WorldWideScience

Sample records for molecular electronic rectification

  1. Molecular rectification, photodiodes and symmetry

    Science.gov (United States)

    Martin, A. Scott; Sambles, J. Roy

    1996-12-01

    We present a review of recent advances in the molecular rectifier project. Using a donor - 0957-4484/7/4/017/img1-bridge - acceptor compound, specifically designed to be a molecular rectifier, drastically improved rectifier characteristics were observed compared with a previously published 0957-4484/7/4/017/img2-bridged compound. In particular the increased `rectification ratio' of the 0957-4484/7/4/017/img1-bridged compound was attributed to more effective current blocking under reverse bias. Furthermore, we demonstrate that photodiode-like properties are possessed by films of the zwitterionic, 0957-4484/7/4/017/img2-bridged compound, 0957-4484/7/4/017/img5 - 0957-4484/7/4/017/img6, using a transparent electrode construction. Finally, we provide an explanation for the observation that all non-centrosymmetric Langmuir - Blodgett film samples exhibit an exponential current-density/voltage dependence.

  2. Terahertz rectification by periodic two-dimensional electron plasma

    International Nuclear Information System (INIS)

    The physics of terahertz rectification by periodic two-dimensional electron plasma is discussed. Two different effects yielding terahertz rectification are studied: the plasmonic drag and plasmonic ratchet. Ultrahigh responsivity of terahertz rectification by periodic two-dimensional electron plasma in semiconductor heterostructures and graphene is predicted.

  3. Controlling the direction of rectification in a molecular diode

    Science.gov (United States)

    Yuan, Li; Nerngchamnong, Nisachol; Cao, Liang; Hamoudi, Hicham; Del Barco, Enrique; Roemer, Max; Sriramula, Ravi K.; Thompson, Damien; Nijhuis, Christian A.

    2015-03-01

    A challenge in molecular electronics is to control the strength of the molecule–electrode coupling to optimize device performance. Here we show that non-covalent contacts between the active molecular component (in this case, ferrocenyl of a ferrocenyl–alkanethiol self-assembled monolayer (SAM)) and the electrodes allow for robust coupling with minimal energy broadening of the molecular level, precisely what is required to maximize the rectification ratio of a molecular diode. In contrast, strong chemisorbed contacts through the ferrocenyl result in large energy broadening, leakage currents and poor device performance. By gradually shifting the ferrocenyl from the top to the bottom of the SAM, we map the shape of the electrostatic potential profile across the molecules and we are able to control the direction of rectification by tuning the ferrocenyl–electrode coupling parameters. Our demonstrated control of the molecule–electrode coupling is important for rational design of materials that rely on charge transport across organic–inorganic interfaces.

  4. Rectification Mechanism in Di-Block Oligomer Molecular Diodes

    CERN Document Server

    Oleynik, I I; Posvyanskii, V S; Yu, L

    2005-01-01

    We investigated a mechanism of rectification in di-block oligomer diode molecules that have recently been synthesized and showed a pronounced asymmetry in the measured I-V spectrum. The observed rectification effect is due to the resonant nature of electron transfer in the system and localization properties of bound state wave functions of resonant states of the tunneling electron interacting with asymmetric molecule in an electric field. The asymmetry of the tunneling wave function is enhanced or weakened depending on the polarity of applied bias. The conceptually new theoretical approach, the Green's function theory of sub-barrier scattering, is able to provide a physically transparent explanation of this rectification effect based on the concept of the bound state spectrum of a tunneling electron. The theory predicts the characteristic features of the I-V spectrum in qualitative agreement with experiment.

  5. Improved molecular rectification from self-assembled monolayers of a sterically hindered dye.

    Science.gov (United States)

    Ashwell, Geoffrey J; Mohib, Abdul

    2005-11-23

    Self-assembled monolayers (SAMs) formed from the reaction of 1-(10-acetylsulfanyldecyl)-4-[2-(4-dimethylaminonaphthalen-1-yl)-vinyl]-quinolinium iodide (1a) and gold-coated substrates exhibit asymmetric current-voltage (I-V) characteristics with a rectification ratio of 50-150 at +/-1 V. It is the highest to date for a molecular diode, and the improved behavior may be assigned in part to the controlled alignment of the donor-(pi-bridge)-acceptor moieties and in part to steric hindrance, which imposes a nonplanar structure and effectively isolates the molecular orbitals of the donor and acceptor end groups. The molecular origin of the rectification is verified by its suppression upon exposure to HCl vapor, which protonates the dimethylamino group and inhibits the electron-donating properties, with restoration upon exposure to NH3. It is also established by a reduced rectification ratio of ca. 2 at +/-1 V when the cationic D-pi-A+ moieties adopt an antiparallel arrangement in self-assembled films of the derivative, bis-[1-(10-decyl)-4-[2-(4-dimethylaminonaphthalen-1-yl)-vinyl]-quinolinium]-disulfide diiodide (1b), which adsorbs via one of its terminal donors without rupture of the sulfur-sulfur bond: Au/D-pi-A+-C10H20-S-S-C10H20-+A-pi-D (I-)2. PMID:16287315

  6. Charge transport and rectification in molecular junctions formed with carbon-based electrodes.

    Science.gov (United States)

    Kim, Taekyeong; Liu, Zhen-Fei; Lee, Chulho; Neaton, Jeffrey B; Venkataraman, Latha

    2014-07-29

    Molecular junctions formed using the scanning-tunneling-microscope-based break-junction technique (STM-BJ) have provided unique insight into charge transport at the nanoscale. In most prior work, the same metal, typically Au, Pt, or Ag, is used for both tip and substrate. For such noble metal electrodes, the density of electronic states is approximately constant within a narrow energy window relevant to charge transport. Here, we form molecular junctions using the STM-BJ technique, with an Au metal tip and a microfabricated graphite substrate, and measure the conductance of a series of graphite/amine-terminated oligophenyl/Au molecular junctions. The remarkable mechanical strength of graphite and the single-crystal properties of our substrates allow measurements over few thousand junctions without any change in the surface properties. We show that conductance decays exponentially with molecular backbone length with a decay constant that is essentially the same as that for measurements with two Au electrodes. More importantly, despite the inherent symmetry of the oligophenylamines, we observe rectification in these junctions. State-of-art ab initio conductance calculations are in good agreement with experiment, and explain the rectification. We show that the highly energy-dependent graphite density of states contributes variations in transmission that, when coupled with an asymmetric voltage drop across the junction, leads to the observed rectification. Together, our measurements and calculations show how functionality may emerge from hybrid molecular-scale devices purposefully designed with different electrodes beyond the so-called "wide band limit," opening up the possibility of assembling molecular junctions with dissimilar electrodes using layered 2D materials. PMID:25024198

  7. Electronic heat current rectification in hybrid superconducting devices

    Science.gov (United States)

    Fornieri, Antonio; Martínez-Pérez, María José; Giazotto, Francesco

    2015-05-01

    In this work, we review and expand recent theoretical proposals for the realization of electronic thermal diodes based on tunnel-junctions of normal metal and superconducting thin films. Starting from the basic rectifying properties of a single hybrid tunnel junction, we will show how the rectification efficiency can be largely increased by combining multiple junctions in an asymmetric chain of tunnel-coupled islands. We propose three different designs, analyzing their performance and their potential advantages. Besides being relevant from a fundamental physics point of view, this kind of devices might find important technological application as fundamental building blocks in solid-state thermal nanocircuits and in general-purpose cryogenic electronic applications requiring energy management.

  8. Terahertz radiation by optical rectification in a hydrogen-bonded organic molecular ferroelectric crystal, 2-phenylmalondialdehyde

    OpenAIRE

    Guan, W.; Kida, N.; Sotome, M.; Kinoshita, Y.; Takeda, R.; Inoue, A.; Horiuchi, S.; Okamoto, H.

    2014-01-01

    Terahertz radiation by optical rectification has been observed at room temperature in a hydrogen-bonded organic molecular ferroelectric crystal, 2-phenyl malondialdehyde (PhMDA). The radiated electromagnetic wave consisted of a single-cycle terahertz pulse with a temporal width of $\\sim$ 0.5 ps. The terahertz radiation amplitude divided by the sample thickness in PhMDA was nearly equivalent to that in a typical terahertz wave emitter ZnTe. This is attributable to a long cohe...

  9. Obvious variation of rectification behaviors induced by isomeric anchoring groups for dipyrimidinyl–diphenyl molecular junctions

    International Nuclear Information System (INIS)

    The rectifying properties modulated by isomeric anchoring groups of dipyrimidinyl–diphenyl co-oligomer diodes sandwiched between two gold electrodes are investigated using density functional theory combined with the nonequilibrium Green's function method. Our results show that the rectifying behaviors of the co-oligomer diode are significantly modulated by isomeric substitution of anchoring groups. When the isomeride nitrile end group is replaced by the isocyanide one, for symmetric arrangement of electrodes, the rectifying direction shows obvious inversion for the isocyanide–diblock–thiol junction, and the rectification ratio is obviously enhanced for the thiol–diblock–isocyanide junction. The influence on rectification induced by asymmetric electrodes is also discussed. The analysis of the transmission spectra and the molecular projected self-consistent Hamiltonian under various external bias voltages gives inside mechanisms of the observed results.

  10. Wave-packet rectification in nonlinear electronic systems: A tunable Aharonov-Bohm diode

    CERN Document Server

    Li, Yunyun; Marchesoni, Fabio; Li, Baowen

    2014-01-01

    Rectification of electron wave-packets propagating along a quasi-one dimensional chain is commonly achieved via the simultaneous action of nonlinearity and longitudinal asymmetry, both confined to a limited portion of the chain termed wave diode. However, it is conceivable that, in the presence of an external magnetic field, spatial asymmetry perpendicular to the direction of propagation suffices to ensure rectification. This is the case of a nonlinear ring-shaped lattice with different upper and lower halves (diode), which is attached to two elastic chains (leads). The resulting device is mirror symmetric with respect to the ring vertical axis, but mirror asymmetric with respect to the chain direction. Wave propagation along the two diode paths can be modeled for simplicity by a discrete Schr\\"odinger equation with cubic nonlinearities. Numerical simulations demonstrate that, thanks to the Aharonov-Bohm effect, such a diode can be operated by tuning the magnetic flux across the ring.

  11. Molecular dynamics study on the thermal conductivity and thermal rectification in graphene with geometric variations of doped boron

    International Nuclear Information System (INIS)

    Thermal conductivity and thermal rectification of graphene with geometric variations have been investigated by using classical non-equilibrium molecular dynamics simulation, and analyzed theoretically the cause of the changes of thermal conductivity and thermal rectification. Two different structural models, triangular single-boron-doped graphene (SBDG) and parallel various-boron-doped graphene (VBDG), were considered. The results indicated that the thermal conductivities of two different models are about 54–63% lower than pristine graphene. And it was also found that the structure of parallel various-boron-doped graphene is inhibited more strongly on the heat transfer than that of triangular single-boron-doped graphene. The reduction in the thermal conductivities of two different models gradually decreases as the temperature rises. The thermal conductivities of triangular boron-doped graphene have a large difference in both directions, and the thermal rectification of this structure shows the downward trend with increasing temperature. However, the thermal conductivities of parallel various-boron-doped graphene are similar in both directions, and the thermal rectification effect is not obvious in this structure. The phenomenon of thermal rectification exits in SBDG. It implies that the SBDG might be a potential promising structure for thermal rectifier by controlling the boron-doped model

  12. Rectification of electronic heat current by a hybrid thermal diode

    OpenAIRE

    Martínez-Pérez, M. J.; Fornieri, A.; Giazotto, F.

    2014-01-01

    We report the realization of an ultra-efficient low-temperature hybrid heat current rectifier, thermal counterpart of the well-known electric diode. Our design is based on a tunnel junction between two different elements: a normal metal and a superconducting island. Electronic heat current asymmetry in the structure arises from large mismatch between the thermal properties of these two. We demonstrate experimentally temperature differences exceeding $60$ mK between the forwa...

  13. Rectification of electronic heat current by a hybrid thermal diode

    Science.gov (United States)

    Martínez-Pérez, Maria José; Fornieri, Antonio; Giazotto, Francesco

    2015-05-01

    Thermal diodes—devices that allow heat to flow preferentially in one direction—are one of the key tools for the implementation of solid-state thermal circuits. These would find application in many fields of nanoscience, including cooling, energy harvesting, thermal isolation, radiation detection and quantum information, or in emerging fields such as phononics and coherent caloritronics. However, both in terms of phononic and electronic heat conduction (the latter being the focus of this work), their experimental realization remains very challenging. A highly efficient thermal diode should provide a difference of at least one order of magnitude between the heat current transmitted in the forward temperature (T) bias configuration (Jfw) and that generated with T-bias reversal (Jrev), leading to ??=?Jfw/Jrev ??1 or ??1. So far, ????1.07–1.4 has been reported in phononic devices, and ????1.1 has been obtained with a quantum-dot electronic thermal rectifier at cryogenic temperatures. Here, we show that unprecedentedly high ratios of ????140 can be achieved in a hybrid device combining normal metals tunnel-coupled to superconductors. Our approach provides a high-performance realization of a thermal diode for electronic heat current that could be successfully implemented in true low-temperature solid-state thermal circuits.

  14. Terahertz radiation by optical rectification in a hydrogen-bonded organic molecular ferroelectric crystal, 2-phenylmalondialdehyde

    CERN Document Server

    Guan, W; Sotome, M; Kinoshita, Y; Takeda, R; Inoue, A; Horiuchi, S; Okamoto, H

    2014-01-01

    Terahertz radiation by optical rectification has been observed at room temperature in a hydrogen-bonded organic molecular ferroelectric crystal, 2-phenyl malondialdehyde (PhMDA). The radiated electromagnetic wave consisted of a single-cycle terahertz pulse with a temporal width of $\\sim$ 0.5 ps. The terahertz radiation amplitude divided by the sample thickness in PhMDA was nearly equivalent to that in a typical terahertz wave emitter ZnTe. This is attributable to a long coherence length in the range of 130 $\\sim$ 800 $\\mu$m for the terahertz radiation from PhMDA. We also discussed the possibility of PhMDA as a terahertz wave emitter in terms of the phase-matching condition.

  15. Rectification Properties of Carbon Nanotube ''Y-Junctions''

    International Nuclear Information System (INIS)

    Quantum conductivity of single-wall carbon nanotube Y-junctions is calculated. The current versus voltage characteristics of these junctions show asymmetry and rectification, in agreement with recent experimental results. Furthermore, rectification is found to be independent of the angle between the branches of these junctions, indicating this to be an intrinsic property of symmetric Y-junctions. The implications for the Y-junction to function as a nanoscale molecular electronic switch are investigated

  16. Theory of Rectification in Tour Wires: The Role of Electrode Coupling

    Science.gov (United States)

    Taylor, Jeremy; Brandbyge, Mads; Stokbro, Kurt

    2002-09-01

    We report first-principles studies of electronic transport and rectification in molecular wires attached to gold electrodes. Our ab initio calculation gives an accurate description of the voltage drop as well as the broadening and alignment of the molecular levels in the metal-molecule-metal complex. We find that the operation range and rectification in such strongly chemisorbed molecules is limited by the width of the transmission resonances and their proximity to the Fermi level.

  17. Theory of Rectification in Tour Wires: The Role of Electrode Coupling

    DEFF Research Database (Denmark)

    Taylor, Jeremy Philip; Brandbyge, Mads

    2002-01-01

    We report first-principles studies of electronic transport and rectification in molecular wires attached to gold electrodes. Our ab initio calculation gives an accurate description of the voltage drop as well as the broadening and alignment of the molecular levels in the metal-molecule-metal complex. We find that the operation range and rectification in such strongly chemisorbed molecules is limited by the width of the transmission resonances and their proximity to the Fermi level.

  18. Theory of Rectification in Tour Wires: The Role of Electrode Coupling

    OpenAIRE

    Taylor, Jeremy Philip; Brandbyge, Mads; Stokbro, Kurt

    2006-01-01

    We report first-principles studies of electronic transport and rectification in molecular wires attached to gold electrodes. Our ab initio calculation gives an accurate description of the voltage drop as well as the broadening and alignment of the molecular levels in the metal-molecule-metal complex. We find that the operation range and rectification in such strongly chemisorbed molecules is limited by the width of the transmission resonances and their proximity to the Fermi level.

  19. Electronic transport properties of phenylacetylene molecular junctions

    International Nuclear Information System (INIS)

    Electronic transport properties of a kind of phenylacetylene compound— (4-mercaptophenyl)-phenylacetylene are calculated by the first-principles method in the framework of density functional theory and the nonequilibrium Green's function formalism. The molecular junction shows an obvious rectifying behaviour at a bias voltage larger than 1.0 V. The rectification effect is attributed to the asymmetry of the interface contacts. Moreover, at a bias voltage larger than 2.0 V, which is not referred to in a relevant experiment [Fang L, Park J Y, Ma H, Jen A K Y and Salmeron M 2007 Langmuir 23 11522], we find a negative differential resistance phenomenon. The negative differential resistance effect may originate from the change of the delocalization degree of the molecular orbitals induced by the bias. (condensed matter: electronic structure, electrical, magnetic, and optical properties)

  20. Introducing molecular electronics

    Directory of Open Access Journals (Sweden)

    Mark A Ratner

    2002-02-01

    In the natural world, molecules are used for many purposes. Using molecule-based materials for electronics, sensing, and optoelectronics is a new endeavor, called molecular electronics, and the subject both of riveting new research and substantial popular press interest.

  1. Measurement and understanding of single-molecule break junction rectification caused by asymmetric contacts

    Science.gov (United States)

    Wang, Kun; Zhou, Jianfeng; Hamill, Joseph M.; Xu, Bingqian

    2014-08-01

    The contact effects of single-molecule break junctions on rectification behaviors were experimentally explored by a systematic control of anchoring groups of 1,4-disubstituted benzene molecular junctions. Single-molecule conductance and I-V characteristic measurements reveal a strong correlation between rectifying effects and the asymmetry in contacts. Analysis using energy band models and I-V calculations suggested that the rectification behavior is mainly caused by asymmetric coupling strengths at the two contact interfaces. Fitting of the rectification ratio by a modified Simmons model we developed suggests asymmetry in potential drop across the asymmetric anchoring groups as the mechanism of rectifying I-V behavior. This study provides direct experimental evidence and sheds light on the mechanisms of rectification behavior induced simply by contact asymmetry, which serves as an aid to interpret future single-molecule electronic behavior involved with asymmetric contact conformation.

  2. Rectification in Y-junctions of Luttinger liquid wires

    OpenAIRE

    Wang, Chenjie; Feldman, D. E.

    2010-01-01

    We investigate rectification of a low-frequency ac bias in Y-junctions of one-channel Luttinger liquid wires with repulsive electron interaction. Rectification emerges due to three scatterers in the wires. We find that it is possible to achieve a higher rectification current in a Y-junction than in a single wire with an asymmetric scatterer at the same interaction strength and voltage bias. The rectification effect is the strongest in the absence of the time-reversal symmetr...

  3. Rectification by Doped Mott-Insulator Junctions

    OpenAIRE

    Sabou, Florian C.; Bodington, Natalie; Marston, J. B.

    2012-01-01

    Junctions of doped Mott insulators offer a route to rectification at frequencies beyond the terahertz range. Mott insulators have strong electronic correlations and therefore short timescales for electron-electron scattering. It is this short time scale that allows for the possibility of rectification at frequencies higher than those of semiconductor devices that are limited by the slow diffusion of charge carriers. We model a junction by a one dimensional chain of electrons...

  4. Thermal Rectification In Asymmetric Graphene Ribbons

    OpenAIRE

    Yang, Nuo; Zhang, Gang; Li, Baowen

    2009-01-01

    In this paper, heat flux in graphene nano ribbons has been studied by using molecular dynamics simulations. It is found that the heat flux runs preferentially along the direction of decreasing width, which demonstrates significant thermal rectification effect in the asymmetric graphene ribbons. The dependence of rectification ratio on the vertex angle and the length are also discussed. Compared to the carbon nanotube based one-dimensional thermal rectifier, graphene nano rib...

  5. Rectification Through Entropic Barriers

    Science.gov (United States)

    Schmid, Gerhard; Burada, P. Sekhar; Talkner, Peter; Hänggi, Peter

    The dynamics of Brownian motion has widespread applications extending from transport in designed micro-channels up to its prominent role for inducing transport in molecular motors and Brownian motors. Here, Brownian transport is studied in micro-sized, two dimensional periodic channels, exhibiting periodically varying cross sections. The particles in addition are subjected to a constant external force acting alongside the direction of the longitudinal channel axis. For a fixed channel geometry, the dynamics of the two dimensional problem is characterized by a single dimensionless parameter which is proportional to the ratio of the applied force and the temperature of the environment. In such structures entropic effects may play a dominant role. Under certain conditions the two dimensional dynamics can be approximated by an effective one dimensional motion of the particle in the longitudinal direction. The Langevin equation describing this reduced, one dimensional process is of the type of the Fick-Jacobs equation. It contains an entropic potential determined by the varying extension of the eliminated transversal channel direction, and a correction to the diffusion constant that introduces a space dependent diffusion. We analyze the influence of broken channel symmetry and the validity of the Fick-Jacobs equation. For the nonlinear mobility we find a temperature dependence which is opposite to that known for particle transport in periodic energetic potentials. The influence of entropic effects is discussed for both, the nonlinear mobility, and the effective diffusion constant. In case of broken reflection symmetry rectification occurs and there is a favored direction for particle transport. The rectification effect could be maximized due to the optimal chosen absolute value of the applied bias.

  6. Inelastic transport and low-bias rectification in a single-molecule diode.

    Science.gov (United States)

    Hihath, Joshua; Bruot, Christopher; Nakamura, Hisao; Asai, Yoshihiro; Díez-Pérez, Ismael; Lee, Youngu; Yu, Luping; Tao, Nongjian

    2011-10-25

    Designing, controlling, and understanding rectification behavior in molecular-scale devices has been a goal of the molecular electronics community for many years. Here we study the transport behavior of a single molecule diode, and its nonrectifying, symmetric counterpart at low temperatures, and at both low and high biases to help elucidate the electron-phonon interactions and transport mechanisms in the rectifying system. We find that the onset of current rectification occurs at low biases, indicating a significant change in the elastic transport pathway. However, the peaks in the inelastic electron tunneling (IET) spectrum are antisymmetric about zero bias and show no significant changes in energy or intensity in the forward or reverse bias directions, indicating that despite the change in the elastic transmission probability there is little impact on the inelastic pathway. These results agree with first principles calculations performed to evaluate the IETS, which also allow us to identify which modes are active in the single molecule junction. PMID:21932824

  7. Electronic Properties of a Phenylacetylene Molecular Junction with Dithiocarboxylate Anchoring Group

    International Nuclear Information System (INIS)

    The electronic transport properties of a kind of phenylacetylene compound (4-mercaptophenyl)-phenylacetylene (MPPA) are studied by the first-principles method. A dithiocarboxylate conjugated linker (?CS2) is used to anchor the molecule to one gold electrode. Rectification behavior is observed, which is mainly brought about by the asymmetrical coupling of electrodes to the molecule. There is a drastic increase in current as the electrode-electrode distance is reduced, and the rectification ratio increases by 40% as the electrode-electrode distance is diminished from 16 Å to 15.7 Å. For comparison, we also perform simulations with the ?CS2 linker replaced by thiol linkage. It shows an obvious reduction in current. We find that the stronger interface coupling induced by the ?CS2 linker broadens transmission resonances near the Fermi energy, which leads to the current enhancement of the molecular junction with ?CS2 linker

  8. A gate controlled conjugated single molecule diode: Its rectification could be reversed

    Science.gov (United States)

    Zhang, Qun

    2014-10-01

    A gate controlled Au/diphenyldipyrimidinyl/Au single molecule diode is simulated by a tight-binding Hamiltonian combined with Green's Function and transport methods. After calculating a number of electronic transport characteristics under various gate voltages, a clear modulation by gate is got and when the positive voltage is high enough, the rectification could be reversed. This is advisable for the designing and building future molecular logic devices and integrated circuits.

  9. Thermal rectification in asymmetric U-shaped graphene flakes

    International Nuclear Information System (INIS)

    In this paper, we study the thermal rectification in asymmetric U-shaped graphene flakes by nonequilibrium molecular dynamics simulations. The graphene flakes are composed of a beam and two asymmetric arms. It is found that the heat flux runs preferentially from the wide arm to the narrow arm, which indicates a strong rectification effect. The dependence of the rectification ratio upon the heat flux, the length and the width of the beam and the two arms is studied. It shows that the two asymmetric arms play the central role in thermal rectification and a proper design is needed to obtain the maximum rectification ratio. The result suggests a possible route to manage the heat dissipation in U-shaped graphene based nanoelectronic devices that have recently been fabricated

  10. Electron scattering on molecular hydrogen

    International Nuclear Information System (INIS)

    The author considers scattering phenomena which occur when a beam of electrons interacts with a molecular hydrogen gas of low density. Depending on the energy loss of the scattered electrons one can distinguish elastic scattering, excitation and (auto)ionization of the H2-molecule. The latter processes may also lead to dissociation. These processes are investigated in four experiments in increasing detail. (Auth.)

  11. Unconventional molecule-resolved current rectification in diamondoid-fullerene hybrids.

    Science.gov (United States)

    Randel, Jason C; Niestemski, Francis C; Botello-Mendez, Andrés R; Mar, Warren; Ndabashimiye, Georges; Melinte, Sorin; Dahl, Jeremy E P; Carlson, Robert M K; Butova, Ekaterina D; Fokin, Andrey A; Schreiner, Peter R; Charlier, Jean-Christophe; Manoharan, Hari C

    2014-01-01

    The unimolecular rectifier is a fundamental building block of molecular electronics. Rectification in single molecules can arise from electron transfer between molecular orbitals displaying asymmetric spatial charge distributions, akin to p-n junction diodes in semiconductors. Here we report a novel all-hydrocarbon molecular rectifier consisting of a diamantane-C60 conjugate. By linking both sp(3) (diamondoid) and sp(2) (fullerene) carbon allotropes, this hybrid molecule opposingly pairs negative and positive electron affinities. The single-molecule conductances of self-assembled domains on Au(111), probed by low-temperature scanning tunnelling microscopy and spectroscopy, reveal a large rectifying response of the molecular constructs. This specific electronic behaviour is postulated to originate from the electrostatic repulsion of diamantane-C60 molecules due to positively charged terminal hydrogen atoms on the diamondoid interacting with the top electrode (scanning tip) at various bias voltages. Density functional theory computations scrutinize the electronic and vibrational spectroscopic fingerprints of this unique molecular structure and corroborate the unconventional rectification mechanism. PMID:25202942

  12. Giant Thermal Rectification from Polyethylene Nanofiber Thermal Diodes

    OpenAIRE

    Zhang, Teng; Luo, Tengfei

    2015-01-01

    The realization of phononic computing is held hostage by the lack of high performance thermal devices. Here we show through theoretical analysis and molecular dynamics simulations that unprecedented thermal rectification factors (as large as 1.20) can be achieved utilizing the phase dependent thermal conductivity of polyethylene nanofibers. More importantly, such high thermal rectifications only need very small temperature differences (< 20 oC) across the device, which is a ...

  13. Unexpected large thermal rectification in asymmetric grain boundary of graphene

    OpenAIRE

    Cao, Hai-Yuan; Xiang, Hongjun; Gong, Xin-Gao

    2011-01-01

    We have investigated the lattice thermal transport across the asymmetric tilt grain boundary between armchair and zigzag graphene by nonequilibrium molecular dynamics (NEMD). We have observed significant temperature drop and ultra-low temperature-dependent thermal boundary resistance. More importantly, we find an unexpected thermal rectification phenomenon. The thermal conductivity and Kapitza conductance is direction-dependent. The effect of thermal rectification could be a...

  14. Silicon-based molecular electronics

    CERN Document Server

    Rakshit, T; Ghosh, A W; Datta, S

    2003-01-01

    Molecular electronics on silicon has distinct advantages over its metallic counterpart. We describe a theoretical formalism for transport through semiconductor-molecule heterostructures, combining a semi-empirical treatment of the bulk silicon bandstructure with a first-principles description of the molecular chemistry and its bonding with silicon. Using this method, we demonstrate that the presence of a semiconducting band-edge can lead to a novel molecular resonant tunneling diode (RTD) that shows negative differential resistance (NDR) when the molecular levels are driven by an STM potential into the semiconducting band-gap. The peaks appear for positive bias on a p-doped and negative for an n-doped substrate. Charging in these devices is compromised by the RTD action, allowing possible identification of several molecular highest occupied (HOMO) and lowest unoccupied (LUMO) levels. Recent experiments by Hersam et al. [1] support our theoretical predictions.

  15. Ionic Current Rectification Through Silica Nanopores

    OpenAIRE

    Cruz-Chu, Eduardo R.; Aksimentiev, Aleksei; Schulten, Klaus

    2009-01-01

    Nanopores immersed in electrolytic solution and under the influence of an electric field can produce ionic current rectification, where ionic currents are higher for one voltage polarity than for the opposite polarity, resulting in an asymmetric current-voltage (I-V) curve. This behavior has been observed in polymer and silicon-based nanopores as well as in theoretically studied continuum models. By means of atomic level molecular dynamics (MD) simulations, we have performed a systematic inve...

  16. Electrical gating and rectification in graphene three-terminal junctions

    International Nuclear Information System (INIS)

    Graphene was grown on semiinsulating silicon carbide at 1800 °C and atmospheric argon pressure. The all carbon T- and Y-shape three terminal junction devices were fabricated using electron beam lithography. All devices featured the negative rectification effect. The exact properties of the devices like the curvature of the output voltage response can be tuned by changing the branch width in the T- and Y-shape devices. Beside the rectification a switching behavior is demonstrated with the same three terminal junctions.

  17. Rectification effect of gradient antiparallel magnetic fields on electron conduction in a gas under a radio-frequency electric field

    Energy Technology Data Exchange (ETDEWEB)

    Sugawara, Hirotake; Osaga, Tsuyoshi; Yamamoto, Hiromori, E-mail: sugawara@ist.hokudai.ac.jp [Division of Electronics for Informatics, Graduate School of Information Science and Technology, Hokkaido University, Sapporo 060-0814 (Japan)

    2011-10-15

    Electron transport in CF{sub 4} under linearly gradient antiparallel magnetic fields was analysed in order to investigate the fundamental properties of magnetic neutral loop discharge plasmas used for material processing. The electron motion was simulated by a Monte Carlo method under a radio-frequency (rf) electric field applied perpendicularly to the directions of both the magnetic field and its gradient. Two typical electron motions, meandering in a weak magnetic field and gyration in a strong magnetic field, were observed with particular directionalities. The meandering electrons drifted forward on average similarly to those under a dc electric field. The gyration induced an electron drift towards the inverse direction. The direction of electron flux was dependent not only on the rf phase but also on the distance from the magnetically neutral midplane between the antiparallel magnetic fields. The electron conduction path formed along the midplane had a structure consisting of forward and inverse lanes. A peculiar result was that the direction of local electron flux was always forward in the strong magnetic field whereas the drift of gyrating electrons was towards the inverse direction. This seemingly paradoxical result can appear in the presence of the density gradient of the electron distribution.

  18. Electrode materials for biphenyl-based rectification devices.

    Science.gov (United States)

    Parashar, Sweta; Srivastava, Pankaj; Pattanaik, Manisha

    2013-10-01

    An ab initio approach was utilized to explore the electronic transport properties of 4'-thiolate-biphenyl-4-dithiocarboxylate (TBDT) sandwiched between two electrodes made of various materials X (X?=?Cu, Ag, and Au). Analysis of current-voltage (I-V) characteristics, rectification performance, transmission functions, and the projected density of states (PDOS) under various external voltage biases showed that the transport properties of these constructed systems are markedly impacted by the choice of electrode materials. Further, Cu electrodes yield the best rectifying behavior, followed by Ag and then Au electrodes. Interestingly, the rectification effects can be tuned by changing the torsion angle between the two phenyl rings, as well as by stretching the contact distances between the end group and the electrodes. For Cu, the maximum rectifying ratio increases by 37 % as the contact distance changes from 1.7 Å to 1.9 Å. This is due to an increase in coupling strength asymmetry between the molecule and the electrodes. Our findings are compared with the results reported for other systems. The present calculations are helpful not only for predicting the optimal electrode material for practical applications but also for achieving better control over rectifying performance in molecular devices. PMID:23929412

  19. Fullerene Derived Molecular Electronic Devices

    Science.gov (United States)

    Menon, Madhu; Srivastava, Deepak; Saini, Subbash

    1998-01-01

    The carbon Nanotube junctions have recently emerged as excellent candidates for use as the building blocks in the formation of nanoscale electronic devices. While the simple joint of two dissimilar tubes can be generated by the introduction of a pair of heptagon-pentagon defects in an otherwise perfect hexagonal grapheme sheet, more complex joints require other mechanisms. In this work we explore structural and electronic properties of complex 3-point junctions of carbon nanotubes using a generalized tight-binding molecular-dynamics scheme.

  20. Carbon Nanotubes: Molecular Electronic Components

    Science.gov (United States)

    Srivastava, Deepak; Saini, Subhash; Menon, Madhu

    1997-01-01

    The carbon Nanotube junctions have recently emerged as excellent candidates for use as the building blocks in the formation of nanoscale molecular electronic networks. While the simple joint of two dissimilar tubes can be generated by the introduction of a pair of heptagon-pentagon defects in an otherwise perfect hexagonal graphene sheet, more complex joints require other mechanisms. In this work we explore structural characteristics of complex 3-point junctions of carbon nanotubes using a generalized tight-binding molecular-dynamics scheme. The study of pi-electron local densities of states (LDOS) of these junctions reveal many interesting features, most prominent among them being the defect-induced states in the gap.

  1. Carbon Nanotube Based Molecular Electronics

    Science.gov (United States)

    Srivastava, Deepak; Saini, Subhash; Menon, Madhu

    1998-01-01

    Carbon nanotubes and the nanotube heterojunctions have recently emerged as excellent candidates for nanoscale molecular electronic device components. Experimental measurements on the conductivity, rectifying behavior and conductivity-chirality correlation have also been made. While quasi-one dimensional simple heterojunctions between nanotubes with different electronic behavior can be generated by introduction of a pair of heptagon-pentagon defects in an otherwise all hexagon graphene sheet. Other complex 3- and 4-point junctions may require other mechanisms. Structural stability as well as local electronic density of states of various nanotube junctions are investigated using a generalized tight-binding molecular dynamics (GDBMD) scheme that incorporates non-orthogonality of the orbitals. The junctions investigated include straight and small angle heterojunctions of various chiralities and diameters; as well as more complex 'T' and 'Y' junctions which do not always obey the usual pentagon-heptagon pair rule. The study of local density of states (LDOS) reveal many interesting features, most prominent among them being the defect-induced states in the gap. The proposed three and four pointjunctions are one of the smallest possible tunnel junctions made entirely of carbon atoms. Furthermore the electronic behavior of the nanotube based device components can be taylored by doping with group III-V elements such as B and N, and BN nanotubes as a wide band gap semiconductor has also been realized in experiments. Structural properties of heteroatomic nanotubes comprising C, B and N will be discussed.

  2. Graphitic silicon nitride: a metal-free ferromagnet with charge and spin current rectification.

    Science.gov (United States)

    Sen, Sabyasachi; Chakrabarti, Swapan

    2014-09-15

    As a first example, herein we show that g-Si(4)N(3) is expected to act as a metal-free ferromagnet featuring both charge and spin current rectification simultaneously. Such rectification is crucial for envisioning devices that contain both logic and memory functionality on a single chip. The spin coherent quantum-transport calculations on g-Si(4)N(3) reveal that the chosen system is a unique molecular spin filter, the current-voltage characteristics of which is asymmetric in nature, which can create a perfect background for synchronous charge and spin current rectification. To shed light on this highly unusual in-silico observation, we have meticulously inspected the bias-dependent modulation of the spin-polarized eigenstates. The results indicate that, whereas only the localized 2p orbitals of the outer-ring (OR) Si atoms participate in the transmission process in the positive bias, both OR Si and N atoms contribute in the reverse bias. Furthermore, we have evaluated the spin-polarized electron-transfer rate in the tunneling regime, and the results demonstrate that the transfer rates are unequal in the positive and negative bias range, leading to the possible realization of a simultaneous logic-memory device. PMID:25044228

  3. RENEWED APPROACH FOR IMAGE RECTIFICATION

    Directory of Open Access Journals (Sweden)

    Sahil Bansal

    2011-08-01

    Full Text Available This paper proposed a new method for image rectification ,it is the process by which the pairs of stereo images of same solid scene taken from different viewpoints in order to produce a pair of “matched epipolar projections” and become parallel to the x-axis of image. A stereo rectified images are helpful for matching algorithms.It restricts that each line parallel to x-axis.The stereo rectification is not unique and actually lead to undesirable distortions. To overcome the drawback of the relative distortion between left image and right image an epipolar line rectification technique is used for point detection and reduce the distortion by minimized the camera rotation angle at each step.By comparative experiments show that the algorithm has an accuracy where other methods fail, namely when the epipolar lines are far from horizontal. Keywords--- Rectification, stereovision, epipolar, distortion, camera rotation.

  4. Giant Thermal Rectification from Polyethylene Nanofiber Thermal Diodes

    CERN Document Server

    Zhang, Teng

    2015-01-01

    The realization of phononic computing is held hostage by the lack of high performance thermal devices. Here we show through theoretical analysis and molecular dynamics simulations that unprecedented thermal rectification factors (as large as 1.20) can be achieved utilizing the phase dependent thermal conductivity of polyethylene nanofibers. More importantly, such high thermal rectifications only need very small temperature differences (< 20 oC) across the device, which is a significant advantage over other thermal diodes which need temperature biases on the order of the operating temperature. Taking this into consideration, we show that the dimensionless temperature-scaled rectification factors of the polymer nanofiber diodes range from 12 to 25 - much larger than other thermal diodes (< 8). The polymer nanofiber thermal diode consists of a crystalline portion whose thermal conductivity is highly phase-sensitive and a cross-linked portion which has a stable phase. Nanoscale size effect can be utilized t...

  5. Theoretical investigation into molecular diodes integrated in series using the non-equilibrium Green's function method.

    Science.gov (United States)

    Liu, Hongmei; Wang, Nan; Li, Peng; Yin, Xing; Yu, Cui; Gao, Nengyue; Zhao, Jianwei

    2011-01-28

    We have conducted a theoretical study on the electronic transport behaviour of two molecular diodes connected in series. The single diode is composed of o-nitrotoluene and o-aminotoluene connecting via a ?-bridge, and the tandem diode is two single diodes connecting via a ?-bridge. It was found that the rectification ratio was greatly improved due to the electronic coupling in the tandem diode. The rectification ratio of the tandem molecular diode can be 20 times higher than that of the single diode, which is quite different from a traditional diode. In addition, we also found that the high rectification ratio correlates with the intramolecular coupling of the tandem system. When long conjugated wires are employed in two single diodes, the rectification ratio is reduced. PMID:21152512

  6. Computer simulation of electron transfer in molecular electronic devices

    OpenAIRE

    Correia, Helena M. G.; Ramos, Marta M. D.

    2005-01-01

    The study of electron transfer through individual molecules bound to metal electrodes has become important due to the potential application in molecular electronic devices. Since the electronic and atomic motions in these molecules influence each other they need to be treated self-consistently. We have used self-consistent quantum chemistry molecular dynamics calculations to discuss some of the issues related to electron transfer through a spatially symmetric [9,10-Bis((2???-para-mercaptophen...

  7. Electronic transport properties of molecular junctions based on the direct binding of aromatic ring to electrodes

    International Nuclear Information System (INIS)

    Highlights: • Transport properties of molecular junction having direct binding of aromatic ring to electrode have been investigated. • The conductance of junction with sp-type electrode is higher than that of junction with sd-type electrode. • The rectifying mechanism critically depends on the nature of benzene–electrode coupling. • The p–n junction-like can be obtained even without heteroatom doping. • The negative differential resistance effect was observed for the case of sp-type electrode. - Abstract: We have used the non-equilibrium Green’s function in combination with the density functional theory to investigate the quantum transport properties of the molecular junctions including a terminated benzene ring directly coupled to surface of metal electrodes (physisorption). The other side of molecule was connected to electrode via thiolate bond (chemisorption). Two different electrodes have been studied, namely Cu and Al. Rectification and negative differential resistance behavior have been observed. We found that the electron transport mechanism is affected by the nature of benzene–electrode coupling. In other words, the transport mechanism depends on the nature of metallic electrode. Changing from sp- to sd-metallic electrode, the molecular junction changes from the Schottky to p–n junction-like diode. The transmission spectra, projected density of state, molecular projected self-consistent Hamiltonian, transmission eigenchannel, and Muliken population have been analyzed for explanation of electronic transport properties. Understanding the transport mechanism in junction having direct coupling of ?-conjugate to electrode will be useful to design the future molecular devices

  8. Molecular electronics studies by synchrotron radiation

    International Nuclear Information System (INIS)

    In molecular electronics research, the molecule-metal interfacial properties crucially control the electronic properties of the devices fabricated. We use synchrotron radiation techniques of PES and NEXAFS, complemented by STM, to study the molecular orientation and interfacial charge transfer processes of model molecule-metal systems.

  9. Resonant optical rectification in bacteriorhodopsin

    Science.gov (United States)

    Groma, Géza I.; Colonna, Anne; Lambry, Jean-Christophe; Petrich, Jacob W.; Váró, György; Joffre, Manuel; Vos, Marten H.; Martin, Jean-Louis

    2004-01-01

    The relative role of retinal isomerization and microscopic polarization in the phototransduction process of bacteriorhodopsin is still an open question. It is known that both processes occur on an ultrafast time scale. The retinal trans?cis photoisomerization takes place on the time scale of a few hundred femtoseconds. On the other hand, it has been proposed that the primary light-induced event is a sudden polarization of the retinal environment, although there is no direct experimental evidence for femtosecond charge displacements, because photovoltaic techniques cannot be used to detect charge movements faster than picoseconds. Making use of the known high second-order susceptibility ?(2) of retinal in proteins, we have used a nonlinear technique, interferometric detection of coherent infrared emission, to study macroscopically oriented bacteriorhodopsin-containing purple membranes. We report and characterize impulsive macroscopic polarization of these films by optical rectification of an 11-fs visible light pulse in resonance with the optical transition. This finding provides direct evidence for charge separation as a precursor event for subsequent functional processes. A simple two-level model incorporating the resonant second-order optical properties of retinal, which are known to be a requirement for functioning of bacteriorhodopsin, is used to describe the observations. In addition to the electronic response, long-lived infrared emission at specific frequencies was observed, reflecting charge movements associated with vibrational motions. The simultaneous and phase-sensitive observation of both the electronic and vibrational signals opens the way to study the transduction of the initial polarization into structural dynamics. PMID:15148391

  10. The role of contacts in molecular electronics

    CERN Document Server

    Cuniberti, G; Gutíerrez, R

    2002-01-01

    Molecular electronic devices are the upmost destiny of the miniaturization trend of electronic components. Although not yet reproducible on large scale, molecular devices are since recently subject of intense studies both experimentally and theoretically, which agree in pointing out the extreme sensitivity of such devices on the nature and quality of the contacts. This chapter intends to provide a general theoretical framework for modelling electronic transport at the molecular scale by describing the implementation of a hybrid method based on Green function theory and density functional algorithms. In order to show the presence of contact-dependent features in the molecular conductance, we discuss three archetypal molecular devices, which are intended to focus on the importance of the different sub-parts of a molecular two-terminal setup.

  11. Valve-Less Rectification Pumps.

    Czech Academy of Sciences Publication Activity Database

    Tesa?, Václav

    Heidelberg : Springer Science+Business Media, LLC, 2008 - (Dongqing, L.), s. 2131-2139 ISBN 978-0-387-48998-8 R&D Projects: GA ?R GA101/07/1499 Institutional research plan: CEZ:AV0Z20760514 Keywords : microfluidics * pumps * fluidic rectification Subject RIV: BK - Fluid Dynamics http://www.springer.com/engineering/book/978-0-387-49000-7

  12. Carbohydrate-actuated nanofluidic diode: switchable current rectification in a nanopipette

    Science.gov (United States)

    Vilozny, Boaz; Wollenberg, Alexander L.; Actis, Paolo; Hwang, Daniel; Singaram, Bakthan; Pourmand, Nader

    2013-09-01

    Nanofluidic structures share many properties with ligand-gated ion channels. However, actuating ion conductance in artificial systems is a challenge. We have designed a system that uses a carbohydrate-responsive polymer to modulate ion conductance in a quartz nanopipette. The cationic polymer, a poly(vinylpyridine) quaternized with benzylboronic acid groups, undergoes a transition from swollen to collapsed upon binding to monosaccharides. As a result, the current rectification in nanopipettes can be reversibly switched depending on the concentration of monosaccharides. Such molecular actuation of nanofluidic conductance may be used in novel sensors and drug delivery systems.Nanofluidic structures share many properties with ligand-gated ion channels. However, actuating ion conductance in artificial systems is a challenge. We have designed a system that uses a carbohydrate-responsive polymer to modulate ion conductance in a quartz nanopipette. The cationic polymer, a poly(vinylpyridine) quaternized with benzylboronic acid groups, undergoes a transition from swollen to collapsed upon binding to monosaccharides. As a result, the current rectification in nanopipettes can be reversibly switched depending on the concentration of monosaccharides. Such molecular actuation of nanofluidic conductance may be used in novel sensors and drug delivery systems. Electronic supplementary information (ESI) available: Experimental details on synthesis of polymer PVP-Bn, optical methods, 1H-NMR spectra, details on pH and ionic strength studies, and examples of current actuation with several different nanopores. See DOI: 10.1039/c3nr02105j

  13. Resolution measures in molecular electron microscopy

    OpenAIRE

    Penczek, Pawel A.

    2010-01-01

    Resolution measures in molecular electron microscopy provide means to evaluate quality of macromolecular structures computed from sets of their two-dimensional line projections. When the amount of detail in the computed density map is low there are no external standards by which the resolution of the result can be judged. Instead, resolution measures in molecular electron microscopy evaluate consistency of the results in reciprocal space and present it as a one-dimensional function of the mod...

  14. Radar image registration and rectification

    Science.gov (United States)

    Naraghi, M.; Stromberg, W. D.

    1983-01-01

    Two techniques for radar image registration and rectification are presented. In the registration method, a general 2-D polynomial transform is defined to accomplish the geometric mapping from one image into the other. The degree and coefficients of the polynomial are obtained using an a priori found tiepoint data set. In the second part of the paper, a rectification procedure is developed that models the distortion present in the radar image in terms of the radar sensor's platform parameters and the topographic variations of the imaged scene. This model, the ephemeris data and the digital topographic data are then used in rectifying the radar image. The two techniques are then used in registering and rectifying two examples of radar imagery. Each method is discussed as to its benefits, shortcomings and registration accuracy.

  15. Spin-excited states and rectification in an organic spin rectifier

    Science.gov (United States)

    Zuo, Meng-Ying; Hu, Gui-Chao; Li, Ying; Ren, Jun-Feng; Wang, Chuan-Kui

    2014-08-01

    Spin-excited states in an asymmetric magnetic organic co-oligomer diode are investigated theoretically. The results demonstrate that the structural asymmetry of the co-oligomer is modulated by the spin-excited states, which is embodied in the wave functions of the eigenstates as well as the spin density wave. By calculating the transport property, a robust spin-current rectification concomitant with a charge-current rectification is observed in all spin-excited states. However, the current through the diode is suppressed distinctly by the spin-excited states, while the rectification ratios may be reduced or enhanced depending on the bias and the excited spins. The intrinsic mechanism is analyzed from the spin-dependent transmission combined with the change of molecular eigenstates under bias. Finally, the temperature-induced spin excitation is simulated. Significant rectification behavior is obtained even at room temperature.

  16. Progress in molecular precursors for electronic materials

    Energy Technology Data Exchange (ETDEWEB)

    Buhro, W.E. [Washington Univ., St. Louis, MO (United States)

    1996-09-01

    Molecular-precursor chemistry provides an essential underpinning to all electronic-materials technologies, including photovoltaics and related areas of direct interest to the DOE. Materials synthesis and processing is a rapidly developing field in which advances in molecular precursors are playing a major role. This article surveys selected recent research examples that define the exciting current directions in molecular-precursor science. These directions include growth of increasingly complex structures and stoichiometries, surface-selective growth, kinetic growth of metastable materials, growth of size-controlled quantum dots and quantum-dot arrays, and growth at progressively lower temperatures. Continued progress in molecular-precursor chemistry will afford precise control over the crystal structures, nanostructures, and microstructures of electronic materials.

  17. Nonlinear optical rectification in cubical quantum dots

    International Nuclear Information System (INIS)

    The optical rectification (OR) coefficient for cubical quantum dots (CQDs), with an applied electric field is theoretically investigated in the framework of the compact-density-matrix approach and an iterative method. The confined wave functions and energies of electrons in the CQDs are calculated in the effective-mass approximation. Numerical calculations are presented for typical GaAs/AlAs CQDs. The results show that the calculation for OR coefficient in the CQDs system can reach a magnitude of 10-4m/V, two orders higher than that in the spherical quantum dots system. The OR coefficient strongly depends on the length of CQDs and the magnitude of electric field. And the peak shifts to the aspect of high energy when considering the electric field.

  18. Electron Dynamics during Strong Field Molecular Ionization

    Science.gov (United States)

    Weinacht, Thomas

    2014-05-01

    Strong Field Ionization plays a central role in the study of ultrafast electron dynamics, both as the first step in attosecond pulse generation and in the launch of electron wave packets in atoms and molecules. This talk will focus on studies of strong field molecular ionization with shaped laser pulses, where the pulse shape dependence yields insight into the electron dynamics during ionization. Coincidence velocity map imaging and close collaboration with theory enable us to examine the role of both neutral and ionic resonances as well as electron correlation. We gratefully acknowledge support from the National Science Foundation under grant number 1205397.

  19. Electron Recombination with Small Molecular Ions

    OpenAIRE

    Brinne Roos, Johanna

    2007-01-01

    In this thesis I have theoretically studied electron recombination processes with small molecular ions. In these kind of processes resonant states are involved. To calculate the potential energy for these states as a function of internuclear distance, structure calculations and scattering calculations have to be performed. So far I have been studying the ion-pair formation with in electron recombination with H3+. The cross section for this process has been calculated using different kind of m...

  20. Projected Quasiparticle Theory for Molecular Electronic Structure

    OpenAIRE

    Scuseria, Gustavo E.; Jimenez-hoyos, Carlos A.; Henderson, Thomas M.; Samanta, Kousik; Ellis, Jason K.

    2011-01-01

    We derive and implement symmetry-projected Hartree-Fock-Bogoliubov (HFB) equations and apply them to the molecular electronic structure problem. All symmetries (particle number, spin, spatial, and complex conjugation) are deliberately broken and restored in a self-consistent variation-after-projection approach. We show that the resulting method yields a comprehensive black-box treatment of strong correlations with effective one-electron (mean-field) computational cost. The e...

  1. Molecular Dissociation Induced by Electron Collisions

    Science.gov (United States)

    Wolf, Andreas

    2009-05-01

    Free electrons can efficiently break molecules or molecular ions in low-energy collisions by the processes of dissociative recombination or attachment. These processes make slow electrons efficient chemical agents in many environments. For dissociative recombination, in particular, studies of the underlying reaction paths and mechanisms have become possible on a uniquely elementary level in recent years both for theory and experiment. On the experimental side, collisions can be prepared at resolved collision energies down to the meV (10 Kelvin) level, increasingly gaining control also over the initial molecular quantum level, and individual events are detected and kinematically analyzed by fast-beam coincidence fragment imaging. Experiments are reported from the ion cooler ring TSR in Heidelberg. Stored beams of molecular ions cooled in their external and internal degrees of freedom are collinearly merged with intense and cold electron beams from cryogenic GaAs photocathodes, recently shown to yield fast cooling of the center-of-mass motion also for heavy and correspondingly slow molecular ion beams. To reconstruct the molecular fragmentation events multiparticle imaging can now be used systematically with collision energies set a wide range, especially aiming at specific electron capture resonances. Thus, for CF^+ it is found that the electronic state of the C fragment (^3P or ^1D) switches resonantly when the collision energy is changed by only a small fraction. As a new powerful tool, an energy-sensitive multi-strip surface-barrier detector (EMU) has been set up to measure with near-unity efficiency the masses of all fragments together with their hit positions in high-multiplicity events. Among many uses, this device allows internal molecular excitations to be derived for individual chemical channels in polyatomic fragmentation. New results will be presented in particular on the breakup of the hydronium ion (D3O^+).

  2. Molecular Electronics : Synthesis of Organic Molecules for Nanoscale Electronics

    DEFF Research Database (Denmark)

    Jennum, Karsten Stein

    2013-01-01

    This thesis includes the synthesis and characterisation of organic compounds designed for molecular electronics. The synthesised organic molecules are mainly based on two motifs, the obigo(phenyleneethynylenes) (OPE)s and tetrathiafulvalene (TTF) as shown below. These two scaffolds (OPE and TTF) are chemically merged together to form cruciform-like structures that are an essential part of the thesis. The cruciform molecules were subjected to molecular conductance measurements to explore their capability towards single-crystal field-effect transistors (Part 1), molecular wires, and single electron transistors (Part 2). The synthetic protocols rely on stepwise Sonogashira coupling reactions. Conductivity studies on various OPE-based molecular wires reveal that mere OPE compounds have a higher electrical resistance compared to the cruciform based wires (up to 9 times higher). The most spectacular result, however, was obtained by a study of a single molecular transistor. The investigated OPE5-TTF compound was captured in a three-terminal experiment, whereby manipulation of the molecule’s electronic spin was possible in different charge states. Thus, we demonstrated how the cruciform molecules could be potential candidates for future molecular electronics Synthesis of a new donor-acceptor chromophore based on a benzoquinone- TTF motif (QuinoneDTF) is also described herein (Part 2). Reaction of this molecule with acid induces a colour change from purple to orange. The purple colour can be restored by addition of base. If the QuinoneDTF chromophore was implemented into a molecular device, it could be possible to switch the conductance through the device by pH alternation.

  3. DNA and microfluidics: Building molecular electronics systems

    International Nuclear Information System (INIS)

    The development of molecular electronics using DNA molecules as the building blocks and using microfluidics to build nanowire arrays is reviewed. Applications of DNA conductivity to build sensors and nanowire arrays, and DNA conjugation with other nanostructures, offers an exciting opportunity to build extremely small analytical devices that are suitable for single-molecule detection and also target screening

  4. Computational Nanotechnology Molecular Electronics, Materials and Machines

    Science.gov (United States)

    Srivastava, Deepak; Biegel, Bryan A. (Technical Monitor)

    2002-01-01

    This presentation covers research being performed on computational nanotechnology, carbon nanotubes and fullerenes at the NASA Ames Research Center. Topics cover include: nanomechanics of nanomaterials, nanotubes and composite materials, molecular electronics with nanotube junctions, kinky chemistry, and nanotechnology for solid-state quantum computers using fullerenes.

  5. Electron-nuclear dynamics of molecular systems

    International Nuclear Information System (INIS)

    The content of an ab initio time-dependent theory of quantum molecular dynamics of electrons and atomic nuclei is presented. Employing the time-dependent variational principle and a family of approximate state vectors yields a set of dynamical equations approximating the time-dependent Schroedinger equation. These equations govern the time evolution of the relevant state vector parameters as molecular orbital coefficients, nuclear positions, and momenta. This approach does not impose the Born-Oppenheimer approximation, does not use potential energy surfaces, and takes into account electron-nuclear coupling. Basic conservation laws are fully obeyed. The simplest model of the theory employs a single determinantal state for the electrons and classical nuclei and is implemented in the computer code ENDyne. Results from this ab-initio theory are reported for ion-atom and ion-molecule collisions

  6. Exploiting plasmon-induced hot electrons in molecular electronic devices.

    Science.gov (United States)

    Conklin, David; Nanayakkara, Sanjini; Park, Tae-Hong; Lagadec, Marie F; Stecher, Joshua T; Chen, Xi; Therien, Michael J; Bonnell, Dawn A

    2013-05-28

    Plasmonic nanostructures can induce a number of interesting responses in devices. Here we show that hot electrons can be extracted from plasmonic particles and directed into a molecular electronic device, which represents a new mechanism of transfer from light to electronic transport. To isolate this phenomenon from alternative and sometimes simultaneous mechanisms of plasmon-exciton interactions, we designed a family of hybrid nanostructure devices consisting of Au nanoparticles and optoelectronically functional porphyin molecules that enable precise control of electronic and optical properties. Temperature- and wavelength-dependent transport measurements are analyzed in the context of optical absorption spectra of the molecules, the Au particle arrays, and the devices. Enhanced photocurrent associated with exciton generation in the molecule is distinguished from enhancements due to plasmon interactions. Mechanisms of plasmon-induced current are examined, and it is found that hot electron generation can be distinguished from other possibilities. PMID:23550717

  7. Effect of nanopore geometry on ion current rectification

    International Nuclear Information System (INIS)

    We present the results of systematic studies of ion current rectification performed on artificial asymmetric nanopores with different geometries and dimensions. The nanopores are fabricated by the ion track etching method using surfactant-doped alkaline solutions. By varying the alkali concentration in the etchant and the etching time, control over the pore profile and dimensions is achieved. The pore geometry is characterized in detail using field-emission scanning electron microscopy. The dependence of the ion current rectification ratio on the pore length, tip diameter, and the degree of pore taper is analysed. The experimental data are compared to the calculations based on the Poisson-Nernst-Planck equations. A strong effect of the tip geometry on the diode-like behaviour is confirmed.

  8. Towards reproducible, scalable lateral molecular electronic devices

    Energy Technology Data Exchange (ETDEWEB)

    Durkan, Colm, E-mail: cd229@eng.cam.ac.uk; Zhang, Qian [Nanoscience Centre, University of Cambridge, 9 JJ Thomson Avenue, Cambridge CB3 0FA (United Kingdom)

    2014-08-25

    An approach to reproducibly fabricate molecular electronic devices is presented. Lateral nanometer-scale gaps with high yield are formed in Au/Pd nanowires by a combination of electromigration and Joule-heating-induced thermomechanical stress. The resulting nanogap devices are used to measure the electrical properties of small numbers of two different molecular species with different end-groups, namely 1,4-butane dithiol and 1,5-diamino-2-methylpentane. Fluctuations in the current reveal that in the case of the dithiol molecule devices, individual molecules conduct intermittently, with the fluctuations becoming more pronounced at larger biases.

  9. Probing electronic excitations in molecular conduction

    CERN Document Server

    Muralidharan, B; Pati, S K; Datta, S

    2005-01-01

    We identify experimental signatures in the current-voltage (I-V) characteristics of weakly contacted molecules directly arising from excitations in their many electron spectrum. We calculate transport properties using a multielectron master equation in the Fock space of an exact diagonalized model many-body Hamiltonian benchmarked for a prototypical molecule (benzene). Using this approach, we quantitatively explain various unique features of molecular conduction that are difficult to capture even qualitatively using standard one-electron self-consistent field (SCF) approaches.

  10. Triazatriangulene as binding group for molecular electronics

    DEFF Research Database (Denmark)

    Wei, Zhongming; Wang, Xintai

    2014-01-01

    The triazatriangulene (TATA) ring system was investigated as a binding group for tunnel junctions of molecular wires on gold surfaces. Self-assembled monolayers (SAMs) of TATA platforms with three different lengths of phenylene wires were fabricated, and their electrical conductance was recorded by both conducting probe-atomic force microscopy (CP-AFM) and scanning tunneling microscopy (STM). Similar measurements were performed for phenylene SAMs with thiol anchoring groups as references. It was found that, despite the presence of a sp3 hybridized carbon atom in the conduction path, the TATA platform displays a contact resistance only slightly larger than the thiols. This surprising finding has not been reported before and was analyzed by theoretical computations of the transmission functions of the TATA anchored molecular wires. The relatively low contact resistance of the TATA platform along with its high stability and directionality make this binding group very attractive for molecular electronic measurements and devices. (Figure Presented).

  11. Electron capture by protons in molecular hydrogen

    International Nuclear Information System (INIS)

    The electron-capture probability at large scattering angles has been calculated for proton-H2 collisions between 1 and 20 keV. The molecular approximation for the triatomic H3+ system is used. The transition probabilities are obtained in the impact-parameter approximation. The theoretical results reproduce the essential features of the low-energy experimental data of Lockwood and Everhart (Phys. Rev.; 125:567 (1962)). (author)

  12. Molecular electronic switch using Carbon nanotube electrodes

    International Nuclear Information System (INIS)

    We propose a stable molecular electronic switch design which contains a double-benzene molecule bridging a pair of CNT electrodes. The effect of different coupling between the molecule and electrodes on the switch function of the system is studied by use of tight-binding Green function approach. The system keeps a stable switch function for a large range of the coupling distance, as long as the ? coupling between the molecule and the CNT remains

  13. High rectification ratios of Fe-porphyrin molecules on Au facets

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Xiaoyu; Wang, Gwo-Ching [Department of Physics, Applied Physics and Astronomy, Rensselaer Polytechnic Institute, 110, 8th Street, Troy, NY 12180 (United States); Lewis, Kim M., E-mail: lewisk2@rpi.edu [Department of Physics, Applied Physics and Astronomy, Rensselaer Polytechnic Institute, 110, 8th Street, Troy, NY 12180 (United States)

    2012-09-14

    We report room temperature measurements of current vs. voltage (I-V) from self-assembled Fe porphyrin [Fe(III) 5,15-di[4-(s-acetylthio)phenyl]-10,20-diphenyl porphine] molecular layers formed on annealed gold crystal facets on glass substrates. I-V curves were measured using an atomic force microscope with a conductive platinum tip. We observed a rectifier effect that shows asymmetric I-V curves from a monolayer of molecules. The majority rectification ratios at {+-}1 V obtained from hundreds of I-V lie in between 20 and 200, with the highest up to 9000. This is in contrast to the symmetric I-V curves measured from a few nm thick multilayer molecular islands. We contribute the observed rectification in ultrathin FeP molecular layers from asymmetric Schottky barriers that result from molecules in different bonding strengths to electrodes of gold and platinum. -- Highlights: Black-Right-Pointing-Pointer FeP molecular layers or islands of different thickness were self-assembled on Au. Black-Right-Pointing-Pointer High rectification ratios up to 9000 observed in sub-nm thick FeP molecular layers. Black-Right-Pointing-Pointer Measured current vs. voltage using a conductive AFM tip as one electrode. Black-Right-Pointing-Pointer Observed rectification of symmetric molecules using two different electrodes.

