Quantum dot single-photon switches of resonant tunneling current for discriminating-photon-number detection

PubMed Central

Weng, Qianchun; An, Zhenghua; Zhang, Bo; Chen, Pingping; Chen, Xiaoshuang; Zhu, Ziqiang; Lu, Wei

2015-01-01

Low-noise single-photon detectors that can resolve photon numbers are used to monitor the operation of quantum gates in linear-optical quantum computation. Exactly 0, 1 or 2 photons registered in a detector should be distinguished especially in long-distance quantum communication and quantum computation. Here we demonstrate a photon-number-resolving detector based on quantum dot coupled resonant tunneling diodes (QD-cRTD). Individual quantum-dots (QDs) coupled closely with adjacent quantum well (QW) of resonant tunneling diode operate as photon-gated switches- which turn on (off) the RTD tunneling current when they trap photon-generated holes (recombine with injected electrons). Proposed electron-injecting operation fills electrons into coupled QDs which turn “photon-switches” to “OFF” state and make the detector ready for multiple-photons detection. With proper decision regions defined, 1-photon and 2-photon states are resolved in 4.2 K with excellent propabilities of accuracy of 90% and 98% respectively. Further, by identifying step-like photon responses, the photon-number-resolving capability is sustained to 77 K, making the detector a promising candidate for advanced quantum information applications where photon-number-states should be accurately distinguished. PMID:25797442

Quantum dot single-photon switches of resonant tunneling current for discriminating-photon-number detection.

PubMed

Weng, Qianchun; An, Zhenghua; Zhang, Bo; Chen, Pingping; Chen, Xiaoshuang; Zhu, Ziqiang; Lu, Wei

2015-03-23

Low-noise single-photon detectors that can resolve photon numbers are used to monitor the operation of quantum gates in linear-optical quantum computation. Exactly 0, 1 or 2 photons registered in a detector should be distinguished especially in long-distance quantum communication and quantum computation. Here we demonstrate a photon-number-resolving detector based on quantum dot coupled resonant tunneling diodes (QD-cRTD). Individual quantum-dots (QDs) coupled closely with adjacent quantum well (QW) of resonant tunneling diode operate as photon-gated switches- which turn on (off) the RTD tunneling current when they trap photon-generated holes (recombine with injected electrons). Proposed electron-injecting operation fills electrons into coupled QDs which turn "photon-switches" to "OFF" state and make the detector ready for multiple-photons detection. With proper decision regions defined, 1-photon and 2-photon states are resolved in 4.2 K with excellent propabilities of accuracy of 90% and 98% respectively. Further, by identifying step-like photon responses, the photon-number-resolving capability is sustained to 77 K, making the detector a promising candidate for advanced quantum information applications where photon-number-states should be accurately distinguished.

Ultrafast Structural Dynamics in Combustion Relevant Model Systems

DOE Office of Scientific and Technical Information (OSTI.GOV)

Weber, Peter M.

2014-03-31

The research project explored the time resolved structural dynamics of important model reaction system using an array of novel methods that were developed specifically for this purpose. They include time resolved electron diffraction, time resolved relativistic electron diffraction, and time resolved Rydberg fingerprint spectroscopy. Toward the end of the funding period, we also developed time-resolved x-ray diffraction, which uses ultrafast x-ray pulses at LCLS. Those experiments are just now blossoming, as the funding period expired. In the following, the time resolved Rydberg Fingerprint Spectroscopy is discussed in some detail, as it has been a very productive method. The binding energymore » of an electron in a Rydberg state, that is, the energy difference between the Rydberg level and the ground state of the molecular ion, has been found to be a uniquely powerful tool to characterize the molecular structure. To rationalize the structure sensitivity we invoke a picture from electron diffraction: when it passes the molecular ion core, the Rydberg electron experiences a phase shift compared to an electron in a hydrogen atom. This phase shift requires an adjustment of the binding energy of the electron, which is measurable. As in electron diffraction, the phase shift depends on the molecular, geometrical structure, so that a measurement of the electron binding energy can be interpreted as a measurement of the molecule’s structure. Building on this insight, we have developed a structurally sensitive spectroscopy: the molecule is first elevated to the Rydberg state, and the binding energy is then measured using photoelectron spectroscopy. The molecule’s structure is read out as the binding energy spectrum. Since the photoionization can be done with ultrafast laser pulses, the technique is inherently capable of a time resolution in the femtosecond regime. For the purpose of identifying the structures of molecules during chemical reactions, and for the analysis of molecular species in the hot environments of combustion processes, there are several features that make the Rydberg ionization spectroscopy uniquely useful. First, the Rydberg electron’s orbit is quite large and covers the entire molecule for most molecular structures of combustion interest. Secondly, the ionization does not change vibrational quantum numbers, so that even complicated and large molecules can be observed with fairly well resolved spectra. In fact, the spectroscopy is blind to vibrational excitation of the molecule. This has the interesting consequence for the study of chemical dynamics, where the molecules are invariably very energetic, that the molecular structures are observed unobstructed by the vibrational congestion that dominates other spectroscopies. This implies also that, as a tool to probe the time-dependent structural dynamics of chemically interesting molecules, Rydberg spectroscopy may well be better suited than electron or x-ray diffraction. With recent progress in calculating Rydberg binding energy spectra, we are approaching the point where the method can be evolved into a structure determination method. To implement the Rydberg ionization spectroscopy we use a molecular beam based, time-resolved pump-probe multi-photon ionization/photoelectron scheme in which a first laser pulse excites the molecule to a Rydberg state, and a probe pulse ionizes the molecule. A time-of-flight detector measures the kinetic energy spectrum of the photoelectrons. The photoelectron spectrum directly provides the binding energy of the electron, and thereby reveals the molecule’s time-dependent structural fingerprint. Only the duration of the laser pulses limits the time resolution. With a new laser system, we have now reached time resolutions better than 100 fs, although very deep UV wavelengths (down to 190 nm) have slightly longer instrument functions. The structural dynamics of molecules in Rydberg-excited states is obtained by delaying the probe ionization photon from the pump photon; the structural dynamics of molecules in their ground state or excited valence states is measured by inducing the dynamics using a near UV laser pulse, and employing a multi-photon ionization scheme via the Rydberg states as a probe process. Thus, the technique is capable of measuring the reaction dynamics in any electronic state of neutral molecules.« less

Determination of the electron-capture coefficients and the concentration of free electrons in GaN from time-resolved photoluminescence

PubMed Central

Reshchikov, M. A.; McNamara, J. D.; Toporkov, M.; Avrutin, V.; Morkoç, H.; Usikov, A.; Helava, H.; Makarov, Yu.

2016-01-01

Point defects in high-purity GaN layers grown by hydride vapor phase epitaxy are studied by steady-state and time-resolved photoluminescence (PL). The electron-capture coefficients for defects responsible for the dominant defect-related PL bands in this material are found. The capture coefficients for all the defects, except for the green luminescence (GL1) band, are independent of temperature. The electron-capture coefficient for the GL1 band significantly changes with temperature because the GL1 band is caused by an internal transition in the related defect, involving an excited state acting as a giant trap for electrons. By using the determined electron-capture coefficients, the concentration of free electrons can be found at different temperatures by a contactless method. A new classification system is suggested for defect-related PL bands in undoped GaN. PMID:27901025

Spatially resolved density and ionization measurements of shocked foams using x-ray fluorescence

DOE Office of Scientific and Technical Information (OSTI.GOV)

MacDonald, M. J.; Keiter, P. A.; Montgomery, D. S.

2016-09-22

We present experiments at the Trident laser facility demonstrating the use of x-ray fluorescence (XRF) to simultaneously measure density, ionization state populations, and electron temperature in shocked foams. An imaging x-ray spectrometer was used to obtain spatially-resolved measurements of Ti K-more » $$\\alpha$$ emission. Density profiles were measured from K-$$\\alpha$$ intensity. Ti ionization state distributions and electron temperatures were inferred by fitting K-$$\\alpha$$ spectra to spectra from CRETIN simulations. This study shows that XRF provides a powerful tool to complement other diagnostics to make equation of state measurements of shocked materials containing a suitable tracer element.« less

Photoelectron angular distributions from rotationally resolved autoionizing states of N 2

DOE PAGES

Chartrand, A. M.; McCormack, E. F.; Jacovella, U.; ...

2017-12-08

The single-photon, photoelectron-photoion coincidence spectrum of N 2 has been recorded at high (~1.5 cm -1) resolution in the region between the N 2 + X 2Σ g +, v + = 0 and 1 ionization thresholds by using a double imaging spectrometer and intense vacuum-ultraviolet light from the Synchrotron SOLEIL. This approach provides the relative photoionization cross section, the photoelectron energy distribution, and the photoelectron angular distribution as a function of photon energy. The region of interest contains autoionizing valence states, vibrationally autoionizing Rydberg states converging to vibrationally excited levels of the N 2 + X 2Σ g +more » ground state, and electronically autoionizing states converging to the N 2 + A 2Π and B 2Σ u + states. The wavelength resolution is sufficient to resolve rotational structure in the autoionizing states, but the electron energy resolution is insufficient to resolve rotational structure in the photoion spectrum. Here, a simplified approach based on multichannel quantum defect theory is used to predict the photoelectron angular distribution parameters, β, and the results are in reasonably good agreement with experiment.« less

Time-resolved study of the electron temperature and number density of argon metastable atoms in argon-based dielectric barrier discharges

NASA Astrophysics Data System (ADS)

Desjardins, E.; Laurent, M.; Durocher-Jean, A.; Laroche, G.; Gherardi, N.; Naudé, N.; Stafford, L.

2018-01-01

A combination of optical emission spectroscopy and collisional-radiative modelling is used to determine the time-resolved electron temperature (assuming Maxwellian electron energy distribution function) and number density of Ar 1s states in atmospheric pressure Ar-based dielectric barrier discharges in presence of either NH3 or ethyl lactate. In both cases, T e values were higher early in the discharge cycle (around 0.8 eV), decreased down to about 0.35 eV with the rise of the discharge current, and then remained fairly constant during discharge extinction. The opposite behaviour was observed for Ar 1s states, with cycle-averaged values in the 1017 m-3 range. Based on these findings, a link was established between the discharge ionization kinetics (and thus the electron temperature) and the number density of Ar 1s state.

ULTRAFAST CHEMISTRY: Using Time-Resolved Vibrational Spectroscopy for Interrogation of Structural Dynamics

NASA Astrophysics Data System (ADS)

Nibbering, Erik T. J.; Fidder, Henk; Pines, Ehud

2005-05-01

Time-resolved infrared (IR) and Raman spectroscopy elucidates molecular structure evolution during ultrafast chemical reactions. Following vibrational marker modes in real time provides direct insight into the structural dynamics, as is evidenced in studies on intramolecular hydrogen transfer, bimolecular proton transfer, electron transfer, hydrogen bonding during solvation dynamics, bond fission in organometallic compounds and heme proteins, cis-trans isomerization in retinal proteins, and transformations in photochromic switch pairs. Femtosecond IR spectroscopy monitors the site-specific interactions in hydrogen bonds. Conversion between excited electronic states can be followed for intramolecular electron transfer by inspection of the fingerprint IR- or Raman-active vibrations in conjunction with quantum chemical calculations. Excess internal vibrational energy, generated either by optical excitation or by internal conversion from the electronic excited state to the ground state, is observable through transient frequency shifts of IR-active vibrations and through nonequilibrium populations as deduced by Raman resonances.

Topological Electride Y2C.

PubMed

Huang, Huaqing; Jin, Kyung-Hwan; Zhang, Shunhong; Liu, Feng

2018-03-14

Two-dimensional (2D) electrides are layered ionic crystals in which anionic electrons are confined in the interlayer space. Here, we report a discovery of nontrivial [Formula: see text] topology in the electronic structures of 2D electride Y 2 C. Based on first-principles calculations, we found a topological [Formula: see text] invariant of (1; 111) for the bulk band and topologically protected surface states in the surfaces of Y 2 C, signifying its nontrivial electronic topology. We suggest a spin-resolved angle-resolved photoemission spectroscopy (ARPES) measurement to detect the unique helical spin texture of the spin-polarized topological surface state, which will provide characteristic evidence for the nontrivial electronic topology of Y 2 C. Furthermore, the coexistence of 2D surface electride states and topological surface state enables us to explain the outstanding discrepancy between the recent ARPES experiments and theoretical calculations. Our findings establish a preliminary link between the electride in chemistry and the band topology in condensed-matter physics, which are expected to inspire further interdisciplinary research between these fields.

Use of multiwavelength emission from hollow cathode lamp for measurement of state resolved atom density of metal vapor produced by electron beam evaporation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Majumder, A.; Dikshit, B.; Bhatia, M. S.

2008-09-15

State resolved atom population of metal vapor having low-lying metastable states departs from equilibrium value. It needs to be experimentally investigated. This paper reports the use of hollow cathode lamp based atomic absorption spectroscopy technique to measure online the state resolved atom density (ground and metastable) of metal vapor in an atomic beam produced by a high power electron gun. In particular, the advantage of availability of multiwavelength emission in hollow cathode lamp is used to determine the atom density in different states. Here, several transitions pertaining to a given state have also been invoked to obtain the mean valuemore » of atom density thereby providing an opportunity for in situ averaging. It is observed that at higher source temperatures the atoms from metastable state relax to the ground state. This is ascribed to competing processes of atom-atom and electron-atom collisions. The formation of collision induced virtual source is inferred from measurement of atom density distribution profile along the width of the atomic beam. The total line-of-sight average atom density measured by absorption technique using hollow cathode lamp is compared to that measured by atomic vapor deposition method. The presence of collisions is further supported by determination of beaming exponent by numerically fitting the data.« less

Unraveling the electronic relaxation dynamics in photoexcited 2,4-difluoroaniline via femtosecond time-resolved photoelectron imaging

NASA Astrophysics Data System (ADS)

Ling, Fengzi; Li, Shuai; Wei, Jie; Liu, Kai; Wang, Yanmei; Zhang, Bing

2018-04-01

Time-resolved photoelectron imaging is employed to investigate the relaxation dynamics of the lowest two excited electronic states S1(ππ*) and S2(π3s/πσ*) in 2,4-difluoroaniline (24DFA). As the S1(ππ*) state is populated directly following 289 nm excitation, the population undergoes ultrafast intramolecular vibrational redistribution on a 540 fs time scale, followed by efficient intersystem crossing from S1(ππ*) to the triplet state within 379 ps, and the subsequent slower deactivation process of the triplet state. For excitation to the S2(π3s/πσ*) state at 238 nm, the population probably bifurcates into two decay channels. The dominant channel with 84 fs involves ultrafast internal conversion to the S1(ππ*) state, from which it relaxes to the electronic ground state on a 116 ps time scale. The other appears to involve motion along the S2(π3s/πσ*) potential energy surface. Our data also determine experimentally the electronic energies of S2(π3s/πσ*), S3(ππ*), and several Rydberg states in 24DFA.

Investigation of temporal-resolved emission spectra of highly charged Al ions from laser-produced plasmas

DOE Office of Scientific and Technical Information (OSTI.GOV)

Su, M. G., E-mail: sumg@nwnu.edu.cn; Sun, D. X.; Dong, C. Z.

2016-03-15

Temporal evolution of extreme ultraviolet emission from laser-produced aluminum (Al) plasma has been experimentally and theoretically investigated. Al plasmas have been measured by using the temporal-spatially resolved laser-produced plasma technique. The emission lines can be identified from 2p-3s, 3d, 4s, 4d, 5d transition lines from Al{sup 3+} to Al{sup 6+} ions. In order to quickly diagnose the plasma, the assumptions of a normalized Boltzmann distribution among the excited states and a steady-state collisional-radiative model are used to estimate the values of electron temperature and electron density in plasma. We succeeded in reproducing the simulated spectra related to the different timemore » delays, which are in good agreement with experiments. Temporal evolution behavior of highly charged Al ions in plasma has been analyzed, and the exponential decay about electron temperature and electron density has been obtained. The results indicate that the temporal-spatially resolved measurement is essential for accurate understanding of evolution behavior of highly charged ions in laser-produced plasmas.« less

Image potential states at transition metal oxide surfaces: A time-resolved two-photon photoemission study on ultrathin NiO films

NASA Astrophysics Data System (ADS)

Gillmeister, K.; Kiel, M.; Widdra, W.

2018-02-01

For well-ordered ultrathin films of NiO(001) on Ag(001), a series of unoccupied states below the vacuum level has been found. The states show a nearly free electron dispersion and binding energies which are typical for image potential states. By time-resolved two-photon photoemission (2PPE), the lifetimes of the first three states and their dependence on oxide film thickness are determined. For NiO film thicknesses between 2 and 4 monolayers (ML), the lifetime of the first state is in the range of 28-42 fs and shows an oscillatory behavior with increasing thickness. The values for the second state decrease monotonically from 88 fs for 2 ML to 33 fs for 4 ML. These differences are discussed in terms of coupling of the unoccupied states to the layer-dependent electronic structure of the growing NiO film.

Electronic and Vibrational Coherence in Charge-Transfer Reactions

NASA Astrophysics Data System (ADS)

Scherer, Norbert

1996-03-01

The ultrafast dynamics associated with optically-induced intervalence charge-transfer reactions in solution and protein environments are reported. These studies include the Fe^(II)-Fe^(III) MMCT complex Prussian blue and the mixed valence dimer (CN)_5Ru^(II)CNRuRu^(III)(NH_3)_5. The protein systems include blue copper proteins and the bacterial photosynthetic reaction center. The experimental approaches include photon echo, wavelength-resolved pump-probe and anisotropy measurements performed with 12-16fs duration optical pulses. Complicated time-domain waveforms reflect the several different p[rocesses and time scales for relaxation of coherences (both electronic and vibrational) and populations within these systems. The photon echo and anisotropy results probe electronic coherence and dephasing prior to back electron transfer. Wavelength-resolved pump-probe results reveal vibrational modes coupled to the CT-coordinate as well as formation of new product states or vibrational cooling in the ground state following back electron transfer.

Elucidating the Nature of the Excited State of a Heteroleptic Copper Photosensitizer by using Time-Resolved X-ray Absorption Spectroscopy.

PubMed

Moonshiram, Dooshaye; Garrido-Barros, Pablo; Gimbert-Suriñach, Carolina; Picón, Antonio; Liu, Cunming; Zhang, Xiaoyi; Karnahl, Michael; Llobet, Antoni

2018-04-25

We report the light-induced electronic and geometric changes taking place within a heteroleptic Cu I photosensitizer, namely [(xant)Cu(Me 2 phenPh 2 )]PF 6 (xant=xantphos, Me 2 phenPh 2 =bathocuproine), by time-resolved X-ray absorption spectroscopy in the ps-μs time regime. Time-resolved X-ray absorption near edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) analysis enabled the elucidation of the electronic and structural configuration of the copper center in the excited state as well as its decay dynamics in different solvent conditions with and without triethylamine acting as a sacrificial electron donor. A three-fold decrease in the decay lifetime of the excited state is observed in the presence of triethylamine, showing the feasibility of the reductive quenching pathway in the latter case. A prominent pre-edge feature is observed in the XANES spectrum of the excited state upon metal to charge ligand transfer transition, showing an increased hybridization of the 3d states with the ligand p orbitals in the tetrahedron around the Cu center. EXAFS and density functional theory illustrate a significant shortening of the Cu-N and an elongation of the Cu-P bonds together with a decrease in the torsional angle between the xantphos and bathocuproine ligand. This study provides mechanistic time-resolved understanding for the development of improved heteroleptic Cu I photosensitizers, which can be used for the light-driven production of hydrogen from water. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Femtosecond Electron Wave Packet Propagation and Diffraction: Towards Making the ``Molecular Movie"

NASA Astrophysics Data System (ADS)

Miller, R. J. Dwayne

2003-03-01

Time-resolved electron diffraction harbors great promise for achieving atomic resolution of the fastest chemical processes. The generation of sufficiently short electron pulses to achieve this real time view of a chemical reaction has been limited by problems in maintaining short electron pulses with realistic electron densities to the sample. The propagation dynamics of femtosecond electron packets in the drift region of a photoelectron gun are investigated with an N-body numerical simulation and mean-field model. This analyis shows that the redistribution of electrons inside the packet, arising from space-charge and dispersion contributions, changes the pulse envelope and leads to the development of a spatially linear axial velocity distribution. These results have been used in the design of femtosecond photoelectron guns with higher time resolution and novel electron-optical methods of pulse characterization that are approaching 100 fs timescales. Time-resolved diffraction studies with electron pulses of approximately 500 femtoseconds have focused on solid-liquid phase transitions under far from equilibrium conditions. This work gives a microscopic description of the melting process and illustrates the promise of atomically resolving transition state processes.

Fine- and hyperfine-structure effects in molecular photoionization. I. General theory and direct photoionization.

PubMed

Germann, Matthias; Willitsch, Stefan

2016-07-28

We develop a model for predicting fine- and hyperfine intensities in the direct photoionization of molecules based on the separability of electron and nuclear spin states from vibrational-electronic states. Using spherical tensor algebra, we derive highly symmetrized forms of the squared photoionization dipole matrix elements from which we derive the salient selection and propensity rules for fine- and hyperfine resolved photoionizing transitions. Our theoretical results are validated by the analysis of the fine-structure resolved photoelectron spectrum of O2 reported by Palm and Merkt [Phys. Rev. Lett. 81, 1385 (1998)] and are used for predicting hyperfine populations of molecular ions produced by photoionization.

Coherent structural trapping through wave packet dispersion during photoinduced spin state switching

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lemke, Henrik T.; Kjær, Kasper S.; Hartsock, Robert

The description of ultrafast nonadiabatic chemical dynamics during molecular photo-transformations remains challenging because electronic and nuclear configurations impact each other and cannot be treated independently. Here we gain experimental insights, beyond the Born–Oppenheimer approximation, into the light-induced spin-state trapping dynamics of the prototypical [Fe(bpy)3]2+ compound by time-resolved X-ray absorption spectroscopy at sub-30-femtosecond resolution and high signal-to-noise ratio. The electronic decay from the initial optically excited electronic state towards the high spin state is distinguished from the structural trapping dynamics, which launches a coherent oscillating wave packet (265 fs period), clearly identified as molecular breathing. Throughout the structural trapping, the dispersionmore » of the wave packet along the reaction coordinate reveals details of intramolecular vibronic coupling before a slower vibrational energy dissipation to the solution environment. These findings illustrate how modern time-resolved X-ray absorption spectroscopy can provide key information to unravel dynamic details of photo-functional molecules.« less

Coherent structural trapping through wave packet dispersion during photoinduced spin state switching

DOE PAGES

Lemke, Henrik T.; Kjær, Kasper S.; Hartsock, Robert; ...

2017-05-24

The description of ultrafast nonadiabatic chemical dynamics during molecular photo-transformations remains challenging because electronic and nuclear configurations impact each other and cannot be treated independently. Here we gain experimental insights, beyond the Born–Oppenheimer approximation, into the light-induced spin-state trapping dynamics of the prototypical [Fe(bpy)3]2+ compound by time-resolved X-ray absorption spectroscopy at sub-30-femtosecond resolution and high signal-to-noise ratio. The electronic decay from the initial optically excited electronic state towards the high spin state is distinguished from the structural trapping dynamics, which launches a coherent oscillating wave packet (265 fs period), clearly identified as molecular breathing. Throughout the structural trapping, the dispersionmore » of the wave packet along the reaction coordinate reveals details of intramolecular vibronic coupling before a slower vibrational energy dissipation to the solution environment. These findings illustrate how modern time-resolved X-ray absorption spectroscopy can provide key information to unravel dynamic details of photo-functional molecules.« less

Coherent structural trapping through wave packet dispersion during photoinduced spin state switching

NASA Astrophysics Data System (ADS)

Lemke, Henrik T.; Kjær, Kasper S.; Hartsock, Robert; van Driel, Tim B.; Chollet, Matthieu; Glownia, James M.; Song, Sanghoon; Zhu, Diling; Pace, Elisabetta; Matar, Samir F.; Nielsen, Martin M.; Benfatto, Maurizio; Gaffney, Kelly J.; Collet, Eric; Cammarata, Marco

2017-05-01

The description of ultrafast nonadiabatic chemical dynamics during molecular photo-transformations remains challenging because electronic and nuclear configurations impact each other and cannot be treated independently. Here we gain experimental insights, beyond the Born-Oppenheimer approximation, into the light-induced spin-state trapping dynamics of the prototypical [Fe(bpy)3]2+ compound by time-resolved X-ray absorption spectroscopy at sub-30-femtosecond resolution and high signal-to-noise ratio. The electronic decay from the initial optically excited electronic state towards the high spin state is distinguished from the structural trapping dynamics, which launches a coherent oscillating wave packet (265 fs period), clearly identified as molecular breathing. Throughout the structural trapping, the dispersion of the wave packet along the reaction coordinate reveals details of intramolecular vibronic coupling before a slower vibrational energy dissipation to the solution environment. These findings illustrate how modern time-resolved X-ray absorption spectroscopy can provide key information to unravel dynamic details of photo-functional molecules.

Time-resolved x-ray absorption spectroscopy: Watching atoms dance

NASA Astrophysics Data System (ADS)

Milne, Chris J.; Pham, Van-Thai; Gawelda, Wojciech; van der Veen, Renske M.; El Nahhas, Amal; Johnson, Steven L.; Beaud, Paul; Ingold, Gerhard; Lima, Frederico; Vithanage, Dimali A.; Benfatto, Maurizio; Grolimund, Daniel; Borca, Camelia; Kaiser, Maik; Hauser, Andreas; Abela, Rafael; Bressler, Christian; Chergui, Majed

2009-11-01

The introduction of pump-probe techniques to the field of x-ray absorption spectroscopy (XAS) has allowed the monitoring of both structural and electronic dynamics of disordered systems in the condensed phase with unprecedented accuracy, both in time and in space. We present results on the electronically excited high-spin state structure of an Fe(II) molecular species, [FeII(bpy)3]2+, in aqueous solution, resolving the Fe-N bond distance elongation as 0.2 Å. In addition an analysis technique using the reduced χ2 goodness of fit between FEFF EXAFS simulations and the experimental transient absorption signal in energy space has been successfully tested as a function of excited state population and chemical shift, demonstrating its applicability in situations where the fractional excited state population cannot be determined through other measurements. Finally by using a novel ultrafast hard x-ray 'slicing' source the question of how the molecule relaxes after optical excitation has been successfully resolved using femtosecond XANES.

Charge Carriers Modulate the Bonding of Semiconductor Nanoparticle Dopants As Revealed by Time-Resolved X-ray Spectroscopy

DOE PAGES

Hassan, Asra; Zhang, Xiaoyi; Liu, Xiaohan; ...

2017-08-28

Understanding the electronic structure of doped semiconductors is essential to realize advancements in electronics and in the rational design of nanoscale devices. Here, we report the results of time-resolved X-ray absorption studies on copper-doped cadmium sulfide nanoparticles that provide an explicit description of the electronic dynamics of the dopants. The interaction of a dopant ion and an excess charge carrier is unambiguously observed via monitoring the oxidation state. The experimental data combined with DFT calculations demonstrate that dopant bonding to the host matrix is modulated by its interaction with charge carriers. Additionally, the transient photoluminescence and the kinetics of dopantmore » oxidation reveal the presence of two types of surface-bound ions that create mid-gap states.« less

Review of the Theoretical Description of Time-Resolved Angle-Resolved Photoemission Spectroscopy in Electron-Phonon Mediated Superconductors

DOE PAGES

Kemper, A. F.; Sentef, M. A.; Moritz, B.; ...

2017-07-13

Here. we review recent work on the theory for pump/probe photoemission spectroscopy of electron-phonon mediated superconductors in both the normal and the superconducting states. We describe the formal developments that allow one to solve the Migdal-Eliashberg theory in nonequilibrium for an ultrashort laser pumping field, and explore the solutions which illustrate the relaxation as energy is transferred from electrons to phonons. We also focus on exact results emanating from sum rules and approximate numerical results which describe rules of thumb for relaxation processes. Additionally, in the superconducting state, we describe how Anderson-Higgs oscillations can be excited due to the nonlinearmore » coupling with the electric field and describe mechanisms where pumping the system enhances superconductivity.« less

Review of the Theoretical Description of Time-Resolved Angle-Resolved Photoemission Spectroscopy in Electron-Phonon Mediated Superconductors

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kemper, A. F.; Sentef, M. A.; Moritz, B.

Here. we review recent work on the theory for pump/probe photoemission spectroscopy of electron-phonon mediated superconductors in both the normal and the superconducting states. We describe the formal developments that allow one to solve the Migdal-Eliashberg theory in nonequilibrium for an ultrashort laser pumping field, and explore the solutions which illustrate the relaxation as energy is transferred from electrons to phonons. We also focus on exact results emanating from sum rules and approximate numerical results which describe rules of thumb for relaxation processes. Additionally, in the superconducting state, we describe how Anderson-Higgs oscillations can be excited due to the nonlinearmore » coupling with the electric field and describe mechanisms where pumping the system enhances superconductivity.« less

Charge Carriers Modulate the Bonding of Semiconductor Nanoparticle Dopants As Revealed by Time-Resolved X-ray Spectroscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hassan, Asra; Zhang, Xiaoyi; Liu, Xiaohan

Understanding the electronic structure of doped semiconductors is essential to realize advancements in electronics and in the rational design of nanoscale devices. Here, we report the results of time-resolved X-ray absorption studies on copper-doped cadmium sulfide nanoparticles that provide an explicit description of the electronic dynamics of the dopants. The interaction of a dopant ion and an excess charge carrier is unambiguously observed via monitoring the oxidation state. The experimental data combined with DFT calculations demonstrate that dopant bonding to the host matrix is modulated by its interaction with charge carriers. Additionally, the transient photoluminescence and the kinetics of dopantmore » oxidation reveal the presence of two types of surface-bound ions that create mid-gap states.« less

Electron-electron interaction in ion-atom collisions studied by projectile state-resolved Auger-electron spectroscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dohyung Lee.

This dissertation addresses the problem of dynamic electron-electron interactions in fast ion-atom collisions using projectile Auger electron spectroscopy. The study was carried out by measuring high-resolution projectile KKL Auger electron spectra as a function of projectile energy for the various collision systems of 0.25-2 MeV/u O{sup q+} and F{sup q+} incident on H{sub 2} and He targets. The electrons were detected in the beam direction, where the kinematic broadening is minimized. A zero-degree tandem electron spectrometer system, was developed and showed the versatility of zero-degree measurements of collisionally-produced atomic states. The zero-degree binary encounter electrons (BEe), quasifree target electrons ionizedmore » by the projectiles in head-on collisions, were observed as a strong background in the KLL Auger electron spectrum. They were studied by treating the target ionization as 180{degree} Rutherford elastic scattering in the projectile frame, and resulted in a validity test of the impulse approximation (IA) and a way to determine the spectrometer efficiency. An anomalous q-dependence, in which the zero-degree BEe yields increase with decreasing projectile charge state (q), was observed. State-resolved KLL Auger cross sections were determined by using the BEe normalization and thus the cross section of the electron-electron interactions such as resonant transfer-excitation (RTE), electron-electron excitation (eeE), and electron-electron ionization (eeI) were determined. Projectile 2l capture with 1s {yields} 2p excitation by the captured target electron was observed as an RTE process with Li-like and He-like projectiles and the measured RTEA (RTE followed by Auger decay) cross sections showed good agreement with an RTE-IA treatment and RTE alignment theory.« less

Rotationally Resolved Electronic Spectroscopy of Biomolecules in the Gas Phase. Melatonin.

NASA Astrophysics Data System (ADS)

Yi, John T.; Pratt, David W.; Brand, Christian; Wollenhaupt, Miriam; Schmitt, Michael; Meerts, W. Leo

2011-06-01

Rotationally resolved electronic spectra of the A and B bands of melatonin have been analyzed using an evolutionary strategy approach. From a comparison of the ab initio calculated structures of energy selected conformers to the experimental rotational constants, the A band could be shown to be due to a gauche structure of the side chain, while the B band is an anti structure. Both bands show a complicated pattern due to a splitting from the three-fold internal rotation of the methyl rotor in the N-acetyl group of the molecules. From a torsional analysis we additionally were able to determine the barriers of the methyl torsion in both electronic states. The electronic nature of the lowest excited singlet state could be determined to be 1LB (as in the chromophore indole) from comparison to the results of ab initio calculations.

Time-Resolved Magnetic Field Effects Distinguish Loose Ion Pairs from Exciplexes

PubMed Central

2013-01-01

We describe the experimental investigation of time-resolved magnetic field effects in exciplex-forming organic donor–acceptor systems. In these systems, the photoexcited acceptor state is predominantly deactivated by bimolecular electron transfer reactions (yielding radical ion pairs) or by direct exciplex formation. The delayed fluorescence emitted by the exciplex is magnetosensitive if the reaction pathway involves loose radical ion pair states. This magnetic field effect results from the coherent interconversion between the electronic singlet and triplet radical ion pair states as described by the radical pair mechanism. By monitoring the changes in the exciplex luminescence intensity when applying external magnetic fields, details of the reaction mechanism can be elucidated. In this work we present results obtained with the fluorophore-quencher pair 9,10-dimethylanthracene/N,N-dimethylaniline (DMA) in solvents of systematically varied permittivity. A simple theoretical model is introduced that allows discriminating the initial state of quenching, viz., the loose ion pair and the exciplex, based on the time-resolved magnetic field effect. The approach is validated by applying it to the isotopologous fluorophore-quencher pairs pyrene/DMA and pyrene-d10/DMA. We detect that both the exciplex and the radical ion pair are formed during the initial quenching stage. Upon increasing the solvent polarity, the relative importance of the distant electron transfer quenching increases. However, even in comparably polar media, the exciplex pathway remains remarkably significant. We discuss our results in relation to recent findings on the involvement of exciplexes in photoinduced electron transfer reactions. PMID:24041160

Electronic structure of dense Pb overlayers on Si(111) investigated using angle-resolved photoemission

NASA Astrophysics Data System (ADS)

Choi, W. H.; Koh, H.; Rotenberg, E.; Yeom, H. W.

2007-02-01

Dense Pb overlayers on Si(111) are important as the wetting layer for anomalous Pb island growth as well as for their own complex “devil’s-staircase” phases. The electronic structures of dense Pb overlayers on Si(111) were investigated in detail by angle-resolved photoemission. Among the series of ordered phases found recently above one monolayer, the low-coverage 7×3 and the high-coverage 14×3 phases are studied; they are well ordered and form reproducibly in large areas. The band dispersions and Fermi surfaces of the two-dimensional (2D) electronic states of these overlayers are mapped out. A number of metallic surface-state bands are identified for both phases with complex Fermi contours. The basic features of the observed Fermi contours can be explained by overlapping 2D free-electron-like Fermi circles. This analysis reveals that the 2D electrons near the Fermi level of the 7×3 and 14×3 phases are mainly governed by strong 1×1 and 3×3 potentials, respectively. The origins of the 2D electronic states and their apparent Fermi surface shapes are discussed based on recent structure models.

Direct observation of spin-resolved full and empty electron states in ferromagnetic surfaces

DOE Office of Scientific and Technical Information (OSTI.GOV)

Berti, G., E-mail: giulia.berti@polimi.it; Calloni, A.; Brambilla, A.

2014-07-15

We present a versatile apparatus for the study of ferromagnetic surfaces, which combines spin-polarized photoemission and inverse photoemission spectroscopies. Samples can be grown by molecular beam epitaxy and analyzed in situ. Spin-resolved photoemission spectroscopy analysis is done with a hemispherical electron analyzer coupled to a 25 kV-Mott detector. Inverse photoemission spectroscopy experiments are performed with GaAs crystals as spin-polarized electron sources and a UV bandpass photon detector. As an example, measurements on the oxygen passivated Fe(100)-p(1×1)O surface are presented.

Asymmetric valley-resolved beam splitting and incident modes in slanted graphene junctions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hsieh, S. H.; Chu, C. S.

2016-01-18

Electron injection into a graphene sheet through a slanted armchair graphene nanoribbon (AGNR) is investigated. An incident mode, or subband, in the AGNR is valley-unpolarized. Our attention is on the valley-resolved nature of the injected electron beams and its connection to the incident mode. It is known for a normal injection that an incident mode will split symmetrically into two valley-resolved beams of equal intensity. We show, in contrast, that slanted injections result in asymmetric valley-resolved beam splitting. The most asymmetric beam splitting cases, when one of the valley-resolved beams has basically disappeared, are found and the condition derived. Thismore » is shown not due to trigonal warping because it holds even in the low incident energy regime, as long as collimation allows. These most asymmetric beam splitting cases occur at energies within an energy interval near and include the subband edge of an incident mode. The physical picture is best illustrated by a projection of the slanted AGNR subband states onto that of the 2D graphene sheet. It follows that the disappearing of a valley-resolved beam coincides with the situation that the group velocities of the projected states in the corresponding valley are in backward directions.« less

Rotationally resolved electronic spectroscopy of biomolecules in the gas phase. Melatonin

NASA Astrophysics Data System (ADS)

Yi, John T.; Brand, Christian; Wollenhaupt, Miriam; Pratt, David W.; Leo Meerts, W.; Schmitt, Michael

2011-07-01

Rotationally resolved electronic spectra of the A and B bands of melatonin have been analyzed using an evolutionary strategy approach. From a comparison of the ab initio calculated structures of energy selected conformers to the experimental rotational constants, the A band could be shown to be due to a gauche structure of the side chain, while the B band is an anti structure. Both bands show a complicated pattern due to a splitting from the threefold internal rotation of the methyl rotor in the N-acetyl group of the molecules. From a torsional analysis we additionally were able to determine the barriers of the methyl torsion in both electronic states of melatonin B and give an estimate for the change of the barrier upon electronic excitation in melatonin A. The electronic nature of the lowest excited singlet state could be determined to be 1Lb (as in the chromophore indole) from comparison to the results of ab initio calculations.

Pervasive electronic nematicity in a cuprate superconductor

NASA Astrophysics Data System (ADS)

Wu, J.; Bollinger, A. T.; He, X.; Božović, I.

2018-06-01

We describe an extensive experimental study of La2-xSrxCuO4 films synthesized by molecular beam epitaxy and investigated by angle-resolved measurements of transverse resistivity (without applied magnetic field). The data show that an unusual metallic state, in which the rotational symmetry of the electron fluid is spontaneously broken, occurs in a large temperature and doping region. The superconducting state always emerges out of this nematic metal state.

Experimental and Theoretical Aspects of Excited State Electron Transfer and Related Phenomena: Conference Held in Honour of Zbigniew R. Grabowski in Pultusk, Poland on September 27-October 2, 1992

DTIC Science & Technology

1992-10-01

DBMBF2 ) undergoes photoreaction with olefins through a partial electron transfer that leads to cycloaddition or sensitized Diels - Alder reactions. We...8217 Fluorescence. 10:00 J.M. WARMAN: Photon-induced Intramolecular Charge Sepaiation Studied byTime-Resolved Microwave Conductivity. 10:30 Coffee 11:)) W...26 Photon-Induced Intramolecular Charge Separation Studied by Time-Resolved Microwave Conductivity John M. Warman IRI, Delft University of Technology

Electronic structure and relaxation dynamics in a superconducting topological material

DOE PAGES

Neupane, Madhab; Ishida, Yukiaki; Sankar, Raman; ...

2016-03-03

Topological superconductors host new states of quantum matter which show a pairing gap in the bulk and gapless surface states providing a platform to realize Majorana fermions. Recently, alkaline-earth metal Sr intercalated Bi2Se3 has been reported to show superconductivity with a Tc~3K and a large shielding fraction. Here we report systematic normal state electronic structure studies of Sr0.06Bi2Se3 (Tc~2.5K) by performing photoemission spectroscopy. Using angle-resolved photoemission spectroscopy (ARPES), we observe a quantum well confined two-dimensional (2D) state coexisting with a topological surface state in Sr0.06Bi2Se3. Furthermore, our time-resolved ARPES reveals the relaxation dynamics showing different decay mechanism between the excitedmore » topological surface states and the two-dimensional states. Our experimental observation is understood by considering the intra-band scattering for topological surface states and an additional electron phonon scattering for the 2D states, which is responsible for the superconductivity. Our first-principles calculations agree with the more effective scattering and a shorter lifetime of the 2D states. In conclusion, our results will be helpful in understanding low temperature superconducting states of these topological materials.« less

Ne matrix spectra of the sym-C6Br3F3+ radical cation

USGS Publications Warehouse

Bondybey, V.E.; Sears, T.J.; Miller, T.A.; Vaughn, C.; English, J.H.; Shiley, R.S.

1981-01-01

The electronic absorption and laser excited, wavelength resolved fluorescence spectra of the title cation have been observed in solid Ne matrix and vibrationally analysed. The vibrational structure of the excited B2A2??? state shows close similarity to the parent compound. The X2E??? ground state structure is strongly perturbed and irregular owing to a large Jahn-Teller distortion. The data are analysed in terms of a recently developed, sophisticated multimode Jahn-Teller theoretical model. We have generated the sym-C6Br3F3+ cations in solid Ne matrix and obtained their wavelength resolved emission and absorption spectra. T ground electronic X2E??? state exhibits an irregular and strongly perturbed vibrational structure, which can be successfully modeled using sophisticated multimode Jahn-Teller theory. ?? 1981.

Spectroscopic Diagnosis of Excited-State Aromaticity: Capturing Electronic Structures and Conformations upon Aromaticity Reversal.

PubMed

Oh, Juwon; Sung, Young Mo; Hong, Yongseok; Kim, Dongho

2018-03-06

Aromaticity, the special energetic stability derived from cyclic [4 n + 2]π-conjugated electronic structures, has been the topic of intense interest in chemistry because it plays a critical role in rationalizing molecular stability, reactivity, and physical/chemical properties. Recently, the pioneering work by Colin Baird on aromaticity reversal, postulating that aromatic (antiaromatic) character in the ground state reverses to antiaromatic (aromatic) character in the lowest excited triplet state, has attracted much scientific attention. The completely reversed aromaticity in the excited state provides direct insight into understanding the photophysical/chemical properties of photoactive materials. In turn, the application of aromatic molecules to photoactive materials has led to numerous studies revealing this aromaticity reversal. However, most studies of excited-state aromaticity have been based on the theoretical point of view. The experimental evaluation of aromaticity in the excited state is still challenging and strenuous because the assessment of (anti)aromaticity with conventional magnetic, energetic, and geometric indices is difficult in the excited state, which practically restricts the extension and application of the concept of excited-state aromaticity. Time-resolved optical spectroscopies can provide a new and alternative avenue to evaluate excited-state aromaticity experimentally while observing changes in the molecular features in the excited states. Time-resolved optical spectroscopies take advantage of ultrafast laser pulses to achieve high time resolution, making them suitable for monitoring ultrafast changes in the excited states of molecular systems. This can provide valuable information for understanding the aromaticity reversal. This Account presents recent breakthroughs in the experimental assessment of excited-state aromaticity and the verification of aromaticity reversal with time-resolved optical spectroscopic measurements. To scrutinize this intriguing and challenging scientific issue, expanded porphyrins have been utilized as the ideal testing platform for investigating aromaticity because they show distinct aromatic and antiaromatic characters with aromaticity-specific spectroscopic features. Expanded porphyrins exhibit perfect aromatic and antiaromatic congener pairs having the same molecular framework but different numbers of π electrons, which facilitates the study of the pure effect of aromaticity by comparative analyses. On the basis of the characteristics of expanded porphyrins, time-resolved electronic and vibrational absorption spectroscopies capture the changes in electronic structure and molecular conformations driven by the change in aromaticity and provide clear evidence for aromaticity reversal in the excited states. The approaches described in this Account pave the way for the development of new and alternative experimental indices for the evaluation of excited-state aromaticity, which will enable overarching and fundamental comprehension of the role of (anti)aromaticity in the stability, dynamics, and reactivity in the excited states with possible implications for practical applications.

Fine- and hyperfine-structure effects in molecular photoionization. I. General theory and direct photoionization

DOE Office of Scientific and Technical Information (OSTI.GOV)

Germann, Matthias; Willitsch, Stefan, E-mail: stefan.willitsch@unibas.ch

2016-07-28

We develop a model for predicting fine- and hyperfine intensities in the direct photoionization of molecules based on the separability of electron and nuclear spin states from vibrational-electronic states. Using spherical tensor algebra, we derive highly symmetrized forms of the squared photoionization dipole matrix elements from which we derive the salient selection and propensity rules for fine- and hyperfine resolved photoionizing transitions. Our theoretical results are validated by the analysis of the fine-structure resolved photoelectron spectrum of O{sub 2} reported by Palm and Merkt [Phys. Rev. Lett. 81, 1385 (1998)] and are used for predicting hyperfine populations of molecular ionsmore » produced by photoionization.« less

Electron-impact electronic-state excitation of para-benzoquinone

NASA Astrophysics Data System (ADS)

Jones, D. B.; da Costa, R. F.; Kossoski, F.; Varella, M. T. do N.; Bettega, M. H. F.; Ferreira da Silva, F.; Limão-Vieira, P.; García, G.; Lima, M. A. P.; White, R. D.; Brunger, M. J.

2018-03-01

Angle resolved electron energy loss spectra (EELS) for para-benzoquinone (C6H4O2) have been recorded for incident electron energies of 20, 30, and 40 eV. Measured differential cross sections (DCSs) for electronic band features, composed of a combination of energetically unresolved electronic states, are subsequently derived from those EELS. Where possible, the obtained DCSs are compared with those calculated using the Schwinger multichannel method with pseudopotentials. These calculations were performed using a minimum orbital basis single configuration interaction framework at the static exchange plus polarisation level. Here, quite reasonable agreement between the experimental cross sections and the theoretical cross sections for the summation of unresolved states was observed.

Magneto-electronic properties and spin-resolved I-V curves of a Co/GeSe heterojunction diode: an ab initio study

NASA Astrophysics Data System (ADS)

Makinistian, Leonardo; Albanesi, Eduardo A.

2013-06-01

We present ab initio calculations of magnetoelectronic and transport properties of the interface of hcp Cobalt (001) and the intrinsic narrow-gap semiconductor germanium selenide (GeSe). Using a norm-conserving pseudopotentials scheme within DFT, we first model the interface with a supercell approach and focus on the spin-resolved densities of states and the magnetic moment (spin and orbital components) at the different atomic layers that form the device. We also report a series of cuts (perpendicular to the plane of the heterojunction) of the electronic and spin densities showing a slight magnetization of the first layers of the semiconductor. Finally, we model the device with a different scheme: using semiinfinite electrodes connected to the heterojunction. These latter calculations are based upon a nonequilibrium Green's function approach that allows us to explore the spin-resolved electronic transport under a bias voltage (spin-resolved I-V curves), revealing features of potential applicability in spintronics.

Manipulating charge transfer excited state relaxation and spin crossover in iron coordination complexes with ligand substitution

DOE PAGES

Zhang, Wenkai; Kjaer, Kasper S.; Alonso-Mori, Roberto; ...

2016-08-25

Developing light-harvesting and photocatalytic molecules made with iron could provide a cost effective, scalable, and environmentally benign path for solar energy conversion. To date these developments have been limited by the sub-picosecond metal-to-ligand charge transfer (MLCT) electronic excited state lifetime of iron based complexes due to spin crossover – the extremely fast intersystem crossing and internal conversion to high spin metal-centered excited states. We revitalize a 30 year old synthetic strategy for extending the MLCT excited state lifetimes of iron complexes by making mixed ligand iron complexes with four cyanide (CN –) ligands and one 2,2'-bipyridine (bpy) ligand. This enablesmore » MLCT excited state and metal-centered excited state energies to be manipulated with partial independence and provides a path to suppressing spin crossover. We have combined X-ray Free-Electron Laser (XFEL) Kβ hard X-ray fluorescence spectroscopy with femtosecond time-resolved UV-visible absorption spectroscopy to characterize the electronic excited state dynamics initiated by MLCT excitation of [Fe(CN) 4(bpy)] 2–. The two experimental techniques are highly complementary; the time-resolved UV-visible measurement probes allowed electronic transitions between valence states making it sensitive to ligand-centered electronic states such as MLCT states, whereas the Kβ fluorescence spectroscopy provides a sensitive measure of changes in the Fe spin state characteristic of metal-centered excited states. Here, we conclude that the MLCT excited state of [Fe(CN) 4(bpy)] 2– decays with roughly a 20 ps lifetime without undergoing spin crossover, exceeding the MLCT excited state lifetime of [Fe(2,2'-bipyridine) 3] 2+ by more than two orders of magnitude.« less

Spin polarized and density modulated phases in symmetric electron-electron and electron-hole bilayers.

PubMed

Kumar, Krishan; Moudgil, R K

2012-10-17

We have studied symmetric electron-electron and electron-hole bilayers to explore the stable homogeneous spin phase and the feasibility of inhomogeneous charge-/spin-density ground states. The former is resolved by comparing the ground-state energies in states of different spin polarizations, while the latter is resolved by searching for a divergence in the wavevector-dependent static charge/spin susceptibility. For this endeavour, we have used the dielectric approach within the self-consistent mean-field theory of Singwi et al. We find that the inter-layer interactions tend to change an abrupt spin-polarization transition of an isolated layer into a nearly gradual one, even though the partially spin-polarized phases are not clearly stable within the accuracy of our calculation. The transition density is seen to decrease with a reduction in layer spacing, implying a suppression of spin polarization by inter-layer interactions. Indeed, the suppression shows up distinctly in the spin susceptibility computed from the spin-polarization dependence of the ground-state energy. However, below a critical layer spacing, the unpolarized liquid becomes unstable against a charge-density-wave (CDW) ground state at a density preceding full spin polarization, with the transition density for the CDW state increasing on further reduction in the layer spacing. Due to attractive e-h correlations, the CDW state is found to be more pronounced in the e-h bilayer. On the other hand, the static spin susceptibility diverges only in the long-wavelength limit, which simply represents a transition to the homogeneous spin-polarized phase.

Channel-resolved photo- and Auger-electron spectroscopy of halogenated hydrocarbons

NASA Astrophysics Data System (ADS)

Ablikim, Utuq; Kaderiya, B.; Kumarapan, V.; Kushawaha, R.; Rudenko, A.; Rolles, D.; Xiong, H.; Berrah, N.; Bomme, C.; Savelyev, E.; Kilcoyne, D.

2016-05-01

Inner-shell photoelectron and Auger electron spectra of polyatomic molecules such as halogenated hydrocarbons are typically hard to interpret and assign due to many overlapping states that form broad bands even in high-resolution measurements. With the help of electron-ion-ion coincidence measurements performed using the velocity map imaging technique, we are able to detect high-energy (<= 150 eV) photo- and Auger electrons in coincidence with two- or many-body ionic fragmentation channels. Such channel-resolved measurements allow disentangling the overlapping electronic structures and help assigning individual components of the electron spectra to specific potential surfaces and final states. In this work, we present measurements on CH3 I, CH2 IBr, and CH2 ICl molecules in the gas-phase using soft x-ray light provided by the Advanced Light Source at LBNL. This project is supported by the DOE, Office of Science, BES, Division of Chemical, Geological and Biological Sciences under Award Number DE-FG02-86ER13491 (U.A., B.K., V.K., A.R., D.R.) and Award Number DE-SC0012376 (H.X., N.B.).

