfer processes are needed to interpret remote sensing data and derive measurements of snow properties such as snow mass. A key requirement and challenge for microwave emission and scattering models is an accurate description of the snow microstructure. The snow microwave radiative transfer model (SMRT) was designed to cater for potential future active and/or passive satellite missions and developed to improve understanding of how to parameterize snow microstructure. SMRT is implemented in Python and is modular to allow easy intercomparison of different theoretical approaches. Separate modules are included for the snow microstructure model, electromagnetic module, radiative transfer solver, substrate, interface reflectivities, atmosphere and permittivities. An object-oriented approach is used with carefully specified exchanges between modules to allow future extensibility i.e. without constraining the parameter list requirements. This presentation illustrates the capabilities of SMRT. At present, five different snow microstructure models have been implemented, and direct insertion of the autocorrelation function from microtomography data is also foreseen with SMRT. Three electromagnetic modules are currently available. While DMRT-QCA and Rayleigh models need specific microstructure models, the Improved Born Approximation may be used with any microstructure representation. A discrete ordinates approach with stream connection is used to solve the radiative transfer equations, although future inclusion of 6-flux and 2-flux solvers are envisioned. Wrappers have been included to allow existing microwave emission models (MEMLS, HUT, DMRT-QMS) to be run with the same inputs and minimal extra code (2 lines). Comparisons between theoretical approaches will be shown, and evaluation against field experiments in the frequency range 5-150 GHz. SMRT is simple and elegant to use whilst providing a framework for future development within the

  8. Intercomparison of shortwave radiative transfer schemes in global aerosol modeling: results from the AeroCom Radiative Transfer Experiment

    Directory of Open Access Journals (Sweden)

    C. A. Randles


    Full Text Available In this study we examine the performance of 31 global model radiative transfer schemes in cloud-free conditions with prescribed gaseous absorbers and no aerosols (Rayleigh atmosphere, with prescribed scattering-only aerosols, and with more absorbing aerosols. Results are compared to benchmark results from high-resolution, multi-angular line-by-line radiation models. For purely scattering aerosols, model bias relative to the line-by-line models in the top-of-the atmosphere aerosol radiative forcing ranges from roughly −10 to 20%, with over- and underestimates of radiative cooling at lower and higher solar zenith angle, respectively. Inter-model diversity (relative standard deviation increases from ~10 to 15% as solar zenith angle decreases. Inter-model diversity in atmospheric and surface forcing decreases with increased aerosol absorption, indicating that the treatment of multiple-scattering is more variable than aerosol absorption in the models considered. Aerosol radiative forcing results from multi-stream models are generally in better agreement with the line-by-line results than the simpler two-stream schemes. Considering radiative fluxes, model performance is generally the same or slightly better than results from previous radiation scheme intercomparisons. However, the inter-model diversity in aerosol radiative forcing remains large, primarily as a result of the treatment of multiple-scattering. Results indicate that global models that estimate aerosol radiative forcing with two-stream radiation schemes may be subject to persistent biases introduced by these schemes, particularly for regional aerosol forcing.

  9. An edge-on charge-transfer design for energy-resolved x-ray detection (United States)

    Shi, Zaifeng; Yang, Haoyu; Cong, Wenxiang; Wang, Ge


    As an x-ray beam goes through the human body, it will collect important information via interaction with tissues. Since this interaction is energy-sensitive, the state-of-the-art spectral CT technologies provide higher quality images of biological tissues with x-ray energy information (or spectral information). With existing energy-integrating technologies, a large fraction of energy information is ignored in the x-ray detection process. Although the recently proposed photon-counting technology promises to achieve higher image quality at a lower radiation dose, it suffers from limitations in counting rate, performance uniformity, and fabrication cost. In this paper, we focus on an alternative approach to resolve the energy distribution of transmitted x-ray photons. First, we analyze the x-ray attenuation in a silicon substrate and describe a linear approximation model for x-ray detection. Then, we design an edge-on architecture based on the proposed energy-resolving model. In our design, the x-ray-photon-induced charges are transferred sequentially resembling the working process of a CCD camera. Finally, we numerically evaluate the linear approximation of x-ray attenuation and derive the energy distribution of x-ray photons. Our simulation results show that the proposed energy-sensing approach is feasible and has the potential to complement the photon-counting technology.

  10. TWILIGHT: A Cellular Framework for Three-Dimensional Radiative Transfer (United States)

    Khatami, David; Madore, Barry


    We describe a new framework for solving three-dimensional radiative transfer of arbitrary geometries, including a full characterisation of the wavelength-dependent anisotropic scattering, absorption, and thermal reemission of light by dust. By adopting a cellular approach to discretising the light and dust, the problem can be efficiently solved through a fully deterministic iterative process. As a proof of concept we present TWILIGHT, our implementation of the cellular approach, in order to demonstrate and benchmark the new method. TWILIGHT simultaneously renders over one hundred unique images of a given environment with no additional slowdown, enabling a close study of inclination effects of three-dimensional dust geometries. In addition to qualitative rendering tests, TWILIGHT is successfully tested against two Monte-Carlo radiative transfer benchmarks, producing similar brightness profiles at varying inclinations. With the proof-of-concept established, we describe the improvements and current developments underway using the cellular framework, including a technique to resolve the subgrid physics of dust radiative transfer from micron-scale grain models to kiloparsec-sized dust environments.

  11. Lattice Boltzmann method for one-dimensional vector radiative transfer. (United States)

    Zhang, Yong; Yi, Hongliang; Tan, Heping


    A one-dimensional vector radiative transfer (VRT) model based on lattice Boltzmann method (LBM) that considers polarization using four Stokes parameters is developed. The angular space is discretized by the discrete-ordinates approach, and the spatial discretization is conducted by LBM. LBM has such attractive properties as simple calculation procedure, straightforward and efficient handing of boundary conditions, and capability of stable and accurate simulation. To validate the performance of LBM for vector radiative transfer, four various test problems are examined. The first case investigates the non-scattering thermal-emitting atmosphere with no external collimated solar. For the other three cases, the external collimated solar and three different scattering types are considered. Particularly, the LBM is extended to solve VRT in the atmospheric aerosol system where the scattering function contains singularities and the hemisphere space distributions for the Stokes vector are presented and discussed. The accuracy and computational efficiency of this algorithm are discussed. Numerical results show that the LBM is accurate, flexible and effective to solve one-dimensional polarized radiative transfer problems.

  12. Channeling and electromagnetic radiation of relativistic charged particles in metal-organic frameworks (United States)

    Zhevago, N. K.; Glebov, V. I.


    We have developed the theory of electromagnetic interaction of relativistic charged particles with metal-organic frameworks (MOFs). The electrostatic potential and electron number density distribution in MOFs were calculated using the most accurate data for the atomic form factors. Peculiarities of axial channeling of fast charged particles and various types of electromagnetic radiation from relativistic particles has been discussed.

  13. Photoinduced charge-transfer electronic excitation of tetracyanoethylene/tetramethylethylene complex in dichloromethane (United States)

    Xu, Long-Kun; Bi, Ting-Jun; Ming, Mei-Jun; Wang, Jing-Bo; Li, Xiang-Yuan


    Based on the previous work on nonequilibrium solvation model by the authors, Intermolecular charge-transfer electronic excitation of tetracyanoethylene (TCE)/tetramethylethylene (TME) π -stacked complex in dichloromethane (DCM) has been investigated. For weak interaction correction, dispersion corrected functional DFT-D3 is adopted for geometry optimization. In order to identify the excitation metric, dipole moment components of each Cartesian direction, atomic charge, charge separation and Δr index are analyzed for TCE/TME complex. Calculation shows that the calculated excitation energy is dependent on the functional choice, when conjuncted with suitable time-dependent density functional, the modified nonequilibrium expression gives satisfied results for intermolecular charge-transfer electronic excitation.

  14. Intersystem crossing mediated by photoinduced intramolecular charge transfer: julolidine-anthracene molecules with perpendicular pi systems. (United States)

    Dance, Zachary E X; Mickley, Sarah M; Wilson, Thea M; Ricks, Annie Butler; Scott, Amy M; Ratner, Mark A; Wasielewski, Michael R


    Time-resolved electron paramagnetic resonance studies show that the primary mechanism of triplet formation following photoexcitation of julolidine-anthracene molecules linked by a single bond and having perpendicular pi systems is a spin-orbit, charge-transfer intersystem crossing mechanism (SOCT-ISC). This mechanism depends on the degree of charge transfer from julolidine to anthracene, the dihedral angle (theta1) between their pi systems, and the magnitude of the electronic coupling between julolidine and anthracene. We compare 4-(9-anthracenyl)-julolidine with the more sterically encumbered 4-(9-anthracenyl)-3,5-dimethyljulolidine and find that fixing theta1 congruent with 90 degrees serves to enhance SOCT-ISC by increasing the change in orbital angular momentum accompanying charge transfer. Given that the requirements for the SOCT-ISC mechanism are quite general, we expect it to occur in a variety of electron donor-acceptor systems.

  15. Organic narrowband near-infrared photodetectors based on intermolecular charge-transfer absorption (United States)

    Siegmund, Bernhard; Mischok, Andreas; Benduhn, Johannes; Zeika, Olaf; Ullbrich, Sascha; Nehm, Frederik; Böhm, Matthias; Spoltore, Donato; Fröb, Hartmut; Körner, Christian; Leo, Karl; Vandewal, Koen


    Blending organic electron donors and acceptors yields intermolecular charge-transfer states with additional optical transitions below their optical gaps. In organic photovoltaic devices, such states play a crucial role and limit the operating voltage. Due to its extremely weak nature, direct intermolecular charge-transfer absorption often remains undetected and unused for photocurrent generation. Here, we use an optical microcavity to increase the typically negligible external quantum efficiency in the spectral region of charge-transfer absorption by more than 40 times, yielding values over 20%. We demonstrate narrowband detection with spectral widths down to 36 nm and resonance wavelengths between 810 and 1,550 nm, far below the optical gap of both donor and acceptor. The broad spectral tunability via a simple variation of the cavity thickness makes this innovative, flexible and potentially visibly transparent device principle highly suitable for integrated low-cost spectroscopic near-infrared photodetection.

  16. Heat transfer from the evaporator outlet to the charge of thermostatic expansion valves

    DEFF Research Database (Denmark)

    Langmaack, Lasse Nicolai; Knudsen, Hans-Jørgen Høgaard


    The bulb of a thermostatic expansion valve (TXV) is basically a temperature-pressure converter. It senses the temperature at the outlet of the evaporator, and the substance in the bulb (charge) generates the corresponding saturation pressure inside the bulb. The bulb is mounted on the evaporator...... outlet with a special mounting strap. The heat transfer is quite complex because it takes place both directly through the contact points between bulb and pipe and indirectly through the mounting strap The TXV has to react to temperature changes at the evaporator outlet. Therefore, the dynamic behavior...... of the valve (and thereby the whole refrigeration system) depends greatly on the heat transfer between the evaporator outlet tube and the charge in the bulb. In this paper a model for the overall heat transfer between the pipe and the charge is presented. Geometrical data and material properties have been kept...

  17. Charge Transfer Properties Through Graphene for Applications in Gaseous Detectors

    CERN Document Server

    Franchino, S.; Hall-Wilton, R.; Jackman, R.B.; Muller, H.; Nguyen, T.T.; de Oliveira, R.; Oliveri, E.; Pfeiffer, D.; Resnati, F.; Ropelewski, L.; Smith, J.; van Stenis, M.; Streli, C.; Thuiner, P.; Veenhof, R.


    Graphene is a single layer of carbon atoms arranged in a honeycomb lattice with remarkable mechanical and electrical properties. Regarded as the thinnest and narrowest conductive mesh, it has drastically different transmission behaviours when bombarded with electrons and ions in vacuum. This property, if confirmed in gas, may be a definitive solution for the ion back-flow problem in gaseous detectors. In order to ascertain this aspect, graphene layers of dimensions of about 2x2cm$^2$, grown on a copper substrate, are transferred onto a flat metal surface with holes, so that the graphene layer is freely suspended. The graphene and the support are installed into a gaseous detector equipped with a triple Gaseous Electron Multiplier (GEM), and the transparency properties to electrons and ions are studied in gas as a function of the electric fields. The techniques to produce the graphene samples are described, and we report on preliminary tests of graphene-coated GEMs.

  18. Photoinduced charge transfer involving a MoMo quadruply bonded complex to a perylene diimide. (United States)

    Alberding, Brian G; Brown-Xu, Samantha E; Chisholm, Malcolm H; Epstein, Arthur J; Gustafson, Terry L; Lewis, Sharlene A; Min, Yong


    Evidence, based on femtosecond transient absorption and time resolved infrared spectroscopy, is presented for photoinduced charge transfer from the Mo2δ orbital of the quadruply bonded molecule trans-Mo2(T(i)PB)2(BTh)2, where T(i)PB = 2,4,6-triisopropyl benzoate and BTh = 2,2'-bithienylcarboxylate, to di-n-octyl perylene diimide and di-n-hexylheptyl perylene diimide in thin films and solutions of the mixtures. The films show a long-lived charge separated state while slow back electron transfer, τBET ~ 500 ps, occurs in solution.

  19. Theory for charge states of energetic oxygen ions in the earth's radiation belts (United States)

    Spjeldvik, W. N.; Fritz, T. A.


    Fluxes of geomagnetically trapped energetic oxygen ions have been studied in detail. Ion distributions in radial locations below the geostationary orbit, energy spectra between 1 keV and 100 MeV, and the distribution over charge states have been computed for equatorially mirroring ions. Both ionospheric and solar wind oxygen ion sources have been considered, and it is found that the charge state distributions in the interior of the radiation belts are largely independent of the charge state characteristics of the sources. In the MeV range, oxygen ions prove to be a more sensitive probe for radiation belt dynamics than helium ions and protons.

  20. Charge of the Electron, and the Constants of Radiation According to J. A. Wheeler's Geometrodynamic Model

    Directory of Open Access Journals (Sweden)

    Belyakov A. V.


    Full Text Available This study suggests a mechanical interpretation of Wheller’s model of the charge. Ac- cording to the suggested interpretation, the oppositely charged particles are connected through the vortical lines of the current thus create a close contour “input-output” whose parameters determine the properties of the charge and spin. Depending on the energetic state of the system, the contour can be structurized into the units of the second and thirs order (photons. It is found that, in the framework of this interpretation, the charge is equivalent to the momentum. The numerical value of the unit charge has also been cal- culated proceeding from this basis. A system of the relations, connecting the charge to the constants of radiation (the Boltzmann, Wien, and Stefan-Boltzmann constants, and the fine structure constant has been obtained: this give a possibility for calculating all these constants through the unit charge.

  1. Transverse Schottky spectra and beam transfer functions of coasting ion beams with space charge

    Energy Technology Data Exchange (ETDEWEB)

    Paret, Stefan


    A study of the transverse dynamics of coasting ion beams with moderate space charge is presented in this work. From the dispersion relation with linear space charge, an analytic model describing the impact of space charge on transverse beam transfer functions (BTFs) and the stability limits of a beam is derived. The dielectric function obtained in this way is employed to describe the transverse Schottky spectra with linear space charge as well. The difference between the action of space charge and impedances is highlighted. The setup and the results of an experiment performed in the heavy ion synchrotron SIS-18 at GSI to detect space-charge effects at different beam intensities are explicated. The measured transverse Schottky spectra and BTFs are compared with the linear space-charge model. The stability diagrams constructed from the BTFs are presented. The space-charge parameters evaluated from the Schottky and BTF measurements are compared with estimations based on measured beam parameters. The impact of collective effects on the Schottky and BTF diagnostics is also investigated through numerical simulations. For this purpose the self-field of beams with linear and non-linear transverse density-distributions is computed on a twodimensional grid. The noise of the random particle distribution causes fluctuations of the dipole moment of the beam which produce the Schottky spectrum. BTFs are simulated by exciting the beam with transverse kicks. The simulation results are used to verify the space-charge model. (orig.)

  2. Note: Charge transfer in a hydrated peptide group is determined mainly by its intrinsic hydrogen-bond energetics

    Energy Technology Data Exchange (ETDEWEB)

    Mirkin, Noemi G.; Krimm, Samuel [LSA Biophysics, University of Michigan, 930 N. University Ave., Ann Arbor, Michigan 48109-1055 (United States)


    Charge transfer in a hydrogen-bonded N-methylacetamide(H{sub 2}O){sub 3} system is obtained from ωB97X-D/6-31++G** and CHelpG atomic charge calculations of individual peptide-water interactions as well as that of the entire complex. In the latter, the electron transfer to water is 0.19 e, influenced primarily by the hydrogen bonds to the C=O group. The values of such charge transfer are paralleled by the corresponding intrinsic hydrogen-bond energies. These results support the desirability of incorporating charge transfer in molecular mechanics energy functions.

  3. Spectral and angular radiation characteristics of a charged particle in the plane monochromatic electromagnetic wave

    Directory of Open Access Journals (Sweden)

    Nikolay S. Akintsov


    Full Text Available Relying upon the solution of the relativistic equation of charged-particle motion that was obtained by Rukhadze et al., the spectral and angular characteristics of ultra-relativistic intensive radiation of a relativistic charged particle have been studied, the particle being linearly accelerated by a superpower laser pulse. The case where the particle propagates in vacuum without brake light was examined. The interaction of the charged particle with the large-amplitude ultra-short laser pulse was analyzed in details using the relativistic consideration. Formulae for the average radiated power of the relativistic charged particle, depending on the initial conditions, the electromagnetic-wave amplitude, intensity and polarization were obtained. For the case where the laser pulse can be represented by a monochromatic plane wave, analytical expressions for the radiation characteristics were put forward and the phase-angular distributions of relativistic radiated power and intensity were found. The Fourier transform of the electric-intensity radiation field of the charged particle and the particle's spectral density radiation in the field of a plane monochromatic wave for different types of polarization (linear and circular ones were determined.

  4. Comparing simulations and test data of a radiation damaged charge-coupled device for the Euclid mission (United States)

    Skottfelt, Jesper; Hall, David J.; Gow, Jason P. D.; Murray, Neil J.; Holland, Andrew D.; Prod'homme, Thibaut


    The visible imager instrument on board the Euclid mission is a weak-lensing experiment that depends on very precise shape measurements of distant galaxies obtained by a large charge-coupled device (CCD) array. Due to the harsh radiative environment outside the Earth's atmosphere, it is anticipated that the CCDs over the mission lifetime will be degraded to an extent that these measurements will be possible only through the correction of radiation damage effects. We have therefore created a Monte Carlo model that simulates the physical processes taking place when transferring signals through a radiation-damaged CCD. The software is based on Shockley-Read-Hall theory and is made to mimic the physical properties in the CCD as closely as possible. The code runs on a single electrode level and takes the three-dimensional trap position, potential structure of the pixel, and multilevel clocking into account. A key element of the model is that it also takes device specific simulations of electron density as a direct input, thereby avoiding making any analytical assumptions about the size and density of the charge cloud. This paper illustrates how test data and simulated data can be compared in order to further our understanding of the positions and properties of the individual radiation-induced traps.

  5. The electric charge of the aerosols under gamma radiation; La charge electrique des aerosols sous irradiation gamma

    Energy Technology Data Exchange (ETDEWEB)

    Gensdarmes, F.; Cetier, P.; Boulaud, D. [CEA/Saclay, Inst. de Protection et de Surete Nucleaire, IPSN/DPEA/SERAC, 91 - Gif-sur-Yvette (France); Renoux, A. [Paris-12 Univ., Lab. de Physique des Aerosols et de Transfert des Contaminations, 94 - Creteil (France)


    During a PWR type reactor accident, the gamma radiation may create a high ionized atmosphere. In such a situation the aerosols properties knowledge is useful to simulate the particles transport and deposit in the enclosed. The aim of this study is to determine the aerosol charges distribution in a high ionized medium, in function of the ionic properties of the medium. (A.L.B.)

  6. Imaging charge and energy transfer in molecules using free-electron lasers (United States)

    Rudenko, Artem


    Charge and energy transfer reactions drive numerous important processes in physics, chemistry and biology, with applications ranging from X-ray astrophysics to artificial photosynthesis and molecular electronics. Experimentally, the central goal in studies of transfer phenomena is to trace the spatial localization of charge at a given time. Because of their element and site sensitivity, ultrafast X-rays provide a promising tool to address this goal. In this talk I will discuss several experiments where free-electron lasers were employed to study charge and energy transfer dynamics in fragmenting molecules. In a first example, we used intense, 70 femtosecond 1.5 keV pulses from the Linac Coherent Light Source (LCLS) to study distance dependence of electron transfer in laser-dissociated methyl iodide molecules. Inducing well-localized positive charge on the heavy iodine atom, we observe signature of electron transition from the separated methyl group up to the distances of 35 atomic units. In a complementary experiment, we studied charge exchange between two partners in a dissociating molecular iodine employing a pump-probe arrangement with two identical 90 eV pulses from the Free-Electron LASer in Hamburg (FLASH). In both cases, the effective spatial range of the electron transfer can be reasonably described by a classical over-the-barrier model developed for ion-atom collisions. Finally, I will discuss a time-resolved measurement on non-local relaxation mechanism based on a long-range energy transfer, the so-called interatomic Coulombic decay. This work was supported by Chemical Sciences, Geosciences, and Biosciences Division, Office of Basic Energy Sciences, Office of Science, US Department of Energy and by the Kansas NSF ``First Award'' program.

  7. Conjugated block copolymers as model materials to examine charge transfer in donor-acceptor systems (United States)

    Gomez, Enrique; Aplan, Melissa; Lee, Youngmin

    Weak intermolecular interactions and disorder at junctions of different organic materials limit the performance and stability of organic interfaces and hence the applicability of organic semiconductors to electronic devices. The lack of control of interfacial structure has also prevented studies of how driving forces promote charge photogeneration, leading to conflicting hypotheses in the organic photovoltaic literature. Our approach has focused on utilizing block copolymer architectures -where critical interfaces are controlled and stabilized by covalent bonds- to provide the hierarchical structure needed for high-performance organic electronics from self-assembled soft materials. For example, we have demonstrated control of donor-acceptor heterojunctions through microphase-separated conjugated block copolymers to achieve 3% power conversion efficiencies in non-fullerene photovoltaics. Furthermore, incorporating the donor-acceptor interface within the molecular structure facilitates studies of charge transfer processes. Conjugated block copolymers enable studies of the driving force needed for exciton dissociation to charge transfer states, which must be large to maximize charge photogeneration but must be minimized to prevent losses in photovoltage in solar cell devices. Our work has systematically varied the chemical structure, energetics, and dielectric constant to perturb charge transfer. As a consequence, we predict a minimum dielectric constant needed to minimize the driving force and therefore simultaneously maximize photocurrent and photovoltage in organic photovoltaic devices.

  8. Hybridization-controlled charge transfer and induced magnetism at correlated oxide interfaces (United States)

    Grisolia, M. N.; Varignon, J.; Sanchez-Santolino, G.; Arora, A.; Valencia, S.; Varela, M.; Abrudan, R.; Weschke, E.; Schierle, E.; Rault, J. E.; Rueff, J.-P.; Barthélémy, A.; Santamaria, J.; Bibes, M.


    At interfaces between conventional materials, band bending and alignment are classically controlled by differences in electrochemical potential. Applying this concept to oxides in which interfaces can be polar and cations may adopt a mixed valence has led to the discovery of novel two-dimensional states between simple band insulators such as LaAlO3 and SrTiO3. However, many oxides have a more complex electronic structure, with charge, orbital and/or spin orders arising from strong Coulomb interactions at and between transition metal and oxygen ions. Such electronic correlations offer a rich playground to engineer functional interfaces but their compatibility with the classical band alignment picture remains an open question. Here we show that beyond differences in electron affinities and polar effects, a key parameter determining charge transfer at correlated oxide interfaces is the energy required to alter the covalence of the metal-oxygen bond. Using the perovskite nickelate (RNiO3) family as a template, we probe charge reconstruction at interfaces with gadolinium titanate GdTiO3. X-ray absorption spectroscopy shows that the charge transfer is thwarted by hybridization effects tuned by the rare-earth (R) size. Charge transfer results in an induced ferromagnetic-like state in the nickelate, exemplifying the potential of correlated interfaces to design novel phases. Further, our work clarifies strategies to engineer two-dimensional systems through the control of both doping and covalence.

  9. Reptation Quantum Monte Carlo calculation of charge transfer: The Na-Cl dimer (United States)

    Yao, Yi; Kanai, Yosuke


    The phenomenon of ion pairing in aqueous solutions is of widespread importance in chemistry and physics, and charge transfer between the ions plays a significant role. We examine the performance of quantum Monte Carlo (QMC) calculations for describing the charge transfer behavior in a NaCl dimer. The influence of the fermion nodes is investigated by obtaining the electron density using the reptation Monte Carlo approach. The fermion nodes are given by single-particle orbitals in Slater-Jastrow trial wavefunctions. We consider the single-particle orbitals from Hartree-Fock and density functional theory calculations with several exchange-correlation approximations. Appreciable dependence of the charge transfer on the fixed-node approximation was found although the total energy was found to be rather insensitive. Our work shows that a careful examination of the fixed-node approximation is necessary for quantifying charge transfer in QMC calculations even when other properties such as reaction energetics are insensitive to the approximation.

  10. On the relation between local and charge-transfer exciton bindingenergies in organic photovoltaic materials

    NARCIS (Netherlands)

    de Gier, Hilde Dorothea; Braam, Henderika; Havenith, Remco


    In organic photovoltaic devices two types of excitons can be generated for which different binding energies can be defined: the binding energy of the local exciton generated immediately after light absorption on the polymer and the binding energy of the charge-transfer exciton generated through the

  11. Charge transfer kinetics in fullerene-oligomer-fullerene triads containing alkylpyrrole units

    NARCIS (Netherlands)

    Beckers, EHA; van Hal, PA; Dhanabalan, A; Meskers, SCJ; Knol, J; Hummelen, JC; Janssen, RAJ; Beckers, Edwin H.A.; Meskers, Stefan C.J.; Janssen, René A.J.


    A photoinduced electron-transfer reaction has been observed in three fullerene-donor-fullerene triads containing an electron-rich pyrrole ring in the donor moiety. The kinetics of charge separation in solution has been investigated by photoluminescence and transient absorption spectroscopy. The

  12. The synthesis of organic charge transfer hetero-microtubules by crack welding. (United States)

    Kim, J; Chung, J; Hyon, J; Kwon, T; Seo, C; Nam, J; Kang, Y


    The strain-induced cracks in organic microtubules composed of an organic charge transfer (CT) complex of 1,2,4,5-tetracyanobenzene (TCNB) and naphthalene were selectively welded via the formation of secondary CT complexes; this process, in turn, led to the formation of organic hetero-microtubules consisting of multiple segments of two organic CT complexes.

  13. Charge-Transfer Complex of p-Aminodiphenylamine with Maleic Anhydride: Spectroscopic, Electrochemical, and Physical Properties. (United States)

    Karaca, Erhan; Kaplan Can, Hatice; Bozkaya, Uğur; Özçiçek Pekmez, Nuran


    A new charge-transfer complex and the amide formed by the interaction between the electron donor of the p-aminodiphenylamine and the electron acceptor of maleic anhydride are investigated by spectroscopic methods. The amidation reaction is caused by proton and charge transfer between the maleic anhydride and p-aminodiphenylamine molecules. The Benesi-Hildebrand equation is used to determine the formation constant, the molar extinction coefficient and the standard Gibbs free energy of the complex by using UV/Vis spectroscopy. To reveal the electronic and spectroscopic properties of these molecules, theoretical computations are performed on the structures of maleic anhydride, p-aminodiphenylamine and the conformers of their charge-transfer complex. The charge-transfer complex and amidation reaction mechanism are also confirmed by IR and NMR spectroscopy and HRMS. The nature of the maleic anhydride-p-aminodiphenylamine complex is characterized by cyclic voltammetry, thermogravimetric analysis, XRD and SEM. Solid microribbons of this complex show higher thermal stability than p-aminodiphenylamine. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. Vibronic coupling in Frenkel and charge-transfer states of oligothiophene crystals

    NARCIS (Netherlands)

    Stradomska, Anna; Kulig, Waldemar; Petelenz, Piotr

    A novel approach, recently proposed to describe exciton phonon coupling in Frenkel states of an infinite molecular crystal, is generalized to incorporate charge-transfer (CT) excitons. Both types of electronic excitations are treated on the same footing. The corresponding Hamiltonian in the Lang

  15. Dynamic self-assembly of charge-transfer nanofibers of tetrathiafulvalene derivatives with F4TCNQ. (United States)

    Jain, Ankit; Rao, K Venkata; Mogera, Umesha; Sagade, Abhay A; George, Subi J


    One-dimensional charge-transfer nanostructures were constructed by the supramolecular coassembly of amphiphilic (Amph-TTF) and hydrophobic (TDD-TTF) tetrathiafulvalene (TTF) donor derivatives with the acceptor 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F(4)TCNQ), in appropriate solvent composition mixtures. Microscopic analyses show that TDD-TTF retains its self-assembled fibrillar morphology even in the charge-transfer state, whereas Amph-TTF undergoes a spherical to nanorod transition upon coassembly. Time-dependent optical spectroscopy studies have shown a spontaneous change in molecular organization in TDD-TTF-based donor-acceptor costacks, which suggests a dynamic behavior, in contrast to the kinetically stable amphiphilic TTF assemblies. We have also tried to get an insight into the observed time-dependent change in molecular packing of these nanostructures through spectroscopic analyses by commenting on whether the TTF-TCNQ pair is cofacially arranged or present in the classical herringbone (orthogonal) fashion. Furthermore, our two-probe electrical measurements showed that these charge-transfer fibers are conducting. A supramolecular approach that yields 1D charge-transfer nanostructures of donor and acceptor molecules will be an alternative to existing crystalline substances with high conductivity and hence can be a viable tool for nanoelectronics. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. Photoinduced energy and charge transfer in layered porphyrin-gold nanoparticle thin films

    NARCIS (Netherlands)

    Kotiaho, Anne; Lahtinen, Riikka; Lehtivuori, Heli; Tkachenko, Nikolai V.; Lemmetyinen, Helge


    In thin films of porphyrin (H2P) and gold nanoparticles (AuNPs), photoexcitation of porphyrins leads to energy and charge transfer to the gold nanoparticles. Alternating layers of porphyrins and octanethiol protected gold nanoparticles (dcore ∼3 nm) were deposited on solid substrates via the

  17. Engineering and Probing Topological Properties of Dirac Semimetal Films by Asymmetric Charge Transfer. (United States)

    Villanova, John W; Barnes, Edwin; Park, Kyungwha


    Dirac semimetals (DSMs) have topologically robust three-dimensional Dirac (doubled Weyl) nodes with Fermi-arc states. In heterostructures involving DSMs, charge transfer occurs at the interfaces, which can be used to probe and control their bulk and surface topological properties through surface-bulk connectivity. Here we demonstrate that despite a band gap in DSM films, asymmetric charge transfer at the surface enables one to accurately identify locations of the Dirac-node projections from gapless band crossings and to examine and engineer properties of the topological Fermi-arc surface states connecting the projections, by simulating adatom-adsorbed DSM films using a first-principles method with an effective model. The positions of the Dirac-node projections are insensitive to charge transfer amount or slab thickness except for extremely thin films. By varying the amount of charge transfer, unique spin textures near the projections and a separation between the Fermi-arc states change, which can be observed by gating without adatoms.

  18. Correlation between charge transfer exciton recombination and photocurrent in polymer/fullerene solar cells

    NARCIS (Netherlands)

    Hallermann, Markus; Da Como, Enrico; Feldmann, Jochen; Izquierdo, Marta; Filippone, Salvatore; Martin, Nazario; Juechter, Sabrina; von Hauff, Elizabeth


    We correlate carrier recombination via charge transfer excitons (CTEs) with the short circuit current, J sc, in polymer/fullerene solar cells. Near infrared photoluminescence spectroscopy of CTE in three blends differing for the fullerene acceptor, gives unique insights into solar cell

  19. Spectral signatures of charge transfer in assemblies of molecularly-linked plasmonic nanoparticles (United States)

    Lerch, Sarah; Reinhard, Björn M.


    Self-assembly of functionalized nanoparticles (NPs) provides a unique class of nanomaterials for exploring and utilizing quantum-plasmonic effects that occur if the interparticle separation between NPs approaches a few nanometers and below. We review recent theoretical and experimental studies of plasmon coupling in self-assembled NP structures that contain molecular linkers between the NPs. Charge transfer through the interparticle gap of an NP dimer results in a significant blue-shift of the bonding dipolar plasmon (BDP) mode relative to classical electromagnetic predictions, and gives rise to new coupled plasmon modes, the so-called charge transfer plasmon (CTP) modes. The blue-shift of the plasmon spectrum is accompanied by a weakening of the electromagnetic field in the gap of the NPs. Due to an optical far-field signature that is sensitive to charge transfer across the gap, plasmonic molecules represent a sensor platform for detecting and characterizing gap conductivity in an optical fashion and for characterizing the role of molecules in facilitating the charge transfer across the gap.

  20. Integer charge transfer at the tetrakis(dimethylamino)ethylene/Au interface

    DEFF Research Database (Denmark)

    Lindell, L.; Unge, Mikael; Osikowicz, W.


    In organic-based electronics, interfacial properties have a profound impact on device performance. The lineup of energy levels is usually dependent on interface dipoles, which may arise from charge transfer reactions. In many applications, metal-organic junctions are prepared under ambient condit...

  1. Laboratory Measurements of Charge Transfer on Atomic Hydrogen at Thermal Energies (United States)

    Havener, C. C.; Vane, C. R.; Krause, H. F.; Stancil, P. C.; Mroczkowski, T.; Savin, D. W.


    We describe our ongoing program to measure velocity dependent charge transfer (CT) cross sections for selected ions on atomic hydrogen using the ion-aloin merged-beams apparatus at Oak Ridge Natioiial Laboralory. Our focus is on those ions for which CT plays an important role in determining the ionization structure, line emis sion, and thermal structure of observed cosmic photoionized plasmas.

  2. Elastic, excitation, ionization and charge transfer cross sections of current interest in fusion energy research

    Energy Technology Data Exchange (ETDEWEB)

    Schultz, D.R.; Krstic, P.S. [Oak Ridge National Lab. TN (United States). Physics Div.


    Due to the present interest in modeling and diagnosing the edge and divertor plasma regions in magnetically confined fusion devices, we have sought to provide new calculations regarding the elastic, excitation, ionization, and charge transfer cross sections in collisions among relevant ions, neutrals, and isotopes in the low-to intermediate-energy regime. We summarize here some of our recent work. (author)

  3. Symmetry-breaking intramolecular charge transfer in the excited state of meso-linked BODIPY dyads

    KAUST Repository

    Whited, Matthew T.


    We report the synthesis and characterization of symmetric BODIPY dyads where the chromophores are attached at the meso position, using either a phenylene bridge or direct linkage. Both molecules undergo symmetry-breaking intramolecular charge transfer in the excited state, and the directly linked dyad serves as a visible-light-absorbing analogue of 9,9′-bianthryl.

  4. Mechanism and Dynamics of Charge Transfer in Donor-Bridge-Acceptor Systems

    NARCIS (Netherlands)

    Gorczak-Vos, N.


    Photoinduced charge transfer in organic materials is a fundamental process in various biological and technological areas. Donor-bridge-acceptor (DBA) molecules are used as model systems in numerous theoretical and experimental work to systematically study and unravel the underlying mechanisms of

  5. A field test of a simple stochastic radiative transfer model

    Energy Technology Data Exchange (ETDEWEB)

    Byrne, N. [Science Applications International Corp., San Diego, CA (United States)


    The problem of determining the effect of clouds on the radiative energy balance of the globe is of well-recognized importance. One can in principle solve the problem for any given configuration of clouds using numerical techniques. This knowledge is not useful however, because of the amount of input data and computer resources required. Besides, we need only the average of the resulting solution over the grid scale of a general circulation model (GCM). Therefore, we are interested in estimating the average of the solutions of such fine-grained problems using only coarse grained data, a science or art called stochastic radiation transfer. Results of the described field test indicate that the stochastic description is a somewhat better fit to the data than is a fractional cloud cover model, but more data are needed. 1 ref., 3 figs.

  6. Estimation of presampling modulation transfer function in synchrotron radiation microtomography

    CERN Document Server

    Mizutani, Ryuta; Takeuchi, Akihisa; Uesugi, Kentaro; Suzuki, Yoshio


    The spatial resolution achieved by recent synchrotron radiation microtomographs should be estimated from the modulation transfer function (MTF) on the micrometer scale. Step response functions of a synchrotron radiation microtomograph were determined by the slanted edge method by using high-precision surfaces of diamond crystal and ion-milled aluminum wire. Tilted reconstruction was introduced to enable any edge to be used as the slanted edge by defining the reconstruction pixel matrix in an arbitrary orientation. MTFs were estimated from the step response functions of the slanted edges. The obtained MTFs coincided with MTF values estimated from square-wave patterns milled on the aluminum surface. Although x-ray refraction influences should be taken into account to evaluate MTFs, any flat surfaces with nanometer roughness can be used to determine the spatial resolutions of microtomographs.

  7. Nonequilibrium Fluctuational Quantum Electrodynamics: Heat Radiation, Heat Transfer, and Force (United States)

    Bimonte, Giuseppe; Emig, Thorsten; Kardar, Mehran; Krüger, Matthias


    Quantum-thermal fluctuations of electromagnetic waves are the cornerstone of quantum statistics and inherent to phenomena such as thermal radiation and van der Waals forces. Although the principles are found in elementary texts, recent experimental and technological advances make it necessary to come to terms with counterintuitive consequences at short scales—the so-called near-field regime. We focus on three manifestations: (a) The Stefan-Boltzmann law describes radiation from macroscopic bodies but fails for small objects. (b) The heat transfer between two bodies at close proximity is dominated by evanescent waves and can be orders of magnitude larger than the classical (propagating) contribution. (c) Casimir forces, dominant at submicron separation, are not sufficiently explored for objects at different temperatures (at least experimentally). We explore these phenomena using fluctuational quantum electrodynamics (QED), introduced by Rytov in the 1950s, combined with scattering formalisms. This enables investigation of different material properties, shapes, separations, and arrangements.