  14. High rectification ratios of Fe–porphyrin molecules on Au facets

    International Nuclear Information System (INIS)

    We report room temperature measurements of current vs. voltage (I–V) from self-assembled Fe porphyrin [Fe(III) 5,15-di[4-(s-acetylthio)phenyl]-10,20-diphenyl porphine] molecular layers formed on annealed gold crystal facets on glass substrates. I–V curves were measured using an atomic force microscope with a conductive platinum tip. We observed a rectifier effect that shows asymmetric I–V curves from a monolayer of molecules. The majority rectification ratios at ±1 V obtained from hundreds of I–V lie in between 20 and 200, with the highest up to 9000. This is in contrast to the symmetric I–V curves measured from a few nm thick multilayer molecular islands. We contribute the observed rectification in ultrathin FeP molecular layers from asymmetric Schottky barriers that result from molecules in different bonding strengths to electrodes of gold and platinum. -- Highlights: ? FeP molecular layers or islands of different thickness were self-assembled on Au. ? High rectification ratios up to 9000 observed in sub-nm thick FeP molecular layers. ? Measured current vs. voltage using a conductive AFM tip as one electrode. ? Observed rectification of symmetric molecules using two different electrodes.

  15. Towards molecular electronics: electron transport through single molecules

    International Nuclear Information System (INIS)

    Full text: Molecular electronics, a new emerging science area in the field of nanotechnology, is seen as a potential replacement for silicon device-technology in the next decade. To enable such a technology, an essential initial requirement is a detailed understanding of the electrical conduction properties of molecules placed between metal electrodes. We recently investigated the electrical conduction of single molecules using first-principle quantum mechanical calculations based on the density functional theory and non-equilibrium Green's function techniques. We demonstrate that each molecule has its own distinct current-voltage characteristic, determined by the positions of the molecular energy levels and the degree of electrode-molecule coupling. We show that the calculated attenuation factors of molecular wires made of polyene dithiol, polyphenyl dithiol and alkane dithiol agree with experimental data. Furthermore we reveal that photo isomerization of azobenzene can be utilized as an electrical molecular switch and that bipyridine dithiol, in the presence of a gate electrode, can function as a single-molecule field-effect transistor. Different experimental techniques that help to elucidate the conduction properties of single molecules will be discussed

  16. Modeling ion sensing in molecular electronics

    International Nuclear Information System (INIS)

    We examine the ability of molecules to sense ions by measuring the change in molecular conductance in the presence of such charged species. The detection of protons (H+), alkali metal cations (M+), calcium ions (Ca2+), and hydronium ions (H3O+) is considered. Density functional theory (DFT) is used within the Keldysh non-equilibrium Green's function framework (NEGF) to model electron transport properties of quinolinedithiol (QDT, C9H7NS2), bridging Al electrodes. The geometry of the transport region is relaxed with DFT. The transport properties of the device are modeled with NEGF-DFT to determine if this device can distinguish among the M+ + QDT species containing monovalent cations, where M+ = H+, Li+, Na+, or K+. Because of the asymmetry of QDT in between the two electrodes, both positive and negative biases are considered. The electron transmission function and conductance properties are simulated for electrode biases in the range from ?0.5?V to 0.5?V at increments of 0.1 V. Scattering state analysis is used to determine the molecular orbitals that are the main contributors to the peaks in the transmission function near the Fermi level of the electrodes, and current-voltage relationships are obtained. The results show that QDT can be used as a proton detector by measuring transport through it and can conceivably act as a pH sensor in solutions. In addition, QDT may be able to distinguish among different monovalent species. This work suggests an approach to design modern molecular electronic conductance sensors with high sensitivity and specificity using well-established quantum chemistry

  17. Thermal conductance and rectification of asymmetric tilt grain boundary in graphene

    CERN Document Server

    Cao, Hai-Yuan; Gong, Xin-Gao

    2011-01-01

    We have investigated the lattice thermal transport across the asymmetry tilt grain boundary between armchair and zigzag grains by using nonequilibrium molecular dynamics (NEMD). We have observed significant temperature drop and ultralow temperature-dependent thermal boundary resistance. Importantly, we find an unexpected thermal rectification phenomenon, i.e, the thermal conductivity and Kapitza conductance is asymmetric with respect to the thermal transport direction. And the effect of thermal rectification could be amplified by increasing the difference of temperature imposed on two sides. Our results propose a new promising kind of thermal rectifier and phonon diodes from polycrystalline graphene without delicate manupulation of the atomic structures.

  18. Projected quasiparticle theory for molecular electronic structure.

    Science.gov (United States)

    Scuseria, Gustavo E; Jiménez-Hoyos, Carlos A; Henderson, Thomas M; Samanta, Kousik; Ellis, Jason K

    2011-09-28

    We derive and implement symmetry-projected Hartree-Fock-Bogoliubov (HFB) equations and apply them to the molecular electronic structure problem. All symmetries (particle number, spin, spatial, and complex conjugation) are deliberately broken and restored in a self-consistent variation-after-projection approach. We show that the resulting method yields a comprehensive black-box treatment of static correlations with effective one-electron (mean-field) computational cost. The ensuing wave function is of multireference character and permeates the entire Hilbert space of the problem. The energy expression is different from regular HFB theory but remains a functional of an independent quasiparticle density matrix. All reduced density matrices are expressible as an integration of transition density matrices over a gauge grid. We present several proof-of-principle examples demonstrating the compelling power of projected quasiparticle theory for quantum chemistry. PMID:21974513

  19. Thermal boundary conductance and thermal rectification in molecules.

    Science.gov (United States)

    Leitner, David M

    2013-10-24

    An approach is presented to calculate thermal boundary resistance in molecules, which occurs, for example, at the interfaces between moieties held at fixed temperatures and a molecular bridge that connects them. If the vibrational frequencies of each moiety lie outside of the band of heat-carrying modes of the bridge, anharmonic interactions mediate thermal conduction at the boundaries. We have expressed thermal boundary conductance in terms of the low-order anharmonic interactions between a moiety and a molecular bridge. Differences in the temperature-dependent boundary conductance at each end of the bridge can be exploited in the design of a molecular thermal diode. The approach is illustrated with the calculation of thermal boundary conductance and thermal rectification in azulene-(CH2)N-anthracene. PMID:23701185

  20. Terahertz Radiation from Phase Matched Optical Rectification in Magnetized Plasmas and Crystals

    Science.gov (United States)

    Gordon, Daniel; Sprangle, Phillip; Ting, Antonio; Kapetanakos, Christos; Alexeev, Ilya; Briscoe, Eldridge

    2004-11-01

    Nonlinear optics in a crystal is described by an expansion of the electronic polarization in powers of the electric field. The second order term in the expansion leads to several frequency conversion effects including optical rectification. Optical rectification of a laser pulse leads to the generation of terahertz radiation when the laser pulse length is on the order of 1 picosecond. We discuss an experiment underway at the Naval Research Laboratory utilizing a phase matched optical rectification process to efficiently generate terahertz radiation in GaSe and other crystals. We also discuss the analogous process in a magnetized plasma, and show that phase matching can be achieved by tuning the laser pulse length, plasma density, and magnetic field strength. Particle-in-cell simulations suggest that relativistic terahertz pulses can be generated in a plasma.

  1. Electron transport in atomic and molecular wires

    Science.gov (United States)

    Xu, Bingqian

    Molecular electronics involves constructing atomic and molecular junctions in which an atomic chain or a single molecule or small number of molecules are bridged between two electrodes, measuring and understanding the current-voltage response of such junctions. Contacts between the atoms or molecules and the electrodes greatly affect the current-voltage characteristics. Other challenges include how to determine the conductance of single molecules. This dissertation presents a study of single atomic/molecular conductance with modified Scanning Tunneling Microscope (STM) and Atomic Force Microscope (AFM). Firstly I describe an electron transport study of atomically-thin Au wires by (1) modulating the electrochemical potential and (2) anion adsorption onto the wire. The potential modulation induces a conductance change around 0.55G0 (G0 = 2e2/h) per V for a wire with conductance quantized near 1G0 in the absence of anion adsorption. However, in the presence of I- adsorption, the conductance changes as much as 1.5G0/V. Second, I present the work of determining single-molecule conductance of various molecules by repeatedly forming thousands of Au-molecule-Au junctions. The molecules tested have either S-atoms or N-atoms on both sides so that they can form Au-S or Au-N bonds chemically to ensure the good contacts. I have determined the tunneling decay constant (betaN) of the N-alkanedithiol molecules to be 1.0 +/- 0.1 per carbon atom and depends on the applied bias very weakly. The forces needed to break down the single N-alkanedithiol molecule junction and the 4,4' bipyridine molecule junction are 1.5 +/- 0.2nN and 0.8 +/- 0.2nN respectively, suggesting that the Au-Au bond broke in the alkanedithiol case while the Au-N bond broke in the 4,4' bipyridine case. I have determined the length and base-pair dependence of the DNA conductance. Electron transport through different base pair DNA molecules decreases exponentially with the number of "AT" base pairs inserted in the G-rich region but inversely proportional to the length of "GC" base pairs. A DNA molecule with mismatch was found to conduct less than its perfectly matched sequences.

  2. Thermoelectric transport with electron-phonon coupling and electron-electron interaction in molecular junctions

    OpenAIRE

    Ren, Jie; Zhu, Jian-Xin; Gubernatis, James E.; WANG, CHEN; Li, Baowen

    2011-01-01

    Within the framework of nonequilibrium Green's functions, we investigate the thermoelectric transport in a single molecular junction with electron-phonon and electron-electron interactions. By transforming into a displaced phonon basis, we are able to deal with these interactions non-perturbatively. Then, by invoking the weak tunneling limit, we are able to calculate the thermoelectricity. Results show that at low temperatures, resonances of the thermoelectric figure of meri...

  3. Electroosmotic flow rectification in conical nanopores

    Science.gov (United States)

    Laohakunakorn, Nadanai; Keyser, Ulrich F.

    2015-07-01

    Recent experimental work has suggested that electroosmotic flows (EOFs) through conical nanopores exhibit rectification in the opposite sense to the well-studied effect of ionic current rectification. A positive bias voltage generates large EOF and small current, while negative voltages generate small EOF and large current. Here we systematically investigate this effect using finite-element simulations. We find that inside the pore, the electric field and salt concentration are inversely correlated, which leads to the inverse relationship between the magnitudes of EOF and current. Rectification occurs when the pore is driven into states characterized by different salt concentrations depending on the sign of the voltage. The mechanism responsible for this behaviour is concentration polarization, which requires the pore to exhibit the properties of permselectivity and asymmetry.

  4. Electroosmotic flow rectification in conical nanopores

    CERN Document Server

    Laohakunakorn, Nadanai

    2015-01-01

    Recent experimental work has suggested that electroosmotic flows (EOF) through conical nanopores exhibit rectification in the opposite sense to the well-studied effect of ionic current rectification. A positive bias voltage generates large EOF and small current, while negative voltages generate small EOF and large current. Here we systematically investigate this effect using finite-element simulations. We find that inside the pore, the electric field and salt concentration are inversely correlated, which leads to the inverse relationship between the magnitudes of EOF and current. Rectification occurs when the pore is driven into states characterized by different salt concentrations depending on the sign of the voltage. The mechanism responsible for this behaviour is concentration polarization, which requires the pore to exhibit the properties of permselectivity and asymmetry.

  5. Time rectification system for in-beam TOF-PET

    International Nuclear Information System (INIS)

    A time rectification system for a In-Beam TOF-PET was described.It consists of a pair of BaF2(?40 mm x 45 mm) crystals coupled to Philips photomultipliers XP2020Q and a time coincidence electronic system using standard NIM modules. The best coincidence timing resolution of the system for pairs of 511 keV gamma rays is 576 ps. Some factors affecting the time resolution were primarily discussed, such as the types of photomultiplier tubes (PMT), the model of signal readout, the effects of different discriminators and timing amplifiers. The experiment results show that the signal read from the PMT dynode can get the optimum resolution; the PMT types, especially the rise time and electronic transmit time greatly affect the system performance. The shorter the rise time and electronic transmit time for the PMTs is, the better the timing performance is. The system timing performance is also related to the electronic combination. (authors)

  6. Thermal rectification in nonlinear quantum circuits

    DEFF Research Database (Denmark)

    Ruokola, T.; Ojanen, T.

    2009-01-01

    We present a theoretical study of radiative heat transport in nonlinear solid-state quantum circuits. We give a detailed account of heat rectification effects, i.e., the asymmetry of heat current with respect to a reversal of the thermal gradient, in a system consisting of two reservoirs at finite temperatures coupled through a nonlinear resonator. We suggest an experimentally feasible superconducting circuit employing the Josephson nonlinearity to realize a controllable low-temperature heat rectifier with a maximal asymmetry of the order of 10%. We also discover a parameter regime where the rectification changes sign as a function of temperature.

  7. Molecular rectification with identical metal electrodes at low temperatures Thin film deposition; Gold; Molecular electronics; Langmuir- Blodgett; Au/LB/Au structures; Fabrication

    CERN Document Server

    Okazaki, N

    2003-01-01

    A gold deposition technique for the fabrication of Au/LB/Au structures has been developed. The kinetic energy of evaporated gold atoms is reduced by scattering the gold atoms from argon gas. Moreover, the samples are cooled down below 173K (-100 deg C) to avoid the diffusion of gold atoms into the LB films and to fabricate electrically continuous thin gold electrodes (This technique has since been used in fabrication of Au/LB/Au structures even with monolayer LB films (Metzger, et al. (2001)). To measure the current-voltage characteristics of the Au/LB/Au structures at liquid helium temperatures, new junction geometries have been explored. To avoid the direct contact of the Gallium-Indium eutectic onto the LB films, which is the cause of the breakdown of the junction at lower temperatures, a cross electrode junction geometry is used. The problem of poor Langmuir-Blodgett film deposition at the penumbra region of the base electrode is avoided by covering the penumbra region with an insulating omega-tricosenoic...

  8. Molecular Self-assembly for Organic Electronics

    Science.gov (United States)

    Wang, Jun; Kaur, Irvinder; Diaconescu, Bogdan; Jazdzyk, Mikael; Miller, Glen P.; Pohl, Karsten

    2009-10-01

    Self-assembled thin films of novel organic molecules hold the promise of emerging technologies and applications ranging from sensors for biological applications to organic electronics and more efficient organic photovoltaics. Self-assembled monolayers (SAMs) form as a result of a delicate balance between competing molecule-substrate and intermolecular interactions. To control such self-assembly processes, it is mandatory to understand how this balance reflects onto the SAM's final structure. Here we present an ultra-high vacuum scanning tunneling microscopy (STM) study of the self-assembly of novel pentacene derivatives and functionalized fullerenes (F-C60) on metal surfaces. Pentacene is known to exhibit large carrier mobility and has been studied extensively as a semiconductor in organic thin film devices. However, it is subject to facile photo-oxidation that limits device lifetime. We recently synthesized novel pentacene derivatives that show a dramatically increased resistance to photo-oxidation. We identified 6,13-dichloropentacene as a promising candidate for organic electronics. On the compact surface of gold, 6,13-dichloropentacene forms self-assembled domains with various high symmetry orientations. The quality of the SAM is seem to dramatically improve when the 6,13-dichloropentacene are deposited on the (788) vicinal surface of gold where the presence of parallel atomic steps will select only one of the possible SAM orientations due to the molecule-step interaction. Thus we observe the formation of very large self-assembled 6,13-dichloropentacene monolayers with perfect single domain orientation. We have also studied the self-assembly of C60 functionalized with alkyl chains of various lengths (F-C60) on Ag(111). We find that as a function of the alkyl chain length various structures are forming, ranging from zigzag like to linear arrays of C60 fullerene cages. The symmetry and unit cell size of the F-C60 SAMs is dictated by the alkyl-surface and the intermolecular interactions. These results show that C60 molecules can be assembled in 2D and non-compact molecular arrays with a surface density controllable via appropriate chemical functionalization. Those structures show promise as candidates for selfassembled molecular junctions.

  9. Radiative thermal rectification using superconducting materials

    Energy Technology Data Exchange (ETDEWEB)

    Nefzaoui, Elyes, E-mail: elyes.nefzaoui@univ-poitiers.fr; Joulain, Karl, E-mail: karl.joulain@univ-poitiers.fr; Drevillon, Jérémie; Ezzahri, Younès [Institut Pprime, Université de Poitiers-CNRS-ENSMA, 2, Rue Pierre Brousse, Bâtiment B25, TSA 41105, 86073 Poitiers Cedex 9 (France)

    2014-03-10

    Thermal rectification can be defined as an asymmetry in the heat flux when the temperature difference between two interacting thermal reservoirs is reversed. In this Letter, we present a far-field radiative thermal rectifier based on high-temperature superconducting materials with a rectification ratio up to 80%. This value is among the highest reported in literature. Two configurations are examined: a superconductor (Tl{sub 2}Ba{sub 2}CaCu{sub 2}O{sub 8}) exchanging heat with (1) a black body and (2) another superconductor, YBa{sub 2}Cu{sub 3}O{sub 7} in this case. The first configuration shows a higher maximal rectification ratio. Besides, we show that the two-superconductor rectifier exhibits different rectification regimes depending on the choice of the reference temperature, i.e., the temperature of the thermostat. Presented results might be useful for energy conversion devices, efficient cryogenic radiative insulators engineering, and thermal logical circuits’ development.

  10. A Quantum Chemical View of Molecular and Nano-Electronics

    OpenAIRE

    Jiang, Jun

    2007-01-01

    This dissertation presents a generalized quantum chemical approach for electron transport in molecular electronic devices based on Green's function scattering theory. It allows to describe both elastic and inelastic electron transport processes at first principles levels of theory, and to treat devices with metal electrodes either chemically or physically bonded to the molecules on equal footing. Special attention has been paid to understand the molecular length dependence of current-voltage ...

  11. Molecular Electronics : A Theoretical Study of Electronic Structure of Bulk and Interfaces

    OpenAIRE

    Unge, Mikael

    2006-01-01

    This thesis deals with theoretical studies of the electronic structure of molecules used in the context of molecular electronics. Both studies with model Hamiltonians and first principle calculations have been performed. The materials studied include molecular crystals of pentacene and DNA, which are used as active material in field-effect transistors and as tentative molecular wires, respectively. The molecular magnet compound TCNE and surface modification by means of chemisorption of TDAE o...

  12. A New Full Adder Cell for Molecular Electronics

    CERN Document Server

    Ghasemi, Mehdi; Navi, Keivan; 10.5121/vlsic.2011.2401

    2012-01-01

    Due to high power consumption and difficulties with minimizing the CMOS transistor size, molecular electronics has been introduced as an emerging technology. Further, there have been noticeable advances in fabrication of molecular wires and switches and also molecular diodes can be used for designing different logic circuits. Considering this novel technology, we use molecules as the active components of the circuit, for transporting electric charge. In this paper, a full adder cell based on molecular electronics is presented. This full adder is consisted of resonant tunneling diodes and transistors which are implemented via molecular electronics. The area occupied by this kind of full adder would be much times smaller than the conventional designs and it can be used as the building block of more complex molecular arithmetic circuits.

  13. Electron Interference in Molecular Circular Polarization Attosecond XUV Photoionization

    Directory of Open Access Journals (Sweden)

    Kai-Jun Yuan

    2015-01-01

    Full Text Available Two-center electron interference in molecular attosecond photoionization processes is investigated from numerical solutions of time-dependent Schrödinger equations. Both symmetric H\\(_2^+\\ and nonsymmetric HHe\\(^{2+}\\ one electron diatomic systems are ionized by intense attosecond circularly polarized XUV laser pulses. Photoionization of these molecular ions shows signature of interference with double peaks (minima in molecular attosecond photoelectron energy spectra (MAPES at critical angles \\(\\vartheta_c\\ between the molecular \\(\\textbf{R}\\ axis and the photoelectron momentum \\(\\textbf{p}\\. The interferences are shown to be a function of the symmetry of electronic states and the interference patterns are sensitive to the molecular orientation and pulse polarization. Such sensitivity offers possibility for imaging of molecular structure and orbitals.

  14. Molecular modeling and multiscaling issues for electronic material applications

    CERN Document Server

    Iwamoto, Nancy; Yuen, Matthew; Fan, Haibo

    Volume 1 : Molecular Modeling and Multiscaling Issues for Electronic Material Applications provides a snapshot on the progression of molecular modeling in the electronics industry and how molecular modeling is currently being used to understand material performance to solve relevant issues in this field. This book is intended to introduce the reader to the evolving role of molecular modeling, especially seen through the eyes of the IEEE community involved in material modeling for electronic applications.  Part I presents  the role that quantum mechanics can play in performance prediction, such as properties dependent upon electronic structure, but also shows examples how molecular models may be used in performance diagnostics, especially when chemistry is part of the performance issue.  Part II gives examples of large-scale atomistic methods in material failure and shows several examples of transitioning between grain boundary simulations (on the atomistic level)and large-scale models including an example ...

  15. Molecular tips for scanning tunneling microscopy: intermolecular electron tunneling for single-molecule recognition and electronics.

    Science.gov (United States)

    Nishino, Tomoaki

    2014-01-01

    This paper reviews the development of molecular tips for scanning tunneling microscopy (STM). Molecular tips offer many advantages: first is their ability to perform chemically selective imaging because of chemical interactions between the sample and the molecular tip, thus improving a major drawback of conventional STM. Rational design of the molecular tip allows sophisticated chemical recognition; e.g., chiral recognition and selective visualization of atomic defects in carbon nanotubes. Another advantage is that they provide a unique method to quantify electron transfer between single molecules. Understanding such electron transfer is mandatory for the realization of molecular electronics. PMID:24420248

  16. Electron-phonon scattering in molecular electronics: from inelastic electron tunnelling spectroscopy to heating effects

    International Nuclear Information System (INIS)

    In this paper, we investigate dissipation in molecular electronic devices. Dissipation is a crucial quantity which determines the stability and heating of the junction. Moreover, several experimental techniques which use inelastically scattered electrons as probes to investigate the geometry in the junction are becoming fundamental in the field. In order to describe such physical effects, a non-equilibrium Green's function (NEGF) method was implemented to include scattering events between electrons and molecular vibrations in current simulations. It is well known that the final heating of the molecule depends also on the ability of the molecule to relax vibrational quanta into the contact reservoirs. A semi-classical rate equation has been implemented and integrated within the NEGF formalism to include this relaxation. The model is based on two quantities: (i) the rate of emission of phonons in the junction by electron-phonon scattering and (ii) a microscopic approach for the computation of the phonon decay rate, accounting for the dynamical coupling between the vibrational modes localized on the molecule and the contact phonons. The method is applied to investigate inelastic electron tunnelling spectroscopy (IETS) signals in CO molecules on Cu(110) substrates as well as dissipation in C60 molecules on Cu(110) and Si(100) surfaces. It is found that the mechanisms of energy relaxation are highly mode-specific and depend crucially on the lead electronic strucend crucially on the lead electronic structure and junction geometry

  17. Fast polaron switching in degenerate molecular quantum dots

    International Nuclear Information System (INIS)

    Devices for nano- and molecular size electronics are currently a focus of research aimed at an efficient current rectification and switching. Current switching due to conformational changes in the molecules is slow, of the order of a few kHz. Fast switching (?1 THz) may be achieved, at least in principle, in a degenerate molecular quantum dot with strong coupling of electrons with vibrational excitations. We show that the mean-field approach fails to properly describe intrinsic molecular switching and present an exact solution to the problem

  18. Thermal conductivity and thermal rectification in unzipped carbon nanotubes.

    Science.gov (United States)

    Ni, Xiaoxi; Zhang, Gang; Li, Baowen

    2011-06-01

    We study the thermal transport in completely unzipped carbon nanotubes, which are called graphene nanoribbons, partially unzipped carbon nanotubes, which can be seen as carbon-nanotube-graphene-nanoribbon junctions, and carbon nanotubes by using molecular dynamics simulations. It is found that the thermal conductivity of a graphene nanoribbon is much less than that of its perfect carbon nanotube counterparts because of the localized phonon modes at the boundary. A partially unzipped carbon nanotube has the lowest thermal conductivity due to additional localized modes at the junction region. More strikingly, a significant thermal rectification effect is observed in both partially unzipped armchair and zigzag carbon nanotubes. Our results suggest that carbon-nanotube-graphene-nanoribbon junctions can be used in thermal energy control. PMID:21555836

  19. Heat transport across a SiGe nanowire axial junction: Interface thermal resistance and thermal rectification

    Science.gov (United States)

    Rurali, Riccardo; Cartoixà, Xavier; Colombo, Luciano

    2014-07-01

    We study thermal transport in SiGe nanowires by means of nonequilibrium molecular dynamics simulations. We calculate the axial interface thermal resistance (ITR) of realistic models of SiGe nanowires that are obtained in different experimental conditions. We study thermal rectification, finding that heat transport from Si to Ge is favored, particularly in sharp junctions, and that this behavior can be explained in terms of the different temperature dependence of the thermal conductivity of the pristine nanowires.

  20. Photoelectrochemical solar conversion systems molecular and electronic aspects

    CERN Document Server

    Munoz, Andres G

    2012-01-01

    Providing new insights into the molecular and electronic processes involved in the conversion of sunlight into chemical products, Photoelectrochemical Solar Conversion Systems: Molecular and Electronic Aspects begins with an historical overview and a survey of recent developments in the electrochemistry of semiconductors and spectroscopic techniques. It then provides a comprehensive introduction to the science of conversion cells, reviews current issues and potential directions, and covers a wide range of materials from organic to inorganic cells.Employing a tutorial organization with balanced

  1. Site-directed deep electronic tunneling through a molecular network

    International Nuclear Information System (INIS)

    Electronic tunneling in a complex molecular network of N(>2) donor/acceptor sites, connected by molecular bridges, is analyzed. The 'deep' tunneling dynamics is formulated using a recursive perturbation expansion, yielding a McConnell-type reduced N-level model Hamiltonian. Applications to models of molecular junctions demonstrate that the donor-bridge contact parameters can be tuned in order to control the tunneling dynamics and particularly to direct the tunneling pathway to either one of the various acceptors

  2. Electron transport in molecular wires with transition metal contacts

    OpenAIRE

    Dalgleish, Hugh

    2006-01-01

    A molecular wire is an organic molecule that forms a conducting bridge between electronic contacts. Single molecules are likely to be the smallest entities to conduct electricity and thus molecular wires present many interesting challenges to fundamental science as well as enormous potential for nanoelectronic technological applications. A particular challenge stems from the realization that the properties of molecular wires are strongly influenced by the combined characteristics of the molec...

  3. A New Full Adder Cell for Molecular Electronics

    OpenAIRE

    Keivan Navi; Mohammad Hossein Moaiyeri; Mehdi Ghasemi

    2012-01-01

    Due to high power consumption and difficulties with minimizing the CMOS transistor size, molecular electronics has been introduced as an emerging technology. Further, there have been noticeable advances in fabrication of molecular wires and switches and also molecular diodes can be used for designing different logic circuits. Considering this novel technology, we use molecules as the active components of the circuit, for transporting electric charge. In this paper, a full ad...

  4. Real-time imaging of acoustic rectification

    Science.gov (United States)

    Danworaphong, S.; Kelf, T. A.; Matsuda, O.; Tomoda, M.; Tanaka, Y.; Nishiguchi, N.; Wright, O. B.; Nishijima, Y.; Ueno, K.; Juodkazis, S.; Misawa, H.

    2011-11-01

    We image gigahertz surface acoustic waves normally incident on a microscopic linear array of triangular holes—a generic "acoustic diode" geometry—with a real-time ultrafast optical technique. Spatiotemporal Fourier transforms reveal wave diffraction orders in k-space. Squared amplitude reflection and transmission coefficients for incidence on both sides of the array are evaluated and compared with numerical simulations. We thereby directly demonstrate acoustic rectification with an asymmetric structure.

  5. Photovoltaic and rectification currents in quantum dots

    Science.gov (United States)

    Vavilov, M. G.; Dicarlo, L.; Marcus, C. M.

    2005-06-01

    We investigate theoretically and experimentally the statistical properties of dc current through an open quantum dot subject to ac excitation of a shape-defining gate. The symmetries of rectification current and photovoltaic current with respect to applied magnetic field are examined. Theory and experiment are found to be in good agreement throughout a broad range of frequency and ac power, ranging from adiabatic to nonadiabatic regimes.

  6. Photovoltaic and Rectification Currents in Quantum Dots

    CERN Document Server

    Vavilov, M G; Marcus, C M

    2004-01-01

    We investigate theoretically and experimentally the statistical properties of dc current through an open quantum dot subject to ac excitation of a shape-defining gate. The symmetries of rectification current and photovoltaic current with respect to applied magnetic field are examined. Theory and experiment are found to be in good agreement throughout a broad range of frequency and ac power, ranging from adiabatic to nonadiabatic regimes.

  7. Research ZCS Synchronous Rectification of Resonant Converter

    OpenAIRE

    Xiao Kui Li

    2014-01-01

    In this study, the application of ZCS synchronous rectification for the IPT resonant converter is researched. A novel control method that AC-DC section of the resonant converter works in ZCS SR state is proposed by using the characteristic of resonant tank current. First, the ZCS working operation of SR is presented, analyzed and equivalent circuits for each operation mode are also given, respectively. Then, the novel control method of ZCS SR for resonant convert...

  8. Current rectification by asymmetric molecules: An ab initio study

    CERN Document Server

    Zhou, Y; Xu, Y; Zeng, Z Y; Zhou, Yan-hong; Zheng, Xiao-hong; Xu, Ying; Zeng, Zhao Yang

    2006-01-01

    We study current rectification effect in an asymmetric molecule HOOC-C$_6$H$_4$-(CH$_2$)$_n$ sandwiched between two Aluminum electrodes using an {\\sl ab initio} nonequilibrium Green function method. The conductance of the system decreases exponentially with the increasing number $n$ of CH$_2$. The phenomenon of current rectification is observed such that a very small current appears at negative bias and a sharp negative differential resistance at a critical positive bias when $n\\ge 2$. The rectification effect arises from the asymmetric structure of the molecule and the molecule-electrode couplings. A significant rectification ratio of $\\sim$38 can be achieved when $n=5$.

  9. Fragmentation of molecular ions in slow electron collisions

    OpenAIRE

    Novotny, Steffen

    2008-01-01

    The fragmentation of positively charged hydrogen molecular ions by the capture of slow electrons, the so called dissociative recombination (DR), has been investigated in storage ring experiments at the TSR, Heidelberg, where an unique twin-electron-beam arrangement was combined with high resolution fragment imaging detection. Provided with well directed cold electrons the fragmentation kinematics were measured down to meV collision energies where pronounced rovibrational Feshbach resonances a...

  10. Molecular dynamics simulations of electron irradiated PVDF nanofibers

    Science.gov (United States)

    Miao, Jiayuan; Bhatta, Ram; Kisielowski, Christian; Lolla, Dinesh; Reneker, Darrell; Tsige, Mesfin; Taylor, Philip

    2014-03-01

    High-resolution, aberration corrected transmission electron microscopy was used to observe morphological changes and segmental motion of electrospun poly(vinylidene fluoride) nanofibers in an 80 kilovolt electron beam. Atomic and molecular scale high-resolution images of fibers were made with an aberration corrected electron microscope. Chemical and morphological changes, which include the breaking of the fiber, loss of fluorine atoms and cross-linking of chains, caused by the high-energy electron beam were observed. We present the results of molecular dynamics (MD) simulations of such atomic and molecular level observations. The calculational models include the influence of chain scission, chain recoiling, and torsional defects on the morphology of a nanofiber. The effects of the loss of fluorine atoms and the applied tension on the morphology of the fibers were also investigated. High-resolution, aberration corrected transmission electron microscopy was used to observe morphological changes and segmental motion of electrospun poly(vinylidene fluoride) nanofibers in an 80 kilovolt electron beam. Atomic and molecular scale high-resolution images of fibers were made with an aberration corrected electron microscope. Chemical and morphological changes, which include the breaking of the fiber, loss of fluorine atoms and cross-linking of chains, caused by the high-energy electron beam were observed. We present the results of molecular dynamics (MD) simulations of such atomic and molecular level observations. The calculational models include the influence of chain scission, chain recoiling, and torsional defects on the morphology of a nanofiber. The effects of the loss of fluorine atoms and the applied tension on the morphology of the fibers were also investigated. Work supported by the Petroleum Research Fund of the American Chemical Society.

  11. Self-assembled nanogaps for molecular electronics

    DEFF Research Database (Denmark)

    Tang, Qingxin; Tong, Yanhong

    2009-01-01

    A nanogap for molecular devices was realized using solution-based self-assembly. Gold nanorods were assembled to gold nanoparticle-coated conducting SnO2:Sb nanowires via thiol end-capped oligo(phenylenevinylene)s (OPVs). The molecular gap was easily created by the rigid molecule itself during self-assembly and the gap length was determined by the molecule length. The gold nanorods and gold nanoparticles, respectively covalently bonded at the two ends of the molecule, had very small dimensions, e. g. a width of similar to 20 nm, and hence were expected to minimize the screening effect. The ultra-long conducting SnO2:Sb nanowires provided the bridge to connect one of the electrodes of the molecular device (gold nanoparticle) to the external circuit. The tip of the atomic force microscope (AFM) was contacted onto the other electrode (gold nanorod) for the electrical measurement of the OPV device. The conductance measurement confirmed that the self-assembly of the molecules and the subsequent self-assembly of the gold nanorods was a feasible method for the fabrication of the nanogap of the molecular devices.

  12. High-Order Harmonic Generation and Molecular Orbital Tomography: Characteristics of Molecular Recollision Electronic Wave Packets

    OpenAIRE

    Chen, Yanjun.; Yan LI; Yang, Shiping; Liu, Jie

    2008-01-01

    We investigate the orientation dependence of molecular high-order harmonic generation (HHG) both numerically and analytically. We show that the molecular recollision electronic wave packets (REWPs) in the HHG are closely related to the ionization potential as well as the particular orbital from which it ionized. As a result, the spectral amplitude of the molecular REWP can be significantly different from its reference atom (i.e., with the same ionization potential as the mol...

  13. Ballistic thermal rectification in nanoscale three-terminal junctions

    OpenAIRE

    Zhang, Lifa; Wang, Jian-sheng; Li, Baowen

    2010-01-01

    We study ballistic thermal transport in three-terminal atomic nanojunctions by the nonequilibrium Green's function method. We find that there is ballistic thermal rectification in asymmetric three-terminal structures because of the incoherent phonon scattering from the control terminal. With spin-phonon interaction, we also find the ballistic thermal rectification even in symmetric three-terminal paramagnetic structures.

  14. Molecular interfaces for plasmonic hot electron photovoltaics

    Science.gov (United States)

    Pelayo García de Arquer, F.; Mihi, Agustín; Konstantatos, Gerasimos

    2015-01-01

    The use of self-assembled monolayers (SAMs) to improve and tailor the photovoltaic performance of plasmonic hot-electron Schottky solar cells is presented. SAMs allow the simultaneous control of open-circuit voltage, hot-electron injection and short-circuit current. To that end, a plurality of molecule structural parameters can be adjusted: SAM molecule's length can be adjusted to control plasmonic hot electron injection. Modifying SAMs dipole moment allows for a precise tuning of the open-circuit voltage. The functionalization of the SAM can also be selected to modify short-circuit current. This allows the simultaneous achievement of high open-circuit voltages (0.56 V) and fill-factors (0.58), IPCE above 5% at the plasmon resonance and maximum power-conversion efficiencies of 0.11%, record for this class of devices.The use of self-assembled monolayers (SAMs) to improve and tailor the photovoltaic performance of plasmonic hot-electron Schottky solar cells is presented. SAMs allow the simultaneous control of open-circuit voltage, hot-electron injection and short-circuit current. To that end, a plurality of molecule structural parameters can be adjusted: SAM molecule's length can be adjusted to control plasmonic hot electron injection. Modifying SAMs dipole moment allows for a precise tuning of the open-circuit voltage. The functionalization of the SAM can also be selected to modify short-circuit current. This allows the simultaneous achievement of high open-circuit voltages (0.56 V) and fill-factors (0.58), IPCE above 5% at the plasmon resonance and maximum power-conversion efficiencies of 0.11%, record for this class of devices. Electronic supplementary information (ESI) available: Contact-potential differentiometry measurements, FTIR characterization, performance statistics and gold devices. See DOI: 10.1039/c4nr06356b

  15. Electron-beam evaporated silicon as a top contact for molecular electronic device fabrication.

    Science.gov (United States)

    Kumar, Rajesh; Yan, Haijun; McCreery, Richard L; Bergren, Adam Johan

    2011-08-28

    This paper discusses the electronic properties of molecular devices made using covalently bonded molecular layers on carbon surfaces with evaporated silicon top contacts. The Cu "top contact" of previously reported carbon/molecule/Cu devices was replaced with e-beam deposited Si in order to avoid Cu oxidation or electromigration, and provide further insight into electron transport mechanisms. The fabrication and characterization of the devices is detailed, including a spectroscopic assessment of the molecular layer integrity after top contact deposition. The electronic, optical, and structural properties of the evaporated Si films are assessed in order to determine the optical gap, work function, and film structure, and show that the electron beam evaporated Si films are amorphous and have suitable conductivity for molecular junction fabrication. The electronic characteristics of Si top contact molecular junctions made using different molecular layer structures and thicknesses are used to evaluate electron transport in these devices. Finally, carbon/molecule/silicon devices are compared to analogous carbon/molecule/metal junctions and the possible factors that control the conductance of molecular devices with differing contact materials are discussed. PMID:21701710

  16. Molecular and electronic structure of molybdenum pentafluoride

    International Nuclear Information System (INIS)

    Using the method of 19F NMR the structure and molecular mobility of glasslike molybdenum pentafluoride are investigated. NMR spectra have been taken at the temperature of 100-370 K. It has been established that in fluid state MoF5 is presented by monomers with the structure of square pyramid, which form endless polymeric chains at hardening. Glass-like MoF5 transformation into crystalline (tetrameric) state is considered

  17. Orthogonally modulated molecular transport junctions for resettable electronic logic gates

    Science.gov (United States)

    Meng, Fanben; Hervault, Yves-Marie; Shao, Qi; Hu, Benhui; Norel, Lucie; Rigaut, Stéphane; Chen, Xiaodong

    2014-01-01

    Individual molecules have been demonstrated to exhibit promising applications as functional components in the fabrication of computing nanocircuits. Based on their advantage in chemical tailorability, many molecular devices with advanced electronic functions have been developed, which can be further modulated by the introduction of external stimuli. Here, orthogonally modulated molecular transport junctions are achieved via chemically fabricated nanogaps functionalized with dithienylethene units bearing organometallic ruthenium fragments. The addressable and stepwise control of molecular isomerization can be repeatedly and reversibly completed with a judicious use of the orthogonal optical and electrochemical stimuli to reach the controllable switching of conductivity between two distinct states. These photo-/electro-cooperative nanodevices can be applied as resettable electronic logic gates for Boolean computing, such as a two-input OR and a three-input AND-OR. The proof-of-concept of such logic gates demonstrates the possibility to develop multifunctional molecular devices by rational chemical design.

  18. Molecular interfaces for plasmonic hot electron photovoltaics.

    Science.gov (United States)

    Pelayo García de Arquer, F; Mihi, Agustín; Konstantatos, Gerasimos

    2015-02-14

    The use of self-assembled monolayers (SAMs) to improve and tailor the photovoltaic performance of plasmonic hot-electron Schottky solar cells is presented. SAMs allow the simultaneous control of open-circuit voltage, hot-electron injection and short-circuit current. To that end, a plurality of molecule structural parameters can be adjusted: SAM molecule's length can be adjusted to control plasmonic hot electron injection. Modifying SAMs dipole moment allows for a precise tuning of the open-circuit voltage. The functionalization of the SAM can also be selected to modify short-circuit current. This allows the simultaneous achievement of high open-circuit voltages (0.56 V) and fill-factors (0.58), IPCE above 5% at the plasmon resonance and maximum power-conversion efficiencies of 0.11%, record for this class of devices. PMID:25578026

  19. Dissociative recombination of an electron and a molecular ion

    International Nuclear Information System (INIS)

    It is shown that the multichannel problem of the recombination of an electron and a molecular ion can be rigorously reduced to the determination of an optical potential for the elastic scattering of an electron by a molecular ion. A method, based on the formalism of many-particle theory, is proposed and makes it possible to construct the optical potential. As a result, formulas are derived for the reasonance part of the dissociative-recombination cross section with allowance for strong channel coupling. These formulas are used to calculate the cross section for dissociative recombination of an electron and a molecular-oxygen ion in various vibrational states. All the quantities in the formula for the cross section are determined by the present method, and are not adjustable parameters. The results are in satisfactory agreement with the experimental data

  20. Microwave power engineering generation, transmission, rectification

    CERN Document Server

    Okress, Ernest C

    1968-01-01

    Microwave Power Engineering, Volume 1: Generation, Transmission, Rectification considers the components, systems, and applications and the prevailing limitations of the microwave power technology. This book contains four chapters and begins with an introduction to the basic concept and developments of microwave power technology. The second chapter deals with the development of the main classes of high-power microwave and optical frequency power generators, such as magnetrons, crossed-field amplifiers, klystrons, beam plasma amplifiers, crossed-field noise sources, triodes, lasers. The third

  1. Research ZVS Synchronous Rectification of Resonant Converter

    OpenAIRE

    Xiao Kui Li

    2014-01-01

    In order to expand the application of synchronous rectification, the technology using ZVS synchronous rectifier is studied which is based on the IPT resonant converter. By using its own resonant characteristic, a novel control method that AC-DC section of the resonant converter works in ZVS SR state is proposed in this study. First of all, the ZVS working operation of SR is analyzed and equivalent circuits for each operation mode are also given. On that basis, the novel control method is prop...

  2. High-Order Harmonic Generation and Molecular Orbital Tomography: Characteristics of Molecular Recollision Electronic Wave Packets

    CERN Document Server

    Chen, Yanjun; Yang, Shiping; Liu, Jie

    2008-01-01

    We investigate the orientation dependence of molecular high-order harmonic generation (HHG) both numerically and analytically. We show that the molecular recollision electronic wave packets (REWPs) in the HHG are closely related to the ionization potential as well as the particular orbital from which it ionized. As a result, the spectral amplitude of the molecular REWP can be significantly different from its reference atom (i.e., with the same ionization potential as the molecule under study) in some energy regions due to the interference between the atomic cores of the molecules. This finding is important for molecular orbital tomography using HHG[Nature \\textbf{432}, 867(2004)].

  3. Spin polarized electron tunneling and magnetoresistance in molecular junctions.

    Science.gov (United States)

    Szulczewski, Greg

    2012-01-01

    This chapter reviews tunneling of spin-polarized electrons through molecules positioned between ferromagnetic electrodes, which gives rise to tunneling magnetoresistance. Such measurements yield important insight into the factors governing spin-polarized electron injection into organic semiconductors, thereby offering the possibility to manipulate the quantum-mechanical spin degrees of freedom for charge carriers in optical/electrical devices. In the first section of the chapter a brief description of the Jullière model of spin-dependent electron tunneling is reviewed. Next, a brief description of device fabrication and characterization is presented. The bulk of the review highlights experimental studies on spin-polarized electron tunneling and magnetoresistance in molecular junctions. In addition, some experiments describing spin-polarized scanning tunneling microscopy/spectroscopy on single molecules are mentioned. Finally, some general conclusions and prospectus on the impact of spin-polarized tunneling in molecular junctions are offered. PMID:21809185

  4. Electron transport and light absorption/emission in molecular complexes

    Science.gov (United States)

    Martinez, Miguel; Mourokh, Lev

    2015-03-01

    In this work, we address photon-assisted electron transport in molecular triads and tetrads connected to the leads. Donor-bridge-acceptor triads are promising candidates for efficient organic solar cells, as the photon absorption makes it possible to transfer electrons against the applied voltage. Deriving and solving numerically the equations of motion for electron creation/annihilation operators, we obtain the parameters of molecular complexes which are optimal for a maximal efficiency of the light harvesting. For donor-bridge-bridge-acceptor tetrads, we determine the conditions for another phenomenon, optical up-conversion. Electron transport along the applied voltage and the photon absorption at one of the bridges facilitates the photon emission at another bridge with higher frequency. Using the same equations of motion approach, we obtain the emitted electromagnetic energy and its dependence on the system parameters.

  5. Electronic Transport in Molecular Diode Heterojunctions

    Science.gov (United States)

    Yee, Shannon; Sun, Jibin; Darancet, Pierre; Tilley, T. Don; Neaton, Jeffrey; Segalman, Rachel A.

    2010-03-01

    Anode-donor, donor-acceptor, and acceptor-cathode interfaces dominate the performance of organic solar cells. However, within thin-film, bulk-heterojunction, or nanostructured morphologies, interfacial transport affects are not well understood. In order to better understand these interfaces, a simplified system consisting of a single, small, diode molecule covalently bound to electrodes (anode-end group-donor-bridge-acceptor-end group-cathode) is considered. The end groups and bridge moities can be interchanged using chemical synthesis technique to understand how these parameters affect electronic transport. Here, we report our findings on single-molecule diode measurements using a conducting atomic force microscope on four newly synthesized molecules consisting of bithiophene donors and naphthalene diimide acceptors with systematic interchange of two end groups and two bridge moities. We explain the electronic structure of these molecules using absorption and fluorescence spectrometry, cyclic voltammetry, and transition voltage spectrometry in conjunction with newly developed theory.

  6. Modeling rectification effects in mesoscopic superconducting devices

    International Nuclear Information System (INIS)

    Model: loop of weak links of RSJ+thermal fluctuations. Good agreement with diode effects measured in Al mesoscopic triangles. Prediction: amplitude of the rectified signal depends strongly on the current contacts configuration in triangle shaped SC. Key ingredients: field induced persistent currents and asymmetry induced by an off-center injection of external currents. Similar effects should be also present in every system with a persistent current and an asymmetric current path. Useful to design and control newer and smaller diode devices. We study thermal fluctuations and capacitive effects on small Josephson Junction Rings (JJR) that mimics the rectification phenomena recently observed in triangular shaped mesoscopic superconductors, due to the superposition of the field induced persistent current with the bias current. At finite temperature we predicted that the amplitude of the rectified signal depends strongly on the current contacts configuration on the JJR, in coincidence with experiments. In addition, we analyze the range of parameters where a closed loop of capacitive junctions is an appropriate model to explain the experimental observations. We conclude that the closed loop of weak links, a JJR, is a simple, robust and good model to explain the observed voltage rectification effects on mesoscopic superconducting samples for a wide range of temperature.

  7. Instrumentation for Molecular Electronics Device Research

    Science.gov (United States)

    Kibel, Ashley Ann

    This dissertation describes work on three projects concerning the design and implementation of instrumentation used to study potential organic electronic devices. The first section describes the conducting atomic force microscope (CAFM) in the study of the mechanical and electronic interactions between DNA bases and nucleosides. Previous STM data suggested that an STM tip could recognize single base pairs through an electronic interaction after a functionalized tip made contact with a self assembled monolayer then was retracted. The conducting AFM was employed in order to understand the mechanical interactions of such a system and how they were affecting electrical responses. The results from the conducting AFM showed that the scanning probe system was measuring multiple base-pair interactions, and thus did not have single base resolution. Further, results showed that the conductance between a single base-nucleoside pair is below the detection limit of a potential commercial sequencing device. The second section describes the modifications of a scanning probe microscope in order to study the conductance of single organic molecules under illumination. Modifications to the scanning probe microscope are described as are the control and data analysis software for an experiment testing the single molecule conductance of an organic molecule under illumination. This instrument was then tested using a novel charge-separation molecule, which is being considered for its potential photovoltaic properties. The experiments showed that the instrumentation is capable of detecting differences in conductance upon laser illumination of the molecule on a transparent conductive surface. The third section describes measurements using the illuminated CAFM, as well as the design and construction of an illuminated mercury drop electrode apparatus. Both instruments were tested by attempting to observe photovoltaic behavior in a novel self-organized film of the charge-separation molecules mentioned in the previous paragraph. Results and calculations show that the conducting AFM is not a useful tool in the examination of these organic photovoltaics, while the mercury drop apparatus measured photovoltaic effects in the film. Although photovoltaic effects were measurable with the mercury drop electrode, it was found that the film exhibited very low photon-to-electron conversion efficiency (IPCE).

  8. Molecular orbital theory of ballistic electron transport through molecules

    Science.gov (United States)

    Ernzerhof, Matthias; Rocheleau, Philippe; Goyer, Francois

    2009-03-01

    Electron transport through molecules occurs, for instance, in STM imaging and in conductance measurements on molecular electronic devices (MEDs). To model these phenomena, we use a non-Hermitian model Hamiltonian [1] for the description of open systems that exchange current density with their environment. We derive qualitative, molecular-orbital-based rules relating molecular structure and conductance. We show how side groups attached to molecular conductors [2] can completely suppress the conductance. We discuss interference effects in aromatic molecules [3] that can also inhibit electron transport. Rules are developed [1] for the prediction of Fano resonances. All these phenomena are explained with a molecular orbital theory [1,4] for molecules attached to macroscopic reservoirs. [1] F. Goyer, M. Ernzerhof, and M. Zhuang, JCP 126, 144104 (2007); M. Ernzerhof, JCP 127, 204709 (2007). [2] M. Ernzerhof, M. Zhuang, and P. Rocheleau, JCP 123, 134704 (2005); G. C. Solomon, D Q. Andrews, R P. Van Duyne, and M A. Ratner, JACS 130, 7788 (2008). [3] M. Ernzerhof, H. Bahmann, F. Goyer, M. Zhuang, and P. Rocheleau, JCTC 2, 1291 (2006); G. C. Solomon, D. Q. Andrews, R. P. Van Duyne, and M. A. Ratner, JCP 129, 054701 (2008). [4] B.T. Pickup, P.W. Fowler, CPL 459, 198 (2008); P. Rocheleau and M. Ernzerhof, JCP, submitted.

  9. Effect of interfacial coupling on rectification in organic spin rectifiers

    Science.gov (United States)

    Hu, Gui-Chao; Zuo, Meng-Ying; Li, Ying; Zhang, Zhao; Ren, Jun-Feng; Wang, Chuan-Kui

    2015-07-01

    The effect of interfacial coupling on rectification in an organic co-oligomer spin diode is investigated theoretically by considering spin-independent and spin-resolved couplings respectively. In the case of spin-independent coupling, an optimal interfacial coupling strength with a significant enhanced rectification ratio is found, whose value depends on the structural asymmetry of the molecule. In the case of spin-resolved coupling, we found that only the variation of the interfacial coupling with specific spin is effective to modulate the rectification, which is due to the spin-filtering property of the central asymmetric magnetic molecule. A transition of the spin-current rectification between parallel spin-current rectification and antiparallel spin-current rectification may be observed with the variation of the spin-resolved interfacial coupling. The interfacial effect on rectification is further analyzed from the spin-dependent transmission spectrum at different biases. Project supported by the National Natural Science Foundation of China (Grant No. 1374195), the Natural Science Foundation of Shandong Province, China (Grant No. ZR2014AM017), and the Excellent Young Scholars Research Fund of Shandong Normal University, China.

  10. Exploring coherent transport through ?-stacked systems for molecular electronic devices

    DEFF Research Database (Denmark)

    Li, Qian; Solomon, Gemma

    2014-01-01

    Understanding electron transport across ?-stacked systems can help to elucidate the role of intermolecular tunneling in molecular junctions and potentially with the design of high-efficiency molecular devices. Here we show how conjugation length and substituent groups influence the electron transport and thermoelectric response in the ?-stacked structures by investigating five representative stacked molecular junctions. We found that a ?-stacked system of two substituted anthracenes exhibits good thermopower and a high power factor, suggesting that increased conjugation can enhance the thermoelectric response. The fully eclipsed structure of quinhydrone exhibits a high power factor at the minimum energy structure and could thus be a better candidate in a thermoelectric device compared with the other ?-stacked systems considered.

  11. Electron energy-loss spectra in molecular fluorine

    Science.gov (United States)

    Nishimura, H.; Cartwright, D. C.; Trajmar, S.

    1979-01-01

    Electron energy-loss spectra in molecular fluorine, for energy losses from 0 to 17.0 eV, have been taken at incident electron energies of 30, 50, and 90 eV and scattering angles from 5 to 140 deg. Features in the spectra above 11.5 eV energy loss agree well with the assignments recently made from optical spectroscopy. Excitations of many of the eleven repulsive valence excited electronic states are observed and their location correlates reasonably well with recent theoretical results. Several of these excitations have been observed for the first time and four features, for which there are no identifications, appear in the spectra.

  12. Theory and Application of Dissociative Electron Capture in Molecular Identification

    CERN Document Server

    Havey, C D; Jones, T; Voorhees, K J; Laramee, J A; Cody, R B; Clougherty, D P; Eberhart, Mark; Voorhees, Kent J.; Laramee, James A.; Cody, Robert B.; Clougherty, Dennis P.

    2006-01-01

    The coupling of an electron monochromator (EM) to a mass spectrometer (MS) has created a new analytical technique, EM-MS, for the investigation of electrophilic compounds. This method provides a powerful tool for molecular identification of compounds contained in complex matrices, such as environmental samples. EM-MS expands the application and selectivity of traditional MS through the inclusion of a new dimension in the space of molecular characteristics--the electron resonance energy spectrum. However, before this tool can realize its full potential, it will be necessary to create a library of resonance energy scans from standards of the molecules for which EM-MS offers a practical means of detection. Here, an approach supplementing direct measurement with chemical inference and quantum scattering theory is presented to demonstrate the feasibility of directly calculating resonance energy spectra. This approach makes use of the symmetry of the transition-matrix element of the captured electron to discriminat...

  13. Chiral molecular films as electron polarizers and polarization modulators

    CERN Document Server

    Medina, Ernesto; Ratner, Mark; Mujica, Vladimiro

    2012-01-01

    Recent experiments on electron scattering through molecular films have shown that chiral molecules can be efficient sources of polarized electrons even in the absence of heavy nuclei as source of a strong spin-orbit interaction. We show that self-assembled monolayers (SAMs) of chiral molecules are strong electron polarizers due to the high density effect of the monolayers and explicitly compute the scattering amplitude off a helical molecular model of carbon atoms. Longitudinal polarization is shown to be the signature of chiral scattering. For elastic scattering, we find that at least double scattering events must take place for longitudinal polarization to arise. We predict energy windows for strong polarization, determined by the energy dependences of spin-orbit strength and multiple scattering probability. An incoherent mechanism for polarization amplification is proposed, that increases the polarization linearly with the number of helix turns, consistent with recent experiments on DNA SAMs.

  14. Calibration-free sinusoidal rectification and uniform retinal irradiance in scanning light ophthalmoscopy.

    Science.gov (United States)

    Yang, Qiang; Yin, Lu; Nozato, Koji; Zhang, Jie; Saito, Kenichi; Merigan, William H; Williams, David R; Rossi, Ethan A

    2015-01-01

    Sinusoidal rectification (i.e., desinusoiding) is necessary for scanning imaging systems and is typically achieved by calculating a rectification transform from a calibration image such as a regular grid. This approach is susceptible to error due to electronic or mechanical instability that can alter the phase of the imaging window with respect to the calibration transform. Here, we show a calibration-free rectification method implemented from live video of a scanning light ophthalmoscope (SLO) with or without adaptive optics (AO). This approach, which capitalizes on positional differences in the images obtained in the forward and backward scan directions, dynamically keeps the imaging window in phase with the motion of the sinusoidal resonant scanner, preventing errors from signal drift over time. A benefit of this approach is that it allows the light power across the field-of-view (FOV) to be modulated inversely to achieve uniform irradiance on the retina, a feature desirable for functional imaging methods and light safety in SLOs. PMID:25531615

  15. Rectification of Uncalibrated Images for Stereo Vision

    Directory of Open Access Journals (Sweden)

    Yang Fengbao

    2013-01-01

    Full Text Available This paper aims at rectification of uncalibrated stereo images. We use the direct method to compute the rectifying transformations, not to deduce from the fundamental matrix, so to reduce the uncertainty; Minimize the distance from the point to its epipolar line to ensue the uniqueness of the two rectifying transformations. We only extract a few correspondent points, make use of the condition of the correspondent points in the rectified images also meet the polar constraint, minimize distance of all of the correspondent points to the corresponding epipolar line, then obtain the system equations, through solving system of equations, thus get the rectifying transformation matrix and rectify the stereo image pairs. Experiments show that, the size of the rectified images change not so seriously, the vertical disparity is eliminated, so the subsequent stereo correspondence can be fulfilled on the horizontal scan line of the rectified images completely.

  16. III - V semiconductor structures for biosensor and molecular electronics applications

    Energy Technology Data Exchange (ETDEWEB)

    Luber, S.M.

    2007-01-15

    The present work reports on the employment of III-V semiconductor structures to biosensor and molecular electronics applications. In the first part a sensor based on a surface-near two dimensional electron gas for a use in biological environment is studied. Such a two dimensional electron gas inherently forms in a molecular beam epitaxy (MBE) grown, doped aluminum gallium arsenide - gallium arsenide (AlGaAs-GaAs) heterostructure. Due to the intrinsic instability of GaAs in aqueous solutions the device is passivated by deposition of a monolayer of 4'-substituted mercaptobiphenyl molecules. The influence of these molecules which bind to the GaAs via a sulfur group is investigated by Kelvin probe measurements in air. They reveal a dependence of GaAs electron affinity on the intrinsic molecular dipole moment of the mercaptobiphenyls. Furthermore, transient surface photovoltage measurements are presented which demonstrate an additional influence of mercaptobiphenyl chemisorption on surface carrier recombination rates. As a next step, the influence of pH-value and salt concentration upon the sensor device is discussed based on the results obtained from sensor conductance measurements in physiological solutions. A dependence of the device surface potential on both parameters due to surface charging is deduced. Model calculations applying Poisson-Boltzmann theory reveal as possible surface charging mechanisms either the adsorption of OH- ions on the surface, or the dissociation of OH groups in surface oxides. A comparison between simulation settings and physical device properties indicate the OH- adsorption as the most probable mechanism. In the second part of the present study the suitability of MBE grown III-V semiconductor structures for molecular electronics applications is examined. In doing so, a method to fabricate nanometer separated, coplanar, metallic electrodes based on the cleavage of a supporting AlGaAs-GaAs heterostructure is presented. This is followed by a thorough topographical and electrical characterization of fabricated devices which includes the electrostatic trapping of single gold nanoclusters between the electrodes. A first application to molecular electronics is presented by conductance measurements on a molecular layer of oligophenylenvinylene derivatives. Simulations on model molecules applying extended Hueckel theory and the nonequilibrium Greens function formalism reveal a good qualitative agreement between theory and experiment. Furthermore, promising extensions to the present fabrication method are discussed. These include the processing and characterization of broken T-shaped electrodes suitable for measurements on single molecules, and the transition to pure semiconductor electrodes based on indium arsenide. (orig.)

  17. Rigorous theory of molecular orientational nonlinear optics

    Science.gov (United States)

    Kwak, Chong Hoon; Kim, Gun Yeup

    2015-01-01

    Classical statistical mechanics of the molecular optics theory proposed by Buckingham [A. D. Buckingham and J. A. Pople, Proc. Phys. Soc. A 68, 905 (1955)] has been extended to describe the field induced molecular orientational polarization effects on nonlinear optics. In this paper, we present the generalized molecular orientational nonlinear optical processes (MONLO) through the calculation of the classical orientational averaging using the Boltzmann type time-averaged orientational interaction energy in the randomly oriented molecular system under the influence of applied electric fields. The focal points of the calculation are (1) the derivation of rigorous tensorial components of the effective molecular hyperpolarizabilities, (2) the molecular orientational polarizations and the electronic polarizations including the well-known third-order dc polarization, dc electric field induced Kerr effect (dc Kerr effect), optical Kerr effect (OKE), dc electric field induced second harmonic generation (EFISH), degenerate four wave mixing (DFWM) and third harmonic generation (THG). We also present some of the new predictive MONLO processes. For second-order MONLO, second-order optical rectification (SOR), Pockels effect and difference frequency generation (DFG) are described in terms of the anisotropic coefficients of first hyperpolarizability. And, for third-order MONLO, third-order optical rectification (TOR), dc electric field induced difference frequency generation (EFIDFG) and pump-probe transmission are presented.