Operando observations of solid-state electrochemical reactions in Li-ion batteries by spatially resolved TEM EELS and electron holography.

PubMed

Yamamoto, Kazuo; Iriyama, Yasutoshi; Hirayama, Tsukasa

2017-02-08

All-solid-state Li-ion batteries having incombustible solid electrolytes are promising energy storage devices because they have significant advantages in terms of safety, lifetime and energy density. Electrochemical reactions, namely, Li-ion insertion/extraction reactions, commonly occur around the nanometer-scale interfaces between the electrodes and solid electrolytes. Thus, transmission electron microscopy (TEM) is an appropriate technique to directly observe such reactions, providing important information for understanding the fundamental solid-state electrochemistry and improving battery performance. In this review, we introduce two types of TEM techniques for operando observations of battery reactions, spatially resolved electron energy-loss spectroscopy in a TEM mode for direct detection of the Li concentration profiles and electron holography for observing the electric potential changes due to Li-ion insertion/extraction reactions. We visually show how Li-ion insertion/extractions affect the crystal structures, electronic structures, and local electric potential during the charge-discharge processes in these batteries. © The Author 2016. Published by Oxford University Press on behalf of The Japanese Society of Microscopy. All rights reserved. For permissions, please e-mail: journals.permissions@oup.com.

Angle-resolved molecular beam scattering of NO at the gas-liquid interface.

PubMed

Zutz, Amelia; Nesbitt, David J

2017-08-07

This study presents first results on angle-resolved, inelastic collision dynamics of thermal and hyperthermal molecular beams of NO at gas-liquid interfaces. Specifically, a collimated incident beam of supersonically cooled NO ( 2 Π 1/2 , J = 0.5) is directed toward a series of low vapor pressure liquid surfaces ([bmim][Tf 2 N], squalane, and PFPE) at θ inc = 45(1)°, with the scattered molecules detected with quantum state resolution over a series of final angles (θ s = -60°, -30°, 0°, 30°, 45°, and 60°) via spatially filtered laser induced fluorescence. At low collision energies [E inc = 2.7(9) kcal/mol], the angle-resolved quantum state distributions reveal (i) cos(θ s ) probabilities for the scattered NO and (ii) electronic/rotational temperatures independent of final angle (θ s ), in support of a simple physical picture of angle independent sticking coefficients and all incident NO thermally accommodating on the surface. However, the observed electronic/rotational temperatures for NO scattering reveal cooling below the surface temperature (T elec < T rot < T S ) for all three liquids, indicating a significant dependence of the sticking coefficient on NO internal quantum state. Angle-resolved scattering at high collision energies [E inc = 20(2) kcal/mol] has also been explored, for which the NO scattering populations reveal angle-dependent dynamical branching between thermal desorption and impulsive scattering (IS) pathways that depend strongly on θ s . Characterization of the data in terms of the final angle, rotational state, spin-orbit electronic state, collision energy, and liquid permit new correlations to be revealed and investigated in detail. For example, the IS rotational distributions reveal an enhanced propensity for higher J/spin-orbit excited states scattered into near specular angles and thus hotter rotational/electronic distributions measured in the forward scattering direction. Even more surprisingly, the average NO scattering angle (⟨θ s ⟩) exhibits a remarkably strong correlation with final angular momentum, N, which implies a linear scaling between net forward scattering propensity and torque delivered to the NO projectile by the gas-liquid interface.

Angle-resolved molecular beam scattering of NO at the gas-liquid interface

NASA Astrophysics Data System (ADS)

Zutz, Amelia; Nesbitt, David J.

2017-08-01

This study presents first results on angle-resolved, inelastic collision dynamics of thermal and hyperthermal molecular beams of NO at gas-liquid interfaces. Specifically, a collimated incident beam of supersonically cooled NO (2 Π 1/2, J = 0.5) is directed toward a series of low vapor pressure liquid surfaces ([bmim][Tf2N], squalane, and PFPE) at θinc = 45(1)°, with the scattered molecules detected with quantum state resolution over a series of final angles (θs = -60°, -30°, 0°, 30°, 45°, and 60°) via spatially filtered laser induced fluorescence. At low collision energies [Einc = 2.7(9) kcal/mol], the angle-resolved quantum state distributions reveal (i) cos(θs) probabilities for the scattered NO and (ii) electronic/rotational temperatures independent of final angle (θs), in support of a simple physical picture of angle independent sticking coefficients and all incident NO thermally accommodating on the surface. However, the observed electronic/rotational temperatures for NO scattering reveal cooling below the surface temperature (Telec < Trot < TS) for all three liquids, indicating a significant dependence of the sticking coefficient on NO internal quantum state. Angle-resolved scattering at high collision energies [Einc = 20(2) kcal/mol] has also been explored, for which the NO scattering populations reveal angle-dependent dynamical branching between thermal desorption and impulsive scattering (IS) pathways that depend strongly on θs. Characterization of the data in terms of the final angle, rotational state, spin-orbit electronic state, collision energy, and liquid permit new correlations to be revealed and investigated in detail. For example, the IS rotational distributions reveal an enhanced propensity for higher J/spin-orbit excited states scattered into near specular angles and thus hotter rotational/electronic distributions measured in the forward scattering direction. Even more surprisingly, the average NO scattering angle (⟨θs⟩) exhibits a remarkably strong correlation with final angular momentum, N, which implies a linear scaling between net forward scattering propensity and torque delivered to the NO projectile by the gas-liquid interface.

Pervasive electronic nematicity in a cuprate superconductor

DOE PAGES

Wu, J.; Bollinger, A. T.; He, X.; ...

2018-03-07

Here, we describe an extensive experimental study of La 2-xSr xCuO 4 films synthesized by molecular beam epitaxy and investigated by angle-resolved measurements of transverse resistivity (without applied magnetic field). The data show that an unusual metallic state, in which the rotational symmetry of the electron fluid is spontaneously broken, occurs in a large temperature and doping region. The superconducting state always emerges out of this nematic metal state.

Pathways of energy transfer in LHCII revealed by room-temperature 2D electronic spectroscopy.

PubMed

Wells, Kym L; Lambrev, Petar H; Zhang, Zhengyang; Garab, Gyözö; Tan, Howe-Siang

2014-06-21

We present here the first room-temperature 2D electronic spectroscopy study of energy transfer in the plant light-harvesting complex II, LHCII. Two-dimensional electronic spectroscopy has been used to study energy transfer dynamics in LHCII trimers from the chlorophyll b Qy band to the chlorophyll a Qy band. Observing cross-peak regions corresponding to couplings between different excitonic states reveals partially resolved fine structure at the exciton level that cannot be isolated by pump-probe or linear spectroscopy measurements alone. Global analysis of the data has been performed to identify the pathways and time constants of energy transfer. The measured waiting time (Tw) dependent 2D spectra are found to be composed of 2D decay-associated spectra with three timescales (0.3 ps, 2.3 ps and >20 ps). Direct and multistep cascading pathways from the high-energy chlorophyll b states to the lowest-energy chlorophyll a states have been resolved occurring on time scales of hundreds of femtoseconds to picoseconds.

Excited state non-adiabatic dynamics of pyrrole: A time-resolved photoelectron spectroscopy and quantum dynamics study

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wu, Guorong; State Key Laboratory of Molecular Reaction Dynamics, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian, Liaoning 116023; Synergetic Innovation Center of Quantum Information and Quantum Physics, University of Science and Technology of China, Hefei, Anhui 230026

The dynamics of pyrrole excited at wavelengths in the range 242-217 nm are studied using a combination of time-resolved photoelectron spectroscopy and wavepacket propagations performed using the multi-configurational time-dependent Hartree method. Excitation close to the origin of pyrrole’s electronic spectrum, at 242 and 236 nm, is found to result in an ultrafast decay of the system from the ionization window on a single timescale of less than 20 fs. This behaviour is explained fully by assuming the system to be excited to the A{sub 2}(πσ{sup ∗}) state, in accord with previous experimental and theoretical studies. Excitation at shorter wavelengths hasmore » previously been assumed to result predominantly in population of the bright A{sub 1}(ππ{sup ∗}) and B{sub 2}(ππ{sup ∗}) states. We here present time-resolved photoelectron spectra at a pump wavelength of 217 nm alongside detailed quantum dynamics calculations that, together with a recent reinterpretation of pyrrole’s electronic spectrum [S. P. Neville and G. A. Worth, J. Chem. Phys. 140, 034317 (2014)], suggest that population of the B{sub 1}(πσ{sup ∗}) state (hitherto assumed to be optically dark) may occur directly when pyrrole is excited at energies in the near UV part of its electronic spectrum. The B{sub 1}(πσ{sup ∗}) state is found to decay on a timescale of less than 20 fs by both N-H dissociation and internal conversion to the A{sub 2}(πσ{sup ∗}) state.« less

Collision-energy-resolved angular distribution of Penning electrons for N 2-He ∗(2 3S)

NASA Astrophysics Data System (ADS)

Hanzawa, Yoshinori; Kishimoto, Naoki; Yamazaki, Masakazu; Ohno, Koichi

2006-07-01

The collision-energy-resolved angular distributions of Penning electrons for individual ionic state of N 2-He ∗(2 3S) were measured. The angular distributions showed increasing intensity in the backward (rebounding) directions with respect to initial He ∗(2 3S) beam vector because Penning ionization occurs with a collision against repulsive interaction wall followed by the electron emission from 2s orbital of He ∗. We also analyzed internal angular distribution by means of fitting parameters using classical trajectory calculations for N 2-He ∗(2 3S) on the modified interaction potential. These internal angular distributions suggested the electron emission from 2s orbital of He ∗ and they depended on collision energy and electron kinetic energy.

Electron Correlation in the Ionization Continuum of Molecules: Photoionization of N2 in the Vicinity of the Hopfield Series of Autoionizing States.

PubMed

Klinker, Markus; Marante, Carlos; Argenti, Luca; González-Vázquez, Jesús; Martín, Fernando

2018-02-15

Direct measurement of autoionization lifetimes by using time-resolved experimental techniques is a promising approach when energy-resolved spectroscopic methods do not work. Attosecond time-resolved experiments have recently provided the first quantitative determination of autoionization lifetimes of the lowest members of the well-known Hopfield series of resonances in N 2 . In this work, we have used the recently developed XCHEM approach to study photoionization of the N 2 molecule in the vicinity of these resonances. The XCHEM approach allows us to describe electron correlation in the molecular electronic continuum at a level similar to that provided by multireference configuration interaction methods in bound state calculations, a necessary condition to accurately describe autoionization, shakeup, and interchannel couplings occurring in this range of photon energies. Our results show that electron correlation leading to interchannel mixing is the main factor that determines the magnitude and shape of the N 2 photoionization cross sections, as well as the lifetimes of the Hopfield resonances. At variance with recent speculations, nonadiabatic effects do not seem to play a significant role. These conclusions are supported by the very good agreement between the calculated cross sections and those determined in synchrotron radiation and attosecond experiments.

Alkali-metal induced band structure deformation investigated by angle-resolved photoemission spectroscopy and first-principles calculations

NASA Astrophysics Data System (ADS)

Ito, S.; Feng, B.; Arita, M.; Someya, T.; Chen, W.-C.; Takayama, A.; Iimori, T.; Namatame, H.; Taniguchi, M.; Cheng, C.-M.; Tang, S.-J.; Komori, F.; Matsuda, I.

2018-04-01

Alkali-metal adsorption on the surface of materials is widely used for in situ surface electron doping, particularly for observing unoccupied band structures by angle-resolved photoemission spectroscopy (ARPES). However, the effects of alkali-metal atoms on the resulting band structures have yet to be fully investigated, owing to difficulties in both experiments and calculations. Here, we combine ARPES measurements on cesium-adsorbed ultrathin bismuth films with first-principles calculations of the electronic charge densities and demonstrate a simple method to evaluate alkali-metal induced band deformation. We reveal that deformation of bismuth surface bands is directly correlated with vertical charge-density profiles at each electronic state of bismuth. In contrast, a change in the quantized bulk bands is well described by a conventional rigid-band-shift picture. We discuss these two aspects of the band deformation holistically, considering spatial distributions of the electronic states and cesium-bismuth hybridization, and provide a prescription for applying alkali-metal adsorption to a wide range of materials.

Spin resolved electronic transport through N@C20 fullerene molecule between Au electrodes: A first principles study

NASA Astrophysics Data System (ADS)

Caliskan, Serkan

2018-05-01

Using first principles study, through Density Functional Theory combined with Non Equilibrium Green's Function Formalism, electronic properties of endohedral N@C20 fullerene molecule joining Au electrodes (Au-N@C20) was addressed in the presence of spin property. The electronic transport behavior across the Au-N@C20 molecular junction was investigated by spin resolved transmission, density of states, molecular orbitals, differential conductance and current-voltage (I-V) characteristics. Spin asymmetric variation was clearly observed in the results due to single N atom encapsulated in the C20 fullerene cage, where the N atom played an essential role in the electronic behavior of Au-N@C20. This N@C20 based molecular bridge, exhibiting a spin dependent I-V variation, revealed a metallic behavior within the bias range from -1 V to 1 V. The induced magnetic moment, spin polarization and other relevant quantities associated with the spin resolved transport were elucidated.

Investigation of electronically excited indole relaxation dynamics via photoionization and fragmentation pump-probe spectroscopy.

PubMed

Godfrey, T J; Yu, Hui; Ullrich, Susanne

2014-07-28

The studies herein investigate the involvement of the low-lying (1)La and (1)Lb states with (1)ππ(*) character and the (1)πσ(*) state in the deactivation process of indole following photoexcitation at 201 nm. Three gas-phase, pump-probe spectroscopic techniques are employed: (1) Time-resolved photoelectron spectroscopy (TR-PES), (2) hydrogen atom (H-atom) time-resolved kinetic energy release (TR-KER), and (3) time-resolved ion yield (TR-IY). Each technique provides complementary information specific to the photophysical processes in the indole molecule. In conjunction, a thorough examination of the electronically excited states in the relaxation process, with particular focus on the involvement of the (1)πσ(*) state, is afforded. Through an extensive analysis of the TR-PES data presented here, it is deduced that the initial excitation of the (1)Bb state decays to the (1)La state on a timescale beyond the resolution of the current experimental setup. Relaxation proceeds on the (1)La state with an ultrafast decay constant (<100 femtoseconds (fs)) to the lower-lying (1)Lb state, which is found to possess a relatively long lifetime of 23 ± 5 picoseconds (ps) before regressing to the ground state. These studies also manifest an additional component with a relaxation time of 405 ± 76 fs, which is correlated with activity along the (1)πσ(*) state. TR-KER and TR-IY experiments, both specifically probing (1)πσ(*) dynamics, exhibit similar decay constants, further validating these observations.

Singlet and triplet trions in WS2 monolayer encapsulated in hexagonal boron nitride.

PubMed

Vaclavkova, D; Wyzula, J; Nogajewski, K; Bartos, M; Slobodeniuk, A O; Faugeras, C; Potemski, M; Molas, M R

2018-08-10

Embedding a WS 2 monolayer in flakes of hexagonal boron nitride allowed us to resolve and study the photoluminescence response due to both singlet and triplet states of negatively charged excitons (trions) in this atomically thin semiconductor. The energy separation between the singlet and triplet states has been found to be relatively small reflecting rather weak effects of the electron-electron exchange interaction for the trion triplet in a WS 2 monolayer, which involves two electrons with the same spin but from different valleys. Polarization-resolved experiments demonstrate that the helicity of the excitation light is better preserved in the emission spectrum of the triplet trion than in that of the singlet trion. Finally, the singlet (intravalley) trions are found to be observable even at ambient conditions whereas the emission due to the triplet (intervalley) trions is only efficient at low temperatures.

Measurement of electron-ion relaxation in warm dense copper

DOE PAGES

Cho, B. I.; Ogitsu, T.; Engelhorn, K.; ...

2016-01-06

Experimental investigation of electron-ion coupling and electron heat capacity of copper in warm and dense states are presented. From time-resolved x-ray absorption spectroscopy, the temporal evolution of electron temperature is obtained for non-equilibrium warm dense copper heated by an intense femtosecond laser pulse. Electron heat capacity and electron-ion coupling are inferred from the initial electron temperature and its decrease over 10 ps. As a result, data are compared with various theoretical models.

Pulsed-field ionization zero electron kinetic energy spectrum of the ground electronic state of BeOBe+.

PubMed

Antonov, Ivan O; Barker, Beau J; Heaven, Michael C

2011-01-28

The ground electronic state of BeOBe(+) was probed using the pulsed-field ionization zero electron kinetic energy photoelectron technique. Spectra were rotationally resolved and transitions to the zero-point level, the symmetric stretch fundamental and first two bending vibrational levels were observed. The rotational state symmetry selection rules confirm that the ground electronic state of the cation is (2)Σ(g)(+). Detachment of an electron from the HOMO of neutral BeOBe results in little change in the vibrational or rotational constants, indicating that this orbital is nonbonding in nature. The ionization energy of BeOBe [65480(4) cm(-1)] was refined over previous measurements. Results from recent theoretical calculations for BeOBe(+) (multireference configuration interaction) were found to be in good agreement with the experimental data.

Application of spectroscopy and super-resolution microscopy: Excited state

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bhattacharjee, Ujjal

Photophysics of inorganic materials and organic molecules in complex systems have been extensively studied with absorption and emission spectroscopy.1-4 Steady-state and time-resolved fluorescence studies are commonly carried out to characterize excited-state properties of fluorophores. Although steady-state fluorescence measurements are widely used for analytical applications, time-resolved fluorescence measurements provide more detailed information about excited-state properties and the environment in the vicinity of the fluorophore. Many photophysical processes, such as photoinduced electron transfer (PET), rotational reorientation, solvent relaxation, and energy transfer, occur on a nanosecond (10 -9 s) timescale, thus affecting the lifetime of the fluorophores. Moreover, time-resolved microscopy methods, such asmore » lifetimeimaging, combine the benefits of the microscopic measurement and information-rich, timeresolved data. Thus, time-resolved fluorescence spectroscopy combined with microscopy can be used to quantify these processes and to obtain a deeper understanding of the chemical surroundings of the fluorophore in a small area under investigation. This thesis discusses various photophysical and super-resolution microscopic studies of organic and inorganic materials, which have been outlined below.« less

Effect of electron-phonon coupling on energy and density of states renormalizations of dynamically screened graphene

NASA Astrophysics Data System (ADS)

Leblanc, J. P. F.; Carbotte, J. P.; Nicol, E. J.

2012-02-01

Motivated by recent tunneling and angle-resolved photoemission (ARPES) work [1,2], we explore the combined effect of electron-electron and electron-phonon couplings on the renormalized energy dispersion, the spectral function, and the density of states of doped graphene. We find that the plasmarons seen in ARPES are also observable in the density of states and appear as structures with quadratic dependence on energy about the minima. Further, we illustrate how knowledge of the slopes of both the density of states and the renormalized dispersion near the Fermi level can allow for the separation of momentum and frequency dependent renormalizations to the Fermi velocity. This analysis should allow for the isolation of the renormalization due to the electron-phonon interaction from that of the electron-electron interaction. [4pt] [1] Brar et al. Phys. Rev. Lett. 104, 036805 (2010) [2] Bostwick et al. Science 328, p.999 (2010)

Unoccupied surface states of LaB6(001) studied by k -resolved inverse photoemission

NASA Astrophysics Data System (ADS)

Morimoto, Osamu; Kunii, Satoru; Kakizaki, Akito

2006-06-01

We have measured k -resolved inverse photoemission spectra of LaB6(001) to study unoccupied surface states. The surface states are observed near the Fermi level (EF) and at 6.8eV above EF , which are originated from La5d and La4f states, respectively. The surface state near EF shows energy dispersion along the Γ - M direction of the surface Brillouin zone, which does not agree with that of a recently reported theoretical calculation. It is deduced that at a LaB6(001) surface, electrons are transferred from the subsurface to the topmost La layer. This charge redistribution can reduce surface dipole moments.

Vibrationally resolved photoelectron spectroscopy of electronic excited states of DNA bases: application to the ã state of thymine cation.

PubMed

Hochlaf, Majdi; Pan, Yi; Lau, Kai-Chung; Majdi, Youssef; Poisson, Lionel; Garcia, Gustavo A; Nahon, Laurent; Al Mogren, Muneerah Mogren; Schwell, Martin

2015-02-19

For fully understanding the light-molecule interaction dynamics at short time scales, recent theoretical and experimental studies proved the importance of accurate characterizations not only of the ground (D0) but also of the electronic excited states (e.g., D1) of molecules. While ground state investigations are currently straightforward, those of electronic excited states are not. Here, we characterized the à electronic state of ionic thymine (T(+)) DNA base using explicitly correlated coupled cluster ab initio methods and state-of-the-art synchrotron-based electron/ion coincidence techniques. The experimental spectrum is composed of rich and long vibrational progressions corresponding to the population of the low frequency modes of T(+)(Ã). This work challenges previous numerous works carried out on DNA bases using common synchrotron and VUV-based photoelectron spectroscopies. We provide hence a powerful theoretical and experimental framework to study the electronic structure of ionized DNA bases that could be generalized to other medium-sized biologically relevant systems.

Quantifying electronic band interactions in van der Waals materials using angle-resolved reflected-electron spectroscopy.

PubMed

Jobst, Johannes; van der Torren, Alexander J H; Krasovskii, Eugene E; Balgley, Jesse; Dean, Cory R; Tromp, Rudolf M; van der Molen, Sense Jan

2016-11-29

High electron mobility is one of graphene's key properties, exploited for applications and fundamental research alike. Highest mobility values are found in heterostructures of graphene and hexagonal boron nitride, which consequently are widely used. However, surprisingly little is known about the interaction between the electronic states of these layered systems. Rather pragmatically, it is assumed that these do not couple significantly. Here we study the unoccupied band structure of graphite, boron nitride and their heterostructures using angle-resolved reflected-electron spectroscopy. We demonstrate that graphene and boron nitride bands do not interact over a wide energy range, despite their very similar dispersions. The method we use can be generally applied to study interactions in van der Waals systems, that is, artificial stacks of layered materials. With this we can quantitatively understand the 'chemistry of layers' by which novel materials are created via electronic coupling between the layers they are composed of.

Influence of molecular designs on polaronic and vibrational transitions in a conjugated push-pull copolymer

NASA Astrophysics Data System (ADS)

Cobet, Christoph; Gasiorowski, Jacek; Menon, Reghu; Hingerl, Kurt; Schlager, Stefanie; White, Matthew S.; Neugebauer, Helmut; Sariciftci, N. Serdar; Stadler, Philipp

2016-10-01

Electron-phonon interactions of free charge-carriers in doped pi-conjugated polymers are conceptually described by 1-dimensional (1D) delocalization. Thereby, polaronic transitions fit the 1D-Froehlich model in quasi-confined chains. However, recent developments in conjugated polymers have diversified the backbones to become elaborate heterocylcic macromolecules. Their complexity makes it difficult to investigate the electron-phonon coupling. In this work we resolve the electron-phonon interactions in the ground and doped state in a complex push-pull polymer. We focus on the polaronic transitions using in-situ spectroscopy to work out the differences between single-unit and push-pull systems to obtain the desired structural- electronic correlations in the doped state. We apply the classic 1D-Froehlich model to generate optical model fits. Interestingly, we find the 1D-approach in push-pull polarons in agreement to the model, pointing at the strong 1D-character and plain electronic structure of the push-pull structure. In contrast, polarons in the single-unit polymer emerge to a multi- dimensional problem difficult to resolve due to their anisotropy. Thus, we report an enhancement of the 1D-character by the push-pull concept in the doped state - an important view in light of the main purpose of push-pull polymers for photovoltaic devices.

Modelling Time-Resolved Two-Dimensional Electronic Spectroscopy of the Primary Photoisomerization Event in Rhodopsin

PubMed Central

2015-01-01

Time-resolved two-dimensional (2D) electronic spectra (ES) tracking the evolution of the excited state manifolds of the retinal chromophore have been simulated along the photoisomerization pathway in bovine rhodopsin, using a state-of-the-art hybrid QM/MM approach based on multiconfigurational methods. Simulations of broadband 2D spectra provide a useful picture of the overall detectable 2D signals from the near-infrared (NIR) to the near-ultraviolet (UV). Evolution of the stimulated emission (SE) and excited state absorption (ESA) 2D signals indicates that the S1 → SN (with N ≥ 2) ESAs feature a substantial blue-shift only after bond inversion and partial rotation along the cis → trans isomerization angle, while the SE rapidly red-shifts during the photoinduced skeletal relaxation of the polyene chain. Different combinations of pulse frequencies are proposed in order to follow the evolution of specific ESA signals. These include a two-color 2DVis/NIR setup especially suited for tracking the evolution of the S1 → S2 transitions that can be used to discriminate between different photochemical mechanisms of retinal photoisomerization as a function of the environment. The reported results are consistent with the available time-resolved pump–probe experimental data, and may be used for the design of more elaborate transient 2D electronic spectroscopy techniques. PMID:24794143

Nonlocal Coulomb correlations in pure and electron-doped Sr2IrO4 : Spectral functions, Fermi surface, and pseudo-gap-like spectral weight distributions from oriented cluster dynamical mean-field theory

NASA Astrophysics Data System (ADS)

Martins, Cyril; Lenz, Benjamin; Perfetti, Luca; Brouet, Veronique; Bertran, François; Biermann, Silke

2018-03-01

We address the role of nonlocal Coulomb correlations and short-range magnetic fluctuations in the high-temperature phase of Sr2IrO4 within state-of-the-art spectroscopic and first-principles theoretical methods. Introducing an "oriented-cluster dynamical mean-field scheme", we compute momentum-resolved spectral functions, which we find to be in excellent agreement with angle-resolved photoemission spectra. We show that while short-range antiferromagnetic fluctuations are crucial to accounting for the electronic properties of Sr2IrO4 even in the high-temperature paramagnetic phase, long-range magnetic order is not a necessary ingredient of the insulating state. Upon doping, an exotic metallic state is generated, exhibiting cuprate-like pseudo-gap spectral properties, for which we propose a surprisingly simple theoretical mechanism.

A Gaussian Wave Packet Propagation Approach to Vibrationally Resolved Optical Spectra at Non-Zero Temperatures.

PubMed

Reddy, Ch Sridhar; Prasad, M Durga

2016-04-28

An effective time dependent approach based on a method that is similar to the Gaussian wave packet propagation (GWP) technique of Heller is developed for the computation of vibrationally resolved electronic spectra at finite temperatures in the harmonic, Franck-Condon/Hertzberg-Teller approximations. Since the vibrational thermal density matrix of the ground electronic surface and the time evolution operator on that surface commute, it is possible to write the spectrum generating correlation function as a trace of the time evolved doorway state. In the stated approximations, the doorway state is a superposition of the harmonic oscillator zero and one quantum eigenfunctions and thus can be propagated by the GWP. The algorithm has an O(N(3)) dependence on the number of vibrational modes. An application to pyrene absorption spectrum at two temperatures is presented as a proof of the concept.

High resolution photoelectron imaging of UO(-) and UO2(-) and the low-lying electronic states and vibrational frequencies of UO and UO2.

PubMed

Czekner, Joseph; Lopez, Gary V; Wang, Lai-Sheng

2014-12-28

We report a study of the electronic and vibrational structures of the gaseous uranium monoxide and dioxide molecules using high-resolution photoelectron imaging. Vibrationally resolved photoelectron spectra are obtained for both UO(-) and UO2(-). The spectra for UO2(-) are consistent with, but much better resolved than a recent study using a magnetic-bottle photoelectron analyzer [W. L. Li et al., J. Chem. Phys. 140, 094306 (2014)]. The electron affinity (EA) of UO is reported for the first time as 1.1407(7) eV, whereas a much more accurate EA is obtained for UO2 as 1.1688(6) eV. The symmetric stretching modes for the neutral and anionic ground states, and two neutral excited states for UO2 are observed, as well as the bending mode for the neutral ground state. These vibrational frequencies are consistent with previous experimental and theoretical results. The stretching vibrational modes for the ground state and one excited state are observed for UO. The current results for UO and UO2 are compared with previous theoretical calculations including relativistic effects and spin-orbit coupling. The accurate experimental data reported here provide more stringent tests for future theoretical methods for actinide-containing species.

Real-time observation of cascaded electronic relaxation processes in p-Fluorotoluene

NASA Astrophysics Data System (ADS)

Hao, Qiaoli; Deng, Xulan; Long, Jinyou; Wang, Yanmei; Abulimiti, Bumaliya; Zhang, Bing

2017-08-01

Ultrafast electronic relaxation processes following two photoexcitation of 400 nm in p-Fluorotoluene (pFT) have been investigated utilizing time-resolved photoelectron imaging coupled with time-resolved mass spectroscopy. Cascaded electronic relaxation processes started from the electronically excited S2 state are directly imaged in real time and well characterized by two distinct time constants of 85 ± 10 fs and 2.4 ± 0.3 ps. The rapid component corresponds to the lifetime of the initially excited S2 state, including the structure relaxation from the Franck-Condon region to the conical intersection of S2/S1 and the subsequent internal conversion to the highly excited S1 state. While, the slower relaxation constant is attributed to the further internal conversion to the high levels of S0 from the secondarily populated S1 locating in the channel three region. Moreover, dynamical differences with benzene and toluene of analogous structures, including, specifically, the slightly slower relaxation rate of S2 and the evidently faster decay of S1, are also presented and tentatively interpreted as the substituent effects. In addition, photoelectron kinetic energy and angular distributions reveal the feature of accidental resonances with low-lying Rydberg states (the 3p, 4s and 4p states) during the multi-photon ionization process, providing totally unexpected but very interesting information for pFT.

Spectroscopy of Vibrational States in Diatomic Iodine Molecules

NASA Astrophysics Data System (ADS)

Mulholland, Mary; Harrill, Charles H.; Smith, R. Seth

2015-04-01

This project is focused on understanding the vibrational structure of iodine, which is a homonuclear diatomic molecule. A 20 mW, 532 nm cw diode laser was used to selectively excite neutral iodine molecules to a higher energy electronic state. By performing spectroscopy on the transitions from this state to a lower energy electronic state, the data only showed those vibrational bands which connect the two electronic states. Since a number of vibrational levels are populated in the higher energy electronic state, the transitions to all of the allowed vibrational levels in the lower energy electronic state provided sufficient data to determine the vibrational structures of both states. Emission spectra were collected with an Ocean Optics USB4000 Compact CCD Spectrometer. The spectrometer had a range of 500 - 770 nm with a resolution of approximately 0.5 nm and was sensitive enough to resolve the vibrational states in diatomic iodine molecules. The results were compared to a simple harmonic oscillator model.

Orbital-occupancy versus charge ordering and the strength of electron correlations in electron-doped CaMnO3.

PubMed

Luo, Weidong; Franceschetti, Alberto; Varela, Maria; Tao, Jing; Pennycook, Stephen J; Pantelides, Sokrates T

2007-07-20

The structural, electronic, and magnetic properties of mixed-valence compounds are believed to be governed by strong electron correlations. Here we report benchmark density-functional calculations in the spin-polarized generalized-gradient approximation (GGA) for the ground-state properties of doped CaMnO(3). We find excellent agreement with all available data, while inclusion of strong correlations in the GGA+U scheme impairs this agreement. We demonstrate that formal oxidation states reflect only orbital occupancies, not charge transfer, and resolve outstanding controversies about charge ordering.

Orbital-Occupancy versus Charge Ordering and the Strength of Electron Correlations in Electron-Doped CaMnO3

NASA Astrophysics Data System (ADS)

Luo, Weidong; Franceschetti, Alberto; Varela, Maria; Tao, Jing; Pennycook, Stephen J.; Pantelides, Sokrates T.

2007-07-01

The structural, electronic, and magnetic properties of mixed-valence compounds are believed to be governed by strong electron correlations. Here we report benchmark density-functional calculations in the spin-polarized generalized-gradient approximation (GGA) for the ground-state properties of doped CaMnO3. We find excellent agreement with all available data, while inclusion of strong correlations in the GGA+U scheme impairs this agreement. We demonstrate that formal oxidation states reflect only orbital occupancies, not charge transfer, and resolve outstanding controversies about charge ordering.

Spatially Resolved Nano-Scale Characterization of Electronic States in SrTiO3(001) Surfaces by STM/STS

NASA Astrophysics Data System (ADS)

Iwaya, Katsuya; Ohsawa, Takeo; Shimizu, Ryota; Hashizume, Tomihiro; Hitosugi, Taro

2012-02-01

We have performed low temperature scanning tunneling microscopy/spectroscopy (STM/STS) measurements on TiO2-terminated SrTiO3(001) thin film surfaces. The conductance map exhibited electronic modulations that were completely different from the surface structure. We also found that the electronic modulations were strongly dependent on temperature and the density of atomic defects associated with oxygen vacancies. These results suggest the existence of strongly correlated two-dimensional electronic states near the SrTiO3 surface, implying the importance of electron correlation at the interfaces of SrTiO3-related heterostructures.

Ultrafast electron and energy transfer in dye-sensitized iron oxide and oxyhydroxide nanoparticles.

PubMed

Gilbert, Benjamin; Katz, Jordan E; Huse, Nils; Zhang, Xiaoyi; Frandsen, Cathrine; Falcone, Roger W; Waychunas, Glenn A

2013-10-28

An emerging area in chemical science is the study of solid-phase redox reactions using ultrafast time-resolved spectroscopy. We have used molecules of the photoactive dye 2',7'-dichlorofluorescein (DCF) anchored to the surface of iron(III) oxide nanoparticles to create iron(II) surface atoms via photo-initiated interfacial electron transfer. This approach enables time-resolved study of the fate and mobility of electrons within the solid phase. However, complete analysis of the ultrafast processes following dye photoexcitation of the sensitized iron(III) oxide nanoparticles has not been reported. We addressed this topic by performing femtosecond transient absorption (TA) measurements of aqueous suspensions of uncoated and DCF-sensitized iron oxide and oxyhydroxide nanoparticles, and an aqueous iron(III)-dye complex. Following light absorption, excited state relaxation times of the dye of 115-310 fs were found for all samples. Comparison between TA dynamics on uncoated and dye-sensitized hematite nanoparticles revealed the dye de-excitation pathway to consist of a competition between electron and energy transfer to the nanoparticles. We analyzed the TA data for hematite nanoparticles using a four-state model of the dye-sensitized system, finding electron and energy transfer to occur on the same ultrafast timescale. The interfacial electron transfer rates for iron oxides are very close to those previously reported for DCF-sensitized titanium dioxide (for which dye-oxide energy transfer is energetically forbidden) even though the acceptor states are different. Comparison of the alignment of the excited states of the dye and the unoccupied states of these oxides showed that the dye injects into acceptor states of different symmetry (Ti t2gvs. Fe eg).

Observation of the spin-polarized surface state in a noncentrosymmetric superconductor BiPd

DOE Office of Scientific and Technical Information (OSTI.GOV)

Neupane, Madhab; Alidoust, Nasser; Hosen, M. Mofazzel

Recently, noncentrosymmetric superconductor BiPd has attracted considerable research interest due to the possibility of hosting topological superconductivity. Here in this paper we report a systematic high-resolution angle-resolved photoemission spectroscopy (ARPES) and spin-resolved ARPES study of the normal state electronic and spin properties of BiPd. Our experimental results show the presence of a surface state at higher-binding energy with the location of Dirac point at around 700 meV below the Fermi level. The detailed photon energy, temperature-dependent and spin-resolved ARPES measurements complemented by our first-principles calculations demonstrate the existence of the spin-polarized surface states at high-binding energy. The absence of suchmore » spin-polarized surface states near the Fermi level negates the possibility of a topological superconducting behaviour on the surface. Our direct experimental observation of spin-polarized surface states in BiPd provides critical information that will guide the future search for topological superconductivity in noncentrosymmetric materials.« less

Observation of the spin-polarized surface state in a noncentrosymmetric superconductor BiPd

DOE PAGES

Neupane, Madhab; Alidoust, Nasser; Hosen, M. Mofazzel; ...

2016-11-07

Recently, noncentrosymmetric superconductor BiPd has attracted considerable research interest due to the possibility of hosting topological superconductivity. Here in this paper we report a systematic high-resolution angle-resolved photoemission spectroscopy (ARPES) and spin-resolved ARPES study of the normal state electronic and spin properties of BiPd. Our experimental results show the presence of a surface state at higher-binding energy with the location of Dirac point at around 700 meV below the Fermi level. The detailed photon energy, temperature-dependent and spin-resolved ARPES measurements complemented by our first-principles calculations demonstrate the existence of the spin-polarized surface states at high-binding energy. The absence of suchmore » spin-polarized surface states near the Fermi level negates the possibility of a topological superconducting behaviour on the surface. Our direct experimental observation of spin-polarized surface states in BiPd provides critical information that will guide the future search for topological superconductivity in noncentrosymmetric materials.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chartrand, A. M.; McCormack, E. F.; Jacovella, U.

The single-photon, photoelectron-photoion coincidence spectrum of N 2 has been recorded at high (~1.5 cm -1) resolution in the region between the N 2 + X 2Σ g +, v + = 0 and 1 ionization thresholds by using a double imaging spectrometer and intense vacuum-ultraviolet light from the Synchrotron SOLEIL. This approach provides the relative photoionization cross section, the photoelectron energy distribution, and the photoelectron angular distribution as a function of photon energy. The region of interest contains autoionizing valence states, vibrationally autoionizing Rydberg states converging to vibrationally excited levels of the N 2 + X 2Σ g +more » ground state, and electronically autoionizing states converging to the N 2 + A 2Π and B 2Σ u + states. The wavelength resolution is sufficient to resolve rotational structure in the autoionizing states, but the electron energy resolution is insufficient to resolve rotational structure in the photoion spectrum. Here, a simplified approach based on multichannel quantum defect theory is used to predict the photoelectron angular distribution parameters, β, and the results are in reasonably good agreement with experiment.« less

Time-resolved EPR study on the photoexcited triplet state of the electron-donor-acceptor complex formed in the system of fac-tris[2-(4-octyl-phenyl) pyridine] iridium(III) and tetracene.

PubMed

Zhebin, Fu; Shuhei, Yoshioka; Hisao, Murai

2014-01-09

The physical properties of the phosphorescent organic light-emitting diode material fac-tris(phenylpyridine) iridium(III), Ir(ppy)3, have been reported with experimental and theoretical studies. Here, the photochemical properties of the excited triplet state of partially modified fac-tris[2-(4-octyl-phenyl) pyridine] iridium(III), Ir(C8ppy)3, were investigated using time-resolved electron paramagnetic resonance (tr-EPR) and optical methods by adding tetracene in the toluene solution. The tr-EPR observation at 77 K revealed the following two species: the excited triplet state of tetracene and another triplet species with zero field splitting parameters of |D| = 0.088 cm(-1) and |E| = 0.018 cm(-1) with characteristic spin polarization. The latter species was assigned to the electron-donor-acceptor (EDA) complex formed between Ir(C8ppy)3 and tetracene. The mechanism of formation and the properties of this EDA complex, including the information on the principal axes of (3)Ir(C8ppy)3*, are discussed.

Atomic-scale luminescence measurement and theoretical analysis unveiling electron energy dissipation at a p-type GaAs(110) surface.

PubMed

Imada, Hiroshi; Miwa, Kuniyuki; Jung, Jaehoon; Shimizu, Tomoko K; Yamamoto, Naoki; Kim, Yousoo

2015-09-11

Luminescence of p-type GaAs was induced by electron injection from the tip of a scanning tunnelling microscope into a GaAs(110) surface. Atomically-resolved photon maps revealed a significant reduction in luminescence intensity at surface electronic states localized near Ga atoms. Theoretical analysis based on first principles calculations and a rate equation approach was performed to describe the perspective of electron energy dissipation at the surface. Our study reveals that non-radiative recombination through the surface states (SS) is a dominant process for the electron energy dissipation at the surface, which is suggestive of the fast scattering of injected electrons into the SS.

Ultrafast above-threshold dynamics of the radical anion of a prototypical quinone electron-acceptor.

PubMed

Horke, Daniel A; Li, Quansong; Blancafort, Lluís; Verlet, Jan R R

2013-08-01

Quinones feature prominently as electron acceptors in nature. Their electron-transfer reactions are often highly exergonic, for which Marcus theory predicts reduced electron-transfer rates because of a free-energy barrier that occurs in the inverted region. However, the electron-transfer kinetics that involve quinones can appear barrierless. Here, we consider the intrinsic properties of the para-benzoquinone radical anion, which serves as the prototypical electron-transfer reaction product involving a quinone-based acceptor. Using time-resolved photoelectron spectroscopy and ab initio calculations, we show that excitation at 400 and 480 nm yields excited states that are unbound with respect to electron loss. These excited states are shown to decay on a sub-40 fs timescale through a series of conical intersections with lower-lying excited states, ultimately to form the ground anionic state and avoid autodetachment. From an isolated electron-acceptor perspective, this ultrafast stabilization mechanism accounts for the ability of para-benzoquinone to capture and retain electrons.

Time resolved Thomson scattering diagnostic of pulsed gas metal arc welding (GMAW) process

NASA Astrophysics Data System (ADS)

Kühn-Kauffeldt, M.; Marquès, J. L.; Schein, J.

2014-11-01

In this work a Thomson scattering diagnostic technique was applied to obtain time resolved electron temperature and density values during a gas metal arc welding (GMAW) process. The investigated GMAW process was run with aluminum wire (AlMg 4,5 Mn) with 1.2 mm diameter as a wire electrode, argon as a shielding gas and peak currents in the range of 400 A. Time resolved measurements could be achieved by triggering the laser pulse at shifted time positions with respect to the current pulse driving the process. Time evaluation of resulting electron temperatures and densities is used to investigate the state of the plasma in different phases of the current pulse and to determine the influence of the metal vapor and droplets on the plasma properties.

Photoelectron Spectroscopy of Substituted Phenylnitrenes

NASA Astrophysics Data System (ADS)

Wijeratne, Neloni R.; Da Fonte, Maria; Wenthold, Paul G.

2009-06-01

Nitrenes are unusual molecular structures with unfilled electronic valences that are isoelectronic with carbenes. Although, both can be generated by either thermal or photochemical decomposition of appropriate precursors they usually exhibit different reactivities. In this work, we carry out spectroscopic studies of substituted phenylnitrene to determine how the introduction of substituents will affect the reactivity and its thermochemical properties. All studies were carried out by using the newly constructed time-of-flight negative ion photoelectron spectrometer (NIPES) at Purdue University. The 355 nm photoelectron spectra of the o-, m-, and p-chlorophenyl nitrene anions are fairly similar to that measured for phenylnitrene anion. All spectra show low energy triplet state and a high energy singlet state. The singlet state for the meta isomer is well-resolved, with a well defined origin and observable vibrational structure. Whereas the singlet states for the ortho and para isomers have lower energy onsets and no resolved structure. The isomeric dependence suggests that the geometry differences result from the resonance interaction between the nitrogen and the substituent. Quinoidal resonance structures are possible for the open-shell singlet states of the o- and p-chlorinated phenyl nitrenes. The advantages of this type of electronic structures for the open-shell singlet states is that the unpaired electrons can be more localized on separate atoms in the molecules, minimizing the repulsion between. Because the meta position is not in resonance with the nitrenes, substitution at that position should not affect the structure of the open-shell singlet state. The measured electron affinities (EA) of the triplet phenylnitrenes are in excellent agreement with the values predicted by electronic structure calculations. The largest EA, 1.82 eV is found for the meta isomer, with para being the smallest, 1.70 eV.

Resonant two-photon ionization and laser induced fluorescence spectroscopy of jet-cooled adenine

NASA Astrophysics Data System (ADS)

Kim, Nam Joon; Jeong, Gawoon; Kim, Yung Sam; Sung, Jiha; Keun Kim, Seong; Park, Young Dong

2000-12-01

Electronic spectra of the jet-cooled DNA base adenine were obtained by the resonant two-photon ionization (R2PI) and the laser induced fluorescence (LIF) techniques. The 0-0 band to the lowest electronically excited state was found to be located at 35 503 cm-1. Well-resolved vibronic structures were observed up to 1100 cm-1 above the 0-0 level, followed by a slow rise of broad structureless absorption. The lowest electronic state was proposed to be of nπ* character, which lies ˜600 cm-1 below the onset of the ππ* state. The broad absorption was attributed to the extensive vibronic mixing between the nπ* state and the high-lying ππ* state.

Direct Imaging of Transient Fano Resonances in N_{2} Using Time-, Energy-, and Angular-Resolved Photoelectron Spectroscopy.

PubMed

Eckstein, Martin; Yang, Chung-Hsin; Frassetto, Fabio; Poletto, Luca; Sansone, Giuseppe; Vrakking, Marc J J; Kornilov, Oleg

2016-04-22

Autoionizing Rydberg states of molecular N_{2} are studied using time-, energy-, and angular-resolved photoelectron spectroscopy. A femtosecond extreme ultraviolet pulse with a photon energy of 17.5 eV excites the resonance and a subsequent IR pulse ionizes the molecule before the autoionization takes place. The angular-resolved photoelectron spectra depend on pump-probe time delay and allow for the distinguishing of two electronic states contributing to the resonance. The lifetime of one of the contributions is determined to be 14±1  fs, while the lifetime of the other appears to be significantly shorter than the time resolution of the experiment. These observations suggest that the Rydberg states in this energy region are influenced by the effect of interference stabilization and merge into a complex resonance.

Scanning photoelectron microscope for nanoscale three-dimensional spatial-resolved electron spectroscopy for chemical analysis.

PubMed

Horiba, K; Nakamura, Y; Nagamura, N; Toyoda, S; Kumigashira, H; Oshima, M; Amemiya, K; Senba, Y; Ohashi, H

2011-11-01

In order to achieve nondestructive observation of the three-dimensional spatially resolved electronic structure of solids, we have developed a scanning photoelectron microscope system with the capability of depth profiling in electron spectroscopy for chemical analysis (ESCA). We call this system 3D nano-ESCA. For focusing the x-ray, a Fresnel zone plate with a diameter of 200 μm and an outermost zone width of 35 nm is used. In order to obtain the angular dependence of the photoelectron spectra for the depth-profile analysis without rotating the sample, we adopted a modified VG Scienta R3000 analyzer with an acceptance angle of 60° as a high-resolution angle-resolved electron spectrometer. The system has been installed at the University-of-Tokyo Materials Science Outstation beamline, BL07LSU, at SPring-8. From the results of the line-scan profiles of the poly-Si/high-k gate patterns, we achieved a total spatial resolution better than 70 nm. The capability of our system for pinpoint depth-profile analysis and high-resolution chemical state analysis is demonstrated. © 2011 American Institute of Physics

Electronic structure of the dilute magnetic semiconductor G a1 -xM nxP from hard x-ray photoelectron spectroscopy and angle-resolved photoemission

NASA Astrophysics Data System (ADS)

Keqi, A.; Gehlmann, M.; Conti, G.; Nemšák, S.; Rattanachata, A.; Minár, J.; Plucinski, L.; Rault, J. E.; Rueff, J. P.; Scarpulla, M.; Hategan, M.; Pálsson, G. K.; Conlon, C.; Eiteneer, D.; Saw, A. Y.; Gray, A. X.; Kobayashi, K.; Ueda, S.; Dubon, O. D.; Schneider, C. M.; Fadley, C. S.

2018-04-01

We have investigated the electronic structure of the dilute magnetic semiconductor (DMS) G a0.98M n0.02P and compared it to that of an undoped GaP reference sample, using hard x-ray photoelectron spectroscopy (HXPS) and hard x-ray angle-resolved photoemission spectroscopy (HARPES) at energies of about 3 keV. We present experimental data, as well as theoretical calculations, to understand the role of the Mn dopant in the emergence of ferromagnetism in this material. Both core-level spectra and angle-resolved or angle-integrated valence spectra are discussed. In particular, the HARPES experimental data are compared to free-electron final-state model calculations and to more accurate one-step photoemission theory. The experimental results show differences between G a0.98M n0.02P and GaP in both angle-resolved and angle-integrated valence spectra. The G a0.98M n0.02P bands are broadened due to the presence of Mn impurities that disturb the long-range translational order of the host GaP crystal. Mn-induced changes of the electronic structure are observed over the entire valence band range, including the presence of a distinct impurity band close to the valence-band maximum of the DMS. These experimental results are in good agreement with the one-step photoemission calculations and a prior HARPES study of G a0.97M n0.03As and GaAs [Gray et al., Nat. Mater. 11, 957 (2012), 10.1038/nmat3450], demonstrating the strong similarity between these two materials. The Mn 2 p and 3 s core-level spectra also reveal an essentially identical state in doping both GaAs and GaP.

Photoelectrical, photophysical and photocatalytic properties of Al based MOFs: MIL-53(Al) and MIL-53-NH{sub 2}(Al)

DOE Office of Scientific and Technical Information (OSTI.GOV)

An, Yang; Li, Huiliang; Liu, Yuanyuan, E-mail: yyliu@sdu.edu.cn

Two Al based MOFs (MIL-53(Al) and MIL-53-NH{sub 2} (Al)) were synthesized, and their photoelectrical, photophysical and photocatalytic properties towards oxygen evolution from water were investigated. Different from the ligand to metal charge transfer process previously reported, we proposes a new photocatalytic mechanism based on electron tunneling according to the results of theoretical calculation, steady state and time resolved fluorescence spectra. The organic linkers absorb photons, giving rise to electrons and holes. Then, the photogenerated electrons tunnel through the AlO{sub 6}-octahedra, which not only inhibit the recombination of photogenerated charge carriers, but also is a key factor to the photocatalytic activitymore » of Al based MOFs. - Graphical abstract: The photoelectrical, photophysical and photocatalytic properties towards oxygen evolution from water of two Al based MOFs were investigated. A new photocatalytic mechanism was proposed based on electron tunneling according to the results of both theoretical calculation and steady state, time resolved fluorescence spectra. The electron tunneling process not only inhibit the recombination of photogenerated charge carriers, but also is a key factor to the photocatalytic activity of Al based MOFs.« less

Birth of a resonant attosecond wavepacket

NASA Astrophysics Data System (ADS)

Argenti, L.; Gruson, V.; Barreau, L.; Jimenez-Galan, A.; Risoud, F.; Caillat, J.; Maquet, A.; Carre, B.; Lepetit, F.; Hergott, J.-F.; Ruchon, T.; Taieb, R.; Martin, F.; Salieres, P.

2016-05-01

Both amplitude and phase are needed to characterize the dynamics of a wavepacket. However, such characterization is difficult when both attosecond and femtosecond timescales are involved, as it is the case for broadband photoionization to a continuum encompassing autoionizing states. Here we demonstrate that Rainbow RABBIT, a new attosecond interferometry, allows the measurement of amplitude and phase of a photoelectron wavepacket created through a Fano resonance with unprecedented precision. In the experiment, a tunable attosecond pulse train is combined with the fundamental laser pulse to induce two-photon transitions in helium via an intermediate autoionizing state. From the energy and time-delay resolved signal, we fully reconstruct the resonant electron wavepacket as it builds up in the continuum. Measurements accurately match the predictions of a new time-resolved multi-photon resonant model, known to reproduce ab initio calculations. This agreement confirms the potential of Rainbow RABBIT to investigate photoemission delays in ultrafast processes governed by electron correlation, as well as to control structured electron wavepackets. now at Univ. Central Florida, Orlando, FL (USA).