  8. Unravelling radiative energy transfer in solid-state lighting (United States)

    Melikov, Rustamzhon; Press, Daniel Aaron; Ganesh Kumar, Baskaran; Sadeghi, Sadra; Nizamoglu, Sedat


    Today, a wide variety of organic and inorganic luminescent materials (e.g., phosphors, quantum dots, etc.) are being used for lighting and new materials (e.g., graphene, perovskite, etc.) are currently under investigation. However, the understanding of radiative energy transfer is limited, even though it is critical to understand and improve the performance levels of solid-state lighting devices. In this study, we derived a matrix approach that includes absorption, reabsorption, inter-absorption and their iterative and combinatorial interactions for one and multiple types of fluorophores, which is simplified to an analytical matrix. This mathematical approach gives results that agree well with the measured spectral and efficiency characteristics of color-conversion light-emitting diodes. Moreover, it also provides a deep physical insight by uncovering the entire radiative interactions and their contribution to the output optical spectrum. The model is universal and applicable for all kinds of fluorophores.

  9. Charge transfer for slow H atoms interacting with Al: Atomic levels and linewidths (United States)

    Merino, J.; Lorente, N.; Pou, P.; Flores, F.


    The charge transfer of slow H atoms colliding with an Al(100) surface is studied by means of a linear combination of atomic orbitals method with local-density many-body contributions. The method is developed in order to calculate atomic levels and associated linewidths. Unlike previous theories, the present method is able to study the effect of the corrugation of the surface, together with the self-consistent potentials involved. This leads to a shift of atomic levels nonlinear on the external charge, contrary to the traditionally assumed image shift. The method works best at very short distances, where the strong coupling between atom and surface promotes molecular orbitals. Thus, the theory expounded in this work can describe the charge-transfer processes of systems in which the atomic levels are near the band edges, as protons scattered off aluminum.

  10. A multilevel method for conductive-radiative heat transfer

    Energy Technology Data Exchange (ETDEWEB)

    Banoczi, J.M.; Kelley, C.T. [North Carolina State Univ., Raleigh, NC (United States)


    We present a fast multilevel algorithm for the solution of a system of nonlinear integro-differential equations that model steady-state combined radiative-conductive heat transfer. The equations can be formulated as a compact fixed point problem with a fixed point map that requires both a solution of the linear transport equation and the linear heat equation for its evaluation. We use fast transport solvers developed by the second author, to construct an efficient evaluation of the fixed point map and then apply the Atkinson-Brakhage, method, with Newton-GMRES as the coarse mesh solver, to the full nonlinear system.

  11. Numerical Radiative Transfer and the Hydrogen Reionization of the Universe (United States)

    Petkova, M.


    One of the most interesting questions in cosmology is to understand how the Universe evolved from its nearly uniform and simple state briefly after the Big Bang to the complex state we see around us today. In particular, we would like to explain how galaxies have formed, and why they have the properties that we observe in the local Universe. Computer simulations play a highly important role in studying these questions, because they allow one to follow the dynamical equations of gravity and hydrodynamics well into the non-linear regime of the growth of cosmic structures. The current generation of simulation codes for cosmological structure formation calculates the self-gravity of dark matter and cosmic gas, and the fluid dynamics of the cosmic gas, but radiation processes are typically not taken into account, or only at the level of a spatially uniform, externally imposed background field. However, we know that the radiation field has been highly inhomogeneous during certain phases of the growth of structure, and may have in fact provided important feedback effects for galaxy formation. In particular, it is well established that the diffuse gas in the universe was nearly fully neutral after recombination at very high redshift, but today this gas is highly ionized. Sometime during the evolution, a transition to the ionized state must have occurred, a process we refer to as reionization. The UV radiation responsible for this reionization is now permeating the universe and may in part explain why small dwarf galaxies have so low luminosities. It is therefore clear that accurate and self-consistent studies of galaxy formation and of the dynamics of the reionization process should ideally be done with simulation codes that directly include a treatment of radiative transfer, and that account for all relevant source and sink terms of the radiation. We present a novel numerical implementation of radiative transfer in the cosmological smoothed particle hydrodynamics (SPH

  12. Charge transfer in dissociating iodomethane and fluoromethane molecules ionized by intense femtosecond X-ray pulses

    Directory of Open Access Journals (Sweden)

    Rebecca Boll


    Full Text Available Ultrafast electron transfer in dissociating iodomethane and fluoromethane molecules was studied at the Linac Coherent Light Source free-electron laser using an ultraviolet-pump, X-ray-probe scheme. The results for both molecules are discussed with respect to the nature of their UV excitation and different chemical properties. Signatures of long-distance intramolecular charge transfer are observed for both species, and a quantitative analysis of its distance dependence in iodomethane is carried out for charge states up to I21+. The reconstructed critical distances for electron transfer are in good agreement with a classical over-the-barrier model and with an earlier experiment employing a near-infrared pump pulse.

  13. [Diffusion and diffusion-osmosis models of the charged macromolecule transfer in barriers of biosystems]. (United States)

    Varakin, A I; Mazur, V V; Arkhipova, N V; Serianov, Iu V


    Mathematical models of the transfer of charged macromolecules have been constructed on the basis of the classical equations of electromigration diffusion of Helmholtz-Smolukhovskii, Goldman, and Goldman-Hodgkin-Katz. It was shown that ion transfer in placental (mimicking lipid-protein barriers) and muscle barriers occurs by different mechanisms. In placental barriers, the electromigration diffusion occurs along lipid-protein channels formed due to the conformational deformation of phospholipid and protein molecules with the coefficients of diffusion D = (2.6-3.6) x 10(-8) cm2/s. The transfer in muscle barriers is due to the migration across charged interfibrillar channels with the negative diffusion activation energy, which is explained by changes in the structure of muscle fibers and expenditures of thermal energy for the extrusion of Cl- from channel walls with the diffusion coefficient D = (6.0-10.0) x 10(-6) cm2/s.

  14. Effect of radiative cooling on collapsing charged grains

    Indian Academy of Sciences (India)

    Thus, numerical picture suggests that most of the radiative effects dominate at large implying condensation and structure formation down to much shorter scales (nearly by a factor of 2) than otherwise possible by purely. Jeans mode (curve 1). Physically, gravitational condensation is inhibited by the 'thermal pressure' (set up ...

  15. Electroluminescence from charge transfer states in Donor/Acceptor solar cells

    DEFF Research Database (Denmark)

    Sherafatipour, Golenaz; Madsen, Morten

    Charge photocurrent generation is a key process in solar energy conversion systems. Effective dissociation of the photo-generated electron-hole pairs (excitons) has a strong influence on the efficiency of the organic solar cells. Charge dissociation takes place at the donor/acceptor interface via...... charge transfer (CT) excitons, which is Coulombically bound interfacial electron- hole pairs residing at the donor/acceptor heterojunctions. The CT state represents an intermediate state between the exciton dissociation and recombination back to the ground state. Since the recombination of photo-generated...... charges is a major limitation for the efficiency of the organic solar cells, a thorough understanding of this loss mechanism is crucial to improve the performance of the devices. Furthermore, examining this interfacial state is of great importance in order to maximize open-circuit voltage and photocurrent...

  16. Synthetic system mimicking the energy transfer and charge separation of natural photosynthesis

    Energy Technology Data Exchange (ETDEWEB)

    Gust, D.; Moore, T.A.


    A synthetic molecular triad consisting of a porphyrin P linked to both a quinone Q and a carotenoid polyene C has been prepared as a mimic of natural photosynthesis for solar energy conversion purposes. Laser flash excitation of the porphyrin moiety yields a charge-separated state Csup(+.)-P-Qsup(-.) within 100 ps with a quantum yield of more than 0.25. This charge-separated state has a lifetime on the microsecond time scale in suitable solvents. The triad also models photosynthetic antenna function and photoprotection from singlet oxygen damge. The successful biomimicry of photosynthetic charge separation is in part the result of multistep electron transfers which rapidly separate the charges and leave the system at high potential, but with a considerable barrier to recombination.

  17. Monovalent counterion distributions at highly charged water interfaces: proton-transfer and Poisson-Boltzmann theory. (United States)

    Bu, Wei; Vaknin, David; Travesset, Alex


    Surface sensitive synchrotron-x-ray scattering studies reveal the distributions of monovalent ions next to highly charged interfaces. A lipid phosphate (dihexadecyl hydrogen phosphate) was spread as a monolayer at the air-water interface, containing CsI at various concentrations. Using anomalous reflectivity off and at the L3 Cs+ resonance, we provide spatial counterion distributions (Cs+) next to the negatively charged interface over a wide range of ionic concentrations. We argue that at low salt concentrations and for pure water the enhanced concentration of hydroniums H3O+ at the interface leads to proton transfer back to the phosphate group by a high contact potential, whereas high salt concentrations lower the contact potential resulting in proton release and increased surface charge density. The experimental ionic distributions are in excellent agreement with a renormalized-surface-charge Poisson-Boltzmann theory without fitting parameters or additional assumptions.

  18. Active pixel sensor having intra-pixel charge transfer with analog-to-digital converter (United States)

    Fossum, Eric R. (Inventor); Mendis, Sunetra K. (Inventor); Pain, Bedabrata (Inventor); Nixon, Robert H. (Inventor); Zhou, Zhimin (Inventor)


    An imaging device formed as a monolithic complementary metal oxide semiconductor integrated circuit in an industry standard complementary metal oxide semiconductor process, the integrated circuit including a focal plane array of pixel cells, each one of the cells including a photogate overlying the substrate for accumulating photo-generated charge in an underlying portion of the substrate, a readout circuit including at least an output field effect transistor formed in the substrate, and a charge coupled device section formed on the substrate adjacent the photogate having a sensing node connected to the output transistor and at least one charge coupled device stage for transferring charge from the underlying portion of the substrate to the sensing node and an analog-to-digital converter formed in the substrate connected to the output of the readout circuit.

  19. Photoinduced charge-transfer dynamics of sequentially aligned donor-acceptor systems in an ionic liquid. (United States)

    Muramatsu, Masayasu; Katayama, Tetsuro; Ito, Syoji; Nagasawa, Yutaka; Matsuo, Daisuke; Suzuma, Yoshinori; Peng, Lifen; Orita, Akihiro; Otera, Junzo; Miyasaka, Hiroshi


    Photoinduced charge separation processes of linear phenyleneethynylene derivatives (PEN) with different sequences of electron-withdrawing perfluorophenyl groups (A) and electron-donating phenyl groups (D) were investigated in an ionic liquid (IL), BmimTFSI, by picosecond time-resolved fluorescence (TRF) and transient absorption (TA) spectroscopies. Very rapid photoinduced charge separation within 10 ps in AADD was followed by the stabilization of the charge-transfer (CT) state by the solvation, while the excited states in ADAD and ADDA were ascribable to the locally excited (LE) state. Equilibrium between the LE and CT states was established for DAAD with time constants of forward and backward processes much faster than the solvation time. The relative population of the CT state increases with time owing to the dynamic stabilization of the CT state by the solvation. The elementary charge separation process, the increase in the CT population, and their relation to the solvation time were discussed.

  20. Quantum radiation produced by a uniformly accelerating charged particle in thermal random motion (United States)

    Oshita, Naritaka; Yamamoto, Kazuhiro; Zhang, Sen


    We investigate the properties of quantum radiation produced by a uniformly accelerating charged particle undergoing thermal random motion, which originates from the coupling to the vacuum fluctuations of the electromagnetic field. Because the thermal random motion is regarded to result from the Unruh effect, the quantum radiation might give us hints of the Unruh effect. The energy flux of the quantum radiation is negative and smaller than that of Larmor radiation by one order in a /m , where a is the constant acceleration and m is the mass of the particle. Thus, the quantum radiation appears to be a suppression of the classical Larmor radiation. The quantum interference effect plays an important role in this unique signature. The results are consistent with the predictions of a model consisting of a particle coupled to a massless scalar field as well as those of the previous studies on the quantum effect on the Larmor radiation.

  1. Charge Transfer and Triplet States in High Efficiency OPV Materials and Devices (United States)

    Dyakonov, Vladimir


    The advantage of using polymers and molecules in electronic devices, such as light-emitting diodes (LED), field-effect transistors (FET) and, more recently, solar cells (SC) is justified by the unique combination of high device performance and processing of the semiconductors used. Power conversion efficiency of nanostructured polymer SC is in the range of 10% on lab scale, making them ready for up-scaling. Efficient charge carrier generation and recombination in SC are strongly related to dissociation of the primary singlet excitons. The dissociation (or charge transfer) process should be very efficient in photovoltaics. The mechanisms governing charge carrier generation, recombination and transport in SC based on the so-called bulk-heterojunctions, i.e. blends of two or more semiconductors with different electron affinities, appear to be very complex, as they imply the presence of the intermediate excited states, neutral and charged ones. Charge transfer states, or polaron pairs, are the intermediate states between free electrons/holes and strongly bound excitons. Interestingly, the mostly efficient OLEDs to date are based on the so-called triplet emitters, which utilize the triplet-triplet annihilation process. In SC, recent investigations indicated that on illumination of the device active layer, not only mobile charges but also triplet states were formed. With respect to triplets, it is unclear how these excited states are generated, via inter-system crossing or via back transfer of the electron from acceptor to donor. Triplet formation may be considered as charge carrier loss channel; however, the fusion of two triplets may lead to a formation of singlet excitons instead. In such case, a generation of charges by utilizing of the so far unused photons will be possible. The fundamental understanding of the processes involving the charge transfer and triplet states and their relation to nanoscale morphology and/or energetics of blends is essential for the

  2. Failures of TDDFT in describing the lowest intramolecular charge-transfer excitation in para-nitroaniline

    DEFF Research Database (Denmark)

    Eriksen, Janus J.; Sauer, Stephan P. A.; Mikkelsen, Kurt V.


    for charge{transfer character, we furthermore conrm that the di¿erence between excitation energies calculated with TDDFT and with the Tamm-Danco¿ approximation (TDA) to TDDFT is indeed correlated with the charge-transfer character of a given electronic transition both in vacuo and in solution...

  3. A low-spin Fe(III) complex with 100-ps ligand-to-metal charge transfer photoluminescence

    DEFF Research Database (Denmark)

    Chabera, Pavel; Liu, Yizhu; Prakash, Om


    Transition-metal complexes are used as photosensitizers(1), in light-emitting diodes, for biosensing and in photocatalysis(2). A key feature in these applications is excitation from the ground state to a charge-transfer state(3,4); the long charge-transfer-state lifetimes typical for complexes...

  4. Radiative transfer model for contaminated slabs : experimental validations

    CERN Document Server

    Andrieu, François; Schmitt, Bernard; Douté, Sylvain; Brissaud, Olivier


    This article presents a set of spectro-goniometric measurements of different water ice samples and the comparison with an approximated radiative transfer model. The experiments were done using the spectro-radiogoniometer described in Brissaud et al. (2004). The radiative transfer model assumes an isotropization of the flux after the second interface and is fully described in Andrieu et al. (2015). Two kind of experiments were conducted. First, the specular spot was closely investigated, at high angular resolution, at the wavelength of $1.5\\,\\mbox{\\mu m}$, where ice behaves as a very absorbing media. Second, the bidirectional reflectance was sampled at various geometries, including low phase angles on 61 wavelengths ranging from $0.8\\,\\mbox{\\mu m}$ to $2.0\\,\\mbox{\\mu m}$. In order to validate the model, we made a qualitative test to demonstrate the relative isotropization of the flux. We also conducted quantitative assessments by using a bayesian inversion method in order to estimate the parameters (e.g. sampl...

  5. Discrete ordinates quadrature schemes for multidimensional radiative transfer (United States)

    Koch, R.; Krebs, W.; Wittig, S.; Viskanta, R.


    The fundamental problem of applying the method of discrete ordinates to radiative transfer predictions is the selection of the discrete directions and their associated weights. Both the accuracy of the solution and the computational effort depend on the angular discretization. This paper provides a sound mathematical methodology for the derivation of angular quadratures. By applying the collocation principle, the errors introduced by a quadrature are analyzed and the constituting equations of angular quadratures are identified. Special emphasis is placed on the rotational invariance of the qudrature schemes. Multidimensional radiative transfer in participating media with isotropic and anisotropic scattering is accounted for thoughout the analysis. A major goal of the present study is the construction of a new principle for multidimensional angular quadratures which is essentially a generalization of the principles employed for the well-known S(sub n) quadratures. The new construction principle has two major advantages. First, it enables a very flexible tailoring of quadratures according to the actual requirements. Second, compared to the S(sub n) quadratures, the new types of quadratures provide a higher accuracy while using the same number of nodal points.

  6. Polarized radiative transfer modeling of warped and clumpy dusty tori (United States)

    Marin, F.; Schartmann, M.


    Context. Active galactic nuclei (AGN) are anisotropic objects surrounded by an optically thick equatorial medium whose true geometry still defies observers. Aims: We aim to explore the optical scattering-induced polarization that emerges from clumpy and warped dusty tori to check whether they can fit the unified model predictions. Methods: We ran polarized radiative transfer simulations in a set of warped and non-warped clumpy tori to explore the differences induced by distorted dust distributions. We then included warped tori in a more complex model representative of an AGN to check, using polarimetry and imaging methods, whether warps can reproduce the expected polarization dichotomy between Seyfert-I and Seyfert-II AGN. Results: The main results from our simulations highlight that isolated warped structures imprint the polarization degree and angle with distinctive signatures at Seyfert-I orientations. Included in an AGN model, the signatures of warps are easily (but not always) washed out by multiple scattering in a clumpy environment. Imaging polarimetry may help to detect warped tori, but we prove that warps can exist in AGN circumnuclear regions without contradicting observations. Conclusions: Two warped tori with a non-significant difference in geometry in terms of photometry or spectroscopy can have entirely different signatures in polarimetry. Testing the geometry of any alternative model to the usual dusty torus using polarized radiative transfer is a necessary approach to verify or reject a hypothesis.

  7. Gravitational energy and radiation of a charged black hole (United States)

    Combi, Luciano; Romero, Gustavo E.


    We investigate the energy configuration of a charged black hole in the teleparallel framework of general relativity. We obtain the energy-momentum tensor of the gravitational field in a stationary frame, and we calculate its contribution to the total energy of the system. We study the same gravitational field measured by an accelerated frame and we analyze how the energy-momentum tensor is transformed. We found that in the accelerated frame, a Poynting-like flux appears for the gravitational field but not for the electromagnetic field.

  8. Charge Transfer Dynamics in Complexes of Light-Absorbing CdS Nanorods and Redox Catalysts (United States)

    Wilker, Molly Bea

    The use of photoexcited electrons and holes in semiconductor nanocrystals as reduction and oxidation reagents is an intriguing way of harvesting photon energy to drive chemical reactions. This dissertation describes research efforts to understand the photoexcited charge transfer kinetics in complexes of colloidal CdS nanorods coupled with either a water oxidation or reduction catalyst. The first project focuses on the charge transfer interactions between photoexcited CdS nanorods and a mononuclear water oxidation catalyst derived from the [Ru(bpy)(tpy)Cl]+ parent structure. The second project details the electron transfer kinetics in complexes of CdS nanorods coupled with [FeFe]-hydrogenase, which catalyzes H+ reduction. These complexes photochemically produce H2 with quantum yields of up to 20%. Kinetics of electron transfer from CdS nanorods to hydrogenase play a critical role in the overall photochemical reactivity, as the quantum efficiency of electron transfer defines the upper limit on the quantum yield of H 2 generation. Insights from these time-resolved spectroscopic studies are used to discuss the intricate kinetic pathways involved in photochemical H2 generation and the mechanism for electron transfer from photoexcited nanorods to hydrogenase in photocatalytic complexes.

  9. Negative Resistance Effect and Charge Transfer Mechanisms in the lon Beam Deposited Diamond Like Carbon Superlattices

    Directory of Open Access Journals (Sweden)



    Full Text Available In the present study DLC:SiOx/DLC/DLC:SiOx/nSi and DLC:SiOx/DLC/DLC:SiOx/pSi structures were fabricated by ion beam deposition using a closed drift ion source. Current-voltage (I-V characteristics of the multilayer samples were measured at room temperature. The main charge transfer mechanisms were considered. Unstable negative resistance effect was observed for some DLC:SiOx/DLC/DLC:SiOx/nSi and DLC:SiOx/DLC/DLC:SiOx/pSi structures. In the case of the diamond like carbon superlattices fabricated on nSi it was observed only during the first measurement. In the case of the some DLC:SiOx/DLC/DLC:SiOx/pSi negative resistance "withstood" several measurements. Changes of the charge carrier mechanisms were observed along with the dissapear of the negative resistance peaks. It seems, that in such a case influence of the bulk related charge transfer mechanisms such as Poole-Frenkel emission increased, while the influence of the contact limited charge transfer mechanisms such as Schottky emission decreased. Observed results were be explained by current flow through the local microconducting channels and subsequent destruction of the localized current pathways as a result of the heating by flowing electric current.

  10. Charge-Transfer Phase Transition of a Cyanide-Bridged Fe(II) /Fe(III) Coordination Polymer. (United States)

    Zhang, Kuirun; Kang, Soonchul; Yao, Zi-Shuo; Nakamura, Kazusa; Yamamoto, Takashi; Einaga, Yasuaki; Azuma, Nobuaki; Miyazaki, Yuji; Nakano, Motohiro; Kanegawa, Shinji; Sato, Osamu


    Heterometallic Prussian blue analogues are known to exhibit thermally induced charge transfer, resulting in switching of optical and magnetic properties. However, charge-transfer phase transitions have not been reported for the simplest FeFe cyanide-bridged systems. A mixed-valence Fe(II) /Fe(III) cyanide-bridged coordination polymer, {[Fe(Tp)(CN)3 ]2 Fe(bpe)⋅5 H2 O}n , which demonstrates a thermally induced charge-transfer phase transition, is described. As a result of the charge transfer during this phase transition, the high-spin state of the whole system does not change to a low-spin state. This result is in contrast to FeCo cyanide-bridged systems that exhibit charge-transfer-induced spin transitions. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. Effect of high linear energy transfer radiation on biological membranes

    Energy Technology Data Exchange (ETDEWEB)

    Choudhary, D.; Srivastava, M.; Kale, R.K. [Radiation Biology Lab., Jawaharlal Nehru Univ., New Delhi (India); Sarma, A. [Nuclear Science Centre, New Delhi (India)


    Cellular membranes are vital elements, and their integrity is extremely essential for the viability of the cells. We studied the effects of high linear energy transfer (LET) radiation on the membranes. Rabbit erythrocytes (1 x 10{sup 7} cells/ml) and microsomes (0.6 mg protein/ml) prepared from liver of rats were irradiated with {sup 7}Li ions of energy 6.42 MeV/u and {sup 16}O ions of energy 4.25 MeV/u having maximum LET values of 354 keV/{mu}m and 1130 keV/{mu}m, respectively. {sup 7}Li- and {sup 16}O-induced microsomal lipid peroxidation was found to increase with fluence. The {sup 16}O ions were more effective than {sup 7}Li ions, which could be due to the denser energy distribution in the track and the yield of free radicals. These findings suggested that the biological membranes could be peroxidized on exposure to high-LET radiation. Inhibition of the lipid peroxidation was observed in the presence of a membrane-active drug, chlorpromazine (CPZ), which could be due to scavenging of free radicals (mainly HO. and ROO.), electron donation, and hydrogen transfer reactions. The {sup 7}Li and {sup 16}O ions also induced hemolysis in erythrocytes. The extent of hemolysis was found to be a function of time and fluence, and showed a characteristic sigmoidal pattern. The {sup 16}O ions were more effective in the lower fluence range than {sup 7}Li ions. These results were compared with lipid peroxidation and hemolysis induced by gamma-radiation. (orig.) With 7 figs., 3 tabs., 30 refs.

  12. Efficient two-step photogeneration of long-lived charges in ground-state charge-transfer complexes of conjugated polymer doped with fullerene

    NARCIS (Netherlands)

    Bakulin, Artem A.; Zapunidy, Sergey A.; Pshenichnikov, Maxim S.; van Loosdrecht, Paul H. M.; Paraschuk, Dmitry Yu.


    Polarization-sensitive time-resolved visible-infrared pump-probe experiments demonstrate that one can efficiently generate long-lived charges in donor-acceptor charge transfer complex (CTC) of conjugated polymer doped with fullerene, MEH-PPV/dinitroanthraquinone/C(60). In particular, a strong

  13. Facile Access to Twisted Intramolecular Charge-Transfer Fluorogens Bearing Highly Pretwisted Donor-Acceptor Systems Together with Readily Fine-Tuned Charge-Transfer Characters. (United States)

    Luo, Yanju; Wang, Yan; Chen, Shiqi; Wang, Ning; Qi, Yige; Zhang, Xiaogen; Yang, Minghui; Huang, Yan; Li, Ming; Yu, Junsheng; Luo, Daibing; Lu, Zhiyun


    Twisted intramolecular charge-transfer (TICT) fluorogens bearing highly pretwisted geometries and readily-fine-tuned charge-transfer characters are quite promising sensor and electroluminescence (EL) materials. In this study, by using 4-aryloxy-1,8-naphthalimide derivatives as the molecular framework, it is demonstrated for the first time that a CO bond could serve as the central bond to construct new TICT D-A systems. Photophysical and quantum chemical studies confirm that rotation around central CO bonds is responsible for the formation of a stable TICT state in these compounds. More importantly, owing to the structural adjustability of the aryl moiety and the strong steric interactions between the naphthalimide and the aryl ring systems, these compounds can display readily-fine-tuned TICT characters, hence exhibiting an adjustable solvent polarity threshold for aggregation-induced emission (AIE) activity, and could be AIE-active even in less-polar toluene and nonpolar cyclohexane. Furthermore, these compounds could possess highly-pretwisted ground-state geometries, hence could show good EL performance. The findings reveal a facile but effective molecular constructive strategy for versatile, high-performance optoelectronic TICT compounds. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. Mass transfer within electrostatic precipitators: in-flight adsorption of mercury by charged suspended particulates. (United States)

    Clack, Herek L


    Electrostatic precipitation is the dominant method of particulate control used for coal combustion, and varying degrees of mercury capture and transformation have been reported across ESPs. Nevertheless, the fate of gas-phase mercury within an ESP remains poorly understood. The present analysis focuses on the gas-particle mass transfer that occurs within a charged aerosol in an ESP. As a necessary step in gas-phase mercury adsorption or transformation, gas-particle mass transfer-particularly in configurations other than fixed beds-has received far less attention than studies of adsorption kinetics. Our previous analysis showed that only a small fraction of gas-phase mercury entering an ESP is likelyto be adsorbed by collected particulate matter on the plate electrodes. The present simplified analysis provides insight into gas-particle mass transfer within an ESP under two limiting conditions: laminar and turbulent fluid flows. The analysis reveals that during the process of particulate collection, gas-particle mass transfer can be quite high, easily exceeding the mass transfer to ESP plate electrodes in most cases. Decreasing particle size, increasing particle mass loading, and increasing temperature all result in increased gas-particle mass transfer. The analysis predicts significantly greater gas-particle mass transfer in the laminar limitthan in the turbulent limit; however, the differences become negligible under conditions where other factors, such as total mass of suspended particulates, are the controlling mass transfer parameters. Results are compared to selected pilot- and full-scale sorbent injection data.

  15. Block-Localized Wavefunction (BLW) Based Two-State Approach for Charge Transfers between Phenyl Rings. (United States)

    Mo, Yirong; Song, Lingchun; Lin, Yuchun; Liu, Minghong; Cao, Zexing; Wu, Wei


    The block-localized wave function (BLW) method is the simplest and most efficient variant of ab initio valence bond (VB) theory which defines electron-localized resonance states following the conventional VB concepts. Here, a BLW-based two-state approach is proposed to probe the charge/hole transfer reactions within the Marcus-Hush model. With this approach, both the electronic coupling and reorganization energies can be derived at the ab initio level. Pilot applications to the electron/hole transfers between two phenyl rings are presented. Good exponential correlation between the electronic coupling energy and the donor-acceptor distance is shown, whereas the inner-sphere reorganization shows little geometric dependency. Computations also support the assumption in Marcus theory that the thermal electron transfer barrier (ΔG*), which is a sum of the reaction barrier (ΔEa) for electron/hole transfer and the coupling energy (VAB), is a quarter of the reorganization energy (λ).

  16. Cluster Dependent Charge-Transfer Dynamics in Iron-Sulfur Proteins. (United States)

    Mao, Ziliang; Liou, Shu-Hao; Khadka, Nimesh; Jenney, Francis E; Goodin, David B; Seefeldt, Lance C; Adams, Michael W W; Cramer, Stephen; Larsen, Delmar S


    Photo-induced charge-transfer dynamics and the influence of cluster size on the dynamics were investigated using five iron-sulfur clusters: the 1Fe-4S cluster in Pyrococcos furiosus rubredoxin, the 2Fe-2S cluster in Pseudomonas putida putidaredoxin, the 4Fe-4S cluster in nitrogenase iron protein, and the 8Fe-7S P-cluster and the 7Fe-9S-1Mo FeMo cofactor in nitrogenase MoFe protein. Laser excitation promotes the iron-sulfur clusters to excited electronic states that relax to lower states. The electronic relaxation lifetimes of the 1Fe-4S, the 8Fe-7S, and the 7Fe-9S-1Mo clusters are in the picoseconds timescale, although the dynamics of the MoFe protein is a mixture of the dynamics of the later two clusters. The lifetimes of the 2Fe-2S and the 4Fe-4S clusters, however, extend to several nanoseconds. A competition between reorganization energies and density of electronic states (thus electronic coupling between states) mediates the charge-transfer lifetimes, with the 2Fe-2S cluster of Pdx and the 4Fe-4S cluster of Fe protein lying at the optimum leading to them having significantly longer lifetimes. Their long lifetimes make them the optimal candidates for long-range electron transfer and as external photosensitizers for other photo-activated chemical reactions like solar hydrogen production. Potential electron-transfer and hole-transfer pathways are proposed that possibly facilitate these charge transfers.

  17. Electrostatic Potential-Based Method of Balancing Charge Transfer Across ONIOM QM:QM Boundaries. (United States)

    Jovan Jose, K V; Raghavachari, Krishnan


    The inability to describe charge redistribution effects between different regions in a large molecule can be a source of error in an ONIOM hybrid calculation. We propose a new and an inexpensive method for describing such charge-transfer effects and for improving reaction energies obtained with the ONIOM method. Our method is based on matching the electrostatic potential (ESP) between the model system and the real system. The ESP difference arising due to charge redistribution is overcome by placing an optimum one electron potential at a defined buffer region. In our current implementation, the link atom nuclear charge is optimized iteratively to produce a model low ESP distribution equal to that in the real low calculation. These optimum charges are relatively small in magnitude and corroborate physical intuition. This new ESP-ONIOM-CT method is independent of any arbitrary definition of charges, is defined on the basis of a physical observable, and is less basis set dependent than previous approaches. The method is easily extended for studying reactions involving multiple link atoms. We present a thorough benchmark of this method on test sets consisting of one- and two-link atom reactions. Using reaction energies of four different test sets each with four different combinations of high:low levels of theory, the accuracy of ESP-ONIOM-CT improved by 40-60% over the ONIOM method.

  18. Charge transfer in the electron donor-acceptor complex BH3NH3. (United States)

    Mo, Yirong; Song, Lingchun; Wu, Wei; Zhang, Qianer


    As a simple yet strongly binding electron donor-acceptor (EDA) complex, BH(3)NH(3) serves as a good example to study the electron pair donor-acceptor complexes. We employed both the ab initio valence bond (VB) and block-localized wave function (BLW) methods to explore the electron transfer from NH(3) to BH(3). Conventionally, EDA complexes have been described by two diabatic states: one neutral state and one ionic charge-transferred state. Ab initio VB self-consistent field (VBSCF) computations generate the energy profiles of the two diabatic states together with the adiabatic (ground) state. Our calculations evidently demonstrated that the electron transfer between NH(3) and BH(3) falls in the abnormal regime where the reorganization energy is less than the exoergicity of the reaction. The nature of the NH(3)-BH(3) interaction is probed by an energy decomposition scheme based on the BLW method. We found that the variation of the charge-transfer energy with the donor-acceptor distance is insensitive to the computation levels and basis sets, but the estimation of the amount of electron transferred heavily depends on the population analysis procedures. The recent resurgence of interest in the nature of the rotation barrier in ethane prompted us to analyze the conformational change of BH(3)NH(3), which is an isoelectronic system with ethane. We found that the preference of the staggered structure over the eclipsed structure of BH(3)NH(3) is dominated by the Pauli exchange repulsion.

  19. Charge transfer kinetics at the solid-solid interface in porous electrodes (United States)

    Bai, Peng; Bazant, Martin Z.


    Interfacial charge transfer is widely assumed to obey the Butler-Volmer kinetics. For certain liquid-solid interfaces, the Marcus-Hush-Chidsey theory is more accurate and predictive, but it has not been applied to porous electrodes. Here we report a simple method to extract the charge transfer rates in carbon-coated LiFePO4 porous electrodes from chronoamperometry experiments, obtaining curved Tafel plots that contradict the Butler-Volmer equation but fit the Marcus-Hush-Chidsey prediction over a range of temperatures. The fitted reorganization energy matches the Born solvation energy for electron transfer from carbon to the iron redox site. The kinetics are thus limited by electron transfer at the solid-solid (carbon-LixFePO4) interface rather than by ion transfer at the liquid-solid interface, as previously assumed. The proposed experimental method generalizes Chidsey’s method for phase-transforming particles and porous electrodes, and the results show the need to incorporate Marcus kinetics in modelling batteries and other electrochemical systems.

  20. Charge transfer kinetics at the solid-solid interface in porous electrodes. (United States)

    Bai, Peng; Bazant, Martin Z


    Interfacial charge transfer is widely assumed to obey the Butler-Volmer kinetics. For certain liquid-solid interfaces, the Marcus-Hush-Chidsey theory is more accurate and predictive, but it has not been applied to porous electrodes. Here we report a simple method to extract the charge transfer rates in carbon-coated LiFePO4 porous electrodes from chronoamperometry experiments, obtaining curved Tafel plots that contradict the Butler-Volmer equation but fit the Marcus-Hush-Chidsey prediction over a range of temperatures. The fitted reorganization energy matches the Born solvation energy for electron transfer from carbon to the iron redox site. The kinetics are thus limited by electron transfer at the solid-solid (carbon-Li(x)FePO4) interface rather than by ion transfer at the liquid-solid interface, as previously assumed. The proposed experimental method generalizes Chidsey's method for phase-transforming particles and porous electrodes, and the results show the need to incorporate Marcus kinetics in modelling batteries and other electrochemical systems.

  1. Strain-induced charge transfer and polarity control of a heterosheet comprising C60 and graphene (United States)

    Saucier, Yamato A.; Okada, Susumu; Maruyama, Mina


    Using density functional theory combined with the effective screening medium method, the energetics and electronic structure of a C60 molecular sheet adsorbed on graphene were studied in terms of biaxial strains. The optimum spacing and interlayer interaction monotonically decreases and increases, respectively, with an increasing biaxial tensile strain. The biaxial compressive strain induces electron transfer from the graphene to C60 at a 2% lateral compression, leading to an all-carbon charge transfer complex. The heterosheet possesses an intrinsic dipole moment along the graphene-to-C60 molecular layer direction.

  2. Temperature-dependent kinetics of charge transfer, hydrogen-atom transfer, and hydrogen-atom expulsion in the reaction of CO+ with CH4 and CD4. (United States)

    Melko, Joshua J; Ard, Shaun G; Johnson, Ryan S; Shuman, Nicholas S; Guo, Hua; Viggiano, Albert A


    We have determined the rate constants and branching ratios for the reactions of CO(+) with CH4 and CD4 in a variable-temperature selected ion flow tube. We find that the rate constants are collisional for all temperatures measured (193-700 K for CH4 and 193-500 K for CD4). For the CH4 reaction, three product channels are identified, which include charge transfer (CH4(+) + CO), H-atom transfer (HCO(+) + CH3), and H-atom expulsion (CH3CO(+) + H). H-atom transfer is slightly preferred to charge transfer at low temperature, with the charge-transfer product increasing in contribution as the temperature is increased (H-atom expulsion is a minor product for all temperatures). Analogous products are identified for the CD4 reaction. Density functional calculations on the CO(+) + CH4 reaction were also conducted, revealing that the relative temperature dependences of the charge-transfer and H-atom transfer pathways are consistent with an initial charge transfer followed by proton transfer.

  3. Charge transfer complex in diketopyrrolopyrrole polymers and fullerene blends: Implication for organic solar cell efficiency (United States)

    Moghe, D.; Yu, P.; Kanimozhi, C.; Patil, S.; Guha, S.


    Copolymers based on diketopyrrolopyrrole (DPP) have recently gained potential in organic photovoltaics. When blended with another acceptor such as PCBM, intermolecular charge transfer occurs which may result in the formation of charge transfer (CT) states. We present here the spectral photocurrent characteristics of two donor-acceptor DPP based copolymers, PDPP-BBT and TDPP-BBT, blended with PCBM to identify the CT states. The spectral photocurrent measured using Fourier-transform photocurrent spectroscopy (FTPS) and monochromatic photocurrent (PC) methods are compared with P3HT:PCBM, where the CT state is well known. PDPP-BBT:PCBM shows a stable CT state while TDPP-BBT does not. Our analysis shows that the larger singlet state energy difference between TDPP-BBT and PCBM along with the lower optical gap of TDPP-BBT obliterates the formation of a midgap CT state resulting in an enhanced photovoltaic efficiency over PDPP-BBT:PCBM.

  4. Specific features of the charge and mass transfer in a silver-intercalated hafnium diselenide (United States)

    Pleshchev, V. G.; Selezneva, N. V.; Baranov, N. V.