  18. Molecular interferometer to decode attosecond electron–nuclear dynamics

    Science.gov (United States)

    Palacios, Alicia; González-Castrillo, Alberto; Martín, Fernando

    2014-01-01

    Understanding the coupled electronic and nuclear dynamics in molecules by using pump–probe schemes requires not only the use of short enough laser pulses but also wavelengths and intensities that do not modify the intrinsic behavior of the system. In this respect, extreme UV pulses of few-femtosecond and attosecond durations have been recognized as the ideal tool because their short wavelengths ensure a negligible distortion of the molecular potential. In this work, we propose the use of two twin extreme UV pulses to create a molecular interferometer from direct and sequential two-photon ionization processes that leave the molecule in the same final state. We theoretically demonstrate that such a scheme allows for a complete identification of both electronic and nuclear phases in the wave packet generated by the pump pulse. We also show that although total ionization yields reveal entangled electronic and nuclear dynamics in the bound states, doubly differential yields (differential in both electronic and nuclear energies) exhibit in addition the dynamics of autoionization, i.e., of electron correlation in the ionization continuum. Visualization of such dynamics is possible by varying the time delay between the pump and the probe pulses. PMID:24591647

  19. Molecular interferometer to decode attosecond electron-nuclear dynamics.

    Science.gov (United States)

    Palacios, Alicia; González-Castrillo, Alberto; Martín, Fernando

    2014-03-18

    Understanding the coupled electronic and nuclear dynamics in molecules by using pump-probe schemes requires not only the use of short enough laser pulses but also wavelengths and intensities that do not modify the intrinsic behavior of the system. In this respect, extreme UV pulses of few-femtosecond and attosecond durations have been recognized as the ideal tool because their short wavelengths ensure a negligible distortion of the molecular potential. In this work, we propose the use of two twin extreme UV pulses to create a molecular interferometer from direct and sequential two-photon ionization processes that leave the molecule in the same final state. We theoretically demonstrate that such a scheme allows for a complete identification of both electronic and nuclear phases in the wave packet generated by the pump pulse. We also show that although total ionization yields reveal entangled electronic and nuclear dynamics in the bound states, doubly differential yields (differential in both electronic and nuclear energies) exhibit in addition the dynamics of autoionization, i.e., of electron correlation in the ionization continuum. Visualization of such dynamics is possible by varying the time delay between the pump and the probe pulses. PMID:24591647

  20. Molecular geometric phase from the exact electron-nuclear factorization

    CERN Document Server

    Requist, Ryan

    2015-01-01

    The topological Longuet-Higgins phase changes into a geometric phase when the adiabatic Born-Oppenheimer product is replaced by the exact electron-nuclear factorization $\\Phi_R(r) \\chi(R)$ in a model pseudorotating molecule. The model provides the first examples of induced vector potentials and molecular geometric phase from the exact factorization. The former contributes to the persistent nuclear current of the state. The exact potential energy surface is calculated and found to contain a term depending on the Fubini-Study metric for the conditional electronic wavefunction.

  1. Molecular switching with strong electron-phonon interaction

    International Nuclear Information System (INIS)

    We have shown that the attractive electron correlations caused by a strong electron-phonon interaction (EPI) in molecular quantum dots (MQDs) weakly coupled with the leads provide a switching effect, when the current-voltage characteristics show two branches with high and low current for the same voltage. Key features of polaronic correlated transport in degenerate MQDs are briefly reviewed fully taking into account both the Coulomb repulsion and EPI. Switching shows up when the effective interaction of polarons is attractive and the state of the dot is multiple degenerate

  2. Determination of hydrogen and electron densities in interstellar molecular clouds

    International Nuclear Information System (INIS)

    The moleular hydrogen densities is six interstellar molecular clouds have been determined from the spectral data for 12CO and 13CO using the radiative transfer model with large scale velocity gradient. The results indicate that in the central part of the cloud the density of H2 decreases exponentially with the distance from the centre. This is physically realistic, as a finite value of hydrogen density at the centre is obtained. The electron density near the centre of the Orion A cloud has been determined from the spectral data for HCN. For other clouds considered by us the electron densities appear to be too low to affect the spectral intensity. (author)

  3. Signature properties of water: Their molecular electronic origins.

    Science.gov (United States)

    Sokhan, Vlad P; Jones, Andrew P; Cipcigan, Flaviu S; Crain, Jason; Martyna, Glenn J

    2015-05-19

    Water challenges our fundamental understanding of emergent materials properties from a molecular perspective. It exhibits a uniquely rich phenomenology including dramatic variations in behavior over the wide temperature range of the liquid into water's crystalline phases and amorphous states. We show that many-body responses arising from water's electronic structure are essential mechanisms harnessed by the molecule to encode for the distinguishing features of its condensed states. We treat the complete set of these many-body responses nonperturbatively within a coarse-grained electronic structure derived exclusively from single-molecule properties. Such a "strong coupling" approach generates interaction terms of all symmetries to all orders, thereby enabling unique transferability to diverse local environments such as those encountered along the coexistence curve. The symmetries of local motifs that can potentially emerge are not known a priori. Consequently, electronic responses unfiltered by artificial truncation are then required to embody the terms that tip the balance to the correct set of structures. Therefore, our fully responsive molecular model produces, a simple, accurate, and intuitive picture of water's complexity and its molecular origin, predicting water's signature physical properties from ice, through liquid-vapor coexistence, to the critical point. PMID:25941394

  4. Modulations to molecular high order harmonic generation by electron de Broglie wave

    OpenAIRE

    Chen, J.; Chen, Y. J.; Fan, J; J Liu; Chen, S.G.; He, X. T.

    2008-01-01

    We present a new theory that the molecular high order harmonic generation in an intense laser field is determined by molecular internal symmetry and momentum distribution of the tunneling-ionized electron. The molecular internal symmetry determines the quantum interference form of the returning electron inside the molecule. The electron momentum distribution determines the relative interference strength of each individual electron de Broglie wave. All individual electron de ...

  5. Two-dimensional electronic spectroscopy of molecular aggregates.

    Science.gov (United States)

    Ginsberg, Naomi S; Cheng, Yuan-Chung; Fleming, Graham R

    2009-09-15

    The properties of molecular aggregates, coupled clusters of small molecules, are often challenging to unravel because of their inherent complexity and disordered environments. Their structure-function relationships are often far from obvious. However, their ability to efficiently channel excitation energy over remarkable distances, as is the case in photosynthetic light harvesting, is a compelling motivation to investigate them. Understanding and subsequently mimicking the processes in photosynthesis, for example, will set the stage for considerable advances in using light harvesting to fuel renewable energy technologies. Two-dimensional (2D) electronic spectroscopy is emerging as a nonlinear optical technique that provides significant insight into the interactions and dynamics of complex molecular systems. In addition to spectrally resolving excitation and emission energies over significant bandwidths with femtosecond resolution, this technique has already enabled discoveries about the structure and dynamics of photosynthetic light-harvesting complexes and other aggregates. Multiple capabilities unique to 2D electronic spectroscopy enable such findings. For example, the spectral resolution of excitation and emission combined with the ability to eliminate the effects of static disorder can reveal the homogeneous line width of a transition and the different dynamic contributions to it. Two dimensional spectroscopy is also sensitive to electronic coherence and has been employed to identify and characterize coherent excitation energy transfer dynamics in photosynthetic systems and conjugated polymers. The presence of cross-peaks, signals for which excitation and emission occur at different wavelengths, provides multiple forms of information. First, it allows the identification of states in congested spectra and reveals correlations between them. Second, we can track excitation energy flow from origin to terminus through multiple channels simultaneously. Finally, 2D electronic spectroscopy is uniquely sensitive to intermolecular electronic coupling through the sign and amplitude of the cross-peaks. This feature makes it possible to reveal spatial molecular configurations by probing electronic transitions. Another means of "resolving" these angstrom-scale arrangements is to manipulate the probing laser pulse polarizations. In this way, we can isolate and modulate specific processes in order to retrieve structural information. In this Account, we demonstrate these capabilities through a close collaboration between experiments and modeling on isolated photosynthetic pigment-protein complexes and also on J-aggregates. Each of the probed systems we describe offers insights that have both increased the utility of 2D electronic spectroscopy and led to discoveries about the molecular aggregates' dynamics and underlying structure. PMID:19691358

  6. Photocurrent, Rectification, and Magnetic Field Symmetry in Quantum Dots

    Science.gov (United States)

    Dicarlo, L.; Marcus, C. M.; Vavilov, M. G.; Harris, J. R.

    2003-03-01

    We present an experimental study of mesoscopic fluctuations of dc current induced by ac excitation applied to a confining gate of an open GaAs quantum dot. The symmetry of current fluctuations with respect to an applied perpendicular magnetic field is investigated over a broad range of frequencies, from the adiabatic regime, where frequency is much less than the inverse dwell time of an electron in the dot, to the high frequency regime, where frequency exceeds the inverse dwell time but is less than or comparable to temperature. We find that while the two-probe dc conductance of the dot is field symmetric over the entire frequency range studied, the induced current is symmetric at lower frequencies, but can be nonsymmetric at higher frequencies. This demonstrates that field symmetry may be used to distinguish mechanisms of dc response to ac excitation (eg., adiabatic rectification is symmetric, photocurrent is nonsymmetric). Direct comparison to theory will be presented. Supported by the NSF under DMR-0072777 and the Harvard NSEC.

  7. Machine Learning of Molecular Electronic Properties in Chemical Compound Space

    CERN Document Server

    Montavon, Grégoire; Gobre, Vivekanand; Vazquez-Mayagoitia, Alvaro; Hansen, Katja; Tkatchenko, Alexandre; Müller, Klaus-Robert; von Lilienfeld, O Anatole

    2013-01-01

    The combination of modern scientific computing with electronic structure theory can lead to an unprecedented amount of data amenable to intelligent data analysis for the identification of meaningful, novel, and predictive structure-property relationships. Such relationships enable high-throughput screening for relevant properties in an exponentially growing pool of virtual compounds that are synthetically accessible. Here, we present a machine learning (ML) model, trained on a data base of \\textit{ab initio} calculation results for thousands of organic molecules, that simultaneously predicts multiple electronic ground- and excited-state properties. The properties include atomization energy, polarizability, frontier orbital eigenvalues, ionization potential, electron affinity, and excitation energies. The ML model is based on a deep multi-task artificial neural network, exploiting underlying correlations between various molecular properties. The input is identical to \\emph{ab initio} methods, \\emph{i.e.} nucle...

  8. Radio frequency rectification on membrane bound pores

    International Nuclear Information System (INIS)

    Probing the interaction of biological systems with radio frequencies holds great promise for research and drug screening applications. While a common assumption is that biological systems do not operate at radio frequencies, we find that currents due to ion transport through channels and pores in cell membranes are in the pA to nA range. These values translate via the average current (I) = (n)e/?d = (n)ef to frequencies in the range of 1 MHz-1 GHz, where (n) is the average number of ions transported and ?d is the dwell time of the ions in the channel. It is thus desirable to have circuitry available which facilitates radio frequency spectroscopy of ion transport. This will yield real-time in vitro information on ion channel operation. Here we present measurements on the local interaction of a radio frequency signal with single ion channels and pores. We find radio frequency rectification and pumping on the channels and pores embedded in suspended bilipid membranes, recorded in direct current measurements. This electromagnetic modulation can be used to probe the dynamics of ion channel conformational changes.

  9. Research ZCS Synchronous Rectification of Resonant Converter

    Directory of Open Access Journals (Sweden)

    Xiao Kui Li

    2014-01-01

    Full Text Available In this study, the application of ZCS synchronous rectification for the IPT resonant converter is researched. A novel control method that AC-DC section of the resonant converter works in ZCS SR state is proposed by using the characteristic of resonant tank current. First, the ZCS working operation of SR is presented, analyzed and equivalent circuits for each operation mode are also given, respectively. Then, the novel control method of ZCS SR for resonant converter is proposed. According to the ZCS working operation of SR and the differential equations of equivalent circuit, a steady-state mathematical model of the circuit is established. On that basis, the calculation method for ZCS operating point of SR is deduced by solving the fixed point function about resonant tank current. Moreover, the specific flow chart for calculating ZCS operating point of SR and the steady-state waveforms of each state variable is also presented and operating principle of control circuit for ZCS SR is described in detail. Finally, experimental results verify the effectiveness of control method proposed in this study.

  10. Research ZVS Synchronous Rectification of Resonant Converter

    Directory of Open Access Journals (Sweden)

    Xiao Kui Li

    2014-01-01

    Full Text Available In order to expand the application of synchronous rectification, the technology using ZVS synchronous rectifier is studied which is based on the IPT resonant converter. By using its own resonant characteristic, a novel control method that AC-DC section of the resonant converter works in ZVS SR state is proposed in this study. First of all, the ZVS working operation of SR is analyzed and equivalent circuits for each operation mode are also given. On that basis, the novel control method is proposed. Then, according to the differential equations of equivalent circuit, the state space model is established. In order to make full-bridge SR network of the secondary circuit work in ZVS state, the ZVS operating point can be obtained by solving the fixed point function which is based on the state space model and stroboscopic mapping method. Moreover, operating principle of control circuit for ZVS SR is also presented. Finally, experimental results verify the effectiveness of control method proposed in this study.

  11. Photocurrent, Rectification, and Magnetic Field Symmetry of Induced Current Through Quantum Dots

    CERN Document Server

    Di Carlo, L

    2003-01-01

    We report mesoscopic dc current generation in an open chaotic quantum dot with ac excitation applied to one of the shape-defining gates. For excitation frequencies large compared to the inverse dwell time of electrons in the dot (i.e., GHz), we find mesoscopic fluctuations of induced current that are fully asymmetric in the applied perpendicular magnetic field, as predicted by recent theory. Conductance, measured simultaneously, is found to be symmetric in field. In the adiabatic (i.e., MHz) regime, in contrast, the induced current is always symmetric in field, suggesting its origin is mesoscopic rectification.

  12. Photocurrent, Rectification, and Magnetic Field Symmetry of Induced Current through Quantum Dots

    Science.gov (United States)

    Dicarlo, L.; Marcus, C. M.; Harris, J. S.

    2003-12-01

    We report mesoscopic dc current generation in an open chaotic quantum dot with ac excitation applied to one of the shape-defining gates. For excitation frequencies large compared to the inverse dwell time of electrons in the dot (i.e., GHz), we find mesoscopic fluctuations of induced current that are fully asymmetric in the applied perpendicular magnetic field, as predicted by recent theory. Conductance, measured simultaneously, is found to be symmetric in field. In the adiabatic (i.e., MHz) regime, in contrast, the induced current is always symmetric in field, suggesting its origin is mesoscopic rectification.

  13. Modulation of rectification and negative differential resistance in graphene nanoribbon by nitrogen doping

    International Nuclear Information System (INIS)

    By applying the nonequilibrium Green's function formalism combined with density functional theory, we have investigated the electronic transport properties of two nitrogen-doped armchair graphene nanoribbon-based junctions M1 and M2. In the left part of M1 and M2, nitrogen atoms are doped at two edges of the nanoribbon. In the right part, nitrogen atoms are doped at one edge and at the center for M1 and M2, respectively. Obvious rectifying and negative differential resistance behaviors are found, which are strongly dependent on the doping position. The maximum rectification and peak-to-valley ratios are up to the order of 104 in M2.

  14. Photocurrent, rectification, and magnetic field symmetry of induced current through quantum dots.

    Science.gov (United States)

    DiCarlo, L; Marcus, C M; Harris, J S

    2003-12-12

    We report mesoscopic dc current generation in an open chaotic quantum dot with ac excitation applied to one of the shape-defining gates. For excitation frequencies large compared to the inverse dwell time of electrons in the dot (i.e., GHz), we find mesoscopic fluctuations of induced current that are fully asymmetric in the applied perpendicular magnetic field, as predicted by recent theory. Conductance, measured simultaneously, is found to be symmetric in field. In the adiabatic (i.e., MHz) regime, in contrast, the induced current is always symmetric in field, suggesting its origin is mesoscopic rectification. PMID:14683146

  15. Dissociative processes in electron-molecular ion collisions

    Science.gov (United States)

    Djuric, Nada; Dunn, Gordon H.

    1998-10-01

    There is renewed interest in dissociation of molecular ions, primarily due to needs for modeling plasma generators for etching and deposition and for modeling edge plasmas for fusion reactors. At the same time, there are improvements in experimental techniques; e.g. use of heavy-ion storage rings has opened possibilities in dissociation studies of vibrationally relaxed molecular ions. At electron energies below the dissociation energy (D_e) of a molecular ion, the most importanat process is dissociative recombination (DR). Once the energy is above D_e, dissociative excitation (DE) is allowed, and at even higher energies dissociative ionization (DI) is energetically possible. In JILA we set up an apparatus wherein light fragment ions from DE of heteronuclear molecular ions are detected. In the heavy-ion storage ring at Stockholm (CRYRING) detection of neutral fragments was used for DE and DR studies. We will discuss the techniques and give examples of DE and DI obtainet at JILA and CRYRING [1,2,3]. Work supported in part by the Office of Fusion Energy of the U. S. DOE under Contract No. DE-A105-86ER53237 with NIST and in part by the Swedish Natural Science Research Council. 1. N. Djuric et al., Phys. Rev. A 56, 2887 (1997). 2. J. Semaniak et al., Ap. J. 498, 886 (1998). 3. J. R. Peterson et al., J. Chem. Phys. 108, 1978 (1998)

  16. Enhanced electron-capture and charge variation of molecular ions

    International Nuclear Information System (INIS)

    The following question is asked: For molecular ions moving within a stopping medium, its atomic-ion components separating under the influence of their mutual repulsion, how do the charges of the atomic ions vary with the dept of penetration? To address this question, the author considers a diatomic, homonuclear molecular ion whose center of mass moves with velocity V in a solid. He can describe this molecular ion as a pair of atomic ions having equal nuclear charges, Z, each carrying a number, N(x), of electrons which are bound to their respective centers of force. Let the displacement of nuclear charge Z1 relative to nuclear charge Z2 be described by the internuclear separation R. For a depth of penetration into the solid, x, the internuclear separation, R(x) = R(t), will be determined by the Coulomb explosion between the interacting charges, q1 = q2 = q(x), where q(x) = Z-N(x). The relative motion of the ion pair may be neglected so that each atomic ion moves with the velocity of the center of mass; i.e., V1 = V2 = V. For the present, he restricts consideration to molecular ions whose internuclear axes are aligned parallel with the direction of the beam. 4 refs., 1 fig

  17. Electron collisions and internal excitation in stored molecular ion beams

    International Nuclear Information System (INIS)

    In storage ring experiments the role, which the initial internal excitation of a molecular ion can play in electron collisions, and the effect of these collisions on the internal excitation are investigated. Dissociative recombination (DR) and inelastic and super-elastic collisions are studied in the system of He+2. The DR rate coefficient at low energies depends strongly on the initial vibrational excitation in this system. Therefore changes in the DR rate coefficient are a very sensitive probe for changes in the vibrational excitation in He+2, which is used to investigate the effects of collisions with electrons and residual gas species. The low-energy DR of HD+ is rich with resonances from the indirect DR process, when certain initial rotational levels in the molecular ion are coupled to levels in neutral Rydberg states lying below the ion state. Using new procedures for high-resolution electron-ion collision spectroscopy developed here, these resonances in the DR cross section can be measured with high energy sensitivity. This allows a detailed comparison with results of a MQDT calculation in an effort to assign some or all of the resonances to certain intermediate Rydberg levels. (orig.)

  18. Electron collisions and internal excitation in stored molecular ion beams

    Energy Technology Data Exchange (ETDEWEB)

    Buhr, H.

    2006-07-26

    In storage ring experiments the role, which the initial internal excitation of a molecular ion can play in electron collisions, and the effect of these collisions on the internal excitation are investigated. Dissociative recombination (DR) and inelastic and super-elastic collisions are studied in the system of He{sup +}{sub 2}. The DR rate coefficient at low energies depends strongly on the initial vibrational excitation in this system. Therefore changes in the DR rate coefficient are a very sensitive probe for changes in the vibrational excitation in He{sup +}{sub 2}, which is used to investigate the effects of collisions with electrons and residual gas species. The low-energy DR of HD{sup +} is rich with resonances from the indirect DR process, when certain initial rotational levels in the molecular ion are coupled to levels in neutral Rydberg states lying below the ion state. Using new procedures for high-resolution electron-ion collision spectroscopy developed here, these resonances in the DR cross section can be measured with high energy sensitivity. This allows a detailed comparison with results of a MQDT calculation in an effort to assign some or all of the resonances to certain intermediate Rydberg levels. (orig.)

  19. Molecular order affecting electron transport through ssDNA

    Energy Technology Data Exchange (ETDEWEB)

    Ehlich, Rudolf, E-mail: phrame@bris.ac.uk [H.H. Wills Physics Laboratory, University of Bristol, Bristol BS8 1TL (United Kingdom); Hoerber, J.K. Heinrich [H.H. Wills Physics Laboratory, University of Bristol, Bristol BS8 1TL (United Kingdom)

    2009-07-15

    DNA is considered to be the ideal model for studies of electron transport in molecule/conductor systems due to its stability, easily controlled structure and the presumed electrical properties. Scanning tunnelling microscope (STM) studies of single-stranded DNA bound to Au (1 1 1) or Au nanodots with a thiol linker were carried out under ambient conditions. The results show that the electron transfer between the STM tip and the gold is governed by the serial resistance of the oligomer strands and a water film. Electron transfer properties also depend on the alignment of the DNA strands. Measurements show that well-ordered parallel arrangement of the molecules protruding from flat crystalline surfaces is favourable for electron transport compared with unordered arrangements of molecules on spherical nanodots. Nanodots are good candidates for effective charge production by absorption of light allowing chemical reactions to happen at the dots, which can be used for storing the light energy. Understanding electron transport through molecular structures is of crucial importance for the development of such novel photovoltaic devices.

  20. Molecular order affecting electron transport through ssDNA

    International Nuclear Information System (INIS)

    DNA is considered to be the ideal model for studies of electron transport in molecule/conductor systems due to its stability, easily controlled structure and the presumed electrical properties. Scanning tunnelling microscope (STM) studies of single-stranded DNA bound to Au (1 1 1) or Au nanodots with a thiol linker were carried out under ambient conditions. The results show that the electron transfer between the STM tip and the gold is governed by the serial resistance of the oligomer strands and a water film. Electron transfer properties also depend on the alignment of the DNA strands. Measurements show that well-ordered parallel arrangement of the molecules protruding from flat crystalline surfaces is favourable for electron transport compared with unordered arrangements of molecules on spherical nanodots. Nanodots are good candidates for effective charge production by absorption of light allowing chemical reactions to happen at the dots, which can be used for storing the light energy. Understanding electron transport through molecular structures is of crucial importance for the development of such novel photovoltaic devices.

  1. Vibrational excitations in molecular layers probed by ballistic electron microscopy

    Energy Technology Data Exchange (ETDEWEB)

    Kajen, Rasanayagam Sivasayan; Chandrasekhar, Natarajan [Institute of Materials Research and Engineering, 3 Research Link, 117602 (Singapore); Feng Xinliang; Muellen, Klaus [Max-Planck-Institut fuer Polymerforschung, Postfach 3148, D-55021 Mainz (Germany); Su Haibin, E-mail: n-chandra@imre.a-star.edu.sg, E-mail: muellen@mpip-mainz.mpg.de, E-mail: hbsu@ntu.edu.sg [Division of Materials Science, Nanyang Technological University, 50 Nanyang Avenue, 639798 (Singapore)

    2011-10-28

    We demonstrate the information on molecular vibrational modes via the second derivative (d{sup 2}I{sub B}/dV{sup 2}) of the ballistic electron emission spectroscopy (BEES) current. The proposed method does not create huge fields as in the case of conventional derivative spectroscopy and maintains a zero bias across the device. BEES studies carried out on three different types of large polycyclic aromatic hydrocarbon (PAH) molecular layers show that the d{sup 2}I{sub B}/dV{sup 2} spectra consist of uniformly spaced peaks corresponding to vibronic excitations. The peak spacing is found to be identical for molecules within the same PAH family though the BEES onset voltage varies for different molecules. In addition, injection into a particular orbital appears to correspond to a specific vibrational mode as the manifestation of the symmetry principle.

  2. Fast Electron Repulsion Integrals for Molecular Coulomb Sturmians

    DEFF Research Database (Denmark)

    Avery, James Emil

    2013-01-01

    A new method is presented for calculating interelectron repulsion integrals for molecular Coulomb Sturmian basis sets. This makes use of an expansion of densities in terms of 2k-Sturmians, and the interelectron repulsion integrals are then calculated by a method based on the theory of hyperspherical harmonics. A rudimentary software library has been implemented and preliminary benchmarks indicate very good performance: On average 40 ns, or approximately 80 clock cycles, per electron repulsion integral. This makes molecular Coulomb Sturmians competitive with Gaussian type orbitals in terms of speed, and is three to four orders of magnitude faster than methods based on expanding the exponential type orbitals in Gaussians. A full software library will be made available during autumn 2013.

  3. Semiclassical theory of electronically nonadiabatic transitions in molecular collision processes

    International Nuclear Information System (INIS)

    An introductory account of the semiclassical theory of the S-matrix for molecular collision processes is presented, with special emphasis on electronically nonadiabatic transitions. This theory is based on the incorporation of classical mechanics with quantum superposition, and in practice makes use of the analytic continuation of classical mechanics into the complex space or time domain. After a brief discussion of the relevant concepts of molecular scattering theory and related dynamical models, the formalism is developed and illustrated with simple examples - collinear collision of the A + BC type. The theory is then extended to include the effects of laser-induced nonadiabatic transitions. The lecture concludes with a discussion of two bound continuum processes - collisional ionization and collision-induced emission - also amenable to the same general semiclassical treatment. (orig.)

  4. Electron transport through catechol-functionalized molecular rods

    International Nuclear Information System (INIS)

    The charge transport properties of a catechol-type dithiol-terminated oligo-phenylene-ethynylene was investigated by cyclic voltammetry (CV) and by the scanning tunnelling microscopy break junction technique (STM-BJ). Single molecule charge transport experiments demonstrated the existence of high and low conductance regions. The junction conductance is rather weakly dependent on the redox state of the bridging molecule. However, a distinct dependence of junction formation probability and of relative stretching distances of the catechol- and quinone-type molecular junctions is observed. Substitution of the central catechol ring with alkoxy-moieties and the combination with a topological analysis of possible ?-electron pathways through the respective molecular skeletons lead to a working hypothesis, which could rationalize the experimentally observed conductance characteristics of the redox-active nanojunctions

  5. Stretched exponential relaxation in molecular and electronic glasses

    International Nuclear Information System (INIS)

    Stretched exponential relaxation, exp[-(t/?)?], fits many relaxation processes in disordered and quenched electronic and molecular systems, but it is widely believed that this function has no microscopic basis, especially in the case of molecular relaxation. For electronic relaxation the appearance of the stretched exponential is often described in the context of dispersive transport, where ? is treated as an adjustable parameter, but in almost all cases it is generally assumed that no microscopic meaning can be assigned to 0g, a glass transition temperature. We show that for molecular relaxation ?(Tg) can be understood, providing that one separates extrinsic and intrinsic effects, and that the intrinsic effects are dominated by two magic numbers, ?SR=3/5 for short-range forces, and ?K=3/7 for long-range Coulomb forces, as originally observed by Kohlrausch for the decay of residual charge on a Leyden jar. Our mathematical model treats relaxation kinetics using the Lifshitz-Kac-Luttinger diffusion to traps depletion model in a configuration space of effective dimensionality, the latter being determined using axiomatic set theory and Phillips-Thorpe constraint theory. The experiments discussed include ns neutron scattering experiments, particularly those based on neutron spin echoes which measure S(Q, t) directly, and the traditional linear response measurements which span the range from ?ements which span the range from ?s to s, as collected and analysed phenomenologically by Angell, Ngai, Boehmer and others. The electronic materials discussed include a-Si:H, granular C60, semiconductor nanocrystallites, charge density waves in TaS3, spin glasses, and vortex glasses in high-temperature semiconductors. The molecular materials discussed include polymers, network glasses, electrolytes and alcohols, Van der Waals supercooled liquids and glasses, orientational glasses, water, fused salts, and heme proteins. In the intrinsic cases the theory of ?(Tg) is often accurate to 2%, which is often better than the quoted experimental accuracies ?5%. The extrinsic cases are identified by explicit structural signatures which are discussed at length. The discussion also includes recent molecular dynamical simulations for metallic glasses, spin glasses, quasicrystals and polymers which have achieved the intermediate relaxed Kohlrausch state and which have obtained values of ? in excellent agreement with the prediction of the microscopic theory. (author)

  6. Probing ultrafast electronic and molecular dynamics with free-electron lasers

    International Nuclear Information System (INIS)

    Molecular dynamics is an active area of research, focusing on revealing fundamental information on molecular structures and photon–molecule interaction and with broad impacts in chemical and biological sciences. Experimental investigation of molecular dynamics has been advanced by the development of new light sources and techniques, deepening our understanding of natural processes and enabling possible control and modification of chemical and biomolecular processes. Free-electron lasers (FELs) deliver unprecedented intense and short photon pulses in the vacuum ultraviolet and x-ray spectral ranges, opening a new era for the study of electronic and nuclear dynamics in molecules. This review focuses on recent molecular dynamics investigations using FELs. We present recent work concerning dynamics of molecular interaction with FELs using an intrinsic clock within a single x-ray pulse as well as using an external clock in a pump–probe scheme. We review the latest developments on correlated and coincident spectroscopy in FEL-based research and recent results revealing photo-induced interaction dynamics using these techniques. We also describe new instrumentations to conduct x-ray pump–x-ray probe experiments with spectroscopy and imaging detectors. (review article)

  7. Molecular and electronic structure of a largely extended tetracyanoquinodimethane

    Energy Technology Data Exchange (ETDEWEB)

    Viruela, R. [Dept. Quimica Fisica, Univ. Valencia (Spain); Viruela, P.M. [Dept. Quimica Fisica, Univ. Valencia (Spain); Orti, E. [Dept. Quimica Fisica, Univ. Valencia (Spain); Martin, N. [Dept. Quimica Organica, Univ. Complutense, Madrid (Spain)

    1995-03-15

    We investigate the molecular structure and electronic properties of 15,15,16,16-tetracyano-6,13-pentacenequinodimethane (TCPQ) using quantum-chemical methods. The molecule is predicted to be severely distorted from planarity adopting a butterfly-type structure. The analysis of the topology of the frontier orbitals justifies the decrease in the acceptor ability of extended TCNQs and assigns the first optical absorption observed for TCPQ to an intramolecular charge-transfer transition. Calculations on negatively charged TCPQ show that the molecule is planarized upon reduction. (orig.)

  8. Electronic Transport of a Molecular Photoswitch with Graphene Nanoribbon Electrodes

    Science.gov (United States)

    Wu, Qiu-Hua; Zhao, Peng; Liu, De-Sheng

    2014-05-01

    Based on non-equilibrium Green's function formalism and density functional theory calculations, we investigate the electronic transport properties of 15,16-dinitrile dihydropyrene/cyclophanediene bridged between two zigzag graphene nanoribbon electrodes. Our results demonstrate that the system can exhibit good switching behavior with the maximum on-off ratio high up to 146 which is improved dramatically compared with the case of gold electrodes. Moreover, an obvious negative differential resistance behavior occurs at 0.3 V, making the system have more potential in near future molecular circuits.

  9. Molecular Electronics: Insight from First-Principles Transport Simulations

    DEFF Research Database (Denmark)

    Paulsson, Magnus; Frederiksen, Thomas

    2010-01-01

    Conduction properties of nanoscale contacts can be studied using first-principles simulations. Such calculations give insight into details behind the conductance that is not readily available in experiments. For example, we may learn how the bonding conditions of a molecule to the electrodes affect the electronic transport. Here we describe key computational ingredients and discuss these in relation to simulations for scanning tunneling microscopy (STM) experiments with C-60 molecules where the experimental geometry is well characterized. We then show how molecular dynamics simulations may be combined with transport calculations to study more irregular situations, such as the evolution of a nanoscale contact with the mechanically controllable break-junction technique. Finally we discuss calculations of inelastic electron tunnelling spectroscopy as a characterization technique that reveals information about the atomic arrangement and transport channels.

  10. Fast electronic structure methods for strongly correlated molecular systems

    International Nuclear Information System (INIS)

    A short review is given of newly developed fast electronic structure methods that are designed to treat molecular systems with strong electron correlations, such as diradicaloid molecules, for which standard electronic structure methods such as density functional theory are inadequate. These new local correlation methods are based on coupled cluster theory within a perfect pairing active space, containing either a linear or quadratic number of pair correlation amplitudes, to yield the perfect pairing (PP) and imperfect pairing (IP) models. This reduces the scaling of the coupled cluster iterations to no worse than cubic, relative to the sixth power dependence of the usual (untruncated) coupled cluster doubles model. A second order perturbation correction, PP(2), to treat the neglected (weaker) correlations is formulated for the PP model. To ensure minimal prefactors, in addition to favorable size-scaling, highly efficient implementations of PP, IP and PP(2) have been completed, using auxiliary basis expansions. This yields speedups of almost an order of magnitude over the best alternatives using 4-center 2-electron integrals. A short discussion of the scope of accessible chemical applications is given

  11. Fragmentation of molecular ions in slow electron collisions

    International Nuclear Information System (INIS)

    The fragmentation of positively charged hydrogen molecular ions by the capture of slow electrons, the so called dissociative recombination (DR), has been investigated in storage ring experiments at the TSR, Heidelberg, where an unique twin-electron-beam arrangement was combined with high resolution fragment imaging detection. Provided with well directed cold electrons the fragmentation kinematics were measured down to meV collision energies where pronounced rovibrational Feshbach resonances appear in the DR cross section. For thermally excited HD+ the fragmentation angle and the kinetic energy release were studied at variable precisely controlled electron collision energies on a dense energy grid from 10 to 80 meV. The anisotropy described for the first time by Legendre polynomials higher 2nd order and the extracted rotational state contributions were found to vary on a likewise narrow energy scale as the rotationally averaged DR rate coefficient. Ro-vibrationally resolved DR experiments were performed on H2+ produced in distinct internal excitations by a novel ion source. Both the low-energy DR rate as well as the fragmentation dynamics at selected resonances were measured individually in the lowest two vibrational and first three excited rotational states. State-specific DR rates and angular dependences are reported. (orig.)

  12. Vibrational coherence transfer in an electronically decoupled molecular dyad.

    Science.gov (United States)

    Schweighöfer, Felix; Dworak, Lars; Braun, Markus; Zastrow, Marc; Wahl, Jan; Burghardt, Irene; Rück-Braun, Karola; Wachtveitl, Josef

    2015-01-01

    The ring opening of a dithienylethene photoswitch incorporated in a bridged boron-dipyrromethene - dithienylethene molecular dyad was investigated with ultrafast spectroscopy. Coherent vibrations in the electronic ground state of the boron-dipyrromethene are triggered after selective photoexcitation of the closed dithienylethene indicating vibrational coupling although the two moieties are electronically isolated. A distribution of short-lived modes and a long-lived mode at 143 cm(-1) are observed. Analysis of the theoretical frequency spectrum indicates two modes at 97 cm(-1) and 147 cm(-1) which strongly modulate the electronic transition energy. Both modes exhibit a characteristic displacement of the bridge suggesting that the mechanical momentum of the initial geometry change after photoexcitation of the dithienylethene is transduced to the boron-dipyrromethene. The relaxation to the dithienylethene electronic ground state is accompanied by significant heat dissipation into the surrounding medium. In the investigated dyad, the boron-dipyrromethene acts as probe for the ultrafast photophysical processes in the dithienylethene. PMID:25797419

  13. Fragmentation of molecular ions in slow electron collisions

    Energy Technology Data Exchange (ETDEWEB)

    Novotny, Steffen

    2008-06-25

    The fragmentation of positively charged hydrogen molecular ions by the capture of slow electrons, the so called dissociative recombination (DR), has been investigated in storage ring experiments at the TSR, Heidelberg, where an unique twin-electron-beam arrangement was combined with high resolution fragment imaging detection. Provided with well directed cold electrons the fragmentation kinematics were measured down to meV collision energies where pronounced rovibrational Feshbach resonances appear in the DR cross section. For thermally excited HD{sup +} the fragmentation angle and the kinetic energy release were studied at variable precisely controlled electron collision energies on a dense energy grid from 10 to 80 meV. The anisotropy described for the first time by Legendre polynomials higher 2{sup nd} order and the extracted rotational state contributions were found to vary on a likewise narrow energy scale as the rotationally averaged DR rate coefficient. Ro-vibrationally resolved DR experiments were performed on H{sub 2}{sup +} produced in distinct internal excitations by a novel ion source. Both the low-energy DR rate as well as the fragmentation dynamics at selected resonances were measured individually in the lowest two vibrational and first three excited rotational states. State-specific DR rates and angular dependences are reported. (orig.)

  14. Rectification inversion in oxygen substituted graphyne-graphene-based heterojunctions.

    Science.gov (United States)

    Zhao, Wen-kai; Cui, Bin; Fang, Chang-feng; Ji, Guo-min; Zhao, Jing-fen; Kong, Xiang-ru; Zou, Dong-qing; Jiang, Xiao-hui; Li, Dong-mei; Liu, De-sheng

    2015-02-01

    Current rectification is found in oxygen-substituted zigzag graphyne nanoribbon/hydrogen-terminated zigzag graphene nanoribbon heterostructure junctions, from the application of nonequilibrium Green's function formalism combined with density functional theory. This behavior could be tuned by varying the number and location of oxygen atoms in the zigzag graphyne nanoribbon parts, and the rectification direction could be reversed due to the parity limitation tunneling effect. Moreover, an obvious negative differential resistance behavior is found and may be explained by two different mechanisms. PMID:25516239

  15. Bounds for the rectification efficiency of solar radiation

    Science.gov (United States)

    Mashaal, Heylal; Gordon, Jeffrey M.

    2013-09-01

    Efficiency bounds for the rectification (AC to DC conversion) efficiency of non-coherent broadband radiation are derived, motivated by determining a basic limit for solar rectifying antennas. The limit is shown to be 2/? for a single full-wave rectifier. We also derive the increase in rectification efficiency that is possible by cascading multiple rectifiers. The approach for deriving the broadband limit follows from an analysis of sinusoidal signals of random phase. This analysis is also germane for harvesting ambient radio-frequency radiation from multiple uncorrelated sources.

  16. Radical and non-radical carbazole derivatives formolecular electronics. Molecular Glasses and Liquid Crystals.

    OpenAIRE

    Castellanos Ortega, Sonia

    2010-01-01

    [eng] Molecular electronics is an emergent area of the new technologies related to the use of organic and biological materials in optoelectronic and electronic devices. Among the materials used in electronic applications, low molecular weight materials, or molecular materials, became of great interest in the last years, due to the advantages they present in front of the traditional polymeric materials, such as, easier synthesis, purification and characterization, and a better processability. ...

  17. Machine learning of molecular electronic properties in chemical compound space

    Science.gov (United States)

    Montavon, Grégoire; Rupp, Matthias; Gobre, Vivekanand; Vazquez-Mayagoitia, Alvaro; Hansen, Katja; Tkatchenko, Alexandre; Müller, Klaus-Robert; Anatole von Lilienfeld, O.

    2013-09-01

    The combination of modern scientific computing with electronic structure theory can lead to an unprecedented amount of data amenable to intelligent data analysis for the identification of meaningful, novel and predictive structure-property relationships. Such relationships enable high-throughput screening for relevant properties in an exponentially growing pool of virtual compounds that are synthetically accessible. Here, we present a machine learning model, trained on a database of ab initio calculation results for thousands of organic molecules, that simultaneously predicts multiple electronic ground- and excited-state properties. The properties include atomization energy, polarizability, frontier orbital eigenvalues, ionization potential, electron affinity and excitation energies. The machine learning model is based on a deep multi-task artificial neural network, exploiting the underlying correlations between various molecular properties. The input is identical to ab initio methods, i.e. nuclear charges and Cartesian coordinates of all atoms. For small organic molecules, the accuracy of such a ‘quantum machine’ is similar, and sometimes superior, to modern quantum-chemical methods—at negligible computational cost.

  18. Machine learning of molecular electronic properties in chemical compound space

    International Nuclear Information System (INIS)

    The combination of modern scientific computing with electronic structure theory can lead to an unprecedented amount of data amenable to intelligent data analysis for the identification of meaningful, novel and predictive structure–property relationships. Such relationships enable high-throughput screening for relevant properties in an exponentially growing pool of virtual compounds that are synthetically accessible. Here, we present a machine learning model, trained on a database of ab initio calculation results for thousands of organic molecules, that simultaneously predicts multiple electronic ground- and excited-state properties. The properties include atomization energy, polarizability, frontier orbital eigenvalues, ionization potential, electron affinity and excitation energies. The machine learning model is based on a deep multi-task artificial neural network, exploiting the underlying correlations between various molecular properties. The input is identical to ab initio methods, i.e. nuclear charges and Cartesian coordinates of all atoms. For small organic molecules, the accuracy of such a ‘quantum machine’ is similar, and sometimes superior, to modern quantum-chemical methods—at negligible computational cost. (paper)

  19. Ab initio quantum mechanical/molecular mechanical simulation of electron transfer process: Fractional electron approach

    Science.gov (United States)

    Zeng, Xiancheng; Hu, Hao; Hu, Xiangqian; Cohen, Aron J.; Yang, Weitao

    2008-03-01

    Electron transfer (ET) reactions are one of the most important processes in chemistry and biology. Because of the quantum nature of the processes and the complicated roles of the solvent, theoretical study of ET processes is challenging. To simulate ET processes at the electronic level, we have developed an efficient density functional theory (DFT) quantum mechanical (QM)/molecular mechanical (MM) approach that uses the fractional number of electrons as the order parameter to calculate the redox free energy of ET reactions in solution. We applied this method to study the ET reactions of the aqueous metal complexes Fe(H2O)62+/3+ and Ru(H2O)62+/3+. The calculated oxidation potentials, 5.82 eV for Fe(II/III) and 5.14 eV for Ru(II/III), agree well with the experimental data, 5.50 and 4.96 eV, for iron and ruthenium, respectively. Furthermore, we have constructed the diabatic free energy surfaces from histogram analysis based on the molecular dynamics trajectories. The resulting reorganization energy and the diabatic activation energy also show good agreement with experimental data. Our calculations show that using the fractional number of electrons (FNE) as the order parameter in the thermodynamic integration process leads to efficient sampling and validate the ab initio QM/MM approach in the calculation of redox free energies.

  20. Probing flexible conformations in molecular junctions by inelastic electron tunneling spectroscopy

    Directory of Open Access Journals (Sweden)

    Mingsen Deng

    2015-01-01

    Full Text Available The probe of flexible molecular conformation is crucial for the electric application of molecular systems. We have developed a theoretical procedure to analyze the couplings of molecular local vibrations with the electron transportation process, which enables us to evaluate the structural fingerprints of some vibrational modes in the inelastic electron tunneling spectroscopy (IETS. Based on a model molecule of Bis-(4-mercaptophenyl-ether with a flexible center angle, we have revealed and validated a simple mathematical relationship between IETS signals and molecular angles. Our results might open a route to quantitatively measure key geometrical parameters of molecular junctions, which helps to achieve precise control of molecular devices.

  1. Electron degradation and yields of initial products. IV. Subexcitation electrons in molecular oxygen

    International Nuclear Information System (INIS)

    Electron slowing-down processes in molecular oxygen gas in the subexcitation domain (below the ionization threshold) are studied by using the Spencer--Fano (SF) equation and its simplification, the continuous-slowing-down approximation (CSDA), both in time-dependent and time-independent representations. Compared to the previously studied cases of N2 and CO2, O2 has the special features in its inelastic cross sections of (i) strong delta-function-like peaks in the vibrational excitation cross section below 1.3 eV and (ii) very low energy thresholds of electronic excitation channels. These features provide a stringent test for the CSDA. Indeed, our results clearly show for the first time that the CSDA fails even qualitatively to reproduce the electron degradation spectrum given by the exact SF method over the whole energy regime studied

  2. The effect of asymmetrical electrode on the transport properties of molecular devices

    Energy Technology Data Exchange (ETDEWEB)

    Wu, X.Z. [School of Physics and Electronics, Central South University, Changsha 410083 (China); School of Materials Science and Engineering, Central South University, Changsha 410083 (China); Institute of Super Microstructure and Ultrafast Process, Central South University, Changsha 410083 (China); Xiao, J. [School of Physics and Electronics, Central South University, Changsha 410083 (China); Institute of Super Microstructure and Ultrafast Process, Central South University, Changsha 410083 (China); Chen, L.N. [Institute of Super Microstructure and Ultrafast Process, Central South University, Changsha 410083 (China); School of Computer Science and Technology, University of South China, Hengyang 421001 (China); Cao, C. [School of Physics and Electronics, Central South University, Changsha 410083 (China); Institute of Super Microstructure and Ultrafast Process, Central South University, Changsha 410083 (China); Xu, H., E-mail: cmpxhg@csu.edu.cn [School of Physics and Electronics, Central South University, Changsha 410083 (China); School of Materials Science and Engineering, Central South University, Changsha 410083 (China); Institute of Super Microstructure and Ultrafast Process, Central South University, Changsha 410083 (China); Long, M.Q., E-mail: mqlong@csu.edu.cn [School of Physics and Electronics, Central South University, Changsha 410083 (China); Institute of Super Microstructure and Ultrafast Process, Central South University, Changsha 410083 (China)

    2013-02-15

    By applying nonequilibrium Green's functions in combination with the density functional theory, we have investigated the electronic transport properties of molecular devices consisting of the carbon atomic chain coupling with symmetry and asymmetry Au electrodes. The asymmetry Au electrodes systems display good rectifying behavior. The main origin of this phenomenon is that a molecular core coupling with asymmetry electrodes can generate two asymmetrical Schottky barriers at both extended molecule regions. This rectification is also explained by the calculated transmission spectrum and the spatial distribution of the LUMO and HOMO states.

  3. A scheme for automatic text rectification in real scene images

    Science.gov (United States)

    Wang, Baokang; Liu, Changsong; Ding, Xiaoqing

    2015-03-01

    Digital camera is gradually replacing traditional flat-bed scanner as the main access to obtain text information for its usability, cheapness and high-resolution, there has been a large amount of research done on camera-based text understanding. Unfortunately, arbitrary position of camera lens related to text area can frequently cause perspective distortion which most OCR systems at present cannot manage, thus creating demand for automatic text rectification. Current rectification-related research mainly focused on document images, distortion of natural scene text is seldom considered. In this paper, a scheme for automatic text rectification in natural scene images is proposed. It relies on geometric information extracted from characters themselves as well as their surroundings. For the first step, linear segments are extracted from interested region, and a J-Linkage based clustering is performed followed by some customized refinement to estimate primary vanishing point(VP)s. To achieve a more comprehensive VP estimation, second stage would be performed by inspecting the internal structure of characters which involves analysis on pixels and connected components of text lines. Finally VPs are verified and used to implement perspective rectification. Experiments demonstrate increase of recognition rate and improvement compared with some related algorithms.

  4. Terahertz pulse generation via optical rectification in photonic crystal microcavities

    OpenAIRE

    Di Falco, Andrea; Conti, Claudio; Assanto, Gaetano

    2005-01-01

    Using a 3D fully-vectorial nonlinear time-domain analysis we numerically investigate the generation of terahertz radiation by pumping a photonic crystal microcavity out of resonance. High quality factors and a quadratic susceptibility lead to few-cycle terahertz pulses via optical rectification. Material dispersion as well as linear and nonlinear anisotropy is fully accounted for.

  5. Symmetry and environment effects on rectification mechanisms in quantum pumps

    CERN Document Server

    Arrachea, L

    2005-01-01

    We consider a paradigmatic model of quantum pumps and discuss its rectification properties in the framework of a symmetry analysis proposed for ratchet systems. We discuss the role of the environment in breaking time-reversal symmetry and the possibility of a finite directed current in the Hamiltonian limit of annular systems.

  6. Symmetry and environment effects on rectification mechanisms in quantum pumps

    Science.gov (United States)

    Arrachea, Liliana

    2005-09-01

    We consider a paradigmatic model of quantum pumps and discuss its rectification properties in the framework of a symmetry analysis proposed for ratchet systems. We discuss the role of the environment in breaking time-reversal symmetry and the possibility of a finite directed current in the Hamiltonian limit of annular systems.

  7. Stereo rectification of calibrated image pairs based on geometric transformation

    Directory of Open Access Journals (Sweden)

    Huihuang Su

    2011-07-01

    Full Text Available The objective of stereo rectification is to make the corresponding epipolar lines of image pairs be parallel to the horizontal direction, so that the efficiency of stereo matching is improved as the corresponding points stay in the same horizontal lines of both images. In this paper?a simple and convenient rectification method of calibrated image pairs based on geometric transformation is proposed, which can avoid the complicated calculation of many previous algorithms such as based on epipolar lines, based on fundamental matrix or directly depend on corresponding points. This method is divided into two steps including coordinate system transformation and re-projection of image points. Firstly, we establish two virtual cameras with parallel optical axis by coordinate system transformation based on the pose relationship of the two cameras from calibration result. Secondly, we re-project the points of the original image onto new image planes of the virtual cameras through geometrical method, and then realized the stereo rectification. Experiments of real stereo image pairs show that the proposed method is able to realize the rectification of stereo image pairs accurately and efficiently.

  8. Fullerene-based Anchoring Groups for Molecular Electronics

    DEFF Research Database (Denmark)

    Martin, Christian A.; Ding, Dapeng

    2008-01-01

    We present results on a new fullerene-based anchoring group for molecular electronics. Using lithographic mechanically controllable break junctions in vacuum we have determined the conductance and stability of single-molecule junctions of 1,4-bis(fullero[c]pyrrolidin-1-yl)benzene. The compound can be self-assembled from solution and has a low-bias conductance of 3 × 10-4 G0. Compared to 1,4-benzenedithiol the fullerene-anchored molecule exhibits a considerably lower conductance spread. In addition, the signature of the new compound in histograms is more significant than that of 1,4-benzenediamine, probably owing to a more stable adsorption motif. Statistical analyses of the breaking of the junctions confirm the stability of the fullerene-gold bond.

  9. Determination of molecular parameters by electron collisions and laser techniques

    International Nuclear Information System (INIS)

    In this work a general procedure to study diatomic molecules in intermediate coupling scheme has been developed. This study allows to obtain expressions to calculate molecular line strengths and rotational transition intensities. These results are used in a numerical program to synthetize vibrational and rotational band spectra of any diatomic molecule. With this technique the experimental spectra of the first negative system of N2+ and the fist positive system of N2 are reproduced theoretically and it is possible to deduce its electronic transition moments values by comparison. Also the method has been applied to compare the synthetized bands with the experimental spectra of the B Ou+-- x1?g+ system of Au2 and the A2?--- x 2? system of OH. From these comparison band intensities and electronic moments can be deduced. The branching ratio method to measure the relative spectral response in the 1100-1560 Ao=wavelength range of a vacuum uv monochromator has been used. Relative intensity of rotational lines with origine in a common upper vibrational-rotational level of Warner and Lyman systems of H2, have been measured. Also in this work, the deexcitation of the B3?+(0+u), v'=14 level of I2 after pulsed laser excitation has been studied. The quenching cross sections by collisions with I2, H2, CO2 and CH4 have been determin-ed. (Author)

  10. Ionic fragmentation channels in electron collisions of small molecular ions

    International Nuclear Information System (INIS)

    Dissociative Recombination (DR) is one of the most important loss processes of molecular ions in the interstellar medium (IM). Ion storage rings allow to investigate these processes under realistic conditions. At the Heidelberg test storage ring TSR a new detector system was installed within the present work in order to study the DR sub-process of ion pair formation (IPF). The new detector expands the existing electron target setup by the possibility to measure strongly deflected negative ionic fragments. At the TSR such measurements can be performed with a uniquely high energy resolution by independently merging two electron beams with the ion beam. In this work IPF of HD+, H3+ and HF+ has been studied. In the case of HD+ the result of the high resolution experiment shows quantum interferences. Analysis of the quantum oscillations leads to a new understanding of the reaction dynamics. For H3+ it was for the first time possible to distinguish different IPF channels and to detect quantum interferences in the data. Finally the IPF of HF+ was investigated in an energy range, where in previous experiments no conclusive results could be obtained. (orig.)

  11. Ionic fragmentation channels in electron collisions of small molecular ions

    Energy Technology Data Exchange (ETDEWEB)

    Hoffmann, Jens

    2009-01-28

    Dissociative Recombination (DR) is one of the most important loss processes of molecular ions in the interstellar medium (IM). Ion storage rings allow to investigate these processes under realistic conditions. At the Heidelberg test storage ring TSR a new detector system was installed within the present work in order to study the DR sub-process of ion pair formation (IPF). The new detector expands the existing electron target setup by the possibility to measure strongly deflected negative ionic fragments. At the TSR such measurements can be performed with a uniquely high energy resolution by independently merging two electron beams with the ion beam. In this work IPF of HD{sup +}, H{sub 3}{sup +} and HF{sup +} has been studied. In the case of HD{sup +} the result of the high resolution experiment shows quantum interferences. Analysis of the quantum oscillations leads to a new understanding of the reaction dynamics. For H{sub 3}{sup +} it was for the first time possible to distinguish different IPF channels and to detect quantum interferences in the data. Finally the IPF of HF{sup +} was investigated in an energy range, where in previous experiments no conclusive results could be obtained. (orig.)

  12. Poly(3-hexylthiophene)/multiwalled carbon hybrid coaxial nanotubes: nanoscale rectification and photovoltaic characteristics.

    Science.gov (United States)

    Kim, Kihyun; Shin, Ji Won; Lee, Yong Baek; Cho, Mi Yeon; Lee, Suk Ho; Park, Dong Hyuk; Jang, Dong Kyu; Lee, Cheol Jin; Joo, Jinsoo

    2010-07-27

    We fabricate hybrid coaxial nanotubes (NTs) of multiwalled carbon nanotubes (MWCNTs) coated with light-emitting poly(3-hexylthiophene) (P3HT). The p-type P3HT material with a thickness of approximately 20 nm is electrochemically deposited onto the surface of the MWCNT. The formation of hybrid coaxial NTs of the P3HT/MWCNT is confirmed by a transmission electron microscope, FT-IR, and Raman spectra. The optical and structural properties of the hybrid NTs are characterized using ultraviolet and visible absorption, Raman, and photoluminescence (PL) spectra where, it is shown that the PL intensity of the P3HT materials decreases after the hybridization with the MWCNTs. The current-voltage (I-V) characteristics of the outer P3HT single NT show the semiconducting behavior, while ohmic behavior is observed for the inner single MWCNT. The I-V characteristics of the hybrid junction between the outer P3HT NT and the inner MWCNT, for the hybrid single NT, exhibit the characteristics of a diode (i.e., rectification), whose efficiency is clearly enhanced with light irradiation. The rectification effect of the hybrid single NT has been analyzed in terms of charge tunneling models. The quasi-photovoltaic effect is also observed at low bias for the P3HT/MWCNT hybrid single NT. PMID:20533839

  13. Theoretical study of molecular vibrations in electron momentum spectroscopy experiments on furan: An analytical versus a molecular dynamical approach

    Science.gov (United States)

    Morini, Filippo; Deleuze, Michael S.; Watanabe, Noboru; Takahashi, Masahiko

    2015-03-01

    The influence of thermally induced nuclear dynamics (molecular vibrations) in the initial electronic ground state on the valence orbital momentum profiles of furan has been theoretically investigated using two different approaches. The first of these approaches employs the principles of Born-Oppenheimer molecular dynamics, whereas the so-called harmonic analytical quantum mechanical approach resorts to an analytical decomposition of contributions arising from quantized harmonic vibrational eigenstates. In spite of their intrinsic differences, the two approaches enable consistent insights into the electron momentum distributions inferred from new measurements employing electron momentum spectroscopy and an electron impact energy of 1.2 keV. Both approaches point out in particular an appreciable influence of a few specific molecular vibrations of A1 symmetry on the 9a1 momentum profile, which can be unravelled from considerations on the symmetry characteristics of orbitals and their energy spacing.

  14. Effect of triangular vacancy defect on thermal conductivity and thermal rectification in graphene nanoribbons

    International Nuclear Information System (INIS)

    We investigate the thermal transport properties of armchair graphene nanoribbons (AGNRs) possessing various sizes of triangular vacancy defect within a temperature range of 200–600 K by using classical molecular dynamics simulation. The results show that the thermal conductivities of the graphene nanoribbons decrease with increasing sizes of triangular vacancy defects in both directions across the whole temperature range tested, and the presence of the defect can decrease the thermal conductivity by more than 40% as the number of removed cluster atoms is increased to 25 (1.56% for vacancy concentration) owing to the effect of phonon–defect scattering. In the meantime, we find the thermal conductivity of defective graphene nanoribbons is insensitive to the temperature change at higher vacancy concentrations. Furthermore, the dependence of temperatures and various sizes of triangular vacancy defect for the thermal rectification ration are also detected. This work implies a possible route to achieve thermal rectifier for 2D materials by defect engineering

  15. Quantum mechanical simulations of polymers for molecular electronics and photonics

    International Nuclear Information System (INIS)

    Ab initio quantum mechanical studies can play an important role in obtaining a detailed understanding of the electronic structure of existing materials, and in predicting the properties of new ones. In this article the authors give a general outline of their research activity in two areas dealing with new materials, specifically, conducting polymers and polymers with non-linear optical properties. The authors present the strategy followed for the study of these molecular systems, and an overview of their findings concerning the structure of the prototypical conducting polymer, i.e. pure and doped polyacetylene (PA). They focused attention on vibrational spectra and infrared and Raman intensities. The results of self-consistent-field (SCF) calculations on charged soliton-like molecules are consistent with experimental observation. In particular, they show that the theoretically established accidental mutual exclusion of infrared and Raman bands invalidates the requirement formulated on the basis of the interpretation of experimental data, that defects in PA must have local C/sub 2h/ symmetry. These conclusions are derived from extensive calculations for which supercomputer performance was imperative and carried out on the parallel supercomputer assembled at IBM-Kingston as a loosely coupled array of processors (LCAP). The authors briefly describe this computer system which has proven to be ideally suited to the methods of ab initio quantum chemistryitio quantum chemistry

  16. Molecular and electronic structure at C60:pentacene interfaces

    Science.gov (United States)

    Robey, S. W.; Dougherty, D. B.; Jin, W.; Cullen, W. G.; Dutton, G. J.; Reutt-Robey, J. E.

    2008-03-01

    Successful utilization of organic donor-acceptor systems for photovoltaic applications requires understanding factors controlling molecular and electronic structure at interfaces. We have used STM, STS, and photoemission to study the donor- acceptor system C60:pentacene. At low coverage, C60 deposited on a well-ordered pentacene bilayer structure on Ag (111) adsorbs in between two adjacent pentacene rows. Isolated C60 molecules are easily observed at room temperature indicating that the mobility of C60 on pentacene is significantly smaller than on metal surfaces. Some images of C60 reveal structure that may indicate a preferred C60 orientation. Electrostatic contributions to intermolecular interactions are discussed to help explain C60 adsorption between pentacene molecules. With increasing coverage, C60 forms linear chains, still locked to underlying pentacene rows. A further increase in coverage results in domains of disordered C60 that we propose result from competing C60- C60 and C60-pentacene interactions. Information on nanoscale transport gaps and band alignment was obtained using constant-current distance-voltage spectroscopy. A gap of 4.5 eV is found over the linear C60 chains compared with a gap of 3.6 eV for the surounding pentacene bilayer.

  17. Rectification of the OPAL Cold Neutron Source Cryogenic System

    International Nuclear Information System (INIS)

    The Cold Neutron Source (CNS) at ANSTO's OPAL Reactor had experienced repeated outages since 2009 due to failures in the cryogenic system. An extensive root cause analysis was initiated in May 2012, led by an ANSTO team that also involved knowledgeable external experts. At the conclusion of the investigation, a set of recommendations was released to address the identified contributing causes. A rectification program was established to implement the solutions. Cryogenic operation of the CNS, providing end users with cold neutrons, successfully returned to service in July 2013. Thanks to the unique stand-by operation mode of the CNS, irradiation activities at the reactor, as well as thermal neutron availability, had not been affected during the year-long investigation/rectification process. Some technical and operational aspects of the investigation, testing and engineering modifications are discussed in this presentation

  18. Rectification of the OPAL Cold Neutron Source Cryogenic System

    Energy Technology Data Exchange (ETDEWEB)

    Lu, Weijian [Australian Nuclear Science and Technology Organisation, Sydney (Australia)

    2013-07-01

    The Cold Neutron Source (CNS) at ANSTO's OPAL Reactor had experienced repeated outages since 2009 due to failures in the cryogenic system. An extensive root cause analysis was initiated in May 2012, led by an ANSTO team that also involved knowledgeable external experts. At the conclusion of the investigation, a set of recommendations was released to address the identified contributing causes. A rectification program was established to implement the solutions. Cryogenic operation of the CNS, providing end users with cold neutrons, successfully returned to service in July 2013. Thanks to the unique stand-by operation mode of the CNS, irradiation activities at the reactor, as well as thermal neutron availability, had not been affected during the year-long investigation/rectification process. Some technical and operational aspects of the investigation, testing and engineering modifications are discussed in this presentation.