Simulating pump-probe photoelectron and absorption spectroscopy on the attosecond timescale with time-dependent density functional theory.

PubMed

De Giovannini, Umberto; Brunetto, Gustavo; Castro, Alberto; Walkenhorst, Jessica; Rubio, Angel

2013-05-10

Molecular absorption and photoelectron spectra can be efficiently predicted with real-time time-dependent density functional theory. We show herein how these techniques can be easily extended to study time-resolved pump-probe experiments, in which a system response (absorption or electron emission) to a probe pulse is measured in an excited state. This simulation tool helps with the interpretation of fast-evolving attosecond time-resolved spectroscopic experiments, in which electronic motion must be followed at its natural timescale. We show how the extra degrees of freedom (pump-pulse duration, intensity, frequency, and time delay), which are absent in a conventional steady-state experiment, provide additional information about electronic structure and dynamics that improve characterization of a system. As an extension of this approach, time-dependent 2D spectroscopy can also be simulated, in principle, for large-scale structures and extended systems. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rameau, J. D.; Freutel, S.; Kemper, A. F.

We report that in complex materials various interactions have important roles in determining electronic properties. Angle-resolved photoelectron spectroscopy (ARPES) is used to study these processes by resolving the complex single-particle self-energy and quantifying how quantum interactions modify bare electronic states. However, ambiguities in the measurement of the real part of the self-energy and an intrinsic inability to disentangle various contributions to the imaginary part of the self-energy can leave the implications of such measurements open to debate. Here we employ a combined theoretical and experimental treatment of femtosecond time-resolved ARPES (tr-ARPES) show how population dynamics measured using tr-ARPES can bemore » used to separate electron–boson interactions from electron–electron interactions. In conclusion, we demonstrate a quantitative analysis of a well-defined electron–boson interaction in the unoccupied spectrum of the cuprate Bi 2Sr 2CaCu 2O 8+x characterized by an excited population decay time that maps directly to a discrete component of the equilibrium self-energy not readily isolated by static ARPES experiments.« less

Energy-resolved attosecond interferometric photoemission from Ag(111) and Au(111) surfaces

NASA Astrophysics Data System (ADS)

Ambrosio, M. J.; Thumm, U.

2018-04-01

Photoelectron emission from solid surfaces induced by attosecond pulse trains into the electric field of delayed phase-coherent infrared (IR) pulses allows the surface-specific observation of energy-resolved electronic phase accumulations and photoemission delays. We quantum-mechanically modeled interferometric photoemission spectra from the (111) surfaces of Au and Ag, including background contributions from secondary electrons and direct emission by the IR pulse, and adjusted parameters of our model to energy-resolved photoelectron spectra recently measured at a synchrotron light source by Roth et al. [J. Electron Spectrosc. 224, 84 (2018), 10.1016/j.elspec.2017.05.008]. Our calculated spectra and photoelectron phase shifts are in fair agreement with the experimental data of Locher et al. [Optica 2, 405 (2015), 10.1364/OPTICA.2.000405]. Our model's not reproducing the measured energy-dependent oscillations of the Ag(111) photoemission phases may be interpreted as evidence for subtle band-structure effects on the final-state photoelectron-surface interaction not accounted for in our simulation.

Femtosecond to picosecond transient effects in WSe 2 observed by pump-probe angle-resolved photoemission spectroscopy.

PubMed

Liu, Ro-Ya; Ogawa, Yu; Chen, Peng; Ozawa, Kenichi; Suzuki, Takeshi; Okada, Masaru; Someya, Takashi; Ishida, Yukiaki; Okazaki, Kozo; Shin, Shik; Chiang, Tai-Chang; Matsuda, Iwao

2017-11-22

Time-dependent responses of materials to an ultrashort optical pulse carry valuable information about the electronic and lattice dynamics; this research area has been widely studied on novel two-dimensional materials such as graphene, transition metal dichalcogenides (TMDs) and topological insulators (TIs). We report herein a time-resolved and angle-resolved photoemission spectroscopy (TRARPES) study of WSe 2 , a layered semiconductor of interest for valley electronics. The results for below-gap optical pumping reveal energy-gain and -loss Floquet replica valence bands that appear instantaneously in concert with the pump pulse. Energy shift, broadening, and complex intensity variation and oscillation at twice the phonon frequency for the valence bands are observed at time scales ranging from the femtosecond to the picosecond and beyond. The underlying physics is rich, including ponderomotive interaction, dressing of the electronic states, creation of coherent phonon pairs, and diffusion of charge carriers - effects operating at vastly different time domains.

Electrical control of flying spin precession in chiral 1D edge states

DOE Office of Scientific and Technical Information (OSTI.GOV)

Nakajima, Takashi; Komiyama, Susumu; Lin, Kuan-Ting

2013-12-04

Electrical control and detection of spin precession are experimentally demonstrated by using spin-resolved edge states in the integer quantum Hall regime. Spin precession is triggered at a corner of a biased metal gate, where electron orbital motion makes a sharp turn leading to a nonadiabatic change in the effective magnetic field via spin-orbit interaction. The phase of precession is controlled by the group velocity of edge-state electrons tuned by gate bias voltage: Spin-FET-like coherent control of spin precession is thus realized by all-electrical means.

Acceptor number-dependent ultrafast photo-physical properties of push-pull chromophores using time-resolved methods

NASA Astrophysics Data System (ADS)

Chi, Xiao-Chun; Wang, Ying-Hui; Gao, Yu; Sui, Ning; Zhang, Li-Quan; Wang, Wen-Yan; Lu, Ran; Ji, Wen-Yu; Yang, Yan-Qiang; Zhang, Han-Zhuang

2018-04-01

Three push-pull chromophores comprising a triphenylamine (TPA) as electron-donating moiety and functionalized β-diketones as electron acceptor units are studied by various spectroscopic techniques. The time-correlated single-photon counting data shows that increasing the number of electron acceptor units accelerates photoluminescence relaxation rate of compounds. Transient spectra data shows that intramolecular charge transfer (ICT) takes place from TPA units to β-diketones units after photo-excitation. Increasing the number of electron acceptor units would prolong the generation process of ICT state, and accelerate the excited molecule reorganization process and the relaxation process of ICT state.

Rotationally resolved fluorescence spectroscopy of molecular iodine

NASA Astrophysics Data System (ADS)

Lemon, Christopher; Canagaratna, Sebastian; Gray, Jeffrey

2008-03-01

Vibration-electronic spectroscopy of I2 vapor is a common, important experiment in physical chemistry lab courses. We use narrow bandwidth diode-pumped solid state (DPSS) lasers to excite specific rotational levels; these lasers are surprisingly stable and are now available at low cost. We also use efficient miniature fiber-optic spectrometers to resolve rotational fluorescence patterns in a vibrational progression. The resolution enables thorough and accurate analysis of spectroscopic constants for the ground electronic state. The high signal-to-noise ratio, which is easily achieved, also enables students to precisely measure fluorescence band intensities, providing further insight into vibrational wavefunctions and the molecular potential function. We will provide a detailed list of parts for the apparatus as well as modeling algorithms with statistical evaluation to facilitate widespread adoption of these experimental improvements by instructors of intermediate and advanced lab courses.

Visualizing One-Dimensional Electronic States and their Scattering in Semi-conducting Nanowires

NASA Astrophysics Data System (ADS)

Beidenkopf, Haim; Reiner, Jonathan; Norris, Andrew; Nayak, Abhay Kumar; Avraham, Nurit; Shtrikman, Hadas

One-dimensional electronic systems constitute a fascinating playground for the emergence of exotic electronic effects and phases, within and beyond the Tomonaga-Luttinger liquid paradigm. More recently topological superconductivity and Majorana modes were added to that long list of phenomena. We report scanning tunneling microscopy and spectroscopy measurements conducted on pristine, epitaxialy grown InAs nanowires. We resolve the 1D electronic band structure manifested both via Van-Hove singularities in the local density-of-states, as well as by the quasi-particle interference patterns, induced by scattering from surface impurities. By studying the scattering of the one-dimensional electronic states off various scatterers, including crystallographic defects and the nanowire end, we identify new one-dimensional relaxation regimes and yet unexplored effects of interactions. Some of these may bear implications on the topological superconducting state and Majorana modes therein. The authors acknowledge support from the Israeli Science Foundation (ISF).

The Negative Ion Photoelectron Spectrum of meta -Benzoquinone Radical Anion (MBQ •– ): A Joint Experimental and Computational Study

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chen, Bo; Hrovat, David A.; Deng, S. H. M.

Negative ion photoelectron (NIPE) spectra of the radical anion of meta-benzoquinone (MBQ, m-OC6H4O) have been obtained at 20 K, using both 355 and 266 nm lasers for electron photodetachment. The spectra show well-resolved peaks and complex spectral patterns. The electron affinity of MBQ is determined from the first resolved peak to be 2.875 ±17 0.010 eV. Single-point, CASPT2/aug-cc-pVTZ//CASPT2/ aug-cc-pVDZ calculations predict accurately the positions of the 0-0 bands in the NIPE spectrum for formation of the four lowest electronic states of neutral MBQ from the 2A2 state of MBQ•-. In addition, the Franck-Condon factors that are computed from the CASPT2/aug-cc-pVDZmore » optimized geometries,vibrational frequencies, and normal mode vectors, successfully simulate the intensities and frequencies of the vibrational peaks in the NIPE spectrum that are associated with each of these electronic states. The successful simulation of the NIPE spectrum of MBQ•- allows the assignment of 3B2 as the ground state of MBQ, followed by the 1B2 and 1A1 electronic states, respectively 9.0 ± 0.2 and 16.6 ± 0.2 kcal/mol higher in energy than the triplet. These experimental energy differences are in good agreement with the calculated values of 9.7 and 15.7 kcal/mol. The relative energies of these two singlet states in MBQ confirm the previous prediction that their relative energies would be reversed from those in meta-benzoquinodimethane (MBQDM, m-CH2C6H4CH2).« less

High resolution photoelectron imaging of UO{sup −} and UO{sub 2}{sup −} and the low-lying electronic states and vibrational frequencies of UO and UO{sub 2}

DOE Office of Scientific and Technical Information (OSTI.GOV)

Czekner, Joseph; Lopez, Gary V.; Wang, Lai-Sheng

2014-12-28

We report a study of the electronic and vibrational structures of the gaseous uranium monoxide and dioxide molecules using high-resolution photoelectron imaging. Vibrationally resolved photoelectron spectra are obtained for both UO{sup −} and UO{sub 2}{sup −}. The spectra for UO{sub 2}{sup −} are consistent with, but much better resolved than a recent study using a magnetic-bottle photoelectron analyzer [W. L. Li et al., J. Chem. Phys. 140, 094306 (2014)]. The electron affinity (EA) of UO is reported for the first time as 1.1407(7) eV, whereas a much more accurate EA is obtained for UO{sub 2} as 1.1688(6) eV. The symmetricmore » stretching modes for the neutral and anionic ground states, and two neutral excited states for UO{sub 2} are observed, as well as the bending mode for the neutral ground state. These vibrational frequencies are consistent with previous experimental and theoretical results. The stretching vibrational modes for the ground state and one excited state are observed for UO. The current results for UO and UO{sub 2} are compared with previous theoretical calculations including relativistic effects and spin-orbit coupling. The accurate experimental data reported here provide more stringent tests for future theoretical methods for actinide-containing species.« less

Quantifying electronic band interactions in van der Waals materials using angle-resolved reflected-electron spectroscopy

PubMed Central

Jobst, Johannes; van der Torren, Alexander J. H.; Krasovskii, Eugene E.; Balgley, Jesse; Dean, Cory R.; Tromp, Rudolf M.; van der Molen, Sense Jan

2016-01-01

High electron mobility is one of graphene's key properties, exploited for applications and fundamental research alike. Highest mobility values are found in heterostructures of graphene and hexagonal boron nitride, which consequently are widely used. However, surprisingly little is known about the interaction between the electronic states of these layered systems. Rather pragmatically, it is assumed that these do not couple significantly. Here we study the unoccupied band structure of graphite, boron nitride and their heterostructures using angle-resolved reflected-electron spectroscopy. We demonstrate that graphene and boron nitride bands do not interact over a wide energy range, despite their very similar dispersions. The method we use can be generally applied to study interactions in van der Waals systems, that is, artificial stacks of layered materials. With this we can quantitatively understand the ‘chemistry of layers' by which novel materials are created via electronic coupling between the layers they are composed of. PMID:27897180

Electronic and geometric structure of thin CoO(100) films studied by angle-resolved photoemission spectroscopy and Auger electron diffraction

NASA Astrophysics Data System (ADS)

Heiler, M.; Chassé, A.; Schindler, K.-M.; Hollering, M.; Neddermeyer, H.

2000-05-01

We have prepared ordered thin films of CoO by evaporating cobalt in an O 2 atmosphere on to a heated (500 K) Ag(100) substrate. The geometric and electronic structure of the films was characterized by means of Auger electron diffraction (AED) and angle-resolved photoemission spectroscopy (ARUPS), respectively. The experimental AED results were compared with simulated data, which showed that the film grows in (100) orientation on the Ag(100) substrate. Synchrotron-radiation-induced photoemission investigations were performed in the photon energy range from 25 eV to 67 eV. The dispersion of the transitions was found to be similar to that of previous results on a single-crystal CoO(100) surface. The resonance behaviour of the photoemission lines in the valence-band region was investigated by constant-initial-state (CIS) spectroscopy. The implications of this behaviour for assignment of the photoemission lines to specific electronic transitions is discussed and compared with published theoretical models of the electronic structure.

Theoretical study of dynamic electron-spin-polarization via the doublet-quartet quantum-mixed state and time-resolved ESR spectra of the quartet high-spin state.

PubMed

Teki, Yoshio; Matsumoto, Takafumi

2011-04-07

The mechanism of the unique dynamic electron polarization of the quartet (S = 3/2) high-spin state via a doublet-quartet quantum-mixed state and detail theoretical calculations of the population transfer are reported. By the photo-induced electron transfer, the quantum-mixed charge-separate state is generated in acceptor-donor-radical triad (A-D-R). This mechanism explains well the unique dynamic electron polarization of the quartet state of A-D-R. The generation of the selectively populated quantum-mixed state and its transfer to the strongly coupled pure quartet and doublet states have been treated both by a perturbation approach and by exact numerical calculations. The analytical solutions show that generation of the quantum-mixed states with the selective populations after de-coherence and/or accompanying the (complete) dephasing during the charge-recombination are essential for the unique dynamic electron polarization. Thus, the elimination of the quantum coherence (loss of the quantum information) is the key process for the population transfer from the quantum-mixed state to the quartet state. The generation of high-field polarization on the strongly coupled quartet state by the charge-recombination process can be explained by a polarization transfer from the quantum-mixed charge-separate state. Typical time-resolved ESR patterns of the quantum-mixed state and of the strongly coupled quartet state are simulated based on the generation mechanism of the dynamic electron polarization. The dependence of the spectral pattern of the quartet high-spin state has been clarified for the fine-structure tensor and the exchange interaction of the quantum-mixed state. The spectral pattern of the quartet state is not sensitive towards the fine-structure tensor of the quantum-mixed state, because this tensor contributes only as a perturbation in the population transfer to the spin-sublevels of the quartet state. Based on the stochastic Liouville equation, it is also discussed why the selective population in the quantum-mixed state is generated for the "finite field" spin-sublevels. The numerical calculations of the elimination of the quantum coherence (de-coherence and/or dephasing) are demonstrated. A new possibility of the enhanced intersystem crossing pathway in solution is also proposed.

The excited spin-triplet state of a charged exciton in quantum dots.

PubMed

Molas, M R; Nicolet, A A L; Piętka, B; Babiński, A; Potemski, M

2016-09-14

We report on spectroscopic studies of resonances related to ladder of states of a charged exciton in single GaAlAs/AlAs quantum dot structures. Polarization-resolved photoluminescence, photoluminescence excitation and photon-correlation measurements were performed at low (T  =  4.2 K) temperature also in magnetic field applied in Faraday configuration. The investigated resonances are assigned to three different configurations of a positively charged exciton. Together with a singlet ground state and a conventional triplet state (involving an electron from the ground state electronic s-shell), an excited triplet state, which involved an electron from the excited electronic p-shell was identified in single dots. The appearance of an emission line related to the latter complex is due to a partially suppressed electron relaxation in the investigated dots. An analysis of this emission line allows us to scrupulously determine properties of the excited triplet state and compare them with those of the conventional triplet state. Both triplets exhibit similar patterns of anisotropic fine structure and Zeeman splitting, however their amplitudes significantly differ for those two states. Presented results emphasize the role of the symmetry of the electronic state on the properties of the triplet states of two holes  +  electron excitonic complex.

Backtracking Depth-Resolved Microstructures for Crystal Plasticity Identification—Part 1: Backtracking Microstructures

NASA Astrophysics Data System (ADS)

Shi, Qiwei; Latourte, Félix; Hild, François; Roux, Stéphane

2017-12-01

In situ mechanical tests performed on polycrystalline materials in a scanning electron microscope suffer from the lack of information on depth-resolved three-dimensional microstructures. The latter ones can be accessed with focused ion beam technology only postmortem, because it is destructive. The present study considers the challenge of backtracking this deformed microstructure to the reference state. This theoretical question is tackled on a numerical (synthetic) test case. A two-dimensional microstructure with one dimension along the depth is considered, and deformed using a crystal plasticity law. The proposed numerical strategy is shown to retrieve accurately the reference state.

Microscopic description of orbital-selective spin ordering in BaMn2As2

NASA Astrophysics Data System (ADS)

Craco, L.; Carara, S. S.

2018-05-01

Using generalized gradient approximation+dynamical mean-field theory, we provide a microscopic description of orbital-selective spin ordering in the tetragonal manganese pnictide BaMn2As2 . We demonstrate the coexistence of local moments and small band-gap electronic states in the parent compound. We also explore the role played by electron/hole doping, showing that the Mott insulating state is rather robust to small removal of electron charge carriers similar to cuprate oxide superconductors. Good qualitative accord between theory and angle-resolved photoemission as well as electrical transport provides support to our view of orbital-selective spin ordering in BaMn2As2 . Our proposal is expected to be an important step to understanding the emergent correlated electronic structure of materials with persisting ordered localized moments coexisting with Coulomb reconstructed nonmagnetic electronic states.

Electronic properties of novel topological quantum materials studied by angle-resolved photoemission spectroscopy (ARPES)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wu, Yun

The discovery of quantum Hall e ect has motivated the use of topology instead of broken symmetry to classify the states of matter. Quantum spin Hall e ect has been proposed to have a separation of spin currents as an analogue of the charge currents separation in quantum Hall e ect, leading us to the era of topological insulators. Three-dimensional analogue of the Dirac state in graphene has brought us the three-dimensional Dirac states. Materials with three-dimensional Dirac states could potentially be the parent compounds for Weyl semimetals and topological insulators when time-reversal or space inversion symmetry is broken. Inmore » addition to the single Dirac point linking the two dispersion cones in the Dirac/Weyl semimetals, Dirac points can form a line in the momentum space, resulting in a topological node line semimetal. These fascinating novel topological quantum materials could provide us platforms for studying the relativistic physics in condensed matter systems and potentially lead to design of new electronic devices that run faster and consume less power than traditional, silicon based transistors. In this thesis, we present the electronic properties of novel topological quantum materials studied by angle-resolved photoemission spectroscopy (ARPES).« less

Wide-band, time-resolved photoacoustic study of electron-transfer reactions. Photoexcited magnesium porphyrin and quinones

DOE Office of Scientific and Technical Information (OSTI.GOV)

Feitelson, J.; Mauzerall, D.C.

1993-08-12

Wide-band, time-resolved, pulsed photoacoustics has been employed to study the electron-transfer reaction between a triplet magnesium porphyrin and various quinones in polar and nonpolar solvents. The reaction rate constants are near encounter limited. The yield of triplet state is 70% in both solvents. The yield of ions is 85% in the former and zero in the latter, in agreement with spin dephasing time and escape times from the Coulomb wells in the two solvents. In methanol the plot of measured heat output versus quinone redox potential is linear. This implies that the entropy of electron transfer is constant through themore » series, but it may not be negligible. 16 refs., 2 figs., 1 tab.« less

Assignment of the photoelectron spectrum of the nitrate anion NO3- and vibronic interactions in the nitrate free radical

NASA Astrophysics Data System (ADS)

Hirota, Eizi

2018-01-01

The unpaired electron orbital of NO3 is of a2‧ symmetry in the ground electronic state, and thus its motion about the symmetry axis of the molecule is free rotation. When a degenerate vibration is excited, however, the free azimuthal rotation of the unpaired electron is perturbed much by nuclear motions of the degenerate mode, as evidenced by high-resolution spectroscopic studies. Thus the ν4 fundamental state, for example, bears some characters of the B ˜ excited electronic state through the Herzberg-Teller (H-T) interaction, and Neumark et al. explained anomalous ν4 progression in the photoelectron spectra of the NO3- anion by the H-T mechanism. However, the interaction parameter Neumark required was too large to reproduce the ν4 molecular parameters in the ground electronic state precisely determined by high-resolution IR spectroscopy. This discrepancy was resolved by the fact that the upper ν4 overtone/combination states of Neumark's photoelectron transitions were primarily of vibrational in nature. The present study thus showed that NO3 bears both vibrational and H-T induced electronic characters in excited states of degenerate modes in the ground electronic state.

Lifetimes and energetics of the first electronically excited states of NaH2O from time-resolved photoelectron imaging

NASA Astrophysics Data System (ADS)

Gartmann, Thomas E.; Yoder, Bruce L.; Chasovskikh, Egor; Signorell, Ruth

2017-09-01

The energetics and lifetimes of the first electronically excited states (;3p-states;) of NaH2O and NaD2O have been measured by pump-probe (740/780 and 400 nm) photoelectron imaging. The photoelectron spectra of NaH2O show two bands at an electron kinetic energy of 0.14 and 0.38 eV, respectively. We assign the former to excitation via the two energetically close lying ;pπ-states; with flat potential curves in the intermolecular degrees of freedom, and the latter to the excitation via the ;pσ-state; characterized by significantly steeper potential curves. The relaxation of all ;p-states; follows a double exponential decay with a lifetime around 110 ps for the dominant fast component.

Unravelling electronic and structural requisites of triplet-triplet energy transfer by advanced electron paramagnetic resonance and density functional theory

NASA Astrophysics Data System (ADS)

Di Valentin, M.; Salvadori, E.; Barone, V.; Carbonera, D.

2013-10-01

Advanced electron paramagnetic resonance (EPR) techniques, in combination with Density Functional theory (DFT), have been applied to the comparative study of carotenoid triplet states in two major photosynthetic antenna complexes, the Peridinin-chlorophyll a-protein of dinoflagellates and the light-harvesting complex II of higher plants. Carotenoid triplet states are populated by triplet-triplet energy transfer (TTET) from chlorophyll molecules to photoprotect the system from singlet oxygen formation under light-stress conditions. The TTET process is strongly dependent on the relative arrangement and on the electronic properties of the triplet states involved. The proposed spectroscopic approach exploits the concept of spin conservation during TTET, which leads to recognisable spin polarisation effects in the time-resolved and field-swept echo-detected EPR spectra. The electron spin polarisation produced at the carotenoid acceptor site depends on the initial polarisation of the chlorophyll donor and on the relative geometrical arrangement of the donor-acceptor zero-field splitting axes. We have demonstrated that a proper analysis of the spectra in the framework of spin angular momentum conservation allows to derive the pathways of TTET and to gain insight into the structural requirements of this mechanism for those antenna complexes, whose X-ray structure is available. We have further proved that this method, developed for natural antenna complexes of known X-ray structure, can be extended to systems lacking structural information in order to derive the relative arrangement of the partners in the energy transfer process. The structural requirements for efficient TTET, obtained from time-resolved and pulse EPR, have been complemented by a detailed description of the electronic structure of the carotenoid triplet state, provided by pulse Electron-Nuclear DOuble Resonance (ENDOR) experiments. Triplet-state hyperfine couplings of the α- and β-protons of the carotenoid conjugated chain have been assigned with the aid of quantum chemical calculation. DFT predictions of the electronic structure of the carotenoid triplet state, in terms of spin density distribution, frontier orbital description and orbital excitation represent suitable building blocks toward a deeper understanding of electronic requirements for efficient TTET.

Observation of inhibited electron-ion coupling in strongly heated graphite

PubMed Central

White, T. G.; Vorberger, J.; Brown, C. R. D.; Crowley, B. J. B.; Davis, P.; Glenzer, S. H.; Harris, J. W. O.; Hochhaus, D. C.; Le Pape, S.; Ma, T.; Murphy, C. D.; Neumayer, P.; Pattison, L. K.; Richardson, S.; Gericke, D. O.; Gregori, G.

2012-01-01

Creating non-equilibrium states of matter with highly unequal electron and lattice temperatures (Tele≠Tion) allows unsurpassed insight into the dynamic coupling between electrons and ions through time-resolved energy relaxation measurements. Recent studies on low-temperature laser-heated graphite suggest a complex energy exchange when compared to other materials. To avoid problems related to surface preparation, crystal quality and poor understanding of the energy deposition and transport mechanisms, we apply a different energy deposition mechanism, via laser-accelerated protons, to isochorically and non-radiatively heat macroscopic graphite samples up to temperatures close to the melting threshold. Using time-resolved x ray diffraction, we show clear evidence of a very small electron-ion energy transfer, yielding approximately three times longer relaxation times than previously reported. This is indicative of the existence of an energy transfer bottleneck in non-equilibrium warm dense matter. PMID:23189238

Persistent order due to transiently enhanced nesting in an electronically excited charge density wave

DOE PAGES

Rettig, L.; Cortés, R.; Chu, J. -H.; ...

2016-01-25

Non-equilibrium conditions may lead to novel properties of materials with broken symmetry ground states not accessible in equilibrium as vividly demonstrated by non-linearly driven mid-infrared active phonon excitation. Potential energy surfaces of electronically excited states also allow to direct nuclear motion, but relaxation of the excess energy typically excites fluctuations leading to a reduced or even vanishing order parameter as characterized by an electronic energy gap. Here, using femtosecond time-and angle-resolved photoemission spectroscopy, we demonstrate a tendency towards transient stabilization of a charge density wave after near-infrared excitation, counteracting the suppression of order in the non-equilibrium state. Analysis of themore » dynamic electronic structure reveals a remaining energy gap in a highly excited transient state. In conclusion, our observation can be explained by a competition between fluctuations in the electronically excited state, which tend to reduce order, and transiently enhanced Fermi surface nesting stabilizing the order.« less

Molecular charge distribution and dispersion of electronic states in the contact layer between pentacene and Cu(119) and beyond

NASA Astrophysics Data System (ADS)

Annese, E.; Fujii, J.; Baldacchini, C.; Zhou, B.; Viol, C. E.; Vobornik, I.; Betti, M. G.; Rossi, G.

2008-05-01

The interaction of pentacene molecules in contact with the Cu(119) stepped surface has been directly imaged by scanning tunneling microscopy and analyzed by angle resolved photoemission spectroscopy. Interacting molecules, which are in contact with copper, generate dispersive electronic states associated with a perturbed electron charge density distribution of the molecular orbitals. In contrast, the electron charge density of molecules of the pentacene on top of the first layer, which is not in direct contact with the Cu surface, shows an intramolecular structure very similar to that of the free molecule. Our results indicate that the delocalization of the molecular states in the pentacene/Cu system is confined to the very first molecular layer at the interface.

2D layered transport properties from topological insulator Bi2Se3 single crystals and micro flakes

PubMed Central

Chiatti, Olivio; Riha, Christian; Lawrenz, Dominic; Busch, Marco; Dusari, Srujana; Sánchez-Barriga, Jaime; Mogilatenko, Anna; Yashina, Lada V.; Valencia, Sergio; Ünal, Akin A.; Rader, Oliver; Fischer, Saskia F.

2016-01-01

Low-field magnetotransport measurements of topological insulators such as Bi2Se3 are important for revealing the nature of topological surface states by quantum corrections to the conductivity, such as weak-antilocalization. Recently, a rich variety of high-field magnetotransport properties in the regime of high electron densities (∼1019 cm−3) were reported, which can be related to additional two-dimensional layered conductivity, hampering the identification of the topological surface states. Here, we report that quantum corrections to the electronic conduction are dominated by the surface states for a semiconducting case, which can be analyzed by the Hikami-Larkin-Nagaoka model for two coupled surfaces in the case of strong spin-orbit interaction. However, in the metallic-like case this analysis fails and additional two-dimensional contributions need to be accounted for. Shubnikov-de Haas oscillations and quantized Hall resistance prove as strong indications for the two-dimensional layered metallic behavior. Temperature-dependent magnetotransport properties of high-quality Bi2Se3 single crystalline exfoliated macro and micro flakes are combined with high resolution transmission electron microscopy and energy-dispersive x-ray spectroscopy, confirming the structure and stoichiometry. Angle-resolved photoemission spectroscopy proves a single-Dirac-cone surface state and a well-defined bulk band gap in topological insulating state. Spatially resolved core-level photoelectron microscopy demonstrates the surface stability. PMID:27270569

Time-resolved single-turnover of caa(3) oxidase from Thermus thermophilus. Fifth electron of the fully reduced enzyme converts O(H) into E(H) state.

PubMed

Siletsky, Sergey A; Belevich, Ilya; Belevich, Nikolai P; Soulimane, Tewfik; Verkhovsky, Michael I

2011-09-01

The oxidative part of the catalytic cycle of the caa(3)-type cytochrome c oxidase from Thermus thermophilus was followed by time-resolved optical spectroscopy. Rate constants, chemical nature and the spectral properties of the catalytic cycle intermediates (Compounds A, P, F) reproduce generally the features typical for the aa(3)-type oxidases with some distinctive peculiarities caused by the presence of an additional 5-th redox-center-a heme center of the covalently bound cytochrome c. Compound A was formed with significantly smaller yield compared to aa(3) oxidases in general and to ba(3) oxidase from the same organism. Two electrons, equilibrated between three input redox-centers: heme a, Cu(A) and heme c are transferred in a single transition to the binuclear center during reduction of the compound F, converting the binuclear center through the highly reactive O(H) state into the final product of the reaction-E(H) (one-electron reduced) state of the catalytic site. In contrast to previous works on the caa(3)-type enzymes, we concluded that the finally produced E(H) state of caa(3) oxidase is characterized by the localization of the fifth electron in the binuclear center, similar to the O(H)→E(H) transition of the aa(3)-type oxidases. So, the fully-reduced caa(3) oxidase is competent in rapid electron transfer from the input redox-centers into the catalytic heme-copper site. 2011 Elsevier B.V. All rights reserved.

Quantum State-Resolved Collision Dynamics of Nitric Oxide at Ionic Liquid and Molten Metal Surfaces

NASA Astrophysics Data System (ADS)

Zutz, Amelia Marie

Detailed molecular scale interactions at the gas-liquid interface are explored with quantum state-to-state resolved scattering of a jet-cooled beam of NO(2pi1/2; N = 0) from ionic liquid and molten metal surfaces. The scattered distributions are probed via laser-induced fluorescence methods, which yield rotational and spin-orbit state populations that elucidate the dynamics of energy transfer at the gas-liquid interface. These collision dynamics are explored as a function of incident collision energy, surface temperature, scattering angle, and liquid identity, all of which are found to substantially affect the degree of rotational, electronic and vibrational excitation of NO via collisions at the liquid surface. Rotational distributions observed reveal two distinct scattering pathways, (i) molecules that trap, thermalize and eventually desorb from the surface (trapping-desorption, TD), and (ii) those that undergo prompt recoil (impulsive scattering, IS) prior to complete equilibration with the liquid surface. Thermally desorbing NO molecules are found to have rotational temperatures close to, but slightly cooler than the surface temperature, indicative of rotational dependent sticking probabilities on liquid surfaces. Nitric oxide is a radical with multiple low-lying electronic states that serves as an ideal candidate for exploring nonadiabatic state-changing collision dynamics at the gas-liquid interface, which induce significant excitation from ground (2pi1/2) to excited (2pi 3/2) spin-orbit states. Molecular beam scattering of supersonically cooled NO from hot molten metals (Ga and Au, Ts = 300 - 1400 K) is also explored, which provide preliminary evidence for vibrational excitation of NO mediated by thermally populated electron-hole pairs in the hot, conducting liquid metals. The results highlight the presence of electronically nonadiabatic effects and build toward a more complete characterization of energy transfer dynamics at gas-liquid interfaces.

Uncovering Highly-Excited State Mixing in Acetone Using Ultrafast VUV Pulses and Coincidence Imaging Techniques

DOE PAGES

Couch, David E.; Kapteyn, Henry C.; Murnane, Margaret M.; ...

2017-03-17

Here, understanding the ultrafast dynamics of highly-excited electronic states of small molecules is critical for a better understanding of atmospheric and astrophysical processes, as well as for designing coherent control strategies for manipulating chemical dynamics. In highly excited states, nonadiabatic coupling, electron-electron interactions, and the high density of states govern dynamics. However, these states are computationally and experimentally challenging to access. Fortunately, new sources of ultrafast vacuum ultraviolet pulses, in combination with electron-ion coincidence spectroscopies, provide new tools to unravel the complex electronic landscape. Here we report time-resolved photoelectron-photoion coincidence experiments using 8 eV pump photons to study the highlymore » excited states of acetone. We uncover for the first time direct evidence that the resulting excited state consists of a mixture of both n y → 3p and π → π* character, which decays with a time constant of 330 fs. In the future, this approach can inform models of VUV photochemistry and aid in designing coherent control strategies for manipulating chemical reactions.« less

Uncovering Highly-Excited State Mixing in Acetone Using Ultrafast VUV Pulses and Coincidence Imaging Techniques

DOE Office of Scientific and Technical Information (OSTI.GOV)

Couch, David E.; Kapteyn, Henry C.; Murnane, Margaret M.

Here, understanding the ultrafast dynamics of highly-excited electronic states of small molecules is critical for a better understanding of atmospheric and astrophysical processes, as well as for designing coherent control strategies for manipulating chemical dynamics. In highly excited states, nonadiabatic coupling, electron-electron interactions, and the high density of states govern dynamics. However, these states are computationally and experimentally challenging to access. Fortunately, new sources of ultrafast vacuum ultraviolet pulses, in combination with electron-ion coincidence spectroscopies, provide new tools to unravel the complex electronic landscape. Here we report time-resolved photoelectron-photoion coincidence experiments using 8 eV pump photons to study the highlymore » excited states of acetone. We uncover for the first time direct evidence that the resulting excited state consists of a mixture of both n y → 3p and π → π* character, which decays with a time constant of 330 fs. In the future, this approach can inform models of VUV photochemistry and aid in designing coherent control strategies for manipulating chemical reactions.« less

Asymmetric band gaps in a Rashba film system

DOE Office of Scientific and Technical Information (OSTI.GOV)

Carbone, C.; Moras, P.; Sheverdyaeva, P. M.

The joint effect of exchange and Rashba spin-orbit interactions is examined on the surface and quantum well states of Ag 2 Bi -terminated Ag films grown on ferromagnetic Fe(110). The system displays a particular combination of time-reversal and translational symmetry breaking that strongly influences its electronic structure. Angle-resolved photoemission reveals asymmetric band-gap openings, due to spin-selective hybridization between Rashba-split surface states and exchange-split quantum well states. This results in an unequal number of states along positive and negative reciprocal space directions. We suggest that the peculiar asymmetry of the discovered electronic structure can have significant influence on spin-polarized transport properties.

Trivial and topological Fermi arcs in the type-II Weyl semimetal candidate MoTe2

NASA Astrophysics Data System (ADS)

Tamai, Anna; Wu, Quansheng; Cucchi, Irene; Bruno, Flavio; Barreteau, Celine; Giannini, Enrico; Soluyanov, Alexey; Baumberger, Felix

Weyl semimetals are commonly identified by detecting their characteristic open surface state Fermi arcs in angle-resolved photoemission (ARPES) experiments. However, in type-II Weyl semimetals the Fermi arcs generally disappear in the bulk carrier pockets before reaching the Weyl points where they terminate - making it harder to unambiguously identify this new electronic state. Using laser-based ARPES, we have resolved multiple distinct Fermi arcs on the inequivalent top and bottom (001) surfaces of the candidate type-II Weyl semimetal MoTe2. By comparing our ARPES data with systematic electronic structure calculations simulating different Weyl point arrangements, we show that some of these arcs are false positives as they can be explained without Weyl points, while others are only reproduced in scenarios with at least eight Weyl points. Our results thus suggest that MoTe2 is the first experimental realisation of a type-II Weyl semimetal.

Antiferroic electronic structure in the nonmagnetic superconducting state of the iron-based superconductors

PubMed Central

Shimojima, Takahiro; Malaeb, Walid; Nakamura, Asuka; Kondo, Takeshi; Kihou, Kunihiro; Lee, Chul-Ho; Iyo, Akira; Eisaki, Hiroshi; Ishida, Shigeyuki; Nakajima, Masamichi; Uchida, Shin-ichi; Ohgushi, Kenya; Ishizaka, Kyoko; Shin, Shik

2017-01-01

A major problem in the field of high-transition temperature (Tc) superconductivity is the identification of the electronic instabilities near superconductivity. It is known that the iron-based superconductors exhibit antiferromagnetic order, which competes with the superconductivity. However, in the nonmagnetic state, there are many aspects of the electronic instabilities that remain unclarified, as represented by the orbital instability and several in-plane anisotropic physical properties. We report a new aspect of the electronic state of the optimally doped iron-based superconductors by using high–energy resolution angle-resolved photoemission spectroscopy. We find spectral evidence for the folded electronic structure suggestive of an antiferroic electronic instability, coexisting with the superconductivity in the nonmagnetic state of Ba1−xKxFe2As2. We further establish a phase diagram showing that the antiferroic electronic structure persists in a large portion of the nonmagnetic phase covering the superconducting dome. These results motivate consideration of a key unknown electronic instability, which is necessary for the achievement of high-Tc superconductivity in the iron-based superconductors. PMID:28875162

Antiferroic electronic structure in the nonmagnetic superconducting state of the iron-based superconductors.

PubMed

Shimojima, Takahiro; Malaeb, Walid; Nakamura, Asuka; Kondo, Takeshi; Kihou, Kunihiro; Lee, Chul-Ho; Iyo, Akira; Eisaki, Hiroshi; Ishida, Shigeyuki; Nakajima, Masamichi; Uchida, Shin-Ichi; Ohgushi, Kenya; Ishizaka, Kyoko; Shin, Shik

2017-08-01

A major problem in the field of high-transition temperature ( T c ) superconductivity is the identification of the electronic instabilities near superconductivity. It is known that the iron-based superconductors exhibit antiferromagnetic order, which competes with the superconductivity. However, in the nonmagnetic state, there are many aspects of the electronic instabilities that remain unclarified, as represented by the orbital instability and several in-plane anisotropic physical properties. We report a new aspect of the electronic state of the optimally doped iron-based superconductors by using high-energy resolution angle-resolved photoemission spectroscopy. We find spectral evidence for the folded electronic structure suggestive of an antiferroic electronic instability, coexisting with the superconductivity in the nonmagnetic state of Ba 1- x K x Fe 2 As 2 . We further establish a phase diagram showing that the antiferroic electronic structure persists in a large portion of the nonmagnetic phase covering the superconducting dome. These results motivate consideration of a key unknown electronic instability, which is necessary for the achievement of high- T c superconductivity in the iron-based superconductors.

Identification of a new low energy 1u state in dicopper with resonant four-wave mixing.

PubMed

Visser, B; Beck, M; Bornhauser, P; Knopp, G; van Bokhoven, J A; Marquardt, R; Gourlaouen, C; Radi, P P

2017-12-07

The low energy electronic structure of the copper dimer has been re-investigated using non-linear four-wave mixing spectroscopy and high level ab initio calculations. In addition to the measurement of the previously reported A, B, and C electronic states, a new state denoted A' is identified with T 0 = 20 100.4090(16) cm -1 ( 63 Cu 2 ). Rotational analysis of the A'-X (0,0) and (1,0) transitions leads to the assignment of A' 1 u . Ab initio calculations present the first theoretical description of the low energy states of the copper dimer in Hund's case (c) and confirm the experimental assignment. The discovery of this new low energy excited state emphasizes that spin-orbit coupling is significant in states with d-hole electronic configurations and resolves a decades-long mystery in the initial assignment of the A state.

Dynamics of dipole- and valence bound anions in iodide-adenine binary complexes: A time-resolved photoelectron imaging and quantum mechanical investigation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Stephansen, Anne B.; King, Sarah B.; Li, Wei-Li

2015-09-14

Dipole bound (DB) and valence bound (VB) anions of binary iodide-adenine complexes have been studied using one-color and time-resolved photoelectron imaging at excitation energies near the vertical detachment energy. The experiments are complemented by quantum chemical calculations. One-color spectra show evidence for two adenine tautomers, the canonical, biologically relevant A9 tautomer and the A3 tautomer. In the UV-pump/IR-probe time-resolved experiments, transient adenine anions can be formed by electron transfer from the iodide. These experiments show signals from both DB and VB states of adenine anions formed on femto- and picosecond time scales, respectively. Analysis of the spectra and comparison withmore » calculations suggest that while both the A9 and A3 tautomers contribute to the DB signal, only the DB state of the A3 tautomer undergoes a transition to the VB anion. The VB anion of A9 is higher in energy than both the DB anion and the neutral, and the VB anion is therefore not accessible through the DB state. Experimental evidence of the metastable A9 VB anion is instead observed as a shape resonance in the one-color photoelectron spectra, as a result of UV absorption by A9 and subsequent electron transfer from iodide into the empty π-orbital. In contrast, the iodide-A3 complex constitutes an excellent example of how DB states can act as doorway state for VB anion formation when the VB state is energetically available.« less

Time-resolved generation of membrane potential by ba3 cytochrome c oxidase from Thermus thermophilus coupled to single electron injection into the O and OH states.

PubMed

Siletsky, Sergey A; Belevich, Ilya; Belevich, Nikolai P; Soulimane, Tewfik; Wikström, Mårten

2017-11-01

Two electrogenic phases with characteristic times of ~14μs and ~290μs are resolved in the kinetics of membrane potential generation coupled to single-electron reduction of the oxidized "relaxed" O state of ba 3 oxidase from T. thermophilus (O→E transition). The rapid phase reflects electron redistribution between Cu A and heme b. The slow phase includes electron redistribution from both Cu A and heme b to heme a 3 , and electrogenic proton transfer coupled to reduction of heme a 3 . The distance of proton translocation corresponds to uptake of a proton from the inner water phase into the binuclear center where heme a 3 is reduced, but there is no proton pumping and no reduction of Cu B . Single-electron reduction of the oxidized "unrelaxed" state (O H →E H transition) is accompanied by electrogenic reduction of the heme b/heme a 3 pair by Cu A in a "fast" phase (~22μs) and transfer of protons in "middle" and "slow" electrogenic phases (~0.185ms and ~0.78ms) coupled to electron redistribution from the heme b/heme a 3 pair to the Cu B site. The "middle" and "slow" electrogenic phases seem to be associated with transfer of protons to the proton-loading site (PLS) of the proton pump, but when all injected electrons reach Cu B the electronic charge appears to be compensated by back-leakage of the protons from the PLS into the binuclear site. Thus proton pumping occurs only to the extent of ~0.1 H + /e - , probably due to the formed membrane potential in the experiment. Copyright © 2017 Elsevier B.V. All rights reserved.

Angle-resolved PED and AED calculations for different structures of the diamond C(111) surface

NASA Astrophysics Data System (ADS)

Niebergall, L.; Rennert, P.; Chassé, A.; Kucherenko, Yu

1998-05-01

Angle-resolved (AR) photoelectron diffraction (PED) spectra for electrons excited from the C 1s core state and angle-resolved KVV Auger electron diffraction (AED) spectra are calculated for the Pandey and the Tsai stucture models of diamond C(111) which extend previous investigations of the ideal structure. It is shown how to decide on the structure model by comparing PE spectra for different directions and by comparing PED and AED spectra. Calculations have been performed by evaluating the scattering path operator for a finite cluster in a curved-wave approximation. The different matrix elements for the photoelectron excitation and for the Auger process, respectively, are included. It is shown that the PED intensities are very sensitive to the surface reconstruction for polar angles in the range of 80°. In the AED intensities, polar scans in the plane perpendicular to the chain direction can be considered.

A review of electron-phonon coupling seen in the high-Tc superconductors by angle-resolved photoemission studies (ARPES)

NASA Astrophysics Data System (ADS)

Cuk, T.; Lu, D. H.; Zhou, X. J.; Shen, Z.-X.; Devereaux, T. P.; Nagaosa, N.

2005-01-01

This issue of pss (b) - basic solid state physics contains a collection of Review Articles on the rather controversially discussed topic of Electron-Phonon Interaction in High-Temperature Superconductors, guest-edited by Miodrag Kuli, Johann Wolfgang Goethe-Universität Frankfurt/Main, Germany, with a Preface written by V. L. Ginzburg and E. G. Maksimov [1].The cover picture, taken from the review [2] by T. Cuk et al., shows plots of the electron-phonon coupling vertex, g2(k, k), where k, k are the initial and final electron momentum for electrons scattered by the bond-buckling phonon B1g (the out-of-phase vibration of the in-plane oxygen) in a tight-binding model of the copper-oxygen plane. The momentum dependence of this vertex, along with the d-wave superconducting gap and the van Hove singularity at the anti-node, accounts for the momentum dependence of the collective mode coupling seen in angle-resolved photoemission data on Bi2212.The present issue also sees the start of our rapid research letters, the fastest peer-reviewed publication medium in solid state physics. For more information see www.pss-rapid.com and the Editorial by the Editor-in-Chief Martin Stutzmann on page 7 [3].

Intrinsic Resolution of Molecular Electronic Wave Functions and Energies in Terms of Quasi-atoms and Their Interactions.

PubMed

West, Aaron C; Schmidt, Michael W; Gordon, Mark S; Ruedenberg, Klaus

2017-02-09

A general intrinsic energy resolution has been formulated for strongly correlated wave functions in the full molecular valence space and its subspaces. The information regarding the quasi-atomic organization of the molecular electronic structure is extracted from the molecular wave function without introducing any additional postulated model state wave functions. To this end, the molecular wave function is expressed in terms of quasi-atomic molecular orbitals, which maximize the overlap between subspaces of the molecular orbital space and the free-atom orbital spaces. As a result, the molecular wave function becomes the superposition of a wave function representing the juxtaposed nonbonded quasi-atoms and a wave function describing the interatomic electron migrations that create bonds through electron sharing. The juxtaposed nonbonded quasi-atoms are shown to consist of entangled quasi-atomic states from different atoms. The binding energy is resolved as a sum of contributions that are due to quasi-atom formation, quasiclassical electrostatic interactions, and interatomic interferences caused by electron sharing. The contributions are further resolved according to orbital interactions. The various transformations that generate the analysis are determined by criteria that are independent of the working orbital basis used for calculating the molecular wave function. The theoretical formulation of the resolution is quantitatively validated by an application to the C 2 molecule.

Electron scattering at interfaces in nano-scale vertical interconnects: A combined experimental and ab initio study

NASA Astrophysics Data System (ADS)

Lanzillo, Nicholas A.; Restrepo, Oscar D.; Bhosale, Prasad S.; Cruz-Silva, Eduardo; Yang, Chih-Chao; Youp Kim, Byoung; Spooner, Terry; Standaert, Theodorus; Child, Craig; Bonilla, Griselda; Murali, Kota V. R. M.

2018-04-01

We present a combined theoretical and experimental study on the electron transport characteristics across several representative interface structures found in back-end-of-line interconnect stacks for advanced semiconductor manufacturing: Cu/Ta(N)/Co/Cu and Cu/Ta(N)/Ru/Cu. In particular, we evaluate the impact of replacing a thin TaN barrier with Ta while considering both Co and Ru as wetting layers. Both theory and experiment indicate a pronounced reduction in vertical resistance when replacing TaN with Ta, regardless of whether a Co or Ru wetting layer is used. This indicates that a significant portion of the total vertical resistance is determined by electron scattering at the Cu/Ta(N) interface. The electronic structure of these nano-sized interconnects is analyzed in terms of the atom-resolved projected density of states and k-resolved transmission spectra at the Fermi level. This work further develops a fundamental understanding of electron transport and material characteristics in nano-sized interconnects.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Alberi, K.; Christian, T. M.; Fluegel, B.

While bismuth-related states are known to localize carriers in GaAs 1-xBi x alloys, the localization behavior of distinct Bi pair, triplet and cluster states bound above the valence band is less well understood. We probe localization at three different Bi complex states in dilute GaAs 1-xBi x alloys using magneto-photoluminescence and time-resolved photoluminescence spectroscopy. The mass of electrons Coulomb-bound to holes trapped at Bi pair states is found to increase relative to the average electron mass in the alloy. This increase is attributed to enhanced local compressive strain in the immediate vicinity of the pairs. The dependence of energy transfermore » between these states on composition is also explored.« less

State-Resolved Metal Nanoparticle Dynamics Viewed through the Combined Lenses of Ultrafast and Magneto-optical Spectroscopies.

PubMed

Zhao, Tian; Herbert, Patrick J; Zheng, Hongjun; Knappenberger, Kenneth L

2018-06-19

Electronic carrier dynamics play pivotal roles in the functional properties of nanomaterials. For colloidal metals, the mechanisms and influences of these dynamics are structure dependent. The coherent carrier dynamics of collective plasmon modes for nanoparticles (approximately 2 nm and larger) determine optical amplification factors that are important to applied spectroscopy techniques. In the nanocluster domain (sub-2 nm), carrier coupling to vibrational modes affects photoluminescence yields. The performance of photocatalytic materials featuring both nanoparticles and nanoclusters also depends on the relaxation dynamics of nonequilibrium charge carriers. The challenges for developing comprehensive descriptions of carrier dynamics spanning both domains are multifold. Plasmon coherences are short-lived, persisting for only tens of femtoseconds. Nanoclusters exhibit discrete carrier dynamics that can persist for microseconds in some cases. On this time scale, many state-dependent processes, including vibrational relaxation, charge transfer, and spin conversion, affect carrier dynamics in ways that are nonscalable but, rather, structure specific. Hence, state-resolved spectroscopy methods are needed for understanding carrier dynamics in the nanocluster domain. Based on these considerations, a detailed understanding of structure-dependent carrier dynamics across length scales requires an appropriate combination of spectroscopic methods. Plasmon mode-specific dynamics can be obtained through ultrafast correlated light and electron microscopy (UCLEM), which pairs interferometric nonlinear optical (INLO) with electron imaging methods. INLO yields nanostructure spectral resonance responses, which capture the system's homogeneous line width and coherence dynamics. State-resolved nanocluster dynamics can be obtained by pairing ultrafast with magnetic-optical spectroscopy methods. In particular, variable-temperature variable-field (VTVH) spectroscopies allow quantification of transient, excited states, providing quantification of important parameters such as spin and orbital angular momenta as well as the energy gaps that separate electronic fine structure states. Ultrafast two-dimensional electronic spectroscopy (2DES) can be used to understand how these details influence state-to-state carrier dynamics. In combination, VTVH and 2DES methods can provide chemists with detailed information regarding the structure-dependent and state-specific flow of energy through metal nanoclusters. In this Account, we highlight recent advances toward understanding structure-dependent carrier dynamics for metals spanning the sub-nanometer to tens of nanometers length scale. We demonstrate the use of UCLEM methods for arresting interband scattering effects. For sub-nanometer thiol-protected nanoclusters, we discuss the effectiveness of VTVH for distinguishing state-specific radiative recombination originating from a gold core versus organometallic protecting layers. This state specificity is refined further using femtosecond 2DES and two-color methods to isolate so-called superatom state dynamics and vibrationally mediated spin-conversion and emission processes. Finally, we discuss prospects for merging VTVH and 2DES methods into a single platform.