    The specific features of the charge transfer in intercalated samples of Ag x HfSe2 have been studied for the first time by alternating current (ac) impedance spectroscopy. It has been found that relaxation processes in an ac field are accelerated with increasing silver content in the samples. The complex conductivity ( Y) shows a frequency dispersion described by power law Y ˜ ω s , which is characteristic of the hopping conductivity mechanism. The Ag x HfSe2 compounds demonstrate shorter relaxation times as compared to those observed in hafnium diselenide intercalated with copper atoms, and this fact indicates that the charge carrier mobility in the silver-intercalated compounds is higher. The possibility of silver ion transfer in Ag x HfSe2 is confirmed by the measurements performed by the method of electrochemical cell emf.

  5. Ultrafast Charge Transfer Processes Accompanying K L L Auger Decay in Aqueous KCl Solution (United States)

    Céolin, D.; Kryzhevoi, N. V.; Nicolas, Ch.; Pokapanich, W.; Choksakulporn, S.; Songsiriritthigul, P.; Saisopa, T.; Rattanachai, Y.; Utsumi, Y.; Palaudoux, J.; Öhrwall, G.; Rueff, J.-P.


    X-ray photoelectron and K L L Auger spectra were measured for the K+ and Cl- ions in aqueous KCl solution. While the XPS spectra of these ions have similar structures, both exhibiting only weak satellites near the main line, the Auger spectra differ dramatically. Contrary to the chloride case, a very strong extra peak was found in the Auger spectrum of K+ at the low kinetic energy side of the D 1 state. Using the equivalent core model and ab initio calculations this spectral feature was assigned to electron transfer processes from solvent water molecules to the solvated cation. The observed charge transfer processes are suggested to play an important role in charge redistribution following single and multiple core-hole creation in atoms and molecules placed into environment.

  6. WO3-reduced graphene oxide composites with enhanced charge transfer for photoelectrochemical conversion. (United States)

    Wu, Haoyu; Xu, Ming; Da, Peimei; Li, Wenjie; Jia, Dingsi; Zheng, Gengfeng


    Hybrid structures between semiconducting metal oxides and carbon with rational synthesis represent unique device building blocks to optimize the light absorption and charge transfer process for the photoelectrochemical conversion. Here we demonstrate the realization of a WO3-reduced graphene oxide (RGO) nanocomposite via hydrothermal growth of ultrathin WO3 nanoplates directly on fluorine-doped tin oxide (FTO) substrates, followed by in situ photo-reduction to deposit RGO layers on WO3 nanoplate surface. Photoanodes made of the WO3-RGO nanocomposites have achieved a photocurrent density of 2.0 mA cm(-2) at 1.23 V vs. reversible hydrogen electrode (RHE), which is among the highest reported values for photoanodes based on hydrothermally grown WO3. Electrochemical impedance spectroscopy reveals that the increase of photoactivity is attributed to the enhanced charge transfer by the incorporation of RGO, thus suggesting a general approach for designing other metal oxide-RGO hybrid architectures.

  7. Histopathology of uveal melanomas treated with charged particle radiation

    Energy Technology Data Exchange (ETDEWEB)

    Crawford, J.B.; Char, D.H.


    The authors have treated 255 uveal melanomas with helium ion radiation. Twenty-three eyes have been enucleated because of complications and five eyes have been obtained at autopsy. We have evaluated 27 of these eyes. Neovascular glaucoma (10 eyes), painful keratitis (6 eyes), continued tumor growth (4 eyes), and vitreous hemorrhage (2 eyes) were the major complications of treatment that led to enucleation. The degree of tumor necrosis correlated with the size, pigmentation, and anterior extent of the tumor. It did not correlate with the interval from irradiation or with the amount of tumor shrinkage. Mitotic figures were extremely rare in treated tumors, suggesting that the tumor cells have lost their ability to cycle.

  8. Incident energy transfer equation and its solution by collocation spectral method for one-dimensional radiative heat transfer (United States)

    Hu, Zhang-Mao; Tian, Hong; Li, Ben-Wen; Zhang, Wei; Yin, Yan-Shan; Ruan, Min; Chen, Dong-Lin


    The ray-effect is a major discretization error in the approximate solution method for the radiative transfer equation (RTE). To overcome this problem, the incident energy transfer equation (IETE) is proposed. The incident energy, instead of radiation intensity, is obtained by directly solving this new equation. Good numerical properties are found for the incident energy transfer equation. To show the properties of numerical solution, the collocation spectral method (CSM) is employed to solve the incident energy transfer equation. Three test cases are taken into account to verify the performance of the incident energy transfer equation. The result shows that the radiative heat flux obtained based on IETE is much more accurate than that based on RTE, which means that the IETE is very effective in eliminating the impacts of ray-effect on the heat flux. However, on the contrary, the radiative intensity obtained based on IETE is less accurate than that based on RTE due to the ray-effect. So, this equation is more suitable for those radiative heat transfer problems, in which the radiation heat flux and incident energy are needed rather than the radiation intensity.

  9. Interfaces between strongly correlated oxides: controlling charge transfer and induced magnetism by hybridization (United States)

    Bibes, Manuel

    At interfaces between conventional materials, band bending and alignment are controlled by differences in electrochemical potential. Applying this concept to oxides in which interfaces can be polar and cations may adopt a mixed valence has led to the discovery of novel two-dimensional states between simple band insulators such as LaAlO3 and SrTiO3. However, many oxides have a more complex electronic structure, with charge, orbital and/or spin orders arising from correlations between transition metal and oxygen ions. Strong correlations thus offer a rich playground to engineer functional interfaces but their compatibility with the classical band alignment picture remains an open question. In this talk we will show that beyond differences in electron affinities and polar effects, a key parameter determining charge transfer at correlated oxide interfaces is the energy required to alter the covalence of the metal-oxygen bond. Using the perovskite nickelate (RNiO3) family as a template, we have probed charge reconstruction at interfaces with gadolinium titanate GdTiO3 using soft X-ray absorption spectroscopy and hard X-ray photoemission spectroscopy. We show that the charge transfer is thwarted by hybridization effects tuned by the rare-earth (R) size. Charge transfer results in an induced ferromagnetic-like state in the nickelate (observed by XMCD), exemplifying the potential of correlated interfaces to design novel phases. Further, our work clarifies strategies to engineer two-dimensional systems through the control of both doping and covalence. Work supported by ERC CoG MINT #615759.

  10. Computational models of an inductive power transfer system for electric vehicle battery charge (United States)

    Anele, A. O.; Hamam, Y.; Chassagne, L.; Linares, J.; Alayli, Y.; Djouani, K.


    One of the issues to be solved for electric vehicles (EVs) to become a success is the technical solution of its charging system. In this paper, computational models of an inductive power transfer (IPT) system for EV battery charge are presented. Based on the fundamental principles behind IPT systems, 3 kW single phase and 22 kW three phase IPT systems for Renault ZOE are designed in MATLAB/Simulink. The results obtained based on the technical specifications of the lithium-ion battery and charger type of Renault ZOE show that the models are able to provide the total voltage required by the battery. Also, considering the charging time for each IPT model, they are capable of delivering the electricity needed to power the ZOE. In conclusion, this study shows that the designed computational IPT models may be employed as a support structure needed to effectively power any viable EV.

  11. Interfacial Charge Transfer and Recombination Dynamics in van der Waals Heterojunctions of 2D Semiconductors (United States)

    Wang, Jue; Zhu, Haiming; Gong, Zizhou; Kim, Young Duck; Gustafsson, Martin; Hone, James; Zhu, Xiaoyang

    Heterojunctions of transition metal dichalcogenides (TMDC) are being explored for optoelectronics, photovoltaics and spin-valleytronics at the 2D limit. Using time-resolved microscopic transient reflectance spectroscopy, we measured the interfacial charge transfer and recombination dynamics in two dimensional MoS2/WSe2 heterojunctions as a function of interlayer momentum mismatch. The observed ultrafast (Science Foundation Grant DMR 1608437 and Grant DMR 1420634 (Materials Research Science and Engineering Center).

  12. Oxidation and metal-insertion in molybdenite surfaces: evaluation of charge-transfer mechanisms and dynamics (United States)

    Ramana, CV; Becker, U; Shutthanandan, V; Julien, CM


    Molybdenum disulfide (MoS2), a layered transition-metal dichalcogenide, has been of special importance to the research community of geochemistry, materials and environmental chemistry, and geotechnical engineering. Understanding the oxidation behavior and charge-transfer mechanisms in MoS2 is important to gain better insight into the degradation of this mineral in the environment. In addition, understanding the insertion of metals into molybdenite and evaluation of charge-transfer mechanism and dynamics is important to utilize these minerals in technological applications. Furthermore, a detailed investigation of thermal oxidation behavior and metal-insertion will provide a basis to further explore and model the mechanism of adsorption of metal ions onto geomedia. The present work was performed to understand thermal oxidation and metal-insertion processes of molybdenite surfaces. The analysis was performed using atomic force microscopy (AFM), scanning electron microscopy (SEM), transmission electron microscopy (TEM), Rutherford backscattering spectrometry (RBS), and nuclear reaction analysis (NRA). Structural studies using SEM and TEM indicate the local-disordering of the structure as a result of charge-transfer process between the inserted lithium and the molybdenite layer. Selected area electron diffraction measurements indicate the large variations in the diffusivity of lithium confirming that the charge-transfer is different along and perpendicular to the layers in molybdenite. Thermal heating of molybenite surface in air at 400°C induces surface oxidation, which is slow during the first hour of heating and then increases significantly. The SEM results indicate that the crystals formed on the molybdenite surface as a result of thermal oxidation exhibit regular thin-elongated shape. The average size and density of the crystals on the surface is dependent on the time of annealing; smaller size and high density during the first one-hour and significant increase in

  13. Oxidation and metal-insertion in molybdenite surfaces: evaluation of charge-transfer mechanisms and dynamics

    Directory of Open Access Journals (Sweden)

    Shutthanandan V


    Full Text Available Abstract Molybdenum disulfide (MoS2, a layered transition-metal dichalcogenide, has been of special importance to the research community of geochemistry, materials and environmental chemistry, and geotechnical engineering. Understanding the oxidation behavior and charge-transfer mechanisms in MoS2 is important to gain better insight into the degradation of this mineral in the environment. In addition, understanding the insertion of metals into molybdenite and evaluation of charge-transfer mechanism and dynamics is important to utilize these minerals in technological applications. Furthermore, a detailed investigation of thermal oxidation behavior and metal-insertion will provide a basis to further explore and model the mechanism of adsorption of metal ions onto geomedia. The present work was performed to understand thermal oxidation and metal-insertion processes of molybdenite surfaces. The analysis was performed using atomic force microscopy (AFM, scanning electron microscopy (SEM, transmission electron microscopy (TEM, Rutherford backscattering spectrometry (RBS, and nuclear reaction analysis (NRA. Structural studies using SEM and TEM indicate the local-disordering of the structure as a result of charge-transfer process between the inserted lithium and the molybdenite layer. Selected area electron diffraction measurements indicate the large variations in the diffusivity of lithium confirming that the charge-transfer is different along and perpendicular to the layers in molybdenite. Thermal heating of molybenite surface in air at 400°C induces surface oxidation, which is slow during the first hour of heating and then increases significantly. The SEM results indicate that the crystals formed on the molybdenite surface as a result of thermal oxidation exhibit regular thin-elongated shape. The average size and density of the crystals on the surface is dependent on the time of annealing; smaller size and high density during the first one-hour and

  14. Impact of speciation on the electron charge transfer properties of nanodiamond drug carriers (United States)

    Sun, Baichuan; Barnard, Amanda S.


    Unpassivated diamond nanoparticles (bucky-diamonds) exhibit a unique surface reconstruction involving graphitization of certain crystal facets, giving rise to hybrid core-shell particles containing both aromatic and aliphatic carbon. Considerable effort is directed toward eliminating the aromatic shell, but persistent graphitization of subsequent subsurface-layers makes perdurable purification a challenge. In this study we use some simple statistical methods, in combination with electronic structure simulations, to predict the impact of different fractions of aromatic and aliphatic carbon on the charge transfer properties of the ensembles of bucky-diamonds. By predicting quality factors for a variety of cases, we find that perfect purification is not necessary to preserve selectivity, and there is a clear motivation for purifying samples to improve the sensitivity of charge transfer reactions. This may prove useful in designing drug delivery systems where the release of (selected) drugs needs to be sensitive to specific conditions at the point of delivery.Unpassivated diamond nanoparticles (bucky-diamonds) exhibit a unique surface reconstruction involving graphitization of certain crystal facets, giving rise to hybrid core-shell particles containing both aromatic and aliphatic carbon. Considerable effort is directed toward eliminating the aromatic shell, but persistent graphitization of subsequent subsurface-layers makes perdurable purification a challenge. In this study we use some simple statistical methods, in combination with electronic structure simulations, to predict the impact of different fractions of aromatic and aliphatic carbon on the charge transfer properties of the ensembles of bucky-diamonds. By predicting quality factors for a variety of cases, we find that perfect purification is not necessary to preserve selectivity, and there is a clear motivation for purifying samples to improve the sensitivity of charge transfer reactions. This may prove

  15. Radiative transfer theory applied to ocean bottom modeling. (United States)

    Quijano, Jorge E; Zurk, Lisa M


    Research on the propagation of acoustic waves in the ocean bottom sediment is of interest for active sonar applications such as target detection and remote sensing. The interaction of acoustic energy with the sea floor sublayers is usually modeled with techniques based on the full solution of the wave equation, which sometimes leads to mathematically intractable problems. An alternative way to model wave propagation in layered media containing random scatterers is the radiative transfer (RT) formulation, which is a well established technique in the electromagnetics community and is based on the principle of conservation of energy. In this paper, the RT equation is used to model the backscattering of acoustic energy from a layered elastic bottom sediment containing distributions of independent scatterers due to a constant single frequency excitation in the water column. It is shown that the RT formulation provides insight into the physical phenomena of scattering and conversion of energy between waves of different polarizations.

  16. Radiative Transfer Theory Verified by Controlled Laboratory Experiments (United States)

    Mishchenko, Michael I.; Goldstein, Dennis H.; Chowdhary, Jacek; Lompado, Arthur


    We report the results of high-accuracy controlled laboratory measurements of the Stokes reflection matrix for suspensions of submicrometer-sized latex particles in water and compare them with the results of a numerically exact computer solution of the vector radiative transfer equation (VRTE). The quantitative performance of the VRTE is monitored by increasing the volume packing density of the latex particles from 2 to 10. Our results indicate that the VRTE can be applied safely to random particulate media with packing densities up to 2. VRTE results for packing densities of the order of 5 should be taken with caution, whereas the polarized bidirectional reflectivity of suspensions with larger packing densities cannot be accurately predicted. We demonstrate that a simple modification of the phase matrix entering the VRTE based on the so-called static structure factor can be a promising remedy that deserves further examination.

  17. Radiative Transfer Analysis of Neptune’s New Dark Vortex (United States)

    Tollefson, Joshua; Luszcz-Cook, Statia H.; Wong, Michael H.; de Pater, Imke


    A new dark spot on Neptune was discovered in late 2015, named: "SDS-2015" for "Southern Dark Spot discovered in 2015". Subsequent observations from Hubble Space Telescope Mid-Cycle 23 (PI: Wong) and the Outer Planetary Atmospheres Legacy (OPAL) programs (PI: Simon-Miller) took the first multispectral data over multiple viewing geometries of a Neptunian dark spot, spanning wavelengths from 336 to 763nm. SDS-2015 is visible at blue wavelengths, with contrast from the background atmosphere peaking at 467nm. In this abstract, we present a radiative transfer analysis of the dark spot and surrounding background atmosphere. We summarize our retrieved properties of Neptune's background atmosphere, including its aerosol structure and methane profile, and compare our findings in the optical wavelengths to those in the near-infrared. We then discuss various hypotheses about the make up of SDS-2015 and its interaction with the background atmosphere.

  18. Muon transfer from muonic hydrogen to heavier atoms; Transfert de charge muonique

    Energy Technology Data Exchange (ETDEWEB)

    Dupays, A


    This work concerns muon transfer from muonic hydrogen to heavier atoms. Recently, a method of measurement of the hyperfine structure of ground-state muonic hydrogen based on the collision energy dependence of the muon transfer rate to oxygen has been proposed. This proposal is based on measurements which where performed at the Paul Scherrer Institute in the early nineties which indicate that the muon transfer from muonic hydrogen to oxygen increases by a factor of 4 going from thermal to 0.12 eV energies. The motivation of our calculations was to confirm this behaviour. To study the collision energy dependence of the muon transfer rate, we have used a time-independent close-coupling method. We have set up an hyperspherical elliptic formalism valid for nonzero total angular momentum which allows accurate computations of state-to-state reactive and charge exchange processes. We have applied this formalism to muon-transfer process to oxygen and neon. The comparison with experimental results is in both cases excellent. Finally, the neon transfer rate dependence with energy suggests to use neon instead of oxygen to perform a measurement of the hyperfine structure of muonic hydrogen. The results of accurate calculations of the muon transfer rates from muonic protium and deuterium atoms to nitrogen, oxygen and neon are also reported. Very good agreement with measured rates is obtained and for the three systems, the isotopic effect is perfectly reproduced. (author)

  19. First measurement of proton's charge form factor at very low Q2 with initial state radiation

    Directory of Open Access Journals (Sweden)

    M. Mihovilovič


    Full Text Available We report on a new experimental method based on initial-state radiation (ISR in e–p scattering, which exploits the radiative tail of the elastic peak to study the properties of electromagnetic processes and to extract the proton charge form factor (GEp at extremely small Q2. The ISR technique was implemented in an experiment at the three-spectrometer facility of the Mainz Microtron (MAMI. This led to a precise validation of radiative corrections far away from elastic line and provided first measurements of GEp for 0.001≤Q2≤0.004(GeV/c2.

  20. Charge-Transfer States in Organic Solar Cells: Understanding the Impact of Polarization, Delocalization, and Disorder

    KAUST Repository

    Zheng, Zilong


    We investigate the impact of electronic polarization, charge delocalization, and energetic disorder on the charge-transfer (CT) states formed at a planar C60/pentacene interface. The ability to examine large complexes containing up to seven pentacene molecules and three C60 molecules allows us to take explicitly into account the electronic polarization effects. These complexes are extracted from a bilayer architecture modeled by molecular dynamics simulations and evaluated by means of electronic-structure calculations based on long-range-separated functionals (ωB97XD and BNL) with optimized range-separation parameters. The energies of the lowest charge-transfer states derived for the large complexes are in very good agreement with the experimentally reported values. The average singlet-triplet energy splittings of the lowest CT states are calculated not to exceed 10 meV. The rates of geminate recombination as well as of dissociation of the triplet excitons are also evaluated. In line with experiment, our results indicate that the pentacene triplet excitons generated through singlet fission can dissociate into separated charges on a picosecond time scale, despite the fact that their energy in C60/pentacene heterojunctions is slightly lower than the energies of the lowest CT triplet states.

  1. Charge constrained density functional molecular dynamics for simulation of condensed phase electron transfer reactions. (United States)

    Oberhofer, Harald; Blumberger, Jochen


    We present a plane-wave basis set implementation of charge constrained density functional molecular dynamics (CDFT-MD) for simulation of electron transfer reactions in condensed phase systems. Following the earlier work of Wu and Van Voorhis [Phys. Rev. A 72, 024502 (2005)], the density functional is minimized under the constraint that the charge difference between donor and acceptor is equal to a given value. The classical ion dynamics is propagated on the Born-Oppenheimer surface of the charge constrained state. We investigate the dependence of the constrained energy and of the energy gap on the definition of the charge and present expressions for the constraint forces. The method is applied to the Ru2+-Ru3+ electron self-exchange reaction in aqueous solution. Sampling the vertical energy gap along CDFT-MD trajectories and correcting for finite size effects, a reorganization free energy of 1.6 eV is obtained. This is 0.1-0.2 eV lower than a previous estimate based on a continuum model for solvation. The smaller value for the reorganization free energy can be explained by the fact that the Ru-O distances of the divalent and trivalent Ru hexahydrates are predicted to be more similar in the electron transfer complex than for the separated aqua ions.

  2. Density functional theory for the description of charge-transfer processes at TTF/TCNQ interfaces

    KAUST Repository

    Van Regemorter, Tanguy


    In the field of organic electronics, a central issue is to assess how the frontier electronic levels of two adjacent organic layers align with respect to one another at the interface. This alignment can be driven by the presence of a partial charge transfer and the formation of an interface dipole; it plays a key role for instance in determining the rates of exciton dissociation or exciton formation in organic solar cells or light-emitting diodes, respectively. Reliably modeling the processes taking place at these interfaces remains a challenge for the computational chemistry community. Here, we review our recent theoretical work on the influence of the choice of density functional theory (DFT) methodology on the description of the charge-transfer character in the ground state of TTF/ TCNQ model complexes and interfaces. Starting with the electronic properties of the isolated TTF and TCNQ molecules and then considering the charge transfer and resulting interface dipole in TTF/TCNQ donor-acceptor stacks and bilayers, we examine the impact of the choice of DFT functional in describing the interfacial electronic structure. Finally, we employ computations based on periodic boundary conditions to highlight the impact of depolarization effects on the interfacial dipole moment. © Springer-Verlag 2012.

  3. Overcoming the Cut-Off Charge Transfer Bandgaps at the PbS Quantum Dot Interface

    KAUST Repository

    El-Ballouli, Ala'a O.


    Light harvesting from large size of semiconductor PbS quantum dots (QDs) with a bandgap of less than 1 eV is one of the greatest challenges precluding the development of PbS QD-based solar cells because the interfacial charge transfer (CT) from such QDs to the most commonly used electron acceptor materials is very inefficient, if it occurs at all. Thus, an alternative electron-accepting unit with a new driving force for CT is urgently needed to harvest the light from large-sized PbS QDs. Here, a cationic porphyrin is utilized as a new electron acceptor unit with unique features that bring the donor–acceptor components into close molecular proximity, allowing ultrafast and efficient electron transfer for QDs of all sizes, as inferred from the drastic photoluminescence quenching and the ultrafast formation of the porphyrin anionic species. The time-resolved results clearly demonstrate the possibility of modulating the electron transfer process between PbS QDs and porphyrin moieties not only by the size quantization effect but also by the interfacial electrostatic interaction between the positively charged porphyrin and the negatively charged QDs. This approach provides a new pathway for engineering QD-based solar cells that make the best use of the diverse photons making up the Sun\\'s broad irradiance spectrum.

  4. Observation of Ground- and Excited-State Charge Transfer at the C60/Graphene Interface. (United States)

    Jnawali, Giriraj; Rao, Yi; Beck, Jonathan H; Petrone, Nicholas; Kymissis, Ioannis; Hone, James; Heinz, Tony F


    We examine charge transfer interactions in the hybrid system of a film of C60 molecules deposited on single-layer graphene using Raman spectroscopy and Terahertz (THz) time-domain spectroscopy. In the absence of photoexcitation, we find that the C60 molecules in the deposited film act as electron acceptors for graphene, yielding increased hole doping in the graphene layer. Hole doping of the graphene film by a uniform C60 film at a level of 5.6 × 10(12)/cm(2) or 0.04 holes per interfacial C60 molecule was determined by the use of both Raman and THz spectroscopy. We also investigate transient charge transfer occurring upon photoexcitation by femtosecond laser pulses with a photon energy of 3.1 eV. The C60/graphene hybrid exhibits a short-lived (ps) decrease in THz conductivity, followed by a long-lived increase in conductivity. The initial negative photoconductivity transient, which decays within 2 ps, reflects the intrinsic photoresponse of graphene. The longer-lived positive conductivity transient, with a lifetime on the order of 100 ps, is attributed to photoinduced hole doping of graphene by interfacial charge transfer. We discuss possible microscopic pathways for hot carrier processes in the hybrid system.

  5. Defect passivation of transition metal dichalcogenides via a charge transfer van der Waals interface. (United States)

    Park, Jun Hong; Sanne, Atresh; Guo, Yuzheng; Amani, Matin; Zhang, Kehao; Movva, Hema C P; Robinson, Joshua A; Javey, Ali; Robertson, John; Banerjee, Sanjay K; Kummel, Andrew C


    Integration of transition metal dichalcogenides (TMDs) into next-generation semiconductor platforms has been limited due to a lack of effective passivation techniques for defects in TMDs. The formation of an organic-inorganic van der Waals interface between a monolayer (ML) of titanyl phthalocyanine (TiOPc) and a ML of MoS 2 is investigated as a defect passivation method. A strong negative charge transfer from MoS 2 to TiOPc molecules is observed in scanning tunneling microscopy. As a result of the formation of a van der Waals interface, the I ON / I OFF in back-gated MoS 2 transistors increases by more than two orders of magnitude, whereas the degradation in the photoluminescence signal is suppressed. Density functional theory modeling reveals a van der Waals interaction that allows sufficient charge transfer to remove defect states in MoS 2 . The present organic-TMD interface is a model system to control the surface/interface states in TMDs by using charge transfer to a van der Waals bonded complex.

  6. The impact of size and shape distributions on the electron charge transfer properties of silver nanoparticles. (United States)

    Sun, Baichuan; Barnard, Amanda S


    Many applications of silver nanoparticles are moderated by the electron charge transfer properties, such as the ionization potential, electron affinity and Fermi energy, which may be tuned by controlling the size and shape of individual particles. However, since producing samples of silver nanoparticles that are perfectly monodispersed in terms of both size and shape can be prohibitive, it is important to understand how these properties are impacted by polydispersivity, and ideally be able to predict the tolerance for variation of different geometric features. In this study, we use straightforward statistical methods, together with electronic structure simulations, to predict the electron charge transfer properties of different types of ensembles of silver nanoparticles and how restricting the structural diversity in different ways can improve or retard performance. In agreement with previous reports, we confirm that restricting the shape distribution will tune the charge transfer properties toward specific reactions, but by including the quality factors for each case we go beyond this assessment and show how targeting specific classes of morphologies and restricting the distribution of size can impact sensitivity.

  7. Charge inversion via concurrent cation and anion transfer: application to corticosteroids. (United States)

    Hassell, Kerry M; LeBlanc, Yves; McLuckey, Scott A


    A novel charge inversion process that involves the removal of an excess cation from an analyte ion and the transfer of an anion to the neutral analyte in a single ion/ion encounter is described. Polyamidoamine (PAMAM) half-generation dendrimer anions that contain small anions, such as the chloride ion, were used as charge inversion reagents. Several competing processes can occur that include removal of the cation to neutralize the analyte, the removal of the excess cation and an additional proton to yield the deprotonated molecule, or removal of the excess cation and transfer of a small anion to the analyte. For the latter process to dominate, several requirements for both the reagent anion and the analyte cation must be met. The reagent anion must form multiply charged anions and must be able to incorporate one or more small anions for transfer. The analyte must have no strongly acidic sites as well as a relatively high affinity for small anion attachment. The PAMAM dendrimer anions must meet the conditions for the reagent anions and the cations of the corticosteroids meet the conditions for the analyte. The estrogenic steroid estrone, on the other hand, does not meet the requirements and, as a result, is largely neutralized when reacted with the reagent anions. This reaction, therefore, is highly selective and might serve as a useful reaction for the screening of appropriate analytes. Copyright © 2011 John Wiley & Sons, Ltd.

  8. Radiative transfer model of snow for bare ice regions (United States)

    Tanikawa, T.; Aoki, T.; Niwano, M.; Hosaka, M.; Shimada, R.; Hori, M.; Yamaguchi, S.


    Modeling a radiative transfer (RT) for coupled atmosphere-snow-bare ice systems is of fundamental importance for remote sensing applications to monitor snow and bare ice regions in the Greenland ice sheet and for accurate climate change predictions by regional and global climate models. Recently, the RT model for atmosphere-snow system was implemented for our regional and global climate models. However, the bare ice region where recently it has been expanded on the Greenland ice sheet due to the global warming, has not been implemented for these models, implying that this region leads miscalculations in these climate models. Thus, the RT model of snow for bare ice regions is needed for accurate climate change predictions. We developed the RT model for coupled atmosphere-snow-bare ice systems, and conducted a sensitivity analysis of the RT model to know the effect of snow, bare ice and geometry parameters on the spectral radiant quantities. The RT model considers snow and bare-ice inherent optical properties (IOPs), including snow grain size, air bubble size and its concentration and bare ice thickness. The conventional light scattering theory, Mie theory, was used for IOP calculations. Monte Carlo method was used for the multiple scattering. The sensitivity analyses showed that spectral albedo for the bare ice increased with increasing the concentration of the air bubble in the bare ice for visible wavelengths because the air bubble is scatterer with no absorption. For near infrared wavelengths, spectral albedo has no dependence on the air bubble due to the strong light absorption by ice. When increasing solar zenith angle, the spectral albedo were increased for all wavelengths. This is the similar trend with spectral snow albedo. Cloud cover influenced the bare ice spectral albedo by covering direct radiation into diffuse radiation. The purely diffuse radiation has an effective solar zenith angle near 50°. Converting direct into diffuse radiation reduces the

  9. Fast radiative transfer modeling for infrared imaging radiometry

    Energy Technology Data Exchange (ETDEWEB)

    Dubuisson, P. [ELICO, Federation de Recherche CNRS 1818, Universite Littoral Cote d' Opale, 32 Av. Foch, 62930 Wimereux (France)]. E-mail:; Giraud, V. [Laboratoire d' Optique Atmospherique, FR1818, Universite de Lille1, 59655 Villeneuve d' Ascq Cedex (France); Chomette, O. [Laboratoire de Meteorologie Dynamique, Ecole Polytechnique, 91128 Palaiseau Cedex (France); Chepfer, H. [Laboratoire de Meteorologie Dynamique, Ecole Polytechnique, 91128 Palaiseau Cedex (France); Pelon, J. [Service d' Aeronomie, Universite Pierre et Marie Curie, 4 Place Jussieu, 75252 Paris Cedex 05 (France)


    Fast radiative transfer codes have been developed for simulating the outgoing radiance (and corresponding brightness temperature) to be measured by the Infrared Imaging Radiometer (IIR) of the space Cloud-Aerosol Lidar and Infrared Pathfinder Satellite Observations (CALIPSO) mission. Two simple codes (FASRAD and FASAA), for which scattering is neglected, as well as an accurate code (FASDOM), accounting for scattering and absorption with the Discrete Ordinate Method (DOM), are presented. Their accuracy has been estimated with a reference code including a line-by-line model and the DOM. Simulations have shown that the accuracy is generally better than 0.3K on the brightness temperature for clear or cloudy atmospheres. This accuracy agrees with the expected one of future IIR measurements. In addition, the impact of scattering on the brightness temperature has been evaluated for semi-transparent liquid clouds in the IIR spectral range. Especially, simulations have shown that cloud microphysics retrieval might be possible with the Brightness Temperature Difference (BTD) between two IIR bands, using the couple of wavelengths (8.7-12{mu}m) or (10.6-12{mu}m). However, scattering strongly influences the radiation for shorter wavelengths. The error on the BTD with (8.7-12{mu}m) can reach 4K when scattering is neglected, leading to large uncertainties in the retrieval of droplet effective radius.

  10. Martian Radiative Transfer Modeling Using the Optimal Spectral Sampling Method (United States)

    Eluszkiewicz, J.; Cady-Pereira, K.; Uymin, G.; Moncet, J.-L.


    The large volume of existing and planned infrared observations of Mars have prompted the development of a new martian radiative transfer model that could be used in the retrievals of atmospheric and surface properties. The model is based on the Optimal Spectral Sampling (OSS) method [1]. The method is a fast and accurate monochromatic technique applicable to a wide range of remote sensing platforms (from microwave to UV) and was originally developed for the real-time processing of infrared and microwave data acquired by instruments aboard the satellites forming part of the next-generation global weather satellite system NPOESS (National Polarorbiting Operational Satellite System) [2]. As part of our on-going research related to the radiative properties of the martian polar caps, we have begun the development of a martian OSS model with the goal of using it to perform self-consistent atmospheric corrections necessary to retrieve caps emissivity from the Thermal Emission Spectrometer (TES) spectra. While the caps will provide the initial focus area for applying the new model, it is hoped that the model will be of interest to the wider Mars remote sensing community.

  11. Analysis of linear energy transfers and quality factors of charged particles produced by spontaneous fission neutrons from 252Cf and 244Pu in the human body. (United States)

    Endo, Akira; Sato, Tatsuhiko


    Absorbed doses, linear energy transfers (LETs) and quality factors of secondary charged particles in organs and tissues, generated via the interactions of the spontaneous fission neutrons from (252)Cf and (244)Pu within the human body, were studied using the Particle and Heavy Ion Transport Code System (PHITS) coupled with the ICRP Reference Phantom. Both the absorbed doses and the quality factors in target organs generally decrease with increasing distance from the source organ. The analysis of LET distributions of secondary charged particles led to the identification of the relationship between LET spectra and target-source organ locations. A comparison between human body-averaged mean quality factors and fluence-averaged radiation weighting factors showed that the current numerical conventions for the radiation weighting factors of neutrons, updated in ICRP103, and the quality factors for internal exposure are valid.

  12. Charge-transfer mobility and electrical conductivity of PANI as conjugated organic semiconductors (United States)

    Zhang, Yahong; Duan, Yuping; Song, Lulu; Zheng, Daoyuan; Zhang, Mingxing; Zhao, Guangjiu


    The intramolecular charge transfer properties of a phenyl-end-capped aniline tetramer (ANIH) and a chloro-substituted derivative (ANICl) as organic semiconductors were theoretically studied through the first-principles calculation based on the Marcus-Hush theory. The reorganization energies, intermolecular electronic couplings, angular resolution anisotropic mobilities, and density of states of the two crystals were evaluated. The calculated results demonstrate that both ANIH and ANICl crystals show the higher electron transfer mobilities than the hole-transfer mobilities, which means that the two crystals should prefer to function as n-type organic semiconductors. Furthermore, the angle dependence mobilities of the two crystals show remarkable anisotropic character. The maximum mobility μmax of ANIH and ANICl crystals is 1.3893 and 0.0272 cm2 V-1 s-1, which appear at the orientation angles near 176°/356° and 119°/299° of a conducting channel on the a-b reference plane. It is synthetically evaluated that the ANIH crystal possesses relatively lower reorganization energy, higher electronic coupling, and electron transfer mobility, which means that the ANIH crystal may be the more ideal candidate as a high performance n-type organic semiconductor material. The systematic theoretical studies on organic crystals should be conducive to evaluating the charge-transport properties and designing higher performance organic semiconductor materials.

  13. Charge transfer dynamics from adsorbates to surfaces with single active electron and configuration interaction based approaches

    Energy Technology Data Exchange (ETDEWEB)

    Ramakrishnan, Raghunathan, E-mail: [Institute of Physical Chemistry, National Center for Computational Design and Discovery of Novel Materials (MARVEL), Department of Chemistry, University of Basel, Klingelbergstrasse 80, CH-4056 Basel (Switzerland); Nest, Mathias [Theoretische Chemie, Technische Universität München, Lichtenbergstr. 4, 85747 Garching (Germany)


    Highlights: • We model electron dynamics across cyano alkanethiolates attached to gold cluster. • We present electron transfer time scales from TD-DFT and TD-CI based simulations. • Both DFT and CI methods qualitatively predict the trend in time scales. • TD-CI predicts the experimental relative time scale very accurately. - Abstract: We employ wavepacket simulations based on many-body time-dependent configuration interaction (TD-CI), and single active electron theories, to predict the ultrafast molecule/metal electron transfer time scales, in cyano alkanethiolates bonded to model gold clusters. The initial states represent two excited states where a valence electron is promoted to one of the two virtual π{sup ∗} molecular orbitals localized on the cyanide fragment. The ratio of the two time scales indicate the efficiency of one charge transfer channel over the other. In both our one-and many-electron simulations, this ratio agree qualitatively with each other as well as with the previously reported experimental time scales (Blobner et al., 2012), measured for a macroscopic metal surface. We study the effect of cluster size and the description of electron correlation on the charge transfer process.

  14. Charge transfer dissociation (CTD) mass spectrometry of peptide cations using kiloelectronvolt helium cations. (United States)

    Hoffmann, William D; Jackson, Glen P


    A kiloelectronvolt beam of helium ions is used to ionize and fragment precursor peptide ions starting in the 1+ charge state. The electron affinity of helium cations (24.6 eV) exceeds the ionization potential of protonated peptides and can therefore be used to abstract an electron from--or charge exchange with--the isolated precursor ions. Kiloelectronvolt energies are used, (1) to overcome the Coulombic repulsion barrier between the cationic reactants, (2) to overcome ion-defocussing effects in the ion trap, and (3) to provide additional activation energy. Charge transfer dissociation (CTD) of the [M+H](+) precursor of Substance P gives product ions such as [M+H](2+•) and a dominant series of a ions in both the 1+ and 2+ charge states. These observations, along with the less-abundant a + 1 ions, are consistent with ultraviolet photodissociation (UVPD) results of others and indicate that C-C(α) cleavages are possible through charge exchange with helium ions. Although the efficiencies and timescale of CTD are not yet suitable for on-line chromatography, this new approach to ion activation provides an additional potential tool for the interrogation of gas phase ions.

  15. Photoinduced Electron Transfer in DNA: Charge Shift Dynamics Between 8-Oxo-Guanine Anion and Adenine. (United States)

    Zhang, Yuyuan; Dood, Jordan; Beckstead, Ashley A; Li, Xi-Bo; Nguyen, Khiem V; Burrows, Cynthia J; Improta, Roberto; Kohler, Bern


    Femtosecond time-resolved IR spectroscopy is used to investigate the excited-state dynamics of a dinucleotide containing an 8-oxoguanine anion at the 5'-end and neutral adenine at the 3'-end. UV excitation of the dinucleotide transfers an electron from deprotonated 8-oxoguanine to its π-stacked neighbor adenine in less than 1 ps, generating a neutral 8-oxoguanine radical and an adenine radical anion. These species are identified by the excellent agreement between the experimental and calculated IR difference spectra. The quantum efficiency of this ultrafast charge shift reaction approaches unity. Back electron transfer from the adenine radical anion to the 8-oxguanine neutral radical occurs in 9 ps, or approximately 6 times faster than between the adenine radical anion and the 8-oxoguanine radical cation (Zhang, Y. et al. Proc. Natl. Acad. Sci. U.S.A. 2014, 111, 11612-11617). The large asymmetry in forward and back electron transfer rates is fully rationalized by semiclassical nonadiabatic electron transfer theory. Forward electron transfer is ultrafast because the driving force is nearly equal to the reorganization energy, which is estimated to lie between 1 and 2 eV. Back electron transfer is highly exergonic and takes place much more slowly in the Marcus inverted region.