  19. Rectification of energy transport in nonlinear metamaterials via ratchets

    International Nuclear Information System (INIS)

    The presence of discrete breathers (DBs) has already been described in nonlinear photonic materials, such as ferroelectrics and metamaterials (MMs) by the Klein–Gordon (K–G) approach. Rectification of energy transport in MMs in the presence of an appropriate external field is studied via symmetry breaking leading to directed energy transport or ratchet behaviour. Based on the earlier development of the K–G equation in a MM system with a split-ring resonator for antenna applications, a theoretical model for current density is worked out by symmetry analysis and its violation to characterize the ratchet effect. The time-averaged current shows interesting results against phase shift in the ac driver. These data are further related to various parameters, such as coupling and damping in the system. For MMs, this opens a new application for rectification using ratchets. (paper)

  20. Nonlinear optical rectification in asymmetric coupled quantum wells

    International Nuclear Information System (INIS)

    The optical rectification (OR) in the asymmetric coupled quantum wells (ACQWs) is calculated theoretically. The dependence of the OR on the width of the right-well and the barrier is studied. The analytical expression of the optical rectification coefficient is obtained by using the compact density-matrix approach and the iterative method, and the numerical calculations are presented for a typical GaAs/AlxGa1-xAs ACQW. The results obtained show that the OR efficient can reach the magnitude of 10-4 m/V in this ACQW system, which is 1-2 orders higher than that in single quantum systems. Moreover, the OR coefficient is strongly dependent on the widths of the barrier and the right-well of the ACQWs. An appropriate choice for the width of the barrier and the right-well of the ACQWs can induce a larger OR coefficient

  1. Exploring Higher-Lying Electronic States of a Molecular Switch by Coherent Triggered-Exchange 2D Electronic Spectroscopy

    OpenAIRE

    Nuernberger P.; Buback J.; Kullmann M.; Ruetzel S.; Brixner T.

    2013-01-01

    We use pump-repump-probe transient absorption spectroscopy to investigate the role of higher-lying electronic states in the photochemistry of a molecular switch. Moreover, replacing the pump pulse by a pulse-shaper-generated phase-stable double pulse, triggered-exchange two-dimensional (TE2D) electronic spectroscopy is established in the visible regime.

  2. Rectification of License Plate Images Based on HT and Projection

    Directory of Open Access Journals (Sweden)

    Jingsong Tao

    2013-07-01

    Full Text Available It is crucial to segment characters correctly and improve rate of correct character recognition when processing automobile license plates corrections. In this paper, two algorithms are proposed to obtain the horizontal tilt and vertical shear angles. The transformation matrix for images rectification is given and the subpixel issue is solved. Some experiments were done to test the algorithms. Experimental results show that the algorithm is robust, flexible and effective.

  3. Suppression of rectification at metal-Mott-insulator interfaces

    OpenAIRE

    Yonemitsu, Kenji; Maeshima, Nobuya; Hasegawa, Tatsuo

    2007-01-01

    Charge transport through metal-Mott-insulator interfaces is studied and compared with that through metal-band-insulator interfaces. For band insulators, rectification has been known to occur owing to a Schottky barrier, which is produced by the work-function difference. For Mott insulators, however, qualitatively different current-voltage characteristics are obtained. Theoretically, we use the one-dimensional Hubbard model for a Mott insulator and attach to it the tight-bind...

  4. Ballistic switching and rectification in single wall carbon nanotube Y junctions

    International Nuclear Information System (INIS)

    Transport properties of various semiconducting zig-zag carbon nanotube Y junctions are studied for the investigations of rectification and switching. Our results indicate that such junctions, when symmetric, can support both ballistic rectification and/or the ballistic switching operating modes. Although structural symmetry of the Y junction is found to be a necessary condition for rectification, it may not be sufficient in all cases

  5. Controllable Thermal Rectification Realized in Binary Phase Change Composites

    Science.gov (United States)

    Chen, Renjie; Cui, Yalong; Tian, He; Yao, Ruimin; Liu, Zhenpu; Shu, Yi; Li, Cheng; Yang, Yi; Ren, Tianling; Zhang, Gang; Zou, Ruqiang

    2015-03-01

    Phase transition is a natural phenomenon happened around our daily life, represented by the process from ice to water. While melting and solidifying at a certain temperature, a high heat of fusion is accompanied, classified as the latent heat. Phase change material (PCM) has been widely applied to store and release large amount of energy attributed to the distinctive thermal behavior. Here, with the help of nanoporous materials, we introduce a general strategy to achieve the binary eicosane/PEG4000 stuffed reduced graphene oxide aerogels, which has two ends with different melting points. It's successfully demonstrated this binary PCM composites exhibits thermal rectification characteristic. Partial phase transitions within porous networks instantaneously result in one end of the thermal conductivity saltation at a critical temperature, and therefore switch on or off the thermal rectification with the coefficient up to 1.23. This value can be further raised by adjusting the loading content of PCM. The uniqueness of this device lies in its performance as a normal thermal conductor at low temperature, only exhibiting rectification phenomenon when temperature is higher than a critical value. The stated technology has broad applications for thermal energy control in macroscopic scale such as energy-efficiency building or nanodevice thermal management.

  6. Preparation and rectification function of multilayer oxide p-i-n junction

    International Nuclear Information System (INIS)

    The all perovskite oxide p-i-n junctions formed by integrating semiconducting p-type (hole-doped) manganite (La,Sr)MnO3 (LSMO) and metallic n-type (electron-doped) cuprate superconductor (La,Ce)2CuO4, in between, the ferroelectric (Ba,Sr)TiO3 (BST) (which is in n-type semiconducting [1]) is sandwiched as the depletion barrier layer (i). It is shown that the perfect interfaces of the integrated layers is the most important factor to determine the rectification function of such p-i-n junction. For the typical p-i-n junction with depletion layer BST?20 nm, under the bias case, the forward current density is in 10?1A cm?2 order. The built-in field is estimated to be ?1.7 V, the depolarization field is ?1.4 V, and the reverse broken field is ??3.3 V.

  7. Air-pressure tunable depletion width, rectification behavior, and charge conduction in oxide nanotubes.

    Science.gov (United States)

    Alivov, Yahya; Funke, Hans H; Singh, Vivek; Nagpal, Prashant

    2015-02-01

    Metal-oxide nanotubes provide large surface areas and functionalizable surfaces for a variety of optical and electronic applications. Here we report air-tunable rectifying behavior, depletion width modulation, and two-dimensional (2D) charge conduction in hollow titanium-dioxide nanotubes. The metal contact forms a Schottky-diode in the nanotubes, and the rectification factor (on/off ratio) can be varied by more than 3 orders of magnitude (1-2 × 10(3)) as the air pressure is increased from 2 mTorr to atmospheric pressure. This behavior is explained using a change in depletion width of these thin nanotubes by adsorption of water vapor on both surfaces of a hollow nanotube, and the resulting formation of a metal-insulator-semiconductor (MIS) junction, which controls the 2D charge conduction properties in thin oxide nanotubes. PMID:25594471

  8. Rectification induced in N2AA-doped armchair graphene nanoribbon device

    International Nuclear Information System (INIS)

    By using non-equilibrium Green function formalism in combination with density functional theory, we investigated the electronic transport properties of armchair graphene nanoribbon devices in which one lead is undoped and the other is N2AA-doped with two quasi-adjacent substitutional nitrogen atoms incorporating pairs of neighboring carbon atoms in the same sublattice A. Two kinds of N2AA-doped style are considered, for N dopants substitute the center or the edge carbon atoms. Our results show that the rectification behavior with a large rectifying ratio can be found in these devices and the rectifying characteristics can be modulated by changing the width of graphene nanoribbons or the position of the N2AA dopant. The mechanisms are revealed to explain the rectifying behaviors.

  9. Dihydroazulene Photochromism:Synthesis, Molecular Electronics and Hammett Correlations

    DEFF Research Database (Denmark)

    Broman, SØren Lindbæk

    2013-01-01

    This thesis describes the development of a versatile synthetic protocol for preparation of a large selection of dihydroazulenes (DHAs) with both electron withdrawing and donating groups. By UV-Vis and NMR spectroscopies and even in a single-molecule junction, their ability to undergo a light-induced ring-opening reaction to vinylheptafulvenes (VHFs) and a thermally induced back-reaction (VHF ? DHA) were studied in detail. The first chapter briefly introduces photoswitches with focus, in particular, on the most well-known photoswitches. Then, the synthesis and properties of the DHA/VHF system will be discussed in detail. The second chapter describes the design and synthesis of DHA/VHFs intended for use in molecular electronics and their solution and single-molecule junction switching properties. By the expansion of the recently reported procedure for functionalization of this system by Suzuki cross-coupling reactions, systems with either one or two “molecular alligator clips” were prepared. These were studied in solution by UV-Vis absorption spectroscopy and in a single-molecule junction, the latter by the group of Danilov and Kubatkin at the Chalmers University of Technology. A single-molecule device was prepared in which reversible switching between states of conductance could be accomplished by either light/heat or light/bias. The third chapter describes the synthesis of a large number of donor and/or acceptor functionalized DHA/VHFs and the systematic dependence of the rate of the thermally induced back-reaction (VHF ? DHA), studied by UV-Vis absorption spectroscopy. In seven different model systems, the rate of back-reaction was found to obey a Hammett correlation when plotting ln(k) against the appropriate ?-values. These plots were used to estimate the ?-value of substituents which have not yet been determined such as heteroaromatics (furan, thiophene, and 1,2,3-triazole) and alkynes (triisopropylsilylethyne, trimethylsilyl- 1,3-butadiyne, and 1,3-butadiyne). It was also shown that the absorption maximum of the VHF and the rate of back-reaction can be conveniently fine-tuned by these donor or acceptor groups. The fourth chapter describes the synthesis and study of a VHF containing two sites for ring-closure in an attempt to overcome the problem of the VHF taking an unreactive conformation which was speculated to cause the relatively slow back-reaction (VHF ? DHA). The study showed that the rate of back-reaction was increased with close to a factor of 2 which is only the statistical improvement of having two possible sites for back-reaction as supposed to just one. The fifth chapter describes, in short, my contributions to an additional seven papers published. Figure 1. Structure of proposed transition state (TS) for the thermally induced ring-closure (VHF ? DHA). This strongly polarized TS is responsible for substituent-dependency of this reaction (left). Reversible switching between the states of the DHA/VHF trapped in a silver nano-gap (right).

  10. Electron degradation and yields on initial products. II. Subexcitation electrons in molecular nitrogen

    International Nuclear Information System (INIS)

    Subexcitation electrons lose their kinetic energy through vibrational excitation, rotational excitation, and elastic collisions in molecular gases. Initial yields of vibrationally and rotationally excited states of nitrogen molecules are calculated by using the Spencer--Fano equation (SFE) and its simplification, the continuous-slowing-down approximation (CSDA), both in time-independent and time-dependent representations. One focus of the present study is a close comparison of the CSDA with the rigorous treatment of the SFE in the subexcitation domain. The present result reveals for the first time distinct energy regions in which either vibrational excitation or rotational excitation dominates. This recognition explains the different time dependence of the yields of vibrational and rotational excitation

  11. EPICEA: Probing High-Energy Electron Emission In The Molecular Frame

    Science.gov (United States)

    Liu, Xiao-Jing; Nicolas, Christophe; Robert, Emmanuel; Miron, Catalin

    2014-04-01

    Electron emission provides an excellent opportunity to probe the electronic structure and the chemical reactivity of materials. For molecules, the most natural way is describing it in the molecular frame. Recently, using the upgraded version of the EPICEA coincidence setup available at PLEIADES beamline at SOLEIL (France), we were able to measure the electron emission in the molecular frame for kinetic energies up to several hundreds of eV. At these high energies the de Broglie wavelength is comparable to or smaller than the inter-nuclear distance, the possibility of observing the intramolecular electron diffraction thus being opened.

  12. Electron spin resonance study on lignin molecular mobility

    International Nuclear Information System (INIS)

    Molecular mobility of grinded wood lignin is studied in the wide temperature range using the recombination-kinetic method. Macroradicals formed during low-temperature ?-radiolysis of lignin, are used as a molecular probe. Analysis of curves of stage-by-stage heating of specimens confirms microheterogeneity of lignin

  13. Electronic and Molecular Surface Structures of Dye-Sensitized TiO2 Interfaces

    OpenAIRE

    Hahlin, Maria

    2010-01-01

    The dye-sensitized solar cell is a promising solar cell technology. In these systems the key process for light to electricity conversion is molecular in nature and is initiated in dye molecules adsorbed at a semiconducting surface. This thesis focuses on the electronic and molecular surface structure of the dye/TiO2 interface, and the experimental results were obtained from surface sensitive X-ray based electron spectroscopic methods. Two families of dyes, triarylamine based organic dyes and ...

  14. Proceedings of the 2. Latin American Meeting on Atomic, Molecular and Electronic Collisions

    International Nuclear Information System (INIS)

    Annals of the II Latin American Meeting on Atomic, Molecular and Electronic Collisions. Over than 50 people from Latin America participated on this meeting giving talks on different subjects (theoretical and experimental), related to atomic and molecular physics, as well as, nuclear physics. (A.C.A.S.)

  15. Computational Nanotechnology of Molecular Materials, Electronics, and Actuators with Carbon Nanotubes and Fullerenes

    Science.gov (United States)

    Srivastava, Deepak; Menon, Madhu; Cho, Kyeongjae; Biegel, Bryan (Technical Monitor)

    2001-01-01

    The role of computational nanotechnology in developing next generation of multifunctional materials, molecular scale electronic and computing devices, sensors, actuators, and machines is described through a brief review of enabling computational techniques and few recent examples derived from computer simulations of carbon nanotube based molecular nanotechnology.

  16. First Principles Study and Theoretical Analysis of a Single Molecular Diode by p - n di-block molecules

    Science.gov (United States)

    Nakamura, Hisao; Asai, Yoshihiro; Hihath, Josh; Tao, Nongjian

    2011-03-01

    The concept of a single molecular diode was first proposed by Aviram and Ratner, and there have been many studies of synthesis D- ? -A or p - n di-block molecules and measurements of the current-voltage (I - V) characteristics for relating molecular junctions. Recently, the I - V measurement in a symmetric tetraphenyl junction and non-symmetric dipyrimidinyl -diphenyl diblock junction was performed, and clear rectification was found in the latter system, which resembles the p - n junction by the covalent connection between electron-deficient bypyrimidinyl and electron-rich biphenyl moieties, though an applied bias is much lower than the resonant level. In this presentation, we performed the first principles calculations of electron transport for the above tetraphenyl and dipyrimidinyl -diphenyl diblock junctions by the self-consistent nonequilibrium Green's function theory with the use of our HiRUNE program module. We carried out the systematic analysis of the rectification behavior and identified the change of electron-pathway in the bridge molecule relating to p - n junction based on the first principles data. The relation between the rectifying action and molecular conformation, particularly, the torsion of diblock, will be discussed.

  17. Testing accelerometer rectification error caused by multidimensional composite inputs with double turntable centrifuge

    Science.gov (United States)

    Guan, W.; Meng, X. F.; Dong, X. M.

    2014-12-01

    Rectification error is a critical characteristic of inertial accelerometers. Accelerometers working in operational situations are stimulated by composite inputs, including constant acceleration and vibration, from multiple directions. However, traditional methods for evaluating rectification error only use one-dimensional vibration. In this paper, a double turntable centrifuge (DTC) was utilized to produce the constant acceleration and vibration simultaneously and we tested the rectification error due to the composite accelerations. At first, we deduced the expression of the rectification error with the output of the DTC and a static model of the single-axis pendulous accelerometer under test. Theoretical investigation and analysis were carried out in accordance with the rectification error model. Then a detailed experimental procedure and testing results were described. We measured the rectification error with various constant accelerations at different frequencies and amplitudes of the vibration. The experimental results showed the distinguished characteristics of the rectification error caused by the composite accelerations. The linear relation between the constant acceleration and the rectification error was proved. The experimental procedure and results presented in this context can be referenced for the investigation of the characteristics of accelerometer with multiple inputs.

  18. Large nonlinear optical rectification in atomic hexagonal layers with broken space inversion symmetry

    International Nuclear Information System (INIS)

    Motivated by possible applications in optoelectronics, we consider nonlinear optical rectification (NOR) in two planar hexagonal lattice structures with broken space inversion symmetry—namely, in graphene epitaxially grown on a SiC substrate and in boronitrene (a monolayer of BN). For both structures, we calculate the second-order nonlinear optical susceptibility ?(2)(0;?, ? ?) relevant to the NOR effect and evaluate a bias voltage V0 appearing at the structure terminals under strong laser irradiation. We show that the reason for the ?(2)(0;?, ? ?) being nonvanishing in the examined structures is their sublattice (inversion) asymmetry combined with the trigonal symmetry of their ?-electron energy bands near the corners of the hexagonal Brillouin zone of those structures. In spite of being rather small, the trigonal warping of the energy bands involved is found to provide a remarkably large magnitude of the NOR susceptibility, reaching the order of 5 × 10?4 esu for the graphene/SiC overlayer system when the pump photon energy ?? approaches the bandgap energy EG (?0.26 eV) of the overlying graphene. For a graphene sample of a few microns length, irradiated by a normally incident laser beam with a relatively moderate power density of 10 kW cm?2, the corresponding optical rectification voltage V0 is estimated to be as large as several millivolts. Moreover, the sign of the voltage (i.e., its polarity) can be sharply reversed by sweeping the photon energy through the inter-?-band resonance condition ?? = EG. This frequency-controlled optical switching, if realized, will be a potent technique for graphene-based photonics and optoelectronics. (paper)

  19. Cascade units for neon isotopes production by rectification method

    International Nuclear Information System (INIS)

    Basics of neon separation into isotopes by distillation method at T = 28 K are discussed. The required numbers of transfer units of the top and bottom column sections at different loads are calculated. The experimental characteristics of packed rectification columns are presented and examples of the cascade outlined. A scheme of cryogenic circuit based on the high-pressure throttle neon cycle with intermediate nitrogen cooling is presented. The necessity and the technical ability to create the driving difference of pressures between columns of various stages demonstrated.

  20. Study of rectification at the metal-cadmium telluride contact

    International Nuclear Information System (INIS)

    The barrier heights at the contact between metals and N or P type cadmium telluride have been determined. Various surface treatments have been used for the semiconductor: lapping, polishing and etching in a bromine in methanol solution. Depending on these preparation differences of about 0.1 eV have been observed for the barrier height which in any case was no more than 0.9 - 1.0 eV. These results can not be explained by only considering the Schottky theory of rectification

  1. Measuring the Density of a Molecular Cluster Injector via Visible Emission from an Electron Beam

    Energy Technology Data Exchange (ETDEWEB)

    Lundberg, D. P.; Kaita, R.; Majeski, R. M.; Stotler, D. P.

    2010-06-28

    A method to measure the density distribution of a dense hydrogen gas jet is pre- sented. A Mach 5.5 nozzle is cooled to 80K to form a flow capable of molecular cluster formation. A 250V, 10mA electron beam collides with the jet and produces H? emission that is viewed by a fast camera. The high density of the jet, several 1016cm?3, results in substantial electron depletion, which attenuates the H? emission. The attenuated emission measurement, combined with a simplified electron-molecule collision model, allows us to determine the molecular density profile via a simple iterative calculation.

  2. Intense Electron Beams from GaAs Photocathodes as a Tool for Molecular and Atomic Physics

    OpenAIRE

    Krantz, Claude

    2009-01-01

    We present cesium-coated GaAs photocathodes as reliable sources of intense, quasi-monoenergetic electron beams in atomic and molecular physics experiments. In long-time operation of the Electron Target of the ion storage ring TSR in Heidelberg, cold electron beams could be realised at steadily improving intensity and reliability. Minimisation of processes degrading the quantum efficiency allowed to increase the extractable current to more than 1mA at stable cathode lifetimes of 24 h or more. ...

  3. Darwin at the molecular scale: selection and variance in electron tunnelling proteins including cytochrome c oxidase

    OpenAIRE

    Moser, Christopher C.; Page, Christopher C.; Dutton, P. Leslie

    2006-01-01

    Biological electron transfer is designed to connect catalytic clusters by chains of redox cofactors. A review of the characterized natural redox proteins with a critical eye for molecular scale measurement of variation and selection related to physiological function shows no statistically significant differences in the protein medium lying between cofactors engaged in physiologically beneficial or detrimental electron transfer. Instead, control of electron tunnelling over long distances relie...

  4. Optically induced transport through semiconductor-based molecular electronics

    Science.gov (United States)

    Li, Guangqi; Fainberg, Boris D.; Seideman, Tamar

    2015-04-01

    A tight binding model is used to investigate photoinduced tunneling current through a molecular bridge coupled to two semiconductor electrodes. A quantum master equation is developed within a non-Markovian theory based on second-order perturbation theory with respect to the molecule-semiconductor electrode coupling. The spectral functions are generated using a one dimensional alternating bond model, and the coupling between the molecule and the electrodes is expressed through a corresponding correlation function. Since the molecular bridge orbitals are inside the bandgap between the conduction and valence bands, charge carrier tunneling is inhibited in the dark. Subject to the dipole interaction with the laser field, virtual molecular states are generated via the absorption and emission of photons, and new tunneling channels open. Interesting phenomena arising from memory are noted. Such a phenomenon could serve as a switch.

  5. Optically induced transport through semiconductor-based molecular electronics.

    Science.gov (United States)

    Li, Guangqi; Fainberg, Boris D; Seideman, Tamar

    2015-04-21

    A tight binding model is used to investigate photoinduced tunneling current through a molecular bridge coupled to two semiconductor electrodes. A quantum master equation is developed within a non-Markovian theory based on second-order perturbation theory with respect to the molecule-semiconductor electrode coupling. The spectral functions are generated using a one dimensional alternating bond model, and the coupling between the molecule and the electrodes is expressed through a corresponding correlation function. Since the molecular bridge orbitals are inside the bandgap between the conduction and valence bands, charge carrier tunneling is inhibited in the dark. Subject to the dipole interaction with the laser field, virtual molecular states are generated via the absorption and emission of photons, and new tunneling channels open. Interesting phenomena arising from memory are noted. Such a phenomenon could serve as a switch. PMID:25903870

  6. Molecular electronic junction transport : some pathways and some ideas

    DEFF Research Database (Denmark)

    Solomon, Gemma C.; Herrmann, Carmen

    2012-01-01

    Whenasinglemolecule,oracollectionofmolecules,isplacedbetween two electrodes and voltage is applied, one has a molecular transport junction. We discuss such junctions, their properties, their description, and some of their applications. The discussion is qualitative rather than quantitative, and focuses on mechanism, structure/function relations, regimes and mechanisms of transport, some molecular regularities, and some substantial challenges facing the field. Because there are many regimes and mechanisms in transport junctions, we will discuss time scales, geometries, and inelastic scattering methods for trying to determine the properties of molecules within these junctions. Finally, we discuss some device applications, some outstanding problems, and some future directions.

  7. Adventures in molecular electronics: how to attach wires to molecules

    International Nuclear Information System (INIS)

    Films of both methoxy-terminated alkanethiols and a molecular wire candidate on Au{1 1 1} substrates were exposed to a variety of transition and alkali earth metals (Al, Au, Ag, Ca, Cr, Fe, Cu, Mg, Ti). The results show that aggressively reacting metals, such as Ti, destroy the organic monolayer and metals of intermediate reactivity, e.g. Cu, react at the termini and also penetrate the monolayer and react with the substrate. The results of these investigations provide a basis by which future construction of molecular devices based on desired chemical reactivity may proceed

  8. Multiple-electron removal and molecular fragmentation of CO by fast F4+ impact

    International Nuclear Information System (INIS)

    Multiple-electron removal from and molecular fragmentation of carbon monoxide molecules caused by collisions with 1-MeV/amu F4+ ions were studied using the coincidence time-of-flight technique. In these collisions, multiple-electron removal of the target molecule is a dominant process. Cross sections for the different levels of ionization of the CO molecule during the collision were determined. The relative cross sections of ionization decrease with increasing number of electrons removed in a similar way as seen in atomic targets. This behavior is in agreement with a two-step mechanism, where first the molecule is ionized by a Franck-Condon ionization and then the molecular ion dissociates. Most of the highly charged intermediate states of the molecule dissociate rapidly. Only CO+ and CO2+ molecular ions have been seen to survive long enough to be detected as molecular ions. The relative cross sections for the different breakup channels were evaluated for collisions in which the molecule broke into two charged fragments as well as for collisions where only a single charged molecular ion or fragment were produced. The average charge state of each fragment resulting from COQ+?Ci++Oj+ breakup increases with the number of electrons removed from the molecule approximately following the relationship bar i=bar j=Q/2 as long as K-shell electrons are not removed. This does not mean that the charge-state distries not mean that the charge-state distribution is exactly symmetric, as, in general, removing electrons from the carbon fragment is slightly more likely than removing electrons from the oxygen due to the difference in binding energy. The cross sections for molecular breakup into a charged fragment and a neutral fragment drop rapidly with an increasing number of electrons removed

  9. Stereo Calibration and Rectification for Omnidirectional Multi-camera Systems

    Directory of Open Access Journals (Sweden)

    Yanchang Wang

    2012-10-01

    Full Text Available Stereo vision has been studied for decades as a fundamental problem in the field of computer vision. In recent years, computer vision and image processing with a large field of view, especially using omnidirectional vision and panoramic images, has been receiving increasing attention. An important problem for stereo vision is calibration. Although various kinds of calibration methods for omnidirectional cameras are proposed, most of them are limited to calibrate catadioptric cameras or fish?eye cameras and cannot be applied directly to multi?camera systems. In this work, we propose an easy calibration method with closed?form initialization and iterative optimization for omnidirectional multi?camera systems. The method only requires image pairs of the 2D target plane in a few different views. A method based on the spherical camera model is also proposed for rectifying omnidirectional stereo pairs. Using real data captured by Ladybug3, we carry out some experiments, including stereo calibration, rectification and 3D reconstruction. Statistical analyses and comparisons of the experimental results are also presented. As the experimental results show, the calibration results are precise and the effect of rectification is promising.

  10. Influences of molecular weight on curing effect of epoxy resin irradiated by electron beam

    International Nuclear Information System (INIS)

    The influences of molecular weight on electron beam (EB) curing in epoxy resins were studied. The rate of radiation reaction in epoxy resin systems decreases with the increasing molecular weight. Under the low radiation dose, the curing thickness and curing degree is small for samples with high molecular weight. The effect of molecular weight decreases with the increasing radiation dose. The glass transition temperature (Tg) and the storage modulus (E') are under the control of curing degree in samples, and the molecular weight will play a role on the samples with similar curing degree. After heat treatment, the Tg and E' of epoxy resins cured by radiation will increase. The molecular weight is directly associated with effect of heat treatment

  11. Molecular double core-hole electron spectroscopy for chemical analysis

    CERN Document Server

    Tashiro, Motomichi; Fukuzawa, Hironobu; Ueda, Kiyoshi; Buth, Christian; Kryzhevoi, Nikolai V; Cederbaum, Lorenz S

    2010-01-01

    We explore the potential of double core hole electron spectroscopy for chemical analysis in terms of x-ray two-photon photoelectron spectroscopy (XTPPS). The creation of deep single and double core vacancies induces significant reorganization of valence electrons. The corresponding relaxation energies and the interatomic relaxation energies are evaluated by CASSCF calculations. We propose a method how to experimentally extract these quantities by the measurement of single and double core-hole ionization potentials (IPs and DIPs). The influence of the chemical environment on these DIPs is also discussed for states with two holes at the same atomic site and states with two holes at two different atomic sites. Electron density difference between the ground and double core-hole states clearly shows the relaxations accompanying the double core-hole ionization. The effect is also compared with the sensitivity of single core hole ionization potentials (IPs) arising in single core hole electron spectroscopy. We have ...

  12. Regularizing the molecular potential in electronic structure calculations. II. Many-body methods

    Science.gov (United States)

    Bischoff, Florian A.

    2014-11-01

    In Paper I of this series [F. A. Bischoff, "Regularizing the molecular potential in electronic structure calculations. I. SCF methods," J. Chem. Phys. 141, 184105 (2014)] a regularized molecular Hamilton operator for electronic structure calculations was derived and its properties in SCF calculations were studied. The regularization was achieved using a correlation factor that models the electron-nuclear cusp. In the present study we extend the regularization to correlated methods, in particular the exact solution of the two-electron problem, as well as second-order many body perturbation theory. The nuclear and electronic correlation factors lead to computations with a smaller memory footprint because the singularities are removed from the working equations, which allows coarser grid resolution while maintaining the precision. Numerical examples are given.

  13. Trimer effects in fragment molecular orbital-linear combination of molecular orbitals calculation of one-electron orbitals for biomolecules

    Science.gov (United States)

    Kobori, Tomoki; Sodeyama, Keitaro; Otsuka, Takao; Tateyama, Yoshitaka; Tsuneyuki, Shinji

    2013-09-01

    The fragment molecular orbital (FMO)-linear combination of molecular orbitals (LCMO) method incorporates as an efficient post-process calculation of one-electron orbitals of the whole system after the FMO total energy calculation. A straightforward way to increase the accuracy is inclusion of the trimer effect. Here, we derive a comprehensive formulation called the FMO3-LCMO method. To keep the computational costs of the trimer term low enough, we use a matrix-size reduction technique. We evaluated the accuracy and efficiency of the FMO3-LCMO scheme in model biological systems (alanine oligomer and chignolin). The results show that delocalized electronic orbitals with covalent and hydrogen bonds are better described at the trimer level, and the FMO3-LCMO method is applicable to quantitative evaluations of a wide range of frontier orbitals in large biosystems.

  14. NATO Advanced Study Institute on Electronic Structure of Polymers and Molecular Crystals

    CERN Document Server

    Ladik, János

    1975-01-01

    The NATO Advanced Study Institute on "Electronic Structure of Polymers and Molecular Crystals" was held at the Facultes Universi­ taires de Namur (F.U.N.) from September 1st till September 14th, 1974. We wish to express our appreciation to the NATO Scientific Affairs Division whose generous support made this Institute possible and to the Facultes Universitaires de Namur and the Societe Chimique de Belgique which provided fellowships and travel grants to a number of students. This volume contains the main lectures about the basic principles of the field and about different recent developments of the theory of the electronic structure of polymers and molecular crystals. The school started with the presentation of the basic SCF-LCAO theory of the electronic structure of periodic polymers and molecular crystals (contributions by Ladik, Andre & Delhalle) showing how a combination of quantum chemical and solid state physical methods can provide band structures for these systems. The numerical aspects of these ...

  15. NATO Advanced Research Workshop on Vectorization of Advanced Methods for Molecular Electronic Structure

    CERN Document Server

    1984-01-01

    That there have been remarkable advances in the field of molecular electronic structure during the last decade is clear not only to those working in the field but also to anyone else who has used quantum chemical results to guide their own investiga­ tions. The progress in calculating the electronic structures of molecules has occurred through the truly ingenious theoretical and methodological developments that have made computationally tractable the underlying physics of electron distributions around a collection of nuclei. At the same time there has been consider­ able benefit from the great advances in computer technology. The growing sophistication, declining costs and increasing accessibi­ lity of computers have let theorists apply their methods to prob­ lems in virtually all areas of molecular science. Consequently, each year witnesses calculations on larger molecules than in the year before and calculations with greater accuracy and more com­ plete information on molecular properties. We can surel...

  16. Molecular shock response of explosives: electronic absorption spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Mcgrne, Shawn D [Los Alamos National Laboratory; Moore, David S [Los Alamos National Laboratory; Whitley, Von H [Los Alamos National Laboratory; Bolme, Cindy A [Los Alamos National Laboratory; Eakins, Daniel E [Los Alamos National Laboratory

    2009-01-01

    Electronic absorption spectroscopy in the range 400-800 nm was coupled to ultrafast laser generated shocks to begin addressing the question of the extent to which electronic excitations are involved in shock induced reactions. Data are presented on shocked polymethylmethacrylate (PMMA) thin films and single crystal pentaerythritol tetranitrate (PETN). Shocked PMMA exhibited thin film interference effects from the shock front. Shocked PETN exhibited interference from the shock front as well as broadband increased absorption. Relation to shock initiation hypotheses and the need for time dependent absorption data (future experiments) is briefly discussed.

  17. Coupled electron-phonon transport from molecular dynamics with quantum baths

    DEFF Research Database (Denmark)

    Lu, Jing Tao; Wang, J. S.

    2009-01-01

    Based on generalized quantum Langevin equations for the tight-binding wavefunction amplitudes and lattice displacements, electron and phonon quantum transport are obtained exactly using molecular dynamics (MD) in the ballistic regime. The electron-phonon interactions can be handled with a quasi-classical approximation. Both charge and energy transport and their interplay can be studied. We compare the MD results with those of a fully quantum mechanical nonequilibrium Green's function (NEGF) approach for the electron currents. We find a ballistic to diffusive transition of the electron conduction in one-dimensional chains as the chain length increases.

  18. Electronic transport properties of a molecular switch with carbon nanotube electrodes: A first-principles study

    International Nuclear Information System (INIS)

    We have studied the electronic transport properties of a new kind of optical molecular switch with two single-walled carbon nanotube (SWCNT) electrodes using first-principles transport calculations. It is shown that the enol form shows an overall higher conductance than the keto form at low-bias voltage, which is independent of the SWCNTs' chirality. Meantime, it is possible to tune the conductance of the molecular switch by changing the chirality of the SWCNTs.

  19. Polaron effects on nonlinear optical rectification in asymmetrical Gaussian potential quantum wells with applied electric fields

    International Nuclear Information System (INIS)

    Polaron effects on nonlinear optical rectification in asymmetrical Gaussian potential quantum wells are studied by the effective mass approximation and the perturbation theory. The numerical results show that nonlinear optical rectification coefficients are strongly dependent on the barrier hight V0 of the Gaussian potential quantum wells, the range L of the confinement potential and the electric field F. Besides, the numerical results show that no matter how V0, L and F change, taking into consideration polaron effects, the optical rectification coefficients ?0(2) get greatly enhanced.

  20. Polaron effects on nonlinear optical rectification in asymmetrical Gaussian potential quantum wells with applied electric fields

    Energy Technology Data Exchange (ETDEWEB)

    Wu, Jinghe [Department of Physics, Henan Institute of Education, Zhengzhou 450046 (China); Guo, Kangxian, E-mail: axguo@sohu.com [Department of Physics, College of Physics and Electronic Engineering, Guangzhou University, Guangzhou 510006 (China); Liu, Guanghui [Department of Physics, College of Physics and Electronic Engineering, Guangzhou University, Guangzhou 510006 (China)

    2014-08-01

    Polaron effects on nonlinear optical rectification in asymmetrical Gaussian potential quantum wells are studied by the effective mass approximation and the perturbation theory. The numerical results show that nonlinear optical rectification coefficients are strongly dependent on the barrier hight V{sub 0} of the Gaussian potential quantum wells, the range L of the confinement potential and the electric field F. Besides, the numerical results show that no matter how V{sub 0}, L and F change, taking into consideration polaron effects, the optical rectification coefficients ?{sub 0}{sup (2)} get greatly enhanced.

  1. Molecular and electronic structure of TiH2

    Science.gov (United States)

    Kudo, Takako; Gordon, Mark S.

    1995-05-01

    Ab initio electronic structure calculations using correlated wave functions have been performed to investigate the structure and energetics of TiH2 in its low-lying electronic states. Several triplet states have been found to lie very close to each other in energy (within 5 kcal/mol) and nearly 1 eV below the lowest singlet state. The lowest quintet states appear to be considerably higher in energy. The ground state of TiH2 is found to be bent 3B1 in C2v symmetry, with the 3A1 state lying only 1 kcal/mol higher in energy. The lowest singlet state, 1A1, is found to be slightly bent, but with a very flat potential energy surface. The Ti-H bond in all TiH2 electronic states is predicted to be strongly polarized Ti+H-. The use of state-averaged multiconfigurational self-consistent field wave functions is essential to obtain a consistent picture of all electronic states of interest.

  2. Distant electron tunneling controlled by external fields in molecular nano structures

    International Nuclear Information System (INIS)

    The influence of stochastic, periodic, and magnetic fields on a long-range electron tunneling in donor - bridge - acceptor and electrode - molecular wire - electrode structures is studied theoretically. The description of a bridge-mediated electron tunneling between donor and acceptor groups is shown to be possible via the introduction of effective transfer rates. The principal distinction in the dependence of low-temperature elastic and inelastic tunnel currents mediated by a molecular wire with bridging paramagnetic ions on an applied magnetic field is considered. The appearance of the field-induced inversion and suppression effects is widely discussed

  3. The roles of electronic and nuclear stopping in the desorption valine negative molecular ions

    International Nuclear Information System (INIS)

    The yield of valine negative molecular ions has been measured as a function of Xe+, Kr+, and Ar+ primary ion velocity. The electronic and nuclear stopping powers are comparable in magnitude and opposite in slope in the experimental velocity region. The yield data are explained in terms of electronic stopping power alone, with no contribution from nuclear stopping power within the experimental error. Low molecular weight atomic species are found to be best described by a nuclear stopping power related process. 18 refs., 3 figs

  4. System of excited electronic states and molecular constants of calcium, strontium and barium monoxides

    International Nuclear Information System (INIS)

    In the framework of spin-limited, spin-unlimited and quasirelativistic variants of X2-PB method the spectroscopic constants of the basic and excited electron states of SrO, CaO, BaO are calculated. Dependences of orbital energies on internuclear distance in molecules are determined; spin-orbital splittings of molecular orbitals and population in molecules being considered. Comparison of calculated and experimental values of molecular constants for SrO is made. It is shown that in case of satisfactory agreement between the values of vibration frequencies and internuclear distances the calculation results in overestimation of energies of all excited electron states

  5. Efficient electronic structure calculation for molecular ionization dynamics at high x-ray intensity

    CERN Document Server

    Hao, Yajiang; Hanasaki, Kota; Son, Sang-Kil; Santra, Robin

    2015-01-01

    We present the implementation of an electronic-structure approach dedicated to ionization dynamics of molecules interacting with x-ray free-electron laser (XFEL) pulses. In our scheme, molecular orbitals for molecular core-hole states are represented by linear combination of numerical atomic orbitals that are solutions of corresponding atomic core-hole states. We demonstrate that our scheme efficiently calculates all possible multiple-hole configurations of molecules formed during XFEL pulses. The present method is suitable to investigate x-ray multiphoton multiple ionization dynamics and accompanying nuclear dynamics, providing essential information on the chemical dynamics relevant for high-intensity x-ray imaging.

  6. Electron Transfer Dynamics in Efficient Molecular Solar Cells

    Energy Technology Data Exchange (ETDEWEB)

    Meyer, Gerald John

    2014-10-01

    This research provided new mechanistic insights into surface mediated photochemical processes relevant to solar energy conversion. In this past three years our research has focused on oxidation photo-redox chemistry and on the role surface electric fields play on basic spectroscopic properties of molecular-semiconductor interfaces. Although this research as purely fundamental science, the results and their interpretation have relevance to applications in dye sensitized and photogalvanic solar cells as well as in the storage of solar energy in the form of chemical bonds.

  7. Electronic Transport Properties of a Naphthopyran-Based Optical Molecular Switch: an ab initio Study

    International Nuclear Information System (INIS)

    The electronic transport properties of a naphthopyran-based molecular optical switch are investigated by using the nonequilibrium Green's function formalism combined with first-principles density functional theory. The molecule that comprises the switch can convert between its open and closed forms upon photoexcitation. Theoretical results show that the current through the open form is significantly larger than that through the closed form, which is different from other optical switches based on ring-opening reactions of the molecular bridge. The maximum on-off ratio (about 90) can be obtained at 1.4 V. The physical origin of the switching behavior is interpreted based on the spatial distributions of molecular orbitals and the HOMO-LUMO gap. Our result shows that the naphthopyran-based molecule is a good candidate for optical molecular switches and will be useful in the near future. (atomic and molecular physics)

  8. Electrochemical current rectification-a novel signal amplification strategy for highly sensitive and selective aptamer-based biosensor.

    Science.gov (United States)

    Feng, Lingyan; Sivanesan, Arumugam; Lyu, Zhaozi; Offenhäusser, Andreas; Mayer, Dirk

    2015-04-15

    Electrochemical aptamer-based (E-AB) sensors represent an emerging class of recently developed sensors. However, numerous of these sensors are limited by a low surface density of electrode-bound redox-oligonucleotides which are used as probe. Here we propose to use the concept of electrochemical current rectification (ECR) for the enhancement of the redox signal of E-AB sensors. Commonly, the probe-DNA performs a change in conformation during target binding and enables a nonrecurring charge transfer between redox-tag and electrode. In our system, the redox-tag of the probe-DNA is continuously replenished by solution-phase redox molecules. A unidirectional electron transfer from electrode via surface-linked redox-tag to the solution-phase redox molecules arises that efficiently amplifies the current response. Using this robust and straight-forward strategy, the developed sensor showed a substantial signal amplification and consequently improved sensitivity with a calculated detection limit of 114nM for ATP, which was improved by one order of magnitude compared with the amplification-free detection and superior to other previous detection results using enzymes or nanomaterials-based signal amplification. To the best of our knowledge, this is the first demonstration of an aptamer-based electrochemical biosensor involving electrochemical rectification, which can be presumably transferred to other biomedical sensor systems. PMID:25460883

  9. Participation of Low Molecular Weight Electron Carriers in Oxidative Protein Folding

    Directory of Open Access Journals (Sweden)

    József Mandl

    2009-03-01

    Full Text Available Oxidative protein folding is mediated by a proteinaceous electron relay system, in which the concerted action of protein disulfide isomerase and Ero1 delivers the electrons from thiol groups to the final acceptor. Oxygen appears to be the final oxidant in aerobic living organisms, although the existence of alternative electron acceptors, e.g. fumarate or nitrate, cannot be excluded. Whilst the protein components of the system are well-known, less attention has been turned to the role of low molecular weight electron carriers in the process. The function of ascorbate, tocopherol and vitamin K has been raised recently. In vitro and in vivo evidence suggests that these redox-active compounds can contribute to the functioning of oxidative folding. This review focuses on the participation of small molecular weight redox compounds in oxidative protein folding.

  10. Self-regulation of photoinduced electron transfer by a molecular nonlinear transducer.

    Science.gov (United States)

    Straight, Stephen D; Kodis, Gerdenis; Terazono, Yuichi; Hambourger, Michael; Moore, Thomas A; Moore, Ana L; Gust, Devens

    2008-05-01

    Organisms must adapt to survive, necessitating regulation of molecular and subcellular processes. Green plant photosynthesis responds to potentially damaging light levels by downregulating the fraction of excitation energy that drives electron transfer. Achieving adaptive, self-regulating behaviour in synthetic molecules is a critical challenge that must be met if the promises of nanotechnology are to be realized. Here we report a molecular pentad consisting of two light-gathering antennas, a porphyrin electron donor, a fullerene electron acceptor and a photochromic control moiety. At low white-light levels, the molecule undergoes photoinduced electron transfer with a quantum yield of 82%. As the light intensity increases, photoisomerization of the photochrome leads to quenching of the porphyrin excited state, reducing the quantum yield to as low as 27%. This self-regulating molecule modifies its function according to the level of environmental light, mimicking the non-photochemical quenching mechanism for photoprotection found in plants. PMID:18654524

  11. Light-induced self-assembly of active rectification devices

    CERN Document Server

    Stenhammar, J; Marenduzzo, D; Cates, M E

    2015-01-01

    Self-propelled colloidal objects, such as motile bacteria or synthetic microswimmers, have microscopically irreversible individual dynamics - a feature they share with all living systems. The incoherent behaviour of individual swimmers can then be harnessed (or "rectified") by microfluidic devices that create systematic motions impossible in equilibrium. Examples include flow of rotor particles round a circuit, steady rotation of a gear wheel in a bacterial bath, and pumping of bacteria between chambers by "funnel gates". Here we present a computational proof-of-concept study, showing that such active rectification devices might be created directly from an unstructured "primordial soup" of motile particles, solely by using spatially modulated illumination to control their local propulsion speed. Alongside both microscopic irreversibility and speed modulation, our mechanism requires spatial symmetry breaking, such as a chevron light pattern, and strong interactions between particles, such as volume exclusion c...

  12. Voltage rectification in two-dimensional Josephson junction arrays

    International Nuclear Information System (INIS)

    We study numerically the directed motion of vortices (antivortices) under an applied ac bias in two-dimensional Josephson junction arrays (JJA) with an asymmetrically modulated periodic vortex pinning potential. We find that the ratchet effect in large 2D JJA can be obtained using the RSJ model for the overdamped vortex dynamics. The rectification effect shows a strong dependence on vortex density as well as an inversion of the vortex flow direction with the ac amplitude, for a wide range of magnetic field around f = 1/2 (f being the vortex density). Our results are in good agreement with very recent experiments by D.E. Shalom and H. Pastoriza [D.E. Shalom, H. Pastoriza, Phys. Rev. Lett. 94 (2005) 177001

  13. Current rectification in temperature-responsive single nanopores.

    Science.gov (United States)

    Guo, Wei; Xia, Hongwei; Xia, Fan; Hou, Xu; Cao, Liuxuan; Wang, Lin; Xue, Jianming; Zhang, Guangzhao; Song, Yanlin; Zhu, Daoben; Wang, Yugang; Jiang, Lei

    2010-03-15

    Herein we demonstrate a fully abiotic smart single-nanopore device that rectifies ionic current in response to the temperature. The temperature-responsive nanopore ionic rectifier can be switched between a rectifying state below 34 degrees C and a non-rectifying state above 38 degrees C actuated by the phase transition of the poly(N-isopropylacrylamide) [PNIPAM] brushes. On the rectifying state, the rectifying efficiency can be enhanced by the dehydration of the attached PNIPAM brushes below the LCST. When the PNIPAM brushes have sufficiently collapsed, the nanopore switches to the non-rectifying state. The concept of the temperature-responsive current rectification in chemically-modified nanopores paves a new way for controlling the preferential direction of the ion transport in nanofluidics by modulating the temperature, which has the potential to build novel nanomachines with smart fluidic communication functions for future lab-on-chip devices. PMID:20140936

  14. CONCURRENT FAULT RECTIFICATION (CFR ARCHITECTURE FOR MOTION ANALYSIS COMPUTING ARRAYS

    Directory of Open Access Journals (Sweden)

    S. Vasanth Vigneshwaran

    2013-10-01

    Full Text Available This paper develops a novel Concurrent Fault Rectification (CFR architecture for Motion Analysis Computing Arrays (MACA. Any single fault in each Processing Element (PE in an MACA can be effectively detected and corrected using the concept of Dual-Remnant codes i.e., Remnant and Proportionate (RP code. A Good Example is the H.264 video compression standard, also known as MPEG-4 Advanced Video Coding application. It uses a context-based adaptive method to speed up the multiple reference frames Motion Analysis by avoiding 76%–96% unnecessary reference frames computation. A large PE array accelerates the computation speed especially in High Resolution devices such as HDTV(High Definition Television.The Visual Quality and Peak Signal-to-Noise Ratio (PSNR at a given bit rate are influenced if a fault occurred in MA process.

  15. Maximal rectification ratios for bi-segment thermal rectifiers

    CERN Document Server

    Shih, Tien-Mo; Guo, Ziquan; Liu, Guangcao; Merlitz, Holger; Pagni, Patrick J; Chen, Zhong

    2014-01-01

    We study bi-segment thermal rectifiers whose forward heat fluxes are greater than reverse counterparts. Presently, a shortcoming of thermal rectifiers is that the rectification ratio, namely the forward flux divided by the reverse flux, remains too small for practical applications. In this study, we have managed to discover and theoretically derive the ultimate limit of such ratios, which are validated by numerical simulations, experiments, and micro-scale Hamiltonian-oscillator analyses. For rectifiers whose thermal conductivities are linear with the temperature, this limit is simply a numerical value of 3. For those whose conductivities are nonlinear with temperatures, the maxima equal $\\kappa_{max}/\\kappa_{min}$, where the two extremes denote values of the solid segment materials that can be possibly found or fabricated within a reasonable temperature range on earth. Recommendations for manufacturing high-ratio rectifiers are also given with examples.

  16. Monitoring molecular dynamics using coherent electrons from high harmonic generation

    OpenAIRE

    Wagner, Nicholas L.; Wüest, Andrea; Christov, Ivan P.; Popmintchev, Tenio; Zhou, Xibin; Murnane, Margaret M.; Kapteyn, Henry C.

    2006-01-01

    We report a previously undescribed spectroscopic probe that makes use of electrons rescattered during the process of high-order harmonic generation. We excite coherent vibrations in SF6 using impulsive stimulated Raman scattering with a short laser pulse. A second, more intense laser pulse generates high-order harmonics of the fundamental laser, at wavelengths of ?20–50 nm. The high-order harmonic yield is observed to oscillate, at frequencies corresponding to all of the Raman-active mode...

  17. Machine learning of molecular electronic properties in chemical compound space

    OpenAIRE

    Gr\\xe9goire Montavon; Matthias Rupp; Vivekanand Gobre; Alvaro Vazquez-Mayagoitia; Katja Hansen; Alexandre Tkatchenko; Klaus-Robert M\\xfcller; O Anatole von Lilienfeld

    2013-01-01

    The combination of modern scientific computing with electronic structure theory can lead to an unprecedented amount of data amenable to intelligent data analysis for the identification of meaningful, novel, and predictive structure-property relationships. Such relationships enable high-throughput screening for relevant properties in an exponentially growing pool of virtual compounds that are synthetically accessible. Here, we present a machine learning (ML) model, trained on...

  18. Rate coefficients for low-energy electron dissociative attachment to molecular hydrogen

    International Nuclear Information System (INIS)

    Calculation of rate constants for dissociative electron attachment to molecular hydrogen is reported. The calculation is based on an improved nonlocal resonance model of Cizek, Horacek and Domcke which takes fully into account the nonlocality of the resonance dynamics and uses potentials with correct asymptotic forms. The rate constants are calculated for all quantum numbers v and J of the target molecules and for electron temperature in the range 0-30000 K. (author)

  19. Ion Current Rectification, Limiting and Overlimiting Conductances in Nanopores

    Science.gov (United States)

    van Oeffelen, Liesbeth; Van Roy, Willem; Idrissi, Hosni; Charlier, Daniel; Lagae, Liesbet; Borghs, Gustaaf

    2015-01-01

    Previous reports on Poisson-Nernst-Planck (PNP) simulations of solid-state nanopores have focused on steady state behaviour under simplified boundary conditions. These are Neumann boundary conditions for the voltage at the pore walls, and in some cases also Donnan equilibrium boundary conditions for concentrations and voltages at both entrances of the nanopore. In this paper, we report time-dependent and steady state PNP simulations under less restrictive boundary conditions, including Neumann boundary conditions applied throughout the membrane relatively far away from the nanopore. We simulated ion currents through cylindrical and conical nanopores with several surface charge configurations, studying the spatial and temporal dependence of the currents contributed by each ion species. This revealed that, due to slow co-diffusion of oppositely charged ions, steady state is generally not reached in simulations or in practice. Furthermore, it is shown that ion concentration polarization is responsible for the observed limiting conductances and ion current rectification in nanopores with asymmetric surface charges or shapes. Hence, after more than a decade of collective research attempting to understand the nature of ion current rectification in solid-state nanopores, a relatively intuitive model is retrieved. Moreover, we measured and simulated current-voltage characteristics of rectifying silicon nitride nanopores presenting overlimiting conductances. The similarity between measurement and simulation shows that overlimiting conductances can result from the increased conductance of the electric double-layer at the membrane surface at the depletion side due to voltage-induced polarization charges. The MATLAB source code of the simulation software is available via the website http://micr.vub.ac.be. PMID:25978328

  20. Ion current rectification, limiting and overlimiting conductances in nanopores.

    Science.gov (United States)

    van Oeffelen, Liesbeth; Van Roy, Willem; Idrissi, Hosni; Charlier, Daniel; Lagae, Liesbet; Borghs, Gustaaf

    2015-01-01

    Previous reports on Poisson-Nernst-Planck (PNP) simulations of solid-state nanopores have focused on steady state behaviour under simplified boundary conditions. These are Neumann boundary conditions for the voltage at the pore walls, and in some cases also Donnan equilibrium boundary conditions for concentrations and voltages at both entrances of the nanopore. In this paper, we report time-dependent and steady state PNP simulations under less restrictive boundary conditions, including Neumann boundary conditions applied throughout the membrane relatively far away from the nanopore. We simulated ion currents through cylindrical and conical nanopores with several surface charge configurations, studying the spatial and temporal dependence of the currents contributed by each ion species. This revealed that, due to slow co-diffusion of oppositely charged ions, steady state is generally not reached in simulations or in practice. Furthermore, it is shown that ion concentration polarization is responsible for the observed limiting conductances and ion current rectification in nanopores with asymmetric surface charges or shapes. Hence, after more than a decade of collective research attempting to understand the nature of ion current rectification in solid-state nanopores, a relatively intuitive model is retrieved. Moreover, we measured and simulated current-voltage characteristics of rectifying silicon nitride nanopores presenting overlimiting conductances. The similarity between measurement and simulation shows that overlimiting conductances can result from the increased conductance of the electric double-layer at the membrane surface at the depletion side due to voltage-induced polarization charges. The MATLAB source code of the simulation software is available via the website http://micr.vub.ac.be. PMID:25978328

  1. Atomic and molecular photoelectron and Auger-electron-spectroscopy studies using synchrotron radiation

    International Nuclear Information System (INIS)

    Electron spectroscopy, combined with synchrotron radiation, was used to measure the angular distributions of photoelectrons and Auger electrons from atoms and molecules as functions of photon energy. The branching ratios and partial cross sections were also measured in certain cases. By comparison with theoretical calculations, the experimental results are interpreted in terms of the characteristic electronic structure and ionization dynamics of the atomic or molecular sample. The time structure of the synchrotron radiation source was used to record time-of-flight (TOF) spectra of the ejected electrons. The double-angle-TOF method for the measurement of photoelectron angular distributions is discussed. This technique offers the advantages of increased electron collection efficiency and the elimination of certain systematic errors. An electron spectroscopy study of inner-shell photoexcitation and ionization of Xe, photoelectron angular distributions from H2 and D2, and photoionization cross sections and photoelectron asymmetries of the valence orbitals of NO are reported

  2. Theory of Photoinduced Phase Transitions in Molecular Conductors: Interplay Between Correlated Electrons, Lattice Phonons and Molecular Vibrations

    Directory of Open Access Journals (Sweden)

    Kenji Yonemitsu

    2012-01-01

    Full Text Available Dynamics of photoinduced phase transitions in molecular conductors are reviewed from the perspective of interplay between correlated electrons and phonons. (1 The charge-transfer complex TTF-CA shows a transition from a neutral paraelectric phase to an ionic ferroelectric phase. Lattice phonons promote this photoinduced transition by preparing short-range lattice dimerization as a precursor. Molecular vibrations stabilize the neutral phase so that the ionic phase, when realized, possesses a large ionicity and the Mott character; (2 The organic salts ?-(BEDT-TTF2RbZn(SCN4 and ?-(BEDT-TTF2I3 show transitions from a charge-ordered insulator to a metal. Lattice phonons make this photoinduced transition hard for the former salt only. Molecular vibrations interfere with intermolecular transfers of correlated electrons at an early stage; (3 The organic salt ?-(d-BEDT-TTF2Cu[N(CN2]Br shows a transition from a Mott insulator to a metal. Lattice phonons modulating intradimer transfer integrals enable photoexcitation-energy-dependent transition pathways through weakening of effective interaction and through introduction of carriers.

  3. How the geometric configuration and the surface charge distribution influence the ionic current rectification in nanopores

    International Nuclear Information System (INIS)

    Asymmetrical properties of ion transport have been found in single conical nanopores and partly charged nano-channels. Recently, nanofluidic diodes based on this novel phenomenon have been fabricated. To generally understand the mechanism of the ionic current rectification, we study the ionic electric behaviours in several kinds of nanopores based on Poisson-Nernst-Planck equations. The calculated results show that for a partly charged nanopore, the geometry of the uncharged section, which might have been overlooked previously, has a substantial influence on current rectification. In addition, surface charge distribution is also an influential factor in current rectification. In particular, for a long homogeneously charged conical nanopore, the electrical and geometric properties of the section near the nanopore tip with a length of hundreds of nanometres are mainly responsible for the ionic current rectification. This result is consistent with the results of recent experiments on nanofluidic diodes

  4. Time-dependent theoretical treatments of the dynamics of electrons and nuclei in molecular systems

    International Nuclear Information System (INIS)

    An overview is presented of methods for time-dependent treatments of molecules as systems of electrons and nuclei. The theoretical details of these methods are reviewed and contrasted in the light of a recently developed time-dependent method called electron-nuclear dynamics. Electron-nuclear dynamics (END) is a formulation of the complete dynamics of electrons and nuclei of a molecular system that eliminates the necessity of constructing potential-energy surfaces. Because of its general formulation, it encompasses many aspects found in other formulations and can serve as a didactic device for clarifying many of the principles and approximations relevant in time-dependent treatments of molecular systems. The END equations are derived from the time-dependent variational principle applied to a chosen family of efficiently parametrized approximate state vectors. A detailed analysis of the END equations is given for the case of a single-determinantal state for the electrons and a classical treatment of the nuclei. The approach leads to a simple formulation of the fully nonlinear time-dependent Hartree-Fock theory including nuclear dynamics. The nonlinear END equations with the ab initio Coulomb Hamiltonian have been implemented at this level of theory in a computer program, ENDyne, and have been shown feasible for the study of small molecular systems. Implementation of the Austin Model 1 semiempirical Hamiltonian is discussed as a route to large molecular systems. The lin route to large molecular systems. The linearized END equations at this level of theory are shown to lead to the random-phase approximation for the coupled system of electrons and nuclei. The qualitative features of the general nonlinear solution are analyzed using the results of the linearized equations as a first approximation. Some specific applications of END are presented, and the comparison with experiment and other theoretical approaches is discussed

  5. Intense electron beams from GaAs photocathodes as a tool for molecular and atomic physics

    Energy Technology Data Exchange (ETDEWEB)

    Krantz, Claude

    2009-10-28

    We present cesium-coated GaAs photocathodes as reliable sources of intense, quasi-monoenergetic electron beams in atomic and molecular physics experiments. In long-time operation of the Electron Target of the ion storage ring TSR in Heidelberg, cold electron beams could be realised at steadily improving intensity and reliability. Minimisation of processes degrading the quantum efficiency allowed to increase the extractable current to more than 1mA at usable cathode lifetimes of 24 h or more. The benefits of the cold electron beam with respect to its application to electron cooling and electron-ion recombination experiments are discussed. Benchmark experiments demonstrate the superior cooling force and energy resolution of the photoelectron beam compared to its thermionic counterparts. The long period of operation allowed to study the long-time behaviour of the GaAs samples during multiple usage cycles at the Electron Target and repeated in-vacuum surface cleaning by atomic hydrogen exposure. An electron emission spectroscopy setup has been implemented at the photocathode preparation chamber of the Electron Target. Among others, this new facility opened the way to a novel application of GaAs (Cs) photocathodes as robust, ultraviolet-driven electron emitters. Based on this principle, a prototype of an electron gun, designed for implementation at the HITRAP setup at GSI, has been built and taken into operation successfully. (orig.)

  6. Intense electron beams from GaAs photocathodes as a tool for molecular and atomic physics

    International Nuclear Information System (INIS)

    We present cesium-coated GaAs photocathodes as reliable sources of intense, quasi-monoenergetic electron beams in atomic and molecular physics experiments. In long-time operation of the Electron Target of the ion storage ring TSR in Heidelberg, cold electron beams could be realised at steadily improving intensity and reliability. Minimisation of processes degrading the quantum efficiency allowed to increase the extractable current to more than 1mA at usable cathode lifetimes of 24 h or more. The benefits of the cold electron beam with respect to its application to electron cooling and electron-ion recombination experiments are discussed. Benchmark experiments demonstrate the superior cooling force and energy resolution of the photoelectron beam compared to its thermionic counterparts. The long period of operation allowed to study the long-time behaviour of the GaAs samples during multiple usage cycles at the Electron Target and repeated in-vacuum surface cleaning by atomic hydrogen exposure. An electron emission spectroscopy setup has been implemented at the photocathode preparation chamber of the Electron Target. Among others, this new facility opened the way to a novel application of GaAs (Cs) photocathodes as robust, ultraviolet-driven electron emitters. Based on this principle, a prototype of an electron gun, designed for implementation at the HITRAP setup at GSI, has been built and taken into operation successfully. (orig.)

  7. The Design, Synthesis and Assessment of Novel Phthalocyanines for Application in Molecular Electronics.

    Science.gov (United States)

    McKeown, Neil B.

    Available from UMI in association with The British Library. Requires signed TDF. The concepts, potential, and problems of molecular electronic materials in general and of phthalocyanines in particular are described briefly in the introductory chapter. Phthalocyanines are recognised as potentially important molecular electronic materials. However, in order to enable their incorporation into devices a method of fabricating well ordered thin films is required. The Langmuir-Blodgett technique produces ordered films of organic materials by the deposition of a monolayer at an air/water interface onto a solid substrate. This technique, its potential role in molecular electronics, and the poor results obtained with phthalocyanine derivatives, to date, are reviewed. The synthesis of a new series of phthalocyanine derivatives (LBPcs) specifically designed for the LB technique is described. The molecular structure of the LBPcs fulfill the requirements of solubility in organic solvents, isomeric purity, and the hydrophobic/hydrophilic interactions known to orientate molecules of fatty acids at the water surface. A variety of physical methods including X-ray diffraction show that the LB films of the LBPcs are well ordered. The molecular orientation and thermal reorganisation within the films is discussed. The phthalocyanine by-products from the preparation of the LBPcs are shown to be thermotropic liquid crystals by optical microscopy and differential scanning calorimetry. The columnar structure within these liquid crystals has been determined by low angle X-ray diffraction.