Nonlinear Optical Spectroscopy in the Time Domain: Studies of Ultrafast Molecular Processes in the Condensed Phase.

NASA Astrophysics Data System (ADS)

Joo, Taiha

Ultrafast molecular processes in the condensed phase at room temperature are studied in the time domain by four wave mixing spectroscopy. The structure/dynamics of various quantum states can be studied by varying the time ordering of the incident fields, their polarization, their colors, etc. In one, time-resolved coherent Stokes Raman spectroscopy of benzene is investigated at room temperature. The reorientational correlation time of benzene as well as the T_2 time of the nu _1 ring-breathing mode have been measured by using two different polarization geometries. Bohr frequency difference beats have also been resolved between the nu_1 modes of ^ {12}C_6H_6 and ^{12}C_5^{13 }CH_6.. The dephasing dynamics of the nu _1 ring-breathing mode of neat benzene is studied by time-resolved coherent anti-Stokes Raman scattering. Ultrafast time resolution reveals deviation from the conventional exponential decay. The correlation time, tau _{rm c}, and the rms magnitude, Delta, of the Bohr frequency modulation are determined for the process responsible for the vibrational dephasing by Kubo dephasing function analysis. The electronic dephasing of two oxazine dyes in ethylene glycol at room temperature is investigated by photon echo experiments. It was found that at least two stochastic processes are responsible for the observed electronic dephasing. Both fast (homogeneous) and slow (inhomogeneous) dynamics are recovered using Kubo line shape analysis. Moreover, the slow dynamics is found to spectrally diffuse over the inhomogeneous distribution on the time scale around a picosecond. Time-resolved degenerate four wave mixing signal of dyes in a population measurement geometry is reported. The vibrational coherences both in the ground and excited electronic states produced strong oscillations in the signal together with the usual population decay from the excited electronic state. Absolute frequencies and their dephasing times of the vibrational modes at ~590 cm^{-1} are obtained. Finally, a new inverse transform procedure is presented that calculates the absorption band (ABS) from an experimental Raman excitation profile (REP). An iterative solution is sought for an integral Hilbert transform relation. An exact ABS is recovered regardless of the starting ABS when sufficient iterations are performed.

Superconductivity and bandwidth-controlled Mott metal-insulator transition in 1T-TaS2-xSex

NASA Astrophysics Data System (ADS)

Ang, R.; Miyata, Y.; Ieki, E.; Nakayama, K.; Sato, T.; Liu, Y.; Lu, W. J.; Sun, Y. P.; Takahashi, T.

2013-09-01

We have performed high-resolution angle-resolved photoemission spectroscopy (ARPES) of layered chalcogenide 1T-TaS2-xSex to elucidate the electronic states especially relevant to the occurrence of superconductivity. We found a direct evidence for a Ta-5d-derived electron pocket associated with the superconductivity, which is fragile against a Mott-gap opening observed in the insulating ground state for S-rich samples. In particular, a strong electron-electron interaction-induced Mott gap driven by a Ta 5d orbital also exists in the metallic ground state for Se-rich samples, while finite ARPES intensity near the Fermi level likely originating from a Se 4p orbital survives, indicative of the orbital-selective nature of the Mott transition. Present results suggest that effective electron correlation and p-d hybridization play a crucial role to tune the superconductivity and Mott metal-insulator transition.

Intramolecular structure and dynamics of mequinol and guaiacol in the gas phase: Rotationally resolved electronic spectra of their S1 states

NASA Astrophysics Data System (ADS)

Ruiz-Santoyo, José Arturo; Rodríguez-Matus, Marcela; Cabellos, José Luis; Yi, John T.; Pratt, David W.; Schmitt, Michael; Merino, Gabriel; Álvarez-Valtierra, Leonardo

2015-09-01

The molecular structures of guaiacol (2-methoxyphenol) and mequinol (4-methoxyphenol) have been studied using high resolution electronic spectroscopy in a molecular beam and contrasted with ab initio computations. Mequinol exhibits two low frequency bands that have been assigned to electronic origins of two possible conformers of the molecule, trans and cis. Guaiacol also shows low frequency bands, but in this case, the bands have been assigned to the electronic origin and vibrational modes of a single conformer of the isolated molecule. A detailed study of these bands indicates that guaiacol has a vibrationally averaged planar structure in the ground state, but it is distorted along both in-plane and out-of-plane coordinates in the first electronically excited state. An intramolecular hydrogen bond involving the adjacent -OH and -OCH3 groups plays a major role in these dynamics.

Intramolecular structure and dynamics of mequinol and guaiacol in the gas phase: Rotationally resolved electronic spectra of their S1 states.

PubMed

Ruiz-Santoyo, José Arturo; Rodríguez-Matus, Marcela; Cabellos, José Luis; Yi, John T; Pratt, David W; Schmitt, Michael; Merino, Gabriel; Álvarez-Valtierra, Leonardo

2015-09-07

The molecular structures of guaiacol (2-methoxyphenol) and mequinol (4-methoxyphenol) have been studied using high resolution electronic spectroscopy in a molecular beam and contrasted with ab initio computations. Mequinol exhibits two low frequency bands that have been assigned to electronic origins of two possible conformers of the molecule, trans and cis. Guaiacol also shows low frequency bands, but in this case, the bands have been assigned to the electronic origin and vibrational modes of a single conformer of the isolated molecule. A detailed study of these bands indicates that guaiacol has a vibrationally averaged planar structure in the ground state, but it is distorted along both in-plane and out-of-plane coordinates in the first electronically excited state. An intramolecular hydrogen bond involving the adjacent   -OH and   -OCH3 groups plays a major role in these dynamics.

Extracting the temperature of hot carriers in time- and angle-resolved photoemission.

PubMed

Ulstrup, Søren; Johannsen, Jens Christian; Grioni, Marco; Hofmann, Philip

2014-01-01

The interaction of light with a material's electronic system creates an out-of-equilibrium (non-thermal) distribution of optically excited electrons. Non-equilibrium dynamics relaxes this distribution on an ultrafast timescale to a hot Fermi-Dirac distribution with a well-defined temperature. The advent of time- and angle-resolved photoemission spectroscopy (TR-ARPES) experiments has made it possible to track the decay of the temperature of the excited hot electrons in selected states in the Brillouin zone, and to reveal their cooling in unprecedented detail in a variety of emerging materials. It is, however, not a straightforward task to determine the temperature with high accuracy. This is mainly attributable to an a priori unknown position of the Fermi level and the fact that the shape of the Fermi edge can be severely perturbed when the state in question is crossing the Fermi energy. Here, we introduce a method that circumvents these difficulties and accurately extracts both the temperature and the position of the Fermi level for a hot carrier distribution by tracking the occupation statistics of the carriers measured in a TR-ARPES experiment.

Tempo-spatially resolved dynamics of elec- trons and holes in bilayer MoS2 -WS2

NASA Astrophysics Data System (ADS)

Galicia-Hernandez, J. M.; Turkowski, V.; Hernandez-Cocoletzi, G.; Rahman, T. S.

We have performed a Density-Matrix Time-Dependent Density-Functional Theory analysis of the response of bilayer MoS2-WS2 to external laser-pulse perturbations. Time-resolved study of the dynamics of electrons and holes, including formation and dissociation of strongly-bound intra- and inter-layer excitonic states, shows that the experimentally observed ultrafast inter-layer MoS2 to WS2 migration of holes may be attributed to unusually large delocalization of the hole state which extends far into the inter-layer region. We also argue that the velocity of the hole transfer may be further enhanced by its interaction with transfer phonon modes. We analyze other possible consequences of the hole delocalization in the system, including reduction of the effects of the electron-electron and hole-hole repulsion in the trions and biexcitons as compared to that in the monolayers Work supported in part by DOE Grant No. DOE-DE-FG02-07ER46354 and by CONACYT Scholarship No. 23210 (J.M.G.H.).

Energy dissipation from a correlated system driven out of equilibrium

DOE PAGES

Rameau, J. D.; Freutel, S.; Kemper, A. F.; ...

2016-12-20

We report that in complex materials various interactions have important roles in determining electronic properties. Angle-resolved photoelectron spectroscopy (ARPES) is used to study these processes by resolving the complex single-particle self-energy and quantifying how quantum interactions modify bare electronic states. However, ambiguities in the measurement of the real part of the self-energy and an intrinsic inability to disentangle various contributions to the imaginary part of the self-energy can leave the implications of such measurements open to debate. Here we employ a combined theoretical and experimental treatment of femtosecond time-resolved ARPES (tr-ARPES) show how population dynamics measured using tr-ARPES can bemore » used to separate electron–boson interactions from electron–electron interactions. In conclusion, we demonstrate a quantitative analysis of a well-defined electron–boson interaction in the unoccupied spectrum of the cuprate Bi 2Sr 2CaCu 2O 8+x characterized by an excited population decay time that maps directly to a discrete component of the equilibrium self-energy not readily isolated by static ARPES experiments.« less

Elucidating light-induced charge accumulation in an artificial analogue of methane monooxygenase enzymes using time-resolved X-ray absorption spectroscopy

DOE PAGES

Moonshiram, Dooshaye; Picon, Antonio; Vazquez-Mayagoitia, Alvaro; ...

2017-02-08

Here, we report the use of time-resolved X-ray absorption spectroscopy in the ns–μs time scale to track the light induced two electron transfer processes in a multi-component photocatalytic system, consisting of [Ru(bpy) 3] 2+/ a diiron(III,III) model/triethylamine. EXAFS analysis with DFT calculations confirms the structural configurations of the diiron(III,III) and reduced diiron(II,II) states.

Elucidating light-induced charge accumulation in an artificial analogue of methane monooxygenase enzymes using time-resolved X-ray absorption spectroscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Moonshiram, Dooshaye; Picon, Antonio; Vazquez-Mayagoitia, Alvaro

Here, we report the use of time-resolved X-ray absorption spectroscopy in the ns–μs time scale to track the light induced two electron transfer processes in a multi-component photocatalytic system, consisting of [Ru(bpy) 3] 2+/ a diiron(III,III) model/triethylamine. EXAFS analysis with DFT calculations confirms the structural configurations of the diiron(III,III) and reduced diiron(II,II) states.

F + H2 collisions on two electronic potential energy surfaces - Quantum-mechanical study of the collinear reaction

NASA Technical Reports Server (NTRS)

Zimmerman, I. H.; Baer, M.; George, T. F.

1979-01-01

Collinear quantum calculations are carried out for reactive F + H2 collisions on two electronic potential energy surfaces. The resulting transmission and reflection probabilities exhibit much greater variation with energy than single-surface studies would lead us to anticipate. Transmission to low-lying product channels is increased by orders of magnitude by the presence of the second surface; however, branching ratios among product states are found to be independent of the initial electronic state of the reactants. These apparently contradictory aspects of the calculation are discussed and a tentative explanation put forward to resolve them.

Electronic spectra of 2- and 3-tolunitrile in the gas phase. I. A study of methyl group internal rotation via rovibronically resolved spectroscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ruiz-Santoyo, José Arturo; Álvarez-Valtierra, Leonardo, E-mail: leoav@fisica.ugto.mx; Wilke, Josefin

2016-01-28

Rotationally resolved fluorescence excitation spectra of the origin bands in the S{sub 1}←S{sub 0} transition of 2-tolunitrile (2TN) and 3-tolunitrile (3TN) have been recorded in the collision-free environment of a molecular beam. Analyses of these data provide the rotational constants of each molecule and the potential energy curves governing the internal rotation of the attached methyl groups in both electronic states. 2TN exhibits much larger barriers along this coordinate than 3TN. Interestingly, the electronic transition dipole moment in both molecules is markedly influenced by the position of the attached methyl group rather than the position of the cyano group; possiblemore » reasons for this intriguing behavior are discussed.« less

Spectroscopic Constants of the Known Electronic States of Lead Monofluoride

DOE Office of Scientific and Technical Information (OSTI.GOV)

McRaven, C.P.; Sivakumar, P.; Shafer-Ray, N.E.

2010-08-01

Based on measurements made by mass-resolved 1 + 1{prime} + 1{double_prime} resonance-enhanced multiphoton ionization spectroscopy, we have determined new molecular constants describing the rotational and fine structure levels of the B, D, E, and F states of the most abundant isotopic variant {sup 208}Pb{sup 19}F, and we summarize the spectroscopic constants for all the know electronic states of the radical. Many spectroscopic constants for the isotopologues {sup 206}Pb{sup 19}F and {sup 207}Pb{sup 19}F have also been determined. The symmetry of the D-state is found to be {sup 2}{pi}{sub 1/2}, and the F-state is found to be an {Omega} = 3/2more » state.« less

Separating Bulk and Surface Contributions to Electronic Excited-State Processes in Hybrid Mixed Perovskite Thin Films via Multimodal All-Optical Imaging.

PubMed

Simpson, Mary Jane; Doughty, Benjamin; Das, Sanjib; Xiao, Kai; Ma, Ying-Zhong

2017-07-20

A comprehensive understanding of electronic excited-state phenomena underlying the impressive performance of solution-processed hybrid halide perovskite solar cells requires access to both spatially resolved electronic processes and corresponding sample morphological characteristics. Here, we demonstrate an all-optical multimodal imaging approach that enables us to obtain both electronic excited-state and morphological information on a single optical microscope platform with simultaneous high temporal and spatial resolution. Specifically, images were acquired for the same region of interest in thin films of chloride containing mixed lead halide perovskites (CH 3 NH 3 PbI 3-x Cl x ) using femtosecond transient absorption, time-integrated photoluminescence, confocal reflectance, and transmission microscopies. Comprehensive image analysis revealed the presence of surface- and bulk-dominated contributions to the various images, which describe either spatially dependent electronic excited-state properties or morphological variations across the probed region of the thin films. These results show that PL probes effectively the species near or at the film surface.

Jet-resolved vibronic structure in the higher excited states of N2O - Ultraviolet three-photon absorption spectroscopy from 80,000 to 90,000/cm

NASA Technical Reports Server (NTRS)

Patsilinakou, E.; Wiedmann, R. T.; Fotakis, C.; Grant, E. R.

1989-01-01

Ionization-detected UV multiphoton absorption spectroscopy of the excited states of N2O is presented, showing Rydberg structure within 20,000/cm of the first ionization threshold. Despite evidence for strong Rydberg-continuum coupling in the form of broadened bands and Fano line-shapes, the Rydberg structure persists, with atomic-like quantum defects and vibration structure well-matched with that of the ion. In the most clearly resolved spectrum, corresponding to the 3p(delta)1Pi state, Renner-Teller and Herzberg-Teller coupling of electronic and vibrational angular momentum are revealed. It is suggested that these mixings are properties of the N2O(+)Pi ion core.

Calculated momentum dependence of Zhang-Rice states in transition metal oxides.

PubMed

Yin, Quan; Gordienko, Alexey; Wan, Xiangang; Savrasov, Sergey Y

2008-02-15

Using a combination of local density functional theory and cluster exact diagonalization based dynamical mean field theory, we calculate many-body electronic structures of several Mott insulating oxides including undoped high T(c) materials. The dispersions of the lowest occupied electronic states are associated with the Zhang-Rice singlets in cuprates and with doublets, triplets, quadruplets, and quintets in more general cases. Our results agree with angle resolved photoemission experiments including the decrease of the spectral weight of the Zhang-Rice band as it approaches k=0.

Coherent Electron Transfer at the Ag / Graphite Heterojunction Interface

NASA Astrophysics Data System (ADS)

Tan, Shijing; Dai, Yanan; Zhang, Shengmin; Liu, Liming; Zhao, Jin; Petek, Hrvoje

2018-03-01

Charge transfer in transduction of light to electrical or chemical energy at heterojunctions of metals with semiconductors or semimetals is believed to occur by photogenerated hot electrons in metal undergoing incoherent internal photoemission through the heterojunction interface. Charge transfer, however, can also occur coherently by dipole coupling of electronic bands at the heterojunction interface. Microscopic physical insights into how transfer occurs can be elucidated by following the coherent polarization of the donor and acceptor states on the time scale of electronic dephasing. By time-resolved multiphoton photoemission spectroscopy (MPP), we investigate the coherent electron transfer from an interface state that forms upon chemisorption of Ag nanoclusters onto graphite to a σ symmetry interlayer band of graphite. Multidimensional MPP spectroscopy reveals a resonant two-photon transition, which dephases within 10 fs completing the coherent transfer.

DataQs analyst guide : best practices for federal and state agency users.

DOT National Transportation Integrated Search

2014-12-01

The DataQs Analyst Guide provides practical guidance and : best practices to address and resolve Requests for Data : Reviews (RDRs) submitted electronically to FMCSA by motor : carriers, commercial drivers, and other persons using the : DataQs system...

A study on the anisole-water complex by molecular beam-electronic spectroscopy and molecular mechanics calculations.

PubMed

Becucci, M; Pietraperzia, G; Pasquini, M; Piani, G; Zoppi, A; Chelli, R; Castellucci, E; Demtroeder, W

2004-03-22

An experimental and theoretical study is made on the anisole-water complex. It is the first van der Waals complex studied by high resolution electronic spectroscopy in which the water is seen acting as an acid. Vibronically and rotationally resolved electronic spectroscopy experiments and molecular mechanics calculations are used to elucidate the structure of the complex in the ground and first electronic excited state. Some internal dynamics in the system is revealed by high resolution spectroscopy. (c) 2004 American Institute of Physics

Photoinduced Charge Shifts and Electron Transfer in Viologen-Tetraphenylborate Complexes: Push-Pull Character of the Exciplex.

PubMed

Santos, Willy G; Budkina, Darya S; Deflon, Victor M; Tarnovsky, Alexander N; Cardoso, Daniel R; Forbes, Malcolm D E

2017-06-14

Viologen-tetraarylborate ion-pair complexes were prepared and investigated by steady-state and time-resolved spectroscopic techniques such as fluorescence and femtosecond transient absorption. The results highlight a charge transfer transition that leads to changes in the viologen structure in the excited singlet state. Femtosecond transient absorption reveals the formation of excited-state absorption and stimulated emission bands assigned to the planar (k obs < 10 12 s -1 ) and twisted (k obs ∼ 10 10 s -1 ) structures between two pyridinium groups in the viologen ion. An efficient photoinduced electron transfer from the tetraphenylborate anionic moiety to the viologen dication was observed less than 1 μs after excitation. This is a consequence of the push-pull character of the electron donor twisted viologen structure, which helps formation of the borate triplet state. The borate triplet state is deactivated further via a second electron transfer process, generating viologen cation radical (V •+ ).

Fourier transform infrared difference and time-resolved infrared detection of the electron and proton transfer dynamics in photosynthetic water oxidation.

PubMed

Noguchi, Takumi

2015-01-01

Photosynthetic water oxidation, which provides the electrons necessary for CO₂ reduction and releases O₂ and protons, is performed at the Mn₄CaO₅ cluster in photosystem II (PSII). In this review, studies that assessed the mechanism of water oxidation using infrared spectroscopy are summarized focusing on electron and proton transfer dynamics. Structural changes in proteins and water molecules between intermediates known as Si states (i=0-3) were detected using flash-induced Fourier transform infrared (FTIR) difference spectroscopy. Electron flow in PSII and proton release from substrate water were monitored using the infrared changes in ferricyanide as an exogenous electron acceptor and Mes buffer as a proton acceptor. Time-resolved infrared (TRIR) spectroscopy provided information on the dynamics of proton-coupled electron transfer during the S-state transitions. In particular, a drastic proton movement during the lag phase (~200μs) before electron transfer in the S3→S0 transition was detected directly by monitoring the infrared absorption of a polarizable proton in a hydrogen bond network. Furthermore, the proton release pathways in the PSII proteins were analyzed by FTIR difference measurements in combination with site-directed mutagenesis, isotopic substitutions, and quantum chemical calculations. Therefore, infrared spectroscopy is a powerful tool for understanding the molecular mechanism of photosynthetic water oxidation. This article is part of a Special Issue entitled: Vibrational spectroscopies and bioenergetic systems. Copyright © 2014 Elsevier B.V. All rights reserved.

Electronic structure and dynamics of thin Ge/GaAs(110) heterostructures

NASA Astrophysics Data System (ADS)

Haight, R.; Silberman, J. A.

1990-10-01

Using angle-resolved picosecond laser photoemission we have investigated both occupied and transiently excited empty states at the surface of Ge grown epitaxially on GaAs(110). We observe a normally unoccupied, Ge layer derived state whose separation from the valence-band maximum of the system is 700±50 meV at six monolayers Ge coverage. The evolution of the electronic structure is followed as a function of coverage and correlated with low-energy electron diffraction. The time dependence of the transiently occupied Ge signal is compared with that of the clean GaAs(110) surface and shows that electrons are prevented from diffusing into the GaAs bulk by the conduction-band offset of 330±40 meV.

a Study on SODIUM(110) and Other Nearly Free Electron Metals Using Angle Resolved Photoemission Spectroscopy.

NASA Astrophysics Data System (ADS)

Lyo, In-Whan

Electronic properties of the epitaxially grown Na(110) film have been studied using angle resolved ultraviolet photoemission spectroscopy with synchrotron radiation as the light source. Na provides an ideal ground to study the fundamental aspects of the electron-electron interactions in metals, because of its simple Fermi surface and small pseudopotential. The absolute band structure of Na(110) using angle resolved photoemission spectroscopy has been mapped out using the extrema searching method. The advantage of this approach is that the usual assumption of the unoccupied state dispersion is not required. We have found that the dispersion of Na(1l0) is very close to the parabolic band with the effective mass 1.21 M_{rm e} at 90 K. Self-consistent calculations of the self-energy for the homogeneous electron gas have been performed using the Green's function technique within the framework of the GW approximation, in the hope of understanding the narrowing mechanism of the bandwidth observed for all the nearly-free-electron (NFE) metals. Good agreements between the experimental data and our calculated self-energy were obtained not only for our data on k-dependency from Na(l10), but also for the total bandwidth corrections for other NFE metals, only if dielectric functions beyond the random phase approximation were used. Our findings emphasize the importance of the screening by long wavelength plasmons. Off-normal spectra of angle resolved photoemission from Na(110) show strong asymmetry of the bulk peak intensity for the wide range of photon energies. Using a simple analysis, we show this asymmetry has an origin in the interference of the surface Umklapp electrons with the normal electrons. We have also performed the detailed experimental studies of the anomalous Fermi level structure observed in the forbidden gap region of Na. This was claimed by A. W. Overhauser as the evidence of the charge density wave in the alkali metal. The possibility of this hypothesis is critically discussed against other explanations.

Nonadiabatic Dynamics May Be Probed through Electronic Coherence in Time-Resolved Photoelectron Spectroscopy.

PubMed

Bennett, Kochise; Kowalewski, Markus; Mukamel, Shaul

2016-02-09

We present a hierarchy of Fermi golden rules (FGRs) that incorporate strongly coupled electronic/nuclear dynamics in time-resolved photoelectron spectroscopy (TRPES) signals at different levels of theory. Expansion in the joint electronic and nuclear eigenbasis yields the numerically most challenging exact FGR (eFGR). The quasistatic Fermi Golden Rule (qsFGR) neglects nuclear motion during the photoionization process but takes into account electronic coherences as well as populations initially present in the pumped matter as well as those generated internally by coupling between electronic surfaces. The standard semiclassical Fermi Golden Rule (scFGR) neglects the electronic coherences and the nuclear kinetic energy during the ionizing pulse altogether, yielding the classical Condon approximation. The coherence contributions depend on the phase-profile of the ionizing field, allowing coherent control of TRPES signals. The photoelectron spectrum from model systems is simulated using these three levels of theory. The eFGR and the qsFGR show temporal oscillations originating from the electronic or vibrational coherences generated as the nuclear wave packet traverses a conical intersection. These oscillations, which are missed by the scFGR, directly reveal the time-evolving splitting between electronic states of the neutral molecule in the curve-crossing regime.

Ultrafast time-resolved spectroscopy of the light-harvesting complex 2 (LH2) from the photosynthetic bacterium Thermochromatium tepidum.

PubMed

Niedzwiedzki, Dariusz M; Fuciman, Marcel; Kobayashi, Masayuki; Frank, Harry A; Blankenship, Robert E

2011-10-01

The light-harvesting complex 2 from the thermophilic purple bacterium Thermochromatium tepidum was purified and studied by steady-state absorption and fluorescence, sub-nanosecond-time-resolved fluorescence and femtosecond time-resolved transient absorption spectroscopy. The measurements were performed at room temperature and at 10 K. The combination of both ultrafast and steady-state optical spectroscopy methods at ambient and cryogenic temperatures allowed the detailed study of carotenoid (Car)-to-bacteriochlorophyll (BChl) as well BChl-to-BChl excitation energy transfer in the complex. The studies show that the dominant Cars rhodopin (N=11) and spirilloxanthin (N=13) do not play a significant role as supportive energy donors for BChl a. This is related with their photophysical properties regulated by long π-electron conjugation. On the other hand, such properties favor some of the Cars, particularly spirilloxanthin (N=13) to play the role of the direct quencher of the excited singlet state of BChl. © Springer Science+Business Media B.V. 2011

Surface and interface effects on non-radiative exciton recombination and relaxation dynamics in CdSe/Cd,Zn,S nanocrystals

NASA Astrophysics Data System (ADS)

Walsh, Brenna R.; Saari, Jonathan I.; Krause, Michael M.; Nick, Robert; Coe-Sullivan, Seth; Kambhampati, Patanjali

2016-06-01

Excitonic state-resolved pump/probe spectroscopy and time correlate single photon counting were used to study exciton dynamics from the femtosecond to nanosecond time scales in CdSe/Cd,Zn,S nanocrystals. These measurements reveal the role of the core/shell interface as well as surface on non-radiative excitonic processes over three time regimes. Time resolved photoluminescence reports on how the interface controls slow non-radiative processes that dictate emission at the single excitonic level. Heterogeneity in decay is minimized by interfacial structure. Pump/probe measurements explore the non-radiative multiexcitonic recombination processes on the picosecond timescale. These Auger based non-radiative processes dictate lifetimes of multiexcitonic states. Finally state-resolved pump/probe measurements on the femtosecond timescale reveal the influence of the interface on electron and hole relaxation dynamics. We find that the interface has a profound influence on all three types of non-radiative processes which ultimately control light emission from nanocrystals.

Pentacene appended to a TEMPO stable free radical: the effect of magnetic exchange coupling on photoexcited pentacene.

PubMed

Chernick, Erin T; Casillas, Rubén; Zirzlmeier, Johannes; Gardner, Daniel M; Gruber, Marco; Kropp, Henning; Meyer, Karsten; Wasielewski, Michael R; Guldi, Dirk M; Tykwinski, Rik R

2015-01-21

Understanding the fundamental spin dynamics of photoexcited pentacene derivatives is important in order to maximize their potential for optoelectronic applications. Herein, we report on the synthesis of two pentacene derivatives that are functionalized with the [(2,2,6,6-tetramethylpiperidin-1-yl)oxy] (TEMPO) stable free radical. The presence of TEMPO does not quench the pentacene singlet excited state, but does quench the photoexcited triplet excited state as a function of TEMPO-to-pentacene distance. Time-resolved electron paramagnetic resonance experiments confirm that triplet quenching is accompanied by electron spin polarization transfer from the pentacene excited state to the TEMPO doublet state in the weak coupling regime.

Control of two-dimensional electronic states at anatase Ti O2(001 ) surface by K adsorption

NASA Astrophysics Data System (ADS)

Yukawa, R.; Minohara, M.; Shiga, D.; Kitamura, M.; Mitsuhashi, T.; Kobayashi, M.; Horiba, K.; Kumigashira, H.

2018-04-01

The nature of the intriguing metallic electronic structures appearing at the surface of anatase titanium dioxide (a-Ti O2 ) remains to be elucidated, mainly owing to the difficulty of controlling the depth distribution of the oxygen vacancies generated by photoirradiation. In this study, K atoms were adsorbed onto the (001) surface of a-Ti O2 to dope electrons into the a-Ti O2 and to confine the electrons in the surface region. The success of the electron doping and its controllability were confirmed by performing in situ angle-resolved photoemission spectroscopy as well as core-level measurements. Clear subband structures were observed in the surface metallic states, indicating the creation of quasi-two-dimensional electron liquid (q2DEL) states in a controllable fashion. With increasing electron doping (K adsorption), the q2DEL states exhibited crossover from polaronic liquid states with multiple phonon-loss structures originating from the long-range Fröhlich interaction to "weakly correlated metallic" states. In the q2DEL states in the weakly correlated metallic region, a kink due to short-range electron-phonon coupling was clearly observed at about 80 ±10 meV . The characteristic energy is smaller than that previously observed for the metallic states of a-Ti O2 with three-dimensional nature (˜110 meV ) . These results suggest that the dominant electron-phonon coupling is modulated by anisotropic carrier screening in the q2DEL states.

Localized-to-extended-states transition below the Fermi level

NASA Astrophysics Data System (ADS)

Tito, M. A.; Pusep, Yu. A.

2018-05-01

Time-resolved photoluminescence is employed to examine a transition from localized to extended electron states below the Fermi level in multiple narrow quantum well GaAs/AlGaAs heterostructures, where disorder was generated by interface roughness. Such a transition resembles the metal-insulator transition profoundly investigated by electric transport measurements. An important distinction distinguishes the localized-to-extended-states transition studied here: it takes place below the Fermi level in an electron system with a constant concentration, which implies unchanging Coulomb correlations. Moreover, for such a localized-to-extended-states transition the temperature is shown to be irrelevant. In the insulating regime the magnetic field was found to cause an additional momentum relaxation which considerably enhanced the recombination rate. Thus, we propose a method to explore the evolution of the localized electron states in a system with a fixed disorder and Coulomb interaction.

Surface electronic structure of the topological Kondo-insulator candidate correlated electron system SmB6.

PubMed

Neupane, M; Alidoust, N; Xu, S-Y; Kondo, T; Ishida, Y; Kim, D J; Liu, Chang; Belopolski, I; Jo, Y J; Chang, T-R; Jeng, H-T; Durakiewicz, T; Balicas, L; Lin, H; Bansil, A; Shin, S; Fisk, Z; Hasan, M Z

2013-01-01

The Kondo insulator SmB6 has long been known to exhibit low-temperature transport anomalies whose origin is of great interest. Here we uniquely access the surface electronic structure of the anomalous transport regime by combining state-of-the-art laser and synchrotron-based angle-resolved photoemission techniques. We observe clear in-gap states (up to ~4 meV), whose temperature dependence is contingent on the Kondo gap formation. In addition, our observed in-gap Fermi surface oddness tied with the Kramers' point topology, their coexistence with the two-dimensional transport anomaly in the Kondo hybridization regime, as well as their robustness against thermal recycling, taken together, collectively provide strong evidence for protected surface metallicity with a Fermi surface whose topology is consistent with the theoretically predicted topological Fermi surface. Our observations of systematic surface electronic structure provide the fundamental electronic parameters for the anomalous Kondo ground state of correlated electron material SmB6.

Angle-resolved photoemission spectroscopy studies of metallic surface and interface states of oxide insulators

NASA Astrophysics Data System (ADS)

Plumb, Nicholas C.; Radović, Milan

2017-11-01

Over the last decade, conducting states embedded in insulating transition metal oxides (TMOs) have served as gateways to discovering and probing surprising phenomena that can emerge in complex oxides, while also opening opportunities for engineering advanced devices. These states are commonly realized at thin film interfaces, such as the well-known case of LaAlO3 (LAO) grown on SrTiO3 (STO). In recent years, the use of angle-resolved photoemission spectroscopy (ARPES) to investigate the k-space electronic structure of such materials led to the discovery that metallic states can also be formed on the bare surfaces of certain TMOs. In this topical review, we report on recent studies of low-dimensional metallic states confined at insulating oxide surfaces and interfaces as seen from the perspective of ARPES, which provides a direct view of the occupied band structure. While offering a fairly broad survey of progress in the field, we draw particular attention to STO, whose surface is so far the best-studied, and whose electronic structure is probably of the most immediate interest, given the ubiquitous use of STO substrates as the basis for conducting oxide interfaces. The ARPES studies provide crucial insights into the electronic band structure, orbital character, dimensionality/confinement, spin structure, and collective excitations in STO surfaces and related oxide surface/interface systems. The obtained knowledge increases our understanding of these complex materials and gives new perspectives on how to manipulate their properties.

Exciplex mediated photoinduced electron transfer reactions of phthalocyanine-fullerene dyads.

PubMed

Niemi, Marja; Tkachenko, Nikolai V; Efimov, Alexander; Lehtivuori, Heli; Ohkubo, Kei; Fukuzumi, Shunichi; Lemmetyinen, Helge

2008-07-31

Evidences of an intramolecular exciplex intermediate in a photoinduced electron transfer (ET) reaction of double-linked free-base and zinc phthalocyanine-C60 dyads were found. This was the first time for a dyad with phthalocyanine donor. Excitation of the phthalocyanine moiety of the dyads results in rapid ET from phthalocyanine to fullerene via an exciplex state in both polar and nonpolar solvents. Relaxation of the charge-separated (CS) state Pc(*+)-C60(*-) in a polar solvent occurs directly to the ground state in 30-70 ps. In a nonpolar solvent, roughly 20% of the molecules undergo transition from the CS state to phthalocyanine triplet state (3)Pc*-C60 before relaxation to the ground state. Formation of the CS state was confirmed with electron spin resonance measurements at low temperature in both polar and nonpolar solvent. Reaction schemes for the photoinduced ET reactions of the dyads were completed with rate constants obtained from the time-resolved absorption and emission measurements and with state energies obtained from the fluorescence, phosphorescence, and voltammetric measurements.

Photoionization of furan from the ground and excited electronic states.

PubMed

Ponzi, Aurora; Sapunar, Marin; Angeli, Celestino; Cimiraglia, Renzo; Došlić, Nađa; Decleva, Piero

2016-02-28

Here we present a comparative computational study of the photoionization of furan from the ground and the two lowest-lying excited electronic states. The study aims to assess the quality of the computational methods currently employed for treating bound and continuum states in photoionization. For the ionization from the ground electronic state, we show that the Dyson orbital approach combined with an accurate solution of the continuum one particle wave functions in a multicenter B-spline basis, at the density functional theory (DFT) level, provides cross sections and asymmetry parameters in excellent agreement with experimental data. On the contrary, when the Dyson orbitals approach is combined with the Coulomb and orthogonalized Coulomb treatments of the continuum, the results are qualitatively different. In excited electronic states, three electronic structure methods, TDDFT, ADC(2), and CASSCF, have been used for the computation of the Dyson orbitals, while the continuum was treated at the B-spline/DFT level. We show that photoionization observables are sensitive probes of the nature of the excited states as well as of the quality of excited state wave functions. This paves the way for applications in more complex situations such as time resolved photoionization spectroscopy.

Divertor electron temperature and impurity diffusion measurements with a spectrally resolved imaging radiometer.

PubMed

Clayton, D J; Jaworski, M A; Kumar, D; Stutman, D; Finkenthal, M; Tritz, K

2012-10-01

A divertor imaging radiometer (DIR) diagnostic is being studied to measure spatially and spectrally resolved radiated power P(rad)(λ) in the tokamak divertor. A dual transmission grating design, with extreme ultraviolet (~20-200 Å) and vacuum ultraviolet (~200-2000 Å) gratings placed side-by-side, can produce coarse spectral resolution over a broad wavelength range covering emission from impurities over a wide temperature range. The DIR can thus be used to evaluate the separate P(rad) contributions from different ion species and charge states. Additionally, synthetic spectra from divertor simulations can be fit to P(rad)(λ) measurements, providing a powerful code validation tool that can also be used to estimate electron divertor temperature and impurity transport.

Photoisomerization and photodissociation dynamics of reactive free radicals

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bise, Ryan T.

2000-08-01

The photofragmentation pathways of chemically reactive free radicals have been examined using the technique of fast beam photofragment translational spectroscopy. Measurements of the photodissociation cross-sections, product branching ratios, product state energy distributions, and angular distributions provide insight into the excited state potential energy surfaces and nonadiabatic processes involved in the dissociation mechanisms. Photodissociation spectroscopy and dynamics of the predissociativemore » $$\\tilde{A}$$ 2A 1 and $$\\tilde{B}$$ 2A 2 states of CH 3S have been investigated. At all photon energies, CH 3 + S( 3P j), was the main reaction channel. The translational energy distributions reveal resolved structure corresponding to vibrational excitation of the CH 3 umbrella mode and the S( 3P j) fine-structure distribution from which the nature of the coupled repulsive surfaces is inferred. Dissociation rates are deduced from the photofragment angular distributions, which depend intimately on the degree of vibrational excitation in the C-S stretch. Nitrogen combustion radicals, NCN, CNN and HNCN have also been studied. For all three radicals, the elimination of molecular nitrogen is the primary reaction channel. Excitation to linear excited triplet and singlet electronic states of the NCN radical generates resolved vibrational structure of the N 2 photofragment. The relatively low fragment rotational excitation suggests dissociation via a symmetric C 2V transition state. Resolved vibrational structure of the N 2 photofragment is also observed in the photodissociation of the HNCN radical. The fragment vibrational and rotational distributions broaden with increased excitation energy. Simple dissociation models suggest that the HNCN radical isomerizes to a cyclic intermediate (c-HCNN) which then dissociates via a tight cyclic transition state. In contrast to the radicals mentioned above, resolved vibrational structure was not observed for the ICNN radical due to extensive fragment rotational excitation, suggesting that intermediate bent states are strongly coupled along the dissociation pathway. The measurements performed in this Thesis have additionally refined the heats of formation and bond dissociation energies of these radicals and have unambiguously confirmed and added to the known electronic spectroscopy.« less

Photoluminescence from narrow InAs-AlSb quantum wells

NASA Technical Reports Server (NTRS)

Brar, Berinder; Kroemer, Herbert; Ibbetson, James; English, John H.

1993-01-01

We report on photoluminescence spectra from narrow InAs-AlSb quantum wells. Strong, clearly resolved peaks for well widths from 2 to 8 monolayers were observed. Transmission electron micrographs show direct evidence for the structural quality of the quantum well structures. The transition energies of the narrowest wells suggest a strong influence of the AlSb X-barrier on the electronic states in the conduction band.

Intrinsic Resolution of Molecular Electronic Wave Functions and Energies in Terms of Quasi-atoms and Their Interactions

DOE Office of Scientific and Technical Information (OSTI.GOV)

West, Aaron C.; Schmidt, Michael W.; Gordon, Mark S.

A general intrinsic energy resolution has been formulated for strongly correlated wave functions in the full molecular valence space and its subspaces. The information regarding the quasi-atomic organization of the molecular electronic structure is extracted from the molecular wave function without introducing any additional postulated model state wave functions. To this end, the molecular wave function is expressed in terms of quasi-atomic molecular orbitals, which maximize the overlap between subspaces of the molecular orbital space and the free-atom orbital spaces. As a result, the molecular wave function becomes the superposition of a wave function representing the non-bonded juxtaposed quasi-atoms andmore » a wave function describing the interatomic electron migrations that create bonds through electron sharing. The juxtaposed nonbonded quasi-atoms are shown to consist of entangled quasi-atomic states from different atoms. The binding energy is resolved as a sum of contributions that are due to quasi-atom formation, quasiclassical electrostatic interactions and interatomic interferences caused by electron sharing. The contributions are further resolved according to orbital interactions. The various transformations that generate the analysis are determined by criteria that are independent of the working orbital basis used for calculating the molecular wave function. Lastly, the theoretical formulation of the resolution is quantitatively validated by an application to the C 2 molecule.« less

Intrinsic Resolution of Molecular Electronic Wave Functions and Energies in Terms of Quasi-atoms and Their Interactions

DOE PAGES

West, Aaron C.; Schmidt, Michael W.; Gordon, Mark S.; ...

2017-01-30

A general intrinsic energy resolution has been formulated for strongly correlated wave functions in the full molecular valence space and its subspaces. The information regarding the quasi-atomic organization of the molecular electronic structure is extracted from the molecular wave function without introducing any additional postulated model state wave functions. To this end, the molecular wave function is expressed in terms of quasi-atomic molecular orbitals, which maximize the overlap between subspaces of the molecular orbital space and the free-atom orbital spaces. As a result, the molecular wave function becomes the superposition of a wave function representing the non-bonded juxtaposed quasi-atoms andmore » a wave function describing the interatomic electron migrations that create bonds through electron sharing. The juxtaposed nonbonded quasi-atoms are shown to consist of entangled quasi-atomic states from different atoms. The binding energy is resolved as a sum of contributions that are due to quasi-atom formation, quasiclassical electrostatic interactions and interatomic interferences caused by electron sharing. The contributions are further resolved according to orbital interactions. The various transformations that generate the analysis are determined by criteria that are independent of the working orbital basis used for calculating the molecular wave function. Lastly, the theoretical formulation of the resolution is quantitatively validated by an application to the C 2 molecule.« less

Time-resolved microplasma excitation temperature in a pulsed microwave discharge

NASA Astrophysics Data System (ADS)

Hopwood, Jeffrey; Monfared, Shabnam; Hoskinson, Alan

2013-09-01

Microwave-driven microplasmas are usually operated in a steady-state mode such that the electron temperature is constant in time. Transient measurements of excitation temperature and helium emission lines, however, suggest that short microwave pulses can be used to raise the electron energy by 20-30% for approximately 100 ns. Time-resolved optical emission spectrometry reveals an initial burst of light emission from the igniting microplasma. This emission overshoot is also correlated with a measured increase in excitation temperature. Excimer emission lags atomic emission, however, and does not overshoot. A simple model demonstrates that an increase in electron temperature is responsible for the overshoot of atomic optical emission at the beginning of each microwave pulse. The formation of dimers and subsequent excimer emission requires slower three-body collisions with the excited rare gas atom; this is why excimer emission does not overshoot the steady state value. Similar experimental and modeling results are observed in argon gas. The overshoot in electron temperature may be used to manipulate the collisional production of species in microplasmas using short, low-duty cycle microwave pulses. This material is based upon work supported by the USAF and Physical Sciences Inc., under contract No. FA8650-C-12-C-2312. Additional support was provided by the DARPA MPD program under award FA9550-12-1-0006.

Spin ordering and electronic texture in the bilayer iridate Sr3Ir2O7

NASA Astrophysics Data System (ADS)

Dhital, Chetan; Khadka, Sovit; Yamani, Z.; de la Cruz, Clarina; Hogan, T. C.; Disseler, S. M.; Pokharel, Mani; Lukas, K. C.; Tian, Wei; Opeil, C. P.; Wang, Ziqiang; Wilson, Stephen D.

2012-09-01

Through a neutron scattering, charge transport, and magnetization study, the correlated ground state in the bilayer iridium oxide Sr3Ir2O7 is explored. Our combined results resolve scattering consistent with a high temperature magnetic phase that persists above 600 K, reorients at the previously defined TAF=280 K, and coexists with an electronic ground state whose phase behavior suggests the formation of a fluctuating charge or orbital phase that freezes below T*≈70 K. Our study provides a window into the emergence of multiple electronic order parameters near the boundary of the metal to insulator phase transition of the 5d Jeff=1/2 Mott phase.

Development of an electron momentum spectrometer for time-resolved experiments employing nanosecond pulsed electron beam

NASA Astrophysics Data System (ADS)

Tang, Yaguo; Shan, Xu; Liu, Zhaohui; Niu, Shanshan; Wang, Enliang; Chen, Xiangjun

2018-03-01

The low count rate of (e, 2e) electron momentum spectroscopy (EMS) has long been a major limitation of its application to the investigation of molecular dynamics. Here we report a new EMS apparatus developed for time-resolved experiments in the nanosecond time scale, in which a double toroidal energy analyzer is utilized to improve the sensitivity of the spectrometer and a nanosecond pulsed electron gun with a repetition rate of 10 kHz is used to obtain an average beam current up to nA. Meanwhile, a picosecond ultraviolet laser with a repetition rate of 5 kHz is introduced to pump the sample target. The time zero is determined by photoionizing the target using a pump laser and monitoring the change of the electron beam current with time delay between the laser pulse and electron pulse, which is influenced by the plasma induced by the photoionization. The performance of the spectrometer is demonstrated by the EMS measurement on argon using a pulsed electron beam, illustrating the potential abilities of the apparatus for investigating the molecular dynamics in excited states when employing the pump-probe scheme.

Localization behavior at bound Bi complex states in GaA s 1 - x B i x

DOE PAGES

Alberi, K.; Christian, T. M.; Fluegel, B.; ...

2017-07-01

While bismuth-related states are known to localize carriers in GaAs 1-xBi x alloys, the localization behavior of distinct Bi pair, triplet and cluster states bound above the valence band is less well understood. We probe localization at three different Bi complex states in dilute GaAs 1-xBi x alloys using magneto-photoluminescence and time-resolved photoluminescence spectroscopy. The mass of electrons Coulomb-bound to holes trapped at Bi pair states is found to increase relative to the average electron mass in the alloy. This increase is attributed to enhanced local compressive strain in the immediate vicinity of the pairs. The dependence of energy transfermore » between these states on composition is also explored.« less

Time-resolved photoelectron spectroscopy of a dinuclear Pt(II) complex: Tunneling autodetachment from both singlet and triplet excited states of a molecular dianion

DOE Office of Scientific and Technical Information (OSTI.GOV)

Winghart, Marc-Oliver, E-mail: marc-oliver.winghart@kit.edu; Unterreiner, Andreas-Neil; Yang, Ji-Ping

2016-02-07

Time-resolved pump-probe photoelectron spectroscopy has been used to study the relaxation dynamics of gaseous [Pt{sub 2}(μ-P{sub 2}O{sub 5}H{sub 2}){sub 4} + 2H]{sup 2−} after population of its first singlet excited state by 388 nm femtosecond laser irradiation. In contrast to the fluorescence and phosphorescence observed in condensed phase, a significant fraction of the photoexcited isolated dianions decays by electron loss to form the corresponding monoanions. Our transient photoelectron data reveal an ultrafast decay of the initially excited singlet {sup 1}A{sub 2u} state and concomitant rise in population of the triplet {sup 3}A{sub 2u} state, via sub-picosecond intersystem crossing (ISC). Wemore » find that both of the electronically excited states are metastably bound behind a repulsive Coulomb barrier and can decay via delayed autodetachment to yield electrons with characteristic kinetic energies. While excited state tunneling detachment (ESETD) from the singlet {sup 1}A{sub 2u} state takes only a few picoseconds, ESETD from the triplet {sup 3}A{sub 2u} state is much slower and proceeds on a time scale of hundreds of nanoseconds. The ISC rate in the gas phase is significantly higher than in solution, which can be rationalized in terms of changes to the energy dissipation mechanism in the absence of solvent molecules. [Pt{sub 2}(μ-P{sub 2}O{sub 5}H{sub 2}){sub 4} + 2H]{sup 2−} is the first example of a photoexcited multianion for which ESETD has been observed following ISC.« less

High-pressure studies with x-rays using diamond anvil cells

DOE Office of Scientific and Technical Information (OSTI.GOV)

Shen, Guoyin; Mao, Ho Kwang

2016-11-22

Pressure profoundly alters all states of matter. The symbiotic development of ultrahigh-pressure diamond anvil cells, to compress samples to sustainable multi-megabar pressures; and synchrotron x-ray techniques, to probe materials' properties in situ, has enabled the exploration of rich high-pressure (HP) science. In this article, we first introduce the essential concept of diamond anvil cell technology, together with recent developments and its integration with other extreme environments. We then provide an overview of the latest developments in HP synchrotron techniques, their applications, and current problems, followed by a discussion of HP scientific studies using x-rays in the key multidisciplinary fields. Thesemore » HP studies include: HP x-ray emission spectroscopy, which provides information on the filled electronic states of HP samples; HP x-ray Raman spectroscopy, which probes the HP chemical bonding changes of light elements; HP electronic inelastic x-ray scattering spectroscopy, which accesses high energy electronic phenomena, including electronic band structure, Fermi surface, excitons, plasmons, and their dispersions; HP resonant inelastic x-ray scattering spectroscopy, which probes shallow core excitations, multiplet structures, and spin-resolved electronic structure; HP nuclear resonant x-ray spectroscopy, which provides phonon densities of state and time-resolved Mössbauer information; HP x-ray imaging, which provides information on hierarchical structures, dynamic processes, and internal strains; HP x-ray diffraction, which determines the fundamental structures and densities of single-crystal, polycrystalline, nanocrystalline, and non-crystalline materials; and HP radial x-ray diffraction, which yields deviatoric, elastic and rheological information. Integrating these tools with hydrostatic or uniaxial pressure media, laser and resistive heating, and cryogenic cooling, has enabled investigations of the structural, vibrational, electronic, and magnetic properties of materials over a wide range of pressure-temperature conditions.« less

High-pressure studies with x-rays using diamond anvil cells

NASA Astrophysics Data System (ADS)

Shen, Guoyin; Mao, Ho Kwang

2017-01-01

Pressure profoundly alters all states of matter. The symbiotic development of ultrahigh-pressure diamond anvil cells, to compress samples to sustainable multi-megabar pressures; and synchrotron x-ray techniques, to probe materials’ properties in situ, has enabled the exploration of rich high-pressure (HP) science. In this article, we first introduce the essential concept of diamond anvil cell technology, together with recent developments and its integration with other extreme environments. We then provide an overview of the latest developments in HP synchrotron techniques, their applications, and current problems, followed by a discussion of HP scientific studies using x-rays in the key multidisciplinary fields. These HP studies include: HP x-ray emission spectroscopy, which provides information on the filled electronic states of HP samples; HP x-ray Raman spectroscopy, which probes the HP chemical bonding changes of light elements; HP electronic inelastic x-ray scattering spectroscopy, which accesses high energy electronic phenomena, including electronic band structure, Fermi surface, excitons, plasmons, and their dispersions; HP resonant inelastic x-ray scattering spectroscopy, which probes shallow core excitations, multiplet structures, and spin-resolved electronic structure; HP nuclear resonant x-ray spectroscopy, which provides phonon densities of state and time-resolved Mössbauer information; HP x-ray imaging, which provides information on hierarchical structures, dynamic processes, and internal strains; HP x-ray diffraction, which determines the fundamental structures and densities of single-crystal, polycrystalline, nanocrystalline, and non-crystalline materials; and HP radial x-ray diffraction, which yields deviatoric, elastic and rheological information. Integrating these tools with hydrostatic or uniaxial pressure media, laser and resistive heating, and cryogenic cooling, has enabled investigations of the structural, vibrational, electronic, and magnetic properties of materials over a wide range of pressure-temperature conditions.