  16. Differential and total cross sections for charge transfer and transfer-excitation in ion-helium collisions (United States)

    Halder, S.; Mondal, A.; Samaddar, S.; Mandal, C. R.; Purkait, M.


    Total cross sections for single charge transfer in collisions of multicharged bare ions with ground-state helium atoms at incident energy ranging from 40 to 5000 keV/amu have been calculated in the framework of a four-body model of final channel distorted-wave (FC-DW-4B) approximation. In this formalism, distortion in the final channel related to the Coulomb continuum of the target and the Coulomb interaction between the passive electron in the target with the projectile are included. In all cases, total single electron-capture cross sections have been calculated by summing over all contributions up to n =3 shells and subshells. It has been observed that the contribution of the capture cross sections into excited states have insignificant contributions for symmetric collisions. Comprehensive comparisons are made between the four body model of boundary corrected continuum intermediate-state approximations [Phys. Rev. A 83, 032706 (2011), 10.1103/PhysRevA.83.032706] and the present FC-DW-4B model. The main purpose of the present study is to investigate the relative importance of dynamic electron correlation and the role of passive electron in the target at intermediate and high impact energies. In addition, projectile angular differential cross sections (DCS) for charge transfer and transfer-excitation in p -He collisions are calculated at different impact energies. At low projectile energies, the present DCS data exhibits the typical steeply decreasing dependence on the projectile scattering angles, whereas at high impact energies, the double-scattering region centered on the Thomas angle is obtained. Detailed comparisons with the available experimental data and other theories are reported with the purpose of further assessing the relevance of the present model at different impact energies. Overall, the calculated cross sections show good agreement with the available experimental findings.

  17. Electronic and vibronic properties of a discotic liquid-crystal and its charge transfer complex (United States)

    Haverkate, Lucas A.; Zbiri, Mohamed; Johnson, Mark R.; Carter, Elizabeth; Kotlewski, Arek; Picken, S.; Mulder, Fokko M.; Kearley, Gordon J.


    Discotic liquid crystalline (DLC) charge transfer (CT) complexes combine visible light absorption and rapid charge transfer characteristics, being favorable properties for photovoltaic (PV) applications. We present a detailed study of the electronic and vibrational properties of the prototypic 1:1 mixture of discotic 2,3,6,7,10,11-hexakishexyloxytriphenylene (HAT6) and 2,4,7-trinitro-9-fluorenone (TNF). It is shown that intermolecular charge transfer occurs in the ground state of the complex: a charge delocalization of about 10-2 electron from the HAT6 core to TNF is deduced from both Raman and our previous NMR measurements [L. A. Haverkate, M. Zbiri, M. R. Johnson, B. Deme, H. J. M. de Groot, F. Lefeber, A. Kotlewski, S. J. Picken, F. M. Mulder, and G. J. Kearley, J. Phys. Chem. B 116, 13098 (2012)], implying the presence of permanent dipoles at the donor-acceptor interface. A combined analysis of density functional theory calculations, resonant Raman and UV-VIS absorption measurements indicate that fast relaxation occurs in the UV region due to intramolecular vibronic coupling of HAT6 quinoidal modes with lower lying electronic states. Relatively slower relaxation in the visible region the excited CT-band of the complex is also indicated, which likely involves motions of the TNF nitro groups. The fast quinoidal relaxation process in the hot UV band of HAT6 relates to pseudo-Jahn-Teller interactions in a single benzene unit, suggesting that the underlying vibronic coupling mechanism can be generic for polyaromatic hydrocarbons. Both the presence of ground state CT dipoles and relatively slow relaxation processes in the excited CT band can be relevant concerning the design of DLC based organic PV systems.

  18. Electronic and vibronic properties of a discotic liquid-crystal and its charge transfer complex

    Energy Technology Data Exchange (ETDEWEB)

    Haverkate, Lucas A.; Mulder, Fokko M. [Reactor Institute Delft, Faculty of Applied Sciences, Delft University of Technology, Mekelweg 15, 2629JB Delft (Netherlands); Zbiri, Mohamed, E-mail:; Johnson, Mark R. [Institut Laue Langevin, 38042 Grenoble Cedex 9 (France); Carter, Elizabeth [Vibrational Spectroscopy Facility, School of Chemistry, The University of Sydney, NSW 2008 (Australia); Kotlewski, Arek; Picken, S. [ChemE-NSM, Faculty of Chemistry, Delft University of Technology, 2628BL/136 Delft (Netherlands); Kearley, Gordon J. [Bragg Institute, Australian Nuclear Science and Technology Organisation, Menai, NSW 2234 (Australia)


    Discotic liquid crystalline (DLC) charge transfer (CT) complexes combine visible light absorption and rapid charge transfer characteristics, being favorable properties for photovoltaic (PV) applications. We present a detailed study of the electronic and vibrational properties of the prototypic 1:1 mixture of discotic 2,3,6,7,10,11-hexakishexyloxytriphenylene (HAT6) and 2,4,7-trinitro-9-fluorenone (TNF). It is shown that intermolecular charge transfer occurs in the ground state of the complex: a charge delocalization of about 10{sup −2} electron from the HAT6 core to TNF is deduced from both Raman and our previous NMR measurements [L. A. Haverkate, M. Zbiri, M. R. Johnson, B. Deme, H. J. M. de Groot, F. Lefeber, A. Kotlewski, S. J. Picken, F. M. Mulder, and G. J. Kearley, J. Phys. Chem. B 116, 13098 (2012)], implying the presence of permanent dipoles at the donor-acceptor interface. A combined analysis of density functional theory calculations, resonant Raman and UV-VIS absorption measurements indicate that fast relaxation occurs in the UV region due to intramolecular vibronic coupling of HAT6 quinoidal modes with lower lying electronic states. Relatively slower relaxation in the visible region the excited CT-band of the complex is also indicated, which likely involves motions of the TNF nitro groups. The fast quinoidal relaxation process in the hot UV band of HAT6 relates to pseudo-Jahn-Teller interactions in a single benzene unit, suggesting that the underlying vibronic coupling mechanism can be generic for polyaromatic hydrocarbons. Both the presence of ground state CT dipoles and relatively slow relaxation processes in the excited CT band can be relevant concerning the design of DLC based organic PV systems.

  19. Synthesis of Stable Interfaces on SnO2 Surfaces for Charge-Transfer Applications (United States)

    Benson, Michelle C.

    The commercial market for solar harvesting devices as an alternative energy source requires them to be both low-cost and efficient to replace or reduce the dependence on fossil fuel burning. Over the last few decades there has been promising efforts towards improving solar devices by using abundant and non-toxic metal oxide nanomaterials. One particular metal oxide of interest has been SnO2 due to its high electron mobility, wide-band gap, and aqueous stability. However SnO2 based solar cells have yet to reach efficiency values of other metal oxides, like TiO2. The advancement of SnO2 based devices is dependent on many factors, including improved methods of surface functionalization that can yield stable interfaces. This work explores the use of a versatile functionalization method through the use of the Cu(I)-catalyzed azide-alkyne cycloaddition (CuAAC) reaction. The CuAAC reaction is capable of producing electrochemically, photochemically, and electrocatalytically active surfaces on a variety of SnO2 materials. The resulting charge-transfer characteristics were investigated as well as an emphasis on understanding the stability of the resulting molecular linkage. We determined the CuAAC reaction is able to proceed through both azide-modified and alkyne-modified surfaces. The resulting charge-transfer properties showed that the molecular tether was capable of supporting charge separation at the interface. We also investigated the enhancement of electron injection upon the introduction of an ultra-thin ZrO2 coating on SnO2. Several complexes were used to fully understand the charge-transfer capabilities, including model systems of ferrocene and a ruthenium coordination complex, a ruthenium mononuclear water oxidation catalyst, and a commercial ruthenium based dye.

  20. Investigation of Improved Methods in Power Transfer Efficiency for Radiating Near-Field Wireless Power Transfer

    Directory of Open Access Journals (Sweden)

    Hesheng Cheng


    Full Text Available A metamaterial-inspired efficient electrically small antenna is proposed, firstly. And then several improving power transfer efficiency (PTE methods for wireless power transfer (WPT systems composed of the proposed antenna in the radiating near-field region are investigated. Method one is using a proposed antenna as a power retriever. This WPT system consisted of three proposed antennas: a transmitter, a receiver, and a retriever. The system is fed by only one power source. At a fixed distance from receiver to transmitter, the distance between the transmitter and the retriever is turned to maximize power transfer from the transmitter to the receiver. Method two is using two proposed antennas as transmitters and one antenna as receiver. The receiver is placed between the two transmitters. In this system, two power sources are used to feed the two transmitters, respectively. By adjusting the phase difference between the two feeding sources, the maximum PTE can be obtained at the optimal phase difference. Using the same configuration as method two, method three, where the maximum PTE can be increased by regulating the voltage (or power ratio of the two feeding sources, is proposed. In addition, we combine the proposed methods to construct another two schemes, which improve the PTE at different extent than classical WPT system.

  1. Bane of Hydrogen-Bond Formation on the Photoinduced Charge-Transfer Process in Donor–Acceptor Systems

    KAUST Repository

    Alsam, Amani Abdu


    Controlling the ultrafast dynamical process of photoinduced charge transfer at donor acceptor interfaces remains a major challenge for physical chemistry and solar cell communities. The process is complicated by the involvement of other complex dynamical processes, including hydrogen bond formation, energy transfer, and solvation dynamics occurring on similar time scales. In this study, we explore the remarkable impact of hydrogen-bond formation on the interfacial charge transfer between a negatively charged electron donating anionic porphyrin and a positively charged electron accepting pi-conjugated polymer, as a model system in solvents with different polarities and capabilities for hydiogen bonding using femtosecond transient absorption spectroscopy. Unlike the conventional understanding of the key role of hydrogen bonding in promoting the charge-transfer process, our steadystate and time-resolved results reveal that the intervening hydrogen-bonding environment and, consequently, the probable longer spacing between the donor and acceptor molecules significantly hinders the charge-transfer process between them. These results show that site-specific hydrogen bonding and geometric considerations between donor and acceptor can be exploited to control both the charge-transfer dynamics and its efficiency not only at donor acceptor interfaces but also in complex biological systems.

  2. Hamiltonian and Lagrangian dynamics of charged particles including the effects of radiation damping (United States)

    Qin, Hong; Burby, Joshua; Davidson, Ronald; Fisch, Nathaniel; Chung, Moses


    The effects of radiation damping (radiation reaction) on accelerating charged particles in modern high-intensity accelerators and high-intensity laser beams have becoming increasingly important. Especially for electron accelerators and storage rings, radiation damping is an effective mechanism and technique to achieve high beam luminosity. We develop Hamiltonian and Lagrangian descriptions of the classical dynamics of a charged particle including the effects of radiation damping in the general electromagnetic focusing channels encountered in accelerators. The direct connection between the classical Hamiltonian and Lagrangian theories and the more fundamental QED description of the synchrotron radiation process is also addressed. In addition to their theoretical importance, the classical Hamiltonian and Lagrangian theories of the radiation damping also enable us to numerically integrate the dynamics using advanced structure-preserving geometric algorithms. These theoretical developments can also be applied to runaway electrons and positrons generated during the disruption or startup of tokamak discharges. This research was supported by the U.S. Department of Energy (DE-AC02-09CH11466).

  3. Charge Versus Energy Transfer in Atomically Thin Graphene-Transition Metal Dichalcogenide van der Waals Heterostructures (United States)

    Froehlicher, Guillaume; Lorchat, Etienne; Berciaud, Stéphane


    Made from stacks of two-dimensional materials, van der Waals heterostructures exhibit unique light-matter interactions and are promising for novel optoelectronic devices. The performance of such devices is governed by near-field coupling through, e.g., interlayer charge and/or energy transfer. New concepts and experimental methodologies are needed to properly describe two-dimensional heterointerfaces. Here, we report an original study of interlayer charge and energy transfer in atomically thin metal-semiconductor [i.e., graphene-transition metal dichalcogenide (TMD, here molybdenum diselenide, MoSe2 )] heterostructures using a combination of microphotoluminescence and Raman scattering spectroscopies. The photoluminescence intensity in graphene /MoSe2 is quenched by more than 2 orders of magnitude and rises linearly with the incident photon flux, demonstrating a drastically shortened (about 1 ps) room-temperature MoSe2 exciton lifetime. Key complementary insights are provided from a comprehensive analysis of the graphene and MoSe2 Raman modes, which reveals net photoinduced electron transfer from MoSe2 to graphene and hole accumulation in MoSe2 . Remarkably, the steady-state Fermi energy of graphene saturates at 290 ±15 meV above the Dirac point. This reproducible behavior is observed both in ambient air and in vacuum and is discussed in terms of intrinsic factors (i.e., band offsets) and environmental effects. In this saturation regime, balanced photoinduced flows of electrons and holes may transfer to graphene, a mechanism that effectively leads to energy transfer. Using a broad range of incident photon fluxes and diverse environmental conditions, we find that the presence of net photoinduced charge transfer has no measurable impact on the near-unity photoluminescence quenching efficiency in graphene /MoSe2 . This absence of correlation strongly suggests that energy transfer to graphene (either in the form of electron exchange or dipole-dipole interaction) is the

  4. Charge Versus Energy Transfer in Atomically Thin Graphene-Transition Metal Dichalcogenide van der Waals Heterostructures

    Directory of Open Access Journals (Sweden)

    Guillaume Froehlicher


    Full Text Available Made from stacks of two-dimensional materials, van der Waals heterostructures exhibit unique light-matter interactions and are promising for novel optoelectronic devices. The performance of such devices is governed by near-field coupling through, e.g., interlayer charge and/or energy transfer. New concepts and experimental methodologies are needed to properly describe two-dimensional heterointerfaces. Here, we report an original study of interlayer charge and energy transfer in atomically thin metal-semiconductor [i.e., graphene-transition metal dichalcogenide (TMD, here molybdenum diselenide, MoSe_{2}] heterostructures using a combination of microphotoluminescence and Raman scattering spectroscopies. The photoluminescence intensity in graphene/MoSe_{2} is quenched by more than 2 orders of magnitude and rises linearly with the incident photon flux, demonstrating a drastically shortened (about 1 ps room-temperature MoSe_{2} exciton lifetime. Key complementary insights are provided from a comprehensive analysis of the graphene and MoSe_{2} Raman modes, which reveals net photoinduced electron transfer from MoSe_{2} to graphene and hole accumulation in MoSe_{2}. Remarkably, the steady-state Fermi energy of graphene saturates at 290±15  meV above the Dirac point. This reproducible behavior is observed both in ambient air and in vacuum and is discussed in terms of intrinsic factors (i.e., band offsets and environmental effects. In this saturation regime, balanced photoinduced flows of electrons and holes may transfer to graphene, a mechanism that effectively leads to energy transfer. Using a broad range of incident photon fluxes and diverse environmental conditions, we find that the presence of net photoinduced charge transfer has no measurable impact on the near-unity photoluminescence quenching efficiency in graphene/MoSe_{2}. This absence of correlation strongly suggests that energy transfer to graphene (either in the form of electron

  5. Assessing the influence of spectral band configuration on automated radiative transfer model inversion

    NARCIS (Netherlands)

    Dorigo, W.A.; Richter, R.; Schneider, T.; Schaepman, M.E.; Müller, A.; Wagner, W.


    The success of radiative transfer model (RTM) inversion strongly depends on various factors, including the choice of a suited radiative transfer model, the followed inversion strategy, and the band configuration of the remote sensing system. Current study aims at addressing the latter, by

  6. Modeling photosynthesis of discontinuous plant canopies by linking Geometric Optical Radiative Transfer model with biochemical processes


    Q. Xin; Gong, P.; W. Li


    Modeling vegetation photosynthesis is essential for understanding carbon exchanges between terrestrial ecosystems and the atmosphere. The radiative transfer process within plant canopies is one of the key drivers that regulate canopy photosynthesis. Most vegetation cover consists of discrete plant crowns, of which the physical observation departs from the underlying assumption of a homogenous and uniform medium in classic radiative transfer theory. Here we a...

  7. Incorporating boundary conditions in the integral form of the radiative transfer equation for transcranial imaging

    DEFF Research Database (Denmark)

    Jha, Abhinav K.; Zhu, Yansong; Kang, Jin U.


    An integral Neumann-series implementation of the Radiative Transfer Equation that accounts for boundary conditions is proposed to simulate photon transport through tissue for transcranial optical imaging.......An integral Neumann-series implementation of the Radiative Transfer Equation that accounts for boundary conditions is proposed to simulate photon transport through tissue for transcranial optical imaging....

  8. A scalable plant-resolving radiative transfer model based on optimized GPU ray tracing (United States)

    A new model for radiative transfer in participating media and its application to complex plant canopies is presented. The goal was to be able to efficiently solve complex canopy-scale radiative transfer problems while also representing sub-plant heterogeneity. In the model, individual leaf surfaces ...

  9. Numerical study of radiative heat transfer and effects of thermal boundary conditions on CLC fuel reactor (United States)

    Ben-Mansour, R.; Li, H.; Habib, M. A.; Hossain, M. M.


    Global warming has become a worldwide concern due to its severe impacts and consequences on the climate system and ecosystem. As a promising technology proving good carbon capture ability with low-efficiency penalty, Chemical Looping Combustion technology has risen much interest. However, the radiative heat transfer was hardly studied, nor its effects were clearly declared. The present work provides a mathematical model for radiative heat transfer within fuel reactor of chemical looping combustion systems and conducts a numerical research on the effects of boundary conditions, solid particles reflectivity, particles size, and the operating temperature. The results indicate that radiative heat transfer has very limited impacts on the flow pattern. Meanwhile, the temperature variations in the static bed region (where solid particles are dense) brought by radiation are also insignificant. However, the effects of radiation on temperature profiles within free bed region (where solid particles are very sparse) are obvious, especially when convective-radiative (mixed) boundary condition is applied on fuel reactor walls. Smaller oxygen carrier particle size results in larger absorption & scattering coefficients. The consideration of radiative heat transfer within fuel reactor increases the temperature gradient within free bed region. On the other hand, the conversion performance of fuel is nearly not affected by radiation heat transfer within fuel reactor. However, the consideration of radiative heat transfer enhances the heat transfer between the gas phase and solid phase, especially when the operating temperature is low.

  10. Numerical study of radiative heat transfer and effects of thermal boundary conditions on CLC fuel reactor (United States)

    Ben-Mansour, R.; Li, H.; Habib, M. A.; Hossain, M. M.


    Global warming has become a worldwide concern due to its severe impacts and consequences on the climate system and ecosystem. As a promising technology proving good carbon capture ability with low-efficiency penalty, Chemical Looping Combustion technology has risen much interest. However, the radiative heat transfer was hardly studied, nor its effects were clearly declared. The present work provides a mathematical model for radiative heat transfer within fuel reactor of chemical looping combustion systems and conducts a numerical research on the effects of boundary conditions, solid particles reflectivity, particles size, and the operating temperature. The results indicate that radiative heat transfer has very limited impacts on the flow pattern. Meanwhile, the temperature variations in the static bed region (where solid particles are dense) brought by radiation are also insignificant. However, the effects of radiation on temperature profiles within free bed region (where solid particles are very sparse) are obvious, especially when convective-radiative (mixed) boundary condition is applied on fuel reactor walls. Smaller oxygen carrier particle size results in larger absorption & scattering coefficients. The consideration of radiative heat transfer within fuel reactor increases the temperature gradient within free bed region. On the other hand, the conversion performance of fuel is nearly not affected by radiation heat transfer within fuel reactor. However, the consideration of radiative heat transfer enhances the heat transfer between the gas phase and solid phase, especially when the operating temperature is low.

  11. An Electronic Structure Approach to Charge Transfer and Transport in Molecular Building Blocks for Organic Optoelectronics (United States)

    Hendrickson, Heidi Phillips

    A fundamental understanding of charge separation in organic materials is necessary for the rational design of optoelectronic devices suited for renewable energy applications and requires a combination of theoretical, computational, and experimental methods. Density functional theory (DFT) and time-dependent (TD)DFT are cost effective ab-initio approaches for calculating fundamental properties of large molecular systems, however conventional DFT methods have been known to fail in accurately characterizing frontier orbital gaps and charge transfer states in molecular systems. In this dissertation, these shortcomings are addressed by implementing an optimally-tuned range-separated hybrid (OT-RSH) functional approach within DFT and TDDFT. The first part of this thesis presents the way in which RSH-DFT addresses the shortcomings in conventional DFT. Environmentally-corrected RSH-DFT frontier orbital energies are shown to correspond to thin film measurements for a set of organic semiconducting molecules. Likewise, the improved RSH-TDDFT description of charge transfer excitations is benchmarked using a model ethene dimer and silsesquioxane molecules. In the second part of this thesis, RSH-DFT is applied to chromophore-functionalized silsesquioxanes, which are currently investigated as candidates for building blocks in optoelectronic applications. RSH-DFT provides insight into the nature of absorptive and emissive states in silsesquioxanes. While absorption primarily involves transitions localized on one chromophore, charge transfer between chromophores and between chromophore and silsesquioxane cage have been identified. The RSH-DFT approach, including a protocol accounting for complex environmental effects on charge transfer energies, was tested and validated against experimental measurements. The third part of this thesis addresses quantum transport through nano-scale junctions. The ability to quantify a molecular junction via spectroscopic methods is crucial to their

  12. Phonon-Assisted Ultrafast Charge Transfer at van der Waals Heterostructure Interface. (United States)

    Zheng, Qijing; Saidi, Wissam A; Xie, Yu; Lan, Zhenggang; Prezhdo, Oleg V; Petek, Hrvoje; Zhao, Jin


    The van der Waals (vdW) interfaces of two-dimensional (2D) semiconductor are central to new device concepts and emerging technologies in light-electricity transduction where the efficient charge separation is a key factor. Contrary to general expectation, efficient electron-hole separation can occur in vertically stacked transition-metal dichalcogenide heterostructure bilayers through ultrafast charge transfer between the neighboring layers despite their weak vdW bonding. In this report, we show by ab initio nonadiabatic molecular dynamics calculations, that instead of direct tunneling, the ultrafast interlayer hole transfer is strongly promoted by an adiabatic mechanism through phonon excitation occurring on 20 fs, which is in good agreement with the experiment. The atomic level picture of the phonon-assisted ultrafast mechanism revealed in our study is valuable both for the fundamental understanding of ultrafast charge carrier dynamics at vdW heterointerfaces as well as for the design of novel quasi-2D devices for optoelectronic and photovoltaic applications.

  13. Coil Design for High Misalignment Tolerant Inductive Power Transfer System for EV Charging

    Directory of Open Access Journals (Sweden)

    Kafeel Ahmed Kalwar


    Full Text Available The inductive power transfer (IPT system for electric vehicle (EV charging has acquired more research interest in its different facets. However, the misalignment tolerance between the charging coil (installed in the ground and pick-up coil (mounted on the car chassis, has been a challenge and fundamental interest in the future market of EVs. This paper proposes a new coil design QDQ (Quad D Quadrature that maintains the high coupling coefficient and efficient power transfer during reasonable misalignment. The QDQ design makes the use of four adjacent circular coils and one square coil, for both charging and pick-up side, to capture the maximum flux at any position. The coil design has been modeled in JMAG software for calculation of inductive parameters using the finite element method (FEM, and its hardware has been tested experimentally at various misaligned positions. The QDQ coils are shown to be capable of achieving good coupling coefficient and high efficiency of the system until the misalignment displacement reaches 50% of the employed coil size.

  14. Single-crystal charge transfer interfaces for efficient photonic devices (Conference Presentation) (United States)

    Alves, Helena; Pinto, Rui M.; Maçôas, Ermelinda M. S.; Baleizão, Carlos; Santos, Isabel C.


    Organic semiconductors have unique optical, mechanical and electronic properties that can be combined with customized chemical functionality. In the crystalline form, determinant features for electronic applications such as molecular purity, the charge mobility or the exciton diffusion length, reveal a superior performance when compared with materials in a more disordered form. Combining crystals of two different conjugated materials as even enable a new 2D electronic system. However, the use of organic single crystals in devices is still limited to a few applications, such as field-effect transistors. In 2013, we presented the first system composed of single-crystal charge transfer interfaces presenting photoconductivity behaviour. The system composed of rubrene and TCNQ has a responsivity reaching 1 A/W, corresponding to an external quantum efficiency of nearly 100%. A similar approach, with a hybrid structure of a PCBM film and rubrene single crystal also presents high responsivity and the possibility to extract excitons generated in acceptor materials. This strategy led to an extended action towards the near IR. By adequate material design and structural organisation of perylediimides, we demonstrate that is possible to improve exciton diffusion efficiency. More recently, we have successfully used the concept of charge transfer interfaces in phototransistors. These results open the possibility of using organic single-crystal interfaces in photonic applications.

  15. Transport, charge exchange and loss of energetic heavy ions in the earth's radiation belts - Applicability and limitations of theory (United States)

    Spjeldvik, W. N.


    Computer simulations of processes which control the relative abundances of ions in the trapping regions of geospace are compared with observations from discriminating ion detectors. Energy losses due to Coulomb collisions between ions and exospheric neutrals are considered, along with charge exchange losses and internal charge exchanges. The time evolution of energetic ion fluxes of equatorially mirroring ions under radial diffusion is modelled to include geomagnetic and geoelectric fluctutations. Limits to the validity of diffusion transport theory are discussed, and the simulation is noted to contain provisions for six ionic charge states and the source effect on the radiation belt oxygen ion distributions. Comparisons are made with ion flux data gathered on Explorer 45 and ISEE-1 spacecraft and results indicate that internal charge exchanges cause the radiation belt ion charge state to be independent of source charge rate characteristics, and relative charge state distribution is independent of the radially diffusive transport rate below the charge state redistribution zone.

  16. Single Molecule Spectroelectrochemistry of Interfacial Charge Transfer Dynamics In Hybrid Organic Solar Cell

    Energy Technology Data Exchange (ETDEWEB)

    Pan, Shanlin [Univ. of Alabama, Tuscaloosa, AL (United States)


    Our research under support of this DOE grant is focused on applied and fundamental aspects of model organic solar cell systems. Major accomplishments are: 1) we developed a spectroelectorchemistry technique of single molecule single nanoparticle method to study charge transfer between conjugated polymers and semiconductor at the single molecule level. The fluorescence of individual fluorescent polymers at semiconductor surfaces was shown to exhibit blinking behavior compared to molecules on glass substrates. Single molecule fluorescence excitation anisotropy measurements showed the conformation of the polymer molecules did not differ appreciably between glass and semiconductor substrates. The similarities in molecular conformation suggest that the observed differences in blinking activity are due to charge transfer between fluorescent polymer and semiconductor, which provides additional pathways between states of high and low fluorescence quantum efficiency. Similar spectroelectrochemistry work has been done for small organic dyes for understand their charge transfer dynamics on various substrates and electrochemical environments; 2) We developed a method of transferring semiconductor nanoparticles (NPs) and graphene oxide (GO) nanosheets into organic solvent for a potential electron acceptor in bulk heterojunction organic solar cells which employed polymer semiconductor as the electron donor. Electron transfer from the polymer semiconductor to semiconductor and GO in solutions and thin films was established through fluorescence spectroscopy and electroluminescence measurements. Solar cells containing these materials were constructed and evaluated using transient absorption spectroscopy and dynamic fluorescence techniques to understand the charge carrier generation and recombination events; 3) We invented a spectroelectorchemistry technique using light scattering and electroluminescence for rapid size determination and studying electrochemistry of single NPs in an

  17. Classification and radiative-transfer modeling of meteorite spectra (United States)

    Pentikäinen, H.; Penttilä, A.; Peltoniemi, J.; Muinonen, K.


    The interpretation of asteroid spectra is closely tied to surface structure and composition. Asteroid surfaces are usually assumed to be covered with a regolith, which is a mixture of mineral grains ranging from micrometers to centimeters in size. The inverse problem of deducing the characteristics of the grains from the scattering of light (e.g., using photometric and polarimetric observations) is difficult. Meteorite spectroscopy can be a valuable alternative source of information considering that unweathered meteoritic ''falls'' are almost pristine samples of their parent bodies. Reflectance spectra of 18 different meteorite samples were measured with the Finnish Geodetic Institute Field Goniospectrometer (FIGIFIGO) covering a wavelength range of 450--2250 nm [1,2]. The measurements expand the database of reflectance spectra obtained by Paton et al. [3] and Gaffey [4]. Principal Component Analysis (PCA) performed on the spectra indicates a separation of the undifferentiated ordinary chondrites and the differentiated achondrites. The principal components also suggest a discrimination between the spectra of ordinary chondrites with petrologic grades 5 and 6. The distinction is not present when the data are supplemented with the spectra from the two other data sets obtained with differing measuring techniques. To further investigate the different classifications, the PCA is implemented with selected spectral features contrary to the previous analyses, which encompassed the complete spectra. Single-scattering albedos for meteoritic fundamental scatterers were derived with a Monte Carlo radiative-transfer model [1]. In the derivation, realistic scattering phase functions were utilized. The functions were obtained by fitting triple Henyey-Greenstein functions to the measured scattering phase functions of olivine powder for two different size distributions [5,6]. The simulated reflectances for different scattering phase functions were matched to the measured meteorite

  18. Lessons Learned from Radiative Transfer Simulations of the Venus Atmosphere (United States)

    Arney, G.; Meadows, V. S.; Lincowski, A.


    The Venus atmosphere is extremely complex, and because of this the spectrum of Earths sister planet is likewise intricate and a challenge to model accurately. However, accurate modeling of Venus spectrum opens up multiple opportunities to better understand the planet next door, and even for understanding Venus-like planets beyond our solar system. Near-infrared (1-2.5 um, NIR) spectral windows observable on the Venus nigthside present the opportunity to probe beneath the Venusian cloud deck and measure thermal emission from the surface and lower atmosphere remotely from Earth or from orbit. These nigthside spectral windows were discovered by Allen and Crawford (1984) and have since been used measure trace gas abundances in the Venus lower atmosphere (less than 45 km), map surface emissivity varisions, and measure properties of the lower cloud deck. These windows sample radiation from below the cloud base at roughly 45 km, and pressures in this region range from roughly Earthlike (approx. 1 bar) up to 90 bars at the surface. Temperatures in this region are high: they range from about 400 K at the base of the cloud deck up to about 740 K at the surface. This high temperature and pressure presents several challenges to modelers attempting radiative transfer simulations of this region of the atmosphere, which we will review. Venus is also important to spectrally model to predict the remote observables of Venus-like exoplanets in anticipation of data from future observatories. Venus-like planets are likely one of the most common types of terrestrial planets and so simulations of them are valuable for planning observatory and detector properties of future telescopes being designed, as well as predicting the types of observations required to characterize them.

  19. Magnetic Field Generation through Angular Momentum Exchange between Circularly Polarized Radiation and Charged Particles

    Energy Technology Data Exchange (ETDEWEB)

    G. Shvets; N.J. Fisch; J.-M. Rax


    The interaction between circularly polarized (CP) radiation and charged particles can lead to generation of magnetic field through an inverse Faraday effect. The spin of the circularly polarized electromagnetic wave can be converted into the angular momentum of the charged particles so long as there is dissipation. We demonstrate this by considering two mechanisms of angular momentum absorption relevant for laser-plasma interactions: electron-ion collisions and ionization. The precise dissipative mechanism, however, plays a role in determining the efficiency of the magnetic field generation.

  20. Modeling of radiation-induced charge trapping in MOS devices under ionizing irradiation

    Energy Technology Data Exchange (ETDEWEB)

    Petukhov, M. A., E-mail:; Ryazanov, A. I. [National Research Center Kurchatov Institute (Russian Federation)


    The numerical model of the radiation-induced charge trapping process in the oxide layer of a MOS device under ionizing irradiation is developed; the model includes carrier transport, hole capture by traps in different states, recombination of free electrons and trapped holes, kinetics of hydrogen ions which can be accumulated in the material during transistor manufacture, and accumulation and charging of interface states. Modeling of n-channel MOSFET behavior under 1 MeV photon irradiation is performed. The obtained dose dependences of the threshold voltage shift and its contributions from trapped holes and interface states are in good agreement with experimental data.

  1. Comparison of the Impact of Zinc Vacancies on Charge Separation and Charge Transfer at ZnO/Sexithienyl and ZnO/Fullerene Interfaces

    Energy Technology Data Exchange (ETDEWEB)

    Li, Hong [School of Chemistry and Biochemistry and Center for Organic Photonics and Electronics, Georgia Institute of Technology, Atlanta GA 30332-0400 USA; Bredas, Jean-Luc [Solar and Photovoltaics Engineering Research Center, Physical Science and Engineering Division, King Abdullah University of Science and Technology-KAUST, Thuwal 23955-6900 Kingdom of Saudi Arabia


    The impact of surface zinc vacancies on charge transfer and charge separation at donor/ZnO and acceptor/ZnO interfaces is identified via density functional theory calculations. The results show their effect to be related to the stronger internal electric field present near these vacancies. Thus, such surface defects can have a significant negative impact on the performance of hybrid solar cells using ZnO as electron acceptors.

  2. Lead methylammonium triiodide perovskite-based solar cells: an interfacial charge-transfer investigation. (United States)

    Xu, Xiaobao; Zhang, Hua; Cao, Kun; Cui, Jin; Lu, Jianfeng; Zeng, Xianwei; Shen, Yan; Wang, Mingkui


    This work reports on an investigation into interfacial charge transfer in CH3NH3PbI3 perovskite solar cells by using anatase TiO2 nanocuboids enclosed by active {100} and {001} facets. The devices show 6.0 and 8.0% power conversion efficiency with and without hole-transport material. Transient photovoltage/photocurrent decay and charge extraction, as well as impedance spectroscopy measurements, reveal that carbon materials are effective counter electrodes in perovskite solar cells. The photogenerated charges are observed to be stored in mesoporous TiO2 film under illumination and in the CH3NH3PbI3 layer in the dark. The use of 2,2',7,7'-tetrakis(N,N-di-p-methoxyphenylamine)-9,9-spirobifluorene (spiro-MeOTAD) as a hole-transport material accelerates interfacial charge recombination between the photogenerated electrons and holes. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. Charge Transfer at Hybrid Interfaces: Plasmonics of Aromatic Thiol-Capped Gold Nanoparticles. (United States)

    Goldmann, Claire; Lazzari, Rémi; Paquez, Xavier; Boissière, Cédric; Ribot, François; Sanchez, Clément; Chanéac, Corinne; Portehault, David


    Although gold nanoparticles stabilized by organic thiols are the building blocks in a wide range of applications, the role of the ligands on the plasmon resonance of the metal core has been mostly ignored until now. Herein, a methodology based on the combination of spectroscopic ellipsometry and UV-vis spectroscopy is applied to extract dielectric functions of the different components. It is shown that aromatic thiols allow a significant charge transfer at the hybrid interface with the s and d bands of the gold core that yields "giant" red shifts of the plasmon band, up to 40 nm for spherical particles in the size range of 3-5 nm. These results suggest that hybrid nanoplasmonic devices may be designed through the suitable choice of metal core and organic components for optimized charge exchange.

  4. Three-dimensional effects in resonant charge transfer between atomic particles and nanosystems (United States)

    Gainullin, I. K.; Sonkin, M. A.


    Resonant charge transfer (RCT) between negative ions and a metallic nanosystem was investigated by means of a high-performance ab initio three-dimensional (3D) numerical solver. During RCT, an electron was shown to occupy succesively nanosystem eigenstates along the z , ρ , and φ coordinates. Electron tunneling into a nanosystem is a reversible process, because after some time the electron propagates back to the ion. RCT efficiency in a nanosystem was found to exhibit quantum-size effects as well as lateral ion position dependence. This means that during ion-surface interaction, the nanosystem's size and the ion trajectory strongly influence the final charge state of the ion. In the case of real 3D systems (without cylindrical symmetry), the electron density currents form quantum vortices; this result is rather nontrivial for static systems. In addition, the limits of the adiabatic approximation (rate equation) for the RCT calculation with nanosystems are defined.


    NARCIS (Netherlands)

    Recent collision experiments are reviewed in which one-electron transfer between laser excited target atoms and (highly charged) keV-ions has been studied. Especially results showing a dependence of the charge exchange on the initial target orbital alignment are discussed. The question to what

  6. Radiative heat transfer in turbulent combustion systems theory and applications

    CERN Document Server

    Modest, Michael F


    This introduction reviews why combustion and radiation are important, as well as the technical challenges posed by radiation. Emphasis is on interactions among turbulence, chemistry and radiation (turbulence-chemistry-radiation interactions – TCRI) in Reynolds-averaged and large-eddy simulations. Subsequent chapters cover: chemically reacting turbulent flows; radiation properties, Reynolds transport equation (RTE) solution methods, and TCRI; radiation effects in laminar flames; TCRI in turbulent flames; and high-pressure combustion systems. This Brief presents integrated approach that includes radiation at the outset, rather than as an afterthought. It stands as the most recent developments in physical modeling, numerical algorithms, and applications collected in one monograph.

  7. Thermal radiation heat transfer in participating media by finite volume discretization using collimated beam incidence (United States)

    Harijishnu, R.; Jayakumar, J. S.