  8. Inward rectification in KATP channels: a pH switch in the pore.

    OpenAIRE

    Baukrowitz, T; Tucker, SJ; Schulte, U.; Benndorf, K.; Ruppersberg, JP; Fakler, B.

    1999-01-01

    Inward-rectifier potassium channels (Kir channels) stabilize the resting membrane potential and set a threshold for excitation in many types of cell. This function arises from voltage-dependent rectification of these channels due to blockage by intracellular polyamines. In all Kir channels studied to date, the voltage-dependence of rectification is either strong or weak. Here we show that in cardiac as well as in cloned KATP channels (Kir6.2 + sulfonylurea receptor) polyamine-mediated rectifi...

  9. Influence of the electron-phonon iinteraction on phonon heat conduction in a molecular nanowire

    Directory of Open Access Journals (Sweden)

    Galovi? Slobodanka P.

    2006-01-01

    Full Text Available A model for phonon heat conduction in a molecular nanowire is developed. The calculation takes into account modification of the acoustic phonon dispersion relation due to the electron-phonon interaction. The results obtained are compared with models based upon a simpler, Callaway formula.

  10. Influence of the electron-phonon iinteraction on phonon heat conduction in a molecular nanowire

    OpenAIRE

    Galovi? Slobodanka P.; ?evizovi? D.; Zekovi? S.; Ivi? Z.

    2006-01-01

    A model for phonon heat conduction in a molecular nanowire is developed. The calculation takes into account modification of the acoustic phonon dispersion relation due to the electron-phonon interaction. The results obtained are compared with models based upon a simpler, Callaway formula.

  11. Electron-molecular cation reactive collisions: from channel mixing to competitive processes

    International Nuclear Information System (INIS)

    The competition between dissociative recombination, vibrational excitation, and dissociative excitation of molecular cations in electron-impact collisions is discussed within the formalism of the Multichannel Quantum Defect Theory. Illustrative results are given for the HD+/HD and CO+/CO systems.

  12. Reduction of the Glauber amplitude for electron impact rotational excitation of quadrupolar molecular ions

    International Nuclear Information System (INIS)

    A reduction of the Glauber amplitude for the rotational excitation of pure quadrupolar molecular ions by electron impact is presented in a form suitable for numerical evaluation. The differential cross-section is expressed in terms of one dimensional integrals over impact parameter. (author)

  13. Molecular mapping by low-energy-loss energy-filtered transmission electron microscopy imaging.

    Science.gov (United States)

    Linares, Elisângela M; Leite, Carlos A P; Valadares, Leonardo F; Silva, Cristiane A; Rezende, Camila A; Galembeck, Fernando

    2009-03-15

    Structure-function relationships in supramolecular systems depend on the spatial distribution of molecules, ions, and particles within complex arrays. Imaging the spatial distribution of molecular components within nanostructured solids is the objective of many recent techniques, and a powerful tool is electron spectroscopy imaging in the transmission electron microscope (ESI-TEM) in the low-energy-loss range, 0-80 eV. This technique was applied to particulate and thin film samples of dielectric polymers and inorganic compounds, providing excellent distinction between areas occupied by various macromolecules and particles. Domains differentiated by small changes in molecular composition and minor differences in elemental contents are clearly shown. Slight changes in the molecules produce intensity variations in molecular spectra that are in turn expressed in sets of low-energy-loss images, using the standard energy-filtered transmission electron microscopy (EFTEM) procedures. The molecular map resolution is in the nanometer range and very close to the bright-field resolution achieved for the same sample, in the same instrument. Moreover, contrast is excellent, even though sample exposure to the electron beam is minimal. PMID:19222212

  14. IR-MALDI OF LOW MOLECULAR WEIGHT COMPOUNDS USING A FREE ELECTRON LASER.

    Science.gov (United States)

    Initial experiments on infrared matrix-assisted laser desorption/ionization mass spectrometry (IR-MALDI) using a free electron laser in the analysis of low-molecular-weight compounds are reported. Mass spectra from samples of ethylenediaminetetraacetic acid (EDTA), nitrilotriacet...

  15. Computer Simulations of Molecular Electronic Devices in Vacuum and in Organic Solvents

    Science.gov (United States)

    Wang, Huachuan

    The main aim of this dissertation is to study the structure and dynamics of molecular electronic devices in vacuum and in solvent environment, with special focus on the mechanical properties and cross-section geometries of the break-junction down to the atomic level. The problem statement relies on how to overcome the limitations of observations from experiments, to interpret and reduce the gap between experiential measurements and theoretical studies. In order to reach this goal, a molecular system involving gold nano-electrodes, organic dithiol molecules and a driving-spring model has been built based on the experimental set-up of the break junction (BJ) technique. This technique can be classified as the mechanical controllable break junction (MCBJ) and scanning tunneling / atomic force microscope break junction (STM/AFM-BJ). We then generated self-assembled monolayers and molecular junctions by combining grand-canonical Monte Carlo (GCMC) and molecular dynamics (MD) simulation. These approaches allow us to calibrate the structure and dynamics of molecular junctions under multiple environmental factors simultaneously. In the final stage, conductance calculations are performed using the density functional theory (DFT) in combination with the Green's function techniques. The intermediate molecular junction structures could be used to perform electronic transport calculations to eventually close the force-structure-conductance loop.

  16. Secondary electron emission from Au by medium energy atomic and molecular ions

    CERN Document Server

    Itoh, A; Obata, F; Hamamoto, Y; Yogo, A

    2002-01-01

    Number distributions of secondary electrons emitted from a Au metal surface have been measured for atomic and molecular ions of H sup + , He sup + , C sup + , N sup + , O sup + , H sup + sub 2 , H sup + sub 3 , HeH sup + , CO sup + and O sup + sub 2 in the energy range 0.3-2.0 MeV. The emission statistics obtained are described fairly well by a Polya function. The Polya parameter b, determining the distribution shape, is found to decrease monotonously with increasing emission yield gamma, revealing a surprising relationship of b gamma approx 1 over the different projectile species and impact energies. This finding supports certainly the electron cascading model. Also we find a strong negative molecular effect for heavier molecular ions, showing a significant reduction of gamma compared to the estimated values using constituent atomic projectile data.

  17. Carbon Nanotube Based Molecular Electronics and Motors: A View from Classical and Quantum Dynamics Simulations

    Science.gov (United States)

    Srivastava, Deepak; Saini, Subhash (Technical Monitor)

    1998-01-01

    The tubular forms of fullerenes popularly known as carbon nanotubes are experimentally produced as single-, multiwall, and rope configurations. The nanotubes and nanoropes have shown to exhibit unusual mechanical and electronic properties. The single wall nanotubes exhibit both semiconducting and metallic behavior. In short undefected lengths they are the known strongest fibers which are unbreakable even when bent in half. Grown in ropes their tensile strength is approximately 100 times greater than steel at only one sixth the weight. Employing large scale classical and quantum molecular dynamics simulations we will explore the use of carbon nanotubes and carbon nanotube junctions in 2-, 3-, and 4-point molecular electronic device components, dynamic strength characterization for compressive, bending and torsional strains, and chemical functionalization for possible use in a nanoscale molecular motor. The above is an unclassified material produced for non-competitive basic research in the nanotechnology area.

  18. Electronic Correlations in Oligo-acene and -thiophene Organic Molecular Crystals

    CERN Document Server

    Brocks, G; Morpurgo, A F; Brocks, Geert; Brink, Jeroen van den; Morpurgo, Alberto F.

    2004-01-01

    From first principles calculations we determine the Coulomb interaction between two holes on oligo-acene and -thiophene molecules in a crystal, as a function of the oligomer length. The relaxation of the molecular geometry in the presence of holes is found to be small. In contrast, the electronic polarization of the molecules that surround the charged oligomer, reduces the bare Coulomb repulsion between the holes by approximately a factor of two. In all cases the effective hole-hole repulsion is much larger than the calculated valence bandwidth, which implies that at high doping levels the properties of these organic semiconductors are determined by electron-electron correlations.

  19. Electron-impact dissociation cross sections of vibrationally excited He2+ molecular ion

    CERN Document Server

    Celiberto, R; Janev, R K; Laporta, V

    2015-01-01

    Electron-impact cross sections for the dissociation process of vibrationally excited He2+ molecular ion, as a function of the incident electron energy are calculated for the dissociative transition X2\\Sigma+u \\to A2\\Sigma+g by using the R-matrix method in the adiabatic-nuclei approximation. The potential energy curves for the involved electronic states and target properties, also calculated with the R-matrix method, were found to be in good agreement with the results reported in literature.

  20. Electronic polarization in solids probed by dissociation of fast molecular ions

    International Nuclear Information System (INIS)

    The interpretation of molecular ion interaction with solid through conventional stopping power theories is criticised. Comparison of experimental data to simulation of proton velocity distribution after 11.2 MeV OH+ dissociation in carbon foils supports this criticism. A different description of the average potential around a moving ion in solid due to electronic polarization is given. The polarization of the Fermi sea of electrons is described by the Coulomb distortion of the single electron wave function due to scattering on the moving ion. The use of such potential for the simulation of experiments agrees favourably with the measured data. (orig.)

  1. Molecular and electronic structure of actinide hexa-cyanoferrates

    International Nuclear Information System (INIS)

    The goal of this work is to improve our knowledge on the actinide-ligand bond properties. To this end, the hexacyanoferrate entities have been used as pre-organized ligand. We have synthesized, using mild chemistry, the following series of complexes: AnIV[FeII(CN)6].xH2O (An = Th, U, Np, Pu); AmIII[FeIII(CN)6].xH2O; Pu III[CoIII(CN)6].xH2O and K(H?)AnIII[FeII(CN)6].xH2O (An = Pu, Am). The metal oxidation states have been obtained thanks to the ?CN, stretching vibration and to the actinide LIII absorption edge studies. As Prussian Blue, the AnIV[FeII(CN)6].xH2O (An = Np, Pu) are class II of Robin and Day compounds. X-ray Diffraction has shown besides that these complexes crystallize in the P63/m space group, as the isomorphic LaKFe(CN)6.4H2O complex used as structural model. The EXAFS oscillations at the iron K edge and at the An LIII edge allowed to determine the An-N, An-O, Fe-C and Fe-N distances. The display of the multiple scattering paths for both edges explains the actinide contribution absence at the iron edge, whereas the iron signature is present at the actinide edge. We have shown that the actinide coordination sphere in actinides hexa-cyanoferrates is comparable to the one of lanthanides. However, the actinides typical behavior towards the lanthanides is brought to the fore by the AnIV versus LnIII ions presence in this family of complexes. Contrarily to the 4f electrons, the 5f electrons influence the electronic properties of the compounds of this family. However, the gap between the An-N and Ln-N distances towards the corresponding metals ionic radii do not show any covalence bond evolution between the actinide and lanthanide series. (author)

  2. Power spectrum of the rectified EMG: when and why is rectification beneficial for identifying neural connectivity?

    Science.gov (United States)

    Negro, Francesco; Keenan, Kevin; Farina, Dario

    2015-06-01

    Objective. The identification of common oscillatory inputs to motor neurons in the electromyographic (EMG) signal power spectrum is often preceded by EMG rectification for enhancing the low-frequency oscillatory components. However, rectification is a nonlinear operator and its influence on the EMG signal spectrum is not fully understood. In this study, we aim at determining when EMG rectification is beneficial in the study of oscillatory inputs to motor neurons. Approach. We provide a full mathematical description of the power spectrum of the rectified EMG signal and the influence of the average shape of the motor unit action potentials on it. We also provide a validation of these theoretical results with both simulated and experimental EMG signals. Main results. Simulations using an advanced computational model and experimental results demonstrated the accuracy of the theoretical derivations on the effect of rectification on the EMG spectrum. These derivations proved that rectification is beneficial when assessing the strength of low-frequency (delta and alpha bands) common synaptic inputs to the motor neurons, when the duration of the action potentials is short, and when the level of cancellation is relatively low. On the other hand, rectification may distort the estimation of common synaptic inputs when studying higher frequencies (beta and gamma), in a way dependent on the duration of the action potentials, and may introduce peaks in the coherence function that do not correspond to physiological shared inputs. Significance. This study clarifies the conditions when rectifying the surface EMG is appropriate for studying neural connectivity.

  3. Electron transfer flavoprotein deficiency: Functional and molecular aspects.

    DEFF Research Database (Denmark)

    Schiff, M; Froissart, R

    2006-01-01

    Multiple acyl-CoA dehydrogenase deficiency (MADD) is a recessively inherited metabolic disorder that can be due to a deficiency of electron transfer flavoprotein (ETF) or its dehydrogenase (ETF-ubiquinone oxidoreductase). ETF is a mitochondrial matrix protein consisting of alpha- (30kDa) and beta- (28kDa) subunits encoded by the ETFA and ETFB genes, respectively. In the present study, we have analysed tissue samples from 16 unrelated patients with ETF deficiency, and we report the results of ETF activity, Western blot analysis and mutation analysis. The ETF assay provides a reliable diagnostic tool to confirm ETF deficiency in patients suspected to suffer from MADD. Activity ranged from less than 1 to 16% of controls with the most severely affected patients disclosing the lowest activity values. The majority of patients had mutations in the ETFA gene while only two of them harboured mutations in the ETFB gene. Nine novel disease-causing ETF mutations are reported.

  4. Electronic structure of the magnesium hydride molecular ion

    International Nuclear Information System (INIS)

    In this paper, using a standard quantum chemistry approach based on pseudopotentials for atomic core representation, Gaussian basis sets and effective core polarization potentials, we investigate the electronic properties of the MgH+ ion. We first determine potential energy curves for several states using different basis sets and discuss their predicted accuracy by comparing our values of the well depths and position with other available results. We then calculate permanent and transition dipole moments for several transitions. Finally, for the first time, we calculate the static dipole polarizability of MgH+ as a function of the interatomic distance. This study represents the first step towards the modelling of collisions between trapped cold Mg+ ions and H2 molecules.

  5. Molecular Imaging Using X-Ray Free-Electron Lasers

    Science.gov (United States)

    Barty, Anton; Küpper, Jochen; Chapman, Henry N.

    2013-04-01

    The opening of hard X-ray free-electron laser facilities, such as the Linac Coherent Light Source (LCLS) at SLAC National Accelerator Laboratory in the United States, has ushered in a new era in structural determination. With X-ray pulse durations down to 10 fs or shorter, and up to 1013 transversely coherent photons per pulse in a narrow spectral bandwidth, focused irradiances of 1018 to 1021 W cm-2 or higher can be produced at X-ray energies ranging from 500 eV to 10 keV. New techniques for determining the structure of systems that cannot be crystallized and for studying the time-resolved behavior of irreversible reactions at femtosecond timescales are now available.

  6. Nonequilibrium electron velocity distribution and temperature in thermalization of low-energy electrons in molecular hydrogen

    International Nuclear Information System (INIS)

    The thermalization of low-energy electrons (epsilon2 at the gas temperature T = 300 or 77 K is studied by the Monte Carlo simulation, where electrons are so diluted in molecules that the electron--electron collision is neglected as compared with the electron--molecule collision. The accuracy of the approximate theory based on the assumption of the local Maxwell velocity distribution (MD) is examined using, for simplicity, the rotational cross section of the Gerjuoy--Stein formula and the elastic cross section of the hard-sphere model, which are a little larger than the experimental cross sections at low electron energy (epsilon< or approx. =0.1 eV); the initial electron velocity distribution is taken to be the MD. The electron velocity distribution significantly deviates from the MD especially at low gas temperature (T = 77 K); consequently the degradation of the electron temperature T/sub e/ is slower than that for the MD and the thermalization time tau/sub th/ when T/sub e//T = 1.1 is larger than that for the MD to the extent of 20% at T = 300 K, where tau/sub th/ is dominated by the rotational collision, and 140% at T = 77 K, where tau/sub th/ is dominated by the elastic collision. tau/sub th/papprox. =1.9 ?s Torr at T = 300 K, where p is the gas pressure, is about 27% larger than the experimental value of 1.5 ?s Torr at T = 296 K for the higher initial electron energy (epsilhe higher initial electron energy (epsilonapprox.1 eV)

  7. Toward optimizing the electronic structure and properties of large-area molecular junctions

    International Nuclear Information System (INIS)

    Full text: Large area molecular electronic junctions that contain ensembles of >1012 molecules sandwiched between two conducting contacts are complex devices with many possible molecule-contact configurations. Several different types of molecules (e.g., nitroazobenzene, biphenyl, nitrobiphenyl, fluorene) and contacts (e.g., pyrolyzed photo resist films or PPF, C, Au, Ag, Cu) have been employed in the construction of these devices. In these devices, often the molecular layer is covalently bonded to one of the electrodes and physisorbed on the other. Electronic structure modeling is very important for understanding the behaviour of these complex systems. We investigate the covalent bonding of molecules to Au (111), Ag (111), Cu (111), Cu (001), Cu (011), and graphene electrodes, and employ advanced concepts, such as binding energy, bond order, DOS, molecular orbital energy level and spatial distribution, to analyze the efficiency of electronic interaction. The physisorption of molecules to metal surfaces is also explored, e.g. nitrobenzene/Cu system. For calculation of the current-voltage dependence and understanding of electron transport, we intend to employ the tandem of ab initio electronic structure methods and non-equilibrium Green functions technique. (author)

  8. VUV diagnostic of electron impact processes in low temperature molecular hydrogen plasma

    CERN Document Server

    Komppula, J

    2015-01-01

    Novel methods for diagnostics of molecular hydrogen plasma processes, such as ionization, production of high vibrational levels, dissociation of molecules via excitation to singlet and triplet states and production of metastable states, are presented for molecular hydrogen plasmas in corona equilibrium. The methods are based on comparison of rate coefficients of plasma processes and optical emission spectroscopy of lowest singlet and triplet transitions, i.e. Lyman-band ($B^1\\Sigma^+_u \\rightarrow X^1\\Sigma^+_g$) and molecular continuum ($a^3\\Sigma^+_g \\rightarrow b^3\\Sigma^+_u$), of the hydrogen molecule in VUV wavelength range. Comparison of rate coefficients of spin-allowed and/or spin-forbidden excitations reduces the uncertainty caused by the non-equilibrium distributions of electron energy and molecular vibrational level, which are typically known poorly in plasma sources. The described methods are applied to estimate the rates of various plasma processes in a filament arc discharge.

  9. Recent Advances in Photoinduced Electron Transfer Processes of Fullerene-Based Molecular Assemblies and Nanocomposites

    Directory of Open Access Journals (Sweden)

    Osamu Ito

    2012-05-01

    Full Text Available Photosensitized electron-transfer processes of fullerenes hybridized with electron donating or other electron accepting molecules have been surveyed in this review on the basis of the recent results reported mainly from our laboratories. Fullerenes act as photo-sensitizing electron acceptors with respect to a wide variety of electron donors; in addition, fullerenes in the ground state also act as good electron acceptors in the presence of light-absorbing electron donors such as porphyrins. With single-wall carbon nanotubes (SWCNTs, the photoexcited fullerenes act as electron acceptor. In the case of triple fullerene/porphyrin/SWCNT architectures, the photoexcited porphyrins act as electron donors toward the fullerene and SWCNT. These mechanisms are rationalized with the molecular orbital considerations performed for these huge supramolecules. For the confirmation of the electron transfer processes, transient absorption methods have been used, in addition to time-resolved fluorescence spectral measurements. The kinetic data obtained in solution are found to be quite useful to predict the efficiencies of photovoltaic cells.

  10. Ab initio molecular dynamics simulation study of dissociative electron attachment to dialanine conformers.

    Science.gov (United States)

    Feng, Wen-Ling; Tian, Shan Xi

    2015-03-12

    Dissociative electron attachment (DEA) processes of six low-lying conformers (1-6) of dialanine in the gas phase are investigated by using ab initio molecular dynamics simulations. The incoming electron is captured and primarily occupies the virtual molecular orbital ?*, which is followed by the different dissociation processes. The electron attachments to conformers 1 and 2 having the stronger N-H···N and O-H···O intramolecular hydrogen bonds do not lead to fragmentations, but two different backbone bonds are broken in the DEAs to conformers 3 (or 4) and 6, respectively. It is interesting that the hydrogen abstraction of -NH from the terminal methyl group -CH3 is found in the roaming dissociation of the temporary anion of conformer 3. The present simulations enable us to have more insights into the peptide backbone bond breaks in the DEA process and demonstrate a promising way toward understanding of the radiation damages of complicated biological system. PMID:25679256

  11. Multimer Radical Ions and Electron/Hole Localization in Polyatomic Molecular Liquids: A critical review

    CERN Document Server

    Shkrob, I A; Sauer, Myran C.; Shkrob, Ilya A.

    2004-01-01

    While ionization of some polyatomic molecular liquids (such as water and aliphatic alcohols) yields so-called "solvated electrons" in which the excess electron density is localized in the interstices between the solvent molecules, most organic and inorganic liquids yield radical anions and cations in which the electron and spin densities reside on the solvent molecule or, more commonly, a group of such molecules. The resulting multimer ions have many unusual properties, such as high rates of diffusive hopping. The "solvated electron" can be regarded as a variant of a multimer radical anion in which the charge, while perturbing the solvent molecules, mainly resides in the space between these molecules. We give several examples of less known modes for electron localization in liquids that yield multimer radical anions (such as C6F6, benzene, acetonitrile, carbon disulfide and dioxide, etc.) and holes localization in liquids that yield multimer radical cations (such as cycloalkanes). Current understanding of the...

  12. Assessment of a nanoparticle bridge platform for molecular electronics measurements

    International Nuclear Information System (INIS)

    A combination of electron beam lithography, photolithography and focused ion beam milling was used to create a nanogap platform, which was bridged by gold nanoparticles in order to make electrical measurements and assess the platform under ambient conditions. Non-functionalized electrodes were tested to determine the intrinsic response of the platform and it was found that creating devices in ambient conditions requires careful cleaning and awareness of the contributions contaminants may make to measurements. The platform was then used to make measurements on octanethiol (OT) and biphenyldithiol (BPDT) molecules by functionalizing the nanoelectrodes with the molecules prior to bridging the nanogap with nanoparticles. Measurements on OT show that it is possible to make measurements on relatively small numbers of molecules, but that a large variation in response can be expected when one of the metal-molecule junctions is physisorbed, which was partially explained by attachment of OT molecules to different sites on the surface of the Au electrode using a density functional theory calculation. On the other hand, when dealing with BPDT, high yields for device creation are very difficult to achieve under ambient conditions. Significant hysteresis in the I-V curves of BPDT was also observed, which was attributed primarily to voltage induced changes at the interface between the molecule and the metal.

  13. Well-ordered monolayers of alkali-doped coronene and picene: molecular arrangements and electronic structures.

    Science.gov (United States)

    Yano, M; Endo, M; Hasegawa, Y; Okada, R; Yamada, Y; Sasaki, M

    2014-07-21

    Adsorptions of alkali metals (such as K and Li) on monolayers of coronene and picene realize the formation of ordered phases, which serve as well-defined model systems for metal-intercalated aromatic superconductors. Upon alkali-doping of the monolayers of coronene and picene, scanning tunneling microscopy and X-ray absorption spectroscopy revealed the rearrangement of the entire molecular layer. The K-induced reconstruction of both monolayers resulted in the formation of a structure with a herringbone-like arrangement of molecules, suggesting the intercalation of alkali metals between molecular planes. Upon reconstruction, a shift in both the vacuum level and core levels of coronene was observed as a result of a charge transfer from alkali metals to coronene. In addition, a new density of states near the Fermi level was formed in both the doped coronene and the doped picene monolayers. This characteristic electronic feature of the ordered monolayer has been also reported in the multilayer picene films, ensuring that the present monolayer can model the properties of the metal-intercalated aromatic hydrocarbons. It is suggested that the electronic structure near the Fermi level is sensitive to the molecular arrangement, and that both the strict control and determinations of the molecular structure in the doped phase should be important for the determination of the electronic structure of these materials. PMID:25053335

  14. Investigation of Terminal Group Effect on Electron Transport Through Open Molecular Structures

    International Nuclear Information System (INIS)

    The effect of terminal groups on the electron transport through metal-molecule-metal system has been investigated using nonequilibrium Green's function (NEGF) formalism combined with extended Huckel theory (EHT). Au-molecule-Au junctions are constructed with borazine and BCN unit structure as core molecule and sulphur (S), oxygen (O), selenium (Se) and cyano-group (CN) as terminal groups. The electron transport characteristics of the borazine and BCN molecular systems are analyzed through the transmission spectra and the current-voltage curve. The results demonstrate that the terminal groups modifying the transport behaviors of these systems in a controlled way. Our result shows that, selenium is the best linker to couple borazine to Au electrode and oxygen is the best one to couple BCN to Au electrode. Furthermore, the results of borazine systems are compared with that of BCN molecular systems and are discussed. Simulation results show that the conductance through BCN molecular systems is four times larger than the borazine molecular systems. Negative differential resistance behavior is observed with borazine-CN system and the saturation feature appears in BCN systems. (condensed matter: electronic structure, electrical, magnetic, and optical properties)

  15. Tuning electron transport through a single molecular junction by bridge modification

    Energy Technology Data Exchange (ETDEWEB)

    Li, Xiao-Fei, E-mail: xf.li@uestc.edu.cn; Qiu, Qi [School of Optoelectronic Information, University of Electronic Science and Technology of China, Chengdu, Sichuan 610054 (China); Luo, Yi [Division of Theoretical Chemistry and Biology, School of Biotechnology, KTH, Royal Institute of Technology, S-106 91 Stockholm (Sweden)

    2014-07-07

    The possibility of controlling electron transport in a single molecular junction represents the ultimate goal of molecular electronics. Here, we report that the modification of bridging group makes it possible to improve the performance and obtain new functions in a single cross-conjugated molecular junction, designed from a recently synthesized bipolar molecule bithiophene naphthalene diimide. Our first principles results show that the bipolar characteristic remains after the molecule was modified and sandwiched between two metal electrodes. Rectifying is the intrinsic characteristic of the molecular junction and its performance can be enhanced by replacing the saturated bridging group with an unsaturated group. A further improvement of the rectifying and a robust negative differential resistance (NDR) behavior can be achieved by the modification of unsaturated bridge. It is revealed that the modification can induce a deviation angle about 4° between the donor and the acceptor ?-conjugations, making it possible to enhance the communication between the two ? systems. Meanwhile, the low energy frontier orbitals of the junction can move close to the Fermi level and encounter in energy at certain biases, thus a transport channel with a considerable transmission can be formed near the Fermi level only at a narrow bias regime, resulting in the improvement of rectifying and the robust NDR behavior. This finding could be useful for the design of single molecular devices.

  16. Tuning electron transport through a single molecular junction by bridge modification

    International Nuclear Information System (INIS)

    The possibility of controlling electron transport in a single molecular junction represents the ultimate goal of molecular electronics. Here, we report that the modification of bridging group makes it possible to improve the performance and obtain new functions in a single cross-conjugated molecular junction, designed from a recently synthesized bipolar molecule bithiophene naphthalene diimide. Our first principles results show that the bipolar characteristic remains after the molecule was modified and sandwiched between two metal electrodes. Rectifying is the intrinsic characteristic of the molecular junction and its performance can be enhanced by replacing the saturated bridging group with an unsaturated group. A further improvement of the rectifying and a robust negative differential resistance (NDR) behavior can be achieved by the modification of unsaturated bridge. It is revealed that the modification can induce a deviation angle about 4° between the donor and the acceptor ?-conjugations, making it possible to enhance the communication between the two ? systems. Meanwhile, the low energy frontier orbitals of the junction can move close to the Fermi level and encounter in energy at certain biases, thus a transport channel with a considerable transmission can be formed near the Fermi level only at a narrow bias regime, resulting in the improvement of rectifying and the robust NDR behavior. This finding could be useful for the design of single molecular devices.

  17. Tuning electron transport through a single molecular junction by bridge modification

    Science.gov (United States)

    Li, Xiao-Fei; Qiu, Qi; Luo, Yi

    2014-07-01

    The possibility of controlling electron transport in a single molecular junction represents the ultimate goal of molecular electronics. Here, we report that the modification of bridging group makes it possible to improve the performance and obtain new functions in a single cross-conjugated molecular junction, designed from a recently synthesized bipolar molecule bithiophene naphthalene diimide. Our first principles results show that the bipolar characteristic remains after the molecule was modified and sandwiched between two metal electrodes. Rectifying is the intrinsic characteristic of the molecular junction and its performance can be enhanced by replacing the saturated bridging group with an unsaturated group. A further improvement of the rectifying and a robust negative differential resistance (NDR) behavior can be achieved by the modification of unsaturated bridge. It is revealed that the modification can induce a deviation angle about 4° between the donor and the acceptor ?-conjugations, making it possible to enhance the communication between the two ? systems. Meanwhile, the low energy frontier orbitals of the junction can move close to the Fermi level and encounter in energy at certain biases, thus a transport channel with a considerable transmission can be formed near the Fermi level only at a narrow bias regime, resulting in the improvement of rectifying and the robust NDR behavior. This finding could be useful for the design of single molecular devices.

  18. Modelling the effect of structure and base sequence on DNA molecular electronics

    International Nuclear Information System (INIS)

    DNA is a material that has the potential to be used in nanoelectronic devices as an active component. However, the electronic properties of DNA responsible for its conducting behaviour remain controversial. Here we use a self-consistent quantum molecular dynamics method to study the effect of DNA structure and base sequence on the energy involved when electrons are added or removed from isolated molecules and the transfer of the injected charge along the molecular axis when an electric field is applied. Our results show that the addition or removal of an electron from DNA molecules is most exothermic for poly(dC)-poly(dG) in its B-form and poly(dA)-poly(dT) in its A-form, and least exothermic in its Z-form. Additionally, when an electric field is applied to a charged DNA molecule along its axis, there is electron transfer through the molecule, regardless of the number and sign of the injected charge, the molecular structure and the base sequence. Results from these simulations provide useful information that is hard to obtain from experiments and needs to be considered for further modelling aiming to improve charge transport efficiency in nanoelectronic devices based on DNA

  19. First-principles study of the electronic transport properties of the anthraquinone-based molecular switch

    Science.gov (United States)

    Zhao, P.; Liu, D. S.; Wang, P. J.; Zhang, Z.; Fang, C. F.; Ji, G. M.

    2011-02-01

    By applying non-equilibrium Green’s function (NEGF) formalism combined with first-principles density functional theory (DFT), we have investigated the electronic transport properties of the anthraquinone-based molecular switch. The molecule that comprises the switch can be converted between the hydroquinone (HQ) and anthraquinone (AQ) forms via redox reactions. The transmission spectra of these two forms are remarkably distinctive. Our results show that the current through the HQ form is significantly larger than that through the AQ form, which suggests that this system has attractive potential application in future molecular switch technology.

  20. First-principles study of the electronic transport properties of the anthraquinone-based molecular switch

    International Nuclear Information System (INIS)

    By applying non-equilibrium Green's function (NEGF) formalism combined with first-principles density functional theory (DFT), we have investigated the electronic transport properties of the anthraquinone-based molecular switch. The molecule that comprises the switch can be converted between the hydroquinone (HQ) and anthraquinone (AQ) forms via redox reactions. The transmission spectra of these two forms are remarkably distinctive. Our results show that the current through the HQ form is significantly larger than that through the AQ form, which suggests that this system has attractive potential application in future molecular switch technology.

  1. First-principles study of the electronic transport properties of the anthraquinone-based molecular switch

    Energy Technology Data Exchange (ETDEWEB)

    Zhao, P., E-mail: ss_zhaop@ujn.edu.c [School of Science, University of Jinan, Jinan 250022 (China); Liu, D.S. [School of Physics, State Key Laboratory of Crystal Materials, Shandong University, Jinan 250100 (China); Department of Physics, Jining University, Qufu 273155 (China); Wang, P.J.; Zhang, Z. [School of Science, University of Jinan, Jinan 250022 (China); Fang, C.F.; Ji, G.M. [School of Physics, State Key Laboratory of Crystal Materials, Shandong University, Jinan 250100 (China)

    2011-02-15

    By applying non-equilibrium Green's function (NEGF) formalism combined with first-principles density functional theory (DFT), we have investigated the electronic transport properties of the anthraquinone-based molecular switch. The molecule that comprises the switch can be converted between the hydroquinone (HQ) and anthraquinone (AQ) forms via redox reactions. The transmission spectra of these two forms are remarkably distinctive. Our results show that the current through the HQ form is significantly larger than that through the AQ form, which suggests that this system has attractive potential application in future molecular switch technology.

  2. Low energy electron induced fragmentation and reactions of DNA and its molecular components

    Science.gov (United States)

    Bass, Andrew

    2005-05-01

    Much research has been stimulated by the recognition that ionizing radiation can, in condensed matter, generate large numbers of secondary electrons with energies less than 20 eV [1] and by the experimental demonstration that such electrons may induce both single and double strand breaks in plasmid DNA [2]. Identifying the underlying mechanisms involves several research methodologies, from further experiments with DNA to studies of the electron interaction with the component `sub-units' of DNA in both the gas and condensed phases [3]. In particular, understanding electron-induced strand break damage, the type of damage most difficult for organisms to repair, necessitates study of the sub-units of DNA back-bone, and here Tetrahyrofuran (THF) and its derivatives, provide a useful model for the furyl ring at the centre of the deoxyribose sugar. In this contribution, we review with particular reference to DNA and related molecules, the use of electron spectroscopy and mass spectrometry to study electron-induced fragmentation and reactions in thin molecular solids. We describe a newly completed instrument that combines laser post-ionization with a time-of-flight mass analyzer for highly sensitive ion and neutral detection. Use of the instrument is illustrated with results for THF and derivatives. Anion desorption measurements reveal the role of transient negative ions (TNI) and Dissociative Electron Attachment in significant molecular fragmentation and permit effective cross sections for this electron-induced damage to be obtained. The neutral yield functions also illustrate the importance of TNI, mirroring features seen in recently measured cross sections for electron induced aldehyde production in THF [4]. 1. J. A. Laverne and S. M. Pimblott, Radiat. Res. 141, 208 (1995) 2. B. Boudaiffa, et al, Science 287, 1658 (2000) 3. L. Sanche. Physica Scripta. 68, C108, (2003) 4. S.-P. Breton, et al.,J. Chem. Phys. 121, 11240 (2004)

  3. From electron microscopy to X-ray crystallography: molecular-replacement case studies

    International Nuclear Information System (INIS)

    Test studies have been conducted on five crystal structures of large molecular assemblies, in which EM maps are used as models for structure solution by molecular replacement using various standard MR packages such as AMoRe, MOLREP and Phaser. Multi-component molecular complexes are increasingly being tackled by structural biology, bringing X-ray crystallography into the purview of electron-microscopy (EM) studies. X-ray crystallography can utilize a low-resolution EM map for structure determination followed by phase extension to high resolution. Test studies have been conducted on five crystal structures of large molecular assemblies, in which EM maps are used as models for structure solution by molecular replacement (MR) using various standard MR packages such as AMoRe, MOLREP and Phaser. The results demonstrate that EM maps are viable models for molecular replacement. Possible difficulties in data analysis, such as the effects of the EM magnification error, and the effect of MR positional/rotational errors on phase extension are discussed

  4. Modulations of electronic tunneling rates through flexible molecular bridges by a dissipative superexchange mechanism

    International Nuclear Information System (INIS)

    Long-range coherent electron transfer between a donor and an acceptor is often assisted by intermediate molecular bridge, via the superexchange tunneling mechanism. The effect of electronic-nuclear coupling intensity on the tunneling rate and mechanism is analyzed using a generalized spin-boson model, in which the two level system, representing the donor and the acceptor is coupled to a dissipative nuclear bath only indirectly, via additional N bridge sites. A Langevin-Schroedinger equation, based on a mean field approximation, is applied in order to study the corresponding many-body dynamics, and the results are supported by numerically exact calculations for a single nuclear bridge mode. At zero temperature and when the electron tunneling is slower than the nuclear motion, the main effect of electronic-nuclear coupling is the dissipation of electronic energy at the bridge into nuclear vibrations. At small coupling intensities, the electronic tunneling rate increases due to this dissipative mechanism, but as the coupling intensity increases the tunneling into the acceptor is suppressed and efficient dissipation leads to electronic trapping (solvation) at the bridge. This analysis agrees with numerous experimental and theoretical studies, emphasizing the importance of the nuclear bridge conformation and the bridge flexibility in controlling the electron transfer rate in donor-bridge-acceptor systems

  5. Electron Microscopy Study and Molecular Dynamics Simulation of Swift Heavy Ion Irradiation Effects in Ceria

    Energy Technology Data Exchange (ETDEWEB)

    C. A. Yablinsky; R. Devanathan; J. Pakarinen; J. Gan; D. Severin; C. Trautmann; T.R. Allen

    2015-03-01

    Swift heavy ion induced radiation damage is investigated for ceria (CeO2), which serves as a UO2 fuel surrogate. Microstructural changes resulting from the irradiation with 940 MeV gold ions of 42 keV/nm electronic energy loss are investigated by means of electron microscopy accompanied by electron energy loss spectroscopy showing that there exists a small density reduction but no chemical change in the ion track core. Classical molecular dynamics simulations of thermal spikes in CeO2 with energy deposition of 12 and 36 keV/nm show damage consisting of isolated point defects at 12 keV/nm and defect clusters at 36 keV/nm, with no amorphization at either energy. Inferences are drawn from modeling about density changes in the ion track and the formation of interstitial loops that shed light on features observed by electron microscopy of swift heavy ion irradiated ceria.

  6. Controllable acoustic rectification in one-dimensional piezoelectric composite plates

    Science.gov (United States)

    Zou, Xin-Ye; Liang, Bin; Yuan, Ying; Zhu, Xue-Feng; Cheng, Jian-Chun

    2013-10-01

    Theoretical studies are presented for the band structures and power transmission spectra for both symmetric and asymmetric Lamb wave modes in a one-dimensional piezoelectric composite plate consisting of piezoelectric ceramics placed periodically in epoxy by the plane wave expansion method and the harmonic response analysis method, respectively. The one-way transmission, two-way transmission, and two-way forbidden models of acoustic rectification for Lamb waves can be established in specific frequency ranges by introducing corresponding modes conversion and selection mechanisms, and the steady-state displacement fields of these models are also calculated for the proposed plate. The numerical results show that the power extinction ratio for one-way transmission model is up to 104. The piezoelectric composite plate can be switched between these models rapidly and efficiently only by applying the open-circuit and short-circuit electric boundary conditions antisymmetrically or symmetrically on the piezoelectric ceramic unit's boundaries instead of changing any geometrical structure, and the composite plate's architecture structure is also simple enough for the on-chip integration in the engineering field.

  7. Heat flux distribution and rectification of complex networks

    International Nuclear Information System (INIS)

    It was recently found that the heterogeneity of complex networks can enhance transport properties such as epidemic spreading, electric energy transfer, etc. A trivial deduction would be that the presence of hubs in complex networks can also accelerate the heat transfer although no concrete research has been done so far. In the present study, we have studied this problem and have found a surprising answer: the heterogeneity does not favor but prevents the heat transfer. We present a model to study heat conduction in complex networks and find that the network topology greatly affects the heat flux. The heat conduction decreases with the increase of heterogeneity of the network caused by both degree distribution and the clustering coefficient. Its underlying mechanism can be understood by using random matrix theory. Moreover, we also study the rectification effect and find that it is related to the degree difference of the network, and the distance between the source and the sink. These findings may have potential applications in real networks, such as nanotube/nanowire networks and biological networks.

  8. Design and Simulation of Molecular Nonvolatile Single-Electron Resistive Switches

    CERN Document Server

    Simonian, Nikita; Likharev, Konstantin K

    2012-01-01

    We have carried out a preliminary design and simulation of a single-electron resistive switch based on a system of two linear, parallel, electrostatically-coupled molecules: one implementing a single-electron transistor and another serving as a single-electron trap. To verify our design, we have performed a theoretical analysis of this "memristive" device, based on a combination of ab-initio calculations of the electronic structures of the molecules and the general theory of single-electron tunneling in systems with discrete energy spectra. Our results show that such molecular assemblies, with a length below 10 nm and a footprint area of about 5 nm$^2$, may combine sub-second switching times with multi-year retention times and high ($> 10^3$) ON/OFF current ratios, at room temperature. Moreover, Monte Carlo simulations of self-assembled monolayers (SAM) based on such molecular assemblies have shown that such monolayers may also be used as resistive switches, with comparable characteristics and, in addition, b...

  9. Electronic Transport Properties of an Anthraquinone-Based Molecular Switch with Carbon Nanotube Electrodes

    International Nuclear Information System (INIS)

    Based on the nonequilibrium Green's function method and density functional theory calculations, we theoretically investigate the electronic transport properties of an anthraquinone-based molecular switch with carbon nanotube electrodes. The molecules that comprise the switch can convert between reduced hydroquinone (HQ) and oxidized anthraquinne (AQ) states via redox reactions. Our results show that the on-off ratio is increased one order of magnitude when compared to the case of gold electrodes. Moreover, an obvious negative differential resistance behavior at much low bias (0.07 V) is observed in the HQ form. (condensed matter: electronic structure, electrical, magnetic, and optical properties)

  10. Surface Phenomena and Chemical Functionalization of Carbon Nanotubes: Implications to Molecular Electronics and Bioelectronics

    Science.gov (United States)

    Shim, Moonsub; Chen, Robert; Wong Shi Kam, Nadine; Dai, Hongjie

    2002-03-01

    This talk will summarize our recent work on the chemistry and physics related to the surfaces of carbon nanotubes. The results to be presented will include:(1) Interactions between nanotube surfaces with small molecules from the gas phase, and polyaromatic molecules, polymer chains and surfactants from solutions. (2)Molecular photodesorption from nanotubes. (3) Physical properties and electronic devices of functionalized nanotubes. And(4)protein-nanotube interactions. The relationship between these work and novel electronic and biological devices based on functionalized nanomaterials will be illustrated.

  11. Communication: Reduced density matrices in molecular systems: Grand-canonical electron states

    International Nuclear Information System (INIS)

    Grand-canonical like descriptions of many electron atomic and molecular open systems which are characterized by a non-integer number of electrons are presented. Their associated reduced density matrices (RDMs) are obtained by introducing the contracting mapping for this type of distributions. It is shown that there is loss of information when connecting RDMs of different order by partial contractions. The energy convexity property of these systems simplifies the description. Consequently, this formulation opens the possibility to a new look for chemical descriptors such as chemical potential and reactivity among others. Examples are presented to discuss the theoretical aspects of this work

  12. Molecular-Atomic Transition in the Deuterium Hugoniot with Coupled Electron Ion Monte Carlo

    CERN Document Server

    Tubman, Norm M; Pierleoni, Carlo; Holzmann, Markus; Ceperley, David M

    2014-01-01

    We have performed accurate simulations of the Deuterium Hugoniot using Coupled Electron Ion Monte Carlo (CEIMC). Using highly accurate quantum Monte Carlo methods for the electrons, we study the region of maximum compression along the principal Hugoniot, where the system undergoes a continuous transition from a molecular fluid to a monatomic fluid. We include all relevant physical corrections so that a direct comparison to experiment can be made. Around 50 GPa we found a maximum compression of 4.85, roughly 10% larger than previous theoretical predictions and experimental data but still compatible with the latter because of their large uncertainty.

  13. Quantum chemistry the development of ab initio methods in molecular electronic structure theory

    CERN Document Server

    Schaefer III, Henry F

    2012-01-01

    This guide is guaranteed to prove of keen interest to the broad spectrum of experimental chemists who use electronic structure theory to assist in the interpretation of their laboratory findings. A list of 150 landmark papers in ab initio molecular electronic structure methods, it features the first page of each paper (which usually encompasses the abstract and introduction). Its primary focus is methodology, rather than the examination of particular chemical problems, and the selected papers either present new and important methods or illustrate the effectiveness of existing methods in predi

  14. Communication: Reduced density matrices in molecular systems: Grand-canonical electron states

    Energy Technology Data Exchange (ETDEWEB)

    Bochicchio, Roberto C., E-mail: rboc@df.uba.ar [Departamento de Física, Facultad de Ciencias Exactas y Naturales, Universidad de Buenos Aires and IFIBA, CONICET, Ciudad Universitaria, 1428 Buenos Aires (Argentina); Miranda-Quintana, Ramón A. [Laboratory of Computational and Theoretical Chemistry, Faculty of Chemistry, University of Havana, Zapata e G y Mazón, 10400 Havana (Cuba); Rial, Diego [Departamento de Matemática, Facultad de Ciencias Exactas y Naturales, Universidad de Buenos Aires and IMAS, CONICET, Ciudad Universitaria, 1428 Buenos Aires (Argentina)

    2013-11-21

    Grand-canonical like descriptions of many electron atomic and molecular open systems which are characterized by a non-integer number of electrons are presented. Their associated reduced density matrices (RDMs) are obtained by introducing the contracting mapping for this type of distributions. It is shown that there is loss of information when connecting RDMs of different order by partial contractions. The energy convexity property of these systems simplifies the description. Consequently, this formulation opens the possibility to a new look for chemical descriptors such as chemical potential and reactivity among others. Examples are presented to discuss the theoretical aspects of this work.

  15. High Temperature Molecular Magnetism Caused by pi-electrons: Copper Phthalocyanine Doped with Alkaline Metals

    CERN Document Server

    Sharoyan, E G

    2005-01-01

    Electron spin resonance spectra of copper phthalocyanine doped with alkaline metals (AxCuPc) have been investigated. The temperature dependence of ESR spectra indicates the ferromagnetic behavior. The Curie-Weiss temperature varies from 30K to 115K depending on the stoichiometry x of samples. Some particles of polycrystalline samples were attracted to a weak magnet at temperature slightly higher than 77K. The observed magnetism is caused by unpaired pi-electrons of phthalocyanine anions on the Eg doubly degenerated molecular orbital. The observed ferromagnetism can be understood within the framework of the McConnell-2 model proposed for organic ferromagnetic charge-transfer complexes. The high-temperature magnetism in AxCuPc is considered to be a result of the Zener mechanism of double exchange between phthalocyanine molecular anions of different valence.

  16. Effects of End Termination on Electronic Transport in a Molecular Switch

    International Nuclear Information System (INIS)

    Based on the non-equilibrium Green's function formalism and first-principles calculations, we investigate the electronic transport properties of an anthracene-based molecular switch with two carbon nanotube electrodes. Our results show that different terminations at the carbon nanotube end strongly affect the transport properties of the switch. In the case of H-termination the current at low biases is dominated by non-resonant tunneling. In the N-termination case the current at low biases is dominated by quasi-resonant tunneling and is increased by several orders of magnitude. The enhancement is discussed by the molecular projected self-consistent Hamiltonian level, transmission function, and local density of states. (condensed matter: electronic structure, electrical, magnetic, and optical properties)

  17. A quantum simulator for molecules: Imaging molecular orbitals and electronic dynamics with ultracold atoms

    CERN Document Server

    Lühmann, Dirk-Sören; Sengstock, Klaus

    2015-01-01

    In the recent years, ultracold atoms in optical lattices have proven their great value as quantum simulators for studying strongly-correlated phases and complex phenomena in solid-state systems. Here we reveal their potential as quantum simulators for molecular physics and propose a technique to image the three-dimensional molecular orbitals with high resolution. The outstanding tunability of ultracold atoms in terms of potential and interaction offer fully-adjustable model systems for gaining deep insight into the electronic structure of molecules. We study the orbitals of an artificial benzene molecule and discuss the effect of tunable interactions in its conjugated pi electron system with special regard to localization and spin order. The dynamical timescale of ultracold atom simulators are on the order milliseconds which allow for the time-resolved monitoring of a broad range of dynamical processes. As an example, we compute the hole dynamics in the conjugated pi system of the artificial benzene molecule.

  18. Electron-molecular vibration coupling effect on the Raman spectrum of organic charge transfer salts

    Science.gov (United States)

    Yamamoto, Kaoru; Yakushi, Kyuya

    2004-04-01

    Vibrational spectra of dimerized and tetramerized radical clusters have been calculated to understand the features of electron-molecular vibration (EMV) coupling effects for the charge ordered system (CO). The calculated spectra show that the totally in-phase Raman band, which is usually used as a measure of the molecular ionicity, approaches to the frequency corresponding to the average molecular ionicity in the cluster, with increasing the EMV coupling constant. On the other hand, when large charge disproportionation (CD) presents, vibronic bands show steep shift for small variation of the CD ratio. These results suggest that concerning to the normal modes with a large EMV coupling constant, we should focus on the frequency of the vibronic bands instead of the totally in-phase mode to discuss the charge distribution. Key words. Charge ordering charge disproportionation Raman spectroscopy vibrational spectroscopy

  19. Importance of electronic self-consistency in the TDDFT based treatment of nonadiabatic molecular dynamics

    CERN Document Server

    Niehaus, T A; Torralva, B; Frauenheim, T; Frauenheim, Th.

    2004-01-01

    A mixed quantum-classical approach to simulate the coupled dynamics of electrons and nuclei in nanoscale molecular systems is presented. The method relies on a second order expansion of the Lagrangian in time-dependent density functional theory (TDDFT) around a suitable reference density. We show that the inclusion of the second order term renders the method a self-consistent scheme and improves the calculated optical spectra of molecules by a proper treatment of the coupled response. In the application to ion-fullerene collisions, the inclusion of self-consistency is found to be crucial for a correct description of the charge transfer between projectile and target. For a model of the photoreceptor in retinal proteins, nonadiabatic molecular dynamics simulations are performed and reveal problems of TDDFT in the prediction of intra-molecular charge transfer excitations.

  20. On the distance dependence of electron transfer through molecular bridges and wires

    CERN Document Server

    Skourtis, S; Skourtis, Spiros; Nitzan, Abraham

    2002-01-01

    The dependence of electron transfer rates and yields in bridged molecular systems on the bridge length, and the dependence of the zero-bias conduction of molecular wires on wire length are discussed. Both phenomena are controlled by tunneling across the molecular bridge and are consequently expected to show exponential decrease with bridge length that is indeed often observed. Deviations from this exponential dependence for long bridges, in particular a crossover to a very weak dependence on bridge length were recently observed experimentally and discussed theoretically in terms of thermal relaxation and dephasing on the bridge. Here we discuss two other factors that potentially affect the bridge length dependence of these phenomena. First, in experiments initiated by an initial preparation of a non-stationary "donor" state the initial energy is not well defined. A small contribution from initially populated eigenstates that are of mostly bridge-level character may dominate transmission for long bridges, resu...

  1. The electronic transport properties in C60 molecular devices with different contact distances

    International Nuclear Information System (INIS)

    By applying non-equilibrium Green's functions in combination with the density-functional theory, we investigate the transport behavior of molecular devices composed by metal electrode-C60 molecule-metal electrode. Our results show that the electronic transport properties are affected obviously by the different contact distances between the electrodes, and the tunneling current decreases approximately exponentially at a certain bias with the increasing of contact distances. The negative differential resistance is observed and the peak-to-valley ratio can be tuned by different contact distances. The mechanisms of the contact distance effect and the negative differential resistance behavior are proposed. - Highlights: ? The I-V properties of C60 molecular device are affected by the contact distances. ? C60 molecular junctions display metallic transport behavior at low biases. ? NDR behavior appears at some bias range and the peak-to-valley ratio can be tuned. ? Current decreases approximately exponentially with the increasing contact distances.

  2. Uncovering a law of corresponding states for electron tunneling in molecular junctions

    Science.gov (United States)

    Bâldea, Ioan; Xie, Zuoti; Frisbie, C. Daniel

    2015-06-01

    Laws of corresponding states known so far demonstrate that certain macroscopic systems can be described in a universal manner in terms of reduced quantities, which eliminate specific substance properties. To quantitatively describe real systems, all these laws of corresponding states contain numerical factors adjusted empirically. Here, we report a law of corresponding states deduced analytically for charge transport via tunneling in molecular junctions, which we validate against current-voltage measurements for conducting probe atomic force microscope junctions based on benchmark molecular series (oligophenylenedithiols and alkanedithiols) and electrodes (silver, gold, and platinum), as well as against transport data for scanning tunneling microscope junctions. Two salient features distinguish the present law of corresponding states from all those known previously. First, it is expressed by a universal curve free of empirical parameters. Second, it demonstrates that a universal behavior is not necessarily affected by strong stochastic fluctuations often observed in molecular electronics. An important and encouraging message of this finding is that transport behavior across different molecular platforms can be similar and extraordinarily reproducible.Laws of corresponding states known so far demonstrate that certain macroscopic systems can be described in a universal manner in terms of reduced quantities, which eliminate specific substance properties. To quantitatively describe real systems, all these laws of corresponding states contain numerical factors adjusted empirically. Here, we report a law of corresponding states deduced analytically for charge transport via tunneling in molecular junctions, which we validate against current-voltage measurements for conducting probe atomic force microscope junctions based on benchmark molecular series (oligophenylenedithiols and alkanedithiols) and electrodes (silver, gold, and platinum), as well as against transport data for scanning tunneling microscope junctions. Two salient features distinguish the present law of corresponding states from all those known previously. First, it is expressed by a universal curve free of empirical parameters. Second, it demonstrates that a universal behavior is not necessarily affected by strong stochastic fluctuations often observed in molecular electronics. An important and encouraging message of this finding is that transport behavior across different molecular platforms can be similar and extraordinarily reproducible. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr02225h

  3. Electronic sputtering of large organic molecules and its application in bio molecular mass spectrometry

    International Nuclear Information System (INIS)

    This is a review of research which has its origin in the discovery of Plasma Desorption Mass Spectrometry (PDMS). Two main fields of research have developed, namely fundamental studies of the ejection process at fast ion impact and studies of applications of the new mass spectrometric technique. In this review the emphasis will be on the process of electronic sputtering of organic solids but also applications of this process in bio molecular mass spectrometry will be discussed. (author)

  4. Non-adiabatic quantum molecular dynamics: Ionization of many electron systems

    OpenAIRE

    Uhlmann, Mathias; Kunert, Thomas; Schmidt, Ruediger

    2005-01-01

    We propose a novel method to describe realistically ionization processes with absorbing boundary conditions in basis expansion within the formalism of the so-called Non-Adiabatic Quantum Molecular Dynamics. This theory couples self-consistently a classical description of the nuclei with a quantum mechanical treatment of the electrons in atomic many-body systems. In this paper we extend the formalism by introducing absorbing boundary conditions via an imaginary potential. It ...

  5. Quantum Simulation of 2p-? Electronic Hamiltonian in Molecular Ethylene by Using an NMR Quantum Computer

    OpenAIRE

    Deniz Türkpençe; Azmi Gençten

    2013-01-01

    Classical simulation of a quantum system is a hard problem. It’s known that these problems can be solved efficiently by using quantum computers. This study demonstrates the simulation of the molecular Hamiltonian of 2p-? electrons of ethylene in order to calculate the ground state energy. The ground state energy is estimated by an iterative phase estimation algorithm. The ground state is prepared by the adiabatic state preparation and the implementation of the procedure is carried out by num...

  6. Krylov Subspace Method for Molecular Dynamics Simulation based on Large-Scale Electronic Structure Theory

    CERN Document Server

    Takayama, R; Fujiwara, T; Takayama, Ryu; Hoshi, Takeo; Fujiwara, Takeo

    2004-01-01

    For large scale electronic structure calculation, the Krylov subspace method is introduced to calculate the one-body density matrix. Its arithmetic structure is studied for its validation. Molecular dynamics simulation of Si(001) surface reconstruction is examined as an example, and the results reproduce the essential mechanism of asymmetric surface dimer. An appropriate choice of controlling parameters is discussed for the efficient and practical calculation.

  7. Non-adiabatic molecular Hamiltonian: Canonical transformation coupling electronic and vibrational motions

    OpenAIRE

    Hubac, Ivan; Babinec, Peter; Polasek, Martin; Urban, Jan; Mach, Pavel; Masik, Jozef; Leszczynski, Jerzy

    1998-01-01

    The coupling of electronic and vibrational motion is studied by two canonical transformations namely normal coordinate transformation and momentum transformation on molecular Hamiltonian. It is shown that by these transformations we can pass from crude approximation to adiabatic approximation and then to non-adiabatic (diabatic) Hamiltonian. This leads to renormalized fermions and renormalized diabatic phonons. Simple calculations on $H_{2}$, $HD$, and $D_{2}$ systems are pe...

  8. The diabatic picture of electron transfer, reaction barriers and molecular dynamics

    OpenAIRE

    Voorhis, Troy; Kowalczyk, Timothy Daniel; Kaduk, Benjamin J.; Wang, Lee-ping; Cheng, Chiao-lun; Wu, Qin

    2009-01-01

    Diabatic states have a long history in chemistry, beginning with early valence bond pictures of molecular bonding and extending through the construction of model potential energy surfaces to the modern proliferation of methods for computing these elusive states. In this review, we summarize the basic principles that define the diabatic basis and demonstrate how they can be applied in the specific context of constrained density functional theory. Using illustrative examples from electron trans...

  9. Dimer Model for Electronic and Molecular Systems and the Intermediate Phase

    CERN Document Server

    Semerianov, F

    2004-01-01

    We introduce a lattice model of dimers with directional interactions as a paradigm of molecular fluids or strongly correlated Cooper pairs in electronic systems. The model supports an intermediate phase that is common to both systems. There are two different ideal glasses having no moblity since they possess zero entropy. A pairing parameter is introduced to study the geometrical distribution of holes in various phases.

  10. A low-loss hybrid rectification technique for piezoelectric energy harvesting

    International Nuclear Information System (INIS)

    Embedded systems have decreased in size and increased in capability; however, small-scale energy storage technologies still significantly limit these advances. Energy neutral operation using small-scale energy harvesting technologies would allow for longer device operation times and smaller energy storage masses. Vibration energy harvesting is an attractive method due to the prevalence of energy sources in many environments. Losses in efficiency due to AC–DC rectification and conditioning circuits limit its application. This work presents a low-loss hybrid rectification technique for piezoelectric vibration energy harvesting using magnetically actuated reed switches and a passive semiconductor full-bridge rectifier. This method shows the capability to have higher efficiency levels and the rectification of low-voltage harvesters without the need for active electrical components. A theoretical model shows that the hybrid rectification technique performance is highly dependent on the proximity delay and the hysteresis behavior of the reed switches. Experimental results validate the model and support the hypothesis of increased performance using the hybrid rectification technique. (paper)

  11. Theoretical Study of Molecular and Electronic Structures of 51 Knot Systems: Two?Layered ONIOM Calculations

    Scientific Electronic Library Online (English)

    Aguinaldo R. de, Souza; Nelson H., Morgon.

    2015-05-01

    Full Text Available In this study we examine the electronic and molecular structures of the [51 knot···(PF6)10]+ pentafoil knot system and report calculated interaction energies that result from halides (X = F, Cl, Br, and I) localized at the center of the [51 knot···(PF6)9]X molecular structure. The equilibrium geomet [...] ries were fully optimized at the ONIOM(M06/6-31G(2d,p):PM6) level of theory, starting from an initial geometry for the pentafoil knot obtained from experimental X-ray data. The molecular systems were divided into two layers, for which the M06/6-31G(2d,p) level of theory was used to describe the high layer ([C4H6]5X- structure) and the PM6 semiempirical method was employed for the low layer. The calculated electronic energies show that the interaction between the fluorine anion and the pentafoil knot produces the most stable structure, whereas an unfavorable interaction is observed for iodide due to the diffuse character of its electronic cloud. Using basis set superposition error (BSSE) correction techniques, the observed values of the interaction are -0.201 hartrees for the fluoride ion and -0.100 hartrees for iodide.

  12. Fabrication of reproducible, integration-compatible hybrid molecular/si electronics.

    Science.gov (United States)

    Yu, Xi; Lovrin?i?, Robert; Kraynis, Olga; Man, Gabriel; Ely, Tal; Zohar, Arava; Toledano, Tal; Cahen, David; Vilan, Ayelet

    2014-12-29

    Reproducible molecular junctions can be integrated within standard CMOS technology. Metal-molecule-semiconductor junctions are fabricated by direct Si-C binding of hexadecane or methyl-styrene onto oxide-free H-Si(111) surfaces, with the lateral size of the junctions defined by an etched SiO2 well and with evaporated Pb as the top contact. The current density, J, is highly reproducible with a standard deviation in log(J) of 0.2 over a junction diameter change from 3 to 100 ?m. Reproducibility over such a large range indicates that transport is truly across the molecules and does not result from artifacts like edge effects or defects in the molecular monolayer. Device fabrication is tested for two n-Si doping levels. With highly doped Si, transport is dominated by tunneling and reveals sharp conductance onsets at room temperature. Using the temperature dependence of current across medium-doped n-Si, the molecular tunneling barrier can be separated from the Si-Schottky one, which is a 0.47 eV, in agreement with the molecular-modified surface dipole and quite different from the bare Si-H junction. This indicates that Pb evaporation does not cause significant chemical changes to the molecules. The ability to manufacture reliable devices constitutes important progress toward possible future hybrid Si-based molecular electronics. PMID:25098545

  13. Control of molecular organization and energy level alignment by an electronically nanopatterned boron nitride template.