Photodissociation studies of the electronic and vibrational spectroscopy of Ni(+)(H2O).

PubMed

Daluz, Jennifer S; Kocak, Abdulkadir; Metz, Ricardo B

2012-02-09

The electronic spectrum of Ni⁺(H₂O) has been measured from 16200 to 18000 cm⁻¹ using photofragment spectroscopy. Transitions to two excited electronic states are observed; they are sufficiently long-lived that the spectrum is vibrationally and partially rotationally resolved. An extended progression in the metal-ligand stretch is observed, and the absolute vibrational quantum numbering is assigned by comparing isotopic shifts between ⁵⁸Ni⁺(H₂O) and ⁶⁰Ni⁺(H₂O). Time-dependent density functional calculations aid in assigning the spectrum. Two electronic transitions are observed, from the ²A₁ ground state (which correlates to the ²D, 3d⁹ ground state of Ni⁺) to the 3²A₁ and 2²A₂ excited states. These states are nearly degenerate and correlate to the ²F, 3d⁸4s excited state of Ni⁺. Both transitions are quite weak, but surprisingly, the transition to the ²A₂ state is stronger, although it is symmetry-forbidden. The 3d⁸4s states of Ni⁺ interact less strongly with water than does the ground state; therefore, the excited states observed are less tightly bound and have a longer metal-ligand bond than the ground state. Calculations at the CCSD(T)/aug-cc-pVTZ level predict that binding to Ni⁺ increases the H-O-H angle in water from 104.2 to 107.5° as the metal removes electron density from the oxygen lone pairs. The photodissociation spectrum shows well-resolved rotational structure due to rotation about the Ni-O axis. This permits determination of the spin rotation constants ε(αα)'' = -12 cm⁻¹ and ε(αα)' = -3 cm⁻¹ and the excited state rotational constant A' = 14.5 cm⁻¹. This implies a H-O-H angle of 104 ± 1° in the 2²A₂ excited state. The O-H stretching frequencies of the ground state of Ni⁺(H₂O) were measured by combining IR excitation with visible photodissociation in a double resonance experiment. The O-H symmetric stretch is ν₁'' = 3616.5 cm⁻¹; the antisymmetric stretch is ν₅'' = 3688 cm⁻¹. These values are 40 and 68 cm⁻¹ lower, respectively, than those in bare H₂O.

Near ultraviolet photodissociation spectroscopy of Mn+(H2O) and Mn+(D2O)

NASA Astrophysics Data System (ADS)

Pearson, Wright L.; Copeland, Christopher; Kocak, Abdulkadir; Sallese, Zachary; Metz, Ricardo B.

2014-11-01

The electronic spectra of Mn+(H2O) and Mn+(D2O) have been measured from 30 000 to 35 000 cm-1 using photodissociation spectroscopy. Transitions are observed from the 7A1 ground state in which the Mn+ is in a 3d54s1 electronic configuration, to the 7B2 (3d54py) and 7B1 (3d54px) excited states with T0 = 30 210 and 32 274 cm-1, respectively. Each electronic transition has partially resolved rotational and extensive vibrational structure with an extended progression in the metal-ligand stretch at a frequency of ˜450 cm-1. There are also progressions in the in-plane bend in the 7B2 state, due to vibronic coupling, and the out-of-plane bend in the 7B1 state, where the calculation illustrates that this state is slightly non-planar. Electronic structure computations at the CCSD(T)/aug-cc-pVTZ and TD-DFT B3LYP/6-311++G(3df,3pd) level are also used to characterize the ground and excited states, respectively. These calculations predict a ground state Mn-O bond length of 2.18 Å. Analysis of the experimentally observed vibrational intensities reveals that this bond length decreases by 0.15 ± 0.015 Å and 0.14 ± 0.01 Å in the excited states. The behavior is accounted for by the less repulsive px and py orbitals causing the Mn+ to interact more strongly with water in the excited states than the ground state. The result is a decrease in the Mn-O bond length, along with an increase in the H-O-H angle. The spectra have well resolved K rotational structure. Fitting this structure gives spin-rotation constants ɛaa″ = -3 ± 1 cm-1 for the ground state and ɛaa' = 0.5 ± 0.5 cm-1 and ɛaa' = -4.2 ± 0.7 cm-1 for the first and second excited states, respectively, and A' = 12.8 ± 0.7 cm-1 for the first excited state. Vibrationally mediated photodissociation studies determine the O-H antisymmetric stretching frequency in the ground electronic state to be 3658 cm-1.

Ultrafast kinetics of linkage isomerism in Na2[Fe(CN)5NO] aqueous solution revealed by time-resolved photoelectron spectroscopy

PubMed Central

Raheem, Azhr A.; Wilke, Martin; Borgwardt, Mario; Engel, Nicholas; Bokarev, Sergey I.; Grell, Gilbert; Aziz, Saadullah G.; Kühn, Oliver; Kiyan, Igor Yu.; Merschjann, Christoph; Aziz, Emad F.

2017-01-01

The kinetics of ultrafast photoinduced structural changes in linkage isomers is investigated using Na2[Fe(CN)5NO] as a model complex. The buildup of the metastable side-on configuration of the NO ligand, as well as the electronic energy levels of ground, excited, and metastable states, has been revealed by means of time-resolved extreme UV (XUV) photoelectron spectroscopy in aqueous solution, aided by theoretical calculations. Evidence of a short-lived intermediate state in the isomerization process and its nature are discussed, finding that the complete isomerization process occurs in less than 240 fs after photoexcitation. PMID:28713840

The determination of potential energy curve and dipole moment of the (5)0{sup +} electronic state of {sup 85}Rb{sup 133}Cs molecule by high resolution photoassociation spectroscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yuan, Jinpeng; Zhao, Yanting, E-mail: zhaoyt@sxu.edu.cn; Ji, Zhonghua

2015-12-14

We present the formation of ultracold {sup 85}Rb{sup 133}Cs molecules in the (5)0{sup +} electronic state by photoassociation and their detection via resonance-enhanced two-photon ionization. Up to v = 47 vibrational levels including the lowest v = 0 vibrational and lowest J = 0 levels are identified with rotationally resolved high resolution photoassociation spectra. Precise Dunham coefficients are determined for the (5)0{sup +} state with high accuracy, then the Rydberg-Klein-Rees potential energy curve is derived. The electric dipole moments with respect to the vibrational numbers of the (5)0{sup +} electronic state of {sup 85}Rb{sup 133}Cs molecule are also measured inmore » the range between 1.9 and 4.8 D. These comprehensive studies on previously unobserved rovibrational levels of the (5)0{sup +} state are helpful to understand the molecular structure and discover suitable transition pathways for transferring ultracold atoms to deeply bound rovibrational levels of the electronic ground state.« less

High-Resolution Two-Dimensional Optical Spectroscopy of Electron Spins

NASA Astrophysics Data System (ADS)

Salewski, M.; Poltavtsev, S. V.; Yugova, I. A.; Karczewski, G.; Wiater, M.; Wojtowicz, T.; Yakovlev, D. R.; Akimov, I. A.; Meier, T.; Bayer, M.

2017-07-01

Multidimensional coherent optical spectroscopy is one of the most powerful tools for investigating complex quantum mechanical systems. While it was conceived decades ago in magnetic resonance spectroscopy using microwaves and radio waves, it has recently been extended into the visible and UV spectral range. However, resolving MHz energy splittings with ultrashort laser pulses still remains a challenge. Here, we analyze two-dimensional Fourier spectra for resonant optical excitation of resident electrons to localized trions or donor-bound excitons in semiconductor nanostructures subject to a transverse magnetic field. Particular attention is devoted to Raman coherence spectra, which allow one to accurately evaluate tiny splittings of the electron ground state and to determine the relaxation times in the electron spin ensemble. A stimulated steplike Raman process induced by a sequence of two laser pulses creates a coherent superposition of the ground-state doublet which can be retrieved only optically because of selective excitation of the same subensemble with a third pulse. This provides the unique opportunity to distinguish between different complexes that are closely spaced in energy in an ensemble. The related experimental demonstration is based on photon-echo measurements in an n -type CdTe /(Cd ,Mg )Te quantum-well structure detected by a heterodyne technique. The difference in the sub-μ eV range between the Zeeman splittings of donor-bound electrons and electrons localized at potential fluctuations can be resolved even though the homogeneous linewidth of the optical transitions is larger by 2 orders of magnitude.

Current Driven Instabilities and Anomalous Mobility in Hall-effect Thrusters

NASA Astrophysics Data System (ADS)

Tran, Jonathan; Eckhardt, Daniel; Martin, Robert

2017-10-01

Due to the extreme cost of fully resolving the Debye length and plasma frequency, hybrid plasma simulations utilizing kinetic ions and quasi-steady state fluid electrons have long been the principle workhorse methodology for Hall-effect thruster (HET) modeling. Plasma turbulence and the resulting anomalous electron transport in HETs is a promising candidate for developing predictive models for the observed anomalous transport. In this work, we investigate the implementation of an anomalous electron cross field transport model for hybrid HET simulations such a HPHall. A theory for anomalous transport in HETs and current driven instabilities has been recently studied by Lafleur et al. This work has shown collective electron-wave scattering due to large amplitude azimuthal fluctuations of the electric field. We will further adapt the previous results for related current driven instabilities to electric propulsion relevant mass ratios and conduct a preliminary study of resolving this instability with a modified hybrid (fluid electron and kinetic ion) simulation with the hope of integration with established hybrid HET simulations. This work is supported by the Air Force Office of Scientific Research award FA9950-17RQCOR465.

Measuring Conformational Dynamics of Single Biomolecules Using Nanoscale Electronic Devices

NASA Astrophysics Data System (ADS)

Akhterov, Maxim V.; Choi, Yongki; Sims, Patrick C.; Olsen, Tivoli J.; Gul, O. Tolga; Corso, Brad L.; Weiss, Gregory A.; Collins, Philip G.

2014-03-01

Molecular motion can be a rate-limiting step of enzyme catalysis, but motions are typically too quick to resolve with fluorescent single molecule techniques. Recently, we demonstrated a label-free technique that replaced fluorophores with nano-electronic circuits to monitor protein motions. The solid-state electronic technique used single-walled carbon nanotube (SWNT) transistors to monitor conformational motions of a single molecule of T4 lysozyme while processing its substrate, peptidoglycan. As lysozyme catalyzes the hydrolysis of glycosidic bonds, two protein domains undergo 8 Å hinge bending motion that generates an electronic signal in the SWNT transistor. We describe improvements to the system that have extended our temporal resolution to 2 μs . Electronic recordings at this level of detail directly resolve not just transitions between open and closed conformations but also the durations for those transition events. Statistical analysis of many events determines transition timescales characteristic of enzyme activity and shows a high degree of variability within nominally identical chemical events. The high resolution technique can be readily applied to other complex biomolecules to gain insights into their kinetic parameters and catalytic function.

Identifying local structural states in atomic imaging by computer vision

DOE Office of Scientific and Technical Information (OSTI.GOV)

Laanait, Nouamane; Ziatdinov, Maxim; He, Qian

The availability of atomically resolved imaging modalities enables an unprecedented view into the local structural states of materials, which manifest themselves by deviations from the fundamental assumptions of periodicity and symmetry. Consequently, approaches that aim to extract these local structural states from atomic imaging data with minimal assumptions regarding the average crystallographic configuration of a material are indispensable to advances in structural and chemical investigations of materials. Here, we present an approach to identify and classify local structural states that is rooted in computer vision. This approach introduces a definition of a structural state that is composed of both localmore » and non-local information extracted from atomically resolved images, and is wholly untethered from the familiar concepts of symmetry and periodicity. Instead, this approach relies on computer vision techniques such as feature detection, and concepts such as scale-invariance. We present the fundamental aspects of local structural state extraction and classification by application to simulated scanning transmission electron microscopy images, and analyze the robustness of this approach in the presence of common instrumental factors such as noise, limited spatial resolution, and weak contrast. Finally, we apply this computer vision-based approach for the unsupervised detection and classification of local structural states in an experimental electron micrograph of a complex oxides interface, and a scanning tunneling micrograph of a defect engineered multilayer graphene surface.« less

Identifying local structural states in atomic imaging by computer vision

DOE PAGES

Laanait, Nouamane; Ziatdinov, Maxim; He, Qian; ...

2016-11-02

The availability of atomically resolved imaging modalities enables an unprecedented view into the local structural states of materials, which manifest themselves by deviations from the fundamental assumptions of periodicity and symmetry. Consequently, approaches that aim to extract these local structural states from atomic imaging data with minimal assumptions regarding the average crystallographic configuration of a material are indispensable to advances in structural and chemical investigations of materials. Here, we present an approach to identify and classify local structural states that is rooted in computer vision. This approach introduces a definition of a structural state that is composed of both localmore » and non-local information extracted from atomically resolved images, and is wholly untethered from the familiar concepts of symmetry and periodicity. Instead, this approach relies on computer vision techniques such as feature detection, and concepts such as scale-invariance. We present the fundamental aspects of local structural state extraction and classification by application to simulated scanning transmission electron microscopy images, and analyze the robustness of this approach in the presence of common instrumental factors such as noise, limited spatial resolution, and weak contrast. Finally, we apply this computer vision-based approach for the unsupervised detection and classification of local structural states in an experimental electron micrograph of a complex oxides interface, and a scanning tunneling micrograph of a defect engineered multilayer graphene surface.« less

Steady state and time resolved optical characterization studies of Zn 2SnO 4 nanowires for solar cell applications

DOE PAGES

Yakami, Baichhabi R.; Poudyal, Uma; Nandyala, Shashank R.; ...

2016-10-25

Nanowires are a promising option for sensitized solar cells, sensors, and display technology. Most of the work thus far has focused on binary oxides for these nanowires, but ternary oxides have advantages in additional control of optical and electronic properties. Here, we report on the diffuse reflectance, Low Temperature and Room Temperature Photoluminescence (PL), PL excitation spectrum, and Time Resolved PL (TRPL) of Zinc Tin Oxide (ZTO) nanowires grown by Chemical Vapor Deposition. The PL from the ZTO nanowires does not exhibit any band gap or near gap emission, and the diffuse reflectance measurement confirms that these ZTO nanowires havemore » a direct forbidden transition. The broad PL spectrum reveals two Gaussian peaks centered at 1.86 eV (red) and 2.81 eV (blue), representing two distinct defect states or complexes. The PL spectra were further studied by the Time Resolved Emission Spectrum and intensity dependent PL and TRPL. The time resolved measurements show complex non-exponential decays at all wavelengths, indicative of defect to defect transitions, and the red emissive states decay much slower than the blue emissive states. The effects of annealing in air and vacuum are studied to investigate the origin of the defect states in the nanowires, showing that the blue states are related to oxygen vacancies. We propose an energy band model for the nanowires containing defect states within the band gap and the associated transitions between these states that are consistent with our measurements.« less

Steady state and time resolved optical characterization studies of Zn 2SnO 4 nanowires for solar cell applications

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yakami, Baichhabi R.; Poudyal, Uma; Nandyala, Shashank R.

Nanowires are a promising option for sensitized solar cells, sensors, and display technology. Most of the work thus far has focused on binary oxides for these nanowires, but ternary oxides have advantages in additional control of optical and electronic properties. Here, we report on the diffuse reflectance, Low Temperature and Room Temperature Photoluminescence (PL), PL excitation spectrum, and Time Resolved PL (TRPL) of Zinc Tin Oxide (ZTO) nanowires grown by Chemical Vapor Deposition. The PL from the ZTO nanowires does not exhibit any band gap or near gap emission, and the diffuse reflectance measurement confirms that these ZTO nanowires havemore » a direct forbidden transition. The broad PL spectrum reveals two Gaussian peaks centered at 1.86 eV (red) and 2.81 eV (blue), representing two distinct defect states or complexes. The PL spectra were further studied by the Time Resolved Emission Spectrum and intensity dependent PL and TRPL. The time resolved measurements show complex non-exponential decays at all wavelengths, indicative of defect to defect transitions, and the red emissive states decay much slower than the blue emissive states. The effects of annealing in air and vacuum are studied to investigate the origin of the defect states in the nanowires, showing that the blue states are related to oxygen vacancies. We propose an energy band model for the nanowires containing defect states within the band gap and the associated transitions between these states that are consistent with our measurements.« less

Excited state X-ray absorption spectroscopy: Probing both electronic and structural dynamics

NASA Astrophysics Data System (ADS)

Neville, Simon P.; Averbukh, Vitali; Ruberti, Marco; Yun, Renjie; Patchkovskii, Serguei; Chergui, Majed; Stolow, Albert; Schuurman, Michael S.

2016-10-01

We investigate the sensitivity of X-ray absorption spectra, simulated using a general method, to properties of molecular excited states. Recently, Averbukh and co-workers [M. Ruberti et al., J. Chem. Phys. 140, 184107 (2014)] introduced an efficient and accurate L 2 method for the calculation of excited state valence photoionization cross-sections based on the application of Stieltjes imaging to the Lanczos pseudo-spectrum of the algebraic diagrammatic construction (ADC) representation of the electronic Hamiltonian. In this paper, we report an extension of this method to the calculation of excited state core photoionization cross-sections. We demonstrate that, at the ADC(2)x level of theory, ground state X-ray absorption spectra may be accurately reproduced, validating the method. Significantly, the calculated X-ray absorption spectra of the excited states are found to be sensitive to both geometric distortions (structural dynamics) and the electronic character (electronic dynamics) of the initial state, suggesting that core excitation spectroscopies will be useful probes of excited state non-adiabatic dynamics. We anticipate that the method presented here can be combined with ab initio molecular dynamics calculations to simulate the time-resolved X-ray spectroscopy of excited state molecular wavepacket dynamics.

Resolving the neutron lifetime puzzle

NASA Astrophysics Data System (ADS)

Mumm, Pieter

2018-05-01

Free electrons and protons are stable, but outside atomic nuclei, free neutrons decay into a proton, electron, and antineutrino through the weak interaction, with a lifetime of ∼880 s (see the figure). The most precise measurements have stated uncertainties below 1 s (0.1%), but different techniques, although internally consistent, disagree by 4 standard deviations given the quoted uncertainties. Resolving this “neutron lifetime puzzle” has spawned much experimental effort as well as exotic theoretical mechanisms, thus far without a clear explanation. On page 627 of this issue, Pattie et al. (1) present the most precise measurement of the neutron lifetime to date. A new method of measuring trapped neutrons in situ allows a more detailed exploration of one of the more pernicious systematic effects in neutron traps, neutron phase-space evolution (the changing orbits of neutrons in the trap), than do previous methods. The precision achieved, combined with a very different set of systematic uncertainties, gives hope that experiments such as this one can help resolve the current situation with the neutron lifetime.

Polaron pair mediated triplet generation in polymer/fullerene blends

PubMed Central

Dimitrov, Stoichko D.; Wheeler, Scot; Niedzialek, Dorota; Schroeder, Bob C.; Utzat, Hendrik; Frost, Jarvist M.; Yao, Jizhong; Gillett, Alexander; Tuladhar, Pabitra S.; McCulloch, Iain; Nelson, Jenny; Durrant, James R.

2015-01-01

Electron spin is a key consideration for the function of organic semiconductors in light-emitting diodes and solar cells, as well as spintronic applications relying on organic magnetoresistance. A mechanism for triplet excited state generation in such systems is by recombination of electron-hole pairs. However, the exact charge recombination mechanism, whether geminate or nongeminate and whether it involves spin-state mixing is not well understood. In this work, the dynamics of free charge separation competing with recombination to polymer triplet states is studied in two closely related polymer-fullerene blends with differing polymer fluorination and photovoltaic performance. Using time-resolved laser spectroscopic techniques and quantum chemical calculations, we show that lower charge separation in the fluorinated system is associated with the formation of bound electron-hole pairs, which undergo spin-state mixing on the nanosecond timescale and subsequent geminate recombination to triplet excitons. We find that these bound electron-hole pairs can be dissociated by electric fields. PMID:25735188

Probing the electronic structure of UO+ with high-resolution photoelectron spectroscopy.

PubMed

Goncharov, Vasiliy; Kaledin, Leonid A; Heaven, Michael C

2006-10-07

The pulsed field ionization-zero kinetic energy photoelectron technique has been used to observe the low-lying energy levels of UO+. Rotationally resolved spectra were recorded for the ground state and the first nine electronically excited states. Extensive vibrational progressions were characterized. Omega+ assignments were unambiguously determined from the first rotational lines identified in each vibronic band. Term energies, vibrational frequencies, and anharmonicity constants for low-lying energy levels of UO+ are reported. In addition, accurate values for the ionization energies for UO [48,643.8(2) cm(-1)] and U [49,957.6(2) cm(-1)] were determined. The pattern of low-lying electronic states for UO+ indicates that they originate from the U3+(5f3)O2- configuration, where the uranium ion-centered interactions between the 5f electrons are significantly stronger than interactions with the intramolecular electric field. The latter lifts the degeneracy of U3+ ion-core states, but the atomic angular momentum quantum numbers remain reasonably well defined.

Spin resolved photoelectron spectroscopy of [Mn6IIICrIII]3 + single-molecule magnets and of manganese compounds as reference layers

NASA Astrophysics Data System (ADS)

Helmstedt, Andreas; Müller, Norbert; Gryzia, Aaron; Dohmeier, Niklas; Brechling, Armin; Sacher, Marc D.; Heinzmann, Ulrich; Hoeke, Veronika; Krickemeyer, Erich; Glaser, Thorsten; Bouvron, Samuel; Fonin, Mikhail; Neumann, Manfred

2011-07-01

Properties of the manganese-based single-molecule magnet [\\mathbf {Mn}^{\\mathbf {I}\\mathbf {I}\\mathbf {I}}_{\\mathbf {6}} \\mathbf {Cr}^{\\mathbf {I}\\mathbf {I}\\mathbf {I}}]^{\\mathbf {3} \\boldsymbol {+}} are studied. It contains six MnIII ions arranged in two bowl-shaped trinuclear triplesalen building blocks linked by a hexacyanochromate and exhibits a large spin ground state of St = 21/2. The dominant structures in the electron emission spectra of [\\mathbf {Mn}^{\\mathbf {I}\\mathbf {I}\\mathbf {I}}_{\\mathbf {6}}\\mathbf {Cr}^{\\mathbf {I}\\mathbf {I}\\mathbf {I}}]^{\\mathbf {3} \\boldsymbol {+}} resonantly excited at the L3-edge are the L3M2, 3M2, 3, L3M2, 3V and L3VV Auger emission groups following the decay of the primary p3/2 core hole state. Significant differences of the Auger spectra from intact and degraded [\\mathbf {Mn}^{\\mathbf {I}\\mathbf {I}\\mathbf {I}}_{\\mathbf {6}}\\mathbf {Cr}^{\\mathbf {I}\\mathbf {I}\\mathbf {I}}]^{\\mathbf {3} \\boldsymbol {+}} show up. First measurements of the electron spin polarization in the L3M2, 3V and L3VV Auger emission peaks from the manganese constituents in [\\mathbf {Mn}^{\\mathbf {I}\\mathbf {I}\\mathbf {I}}_{\\mathbf {6}} \\mathbf {Cr}^{\\mathbf {I}\\mathbf {I}\\mathbf {I}}]^{\\mathbf {3} \\boldsymbol {+}} resonantly excited at the L3-edge near 640 eV by circularly polarized synchrotron radiation are reported. In addition spin resolved Auger electron spectra of the reference substances MnO, Mn2O3 and MnII(acetate)2·4H2O are given. The applicability of spin resolved electron spectroscopy for characterizing magnetic states of constituent atoms compared to magnetic circular dichroism (MCD) is verified: the spin polarization obtained from MnII(acetate)2·4H2O at room temperature in the paramagnetic state compares to the MCD asymmetry revealed for a star-shaped molecule with a Mn4IIO6 core at 5 K in an external magnetic field of 5 T.

Anion photoelectron spectroscopy of radicals and clusters

DOE Office of Scientific and Technical Information (OSTI.GOV)

Travis, Taylor R.

1999-12-01

Anion photoelectron spectroscopy is used to study free radicals and clusters. The low-lying 2Σ and 2π states of C 2nH (n = 1--4) have been studied. The anion photoelectron spectra yielded electron affinities, term values, and vibrational frequencies for these combustion and astrophysically relevant species. Photoelectron angular distributions allowed the author to correctly assign the electronic symmetry of the ground and first excited states and to assess the degree of vibronic coupling in C 2H and C 4H. Other radicals studied include NCN and I 3. The author was able to observe the low-lying singlet and triplet states of NCNmore » for the first time. Measurement of the electron affinity of I 3 revealed that it has a bound ground state and attachment of an argon atom to this moiety enabled him to resolve the symmetric stretching progression.« less

Highly Charged Rydberg Ions from the Coulomb Explosion of Clusters

NASA Astrophysics Data System (ADS)

Komar, D.; Kazak, L.; Almassarani, M.; Meiwes-Broer, K.-H.; Tiggesbäumker, J.

2018-03-01

Ion emission from a nanoplasma produced in the interaction of intense optical laser pulses with argon clusters is studied resolving simultaneously charge states and recoil energies. By applying appropriate static electric fields we observe that a significant fraction of the ions Arq + (q =1 - 7 ) has electrons with binding energies lower than 150 meV; i.e., nRyd≥15 levels are populated. Charge state changes observed on a μ s time scale can be attributed to electron emission due to autoionizing Rydberg states, indicating that high-ℓ Rydberg levels are populated as well. The experiments support theoretical predictions that a significant fraction of delocalized electrons, which are bound with hundreds of eV to the nanoplasma after the laser exposure, fill up meV bound ion states in the adiabatic expansion. We expect the process to be relevant for the long-term evolution of expanding laser-induced dense plasmas in general.

Ultrafast dynamics of photoactive yellow protein via the photoexcitation and emission processes.

PubMed

Nakamura, Ryosuke; Hamada, Norio; Ichida, Hideki; Tokunaga, Fumio; Kanematsu, Yasuo

2007-01-01

Pump-dump fluorescence spectroscopy was performed for photoactive yellow protein (PYP) at room temperature. The effect of the dump pulse on the population of the potential energy surface of the electronic excited state was examined as depletion in the stationary fluorescence intensity. The dynamic behavior of the population in the electronic excited state was successfully probed in the various combinations of the pump-dump delay, the dump-pulse wavelength, the dump-pulse energy and the observation wavelength. The experimental results were compared with the results obtained by the femtosecond time-resolved fluorescence spectroscopy.

UVA radiation induced ultrafast electron transfer from a food carcinogen benzo[a]pyrene to organic molecules, biological macromolecules, and inorganic nano structures.

PubMed

Banerjee, Soma; Sarkar, Soumik; Lakshman, Karthik; Dutta, Joydeep; Pal, Samir Kumar

2013-04-11

Reactions involving electron transfer (ET) and reactive oxygen species (ROS) play a pivotal role in carcinogenesis and cancer biochemistry. Our present study emphasizes UVA radiation induced ET reaction as one of the key aspects of a potential carcinogen, benzo[a]pyrene (BP), in the presence of a wide variety of molecules covering organic p-benzoquinone (BQ), biological macromolecules like calf-thymus DNA (CT-DNA), human serum albumin (HSA) protein, and inorganic zinc oxide (ZnO) nanorods (NRs). Steady-state and picosecond-resolved fluorescence spectroscopy have been used to monitor such ET reactions. Physical consequences of BP association with CT-DNA have been investigated through temperature-dependent circular dichroism (CD) spectroscopy. The temperature-dependent steady-state, picosecond-resolved fluorescence lifetime and anisotropy studies reveal the effect of temperature on the perturbation of such ET reactions from BP to biological macromolecules, highlighting their temperature-dependent association. Furthermore, the electron-donating property of BP has been corroborated by measuring wavelength-dependent photocurrent in a BP-anchored ZnO NR-based photodevice, offering new physical insights for the carcinogenic study of BP.

Time-resolved X-ray Absorption Spectroscopy for Electron Transport Study in Warm Dense Gold

NASA Astrophysics Data System (ADS)

Lee, Jong-Won; Bae, Leejin; Engelhorn, Kyle; Heimann, Philip; Ping, Yuan; Barbrel, Ben; Fernandez, Amalia; Beckwith, Martha Anne; Cho, Byoung-Ick; GIST Team; IBS Team; LBNL Collaboration; SLAC Collaboration; LLNL Collaboration

2015-11-01

The warm dense Matter represents states of which the temperature is comparable to Fermi energy and ions are strongly coupled. One of the experimental techniques to create such state in the laboratory condition is the isochoric heating of thin metal foil with femtosecond laser pulses. This concept largely relies on the ballistic transport of electrons near the Fermi-level, which were mainly studied for the metals in ambient conditions. However, they were barely investigated in warm dense conditions. We present a time-resolved x-ray absorption spectroscopy measured for the Au/Cu dual layered sample. The front Au layer was isochorically heated with a femtosecond laser pulse, and the x-ray absorption changes around L-edge of Cu, which was attached on the backside of Au, was measured with a picosecond resolution. Time delays between the heating of the `front surface' of Au layer and the alternation of x-ray spectrum of Cu attached on the `rear surface' of Au indicate the energetic electron transport mechanism through Au in the warm dense conditions. IBS (IBS-R012-D1) and the NRF (No. 2013R1A1A1007084) of Korea.

Intramolecular structure and dynamics of mequinol and guaiacol in the gas phase: Rotationally resolved electronic spectra of their S{sub 1} states

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ruiz-Santoyo, José Arturo; Rodríguez-Matus, Marcela; Álvarez-Valtierra, Leonardo, E-mail: leoav@fisica.ugto.mx, E-mail: gmerino@mda.cinvestav.mx

2015-09-07

The molecular structures of guaiacol (2-methoxyphenol) and mequinol (4-methoxyphenol) have been studied using high resolution electronic spectroscopy in a molecular beam and contrasted with ab initio computations. Mequinol exhibits two low frequency bands that have been assigned to electronic origins of two possible conformers of the molecule, trans and cis. Guaiacol also shows low frequency bands, but in this case, the bands have been assigned to the electronic origin and vibrational modes of a single conformer of the isolated molecule. A detailed study of these bands indicates that guaiacol has a vibrationally averaged planar structure in the ground state, butmore » it is distorted along both in-plane and out-of-plane coordinates in the first electronically excited state. An intramolecular hydrogen bond involving the adjacent   –OH and   –OCH{sub 3} groups plays a major role in these dynamics.« less

The valence-fluctuating ground state of plutonium

DOE PAGES

Janoschek, Marc; Das, Pinaki; Chakrabarti, Bismayan; ...

2015-07-10

A central issue in material science is to obtain understanding of the electronic correlations that control complex materials. Such electronic correlations frequently arise because of the competition of localized and itinerant electronic degrees of freedom. Although the respective limits of well-localized or entirely itinerant ground states are well understood, the intermediate regime that controls the functional properties of complex materials continues to challenge theoretical understanding. We have used neutron spectroscopy to investigate plutonium, which is a prototypical material at the brink between bonding and nonbonding configurations. In addition, our study reveals that the ground state of plutonium is governed bymore » valence fluctuations, that is, a quantum mechanical superposition of localized and itinerant electronic configurations as recently predicted by dynamical mean field theory. Our results not only resolve the long-standing controversy between experiment and theory on plutonium’s magnetism but also suggest an improved understanding of the effects of such electronic dichotomy in complex materials.« less

Coherent Nuclear Wave Packets in Q States by Ultrafast Internal Conversions in Free Base Tetraphenylporphyrin.

PubMed

Kim, So Young; Joo, Taiha

2015-08-06

Persistence of vibrational coherence in electronic transition has been noted especially in biochemical systems. Here, we report the dynamics between electronic excited states in free base tetraphenylporphyrin (H2TPP) by time-resolved fluorescence with high time resolution. Following the photoexcitation of the B state, ultrafast internal conversion occurs to the Qx state directly as well as via the Qy state. Unique and distinct coherent nuclear wave packet motions in the Qx and Qy states are observed through the modulation of the fluorescence intensity in time. The instant, serial internal conversions from the B to the Qy and Qx states generate the coherent wave packets. Theory and experiment show that the observed vibrational modes involve the out-of-plane vibrations of the porphyrin ring that are strongly coupled to the internal conversion of H2TPP.

Photodissociation of CS from Excited Rovibrational Levels

NASA Astrophysics Data System (ADS)

Pattillo, R. J.; Cieszewski, R.; Stancil, P. C.; Forrey, R. C.; Babb, J. F.; McCann, J. F.; McLaughlin, B. M.

2018-05-01

Accurate photodissociation cross sections have been computed for transitions from the X 1Σ+ ground electronic state of CS to six low-lying excited electronic states. New ab initio potential curves and transition dipole moment functions have been obtained for these computations using the multi-reference configuration interaction approach with the Davidson correction (MRCI+Q) and aug-cc-pV6Z basis sets. State-resolved cross sections have been computed for transitions from nearly the full range of rovibrational levels of the X 1Σ+ state and for photon wavelengths ranging from 500 Å to threshold. Destruction of CS via predissociation in highly excited electronic states originating from the rovibrational ground state is found to be unimportant. Photodissociation cross sections are presented for temperatures in the range between 1000 and 10,000 K, where a Boltzmann distribution of initial rovibrational levels is assumed. Applications of the current computations to various astrophysical environments are briefly discussed focusing on photodissociation rates due to the standard interstellar and blackbody radiation fields.

Separating Bulk and Surface Contributions to Electronic Excited-State Processes in Hybrid Mixed Perovskite Thin Films via Multimodal All-Optical Imaging

DOE PAGES

Simpson, Mary Jane; Doughty, Benjamin; Das, Sanjib; ...

2017-07-04

A comprehensive understanding of electronic excited-state phenomena underlying the impressive performance of solution-processed hybrid halide perovskite solar cells requires access to both spatially resolved electronic processes and corresponding sample morphological characteristics. In this paper, we demonstrate an all-optical multimodal imaging approach that enables us to obtain both electronic excited-state and morphological information on a single optical microscope platform with simultaneous high temporal and spatial resolution. Specifically, images were acquired for the same region of interest in thin films of chloride containing mixed lead halide perovskites (CH 3NH 3PbI 3–xCl x) using femtosecond transient absorption, time-integrated photoluminescence, confocal reflectance, and transmissionmore » microscopies. Comprehensive image analysis revealed the presence of surface- and bulk-dominated contributions to the various images, which describe either spatially dependent electronic excited-state properties or morphological variations across the probed region of the thin films. Finally, these results show that PL probes effectively the species near or at the film surface.« less

The Pfi-Zeke Spectroscopy Study of HfS+ and the Ionization Energy of HfS

NASA Astrophysics Data System (ADS)

Antonov, I. O.; Barker, B. J.; Heaven, M. C.

2011-06-01

Spectroscopic data for the ground and low-lying states HfS+ have been obtained using the technique of pulse field ionization - zero electron kinetic energy (PFI-ZEKE) spectroscopy. PFI-ZEKE spectra were recorded for the levels X2Σ+ (v=0-18), 2Δ5/2 (v=0-8) and 2Δ3/2 (v=0-3). Assignments of the electronically excited states of HfS+ are based on CCSD(T) and DFT calculations with SDB-aug-cc-pVTZ basis set. Rotationally resolved spectra were recorded for the X2Σ+ (v=0) state using single rotational line excitation of the intermediate state. The ionization energy for HfS, term energies and molecular constants for the ground and low-lying states of HfS+ will be reported.

Photoionization and Electron Transfer of Biphenyl within the Channels of Al-ZSM-5 Zeolites.

PubMed

Gener, Isabelle; Buntinx, Guy; Brémard, Claude

1999-06-14

Evidence of the photogenerated long-lived biphenyl radical and a trapped electron in the void space of aluminated nonacidic ZSM-5 zeolites has been obtained from the time-resolved UV/Vis absorption, Raman scattering, and EPR spectra. The restoration of the ground states implicates the existence of long-lived positive holes in the framework. © 1999 WILEY-VCH Verlag GmbH, Weinheim, Fed. Rep. of Germany.

Angle-resolved studies of inner shell excitations for argon, krypton and xenon using third-generation synchrotron sources

NASA Astrophysics Data System (ADS)

Farhat, Ahmad H.

This dissertation, which is in the area of atomic physics, concentrates on the study of the interaction between VUV-soft X-ray radiation and atoms in the gas phase. The main area of interest is the study of Auger decay in atoms utilizing the process known as the resonance Auger effect, where an inner shell electron is excited to an unfilled orbital followed by the ejection of an Auger electron. The measurements in this thesis were performed by using the high resolution Atomic, Molecular and Optical Physics undulator beam line, which utilizes a spherical grating monochromator at the Advanced Light Source at Lawrence Berkeley National Laboratory. The research focused on three rare gases, argon, krypton and xenon. For argon, high resolution angular-resolved measurements of the 2p → 4s, 3d, 4d resonant Auger lines have been achieved. By measuring photoelectron spectra simultaneously at two different angles using efficient time of flight spectrometers, the angular distributions anisotropy parameters β have been measured, and relative intensities have been evaluated for each of the resolved final ionic states. For krypton, the resonant Auger decay of all the photoexcited Kr 3d3/2,5/2-1 nl (n = 5-9) states have been studied using an angle resolved two dimensional photoelectron spectroscopic technique, in which the electron yield was measured as a function of both photon energy and electron kinetic energy. Angular distributions, spectator and shake probabilities have been derived for the Kr 3d-1np/to4s- 14p-1mp + e/sp- (n = 5-9, m = 5-11) resonance Auger decay. The results show that the spectator-core coupling is strong at lower n (n = 5,6) but it lessens for higher n, with a shake up of m = n + 1 preferred. Finally for xenon, the autoionization resonances and angular distribution of the 4d → 6p decay spectrum were studied utilizing the Auger resonant Raman effect. Using this technique, β parameters of almost all 5p4/ (3P,/ 1D,/ 1S) 6p final ionic states were determined. These results contribute to our understanding of atomic structure and dynamics of inner shell processes and hopefully will stimulate further experimental and theoretical work.

Apparatus for time-resolved and energy-resolved measurement of internal conversion electron emission induced by nuclear resonant excitation with synchrotron radiation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kawauchi, Taizo; Matsumoto, Masuaki; Fukutani, Katsuyuki

2007-01-15

A high-energy and large-object-spot type cylindrical mirror analyzer (CMA) was constructed with the aid of electron trajectory simulations. By adopting a particular shape for the outer cylinder, an energy resolution of 7% was achieved without guide rings as used in conventional CMAs. Combined with an avalanche photodiode as an electron detector, the K-shell internal conversion electrons were successfully measured under irradiation of synchrotron radiation at 14.4 keV in an energy-resolved and time-resolved manner.

The Key Ingredients of the Electronic Structure of FeSe

NASA Astrophysics Data System (ADS)

Coldea, Amalia I.; Watson, Matthew D.

2018-03-01

FeSe is a fascinating superconducting material at the frontier of research in condensed matter physics. Here, we provide an overview of the current understanding of the electronic structure of FeSe, focusing in particular on its low-energy electronic structure as determined from angle-resolved photoemission spectroscopy, quantum oscillations, and magnetotransport measurements of single-crystal samples. We discuss the unique place of FeSe among iron-based superconductors, as it is a multiband system exhibiting strong orbitally dependent electronic correlations and unusually small Fermi surfaces and is prone to different electronic instabilities. We pay particular attention to the evolution of the electronic structure that accompanies the tetragonal-orthorhombic structural distortion of the lattice around 90 K, which stabilizes a unique nematic electronic state. Finally, we discuss how the multiband multiorbital nematic electronic structure impacts our understanding of the superconductivity, and show that the tunability of the nematic state with chemical and physical pressure helps to disentangle the role of different competing interactions relevant for enhancing superconductivity.

Ultrafast electron diffraction study of ab-plane dynamics in superconducting Bi2Sr<2CaCu2O8+d

NASA Astrophysics Data System (ADS)

Konstantinova, Tatiana; Reid, Alexander; Wu, Lijun; Durr, Hermann; Wang, Xijie; Zhu, Yimei

The role of phonons and other collective modes in cooperative electron phenomena in high-TC cuprate superconductors is an extensively interesting topic. Time-resolved experiments provide temporal hierarchy of the bosonic modes interacting with electrons. However, majority of research in this field explore dynamics of electronic states and can only make indirect conclusion about involvement of the lattice. We report time-resolved study of optimally doped Bi2Sr2CaCu2O8+d lattice response to photo-excitation by means of ultrafast electron diffraction that is directly sensitive to atomic motion. Data analysis utilizing Bloch-wave calculation of diffraction peak intensity allows separation of Cu-O in-plane vibration building up on the sub picosecond time scale from the low energy phonon population growth with a much slower rate. This study confirms the assumption of strong electron coupling to the Cu-O plane phonons. This work was supported by the US DOE, Office of Science, Basic Energy Science, Materials Science and Engineering Division under Contract No: DE-AC02-98CH10886; DOE LDRD funding under contract DE-AC02-76SF00515 and BNL.

Nonequilibrium electron and lattice dynamics of strongly correlated Bi2Sr2CaCu2O8+δ single crystals

PubMed Central

Li, Renkai; Gu, Genda; Avigo, Isabella; Dürr, Hermann A.; Johnson, Peter D.; Wang, Xijie

2018-01-01

The interplay between the electronic and lattice degrees of freedom in nonequilibrium states of strongly correlated systems has been debated for decades. Although progress has been made in establishing a hierarchy of electronic interactions with the use of time-resolved techniques, the role of the phonons often remains in dispute, a situation highlighting the need for tools that directly probe the lattice. We present the first combined megaelectron volt ultrafast electron diffraction and time- and angle-resolved photoemission spectroscopy study of optimally doped Bi2Sr2CaCu2O8+δ. Quantitative analysis of the lattice and electron subsystems’ dynamics provides a unified picture of nonequilibrium electron-phonon interactions in the cuprates beyond the N-temperature model. The work provides new insights on the specific phonon branches involved in the nonequilibrium heat dissipation from the high-energy Cu–O bond stretching “hot” phonons to the lowest-energy acoustic phonons with correlated atomic motion along the <110> crystal directions and their characteristic time scales. It reveals a highly nonthermal phonon population during the first several picoseconds after the photoexcitation. The approach, taking advantage of the distinct nature of electrons and photons as probes, is applicable for studying energy relaxation in other strongly correlated electron systems. PMID:29719862

Observation of dx2-y-Like Superconducting Gap in an Electron-Doped High-Temperature Superconductor

NASA Astrophysics Data System (ADS)

Sato, T.; Kamiyama, T.; Takahashi, T.; Kurahashi, K.; Yamada, K.

2001-02-01

High-resolution angle-resolved photoemission spectroscopy of the electron-doped high-temperature superconductor Nd2-xCexCuO4 (x = 0.15, transition temperature Tc = 22 K) has found the quasiparticle signature as well as the anisotropic dx2-y-like superconducting gap. The spectral line shape at the superconducting state shows a strong anisotropic nature of the many-body interaction. The result suggests that the electron-hole symmetry is present in the high-temperature superconductors.

Disentangling the surface and bulk electronic structures of LaOFeAs

DOE PAGES

Zhang, P.; Ma, J.; Qian, T.; ...

2016-09-20

We performed a comprehensive angle-resolved photoemission spectroscopy study of the electronic band structure of LaOFeAs single crystals. We found that samples cleaved at low temperature show an unstable and very complicated band structure, whereas samples cleaved at high temperature exhibit a stable and clearer electronic structure. Using in situ surface doping with K and supported by first-principles calculations, we identify both surface and bulk bands. Our assignments are confirmed by the difference in the temperature dependence of the bulk and surface states.

Security aspects of electronic data interchange between a state health department and a hospital emergency department.

PubMed

Magnuson, J A; Klockner, Rocke; Ladd-Wilson, Stephen; Zechnich, Andrew; Bangs, Christopher; Kohn, Melvin A

2004-01-01

Electronic emergency department reporting provides the potential for enhancing local and state surveillance capabilities for a wide variety of syndromes and reportable conditions. The task of protecting data confidentiality and integrity while developing electronic data interchange between a hospital emergency department and a state public health department proved more complex than expected. This case study reports on the significant challenges that had to be resolved to accomplish this goal; these included application restrictions and incompatibilities, technical malfunctions, changing standards, and insufficient dedicated resources. One of the key administrative challenges was that of coordinating project security with enterprise security. The original project has evolved into an ongoing pilot, with the health department currently receiving secure data from the emergency department at four-hour intervals. Currently, planning is underway to add more emergency departments to the project.

Insulator at the ultrathin limit: MgO on Ag(001).

PubMed

Schintke, S; Messerli, S; Pivetta, M; Patthey, F; Libioulle, L; Stengel, M; De Vita, A; Schneider, W D

2001-12-31

The electronic structure and morphology of ultrathin MgO films epitaxially grown on Ag(001) were investigated using low-temperature scanning tunneling spectroscopy and scanning tunneling microscopy. Layer-resolved differential conductance (dI/dU) measurements reveal that, even at a film thickness of three monolayers, a band gap of about 6 eV is formed corresponding to that of the MgO(001) single-crystal surface. This finding is confirmed by layer-resolved calculations of the local density of states based on density functional theory.

An ultrafast angle-resolved photoemission apparatus for measuring complex materials

NASA Astrophysics Data System (ADS)

Smallwood, Christopher L.; Jozwiak, Christopher; Zhang, Wentao; Lanzara, Alessandra

2012-12-01

We present technical specifications for a high resolution time- and angle-resolved photoemission spectroscopy setup based on a hemispherical electron analyzer and cavity-dumped solid state Ti:sapphire laser used to generate pump and probe beams, respectively, at 1.48 and 5.93 eV. The pulse repetition rate can be tuned from 209 Hz to 54.3 MHz. Under typical operating settings the system has an overall energy resolution of 23 meV, an overall momentum resolution of 0.003 Å-1, and an overall time resolution of 310 fs. We illustrate the system capabilities with representative data on the cuprate superconductor Bi2Sr2CaCu2O8+δ. The descriptions and analyses presented here will inform new developments in ultrafast electron spectroscopy.

Dynamic spin injection into a quantum well coupled to a spin-split bound state

NASA Astrophysics Data System (ADS)

Maslova, N. S.; Rozhansky, I. V.; Mantsevich, V. N.; Arseyev, P. I.; Averkiev, N. S.; Lähderanta, E.

2018-05-01

We present a theoretical analysis of dynamic spin injection due to spin-dependent tunneling between a quantum well (QW) and a bound state split in spin projection due to an exchange interaction or external magnetic field. We focus on the impact of Coulomb correlations at the bound state on spin polarization and sheet density kinetics of the charge carriers in the QW. The theoretical approach is based on kinetic equations for the electron occupation numbers taking into account high order correlation functions for the bound state electrons. It is shown that the on-site Coulomb repulsion leads to an enhanced dynamic spin polarization of the electrons in the QW and a delay in the carriers tunneling into the bound state. The interplay of these two effects leads to nontrivial dependence of the spin polarization degree, which can be probed experimentally using time-resolved photoluminescence experiments. It is demonstrated that the influence of the Coulomb interactions can be controlled by adjusting the relaxation rates. These findings open a new way of studying the Hubbard-like electron interactions experimentally.

Exploring the Bermuda triangle of homonuclear diatomic spectroscopy: The electronic spectrum and structure of Ge2

NASA Astrophysics Data System (ADS)

Hostutler, David A.; Li, Haiyang; Clouthier, Dennis J.; Wannous, Ghassan

2002-03-01

The optical spectrum of jet-cooled Ge2 has been observed for the first time. Laser-induced fluorescence (LIF) and wavelength resolved emission spectra were recorded using the pulsed discharge technique with a tetramethylgermane precursor. Analysis of the spectra yielded the vibrational constants ωe″=287.9(47), ωexe″=0.81(55), ωeye″=0.0037(18), ωe'=189.0(15), ωexe'=6.41(30), and Te'=20 610.8(16) cm-1. High-resolution rotationally resolved spectra of several bands of 74Ge2 show two strong P and R branches and two very weak Q branches. We have assigned the band system as a Hund's case (c) Ω'=1-Ω″=1 transition from the ground 3Σg- state to a 3Σu- excited state. The bond lengths derived from the rotational constants are r0″=2.3680(1) Å and re'=2.5244(18) Å, an ˜0.16 Å increase on electronic excitation. Arguments are presented for assigning the transition to a σg2πu2→σg2πuπg electron promotion, although the observed increase in the bond length is much less than predicted by previous ab initio calculations. The absence of the 0u+-0g+ component in the spectra has been attributed to an excited state predissociation.

Ultrafast demagnetization enhancement in CoFeB/MgO/CoFeB magnetic tunneling junction driven by spin tunneling current.

PubMed

He, Wei; Zhu, Tao; Zhang, Xiang-Qun; Yang, Hai-Tao; Cheng, Zhao-Hua

2013-10-07

The laser-induced ultrafast demagnetization of CoFeB/MgO/CoFeB magnetic tunneling junction is exploited by time-resolved magneto-optical Kerr effect (TRMOKE) for both the parallel state (P state) and the antiparallel state (AP state) of the magnetizations between two magnetic layers. It was observed that the demagnetization time is shorter and the magnitude of demagnetization is larger in the AP state than those in the P state. These behaviors are attributed to the ultrafast spin transfer between two CoFeB layers via the tunneling of hot electrons through the MgO barrier. Our observation indicates that ultrafast demagnetization can be engineered by the hot electrons tunneling current. It opens the door to manipulate the ultrafast spin current in magnetic tunneling junctions.

Electronic structure of hydrogenated diamond: Microscopical insight into surface conductivity

NASA Astrophysics Data System (ADS)

Iacobucci, S.; Alippi, Paola; Calvani, P.; Girolami, M.; Offi, F.; Petaccia, L.; Trucchi, D. M.

2016-07-01

We have correlated the surface conductivity of hydrogen-terminated diamond to the electronic structure in the Fermi region. Significant density of electronic states (DOS) in proximity of the Fermi edge has been measured by photoelectron spectroscopy (PES) on surfaces exposed to air, corresponding to a p -type electric conductive regime, while upon annealing a depletion of the DOS has been achieved, resembling the diamond insulating state. The surface and subsurface electronic structure has been determined, exploiting the different probing depths of PES applied in a photon energy range between 7 and 31 eV. Ab initio density functional calculations including surface charge depletion and band-bending effects favorably compare with electronic states measured by angular-resolved photoelectron spectroscopy. Such states are organized in the energy-momentum space in a twofold structure: one, bulk-derived, band disperses in the Γ -X direction with an average hole effective mass of (0.43 ±0.02 ) m0 , where m0 is the bare electron mass; a second flatter band, with an effective mass of (2.2 ±0.9 ) m0 , proves that a hole gas confined in the topmost layers is responsible for the conductivity of the (2 ×1 ) hydrogen-terminated diamond (100 ) surface.