    The main objective of this paper is to study the heat transfer rate of thermal radiation in participating media. For that, a generated collimated beam has been passed through a two dimensional slab model of flint glass with a refractive index 2. Both Polar and azimuthal angle have been varied to generate such a beam. The Temperature of the slab and Snells law has been validated by Radiation Transfer Equation (RTE) in OpenFOAM (Open Field Operation and Manipulation), a CFD software which is the major computational tool used in Industry and research applications where the source code is modified in which radiation heat transfer equation is added to the case and different radiation heat transfer models are utilized. This work concentrates on the numerical strategies involving both transparent and participating media. Since Radiation Transfer Equation (RTE) is difficult to solve, the purpose of this paper is to use existing solver buoyantSimlpeFoam to solve radiation model in the participating media by compiling the source code to obtain the heat transfer rate inside the slab by varying the Intensity of radiation. The Finite Volume Method (FVM) is applied to solve the Radiation Transfer Equation (RTE) governing the above said physical phenomena.

  8. Remote sensing data assimilation using coupled radiative transfer models (United States)

    Verhoef, Wout; Bach, Heike

    This paper discusses data assimilation of biophysical parameters retrieved from optical remote sensing images in land surface process models by means of image simulation and model inversion. Two different approaches are presented. The first is based on model inversion of atmospherically corrected Landsat TM surface reflectance images and assimilation of the retrieved parameters in a crop growth model. In the second approach top-of-atmosphere (TOA) hyperspectral radiance images have been simulated for the future ESA mission SPECTRA. In this case only the simulation of the images has been executed in order to demonstrate the feasibility of this task with existing software running on a PC. The radiative transfer models that have been used are PROSPECT (leaf level), GeoSAIL (canopy level) and MODTRAN4 (atmosphere). Coupling of this chain of models to land use information of the area can be used to generate TOA radiance images. Comparison of simulated images with actual remote sensing data can be applied to retrieve biophysical parameters and in turn these can be employed to update process models of crop growth.

  9. Inversion of the radiative transfer equation for polarized light

    Directory of Open Access Journals (Sweden)

    Jose Carlos del Toro Iniesta


    Full Text Available Abstract Since the early 1970s, inversion techniques have become the most useful tool for inferring the magnetic, dynamic, and thermodynamic properties of the solar atmosphere. Inversions have been proposed in the literature with a sequential increase in model complexity: astrophysical inferences depend not only on measurements but also on the physics assumed to prevail both on the formation of the spectral line Stokes profiles and on their detection with the instrument. Such an intrinsic model dependence makes it necessary to formulate specific means that include the physics in a properly quantitative way. The core of this physics lies in the radiative transfer equation (RTE, where the properties of the atmosphere are assumed to be known while the unknowns are the four Stokes profiles. The solution of the (differential RTE is known as the direct or forward problem. From an observational point of view, the problem is rather the opposite: the data are made up of the observed Stokes profiles and the unknowns are the solar physical quantities. Inverting the RTE is therefore mandatory. Indeed, the formal solution of this equation can be considered an integral equation. The solution of such an integral equation is called the inverse problem. Inversion techniques are automated codes aimed at solving the inverse problem. The foundations of inversion techniques are critically revisited with an emphasis on making explicit the many assumptions underlying each of them.

  10. Double-delta-function adjustment in thermal radiative transfer (United States)

    Wu, Kun; Zhang, Feng; Iwabuchi, Hironobu; Shi, Yi-Ning; Duan, Mingkeng


    For atmospheric scattering, the weak backward scattering peak is always ignored, in contrast with the strong forward scattering peak. In this paper, the backward peak contribution is incorporated in multiple scattering, along with the forward peak contribution. Thus, a new parameterization, the double- δ -function adjustment, is proposed and its application in a two-stream approximation for infrared radiative transfer is shown. The accuracy of the adding method for the double- δ -two-stream discrete-ordinates approximation (2 δ -2DDA) is evaluated by the emissivities in a single layer of atmosphere and the fluxes and heating rate in a multi-layer atmosphere with a realistic atmospheric profile. The results show that 2 δ -2DDA produces less bias than the δ -two-stream approximation (δ -2DDA) for thick optical depths, such as water cloud conditions. For thin optical depths, such as ice cloud, δ -2DDA and 2 δ -2DDA produce similar errors. Generally, 2 δ -2DDA is more accurate than δ -2DDA, and it can be easily applied in climate models.

  11. Algorithmic vs. finite difference Jacobians for infrared atmospheric radiative transfer (United States)

    Schreier, Franz; Gimeno García, Sebastián; Vasquez, Mayte; Xu, Jian


    Jacobians, i.e. partial derivatives of the radiance and transmission spectrum with respect to the atmospheric state parameters to be retrieved from remote sensing observations, are important for the iterative solution of the nonlinear inverse problem. Finite difference Jacobians are easy to implement, but computationally expensive and possibly of dubious quality; on the other hand, analytical Jacobians are accurate and efficient, but the implementation can be quite demanding. GARLIC, our "Generic Atmospheric Radiation Line-by-line Infrared Code", utilizes algorithmic differentiation (AD) techniques to implement derivatives w.r.t. atmospheric temperature and molecular concentrations. In this paper, we describe our approach for differentiation of the high resolution infrared and microwave spectra and provide an in-depth assessment of finite difference approximations using "exact" AD Jacobians as a reference. The results indicate that the "standard" two-point finite differences with 1 K and 1% perturbation for temperature and volume mixing ratio, respectively, can exhibit substantial errors, and central differences are significantly better. However, these deviations do not transfer into the truncated singular value decomposition solution of a least squares problem. Nevertheless, AD Jacobians are clearly recommended because of the superior speed and accuracy.

  12. Test plan for validation of the radiative transfer equation.

    Energy Technology Data Exchange (ETDEWEB)

    Ricks, Allen Joseph; Grasser, Thomas W.; Kearney, Sean Patrick; Jernigan, Dann A.; Blanchat, Thomas K.


    As the capabilities of numerical simulations increase, decision makers are increasingly relying upon simulations rather than experiments to assess risks across a wide variety of accident scenarios including fires. There are still, however, many aspects of fires that are either not well understood or are difficult to treat from first principles due to the computational expense. For a simulation to be truly predictive and to provide decision makers with information which can be reliably used for risk assessment the remaining physical processes must be studied and suitable models developed for the effects of the physics. A set of experiments are outlined in this report which will provide soot volume fraction/temperature data and heat flux (intensity) data for the validation of models for the radiative transfer equation. In addition, a complete set of boundary condition measurements will be taken to allow full fire predictions for validation of the entire fire model. The experiments will be performed with a lightly-sooting liquid hydrocarbon fuel fire in the fully turbulent scale range (2 m diameter).

  13. Enabling Radiative Transfer on AMR grids in CRASH (United States)

    Hariharan, N.; Graziani, L.; Ciardi, B.; Miniati, F.; Bungartz, H.-J.


    We introduce crash-amr, a new version of the cosmological radiative transfer (RT) code crash, enabled to use refined grids. This new feature allows us to attain higher resolution in our RT simulations and thus to describe more accurately ionization and temperature patterns in high-density regions. We have tested crash-amr by simulating the evolution of an ionized region produced by a single source embedded in gas at constant density, as well as by a more realistic configuration of multiple sources in an inhomogeneous density field. While we find an excellent agreement with the previous version of crash when the adaptive mesh refinement (AMR) feature is disabled, showing that no numerical artefact has been introduced in crash-amr, when additional refinement levels are used the code can simulate more accurately the physics of ionized gas in high-density regions. This result has been attained at no computational loss, as RT simulations on AMR grids with maximum resolution equivalent to that of a uniform Cartesian grid can be run with a gain of up to 60 per cent in computational time.

  14. Analytical solutions in rotating linear dilaton black holes: Hawking radiation of charged massive scalar particles

    CERN Document Server

    Sakalli, I


    Hawking radiation of charged massive spin-0 particles are studied in the gravitational, electromagnetic, dilaton, and axion fields of rotating linear dilaton black holes. In this geometry, we separate the covariant Klein--Gordon equation into radial and angular parts and obtain the exact solutions of both the equations in terms of the confluent Heun functions. Using the radial solution, we analyze the behavior of the wave solutions near the event horizon of the rotating linear dilaton black hole and derive its Hawking radiation spectrum via the Damour--Ruffini--Sannan method.

  15. Energy and charge distribution of energetic helium ions in the outer radiation belt of the earth (United States)

    Klecker, B.; Hovestadt, D.; Scholer, M.; Gloeckler, G.; Ipavich, F. M.; Fan, C. Y.


    The first direct measurement of the charge states of helium at energies greater than 0.5 MeV/nucleon in the outer radiation belt, obtained aboard the ISEE-1 spacecraft in 1977, is reported. High abundances of singly ionized helium, with He(+)/He(2+) = 0.4 + or - 0.1 at L = 3.3 was found during one perigee pass, with a sudden decrease of that ratio by a factor of about 10 between L = 3.3 and 3.7. It is shown that nonstationary and/or nonadiabatic processes may play an important role for the distribution of helium ions in the outer radiation belt.

  16. Classical radiation by free-falling charges in de Sitter spacetime

    CERN Document Server

    Akhmedov, E T; Sadofyev, A


    We study the classical radiation emitted by free-falling charges in de Sitter spacetime coupled to different kinds of fields. Specifically we consider the cases of the electromagnetic field, linearized gravity and scalar fields with arbitrary mass and curvature coupling. Given an arbitrary set of such charges, there is a generic result for sufficiently late times which corresponds to each charge being surrounded by a field zone with negligible influence from the other charges. Furthermore, we explicitly find a static solution in the static patch adapted to a charge (implying no energy loss by the charge) which can be regularly extended beyond the horizon to the full de Sitter spacetime, and show that any other solution decays at late times to this one. On the other hand, for non-conformal scalar fields the inertial observers naturally associated with spatially flat coordinates will see a non-vanishing flux far from the horizon, which will fall off more slowly than the inverse square of the distance for suffic...

  17. Laser-induced charge transfer in the HeH/sup 2 +/ quasimolecule

    Energy Technology Data Exchange (ETDEWEB)

    Errea, L.F.; Mendez, L.; Riera, A.


    In a recent publication, the charge transfer cross section for He/sup 2 +/+H(ls) collisions through photon-assisted 2psigma--3dsigma transitions was calculated; this calculation, however, contained several errors whose quantitative--even qualitative effect on the results is not obvious. We present a correct evaluation of this laser-induced cross section, which turns out to be larger, and present a maximum for longer wavelengths, than the values previously reported. In addition, we have checked the applicability of perturbation theory, of the stationary phase, uniform and Landau--Zener approximations, and the importance of potentially competitive photon-assisted reactions.

  18. Molecular distortion and charge transfer effects in ZnPc/Cu(111)

    KAUST Repository

    Amin, B.


    The adsorption geometry and electronic properties of a zinc-phthalocyanine molecule on a Cu(111) substrate are studied by density functional theory. In agreement with experiment, we find remarkable distortions of the molecule, mainly as the central Zn atom tends towards the substrate to minimize the Zn-Cu distance. As a consequence, the Zn-N chemical bonding and energy levels of the molecule are significantly modified. However, charge transfer induces metallic states on the molecule and therefore is more important for the ZnPc/Cu(111) system than the structural distortions.

  19. Surface characterization and surface electronic structure of organic quasi-one-dimensional charge transfer salts

    DEFF Research Database (Denmark)

    Sing, M.; Schwingenschlögl, U.; Claessen, R.


    We have thoroughly characterized the surfaces of the organic charge-transfer salts TTF-TCNQ and (TMTSF)(2)PF6 which are generally acknowledged as prototypical examples of one-dimensional conductors. In particular x-ray-induced photoemission spectroscopy turns out to be a valuable nondestructive...... diagnostic tool. We show that the observation of generic one-dimensional signatures in photoemission spectra of the valence band close to the Fermi level can be strongly affected by surface effects. Especially, great care must be exercised taking evidence for an unusual one-dimensional many-body state...

  20. Surface charges and J H Poynting’s disquisitions on energy transfer in electrical circuits (United States)

    Matar, M.; Welti, R.


    In this paper we review applications given by J H Poynting (1884) on the transfer of electromagnetic energy in DC circuits. These examples were strongly criticized by O Heaviside (1887). Heaviside stated that Poynting had a misconception about the nature of the electric field in the vicinity of a wire through which a current flows. The historical review of this conflict and its resolution based on the consideration of electrical charges on the surface of the wires can be useful for student courses on electromagnetism or circuit theory.

  1. Mechanism of the Primary Charge Transfer Reaction in the Cytochrome bc1 Complex

    DEFF Research Database (Denmark)

    Barragan, Angela M; Schulten, Klaus; Solov'yov, Ilia A


    The bc1 complex is a critical enzyme for the ATP production in photosynthesis and cellular respiration. Its biochemical function relies on the so-called Q-cycle, which is well established and operates via quinol substrates that bind inside the protein complex. Despite decades of research, the qui...... the conclusion. Finally, key structural elements of the bc1 complex that trigger the charge transfer reactions were established, manifesting the importance of the environment in the process, which is furthermore evidenced by free energy calculations....

  2. Coloration of tyrosine by organic-semiconductor interfacial charge-transfer transitions (United States)

    Fujisawa, Jun-ichi; Kikuchi, Natsumi; Hanaya, Minoru


    L-tyrosine (Tyr) plays a crucial role as a proteinogenic amino acid and also as a precursor to several neurotransmitters and hormones. Here we demonstrate coloration of Tyr based on organic-semiconductor interfacial charge-transfer (ICT) transitions. The ICT transitions from Tyr to TiO2 are induced by the chemisorption of Tyr on TiO2 surfaces via the hydroxy group of the phenol moiety. Because other amino acids possess no chemical group to induce ICT transitions, this coloration method enables to detect Tyr selectively without drastic structural change in contrast to the conventional coloration methods.

  3. Electronic, structural and chemical effects of charge-transfer at organic/inorganic interfaces (United States)

    Otero, R.; Vázquez de Parga, A. L.; Gallego, J. M.


    During the last decade, interest on the growth and self-assembly of organic molecular species on solid surfaces spread over the scientific community, largely motivated by the promise of cheap, flexible and tunable organic electronic and optoelectronic devices. These efforts lead to important advances in our understanding of the nature and strength of the non-bonding intermolecular interactions that control the assembly of the organic building blocks on solid surfaces, which have been recently reviewed in a number of excellent papers. To a large extent, such studies were possible because of a smart choice of model substrate-adsorbate systems where the molecule-substrate interactions were purposefully kept low, so that most of the observed supramolecular structures could be understood simply by considering intermolecular interactions, keeping the role of the surface always relatively small (although not completely negligible). On the other hand, the systems which are more relevant for the development of organic electronic devices include molecular species which are electron donors, acceptors or blends of donors and acceptors. Adsorption of such organic species on solid surfaces is bound to be accompanied by charge-transfer processes between the substrate and the adsorbates, and the physical and chemical properties of the molecules cannot be expected any longer to be the same as in solution phase. In recent years, a number of groups around the world have started tackling the problem of the adsorption, self- assembly and electronic and chemical properties of organic species which interact rather strongly with the surface, and for which charge-transfer must be considered. The picture that is emerging shows that charge transfer can lead to a plethora of new phenomena, from the development of delocalized band-like electron states at molecular overlayers, to the existence of new substrate-mediated intermolecular interactions or the strong modification of the chemical

  4. Charge transfer in energetic Li2+-H and He+-He+ collisions (United States)

    Mančev, I.


    The total cross sections for charge transfer in Li2+-H and He+-He+ collisions have been calculated, using the four body first Born approximation with correct boundary conditions (CB1-4B) and four body continuum distorted wave method (CDW-4B) in the energy range 10-5000 keV/amu. The role of dynamic electron correlations is examined as a function of the impact energy. The present results call for additional experimental data at higher impact energies than presently available.

  5. The 1:1 charge-transfer complex dibenzotetrathiafulvalene–pyromellitic dianhydride (DBTTF–PMDA

    Directory of Open Access Journals (Sweden)

    Margaret E. Payne


    Full Text Available The title charge-transfer (CT complex, C10H2O6·C14H8S4, composed of donor dibenzotetrathiafulvalene (DBTTF and acceptor pyromellitic dianhydride (PMDA, forms a mixed stacking pattern along the [-110] direction. The constituent molecules occupy crystallographic inversion centers. They are nearly parallel and lie ca.3.41 Å from each other. The crystals exhibit a high degree of donor/acceptor overlap [88.20 (4%] in the long direction of the DBTTF and PMDA molecules as compared with 51.27 (5% in the shortest direction of the molecules.

  6. Polarization and charge-transfer effects in aqueous solution via ab initio QM/MM simulations. (United States)

    Mo, Yirong; Gao, Jiali


    Combined ab initio quantum mechanical and molecular mechanical (QM/MM) simulations coupled with the block-localized wave function energy decomposition (BLW-ED) method have been conducted to study the solvation of two prototypical ionic systems, acetate and methylammonium ions in aqueous solution. Calculations reveal that the electronic polarization between the targeted solutes and water is the primary many-body effect, whereas the charge-transfer term only makes a small fraction of the total solute-solvent interaction energy. In particular, the polarization effect is dominated by the solvent (water) polarization.

  7. Conjugated iminopyridine based Azo dye derivatives with efficient charge transfer for third order nonlinearities (United States)

    Kerasidou, A. P.; Khammar, F.; Iliopoulos, K.; Ayadi, A.; El-Ghayoury, A.; Zouari, N.; Mhiri, T.; Sahraoui, B.


    The third order nonlinearities of two azobenzene-iminopyridine molecular systems have been investigated employing the Z-scan technique at 532 nm, 30 ps. The objective of the work has been to study and to compare the nonlinearity of two iminopyridine based ligands substituted with one (NO2AzoIminoPy, A) and two azobenzene units ((NO2Azo)2IminoPy, B). The ligand B exhibits an extended conjugated structure and higher charge transfer within the molecule. Our results show high dependence of the nonlinearity on both the conjugation length within the molecule and on the number of the electron accepting units.

  8. Recombination of charge carriers on radiation-induced defects in silicon doped by transition metals impurities

    CERN Document Server

    Kazakevich, L A


    It has been studied the peculiarities of recombination of nonequilibrium charge carriers on radiation-induced defects in received according to Czochralski method p-silicon (p approx 3 - 20 Ohm centre dot cm), doped by one of the impurities of transition metals of the IV-th group of periodic table (titanium, zirconium, hafnium). Experimental results are obtained out of the analysis of temperature and injection dependence of the life time of charge carriers. The results are explained taking into consideration the influences of elastic stress fields created by the aggregates of transition metals atoms on space distribution over the crystal of oxygen and carbon background impurities as well as on the migration of movable radiation-induced defects during irradiation. (authors).

  9. Apolipoprotein E expression and behavioral toxicity of high charge, high energy (HZE) particle radiation (United States)

    Higuchi, Yoshinori; Nelson, Gregory A.; Vazquez, Marcelo; Laskowitz, Daniel T.; Slater, James M.; Pearlstein, Robert D.


    Apolipoprotein E (apoE) is a lipid binding protein that plays an important role in tissue repair following brain injury. In the present studies, we have investigated whether apoE affects the behavioral toxicity of high charge, high energy (HZE) particle radiation. METHODS: Sixteen male apoE knockout (KO) mice and sixteen genetically matched wild-type (WT) C57BL mice were used in this experiment. Half of the KO and half of the WT animals were irradiated with 600 MeV/amu iron particles (2 Gy whole body). The effect of irradiation on motor coordination and stamina (Rotarod test), exploratory behavior (open field test), and spatial working and reference memory (Morris water maze) was assessed. ROTAROD TEST: Performance was adversely affected by radiation exposure in both KO and WT groups at 30 d after irradiation. By 60 d after radiation, the radiation effect was lost in WT, but still apparent in irradiated KO mice. OPEN FIELD TEST: Radiation reduced open field exploratory activity 14, 28, 56, 84, and 168 d after irradiation of KO mice, but had no effect on WT mice. MORRIS WATER MAZE: Radiation adversely affected spatial working memory in the KO mice, but had no discernible effect in the WT mice as assessed 180 d after irradiation. In contrast, irradiated WT mice showed marked impairment of spatial reference memory in comparison to non-irradiated mice, while no effect of radiation was observed in KO mice. CONCLUSIONS: These studies show that apoE expression influences the behavioral toxicity of HZE particle radiation and suggest that apoE plays a role in the repair/recovery from radiation injury of the CNS. ApoE deficiency may exacerbate the previously reported effects of HZE particle radiation in accelerating the brain aging process.

  10. 29 CFR 102.33 - Transfer of charge and proceeding from region to region; consolidation of proceedings in same... (United States)


    ...; consolidation of proceedings in same region; severance. 102.33 Section 102.33 Labor Regulations Relating to... § 102.33 Transfer of charge and proceeding from region to region; consolidation of proceedings in same... with any other proceeding which may have been instituted in the same region; or (3) Be transferred to...

  11. Intramolecular photoassociation and photoinduced charge transfer in bridged diaryl compounds. 2. Charge-transfer interactions in the lowest excited singlet state of dinaphthylamines

    Energy Technology Data Exchange (ETDEWEB)

    Dresner, J.; Modiano, S.H.; Lim, E.C. [Univ. of Akron, OH (United States)


    The formation of an intramolecular charge-transfer (CT) exciplex is demonstrated for 1,1{prime}-dinaphthylamine (1,1{prime}-DNA) and 2,2{prime}-dinaphthylamine (2,2{prime}-DNA) in the lowest excited singlet state using steady-state and picosecond time-resolved fluorescence spectroscopy. The exciplex is formed through a mutual reorientation of the two naphthalene rings. Differences in the rate of formation and relaxation of the CT state for 1,1{prime}-DNA and 2,2{prime}-DNA indicate the importance of the bridge position in this process. The comparison of the steady-state fluorescence of 2,2{prime}-DNA with that of its protonated form, as well as the fluorescence of 2,2{prime}-dinaphthyl ether and 2,2{prime}-dinaphthylmethane, show the role of the lone-pair electrons of the nitrogen atom in the exciplex formation. 18 refs., 20 figs., 5 tabs.

  12. High-order solution methods for grey discrete ordinates thermal radiative transfer

    Energy Technology Data Exchange (ETDEWEB)

    Maginot, Peter G., E-mail: [Lawrence Livermore National Laboratory, Livermore, CA 94551 (United States); Ragusa, Jean C., E-mail: [Department of Nuclear Engineering, Texas A& M University, College Station, TX 77843 (United States); Morel, Jim E., E-mail: [Department of Nuclear Engineering, Texas A& M University, College Station, TX 77843 (United States)


    This work presents a solution methodology for solving the grey radiative transfer equations that is both spatially and temporally more accurate than the canonical radiative transfer solution technique of linear discontinuous finite element discretization in space with implicit Euler integration in time. We solve the grey radiative transfer equations by fully converging the nonlinear temperature dependence of the material specific heat, material opacities, and Planck function. The grey radiative transfer equations are discretized in space using arbitrary-order self-lumping discontinuous finite elements and integrated in time with arbitrary-order diagonally implicit Runge–Kutta time integration techniques. Iterative convergence of the radiation equation is accelerated using a modified interior penalty diffusion operator to precondition the full discrete ordinates transport operator.

  13. High-order solution methods for grey discrete ordinates thermal radiative transfer (United States)

    Maginot, Peter G.; Ragusa, Jean C.; Morel, Jim E.


    This work presents a solution methodology for solving the grey radiative transfer equations that is both spatially and temporally more accurate than the canonical radiative transfer solution technique of linear discontinuous finite element discretization in space with implicit Euler integration in time. We solve the grey radiative transfer equations by fully converging the nonlinear temperature dependence of the material specific heat, material opacities, and Planck function. The grey radiative transfer equations are discretized in space using arbitrary-order self-lumping discontinuous finite elements and integrated in time with arbitrary-order diagonally implicit Runge-Kutta time integration techniques. Iterative convergence of the radiation equation is accelerated using a modified interior penalty diffusion operator to precondition the full discrete ordinates transport operator.

  14. HELIOS: A new open-source radiative transfer code (United States)

    Malik, Matej; Grosheintz, Luc; Lukas Grimm, Simon; Mendonça, João; Kitzmann, Daniel; Heng, Kevin


    I present the new open-source code HELIOS, developed to accurately describe radiative transfer in a wide variety of irradiated atmospheres. We employ a one-dimensional multi-wavelength two-stream approach with scattering. Written in Cuda C++, HELIOS uses the GPU’s potential of massive parallelization and is able to compute the TP-profile of an atmosphere in radiative equilibrium and the subsequent emission spectrum in a few minutes on a single computer (for 60 layers and 1000 wavelength bins).The required molecular opacities are obtained with the recently published code HELIOS-K [1], which calculates the line shapes from an input line list and resamples the numerous line-by-line data into a manageable k-distribution format. Based on simple equilibrium chemistry theory [2] we combine the k-distribution functions of the molecules H2O, CO2, CO & CH4 to generate a k-table, which we then employ in HELIOS.I present our results of the following: (i) Various numerical tests, e.g. isothermal vs. non-isothermal treatment of layers. (ii) Comparison of iteratively determined TP-profiles with their analytical parametric prescriptions [3] and of the corresponding spectra. (iii) Benchmarks of TP-profiles & spectra for various elemental abundances. (iv) Benchmarks of averaged TP-profiles & spectra for the exoplanets GJ1214b, HD189733b & HD209458b. (v) Comparison with secondary eclipse data for HD189733b, XO-1b & Corot-2b.HELIOS is being developed, together with the dynamical core THOR and the chemistry solver VULCAN, in the group of Kevin Heng at the University of Bern as part of the Exoclimes Simulation Platform (ESP) [4], which is an open-source project aimed to provide community tools to model exoplanetary atmospheres.-----------------------------[1] Grimm & Heng 2015, ArXiv, 1503.03806[2] Heng, Lyons & Tsai, Arxiv, 1506.05501Heng & Lyons, ArXiv, 1507.01944[3] e.g. Heng, Mendonca & Lee, 2014, ApJS, 215, 4H[4]

  15. Modeling photosynthesis of discontinuous plant canopies by linking Geometric Optical Radiative Transfer model with biochemical processes (United States)

    Xin, Q.; Gong, P.; Li, W.


    Modeling vegetation photosynthesis is essential for understanding carbon exchanges between terrestrial ecosystems and the atmosphere. The radiative transfer process within plant canopies is one of the key drivers that regulate canopy photosynthesis. Most vegetation cover consists of discrete plant crowns, of which the physical observation departs from the underlying assumption of a homogenous and uniform medium in classic radiative transfer theory. Here we advance the Geometric Optical Radiative Transfer (GORT) model to simulate photosynthesis activities for discontinuous plant canopies. We separate radiation absorption into two components that are absorbed by sunlit and shaded leaves, and derive analytical solutions by integrating over the canopy layer. To model leaf-level and canopy-level photosynthesis, leaf light absorption is then linked to the biochemical process of gas diffusion through leaf stomata. The canopy gap probability derived from GORT differs from classic radiative transfer theory, especially when the leaf area index is high, due to leaf clumping effects. Tree characteristics such as tree density, crown shape, and canopy length affect leaf clumping and regulate radiation interception. Modeled gross primary production (GPP) for two deciduous forest stands could explain more than 80% of the variance of flux tower measurements at both near hourly and daily time scales. We also demonstrate that the ambient CO2 concentration influences daytime vegetation photosynthesis, which needs to be considered in state-of-the-art biogeochemical models. The proposed model is complementary to classic radiative transfer theory and shows promise in modeling the radiative transfer process and photosynthetic activities over discontinuous forest canopies.

  16. Real-time observation of intersystem crossing induced by charge recombination during bimolecular electron transfer reactions

    KAUST Repository

    Alsam, Amani Abdu


    Real-time probing of intersystem crossing (ISC) and triplet-state formation after photoinduced electron transfer (ET) is a particularly challenging task that can be achieved by time-resolved spectroscopy with broadband capability. Here, we examine the mechanism of charge separation (CS), charge recombination (CR) and ISC of bimolecular photoinduced electron transfer (PET) between poly[(9,9-di(3,3′-N,N’-trimethyl-ammonium) propyl fluorenyl-2,7-diyl)-alt-co-(9,9-dioctyl-fluorenyl-2,7-diyl)] diiodide salt (PFN) and dicyanobenzene (DCB) using time-resolved spectroscopy. PET from PFN to DCB is confirmed by monitoring the transient absorption (TA) and infrared spectroscopic signatures for the radical ion pair (DCB─•-PFN+•). In addition, our time-resolved results clearly demonstrate that CS takes place within picoseconds followed by CR within nanoseconds. The ns-TA data exhibit the clear spectroscopic signature of PFN triplet-triplet absorption, induced by the CR of the radical ion pairs (DCB─•-PFN+•). As a result, the triplet state of PFN (3PFN*) forms and subsequently, the ground singlet state is replenished within microseconds. © 2016

  17. Charge transfer in high velocity C{sub n}{sup +} + He collisions

    Energy Technology Data Exchange (ETDEWEB)

    Chabot, M [Institut de Physique Nucleaire, Universite Paris Sud et CNRS, 91406 Orsay Cedex (France); Martinet, G [Institut de Physique Nucleaire, Universite Paris Sud et CNRS, 91406 Orsay Cedex (France); Mezdari, F [Laboratoire des Collisions Atomiques et Moleculaires, UMR 8625, Universite Paris Sud et CNRS, 91405 Orsay Cedex (France); Diaz-Tendero, S [Departamento de Quimica, Universidad Autonoma de Madrid, 28049 Madrid (Spain); Beroff-Wohrer, K [Laboratoire des Collisions Atomiques et Moleculaires, UMR 8625, Universite Paris Sud et CNRS, 91405 Orsay Cedex (France); Desesquelles, P [Centre de Spectrometrie Nucleaire et de Spectrometrie de Masse, Universite Paris Sud et CNRS, 91405 Orsay Cedex (France); Della-Negra, S [Institut de Physique Nucleaire, Universite Paris Sud et CNRS, 91406 Orsay Cedex (France); Hamrita, H [Institut de Physique Nucleaire, Universite Paris Sud et CNRS, 91406 Orsay Cedex (France); LePadellec, A [IRSAMC, Universite Paul Sabatier et CNRS, 31062 Toulouse Cedex 4 (France); Tuna, T [Institut de Physique Nucleaire, Universite Paris Sud et CNRS, 91406 Orsay Cedex (France); Montagnon, L [IRSAMC, Universite Paul Sabatier et CNRS, 31062 Toulouse Cedex 4 (France); Barat, M [Laboratoire des Collisions Atomiques et Moleculaires, UMR 8625, Universite Paris Sud et CNRS, 91405 Orsay Cedex (France); Simon, M [Laboratoire de Chimie Physique-Matiere et Rayonnement, UMR 7614, Universite Paris 6 et CNRS, 11 rue P et M Curie, 75231 Paris Cedex 05 (France); Ismail, I [Laboratoire des Collisions Atomiques et Moleculaires, UMR 8625, Universite Paris Sud et CNRS, 91405 Orsay Cedex (France)


    Dissociative and non-dissociative charge transfer cross sections in high velocity (v = 2.6 au) collisions between ionic carbon clusters C{sub n}{sup +} (n 2-10) and helium atoms have been measured. The sum of the cross sections has been found to increase significantly with n. Measurements of branching ratios for all fragmentation channels of excited C{sub n} clusters are reported. The summed branching ratios associated with a given number of emitted fragments exhibit odd-even alternations reflecting the higher stability of the species having an odd number of atoms. From an analysis of the summed branching ratios within the statistical microcanonical metropolis Monte Carlo model, and knowing the temperature of the incident clusters, deposited energy distributions due to the charge transfer process are deduced (n = 5-9). These distributions, of similar characteristics whatever n, peak around 4-5 eV and exhibit a large percentage of superexcited states situated above the continuum.

  18. On the morphology of a discotic liquid crystalline charge transfer complex. (United States)

    Haverkate, Lucas A; Zbiri, Mohamed; Johnson, Mark R; Deme, Bruno; de Groot, Huub J M; Lefeber, Fons; Kotlewski, Arkadiusz; Picken, Stephen J; Mulder, Fokko M; Kearley, Gordon J


    Discotic liquid crystalline (DLC) charge transfer (CT) complexes, which combine visible light absorption with rapid charge transfer characteristics within the CT complex, can have a great potential for photovoltaic applications when they can be made to self-assemble in a bulk heterojunction arrangement with separate channels for electron and hole conduction. However, the morphology of some liquid crystalline CT complexes has been under debate for many years. In particular, the liquid crystalline CT complex built from the electron acceptor 2,4,7-trinitro-9-fluorenone (TNF) and discotic molecules has been reported to have the TNF "sandwiched" either between the discotic molecules within the same column or between the columns within the aliphatic tails of the discotic molecules. We present a detailed structural study of the prototypic 1:1 mixture of the discotic 2,3,6,7,10,11-hexakis(hexyloxy)triphenylene (HAT6) and TNF. Nuclear magnetic resonance (NMR) line widths and cross-polarization rates are consistent with the picosecond time scale anisotropic thermal motions of the HAT6 and TNF molecules previously observed. By computational integration of Rietveld refinement analyses of neutron diffraction patterns with density experiments and short-range structural constraints from heteronuclear 2D NMR, we determine that the TNF molecules are vertically oriented between HAT6 columns. The data provide the insight that a morphology of separate hole conducting channels of HAT6 molecules can be realized in the liquid crystalline CT complex.

  19. Excited State Structural Dynamics of Carotenoids and ChargeTransfer Systems

    Energy Technology Data Exchange (ETDEWEB)

    Van Tassle, Aaron Justin [Univ. of California, Berkeley, CA (United States)


    This dissertation describes the development andimplementation of a visible/near infrared pump/mid-infrared probeapparatus. Chapter 1 describes the background and motivation ofinvestigating optically induced structural dynamics, paying specificattention to solvation and the excitation selection rules of highlysymmetric molecules such as carotenoids. Chapter 2 describes thedevelopment and construction of the experimental apparatus usedthroughout the remainder of this dissertation. Chapter 3 will discuss theinvestigation of DCM, a laser dye with a fluorescence signal resultingfrom a charge transfer state. By studying the dynamics of DCM and of itsmethyl deuterated isotopomer (an otherwise identical molecule), we areable to investigate the origins of the charge transfer state and provideevidence that it is of the controversial twisted intramolecular (TICT)type. Chapter 4 introduces the use of two-photon excitation to the S1state, combined with one-photon excitation to the S2 state of thecarotenoid beta-apo-8'-carotenal. These 2 investigations show evidencefor the formation of solitons, previously unobserved in molecular systemsand found only in conducting polymers Chapter 5 presents an investigationof the excited state dynamics of peridinin, the carotenoid responsiblefor the light harvesting of dinoflagellates. This investigation allowsfor a more detailed understanding of the importance of structuraldynamics of carotenoids in light harvesting.

  20. Charge Transfer Mechanism in Titanium-Doped Microporous Silica for Photocatalytic Water-Splitting Applications

    Directory of Open Access Journals (Sweden)

    Wendi Sapp


    Full Text Available Solar energy conversion into chemical form is possible using artificial means. One example of a highly-efficient fuel is solar energy used to split water into oxygen and hydrogen. Efficient photocatalytic water-splitting remains an open challenge for researchers across the globe. Despite significant progress, several aspects of the reaction, including the charge transfer mechanism, are not fully clear. Density functional theory combined with density matrix equations of motion were used to identify and characterize the charge transfer mechanism involved in the dissociation of water. A simulated porous silica substrate, using periodic boundary conditions, with Ti4+ ions embedded on the inner pore wall was found to contain electron and hole trap states that could facilitate a chemical reaction. A trap state was located within the silica substrate that lengthened relaxation time, which may favor a chemical reaction. A chemical reaction would have to occur within the window of photoexcitation; therefore, the existence of a trapping state may encourage a chemical reaction. This provides evidence that the silica substrate plays an integral part in the electron/hole dynamics of the system, leading to the conclusion that both components (photoactive materials and support of heterogeneous catalytic systems are important in optimization of catalytic efficiency.

  1. Oscillatory Noncollinear Magnetism Induced by Interfacial Charge Transfer in Superlattices Composed of Metallic Oxides

    Directory of Open Access Journals (Sweden)

    Jason D. Hoffman


    Full Text Available Interfaces between correlated complex oxides are promising avenues to realize new forms of magnetism that arise as a result of charge transfer, proximity effects, and locally broken symmetries. We report on the discovery of a noncollinear magnetic structure in superlattices of the ferromagnetic metallic oxide La_{2/3}Sr_{1/3}MnO_{3} (LSMO and the correlated metal LaNiO_{3} (LNO. The exchange interaction between LSMO layers is mediated by the intervening LNO, such that the angle between the magnetization of neighboring LSMO layers varies in an oscillatory manner with the thickness of the LNO layer. The magnetic field, temperature, and spacer thickness dependence of the noncollinear structure are inconsistent with the bilinear and biquadratic interactions that are used to model the magnetic structure in conventional metallic multilayers. A model that couples the LSMO layers to a helical spin state within the LNO fits the observed behavior. We propose that the spin-helix results from the interaction between a spatially varying spin susceptibility within the LNO and interfacial charge transfer that creates localized Ni^{2+} states. Our work suggests a new approach to engineering noncollinear spin textures in metallic oxide heterostructures.

  2. The R package 'RLumModel': Simulating charge transfer in quartz (United States)

    Friedrich, Johannes; Kreutzer, Sebastian; Schmidt, Christoph


    Kinetic models of quartz luminescence have gained an important role for predicting experimental results and for understanding charge transfers in (natural) quartz as well as for other dosimetric materials, e.g., Al2O3:C. We present the R package 'RLumModel', offering an easy-to-use tool for simulating quartz luminescence signals (TL, OSL, LM-OSL and RF) based on five integrated and published parameter sets as well as the possibility to use own parameters. Simulation commands can be created (a) using the Risø Sequence Editor, (b) a built-in SAR sequence generator or (c) self-explanatory keywords for customised sequences. Results can be analysed seamlessly using the R package 'Luminescence' along with a visualisation of concentrations of electrons and holes in every trap/centre as well as in the valence and conduction band during all stages of the simulation. Modelling luminescence signals can help understanding charge transfer processes occurring in nature or during measurements in the laboratory. This will lead to a better understanding of several processes concerning geoscientific questions, because quartz is the second most abundant mineral in the Earth's continental crust.