    Science.gov (United States)

    Joshi, Sushobhan; Bischoff, Felix; Koitz, Ralph; Ecija, David; Seufert, Knud; Seitsonen, Ari Paavo; Hutter, Jürg; Diller, Katharina; Urgel, José I; Sachdev, Hermann; Barth, Johannes V; Auwärter, Willi

    2014-01-28

    Suitable templates to steer the formation of nanostructure arrays on surfaces are indispensable in nanoscience. Recently, atomically thin sp(2)-bonded layers such as graphene or boron nitride (BN) grown on metal supports have attracted considerable interest due to their potential geometric corrugation guiding the positioning of atoms, metallic clusters or molecules. Here, we demonstrate three specific functions of a geometrically smooth, but electronically corrugated, sp(2)/metal interface, namely, BN/Cu(111), qualifying it as a unique nanoscale template. As functional adsorbates we employed free-base porphine (2H-P), a prototype tetrapyrrole compound, and tetracyanoquinodimethane (TCNQ), a well-known electron acceptor. (i) The electronic moirons of the BN/Cu(111) interface trap both 2H-P and TCNQ, steering self-organized growth of arrays with extended molecular assemblies. (ii) We report an effective decoupling of the trapped molecules from the underlying metal support by the BN, which allows for a direct visualization of frontier orbitals by scanning tunneling microscopy (STM). (iii) The lateral molecular positioning in the superstructured surface determines the energetic level alignment; i.e., the energy of the frontier orbitals, and the electronic gap are tunable. PMID:24328081

  14. Effect of an electric field on the nonlinear optical rectification of a quantum ring

    International Nuclear Information System (INIS)

    We have studied the effects of an external electric field on the nonlinear optical rectification of a semiconductor quantum ring. An electric field applied in the ring plane destroys the rotational invariance. Calculations are performed by using the matrix diagonalization method and the compact density-matrix approach within the effective-mass approximation. The results indicate that an increase of electric field gives the red shift of the peak positions of nonlinear optical rectification. The roles of ring size and magnetic field strength as control parameters on this nonlinear property have been investigated. Our results show rich nonlinear optical rectification for quantum rings in the presence of electric fields, which effectively displays the signature of the Aharonov–Bohm oscillation.

  15. Radiative Thermal Rectification between SiC and SiO2

    CERN Document Server

    Joulain, Karl; Drevillon, Jérémie; Rousseau, Benoit; Meneses, Domingos De Sousa

    2015-01-01

    By means of fluctuationnal electrodynamics, we calculate radiative heat flux between two planar materials respectively made of SiC and SiO2. More specifically, we focus on a first (direct) situation where one of the two materials (for example SiC) is at ambient temperature whereas the second material is at a higher one, then we study a second (reverse) situation where the material temperatures are inverted. When the two fluxes corresponding to the two situations are different, the materials are said to exhibit a thermal rectification, a property with potential applications in thermal regulation. Rectification variations with temperature and separation distance are here reported. Calculations are performed using material optical data experimentally determined by Fourier transform emission spectrometry of heated materials between ambient temperature (around 300 K) and 1480 K. It is shown that rectification is much more important in the near-field domain, i.e. at separation distances smaller than the thermal wav...

  16. Resonanant enhancement of molecular excitation intensity in inelastic electron scattering spectrum owing to interaction with plasmons in metallic nanoshell

    CERN Document Server

    Goliney, I Yu

    2014-01-01

    A quantum-mechanical model to calculate the electron energy-loss spectra (EELS) for the system of a closely located metallic nanoshell and a molecule has been developed. At the resonance between the molecular excitation and plasmon modes in the nanoshell, which can be provided by a proper choice of the ratio of the inner and outer nanoshell radii, the cross-section of inelastic electron scattering at the molecular excitation energy is shown to grow significantly, because the molecular transition borrows the oscillator strength from a plasmon. The enhancement of the inelastic electron scattering by the molecule makes it possible to observe molecular transitions with an electron microscope. The dependences of the EEL spectra on the relative arrangement of the molecule and the nanoshell, the ratio between the inner and outer nanoshell radii, and the scattering angle are plotted and analyzed.

  17. Connections between molecular photoionization and electron-molecule scattering with emphasis on shape resonances

    International Nuclear Information System (INIS)

    Most of our detailed information on the spectroscopy and dynamics of the electronic continuum of molecules is based on the complementary probes - photoionization and electron scattering. Though usually studied separately, it is most useful to appreciate the connections between these two processes since our understanding of one is often the key to interpreting or even generating new results in the other. We approach this subject in two steps. First, we very briefly outline the well-established connections, e.g., the Bethe-Born theory and comparisons of isoelectronic systems. Then we focus on a point of contact - the role of shape resonances in molecular photoionization and electron-molecule scattering - for which a substantial amount of new information has become available. Specific topics include mapping of resonances from the neutral (h? + molecule) to the negative ion (e + molecule) system, angular distributions, and interaction with vibration

  18. Molecular states of correlated electrons in a quantum dot. Theory and inelastic light scattering experiments

    International Nuclear Information System (INIS)

    Complete text of publication follows. The paradigm of few-electron complexes in semiconductor quantum dots relies on the 'particle-in-a-box' idea that the lowest-energy orbitals are filled according to Pauli's exclusion principle. If Coulomb repulsion is sufficiently strong to overcome the kinetic energy cost of localization, a different scenario is predicted: a 'Wigner' molecule forms, made of electrons frozen in space according to a geometrical pattern. In this talk I will provide evidence of correlated molecular behaviour in dots populated by two, three, and four electrons, which is based on inelastic light scattering measurements combined with configuration-interaction calculations. Our spectroscopy measures the neutral few-body excitations of the electron molecule, which are either vibrations of the electrons around their relative equilibrium positions - fixed by Coulomb interaction - or rigid-body rotations. We find that spectra of low-lying excitations associated with changes of the relative-motion wave function - the analogues of the vibration modes of a conventional molecule - do not depend on the rotational state represented by the angular momentum. In the case of a molecular dimer, we observe the fundamental breathing mode. For three electrons, we see the emergence of a fully spin-polarized state, which is the simplest possible realization of Stoner ferromagnetism. This work is done in collaboration with V. Pellegrini, A. Pinczuk, E. Molinari, G. Goldoni, Lni, A. Pinczuk, E. Molinari, G. Goldoni, L. N. Pfeiffer, B. S. Dennis, K. W. West, A. Gamucci, S. Kalliakos, C. P. Garcia, A. Singha, and it is supported by Projects MIUR-PRIN no. 2008H9ZAZR, CINECA-ISCRA-B FERMIFEW, and Fondazione Cassa di Risparmio di Modena COLDandFEW.

  19. ab initio modeling of open systems: charge transfer, electron conduction, and molecular switching of a C_{60} device

    OpenAIRE

    Taylor, J; Guo, H.; WANG, J

    2000-01-01

    We present an {\\it ab initio} analysis of electron conduction through a $C_{60}$ molecular device. Charge transfer from the device electrodes to the molecular region is found to play a crucial role in aligning the lowest unoccupied molecular orbital (LUMO) of the $C_{60}$ to the Fermi level of the electrodes. This alignment induces a substantial device conductance of $\\sim 2.2 \\times (2e^2/h)$. A gate potential can inhibit charge transfer and introduce a conductance gap near...

  20. [Non-linear rectification of sensor based on immune genetic Algorithm].

    Science.gov (United States)

    Lu, Lirong; Zhou, Jinyang; Niu, Xiaodong

    2014-08-01

    A non-linear rectification based on immune genetic algorithm (IGA) is proposed in this paper, for the shortcoming of the non-linearity rectification. This algorithm introducing the biologic immune mechanism into the genetic algorithm can restrain the disadvantages that the poor precision, slow convergence speed and early maturity of the genetic algorithm. Computer simulations indicated that the algorithm not only keeps population diversity, but also increases the convergent speed, precision and the stability greatly. The results have shown the correctness and effectiveness of the method. PMID:25508412

  1. Size dependence rectification performances induced by boron and nitrogen co-doping in rhombic graphene nanoribbons

    International Nuclear Information System (INIS)

    Rectification performances of rhombic graphene nanoribbons coupled to gold electrodes through thiolate bonds with left and right vertical carbon atoms substituted by one nitrogen or boron atom are analyzed by performing theoretical calculations using a self-consistent ab initio approach that combines the density functional theory with the non-equilibrium Green's function formalism. Increasing the size of graphene nanoribbon markedly improves the rectification effect because of the asymmetric potential profile distribution in rhombic graphene for polarization near the boron and nitrogen atoms.

  2. Rectification cleaning AsCl3 from the admixture of oxygen

    Directory of Open Access Journals (Sweden)

    Maznitska O. V.

    2008-06-01

    Full Text Available The process of the rectification cleaning of three-chlorous arsenic from the admixtures of products of his hydrolysis in the atmosphere of chlorous hydrogen has been considered in the article. Dependence of coefficient of relative volatility a three-chlorous arsenic from his concentration in muriatic solution is explored. The conduct of coefficient of relative volatility with concentrations of HCl and AsCl3 is compared. Saving of equalization of balance and equalization of working curve of column at such conduct of process of rectification is shown.

  3. Uncovering a law of corresponding states for electron tunneling in molecular junctions.

    Science.gov (United States)

    Bâldea, Ioan; Xie, Zuoti; Frisbie, C Daniel

    2015-06-01

    Laws of corresponding states known so far demonstrate that certain macroscopic systems can be described in a universal manner in terms of reduced quantities, which eliminate specific substance properties. To quantitatively describe real systems, all these laws of corresponding states contain numerical factors adjusted empirically. Here, we report a law of corresponding states deduced analytically for charge transport via tunneling in molecular junctions, which we validate against current-voltage measurements for conducting probe atomic force microscope junctions based on benchmark molecular series (oligophenylenedithiols and alkanedithiols) and electrodes (silver, gold, and platinum), as well as against transport data for scanning tunneling microscope junctions. Two salient features distinguish the present law of corresponding states from all those known previously. First, it is expressed by a universal curve free of empirical parameters. Second, it demonstrates that a universal behavior is not necessarily affected by strong stochastic fluctuations often observed in molecular electronics. An important and encouraging message of this finding is that transport behavior across different molecular platforms can be similar and extraordinarily reproducible. PMID:26008991

  4. Density functional theory studies on molecular structure, vibrational spectra and electronic properties of cyanuric acid

    Science.gov (United States)

    Prabhaharan, M.; Prabakaran, A. R.; Srinivasan, S.; Gunasekaran, S.

    2015-03-01

    The present work has been carried out a combined experimental and theoretical study on molecular structure, vibrational spectra and NBO analysis of cyanuric acid. The FT-IR (100-4000 cm-1) and FT-Raman spectra (400-4000 cm-1) of cyanuric acid were recorded. In DFT methods, Becke's three parameter exchange-functional (B3) combined with gradient-corrected correlation functional of Lee, Yang and Parr (LYP) by implementing the split-valence polarized 6-31G(d,p) and 6-31++G(d,p) basis sets have been considered for the computation of the molecular structure optimization, vibrational frequencies, thermodynamic properties and energies of the optimized structures. The density functional theory (DFT) result complements the experimental findings. The electronic properties, such as HOMO-LUMO energies and molecular electrostatic potential (MESP) are also performed. Mulliken population analysis on atomic charges is also calculated. The first order hyperpolarizability (?total) of this molecular system and related properties (?, ? and ??) are calculated using DFT/B3LYP/6-31G (d,p) and B3LYP/6-311++G(d,p) methods. The thermodynamic functions (heat capacity, entropy and enthalpy) from spectroscopic data by statistical methods were also obtained for the range of temperature 50-1000 K.

  5. Density functional theory studies on molecular structure, vibrational spectra and electronic properties of cyanuric acid.

    Science.gov (United States)

    Prabhaharan, M; Prabakaran, A R; Srinivasan, S; Gunasekaran, S

    2015-03-01

    The present work has been carried out a combined experimental and theoretical study on molecular structure, vibrational spectra and NBO analysis of cyanuric acid. The FT-IR (100-4000cm(-1)) and FT-Raman spectra (400-4000cm(-1)) of cyanuric acid were recorded. In DFT methods, Becke's three parameter exchange-functional (B3) combined with gradient-corrected correlation functional of Lee, Yang and Parr (LYP) by implementing the split-valence polarized 6-31G(d,p) and 6-31++G(d,p) basis sets have been considered for the computation of the molecular structure optimization, vibrational frequencies, thermodynamic properties and energies of the optimized structures. The density functional theory (DFT) result complements the experimental findings. The electronic properties, such as HOMO-LUMO energies and molecular electrostatic potential (MESP) are also performed. Mulliken population analysis on atomic charges is also calculated. The first order hyperpolarizability (?total) of this molecular system and related properties (?, ? and ??) are calculated using DFT/B3LYP/6-31G (d,p) and B3LYP/6-311++G(d,p) methods. The thermodynamic functions (heat capacity, entropy and enthalpy) from spectroscopic data by statistical methods were also obtained for the range of temperature 50-1000K. PMID:25544187

  6. Electron capture and loss processes in heavy ion and molecular ion collisions with solids

    International Nuclear Information System (INIS)

    Angular (theta) and velocity (v /SUB e/ ) distributions of convoy electrons have been measured with monoatomic and molecular projectile ions (H+, D+, H2+, D2+, H3+, He+, He++ at 1.7 MeV/U and U+44, Ti+14 at 1.4 MeV/U) as a function of the projectile dwell time t /SUB D/ in carbon foils (2 to 50 ?g/cm2). The spectra with light projectiles from carbon foils are compared with those of gaseous CH4 targets. For the light and molecular projectiles the shapes and yield of convoy electrons depend strongly on the dwell time. A narrow, strongly theta-dependent contribution at v /SUB e/ = v /SUB p/ can be distinguished from a theta-independent part at v /SUB e/ 2+ at v /SUB e/ = v /SUB p/ and under zero degrees is found to be more than about 20 times as large as is expected from the contribution of loss electrons in last layer collisions

  7. Studies of the surface structures of molecular crystals and of adsorbed molecular monolayers on the (111) crystal faces of platinum and silver by low-energy electron diffraction

    International Nuclear Information System (INIS)

    The structures of molecular crystal surfaces were investigated for the first time by the use of low-energy electron diffraction (LEED). The experimental results from a variety of molecular crystals were examined and compared as a first step towards understanding the properties of these surfaces on a microscopic level. The method of sample preparation employed, vapor deposition onto metal single-crystal substrates at low temperatures in ultrahigh vacuum, allowed concurrent study of the structures of adsorbed monolayers on metal surfaces and of the growth processes of molecular films on metal substrates. The systems investigated were ice, ammonia, naphthalene, benzene, the n-paraffins (C3 to C8), cyclohexane, trioxane, acetic acid, propionic acid, methanol, and methylamine adsorbed and condensed on both Pt(111) and Ag(111) surfaces. Electron-beam-induced damage of the molecular surfaces was observed after electron exposures of 10-4 A sec cm-2 at 20 eV. Aromatic molecular crystal samples were more resistant to damage than samples of saturated molecules. The quality and orientation of the grown molecular crystal films were influenced by substrate preparation and growth conditions. Forty ordered monolayer structures were observed. 110 figures, 22 tables, 162 references

  8. Electron-beam-induced changes in ultra-high-molecular weight polyethylene

    Science.gov (United States)

    Mathad, R. D.; Harish Kumar, H. G.; Sannakki, Basavaraj; Sanjeev, Ganesh; Sarma, K. S. S.; Francis, Sanju

    Post-irradiation studies have been carried out to elucidate the effects of electron beam irradiation on the structural, optical, dielectric and thermal properties of ultra-high-molecular weight polyethylene (UHMWPE) films. The modifications in the optical band gap, activation energy, oscillator strength, and transition dipole moment have been investigated as a function of electron radiation dose using UV-Vis absorption spectra of UHMWPE films. The spectral analysis showed a decrease in both the optical band gap and activation energy, whereas the oscillator strength and the transition dipole moment increased with the increase in electron radiation doses. Further, the dielectric measurements indicated a slight increase in the dielectric constant and the ac conductivity of the UHMWPE films upon electron irradiation. The thermal analysis carried out by differential scanning calorimeter and thermo-gravimetric analyzer revealed that the melting temperature, degree of crystallinity and thermal stability of the UHMWPE films increased, obviously, due to the predominant cross-linking following high doses of electron radiation.

  9. Investigation of electron localization in harmonic emission from asymmetric molecular ion

    Science.gov (United States)

    Zhang, Cai-Ping; Miao, Xiang-Yang

    2015-04-01

    We theoretically investigate the electron localization around two nuclei in harmonic emission from asymmetric molecular ion. The results show that the ionization process of electron localized around one nucleus competes with its transfer process to the other nucleus. By increasing the initial vibrational level, more electrons localized around the nucleus D+ tend to transfer to the nucleus He2+ so that the ionizations of electrons localized around the nucleus He2+ increase. In this case, the difference in harmonic efficiency between HeH2+ and HeD2+ decreases while the difference in harmonic spectral structure increases. The evident minimum can be observed in the harmonic spectrum of HeH2+ compared with that in the spectral structure of HeD2+, which is due to the strong interference of multiple recombination channels originating from two nuclei. Time-dependent nuclear probability density, electron-nuclear probability density, double-well model, and time-frequency maps are presented to explain the underlying mechanisms. Project supported by the National Natural Science Foundation of China (Grant No. 11404204), the Key Project of Chinese Ministry of Education (Grant No. 211025), the Research Fund for the Doctoral Program of Higher Education of China (Grant No. 20111404120004), the Natural Science Foundation for Young Scientists of Shanxi Province, China (Grant No. 2009021005), and the Innovation Project for Postgraduates of Shanxi Province, China (Grant No. 20133081).

  10. Long-range electron tunnelling in oligo-porphyrin molecular wires

    Science.gov (United States)

    Sedghi, Gita; García-Suárez, Víctor M.; Esdaile, Louisa J.; Anderson, Harry L.; Lambert, Colin J.; Martín, Santiago; Bethell, Donald; Higgins, Simon J.; Elliott, Martin; Bennett, Neil; MacDonald, J. Emyr; Nichols, Richard J.

    2011-08-01

    Short chains of porphyrin molecules can mediate electron transport over distances as long as 5-10 nm with low attenuation. This means that porphyrin-based molecular wires could be useful in nanoelectronic and photovoltaic devices, but the mechanisms responsible for charge transport in single oligo-porphyrin wires have not yet been established. Here, based on electrical measurements of single-molecule junctions, we show that the conductance of the oligo-porphyrin wires has a strong dependence on temperature, and a weak dependence on the length of the wire. Although it is widely accepted that such behaviour is a signature of a thermally assisted incoherent (hopping) mechanism, density functional theory calculations and an accompanying analytical model strongly suggest that the observed temperature and length dependence is consistent with phase-coherent tunnelling through the whole molecular junction.

  11. Intramolecular electronic interactions in conjugated ferrocene-pi-extended-tetrathiafulvalene donor-pi-donor molecular hybrids

    Science.gov (United States)

    Liu; Perez; Martin; Echegoyen

    2000-12-29

    The synthesis of new hybrid ferrocene and pi-extended tetrathiafulvalene (TTF) donor(1)-pi-donor(2) molecular assemblies 16a-c has been carried out by a Wittig-Horner reaction of the respective phosphonate esters 15a-c with 2-(2-ferrocenylvinyl)-9, 10-anthraquinone (18) prepared by olefination of ferrocenecarboxaldehyde (14) and the anthraquinone phosphonium salt 17. Electrochemical studies show that the D(1)-pi-D(2) (D = donor) molecular assemblies 16a-c essentially retain the redox characteristics of both ferrocene and the pi-extended TTF components and the effects of solvent, temperature, scan rate, and working electrode are significant. Most importantly, pronounced intramolecular electronic interactions between the two donor moieties were observed by cyclic voltammetry and Osteryoung square wave voltammetry in both the ground and charged states. Semiempirical calculations support the electrochemical observations. PMID:11149856

  12. Self-assembling monolayers of helical oligopeptides with applications in molecular electronics

    CERN Document Server

    Strong, A E

    1997-01-01

    prepared. Transformation of the two (Trt)Cys residues of the resin-bound peptide to the intramolecular disulphide by iodine was achieved in acetonitrile but not in DMF. CD suggested that the conformation of this peptide was a mixture of helix and random coil. Films of the peptide-disulphide and the peptide-dithiol adsorbed from protic solvents were characterised as multilayers by ellipsometry. However CV and ellipsometry showed that a monolayer was successfully prepared from acetonitrile. Future targets for improving and extending this method to form monolayers of linked disulphides are presented. The aim of this project was to develop a generic method of preparing a 'molecular architecture' containing functional groups on a surface at predetermined relative positions several nm apart. This would be of great utility in molecular electronics, chemical sensors and other fields. It was proposed that such an architecture could be prepared on gold using linked, helical oligopeptides that contained the components o...

  13. Electronic and transport properties of azobenzene monolayer junctions as molecular switches

    CERN Document Server

    Wang, Yan

    2012-01-01

    We investigate from first-principles the change in transport properties of a two-dimensional azobenzene monolayer sandwiched between two Au electrodes that undergoes molecular switching. We focus on transport differences between a chemisorbed and physisorbed top monolayer-electrode contact. The conductance of the monolayer junction with a chemisorbed top contact is higher in \\textit{trans} configuration, in agreement with the previous theoretical predictions of one-dimensional single molecule junctions. However, with a physisorbed top contact, the "ON" state with larger conductance is associated with the \\textit{cis} configuration due to a reduced effective tunneling pathway by switching from \\textit{trans} to \\textit{cis}, which successfully explains recently experimental measurements of azobenzene monolayer junctions. A simple model is developed to explain electron transmission across subsystems in the molecular junction. We also discuss the effects of monolayer packing density, molecule tilt angle, and con...

  14. Theoretical estimation of the electron molecular vibration coupling in several organic donor molecules

    Science.gov (United States)

    Taniguchi, M.; Misaki, Y.; Tanaka, K.

    2000-03-01

    The electron-molecular vibration (EMV) coupling constants and the accompanying vibronic energy values of five kinds of organic donor molecules (TTF +1, TTP +1, TTPY +1, TOF +1 and TSF +1) are crucial ingredients of metallic organic salts, and have been theoretically estimated in order to systematically investigate their dependencies on the molecular structures. The effect of the replacement of sulfur atoms in TTF +1 with oxygen and selenium atoms (TOF +1 and TSF +1) has been paid particular attention. It has been found that the EMV coupling constant decreases in the order of TOF +1>TTF +1>TSF +1>TTP +1>TTPY +1. That is, the smaller coupling constants appear in the larger-sized molecule with heavier atoms.

  15. Electronic transport in a molecular junction as XOR and OR gates

    Science.gov (United States)

    Mirzanian, S. M.; Shokri, A. A.

    2015-02-01

    In this work, XOR and OR gate responses are investigated theoretically in a benzene molecule threaded by a magnetic flux. The molecule is attached to two semi-infinite one dimensional metallic electrodes. In addition, there are two gate voltages applied to the molecule as the two inputs of the logical gates. The calculations are based on the tight-binding model and generalized Green's function method within the phase coherent transport regime. The hopping integral between two neighboring atoms in the benzene molecule is quantitatively estimated using fully self-consistence DFT based calculations as implemented in SIESTA package. Our numerical study predicts that the XOR and OR responses are explored through our molecular junction for a typical value of the magnetic flux ? =?0 / 2. The application of these results can be a base for the designing of molecular electronics devices.

  16. Non-adiabatic quantum molecular dynamics: Ionization of many electron systems

    CERN Document Server

    Uhlmann, M; Schmidt, R; Uhlmann, Mathias; Kunert, Thomas; Schmidt, Ruediger

    2005-01-01

    We propose a novel method to describe realistically ionization processes with absorbing boundary conditions in basis expansion within the formalism of the so-called Non-Adiabatic Quantum Molecular Dynamics. This theory couples self-consistently a classical description of the nuclei with a quantum mechanical treatment of the electrons in atomic many-body systems. In this paper we extend the formalism by introducing absorbing boundary conditions via an imaginary potential. It is shown how this potential can be constructed in time-dependent density functional theory in basis expansion. The approach is first tested on the hydrogen atom and the pre-aligned hydrogen molecular ion H2+ in intense laser fields where reference calculations are available. It is then applied to study the ionization of non-aligned H2+ and H2. Striking differences in the orientation dependence between both molecules are found. Surprisingly, enhanced ionization is predicted for perpendicularly aligned molecules.

  17. Non-adiabatic quantum molecular dynamics: ionization of many-electron systems

    International Nuclear Information System (INIS)

    We propose a novel method to describe realistically ionization processes with absorbing boundary conditions in basis expansion within the formalism of so-called non-adiabatic quantum molecular dynamics. This theory couples self-consistently a classical description of the nuclei with a quantum-mechanical treatment of the electrons in atomic many-body systems. In this paper, we extend the formalism by introducing absorbing boundary conditions via an imaginary potential. It is shown how this potential can be constructed in time-dependent density functional theory in basis expansion. The approach is first tested on the hydrogen atom and the pre-aligned hydrogen molecular ion H2+ in intense laser fields where reference calculations are available. It is then applied to study the ionization of non-aligned H2+ and H2. Striking differences in the orientation dependence between both molecules are found. Surprisingly, enhanced ionization is predicted for perpendicularly aligned molecules

  18. Electron-correlated fragment-molecular-orbital calculations for biomolecular and nano systems.

    Science.gov (United States)

    Tanaka, Shigenori; Mochizuki, Yuji; Komeiji, Yuto; Okiyama, Yoshio; Fukuzawa, Kaori

    2014-06-14

    Recent developments in the fragment molecular orbital (FMO) method for theoretical formulation, implementation, and application to nano and biomolecular systems are reviewed. The FMO method has enabled ab initio quantum-mechanical calculations for large molecular systems such as protein-ligand complexes at a reasonable computational cost in a parallelized way. There have been a wealth of application outcomes from the FMO method in the fields of biochemistry, medicinal chemistry and nanotechnology, in which the electron correlation effects play vital roles. With the aid of the advances in high-performance computing, the FMO method promises larger, faster, and more accurate simulations of biomolecular and related systems, including the descriptions of dynamical behaviors in solvent environments. The current status and future prospects of the FMO scheme are addressed in these contexts. PMID:24740821

  19. Attosecond-magnetic-field-pulse generation by coherent circular molecular electron wave packets

    Science.gov (United States)

    Yuan, Kai-Jun; Bandrauk, André D.

    2015-04-01

    Attosecond-magnetic-field-pulse generation is investigated using numerical solutions of the time-dependent Schrödinger equation for oriented H2 + excited and ionized by intense 2 ×1016 W /cm2 circularly polarized attosecond UV pulses. The results show that localized attosecond-magnetic-field pulses B at the molecular center (r =0 ) decrease in intensity with increasing attosecond-pulse wavelength, following a classical model. Magnetic-field minima are obtained at a specific laser-pulse wavelength ? =55 nm, which is attributed to ionization suppression. It is found that spatially localized coherent circular electron currents and wave packets are created and induce magnetic-field minima. At ? =55 nm, coherent excitation between the ground state and Rydberg states is created, giving rise to partial Rabi oscillations in population and doublets in molecular above-threshold-ionization photoelectron energy spectra. Pulse intensities are shown to influence these effects on the attosecond time scale through population variations.

  20. A morphological study of molecularly imprinted polymers using the scanning electron microscope

    International Nuclear Information System (INIS)

    Molecular imprinting is an emerging technique for producing polymers with applications in affinity-based separation, in biomimetic sensors, in catalysis, etc. This variety of uses relies upon the production of polymers with different affinities, specificities, sensitivities and loading capacities. Research into the development of molecular imprinted polymers (MIPs) with new or improved morphologies - which involves modification of the polymerisation process - is therefore underway. This paper reports a comparative study of non-covalent MIPs synthesised by 'bulk' polymerisation using digoxin as template. These were synthesised under different conditions, i.e., changing the functional monomers employed (methacrylic acid or 2-vinylpyridine), the porogens (acetonitrile or dichloromethane) used, and by altering the volume of the latter. The polymerisation process was allowed to proceed either under UV light or in a thermostat-controlled waterbath. The surface morphology (was determined by scanning electron microscopy) and the ability of the different polymers to selectively rebind the template was then evaluated

  1. A morphological study of molecularly imprinted polymers using the scanning electron microscope

    Energy Technology Data Exchange (ETDEWEB)

    Paniagua Gonzalez, Gema [Departamento de Ciencias Analiticas, Facultad de Ciencias, Universidad Nacional de Educacion a Distancia (UNED), 28040 Madrid (Spain)]. E-mail: gpaniagua@pas.uned.es; Fernandez Hernando, Pilar [Departamento de Ciencias Analiticas, Facultad de Ciencias, Universidad Nacional de Educacion a Distancia (UNED), 28040 Madrid (Spain); Durand Alegria, J.S. [Departamento de Ciencias Analiticas, Facultad de Ciencias, Universidad Nacional de Educacion a Distancia (UNED), 28040 Madrid (Spain)

    2006-01-31

    Molecular imprinting is an emerging technique for producing polymers with applications in affinity-based separation, in biomimetic sensors, in catalysis, etc. This variety of uses relies upon the production of polymers with different affinities, specificities, sensitivities and loading capacities. Research into the development of molecular imprinted polymers (MIPs) with new or improved morphologies - which involves modification of the polymerisation process - is therefore underway. This paper reports a comparative study of non-covalent MIPs synthesised by 'bulk' polymerisation using digoxin as template. These were synthesised under different conditions, i.e., changing the functional monomers employed (methacrylic acid or 2-vinylpyridine), the porogens (acetonitrile or dichloromethane) used, and by altering the volume of the latter. The polymerisation process was allowed to proceed either under UV light or in a thermostat-controlled waterbath. The surface morphology (was determined by scanning electron microscopy) and the ability of the different polymers to selectively rebind the template was then evaluated.

  2. New Materials, Methods, and Molecules for Microelectronic and Molecular Electronic Devices

    Science.gov (United States)

    Miller, Michael Stephen

    This dissertation reports a variety of new methods and materials for the fabrication of electronic devices. Particular emphasis is placed on low-cost, solution based methods for flexible electronic device fabrication, and new substrates and molecules for molecular electronic tunnel junctions. Chapter 2 reports a low-cost, solution based method for depositing patterned metal circuitry onto a variety of flexible polymer substrates. Microcontact printing an aluminum (III) porphyrin complex activates selected areas of an oxidized polymer substrate to electroless copper metallization. Chapter 3 reports a new transparent conductive electrode for use in optoelectronic devices. A highly conductive, transparent silver nanowire network is embedded at the surface of an optical adhesive, which can be applied to a variety of rigid and flexible polymer substrates. Chapter 4 describes a new approach to the self-assembly of mesoscale components into two-dimensional arrays. Unlike most previously reported self-assembly motifs, this method is completely dry; eliminating solvent makes this method compatible with the assembly of electronic components. Chapter 5 describes a new class of self-assembled monolayer (SAM) on gold formed from dihexadecyldithiophosphinic acid ((C16) 2DTPA) adsorbate molecules. The binding and structure (C16) 2DTPA SAMs is dependent upon the roughness and morphology of the underlying gold substrate. Chapter 6 investigates the influence of chain length on the binding and structure of dialkyl-DTPA SAMs on smooth, template-stripped (TS) gold. Binding of the DTPA head group is independent of the length of the alkyl chain, while the structure of the organic layer has a counter-intuitive dependence: As the length of the alkyl chain increases, these SAMs become more disordered and liquid-like. Chapter 7 describes the fabrication of ultra smooth gold substrates using chemical mechanical polishing (CMP). These substrates are smooth, uniform, and prove to be ideal candidates for bottom electrodes within SAM-based molecular electronic tunnel junctions. Chapter 8 investigates the charge transport properties of new diphenyldithiophosphinic acid (Ph 2DTPA) SAMs on TS gold within metal-SAM//Ga2O3/EGaIn molecular tunnel junctions. A computational investigation provides insight into the electronic structure of the junction.

  3. Control of electron localization to isolate and enhance molecular harmonic plateau in asymmetric HeH2+ system

    International Nuclear Information System (INIS)

    High-order harmonic generation from the asymmetric molecular ion HeH2+ exposed to intense laser fields was investigated by quantum wave packet calculations in which the initial wave packet of HeH2+ was prepared in the first excited 2p? state. The calculated molecular harmonic plateau at low frequencies was effectively isolated and enhanced by adjusting the carrier-envelope phase (CEP) of the laser field. Furthermore, double-well model, time-dependent electronic density, electronic state population, and time-frequency analyses were presented to explain the underlying mechanism of the efficient isolated molecular plateau. By taking advantage of the CEP effect to control the electronic dynamics, this isolated molecular plateau can be used to generate high-intensity single attosecond pulses.

  4. Electronic Transport Properties of an Anthraquinone-Based Molecular Switch with Carbon Nanotube Electrodes

    Science.gov (United States)

    Zhao, Peng; Liu, De-Sheng

    2012-04-01

    Based on the nonequilibrium Green's function method and density functional theory calculations, we theoretically investigate the electronic transport properties of an anthraquinone-based molecular switch with carbon nanotube electrodes. The molecules that comprise the switch can convert between reduced hydroquinone (HQ) and oxidized anthraquinne (AQ) states via redox reactions. Our results show that the on-off ratio is increased one order of magnitude when compared to the case of gold electrodes. Moreover, an obvious negative differential resistance behavior at much low bias (0.07 V) is observed in the HQ form.

  5. Proton-Coupled Electron Transfer in Molecular Electrocatalysis: Theoretical Methods and Design Principles

    Energy Technology Data Exchange (ETDEWEB)

    Solis, Brian H.; Hammes-Schiffer, Sharon

    2014-07-07

    Molecular electrocatalysts play an essential role in a wide range of energy conversion processes. The objective of electrocatalyst design is to maximize the turnover frequency and minimize the overpotential for the overall catalytic cycle. Typically the catalytic cycle is dominated by key proton-coupled electron transfer (PCET) processes comprised of sequential or concerted electron transfer and proton transfer steps. A variety of theoretical methods have been developed to investigate the mechanisms, thermodynamics, and kinetics of PCET processes in electrocatalytic cycles. Electronic structure methods can be used to calculate the reduction potentials and pKa’s and to generate thermodynamic schemes, free energy reaction pathways, and Pourbaix diagrams, which indicate the most stable species at each pH and potential. These types of calculations have assisted in identifying the thermodynamically favorable mechanisms under specified experimental conditions, such as acid strength and overpotential. Such calculations have also revealed linear correlations among the thermodynamic properties, which can be used to predict the impact of modifying the ligand, substituents, or metal center. The role of non-innocent ligands, namely ligand protonation or reduction, has also been examined theoretically. In addition, the rate constants for electron and proton transfer reactions, as well as concerted PCET reactions, have been calculated to investigate the kinetics of molecular electrocatalysts. The concerted PCET mechanism is thought to lower the overpotential required for catalysis by avoiding high-energy intermediates. Rate constant calculations have revealed that the concerted mechanism involving intramolecular proton transfer will be favored by designing more flexible ligands that facilitate the proton donor-acceptor motion while also maintaining a sufficiently short equilibrium proton donor-acceptor distance. Overall, theoretical methods have assisted in the interpretation of experimental data and the design of more effective molecular electrocatalysts. The research on the Ni(P2N2)2 catalysts was supported as part of the Center for Molecular Electrocatalysis, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences.

  6. Molecular fingerprints in the electronic properties of crystalline organic semiconductors : From experiment to theory

    DEFF Research Database (Denmark)

    Ciuchi, S.; Hatch, R.C.

    2012-01-01

    By comparing photoemission spectroscopy with a non-perturbative dynamical mean field theory extension to many-body ab initio calculations, we show in the prominent case of pentacene crystals that an excellent agreement with experiment for the bandwidth, dispersion and lifetime of the hole carrier bands can be achieved in organic semiconductors provided that one properly accounts for the coupling to molecular vibrational modes and the presence of disorder. Our findings rationalize the growing experimental evidence that even the best band structure theories based on a many-body treatment of electronic interactions cannot reproduce the experimental photoemission data in this important class of materials.

  7. Carbon auger electron line shape after beam-foil excitation of molecular ions

    International Nuclear Information System (INIS)

    Auger electrons of beam-foil excited C-projectiles and C-fragments of Coulomb exploding molecular CO-projectiles at 83 keV/u yield information on the excitation mechanisms and the interaction with the solid. A numerical procedure is developed to calculate the mean energy of the Coulomb explosion, the charge states of the fragment ions and their angular straggling behaviour inside the solid. The calculated results are compared with experimental data. From a detailed line shape calculation the magnitude of directional effects induced by the Wake-potential can be predicted. (orig.)

  8. Enhancement of molecular modes by electronically resonant multipulse excitation: further progress towards mode selective chemistry.

    Science.gov (United States)

    Hauer, Jürgen; Buckup, Tiago; Motzkus, Marcus

    2006-08-14

    We show that molecular vibrations induced by resonant excitation pulses can be enhanced by pulse trains, compared to Fourier-limited pulses of equal pulse energy. As a proof-of-principle, a low frequency mode of Nile Blue at 600 cm(-1) is observed and amplified in a pump and probe experiment. In addition to previous experiments in our group, an increased population transfer to the excited electronic state is identified as an important element of the underlying physical mechanism. These results suggest an enhancement on the level of individual molecules rather than a macroscopic effect. PMID:16942265

  9. ab initio modeling of open systems charge transfer, electron conduction, and molecular switching of a C_{60} device

    CERN Document Server

    Taylor, J; Wang, J; Taylor, Jeremy; Guo, Hong; Wang, Jian

    2001-01-01

    We present an {\\it ab initio} analysis of electron conduction through a $C_{60}$ molecular device. Charge transfer from the device electrodes to the molecular region is found to play a crucial role in aligning the lowest unoccupied molecular orbital (LUMO) of the $C_{60}$ to the Fermi level of the electrodes. This alignment induces a substantial device conductance of $\\sim 2.2 \\times (2e^2/h)$. A gate potential can inhibit charge transfer and introduce a conductance gap near $E_F$, changing the current-voltage characteristics from metallic to semi-conducting, thereby producing a field effect molecular current switch.

  10. A molecular Debye-Hückel approach to the reorganization energy of electron transfer reactions in an electric cell

    Science.gov (United States)

    Xiao, Tiejun; Song, Xueyu

    2014-10-01

    Electron transfer near an electrode immersed in ionic fluids is studied using the linear response approximation, namely, mean value of the vertical energy gap can be used to evaluate the reorganization energy, and hence any linear response model that can treat Coulomb interactions successfully can be used for the reorganization energy calculation. Specifically, a molecular Debye-Hückel theory is used to calculate the reorganization energy of electron transfer reactions in an electric cell. Applications to electron transfer near an electrode in molten salts show that the reorganization energies from our molecular Debye-Hückel theory agree well with the results from MD simulations.

  11. Young-type interference pattern in molecular inner-shell excitations by electron impact

    International Nuclear Information System (INIS)

    Recently, Tyliszczak et al. [J. Electron Spectrosc. Rel. Phenom. 114, 93 (2001)] have observed oscillations in the generalized oscillator strength (GOS) profile of molecular inner-shell excitations by electron impact. In order to check the mechanism that gives rise to these oscillations, we have calculated GOS profiles for different inner-shell?Rydberg excitation processes in CO2 and butadiene. The comparison of the oscillations appearing in these ab initio results with a simple analytical model in which the interference term is explicit brings out very strong evidence favorable to the hypothesis that the observed oscillations in the GOS are due to Young-type quantum interference related to symmetry-equivalent atoms

  12. Electron spin resonance studies on reduction process of nitroxyl spin radicals used in molecular imaging

    International Nuclear Information System (INIS)

    The Electron spin resonance studies on the reduction process of nitroxyl spin probes were carried out for 1mM 14N labeled nitroxyl radicals in pure water and 1 mM concentration of ascorbic acid as a function of time. The electron spin resonance parameters such as signal intensity ratio, line width, g-value, hyperfine coupling constant and rotational correlation time were determined. The half life time was estimated for 1mM 14N labeled nitroxyl radicals in 1 mM concentration of ascorbic acid. The ESR study reveals that the TEMPONE has narrowest line width and fast tumbling motion compared with TEMPO and TEMPOL. From the results, TEMPONE has long half life time and high stability compared with TEMPO and TEMPOL radical. Therefore, this study reveals that the TEMPONE radical can act as a good redox sensitive spin probe for molecular imaging

  13. Calculated Cross Sections for the Electron Impact Ionization of Simple Molecular Ions

    Science.gov (United States)

    Deutsch, H.; Becker, K.; Defrance, P.; Onthong, U.; Probst, M.; Matt, S.; Mark, T.

    2001-10-01

    We applied the semi-classical Deutsch-Märk (DM) formalism, which was originally developed for the calculation of atomic electron-impact ionization cross sections and later extended to molecules, radicals, and clusters, to the calculation of absolute electron-impact ionization cross sections of simple molecular ions such as CO2+, H3O+, and H2+. A comparison with available experimental data reveals significant discrepancies in the case of CO2+ and H3O+ which can be attributed (i) to appreciable contributions to some of the measured cross sections due to dissociative excitation channels which are not described by the DM formalism and (ii) the omission of some important dissociative ionization channels in the experiments which are, on the other hand, included in the calculated cross sections. Work supported in part by NASA, the FWF, Wien, Austria and carried out within the Association EURATOM/ÖAW, Wien, Austria.

  14. Formation of molecular nitrogen and diazene by electron irradiation of solid ammonia

    International Nuclear Information System (INIS)

    We present an experimental study on 500–3000 eV energy electron irradiation of ammonia ice at 20 K. While molecular nitrogen and diazene (N2H2) were detected during post-irradiation thermal desorption no appreciable traces of hydrazine (N2H4) were observed. We suggest that the recombination between adjacent nitrogen atoms and between neighboring NH radicals can be the main mechanism responsible for the formation of the observed molecules, whereas hydrazine formed by two amino radicals is probably in an excited state and decays into diazene and hydrogen. - Highlights: ? Experimental study on 500–3000 eV electron irradiation of ammonia ice at 20 K. ? Observation of nitrogen and diazene during post-irradiation thermal desorption. ? No appreciable traces of hydrazine (N2H4).

  15. Molecular imaging with X-ray free electron lasers: dream or reality?

    CERN Document Server

    Fratalocchi, Andrea

    2010-01-01

    X-ray Free Electron Lasers (XFEL) are revolutionary photons sources, whose ultrashort, brilliant pulses are expected to allow single molecule diffraction experiments providing structural information on the atomic length scale. This ultimate goal, however, is currently hampered by several challenging questions basically concerning sample damage, Coulomb explosion and the role of nonlinearity. By employing an original \\emph{ab-initio} approach, as well as exceptional resources of parallel computing, we address these issues showing that accurate XFEL-based single molecule imaging will be only possible with ultrashort pulses of half of femtosecond, due to significant radiation damage and the formation of preferred multi-soliton clusters which reshape the overall electronic density of the molecular system at the femtosecond scale.

  16. Fabrication of dissimilar metal electrodes with nanometer interelectrode distance for molecular electronic device characterization

    International Nuclear Information System (INIS)

    We report a versatile process for the fabrication of dissimilar metal electrodes with a minimum interelectrode distance of less than 6 nm using electron beam lithography and liftoff pattern transfer. This technique provides a controllable and reproducible method for creating structures suited for the electrical characterization of asymmetric molecules for molecular electronics applications. Electrode structures employing pairs of Au electrodes and non-Au electrodes were fabricated in three different patterns. Parallel electrode structures 300 ?m long with interelectrode distances as low as 10 nm, 75 nm wide electrode pairs with interelectrode distances less than 6 nm, and a multiterminal electrode structure with reproducible interelectrode distances of 8 nm were realized using this technique. The processing issues associated with the fabrication of these structures are discussed along with the intended application of these devices. (c) 2000 American Vacuum Society

  17. Auger electrons - A nano-probe for structural, molecular and cellular processes

    International Nuclear Information System (INIS)

    This paper provides a brief review of recently published work on biophysical and biological aspects of Auger processes. Three specific questions have been considered. (1) Does charge neutralisation contribute to molecular damage such as DNA strand breaks? (2) How many DNA double strand breaks are produced by a single decay of DNA bound 125I? (3) What is the correlation between number of ?H2AX foci and number of double strand breaks (DSB)? The paper also gives preliminary reports on two new calculations: (a) calculation of the spectrum of Auger electrons released during decay of 124I and (b) the use of Auger electrons in the decay of 125I as a probing agent of novel DNA structures. (authors)

  18. Electronic structure and partial charge distribution of Doxorubicin in different molecular environments.

    Science.gov (United States)

    Poudel, Lokendra; Wen, Amy M; French, Roger H; Parsegian, V Adrian; Podgornik, Rudolf; Steinmetz, Nicole F; Ching, Wai-Yim

    2015-05-18

    The electronic structure and partial charge of doxorubicin (DOX) in three different molecular environments-isolated, solvated, and intercalated in a DNA complex-are studied by first-principles density functional methods. It is shown that the addition of solvating water molecules to DOX, together with the proximity to and interaction with DNA, has a significant impact on the electronic structure as well as on the partial charge distribution. Significant improvement in estimating the DOX-DNA interaction energy is achieved. The results are further elucidated by resolving the total density of states and surface charge density into different functional groups. It is concluded that the presence of the solvent and the details of the interaction geometry matter greatly in determining the stability of DOX complexation. Ab initio calculations on realistic models are an important step toward a more accurate description of the long-range interactions in biomolecular systems. PMID:25728554

  19. Focus: Two-dimensional electron-electron double resonance and molecular motions: The challenge of higher frequencies

    Science.gov (United States)

    Franck, John M.; Chandrasekaran, Siddarth; Dzikovski, Boris; Dunnam, Curt R.; Freed, Jack H.

    2015-06-01

    The development, applications, and current challenges of the pulsed ESR technique of two-dimensional Electron-Electron Double Resonance (2D ELDOR) are described. This is a three-pulse technique akin to 2D Exchange Nuclear Magnetic Resonance, but involving electron spins, usually in the form of spin-probes or spin-labels. As a result, it required the extension to much higher frequencies, i.e., microwaves, and much faster time scales, with ?/2 pulses in the 2-3 ns range. It has proven very useful for studying molecular dynamics in complex fluids, and spectral results can be explained by fitting theoretical models (also described) that provide a detailed analysis of the molecular dynamics and structure. We discuss concepts that also appear in other forms of 2D spectroscopy but emphasize the unique advantages and difficulties that are intrinsic to ESR. Advantages include the ability to tune the resonance frequency, in order to probe different motional ranges, while challenges include the high ratio of the detection dead time vs. the relaxation times. We review several important 2D ELDOR studies of molecular dynamics. (1) The results from a spin probe dissolved in a liquid crystal are followed throughout the isotropic ? nematic ? liquid-like smectic ? solid-like smectic ? crystalline phases as the temperature is reduced and are interpreted in terms of the slowly relaxing local structure model. Here, the labeled molecule is undergoing overall motion in the macroscopically aligned sample, as well as responding to local site fluctuations. (2) Several examples involving model phospholipid membranes are provided, including the dynamic structural characterization of the boundary lipid that coats a transmembrane peptide dimer. Additionally, subtle differences can be elicited for the phospholipid membrane phases: liquid disordered, liquid ordered, and gel, and the subtle effects upon the membrane, of antigen cross-linking of receptors on the surface of plasma membrane, vesicles can be observed. These 2D ELDOR experiments are performed as a function of mixing time, Tm, i.e., the time between the second and third ?/2 pulses, which provides a third dimension. In fact, a fourth dimension may be added by varying the ESR frequency/magnetic field combination. Therefore, (3) it is shown how continuous-wave multifrequency ESR studies enable the decomposition of complex dynamics of, e.g., proteins by virtue of their respective time scales. These studies motivate our current efforts that are directed to extend 2D ELDOR to higher frequencies, 95 GHz in particular (from 9 and 17 GHz), in order to enable multi-frequency 2D ELDOR. This required the development of quasi-optical methods for performing the mm-wave experiments, which are summarized. We demonstrate state-of-the-art 95 GHz 2D ELDOR spectroscopy through its ability to resolve the two signals from a spin probe dissolved in both the lipid phase and the coexisting aqueous phase. As current 95 GHz experiments are restricted by limited spectral coverage of the ?/2 pulse, as well as the very short T2 relaxation times of the electron spins, we discuss how these limitations are being addressed.

  20. Electron and Ion Reactions in Molecular Solids: from water ice to DNA

    Science.gov (United States)

    Huels, Michael A.

    2002-05-01

    Wherever ionizing radiation interacts with matter, it initiates reaction cascades involving non-thermal ions, radicals, and ballistic secondary electrons, which in turn may lead to substantial physical and chemical modifications of a medium. The detailed study of the fundamental reaction mechanisms which occur on a molecular level aids our general understanding of radiation induced processes in a variety of contexts, ranging from radiobiology to astrochemistry. Here I present measurements of electron (1 - 80 eV) and some ion (1 - 8 eV) mediated reactions in molecular films that resemble biological model systems. These consist of cryogenic films (pure or mixed) of rare gases, oxygen, water, methane, or aromatic hydrocarbons of increasing complexity, including bases, sugars, single and double stranded DNA. Although the basic nature of the electron or ion reaction mechanisms are found to be similar to those in the gas phase, they are often modulated by the physico-chemical characteristics of the medium. Depending on the latter, some reaction channels may be strongly enhanced, some may be quenched, and new reaction pathways, unavailable in the gas phase, may open. Thus, a given reaction cascade may lead to different end-points even in the same target. Although the goal of these studies is to unravel some of the nascent secondary-electron and reactive-ion induced events that contribute to radiation damage in living tissue, the basic observed reactions relate to other areas of application which will be briefly discussed. This research is supported by the Canadian Institutes of Health Research (CIHR), the National Cancer Institutes of Canada, the Natural Science and Engineering Research Council, and NATO.

  1. Magnetization dependent rectification in (Ga,Mn)As tri-layer tunnel junctions

    Science.gov (United States)

    Hashimoto, Y.; Amano, H.; Iye, Y.; Katsumoto, S.

    2012-12-01

    Current rectification in (Ga,Mn)As tri-layer magnetic tunnel junctions (MTJs) is found to be controllable through the alignment of magnetizations, which can be changed with small current injections. The tunneling magnetoresistance (TMR) at 4.2K is 120% in amplitude, showing three step structure, which corresponds to the alignment of magnetizations. With a minor field loop, the alignment of magnetization can be anti-parallel for the top and the bottom layers and then current injections with alternative direction can reverse the direction of the magnetization in the middle layer. The threshold current is as low as 2 × 104A/cm2. We have found the junctions have small rectification effect up to 8GHz, which is strongly dependent on the alignment of the magnetization. Hence the direction of the rectification as well as the amplitude can be switched by the bi-directional current injections. The rectification can be explained within the Julliere model with enegy dependence of the density of states. To check this we performed tunneling measurements and obtained positive results.

  2. The rectification of textile wastes on dewed base after radiation and ozone treatment

    International Nuclear Information System (INIS)

    The influence of the radiation and ozone treatment of textile wastes on further stages of rectification on dewed base is discussed. Different variants of the treatment are related to the removal of contaminants from the wastes. The radiation and ozone treatment is found to improve the performance of the base considerably. 1 fig., 2 tabs., 15 refs. (author)

  3. Nonlinearities and Noise Properties of Electronic Heat Transfer in Molecular Junctions

    Science.gov (United States)

    Luniewski, Arthur; Aghjayan, Rita; Walczak, Kamil; Nanoscale Physics Division Team

    2015-03-01

    We examine the electronic heat transport phenomena in nanoscale junctions composed of organic molecules weakly coupled to two heat reservoirs of different temperatures. The electronic heat flux and its dynamical noise properties are calculated within the scattering (Landauer) formalism with the transmission probability determined by using non-equilibrium Green's functions technique. The perturbative computational scheme is used to determine nonlinear corrections to the electronic heat flux and its noise power spectral density with up to the second order terms in relation to the temperature difference. Our results show the limited applicability of ballistic Fourier's law and the fluctuation-dissipation relations to nanoscale heat flow carried by electrons. Further, we discuss the influence of quantum interference and dimensionality of heat reservoirs onto the transport characteristics and shot noise spectra related to molecular systems under consideration. Importantly, the nonlinear transport theory developed by us may be extended to higher order terms to address a huge variety of problems associated with nonlinear thermal effects, which may occur at nanoscale. This research is supported by Pace University Start-up Grant.

  4. Effects of electron-phonon interaction on thermal and electrical transport through molecular nano-conductors

    Directory of Open Access Journals (Sweden)

    Jing-Tao Lü

    2015-05-01

    Full Text Available The topic of this review is the effects of electron-phonon interaction (EPI on the transport properties of molecular nano-conductors. A nano-conductor connects to two electron leads and two phonon leads, possibly at different temperatures or chemical potentials. The EPI appears only in the nano-conductor. We focus on its effects on charge and energy transport. We introduce three approaches. For weak EPI, we use the nonequilibrium Green’s function method to treat it perturbatively. We derive the expressions for the charge and heat currents. For weak system-lead couplings, we use the quantum master equation approach. In both cases, we use a simple single level model to study the effects of EPI on the system’s thermoelectric transport properties. It is also interesting to look at the effect of currents on the dynamics of the phonon system. For this, we derive a semi-classical generalized Langevin equation to describe the nano-conductor’s atomic dynamics, taking the nonequilibrium electron system, as well as the rest of the atomic degrees of freedom as effective baths. We show simple applications of this approach to the problem of energy transfer between electrons and phonons.

  5. Effects of electron-phonon interaction on thermal and electrical transport through molecular nano-conductors

    Science.gov (United States)

    Lü, Jing-Tao; Zhou, Hangbo; Jiang, Jin-Wu; Wang, Jian-Sheng

    2015-05-01

    The topic of this review is the effects of electron-phonon interaction (EPI) on the transport properties of molecular nano-conductors. A nano-conductor connects to two electron leads and two phonon leads, possibly at different temperatures or chemical potentials. The EPI appears only in the nano-conductor. We focus on its effects on charge and energy transport. We introduce three approaches. For weak EPI, we use the nonequilibrium Green's function method to treat it perturbatively. We derive the expressions for the charge and heat currents. For weak system-lead couplings, we use the quantum master equation approach. In both cases, we use a simple single level model to study the effects of EPI on the system's thermoelectric transport properties. It is also interesting to look at the effect of currents on the dynamics of the phonon system. For this, we derive a semi-classical generalized Langevin equation to describe the nano-conductor's atomic dynamics, taking the nonequilibrium electron system, as well as the rest of the atomic degrees of freedom as effective baths. We show simple applications of this approach to the problem of energy transfer between electrons and phonons.

  6. Non-adiabatic molecular dynamics of electron transfer in dye-sensitized semiconductor systems

    Science.gov (United States)

    Stier, William Michael

    A relatively new type of photovoltaic device is the dye sensitized solar cell (DSSC), or Graetzel cell. Although less expensive to produce than traditional solar cells, the efficiency of DSSCs must be improved substantially to compete effectively with the more expensive conventional silicon-based cells. A considerable amount of research has been done to elucidate the chemistry that takes place in DSSCs, and thereby determine how efficiency may be improved. Two competing mechanisms, which require different conditions for optimum performance, have been proposed to explain the observed ultrafast electron transfer (ET) between the dye and the semiconductor. In order to investigate the importance of these two proposed mechanisms with computational chemistry, it is necessary to apply a method in which the population of the various adiabatic states may evolve over time. Non-adiabatic (NA) molecular dynamics (MD), in which transitions between adiabatic states are calculated via the NA coupling, provides a manner in which the relative importance of the adiabatic and NA pathways may be evaluated. Three computational chemistry studies of the ultrafast ET in DSSCs using a quantum-classical mean-field approach are presented. The first study simulates ultra-high vacuum (UHV) conditions and uses isonicotinic acid as the molecular electron donor (MED). The second study investigates room temperature conditions using isonicotinic acid silver cyanide as the MED. The third study reproduces the experimental results reported for the alizarin TiO2 system.

  7. Mass Spectrometric Study of Molecular Ions of Ethylamine, Diethylamin and Triethylamine Using Electron Impact

    International Nuclear Information System (INIS)

    Electron impact mass spectra of ethylamine, diethylamine, and triethylamine at 70 and 14 eV have been recorded and investigated. The fragmentation pathways for the formation of different immonium ions (Cn H2n+2N)+ are elucidated with the aid of metastable ions . also, ionization efficiency (LE) curves for the three molecular ions are reported, using Deconvoluted First Differential (DFD) technique have been measured. The presently values of ionization energies at threshold are measured at 8.95 +- 0.07, 8.15+-0.08 and 7.63+-0.07 eV for ethylamine, diethylamine and triethylamine, respectively and are explained as due to removal of one lone pair electron of the nitrogen atom. Molecular energy levels have been also detected in the LE curves. Modified Neglect of Diatomic Overlap (MNDO) calculations have been carried out on the three precursors to estimate ionization energies and heats of formation and compared with experimental work. Also, charge distribution on different atoms are calculated in order to interpret some fragmentation mechanisms

  8. Molecular structure, vibrational, electronic and thermal properties of 4-vinylcyclohexene by quantum chemical calculations

    Science.gov (United States)

    Nagabalasubramanian, P. B.; Periandy, S.; Karabacak, Mehmet; Govindarajan, M.

    2015-06-01

    The solid phase FT-IR and FT-Raman spectra of 4-vinylcyclohexene (abbreviated as 4-VCH) have been recorded in the region 4000-100 cm-1. The optimized molecular geometry and vibrational frequencies of the fundamental modes of 4-VCH have been precisely assigned and analyzed with the aid of structure optimizations and normal coordinate force field calculations based on density functional theory (DFT) method at 6-311++G(d,p) level basis set. The theoretical frequencies were properly scaled and compared with experimentally obtained FT-IR and FT-Raman spectra. Also, the effect due the substitution of vinyl group on the ring vibrational frequencies was analyzed and a detailed interpretation of the vibrational spectra of this compound has been made on the basis of the calculated total energy distribution (TED). The time dependent DFT (TD-DFT) method was employed to predict its electronic properties, such as electronic transitions by UV-Visible analysis, HOMO and LUMO energies, molecular electrostatic potential (MEP) and various global reactivity and selectivity descriptors (chemical hardness, chemical potential, softness, electrophilicity index). Stability of the molecule arising from hyper conjugative interaction, charge delocalization has been analyzed using natural bond orbital (NBO) analysis. Atomic charges obtained by Mulliken population analysis and NBO analysis are compared. Thermodynamic properties (heat capacity, entropy and enthalpy) of the title compound at different temperatures are also calculated.

  9. Fragmentation and electronic decay of vacuum-ultraviolet-excited resonant states of molecular CsCl

    International Nuclear Information System (INIS)

    Electronic and nuclear relaxation of molecular CsCl following photoexcitation in the vacuum ultraviolet region is investigated. From the total ion yield and the Cs+ and Cl+ partial ion yield spectra covering the 8 - 22 eV photon energy range, a number of resonating excited states are identified. The fragmentation patterns of the excited and ionized CsCl molecules and also the Cs2Cl2 dimers are studied in detail from ion time-of-flight mass spectra recorded at and around the resonances. Molecular dissociation following the resonant excitation is discussed and an ionic model is applied to explain the observations, emphasizing some principal differences from other alkali chloride molecules (KCl). The valence photoelectron spectra are found to show strong enhancement and pronounced new structures at resonant photon energies. These effects are assigned to a 'cross-ionic' autoionization decay process and are found to be due to a lifetime-dependent interplay between the electronic and nuclear relaxation

  10. Molecular structure, vibrational, electronic and thermal properties of 4-vinylcyclohexene by quantum chemical calculations.