Rotationally resolved electronic spectroscopy study of the conformational space of 3-methoxyphenol

NASA Astrophysics Data System (ADS)

Wilke, Martin; Schneider, Michael; Wilke, Josefin; Ruiz-Santoyo, José Arturo; Campos-Amador, Jorge J.; González-Medina, M. Elena; Álvarez-Valtierra, Leonardo; Schmitt, Michael

2017-07-01

Conformational preferences are determined by (de-)stabilization effects like intramolecular hydrogen bonds or steric hindrance of adjacent substituents and thus, influence the stability and reactivity of the conformers. In the present contribution, we investigate the conformational landscape of 3-methoxyphenol using a combination of high resolution electronic spectroscopy and ab initio calculations. Three of the four possible conformational isomers were characterized in their electronic ground and lowest excited singlet states on the basis of their rotational constants and other molecular parameters. The absence of one conformer in molecular beam studies can be explained by its non-planar structure in the excited state, which leads to a vanishingly small Franck-Condon factor of the respective origin excitation.

Dissociative excitation of the N(+)(5S) state by electron impact on N2 - Excitation function and quenching

NASA Technical Reports Server (NTRS)

Erdman, P. W.; Zipf, E. C.

1986-01-01

Metastable N(+)(5S) ions were produced in the laboratory by dissociative excitation of N2 with energetic electrons. The resulting radiative decay of the N(+)(5S) state was observed with sufficient resolution to completely resolve the doublet from the nearby N2 molecular radiation. The excitation function was measured from threshold to 500 eV. The cross section peaks at a high electron energy and also exhibits a high threshold energy both of which are typical of dissociative excitation-ionization processes. This finding complicates the explanation of electron impact on N2 as the mechanism for the source of the 2145 A 'auroral mystery feature' by further increasing the required peak cross section. It is suggested that the apparent N(+)(5S) quenching in auroras may be an artifact due to the softening of the electron energy spectrum in the auroral E region.

Kinks in the σ band of graphene induced by electron-phonon coupling.

PubMed

Mazzola, Federico; Wells, Justin W; Yakimova, Rositza; Ulstrup, Søren; Miwa, Jill A; Balog, Richard; Bianchi, Marco; Leandersson, Mats; Adell, Johan; Hofmann, Philip; Balasubramanian, T

2013-11-22

Angle-resolved photoemission spectroscopy reveals pronounced kinks in the dispersion of the σ band of graphene. Such kinks are usually caused by the combination of a strong electron-boson interaction and the cutoff in the Fermi-Dirac distribution. They are therefore not expected for the σ band of graphene that has a binding energy of more than ≈3.5 eV. We argue that the observed kinks are indeed caused by the electron-phonon interaction, but the role of the Fermi-Dirac distribution cutoff is assumed by a cutoff in the density of σ states. The existence of the effect suggests a very weak coupling of holes in the σ band not only to the π electrons of graphene but also to the substrate electronic states. This is confirmed by the presence of such kinks for graphene on several different substrates that all show a strong coupling constant of λ≈1.

Direct observation of electronic-liquid-crystal phase transitions and their microscopic origin in La 1/3Ca 2/3MnO 3

DOE PAGES

Tao, J.; Sun, K.; Yin, W. -G.; ...

2016-11-22

The ground-state electronic order in doped manganites is frequently associated with a lattice modulation, contributing to their many interesting properties. However, measuring the thermal evolution of the lattice superstructure with reciprocal-space probes alone can lead to ambiguous results with competing interpretations. Here, we provide direct observations of the evolution of the superstructure in La 1/3Ca 2/3MnO 3 in real space, as well as reciprocal space, using transmission electron microscopic (TEM) techniques. We show that the transitions are the consequence of a proliferation of dislocations plus electronic phase separation. The resulting states are well described by the symmetries associated with electronic-liquid-crystalmore » (ELC) phases. Furthermore, our results resolve the long-standing controversy over the origin of the incommensurate superstructure and suggest a new structural model that is consistent with recent theoretical calculations.« less

A multi-timescale map of radiative and nonradiative decay pathways for excitons in CdSe quantum dots.

PubMed

Knowles, Kathryn E; McArthur, Eric A; Weiss, Emily A

2011-03-22

A combination of transient absorption (TA) and time-resolved photoluminescence (TRPL) spectroscopies performed on solution-phase samples of colloidal CdSe quantum dots (QDs) allows the construction of a time-resolved, charge carrier-resolved map of decay from the first excitonic state of the QD. Data from TA and TRPL yield the same six exponential components, with time constants ranging from ∼1 ps to 50 ns, for excitonic decay. Comparison of TA signals in the visible and near-infrared (NIR) spectral regions enables determination of the relative contributions of electron and hole dynamics to each decay component, and comparison of TA and TRPL reveals that each component represents a competition between radiative and nonradiative decay pathways. In total, these data suggest that the QD sample comprises at least three distinct populations that differ in both the radiative and nonradiative decay pathways available to the excitonic charge carriers, and provide evidence for multiple emissive excitonic states in which the hole is not in the valence band, but rather a relaxed or trapped state.

Vibrationally-Resolved Kinetic Isotope Effects in the Proton-Transfer Dynamics of Ground-State Tropolone

NASA Astrophysics Data System (ADS)

Chew, Kathryn; Vealey, Zachary; Vaccaro, Patrick

2015-06-01

The vibrational and isotopic dependence of the hindered (tunneling-mediated) proton-transfer reaction taking place in the ground electronic state ( X1{A}1) of monodeuterated tropolone (TrOD) has been explored under ambient (bulk-gas) conditions by applying two-color variants of resonant four-wave mixing (RFWM) spectroscopy in conjunction with polarization-resolved detection schemes designed to alleviate spectral complexity and facilitate rovibrational assignments. Full rotation-tunneling analyses of high-resolution spectral profiles acquired for the fundamental and first-overtone bands of a reaction-promoting O-D\\cdotsO deformation/ring-breathing mode, νb{36}(a1), were performed, thereby extracting refined structural and dynamical information that affords benchmarks for the quantitative interpretation of tunneling-induced signatures found in long-range scans of X1{A}1 vibrational levels residing below Etilde{X}vib = 1700 wn}. Observed kinetic isotope effects, which reflect changes in both reaction kinematics and vibrational displacements, will be discussed, with high-level quantum-chemical calculations serving to elucidate state-resolved propensities for proton transfer in TrOH and TrOD.

Serial Femtosecond Crystallography and Ultrafast Absorption Spectroscopy of the Photoswitchable Fluorescent Protein IrisFP.

PubMed

Colletier, Jacques-Philippe; Sliwa, Michel; Gallat, François-Xavier; Sugahara, Michihiro; Guillon, Virginia; Schirò, Giorgio; Coquelle, Nicolas; Woodhouse, Joyce; Roux, Laure; Gotthard, Guillaume; Royant, Antoine; Uriarte, Lucas Martinez; Ruckebusch, Cyril; Joti, Yasumasa; Byrdin, Martin; Mizohata, Eiichi; Nango, Eriko; Tanaka, Tomoyuki; Tono, Kensuke; Yabashi, Makina; Adam, Virgile; Cammarata, Marco; Schlichting, Ilme; Bourgeois, Dominique; Weik, Martin

2016-03-03

Reversibly photoswitchable fluorescent proteins find growing applications in cell biology, yet mechanistic details, in particular on the ultrafast photochemical time scale, remain unknown. We employed time-resolved pump-probe absorption spectroscopy on the reversibly photoswitchable fluorescent protein IrisFP in solution to study photoswitching from the nonfluorescent (off) to the fluorescent (on) state. Evidence is provided for the existence of several intermediate states on the pico- and microsecond time scales that are attributed to chromophore isomerization and proton transfer, respectively. Kinetic modeling favors a sequential mechanism with the existence of two excited state intermediates with lifetimes of 2 and 15 ps, the second of which controls the photoswitching quantum yield. In order to support that IrisFP is suited for time-resolved experiments aiming at a structural characterization of these ps intermediates, we used serial femtosecond crystallography at an X-ray free electron laser and solved the structure of IrisFP in its on state. Sample consumption was minimized by embedding crystals in mineral grease, in which they remain photoswitchable. Our spectroscopic and structural results pave the way for time-resolved serial femtosecond crystallography aiming at characterizing the structure of ultrafast intermediates in reversibly photoswitchable fluorescent proteins.

Experimental evaluation of analyte excitation mechanisms in the inductively coupled plasma

NASA Astrophysics Data System (ADS)

Lehn, Scott A.; Hieftje, Gary M.

2003-10-01

The inductively coupled plasma (ICP) is a justifiably popular source for atomic emission spectrometry. However, despite its popularity, the ICP is still only partially understood. Even the mechanisms of analyte excitation remain unclear; some energy levels are quite clearly populated by charge transfer while others might be populated by electron-ion recombination, by electron impact, or by Penning processes. Distinguishing among these alternatives is possible by means of a steady-state kinetics approach that examines correlations between the emission of a selected atom, ion, or level and the local number densities of species assumed to produce the excitation. In an earlier investigation, strong correlations were found between either calcium atom or ion emission and selected combinations of calcium atom or ion number densities and electron number densities in the plasma. However, all radially resolved data employed in the earlier study were produced from Abel inversion and from measurements that were crude by today's standards. Now, by means of tomographic imaging, laser-saturated atomic fluorescence, and Thomson and Rayleigh scattering, it is possible to measure the required radially resolved data without Abel inversion and with far greater fidelity. The correlations previously studied for calcium have been investigated with these more reliable data. Ion-electron recombination, either radiative or with argon as a third body, was determined to be the most likely excitation mechanism for calcium atom, while electron impact appeared to be the most important process to produce excite-state calcium ions. These results were consistent with the previous study. However, the present study suggests that collisional deactivation, rather than radiative decay, is the most likely mode of returning both calcium atoms and ions to the ground state.

Steady-state and time-resolved studies on the photophysical properties of fullerene-pyropheophorbide a complexes in polar and nonpolar solvents

NASA Astrophysics Data System (ADS)

Ermilov, E. A.; Al-Omari, S.; Helmreich, M.; Jux, N.; Hirsch, A.; Röder, B.

2004-04-01

A novel monofullerene-bis(pyropheophorbide a) dyad has been photophysically characterized by steady-state as well as time-resolved techniques. It was revealed that in this complex strong and fast quenching of the first excited singlet state of the pyropheophorbide a (pyroPheo) molecule occurs by efficient photoinduced electron transfer to the fullerene moiety in both polar (DMF) and nonpolar (toluene) solvents. In DMF the energy of the charge-separated state is 0.94 eV and it undergoes directly transition to the ground state resulting in a very low value of photosensitized singlet oxygen generation. In contrast to the situation in a polar solvent, in toluene the charge-separated state lies above the exited triplet state of pyroPheo as well as that of C 60. It has been shown that in a nonpolar solvent a sufficient amount of singlet oxygen was generated by energy transfer from the excited triplet state of pyroPheo which has been populated via relaxation of the charge-separated state.

Magnetic Control of the Charge-Separated State Lifetime Realized by Covalent Attachment of a Platinum Complex.

PubMed

Miura, Tomoaki; Fujiwara, Dai; Akiyama, Kimio; Horikoshi, Takafumi; Suzuki, Shuichi; Kozaki, Masatoshi; Okada, Keiji; Ikoma, Tadaaki

2017-02-02

Dynamics of the photogenerated charge-separated (CS) state is studied for a newly synthesized molecular triad, in which the donor (D) dimethoxytriphenylamine, 1,3-bis(2-pyridylimino)isoindolate platinum (BPIPt), and the acceptor (A) naphthaldiimide are linked with a triethynylbenzene unit (BPIPt-DA). Photoexcitation of BPIPt gives rise to generation of a long-lived (∼4 μs) CS state BPIPt-D + A - , of which the lifetime is considerably increased by an applied magnetic field of 270 mT. The positive magnetic field effect (MFE) is in contrast to the negative MFE for the reference DA molecule, which indicates successful switching of the initial spin state of the CS state from singlet to triplet. Simulations of the MFE and time-resolved electron paramagnetic resonance show that spin-selective charge recombination and spin relaxation are unaffected by attachment of BPIPt. The minimum impact of heavy atom substitution on the electronic and magnetic properties has been realized by the small electronic coupling mediated by the rigid meta-triethynylbenzene.

Ultrafast Spectroscopic Studies of Two-Photon States in Third Order Optical Processes of Dye Chromophores.

NASA Astrophysics Data System (ADS)

Yu, Yi-Zhong

1995-01-01

Conjugated organic and polymeric materials usually have large, nonresonant third order optical nonlinearity due to correlations of their delocalized pi -electrons. Most materials studied so far show positive values of third order nonlinear susceptibility when all frequencies that generate the third order effect are below any optical transition. A new class of organic molecules, namely indole squarylium (ISQ) and anilinium squarylium (BSQ), exhibit negative < gamma(-omega_4;omega_1, omega_2,omega_3)> when all three frequencies, omega_1, omega_2 and omega_3, lie below the first electronic transition. Although quantum many-electron calculations based on multiple-excitation configuration interaction have shown that the negative third order coefficient is essentially due to the contribution from high-lying two-photon states, the field of experimental studies exploring the microscopic origins of the negative squaraines remains uncultivated. The work presented in this thesis involves extensive experimental investigation of squaraines using techniques such as time-resolved transit absorption spectroscopy and saturable absorption. Theoretical simulations studying nonlinear absorption behavior of a simplified two-level system with ultrashort pulses are also presented. Part of the thesis is dedicated to the development, fabrication and characterization of our ultrafast laser system which offers tunable femtosecond pulses at wavelengths from UV to IR and served as a major tool in the experimental measurements. The dynamics of the population inversion between the ground state and the first excited state was also investigated through time-resolved experiments. The experiment results agree well with the theoretical predictions. Strong couplings between the gateway state and high-lying two-photon states were observed in BSQ squarylium molecules, which suggested a complete quantum calculation with multiple energy levels is required to correctly describe the negative third order effect.

Time-resolved photoluminescence characterization of oxygen-related defect centers in AlN

DOE Office of Scientific and Technical Information (OSTI.GOV)

Genji, Kumihiro; Uchino, Takashi, E-mail: uchino@kobe-u.ac.jp

2016-07-11

Time-resolved photoluminescence (PL) spectroscopy has been employed to investigate the emission characteristics of oxygen-related defects in AlN in the temperature region from 77 to 500 K. Two PL components with different decay constants are observed in the near-ultraviolet to visible regions. One is the PL component with decay time of <10 ns and its peak position shifts to longer wavelengths from ∼350 to ∼500 nm with increasing temperature up to 500 K. This PL component is attributed to the radiative relaxation of photoexcited electrons from the band-edge states to the ground state of the oxygen-related emission centers. In the time region from tens tomore » hundreds of nanoseconds, the second PL component emerges in the wavelength region from 300 to 400 nm. The spectral shape and the decay profiles are hardly dependent on temperature. This temperature-independent PL component most likely results from the transfer of photoexcited electrons from the band-edge states to the localized excited state of the oxygen-related emission centers. These results provide a detailed insight into the radiative relaxation processes of the oxygen-related defect centers in AlN immediately after the photoexcitation process.« less

Direct measurement of discrete valley and orbital quantum numbers in bilayer graphene.

PubMed

Hunt, B M; Li, J I A; Zibrov, A A; Wang, L; Taniguchi, T; Watanabe, K; Hone, J; Dean, C R; Zaletel, M; Ashoori, R C; Young, A F

2017-10-16

The high magnetic field electronic structure of bilayer graphene is enhanced by the spin, valley isospin, and an accidental orbital degeneracy, leading to a complex phase diagram of broken symmetry states. Here, we present a technique for measuring the layer-resolved charge density, from which we directly determine the valley and orbital polarization within the zero energy Landau level. Layer polarization evolves in discrete steps across 32 electric field-tuned phase transitions between states of different valley, spin, and orbital order, including previously unobserved orbitally polarized states stabilized by skew interlayer hopping. We fit our data to a model that captures both single-particle and interaction-induced anisotropies, providing a complete picture of this correlated electron system. The resulting roadmap to symmetry breaking paves the way for deterministic engineering of fractional quantum Hall states, while our layer-resolved technique is readily extendable to other two-dimensional materials where layer polarization maps to the valley or spin quantum numbers.The phase diagram of bilayer graphene at high magnetic fields has been an outstanding question, with orders possibly between multiple internal quantum degrees of freedom. Here, Hunt et al. report the measurement of the valley and orbital order, allowing them to directly reconstruct the phase diagram.

Optical Manipulation and Detection of Emergent Phenomena in Topological Insulators

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gedik, Nuh

The three-dimensional topological insulator (TI) is a new quantum phase of matter that exhibits quantum-Hall-like properties, even in the absence of an external magnetic field. These materials are insulators in the bulk but have a topologically protected conducting state at the surface. Charge carriers on these surface states behave like a two-dimensional gas of massless helical Dirac fermions for which the spin is ideally locked perpendicular to the momentum. The purpose of this project is to probe the unique collective electronic behaviors of topological insulators by developing and using advanced time resolved spectroscopic techniques with state-of-the-art temporal and spatial resolutions.more » The nature of these materials requires development of specialized ultrafast techniques (such as time resolved ARPES that also has spin detection capability, ultrafast electron diffraction that has sub-100 fs time resolution and THz magneto-spectroscopy). The focus of this report is to detail our achievements in terms of establishing state of the art experimental facilities. Below, we will describe achievements under this award for the entire duration of five years. We will focus on detailing the development of ultrafast technqiues here. The details of the science that was done with these technqiues can be found in the publications referencing this grant.« less

State-specific transport properties of electronically excited Ar and C

NASA Astrophysics Data System (ADS)

Istomin, V. A.; Kustova, E. V.

2018-05-01

In the present study, a theoretical model of state-resolved transport properties in electronically excited atomic species developed earlier is applied to argon and carbon atomic species. It is shown that for Ar and C, similarly to the case of atomic nitrogen and oxygen, the Slater-like models can be applied to calculate diameters of electronically excited atoms. Using the Slater-like model it is shown that for half-filled N (2 px1py1pz1) and full-filled Ar (3 px2py2pz2) electronic shells the growth of atomic radius goes slowly compared to C (2 px1py1) and O (2 px2py1pz1). The effect of collision diameters on the transport properties of Ar and C is evaluated. The influence of accounted number of electronic levels on the transport coefficients is examined for the case of Boltzmann distributions over electronic energy levels. It is emphasized that in the temperature range 1000-14000 K, for Boltzmann-like distributions over electronic states the number of accounted electronic levels do not influence the transport coefficients. Contrary to this, for higher temperatures T > 14000 K this effect becomes of importance, especially for argon.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tao, J.; Sun, K.; Yin, W. -G.

The ground-state electronic order in doped manganites is frequently associated with a lattice modulation, contributing to their many interesting properties. However, measuring the thermal evolution of the lattice superstructure with reciprocal-space probes alone can lead to ambiguous results with competing interpretations. Here, we provide direct observations of the evolution of the superstructure in La 1/3Ca 2/3MnO 3 in real space, as well as reciprocal space, using transmission electron microscopic (TEM) techniques. We show that the transitions are the consequence of a proliferation of dislocations plus electronic phase separation. The resulting states are well described by the symmetries associated with electronic-liquid-crystalmore » (ELC) phases. Furthermore, our results resolve the long-standing controversy over the origin of the incommensurate superstructure and suggest a new structural model that is consistent with recent theoretical calculations.« less

Electronic Transitions of Palladium Monoboride and Platinum Monoboride

NASA Astrophysics Data System (ADS)

Ng, Y. W.; Pang, H. F.; Wong, Y. S.; Qian, Yue; Cheung, A. S.-C.

2012-06-01

Electronic transition spectrum of palladium monoboride (PdB) and platinum (PtB) monoboride have been studied using the technique of laser-ablation/reaction free jet expansion and laser induced fluorescence spectroscopy. The metal monoborides were produced by reacting laser ablated metal atoms and diborane ((B_2H_6) seeded in argon. Five and six vibrational bands were observed respectively for the PdB and PtB molecules. Preliminary analysis of the rotationally resolved structure showed that both molecules have X2 Σ+ ground state. Least-squares fit of the measured line positions yielded molecular constants for the electronic states involved. Molecular and electronic structures of PdB and PtB are discussed using a molecular orbital energy level diagram. Financial support from the Research Grants Council of the Hong Kong Special Administrative Region, China (Project No. HKU 701008P) is gratefully acknowledged.

Reconstruction of Band Structure Induced by Electronic Nematicity in an FeSe Superconductor

NASA Astrophysics Data System (ADS)

Nakayama, K.; Miyata, Y.; Phan, G. N.; Sato, T.; Tanabe, Y.; Urata, T.; Tanigaki, K.; Takahashi, T.

2014-12-01

We have performed high-resolution angle-resolved photoemission spectroscopy on an FeSe superconductor (Tc˜8 K ), which exhibits a tetragonal-to-orthorhombic structural transition at Ts˜90 K . At low temperature, we found splitting of the energy bands as large as 50 meV at the M point in the Brillouin zone, likely caused by the formation of electronically driven nematic states. This band splitting persists up to T ˜110 K , slightly above Ts, suggesting that the structural transition is triggered by the electronic nematicity. We have also revealed that at low temperature the band splitting gives rise to a van Hove singularity within 5 meV of the Fermi energy. The present result strongly suggests that this unusual electronic state is responsible for the unconventional superconductivity in FeSe.

Electronic structure reconstruction across the antiferromagnetic transition in TaFe₁̣₂₃Te₃ spin ladder

DOE PAGES

Xu, Min; Wang, Li -Min; Peng, Rui; ...

2015-02-01

With angle-resolved photoemission spectroscopy, we studied the electronic structure of TaFe₁̣₂₃Te₃, a two-leg spin ladder compound with a novel antiferromagnetic ground state. Quasi-two-dimensional Fermi surface is observed, with sizable inter-ladder hopping. Moreover, instead of observing an energy gap at the Fermi surface in the antiferromagnetic state, we observed the shifts of various bands. Combining these observations with density-functional-theory calculations, we propose that the large scale reconstruction of the electronic structure, caused by the interactions between coexisting itinerant electrons and local moments, is most likely the driving force of the magnetic transition. Thus TaFe₁̣₂₃Te₃ serves as a simpler platform that containsmore » similar ingredients as the parent compounds of iron-based superconductors.« less

Spin-polarized surface resonances accompanying topological surface state formation

PubMed Central

Jozwiak, Chris; Sobota, Jonathan A.; Gotlieb, Kenneth; Kemper, Alexander F.; Rotundu, Costel R.; Birgeneau, Robert J.; Hussain, Zahid; Lee, Dung-Hai; Shen, Zhi-Xun; Lanzara, Alessandra

2016-01-01

Topological insulators host spin-polarized surface states born out of the energetic inversion of bulk bands driven by the spin-orbit interaction. Here we discover previously unidentified consequences of band-inversion on the surface electronic structure of the topological insulator Bi2Se3. By performing simultaneous spin, time, and angle-resolved photoemission spectroscopy, we map the spin-polarized unoccupied electronic structure and identify a surface resonance which is distinct from the topological surface state, yet shares a similar spin-orbital texture with opposite orientation. Its momentum dependence and spin texture imply an intimate connection with the topological surface state. Calculations show these two distinct states can emerge from trivial Rashba-like states that change topology through the spin-orbit-induced band inversion. This work thus provides a compelling view of the coevolution of surface states through a topological phase transition, enabled by the unique capability of directly measuring the spin-polarized unoccupied band structure. PMID:27739428

orbital selective correlation reduce in collapse tetragonal phase of CaFe2(As0.935P0.065)2 and electronic structure reconstruction studied by angel resolved photoemission spectroscopy

NASA Astrophysics Data System (ADS)

Zeng, Lingkun

We performed an angle-resolved photoemission spectroscopy (ARPES) study of the CaFe2(As0.935P0.065)2 in the collapse tetragonal(CT) phase and uncollapse tetragonal(UCT) phase. We find in the CT phase the electronic correlation dramatically reduces respective to UCT phase. Meanwhile, the reduction of correlation in CT phase show an orbital selective effect: correlation in dxy reduces the most, and then dxz/yz, while the one in dz2-r2 almost keeps the same. In CT phase, almost all bands sink downwards to higher binding energy, leading to the hole like bands around Brillouin zone(BZ) center sink below EF compared with UCT phase. However, the electron pocket around Brillouin Zone(BZ) corner(M) in UCT phase, forms a hole pocket around BZ center(Z point) in CT phase. Moreover, the dxy exhibits larger movement down to higher binding energy, resulting in farther away from dyz/xz and closer to dxy.We propose the electron filling ,namely high spin state in UCT phase to low spin state in CT phase(due to competing between crystal structure field and Hund's coupling), other than the Fermi surface nesting might be responsible for the absent of magnetic ordering.

Direct measurement of ferromagnetic ordering in biaxially strained LaCoO3 thin films

NASA Astrophysics Data System (ADS)

Klie, R. F.; Yuan, T.; Tanase, M.; Yang, G.; Ramasse, Q.

2010-02-01

LaCoO3 undergoes a transition from a nonmagnetic to a paramagnetic semiconductor at 80 K, associated with a spin-state transition of the Co3+ ions. It was proposed that the temperature of the spin-state transition depends strongly on the LaCoO3 lattice parameter, suggesting that strain can stabilize different spin states at different temperatures. By combining atomic-resolution Z-contrast imaging, electron diffraction, and angular-resolved electron energy-loss spectroscopy (EELS) with in situ cooling experiments, we show that epitaxially strained LaCoO3 (001) thin films grown on LaAlO3 (001) do not undergo a low temperature spin-state transition. Our EELS study explores the origins of the ferromagnetic ordering in strained LaCoO3 films.

Direct observation of self-energy signatures of the resonant collective mode in Bi 2 Sr 2 CaCu 2 O 8 + δ

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mou, Daixiang; Kaminski, Adam; Gu, Genda

Here, we use high-resolution angle-resolved photoemission spectroscopy to study the resonant, collective excitation mode in the superconducting state of Bi2212. By collecting very high-quality data we found noteworthy features in the self-energy in the antinodal region, where the interaction of electrons with the mode is the strongest. This interaction leads to a pronounced peak in the scattering rate and we demonstrate that this feature is directly responsible for the well-known peak-dip-hump structure in cuprates. By studying how the weight of this peak changes with temperature we unequivocally demonstrate that interaction of electrons with the resonant mode in cuprates vanishes atmore » T c and is very much localized in the momentum space close to the antinode. These findings present a consistent picture of line shape and self-energy signatures of the electron-boson coupling in cuprates and resolve long-standing controversy surrounding this issue. The momentum dependence of the strength of electron-mode interaction enables development of quantitative theory of this phenomenon in cuprates.« less

Direct observation of self-energy signatures of the resonant collective mode in Bi 2 Sr 2 CaCu 2 O 8 + δ

DOE PAGES

Mou, Daixiang; Kaminski, Adam; Gu, Genda

2017-05-01

Here, we use high-resolution angle-resolved photoemission spectroscopy to study the resonant, collective excitation mode in the superconducting state of Bi2212. By collecting very high-quality data we found noteworthy features in the self-energy in the antinodal region, where the interaction of electrons with the mode is the strongest. This interaction leads to a pronounced peak in the scattering rate and we demonstrate that this feature is directly responsible for the well-known peak-dip-hump structure in cuprates. By studying how the weight of this peak changes with temperature we unequivocally demonstrate that interaction of electrons with the resonant mode in cuprates vanishes atmore » T c and is very much localized in the momentum space close to the antinode. These findings present a consistent picture of line shape and self-energy signatures of the electron-boson coupling in cuprates and resolve long-standing controversy surrounding this issue. The momentum dependence of the strength of electron-mode interaction enables development of quantitative theory of this phenomenon in cuprates.« less

Real-time visualization of the vibrational wavepacket dynamics in electronically excited pyrimidine via femtosecond time-resolved photoelectron imaging

NASA Astrophysics Data System (ADS)

Li, Shuai; Long, Jinyou; Ling, Fengzi; Wang, Yanmei; Song, Xinli; Zhang, Song; Zhang, Bing

2017-07-01

The vibrational wavepacket dynamics at the very early stages of the S1-T1 intersystem crossing in photoexcited pyrimidine is visualized in real time by femtosecond time-resolved photoelectron imaging and time-resolved mass spectroscopy. A coherent superposition of the vibrational states is prepared by the femtosecond pump pulse at 315.3 nm, resulting in a vibrational wavepacket. The composition of the prepared wavepacket is directly identified by a sustained quantum beat superimposed on the parent-ion transient, possessing a frequency in accord with the energy separation between the 6a1 and 6b2 states. The dephasing time of the vibrational wavepacket is determined to be 82 ps. More importantly, the variable Franck-Condon factors between the wavepacket components and the dispersed cation vibrational levels are experimentally illustrated to identify the dark state and follow the energy-flow dynamics on the femtosecond time scale. The time-dependent intensities of the photoelectron peaks originated from the 6a1 vibrational state exhibit a clear quantum beating pattern with similar periodicity but a phase shift of π rad with respect to those from the 6b2 state, offering an unambiguous picture of the restricted intramolecular vibrational energy redistribution dynamics in the 6a1/6b2 Fermi resonance.

Rates and equilibrium constants of the ligand-induced conformational transition of an HCN ion channel protein domain determined by DEER spectroscopy.

PubMed

Collauto, Alberto; DeBerg, Hannah A; Kaufmann, Royi; Zagotta, William N; Stoll, Stefan; Goldfarb, Daniella

2017-06-14

Ligand binding can induce significant conformational changes in proteins. The mechanism of this process couples equilibria associated with the ligand binding event and the conformational change. Here we show that by combining the application of W-band double electron-electron resonance (DEER) spectroscopy with microfluidic rapid freeze quench (μRFQ) it is possible to resolve these processes and obtain both equilibrium constants and reaction rates. We studied the conformational transition of the nitroxide labeled, isolated carboxy-terminal cyclic-nucleotide binding domain (CNBD) of the HCN2 ion channel upon binding of the ligand 3',5'-cyclic adenosine monophosphate (cAMP). Using model-based global analysis, the time-resolved data of the μRFQ DEER experiments directly provide fractional populations of the open and closed conformations as a function of time. We modeled the ligand-induced conformational change in the protein using a four-state model: apo/open (AO), apo/closed (AC), bound/open (BO), bound/closed (BC). These species interconvert according to AC + L ⇌ AO + L ⇌ BO ⇌ BC. By analyzing the concentration dependence of the relative contributions of the closed and open conformations at equilibrium, we estimated the equilibrium constants for the two conformational equilibria and the open-state ligand dissociation constant. Analysis of the time-resolved μRFQ DEER data gave estimates for the intrinsic rates of ligand binding and unbinding as well as the rates of the conformational change. This demonstrates that DEER can quantitatively resolve both the thermodynamics and the kinetics of ligand binding and the associated conformational change.

The laser versus the lamp: Reactivity of the diphenyl ketyl radical in the ground and excited states

NASA Astrophysics Data System (ADS)

Baumann, H.; Merckel, C.; Timpe, H.-J.; Graness, A.; Kleinschmidt, J.; Gould, I. R.; Turro, N. J.

1984-01-01

The diphenyl ketyl radical which is formed upon photolysis of α-phenyl benzoin is produced in its excited state upon intense pulsed laser irradiation. Using the techniques of time-resolved absorption and emission spectroscopy, reaction rate constants for the ground and excited states of this radical were obtained. For the radical quenchers employed, the excited state reactivity is found to be typically several orders of magnitude greater than that of the ground state. It is concluded that the excited state of diphenyl ketyl radical reacts predominantly by electron transfer processes.

Electronic Interactions of Michler's Ketone with DNA Bases in Synthetic Hairpins.

PubMed

Jalilov, Almaz S; Young, Ryan M; Eaton, Samuel W; Wasielewski, Michael R; Lewis, Frederick D

2015-01-01

The mechanism and dynamics of photoinduced electron transfer in two families of DNA hairpins possessing Michler's ketone linkers have been investigated by means of steady state and time-resolved transient absorption and emission spectroscopies. The excited state behavior of the diol linker employed in hairpin synthesis is similar to that of Michler's ketone in methanol solution. Hairpins possessing only a Michler's ketone linker undergo fast singlet state charge separation and charge recombination with an adjacent purine base, attributed to well-stacked ground state conformations, and intersystem crossing to the triplet state, attributed to poorly stacked ground state conformations. The failure of the triplet to undergo electron transfer reactions on the 7 ns time scale of our measurements is attributed to the low triplet energy and reduction potential of the twisted triplet state. Hairpins possessing both a Michler's ketone linker and a perylenediimide base surrogate separated by four base pairs undergo photoinduced hole transport from the diimide to Michler's ketone upon excitation of the diimide. The efficiency of hole transport is dependent upon the sequence of the intervening purine bases. © 2014 The American Society of Photobiology.

Electronic transitions of tantalum monofluoride

NASA Astrophysics Data System (ADS)

Ng, K. F.; Zou, Wenli; Liu, Wenjian; Cheung, A. S.-C.

2017-03-01

The electronic transition spectrum of the tantalum monofluoride (TaF) molecule in the spectral region between 448 and 560 nm has been studied using the technique of laser-ablation/reaction free jet expansion and laser induced fluorescence spectroscopy. The TaF molecule was produced by reacting laser-ablated tantalum atoms with sulfur hexafluoride gas seeded in argon. Twenty-two vibrational bands with resolved rotational structure have been recorded and analyzed, which were organized into seven electronic transitions. The X3Σ-(0+) state has been identified to be the ground state and the determined equilibrium bond length, re, and vibrational frequency, ωe, are 1.8184 Å and 700.1 cm-1, respectively. The low-lying Λ-S states and Ω sub-states of TaF were also theoretically studied at the MRCISD+Q level of theory with spin-orbit coupling. The Ω = 0+ and 2 sub-states from the -3Σ and 3Φ state have been found to be the ground and the first excited states, respectively, which agrees well with our experimental determinations. This work represents the first experimental investigation of the molecular structure of the TaF molecule.

Time-resolved fluorescence spectroscopy for chemical sensors

NASA Astrophysics Data System (ADS)

Draxler, Sonja; Lippitsch, Max E.

1996-07-01

A family of sensors is presented with fluorescence decay-time measurements used as the sensing technique. The concept is to take a single fluorophore with a suitably long fluorescence decay time as the basic building block for numerous different sensors. Analyte recognition can be performed by different functional groups that are necessary for selective interaction with the analyte. To achieve this, the principle of excited-state electron transfer is applied with pyrene as the fluorophore. Therefore the same instrumentation based on a small, ambient air-nitrogen laser and solid-state electronics can be used to measure different analytes, for example, oxygen, pH, carbon dioxide, potassium, ammonium, lead, cadmium, zinc, and phosphate.

Light-matter interaction in doped microcavities

NASA Astrophysics Data System (ADS)

Averkiev, N. S.; Glazov, M. M.

2007-07-01

We discuss theoretically the light-matter coupling in a microcavity containing a quantum well with a two-dimensional electron gas. The high density limit where the bound exciton states are absent is considered. The matrix element of an interband optical absorption demonstrates the Mahan singularity [Phys. Rev. B153, 882 (1967); 163, 612 (1967)] due to strong Coulomb effect between the electrons and a photocreated hole. We extend the nonlocal dielectric response theory to calculate the quantum well reflection and transmission coefficients as well as the microcavity transmission spectra. The new eigenmodes of the system are discussed. Their implications for the steady state and time-resolved spectroscopy experiments are analyzed.

Unoccupied electronic structure of Ni 2MnGa ferromagnetic shape memory alloy

DOE PAGES

Maniraj, M.; D׳Souza, S. W.; Rai, Abhishek; ...

2015-08-20

Momentum resolved inverse photoemission spectroscopy measurements show that the dispersion of the unoccupied bands of Ni 2MnGa is significant in the austenite phase. Furthermore, in the martensite phase, it is markedly reduced, which is possibly related to the structural transition to an incommensurate modulated state in the martensite phase. Finally, based on the first principle calculations of the electronic structure of Ni–Mn–Ga, we show that the modification of the spectral shape with surface composition is related to change in the hybridization between the Mn 3d and Ni 3d-like states that dominate the unoccupied conduction band.

Unoccupied electronic structure of Ni2MnGa ferromagnetic shape memory alloy

NASA Astrophysics Data System (ADS)

Maniraj, M.; D`Souza, S. W.; Rai, Abhishek; Schlagel, D. L.; Lograsso, T. A.; Chakrabarti, Aparna; Barman, S. R.

2015-11-01

Momentum resolved inverse photoemission spectroscopy measurements show that the dispersion of the unoccupied bands of Ni2MnGa is significant in the austenite phase. In the martensite phase, it is markedly reduced, which is possibly related to the structural transition to an incommensurate modulated state in the martensite phase. Based on the first principle calculations of the electronic structure of Ni-Mn-Ga, we show that the modification of the spectral shape with surface composition is related to change in the hybridization between the Mn 3d and Ni 3d-like states that dominate the unoccupied conduction band.

Rabi oscillation and electron-spin-echo envelope modulation of the photoexcited triplet spin system in silicon

NASA Astrophysics Data System (ADS)

Akhtar, Waseem; Sekiguchi, Takeharu; Itahashi, Tatsumasa; Filidou, Vasileia; Morton, John J. L.; Vlasenko, Leonid; Itoh, Kohei M.

2012-09-01

We report on a pulsed electron paramagnetic resonance (EPR) study of the photoexcited triplet state (S=1) of oxygen-vacancy centers in silicon. Rabi oscillations between the triplet sublevels are observed using coherent manipulation with a resonant microwave pulse. The Hahn echo and stimulated echo decay profiles are superimposed with strong modulations known as electron-spin-echo envelope modulation (ESEEM). The ESEEM spectra reveal a weak but anisotropic hyperfine coupling between the triplet electron spin and a 29Si nuclear spin (I=1/2) residing at a nearby lattice site, that cannot be resolved in conventional field-swept EPR spectra.

Electron injection from graphene quantum dots to poly(amido amine) dendrimers

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lin, T. N.; Inciong, M. R.; Santiago, S. R.

2016-04-18

The steady-state and time-resolved photoluminescence (PL) are used to study the electron injection from graphene quantum dots (GQDs) to poly(amido amine) (PAMAM) dendrimers. The PL is enhanced by depositing GQDs on the surfaces of the PAMAM dendrimers. The maximum enhancement of PL with a factor of 10.9 is achieved at a GQD concentration of 0.9 mg/ml. The dynamics of PL in the GQD/PAMAM composite are analyzed, evidencing the existence of electron injection. On the basis of Kelvin probe measurements, the electron injection from the GQDs to the PAMAM dendrimers is accounted for by the work function difference between them.

Influence of electron correlation on the cross section and linear polarization of radiation emitted by electron-impact excitation of Ca+ and Ba+ ions

NASA Astrophysics Data System (ADS)

Chen, Zhan-Bin

2018-04-01

Calculations of the electron-impact excitation (EIE) of singly charged Ca+ and Ba+ ions and subsequent de-excitation process are performed using a fully relativistic distorted wave (RDW) method. To resolve the discrepancy between previous theory and experiment, careful consideration is given to the generation of the target state wave-functions through the systematic inclusion of electron correlations. It is found that the electron correlation effects play a significant role on the cross section, while the effects on the linear polarization of the emitted radiation are relatively small. Good agreement between our result and experiment is obtained.

Controlling the surface photovoltage on WSe2 by surface chemical modification

NASA Astrophysics Data System (ADS)

Liu, Ro-Ya; Ozawa, Kenichi; Terashima, Naoya; Natsui, Yuto; Feng, Baojie; Ito, Suguru; Chen, Wei-Chuan; Cheng, Cheng-Maw; Yamamoto, Susumu; Kato, Hiroo; Chiang, Tai-Chang; Matsuda, Iwao

2018-05-01

The surface photovoltage (SPV) effect is key to the development of opto-electronic devices such as solar-cells and photo-detectors. For the prototypical transition metal dichalcogenide WSe2, core level and valence band photoemission measurements show that the surface band bending of pristine cleaved surfaces can be readily modified by adsorption with K (an electron donor) or C60 (an electron acceptor). Time-resolved pump-probe photoemission measurements reveal that the SPV for pristine cleaved surfaces is enhanced by K adsorption, but suppressed by C60 adsorption, and yet the SPV relaxation time is substantially shortened in both cases. Evidently, adsorbate-induced electronic states act as electron-hole recombination centers that shorten the carrier lifetime.

Monitoring one-electron photo-oxidation of guanine in DNA crystals using ultrafast infrared spectroscopy

NASA Astrophysics Data System (ADS)

Hall, James P.; Poynton, Fergus E.; Keane, Páraic M.; Gurung, Sarah P.; Brazier, John A.; Cardin, David J.; Winter, Graeme; Gunnlaugsson, Thorfinnur; Sazanovich, Igor V.; Towrie, Michael; Cardin, Christine J.; Kelly, John M.; Quinn, Susan J.

2015-12-01

To understand the molecular origins of diseases caused by ultraviolet and visible light, and also to develop photodynamic therapy, it is important to resolve the mechanism of photoinduced DNA damage. Damage to DNA bound to a photosensitizer molecule frequently proceeds by one-electron photo-oxidation of guanine, but the precise dynamics of this process are sensitive to the location and the orientation of the photosensitizer, which are very difficult to define in solution. To overcome this, ultrafast time-resolved infrared (TRIR) spectroscopy was performed on photoexcited ruthenium polypyridyl-DNA crystals, the atomic structure of which was determined by X-ray crystallography. By combining the X-ray and TRIR data we are able to define both the geometry of the reaction site and the rates of individual steps in a reversible photoinduced electron-transfer process. This allows us to propose an individual guanine as the reaction site and, intriguingly, reveals that the dynamics in the crystal state are quite similar to those observed in the solvent medium.

Exploring the Electronic Structure and Chemical Homogeneity of Individual Bi2Te3 Nanowires by Nano-Angle-Resolved Photoemission Spectroscopy.

PubMed

Krieg, Janina; Chen, Chaoyu; Avila, José; Zhang, Zeying; Sigle, Wilfried; Zhang, Hongbin; Trautmann, Christina; Asensio, Maria Carmen; Toimil-Molares, Maria Eugenia

2016-07-13

Due to their high surface-to-volume ratio, cylindrical Bi2Te3 nanowires are employed as model systems to investigate the chemistry and the unique conductive surface states of topological insulator nanomaterials. We report on nanoangle-resolved photoemission spectroscopy (nano-ARPES) characterization of individual cylindrical Bi2Te3 nanowires with a diameter of 100 nm. The nanowires are synthesized by electrochemical deposition inside channels of ion-track etched polymer membranes. Core level spectra recorded with submicron resolution indicate a homogeneous chemical composition along individual nanowires, while nano-ARPES intensity maps reveal the valence band structure at the single nanowire level. First-principles electronic structure calculations for chosen crystallographic orientations are in good agreement with those revealed by nano-ARPES. The successful application of nano-ARPES on single one-dimensional nanostructures constitutes a new avenue to achieve a better understanding of the electronic structure of topological insulator nanomaterials.

Electron phonon couplings in 2D perovskite probed by ultrafast photoinduced absorption spectroscopy

NASA Astrophysics Data System (ADS)

Huynh, Uyen; Ni, Limeng; Rao, Akshay

We use the time-resolved photoinduced absorption (PIA) spectroscopy with 20fs time resolution to investigate the electron phonon coupling in the self-assembled hybrid organic layered perovskite, the hexyl ammonium lead iodide compound (C6H13NH3)2 (PbI4) . The coupling results in the broadening and asymmetry of its temperature-dependence photoluminescence spectra. The exact time scale of this coupling, however, wasn't reported experimentally. Here we show that using an ultrashort excitation pulse allows us to resolve from PIA kinetics the oscillation of coherent longitudinal optical phonons that relaxes and self-traps electrons to lower energy states within 200 fs. The 200fs relaxation time is equivalent to a coupling strength of 40meV. Two coupled phonon modes are also identified as about 100 cm-1 and 300 cm-1 from the FFT spectrum of the PIA kinetics. The lower energy mode is consistent with previous reports and Raman spectrum but the higher energy one hasn't been observed before.

Monitoring one-electron photo-oxidation of guanine in DNA crystals using ultrafast infrared spectroscopy.

PubMed

Hall, James P; Poynton, Fergus E; Keane, Páraic M; Gurung, Sarah P; Brazier, John A; Cardin, David J; Winter, Graeme; Gunnlaugsson, Thorfinnur; Sazanovich, Igor V; Towrie, Michael; Cardin, Christine J; Kelly, John M; Quinn, Susan J

2015-12-01

To understand the molecular origins of diseases caused by ultraviolet and visible light, and also to develop photodynamic therapy, it is important to resolve the mechanism of photoinduced DNA damage. Damage to DNA bound to a photosensitizer molecule frequently proceeds by one-electron photo-oxidation of guanine, but the precise dynamics of this process are sensitive to the location and the orientation of the photosensitizer, which are very difficult to define in solution. To overcome this, ultrafast time-resolved infrared (TRIR) spectroscopy was performed on photoexcited ruthenium polypyridyl-DNA crystals, the atomic structure of which was determined by X-ray crystallography. By combining the X-ray and TRIR data we are able to define both the geometry of the reaction site and the rates of individual steps in a reversible photoinduced electron-transfer process. This allows us to propose an individual guanine as the reaction site and, intriguingly, reveals that the dynamics in the crystal state are quite similar to those observed in the solvent medium.

Optical properties and electronic energy relaxation of metallic Au144(SR)60 nanoclusters.

PubMed

Yi, Chongyue; Tofanelli, Marcus A; Ackerson, Christopher J; Knappenberger, Kenneth L

2013-12-04

Electronic energy relaxation of Au144(SR)60(q) ligand-protected nanoclusters, where SR = SC6H13 and q = -1, 0, +1, and +2, was examined using femtosecond time-resolved transient absorption spectroscopy. The observed differential transient spectra contained three distinct components: (1) transient bleaches at 525 and 600 nm, (2) broad visible excited-state absorption (ESA), and (3) stimulated emission (SE) at 670 nm. The bleach recovery kinetics depended upon the excitation pulse energy and were thus attributed to electron-phonon coupling typical of metallic nanostructures. The prominent bleach at 525 nm was assigned to a core-localized plasmon resonance (CLPR). ESA decay kinetics were oxidation-state dependent and could be described using a metal-sphere charging model. The dynamics, emission energy, and intensity of the SE peak exhibited dielectric-dependent responses indicative of Superatom charge transfer states. On the basis of these data, the Au144(SR)60 system is the smallest-known nanocluster to exhibit quantifiable electron dynamics and optical properties characteristic of metals.

Spatially resolved NMR spectra for the Swiss cheese model in heavy fermion PuCoGa5 superconductor

NASA Astrophysics Data System (ADS)

Das, Tanmoy; Zhu, Jian-Xin; Balatsky, A. V.; Graf, M. J.

2011-03-01

Spatially resolved NMR experiments, which probe the local electronic excitations, play a vital role for studying the pairing symmetry of unconventional superconductors. Here we calculate the spatial modulation of the NMR spin-lattice relaxation rate (1/T1) for the Swiss cheese model as a function of impurity concentration in PuCoGa5 superconductor. The local suppression of the superconducting order parameter due to impurities is related to the number of holes in the Swiss cheese model. Our results indicate that Friedel-like oscillations,as seen in the local-density of states near an impurity, are also present in the behavior of 1/T1 as one moves away from the impurity site. We demonstrate that the gap nodes, which are filled by disorder, can be probed by NMR through the local information encoded in the spectra. The advantage of spatially resolved NMR compared to STM measurements is that the former probe is not sensitive to surface states. Work is supported by US DOE.

A single-atom quantum memory in silicon

DOE Office of Scientific and Technical Information (OSTI.GOV)

Freer, Solomon; Simmons, Stephanie; Laucht, Arne

Long coherence times and fast gate operations are desirable but often conflicting requirements for physical qubits. This conflict can be resolved by resorting to fast qubits for operations, and by storing their state in a ‘quantum memory’ while idle. The 31P donor in silicon comes naturally equipped with a fast qubit (the electron spin) and a long-lived qubit (the 31P nuclear spin), coexisting in a bound state at cryogenic temperatures. Here, we demonstrate storage and retrieval of quantum information from a single donor electron spin to its host phosphorus nucleus in isotopically-enriched 28Si. The fidelity of the memory process ismore » characterised via both state and process tomography. We report an overall process fidelity Fp ! 81%, a memory fidelity Fm ! 92%, and memory storage times up to 80 ms. These values are limited by a transient shift of the electron spin resonance frequency following highpower radiofrequency pulses.« less

A single-atom quantum memory in silicon

DOE PAGES

Freer, Solomon; Simmons, Stephanie; Laucht, Arne; ...

2017-03-20

Long coherence times and fast gate operations are desirable but often conflicting requirements for physical qubits. This conflict can be resolved by resorting to fast qubits for operations, and by storing their state in a ‘quantum memory’ while idle. The 31P donor in silicon comes naturally equipped with a fast qubit (the electron spin) and a long-lived qubit (the 31P nuclear spin), coexisting in a bound state at cryogenic temperatures. Here, we demonstrate storage and retrieval of quantum information from a single donor electron spin to its host phosphorus nucleus in isotopically-enriched 28Si. The fidelity of the memory process ismore » characterised via both state and process tomography. We report an overall process fidelity Fp ! 81%, a memory fidelity Fm ! 92%, and memory storage times up to 80 ms. These values are limited by a transient shift of the electron spin resonance frequency following highpower radiofrequency pulses.« less

Charge state distribution and emission characteristics in a table top reflex discharge - Effect of ion confinement and electrons accelerated across the sheath

DOE PAGES

Kumar, Deepak; Englesbe, Alexander; Parman, Matthew; ...

2015-11-05

Tabletop reflex discharges in a Penning geometry have many applications including ion sources and eXtreme Ultra-Violet (XUV) sources. The presence of primary electrons accelerated across the cathode sheaths is responsible for the distribution of ion charge states and of the unusually high XUV brightness of these plasmas. Absolutely calibrated space resolved XUV spectra from a table top reflex discharge operating with Al cathodes and Ne gas are presented. The spectra are analyzed with a new and complete model for ion charge distribution in similar reflex discharges. The plasma in the discharge was found to have a density of ~10 18mmore » –3 with a significant fraction >0.01 of fast primary electrons. As a result, the implications of the new model on the ion states achievable in a tabletop reflex plasma discharge are also discussed.« less

Photosynthesis. Electronic structure of the oxygen-evolving complex in photosystem II prior to O-O bond formation.

PubMed

Cox, Nicholas; Retegan, Marius; Neese, Frank; Pantazis, Dimitrios A; Boussac, Alain; Lubitz, Wolfgang

2014-08-15

The photosynthetic protein complex photosystem II oxidizes water to molecular oxygen at an embedded tetramanganese-calcium cluster. Resolving the geometric and electronic structure of this cluster in its highest metastable catalytic state (designated S3) is a prerequisite for understanding the mechanism of O-O bond formation. Here, multifrequency, multidimensional magnetic resonance spectroscopy reveals that all four manganese ions of the catalyst are structurally and electronically similar immediately before the final oxygen evolution step; they all exhibit a 4+ formal oxidation state and octahedral local geometry. Only one structural model derived from quantum chemical modeling is consistent with all magnetic resonance data; its formation requires the binding of an additional water molecule. O-O bond formation would then proceed by the coupling of two proximal manganese-bound oxygens in the transition state of the cofactor. Copyright © 2014, American Association for the Advancement of Science.