  3. Observation of excited state charge transfer with fs/ps-CARS

    Energy Technology Data Exchange (ETDEWEB)

    Blom, Alex Jason [Iowa State Univ., Ames, IA (United States)


    Excited state charge transfer processes are studied using the fs/ps-CARS probe technique. This probe allows for multiplexed detection of Raman active vibrational modes. Systems studied include Michler's Ketone, Coumarin 120, 4-dimethylamino-4'-nitrostilbene, and several others. The vibrational spectrum of the para di-substituted benzophenone Michler's Ketone in the first excited singlet state is studied for the first time. It is found that there are several vibrational modes indicative of structural changes of the excited molecule. A combined experimental and theoretical approach is used to study the simplest 7-amino-4-methylcoumarin, Coumarin 120. Vibrations observed in FTIR and spontaneous Raman spectra are assigned using density functional calculations and a continuum solvation model is used to predict how observed modes are affected upon inclusion of a solvent. The low frequency modes of the excited state charge transfer species 4-dimethylamino-4{prime}-nitrostilbene are studied in acetonitrile. Results are compared to previous work on this molecule in the fingerprint region. Finally, several partially completed projects and their implications are discussed. These include the two photon absorption of Coumarin 120, nanoconfinement in cyclodextrin cavities and sensitization of titania nanoparticles.

  4. On the variably-charged black holes in general relativity: Hawking's radiation and naked singularities

    CERN Document Server

    Ibohal, N


    In this paper variably-charged non-rotating Reissner-Nordstrom and rotating Kerr-Newman black holes are discussed. Such a variable charge e with respect to the polar coordinate r in the field equations is referred to as an electrical radiation of the black hole. It is shown that every electrical radiation e(r) of the non-rotating black hole leads to a reduction in its mass M by some quantity. If one considers such electrical radiation taking place continuously for a long time, then a continuous reduction of the mass may take place in the black-hole body and the original mass of the black hole may be evaporated completely. At that stage, the gravity of the object may depend only on the electromagnetic field, not on the mass. Immediately after the complete evaporation of the mass, if the next radiation continues, there may be creation of a new mass leading to the formation of a negative mass naked singularity. It appears that this new mass of the naked singularity would never decrease, but might increase gradua...

  5. Magnetic field and radiative transfer modelling of a quiescent prominence (United States)

    Gunár, S.; Schwartz, P.; Dudík, J.; Schmieder, B.; Heinzel, P.; Jurčák, J.


    Aims: The aim of this work is to analyse the multi-instrument observations of the June 22, 2010 prominence to study its structure in detail, including the prominence-corona transition region and the dark bubble located below the prominence body. Methods: We combined results of the 3D magnetic field modelling with 2D prominence fine structure radiative transfer models to fully exploit the available observations. Results: The 3D linear force-free field model with the unsheared bipole reproduces the morphology of the analysed prominence reasonably well, thus providing useful information about its magnetic field configuration and the location of the magnetic dips. The 2D models of the prominence fine structures provide a good representation of the local plasma configuration in the region dominated by the quasi-vertical threads. However, the low observed Lyman-α central intensities and the morphology of the analysed prominence suggest that its upper central part is not directly illuminated from the solar surface. Conclusions: This multi-disciplinary prominence study allows us to argue that a large part of the prominence-corona transition region plasma can be located inside the magnetic dips in small-scale features that surround the cool prominence material located in the dip centre. We also argue that the dark prominence bubbles can be formed because of perturbations of the prominence magnetic field by parasitic bipoles, causing them to be devoid of the magnetic dips. Magnetic dips, however, form thin layers that surround these bubbles, which might explain the occurrence of the cool prominence material in the lines of sight intersecting the prominence bubbles. Movie and Appendix A are available in electronic form at

  6. Dissociation of charge-transfer states at donor-acceptor interfaces of organic heterojunctions (United States)

    Inche Ibrahim, M. L.


    The dissociation of charge-transfer (CT) states into free charge carriers at donor-acceptor (DA) interfaces is an important step in the operation of organic solar cells and related devices. In this paper, we show that the effect of DA morphology and architecture means that the directions of CT states (where a CT state’s direction is defined as the direction from the electron to the hole of the CT state) may deviate from the direction of the applied electric field. The deviation means that the electric field is not fully utilized to assist, and could even hinder the dissociation process. Furthermore, we show that the correct charge carrier mobilities that should be used to describe CT state dissociation are the actual mobilites at DA interfaces. The actual mobilities are defined in this paper, and in general are not the same as the mobilities that are used to calculate electric currents which are the mobilites along the direction of the electric field. Then, to correctly describe CT state dissociation, we modify the widely used Onsager-Braun (OB) model by including the effect of DA morphology and architecture, and by employing the correct mobilities. We verify that when the modified OB model is used to describe CT state dissociation, the fundamental issues that concern the original OB model are resolved. This study demonstrates that DA morphology and architecture play an important role by strongly influencing the CT state dissociation as well as the mobilites along the direction of the electric field.

  7. Large impact of reorganization energy on photovoltaic conversion due to interfacial charge-transfer transitions. (United States)

    Fujisawa, Jun-ichi


    Interfacial charge-transfer (ICT) transitions are expected to be a novel charge-separation mechanism for efficient photovoltaic conversion featuring one-step charge separation without energy loss. Photovoltaic conversion due to ICT transitions has been investigated using several TiO2-organic hybrid materials that show organic-to-inorganic ICT transitions in the visible region. In applications of ICT transitions to photovoltaic conversion, there is a significant problem that rapid carrier recombination is caused by organic-inorganic electronic coupling that is necessary for the ICT transitions. In order to solve this problem, in this work, I have theoretically studied light-to-current conversions due to the ICT transitions on the basis of the Marcus theory with density functional theory (DFT) and time-dependent DFT (TD-DFT) calculations. An apparent correlation between the reported incident photon-to-current conversion efficiencies (IPCE) and calculated reorganization energies was clearly found, in which the IPCE increases with decreasing the reorganization energy consistent with the Marcus theory in the inverted region. This activation-energy dependence was systematically explained by the equation formulated by the Marcus theory based on a simple excited-state kinetic scheme. This result indicates that the reduction of the reorganization energy can suppress the carrier recombination and enhance the IPCE. The reorganization energy is predominantly governed by the structural change in the chemical-adsorption moiety between the ground and ICT excited states. This work provides crucial knowledge for efficient photovoltaic conversion due to ICT transitions.

  8. Charged Particle Measurements with the Mars Science Laboratory's Radiation Assessment Detector (MSL/RAD) (United States)

    Ehresmann, B.; Hassler, D.; Zeitlin, C. J.; Kohler, J.; Wimmer-Schweingruber, R. F.; Appel, J. K.; Boehm, E.; Böttcher, S. I.; Brinza, D. E.; Burmeister, S.; Guo, J.; Lohf, H.; Martin-Garcia, C.; Matthiae, D.; Posner, A.; Rafkin, S. C.; Reitz, G.


    Since the Curiosity rover's landing in Gale crater on the surface of Mars, the Radiation Assessment Detector (RAD) on board the rover has been conducting the first-ever measurements of the Martian surface radiation field. This field is induced by Galactic Cosmic Rays (GCRs) and their interactions with the atoms of the Martian atmosphere and soil. Furthermore, sporadic Solar Energetic Particle (SEP) events can lead to large, but short-term enhancements in the intensity of the radiation field. A large part of the radiation environment is made up of charged particles, e.g., ions and their isotopes, electrons, and positrons amongst others. There are mainly two factors influencing the surface radiation field: the modulation of the incoming GCR flux due to the solar magnetic field correlating with the solar cycle; the amount of atmospheric column mass above Gale crater resulting in changes of GCR penetration depth into the atmosphere, as well as influencing the secondary particle production rate. Here, we focus on the temporal evolution of the radiation environment since the landing, analyzing changes in the measured particle spectra for different phases in the Martian seasonal cycle and solar activity. Furthermore, we present enhancements in the proton flux during directly observed SEP events.

  9. Porous Silicon Structures under action microwave Radiation: Charge Carrier Heating Effects (United States)

    Shatkovskis, Eugenijus; Gradauskas, Jonas; Cesnys, Antanas


    Porous silicon (por-Si) is one of modern nanomaterials, which is intensively investigated recently. The action of microwave radiation is only slightly investigated on por-Si, however. Basically there are papers intended to application of por-Si as substrates in microwave and opto-electronic interconnects. Action microwave radiation (MW) often manifests itself through effects of charge carrier heating in semiconductors. Since the energy quanta of MW radiation are too small to challenge any quantum jumps in common semiconductors, it is likely that carrier heating can be responsible for effects arising in por-Si under MW radiation also. This question is discussed in present contribution based on experimental study of electrical conductivity and electromotive force (emf) in por-Si structures under the action of 10 GHz frequency MW radiation pulses. Two-terminal por-Si containing structures were made by usual technology of electrochemical etching of p-type, 0, 4 Si plates in the HF: Ethanol=1:2 electrolyte. It has been shown that experimentally observed decrease of the resistance of the samples and rise of emf can be explained both assuming concept of hole heating, by MW radiation in fractal-like percolation grid of por-Si structure.

  10. Smith-Purcell radiation from a charge moving above a grating of finite length and width

    Directory of Open Access Journals (Sweden)

    Amit S. Kesar


    Full Text Available Smith-Purcell radiation (SPR, emitted when a charge passes above a periodic grating, is important for applications such as terahertz production and nondestructive bunch-length diagnostics. The grating width is shown to become an important parameter for accurately predicting the radiation, and especially in the highly relativistic regime where the charge wakefield considerably stretches in the transverse direction. The SPR radiation is rigorously calculated by the electric-field integral equation (EFIE method for a grating of finite width and length. The integral equation is arranged as a multilevel block-Toeplitz matrix by using symmetry under translation with respect to the grating period and width directions. Following Barrowes et al. [Microw. Opt. Technol. Lett. 31, 28 (2001MOTLEO0895-247710.1002/mop.1348] enhanced computational efficiency can be achieved by matrix to vector projection of the essential matrix elements. A numerical example is calculated for a relativistic (γ=36, 1-mm long, bunch traveling 0.6-mm above a ten-period grating with a period of 2.0 mm and width of 10 mm. The SPR resonance relationship and its broadening due to the finite number of grooves are consistent with the closed-form formulations. The surface current was shown to be concentrated along the center of the grating and decreasing towards its edges. The surface current, power spectrum, and radiated energy were compared to the EFIE formulation in which an infinitely wide grating was assumed. The above parameters resulted in considerable difference of up to a factor of 2.5 between the finite width and the infinitely wide grating assumption, which means that for accurate calculations the grating width should be taken into consideration. A general rule for the required grating width to achieve an accurate SPR radiation result relative to the infinite width result, and the expected accuracy by the infinite width assumption for most radiation angles, is provided.

  11. Properties of a radiation-induced charge multiplication region in epitaxial silicon diodes

    Energy Technology Data Exchange (ETDEWEB)

    Lange, J., E-mail: joern.lange@desy.d [Institute for Experimental Physics, University of Hamburg, Luruper Chaussee 149, 22761 Hamburg (Germany); Becker, J.; Fretwurst, E.; Klanner, R.; Lindstroem, G. [Institute for Experimental Physics, University of Hamburg, Luruper Chaussee 149, 22761 Hamburg (Germany)


    Charge multiplication (CM) in p{sup +}n epitaxial silicon pad diodes of 75, 100 and 150{mu}m thickness at high voltages after proton irradiation with 1 MeV neutron equivalent fluences in the order of 10{sup 16} cm{sup -2} was studied as an option to overcome the strong trapping of charge carriers in the innermost tracking region of future Super-LHC detectors. Charge collection efficiency (CCE) measurements using the Transient Current Technique (TCT) with radiation of different penetration (670, 830, 1060 nm laser light and {alpha}-particles with optional absorbers) were used to locate the CM region close to the p{sup +}-implantation. The dependence of CM on material, thickness of the epitaxial layer, annealing and temperature was studied. The collected charge in the CM regime was found to be proportional to the deposited charge, uniform over the diode area and stable over a period of several days. Randomly occurring micro-discharges at high voltages turned out to be the largest challenge for operation of the diodes in the CM regime. Although at high voltages an increase of the TCT baseline noise was observed, the signal-to-noise ratio was found to improve due to CM for laser light. Possible effects on the charge spectra measured with laser light due to statistical fluctuations in the CM process were not observed. In contrast, the relative width of the spectra increased in the case of {alpha}-particles, probably due to varying charge deposited in the CM region.

  12. Heat transfer performance of a pulsating heat pipe charged with acetone-based mixtures (United States)

    Wang, Wenqing; Cui, Xiaoyu; Zhu, Yue


    Pulsating heat pipes (PHPs) are used as high efficiency heat exchangers, and the selection of working fluids in PHPs has a great impact on the heat transfer performance. This study investigates the thermal resistance characteristics of the PHP charged with acetone-based binary mixtures, where deionized water, methanol and ethanol were added to and mixed with acetone, respectively. The volume mixing ratios were 2:1, 4:1 and 7:1, and the heating power ranged from 10 to 100 W with filling ratios of 45, 55, 62 and 70%. At a low filling ratio (45%), the zeotropic characteristics of the binary mixtures have an influence on the heat transfer performance of the PHP. Adding water, which has a substantially different boiling point compared with that of acetone, can significantly improve the anti-dry-out ability inside the PHP. At a medium filling ratio (55%), the heat transfer performance of the PHP is affected by both phase transition characteristics and physical properties of working fluids. At high heating power, the thermal resistance of the PHP with acetone-water mixture is between that with pure acetone and pure water, whereas the thermal resistance of the PHP with acetone-methanol and acetone-ethanol mixtures at mixing ratios of 2:1 and 4:1 is less than that with the corresponding pure fluids. At high filling ratios (62 and 70%), the heat transfer performance of the PHP is mainly determined by the properties of working fluids that affects the flow resistance. Thus, the PHP with acetone-methanol and acetone-ethanol mixtures that have a lower flow resistance shows better heat transfer performance than that with acetone-water mixture.

  13. Photophysical investigations on supramolecular fullerene/phthalocyanine charge transfer interactions in solution. (United States)

    Ray, Anamika; Pal, Haridas; Bhattacharya, Sumanta


    The photophysical features of non-covalently linked fullerenes C60 and C70 with a designed free-base phthalocyanine, namely, 2,3,9,10,16,17,23,24-octakis-(octyloxy)-29H,31H-phthalocyanine (1) have been investigated employing various spectroscopic tools like UV-vis absorption spectrophotometry, steady state and time resolved fluorescence along with proton NMR measurements in toluene. The ground state interaction between fullerenes and 1 is nicely demonstrated with the appearance of well defined charge transfer absorption bands in the visible region of the electronic spectra. Steady state fluorescence experiment reveals efficient quenching of the excited singlet state of 1 in presence of both C60 and C70. The average values of binding constants for the non-covalent complexes of C60 and C70 with 1 are determined to be ~18,150 and ~32,000 dm(3) mol(-1), respectively. The magnitude of K suggests that 1 preferentially binds C70 in comparison to C60 although average value of selectivity in binding is measured to be low (~1.75). Time resolved emission measurements establish photoinduced energy transfer from the excited singlet state of 1 to fullerene in toluene. Measurements of free energy of electron transfer and free energy of radical ion-pair formation elicit that C70/1 complex is stabilized more in comparison to C60/1 complex regarding generation of charge-separated state. Proton NMR studies provide very good support in favor of effective ground state complexation between fullerenes and 1. Semi empirical theoretical calculations on fullerene/1 systems in vacuo substantiate the stronger binding between C70 and 1 in comparison to C60/1 system in terms of heat of formation value of the respective complexes, and determine the orientation of bound guest (here C70) towards the plane of 1 during complexation. Copyright © 2013 Elsevier B.V. All rights reserved.

  14. Molecular Engineering for Enhanced Charge Transfer in Thin-Film Photoanode. (United States)

    Kim, Jeong Soo; Kim, Byung-Man; Kim, Un-Young; Shin, HyeonOh; Nam, Jung Seung; Roh, Deok-Ho; Park, Jun-Hyeok; Kwon, Tae-Hyuk


    We developed three types of dithieno[3,2-b;2',3'-d]thiophene (DTT)-based organic sensitizers for high-performance thin photoactive TiO2 films and investigated the simple but powerful molecular engineering of different types of bonding between the triarylamine electron donor and the conjugated DTT π-bridge by the introduction of single, double, and triple bonds. As a result, with only 1.3 μm transparent and 2.5-μm TiO2 scattering layers, the triple-bond sensitizer (T-DAHTDTT) shows the highest power conversion efficiency (η = 8.4%; VOC = 0.73 V, JSC = 15.4 mA·cm(-2), and FF = 0.75) in an iodine electrolyte system under one solar illumination (AM 1.5, 1000 W·m(-2)), followed by the single-bond sensitizer (S-DAHTDTT) (η = 7.6%) and the double-bond sensitizer (D-DAHTDTT) (η = 6.4%). We suggest that the superior performance of T-DAHTDTT comes from enhanced intramolecular charge transfer (ICT) induced by the triple bond. Consequently, T-DAHTDTT exhibits the most active photoelectron injection and charge transport on a TiO2 film during operation, which leads to the highest photocurrent density among the systems studied. We analyzed these correlations mainly in terms of charge injection efficiency, level of photocharge storage, and charge-transport kinetics. This study suggests that the molecular engineering of a triple bond between the electron donor and the π-bridge of a sensitizer increases the performance of dye-sensitized solar cell (DSC) with a thin photoactive film by enhancing not only JSC through improved ICT but also VOC through the evenly distributed sensitizer surface coverage.

  15. Looking at Photoinduced Charge Transfer Processes in the IR: Answers to Several Long-Standing Questions. (United States)

    Dereka, Bogdan; Koch, Marius; Vauthey, Eric


    Because of its crucial role in many areas of science and technology, photoinduced electron transfer is the most investigated photochemical reaction. Despite this, several important questions remain open. We present recent efforts to answer some of them, which concern both inter- and intramolecular processes. The decisive factor that allowed these issues to be successfully addressed was the use of time-resolved infrared (TRIR) spectroscopy. Many different transient species, such as tight and loose ion pairs (TIPs and LIPs) and exciplexes, have been invoked to explain the dynamics of intermolecular photoinduced charge separation reactions (i.e., electron transfer between two neutral species) and the production of free ions. However, their structures are essentially unknown, and their exact roles in the reaction mechanism are unclear. Indeed, the commonly used transient electronic absorption spectroscopy does not give much structural insight and cannot clearly distinguish ion pairs from free ions, at least in the visible region. Unambiguous spectral signatures of TIPs, LIPs, and exciplexes could be observed in the IR using electron donor/acceptor (D/A) pairs with adequate vibrational marker modes. The ability to spectrally distinguish these intermediates allowed their dynamics to be disentangled and their roles to be determined. Structural information could be obtained using polarization-resolved TRIR spectroscopy. Our investigations reveal that moderately to highly exergonic reactions result in the formation of both TIPs and LIPs. TIPs are not only generated upon direct charge-transfer excitation of DA complexes, as usually assumed, but are also formed upon static quenching with reactant pairs at distances and orientations enabling charge separation without diffusion. On the other hand, dynamic quenching produces primarily LIPs. In the case of highly exergonic reactions, strong indirect evidence for the generation of ion pairs in an electronic excited state was found

  16. Electron transfer processes of atomic and molecular doubly charged ions: information from beam experiments (United States)

    Herman, Zdenek


    Single-electron transfer reactions in collisions of atomic and molecular doubly charged ions, with atoms and molecules, were investigated in a series of crossed-beam scattering, translational spectroscopy and product luminescence experiments. Investigation of a series of atomic dication-atom electron transfer at collision energies of 0.1-10 eV provided data on differential and relative total cross sections of state-to-state processes. Populations of electronic and vibrational states and rotational temperatures of molecular product ions were obtained from studies of non-dissociative electron transfer in systems containing simple molecular dications and/or molecular targets. The product electronic states populated with highest probability were those for which the translational energy release was 3-5 eV, indicating that the 'reaction window' concept, based on the Landau-Zener formalism, is applicable also to molecular systems. Population of the vibrational states of the molecular products could be described by Franck-Condon factors of the vertical transitions between the reactant and product states, especially at higher (keV) collision energies. Rotational temperature of the product molecular cations was found to be surprisingly low, mostly 400-500 K, practically the temperature of the ion source.

  17. Mechanism of charge transfer/disproportionation in LnCu3Fe4O12 (Ln = lanthanides) (United States)

    Rezaei, N.; Hansmann, P.; Bahramy, M. S.; Arita, R.


    The Fe-Cu intersite charge transfer and Fe charge disproportionation are interesting phenomena observed in some LnCu3Fe4O12 (Ln = lanthanides) compounds containing light and heavy Ln atoms, respectively. We show that a change in the spin state is responsible for the intersite charge transfer in the light Ln compounds. At the high-spin state, such systems prefer an unusual Cu d8 configuration, whereas at the low-spin state they retreat to the normal Cu d9 configuration through a charge transfer from Fe to the Cu 3dxy orbital. We find that the strength of the crystal-field splitting and the relative energy ordering between Cu 3dxy and Fe 3d states are the key parameters determining the intersite charge transfer (charge disproportionation) in light (heavy) Ln compounds. It is further proposed that the size of Ln affects the on-site interaction strength of Cu 3d states, leading to a strong modification of the Cu L3-edge spectrum, as observed by the x-ray-absorption spectroscopy.

  18. Scientific Computation Application Partnerships in Materials and Chemical Sciences, Charge Transfer and Charge Transport in Photoactivated Systems, Developing Electron-Correlated Methods for Excited State Structure and Dynamics in the NWChem Software Suite

    Energy Technology Data Exchange (ETDEWEB)

    Cramer, Christopher J. [Univ. of Minnesota, Minneapolis, MN (United States)


    Charge transfer and charge transport in photoactivated systems are fundamental processes that underlie solar energy capture, solar energy conversion, and photoactivated catalysis, both organometallic and enzymatic. We developed methods, algorithms, and software tools needed for reliable treatment of the underlying physics for charge transfer and charge transport, an undertaking with broad applicability to the goals of the fundamental-interaction component of the Department of Energy Office of Basic Energy Sciences and the exascale initiative of the Office of Advanced Scientific Computing Research.

  19. Comparative study of Green's function matrix elements and charge transfers obtained from different partitioning schemes of molecular charge in hydrogen-bonded complexes

    Directory of Open Access Journals (Sweden)

    Parnaíba-da Silva Antenor J.


    Full Text Available RHF and MP2 ab initio molecular orbital calculations using the 4-31G**, 6-311G** and cc-pVTZ basis sets have revealed that the Green's function matrix element (G D,A values show a good correlation with the amount of intermolecular transferred charges obtained from different charge partitioning schemes for the CNH?CNH, NCH?CNH, CNH?NCH and NCH?NCH hydrogen bonded complexes. This is evident specially when the hydrogen bond distance is progressively increased from the equilibrium position until 4.5 Å. However, G D,A values show a better linear correlation with deltaQ values using corrected Mülliken charges, which are obtained from the charge-charge flux-overlap (CCFO model for infrared intensities. In this case, both G D,A and deltaQcorr form two practically superposed exponential curves. On the other hand, G D,A values show a smaller agreement with deltaQ values obtained from atomic charges derived from natural bonding orbitals. This is clearly verified when considering the first order exponential decay rate of G D,A versus deltaQ obtained from different charge partitioning schemes.

  20. Oscillator based analog to digital converters applied for charge based radiation detectors in positron emission tomography


    Völker, M.


    This thesis presents the development of a readout strategy and a front-end for radiation detectors especially adapted for positron emission tomography. The developed front-end is optimized for the implementation in modern CMOS technologies. On one hand, most of the signal processing is transferred into the digital domain to benefit from the high digital integration density. On the other hand, the circuits have to be robust against cross-talk and power supply noise. Low-power design methods ar...

  1. Near-field radiative heat transfer under temperature gradients and conductive transfer

    Energy Technology Data Exchange (ETDEWEB)

    Jin, Weiliang; Rodriguez, Alejandro W. [Princeton Univ., NJ (United States). Dept. of Electrical Engineering; Messina, Riccardo [CNRS-Univ. de Montpellier (France). Lab. Charles Coulomb


    We describe a recently developed formulation of coupled conductive and radiative heat transfer (RHT) between objects separated by nanometric, vacuum gaps. Our results rely on analytical formulas of RHT between planar slabs (based on the scattering-matrix method) as well as a general formulation of RHT between arbitrarily shaped bodies (based on the fluctuating-volume current method), which fully captures the existence of temperature inhomogeneities. In particular, the impact of RHT on conduction, and vice versa, is obtained via self-consistent solutions of the Fourier heat equation and Maxwell's equations. We show that in materials with low thermal conductivities (e.g. zinc oxides and glasses), the interplay of conduction and RHT can strongly modify heat exchange, exemplified for instance by the presence of large temperature gradients and saturating flux rates at short (nanometric) distances. More generally, we show that the ability to tailor the temperature distribution of an object can modify the behaviour of RHT with respect to gap separations, e.g. qualitatively changing the asymptotic scaling at short separations from quadratic to linear or logarithmic. Our results could be relevant to the interpretation of both past and future experimental measurements of RHT at nanometric distances.

  2. Analysis of Radiation Levels Associated with Operation of the RHIC Transfer Line

    Energy Technology Data Exchange (ETDEWEB)

    Stevens, A. J. [Brookhaven National Lab. (BNL), Upton, NY (United States)


    This note is intended to document calculations of prompt radiation dose in regions exterior to the berm which now exists over the Transfer Line between the AGS and the Relativistic Heavy Ion Collider.

  3. A Numerical Study of Combined Convective and Radiative Heat Transfer in a Rocket Engine Combustion Chamber

    National Research Council Canada - National Science Library

    Savur, Mehmet


    A numerical study was conducted to predict the combined convective and radiative heat transfer rates on the walls of a small aspect ratio cylinder representative of the scaled model of a rocket engine combustion chamber...

  4. Directional radiometry and radiative transfer: The convoluted path from centuries-old phenomenology to physical optics (United States)

    Mishchenko, Michael I.


    This Essay traces the centuries-long history of the phenomenological disciplines of directional radiometry and radiative transfer in turbid media, discusses their fundamental weaknesses, and outlines the convoluted process of their conversion into legitimate branches of physical optics.

  5. Chebyshev collocation spectral method for radiative transfer in participating media with variable physical properties (United States)

    Li, Guo-jun; Wei, Lin-Yang


    Chebyshev collocation spectral method based on discrete ordinates equation is employed to solve radiative heat transfer problems in participating media with variable physical prosperities (including space-dependent or temperature-dependent refractive index, absorption coefficient and scattering coefficient). Discrete ordinates method is employed to discretize the solid angle domain. Chebyshev polynomial and collocation spectral method are adopted to express and discretize space domain, respectively. Numerical results obtained by the Chebyshev collocation spectral-discrete ordinates method (CCS-DOM) are presented in this paper and the results show the CCS-DOM has a good accuracy and efficiency for radiative heat transfer problems in participating media. At last, the effects of variable physical properties on radiative heat transfer are analyzed and it can be found that the distributions of refractive index, absorption coefficient and scattering coefficient have a significant effect on radiative transfer and energy distribution.

  6. Directional Radiometry and Radiative Transfer: the Convoluted Path From Centuries-old Phenomenology to Physical Optics (United States)

    Mishchenko, Michael I.


    This Essay traces the centuries-long history of the phenomenological disciplines of directional radiometry and radiative transfer in turbid media, discusses their fundamental weaknesses, and outlines the convoluted process of their conversion into legitimate branches of physical optics.

  7. Axially Bound Ruthenium Phthalocyanine Monolayers on Indium Tin Oxide: Structure, Energetics, and Charge Transfer Properties. (United States)

    Ehamparam, Ramanan; Oquendo, Luis E; Liao, Michael W; Brynnel, Ambjorn K; Ou, Kai-Lin; Armstrong, Neal R; McGrath, Dominic V; Saavedra, S Scott


    The efficiency of charge collection at the organic/transparent conducting oxide (TCO) interface in organic photovoltaic (OPV) devices affects overall device efficiency. Modifying the TCO with an electrochemically active molecule may enhance OPV efficiency by providing a charge-transfer pathway between the electrode and the organic active layer, and may also mitigate surface recombination. The synthesis and characterization of phosphonic acid-ruthenium phthalocyanine (RuPcPA) monolayer films on indium tin oxide (ITO), designed to facilitate charge harvesting at ITO electrodes, is presented in this work. The PA group was installed axially relative to the Pc plane so that upon deposition, RuPcPA molecules were preferentially aligned with the ITO surface plane. The tilt angle of 22° between the normal axes to the Pc plane and the ITO surface plane, measured by attenuated total reflectance (ATR) spectroscopy, is consistent with a predominately in-plane orientation. The effect of surface roughness on RuPcPA orientation was modeled, and a correlation was obtained between experimental and theoretical mean tilt angles. Based on electrochemical and spectroelectrochemical studies, RuPcPA monolayers are composed predominately of monomers. Electrochemical impedance spectroscopy (EIS) and potential modulated-ATR (PM-ATR) spectroscopy were used to characterize the electron-transfer (ET) kinetics of these monolayers. A rate constant of 4.0 × 10 3 s -1 was measured using EIS, consistent with a short tunneling distance between the chromophore and the electrode surface. Using PM-ATR, k s,opt values of 2.2 × 10 3 and 2.4 × 10 3 s -1 were measured using TE and TM polarized light, respectively; the similarity of these values is consistent with a narrow molecular orientation distribution and narrow range of tunneling distances. The ionization potential of RuPcPA-modified ITO was measured using ultraviolet photoelectron spectroscopy and the results indicate favorable energetics for

  8. Radiating heat transfer in the power boiler downtake gas duct when firing high-ash coal

    Energy Technology Data Exchange (ETDEWEB)

    Sudarev, A.V.; Antonovsky, V.I.; Kiselev, O.V.; Sivchikov, S.B. (VTUS-Leningrad Metal Plant-LMZ, Leningrad (USSR))


    The experimental study of radiation heat transfer in the downtake gas duct of the pulverized-coal fired steam boiler for 500 MW power unit when firing high-ash (40% ash content) coal from Ekibastuz coal field was carried out by means of the radiometer probe with rotary optical axis. The local values of the combustion product temperature were measured simultaneously in the down-take and the operation parameters for boiler gas and steam ducts were registered. The dependence of the extinction coefficient of combustion products on the radiating layer thickness was obtained. The radiating power, generated in the gas space, remote from the steam superheater and reaching the super heater boundaries, was measured. The heat release coefficients from radiation and heat transfer coefficients, were determined for definite operation conditions of the superheater working. The contribution of the gas space outside the steam superheater into the radiating heat transfer negligible.

  9. Mathematical modeling of radiative-conductive heat transfer in semitransparent medium with phase change (United States)

    Savvinova, Nadezhda A.; Sleptsov, Semen D.; Rubtsov, Nikolai A.


    A mathematical phase change model is a formulation of the Stefan problem. Various formulations of the Stefan problem modeling of radiative-conductive heat transfer during melting or solidification of a semitransparent material are presented. Analysis of numerical results show that the radiative heat transfer has a significant effect on temperature distributions during melting (solidification) of the semitransparent material. In this paper conditions for application of various statements of the Stefan problem are analyzed.

  10. Radiative Transfer in the Refractive Atmospheres of Very Cool White Dwarfs


    Piotr Kowalski; Saumon, D.; [Philo-Dicaeus] 


    We consider the problem of radiative transfer in stellar atmospheres where the index of refraction departs from unity and is a function of density and temperature. We present modified Feautrier and Lambda-iteration methods to solve the equation of radiative transfer with refraction in a plane parallel atmosphere. These methods are general and can be used in any problem with 1-D geometry where the index of refraction is a monotonically varying function of vertical optical depth. We present an ...

  11. Nanoscale Heat Transfer Due to Near Field Radiation and Nanofluidic Flows (United States)


    AFRL-OSR-VA-TR-2015-0205 Nanoscale heat transfer due to near field radiation and nanofluidic flows Peter Taborek UNIVERSITY OF CALIFORNIA IRVINE...TITLE AND SUBTITLE Nanoscale heat transfer due to near field radiation and nanofluidic flows 5a. CONTRACT NUMBER 5b. GRANT NUMBER FA9550-12-1-0065...ballistic to hydrodynamic flow in the smallest pipes ever investigated. Because of the vacuum conditions at the low pressure end of our nanopipes

  12. On the maximum charge state and proton transfer reactivity of peptide and protein ions formed by electrospray ionization. (United States)

    Schnier, P D; Gross, D S; Williams, E R


    A relatively simple model for calculation of the energetics of gas-phase proton transfer reactions and the maximum charge state of multiply protonated ions formed by electrospray ionization is presented. This model is based on estimates of the intrinsic proton transfer reactivity of sites of protonation and point charge Coulomb interactions. From this model, apparent gas-phase basicities (GB(app)) of multiply protonated ions are calculated. Comparison of this value to the gas-phase basicity of the solvent from which an ion is formed enables a maximum charge state to be calculated. For 13 commonly electrosprayed proteins, our calculated maximum charge states are within an average of 6% of the experimental values reported in the literature. This indicates that the maximum charge state for proteins is determined by their gas-phase reactivity. Similar results are observed for peptides with many basic residues. For peptides with few basic residues, we find that the maximum charge state is better correlated to the charge state in solution. For low charge state ions, we find that the most basic sites Arg, Lys, and His are preferentially protonated. A significant fraction of the less basic residues Pro, Trp, and Gln are protonated in high charge state ions. The calculated GB(app) of individual protonation sites varies dramatically in the high charge state ions. From these values, we calculate a reduced cross section for proton transfer reactivity that is significantly lower than the Langevin collision frequency when the GB(app) of the ion is approximately equal to the GB of the neutral base.

  13. Evaluation of Radiation Belt Space Weather Forecasts for Internal Charging Analyses (United States)

    Minow, Joseph I.; Coffey, Victoria N.; Jun, Insoo; Garrett, Henry B.


    A variety of static electron radiation belt models, space weather prediction tools, and energetic electron datasets are used by spacecraft designers and operations support personnel as internal charging code inputs to evaluate electrostatic discharge risks in space systems due to exposure to relativistic electron environments. Evaluating the environment inputs is often accomplished by comparing whether the data set or forecast tool reliability predicts measured electron flux (or fluence over a given period) for some chosen period. While this technique is useful as a model metric, it does not provide the information necessary to evaluate whether short term deviances of the predicted flux is important in the charging evaluations. In this paper, we use a 1-D internal charging model to compute electric fields generated in insulating materials as a function of time when exposed to relativistic electrons in the Earth's magnetosphere. The resulting fields are assumed to represent the "true" electric fields and are compared with electric field values computed from relativistic electron environments derived from a variety of space environment and forecast tools. Deviances in predicted fields compared to the "true" fields which depend on insulator charging time constants will be evaluated as a potential metric for determining the importance of predicted and measured relativistic electron flux deviations over a range of time scales.

  14. Radiation and Heat Transfer in the Atmosphere: A Comprehensive Approach on a Molecular Basis

    Directory of Open Access Journals (Sweden)

    Hermann Harde


    Full Text Available We investigate the interaction of infrared active molecules in the atmosphere with their own thermal background radiation as well as with radiation from an external blackbody radiator. We show that the background radiation can be well understood only in terms of the spontaneous emission of the molecules. The radiation and heat transfer processes in the atmosphere are described by rate equations which are solved numerically for typical conditions as found in the troposphere and stratosphere, showing the conversion of heat to radiation and vice versa. Consideration of the interaction processes on a molecular scale allows to develop a comprehensive theoretical concept for the description of the radiation transfer in the atmosphere. A generalized form of the radiation transfer equation is presented, which covers both limiting cases of thin and dense atmospheres and allows a continuous transition from low to high densities, controlled by a density dependent parameter. Simulations of the up- and down-welling radiation and its interaction with the most prominent greenhouse gases water vapour, carbon dioxide, methane, and ozone in the atmosphere are presented. The radiative forcing at doubled CO2 concentration is found to be 30% smaller than the IPCC-value.

  15. Erosion of carbon/carbon by solar wind charged particle radiation during a solar probe mission (United States)

    Sokolowski, Witold; O'Donnell, Tim; Millard, Jerry


    The possible erosion of a carbon/carbon thermal shield by solar wind-charged particle radiation is reviewed. The present knowledge of erosion data for carbon and/or graphite is surveyed, and an explanation of erosion mechanisms under different charged particle environments is discussed. The highest erosion is expected at four solar radii. Erosion rates are analytically estimated under several conservative assumptions for a normal quiet and worst case solar wind storm conditions. Mass loss analyses and comparison studies surprisingly indicate that the predicted erosion rate by solar wind could be greater than by nominal free sublimation during solar wind storm conditions at four solar radii. The predicted overall mass loss of a carbon/carbon shield material during the critical four solar radii flyby can still meet the mass loss mission requirement of less than 0.0025 g/sec.

  16. Influence of semiclassical plasma on the energy levels and radiative transitions in highly charged ions★ (United States)

    Hu, Hong-Wei; Chen, Zhan-Bin; Chen, Wen-Cong; Liu, Xiao-Bin; Fu, Nian; Wang, Kai


    Considering the quantum effects of diffraction and the collective screening effects, the potential of test charge in semiclassical plasmas is derived. It is generalized exponential screened Coulomb potential. Using the Ritz variational method incorporating this potential, the effects of semiclassical plasma on the energy levels and radiative transitions are investigated systematically, taking highly charged H-like ion as an example. The Debye plasma model is also employed for comparison purposes. Comparisons and analysis are made between these two sets of results and the differences are discussed. Contribution to the Topical Issue "Atomic and Molecular Data and their Applications", edited by Gordon W.F. Drake, Jung-Sik Yoon, Daiji Kato, Grzegorz Karwasz.