    Science.gov (United States)

    Nagabalasubramanian, P B; Periandy, S; Karabacak, Mehmet; Govindarajan, M

    2015-06-15

    The solid phase FT-IR and FT-Raman spectra of 4-vinylcyclohexene (abbreviated as 4-VCH) have been recorded in the region 4000-100cm(-1). The optimized molecular geometry and vibrational frequencies of the fundamental modes of 4-VCH have been precisely assigned and analyzed with the aid of structure optimizations and normal coordinate force field calculations based on density functional theory (DFT) method at 6-311++G(d,p) level basis set. The theoretical frequencies were properly scaled and compared with experimentally obtained FT-IR and FT-Raman spectra. Also, the effect due the substitution of vinyl group on the ring vibrational frequencies was analyzed and a detailed interpretation of the vibrational spectra of this compound has been made on the basis of the calculated total energy distribution (TED). The time dependent DFT (TD-DFT) method was employed to predict its electronic properties, such as electronic transitions by UV-Visible analysis, HOMO and LUMO energies, molecular electrostatic potential (MEP) and various global reactivity and selectivity descriptors (chemical hardness, chemical potential, softness, electrophilicity index). Stability of the molecule arising from hyper conjugative interaction, charge delocalization has been analyzed using natural bond orbital (NBO) analysis. Atomic charges obtained by Mulliken population analysis and NBO analysis are compared. Thermodynamic properties (heat capacity, entropy and enthalpy) of the title compound at different temperatures are also calculated. PMID:25795608

  11. Exploring the vibrational fingerprint of the electronic excitation energy via molecular dynamics

    International Nuclear Information System (INIS)

    A Fourier-based method is presented to relate changes of the molecular structure during a molecular dynamics simulation with fluctuations in the electronic excitation energy. The method implies sampling of the ground state potential energy surface. Subsequently, the power spectrum of the velocities is compared with the power spectrum of the excitation energy computed using time-dependent density functional theory. Peaks in both spectra are compared, and motions exhibiting a linear or quadratic behavior can be distinguished. The quadratically active motions are mainly responsible for the changes in the excitation energy and hence cause shifts between the dynamic and static values of the spectral property. Moreover, information about the potential energy surface of various excited states can be obtained. The procedure is illustrated with three case studies. The first electronic excitation is explored in detail and dominant vibrational motions responsible for changes in the excitation energy are identified for ethylene, biphenyl, and hexamethylbenzene. The proposed method is also extended to other low-energy excitations. Finally, the vibrational fingerprint of the excitation energy of a more complex molecule, in particular the azo dye ethyl orange in a water environment, is analyzed

  12. Nanoscale heat transport via electrons and phonons by molecular dynamics simulations

    Science.gov (United States)

    Lin, Keng-Hua

    Nanoscale heat transport has become a crucial research topic due to the growing importance of nanotechnology for manufacturing, energy conversion, medicine and electronics. Thermal transport properties at the nanoscale are distinct from the macroscopic ones since the sizes of nanoscale features, such as free surfaces and interfaces, are comparable to the wavelengths and mean free paths of the heat carriers (electrons and phonons), and lead to changes in thermal transport properties. Therefore, understanding how the nanoscale features and energy exchange between the heat carriers affect thermal transport characteristics are the goals of this research. Molecular dynamics (MD) is applied in this research to understand the details of nanoscale heat transport. The advantage of MD is that the size effect, anharmonicity, atomistic structure, and non-equilibrium behavior of the system can all be captured since the dynamics of atoms are described explicitly in MD. However, MD neglects the thermal role of electrons and therefore it is unable to describe heat transport in metal or metal-semiconductor systems accurately. To address this limitation of MD, we develop a method to simulate electronic heat transport by implementing electronic degrees of freedom to MD. In this research, nanoscale heat transport in semiconductor, metal, and metal-semiconductor systems is studied. Size effects on phonon thermal transport in SiGe superlattice thin films and nanowires are studied by MD. We find that, opposite to the macroscopic trend, superlattice thin films can achieve lower thermal conductivity than nanowires at small scales due to the change of phonon nature caused by adjusting the superlattice periodic length and specimen length. Effects of size and electron-phonon coupling rate on thermal conductivity and thermal interface resistivity in Al and model metal-semiconductor systems are studied by MD with electronic degrees of freedom. The results show that increasing the specimen length or the electron-phonon coupling rate increases the electronic contribution in thermal transport and therefore increases the thermal conductivity; moreover, the thermal interface resistivity in metal-semiconductor systems is observed to depend on the heat flux direction due to the direction-dependent energy transfer pathways between electrons and phonons at the interface. MD with electronic degrees of freedom is also applied to simulate heat transport across the metal-semiconductor interface under the non-equilibrium conditions, mimicking the ultrafast laser heating in transient thermoreflectance measurements. The effect of local and non-local electron-phonon coupling across the interface are examined, since the experimental evidence suggests that non-local electron-phonon coupling occurs under the non-equilibrium conditions. Our results show that non-local electron-phonon coupling not only facilitates energy transfer across the interface but also enhances ballistic transport of the high frequency phonon modes in a semiconductor. In summary, our study provides an insight into the details of nanoscale heat transport in various systems by MD and MD with electronic degrees of freedom.

  13. Research Update: Molecular electronics: The single-molecule switch and transistor

    Directory of Open Access Journals (Sweden)

    Kai Sotthewes

    2014-01-01

    Full Text Available In order to design and realize single-molecule devices it is essential to have a good understanding of the properties of an individual molecule. For electronic applications, the most important property of a molecule is its conductance. Here we show how a single octanethiol molecule can be connected to macroscopic leads and how the transport properties of the molecule can be measured. Based on this knowledge we have realized two single-molecule devices: a molecular switch and a molecular transistor. The switch can be opened and closed at will by carefully adjusting the separation between the electrical contacts and the voltage drop across the contacts. This single-molecular switch operates in a broad temperature range from cryogenic temperatures all the way up to room temperature. Via mechanical gating, i.e., compressing or stretching of the octanethiol molecule, by varying the contact's interspace, we are able to systematically adjust the conductance of the electrode-octanethiol-electrode junction. This two-terminal single-molecule transistor is very robust, but the amplification factor is rather limited.

  14. Research Update: Molecular electronics: The single-molecule switch and transistor

    International Nuclear Information System (INIS)

    In order to design and realize single-molecule devices it is essential to have a good understanding of the properties of an individual molecule. For electronic applications, the most important property of a molecule is its conductance. Here we show how a single octanethiol molecule can be connected to macroscopic leads and how the transport properties of the molecule can be measured. Based on this knowledge we have realized two single-molecule devices: a molecular switch and a molecular transistor. The switch can be opened and closed at will by carefully adjusting the separation between the electrical contacts and the voltage drop across the contacts. This single-molecular switch operates in a broad temperature range from cryogenic temperatures all the way up to room temperature. Via mechanical gating, i.e., compressing or stretching of the octanethiol molecule, by varying the contact's interspace, we are able to systematically adjust the conductance of the electrode-octanethiol-electrode junction. This two-terminal single-molecule transistor is very robust, but the amplification factor is rather limited

  15. Molecular modeling of polymer composite-analyte interactions in electronic nose sensors

    Science.gov (United States)

    Shevade, A. V.; Ryan, M. A.; Homer, M. L.; Manfreda, A. M.; Zhou, H.; Manatt, K. S.

    2003-01-01

    We report a molecular modeling study to investigate the polymer-carbon black (CB) composite-analyte interactions in resistive sensors. These sensors comprise the JPL electronic nose (ENose) sensing array developed for monitoring breathing air in human habitats. The polymer in the composite is modeled based on its stereoisomerism and sequence isomerism, while the CB is modeled as uncharged naphthalene rings with no hydrogens. The Dreiding 2.21 force field is used for the polymer, solvent molecules and graphite parameters are assigned to the carbon black atoms. A combination of molecular mechanics (MM) and molecular dynamics (NPT-MD and NVT-MD) techniques are used to obtain the equilibrium composite structure by inserting naphthalene rings in the polymer matrix. Polymers considered for this work include poly(4-vinylphenol), polyethylene oxide, and ethyl cellulose. Analytes studied are representative of both inorganic and organic compounds. The results are analyzed for the composite microstructure by calculating the radial distribution profiles as well as for the sensor response by predicting the interaction energies of the analytes with the composites. c2003 Elsevier Science B.V. All rights reserved.

  16. Carrier-envelope phase control of electron dynamics in atomic and molecular systems

    International Nuclear Information System (INIS)

    Complete test of publication follows. The availability of laser pulses with a duration down to about hundred attoseconds (= 10-16 seconds) has raised the prospect of studying the motion of electrons on the timescales where this motion occurs in nature and to study how electron motion drives structural dynamics in molecular systems. The type and amount of information that can be extracted from the electrons or ions that leave an atom, molecule or cluster upon irradiation with intense laser light is crucial for an understanding of the processes that led to their release and determined their final properties. Velocity-map imaging (VMI) has shown great promise for sub-femtosecond studies on complex systems, as the full 3D-momentum distribution can be extracted that contains not only spectral but also angular information. In a recent study using VMI it was shown that a suitable interference of attosecond electron wave packets generated in the continuum by ionization may yield information on the wavefunction of the system. Laser light with a controlled evolution of the electric field E(t) = a(t) · cos(?t + ?), where in addition to the amplitude a(t) and frequency ? control of the carrier-envelope phase ? is accomplished, permitted the reliable and reproducible generation of single sub-femtosecond pulses by means of high-order harmonic generation, controlled electron emission from atoms and made possible precision attosecond metrology. These achievements have been a direct consequence of the capability of steering the motion of bound electrons in atoms as well as those having been set free from their atomic bound state. Applications of VMI for the observation of the carrier-envelope phase control of electron dynamics in atomic and molecular systems will be highlighted. Results will be presented on electron emission from above-threshold ionization (ATI) of rare-gases (Xe, Ar and Kr) with phase-stabilized intense few-cycle laser pulses. In particular, the changes in the angular distributions with the laser phase will be compared to results from SFA and TDSE calculations. Control of chemical reactions or photo-biology has been achieved by using laser fields as photonic reagents, which interact with a medium in a manner that is determined by their duration, intensity, frequency, chirp, and polarization. The introduction of a stabilized carrier-envelope phase adds a new functionality to photonic reagents that can be used to control electronic motion. We have performed experiments, where the dissociation of D2+ into D+ + D was driven by intense few-cycle laser pulses with controlled field evolution and observed a pronounced dependence of the direction of the D+ ejection (and hence of the localization of the electron in the system). The possibility to steer electron localization in a molecule and control its dissociation, comprises a completely new way of coherent control that takes place on a sub-femtosecond time scale.

  17. Numerical study of electronic density of states and conductance of a molecular wire coupled with an external molecule

    Directory of Open Access Journals (Sweden)

    S. A. Ketabi

    2006-12-01

    Full Text Available   There is a great interest in the electronic properties of conjugated polymers. Numerous works on the electronic and conduction properties of single-chain conjugated polymers have been published. From an electronic conduction point of view, these systems are quasi-one dimensional. The aim of this paper is to try to investigate corresponding properties in conducting polymers in higher of one-dimension. We study the electronic properties of a polyacetylene chain connected to other molecules. The effect of the size of the molecule and the strength of the coupling to the molecular wire is investigated. The results show that with the increase of the strength of the molecular wire/molecule coupling, the band gap of the system decreases and causes high electronic conduction.

  18. Electron and nuclear dynamics of molecular clusters in ultraintense laser fields. IV. Coulomb explosion of molecular heteroclusters.

    Science.gov (United States)

    Last, Isidore; Jortner, Joshua

    2004-11-01

    In this paper we present a theoretical and computational study of the temporal dynamics and energetics of Coulomb explosion of (CD4)(n) and (CH4)(n) (n=55-4213) molecular heteroclusters in ultraintense (I=10(16)-10(19) W cm(-2)) laser fields, addressing the manifestation of electron dynamics, together with nuclear energetic and kinematic effects on the heterocluster Coulomb instability. The manifestations of the coupling between electron and nuclear dynamics were explored by molecular dynamics simulations for these heteroclusters coupled to Gaussian laser fields (pulse width tau=25 fs), elucidating outer ionization dynamics, nanoplasma screening effects (being significant for Icharges and masses. Nonuniform heterocluster Coulomb explosion (eta >1) manifests an overrun effect of the light ions relative to the heavy ions, exhibiting the expansion of two spatially separated subclusters, with the light ions forming the outer subcluster at the outer edge of the spatial distribution. Important features of the energetics of heterocluster Coulomb explosion originate from energetic triggering effects of the driving of the light ions by the heavy ions (C(4+) for I=10(17)-10(18) W cm(-2) and C(6+) for I=10(19) W cm(-2)), as well as for kinematic effects. Based on the CVI assumption, scaling laws for the cluster size (radius R(0)) dependence of the energetics of uniform Coulomb explosion of heteroclusters (eta=1) were derived, with the size dependence of the average (E(j,av)) and maximal (E(j,M)) ion energies being E(j,av)=aR(0) (2) and E(j,M)=(5a/3)R(0) (2), as well as for the ion energy distributions P(E(j)) proportional to E(j) (1/2); E(j)1) result in an isotope effect, predicting the enhancement (by 9%-11%) of E(H,av) for Coulomb explosion of (C(4+)H(4) (+))(eta) (eta=3) relative to E(D,av) for Coulomb explosion of (C(4+)D(4) (+))(eta) (eta=1.5), with the isotope effect being determined by the ratio of the kinematic parameters for the pair of Coulomb exploding clusters. Kinematic effects for nonuniform explosion also result in a narrow isotope dependent energy distribution (of width DeltaE) of the light ions (with DeltaE/E(H,av) approximately 0.3 and DeltaE/E(D,av) approximately 0.4), with the distribution peaking at the high energy edge, in marked contrast with the uniform explosion case. Features of laser-heterocluster interactions were inferred from the analyses of the intensity dependent boundary radii (R(0))(I) and the corresponding average D+ ion energies (E(D,av))(I), which provide a measure for optimization of the cluster size at intensity I for the neutron yield from dd nuclear fusion driven by Coulomb explosion (NFDCE) of these heteroclusters. We infer on the advantage of deuterium containing heteronuclear clusters, e.g., (CD4)(n) in comparison to homonuclear clusters, e.g., (D2)(n/2), for dd NFDCE, where the highly charged heavy ions (e.g., C4+ or C6+) serve as energetic and kinematic triggers driving the D+ ions to a high (10-200 keV) energy domain. PMID:15511153

  19. High harmonic spectroscopy of electron localization in the hydrogen molecular ion

    International Nuclear Information System (INIS)

    Interaction of a laser pulse with a centrally symmetric medium, such as an isotropic gas of atoms, leads to the generation of harmonic emission which contains exclusively odd harmonics of the incident field. This result is the consequence of both the central symmetry of the medium and the temporal symmetry of the oscillating electric field, E(t+?/?l)=?E(t), where ?l is the laser frequency. In the case of oriented heteronuclear molecules, the spatial symmetry no longer holds and both odd and even harmonics become allowed. Here we show, by solving the time-dependent Schrödinger equation for H2+, D2+, and T2+, that even-order harmonic generation is also possible for sufficiently long infrared (IR) laser pulses in homonuclear molecules. The appearance of even harmonics is a signature of the coupled electron-nuclear dynamics and reflects field-induced electron localization initiated by the strong laser field, which breaks the spatial symmetry in the system. The analysis of even harmonics generated by pulses of different durations might therefore provide information on correlated electron-nuclear dynamics and charge migration in more complex un-oriented molecular ensembles. (paper)

  20. Geometric and electronic factors in the rational design of transition-metal-centered boron molecular wheels.

    Science.gov (United States)

    Romanescu, Constantin; Galeev, Timur R; Li, Wei-Li; Boldyrev, Alexander I; Wang, Lai-Sheng

    2013-04-01

    The effects of the electronic and geometric factors on the global minimum structures of MB9(-) (M = V, Nb, Ta) are investigated using photoelectron spectroscopy and ab initio calculations. Photoelectron spectra are obtained for MB9(-) at two photon energies, and similar spectral features are observed for all three species. The structures for all clusters are established by global minima searches and confirmed by comparison of calculated and experimental vertical electron detachment energies. The VB9(-) cluster is shown to have a planar C2v V©B9(-) structure, whereas both NbB9(-) and TaB9(-) are shown to have Cs M©B9(-) type structures with the central metal atom slightly out of plane. Theoretical calculations suggest that the V atom fits perfectly inside the B9 ring forming a planar D(9h) V©B9(2-) structure, while the lower symmetry of V©B9(-) is due to the Jahn-Teller effect. The Nb and Ta atoms are too large to fit in the B9 ring, and they are squeezed out of the plane slightly even in the M©B9(2-) dianions. Thus, even though all three M©B9(2-) dianions fulfill the electronic design principle for the doubly aromatic molecular wheels, the geometric effect lowers the symmetry of the Nb and Ta clusters. PMID:23574235

  1. The Development of Molecular-Based Materials for Electrical and Electronic Applications

    Science.gov (United States)

    Babalola, P. O.; Inegbenebor, A. O.; Bolu, C. A.; Inegbenebor, A. I.

    2015-04-01

    Aluminum silicon carbide (AlSiC) metal matrix composite materials have a unique set of material properties that are ideally suited for electronics, hence the development of molecular-based materials (MBM) for the electrical and electronic industries. The low material density of AlSiC (3 g/cm3) makes it ideal for weight-sensitive applications such as portable devices over traditional thermal management materials like copper molybdenum (10 g/cm3) and copper tungsten (16 g/cm3). The aim of this work is to develop MBM for electrical and electronic industries. Aluminum (99.66% C.P.) and silicon carbide (SiC) particulates of 240 grit (45 µm), 320 grit (29 µm), 600 grit (9 µm) and 1200 grit (3 µm) at 2.5% weight fraction were used to achieve the objective. The aluminum was melted at 750°C for 25 min in a graphite crucible tilting furnace designed for this work using oil as a firing medium. After melting, a two-step mixing method of stir casting technique was adopted. The cast samples were further analyzed for mechanical and electrical properties. The electrical properties were carried out by using a 4-point probe machine. The result showed that hardness increases at lower grit level, while the electrical properties marginally increased at higher grit. It is therefore recommended that, to make AlSiC composite materials for electrical industries, the higher grit of SiC should be preferred.

  2. Stopping power for hydrogen molecular ions in solids: Influence of the inner-shell electrons of target atoms

    International Nuclear Information System (INIS)

    We present calculations of the electronic stopping power for hydrogen molecular ions H2+ in solids. These calculations include contributions from both valence electrons and inner-shell electrons of target atoms with the linear dielectric theory and the local-density approximation method. The screened Coulomb potential is used to describe the repulsion process of the two protons. The values of the stopping-power ratio Q for H2+ at the high velocities are decreased, obviously due to the contributions of the inner-shell electrons. The theoretical results are compared with some experimental data

  3. Molecular double slit and Young-type electron interference in ionization

    International Nuclear Information System (INIS)

    We provide a brief review of the electron spectroscopic investigation of fast ion-atom collision. Particularly we focus on the investigation of the collisions involving homo-nuclear diatomic molecules. It has been demonstrated that coherent electron emission from the two identical atomic centers can be visualized as a emission from a molecular double slit. The fast charged particle impact ionization and double differential electron emission spectrum then can be used not only to explore more about the ionization mechanisms but also the Young type electron interference. Although such a mechanism was predicted earlier, by Cohen and Fano in 1966, but it took about 40 years to have a clear experimental confirmation. Since then it has been an active field of research worldwide. The fast ion beams from Pelletron accelerator, with velocity about 10% of velocity of light, and the slower ions at intermediate velocity obtained from an ECR based ion-accelerator at TIFR are used for some of these studies. The brief overview includes mainly our experimental results over last several years on the derivation of the interference induced oscillations in the electron spectrum. The use of forward backward asymmetry in electron emission spectrum is an innovative and unambiguous way to study the interference. In addition, the double frequency component of the oscillation is also observed and has been explained in terms of a double scattering mechanism i.e. including the second order effect in the Born series for scattering amplitude. Clear differences in the results for and those for O2 and N2 are explained in terms of ab-initio theoretical models based on the linear combination of atomic orbitals for the target and the distortion of the initial and final states due to the moving Coulomb field of highly charged projectiles. The comparison between fast heavy ions and fast electrons as projectiles are also investigated regarding the structure of the interference oscillations. This is mainly a brief review of our own contribution in this field of research. The work of other international groups are also referred to some extent. (author)

  4. Excitation and charge transfer in He/sup +/ + H collisions. A molecular approach including two-electron translation factors

    Energy Technology Data Exchange (ETDEWEB)

    Errea, L.F.; Mendez, L.; Riera, A.

    1983-06-01

    In a previous paper we have pointed out that the common-translation-factor (CTF) method is the only one which, at present, and within the framework of the molecular model of atomic collisions, can be shown to be both convergent and computationally fast, even for many-electron systems. In this Communication we check that this second statement is correct, presenting, for the first time, a molecular calculation involving two-electron translation factors, for He/sup +/ + H collisions. A careful study of the sensitivity of the calculated cross sections to the choice of the CTF is performed, and conclusions on that sensitivity are drawn, for several types of processes.

  5. Exploring the Tilt-Angle Dependence of electron tunneling across Molecular junction of Self-Assembled Alkanethiols

    DEFF Research Database (Denmark)

    Frederiksen, Thomas; Munuera, C.

    2009-01-01

    Electronic transport mechanisms in molecular junctions are investigated by a combination of first-principles calculations and current?voltage measurements of several well-characterized structures. We study self-assembled layers of alkanethiols grown on Au(111) and form tunnel junctions by contacting the molecular layers with the tip of a conductive force microscope. Measurements done under low-load conditions permit us to obtain reliable tilt-angle and molecular length dependencies of the low-bias conductance through the alkanethiol layers. The observed dependence on tilt-angle is stronger for the longer molecular chains. Our calculations confirm the observed trends and explain them as a result of two mechanisms, namely, a previously proposed intermolecular tunneling enhancement as well as a hitherto overlooked tilt-dependent molecular gate effect.

  6. Changes of molecular mass of humus acids and their systems of polyconjugation upon peat modification by flow of fast electrons

    International Nuclear Information System (INIS)

    It has been studied that while treating peat humus acids in a moist state with the flow of electrons one can observe along with an absorbed dose an increase of averaged molecular masses, high-molecular fractions share, decrease of low-molecular constituent share and insignificant reduction of samples poly-dispersion ability, thus testifying to the polymerization process run. By the ESR-spectroscopy method it has been shown that peat humus acid radiation modification is accompanied by the formation of new structures of polyconjugation (authors)

  7. Depth-Assisted Rectification of Patches Using RGB-D Consumer Devices to Improve Real-Time Keypoint Matching

    OpenAIRE

    Lima, Joa?o Paulo; Simoes, Francisco; Uchiyama, Hideaki; Teichrieb, Veronica; Marchand, Eric

    2013-01-01

    This paper presents a method named Depth-Assisted Rectification of Patches (DARP), which exploits depth information available in RGB-D consumer devices to improve keypoint matching of perspectively distorted images. This is achieved by generating a projective rectification of a patch around the keypoint, which is normalized with respect to perspective distortions and scale. The DARP method runs in real-time and can be used with any local feature detector and descriptor. Evaluations with plana...

  8. Coupling of electrons to intermolecular phonons in molecular charge transfer dimers: A resonance Raman study

    Science.gov (United States)

    Pedron, D.; Speghini, A.; Mulloni, V.; Bozio, R.

    1995-08-01

    We report resonance Raman scattering (RRS) spectra and Raman excitation profiles (REP) of a system containing ? dimers of identical molecular radical ions measured with laser excitation in resonance with the charge transfer (CT) transition. A Peierls-Hubbard (PH) Hamiltonian has been used to model the investigated system and to calculate its optical and RRS properties. Results are reported for two polyoxometallate salts of tetrathiafulvalene (TTF), namely (TTF)2(W6O19) and (TTF)2(Mo6O19) whose structures contain almost isolated (TTF+)2 dimers. The RRS spectra of (TTF)2(W6O19), measured in resonance with the CT absorption band centered at 832 nm, show three phonon modes located at 55, 90, and 116 cm-1 which are strongly resonance enhanced. These modes have been associated to the out-of-phase combinations of the translational motions of the two molecules composing the dimer. Such modes are effective in modulating the intradimer transfer integral, thus providing an efficient mechanism for coupling with the electronic system and for enhancement of the scattering intensity at resonance with the CT transition. The REP for the three strongly coupled modes of (TTF)2(W6O19) have been measured with laser excitation wavelengths ranging from 740 to 930 nm. Quantitative analysis of the REP data has been performed based on a perturbative solution of the PH model to second order in the electron-molecular-vibration (EMV) and electron-intermolecular-phonon (EIP) interactions. The CT absorption profile and the REP's have been calculated using a time correlator technique and the model parameters have been optimized in order to fit the experimental REP data. Infrared vibronic absorptions of (TTF)2(W6O19), originated by the EMV coupling, have been measured and independent information on the electronic parameters of the PH model have been derived. This has made the choice of the fitting parameters used for the REP calculations rather unambiguous and has allowed us to obtain, for the first time, reliable experimental estimates of the EIP coupling constants.

  9. A quasi-classical mapping approach to vibrationally coupled electron transport in molecular junctions

    Energy Technology Data Exchange (ETDEWEB)

    Li, Bin; Miller, William H. [Department of Chemistry and Kenneth S. Pitzer Center for Theoretical Chemistry, University of California, and Chemical Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720 (United States); Wilner, Eli Y. [School of Physics and Astronomy, The Sackler Faculty of Exact Sciences, Tel Aviv University, Tel Aviv 69978 (Israel); Thoss, Michael [Institute for Theoretical Physics and Interdisciplinary Center for Molecular Materials, Friedrich-Alexander-Universität Erlangen-Nürnberg, Staudtstr. 7/B2, 91058 Erlangen (Germany); Rabani, Eran [School of Chemistry, The Sackler Faculty of Exact Sciences, Tel Aviv University, Tel Aviv 69978 (Israel)

    2014-03-14

    We develop a classical mapping approach suitable to describe vibrationally coupled charge transport in molecular junctions based on the Cartesian mapping for many-electron systems [B. Li and W. H. Miller, J. Chem. Phys. 137, 154107 (2012)]. To properly describe vibrational quantum effects in the transport characteristics, we introduce a simple transformation rewriting the Hamiltonian in terms of occupation numbers and use a binning function to facilitate quantization. The approach provides accurate results for the nonequilibrium Holstein model for a range of bias voltages, vibrational frequencies, and temperatures. It also captures the hallmarks of vibrational quantum effects apparent in step-like structure in the current-voltage characteristics at low temperatures as well as the phenomenon of Franck-Condon blockade.

  10. Exploring nuclear pore complex molecular architecture by immuno-electron microscopy using Xenopus oocytes.

    Science.gov (United States)

    Panté, Nelly; Fahrenkrog, Birthe

    2014-01-01

    Xenopus oocytes are large in size and perfectly suited for microinjection experiments. Their nuclei, which can be readily isolated manually, are characterized by an extremely high density of nuclear pore complexes (NPCs). Therefore, Xenopus oocytes are an excellent system to study NPC structure and molecular architecture, as well as nucleocytoplasmic transport on an ultrastructural level. A wide range of electron microscopy (EM) techniques can be employed to do so and thin-sectioning immuno-EM has been proven to be a powerful tool in this context. NPCs are composed of multiple copies of a set of about 30 different nucleoporins, which are often large, multidomain proteins. Their complex organization within NPCs can be unraveled by using domain-specific antibodies to individual nucleoporins in combination with microinjection and expression of epitope-tagged nucleoporins. Here, we describe the immuno-EM methods using Xenopus oocyte that allow for precise ultrastructural localization of nucleoporins within the structure of the NPC. PMID:24857726

  11. Molecular Dynamics Simulations of Electron-Ion Temperature Equilibration in an SF6 Plasma

    International Nuclear Information System (INIS)

    We use classical molecular dynamics to investigate electron-ion temperature equilibration in a two-temperature SF6 plasma. We choose a density of 1.0x1019SF6 molecules per cm3 and initial temperatures of Te=100 eV and TS=TF=15 eV, in accordance with experiments currently underway at Los Alamos National Laboratory. Our computed relaxation time lies between two oft-used variants of the Landau-Spitzer relaxation formula which invoke static screening. Discrepancies are also found when comparing to the predictions made by more recent theoretical approaches. These differences should be large enough to be measured in the upcoming experiments.

  12. Fabrication of a Few-Layer Graphene Electrodes for Molecular Electronics Devices

    Directory of Open Access Journals (Sweden)

    Holovchenko A.

    2014-08-01

    Full Text Available We report on thefabrication of a molecular transistor based on a single molecule trapped in a few-layergraphene nanogap. The device is pre-patterned with He-ion beam milling oroxygen plasma etching prior to nanogap formation. Pre-patterning helps tolocalize the gap, and to make it narrower, so that only a few or a singlemolecule can be trapped in it. The nanogap is formed by an electroburning techniqueat room temperature. In order to test the functionality of the device wedeposited diamino-terphenyl molecules in the nanogap. Three-terminal electricalmeasurements showed an increase of the current after deposition, and a gatevoltage dependence at low temperatures. Hence, pre-patterned few-layer graphenejunctions can be used for electron transport measurements through a terphenylmolecule with a future prospective towards more complex molecularconfigurations.

  13. Density functional theory study on LBDOB and its derivatives: Electronic structures, energies, and molecular properties

    International Nuclear Information System (INIS)

    Theoretical studies on unsymmetrical electrolyte salts, lithium [1,2-benzenediolato(2-)-O,O' oxalato]borate (LBDOB), and its derivatives, lithium bis[1,2-benzenediolato(2-)-O,O']borate (LBBB), and lithium bis(oxalate)borate (LBOB) are carried out using density functional theory (DFT) method and B3LYP theory level. Bidentate structures involving two oxygen atoms are preferred. Based on these conformations, a linear correlation was observed between the highest occupied molecular orbital (HOMO) energies and the limiting oxidation potentials measured by linear sweep voltammetry, which supports experimental results that strongly electron-withdrawing substituent anions are more resistant against oxidation. The correlations were also observed between ionic conductivity and binding energy solubility and theoretical set of parameters of anion, thermal stability and the hardness (?). Wave function analyses have been performed by natural bond orbital (NBO) method to further investigate the cation-anion interactions.

  14. Electronic structures and molecular properties of FLBDOB and its derivatives: A combined experimental and theoretical study

    International Nuclear Information System (INIS)

    Theoretical studies on a new unsymmetrical electrolyte salt, lithium [3-fluoro-1,2-benzenediolato(2-)-o,o' oxalato]borate (FLBDOB), and its derivatives, lithium bis[3-fluoro-1,2-benzenediolato(2-)-o,o]borate (FLBBB), and lithium bis(oxalate)borate (LBOB) are carried out using density functional theory (DFT) method and B3LYP theory level. Bidentate structures involving two oxygen atoms are preferred. Based on these conformations, a linear correlation is observed between the highest occupied molecular orbital (HOMO) energies and the limiting oxidation potentials measured by linear sweep voltammetry, which supports experimental results that strongly electron-withdrawing substituent anions are more resistant against oxidation. The correlations are also observed between ionic conductivity and binding energy, solubility and theoretical set of parameters of anion, thermal stability and the hardness (?). Wave function analyses are performed by natural bond orbital (NBO) method to further investigate the cation-anion interactions.

  15. Electron-molecular mechanism underlying an increase of photo-sensitivity of CdSe films

    International Nuclear Information System (INIS)

    Mechanism underlying an increase of photosensitivity of cadmium selenide films and explaining ? growth due to electron-molecular processes on their surface, taking place during oxygen chemisorption (?=Iph/Id (Iph - photocurrent, Id - dark current), is presented. Oxygen effect on photoconductivity of CdSe type semiconductor was analyzed with regard to the relationship between adsorption center and the form of oxygen chemisorption. The analysis enables to explain semiconductor sensitization and desensitization using the unified model, including both composite effects (redistribution of recombination flows among r- and s-centers owing to the change of surface potential barrier) and local oxygen interaction with adsorption center (change of composition of the basic donor-acceptor complex)

  16. A micro seismometer based on molecular electronic transducer technology for planetary exploration

    International Nuclear Information System (INIS)

    This letter describes an implementation of micromachined seismometer based on molecular electronic transducer (MET) technology. As opposed to a solid inertial mass, MET seismometer senses the movement of liquid electrolyte relative to fixed electrodes. The employment of micro-electro-mechanical systems techniques reduces the internal size of the sensing cell to 1?m and improves the reproducibility of the device. For operating bias of 600 mV, a sensitivity of 809 V/(m/s2) was measured under acceleration of 400?g(g?9.81m/s2) at 0.32 Hz. A ?115 dB (relative to (m/s2)/?(Hz)) noise level at 1 Hz was achieved. This work develops an alternative paradigm of seismic sensing device with small size, high sensitivity, low noise floor, high shock tolerance, and independence of installation angle, which is promising for next generation seismometers for planetary exploration.

  17. Hydrostatic pressure and temperature effects on nonlinear optical rectification in a lens shape InAs/GaAs quantum dot

    International Nuclear Information System (INIS)

    We have performed theoretical calculation of the nonlinear optical rectification in a lens shape InAs/GaAs quantum dot (0D). The combined effects of hydrostatic pressure and temperature on the nonlinear optical rectification in lens-shaped InAs QDs are studied under the compact density matrix formalism and the effective mass approximation. From our calculation, it is found that the subband energies and optical rectification susceptibility are quite sensitive to the applied hydrostatic pressure and temperature. The results show that the resonant peak of the optical rectification can be red-shifted or blue-shifted and their intensity also varied by external probes such as hydrostatic pressure and temperature. In addition, the oscillator strength is strongly affected by these parameters. - Highlights: ? Theoretical calculation of the nonlinear optical rectification in a lens shape InAs/GaAs quantum dot was performed. ? Optical rectification susceptibility is quite sensitive to the applied hydrostatic pressure and temperature. ? The oscillator strength is strongly affected by the applied hydrostatic pressure and temperature.

  18. The reorganization energy of electron transfer in nonpolar solvents: Molecular level treatment of the solvent

    International Nuclear Information System (INIS)

    The intermolecular electron transfer in a solute pair consisting of pyrene and dimethylaniline is investigated in a nonpolar solvent, n-hexane. The earlier elaborated approach [M. Tachiya, J. Phys Chem. 97, 5911 (1993)] is used; this method provides a physically relevant background for separating inertial and inertialess polarization responses for both nonpolarizable and polarizable molecular level simulations. The molecular-dynamics technique was implemented for obtaining the equilibrium ensemble of solvent configurations. The nonpolar solvent, n-hexane, was treated in terms of OPLS-AA parametrization. Solute Lennard-Jones parameters were taken from the same parametrization. Solute charge distributions of the initial and final states were determined using ab initio level [HF/6-31G(d,p)] quantum-chemical calculations. Configuration analysis was performed explicitly taking into account the anisotropic polarizability of n-hexane. It is shown that the Gaussian law well describes calculated distribution functions of the solvent coordinate, therefore, the rate constant of the ET reaction can be characterized by the reorganization energy. Evaluated values of the reorganization energies are in a range of 0.03-0.11 eV and significant contribution (more then 40% of magnitude) comes from anisotropic polarizability. Investigation of the reorganization energy ? dependence on the solute pair separation distance d revealed unexpected behavior. The dependence has a very sharp peak or. The dependence has a very sharp peak at the distance d=7 A where solvent molecules are able to penetrate into the intermediate space between the solute pair. The reason for such behavior is clarified. This new effect has a purely molecular origin and cannot be described within conventional continuum solvent models

  19. A comprehensive study of extended tetrathiafulvalene cruciform molecules for molecular electronics: synthesis and electrical transport measurements.

    Science.gov (United States)

    Parker, Christian R; Leary, Edmund; Frisenda, Riccardo; Wei, Zhongming; Jennum, Karsten S; Glibstrup, Emil; Abrahamsen, Peter Bæch; Santella, Marco; Christensen, Mikkel A; Della Pia, Eduardo Antonio; Li, Tao; Gonzalez, Maria Teresa; Jiang, Xingbin; Morsing, Thorbjørn J; Rubio-Bollinger, Gabino; Laursen, Bo W; Nørgaard, Kasper; van der Zant, Herre; Agrait, Nicolas; Nielsen, Mogens Brøndsted

    2014-11-26

    Cruciform-like molecules with two orthogonally placed ?-conjugated systems have in recent years attracted significant interest for their potential use as molecular wires in molecular electronics. Here we present synthetic protocols for a large selection of cruciform molecules based on oligo(phenyleneethynylene) (OPE) and tetrathiafulvalene (TTF) scaffolds, end-capped with acetyl-protected thiolates as electrode anchoring groups. The molecules were subjected to a comprehensive study of their conducting properties as well as their photophysical and electrochemical properties in solution. The complex nature of the molecules and their possible binding in different configurations in junctions called for different techniques of conductance measurements: (1) conducting-probe atomic force microscopy (CP-AFM) measurements on self-assembled monolayers (SAMs), (2) mechanically controlled break-junction (MCBJ) measurements, and (3) scanning tunneling microscopy break-junction (STM-BJ) measurements. The CP-AFM measurements showed structure-property relationships from SAMs of series of OPE3 and OPE5 cruciform molecules; the conductance of the SAM increased with the number of dithiafulvene (DTF) units (0, 1, 2) along the wire, and it increased when substituting two arylethynyl end groups of the OPE3 backbone with two DTF units. The MCBJ and STM-BJ studies on single molecules both showed that DTFs decreased the junction formation probability, but, in contrast, no significant influence on the single-molecule conductance was observed. We suggest that the origins of the difference between SAM and single-molecule measurements lie in the nature of the molecule-electrode interface as well as in effects arising from molecular packing in the SAMs. This comprehensive study shows that for complex molecules care should be taken when directly comparing single-molecule measurements and measurements of SAMs and solid-state devices thereof. PMID:25375316

  20. Non-adiabatic quantum molecular dynamics: ionization of many-electron systems

    Energy Technology Data Exchange (ETDEWEB)

    Uhlmann, Mathias; Kunert, Thomas; Schmidt, Ruediger [Institut fuer Theoretische Physik, Technische Universitaet Dresden, D-01062 Dresden (Germany)

    2006-07-28

    We propose a novel method to describe realistically ionization processes with absorbing boundary conditions in basis expansion within the formalism of so-called non-adiabatic quantum molecular dynamics. This theory couples self-consistently a classical description of the nuclei with a quantum-mechanical treatment of the electrons in atomic many-body systems. In this paper, we extend the formalism by introducing absorbing boundary conditions via an imaginary potential. It is shown how this potential can be constructed in time-dependent density functional theory in basis expansion. The approach is first tested on the hydrogen atom and the pre-aligned hydrogen molecular ion H{sub 2}{sup +} in intense laser fields where reference calculations are available. It is then applied to study the ionization of non-aligned H{sub 2}{sup +} and H{sub 2}. Striking differences in the orientation dependence between both molecules are found. Surprisingly, enhanced ionization is predicted for perpendicularly aligned molecules.

  1. Advances in the MQDT approach of electron/molecular cation reactive collisions: High precision extensive calculations for applications

    Directory of Open Access Journals (Sweden)

    Motapon O.

    2015-01-01

    Full Text Available Recent advances in the stepwise multichannel quantum defect theory approach of electron/molecular cation reactive collisions have been applied to perform computations of cross sections and rate coefficients for dissociative recombination and electron-impact ro-vibrational transitions of H2+, BeH+ and their deuterated isotopomers. At very low energy, rovibronic interactions play a significant role in the dynamics, whereas at high energy, the dissociative excitation strongly competes with all other reactive processes.

  2. Seebeck rectification enabled by intrinsic thermoelectrical coupling in magnetic tunneling junctions.

    Science.gov (United States)

    Zhang, Z H; Gui, Y S; Fu, L; Fan, X L; Cao, J W; Xue, D S; Freitas, P P; Houssameddine, D; Hemour, S; Wu, K; Hu, C-M

    2012-07-20

    An intrinsic thermoelectric coupling effect in the linear response regime of magnetic tunneling junctions (MTJ) is reported. In the dc response, it leads to a nonlinear correction to Ohm's law. Dynamically, it enables a novel Seebeck rectification and second harmonic generation, which apply for a broad frequency range and can be magnetically controlled. A phenomenological model on the footing of the Onsager reciprocal relation and the principle of energy conservation explains very well the experimental results obtained from both dc and frequency-dependent transport measurements performed up to GHz frequencies. Our work refines previous understanding of magnetotransport and microwave rectification in MTJs. It forms a new foundation for utilizing spin caloritronics in high-frequency applications. PMID:22861893

  3. Theoretical analysis of thermal rectification in a bulk Si/nanoporous Si device

    International Nuclear Information System (INIS)

    We present a theoretical analysis of thermal rectification in a porous Si/bulk Si device, taking into account ballistic effects in phonon-pore collisions when phonon mean free path is much longer than the radius of the pores. Starting from an approximate analytical expression for the effective thermal conductivity of porous Si, we obtain the thermal rectifying coefficient of the device as a function of porosity, pore size, temperature interval, and relative lengths of porous and bulk samples. -- Highlights: ? Heat conductivity of porous Si depends on the pore size. ? Thermal rectification for nanoporous Si/bulk Si is predicted. ? Thermal rectifying coefficient is calculated. ? It is shown to be comparable or higher to that of systems previously considered.

  4. Extremely low-loss rectification methodology for low-power vibration energy harvesters

    Science.gov (United States)

    Tiwari, R.; Ryoo, K.; Schlichting, A.; Garcia, E.

    2013-06-01

    Because of its promise for the generation of wireless systems, energy harvesting technology using smart materials is the focus of significant reported effort. Various techniques and methodologies for increasing power extraction have been tested. One of the key issues with the existing techniques is the use of diodes in the harvesting circuits with a typical voltage drop of 0.7 V. Since most of the smart materials, and other transducers, do not produce large voltage outputs, this voltage drop becomes significant in most applications. Hence, there is a need for designing a rectification method that can convert AC to DC with minimal losses. This paper describes a new mechanical rectification scheme, designed using reed switches, in a full-bridge configuration that shows the capability of working with signals from millivolts to a few hundred volts with extremely low losses. The methodology has been tested for piezoelectric energy harvesters undergoing mechanical excitation.

  5. Rectification of DNA films self-assembled in the presence of electric field

    Science.gov (United States)

    Chan, Zhijian; Ahgilan, Aarthi; Sabaratnam, Vikineswary; Tan, Yee Shin; Periasamy, Vengadesh

    2015-04-01

    We report rectification phenomena in electric field induced self-assembled thin films of DNA that were employed in the development of an ITO/DNA/Al sensor. The prototype sensor was subjected to electrical characterization involving the acquisition of current–voltage graphs. Electric field aligned DNA films exhibited reduced potential barrier of 0.780 eV while the potential barrier for non-aligned films was 0.796 eV. Similar reduction was also observed for the measured ideality factor and series resistance. This enhanced rectification following electric field induced self-assembly of DNA films may prove beneficial for generating accurate and rapid response in DNA-based devices.

  6. Synthesis and Studies of Sulfur-Containing Heterocyclic Molecules for Molecular Electronics

    DEFF Research Database (Denmark)

    Mazzanti, Virginia

    2014-01-01

    This work describes the synthesis and studies of sulfur containing ? conjugated heterocycles, which are considered interesting motifs in the field of molecular electronics. The first project, which is covered in Chapter 1, concerns the functionalization of tetracycle dibenzo[bc,fg][1,4]dithiapentalene (DDP). Attempts to prepare the S-O analog are also discussed. Chapter 2, focuses upon the studies performed on DDP and other sulfur containing ? conjugated organic molecules. Organic Field Effect Transistor devices were fabricated and their performances were evaluated. Chapter 3 entails the synthesis of dimeric structures of redox active system tetrathiafulvalene (TTF). Molecules with different conjugation pathways bridging two TTFs were synthesized and studied using CV and DPV in order to probe the electronic interaction between these two redox units. The last aspect of this thesis, which is presented in Chapter 4, deals with the incorporation of two TTF units into acetylenic scaffolds to generate greater redox active cyclic systems. Improvements of a previously reported macrocycle synthesis and development of asymmetric macrocyclic systems incorporating two TTF moieties were achieved. The instability issue of synthetic intermediates bearing free acetylenes was overcome employing a new strategy. This involved the end–capping of the acetylenic functionality with triphenylphosphine gold motif producing stable organometallic complexes, which could be subsequently used in Sonogashira cross coupling reactions to construct such macrocycles.

  7. First principles study on the electronic transport properties of C60 and B80 molecular bridges

    Science.gov (United States)

    Zheng, X. H.; Hao, H.; Lan, J.; Wang, X. L.; Shi, X. Q.; Zeng, Z.

    2014-08-01

    The electronic transport properties of molecular bridges constructed by C60 and B80 molecules which have the same symmetry are investigated by first principles calculations combined with a non-equilibrium Green's function technique. It is found that, like C60, monomer B80 is a good conductor arising from the charge transfer from the leads to the molecule, while the dimer (B80)2 and (C60)2 are both insulators due to the potential barrier formed at the molecule-molecule interface. Our further study shows that, although both the homogeneous dimer (B80)2 and (C60)2 display poor conductivity, the heterogeneous dimer B80C60 shows a very high conductance as a result from the decreased HOMO-LUMO gap and the excess charge redistribution. Finally, we find that the conductivity of both (B80)2 and (C60)2 can be significantly improved by electron doping, for example, by doping C in (B80)2 and doping N in (C60)2.

  8. Fullerene-based anchoring groups for molecular electronics: insights from theory

    Science.gov (United States)

    Bagrets, Alexei; Seiler, Christian; Meded, Velimir; Evers, Ferdinand

    2010-03-01

    Recent experiments [1] have explored the idea of using C60 as anchoring groups to increase the stability of single molecule junctions. To further explore this concept, we have performed elaborated electronic structure calculations based on the density functional theory. First, the influence of dispersive interactions on the location of C60 with respect to the electrode surface is carefully investigated. Second, the transmission of C60 and BDC60 [=1,4-bis(fullero[c]pyrrolidin-1-yl)benzene] junctions is obtained. We find that a mismatch of the chemical potential of Au electrodes and frontier molecular orbitals of C60 generates a tunneling barrier. As a consequence, BDC60 acts as a sequence of three weakly coupled quantum dots. Specifically, the small conductance values (˜10-3 -- 10-4 G0) observed experimentally [1], arise from the small broadening of the HOMO level of the inner molecule capped by C60 moieties. Third, electrode materials with a smaller work function (e.g. Ag instead of Au) are discussed, which might provide better matching to C60 and therefore establish more favorable conditions for electron transfer. [1] C.A. Martin, D. Ding, J.K. Sørensen, T. Bjørnholm, J. van Ruitenbeek, H.S.J. van der Zant, JACS 130, 13198-13199 (2008).

  9. Quinazolin-4-yl-sulfanylacetyl-hydrazone derivatives; Synthesis, molecular structure and electronic properties

    Science.gov (United States)

    Hagar, Mohamed; Soliman, Saied M.; Ibid, Farahate; El Ashry, El Sayed H.

    2013-10-01

    Four new acetylhydrazone derivatives of quinazoline have been synthesized and characterized. The molecular structures and relative stabilities of four possible isomers for each acetylhydrazone are calculated using DFT/B3LYP/6-31G(d,p) method. The calculations results predicted higher stability of the E-isomers compared to the Z-isomers in the gas phase. The syn-E isomer is the predominant form in gaseous phase for all the studied hydrazones except for the hydrazone derived from salicylaldehyde where the anti-E is the most stable isomer. The latter is stabilized by two strong intramolecular H-bonds instead of one in the others. The electronic and spectroscopic properties of the most stable isomers were also calculated using the same level of theory. The calculated atomic polar tensor (APT) charges indicated an increase of the positive charge density at the H-sites involved in the H-bonding interactions. The HOMO and LUMO energies are negative indicating that the compounds under investigation are stable. The electronic transition from the ground state to the excited state belongs to ?-?* transition. The calculated vibrational spectra showed strong red shifts and increase in the vibrational intensity of the Nsbnd H and Osbnd H stretching modes due to the intramolecular H-bonding interactions. In DMSO solution, the NMR spectra of the studied hydrazones revealed that such polar solvents stabilize the syn isomers for all the studied hydrazones except for the hydrazone derived from salicylaldehyde where the anti isomer is the major.

  10. EDF: Computing electron number probability distribution functions in real space from molecular wave functions

    Science.gov (United States)

    Francisco, E.; Pendás, A. Martín; Blanco, M. A.

    2008-04-01

    Given an N-electron molecule and an exhaustive partition of the real space ( R) into m arbitrary regions ?,?,…,? ( ?i=1m?=R), the edf program computes all the probabilities P(n,n,…,n) of having exactly n electrons in ?, n electrons in ?,…, and n electrons ( n+n+⋯+n=N) in ?. Each ? may correspond to a single basin (atomic domain) or several such basins (functional group). In the later case, each atomic domain must belong to a single ?. The program can manage both single- and multi-determinant wave functions which are read in from an aimpac-like wave function description ( .wfn) file (T.A. Keith et al., The AIMPAC95 programs, http://www.chemistry.mcmaster.ca/aimpac, 1995). For multi-determinantal wave functions a generalization of the original .wfn file has been introduced. The new format is completely backwards compatible, adding to the previous structure a description of the configuration interaction (CI) coefficients and the determinants of correlated wave functions. Besides the .wfn file, edf only needs the overlap integrals over all the atomic domains between the molecular orbitals (MO). After the P(n,n,…,n) probabilities are computed, edf obtains from them several magnitudes relevant to chemical bonding theory, such as average electronic populations and localization/delocalization indices. Regarding spin, edf may be used in two ways: with or without a splitting of the P(n,n,…,n) probabilities into ? and ? spin components. Program summaryProgram title: edf Catalogue identifier: AEAJ_v1_0 Program summary URL:http://cpc.cs.qub.ac.uk/summaries/AEAJ_v1_0.html Program obtainable from: CPC Program Library, Queen's University, Belfast, N. Ireland Licensing provisions: Standard CPC licence, http://cpc.cs.qub.ac.uk/licence/licence.html No. of lines in distributed program, including test data, etc.: 5387 No. of bytes in distributed program, including test data, etc.: 52 381 Distribution format: tar.gz Programming language: Fortran 77 Computer: 2.80 GHz Intel Pentium IV CPU Operating system: GNU/Linux RAM: 55 992 KB Word size: 32 bits Classification: 2.7 External routines: Netlib Nature of problem: Let us have an N-electron molecule and define an exhaustive partition of the physical space into m three-dimensional regions. The edf program computes the probabilities P(n,n,…,n)?P({n}) of all possible allocations of n electrons to ?, n electrons to ?,…, and n electrons to ?,{n} being integers. Solution method: Let us assume that the N-electron molecular wave function, ?(1,N), is a linear combination of M Slater determinants, ?(1,N)=?rMC?(1,N). Calling S?rs the overlap matrix over the 3D region ? between the (real) molecular spin-orbitals (MSO) in ?(?1r,…?Nr) and the MSOs in ?,(?1s,…,?Ns), edf finds all the P({n})'s by solving the linear system ?{n}{?kmtkn}P({n})=?r,sMCCdet[?kmtS?rs], where t=1 and t,…,t are arbitrary real numbers. Restrictions: The number of {n} sets grows very fast with m and N, so that the dimension of the linear system (1) soon becomes very large. Moreover, the computer time required to obtain the determinants in the second member of Eq. (1) scales quadratically with M. These two facts limit the applicability of the method to relatively small molecules. Unusual features: Most of the real variables are of precision real*16. Running time: 0.030, 2.010, and 0.620 seconds for Test examples 1, 2, and 3, respectively. References: [1] A. Martín Pendás, E. Francisco, M.A. Blanco, Faraday Discuss. 135 (2007) 423-438. [2] A. Martín Pendás, E. Francisco, M.A. Blanco, J. Phys. Chem. A 111 (2007) 1084-1090. [3] A. Martín Pendás, E. Francisco, M.A. Blanco, Phys. Chem. Chem. Phys. 9 (2007) 1087-1092. [4] E. Francisco, A. Martín Pendás, M.A. Blanco, J. Chem. Phys. 126 (2007) 094102. [5] A. Martín Pendás, E. Francisco, M.A. Blanco, C. Gatti, Chemistry: A European Journal 113 (2007) 9362-9371.

  11. Graded anharmonic crystals as genuine thermal diodes: analytical description of rectification and negative differential thermal resistance.

    Science.gov (United States)

    Pereira, Emmanuel

    2010-10-01

    We address the heat flow study starting from microscopic models of matter: we develop an approach and investigate some anharmonic graded mass crystals, with weak interparticle interactions. We calculate the thermal conductivity, and show the existence of rectification and negative differential thermal resistance. Our formalism allows us to understand the mechanism behind the phenomena, and shows that the properties of graded materials make them genuine thermal diodes. PMID:21230221

  12. Graded anharmonic crystals as genuine thermal diodes: Analytical description of rectification and negative differential thermal resistance

    OpenAIRE

    Pereira, Emmanuel

    2011-01-01

    We address the heat flow study starting from microscopic models of matter: we develop an approach and investigate some anharmonic graded mass crystals, with weak interparticle interactions. We calculate the thermal conductivity, and show the existence of rectification and negative differential thermal resistance. Our formalism allows us to understand the mechanism behind the phenomena, and shows that the properties of graded materials make them genuine thermal diodes.

  13. The effect of flap parameters on fluid rectification in a microfluidic diode

    OpenAIRE

    Singh, Kunwar Pal; Kumar, Manoj

    2010-01-01

    We have studied the effect of flap parameters on fluid rectification in a microfluidic diode. We use Navier–Stokes equations and arbitrary Lagrangian–Eulerian formulation to obtain dynamics of fluid flow and motion of the flap. The flap opens during forward flow and seals against a stopper during reverse flow. This allows flow in the forward direction and prevents it in the reverse direction. The rectifier is fluidic analog to a semiconductor diode in function because it rectifies fluid f...

  14. Rectification of skeletal muscle ryanodine receptor mediated by FK506 binding protein.

    OpenAIRE

    Ma, J.; Bhat, M. B.; Zhao, J.

    1995-01-01

    The cytosolic receptor for immunosuppressant drugs, FK506 binding protein (FKBP12), maintains a tight association with ryanodine receptors of sarcoplasmic reticulum (SR) membrane in skeletal muscle. The interaction between FKBP12 and ryanodine receptors resulted in distinct rectification of the Ca release channel. The endogenous FKBP-bound Ca release channel conducted current unidirectionally from SR lumen to myoplasm; in the opposite direction, the channel deactivated with fast kinetics. The...

  15. Theory of Optical Rectification Effect in Metallic Thin Film with Periodic Modulation

    CERN Document Server

    Hiroyuki, Kurosawa; Nakayama, Kazuyuki

    2014-01-01

    We carried out theoretical and numerical investigation of optical rectification (OR) effect in metallic structure with periodic modulation. A new formulation of the OR effect is presented and the generation mechanism of OR effect, which was a controversy issue in previous works, is clarified. We revealed that OR effect is strongly enhanced by the combination of spatial variation of metallic structure and local electric field enhancement. Our theory was numerically evaluated and showed fairly well agreement with experiment.

  16. Kinetic method of simulation of the multicomponent rectification process of hydrogen isotopes

    International Nuclear Information System (INIS)

    Alternative kinetic method for calculation of the rectification process is represented. In accordance with that the system of differential equations of mass transfer via every mixture component is solved. Mass output coefficients needed for mass transfer coefficients determination are calculated using empirical dependences. Equations of the heat distribution correcting the inner flows in column are solved taking into account the evolution of heat due to tritium decay whereof affects on general separation efficiency at high concentrations

  17. Rectification and diffusion of self-propelled particles in a two-dimensional corrugated channel

    OpenAIRE

    Ai, Bao-quan; Chen, Qiu-Yan; He, Ya-feng; Li, Feng-guo; Zhong, Wei-rong

    2014-01-01

    Rectification and diffusion of non-interacting self-propelled particles is numerically investigated in a two-dimensional corrugated channel. From numerical simulations, we obtain the average velocity and the effective diffusion coefficient. It is found that the self-propelled particles can be rectified by the self-propelled velocity. There exist optimal values of the parameters (the self-propelled velocity, the translational diffusion constant, and the height of the potentia...

  18. Camera array image rectification and calibration for stereoscopic and autostereoscopic displays

    OpenAIRE

    Nozick, Vincent

    2013-01-01

    This paper presents an image rectification method for an arbitrary number of views with aligned camera center. This paper also describes how to extend this method to easily perform a robust camera calibration. These two techniques can be used for stereoscopic rendering to enhance the perception comfort or for depth from stereo. In this paper, we first expose why epipolar geometry is not suited to solve this problem. Second, we propose a nonlinear method that includes all the images in the rec...

  19. Towards real-time stereoscopic image rectification for 3D visualization

    OpenAIRE

    Marrero, Tony; Mallon, John; Whelan, Paul F.

    2010-01-01

    This paper describes a method for stereoscopic rectification with geometric distortion minimisation, to generate suitable image pairs for 3D viewing applications. The current state of the art technique is not optimal as it lacks appropriate mathematical constraints. We present a new approach that enforces the same distortion minimisation criterion with more computational e±ciency whilst also achieving superior distortion removal. Detailed mathematical expressions have been developed that ful...

  20. Intrinsic rectification of ion flux in alamethicin channels: studies with an alamethicin dimer.

    OpenAIRE

    Woolley, G A; Biggin, P C; A. Schultz; L. Lien; Jaikaran, D C; Breed, J.; Crowhurst, K; Sansom, M. S.

    1997-01-01

    Covalent dimers of alamethicin form conducting structures with gating properties that permit measurement of current-voltage (I-V) relationships during the lifetime of a single channel. These I-V curves demonstrate that the alamethicin channel is a rectifier that passes current preferentially, with voltages of the same sign as that of the voltage that induced opening of the channel. The degree of rectification depends on the salt concentration; single-channel I-V relationships become almost li...

  1. Nonlinear heat transport in mesoscopic conductors: Rectification, Peltier effect and Wiedemann-Franz law

    OpenAIRE

    Lopez, Rosa; Sanchez, David

    2013-01-01

    We investigate nonlinear heat properties in mesoscopic conductors using a scattering theory of transport. Our approach is based on a leading-order expansion in both the electrical and thermal driving forces. Beyond linear response, the transport coefficients are functions of the nonequilibrium screening potential that builds up in the system due to interactions. Within a mean-field approximation, we self-consistently calculate the heat rectification properties of a quantum d...

  2. Design of high power rectification power supply based on digital control

    International Nuclear Information System (INIS)

    For typical high power rectification power supply, a design based on digital control is introduced. The feasibility and superiority of the digital control scheme were verified through the design and experimental results of the filament power supply for high current ion source of NBI. The application of digital control scheme, making the filament power supply design is more intelligent and simple, as related applications provide a reference. (authors)

  3. Optical rectification coefficient of a two-dimensional parabolic quantum dot: Effects of hydrogenic impurity, external fields, hydrostatic pressure and temperature

    Science.gov (United States)

    Rezaei, G.; Kish, S. Shojaeian; Vaseghi, B.; Taghizadeh, S. F.

    2014-10-01

    Simultaneous effects of hydrogenic impurity, hydrostatic pressure, temperature and external electric and magnetic fields on the intersubband optical rectification coefficient of a two-dimensional parabolic quantum dot are studied. Energy eigenvalues and eigenvectors are calculated using the direct matrix diagonalization method and optical rectification coefficient is obtained via the compact density matrix approach. The results indicate that the optical rectification coefficient is affected by the hydrogenic impurity, hydrostatic pressure, temperature and external fields.

  4. Electric and Magnetic Field Tunable Rectification and Magnetoresistance in FexGe1?x/Ge Heterojunction Diodes

    International Nuclear Information System (INIS)

    FexGe1?x/Ge amorphous heterojunction diodes with p-FexGe1?x ferromagnetic semiconductor layers are grown on single-crystal Ge substrates of p-type, n-type and intrinsic semiconductors, respectively. The I—V curves of p-Fe0.4Ge0.6/p-Ge diodes only show slight changes with temperature or with magnetic field. For the p-Fe0.4Ge0.6/n-Ge diode, good rectification is maintained at room temperature. More interestingly, the I—V curve of the p-Fe0.4Ge0.6/i-Ge diode can be tuned by the magnetic field, indicating a large positive magnetoresistance. The resistances of the junctions decrease with the increasing temperature, suggesting a typical semiconductor transport behavior. The origin of the positive magnetoresistance is discussed based on the effect of the electric and magnetic field on the energy band structures of the interface. (condensed matter: electronic structure, electrical, magnetic, and optical properties)

  5. On the molecular and electronic structure of matrine-type alkaloids

    International Nuclear Information System (INIS)

    A systematic study of the molecular and electronic structure of the eight possible members in the trans-matrine series and of two dehydro-derivatives, sophocarpine and sophoramine, has been performed. According to density functional theory (DFT) calculations these alkaloids exhibit a variety of form and junction of the four six-membered rings and all but sophocarpine have a strong preference for one conformation. Sophocarpine is predicted to have a marked conformational flexibility at the lactamic nitrogen and to exist as a mixture of two nearly isoenergetic conformers (C/D-trans and -cis) in the gas phase or solution. The theoretical predictions are consistent with the available X-ray experimental results as well as IR and NMR evidence. The absolute configuration of the preferred conformer of each compound has been established theoretically and corroborated with the specific optical rotation calculated at the sodium D line. The conformational equilibrium of sophocarpine has also been supported by this physical property. The computed gas-phase proton affinity of matrines indicates a basicity comparable to that of other polycyclic proton sponges. The lowest-energy electronic transitions have been characterized by time-dependent DFT calculations as mainly due to excitations spanning the frontier orbitals ?(NCO), n(O), n(Naminic), and ?*(CO). The electronic structures have also been studied by measuring and calculating significant features of the NMR and pho significant features of the NMR and photoelectron spectra. In particular, a representative set of NMR chemical shifts and nuclear spin-spin coupling constants, obtained with DFT formalisms, compares favourably with experiment. Notably, the stereoelectronic hyperconjugative effects on ??(Heq/Hax) and ?1 J(CHeq/CHax) of the >N-CO- groups is correctly accounted for by the theoretical results. Based on ab initio outer valence Green's function calculations, a reliable description of the uppermost bands in the photoelectron spectra has been advanced. The splitting and sequence of the ionization energies reflect a complex interaction of the n and ? chromophores

  6. Effect of thermal rectification on colors of Eucalyptus Saligna and Pinus caribaea Woods

    Scientific Electronic Library Online (English)

    Ana Lúcia Piedade, Sodero Martins Pincelli; Luiz Fernando, de Moura; José Otávio, Brito.

    Full Text Available Eucalyptus saligna and Pinus caribaea var. hondurensis woods underwent a variety of thermal rectification treatments (from 120ºC to 180ºC) to evaluate the effect of heating on their colorimetric properties. The following color parameters were measured: lightness (L), a* coordinate (green-red coordin [...] ate), b* coordinate (blue-yellow coordinate), saturation (C), and tonality angle (H). This study demonstrates that thermal rectification can be regarded as a tool for adding value to wood through color modification by heating. Results also suggest that thermal rectification might be a tool for homogenizing wood tonality and reddish color between species. Both tested species have shown very distinct colorimetric behaviors as a function of thermal treatments. The conifer was more resistant to thermal darkening than the hardwood while exposed to temperatures below 160ºC. The green-red coordinate (a*) and the tonality angle (H) tended to be homogenized for both species, as they decreased in eucalyptus, and increased in pinus, as a function of heating. The effect of wood heating on the blue-yellow coordinate (b*), saturation (C), and tonality angle (H) was likely to be opposite between both tested species.