Re-Visiting the Electronic Energy Map of the Copper Dimer by Double-Resonant Four-Wave Mixing

NASA Astrophysics Data System (ADS)

Visser, Bradley; Bornhauser, Peter; Beck, Martin; Knopp, Gregor; Marquardt, Roberto; Gourlaouen, Christophe; van Bokhoven, Jeroen A.; Radi, Peter

2017-06-01

The copper dimer is one of the most studied transition metal (TM) diatomics due to its alkali-metal like electronic shell structure, strongly bound ground state and chemical reactivity. The high electronic promotion energy in the copper atom yields numerous low-lying electronic states compared to TM dimers with d)-hole electronic configurations. Thus, through extensive study the excited electronic structure of Cu_2 is relatively well known, however in practice few excited states have been investigated with rotational resolution or even assigned term symbols or dissociation limits. The spectroscopic methods that have been used to investigate the copper dimer until now have not possessed sufficient spectral selectivity, which has complicated the analysis of the often overlapping transitions. Resonant four-wave mixing is a non-linear absorption based spectroscopic method. In favorable cases, the two-color version (TC-RFWM) enables purely optical mass selective spectral measurements in a mixed molecular beam. Additionally, by labelling individual rotational levels in the common intermediate state the spectra are dramatically simplified. In this work, we report on the rotationally resolved characterization of low-lying electronic states of dicopper. Several term symbols have been assigned unambiguously. De-perturbation studies performed shed light on the complex electronic structure of the molecule. Furthermore, a new low-lying electronic state of Cu_2 is discovered and has important implications for the high-level theoretical structure calculations performed in parallel. In fact, the ab initio methods applied yield relative energies among the electronic levels that are almost quantitative and allow assignment of the newly observed state that is governed by spin-orbit interacting levels.

Laser angle-resolved photoemission as a probe of initial state k z dispersion, final-state band gaps, and spin texture of Dirac states in the Bi 2Te 3 topological insulator

DOE PAGES

Ärrälä, Minna; Hafiz, Hasnain; Mou, Daixiang; ...

2016-10-27

Here, we have obtained angle-resolved photoemission (ARPES) spectra from single crystals of the topological insulator material Bi 2Te 3 using tunable laser spectrometer. The spectra were collected for eleven different photon energies ranging from 5.57 to 6.70 eV for incident light polarized linearly along two different in-plane directions. Parallel first-principles, fully relativistic computations of photo-intensities were carried out using the experimental geometry within the framework of the one-step model of photoemission. Good overall accord between theory and experiment is used to gain insight into how properties of the initial and final state band structures as well as those of themore » topological surface states and their spin-textures are reflected in the laser-ARPES spectra. In conclusion, our analysis reveals that laser-ARPES is sensitive to both the initial state k z dispersion and the presence of delicate gaps in the final state electronic spectrum.« less

Dynamical photo-induced electronic properties of molecular junctions

NASA Astrophysics Data System (ADS)

Beltako, K.; Michelini, F.; Cavassilas, N.; Raymond, L.

2018-03-01

Nanoscale molecular-electronic devices and machines are emerging as promising functional elements, naturally flexible and efficient, for next-generation technologies. A deeper understanding of carrier dynamics in molecular junctions is expected to benefit many fields of nanoelectronics and power devices. We determine time-resolved charge current flowing at the donor-acceptor interface in molecular junctions connected to metallic electrodes by means of quantum transport simulations. The current is induced by the interaction of the donor with a Gaussian-shape femtosecond laser pulse. Effects of the molecular internal coupling, metal-molecule tunneling, and light-donor coupling on photocurrent are discussed. We then define the time-resolved local density of states which is proposed as an efficient tool to describe the absorbing molecule in contact with metallic electrodes. Non-equilibrium reorganization of hybridized molecular orbitals through the light-donor interaction gives rise to two phenomena: the dynamical Rabi shift and the appearance of Floquet-like states. Such insights into the dynamical photoelectronic structure of molecules are of strong interest for ultrafast spectroscopy and open avenues toward the possibility of analyzing and controlling the internal properties of quantum nanodevices with pump-push photocurrent spectroscopy.

Impact of metal ions in porphyrin-based applied materials for visible-light photocatalysis: key information from ultrafast electronic spectroscopy.

PubMed

Kar, Prasenjit; Sardar, Samim; Alarousu, Erkki; Sun, Jingya; Seddigi, Zaki S; Ahmed, Saleh A; Danish, Ekram Y; Mohammed, Omar F; Pal, Samir Kumar

2014-08-11

Protoporphyrin IX-zinc oxide (PP-ZnO) nanohybrids have been synthesized for applications in photocatalytic devices. High-resolution transmission electron microscopy (HRTEM), X-ray diffraction (XRD), and steady-state infrared, absorption, and emission spectroscopies have been used to analyze the structural details and optical properties of these nanohybrids. Time-resolved fluorescence and transient absorption techniques have been applied to study the ultrafast dynamic events that are key to photocatalytic activities. The photocatalytic efficiency under visible-light irradiation in the presence of naturally abundant iron(III) and copper(II) ions has been found to be significantly retarded in the former case, but enhanced in the latter case. More importantly, femtosecond (fs) transient absorption data have clearly demonstrated that the residence of photoexcited electrons from the sensitizer PP in the centrally located iron moiety hinders ground-state bleach recovery of the sensitizer, affecting the overall photocatalytic rate of the nanohybrid. The presence of copper(II) ions, on the other hand, offers additional stability against photobleaching and eventually enhances the efficiency of photocatalysis. In addition, we have also explored the role of UV light in the efficiency of photocatalysis and have rationalized our observations from femtosecond- to picosecond-resolved studies. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Element-resolved Kikuchi pattern measurements of non-centrosymmetric materials

DOE Office of Scientific and Technical Information (OSTI.GOV)

Vos, Maarten, E-mail: maarten.vos@anu.edu.au

2017-01-15

Angle-resolved electron Rutherford backscattering (ERBS) measurements using an electrostatic electron energy analyser can provide unique access to element-resolved crystallographic information. We present Kikuchi pattern measurements of the non-centrosymmetric crystal GaP, separately resolving the contributions of electrons backscattered from Ga and P. In comparison to element-integrated measurements like in the method of electron backscatter diffraction (EBSD), the effect of the absence of a proper 4-fold rotation axis in the point group of GaP can be sensed with a much higher visibility via the element-resolved Ga to P intensity ratio. These element-resolved measurements make it possible to experimentally attribute the previously observedmore » point-group dependent effect in element-integrated EBSD measurements to the larger contribution of electrons scattered from Ga compared to P. - Highlights: •Element specific Kikuchi patterns are presented for GaP. •Absence of a proper four-fold rotation axis is demonstrated. •Ga and P intensity variations after 90 degree rotation have opposite phase. •The asymmetry in the total intensity distribution resembles that of Ga.« less

Charge transfer excitons and image potential states on organic semiconductor surfaces

NASA Astrophysics Data System (ADS)

Yang, Qingxin; Muntwiler, Matthias; Zhu, X.-Y.

2009-09-01

We report two types of excited electronic states on organic semiconductor surfaces: image potential states (IPS) and charge transfer excitons (CTE). In the former, an excited electron is localized in the surface-normal direction by the image potential and delocalized in the surface plane. In the latter, the electron is localized in all directions by both the image potential and the Coulomb potential from a photogenerated hole on an organic molecule. We use crystalline pentacene and tetracene surfaces as model systems, and time- and angle-resolved two-photon photoemission spectroscopy to probe the energetics and dynamics of both the IPS and the CTE states. On either pentacene or tetracene surfaces, we observe delocalized image bands and a series of CT excitons with binding energies <0.5eV below the image-band minimum. The binding energies of these CT excitons agree well with solutions to the atomic-H-like Schrödinger equation based on the image potential and the electron-hole Coulomb potential. We hypothesize that the formation of CT excitons should be general to the surfaces of organic semiconductors where the relatively narrow valance-band width facilitates the localization of the hole and the low dielectric constant ensures strong electron-hole attraction.

Photodissociation spectroscopy of the dysprosium monochloride molecular ion

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dunning, Alexander, E-mail: alexander.dunning@gmail.com; Schowalter, Steven J.; Puri, Prateek

2015-09-28

We have performed a combined experimental and theoretical study of the photodissociation cross section of the molecular ion DyCl{sup +}. The photodissociation cross section for the photon energy range 35 500 cm{sup −1} to 47 500 cm{sup −1} is measured using an integrated ion trap and time-of-flight mass spectrometer; we observe a broad, asymmetric profile that is peaked near 43 000 cm{sup −1}. The theoretical cross section is determined from electronic potentials and transition dipole moments calculated using the relativistic configuration-interaction valence-bond and coupled-cluster methods. The electronic structure of DyCl{sup +} is extremely complex due to the presence of multiple open electronic shells,more » including the 4f{sup 10} configuration. The molecule has nine attractive potentials with ionically bonded electrons and 99 repulsive potentials dissociating to a ground state Dy{sup +} ion and Cl atom. We explain the lack of symmetry in the cross section as due to multiple contributions from one-electron-dominated transitions between the vibrational ground state and several resolved repulsive excited states.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sessler, J. L.; Sathiosatham, M.; Brown, C. T.

The synthesis of a new, noncovalent anthracene-dimethylaniline dyad (ensemble I) held together via guanosine-cytidine Watson-Crick base-pairing interactions is reported. Upon excitation at 420 nm, photoinduced electron-transfer from the dimethylaniline donor to the singlet excited state of the anthracene acceptor occurs, as inferred from a combination of time-resolved fluorescence quenching and transient absorption measurements. In toluene at room temperature, the rate constants for photoinduced intraensemble electron-transfer and subsequent back-electron-transfer (charge recombination) are k{sub CS} = (3.5 {+-} 0.03) x 10{sup 10} s{sup -1} and k{sub CR} = (1.42 {+-} 0.03) x 10{sup 9} s{sup -1}, respectively.

Anomalously large effects of pressure on electron transfer kinetics in solution: The aqueous manganate(VI)-permanganate(VII) system

NASA Astrophysics Data System (ADS)

Swaddle, T. W.; Spiccia, L.

1986-05-01

The classical Stranks-Hush-Marcus theory of pressure effects on the rates of outer-sphere electron transfer reaction rates in solution underestimates |ΔV ∗| specifically, for the MnO 4/MnO 42- (aq) exchange, ΔV ∗=-21.2 (observed) vs. -6.6 cm3mol-1 (calculated). This discrepancy can best be resolved by conceding that the Mn-Mn separation σ in the transition state is variable and pressure-sensitive in the context of non-adiabatic electron transfer within an ellipsoidal cavity with σ ∼ 550 pm.

Quantum theoretical study of electron solvation dynamics in ice layers on a Cu(111) surface.

PubMed

Andrianov, I; Klamroth, T; Saalfrank, P; Bovensiepen, U; Gahl, C; Wolf, M

2005-06-15

Recent experiments using time- and angle-resolved two-photon photoemission (2PPE) spectroscopy at metal/polar adsorbate interfaces succeeded in time-dependent analysis of the process of electron solvation. A fully quantum mechanical, two-dimensional simulation of this process, which explicitly includes laser excitation, is presented here, confirming the origin of characteristic features, such as the experimental observation of an apparently negative dispersion. The inference of the spatial extent of the localized electron states from the angular dependence of the 2PPE spectra has been found to be non-trivial and system-dependent.

Hydride ions in oxide hosts hidden by hydroxide ions

PubMed Central

Hayashi, Katsuro; Sushko, Peter V.; Hashimoto, Yasuhiro; Shluger, Alexander L.; Hosono, Hideo

2014-01-01

The true oxidation state of formally ‘H−’ ions incorporated in an oxide host is frequently discussed in connection with chemical shifts of 1H nuclear magnetic resonance spectroscopy, as they can exhibit values typically attributed to H+. Here we systematically investigate the link between geometrical structure and chemical shift of H− ions in an oxide host, mayenite, with a combination of experimental and ab initio approaches, in an attempt to resolve this issue. We demonstrate that the electron density near the hydrogen nucleus in an OH− ion (formally H+ state) exceeds that in an H− ion. This behaviour is the opposite to that expected from formal valences. We deduce a relationship between the chemical shift of H− and the distance from the H− ion to the coordinating electropositive cation. This relationship is pivotal for resolving H− species that are masked by various states of H+ ions. PMID:24662678

Photoinduced triplet-triplet energy transfer in a 2-ureido-4(1H)-pyrimidinone-bridged, quadruply hydrogen-bonded ferrocene-fullerene assembly.

PubMed

Feng, Ke; Yu, Mao-Lin; Wang, Su-Min; Wang, Ge-Xia; Tung, Chen-Ho; Wu, Li-Zhu

2013-01-14

2-Ureido-4(1H)-pyrimidinone-bridged ferrocene-fullerene assembly I is designed and synthesized for elaborating the photoinduced electron-transfer processes in self-complementary quadruply hydrogen-bonded modules. Unexpectedly, steady-state and time-resolved spectroscopy reveal an inefficient electron-transfer process from the ferrocene to the singlet or triplet excited state of the fullerene, although the electron-transfer reactions are thermodynamically feasible. Instead, an effective intra-assembly triplet-triplet energy-transfer process is found to be operative in assembly I with a rate constant of 9.2×10(5) s(-1) and an efficiency of 73% in CH(2)Cl(2) at room temperature. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Nonequilibrium electron and lattice dynamics of strongly correlated Bi 2Sr 2CaCu 2O 8+δ single crystals

DOE Office of Scientific and Technical Information (OSTI.GOV)

Konstantinova, Tatiana; Rameau, Jonathan D.; Reid, Alexander H.

Here, the interplay between the electronic and lattice degrees of freedom in nonequilibrium states of strongly correlated systems has been debated for decades. Although progress has been made in establishing a hierarchy of electronic interactions with the use of time-resolved techniques, the role of the phonons often remains in dispute, a situation highlighting the need for tools that directly probe the lattice. We present the first combined megaelectron volt ultrafast electron diffraction and time- and angle-resolved photoemission spectroscopy study of optimally doped Bi 2Sr 2CaCu 2O 8+δ. Quantitative analysis of the lattice and electron subsystems’ dynamics provides a unified picturemore » of nonequilibrium electron-phonon interactions in the cuprates beyond the N-temperature model. The work provides new insights on the specific phonon branches involved in the nonequilibrium heat dissipation from the high-energy Cu–O bond stretching “hot” phonons to the lowest-energy acoustic phonons with correlated atomic motion along the <110> crystal directions and their characteristic time scales. It reveals a highly nonthermal phonon population during the first several picoseconds after the photoexcitation. The approach, taking advantage of the distinct nature of electrons and photons as probes, is applicable for studying energy relaxation in other strongly correlated electron systems.« less

Nonequilibrium electron and lattice dynamics of strongly correlated Bi 2Sr 2CaCu 2O 8+δ single crystals

DOE PAGES

Konstantinova, Tatiana; Rameau, Jonathan D.; Reid, Alexander H.; ...

2018-04-27

Here, the interplay between the electronic and lattice degrees of freedom in nonequilibrium states of strongly correlated systems has been debated for decades. Although progress has been made in establishing a hierarchy of electronic interactions with the use of time-resolved techniques, the role of the phonons often remains in dispute, a situation highlighting the need for tools that directly probe the lattice. We present the first combined megaelectron volt ultrafast electron diffraction and time- and angle-resolved photoemission spectroscopy study of optimally doped Bi 2Sr 2CaCu 2O 8+δ. Quantitative analysis of the lattice and electron subsystems’ dynamics provides a unified picturemore » of nonequilibrium electron-phonon interactions in the cuprates beyond the N-temperature model. The work provides new insights on the specific phonon branches involved in the nonequilibrium heat dissipation from the high-energy Cu–O bond stretching “hot” phonons to the lowest-energy acoustic phonons with correlated atomic motion along the <110> crystal directions and their characteristic time scales. It reveals a highly nonthermal phonon population during the first several picoseconds after the photoexcitation. The approach, taking advantage of the distinct nature of electrons and photons as probes, is applicable for studying energy relaxation in other strongly correlated electron systems.« less

Serial time-resolved crystallography of photosystem II using a femtosecond X-ray laser

PubMed Central

Kupitz, Christopher; Basu, Shibom; Grotjohann, Ingo; Fromme, Raimund; Zatsepin, Nadia A.; Rendek, Kimberly N.; Hunter, Mark S.; Shoeman, Robert L.; White, Thomas A.; Wang, Dingjie; James, Daniel; Yang, Jay-How; Cobb, Danielle E.; Reeder, Brenda; Sierra, Raymond G.; Liu, Haiguang; Barty, Anton; Aquila, Andrew L.; Deponte, Daniel; Kirian, Richard A.; Bari, Sadia; Bergkamp, Jesse J.; Beyerlein, Kenneth R.; Bogan, Michael J.; Caleman, Carl; Chao, Tzu-Chiao; Conrad, Chelsie E.; Davis, Katherine M.; Fleckenstein, Holger; Galli, Lorenzo; Hau-Riege, Stefan P.; Kassemeyer, Stephan; Laksmono, Hartawan; Liang, Mengning; Lomb, Lukas; Marchesini, Stefano; Martin, Andrew V.; Messerschmidt, Marc; Milathianaki, Despina; Nass, Karol; Ros, Alexandra; Roy-Chowdhury, Shatabdi; Schmidt, Kevin; Seibert, Marvin; Steinbrener, Jan; Stellato, Francesco; Yan, Lifen; Yoon, Chunhong; Moore, Thomas A.; Moore, Ana L.; Pushkar, Yulia; Williams, Garth J.; Boutet, Sébastien; Doak, R. Bruce; Weierstall, Uwe; Frank, Matthias; Chapman, Henry N.; Spence, John C. H.; Fromme, Petra

2015-01-01

Photosynthesis, a process catalysed by plants, algae and cyanobacteria converts sunlight to energy thus sustaining all higher life on Earth. Two large membrane protein complexes, photosystem I and II (PSI and PSII), act in series to catalyse the light-driven reactions in photosynthesis. PSII catalyses the light-driven water splitting process, which maintains the Earth’s oxygenic atmosphere1. In this process, the oxygen-evolving complex (OEC) of PSII cycles through five states, S0 to S4, in which four electrons are sequentially extracted from the OEC in four light-driven charge-separation events. Here we describe time resolved experiments on PSII nano/microcrystals from Thermosynechococcus elongatus performed with the recently developed2 technique of serial femtosecond crystallography. Structures have been determined from PSII in the dark S1 state and after double laser excitation (putative S3 state) at 5 and 5.5 Å resolution, respectively. The results provide evidence that PSII undergoes significant conformational changes at the electron acceptor side and at the Mn4CaO5 core of the OEC. These include an elongation of the metal cluster, accompanied by changes in the protein environment, which could allow for binding of the second substrate water molecule between the more distant protruding Mn (referred to as the ‘dangler’ Mn) and the Mn3CaOx cubane in the S2 to S3 transition, as predicted by spectroscopic and computational studies3,4. This work shows the great potential for time-resolved serial femtosecond crystallography for investigation of catalytic processes in biomolecules. PMID:25043005

Topological surface state of α -Sn on InSb(001) as studied by photoemission

NASA Astrophysics Data System (ADS)

Scholz, M. R.; Rogalev, V. A.; Dudy, L.; Reis, F.; Adler, F.; Aulbach, J.; Collins-McIntyre, L. J.; Duffy, L. B.; Yang, H. F.; Chen, Y. L.; Hesjedal, T.; Liu, Z. K.; Hoesch, M.; Muff, S.; Dil, J. H.; Schäfer, J.; Claessen, R.

2018-02-01

We report on the electronic structure of the elemental topological semimetal α -Sn on InSb(001). High-resolution angle-resolved photoemission data allow us to observe the topological surface state (TSS) that is degenerate with the bulk band structure and show that the former is unaffected by different surface reconstructions. An unintentional p -type doping of the as-grown films was compensated by deposition of potassium or tellurium after the growth, thereby shifting the Dirac point of the surface state below the Fermi level. We show that, while having the potential to break time-reversal symmetry, iron impurities with a coverage of up to 0.25 monolayers do not have any further impact on the surface state beyond that of K or Te. Furthermore, we have measured the spin-momentum locking of electrons from the TSS by means of spin-resolved photoemission. Our results show that the spin vector lies fully in-plane, but it also has a finite radial component. Finally, we analyze the decay of photoholes introduced in the photoemission process, and by this gain insight into the many-body interactions in the system. Surprisingly, we extract quasiparticle lifetimes comparable to other topological materials where the TSS is located within a bulk band gap. We argue that the main decay of photoholes is caused by intraband scattering, while scattering into bulk states is suppressed due to different orbital symmetries of bulk and surface states.

Electron-Phonon Coupling and Resonant Relaxation from 1D and 1P States in PbS Quantum Dots.

PubMed

Kennehan, Eric R; Doucette, Grayson S; Marshall, Ashley R; Grieco, Christopher; Munson, Kyle T; Beard, Matthew C; Asbury, John B

2018-05-31

Observations of the hot-phonon bottleneck, which is predicted to slow the rate of hot carrier cooling in quantum confined nanocrystals, have been limited to date for reasons that are not fully understood. We used time-resolved infrared spectroscopy to directly measure higher energy intraband transitions in PbS colloidal quantum dots. Direct measurements of these intraband transitions permitted detailed analysis of the electronic overlap of the quantum confined states that may influence their relaxation processes. In smaller PbS nanocrystals, where the hot-phonon bottleneck is expected to be most pronounced, we found that relaxation of parity selection rules combined with stronger electron-phonon coupling led to greater spectral overlap of transitions among the quantum confined states. This created pathways for fast energy transfer and relaxation that may bypass the predicted hot-phonon bottleneck. In contrast, larger, but still quantum confined nanocrystals did not exhibit such relaxation of the parity selection rules and possessed narrower intraband states. These observations were consistent with slower relaxation dynamics that have been measured in larger quantum confined systems. These findings indicated that, at small radii, electron-phonon interactions overcome the advantageous increase in energetic separation of the electronic states for PbS quantum dots. Selection of appropriately sized quantum dots, which minimize spectral broadening due to electron-phonon interactions while maximizing electronic state separation, is necessary to observe the hot-phonon bottleneck. Such optimization may provide a framework for achieving efficient hot carrier collection and multiple exciton generation.

Unravelling the Electronic State of NO2 Product in Ultrafast Photodissociation of Nitromethane.

PubMed

Adachi, Shunsuke; Kohguchi, Hiroshi; Suzuki, Toshinori

2018-01-18

The primary photochemical reaction of nitromethane (NM) after ππ* excitation is known to be C-N bond cleavage (CH 3 NO 2 + hν → CH 3 + NO 2 ). On the other hand, NO 2 can be formed in both the ground and excited states, and identification of the electronic state of the NO 2 product has been a central subject in the experimental and theoretical studies. Here we present time-resolved photoelectron spectroscopy using vacuum-ultraviolet probe pulses to observe all transient electronic states of NM and the reaction products. The result indicates that ultrafast internal conversion occurs down to S 1 and S 0 within 24 fs, and the dissociation proceeds on the S 1 surface (τ diss ≲ 50 fs), leading to comparable product yields of NO 2 (A) and NO 2 (X). The overall dissociation quantum yield within our observation time window (<2 ps) is estimated to be 0.29.

Imaging electronic trap states in perovskite thin films with combined fluorescence and femtosecond transient absorption microscopy

DOE PAGES

Xiao, Kai; Ma, Ying -Zhong; Simpson, Mary Jane; ...

2016-04-22

Charge carrier trapping degrades the performance of organometallic halide perovskite solar cells. To characterize the locations of electronic trap states in a heterogeneous photoactive layer, a spatially resolved approach is essential. Here, we report a comparative study on methylammonium lead tri-iodide perovskite thin films subject to different thermal annealing times using a combined photoluminescence (PL) and femtosecond transient absorption microscopy (TAM) approach to spatially map trap states. This approach coregisters the initially populated electronic excited states with the regions that recombine radiatively. Although the TAM images are relatively homogeneous for both samples, the corresponding PL images are highly structured. Themore » remarkable variation in the PL intensities as compared to transient absorption signal amplitude suggests spatially dependent PL quantum efficiency, indicative of trapping events. Furthermore, detailed analysis enables identification of two trapping regimes: a densely packed trapping region and a sparse trapping area that appear as unique spatial features in scaled PL maps.« less

Ultrafast Gap Dynamics and Electronic Interactions in a Photoexcited Cuprate Superconductor

DOE PAGES

Parham, S.; Li, H.; Nummy, T. J.; ...

2017-10-20

We perform time- and angle-resolved photoemission spectroscopy (trARPES) on optimally doped Bi 2Sr 2CaCu 2O 8+δ (BSCCO-2212) using sufficient energy resolution (9 meV) to resolve the k-dependent near-nodal gap structure on time scales where the concept of an electronic pseudotemperature is a useful quantity, i.e., after electronic thermalization has occurred. We study the ultrafast evolution of this gap structure, uncovering a very rich landscape of decay rates as a function of angle, temperature, and energy. We explicitly focus on the quasiparticle states at the gap edge as well as on the spectral weight inside the gap that “fills” the gap—understoodmore » as an interaction, or self-energy effect—and we also make high resolution measurements of the nodal states, enabling a direct and accurate measurement of the electronic temperature (or pseudotemperature) of the electrons in the system. Rather than the standard method of interpreting these results using individual quasiparticle scattering rates that vary significantly as a function of angle, temperature, and energy, we show that the entire landscape of relaxations can be understood by modeling the system as following a nonequilibrium, electronic pseudotemperature that controls all electrons in the zone. Furthermore, this model has zero free parameters, as we obtain the crucial information of the SC gap Δ and the gap-filling strength Γ TDoS by connecting to static ARPES measurements. The quantitative and qualitative agreement between data and model suggests that the critical parameters and interactions of the system, including the pairing interactions, follow parametrically from the electronic pseudotemperature. In conclusion, we expect that this concept will be relevant for understanding the ultrafast response of a great variety of electronic materials, even though the electronic pseudotemperature may not be directly measurable.« less

Ultrafast Gap Dynamics and Electronic Interactions in a Photoexcited Cuprate Superconductor

DOE Office of Scientific and Technical Information (OSTI.GOV)

Parham, S.; Li, H.; Nummy, T. J.

We perform time- and angle-resolved photoemission spectroscopy (trARPES) on optimally doped Bi 2Sr 2CaCu 2O 8+δ (BSCCO-2212) using sufficient energy resolution (9 meV) to resolve the k-dependent near-nodal gap structure on time scales where the concept of an electronic pseudotemperature is a useful quantity, i.e., after electronic thermalization has occurred. We study the ultrafast evolution of this gap structure, uncovering a very rich landscape of decay rates as a function of angle, temperature, and energy. We explicitly focus on the quasiparticle states at the gap edge as well as on the spectral weight inside the gap that “fills” the gap—understoodmore » as an interaction, or self-energy effect—and we also make high resolution measurements of the nodal states, enabling a direct and accurate measurement of the electronic temperature (or pseudotemperature) of the electrons in the system. Rather than the standard method of interpreting these results using individual quasiparticle scattering rates that vary significantly as a function of angle, temperature, and energy, we show that the entire landscape of relaxations can be understood by modeling the system as following a nonequilibrium, electronic pseudotemperature that controls all electrons in the zone. Furthermore, this model has zero free parameters, as we obtain the crucial information of the SC gap Δ and the gap-filling strength Γ TDoS by connecting to static ARPES measurements. The quantitative and qualitative agreement between data and model suggests that the critical parameters and interactions of the system, including the pairing interactions, follow parametrically from the electronic pseudotemperature. In conclusion, we expect that this concept will be relevant for understanding the ultrafast response of a great variety of electronic materials, even though the electronic pseudotemperature may not be directly measurable.« less

Electronic cooling via interlayer Coulomb coupling in multilayer epitaxial graphene

PubMed Central

Mihnev, Momchil T.; Tolsma, John R.; Divin, Charles J.; Sun, Dong; Asgari, Reza; Polini, Marco; Berger, Claire; de Heer, Walt A.; MacDonald, Allan H.; Norris, Theodore B.

2015-01-01

In van der Waals bonded or rotationally disordered multilayer stacks of two-dimensional (2D) materials, the electronic states remain tightly confined within individual 2D layers. As a result, electron–phonon interactions occur primarily within layers and interlayer electrical conductivities are low. In addition, strong covalent in-plane intralayer bonding combined with weak van der Waals interlayer bonding results in weak phonon-mediated thermal coupling between the layers. We demonstrate here, however, that Coulomb interactions between electrons in different layers of multilayer epitaxial graphene provide an important mechanism for interlayer thermal transport, even though all electronic states are strongly confined within individual 2D layers. This effect is manifested in the relaxation dynamics of hot carriers in ultrafast time-resolved terahertz spectroscopy. We develop a theory of interlayer Coulomb coupling containing no free parameters that accounts for the experimentally observed trends in hot-carrier dynamics as temperature and the number of layers is varied. PMID:26399955

Core Perylene Diimide Designs via Direct Bay- and ortho-(Poly)trifluoromethylation: Synthesis, Isolation, X-Ray Structures, Optical and Electronic Properties

DOE Office of Scientific and Technical Information (OSTI.GOV)

Clikeman, Tyler T.; Bukovsky, Eric V.; Wang, Xue-Bin

2015-09-22

We developed an efficient solvent- and catalyst-free direct polytrifluoromethylation of solid perylene-3,4,9,10-tetracarboxylic dianhydride that produced a new family of (poly)perfluoroalkyl bay- and ortho-substituted PDIs with two different imide substituents. Direct hydrogen substitution with CN group led to the synthesis of a cyanated perfluoroalkyl PDI derivative for the first time. Absorption, steady-state and time-resolved emission, X-ray diffraction, electrochemical, and gas-phase electron affinity data allowed for systematic studies of substitution effects at bay, ortho, and imide positions in the new PDIs. Solid-state packing showed remarkable variations in the intermolecular interactions that are important for charge transport and photophysical properties. Moreover, analysis ofmore » the electrochemical data for 143 electron poor PDIs, including newly reported compounds, revealed some general trends and peculiar effects from substituting electron-withdrawing groups at all three positions.« less

Core Perylene Diimide Designs via Direct Bay and Ortho (Poly)trifluoromethylation: Synthesis, Isolation, X-ray Structures, Optical and Electronic Properties

DOE Office of Scientific and Technical Information (OSTI.GOV)

Clikeman, Tyler T.; Bukovsky, Eric V.; Wang, Xue B.

2015-09-22

We developed an efficient solvent- and catalyst-free direct polytrifluoromethylation of solid perylene-3,4,9,10-tetracarboxylic dianhydride that produced a new family of (poly)perfluoroalkyl bay and ortho substituted PDIs with two different imide substituents. Direct hydrogen substitution with CN group led to the synthesis of a cyanated perfluoroalkyl PDI derivative for the first time. Absorption, steady-state and time-resolved emission, X-ray diffraction, electrochemical, and gas-phase electron affinity data allowed for systematic studies of substitution effects at bay, ortho, and imide positions in the new PDIs. Solid-state packing showed remarkable variations in the intermolecular interactions that are important for charge transport and photophysical properties. Analysis ofmore » the electrochemical data for 143 electron poor PDIs, including newly reported compounds, revealed some general trends and peculiar effects of electron withdrawing group substitution at all three positions.« less

High-Field Asymmetric-Waveform Ion Mobility Spectrometry and Electron Detachment Dissociation of Isobaric Mixtures of Glycosaminoglycans

NASA Astrophysics Data System (ADS)

Kailemia, Muchena J.; Park, Melvin; Kaplan, Desmond A.; Venot, Andre; Boons, Geert-Jan; Li, Lingyun; Linhardt, Robert J.; Amster, I. Jonathan

2014-02-01

High-field asymmetric waveform ion mobility spectrometry (FAIMS) is shown to be capable of resolving isomeric and isobaric glycosaminoglycan negative ions and to have great utility for the analysis of this class of molecules when combined with Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS) and tandem mass spectrometry. Electron detachment dissociation (EDD) and other ion activation methods for tandem mass spectrometry can be used to determine the sites of labile sulfate modifications and for assigning the stereochemistry of hexuronic acid residues of glycosaminoglycans (GAGs). However, mixtures with overlapping mass-to-charge values present a challenge, as their precursor species cannot be resolved by a mass analyzer prior to ion activation. FAIMS is shown to resolve two types of mass-to-charge overlaps. A mixture of chondroitin sulfate A (CSA) oligomers with 4-10 saccharides units produces ions of a single mass-to-charge by electrospray ionization, as the charge state increases in direct proportion to the degree of polymerization for these sulfated carbohydrates. FAIMS is shown to resolve the overlapping charge. A more challenging type of mass-to-charge overlap occurs for mixtures of diastereomers. FAIMS is shown to separate two sets of epimeric GAG tetramers. For the epimer pairs, the complexity of the separation is reduced when the reducing end is alkylated, suggesting that anomers are also resolved by FAIMS. The resolved components were activated by EDD and the fragment ions were analyzed by FTICR-MS. The resulting tandem mass spectra were able to distinguish the two epimers from each other.

Femtosecond transient absorption spectroscopy of silanized silicon quantum dots

NASA Astrophysics Data System (ADS)

Kuntermann, Volker; Cimpean, Carla; Brehm, Georg; Sauer, Guido; Kryschi, Carola; Wiggers, Hartmut

2008-03-01

Excitonic properties of colloidal silicon quantum dots (Si qdots) with mean sizes of 4nm were examined using stationary and time-resolved optical spectroscopy. Chemically stable silicon oxide shells were prepared by controlled surface oxidation and silanization of HF-etched Si qdots. The ultrafast relaxation dynamics of photogenerated excitons in Si qdot colloids were studied on the picosecond time scale from 0.3psto2.3ns using femtosecond-resolved transient absorption spectroscopy. The time evolution of the transient absorption spectra of the Si qdots excited with a 150fs pump pulse at 390nm was observed to consist of decays of various absorption transitions of photoexcited electrons in the conduction band which overlap with both the photoluminescence and the photobleaching of the valence band population density. Gaussian deconvolution of the spectroscopic data allowed for disentangling various carrier relaxation processes involving electron-phonon and phonon-phonon scatterings or arising from surface-state trapping. The initial energy and momentum relaxation of hot carriers was observed to take place via scattering by optical phonons within 0.6ps . Exciton capturing by surface states forming shallow traps in the amorphous SiOx shell was found to occur with a time constant of 4ps , whereas deeper traps presumably localized in the Si-SiOx interface gave rise to exciton trapping processes with time constants of 110 and 180ps . Electron transfer from initially populated, higher-lying surface states to the conduction band of Si qdots (>2nm) was observed to take place within 400 or 700fs .

DOE Office of Scientific and Technical Information (OSTI.GOV)

Argondizzo, Adam; Cui, Xuefeng; Wang, Cong

We investigate the spectroscopy and photoinduced electron dynamics within the conduction band of reduced rutile TiO2(110) surface by multiphoton photoemission (mPP) spectroscopy with wavelength tunable ultrafast (!20 fs) laser pulse excitation. Tuning the mPP photon excitation energy between 2.9 and 4.6 eV reveals a nearly degenerate pair of new unoccupied states located at 2.73 ± 0.05 and 2.85 ± 0.05 eV above the Fermi level, which can be analyzed through the polarization and sample azimuthal orientation dependence of the mPP spectra. Based on the calculated electronic structure and optical transition moments, as well as related spectroscopic evidence, we assign thesemore » resonances to transitions between Ti 3d bands of nominally t2g and eg symmetry, which are split by crystal field. The initial states for the optical transition are the reduced Ti3+ states of t2g symmetry populated by formation oxygen vacancy defects, which exist within the band gap of TiO2. Furthermore,we studied the electron dynamics within the conduction band of TiO2 by three-dimensional time-resolved pump-probe interferometric mPP measurements. The spectroscopic and time-resolved studies reveal competition between 2PP and 3PP processes where the t2g-eg transitions in the 2PP process saturate, and are overtaken by the 3PP process initiated by the band-gap excitation from the valence band of TiO2.« less

Excited state non-adiabatic dynamics of the smallest polyene, trans 1,3-butadiene. I. Time-resolved photoelectron-photoion coincidence spectroscopy

NASA Astrophysics Data System (ADS)

Boguslavskiy, Andrey E.; Schalk, Oliver; Gador, Niklas; Glover, William J.; Mori, Toshifumi; Schultz, Thomas; Schuurman, Michael S.; Martínez, Todd J.; Stolow, Albert

2018-04-01

The ultrafast excited state dynamics of the smallest polyene, trans-1,3-butadiene, were studied by femtosecond time-resolved photoelectron-photoion coincidence (TRPEPICO) spectroscopy. The evolution of the excited state wavepacket, created by pumping the bright 1Bu (ππ*) electronic state at its origin of 216 nm, is projected via one- and two-photon ionization at 267 nm onto several ionization continua. The results are interpreted in terms of Koopmans' correlations and Franck-Condon factors for the excited and cationic states involved. The known predissociative character of the cation excited states is utilized to assign photoelectron bands to specific continua using TRPEPICO spectroscopy. This permits us to report the direct observation of the famously elusive S1(21Ag) dark electronic state during the internal conversion of trans 1,3-butadiene. Our phenomenological analysis permits the spectroscopic determination of several important time constants. We report the overall decay lifetimes of the 11Bu and 21Ag states and observe the re-appearance of the hot ground state molecule. We argue that the apparent dephasing time of the S2(11Bu) state, which leads to the extreme breadth of the absorption spectrum, is principally due to large amplitude torsional motion on the 1Bu surface in conjunction with strong non-adiabatic couplings via conical intersections, whereupon nuclear wavepacket revivals to the initial Franck-Condon region become effectively impossible. In Paper II [W. J. Glover et al., J. Chem. Phys. 148, 164303 (2018)], ab initio multiple spawning is used for on-the-fly computations of the excited state non-adiabatic wavepacket dynamics and their associated TRPEPICO observables, allowing for direct comparisons of experiment with theory.

Excited state non-adiabatic dynamics of the smallest polyene, trans 1,3-butadiene. I. Time-resolved photoelectron-photoion coincidence spectroscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Boguslavskiy, Andrey E.; Schalk, Oliver; Gador, Niklas

The ultrafast excited state dynamics of the smallest polyene, trans-1,3-butadiene, were studied by femtosecond time-resolved photoelectron-photoion coincidence (TRPEPICO) spectroscopy. The evolution of the excited state wavepacket, created by pumping the bright 1B u (ππ*) electronic state at its origin of 216 nm, is projected via one- and two-photon ionization at 267 nm onto several ionization continua. The results are interpreted in terms of Koopmans’ correlations and Franck-Condon factors for the excited and cationic states involved. The known predissociative character of the cation excited states is utilized to assign photoelectron bands to specific continua using TRPEPICO spectroscopy. This permits us tomore » report the direct observation of the famously elusive S 1(2 1A g) dark electronic state during the internal conversion of trans 1,3-butadiene. Our phenomenological analysis permits the spectroscopic determination of several important time constants. We report the overall decay lifetimes of the 1 1B u and 2 1A g states and observe the re-appearance of the hot ground state molecule. We argue that the apparent dephasing time of the S 2(1 1B u) state, which leads to the extreme breadth of the absorption spectrum, is principally due to large amplitude torsional motion on the 1B u surface in conjunction with strong non-adiabatic couplings via conical intersections, whereupon nuclear wavepacket revivals to the initial Franck-Condon region become effectively impossible. Lastly, in Paper II [W. J. Glover et al., J. Chem. Phys. 148, 164303 (2018)], ab initio multiple spawning is used for on-the-fly computations of the excited state non-adiabatic wavepacket dynamics and their associated TRPEPICO observables, allowing for direct comparisons of experiment with theory.« less

Excited state non-adiabatic dynamics of the smallest polyene, trans 1,3-butadiene. I. Time-resolved photoelectron-photoion coincidence spectroscopy

DOE PAGES

Boguslavskiy, Andrey E.; Schalk, Oliver; Gador, Niklas; ...

2018-04-27

The ultrafast excited state dynamics of the smallest polyene, trans-1,3-butadiene, were studied by femtosecond time-resolved photoelectron-photoion coincidence (TRPEPICO) spectroscopy. The evolution of the excited state wavepacket, created by pumping the bright 1B u (ππ*) electronic state at its origin of 216 nm, is projected via one- and two-photon ionization at 267 nm onto several ionization continua. The results are interpreted in terms of Koopmans’ correlations and Franck-Condon factors for the excited and cationic states involved. The known predissociative character of the cation excited states is utilized to assign photoelectron bands to specific continua using TRPEPICO spectroscopy. This permits us tomore » report the direct observation of the famously elusive S 1(2 1A g) dark electronic state during the internal conversion of trans 1,3-butadiene. Our phenomenological analysis permits the spectroscopic determination of several important time constants. We report the overall decay lifetimes of the 1 1B u and 2 1A g states and observe the re-appearance of the hot ground state molecule. We argue that the apparent dephasing time of the S 2(1 1B u) state, which leads to the extreme breadth of the absorption spectrum, is principally due to large amplitude torsional motion on the 1B u surface in conjunction with strong non-adiabatic couplings via conical intersections, whereupon nuclear wavepacket revivals to the initial Franck-Condon region become effectively impossible. Lastly, in Paper II [W. J. Glover et al., J. Chem. Phys. 148, 164303 (2018)], ab initio multiple spawning is used for on-the-fly computations of the excited state non-adiabatic wavepacket dynamics and their associated TRPEPICO observables, allowing for direct comparisons of experiment with theory.« less

Tracking the photodissociation dynamics of liquid nitromethane at 266 nm by femtosecond time-resolved broadband transient grating spectroscopy

NASA Astrophysics Data System (ADS)

Wu, Honglin; Song, Yunfei; Yu, Guoyang; Wang, Yang; Wang, Chang; Yang, Yanqiang

2016-05-01

Femtosecond time-resolved transient grating (TG) technique was employed to get insight into the photodissociation mechanism of liquid nitromethane (NM). Broadband white-light continuum was introduced as the probe to observe the evolution of electronic excited states of NM molecules and the formation of photodissociation products simultaneously. The reaction channel of liquid NM under 266 nm excitation was obtained that NM molecules in excited state S2 relax through two channels: about 73% relax to low lying S1 state through S2/S1 internal conversion with a time constant of 0.24 ps and then go back to the ground state through S1/S0 internal conversion; the other 27% will dissociate with a time constant of 2.56 ps. NO2 was found to be one of the products from the experimental TG spectra, which confirmed that C-N bond rupture was the primary dissociation channel of liquid NM.

DOE Office of Scientific and Technical Information (OSTI.GOV)

S. K. Kushwaha; Pletikosic, I.; Liang, T.

A long-standing issue in topological insulator research has been to find a bulk single crystal material that provides a high quality platform for characterizing topological surface states without interference from bulk electronic states. This material would ideally be a bulk insulator, have a surface state Dirac point energy well isolated from the bulk valence and conduction bands, display quantum oscillations from the surface state electrons, and be growable as large, high quality bulk single crystals. Here we show that this materials obstacle is overcome by bulk crystals of lightly Sn-doped Bi 1.1Sb 0.9Te 2S grown by the Vertical Bridgeman method.more » We characterize Sn-BSTS via angle-resolved photoemission spectroscopy, scanning tunneling microscopy, transport studies, X-ray diffraction, and Raman scattering. We present this material as a high quality topological insulator that can be reliably grown as bulk single crystals and thus studied by many researchers interested in topological surface states.« less

Monolithic Microfluidic Mixing-Spraying Devices for Time-Resolved Cryo-Electron Microscopy

PubMed Central

Lu, Zonghuan; Shaikh, Tanvir R.; Barnard, David; Meng, Xing; Mohamed, Hisham; Yassin, Aymen; Mannella, Carmen A.; Agrawal, Rajendra K.; Lu, Toh-Ming

2009-01-01

The goal of time-resolved cryo-electron microscopy is to determine structural models for transient functional states of large macromolecular complexes such as ribosomes and viruses. The challenge of time-resolved cryo-electron microscopy is to rapidly mix reactants, and then, following a defined time interval, to rapidly deposit them as a thin film and freeze the sample to the vitreous state. Here we describe a methodology in which reaction components are mixed and allowed to react, and are then sprayed onto an EM grid as it is being plunged into cryogen. All steps are accomplished by a monolithic, microfabricated silicon device that incorporates a mixer, reaction channel, and pneumatic sprayer in a single chip. We have found that microdroplets produced by air atomization spread to sufficiently thin films on a millisecond time scale provided that the carbon supporting film is made suitably hydrophilic. The device incorporates two T-mixers flowing into a single channel of four butterfly-shaped mixing elements that ensure effective mixing, followed by a microfluidic reaction channel whose length can be varied to achieve the desired reaction time. The reaction channel is flanked by two ports connected to compressed humidified nitrogen gas (at 50 psi) to generate the spray. The monolithic mixer-sprayer is incorporated into a computer-controlled plunging apparatus. To test the mixing performance and the suitability of the device for preparation of biological macromolecules for cryo-EM, ribosomes and ferritin were mixed in the device and sprayed onto grids. Three-dimensional reconstructions of the ribosomes demonstrated retention of native structure, and 30S and 50S subunits were shown to be capable of reassociation into ribosomes after passage through the device. PMID:19683579

Extreme ultraviolet probing of nonequilibrium dynamics in high energy density germanium

NASA Astrophysics Data System (ADS)

Principi, E.; Giangrisostomi, E.; Mincigrucci, R.; Beye, M.; Kurdi, G.; Cucini, R.; Gessini, A.; Bencivenga, F.; Masciovecchio, C.

2018-05-01

Intense femtosecond infrared laser pulses induce a nonequilibrium between thousands of Kelvin hot valence electrons and room-temperature ions in a germanium sample foil. The evolution of this exotic state of matter is monitored with time-resolved extreme ultraviolet absorption spectroscopy across the Ge M2 ,3 edge (≃30 eV ) using the FERMI free-electron laser. We analyze two distinct regimes in the ultrafast dynamics in laser-excited Ge: First, on a subpicosecond time scale, the electron energy distribution thermalizes to an extreme temperature unreachable in equilibrium solid germanium; then, during the following picoseconds, the lattice reacts strongly altering the electronic structure and resulting in melting to a metallic state alongside a breakdown of the local atomic order. Data analysis, based on a hybrid approach including both numerical and analytical calculations, provides an estimation of the electron and ion temperatures, the electron density of states, the carrier-phonon relaxation time, as well as the carrier density and lattice heat capacity under those extreme nonequilibrium conditions. Related structural anomalies, such as the occurrence of a transient low-density liquid phase and the possible drop in lattice heat capacity are discussed.

Massive Dirac fermions in a ferromagnetic kagome metal

NASA Astrophysics Data System (ADS)

Ye, Linda; Kang, Mingu; Liu, Junwei; von Cube, Felix; Wicker, Christina R.; Suzuki, Takehito; Jozwiak, Chris; Bostwick, Aaron; Rotenberg, Eli; Bell, David C.; Fu, Liang; Comin, Riccardo; Checkelsky, Joseph G.

2018-03-01

The kagome lattice is a two-dimensional network of corner-sharing triangles that is known to host exotic quantum magnetic states. Theoretical work has predicted that kagome lattices may also host Dirac electronic states that could lead to topological and Chern insulating phases, but these states have so far not been detected in experiments. Here we study the d-electron kagome metal Fe3Sn2, which is designed to support bulk massive Dirac fermions in the presence of ferromagnetic order. We observe a temperature-independent intrinsic anomalous Hall conductivity that persists above room temperature, which is suggestive of prominent Berry curvature from the time-reversal-symmetry-breaking electronic bands of the kagome plane. Using angle-resolved photoemission spectroscopy, we observe a pair of quasi-two-dimensional Dirac cones near the Fermi level with a mass gap of 30 millielectronvolts, which correspond to massive Dirac fermions that generate Berry-curvature-induced Hall conductivity. We show that this behaviour is a consequence of the underlying symmetry properties of the bilayer kagome lattice in the ferromagnetic state and the atomic spin–orbit coupling. This work provides evidence for a ferromagnetic kagome metal and an example of emergent topological electronic properties in a correlated electron system. Our results provide insight into the recent discoveries of exotic electronic behaviour in kagome-lattice antiferromagnets and may enable lattice-model realizations of fractional topological quantum states.

Gigantic 2D laser-induced photovoltaic effect in magnetically doped topological insulators for surface zero-bias spin-polarized current generation

NASA Astrophysics Data System (ADS)

Shikin, A. M.; Voroshin, V. Yu; Rybkin, A. G.; Kokh, K. A.; Tereshchenko, O. E.; Ishida, Y.; Kimura, A.

2018-01-01

A new kind of 2D photovoltaic effect (PVE) with the generation of anomalously large surface photovoltage up to 210 meV in magnetically doped topological insulators (TIs) has been studied by the laser time-resolved pump-probe angle-resolved photoelectron spectroscopy. The PVE has maximal efficiency for TIs with high occupation of the upper Dirac cone (DC) states and the Dirac point located inside the fundamental energy gap. For TIs with low occupation of the upper DC states and the Dirac point located inside the valence band the generated surface photovoltage is significantly reduced. We have shown that the observed giant PVE is related to the laser-generated electron-hole asymmetry followed by accumulation of the photoexcited electrons at the surface. It is accompanied by the 2D relaxation process with the generation of zero-bias spin-polarized currents flowing along the topological surface states (TSSs) outside the laser beam spot. As a result, the spin-polarized current generates an effective in-plane magnetic field that is experimentally confirmed by the k II-shift of the DC relative to the bottom non-spin-polarized conduction band states. The realized 2D PVE can be considered as a source for the generation of zero-bias surface spin-polarized currents and the laser-induced local surface magnetization developed in such kind 2D TSS materials.

Excitation wavelength dependence of excited state intramolecular proton transfer reaction of 4'-N,N-diethylamino-3-hydroxyflavone in room temperature ionic liquids studied by optical Kerr gate fluorescence measurement.

PubMed

Suda, Kayo; Terazima, Masahide; Sato, Hirofumi; Kimura, Yoshifumi

2013-10-17

Excited state intramolecular proton transfer reactions (ESIPT) of 4'-N,N-diethylamino-3-hydroxyflavone (DEAHF) in ionic liquids have been studied by steady-state and time-resolved fluorescence measurements at different excitation wavelengths. Steady-state measurements show the relative yield of the tautomeric form to the normal form of DEAHF decreases as excitation wavelength is increased from 380 to 450 nm. The decrease in yield is significant in ionic liquids that have cations with long alkyl chains. The extent of the decrease is correlated with the number of carbon atoms in the alkyl chains. Time-resolved fluorescence measurements using optical Kerr gate spectroscopy show that ESIPT rate has a strong excitation wavelength dependence. There is a large difference between the spectra at a 200 ps delay from different excitation wavelengths in each ionic liquid. The difference is pronounced in ionic liquids having a long alkyl chain. The equilibrium constant in the electronic excited state obtained at a 200 ps delay and the average reaction rate are also correlated with the alkyl chain length. Considering the results of the steady-state fluorescence and time-resolved measurements, the excitation wavelength dependence of ESIPT is explained by state selective excitation due to the difference of the solvation, and the number of alkyl chain carbon atoms is found to be a good indicator of the effect of inhomogeneity for this reaction.