  17. Radiative transfer solutions for coupled atmosphere ocean systems using the matrix operator technique (United States)

    Hollstein, André; Fischer, Jürgen


    Accurate radiative transfer models are the key tools for the understanding of radiative transfer processes in the atmosphere and ocean, and for the development of remote sensing algorithms. The widely used scalar approximation of radiative transfer can lead to errors in calculated top of atmosphere radiances. We show results with errors in the order of±8% for atmosphere ocean systems with case one waters. Variations in sea water salinity and temperature can lead to variations in the signal of similar magnitude. Therefore, we enhanced our scalar radiative transfer model MOMO, which is in use at Freie Universität Berlin, to treat these effects as accurately as possible. We describe our one-dimensional vector radiative transfer model for an atmosphere ocean system with a rough interface. We describe the matrix operator scheme and the bio-optical model for case one waters. We discuss some effects of neglecting polarization in radiative transfer calculations and effects of salinity changes for top of atmosphere radiances. Results are shown for the channels of the satellite instruments MERIS and OLCI from 412.5 nm to 900 nm.

  18. 3D radiative transfer code for polarized scattered light with aligned grains (United States)

    Pelkonen, V.-M.; Penttilä, A.; Juvela, M.; Muinonen, K.


    We are working on a 3D Monte Carlo radiative transfer code which incorporates hierarchical grid structure (octree) and the full Stokes vector for both the incoming radiation and the radiation scattered by dust grains. The dust model can include different populations of dust, differing in composition, size distribution, shapes, and orientation. The non-spherical dust grains can be randomly aligned, or a fraction of them can be aligned with the magnetic fields (in particular, by the radiation field via radiative torques, RATs). The code will be a valuable tool in studying polarized scattered light from cometary comae in the solar system and from protoplanetary disks in the exoplanetary context.

  19. Enhanced Three-Photon Absorption by Symmetric Twisted Intramolecular Charge Transfer (United States)

    Guo, Fu-Quan; Yang, Jun; Zhang, Qi-Jin; Ming, Hai


    We report on a novel organic chromophore with symmetric twisted intramolecular charge transfer (TICT) state on excitation. The properties of nonlinear transmission induced by three-photon absorption (3 PA) are demonstrated pumped with nanosecond laser pulse. Large 3 PA cross sections as high as the order of 10-74 cm6s2 have been obtained for nanosecond and picosecond laser pulses at 1064 nm from intensity-dependent transmission measurements. Similar two emissive behaviours from one-photon and three-photon excited fluorescence spectra indicate that the linear and nonlinear fluorescences share the same TICT relaxation process from the excited states. The intensity dependence of upconversion fluorescence on the incident intensity obeys the cubic law that characterizes the three-photon absorption.

  20. Charge transfer state in DBP:C70 organic solar cells

    DEFF Research Database (Denmark)

    Sherafatipour, Golenaz; Benduhn, Johannes; Spoltore, Donato

    Organic solar cells (OSC) are green solar energy technology, which can be fabricated from organic compounds with cheep techniques and on flexible or transparent substrates such as plastic or glass. OSCs are cost efficient, and lightweight devices that can exhibit high power conversion efficiency...... of the CT states from which the maximum open circuit can be calculated and will set the base for modeling and optimizing the stability of the solar cells. 1. Cao, H. et al. Recent progress in degradation and stabilization of organic solar cells. J. Power Sources 264, 168–183 (2014). 2. Tvingstedt, K. et al....... Electroluminescence from charge transfer states in polymer solar cells. J. Am. Chem. Soc. 131, 11819–11824 (2009)....

  1. Sodium dodecyl benzene sulphonate mediated tautomerism of Eriochrome Black-T: Effect of charge transfer interaction (United States)

    Ghosh, Sumit


    Interaction between anionic surfactant, sodium dodecyl benzene sulphonate, (SDBS) and an anionic dye Eriochrome Black-T, (EBT) has been investigated by visible spectroscopy, conductometry, dynamic light scattering and zeta potential measurements. Spectral changes of EBT observed on addition of SDBS indicate formation of quinone-hydrazone tautomer at pH 7.0, whereas in absence of SDBS this change appears at pH ˜ 9.45. However, at pH 7.0 this change in tautomerism is not observed in presence of sodium dodecyl sulphate (SDS). Experimental results indicate presence of charge transfer interaction between less stable quinone-hydrazone tautomer of EBT and SDBS molecules, which is confirmed using Benesi-Hildebrand and Scott equations.

  2. Laser-induced charge transfer in the CH/sup 6 +/ quasimolecule

    Energy Technology Data Exchange (ETDEWEB)

    Errea, L.F.; Mendez, L.; Riera, A.


    The charge transfer cross section is calculated for C/sup 6 +/+CH(1s) collisions, through photon assisted 5gsigma--6hsigma, 5gsigma--4fsigma, 5gsigma--4f..pi.., and 5gsigma--4dsigma transitions. The theory developed by Copeland and Tang, and ourselves, is employed, and the validity of the approximations used is tested. The four processes considered have widely different characteristics with regards to the laser wavelength needed, the collision dynamics and the applicability of back-of-the-envelope estimates based on the Landau--Zener approximation. We point out the relevance of those processes to the impurity diagnostics of magnetically confined fusion plasmas and to the development of short wavelength lasers.

  3. Restoration of Conductivity with TTF-TCNQ Charge-Transfer Salts

    Energy Technology Data Exchange (ETDEWEB)

    Odom, Susan A.; Caruso, Mary M.; Finke, Aaron D.; Prokup, Alex M.; Ritchey, Joshua A.; Leonard, Francois; White, Scott R.; Sottos, Nancy R.; Moore, Jeffrey S.


    The formation of the conductive TTF-TCNQ (tetrathiafulvalene–tetracyanoquinodimethane) charge-transfer salt via rupture of microencapsulated solutions of its individual components is reported. Solutions of TTF and TCNQ in various solvents are separately incorporated into poly(urea-formaldehyde) core–shell microcapsules. Rupture of a mixture of TTF-containing microcapsules and TCNQ-containing microcapsules results in the formation of the crystalline salt, as verified by FTIR spectroscopy and powder X-ray diffraction. Preliminary measurements demonstrate the partial restoration of conductivity of severed gold electrodes in the presence of TTF-TCNQ derived in situ. This is the first microcapsule system for the restoration of conductivity in mechanically damaged electronic devices in which the repairing agent is not conductive until its release.

  4. Charge-Transfer within Zr-Based MOF: The Role of Polar Node. (United States)

    Van Wyk, Andrea; Smith, Tanner; Park, Jaehong; Deria, Pravas


    Metal-organic frameworks (MOFs) are emerging materials for electro- and photo- chemical applications, where understanding of underlying charge-transfer (CT) process will facilitate designing new materials. However, involvement of counter-ions in traditional electrochemical experiments complicates the probe on the role of various components during a CT event. A CT reaction between photo-excited MOF linker and a node-anchored ferrocene, within mesoporous framework NU-1000, was spectroscopically probed without the involvement of electrolyte based counter ions. Dielectric dependent CT kinetics indicate that the process involves a high reorganization energy that is required to polarize the node bound hydroxyl/aqua ligands. The findings have clear implication on the design of MOF-based electrocatalysis and photoelectrochemical devices.

  5. Manipulation of charge transfer and transport in plasmonic-ferroelectric hybrids for photoelectrochemical applications (United States)

    Wang, Zhijie; Cao, Dawei; Wen, Liaoyong; Xu, Rui; Obergfell, Manuel; Mi, Yan; Zhan, Zhibing; Nasori, Nasori; Demsar, Jure; Lei, Yong


    Utilizing plasmonic nanostructures for efficient and flexible conversion of solar energy into electricity or fuel presents a new paradigm in photovoltaics and photoelectrochemistry research. In a conventional photoelectrochemical cell, consisting of a plasmonic structure in contact with a semiconductor, the type of photoelectrochemical reaction is determined by the band bending at the semiconductor/electrolyte interface. The nature of the reaction is thus hard to tune. Here instead of using a semiconductor, we employed a ferroelectric material, Pb(Zr,Ti)O3 (PZT). By depositing gold nanoparticle arrays and PZT films on ITO substrates, and studying the photocurrent as well as the femtosecond transient absorbance in different configurations, we demonstrate an effective charge transfer between the nanoparticle array and PZT. Most importantly, we show that the photocurrent can be tuned by nearly an order of magnitude when changing the ferroelectric polarization in PZT, demonstrating a versatile and tunable system for energy harvesting.

  6. Charge transfer from and to manganese phthalocyanine: bulk materials and interfaces

    Directory of Open Access Journals (Sweden)

    Florian Rückerl


    Full Text Available Manganese phthalocyanine (MnPc is a member of the family of transition-metal phthalocyanines, which combines interesting electronic behavior in the fields of organic and molecular electronics with local magnetic moments. MnPc is characterized by hybrid states between the Mn 3d orbitals and the π orbitals of the ligand very close to the Fermi level. This causes particular physical properties, different from those of the other phthalocyanines, such as a rather small ionization potential, a small band gap and a large electron affinity. These can be exploited to prepare particular compounds and interfaces with appropriate partners, which are characterized by a charge transfer from or to MnPc. We summarize recent spectroscopic and theoretical results that have been achieved in this regard.

  7. Charge-transfer excited states in aqueous DNA: Insights from many-body Green's function theory. (United States)

    Yin, Huabing; Ma, Yuchen; Mu, Jinglin; Liu, Chengbu; Rohlfing, Michael


    Charge-transfer (CT) excited states play an important role in the excited-state dynamics of DNA in aqueous solution. However, there is still much controversy on their energies. By ab initio many-body Green's function theory, together with classical molecular dynamics simulations, we confirm the existence of CT states at the lower energy side of the optical absorption maximum in aqueous DNA as observed in experiments. We find that the hydration shell can exert strong effects (∼1  eV) on both the electronic structure and CT states of DNA molecules through dipole electric fields. In this case, the solvent cannot be simply regarded as a macroscopic screening medium as usual. The influence of base stacking and base pairing on the CT states is also discussed.

  8. Charge-transfer interaction mediated organogels from 18β-glycyrrhetinic acid appended pyrene

    Directory of Open Access Journals (Sweden)

    Jun Hu


    Full Text Available We describe herein the two-component charge-transfer (CT interaction induced organogel formation with 18β-glycyrrhetinic acid appended pyrene (GA-pyrene, 3 as the donor, and 2,4,7-trinitrofluorenone (TNF, 4 as the acceptor. The use of TNF (4 as a versatile electron acceptor in the formation of CT gels is demonstrated through the formation of gels in a variety of solvents. Thermal stability, stoichiometry, scanning electron microscopy (SEM, optical micrographs, and circular dichroism (CD are performed on these CT gels to investigate their thermal and assembly properties. UV–vis, fluorescence, mass spectrometric as well as variable-temperature 1H NMR experiments on these gels suggest that the CT interaction is one of the major driving forces for the formation of these organogels.

  9. Mutual Charge Transfer for Estimating Salinity Ratio for Offshore Icing Sensors

    Directory of Open Access Journals (Sweden)

    Umair N. Mughal


    Full Text Available For offshore measurements in Cold Regions, salinity of ice is also a critical parameter (together with many other parameters such as icing type, load, icing rate and melting rate to be identified in order to optimize the performance of anti/de icing systems. Although there are some available sensory solutions in the market to measure real time salinity levels of water, however there are still not many real time techniques or solutions to measure the salinity of ice. In this research task, mutual charge transfer technique is utilized to measure the zero crossover values of different samples of ice and water with varying salt ratios. An analytical relation between percentage salinity ratio of ice and zero crossover values is established. The aim of this paper is therefore a feasibility study to discuss the testing methodology and testing results.

  10. Mechanisms for charge-transfer processes at electrode/solid-electrolyte interfaces.

    Energy Technology Data Exchange (ETDEWEB)

    Chueh, William; El Gabaly Marquez, Farid; Whaley, Josh A.; McCarty, Kevin F.; McDaniel, Anthony H.; Farrow, Roger L.


    This report summarizes the accomplishments of a Laboratory-Directed Research and Development (LDRD) project focused on developing and applying new x-ray spectroscopies to understand and improve electric charge transfer in electrochemical devices. Our approach studies the device materials as they function at elevated temperature and in the presence of sufficient gas to generate meaningful currents through the device. We developed hardware and methods to allow x-ray photoelectron spectroscopy to be applied under these conditions. We then showed that the approach can measure the local electric potentials of the materials, identify the chemical nature of the electrochemical intermediate reaction species and determine the chemical state of the active materials. When performed simultaneous to traditional impedance-based analysis, the approach provides an unprecedented characterization of an operating electrochemical system.

  11. Implementation of Constrained DFT for Computing Charge Transfer Rates within the Projector Augmented Wave Method

    DEFF Research Database (Denmark)

    Melander, Marko; Jónsson, Elvar Örn; Mortensen, Jens Jørgen


    frozen-core electron description across the whole periodic table, with good transferability, as well as facilitate the extraction of all-electron quantities. The present implementation is applicable to two different wave function representations, atomic-centered basis sets (LCAO) and the finite...... of Marcus theory. Here, the combined method is applied to important test cases where practical implementations of DFT fail due to the self-interaction error, such as the dissociation of the helium dimer cation, and it is compared to other established cDFT codes. Moreover, for charge localization...... in a diamine cation, where it was recently shown that the commonly used generalized gradient and hybrid functionals of DFT failed to produce the localized state, cDFT produces qualitatively and quantitatively accurate results when benchmarked against self-interaction corrected DFT and high-level CCSD...

  12. Spectroscopic and thermodynamic study of charge transfer complexes of cloxacillin sodium in aqueous ethanol medium (United States)

    Roy, Dalim Kumar; Saha, Avijit; Mukherjee, Asok K.


    Cloxacillin sodium has been shown to form charge transfer (CT) complexes of 1:1 stoichiometry with a number of electron acceptors in 50% (v/v) aqueous ethanol medium. From the trends in the CT absorption bands, the vertical ionization potential of the drug molecule (cloxacillin sodium) has been estimated to be 7.89 eV. The enthalpies and entropies of formation of two such complexes have been determined by estimating the formation constants spectrophotometrically at five different temperatures. The oscillator strengths and transition dipole moments of these complexes have been determined. It has further been noted that the reduction of o-chloranil by aqueous ethanol is completely inhibited by cloxacillin sodium, a phenomenon that makes the present study of formation equilibrium possible.

  13. ZnO nanowires: Synthesis and charge transfer mechanism in the detection of ammonia vapour (United States)

    Nancy Anna Anasthasiya, A.; Ramya, S.; Rai, P. K.; Jeyaprakash, B. G.


    ZnO nanowires with hexagonal wurtzite structure were grown on the glass substrate using Successive Ionic Layer Adsorption and Reaction (SILAR) method. Both experimental and theoretical studies demonstrated that NH3 chemisorbed and transferred the charge to the surface of the nanowire via its nitrogen site to the zinc site of ZnO nanowires, leading to the detection of NH3 vapour. The adsorbed ammonia dissociated into NH2 and H due to steric repulsion, and then into N2 and H2 gas. The formation of the N2 gas during the desorption process confirmed by observing peak at 14 and 28 m/z in the GC-MS spectrum.

  14. Charge transfer in carbon composites based on fullerenes and exfoliated graphite (United States)

    Berezkin, V. I.


    Kinetic processes have been studied in composites based on fullerenes and exfoliated graphite at the initial proportions of components from 1: 16 to 16: 1 in mass. The samples are produced by heat treatment of initial dispersed mixtures in vacuum in the diffusion-adsorption process, their further cold pressing, and annealing. It is shown that the annealing almost does not influence the conduction mechanisms and only induces additional structural defects acting as electron traps. As a whole, the results obtained at the noted proportions of components make it possible to consider the material as a compensated metallic system with a structural disorder in which the charge transfer at temperatures from 4.2 K to room temperature is controlled by quantum interference phenomena. At low temperatures, the effect of a weak localization is observed, and the electron-electron interactions take place at medium and high temperatures.

  15. Correlation between the Open-Circuit Voltage and Charge Transfer State Energy in Organic Photovoltaic Cells. (United States)

    Zou, Yunlong; Holmes, Russell J


    In order to further improve the performance of organic photovoltaic cells (OPVs), it is essential to better understand the factors that limit the open-circuit voltage (VOC). Previous work has sought to correlate the value of VOC in donor-acceptor (D-A) OPVs to the interface energy level offset (EDA). In this work, measurements of electroluminescence are used to extract the charge transfer (CT) state energy for multiple small molecule D-A pairings. The CT state as measured from electroluminescence is found to show better correlation to the maximum VOC than EDA. The difference between EDA and the CT state energy is attributed to the Coulombic binding energy of the CT state. This correlation is demonstrated explicitly by inserting an insulating spacer layer between the donor and acceptor materials, reducing the binding energy of the CT state and increasing the measured VOC. These results demonstrate a direct correlation between maximum VOC and CT state energy.

  16. Dynamics of charge-transfer excited states relevant to photochemical energy conversion

    Energy Technology Data Exchange (ETDEWEB)

    Lim, E.C.


    A systematic study of intramolecular photoassociation and photoinduced charge transfer (CT) was initiated in bichromophoric systems of M-X-M, where two identical aromatic hydrocarbons M are joined by X=CH[sub 2], O, NH, etc. Dinaphthylamines, dinaphthylethers, and dinaphthylmethanes in nonpolar solvents form triplet excimers, following inter system crossing of singlets to the triplet manifold; in polar solvents, the molecule forms an intramolecular CT state. The interchromophore interaction study was extended to N-phenyl-2-naphthylamine. The lowest excited singlet states of the dinaphthylamines were studied by semiempirical quantum chemical methods. Exciplex formation was studied in excited states of jet-cooled van der Waals complexes, such as fluorene/substituted benzenes and 1-cyanonaphthalene-aliphatic amines.

  17. Charge transfer and magnetization of a MoS2 monolayer at the Co(0001)/MoS2 interface (United States)

    Garandel, T.; Arras, R.; Marie, X.; Renucci, P.; Calmels, L.


    The Co/MoS2 system may constitute a fundamental building block for future spintronic devices based on a single MoS2 transition metal dichalcogenide monolayer. Here, the hcp Co(0001)/MoS2 interface electronic structure as well as magnetic properties are investigated by first principles calculations based on the density functional theory. The charge transfer due to covalent bonding between S and Co atoms at the interface has been calculated for the lowest energy configuration obtained after optimization of the atomic coordinates. This charge transfer is different for majority and minority spin electrons, which induces a magnetization of the MoS2 layer bellow the Cobalt contact. The connection between the charge transfers at the interface and the modification of the magnetic properties is discussed.

  18. Spectroscopic study of the charge-transfer complexes TiCl4/styrene and TiCl4/polystyrene (United States)

    Gonçalves, Norberto S.; Noda, Lúcia. K.


    In this work, solutions of TiCl4/styrene and TiCl4/polystyrene charge-transfer complexes in CHCl3 or CDCl3 were investigated by UV-vis, resonance Raman and 1H NMR spectroscopies in order to study their molecular and electronic structures. Both show a yellow colour due to absorption in the 400 nm region, related to a charge-transfer transition. In Raman spectra, as the excitation approaches the resonance region, the primary enhancement of aromatic ring modes was mainly observed, rather than intensification of the vinylic double-bond stretch. Under the experimental conditions it was observed that formation of polystyrene takes place, as showed by 1H NMR spectra, and the most significant interaction occurs at the aromatic ring, as supported by the results from interaction of TiCl4 with polystyrene, as indicated by the charge-transfer band and resonant intensification of the aromatic ring modes.

  19. Radiation of a uniformly moving line charge in a zero-index metamaterial and other periodic media. (United States)

    Yanai, Avner; Levy, Uriel


    Radiation of electromagnetic waves by a uniformly moving charge is the subject of extensive research over the last several decades. Fascinating effects such as Vavilov-Cherenkov radiation, transition radiation and the Smith-Purcell effect were discovered and studied in depth. In this letter we study the radiation of a line charge moving with relativistic constant velocity within an average zero index metamaterial consisting of periodically alternating layers with negative and positive refractive index. We observe a strong radiation enhancement, ~3 orders of magnitude, for specific combinations of velocities and radiation frequencies. This surprising finding is attributed to a gigantic increase in the density of states at the positive/negative index boundary. Furthermore, we shed light on radiation effects of such a line charge propagating within the more "traditional" structure of periodically alternating layers consisting of positive and different refractive index with focus on frequencies satisfying the quarter wave stack and the half wave stack conditions. We show that the quarter-wave-stack case results in emission propagating vertically to the line charge trajectory, while the half-wave-stack results in negligible radiation. All these findings were obtained using a computationally efficient and conceptually intuitive computation method, based on eigenmode expansion of specific frequency components. For validation purposes this method was compared with the finite-difference-time-domain method.

  20. Analytical study for the charge-transfer complexes of losartan potassium

    Energy Technology Data Exchange (ETDEWEB)

    Darwish, Ibrahim A. [Department of Pharmaceutical Analytical Chemistry, Faculty of Pharmacy, Assiut University, Assiut 71526 (Egypt)]. E-mail:


    Studies were carried out, for the first time, to investigate the charge-transfer reactions of losartan potassium (LOS-K) as n-electron donor with the {sigma}-acceptor iodine and various {pi}-acceptors: 7,7,8,8-tetracyanoquinodimethane, 1,3,5-trinitrobenzene, 2,3-dichloro-5,6-dicyano-1,4-benzoquinone, p-chloranilic acid, tetracyanoethylene, 2,3,5,6-tetrabromo-1,4-benzoquinone, 2,3,5,6-tetrachloro-1,4-benzoquinone, and 2,4,7-trinitro-9-fluorenone. Different colored charge-transfer complexes and radical anions were obtained. Different variables affecting the reactions were studied and optimized. The formed complexes and the site of interaction were examined by UV-vis, IR, and {sup 1}H NMR techniques, and computational molecular modeling. The formation of the colored complexes were utilized in the development of simple, rapid and accurate spectrophotometric methods for the analysis of LOS-K in pure form as well as in its pharmaceutical tablets. Under the optimum reaction conditions, linear relationships with good correlation coefficients (0.9985-0.9998) were found between the absorbances and the concentrations of LOS-K in the range of 2-200 {mu}g ml{sup -1}. The limits of assays detection ranged from 0.61 to 19.65 {mu}g ml{sup -1}. No interference could be observed from the co-formulated hydrochlorothiazide (HCTZ), as well as from the additives commonly present in the tablets. The methods were successfully applied to the analysis of tablets from different manufacturers that contain LOS-K, alone or combined with HCTZ, with good accuracy and precision; the recovery percentages ranged from 98.96 {+-} 1.62% to 101.58 {+-} 1.29%. The results were compared favourably with the reported method.

  1. Space charge effect measurements for a multi-channel ionization chamber used for synchrotron radiation

    Energy Technology Data Exchange (ETDEWEB)

    Nasr, Amgad


    In vivo coronary angiography is one of the techniques used to investigate the heart diseases, by using catheter to inject a contrast medium of a given absorption coefficient into the heart vessels. Taking X-ray images produced by X-ray tube or synchrotron radiation for visualizing the blood in the coronary arteries. As the synchrotron radiation generated by the relativistic charged particle at the bending magnets, which emits high intensity photons in comparison with the X-ray tube. The intensity of the synchrotron radiation is varies with time. However for medical imaging it's necessary to measure the incoming intensity with the integrated time. The thesis work includes building a Multi-channel ionization chamber which can be filled with noble gases N{sub 2}, Ar and Xe with controlled inner pressure up to 30 bar. This affects the better absorption efficiency in measuring the high intensity synchrotron beam fluctuation. The detector is a part of the experimental setup used in the k-edge digital subtraction angiography project, which will be used for correcting the angiography images taken by another detector at the same time. The Multi-channel ionization chamber calibration characteristics are measured using 2 kW X-ray tube with molybdenum anode with characteristic energy of 17.44 keV. According to the fast drift velocity of the electrons relative to the positive ions, the electrons will be collected faster at the anode and will induce current signals, while the positive ions is still drifting towards the cathode. However the accumulation of the slow ions inside the detector disturbs the homogeneous applied electric field and leads to what is known a space charge effect. In this work the space charge effect is measured with very high synchrotron photons intensity from EDR beam line at BESSYII. The strong attenuation in the measured amplitude signal occurs when operating the chamber in the recombination region. A plateau is observed at the amplitude signal when

  2. Frequency dependent magneto-transport in charge transfer Co(II) complex

    Energy Technology Data Exchange (ETDEWEB)

    Shaw, Bikash Kumar; Saha, Shyamal K., E-mail:


    A charge transfer chelated system containing ferromagnetic metal centers is the ideal system to investigate the magneto-transport and magneto-dielectric effects due to the presence of both electronic as well as magnetic properties and their coupling. Magneto-transport properties in materials are usually studied through dc charge transport under magnetic field. As frequency dependent conductivity is an essential tool to understand the nature of carrier wave, its spatial extension and their mutual interaction, in the present work, we have investigated frequency dependent magneto-transport along with magnetization behavior in [Co{sub 2}(II)-(5-(4-PhMe)-1,3,4-oxadiazole-H{sup +}-2-thiolate){sub 5}](OAc){sub 4} metal complex to elucidate the nature of above quantities and their response under magnetic field in the transport property. We have used the existing model for ac conduction incorporating the field dependence to explain the frequency dependent magneto-transport. It is seen that the frequency dependent magneto-transport could be well explained using the existing model for ac conduction. -Highlights: • Chelated Co(II) complex is synthesized for magneto-transport applications. • Frequency dependent magneto-transport and magnetization behavior are studied. • Nature of carrier wave, its spatial extension is investigated under magnetic field. • Existing model for ac conduction is used with magnetic field dependence.

  3. Pseudocapacitive hausmannite nanoparticles with (101) facets: synthesis, characterization, and charge-transfer mechanism. (United States)

    Yeager, Matthew P; Du, Wenxin; Wang, Qi; Deskins, N Aaron; Sullivan, Matthew; Bishop, Brendan; Su, Dong; Xu, Wenqian; Senanayake, Sanjaya D; Si, Rui; Hanson, Jonathan; Teng, Xiaowei


    Hausmannite Mn3 O4 octahedral nanoparticles of 18.3 ± 7.0 nm with (101) facets have been prepared by an oxygen-mediated growth. The electrochemical properties of the Mn3 O4 particles as pseudocapacitive cathode materials were characterized both in half-cells and in button-cells. The Mn3 O4 nanoparticles exhibited a high mass-specific capacitance of 261 F g(-1), which was calculated from cyclic voltammetry analyses, and a capacitive retention of 78% after 10,000 galvanostatic charge-discharge cycles. The charge-transfer mechanisms of the Mn3 O4 nanoparticles were further studied by using synchrotron-based in situ X-ray absorption near edge spectroscopy and XRD. Both measurements showed concurrently that throughout the potential window of 0-1.2 V (vs. Ag/AgCl), a stable spinel structure of Mn3 O4 remained, and a reversible electrochemical conversion between tetrahedral [Mn(II) O4 ] and octahedral [Mn(III) O6 ] units accounted for the redox activity. Density functional theory calculations further corroborated this mechanism by confirming the enhanced redox stability afforded by the abundant and exposed (101) facets of Mn3 O4 octahedra. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. A charge transfer complex nematic liquid crystalline gel with high electrical conductivity (United States)

    Bhargavi, R.; Nair, Geetha G.; Krishna Prasad, S.; Majumdar, R.; Bag, Braja G.


    We describe the rheological, dielectric and elastic properties of a nematic liquid crystal gel created using an anthrylidene derivative of arjunolic acid, a chiral triterpenoid, obtained from the extracts of the wood of Terminalia arjuna. In this novel gel, having the electron-donor and acceptor components as minority constituents, the gelation and strengthening of charge-transfer complex (CTC) formation are seen to be occurring concomitantly. In addition to being mechanically strong with a large storage modulus, the gel with the maximized CTC exhibits Frank bend elastic constant values that approach nanonewton levels. The highlight of the study is the observation of 4-5 orders of magnitude increase in electrical conductivity for this gel, a value that is higher than even in the CT complexes of 2-d ordered columnar structures. A further important advantage of the present system over the columnar complex is that the high conductivity is seen for ac probing also, and owing to the nematic nature can be switched between its anisotropic limits. Some of these features are ascribed to a specific molecular packing architecture, which reduces the trapping of the charge carriers.

  5. A charge transfer complex nematic liquid crystalline gel with high electrical conductivity

    Energy Technology Data Exchange (ETDEWEB)

    Bhargavi, R.; Nair, Geetha G., E-mail:, E-mail:; Krishna Prasad, S., E-mail:, E-mail: [Centre for Nano and Soft Matter Sciences, Jalahalli, Bangalore 560013 (India); Majumdar, R.; Bag, Braja G. [Department of Chemistry and Chemical Technology, Vidyasagar University, Midnapore (W) 721 102 (India)


    We describe the rheological, dielectric and elastic properties of a nematic liquid crystal gel created using an anthrylidene derivative of arjunolic acid, a chiral triterpenoid, obtained from the extracts of the wood of Terminalia arjuna. In this novel gel, having the electron-donor and acceptor components as minority constituents, the gelation and strengthening of charge-transfer complex (CTC) formation are seen to be occurring concomitantly. In addition to being mechanically strong with a large storage modulus, the gel with the maximized CTC exhibits Frank bend elastic constant values that approach nanonewton levels. The highlight of the study is the observation of 4–5 orders of magnitude increase in electrical conductivity for this gel, a value that is higher than even in the CT complexes of 2-d ordered columnar structures. A further important advantage of the present system over the columnar complex is that the high conductivity is seen for ac probing also, and owing to the nematic nature can be switched between its anisotropic limits. Some of these features are ascribed to a specific molecular packing architecture, which reduces the trapping of the charge carriers.

  6. Engineering Interfacial Charge Transfer in CsPbBr3 Perovskite Nanocrystals by Heterovalent Doping

    KAUST Repository

    Begum, Raihana


    Since compelling device efficiencies of perovskite solar cells have been achieved, investigative efforts have turned to understand other key challenges in these systems, such as engineering interfacial energy-level alignment and charge transfer (CT). However, these types of studies on perovskite thin-film devices are impeded by the morphological and compositional heterogeneity of the films and their ill-defined surfaces. Here, we use well-defined ligand-protected perovskite nanocrystals (NCs) as model systems to elucidate the role of heterovalent doping on charge-carrier dynamics and energy level alignment at the interface of perovskite NCs with molecular acceptors. More specifically, we develop an in situ doping approach for colloidal CsPbBr3 perovskite NCs with heterovalent Bi3+ ions by hot injection to precisely tune their band structure and excited-state dynamics. This synthetic method allowed us to map the impact of doping on CT from the NCs to different molecular acceptors. Using time-resolved spectroscopy with broadband capability, we clearly demonstrate that CT at the interface of NCs can be tuned and promoted by metal ion doping. We found that doping increases the energy difference between states of the molecular acceptor and the donor moieties, subsequently facilitating the interfacial CT process. This work highlights the key variable components not only for promoting interfacial CT in perovskites, but also for establishing a higher degree of precision and control over the surface and the interface of perovskite molecular acceptors.

  7. IR spectroscopic investigation of charge transfer at interfaces of organic semiconductors (Conference Presentation) (United States)

    Beck, Sebastian; Hillebrandt, Sabina; Pucci, Annemarie


    In organic electronics, the interactions at interfaces between different organic and inorganic layers play a decisive role for device functionality and performance. Therefore, more detailed, quantitative studies of charge transfer (CT) at such interfaces are needed to improve the understanding of the underlying mechanisms. In this study we show that in-situ infrared spectroscopy can be used to investigate CT effects at organic/organic as well as inorganic/organic interfaces quantitatively. For different combinations of commonly used organic semiconductors such as 4,4´-bis(N-carbazolyl)-1,1´-biphenyl (CBP) or fluorinated zinc phthalocyanine (F4ZnPc) and inorganic contact materials such as molybdenum oxide (MoO3) or indium tin oxide (ITO) the CT at the interface was investigated using in-situ IR spectroscopy. The measurements were carried out under UHV conditions during film growth what enables a careful study of the influence of different parameters such as substrate temperature and layer thickness in a controlled way even on a nanometer scale. When the organic molecules are deposited onto the underlying layer charged and non-charged species form which can be identified and quantitatively analyzed in the IR spectra. It was also found that the deposition sequence can strongly influence the interface properties what might have strong implications on the layer stack design. For example, when MoO3 is deposited onto CBP, the CBP layer is strongly doped, due to diffusion of the deposited transition metal oxide clusters into the organic layer. Financial support by BMBF (project INTERPHASE) is gratefully acknowledged.

  8. A how-to approach for a 3D simulation of charge transfer characteristics in a gas electron multiplier (GEM)

    CERN Document Server

    Sharma, A


    In this paper a detailed description of how to simulate charge transfer processes in a gaseous device is presented, taking the gas electron multiplier (GEM) as an example. A 3-dimensional simulation of the electric field and avalanche is performed. Results on charge transport are compared to experiment and agree within experimental errors; the avalanche mechanism and positive ion feedback are studied. The procedures used in the simulation are described in detail, and program scripts are appended. (15 refs).

  9. Engineering interfacial photo-induced charge transfer based on nanobamboo array architecture for efficient solar-to-chemical energy conversion. (United States)

    Wang, Xiaotian; Liow, Chihao; Bisht, Ankit; Liu, Xinfeng; Sum, Tze Chien; Chen, Xiaodong; Li, Shuzhou


    Engineering interfacial photo-induced charge transfer for highly synergistic photocatalysis is successfully realized based on nanobamboo array architecture. Programmable assemblies of various components and heterogeneous interfaces, and, in turn, engineering of the energy band structure along the charge transport pathways, play a critical role in generating excellent synergistic effects of multiple components for promoting photocatalytic efficiency. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. Assignment of the Charge-Transfer Excited States of Bis(N-Heterocyclic) Complexes of Copper(I) (United States)


    Excited States of Bis (N-Heterocyclic) Complexes of Copper ( I) 12 PERSONAL AUTHOR(S( W. L. Parker and G. A. Crosby 3a 7YPE OF REPORT i b ’!ME COVERED ~ aDATE...Assignment of the Charge-Transfer Excited States of Bis (N-Heterocyclic) Complexes of Copper (I) by W. L. Parker and G. A. Crosby Prepared for Publication in...IHmited. Assignment of the Charge-Transfer Excited States of Bis (N-Heterocycl ic) Complexes of Copper (I) W. L. Parker and G. A. Crosby* Chemical

  11. Change of electric dipole moment in charge transfer transitions of ferrocene oligomers studied by ultrafast two-photon absorption (United States)

    Mikhaylov, Alexander; Arias, Eduardo; Moggio, Ivana; Ziolo, Ronald; Uudsemaa, Merle; Trummal, Aleksander; Cooper, Thomas; Rebane, Aleksander


    Change of permanent electric dipole moment in the lower-energy charge transfer transitions for a series of symmetrical and non-symmetrical ferrocene-phenyleneethynylene oligomers were studied by measuring the corresponding femtosecond two-photon absorption cross section spectra, and were determined to be in the range Δμ = 3 - 10 D. Quantum-chemical calculations of Δμ for the non-symmetrical oligomers show good quantitative agreement with the experimental results, thus validating two-photon absorption spectroscopy as a viable experimental approach to study electrostatic properties of organometallics and other charge transfer systems.

  12. Secondary radiation measurements for particle therapy applications: charged particles produced by 4He and 12C ion beams in a PMMA target at large angle. (United States)

    Rucinski, Antoni; Battistoni, Giuseppe; Collamati, Francesco; De Lucia, Erika; Faccini, Riccardo; Frallicciardi, Paola Maria; Mancini-Terracciano, Carlo; Marafini, Michela; Mattei, Ilaria; Muraro, Silvia; Paramatti, Riccardo; Piersanti, Luca; Pinci, Davide; Russomando, Andrea; Sarti, Alessio; Sciubba, Adalberto; Solfaroli Camillocci, Elena; Toppi, Marco; Traini, Giacomo; Voena, Cecilia; Patera, Vincenzo


    Proton and Carbon ion beams are used in the clinical practice for external radiotherapy treatments achieving, for selected indications, promising and superior clinical results with respect to X-ray based radiotherapy. Other ions, like 4He are recently being considered as projectiles in particle therapy centres and might represent a good compromise between the linear energy transfer and the radiobiological effectiveness of 12C ion and proton beams allowing improved tumour control probability and minimising normal tissue complication probability. All the currently used p, 4He and 12C ion beams allow to achieve sharp dose gradients on the boundary of the target volume, however the accurate dose delivery is more sensitive to the patient positioning and to anatomical variations with respect to photon therapy. This requires beam range and/or dose release measurement during patient irradiation and therefore the development of dedicated monitoring techniques. All the proposed methods make use of the secondary radiation created by the beam interaction with the patient and, in particular, in case of 12C ion beams are able to exploits also the significant charged radiation component. Measurements performed to characterise the charged secondary radiation created by 12C and 4He particle therapy beams are reported. Charged secondary yields, energy spectra and emission profiles produced in poly-methyl methacrylate (PMMA) target by 4He and 12C beams of different therapeutic energies were measured at 60° and 90° with respect to the primary beam direction. The secondary yield of protons produced along the primary beam path in PMMA target was obtained. The energy spectra of charged secondaries were obtained from time-of-flight information, whereas the emission profiles were reconstructed exploiting tracking detector information. Obtained measurements are in agreement with results reported in literature and suggests the feasibility of range monitoring based on charged secondary

  13. Electronic hole transfer in rutile and anatase TiO2: Effect of a delocalization error in the density functional theory on the charge transfer barrier height

    DEFF Research Database (Denmark)

    Zawadzki, Pawel; Rossmeisl, Jan; Jacobsen, Karsten Wedel


    where charge localization is strongly coupled to lattice distortion. As an example we calculate the adiabatic PES for the hole transfer process in rutile and anatase TiO2. (Semi) local DFT leads to qualitatively wrong, barrierless curves. Removal of the nonlinearity improves the PES shape and allows us...