  7. GPU-based rectification of high-resolution remote sensing stereo images

    Science.gov (United States)

    Luka?, Niko; Žalik, Borut

    2014-10-01

    One of the major challenges in the topographic mapping and fast generation of digital terrain or surface models from stereo optical aerial or satellite imagery is the stereo rectification preprocessing step. The general case is the use of extrinsic and intrinsic parameters from each calibrated camera, in order to establish epipolar geometry. Stereo rectification consists of geometric transformation and image sub-pixel resampling. Such a task is computationally demanding when dealing with high-resolution optical imagery. This presents an increasingly evident problem as the remote sensing technologies are becoming more accurate, causing even higher computational demands. This paper proposes a novel method for fast rectification of stereo images pairs to epipolar geometry by using General Purpose computing on Graphics Processing Units (GPGPU). The method is capable of resampling large high-resolution imagery on-the-fly, due to efficient out-of-core processing. In the experiments a runtime comparison was made between the proposed GPU-based and multi-core CPU methods over a dataset consisting of 420 stereo aerial images, where the proposed method achieved a significant speedup.

  8. The mechanism of rectification at the electrotonic motor giant synapse of the crayfish.

    Science.gov (United States)

    Jaslove, S W; Brink, P R

    The synapse between the giant interneurone and the motor giant axon of the crayfish is a well-known example of the rare class of current-rectifying electrotonic synapses. One early proposal for the basis of this rectification was that rectifying junctions are like diodes. Biological correlates of diodes can exist, such as constant-field channels which rectify by very high-speed rearrangements of charge carriers, but these require high selectivity and large concentration gradients. Electrotonic synapses are believed to be composed of wide-bore (1-2 nm) gap-junction channels which have poor selectivity and bridge similar intracellular compartments. An alternative mechanism for rectification would be by voltage-dependent gates that sense trans-synaptic potential. These two mechanisms can be distinguished because a diode should rectify instantaneously (on a biological time-scale) while a gated channel should show kinetic processes. Although a gating model is more consistent with the known behaviour of channels than a diode model, previous work has failed to find any time course for the rectification. We have now developed a high-quality voltage clamp and by working at reduced temperatures we are able to demonstrate channel kinetics. These results support the hypothesis that this rectifying synapse contains voltage-dependent gates. PMID:3748182

  9. Field induced rectification and memristive behavior of TlGaSe2 layered semiconductor

    Science.gov (United States)

    Seyidov, MirHasan Yu.; Suleymanov, R. A.; Balaban, Ertan; ?ale, Y.

    2014-10-01

    We report the internal electric field induced rectification in TlGaSe2 layered semiconductor. This built-in internal electric field was imprinted into the TlGaSe2 sample prior to the measurements while cooling the samples under the external electric field. We employ various pairs of metallic electrodes (In-In, Au-In, Au-Cu), which are deposited on a smooth mirror-like surfaces of TlGaSe2 crystal, respectively, and used to measure the current flow in two directions, parallel and perpendicular to the plane of layers. The current-voltage (I-V) characteristics were measured on the samples with imprinted internal electric field. The diode-like I-V characteristics was observed with the rectification polarity coinciding with the direction of the imprinted electric field. This effect was observed in both directions parallel and perpendicular to the plane of layers. Our results support that near the metal-TlGaSe2 interface the barrier is formed after the pretreatment of the sample in the electric field. So, the diode with a controlled rectification direction, which is achieved by changing the polarization direction using an external bias, is fabricated. The field induced motion of the charge, which piles up under the respective contact that forms a barrier is assumed. The memristive behavior with characteristic pinched hysteresis loop is also observed.

  10. Effect of dielectric barrier on rectification, injection and transport properties of printed organic diodes

    Energy Technology Data Exchange (ETDEWEB)

    Lilja, K E; Heljo, P; Tuukkanen, S; Joutsenoja, T; Lupo, D [Tampere University of Technology, Department of Electronics, PO Box 692, FI-33101 Tampere (Finland); Majumdar, H S; Oesterbacka, R [Abo Akademi University, Department of Natural Science and Center for Functional Materials, Porthansgatan 3, FI-20500, Turku (Finland); Lahtonen, K; Valden, M, E-mail: kaisa.lilja@tut.fi [Tampere University of Technology, Surface Science Laboratory, PO Box 692, FI-33101 Tampere (Finland)

    2011-07-27

    Rectification ratios of 10{sup 5} were observed in printed organic copper/polytriarylamine (PTAA)/silver diodes with a thin insulating barrier layer at the copper/PTAA interface. To clarify the origin of the high rectification ratio in the diodes, the injection, transport and structure of the diodes with two different copper cathodes were examined using impedance spectroscopy and x-ray photoelectron spectroscopy (XPS). The impedance data confirm that the difference in diode performance arises from the copper/PTAA interface. The XPS measurements show that the copper surface in both diode structures is covered by a layer of Cu{sub 2}O topped by an organic layer. The organic layer is thicker on one of the surfaces, which results in lower reverse currents and higher rectification ratios in the printed diodes. We suggest a model where a dipole at the dual insulating layer induces a shift in the semiconductor energy levels explaining the difference between the diodes with different cathodes.

  11. Spectroscopic mapping and selective electronic tuning of molecular orbitals in phosphorescent organometallic complexes – a new strategy for OLED materials

    Science.gov (United States)

    Ewen, Pascal R; Sanning, Jan; Koch, Tobias; Doltsinis, Nikos L

    2014-01-01

    Summary The improvement of molecular electronic devices such as organic light-emitting diodes requires fundamental knowledge about the structural and electronic properties of the employed molecules as well as their interactions with neighboring molecules or interfaces. We show that highly resolved scanning tunneling microscopy (STM) and spectroscopy (STS) are powerful tools to correlate the electronic properties of phosphorescent complexes (i.e., triplet emitters) with their molecular structure as well as the local environment around a single molecule. We used spectroscopic mapping to visualize several occupied and unoccupied molecular frontier orbitals of Pt(II) complexes adsorbed on Au(111). The analysis showed that the molecules exhibit a peculiar localized strong hybridization that leads to partial depopulation of a dz² orbital, while the ligand orbitals are almost unchanged. We further found that substitution of functional groups at well-defined positions can alter specific molecular orbitals without influencing the others. The results open a path toward the tailored design of electronic and optical properties of triplet emitters by smart ligand substitution, which may improve the performance of future OLED devices. PMID:25551053

  12. Static Dipole Polarizability for the $1S\\sigma$ electronic state of the $H^+_2$ molecular ion

    OpenAIRE

    Tsogbayar, Ts.

    2008-01-01

    The static dipole polarizabibility for the $1s\\sigma$ electron state of the $\\mathrm{H}_{2}^{+}$ hydrogen molecular ion is calculated within Born-Oppenheimer approximation. The variational expansion with randomly chosen exponents has been used for numerical studies. The results obtained for the dipole polarizability are accurate to the nine digits.

  13. Molecular projectile effects for kinetic electron emission from carbon- and metal-surfaces bombarded by slow hydrogen ions

    CERN Document Server

    Cernusca, S; Aumayr, F; Diez-Muino, R; Juaristi, J I

    2003-01-01

    Total yields for kinetic electron emission (KE) have been determined for impact of hydrogen monomer-, dimer- and trimer-ions (impact energy <10 keV) on atomically clean surfaces of carbon-fiber inforced graphite used as first-wall armour in magnetic fusion devices. The data are compared with KE yields for impact of same projectile ions on atomically clean highly oriented pyrolytic graphite and polycrystalline gold. We discuss KE yields for the different targets if bombarded by equally fast molecular and atomic ions in view to 'projectile molecular effects' (different yields per proton for equally fast atomic and molecular ions), which are expected from calculated electronic projectile energy losses in these target materials.

  14. Molecular dynamics simulation of electron-ion temperature relaxation in dense hydrogen: A scheme of truncated Coulomb potential

    Science.gov (United States)

    Ma, Qian; Dai, Jiayu; Kang, Dongdong; Zhao, Zengxiu; Yuan, Jianmin; Zhao, Xueqing

    2014-12-01

    Molecular dynamics (MD) simulations are performed to investigate the temperature relaxation between electrons and ions in a fully ionized, dense hydrogen plasma. We used HM (J. P. Hansen and I. R. McDonald) potential and introduced a truncated Coulomb interaction, which can avoid Coulomb catastrophe by choosing an appropriate cutting radius. The calculated results are compared with those from theoretical models (LS, GMS, BPS), whose applicability is also discussed. The effect of the interaction between ions and electrons on the temperature relaxation process is also investigated in the strong collision region. Finally, we discuss the effect of exchange interaction of electrons to the temperature relaxation.

  15. A divide and conquer real-space approach for all-electron molecular electrostatic potentials and interaction energies

    DEFF Research Database (Denmark)

    Losilla, Sergio Alberto; Sundholm, D

    2012-01-01

    A computational scheme to perform accurate numerical calculations of electrostatic potentials and interaction energies for molecular systems has been developed and implemented. Molecular electron and energy densities are divided into overlapping atom-centered atomic contributions and a three-dimensional molecular remainder. The steep nuclear cusps are included in the atom-centered functions making the three-dimensional remainder smooth enough to be accurately represented with a tractable amount of grid points. The one-dimensional radial functions of the atom-centered contributions as well as the three-dimensional remainder are expanded using finite element functions. The electrostatic potential is calculated by integrating the Coulomb potential for each separate density contribution, using our tensorial finite element method for the three-dimensional remainder. We also provide algorithms to compute accurate electron-electron and electron-nuclear interactions numerically using the proposed partitioning. The methods have been tested on all-electron densities of 18 reasonable large molecules containing elements up to Zn. The accuracy of the calculated Coulomb interaction energies is in the range of 10(-3) to 10(-6) E(h) when using an equidistant grid with a step length of 0.05 a(0).

  16. Monitoring attosecond dynamics of coherent electron-nuclear wave packets by molecular high-order-harmonic generation

    Energy Technology Data Exchange (ETDEWEB)

    Bredtmann, Timm [Laboratoire de Chimie Theorique, Faculte des Sciences, Universite de Sherbrooke, Sherbrooke, Quebec, J1K 2R1 (Canada); Institut fuer Chemie und Biochemie, Freie Universitaet Berlin, Takustrasse 3, D-14195 Berlin (Germany); Chelkowski, Szczepan; Bandrauk, Andre D. [Laboratoire de Chimie Theorique, Faculte des Sciences, Universite de Sherbrooke, Sherbrooke, Quebec, J1K 2R1 (Canada)

    2011-08-15

    A pump-probe scheme for preparing and monitoring electron-nuclear motion in a dissociative coherent electron-nuclear wave packet is explored from numerical solutions of a non-Born-Oppenheimer time-dependent Schroedinger equation. A mid-ir intense few-cycle probe pulse is used to generate molecular high-order-harmonic generation (MHOHG) from a coherent superposition of two or more dissociative coherent electronic-nuclear wave packets, prepared by a femtosecond uv pump pulse. Varying the time delay between the intense ir probe pulse and the uv pump pulse by a few hundreds of attoseconds, the MHOHG signal intensity is shown to vary by orders of magnitude, thus showing the high sensitivity to electron-nuclear dynamics in coherent electron-nuclear wave packets. We relate this high sensitivity of MHOHG spectra to opposing electron velocities (fluxes) in the electron wave packets of the recombining (recolliding) ionized electron and of the bound electron in the initial coherent superposition of two electronic states.

  17. Communication: Electronic and transport properties of molecular junctions under a finite bias: A dual mean field approach

    International Nuclear Information System (INIS)

    We show that when a molecular junction is under an external bias, its properties cannot be uniquely determined by the total electron density in the same manner as the density functional theory for ground state properties. In order to correctly incorporate bias-induced nonequilibrium effects, we present a dual mean field (DMF) approach. The key idea is that the total electron density together with the density of current-carrying electrons are sufficient to determine the properties of the system. Two mean fields, one for current-carrying electrons and the other one for equilibrium electrons can then be derived. Calculations for a graphene nanoribbon junction show that compared with the commonly used ab initio transport theory, the DMF approach could significantly reduce the electric current at low biases due to the non-equilibrium corrections to the mean field potential in the scattering region

  18. A molecular dynamics simulation of the two-dimensional ion-electron plasma in the strong coupling regime

    International Nuclear Information System (INIS)

    We have carried out Molecular Dynamics simulations on a two-dimensional plasma made up of ions of charge +e and size d held fixed (infinite mass) on the sites of a hexagonal lattice, and of classical electrons of charge -e moving in the periodic field of the ions. This fixed-ion model maps the dielectric-plasma transition of the two-dimensional Coulomb gas onto a delocalization transition of the electrons. The main diagnostics in our simulations are the electron self-diffusion constant D and the d.c conductivity ?, which vanish below a density dependent threshold temperature T1. The simulations amount to integrating the coupled classical equations of motion on the CRAY-1 over times spanning up to 103 plasma oscillations, and allow a detailed study of ion-electron recombinations and the single-particle and collective motions of the electrons

  19. Self-assembling monolayers of helical oligopeptides with applications in molecular electronics

    International Nuclear Information System (INIS)

    The aim of this project was to develop a generic method of preparing a 'molecular architecture' containing functional groups on a surface at predetermined relative positions several nm apart. This would be of great utility in molecular electronics, chemical sensors and other fields. It was proposed that such an architecture could be prepared on gold using linked, helical oligopeptides that contained the components of interest and sulphur functions able to form monolayers on gold by the self-assembly technique. Towards this ultimate aim Self-Assembled Monolayers (SAMs) of monomeric oligopeptides (13-17 residues) were prepared and characterised. Peptides containing three Met residues spaced in the sequence so that their side-chains lay on the same side of the helix were shown by circular dichroism (CD) to be strongly helical in organic solvents. Their self-assembled films on gold were characterised by Reflection-Absorption Infrared Spectroscopy (RAIRS) which showed the peptides adsorbed with the helix axes parallel to the surface, the orientation expected for self-assembly. However the surface coverage measured by cyclic voltammetry (CV) of the peptides' ferrocenyl derivatives on gold electrodes were less than expected for monolayers. Comparison of the films of ferrocenyl derivatives of Met and Cys showed that the thiolate bound more strongly than the thioether. Accordingly an oligopeptide containing two Cys residues at i, i+3, designed to be 310-helical, wasdesigned to be 310-helical, was prepared. Transformation of the two (Trt)Cys residues of the resin-bound peptide to the intramolecular disulphide by iodine was achieved in acetonitrile but not in DMF. CD suggested that the conformation of this peptide was a mixture of helix and random coil. Films of the peptide-disulphide and the peptide-dithiol adsorbed from protic solvents were characterised as multilayers by ellipsometry. However CV and ellipsometry showed that a monolayer was successfully prepared from acetonitrile. Future targets for improving and extending this method to form monolayers of linked disulphides are presented. (author)

  20. Radio-sensibility study of pseudo cereals by means of molecular markers and electronic microscopy

    International Nuclear Information System (INIS)

    With the purpose of observing the radio sensibility in two species of pseudo cereals group (Amaranthus hypochondria cus and Chenopodium berlandieri subsp. nuttalliae), germplasm of 4 amaranth genotypes was irradiated (A-21-0-10, Mixquic-09, M-2 and M-6) and 4 huauzontle genotypes (H-18, H-19, H-10 and red Chia) in the Gamma Irradiator of the ININ in a dose range of 50 to 500 Gy with intervals each 50 Gy and a treatment witness without irradiating. The evaluation of the material was carried out in three stages: 1) the pheno logy and morphology was evaluated during the plants development in each treatment under greenhouse conditions; 2) the radio sensibility was evaluated at molecular level by means of molecular markers type Ssr (Simple Sequence Repeats); and 3) the irradiated seeds were analyzed by under vacuum electronic microscopy. According to the results, the pheno logy phases were ahead in lower doses to 250 Gy for amaranth and higher doses to 150 Gy for huauzontle, there being a morphological variation in leaves and cob. The morphological variables were favored in dose from 50 to 200 Gy for amaranth, while in huauzontle the morphology presented more response variation to the radiation. In the DNA, the 21 Ssr were 100% polymorphic in amaranth and 97% polymorphic in huauzontle, being one of the more polymorphic the QCA0005 in amaranth and QCA0005 in huauzontle. The generated dendrograms showed greater similarity between Mixquic-09 and M-2 (amaranth) and between H-19 and H-10 (huauzontle). While by treatments, in amaranth the dose of 500 Gy presented most polymorphic difference and in huauzontle was the dose of 200 Gy. The under vacuum electronic microscopy did not show differences in the seed structure while the elemental analysis showed the presence of carbon, oxygen, aluminum, sulfur and calcium as the most common elements and in more concentration carbon and oxygen. For A. hypochondria cus the dose DL50 (median lethal dose) was between 50 and 100 Gy and for C. berlandieri subsp. nuttalliae was between 250 and 300 Gy, ranges that are recommended as good for future works of genetic improvement. (Author)

  1. Theoretical analysis of structures and electronic spectra in molecular cadmium chalcogenide clusters

    Science.gov (United States)

    Nguyen, Kiet A.; Pachter, Ruth; Day, Paul N.; Su, Haibin

    2015-06-01

    We present calculated structural and optical properties of molecular cadmium chalcogenide nonstoichiometric clusters with a size range of less than 1 nm to more than 2 nm with well-defined chemical compositions and structures in comparison to experimental characterization and previous theoretical work. A unified treatment of these clusters to obtain a fundamental understanding of the size, ligand, and solvation effects on their optical properties has not been heretofore presented. The clusters belong to three topological classes, specifically supertetrahedral (Tn), penta-supertetrahedral (Pn), and capped supertetrahedral (Cn), where n is the number of metal layers in each cluster. The tetrahedrally shaped Tn clusters examined in this work are Cd(ER)42- (T1), Cd4(ER)102- (T2), and Cd 10 E4 ' ( ER ) 16 4 - (T3), where R is an organic group, E and E' are chalcogen atoms (sulfur or selenium). The first member of the Pn series considered is M8E'(ER)162-. For the Cn series, we consider the first three members, M 17 E4 ' ( ER ) 28 2 - , M 32 E14 ' ( ER ) 36 L 4 , and M 54 E32 ' ( ER ) 48 L 4 4 - (L = neutral ligand). Mixed ligand clusters with capping ER groups replaced by halogen or neutral ligands were also considered. Ligands and solvent were found to have a large influence on the color and intensity of the electronic absorption spectra of small clusters. Their effects are generally reduced with increasing cluster sizes. Blueshifts were observed for the first electronic transition with reduced size for both cadmium sulfide and cadmium selenide series. Due to weakly absorbing and forbidden transitions underlying the one-photon spectra, more care is needed in interpreting the quantum confinement from the clusters' lowest-energy absorption bands.

  2. A Molecular Electronic Transducer based Low-Frequency Accelerometer with Electrolyte Droplet Sensing Body

    Science.gov (United States)

    Liang, Mengbing

    "Sensor Decade" has been labeled on the first decade of the 21st century. Similar to the revolution of micro-computer in 1980s, sensor R&D developed rapidly during the past 20 years. Hard workings were mainly made to minimize the size of devices with optimal the performance. Efforts to develop the small size devices are mainly concentrated around Micro-electro-mechanical-system (MEMS) technology. MEMS accelerometers are widely published and used in consumer electronics, such as smart phones, gaming consoles, anti-shake camera and vibration detectors. This study represents liquid-state low frequency micro-accelerometer based on molecular electronic transducer (MET), in which inertial mass is not the only but also the conversion of mechanical movement to electric current signal is the main utilization of the ionic liquid. With silicon-based planar micro-fabrication, the device uses a sub-micron liter electrolyte droplet sealed in oil as the sensing body and a MET electrode arrangement which is the anode-cathode-cathode-anode (ACCA) in parallel as the read-out sensing part. In order to sensing the movement of ionic liquid, an imposed electric potential was applied between the anode and the cathode. The electrode reaction, I3-- + 2e-- ? 3I --, occurs around the cathode which is reverse at the anodes. Obviously, the current magnitude varies with the concentration of ionic liquid, which will be effected by the movement of liquid droplet as the inertial mass. With such structure, the promising performance of the MET device design is to achieve 10.8 V/G (G=9.81 m/s2) sensitivity at 20 Hz with the bandwidth from 1 Hz to 50 Hz, and a low noise floor of 100 microg/sqrt(Hz) at 20 Hz.

  3. Ab initio electron propagator calculations in molecular transport junctions: predictions of negative differential resistance.

    Science.gov (United States)

    Kletsov, Aleksey; Dahnovsky, Yuri

    2007-10-14

    In this work we study current-voltage characteristics in transport molecular junctions with a 1,4-benzene dithiol molecule as a bridge by using different ab initio electron propagator methods such as OVGF and P3 which are both programs in a Gaussian software package. The current-voltage characteristics are calculated for different values of Fermi energy in various basis sets such as 6-311++G(p,d) and cc-pVDZ and are compared with the experimental data. A good agreement is found in almost the entire voltage range. In addition, the results of our calculations indicate that the accuracy of ab initio electron propagator methods is in the range of 0.2-0.3 eV. Since the computational methods are truly ab initio, implying no adjustable parameters, functions, or functionals, the theoretical predictions can be improved only by changing the model of a transport device. The current-voltage characteristics predict peaks, i.e., negative differential resistances, for the various values of Fermi energy. As shown, the origin of the negative differential resistances is related to the voltage dependences of overlap integrals for the active terminal orbitals, expansion coefficients of partial atomic wavefunctions in Dyson orbitals, and the voltage dependences of Dyson poles (ionization potentials). We find that two peak behavior in the current-voltage characteristics can be explained by the anharmonicity of potential energy surfaces. As a result of our studies, we predict that negative differential resistances can be experimentally found by changing a position of Fermi level, i.e., by using different metal electrodes coated by a gold atomic monolayer. PMID:17935432

  4. Enhanced production of runaway electrons during electron cyclotron resonance heating and in the presence of supersonic molecular beam injection in the HL-2A tokamak

    International Nuclear Information System (INIS)

    In the present paper, it is reported that a large production of runaway electrons has been observed during the flattop phase of electron cyclotron resonance heating (ECRH) discharges and in the presence of supersonic molecular beam injection (SMBI) in the HuanLiuqi-2A (commonly referred to as HL-2A) [Q. W. Yang, Nucl. Fusion 47, S635 (2007)] tokamak. For the set of discharges carried out in the present experiment, the ranges of ECRH power and plasma electron density are 0.8-1.0 MW and (3.0-4.0)x1019 m-3, respectively. A large number of superthermal electrons are produced through the avalanche effect [A. Lazaros, Phys. Plasmas 8, 1263 (2001)] during ECRH. The loop voltage increase due to SMBI gives rise to a decline in the critical runaway energy, which leads to that many superthermal electrons could be converted into runaway region. Therefore, this phenomenon may come from the synergetic effects of ECRH and SMBI. That is, the superthermal electrons created by ECRH are accelerated into runaway regime via the Dreicer process which is triggered by SMBI. The experimental results are in well agreement with the calculational ones based on the superthermal electron avalanche effect and the Dreicer runaway theory.

  5. Characterization of the electrical and optical properties of viologen devices using chlorophyll a as an electron excimer

    International Nuclear Information System (INIS)

    This paper uses self-assembled monolayers (SAMs) on an Au(111) substrate to detect the unique characteristics of viologen molecules using scanning tunneling microscopy (STM), and reports the orientation and surface changes of molecules at the nanolevel in real-time. In particular, the rectification characteristics of the viologen molecule were observed at the molecular level using scanning tunneling spectroscopy (STS). After verifying the rectification characteristics of viologen molecules, an experiment was carried out to demonstrate the possibility of applying viologen to photodiodes and switching devices by forming a thin film of chlorophyll a on the viologen SAMs using the Langmuir-Blodgett (LB) method. This material mimics the photoinduced electron transport phenomenon in the early stage of photosynthesis in living plants. This study demonstrates the applicability of viologen to bioelectronic photodiodes and switching devices based on photo effects by observing the topography, current sensing, and current-voltage (I-V) characteristics using current-sensing atomic force microscopy (CS-AFM) by introducing light to the AFM-tip/chlorophyll a/viologen/Au(1 1 1) substrate structure.

  6. Multiphoton Ionization as a clock to Reveal Molecular Dynamics with Intense Short X-ray Free Electron Laser Pulses

    CERN Document Server

    Fang, L; Murphy, B; Tarantelli, F; Kukk, E; Cryan, J P; Glownia, M; Bucksbaum, P H; Coffee, R N; Chen, M; Buth, C; Berrah, N

    2013-01-01

    We investigate molecular dynamics of multiple ionization in N2 through multiple core-level photoabsorption and subsequent Auger decay processes induced by intense, short X-ray free electron laser pulses. The timing dynamics of the photoabsorption and dissociation processes is mapped onto the kinetic energy of the fragments. Measurements of the latter allow us to map out the average internuclear separation for every molecular photoionization sequence step and obtain the average time interval between the photoabsorption events. Using multiphoton ionization as a tool of multiple-pulse pump-probe scheme, we demonstrate the modi?cation of the ionization dynamics as we vary the x-ray laser pulse duration.

  7. Effect of electron beam radiation on the structure and mechanical properties of ultra high molecular weight polyethylene fibers

    International Nuclear Information System (INIS)

    Ultra high molecular weight polyethylene fibers have been crosslinked by electron beam. The structure and mechanical properties of them have been investigated in different irradiation atmospheres. The obtained results show that the gel content and crosslinking density increase with the increase of dose, the swelling ratio and average molecular weight of crosslinked net decrease with the increase of dose, the tensile strength and failure elongation decrease with the increase of dose, the tensile modulus increases with the increase of dose. When the samples are irradiated in air, vacuum and acetylene atmospheres, the effect of irradiation in acetylene atmosphere is best

  8. Molecular weight distribution of electron and ?-ray irradiated PEEK measured by very high temperature GPC

    International Nuclear Information System (INIS)

    Poly(ether ether ketone)(PEEK) films were irradiated with electron beam in air and in helium. Gel fractions of the PEEK samples were determined as the ratio of the weight of insoluble fraction/total weigh by extracting the samples with 1-chloronaphthalene (1-CN) at 260degC. While unirradiated PEEK samples were dissolved in 1-CN completely, PEEK samples highly (10 - 50 MGy) irradiated in air were almost insoluble in the solvent. The weight-average molecular weight Mw of soluble fractions of the samples were measured by very high temperature gel permeation chromatography (VHTGPC): it was found that the Mw decreases with increasing dose. On the other hand, PEEK samples irradiated in helium gave gel fractions at lower doses (0 - 5 MGy) than in air. The PEEK films were also irradiated with 60Co ?-rays in the dose range, i.e. from 0 to 5 MGy. The ?-irradiated PEEK samples were completely dissolved in 1-CN at 260degC. Their Mw measured by VHTGPC decreases with increasing dose. (author)

  9. Effect of solvent polarization on the reorganization energy of electron transfer from molecular dynamics simulations

    International Nuclear Information System (INIS)

    The solvent contribution ?s to the reorganization energy of electron transfer can be estimated from averages of the potential energy gaps between neutral-pair and ion-pair states over an ensemble of structures generated from molecular dynamics simulations. Invoking a Marcus-type two-sphere model for charge separation and recombination in an aqueous environment, we explored the effect of a polarizable force field and noted a strong reduction of ?s (by ?45%) compared to the corresponding value obtained with a standard nonpolarizable force field. Both types of force fields yield ?s values that in agreement with the Marcus theory, vary strictly linearly with the inverse of the donor-acceptor distance; the corresponding slopes translate into appropriate effective optical dielectric constants, ???1.0±0.2 for a nonpolarizable and ???1.7±0.4 for a polarizable force field. The reduction in the solvent reorganization energy due to a polarizable force field translates into a scaling factor that is essentially independent of the donor-acceptor distance. The corresponding effective optical dielectric constant, ???1.80, is in excellent agreement with experiment for water.

  10. NATO Advanced Study Institute on Lower-Dimensional Systems and Molecular Electronics

    CERN Document Server

    Day, Peter; Papavassiliou, George

    1990-01-01

    This volume represents the written account of the NATO Advanced Study Institute "Lower-Dimensional Systems and Molecular Electronics" held at Hotel Spetses, Spetses Island, Greece from 12 June to 23 June 1989. The goal of the Institute was to demonstrate the breadth of chemical and physical knowledge that has been acquired in the last 20 years in inorganic and organic crystals, polymers, and thin films, which exhibit phenomena of reduced dimensionality. The interest in these systems started in the late 1960's with lower-dimensional inorganic conductors, in the early 1970's with quasi-one-dimensional crystalline organic conductors. which by 1979 led to the first organic superconductors, and, in 1977, to the fITSt conducting polymers. The study of monolayer films (Langmuir-Blodgett films) had progressed since the 1930's, but reached a great upsurge in . the early 1980's. The pursuit of non-linear optical phenomena became increasingly popular in the early 1980's, as the attention turned from inorganic crystals t...

  11. Amorphous ZrO2 from Ab-initio molecular dynamics: Structural, electronic and dielectric properties

    CERN Document Server

    Zhao, X

    2004-01-01

    Realistic models of amorphous ZrO2 are generated in a ``melt-and-quench'' fashion using ab-initio molecular dynamics in a plane-wave pseudopotential formulation of density-functional theory. The structural properties of the resulting amorphous models are analyzed, with special attention to coordination statistics. The vibrational and dielectric properties of one of these models are then investigated from first principles using linear-response methods. The electronic dielectric response is found to be very close to that of the crystalline phases, but the Born effective charges are found to be smaller, and partly as a result, the overall static dielectric constant turns out to be disappointingly low. A spatial decomposition of the lattice dielectric response indicates that the strongest contributors are 4-coordinated oxygen atoms. This work is motivated by the search for improved gate dielectric materials for sub-0.1 micron CMOS technology, and may also have implications for HfO2 and for silicates of ZrO2 and H...

  12. Scanning electron microscopy and molecular dynamics of surfaces of growing and ablating hexagonal ice crystals

    Directory of Open Access Journals (Sweden)

    W. C. Pfalzgraff

    2009-10-01

    Full Text Available Optical properties of cirrus ice clouds play an important role in regulating Earth's radiative balance. It has been hypothesized that the surfaces of cirrus ice crystals may be characterized by mesoscopic (micrometer-scale texturing, or roughness, in order to explain discrepancies between theoretical and observed light-scattering properties. Here, we present the first clearly resolved observations of surfaces of hexagonal ice crystals, using variable-pressure scanning electron microscopy. During growth conditions, the ice surface develops trans-prismatic strands, separated from one another by distances of 5–10 ?m. These strands become more pronounced during ablation, and exhibit a wider range of separations. Under re-growth conditions, faceting is re-established initially at prismatic edges. Molecular dynamics studies of a free-standing ice Ih nanocolumn showed no trans-prismatic strands at the atomistic level, suggesting that these strands originate at a spatial scale greater than 10 nm. The observed surface roughness could be used to construct more realistic representations of cirrus clouds in climate models, and constrain theories of ice crystal growth and ablation.

  13. Self-consistent GW calculations of electronic transport in thiol- and amine-linked molecular junctions

    DEFF Research Database (Denmark)

    Strange, M.; Rostgaard, Carsten

    2011-01-01

    The electronic conductance of a benzene molecule connected to gold electrodes via thiol, thiolate, or amino anchoring groups is calculated using nonequilibrium Green functions in combination with the fully self-consistent GW approximation for exchange and correlation. The calculated conductance of benzenedithiol and benzenediamine is one-fifth that predicted by standard density functional theory (DFT), in very good agreement with experiments. In contrast, the widely studied benzenedithiolate structure is found to have a significantly higher conductance due to the unsaturated sulfur bonds. These findings suggest that more complex gold-thiolate structures where the thiolate anchors are chemically passivated by Au adatoms are responsible for the measured conductance. Analysis of the energy level alignment obtained with DFT, Hartree-Fock, and GW reveals the importance of self-interaction corrections (exchange) on the molecule and dynamical screening at the metal-molecule interface. The main effect of the GW self-energy is to renormalize the level positions; however, its influence on the shape of molecular resonances also affects the conductance. Non-self-consistent G(0)W(0) calculations, starting from either DFT or Hartree-Fock, yield conductance values within 50% of the self-consistent GW results.

  14. RESEARCH ON THE ELECTRONIC AND OPTICAL PROPERTIES OF POLYMER AND OTHER ORGANIC MOLECULAR THIN FILMS

    Energy Technology Data Exchange (ETDEWEB)

    ALEXEI G. VITUKHNOVSKY; IGOR I. SOBELMAN - RUSSIAN ACADEMY OF SCIENCES

    1995-09-06

    Optical properties of highly ordered films of poly(p-phenylene) (PPP) on different substrates, thin films of mixtures of conjugated polymers, of fullerene and its composition with polymers, molecular J-aggregates of cyanine dyes in frozen matrices have been studied within the framework of the Agreement. Procedures of preparation of high-quality vacuum deposited PPP films on different substrates (ITO, Si, GaAs and etc.) were developed. Using time-correlated single photon counting technique and fluorescence spectroscopy the high quality of PPP films has been confirmed. Dependence of structure and optical properties on the conditions of preparation were investigated. The fluorescence lifetime and spectra of highly oriented vacuum deposited PPP films were studied as a function of the degree of polymerization. It was shown for the first time that the maximum fluorescence quantum yield is achieved for the chain length approximately equal to 35 monomer units. The selective excitation of luminescence of thin films of PPP was performed in the temperature range from 5 to 300 K. The total intensity of luminescence monotonically decreases with decreasing temperature. Conditions of preparation of highly cristallyne fullerene C{sub 60} films by the method of vacuum deposition were found. Composites of C{sub 60} with conjugated polymers PPV and polyacetylene (PA) were prepared. The results on fluorescence quenching, IR and resonant Raman spectroscopy are consistent with earlier reported ultrafast photoinduced electron transfer from PPV to C{sub 60} and show that the electron transfer is absent in the case of the PA-C{sub 60} composition. Strong quenching of PPV fluorescence was observed in the PPV-PA blends. The electron transfer from PPV to PA can be considered as one of the possible mechanisms of this quenching. The dynamics of photoexcitations in different types of J-aggregates of the carbocyanine dye was studied at different temperatures in frozen matrices. The optical properties of relatively simple J-aggregates with pure intrasegment relaxation, which they have found, may clarify the problem of the relationship between intrasegment and intersegment processes in the formation of luminescent states in more complicated conjugated polymers, which is important for construction of electroluminescence and photosensitive devices.

  15. Polarization effects in electron collisions with Li2: application of the molecular R-matrix method with pseudostates

    International Nuclear Information System (INIS)

    Li2 has a huge polarizability and a huge elastic cross section for collisions with low-energy electrons. The recently developed molecular R-matrix with pseudostates (MRMPS) method is applied to electron collisions with Li2 at energies below 5 eV. The calculations, which are shown to be stable with respect to the choice of pseudostate basis, demonstrate the power of the MRMPS method for representing target polarizabilities and polarization effects in general. A previously identified low-lying 2?u shape resonance is found at about 0.05 eV and several other low-lying resonances and resonance-like features are identified. Cross sections for elastic and electronically inelastic electron collisions are calculated and compared with previous studies.

  16. Electron induced formation and stability of molecular and cluster ions in gas phase and superfluid helium nanodroplets

    International Nuclear Information System (INIS)

    The present PhD thesis represents a broad range study of electron induced formation and stability of positive and negative ions in gas phase and superfluid helium nanodroplets. The molecules studied are of industrial, environmental, plasma and biological relevance. The knowledge obtained from the study provides new insight for the proper understanding and control on energetics and dynamics of the reactions involved in the formation and fragmentation processes of the studied molecules and clusters. The experiments are accomplished and investigated using mass spectrometric techniques for the formation of molecular and cluster ions using different mass spectrometers available in our laboratory. One part of the work is focused on electron-induced reactions of the molecules in gas phase. Especially focus is laid to electron attachment to the isomers of mononitrotolouene used as an additive to explosives. The fragile nature and high internal energy of these molecules has lead to extensive fragmentation following the ionisation process. Dissociative electron attachment to the three different isomers has shown different resonances and therefore this process can be utilized to explicitly distinguish these isomers. Anion efficiency curves of the isomers have been studied using effusive molecular beam source in combination with a hemispherical electron monochromator as well as a Nier-type ion source attached to a sector field mass spectrometer. The outcome of the experiment is aometer. The outcome of the experiment is a reliable and effective detection method highly desirable for environmental and security reasons. Secondly, dissociative electron ionization of acetylene and propene is studied and their data is directly related to the plasma modelling for plasma fusion and processing reactors. Temperature effects for dissociative electron attachment to halo-hydrocarbons are also measured using a trochoidal electron monochromator. The second part of the work is concerned with the investigation of electron-induced reactions of the molecules doped into superfluid helium nanodroplets. Pick up of more than one molecule has lead to the formation of ultracold neutral clusters inside the helium droplets. Electron attachment to He nanodroplets doped with ammonia has embarked a synthetic chemistry, forming hydrazine anions, followed by intermediate ion complexes at freezing temperature of 0.37 K of the helium environment. Also a concomitant solvation effect for hydrazine anions has been observed. Electron ionization of He droplets containing ammonia and water co-doped with fullerenes has shown unique sequence of the formation and fragmentation of cluster ions following electron-induced ionization processes. A novel ion-molecule reaction has been observed and established following electron ionization of water and fullerene co-doped into helium nanodroplets. (author)

  17. Probing the shape and stereochemistry of molecular orbitals in locally flexible aromatic chains: a penning ionization electron spectroscopy and Green's function study of the electronic structure of biphenyl.

    Science.gov (United States)

    Kishimoto, Naoki; Hagihara, Yusuke; Ohno, Koichi; Knippenberg, Stefan; François, Jean-Pierre; Deleuze, Michael S

    2005-11-24

    We report on the results of an exhaustive study of the interplay between the valence electronic structure, the topology and reactivity of orbitals, and the molecular structure of biphenyl by means of Penning ionization electron spectroscopy in the gas phase upon collision with metastable He*(2(3)S) atoms. The measurements are compared with one-particle Green's function calculations of one-electron and shake-up valence ionization spectra employing the third-order algebraic diagrammatic construction scheme [ADC(3)]. Penning ionization intensities are also analyzed by means of the exterior electron-density model and comparison with photoelectron spectra: in contrast with the lines originating from sigma orbitals, ionization lines belonging to the pi-band system have large Penning ionization cross sections due to their greater extent outside the molecular van der Waals surface. The involved chemi-ionization processes are further experimentally investigated using collision-energy-resolved Penning ionization electron spectroscopy. The cross sections of pi-ionization bands exhibit a markedly negative collision-energy dependence and indicate that the interaction potential that prevails between the molecule and the He*(2(3)S) atom is strongly attractive in the pi-orbital region. On the other hand, the partial ionization cross sections pertaining to sigma-ionization channels are characterized by more limited collision-energy dependencies, as a consequence of rather repulsive interactions within the sigma-orbital region. A comparison of ADC(3) simulations with the Penning ionization electron spectra and UV photoelectron spectra measured by Kubota et al. [Chem. Phys. Lett. 1980, 74, 409] on thin films of biphenyl deposited at 170 and 109 K on copper demonstrates that biphenyl molecules lying at the surface of polycrystalline layers adopt predominantly a planar configuration, whereas within an amorphous sample most molecules have twisted structures similar to those prevailing in the gas phase. PMID:16834309

  18. Controlling the electron energy distribution function of electron beam generated plasmas with molecular gas concentration: II. Numerical modeling

    International Nuclear Information System (INIS)

    In this work, the second in a series of two, a spatially averaged model of an electron beam generated Ar–N2 plasma is developed to identify the processes behind the measured influence of trace amounts of N2 on the development of the electron energy distribution function. The model is based on the numerical solution of the electron Boltzmann equation self-consistently coupled to a set of rate balance equations for electrons, argon and nitrogen species. Like the experiments, the calculations cover only the low-energy portion (<50 eV) of the electron energy distribution, and therefore a source term is added to the Boltzmann equation to represent ionization by the beam. Similarly, terms representing ambipolar diffusion along and across the magnetic field are added to allow for particle loss and electrostatic cooling from the ambipolar electric field. This work focuses on the changes introduced by adding a small admixture of nitrogen to an argon background. The model predictions for the electron energy distribution function, electron density and temperature are in good agreement with the experimentally measured data reported in part I, where it was found that the electron and ion energy distributions can be controlled by adjusting the fraction of nitrogen in the gas composition. (paper)

  19. Synchrotron radiation X-ray spectroscopic studies of interface electronic structure in molecular organic photovoltaic thin films

    International Nuclear Information System (INIS)

    Highlights: ? Synchrotron radiation spectroscopies are applied to organic solar cell materials. ? Interface electronic structure of small molecule bilayers is measured. ? Beam damage is avoided by sample translation -- Abstract: This paper reviews the application of synchrotron radiation-excited soft X-ray spectroscopies in the study of the interface electronic structure of small molecule organic photovoltaic materials. Recent results of photoemission, X-ray emission, and X-ray absorption experiments on a variety of bilayer systems grown in situ using organic molecular beam deposition will be discussed

  20. Molecular structure, anharmonic vibrational analysis and electronic spectra of o-, m-, p-iodonitrobenzene using DFT calculations

    Science.gov (United States)

    Alam, Mohammad Jane; Ahmad, Shabbir

    2014-02-01

    In the present work, molecular geometry and anharmonic vibrational spectra of o-, m-, p-iodonitrobenzene have been studied. The anharmonic frequencies were calculated using second order perturbative (PT2) approach with basis set 3-21G? on iodine and 6-311G(d,p) on other atoms at DFT(B3LYP) level of theory and were compared to experimental values. The assignments of vibrational modes of isomeric iodonitrobenzenes were done by using potential energy distribution (PED) and vibrational assignments of benzene, nitrobenzene and iodobenzene. The combination and overtone bands are also assigned. The electronic spectra were recorded as well as simulated using polarizable continuum model (PCM) at TD-B3LYP/6-311G(d,p)/3-21G? level of theory. The vibrational and electronic spectra are interpreted. Moreover, atomic charges, MEP mapping, HOMO-LUMO, NBO analysis and various thermodynamics and molecular properties are reported.

  1. Contribution of the metal/SiO2 interface potential to photoinduced switching in molecular single-electron tunneling junctions

    International Nuclear Information System (INIS)

    Photoinduced switching of the Coulomb staircase in molecular single-electron tunneling junctions was previously observed. These junctions consisted of evaporated SiO2 insulator (?5 nm), with tetrakis-3,5-di-t-butylphenyl-porphyrin (H2-TBPP) molecules as Coulomb islands, sandwiched between top and bottom electrodes. The reversible response and the relaxation time of the photoinduced switching suggest that this phenomenon depends on the properties of the metal/SiO2 interface rather than those of the H2-TBPP molecule or SiO2 tunneling layer. We analyzed the photoinduced switching according to the theory of single-electron tunneling taking into account the discrete molecular energy states and the metal/SiO2 interfacial electrostatic phenomena. We conclude that the main contributor to the photoinduced shift was the electrostatic potential formed through the space-charge exchange at the metal/SiO2 interface

  2. Structure impact on the thermal and electronic properties of bismuth telluride by ab-initio and molecular dynamics calculations

    Science.gov (United States)

    Termentzidis, K.; Pokropivny, A.; Woda, M.; Xiong, S.-Y.; Chumakov, Y.; Cortona, P.; Volz, S.

    2012-11-01

    We use molecular dynamics and ab-initio methods to predict the thermal and electronic properties of new materials with high figures of merit. The simulated systems are bulk bismuth tellurides with antisite and vacancy defects. Optimizations of the materials under investigation are performed by the SIESTA code for subsequent calculations of force constants, electronic properties, and Seebeck coefficients. The prediction of the thermal conductivity is made by Non-Equilibrium Molecular Dynamics (NEMD) using the LAMMPS code. The thermal conductivity of bulk bismuth telluride with different stoichiometry and with a number of substitution defects is calculated. We have found that the thermal conductivity can be decreased by 60% by introducing vacancy defects. The calculated thermal conductivities for the different structures are compared with the available experimental and theoretical results.

  3. The calculation of the conductance and electron tunneling characteristic time from metal-molecule contact in a molecular wire

    Directory of Open Access Journals (Sweden)

    S. A. Ketabi

    2003-12-01

    Full Text Available   In this paper, on the basis of tight-binding model and a generalized Green- function method as well as Lanczos algorithm procedure, the effects of the metal-molecule coupling(MMC strength on the electronic transmission through a metal-single molecule-metal(MMM system is investigated. Using the Landauer formalism we study some of the significant conductance properties of this system as a molecular wire. Our results show that with the increase of the length of the molecule, the conductance of the molecular wire decreases exponentially. With trans-polyacetylene (trans-PA as the molecule, we calculate a characteristic time for electron transmission through the MMM system. This time scale measures the delay caused by tunneling through the MMC. Our calculations show that the conductance is sensitive to the MMC strength. The focus is on the significant relationship between this time scale and the strength of the metal-molecule(trans-PA coupling.

  4. On the valve nature of a monolayer of aligned molecular magnets in tunneling spin-polarized electrons: Towards organic molecular spintronics

    Energy Technology Data Exchange (ETDEWEB)

    Chakrabarti, Sudipto; Pal, Amlan J., E-mail: sspajp@iacs.res.in [Department of Solid State Physics, Indian Association for the Cultivation of Science, Jadavpur, Kolkata 700032 (India)

    2014-01-06

    We form a monolayer of magnetic organic molecules and immobilize their moments pointing either upwards or downwards with respect to the substrate through an electrostatic-binding process. Such a monolayer is probed with a scanning tunneling microscope tip, which is also magnetized with the magnetization vector pointing towards (or away from) apex of the tip. From spin-polarized tunneling current, we show that the current was higher when magnetization vectors of the tip and molecules were parallel as compared to that when they were anti-parallel. We show that for tunneling of spin-polarized electrons, aligned organic molecular magnets can act as a valve.

  5. On the valve nature of a monolayer of aligned molecular magnets in tunneling spin-polarized electrons: Towards organic molecular spintronics

    International Nuclear Information System (INIS)

    We form a monolayer of magnetic organic molecules and immobilize their moments pointing either upwards or downwards with respect to the substrate through an electrostatic-binding process. Such a monolayer is probed with a scanning tunneling microscope tip, which is also magnetized with the magnetization vector pointing towards (or away from) apex of the tip. From spin-polarized tunneling current, we show that the current was higher when magnetization vectors of the tip and molecules were parallel as compared to that when they were anti-parallel. We show that for tunneling of spin-polarized electrons, aligned organic molecular magnets can act as a valve

  6. Detection of atomic and molecular mega-electron-volt projectiles using an x-ray charged coupled device camera.

    Science.gov (United States)

    Chabot, M; Martinet, G; Béroff, K; Pino, T; Bouneau, S; Genolini, B; Grave, X; Nguyen, K; le Gailliard, C; Rosier, P; Féraud, G; Friha, H; Villier, B

    2011-10-01

    We show that an x-ray charge coupled device (CCD) may be used as a particle detector for atomic and molecular mega-electron-volt (MeV) projectiles of around a few hundred keV per atomic mass unit. For atomic species, spectroscopic properties in kinetic energy measurements (i.e., linearity and energy resolution) are found to be close to those currently obtained with implanted or surface barrier silicon particle detectors. For molecular species, in order to increase the maximum kinetic energy detection limit, we propose to put a thin foil in front of the CCD. This foil breaks up the molecules into atoms and spreads the charges over many CCD pixels and therefore avoiding saturation effects. This opens new perspectives in high velocity molecular dissociation studies with accelerator facilities. PMID:22047285

  7. Nonlinear optical rectification of hydrogenic impurity in a disk-like parabolic quantum dot: The role of applied magnetic field

    Science.gov (United States)

    Shojaei, S.; Soltani Vala, A.

    2015-06-01

    We report a detailed theoretical study of the effect of combined electric and magnetic field on the nonlinear optical rectification of a hydrogenic impurity, confined in a two dimensional disk-like quantum dot, with parabolic confinement potential. We use the compact density matrix formalism and iterative method to obtain nonlinear optical rectification and absorption coefficients. To find energy levels and wave functions, we employ exact diagonalization method in the effective mass approximation. As main result, we found that the transition energy from ground to first excited state redshifts with increasing the magnetic field while blueshifts for transition from ground to second excited state, moreover, for former transition, nonlinear optical rectification coefficient decreases with increasing magnetic field in contrast to that occurs for latter one.

  8. Electronic transport through zigzag/armchair graphene nanoribbon heterojunctions

    International Nuclear Information System (INIS)

    The electronic transport properties of a graphene nanoribbon (GNR) are known to be sensitive to its width, edges and defects. We investigate the electronic transport properties of a graphene nanoribbon heterojunction constructed by fusing a zigzag and an armchair graphene nanoribbon (zGNR/aGNR) side by side. First principles results reveal that the heterojunction can be either metallic or semiconducting, depending on the width of the nanoribbons. Intrinsic rectification behaviors have been observed, which are largely sensitive to the connection length between the zGNR and aGNR. The microscopic origins of the rectification behavior have been revealed. We find that the carrier type can alter from electrons to holes with the bias voltage changing from negative to positive; the asymmetrical transmission spectra of electrons and holes induced by the interface defects directly results in the rectification behavior. The results suggest that any methods which can enhance the asymmetry of the transmission spectra between holes and electrons could be used to improve the rectification behavior in the zGNR/aGNR heterojunction. Our findings could be useful for designing graphene based electronic devices. (paper)

  9. Electronic transport through zigzag/armchair graphene nanoribbon heterojunctions.

    Science.gov (United States)

    Li, Xiao-Fei; Wang, Ling-Ling; Chen, Ke-Qiu; Luo, Yi

    2012-03-01

    The electronic transport properties of a graphene nanoribbon (GNR) are known to be sensitive to its width, edges and defects. We investigate the electronic transport properties of a graphene nanoribbon heterojunction constructed by fusing a zigzag and an armchair graphene nanoribbon (zGNR/aGNR) side by side. First principles results reveal that the heterojunction can be either metallic or semiconducting, depending on the width of the nanoribbons. Intrinsic rectification behaviors have been observed, which are largely sensitive to the connection length between the zGNR and aGNR. The microscopic origins of the rectification behavior have been revealed. We find that the carrier type can alter from electrons to holes with the bias voltage changing from negative to positive; the asymmetrical transmission spectra of electrons and holes induced by the interface defects directly results in the rectification behavior. The results suggest that any methods which can enhance the asymmetry of the transmission spectra between holes and electrons could be used to improve the rectification behavior in the zGNR/aGNR heterojunction. Our findings could be useful for designing graphene based electronic devices. PMID:22317831

  10. The molecular structure of difluorophosphine selenide, determined using a combination of gas electron diffraction and liquid-crystal NMR data

    International Nuclear Information System (INIS)

    The molecular structure of difluorophosphine selenide has been determined by a combined analysis of gas-phase electron diffraction data and dipolar couplings obtained for a solution in a nematic phase. Geometrical parameters (rsub(a)) are: r(P = Se) 202.6(4), r(P - F) 155.7(3), r(P - H) 142.2(7) pm, SePH 118.6(7)0. (orig.)

  11. 1H NMR study of the effect of variable ligand on heme oxygenase electronic and molecular structure

    OpenAIRE

    Ma, Li-Hua; Liu, Yangzhong; Zhang, Xuhong; Yoshida, Tadashi; La Mar, Gerd N.

    2008-01-01

    Heme oxygenase carries out stereospecific catabolism of protohemin to yield iron, CO and biliverdin. Instability of the physiological oxy complex has necessitated the use of model ligands, of which cyanide and azide are amenable to solution NMR characterization. Since cyanide and azide are contrasting models for bound oxygen, it is of interest to characterize differences in their molecular and/or electronic structures. We report on detailed 2D NMR comparison of the azide and cyanide substrate...

  12. Molecular design of organic semiconductors for electronic devices and their application in flexible light emitting diodes

    Science.gov (United States)

    Pandya, Hermona K.

    The focus of the studies investigated in this work has been two-fold. In the first part, a structure-property study of three novel two-dimensional conjugated phenylenevinylene (PV) based isomers containing oxadiazole moieties for optoelectronic applications has been carried out. The compounds have been designed to serve as a model to study charge delocalization and transport as well as molecular symmetry in organic semiconductor molecules. These molecules are tetra-substituted at the central phenyl ring with two PV based arms and two oxadiazole derivatized PV (OXAPPV) arms. In the three molecules, termed p-, o-, and m-OXA-X, the OXAPPV arms are positioned in a para-, ortho- or meta-position, respectively, in relation to each other. Comparing these molecules, the role of symmetry and charge delocalization in this class of compounds has been explored. Despite having different linear segments, they have nearly identical photophysical properties suggesting a similar charge delocalization mechanism. However, in a LED with the molecules as emissive layers between aluminum and ITO electrodes and with poly(3,4-ethylenedioxythiophene) with poly(styrenesulfonate) (PEDOT:PSS) and lithium fluoride to aid in hole and electron injection, respectively, o-OXA-X exhibited the highest external quantum, luminance and power efficiencies. We explain these differences based on the changes in the film morphology between the three molecules. Supporting data from cyclic voltammetry and morphological data from atomic force microscopy, NMR studies, thermal characterization and x-ray diffraction studies are also reported. In the second part, in an effort to construct stable and high efficiency devices with a single emissive layer and with a stable cathode, flexible LEDs have been fabricated and tested in simple device configurations. Devices on flexible substrates have been made using either the 2D conjugated molecules or a soluble poly(phenylenevinylene) (PPV) and oxadiazole substituted PPV derivatized random copolymer, RC30, as the emissive layer and higher work function aluminum cathodes and compared with control devices on glass substrates. In all devices PEDOT:TSS has been used as the hole transporting layer and a thin layer of cesium fluoride or lithium fluoride has been employed at the polymer/cathode interface to aid in electron injection. For the RC30 polymer, devices on plastic substrates with a lithium fluoride interlayer performed the best, exhibiting up to 1% external quantum efficiency and an average of 0.8% and luminance of 1600 cd/m2 at 40 mA/cm2 (7.8 V). Stability of this device and morphology of the emissive film have also been investigated.

  13. High conversion efficiency, high energy terahertz pulses by optical rectification in cryogenically cooled lithium niobate.

    Science.gov (United States)

    Huang, Shu-Wei; Granados, Eduardo; Huang, Wenqian Ronny; Hong, Kyung-Han; Zapata, Luis E; Kärtner, Franz X

    2013-03-01

    We demonstrate highly efficient terahertz (THz) generation by optical rectification (OR) of near-optimum pump pulses centered at 1.03 ?m in cryogenically cooled lithium niobate. Using a close to optimal pulse duration of 680 fs and a pump energy of 1.2 mJ, we report conversion efficiencies above 3.8±0.4%, which is more than an order of magnitude higher than previously reported. The results confirm the advantage of using cryogenic cooling of the lithium niobate crystal that significantly reduces the THz absorption, enabling the scaling of THz pulse energies to the millijoule level via OR. PMID:23455302

  14. Towards generation of mJ-level ultrashort THz pulses by optical rectification

    OpenAIRE

    Fülöp, József András; Pálfalvi, László; Hoffmann, Matthias C.; Hebling, János

    2011-01-01

    Optical rectification of ultrashort laser pulses in LiNbO3 by tilted-pulse-front excitation is a powerful way to generate near single-cycle terahertz (THz) pulses. Motivated by various applications, calculations were carried out to optimize the THz peak electric field strength. The results predict THz output with peak electric field strength on the MV/cm level in the 0.3-1.5 THz frequency range by using optimal pump pulse duration of about 500 fs, optimal crystal length, and...

  15. Note: Electrical detection and quantification of spin rectification effect enabled by shorted microstrip transmission line technique

    Energy Technology Data Exchange (ETDEWEB)

    Soh, Wee Tee; Ong, C. K. [Center for Superconducting and Magnetic Materials, Department of Physics, National University of Singapore, 2 Science Drive 3, Singapore 117551 (Singapore); Peng, Bin [Center for Superconducting and Magnetic Materials, Department of Physics, National University of Singapore, 2 Science Drive 3, Singapore 117551 (Singapore); State Key Laboratory of Electronic Thin Films and Integrated Devices, University of Electronic Science and Technology of China, Chengdu 610054 (China); Chai, Guozhi [Temasek Laboratories, National University of Singapore, 5A Engineering Drive 2, Singapore 117411 (Singapore)

    2014-02-15

    We describe a shorted microstrip method for the sensitive quantification of Spin Rectification Effect (SRE). SRE for a Permalloy (Ni{sub 80}Fe{sub 20}) thin film strip sputtered onto SiO{sub 2} substrate is demonstrated. Our method obviates the need for simultaneous lithographic patterning of the sample and transmission line, therefore greatly simplifying the SRE measurement process. Such a shorted microstrip method can allow different contributions to SRE (anisotropic magnetoresistance, Hall effect, and anomalous Hall effect) to be simultaneously determined. Furthermore, SRE signals from unpatterned 50 nm thick Permalloy films of area dimensions 5 mm × 10 mm can even be detected.

  16. Note: electrical detection and quantification of Spin Rectification Effect enabled by shorted microstrip transmission line technique.

    Science.gov (United States)

    Soh, Wee Tee; Peng, Bin; Chai, Guozhi; Ong, C K

    2014-02-01

    We describe a shorted microstrip method for the sensitive quantification of Spin Rectification Effect (SRE). SRE for a Permalloy (Ni80Fe20) thin film strip sputtered onto SiO2 substrate is demonstrated. Our method obviates the need for simultaneous lithographic patterning of the sample and transmission line, therefore greatly simplifying the SRE measurement process. Such a shorted microstrip method can allow different contributions to SRE (anisotropic magnetoresistance, Hall effect, and anomalous Hall effect) to be simultaneously determined. Furthermore, SRE signals from unpatterned 50 nm thick Permalloy films of area dimensions 5 mm × 10 mm can even be detected. PMID:24593409

  17. Physicochemical fundamentals of high purification of volatile inorganic hydrides by rectification method at elevated pressures

    International Nuclear Information System (INIS)

    Results of calculations and experimental measurements of equilibrium distribution factor (?) of volatile microimpurities (CH4, C2H4, C2H6, C3H8, C4H10, HCl, BCl3, CH3Cl) between liquid and vapor phases of boron hydride B2H6 in the temperature range from Tboil to 0.8 Tcr are given. Coefficients of ? temperature dependence regression are determined. The results of the investigation are of interest for optimization of the process of rectification purifying of hydrides in terms of temperature

  18. Note: Electrical detection and quantification of spin rectification effect enabled by shorted microstrip transmission line technique

    International Nuclear Information System (INIS)

    We describe a shorted microstrip method for the sensitive quantification of Spin Rectification Effect (SRE). SRE for a Permalloy (Ni80Fe20) thin film strip sputtered onto SiO2 substrate is demonstrated. Our method obviates the need for simultaneous lithographic patterning of the sample and transmission line, therefore greatly simplifying the SRE measurement process. Such a shorted microstrip method can allow different contributions to SRE (anisotropic magnetoresistance, Hall effect, and anomalous Hall effect) to be simultaneously determined. Furthermore, SRE signals from unpatterned 50 nm thick Permalloy films of area dimensions 5 mm × 10 mm can even be detected

  19. Rectification of catalyst separation column at HWP, Thal (Paper No. 5.7)

    International Nuclear Information System (INIS)

    Heavy Water Plant, Thal is based on the monothermal ammonia hydrogen process. Liquid ammonia containing potassium amide catalyst is contacted with the synthesis gas where-in deuterium from hydrogen gets transferred to liquid phase. There are two parallel streams A and B with a common ammonia synthesis unit. The system is provided with an ammonia cracker and ammonia synthesis for providing the reflux gas and liquid for the enrichment process. The parameters such as steam valve opening, column pressure, reflux, condensate valve opening, cooling water valve position, cracking load of the unit before and after the rectification, etc. are discussed. (author). 2 tabs., 2 figs

  20. Stability optimisation of molecular electronic devices based on  nanoelectrode–nanoparticle bridge platform in air and different storage liquids

    Energy Technology Data Exchange (ETDEWEB)

    Jafri, S. H. M. [Mirpur University of Science and Technology, Department of Electrical Engineering (Pakistan); Blom, T. [Uppsala University, The Ångström Laboratory, Department of Engineering Sciences (Sweden); Wallner, A.; Ottosson, H., E-mail: Henrik.Ottosson@kemi.uu.se [Uppsala University, The Biomedical Centre, Department of Chemistry (Sweden); Leifer, K., E-mail: Klaus.Leifer@angstrom.uu.se [Uppsala University, The Ångström Laboratory, Department of Engineering Sciences (Sweden)

    2014-12-15

    The long-term stability of metal nanoparticle–molecule junctions in molecular electronic devices based on nanoelectrodes (NEL) is a major challenge in the effort to bring related molecular electronic devices to application. To optimize the reproducibility of molecular electronic nanodevices, the time-dependent modification of such junctions as exposed to different media needs to be known. Here, we have studied (1) the stability of Au-NEL and (2) the electrical stability of molecule–Au nanoparticle (AuNP) junctions themselves with the molecule being  1,8-octanedithiol (ODT). Both the NELs only and the junctions were exposed to air and liquids such as deionized water, tetrahydrofuran, toluene and tetramethylethylenediamine (TMEDA) over a period of 1 month. The nanogaps remained stable in width when stored in either deionized water or toluene, whereas the current through 1,8-octanedithiol–NP junctions remained most stable when stored in TMEDA as compared to other solvents. Although it is difficult to follow the chemical processes in such devices in the 10-nm range with analytical methods, the behavior can be interpreted from known interactions of solvent molecules with electrodes and ODT.