  14. Ultrafast Charge Transfer in Nickel Phthalocyanine Probed by Femtosecond Raman-Induced Kerr Effect Spectroscopy (United States)


    The recently developed technique of femtosecond stimulated Raman spectroscopy, and its variant, femtosecond Raman-induced Kerr effect spectroscopy (FRIKES), offer access to ultrafast excited-state dynamics via structurally specific vibrational spectra. We have used FRIKES to study the photoexcitation dynamics of nickel(II) phthalocyanine with eight butoxy substituents, NiPc(OBu)8. NiPc(OBu)8 is reported to have a relatively long-lived ligand-to-metal charge-transfer (LMCT) state, an essential characteristic for efficient electron transfer in photocatalysis. Following photoexcitation, vibrational transitions in the FRIKES spectra, assignable to phthalocyanine ring modes, evolve on the femtosecond to picosecond time scales. Correlation of ring core size with the frequency of the ν10 (asymmetric C–N stretching) mode confirms the identity of the LMCT state, which has a ∼500 ps lifetime, as well as that of a precursor d-d excited state. An even earlier (∼0.2 ps) transient is observed and tentatively assigned to a higher-lying Jahn–Teller-active LMCT state. This study illustrates the power of FRIKES spectroscopy in elucidating ultrafast molecular dynamics. PMID:24841906

  15. Thickness dependent charge transfer states and dark carriers density in vacuum deposited small molecule organic photocell (United States)

    Shekhar, Himanshu; Tzabari, Lior; Solomeshch, Olga; Tessler, Nir


    We have investigated the influence of the active layer thickness on the balance of the internal mechanisms affecting the efficiency of copper phthalocyanine - fullerene (C60) based vacuum deposited bulk heterojunction organic photocell. We fabricated a range of devices for which we varied the thickness of the active layer from 40 to 120 nm and assessed their performance using optical and electrical characterization techniques. As reported previously for phthalocyanine:C60, the performance of the device is highly dependent on the active layer thickness and of all the thicknesses we tried, the 40 nm thin active layer device showed the best solar cell characteristic parameters. Using the transfer matrix based optical model, which includes interference effects, we calculated the optical power absorbed in the active layers for the entire absorption band, and we found that this cannot explain the trend with thickness. Measurement of the cell quantum efficiency as a function of light intensity showed that the relative weight of the device internal processes changes when going from 40 nm to 120 nm thick active layer. Electrical modeling of the device, which takes different internal processes into account, allowed to quantify the changes in the processes affecting the generation - recombination balance. Sub gap external quantum efficiency and morphological analysis of the surface of the films agree with the model's result. We found that as the thickness grows the density of charge transfer states and of dark carriers goes up and the uniformity in the vertical direction is reduced.

  16. Correlation between charge transfer and exchange coupling in carbon-based magnetic materials

    Energy Technology Data Exchange (ETDEWEB)

    Nguyen, Anh Tuan, E-mail: [Faculty of Physics, VNU University of Science, 334 Nguyen Trai, Thanh Xuan, Ha Noi (Viet Nam); Science and Technology Department, Vietnam National University, Hanoi, 144 Xuan Thuy, Cau Giay, Hanoi (Viet Nam); Japan Advanced Institute of Science and Technology, 1-1, Asahidai, Nomi, Ishikawa, 923-1292 Japan (Japan); Nguyen, Van Thanh; Nguyen, Huy Sinh [Faculty of Physics, VNU University of Science, 334 Nguyen Trai, Thanh Xuan, Ha Noi (Viet Nam); Pham, Thi Tuan Anh [Faculty of Physics, VNU University of Science, 334 Nguyen Trai, Thanh Xuan, Ha Noi (Viet Nam); Faculty of Science, College of Hai Duong, Nguyen Thi Due, Hai Duong (Viet Nam); Do, Viet Thang [Faculty of Physics, VNU University of Science, 334 Nguyen Trai, Thanh Xuan, Ha Noi (Viet Nam); Faculty of Science, Haiphong University, 171 Phan Dang Luu, Kien An, Hai Phong (Viet Nam); Dam, Hieu Chi [Japan Advanced Institute of Science and Technology, 1-1, Asahidai, Nomi, Ishikawa, 923-1292 Japan (Japan)


    Several forms of carbon-based magnetic materials, i.e. single radicals, radical dimers, and alternating stacks of radicals and diamagnetic molecules, have been investigated using density-functional theory with dispersion correction and full geometry optimization. Our calculated results demonstrate that the C{sub 31}H{sub 15} (R{sub 4}) radical has a spin of ½. However, in its [R{sub 4}]{sub 2} dimer structure, the net spin becomes zero due to antiferromagnetic spin-exchange between radicals. To avoid antiferromagnetic spin-exchange of identical face-to-face radicals, eight alternating stacks, R{sub 4}/D{sub 2m}/R{sub 4} (with m = 3-10), were designed. Our calculated results show that charge transfer (Δn) between R{sub 4} radicals and the diamagnetic molecule D{sub 2m} occurs with a mechanism of spin exchange (J) in stacks. The more electrons that transfer from R{sub 4} to D{sub 2m}, the stronger the ferromagnetic spin-exchange in stacks. In addition, our calculated results show that Δn can be tailored by adjusting the electron affinity (E{sub a}) of D{sub 2m}. The correlation between Δn, E{sub a}, m, and J is discussed. These results give some hints for the design of new ferromagnetic carbon-based materials.

  17. Correlation between charge transfer and exchange coupling in carbon-based magnetic materials

    Directory of Open Access Journals (Sweden)

    Anh Tuan Nguyen


    Full Text Available Several forms of carbon-based magnetic materials, i.e. single radicals, radical dimers, and alternating stacks of radicals and diamagnetic molecules, have been investigated using density-functional theory with dispersion correction and full geometry optimization. Our calculated results demonstrate that the C31H15 (R4 radical has a spin of ½. However, in its [R4]2 dimer structure, the net spin becomes zero due to antiferromagnetic spin-exchange between radicals. To avoid antiferromagnetic spin-exchange of identical face-to-face radicals, eight alternating stacks, R4/D2m/R4 (with m = 3-10, were designed. Our calculated results show that charge transfer (Δn between R4 radicals and the diamagnetic molecule D2m occurs with a mechanism of spin exchange (J in stacks. The more electrons that transfer from R4 to D2m, the stronger the ferromagnetic spin-exchange in stacks. In addition, our calculated results show that Δn can be tailored by adjusting the electron affinity (Ea of D2m. The correlation between Δn, Ea, m, and J is discussed. These results give some hints for the design of new ferromagnetic carbon-based materials.

  18. Characterization and Modeling of Received Signal Strength and Charging Time for Wireless Energy Transfer

    Directory of Open Access Journals (Sweden)

    Uthman Baroudi


    Full Text Available Wireless sensor networks can provide effective means for monitoring and controlling a wide range of applications. Recently, tremendous effort was directed towards devising sensors powered from ambient sources such as heat, wind, and vibration. Wireless energy transfer is another source that has attractive features that make it a promising candidate for supplying power to wireless sensor nodes. This paper is concerned with characterizing and modeling the charging time and received signal strength indicator for wireless energy transfer system. These parameters play a vital role in deciding the geometry of sensor network and the routing protocols to be deployed. The development of communication protocols for wireless-powered wireless sensor networks is also improved with the knowledge of such models. These two quantities were computed from data acquired at various coordinates of the harvester relative to a fixed position of RF energy source. Data was acquired for indoor and outdoor scenarios using the commercially available PowerCast energy harvester and evaluation board. Mathematical models for both indoor and outdoor environments were developed and analyzed. A few guidelines on how to use these models were suggested. Finally, the possibility of harvesting the energy from the ambient RF power to energize wireless sensor nodes was also investigated.

  19. Cooperative coupling of the Li cation and groups to amplify the charge transfer between C60 and corannulene (United States)

    Sun, Gang; Xu, Jing; Chen, Zhi-Yuan; Lei, E.; Liu, Xiang-Shuai; Liu, Chun-Guang


    In present work, four complexes have been designed to investigate the effect of Li+ cation and substituent on the geometric structures and a series of electronic properties using density functional theory. The calculated results indicate that the charge decomposition (CDA) analysis and extend charge decomposition analysis (ECDA) of four complexes have the same sequence. The average d values defined the distances between C60 and corannulene display the inverse sequence. Consequently, the cooperative coupling of the Li+ cation and appropriate substituent is predicted to be an effective way to enhance the charge transfer between the C60 and corannulene derivatives.

  20. Comment on ‘Poynting flux in the neighbourhood of a point charge in arbitrary motion and radiative power losses’ (United States)

    Rowland, David R.


    Based on a calculation of the Poynting vector flux in the neighbourhood of an accelerating point charge, Singal (2016 Eur. J. Phys. 37 045210) has claimed that the instantaneous rate of energy radiated by the charge differs from the Larmor formula. It is argued in this comment that Singal’s proposed formula for the radiated power is physically untenable because it predicts a negative rate of energy loss in physically realisable situations. The cause of Singal’s erroneous conclusion is identified as being a failure to realise that the bound electromagnetic field energy of an accelerating charge differs by the Schott energy from the bound field energy of a charge moving at a constant velocity equal to the current velocity of the accelerating charge. References to the salient literature are provided.

  1. On the interfacial charge transfer between solid and liquid Li(+) electrolytes. (United States)

    Schleutker, Marco; Bahner, Jochen; Tsai, Chih-Long; Stolten, Detlef; Korte, Carsten


    The Li(+) ion transfer between a solid and a liquid Li(+) electrolyte has been investigated by DC polarisation techniques. The current density i is measured as a function of the electrochemical potential drop Δ[small mu, Greek, tilde]Li(+) at the interface, using a liquid electrolyte with different Li(+) concentrations. The subject of this experimental study is the interface between the solid electrolyte Ta-substituted lithium lanthanum zirconate (Li6.6La3Zr1.6Ta0.4O12) and a liquid electrolyte consisting of LiPF6 dissolved in ethylene carbonate/dimethyl carbonate (1 : 1). The functional course of i vs. Δ[small mu, Greek, tilde]Li(+) can be described by a serial connection between a constant ohmic resistance Rslei and a current dependent thermally activated ion transfer process. For the present solid-liquid electrolyte interface the areal resistance Rslei of the surface layer is independent of the Li(+) concentration in the liquid electrolyte. At room temperature a value of about 300 Ω cm(2) is found. The constant ohmic resistance Rslei can be attributed to a surface layer on the solid electrolyte with a (relatively) low conductivity (solid-liquid electrolyte interphase). The low conducting surface layer is formed by degradation reactions with the liquid electrolyte. Rslei is considerably increased if a small amount (ppm) of water is added to the liquid electrolyte. The thermally activated ionic transfer process obeys a Butler-Volmer like behaviour, resulting in an exchange current density i0 depending on the Li(+) concentration in the liquid electrolyte by a power-law. At a Li(+) concentration of 1 mol l(-1) a value of 53.1 μA cm(-2) is found. A charge transfer coefficient α of ∼0.44 is measured. The finding of a superposed constant ohmic resistance due to a solid-liquid electrolyte interphase and a current dependent thermally activated ion transfer process is confirmed by the results of two former experimental studies from the literature, performing AC

  2. Radiative transfer modeling through terrestrial atmosphere and ocean accounting for inelastic processes: Software package SCIATRAN (United States)

    Rozanov, V. V.; Dinter, T.; Rozanov, A. V.; Wolanin, A.; Bracher, A.; Burrows, J. P.


    SCIATRAN is a comprehensive software package which is designed to model radiative transfer processes in the terrestrial atmosphere and ocean in the spectral range from the ultraviolet to the thermal infrared (0.18-40 μm). It accounts for multiple scattering processes, polarization, thermal emission and ocean-atmosphere coupling. The main goal of this paper is to present a recently developed version of SCIATRAN which takes into account accurately inelastic radiative processes in both the atmosphere and the ocean. In the scalar version of the coupled ocean-atmosphere radiative transfer solver presented by Rozanov et al. [61] we have implemented the simulation of the rotational Raman scattering, vibrational Raman scattering, chlorophyll and colored dissolved organic matter fluorescence. In this paper we discuss and explain the numerical methods used in SCIATRAN to solve the scalar radiative transfer equation including trans-spectral processes, and demonstrate how some selected radiative transfer problems are solved using the SCIATRAN package. In addition we present selected comparisons of SCIATRAN simulations with those published benchmark results, independent radiative transfer models, and various measurements from satellite, ground-based, and ship-borne instruments. The extended SCIATRAN software package along with a detailed User's Guide is made available for scientists and students, who are undertaking their own research typically at universities, via the web page of the Institute of Environmental Physics (IUP), University of Bremen:

  3. Monte Carlo simulation of radiative heat transfer in coarse fibrous media

    Energy Technology Data Exchange (ETDEWEB)

    Nisipeanu, E.; Jones, P.D.


    Radiative transfer through a medium made up of a multitude of randomly oriented opaque cylindrical fibers is examined using Monte Carlo simulation of multiple surface radiative exchange for energy bundles interacting with each fiber in their path. The method is termed Monte Carlo Discontinuous Medium (MCDM). As compared to radiative continuum methods, the present approach does not require specification of extinction coefficient, scattering albedo, or scattering phase function. Instead, only volume fraction, fiber diameter, and fiber material complex index of refraction are required as parameters. Although the MCDM method is only strictly valid for the geometric limit, comparison with previous experiments on the edge of this limit (5 {lt} x {lt} 11) is qualitatively good. For the low (solid) volume fractions considered here, comparison is excellent between MCDM results and radiative continuum results, the later being solved by both Monte Carlo simulation and by exact integral solution of the Radiative Transfer Equation (RTE). MCDM results show a sensitivity to directional bias of the fibers in the medium, suggesting that bias parameters are necessary to solve radiative transfer in media with non-random fiber orientations. MCDM results for fibrous media are very similar to those for spherical suspensions at the same volume fraction and scatterer diameter, suggesting that the precise shape of a scattering particle may be relatively less important for radiation heat transfer through randomly oriented solid matrix materials.

  4. Theory of chemical kinetics and charge transfer based on nonequilibrium thermodynamics. (United States)

    Bazant, Martin Z


    Advances in the fields of catalysis and electrochemical energy conversion often involve nanoparticles, which can have kinetics surprisingly different from the bulk material. Classical theories of chemical kinetics assume independent reactions in dilute solutions, whose rates are determined by mean concentrations. In condensed matter, strong interactions alter chemical activities and create variations that can dramatically affect the reaction rate. The extreme case is that of a reaction coupled to a phase transformation, whose kinetics must depend not only on the order parameter but also on its gradients at phase boundaries. Reaction-driven phase transformations are common in electrochemistry, when charge transfer is accompanied by ion intercalation or deposition in a solid phase. Examples abound in Li-ion, metal-air, and lead-acid batteries, as well as metal electrodeposition-dissolution. Despite complex thermodynamics, however, the standard kinetic model is the Butler-Volmer equation, based on a dilute solution approximation. The Marcus theory of charge transfer likewise considers isolated reactants and neglects elastic stress, configurational entropy, and other nonidealities in condensed phases. The limitations of existing theories recently became apparent for the Li-ion battery material LixFePO4 (LFP). It has a strong tendency to separate into Li-rich and Li-poor solid phases, which scientists believe limits its performance. Chemists first modeled phase separation in LFP as an isotropic "shrinking core" within each particle, but experiments later revealed striped phase boundaries on the active crystal facet. This raised the question: What is the reaction rate at a surface undergoing a phase transformation? Meanwhile, dramatic rate enhancement was attained with LFP nanoparticles, and classical battery models could not predict the roles of phase separation and surface modification. In this Account, I present a general theory of chemical kinetics, developed over

  5. Impact of exact exchange in the description of the electronic structure of organic charge-transfer molecular crystals

    KAUST Repository

    Fonari, Alexandr


    We evaluate the impact that the amount of nonlocal Hartree-Fock (%HF) exchange included in a hybrid density functional has on the microscopic parameters (transfer integrals, band gaps, bandwidths, and effective masses) describing charge transport in high-mobility organic crystals. We consider both crystals based on a single molecule, such as pentacene, and crystals based on mixed-stack charge-transfer systems, such as dibenzo-TTF–TCNQ. In the pentacene crystal, the band gap decreases and the effective masses increase linearly with an increase in the amount of %HF exchange. In contrast, in the charge-transfer crystals, while the band gap increases linearly, the effective masses vary only slightly with an increase in %HF exchange. We show that the superexchange nature of the electronic couplings in charge-transfer systems is responsible for this peculiar evolution of the effective masses. We compare the density functional theory results with results obtained within the G0W0 approximation as a way of benchmarking the optimal amount of %HF exchange needed in a given functional.

  6. Coherence, energy and charge transfers in de-excitation pathways of electronic excited state of biomolecules in photosynthesis

    DEFF Research Database (Denmark)

    Bohr, Henrik; Malik, F. Bary


    The observed multiple de-excitation pathways of photo-absorbed electronic excited state in the peridinin–chlorophyll complex, involving both energy and charge transfers among its constituents, are analyzed using the bio-Auger (B-A) theory. It is also shown that the usually used F¨orster–Dexter th...

  7. Numerical test of an inverse polarized radiative transfer algorithm

    CERN Document Server

    Viik, T


    A procedure is tested with which to determine the single-scattering albedo from polarization measurements of the angle-dependent intensity at two locations within, or on the boundaries of, a homogeneous finite or infinite atmosphere that scatters radiation according to the Rayleigh law with true absorption.

  8. CoPc and CoPcF16 on gold: Site-specific charge-transfer processes

    Directory of Open Access Journals (Sweden)

    Fotini Petraki


    Full Text Available Interface properties of cobalt(II phthalocyanine (CoPc and cobalt(II hexadecafluoro-phthalocyanine (CoPcF16 to gold are investigated by photo-excited electron spectroscopies (X-ray photoemission spectroscopy (XPS, ultraviolet photoemission spectroscopy (UPS and X-ray excited Auger electron spectroscopy (XAES. It is shown that a bidirectional charge transfer determines the interface energetics for CoPc and CoPcF16 on Au. Combined XPS and XAES measurements allow for the separation of chemical shifts based on different local charges at the considered atom caused by polarization effects. This facilitates a detailed discussion of energetic shifts of core level spectra. The data allow the discussion of site-specific charge-transfer processes.

  9. Enhanced Bulk and Interfacial Charge Transfer Dynamics for Efficient Photoelectrochemical Water Splitting: The Case of Hematite Nanorod Arrays. (United States)

    Wang, Jian; Feng, Bo; Su, Jinzhan; Guo, Liejin


    Charge transport in the bulk and across the semiconductor/electrolyte interface is one of the major issues that limits photoelectrochemical (PEC) performance in hematite photoelectrodes. Efficient charge transport in the entire hematite is of great importance to obtaining high photoelectrochemical properties. Herein, to reach this goal, we employed both TiO2 underlayer and overlayer deposition on hematite nanorod films, followed by a fast annealing treatment. The TiO2 underlayer and overlayer not only serve as dopant sources for carrier density increase but also reduce charge recombination at the fluorine-doped tin oxide (FTO)/hematite interface and accelerate charge transfer across the hematite/electrolyte interface. This synergistic doping and interface modifying effects give rise to an enhanced photoelectrochemical water oxidation performance of hematite nanorod arrays, generating an impressive photocurrent density of 1.49 mA cm(-2) at 1.23 V vs RHE. This is the first report on using both underlayer and overlayer modification with the same material to improve charge transport through the entire electron transport path in hematite, which provides a novel way to manipulate charge transfer across the semiconductor interface for a high-performance photoelectrode.

  10. Near-field radiative heat transfer in graphene plasmonic nanodisk dimers (United States)

    Ramirez, Francisco V.; Shen, Sheng; McGaughey, Alan J. H.


    Near-field thermal radiation mediated by surface plasmons in parallel graphene nanodisk dimers is studied using a semianalytical model under the electrostatic approximation. The radiative heat transfer between two disks as a function of the distance between them in coaxial and coplanar configurations is first considered. Three regimes are identified and their extents determined using nondimensional analysis. When the edge-to-edge separation is smaller than the disk diameter, near-field coupling and surface plasmon hybridization lead to an enhancement of the radiative heat transfer by up to four orders of magnitude compared to the Planck blackbody limit. A mismatch in the disk diameters affects the plasmonic mode hybridization and can either diminish or enhance the near-field radiation. Destructive interference between eigenmodes that emerge when the relative orientation between disks is varied can induce a twofold reduction in the radiative heat transfer. In all configurations, the radiative heat transfer properties can be controlled by tuning the disk size/orientation, the substrate optical properties, and graphene's doping concentration and electron mobility.

  11. Free Thyroid Transfer: A Novel Procedure to Prevent Radiation-induced Hypothyroidism

    Energy Technology Data Exchange (ETDEWEB)

    Harris, Jeffrey [Division of Otolaryngology-Head and Neck Surgery, Department of Surgery, University of Alberta, Edmonton, Alberta (Canada); Almarzouki, Hani [Division of Otolaryngology-Head and Neck Surgery, Department of Surgery, University of Alberta, Edmonton, Alberta (Canada); Department of Otolaryngology-Head and Neck Surgery, King Abdulaziz University, Jeddah (Saudi Arabia); Barber, Brittany, E-mail: [Division of Otolaryngology-Head and Neck Surgery, Department of Surgery, University of Alberta, Edmonton, Alberta (Canada); Scrimger, Rufus [Division of Radiation Oncology, Department of Oncology, University of Alberta, Edmonton, Alberta (Canada); Romney, Jacques [Division of Endocrinology and Metabolism, Department of Medicine, University of Alberta, Edmonton, Alberta (Canada); O' Connell, Daniel [Division of Otolaryngology-Head and Neck Surgery, Department of Surgery, University of Alberta, Edmonton, Alberta (Canada); Urken, Mark [Institute for Head and Neck and Thyroid Cancers, Icahn School of Medicine, Mount Sinai Hospital, New York, New York (United States); Seikaly, Hadi [Division of Otolaryngology-Head and Neck Surgery, Department of Surgery, University of Alberta, Edmonton, Alberta (Canada)


    Purpose: The incidence of hypothyroidism after radiation therapy for head and neck cancer (HNC) has been found to be ≤53%. Medical treatment of hypothyroidism can be costly and difficult to titrate. The aim of the present study was to assess the feasibility of free thyroid transfer as a strategy for the prevention of radiation-induced damage to the thyroid gland during radiation therapy for HNC. Methods and Materials: A prospective feasibility study was performed involving 10 patients with a new diagnosis of advanced HNC undergoing ablative surgery, radial forearm free-tissue transfer reconstruction, and postoperative adjuvant radiation therapy. During the neck dissection, hemithyroid dissection was completed with preservation of the thyroid arterial and venous supply for implantation into the donor forearm site. All patients underwent a diagnostic thyroid technetium scan 6 weeks and 12 months postoperatively to examine the functional integrity of the transferred thyroid tissue. Results: Free thyroid transfer was executed in 9 of the 10 recruited patients with advanced HNC. The postoperative technetium scans demonstrated strong uptake of technetium at the forearm donor site at 6 weeks and 12 months for all 9 of the transplanted patients. Conclusions: The thyroid gland can be transferred as a microvascular free transfer with maintenance of function. This technique could represent a novel strategy for maintenance of thyroid function after head and neck irradiation.

  12. Alterations of CNS structure & function by charged particle radiation & resultant oxidative stress (United States)

    Nelson, Gregory; Chang, Polly; Favre, Cecile; Fike, John; Komarova, Natalia; Limoli, Charles; Mao, Xiao-Wen; Obenaus, Andre; Raber, Jacob; Spigelman, Igor; Soltesz, Ivan; Song, Sheng-Kwei; Stampanoni, Marco; Vlkolinsky, Roman; Wodarz, Dominik

    The NSCOR program project is transitioning from establishing the existence of CNS responses to low doses of charged particles, to an investigation of mechanisms underlying these changes and extending the irradiation paradigm to more space-like exposures. In earlier experiments we examined radiation responses of the mouse brain (hippocampus) following exposure to 250 MeV protons and 600 MeV/n iron ions. Our key findings on structural changes were: 1) Significant dose and time dependent loss of en-dothelial cells and microvessel network remodeling occurs suggesting that vascular insufficiency is produced. 2) Significant dose dependent losses of neural precursor cells were observed in a lineage specific pattern which may be associated with cognitive impairment. 3) Evaluation of DNA damage showed dose and time dependent accumulation of mutations with region-specific mutation structures and gene expression profiling demonstrated activation of neurotrophic and adhesion factors as well as chemokine receptors associated with inflammation. Our key find-ings on functional changes were: 1) Time and dose dependent modifications to neural output expressed as enhanced excitability but reduced synaptic efficacy and plasticity (including long term potentiation). 2) Intrinsic membrane properties of neurons were not significantly modi-fied by radiation exposure but pharmacological treatments demonstrated changes in inhibitory synapses. 3) MRI imaging visualized brain structural changes based on altered water diffu-sion properties and patterns were consistent with demyelination or gliosis. Our key findings on neurodegeneration and fidelity of homeostasis were: 1) APP23 transgenic mice exhibited accelerated APP-type electrophysiological pathology over several months. 2) Microvessel net-work changes following irradiation were suggestive of poor tissue oxygenation. 3) The ability of the brain to respond a controlled septic shock was altered by irradiation; the septic shock reactions

  13. Direct in Situ Measurement of Charge Transfer Processes During Photoelectrochemical Water Oxidation on Catalyzed Hematite. (United States)

    Qiu, Jingjing; Hajibabaei, Hamed; Nellist, Michael R; Laskowski, Forrest A L; Hamann, Thomas W; Boettcher, Shannon W


    Electrocatalysts improve the efficiency of light-absorbing semiconductor photoanodes driving the oxygen evolution reaction, but the precise function(s) of the electrocatalysts remains unclear. We directly measure, for the first time, the interface carrier transport properties of a prototypical visible-light-absorbing semiconductor, α-Fe2O3, in contact with one of the fastest known water oxidation catalysts, Ni0.8Fe0.2O x , by directly measuring/controlling the current and/or voltage at the Ni0.8Fe0.2O x catalyst layer using a second working electrode. The measurements demonstrate that the majority of photogenerated holes in α-Fe2O3 directly transfer to the catalyst film over a wide range of conditions and that the Ni0.8Fe0.2O x is oxidized by photoholes to an operating potential sufficient to drive water oxidation at rates that match the photocurrent generated by the α-Fe2O3. The Ni0.8Fe0.2O x therefore acts as both a hole-collecting contact and a catalyst for the photoelectrochemical water oxidation process. Separate measurements show that the illuminated junction photovoltage across the α-Fe2O3|Ni0.8Fe0.2O x interface is significantly decreased by the oxidation of Ni(2+) to Ni(3+) and the associated increase in the Ni0.8Fe0.2O x electrical conductivity. In sum, the results illustrate the underlying operative charge-transfer and photovoltage generation mechanisms of catalyzed photoelectrodes, thus guiding their continued improvement.

  14. Neutralized ion beam modification of cellulose membranes for study of ion charge effect on ion-beam-induced DNA transfer

    Energy Technology Data Exchange (ETDEWEB)

    Prakrajang, K., E-mail: [Plasma and Beam Physics Research Facility, Department of Physics and Materials Science, Faculty of Science, Chiang Mai University, Chiang Mai 50200 (Thailand); Sangwijit, K.; Anuntalabhochai, S. [Molecular Biology Laboratory, Department of Biology, Faculty of Science, Chiang Mai University, Chiang Mai 50200 (Thailand); Wanichapichart, P. [Membrane Science and Technology Research Center, Department of Physics, Faculty of Science, Prince of Songkla University, Hat Yai, Songkla 90110 (Thailand); Thailand Center of Excellence in Physics, Commission on Higher Education, 328 Si Ayutthaya Road, Bangkok 10400 (Thailand); Yu, L.D., E-mail: [Plasma and Beam Physics Research Facility, Department of Physics and Materials Science, Faculty of Science, Chiang Mai University, Chiang Mai 50200 (Thailand); Thailand Center of Excellence in Physics, Commission on Higher Education, 328 Si Ayutthaya Road, Bangkok 10400 (Thailand)


    Low-energy ion beam biotechnology (IBBT) has recently been rapidly developed worldwide. Ion-beam-induced DNA transfer is one of the important applications of IBBT. However, mechanisms involved in this application are not yet well understood. In this study plasma-neutralized ion beam was applied to investigate ion charge effect on induction of DNA transfer. Argon ion beam at 7.5 keV was neutralized by RF-driven plasma in the beam path and then bombarded cellulose membranes which were used as the mimetic plant cell envelope. Electrical properties such as impedance and capacitance of the membranes were measured after the bombardment. An in vitro experiment on plasmid DNA transfer through the cellulose membrane was followed up. The results showed that the ion charge input played an important role in the impedance and capacitance changes which would affect DNA transfer. Generally speaking, neutral particle beam bombardment of biologic cells was more effective in inducing DNA transfer than charged ion beam bombardment.

  15. pi-Conjugated chelating polymers with charged iridium complexes in the backbones: synthesis, characterization, energy transfer, and electrochemical properties. (United States)

    Liu, Shu-Juan; Zhao, Qiang; Chen, Run-Feng; Deng, Yun; Fan, Qu-Li; Li, Fu-You; Wang, Lian-Hui; Huang, Chun-Hui; Huang, Wei


    A series of pi-conjugated chelating polymers with charged iridium (Ir) complexes in the backbones were synthesized by a Suzuki polycondensation reaction, leading to homogeneous polymeric materials that phosphoresce red light. The fluorene and bipyridine (bpy) segments were used as polymer backbones. 5,5'-Dibromobipyridine served as a ligand to form a charged iridium complex monomer with 1-(9'9-dioctylfluorene-2-yl)isoquinoline (Fiq) as the cyclometalated ligand. Chemical and photophysical characterization confirmed that Ir complexes were incorporated into the backbones as one of the repeat units by means of the 5,5'-dibromobipyridine ligand. Chelating polymers showed almost complete energy transfer from the host fluorene segments to the guest Ir complexes in the solid state when the feed ratio was 2 mol %. In the films of the corresponding blend system, however, energy transfer was not complete even when the content of Ir complexes was as high as 16 mol %. Both intra- and intermolecular energy-transfer processes existed in this host-guest system, and the intramolecular energy transfer was a more efficient process. All chelating polymers displayed good thermal stability, redox reversibility, and film formation. These chelating polymers also showed more efficient energy transfer than the corresponding blended system and the mechanism of incorporation of the charged Ir complexes into the pi-conjugated polymer backbones efficiently avoided the intrinsic problems associated with the blend system, thus offering promise in optoelectronic applications.

  16. A low-spin Fe(III) complex with 100-ps ligand-to-metal charge transfer photoluminescence (United States)

    Chábera, Pavel; Liu, Yizhu; Prakash, Om; Thyrhaug, Erling; Nahhas, Amal El; Honarfar, Alireza; Essén, Sofia; Fredin, Lisa A.; Harlang, Tobias C. B.; Kjær, Kasper S.; Handrup, Karsten; Ericson, Fredric; Tatsuno, Hideyuki; Morgan, Kelsey; Schnadt, Joachim; Häggström, Lennart; Ericsson, Tore; Sobkowiak, Adam; Lidin, Sven; Huang, Ping; Styring, Stenbjörn; Uhlig, Jens; Bendix, Jesper; Lomoth, Reiner; Sundström, Villy; Persson, Petter; Wärnmark, Kenneth


    Transition-metal complexes are used as photosensitizers, in light-emitting diodes, for biosensing and in photocatalysis. A key feature in these applications is excitation from the ground state to a charge-transfer state; the long charge-transfer-state lifetimes typical for complexes of ruthenium and other precious metals are often essential to ensure high performance. There is much interest in replacing these scarce elements with Earth-abundant metals, with iron and copper being particularly attractive owing to their low cost and non-toxicity. But despite the exploration of innovative molecular designs, it remains a formidable scientific challenge to access Earth-abundant transition-metal complexes with long-lived charge-transfer excited states. No known iron complexes are considered photoluminescent at room temperature, and their rapid excited-state deactivation precludes their use as photosensitizers. Here we present the iron complex [Fe(btz)3]3+ (where btz is 3,3‧-dimethyl-1,1‧-bis(p-tolyl)-4,4‧-bis(1,2,3-triazol-5-ylidene)), and show that the superior σ-donor and π-acceptor electron properties of the ligand stabilize the excited state sufficiently to realize a long charge-transfer lifetime of 100 picoseconds (ps) and room-temperature photoluminescence. This species is a low-spin Fe(III) d5 complex, and emission occurs from a long-lived doublet ligand-to-metal charge-transfer (2LMCT) state that is rarely seen for transition-metal complexes. The absence of intersystem crossing, which often gives rise to large excited-state energy losses in transition-metal complexes, enables the observation of spin-allowed emission directly to the ground state and could be exploited as an increased driving force in photochemical reactions on surfaces. These findings suggest that appropriate design strategies can deliver new iron-based materials for use as light emitters and photosensitizers.

  17. A new type of charge-transfer salts based on tetrathiafulvalene-tetracarboxylate coordination polymers and methyl viologen. (United States)

    Huang, Yu-De; Huo, Peng; Shao, Ming-Yan; Yin, Jing-Xue; Shen, Wei-Chun; Zhu, Qin-Yu; Dai, Jie


    Although charge-transfer compounds based on tetrathiafulvalene (TTF) derivatives have been intensively studied, {[cation](n+)·[TTFs](n-)} ion pair charge-transfer (IPCT) salts have not been reported. The aim of this research is to introduce functional organic cations, such as photoactive methyl viologen (MV(2+)), into the negatively charged TTF-metal coordination framework to obtain this new type of IPCT complex. X-ray structural analysis of the four compounds (MV)2[Li4(L)2(H2O)6] (1), {(MV)(L)[Na2(H2O)8]·4H2O}n (2), {(MV)[Mn(L)(H2O)2]·2H2O}n (3), and {(MV)[Mn(L)(H2O)2]}n (4), reveals that the electron donor (D) TTF moiety and the electron acceptor (A) MV(2+) form a regular mixed-stack arrangement in alternating DADA fashion. The TTF moiety and the MV(2+) cation are essentially parallel stacked to form the column structures. The strong electrostatic interaction is a main force to shorten the distance between the cation and anion planes. Optical diffuse-reflection spectra indicate that charge transfer occurs in these complexes. The ESR and magnetic measurements confirm that there is strong charge-transfer-induced partial electron transfer. Compounds 2, 3, and 4 show an effective and repeatable photocurrent response. The current intensities of 3 and 4 are higher than that of 2, which reflects that the coordination center of the Mn(II) ion has a great effect on the increasing photocurrent response.

  18. Effect of Conjugation Length on Photoinduced Charge-Transfer in π-Conjugated Oligomer-Acceptor Dyads

    KAUST Repository

    Jiang, Junlin


    A series of -conjugated oligomer-acceptor dyads were synthesized that feature oligo(phenylene ethynylene) (OPE) conjugated backbones end-capped with a naphthalene diimide (NDI) acceptor. The OPE segments vary in length from 4 to 8 phenylene ethynene units (PEn-NDI, where n = 4, 6 and 8). Fluorescence and transient absorption spectroscopy reveals that intramolecular OPE NDI charge transfer dominates the deactivation of excited states of the PEn-NDI oligomers. Both charge separation (CS) and charge recombination (CR) are strongly exothermic (G0CS ~ -1.1 and G0CR ~ -2.0 eV), and the driving forces do not vary much across the series because the oxidation and reduction potentials and singlet energies of the OPEs do not vary much with their length. Bimolecular photoinduced charge transfer between model OPEs that do not contain the NDI acceptors with methyl viologen was studied, and the results reveal that the absorption of the cation radical state (OPE+•) remains approximately constant ( ~ 575 nm) regardless of oligomer length. This finding suggests that the cation radical (polaron) of the OPE is relatively localized, effectively occupying a confined segment of n 4 repeat units in the longer oligomers. Photoinduced intramolecular electron transfer dynamics in the PEn-NDI series was investigated by UV-visible femtosecond transient absorption spectroscopy with visible and mid-infrared probes. Charge separation occurs on the 1 – 10 ps timescale, with the rates decreasing slightly with increased oligomer length (βCS ~ 0.15 Å-1). The rate for charge-recombination decreases in the sequence PE4-NDI > PE6-NDI ~ PE8-NDI. The discontinuous distance dependence in the rate for charge recombination may be related to the spatial localization of the positive polaron state in the longer oligomers.

  19. DNA Films Containing the Artificial Nucleobase Imidazole Mediate Charge Transfer in a Silver(I)-Responsive Way. (United States)

    Léon, J Christian; She, Zhe; Kamal, Ajar; Shamsi, Mohtashim Hassan; Müller, Jens; Kraatz, Heinz-Bernhard


    The first sequence-dependent study of DNA films containing metal-mediated base pairs was performed to investigate the charge transfer resistance (RCT ) of metal-modified DNA. The imidazole (Im) deoxyribonucleoside was chosen as a highly Ag(I) -specific ligandoside for the formation of Im-Ag(I) -Im complexes within the duplexes. This new class of site-specifically metal-modified DNA films was characterized by UV, circular dichroism (CD), and X-ray photoelectron spectroscopy (XPS). The electrochemical properties of these systems were investigated by means of electron impedance spectroscopy and scanning electrochemical microscopy. Taken together, these experiments indicated that the incorporation of Ag(I) ions into the DNA films leads to reduced electron transfer through the DNA films. A simple device was proposed that can be switched reversibly between two distinct states with different charge transfer resistance. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. Overpotential-induced lability of the electronic overlap factor in long-range electrochemical electron transfer: charge and distance dependence

    DEFF Research Database (Denmark)

    Kornyshev, A. A.; Kuznetsov, A. M.; Nielsen, Jens Ulrik


    Long-distance electrochemical electron transfer exhibits approximately exponential dependence on the electron transfer distance. On the basis of a jellium model of the metal surface we show that the slope of the logarithm of the current vs. the transfer distance also depends strongly...... on the electrode charge. The slope is smaller the more negative the charge density due to enhanced extension of the surface electronic density profile on the solution side, and thereby better electronic overlap with the reacting molecule. The effect is sensitive to the bulk electron density of the metal...... and the localization of the electronic state at the molecular reactant site. Effects similar to these have been observed experimentally and could be common for electronically light metals....