Charge Separation and Triplet Exciton Formation Pathways in Small-Molecule Solar Cells as Studied by Time-Resolved EPR Spectroscopy

DOE PAGES

Thomson, Stuart A. J.; Niklas, Jens; Mardis, Kristy L.; ...

2017-09-13

Organic solar cells are a promising renewable energy technology, offering the advantages of mechanical flexibility and solution processability. An understanding of the electronic excited states and charge separation pathways in these systems is crucial if efficiencies are to be further improved. Here we use light induced electron paramagnetic resonance (LEPR) spectroscopy and density functional theory calculations (DFT) to study the electronic excited states, charge transfer (CT) dynamics and triplet exciton formation pathways in blends of the small molecule donors (DTS(FBTTh 2) 2, DTS(F2BTTh 2) 2, DTS(PTTh 2) 2, DTG(FBTTh 2) 2 and DTG(F2BTTh 2) 2) with the fullerene derivative PCmore » 61BM. Using high frequency EPR the g-tensor of the positive polaron on the donor molecules was determined. The experimental results are compared with DFT calculations which reveal that the spin density of the polaron is distributed over a dimer or trimer. Time-resolved EPR (TR-EPR) spectra attributed to singlet CT states were identified and the polarization patterns revealed similar charge separation dynamics in the four fluorobenzothiadiazole donors, while charge separation in the DTS(PTTh 2) 2 blend is slower. Using TR-EPR we also investigated the triplet exciton formation pathways in the blend. The polarization patterns reveal that the excitons originate from both intersystem crossing (ISC) and back electron transfer (BET) processes. The DTS(PTTh 2) 2 blend was found to contain substantially more triplet excitons formed by BET than the fluorobenzothiadiazole blends. As a result, the higher BET triplet exciton population in the DTS(PTTh 2) 2 blend is in accordance with the slower charge separation dynamics observed in this blend.« less

Charge Separation and Triplet Exciton Formation Pathways in Small Molecule Solar Cells as Studied by Time-resolved EPR Spectroscopy.

PubMed

Thomson, Stuart A J; Niklas, Jens; Mardis, Kristy L; Mallares, Christopher; Samuel, Ifor D W; Poluektov, Oleg G

2017-10-19

Organic solar cells are a promising renewable energy technology, offering the advantages of mechanical flexibility and solution processability. An understanding of the electronic excited states and charge separation pathways in these systems is crucial if efficiencies are to be further improved. Here we use light induced electron paramagnetic resonance (LEPR) spectroscopy and density functional theory calculations (DFT) to study the electronic excited states, charge transfer (CT) dynamics and triplet exciton formation pathways in blends of the small molecule donors (DTS(FBTTh 2 ) 2 , DTS(F 2 BTTh 2 ) 2 , DTS(PTTh 2 ) 2 , DTG(FBTTh 2 ) 2 and DTG(F 2 BTTh 2 ) 2 ) with the fullerene derivative PC 61 BM. Using high frequency EPR the g-tensor of the positive polaron on the donor molecules was determined. The experimental results are compared with DFT calculations which reveal that the spin density of the polaron is distributed over a dimer or trimer. Time-resolved EPR (TR-EPR) spectra attributed to singlet CT states were identified and the polarization patterns revealed similar charge separation dynamics in the four fluorobenzothiadiazole donors, while charge separation in the DTS(PTTh 2 ) 2 blend is slower. Using TR-EPR we also investigated the triplet exciton formation pathways in the blend. The polarization patterns reveal that the excitons originate from both intersystem crossing (ISC) and back electron transfer (BET) processes. The DTS(PTTh 2 ) 2 blend was found to contain substantially more triplet excitons formed by BET than the fluorobenzothiadiazole blends. The higher BET triplet exciton population in the DTS(PTTh 2 ) 2 blend is in accordance with the slower charge separation dynamics observed in this blend.

Charge Separation and Triplet Exciton Formation Pathways in Small-Molecule Solar Cells as Studied by Time-Resolved EPR Spectroscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Thomson, Stuart A. J.; Niklas, Jens; Mardis, Kristy L.

Organic solar cells are a promising renewable energy technology, offering the advantages of mechanical flexibility and solution processability. An understanding of the electronic excited states and charge separation pathways in these systems is crucial if efficiencies are to be further improved. Here we use light induced electron paramagnetic resonance (LEPR) spectroscopy and density functional theory calculations (DFT) to study the electronic excited states, charge transfer (CT) dynamics and triplet exciton formation pathways in blends of the small molecule donors (DTS(FBTTh 2) 2, DTS(F2BTTh 2) 2, DTS(PTTh 2) 2, DTG(FBTTh 2) 2 and DTG(F2BTTh 2) 2) with the fullerene derivative PCmore » 61BM. Using high frequency EPR the g-tensor of the positive polaron on the donor molecules was determined. The experimental results are compared with DFT calculations which reveal that the spin density of the polaron is distributed over a dimer or trimer. Time-resolved EPR (TR-EPR) spectra attributed to singlet CT states were identified and the polarization patterns revealed similar charge separation dynamics in the four fluorobenzothiadiazole donors, while charge separation in the DTS(PTTh 2) 2 blend is slower. Using TR-EPR we also investigated the triplet exciton formation pathways in the blend. The polarization patterns reveal that the excitons originate from both intersystem crossing (ISC) and back electron transfer (BET) processes. The DTS(PTTh 2) 2 blend was found to contain substantially more triplet excitons formed by BET than the fluorobenzothiadiazole blends. As a result, the higher BET triplet exciton population in the DTS(PTTh 2) 2 blend is in accordance with the slower charge separation dynamics observed in this blend.« less

Mechanisms of transport and electron transfer at conductive polymer/liquid interfaces

NASA Astrophysics Data System (ADS)

Ratcliff, Erin

Organic semiconductors (OSCs) have incredible prospects for next-generation, flexible electronic devices including bioelectronics, thermoelectrics, opto-electronics, and energy storage and conversion devices. Yet many fundamental challenges still exist. First, solution processing prohibits definitive control over microstructure, which is fundamental for controlling electrical, ionic, and thermal transport properties. Second, OSCs generally suffer from poor electrical conductivities due to a combination of low carriers and low mobility. Third, polymeric semiconductors have potential-dependent, dynamically evolving electronic and chemical states, leading to complex interfacial charge transfer properties in contact with liquids. This talk will focus on the use of alternative synthetic strategies of oxidative chemical vapor deposition and electrochemical deposition to control physical, electronic, and chemical structure. We couple our synthetic efforts with energy-, time-, and spatially resolved spectroelectrochemical and microscopy techniques to understand the critical interfacial chemistry-microstructure-property relationships: first at the macroscale, and then moving towards the nanoscale. In particular, approaches to better understand electron transfer events at polymer/liquid interfaces as a function of: 1.) chemical composition; 2.) electronic density of states (DOS); and 3.) crystallinity and microstructure will be discussed.

Atomically precise lateral modulation of a two-dimensional electron liquid in anatase TiO 2 thin films

DOE PAGES

Wang, Zhiming; Zhong, Z.; Walker, S. McKeown; ...

2017-03-10

Engineering the electronic band structure of two-dimensional electron liquids (2DELs) confined at the surface or interface of transition metal oxides is key to unlocking their full potential. Here we describe a new approach to tailoring the electronic structure of an oxide surface 2DEL demonstrating the lateral modulation of electronic states with atomic scale precision on an unprecedented length scale comparable to the Fermi wavelength. To this end, we use pulsed laser deposition to grow anatase TiO 2 films terminated by a (1 x 4) in-plane surface reconstruction. Employing photo-stimulated chemical surface doping we induce 2DELs with tunable carrier densities thatmore » are confined within a few TiO 2 layers below the surface. Subsequent in situ angle resolved photoemission experiments demonstrate that the (1 x 4) surface reconstruction provides a periodic lateral perturbation of the electron liquid. Furthermore, this causes strong backfolding of the electronic bands, opening of unidirectional gaps and a saddle point singularity in the density of states near the chemical potential.« less

Quasiparticles and charge transfer at the two surfaces of the honeycomb iridate Na2IrO3

NASA Astrophysics Data System (ADS)

Moreschini, L.; Lo Vecchio, I.; Breznay, N. P.; Moser, S.; Ulstrup, S.; Koch, R.; Wirjo, J.; Jozwiak, C.; Kim, K. S.; Rotenberg, E.; Bostwick, A.; Analytis, J. G.; Lanzara, A.

2017-10-01

Direct experimental investigations of the low-energy electronic structure of the Na2IrO3 iridate insulator are sparse and draw two conflicting pictures. One relies on flat bands and a clear gap, the other involves dispersive states approaching the Fermi level, pointing to surface metallicity. Here, by a combination of angle-resolved photoemission, photoemission electron microscopy, and x-ray absorption, we show that the correct picture is more complex and involves an anomalous band, arising from charge transfer from Na atoms to Ir-derived states. Bulk quasiparticles do exist, but in one of the two possible surface terminations the charge transfer is smaller and they remain elusive.

Interaction of proflavin with aromatic amines in homogeneous and micellar media: Photoinduced electron transfer probed by magnetic field effect

NASA Astrophysics Data System (ADS)

Chakraborty, Brotati; Basu, Samita

2010-02-01

Photoinduced electron transfer (PET) between proflavin (PF +) and two aromatic amines viz., dimethylaniline (DMA) and 4,4'-bis(dimethylamino)diphenylmethane (DMDPM) is studied in homogeneous and heterogeneous media using steady-state as well as time-resolved fluorescence spectroscopy and laser flash photolysis with an associated magnetic field. Ionic micelles have been used to study the effect of charge of proflavin on PET with amines. Magnetic field effect on PET reactions reveals that the parent spin-state of precursors of PET for DMA-PF + system is singlet while for DMDPM-PF + system is triplet, implying that the dynamics of PET is influenced by the structure of the donor.

Momentum space view of the ultrafast dynamics of surface photocurrents on topological insulators

NASA Astrophysics Data System (ADS)

Kuroda, K.; Reimann, J.; Güdde, J.; Höfer, U.

2017-02-01

The Dirac-cone surface states of topological insulators are characterized by a chiral spin texture in k-space with the electron spin locked to its parallel momentum. Mid-infrared pump pulses can induce spin-polarized photocurrents in such a topological surface state by optical transitions between the occupied and unoccupied part of the Dirac cone. We monitor the ultrafast dynamics of the corresponding asymmetric electron population in momentum space directly by time- and angle-resolved two-photon photoemission (2PPE). The elastic scattering times of 2.5 ps deduced for Sb2Te3 corresponds to a mean-fee path of 0.75 μm in real space.

PAINeT: An object-oriented software package for simulations of flow-field, transport coefficients and flux terms in non-equilibrium gas mixture flows

NASA Astrophysics Data System (ADS)

Istomin, V. A.

2018-05-01

The software package Planet Atmosphere Investigator of Non-equilibrium Thermodynamics (PAINeT) has been devel-oped for studying the non-equilibrium effects associated with electronic excitation, chemical reactions and ionization. These studies are necessary for modeling process in shock tubes, in high enthalpy flows, in nozzles or jet engines, in combustion and explosion processes, in modern plasma-chemical and laser technologies. The advantages and possibilities of the package implementation are stated. Within the framework of the package implementation, based on kinetic theory approximations (one-temperature and state-to-state approaches), calculations are carried out, and the limits of applicability of a simplified description of shock-heated air flows and any other mixtures chosen by the user are given. Using kinetic theory algorithms, a numerical calculation of the heat fluxes and relaxation terms can be performed, which is necessary for further comparison of engineering simulation with experi-mental data. The influence of state-to-state distributions over electronic energy levels on the coefficients of thermal conductivity, diffusion, heat fluxes and diffusion velocities of the components of various gas mixtures behind shock waves is studied. Using the software package the accuracy of different approximations of the kinetic theory of gases is estimated. As an example state-resolved atomic ionized mixture of N/N+/O/O+/e- is considered. It is shown that state-resolved diffusion coefficients of neutral and ionized species vary from level to level. Comparing results of engineering applications with those given by PAINeT, recommendations for adequate models selection are proposed.

Detection of pulsed neutrons with solid-state electronics

NASA Astrophysics Data System (ADS)

Chatzakis, J.; Rigakis, I.; Hassan, S. M.; Clark, E. L.; Lee, P.

2016-09-01

Measurements of the spatial and time-resolved characteristics of pulsed neutron sources require large area detection materials and fast circuitry that can process the electronic pulses readout from the active region of the detector. In this paper, we present a solid-state detector based on the nuclear activation of materials by neutrons, and the detection of the secondary particle emission of the generated radionuclides’ decay. The detector utilizes a microcontroller that communicates using a modified SPI protocol. A solid-state, pulse shaping filter follows a charge amplifier, and it is designed as an inexpensive, low-noise solution for measuring pulses measured by a digital counter. An imaging detector can also be made by using an array of these detectors. The system can communicate with an interface unit and pass an image to a personal computer.

Measurement Of Molecular Mobilities Of Polymers

NASA Technical Reports Server (NTRS)

Kim, Soon Sam; Tsay, Fun-Dow

1989-01-01

New molecular-probe technique used to measure molecular mobility of polymer. Method based on use of time-resolved electron-spin resonance (ESR) spectroscopy to monitor decay of transient nutation amplitudes from photoexcited triplet states of probe molecules with which polymer is doped. The higher molecular mobility of polymer matrix, the faster nutation amplitudes of the probe molecules decay.

Surface electronic states of low-temperature H-plasma-exposed Ge(100)

NASA Astrophysics Data System (ADS)

Cho, Jaewon; Nemanich, R. J.

1992-11-01

The surface of low-temperature H-plasma-cleaned Ge(100) was studied by angle-resolved UV-photoemission spectroscopy and low-energy electron diffraction (LEED). The surface was prepared by an ex situ preclean followed by an in situ H-plasma exposure at a substrate temperature of 150-300 °C. Auger-electron spectroscopy indicated that the in situ H-plasma clean removed the surface contaminants (carbon and oxygen) from the Ge(100) surface. The LEED pattern varied from a 1×1 to a sharp 2×1, as the substrate temperature was increased. The H-induced surface state was identified at ~5.6 eV below EF, which was believed to be mainly due to the ordered or disordered monohydride phases. The annealing dependence of the spectra showed that the hydride started to dissociate at a temperature of 190 °C, and the dangling-bond surface state was identified. A spectral shift upon annealing indicated that the H-terminated surfaces were unpinned. After the H-plasma clean at 300 °C the dangling-bond surface state was also observed directly with no evidence of H-induced states.

Role of Emission Character in Auger Electron Diffraction

NASA Astrophysics Data System (ADS)

Idzerda, Y. U.

A review of the interpretation of the angle-dependent Auger intensity pattern by both Auger electron diffraction (AED), which is concerned with identifying the nearby atomic structure, and angle-resolved Auger electron spectroscopy (ARAES), which is concerned with identifying the character of the emitted electron source function, is presented. The importance of the emission character of the Auger electron (in terms of its angular momentum, l, and its magnetic quantum number, m) in understanding the generation of the AED and ARAES patterns is described. Understanding of how the various direct and secondary mechanisms for the Auger electron generation can affect the populations of these states can also be used to help identify the multiplet structure within the Auger lineshape as well as elucidate the core hole generation process.

Room-temperature ultrafast nonlinear spectroscopy of a single molecule

NASA Astrophysics Data System (ADS)

Liebel, Matz; Toninelli, Costanza; van Hulst, Niek F.

2018-01-01

Single-molecule spectroscopy aims to unveil often hidden but potentially very important contributions of single entities to a system's ensemble response. Albeit contributing tremendously to our ever growing understanding of molecular processes, the fundamental question of temporal evolution, or change, has thus far been inaccessible, thus painting a static picture of a dynamic world. Here, we finally resolve this dilemma by performing ultrafast time-resolved transient spectroscopy on a single molecule. By tracing the femtosecond evolution of excited electronic state spectra of single molecules over hundreds of nanometres of bandwidth at room temperature, we reveal their nonlinear ultrafast response in an effective three-pulse scheme with fluorescence detection. A first excitation pulse is followed by a phase-locked de-excitation pulse pair, providing spectral encoding with 25 fs temporal resolution. This experimental realization of true single-molecule transient spectroscopy demonstrates that two-dimensional electronic spectroscopy of single molecules is experimentally within reach.

Effects of strain on the electronic structure, superconductivity, and nematicity in FeSe studied by angle-resolved photoemission spectroscopy

NASA Astrophysics Data System (ADS)

Phan, G. N.; Nakayama, K.; Sugawara, K.; Sato, T.; Urata, T.; Tanabe, Y.; Tanigaki, K.; Nabeshima, F.; Imai, Y.; Maeda, A.; Takahashi, T.

2017-06-01

One of central issues in iron-based superconductors is the role of structural change to the superconducting transition temperature (Tc). It was found in FeSe that the lattice strain leads to a drastic increase in Tc, accompanied by suppression of nematic order. By angle-resolved photoemission spectroscopy on tensile- or compressive-strained and strain-free FeSe, we experimentally show that the in-plane strain causes a marked change in the energy overlap (Δ Eh -e ) between the hole and electron pockets in the normal state. The change in Δ Eh -e modifies the Fermi-surface volume, leading to a change in Tc. Furthermore, the strength of nematicity is also found to be characterized by Δ Eh -e . These results suggest that the key to understanding the phase diagram is the fermiology and interactions linked to the semimetallic band overlap.

Exploring size and state dynamics in CdSe quantum dots using two-dimensional electronic spectroscopy

PubMed Central

Caram, Justin R.; Zheng, Haibin; Dahlberg, Peter D.; Rolczynski, Brian S.; Griffin, Graham B.; Dolzhnikov, Dmitriy S.; Talapin, Dmitri V.; Engel, Gregory S.

2014-01-01

Development of optoelectronic technologies based on quantum dots depends on measuring, optimizing, and ultimately predicting charge carrier dynamics in the nanocrystal. In such systems, size inhomogeneity and the photoexcited population distribution among various excitonic states have distinct effects on electron and hole relaxation, which are difficult to distinguish spectroscopically. Two-dimensional electronic spectroscopy can help to untangle these effects by resolving excitation energy and subsequent nonlinear response in a single experiment. Using a filament-generated continuum as a pump and probe source, we collect two-dimensional spectra with sufficient spectral bandwidth to follow dynamics upon excitation of the lowest three optical transitions in a polydisperse ensemble of colloidal CdSe quantum dots. We first compare to prior transient absorption studies to confirm excitation-state-dependent dynamics such as increased surface-trapping upon excitation of hot electrons. Second, we demonstrate fast band-edge electron-hole pair solvation by ligand and phonon modes, as the ensemble relaxes to the photoluminescent state on a sub-picosecond time-scale. Third, we find that static disorder due to size polydispersity dominates the nonlinear response upon excitation into the hot electron manifold; this broadening mechanism stands in contrast to that of the band-edge exciton. Finally, we demonstrate excitation-energy dependent hot-carrier relaxation rates, and we describe how two-dimensional electronic spectroscopy can complement other transient nonlinear techniques. PMID:24588185

Detailed Characterization of a Nanosecond-Lived Excited State: X-ray and Theoretical Investigation of the Quintet State in Photoexcited [Fe(terpy)2]2+

PubMed Central

2015-01-01

Theoretical predictions show that depending on the populations of the Fe 3dxy, 3dxz, and 3dyz orbitals two possible quintet states can exist for the high-spin state of the photoswitchable model system [Fe(terpy)2]2+. The differences in the structure and molecular properties of these 5B2 and 5E quintets are very small and pose a substantial challenge for experiments to resolve them. Yet for a better understanding of the physics of this system, which can lead to the design of novel molecules with enhanced photoswitching performance, it is vital to determine which high-spin state is reached in the transitions that follow the light excitation. The quintet state can be prepared with a short laser pulse and can be studied with cutting-edge time-resolved X-ray techniques. Here we report on the application of an extended set of X-ray spectroscopy and scattering techniques applied to investigate the quintet state of [Fe(terpy)2]2+ 80 ps after light excitation. High-quality X-ray absorption, nonresonant emission, and resonant emission spectra as well as X-ray diffuse scattering data clearly reflect the formation of the high-spin state of the [Fe(terpy)2]2+ molecule; moreover, extended X-ray absorption fine structure spectroscopy resolves the Fe–ligand bond-length variations with unprecedented bond-length accuracy in time-resolved experiments. With ab initio calculations we determine why, in contrast to most related systems, one configurational mode is insufficient for the description of the low-spin (LS)–high-spin (HS) transition. We identify the electronic structure origin of the differences between the two possible quintet modes, and finally, we unambiguously identify the formed quintet state as 5E, in agreement with our theoretical expectations. PMID:25838847

Detailed Characterization of a Nanosecond-Lived Excited State: X-ray and Theoretical Investigation of the Quintet State in Photoexcited [Fe(terpy) 2 ] 2+

DOE Office of Scientific and Technical Information (OSTI.GOV)

Vankó, György; Bordage, Amélie; Pápai, Mátyás

2015-03-19

Theoretical predictions show that depending on the populations of the Fe 3dxy, 3dxz, and 3dyz orbitals two possible quintet states can exist for the high-spin state of the photoswitchable model system [Fe(terpy)2]2+. The differences in the structure and molecular properties of these 5B2 and 5E quintets are very small and pose a substantial challenge for experiments to resolve them. Yet for a better understanding of the physics of this system, which can lead to the design of novel molecules with enhanced photoswitching performance, it is vital to determine which high-spin state is reached in the transitions that follow the lightmore » excitation. The quintet state can be prepared with a short laser pulse and can be studied with cutting-edge time-resolved X-ray techniques. Here we report on the application of an extended set of X-ray spectroscopy and scattering techniques applied to investigate the quintet state of [Fe(terpy)2]2+ 80 ps after light excitation. High-quality X-ray absorption, nonresonant emission, and resonant emission spectra as well as X-ray diffuse scattering data clearly reflect the formation of the high-spin state of the [Fe(terpy)2]2+ molecule; moreover, extended X-ray absorption fine structure spectroscopy resolves the Fe-ligand bond-length variations with unprecedented bondlength accuracy in time-resolved experiments. With ab initio calculations we determine why, in contrast to most related systems, one configurational mode is insufficient for the description of the low-spin (LS)-high-spin (HS) transition. We identify the electronic structure origin of the differences between the two possible quintet modes, and finally, we unambiguously identify the formed quintet state as 5E, in agreement with our theoretical expectations.« less

Detailed Characterization of a Nanosecond-Lived Excited State: X-ray and Theoretical Investigation of the Quintet State in Photoexcited [Fe(terpy) 2 ] 2+

DOE PAGES

Vanko, Gyorgy; Bordage, Amelie; Papai, Matyas; ...

2015-03-19

Theoretical predictions show that depending on the populations of the Fe 3d xy, 3d xz, and 3d yz orbitals two possible quintet states can exist for the high-spin state of the photoswitchable model system [Fe(terpy) 2] 2+. The differences in the structure and molecular properties of these 5B2 and 5E quintets are very small and pose a substantial challenge for experiments to resolve them. Yet for a better understanding of the physics of this system, which can lead to the design of novel molecules with enhanced photoswitching performance, it is vital to determine which high-spin state is reached in themore » transitions that follow the light excitation. The quintet state can be prepared with a short laser pulse and can be studied with cutting-edge time-resolved X-ray techniques. Here we report on the application of an extended set of X-ray spectroscopy and scattering techniques applied to investigate the quintet state of [Fe(terpy) 2] 2+ 80 ps after light excitation. High-quality X-ray absorption, nonresonant emission, and resonant emission spectra as well as X-ray diffuse scattering data clearly reflect the formation of the high-spin state of the [Fe(terpy) 2] 2+ molecule; moreover, extended X-ray absorption fine structure spectroscopy resolves the Fe–ligand bond-length variations with unprecedented bond-length accuracy in time-resolved experiments. With ab initio calculations we determine why, in contrast to most related systems, one configurational mode is insufficient for the description of the low-spin (LS)–high-spin (HS) transition. We identify the electronic structure origin of the differences between the two possible quintet modes, and finally, we unambiguously identify the formed quintet state as 5E, in agreement with our theoretical expectations.« less

Probing Interfacial Electronic States in CdSe Quantum Dots using Second Harmonic Generation Spectroscopy

DOE PAGES

Doughty, Benjamin L.; Ma, Yingzhong; Shaw, Robert W

2015-01-07

Understanding and rationally controlling the properties of nanomaterial surfaces is a rapidly expanding field of research due to the dramatic role they play on the optical and electronic properties vital to light harvesting, emitting and detection technologies. This information is essential to the continued development of synthetic approaches designed to tailor interfaces for optimal nanomaterial based device performance. In this work, closely spaced electronic excited states in model CdSe quantum dots (QDs) are resolved using second harmonic generation (SHG) spectroscopy, and the corresponding contributions from surface species to these states are assessed. Two distinct spectral features are observed in themore » SHG spectra, which are not readily identified in linear absorption and photoluminescence excitation spectra. These features include a weak band at 395 6 nm, which coincides with transitions to the 2S1/2 1Se state, and a much more pronounced band at 423 4 nm arising from electronic transitions to the 1P3/2 1Pe state. Chemical modification of the QD surfaces through oxidation resulted in disappearance of the SHG band corresponding to the 1P3/2 1Pe state, indicating prominent surface contributions. Signatures of deep trap states localized on the surfaces of the QDs are also observed. We further find that the SHG signal intensities depend strongly on the electronic states being probed and their relative surface contributions, thereby offering additional insight into the surface specificity of SHG signals from QDs.« less

A direct electron detector for time-resolved MeV electron microscopy

DOE PAGES

Vecchione, T.; Denes, P.; Jobe, R. K.; ...

2017-03-15

The introduction of direct electron detectors enabled the structural biology revolution of cryogenic electron microscopy. Direct electron detectors are now expected to have a similarly dramatic impact on time-resolved MeV electron microscopy, particularly by enabling both spatial and temporal jitter correction. Here in this paper, we report on the commissioning of a direct electron detector for time-resolved MeV electron microscopy. The direct electron detector demonstrated MeV single electron sensitivity and is capable of recording megapixel images at 180 Hz. The detector has a 15-bit dynamic range, better than 30-μm spatial resolution and less than 20 analogue-to-digital converter count RMS pixelmore » noise. The unique capabilities of the direct electron detector and the data analysis required to take advantage of these capabilities are presented. The technical challenges associated with generating and processing large amounts of data are also discussed.« less

A direct electron detector for time-resolved MeV electron microscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Vecchione, T.; Denes, P.; Jobe, R. K.

The introduction of direct electron detectors enabled the structural biology revolution of cryogenic electron microscopy. Direct electron detectors are now expected to have a similarly dramatic impact on time-resolved MeV electron microscopy, particularly by enabling both spatial and temporal jitter correction. Here we report on the commissioning of a direct electron detector for time-resolved MeV electron microscopy. The direct electron detector demonstrated MeV single electron sensitivity and is capable of recording megapixel images at 180 Hz. The detector has a 15-bit dynamic range, better than 30-μmμm spatial resolution and less than 20 analogue-to-digital converter count RMS pixel noise. The uniquemore » capabilities of the direct electron detector and the data analysis required to take advantage of these capabilities are presented. The technical challenges associated with generating and processing large amounts of data are also discussed.« less

A direct electron detector for time-resolved MeV electron microscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Vecchione, T.; Denes, P.; Jobe, R. K.

The introduction of direct electron detectors enabled the structural biology revolution of cryogenic electron microscopy. Direct electron detectors are now expected to have a similarly dramatic impact on time-resolved MeV electron microscopy, particularly by enabling both spatial and temporal jitter correction. Here in this paper, we report on the commissioning of a direct electron detector for time-resolved MeV electron microscopy. The direct electron detector demonstrated MeV single electron sensitivity and is capable of recording megapixel images at 180 Hz. The detector has a 15-bit dynamic range, better than 30-μm spatial resolution and less than 20 analogue-to-digital converter count RMS pixelmore » noise. The unique capabilities of the direct electron detector and the data analysis required to take advantage of these capabilities are presented. The technical challenges associated with generating and processing large amounts of data are also discussed.« less

Electron transfer triggered by optical excitation of phenothiazine-tris(meta-phenylene-ethynylene)-(tricarbonyl)(bpy)(py)rhenium(I).

PubMed

Bingöl, Bahar; Durrell, Alec C; Keller, Gretchen E; Palmer, Joshua H; Grubbs, Robert H; Gray, Harry B

2013-04-25

We have investigated excited-state electron transfer in a donor-bridge-acceptor complex containing phenothiazine (PTZ) linked via tris(meta-phenylene-ethynylene) to a tricarbonyl(bipyridine)(pyridine)Re(I) unit. Time-resolved luminescence experiments reveal two excited-state (*Re) decay regimes, a multiexponential component with a mean lifetime of 2.7 ns and a longer monoexponential component of 530 ns in dichloromethane solution. The faster decay is attributed to PTZ → *Re electron transfer in a C-shaped PTZ-bridge-Re conformer (PTZ-Re ≈ 7.5 Å). We assign the longer lifetime, which is virtually identical to that of free *Re, to an extended conformer (PTZ-Re > 20 Å). The observed biexponential *Re decay requires that interconversion of PTZ-bridge-Re conformers be slower than 10(6) s(-1).

Single-electron thermal devices coupled to a mesoscopic gate

NASA Astrophysics Data System (ADS)

Sánchez, Rafael; Thierschmann, Holger; Molenkamp, Laurens W.

2017-11-01

We theoretically investigate the propagation of heat currents in a three-terminal quantum dot engine. Electron-electron interactions introduce state-dependent processes which can be resolved by energy-dependent tunneling rates. We identify the relevant transitions which define the operation of the system as a thermal transistor or a thermal diode. In the former case, thermal-induced charge fluctuations in the gate dot modify the thermal currents in the conductor with suppressed heat injection, resulting in huge amplification factors and the possible gating with arbitrarily low energy cost. In the latter case, enhanced correlations of the state-selective tunneling transitions redistribute heat flows giving high rectification coefficients and the unexpected cooling of one conductor terminal by heating the other one. We propose quantum dot arrays as a possible way to achieve the extreme tunneling asymmetries required for the different operations.

Ab Initio Studies of Halogen and Nitrogen Oxide Species of Interest in Stratospheric Chemistry

NASA Technical Reports Server (NTRS)

Lee, Timothy J.; Langhoff, Stephen R. (Technical Monitor)

1995-01-01

The ability of modern state-of-the art ab initio quantum chemical techniques to characterize reliably the gas-phase molecular structure, vibrational spectrum, electronic spectrum, and thermal stability of fluorine, chlorine, bromine and nitrogen oxide species will be demonstrated by presentation of some example studies. The ab initio results are shown to be in excellent agreement with the available experimental data, and where the experimental data are either not known or are inconclusive, the theoretical results are shown to fill in the gaps and to resolve experimental controversies. In addition, ab initio studies in which the electronic spectra and the characterization of excited electronic states of halogen oxide species will also be presented. Again where available, the ab initio results are compared to experimental observations, and are used to aid in the interpretation of experimental studies.

Spin-polarized surface resonances accompanying topological surface state formation

DOE PAGES

Jozwiak, Chris; Sobota, Jonathan A.; Gotlieb, Kenneth; ...

2016-10-14

Topological insulators host spin-polarized surface states born out of the energetic inversion of bulk bands driven by the spin-orbit interaction. Here we discover previously unidentified consequences of band-inversion on the surface electronic structure of the topological insulator Bi 2Se 3. By performing simultaneous spin, time, and angle-resolved photoemission spectroscopy, we map the spin-polarized unoccupied electronic structure and identify a surface resonance which is distinct from the topological surface state, yet shares a similar spin-orbital texture with opposite orientation. Its momentum dependence and spin texture imply an intimate connection with the topological surface state. Calculations show these two distinct states canmore » emerge from trivial Rashba-like states that change topology through the spin-orbit-induced band inversion. As a result, this work thus provides a compelling view of the coevolution of surface states through a topological phase transition, enabled by the unique capability of directly measuring the spin-polarized unoccupied band structure.« less

The properties of 4'-N,N-dimethylaminoflavonol in the ground and excited states

NASA Astrophysics Data System (ADS)

Moroz, V. V.; Chalyi, A. G.; Roshal, A. D.

2008-09-01

The mechanism of protonation of 4-N,N-dimethylaminoflavonol and the structure of its protolytic forms in the ground and excited states were studied by electron absorption and fluorescence (steady-state and time-resolved) spectroscopy and with the use of the RM1 quantum-chemical method. A comparison of equilibrium constants and the theoretical enthalpies of formation showed that excitation should be accompanied by the inversion of the basicity of the electron acceptor groups of this compound and, as a consequence, changes in the structure of its monocationic form. An analysis of the spectral parameters of the protolytic 4-N,N-dimethylaminoflavonol forms, however, showed that their structure and the sequence of protonation in the excited state were the same as in the ground state. Changes in the structure of the monocation in the excited state were not observed because of the fast radiationless deactivation of this form and the occurrence of excited state intramolecular proton transfer in aprotic solvents.

Real-time observation of valence electron motion.

PubMed

Goulielmakis, Eleftherios; Loh, Zhi-Heng; Wirth, Adrian; Santra, Robin; Rohringer, Nina; Yakovlev, Vladislav S; Zherebtsov, Sergey; Pfeifer, Thomas; Azzeer, Abdallah M; Kling, Matthias F; Leone, Stephen R; Krausz, Ferenc

2010-08-05

The superposition of quantum states drives motion on the atomic and subatomic scales, with the energy spacing of the states dictating the speed of the motion. In the case of electrons residing in the outer (valence) shells of atoms and molecules which are separated by electronvolt energies, this means that valence electron motion occurs on a subfemtosecond to few-femtosecond timescale (1 fs = 10(-15) s). In the absence of complete measurements, the motion can be characterized in terms of a complex quantity, the density matrix. Here we report an attosecond pump-probe measurement of the density matrix of valence electrons in atomic krypton ions. We generate the ions with a controlled few-cycle laser field and then probe them through the spectrally resolved absorption of an attosecond extreme-ultraviolet pulse, which allows us to observe in real time the subfemtosecond motion of valence electrons over a multifemtosecond time span. We are able to completely characterize the quantum mechanical electron motion and determine its degree of coherence in the specimen of the ensemble. Although the present study uses a simple, prototypical open system, attosecond transient absorption spectroscopy should be applicable to molecules and solid-state materials to reveal the elementary electron motions that control physical, chemical and biological properties and processes.

Electronic properties of conductive pili of the metal-reducing bacterium Geobacter sulfurreducens probed by scanning tunneling microscopy.

PubMed

Veazey, Joshua P; Reguera, Gemma; Tessmer, Stuart H

2011-12-01

The metal-reducing bacterium Geobacter sulfurreducens produces conductive protein appendages known as "pilus nanowires" to transfer electrons to metal oxides and to other cells. These processes can be harnessed for the bioremediation of toxic metals and the generation of electricity in bioelectrochemical cells. Key to these applications is a detailed understanding of how these nanostructures conduct electrons. However, to the best of our knowledge, their mechanism of electron transport is not known. We used the capability of scanning tunneling microscopy (STM) to probe conductive materials with higher spatial resolution than other scanning probe methods to gain insights into the transversal electronic behavior of native, cell-anchored pili. Despite the presence of insulating cellular components, the STM topography resolved electronic molecular substructures with periodicities similar to those reported for the pilus shaft. STM spectroscopy revealed electronic states near the Fermi level, consistent with a conducting material, but did not reveal electronic states expected for cytochromes. Furthermore, the transversal conductance was asymmetric, as previously reported for assemblies of helical peptides. Our results thus indicate that the Geobacter pilus shaft has an intrinsic electronic structure that could play a role in charge transport.

Insulating ferromagnetic oxide films: the controlling role of oxygen vacancy ordering

DOE Office of Scientific and Technical Information (OSTI.GOV)

Salafranca Laforga, Juan I; Salafranca, Juan; Biskup, Nevenko

2014-01-01

The origin of ferromagnetism in strained epitaxial LaCoO3 films has been a long-standing mystery. Here, we combine atomically resolved Z-contrast imaging, electron-energy-loss spectroscopy, and density-functional calculations to demonstrate that, in epitaxial LaCoO3 films, oxygen-vacancy superstructures release strain, control the film s electronic properties, and produce the observed ferromagnetism via the excess electrons in the Co d states. Although oxygen vacancies typically dope a material n-type, we find that ordered vacancies induce Peierls-like minigaps which, combined with strain relaxation, trigger a nonlinear rupture of the energy bands, resulting in insulating behavior.

Insulating Ferromagnetic LaCoO3-δ Films: A Phase Induced by Ordering of Oxygen Vacancies

NASA Astrophysics Data System (ADS)

Biškup, Neven; Salafranca, Juan; Mehta, Virat; Oxley, Mark P.; Suzuki, Yuri; Pennycook, Stephen J.; Pantelides, Sokrates T.; Varela, Maria

2014-02-01

The origin of ferromagnetism in strained epitaxial LaCoO3 films has been a long-standing mystery. Here, we combine atomically resolved Z-contrast imaging, electron-energy-loss spectroscopy, and density-functional calculations to demonstrate that, in epitaxial LaCoO3 films, oxygen-vacancy superstructures release strain, control the film's electronic properties, and produce the observed ferromagnetism via the excess electrons in the Co d states. Although oxygen vacancies typically dope a material n-type, we find that ordered vacancies induce Peierls-like minigaps which, combined with strain relaxation, trigger a nonlinear rupture of the energy bands, resulting in insulating behavior.

Exact Time-Dependent Exchange-Correlation Potential in Electron Scattering Processes

NASA Astrophysics Data System (ADS)

Suzuki, Yasumitsu; Lacombe, Lionel; Watanabe, Kazuyuki; Maitra, Neepa T.

2017-12-01

We identify peak and valley structures in the exact exchange-correlation potential of time-dependent density functional theory that are crucial for time-resolved electron scattering in a model one-dimensional system. These structures are completely missed by adiabatic approximations that, consequently, significantly underestimate the scattering probability. A recently proposed nonadiabatic approximation is shown to correctly capture the approach of the electron to the target when the initial Kohn-Sham state is chosen judiciously, and it is more accurate than standard adiabatic functionals but ultimately fails to accurately capture reflection. These results may explain the underestimation of scattering probabilities in some recent studies on molecules and surfaces.

Excitation transfer and trapping kinetics in plant photosystem I probed by two-dimensional electronic spectroscopy.

PubMed

Akhtar, Parveen; Zhang, Cheng; Liu, Zhengtang; Tan, Howe-Siang; Lambrev, Petar H

2018-03-01

Photosystem I is a robust and highly efficient biological solar engine. Its capacity to utilize virtually every absorbed photon's energy in a photochemical reaction generates great interest in the kinetics and mechanisms of excitation energy transfer and charge separation. In this work, we have employed room-temperature coherent two-dimensional electronic spectroscopy and time-resolved fluorescence spectroscopy to follow exciton equilibration and excitation trapping in intact Photosystem I complexes as well as core complexes isolated from Pisum sativum. We performed two-dimensional electronic spectroscopy measurements with low excitation pulse energies to record excited-state kinetics free from singlet-singlet annihilation. Global lifetime analysis resolved energy transfer and trapping lifetimes closely matches the time-correlated single-photon counting data. Exciton energy equilibration in the core antenna occurred on a timescale of 0.5 ps. We further observed spectral equilibration component in the core complex with a 3-4 ps lifetime between the bulk Chl states and a state absorbing at 700 nm. Trapping in the core complex occurred with a 20 ps lifetime, which in the supercomplex split into two lifetimes, 16 ps and 67-75 ps. The experimental data could be modelled with two alternative models resulting in equally good fits-a transfer-to-trap-limited model and a trap-limited model. However, the former model is only possible if the 3-4 ps component is ascribed to equilibration with a "red" core antenna pool absorbing at 700 nm. Conversely, if these low-energy states are identified with the P 700 reaction centre, the transfer-to-trap-model is ruled out in favour of a trap-limited model.

Epitaxial Growth and Electronic Structure of Half Heuslers Co1-xNixTiSb (001), Ni1-xCoxTiSn, and PtLuSb

DTIC Science & Technology

2016-01-09

studied in detail using scanning tunneling microscopy and angle resolved photoemission. For the doping levels achieved in cobalt titanium antimony, the...angle resolved photoemission. For the doping levels achieved in cobalt titanium antimony, the electron mobility at room temperature was comparable...scanning tunneling microscopy and angle resolved photoemission. For the doping levels achieved in cobalt titanium antimony, the electron mobility at room

The electronically excited states of LH2 complexes from Rhodopseudomonas acidophila strain 10050 studied by time-resolved spectroscopy and dynamic Monte Carlo simulations. II. Homo-arrays of LH2 complexes reconstituted into phospholipid model membranes.

PubMed

Pflock, Tobias J; Oellerich, Silke; Krapf, Lisa; Southall, June; Cogdell, Richard J; Ullmann, G Matthias; Köhler, Jürgen

2011-07-21

We performed time-resolved spectroscopy on homoarrays of LH2 complexes from the photosynthetic purple bacterium Rhodopseudomonas acidophila. Variations of the fluorescence transients were monitored as a function of the excitation fluence and the repetition rate of the excitation. These parameters are directly related to the excitation density within the array and to the number of LH2 complexes that still carry a triplet state prior to the next excitation. Comparison of the experimental observations with results from dynamic Monte Carlo simulations for a model cluster of LH2 complexes yields qualitative agreement without the need for any free parameter and reveals the mutual relationship between energy transfer and annihilation processes.

The Mystery of the Electronic Spectrum of Ruthenium Monophosphide

NASA Astrophysics Data System (ADS)

Adam, Allan G.; Christensen, Ryan M.; Dore, Jacob M.; Konder, Ricarda M.; Tokaryk, Dennis W.

2016-06-01

Using PH3 as a reactant gas and ruthenium as the target metal in the UNB laser ablation spectrometer, the ruthenium monophosphide molecule (RuP) has been detected. Dispersed fluorescence experiments have been performed to determine ground state vibrational frequencies and the presence of any low-lying electronic states. Rotationally resolved spectra of two vibrational bands at 577nm and 592nm have been taken; the bands have been identified as 1-0 and 0-0 bands based on isotopic shifts. Ruthenium has seven stable isotopes and rotational transitions have been observed for six of the RuP isotopologues. RuP is isoelectronic to RuN so it is expected that RuP will have a 2Σ+ ground state and low resolution spectra indicated a likely 2Σ+ - 2Σ+ electronic transition. Further investigation has led us to believe we are observing a 2Π - 2Σ+ transition but mysteriously some important rotational branches are missing. It is hoped that new data to be recorded on a second electronic system we have observed at 535nm will help shed light on this mystery.

Fermi Surface of Metallic V_{2}O_{3} from Angle-Resolved Photoemission: Mid-level Filling of e_{g}^{π} Bands.

PubMed

Lo Vecchio, I; Denlinger, J D; Krupin, O; Kim, B J; Metcalf, P A; Lupi, S; Allen, J W; Lanzara, A

2016-10-14

Using angle resolved photoemission spectroscopy, we report the first band dispersions and distinct features of the bulk Fermi surface (FS) in the paramagnetic metallic phase of the prototypical metal-insulator transition material V_{2}O_{3}. Along the c axis we observe both an electron pocket and a triangular holelike FS topology, showing that both V 3d a_{1g} and e_{g}^{π} states contribute to the FS. These results challenge the existing correlation-enhanced crystal field splitting theoretical explanation for the transition mechanism and pave the way for the solution of this mystery.

Time-resolved measurement of intramolecular photoinduced electron transfer processes in perylene diimides (Conference Presentation)

NASA Astrophysics Data System (ADS)

Döring, Robin Carl; Baal, Eduard; Sundermeyer, Jörg; Chatterjee, Sangam

2017-02-01

Perylene-3,4,9,10-tetracarboxylic acid (PTCDA) and respective derivatives (e.g. perylene diimide - PDI) are widely used as dyes but also for device applications such as organic field effect transistors or in organic photovoltaics. Due to their intrinsically high quantum efficiencies they are also used as spectroscopic standards. One major drawback of these materials is their low solubility in organic solvents which can be addressed by long alkyl substitutions. When introducing a tertiary amine into the molecule a mechanism known as photoinduced electron transfer (PET) can occur. Here, following an optically excited HOMO-LUMO transition of the core, an electron from the electron lone pair of the amine is transferred to the HOMO of the perylene core. Hence, radiative recombination is disallowed and photoluminescence effectively quenched. Here, we perform a systematic study of the distance dependence of the PET by introducing alkyle groups as spacer units between PDI core and the tertiary amine. Dynamics of the PET are extracted from ultrafast time-resolved photoluminescence measurement data. A rate equation model, simulating a three level system, reveals rate constant of the back electron transfer, otherwise not accessible with our experimental methods. Assuming a Marcus model of electron transfer, electronic coupling strength between the electronic states involved in the respective transitions can be calculated. In addition to the distance dependence, the effects of protonation and methylation of the the tertiary amine units are studied.

Picosecond rotationally resolved stimulated emission pumping spectroscopy of nitric oxide

NASA Astrophysics Data System (ADS)

Tanjaroon, Chakree; Reeve, Scott W.; Ford, Alan; Murry, W. Dean; Lyon, Kevin; Yount, Bret; Britton, Dan; Burns, William A.; Allen, Susan D.; Bruce Johnson, J.

2012-01-01

Stimulated emission pumping (SEP) experiments were performed on the nitric oxide molecule in a flow cell environment using lasers with pulse widths of 17-25 ps. A lambda excitation scheme, or ''pump-dump" arrangement, was employed with the pump laser tuned to the T 00 vibronic band origin ( λ=226.35(1)nm) of the A2Σ+( v' = 0, J') ← X2Π1/2( v″ = 0, J″) and the dump laser scanned from 246-248 nm within the A2Σ+( v' = 0, J') → X2Π1/2( v″ = 2, J″) transition. The rotationally resolved SEP spectra were measured by observing the total fluorescence within the A2Σ+( v' = 0, J') → X2Π1/2( v″ = 1, J″) transition between 235 nm and 237.2 nm while scanning the dump laser wavelengths. Multiple rotational states were excited due to the broad laser bandwidth. Measurements showed that the resolved rotational structure depended on the energy and bandwidth of the applied pump and dump laser pulses. Analysis of the observed fluorescence depletion signals yielded an average percent fluorescence depletion of about 19% when λ=226.35(1)nm and λ=247.91(1)nm. This value reflects the percent transfer of the NO population from the A2Σ+( V' = 0, J') excited electronic state to the X2Π1/2( v″ = 2, J″) ground electronic state. The maximum expected depletion is 50% in the limit of dump saturation. Selective excitation of NO at the bandhead provides good spectral discrimination from the background emission and noise and unambiguously confirms the identity of the emitter.

The fifth electron in the fully reduced caa(3) from Thermus thermophilus is competent in proton pumping.

PubMed

Siletsky, Sergey A; Belevich, Ilya; Soulimane, Tewfik; Verkhovsky, Michael I; Wikström, Mårten

2013-01-01

The time-resolved kinetics of membrane potential generation coupled to oxidation of the fully reduced (five-electron) caa(3) cytochrome oxidase from Thermus thermophilus by oxygen was studied in a single-turnover regime. In order to calibrate the number of charges that move across the vesicle membrane in the different reaction steps, the reverse electron transfer from heme a(3) to heme a and further to the cytochrome c/Cu(A) has been resolved upon photodissociation of CO from the mixed valence enzyme in the absence of oxygen. The reverse electron transfer from heme a(3) to heme a and further to the cytochrome c/Cu(A) pair is resolved as a single transition with τ~40 μs. In the reaction of the fully reduced cytochrome caa(3) with oxygen, the first electrogenic phase (τ~30 μs) is linked to OO bond cleavage and generation of the P(R) state. The next electrogenic component (τ~50 μs) is associated with the P(R)→F transition and together with the previous reaction step it is coupled to translocation of about two charges across the membrane. The three subsequent electrogenic phases, with time constants of ~0.25 ms, ~1.4 ms and ~4 ms, are linked to the conversion of the binuclear center through the F→O(H)→E(H) transitions, and result in additional transfer of four charges through the membrane dielectric. This indicates that the delivery of the fifth electron from heme c to the binuclear center is coupled to pumping of an additional proton across the membrane. Copyright © 2012 Elsevier B.V. All rights reserved.

A simple model of solvent-induced symmetry-breaking charge transfer in excited quadrupolar molecules

NASA Astrophysics Data System (ADS)

Ivanov, Anatoly I.; Dereka, Bogdan; Vauthey, Eric

2017-04-01

A simple model has been developed to describe the symmetry-breaking of the electronic distribution of AL-D-AR type molecules in the excited state, where D is an electron donor and AL and AR are identical acceptors. The origin of this process is usually associated with the interaction between the molecule and the solvent polarization that stabilizes an asymmetric and dipolar state, with a larger charge transfer on one side than on the other. An additional symmetry-breaking mechanism involving the direct Coulomb interaction of the charges on the acceptors is proposed. At the same time, the electronic coupling between the two degenerate states, which correspond to the transferred charge being localised either on AL or AR, favours a quadrupolar excited state with equal amount of charge-transfer on both sides. Because of these counteracting effects, symmetry breaking is only feasible when the electronic coupling remains below a threshold value, which depends on the solvation energy and the Coulomb repulsion energy between the charges located on AL and AR. This model allows reproducing the solvent polarity dependence of the symmetry-breaking reported recently using time-resolved infrared spectroscopy.

Electronic structure of single crystalline Bi 2(Sr,Ca,La) 3Cu 2O 8

NASA Astrophysics Data System (ADS)

Lindberg, P. A. P.; Shen, Z.-X.; Dessau, D. S.; Wells, B. O.; Borg, A.; Mitzi, D. B.; Lindau, I.; Spicer, W. E.; Kapitulnik, A.

1989-12-01

Angle-resolved photoemission experiments on single crystals of Bi 2(Sr,Ca,La) 3Cu 2O 8 are reported. The data show a dispersionless behaviour of the valence band states as a function of the perpendicular component of the wave vector (along the c-axis), while as a function of the parallel component (in the a-b plane) clear dispersion occurs. Furthermore, polarization-dependent excitations reveal information on the symmetry of the unoccupied states.

A comprehensive study of LiF TL response to high energy photons and electrons.

PubMed

Bagne, F

1977-06-01

Effects of beam quality, cavity size, TLD state, and medium on the response of thermoluminescent dosimeters were studied. LiF TL-700 powder, extruded rods, and ribbons were irradiated with Co-60 gamma rays, 4, 6, 8, 33, and 45 -MV x rays, and 3, 5, 10, 15, 20, 25, 30, 35, 40, and 45-MeV electrons. Relative TL responses were assessed in water and Lucite, and the results compared. The results of this study were compared with those of previously published studies, and certain discrepancies resolved.

Measurement and dynamics of the spatial distribution of an electron localized at a metal-dielectric interface

NASA Astrophysics Data System (ADS)

Bezel, Ilya; Gaffney, Kelly J.; Garrett-Roe, Sean; Liu, Simon H.; Miller, André D.; Szymanski, Paul; Harris, Charles B.

2004-01-01

The ability of time- and angle-resolved two-photon photoemission to estimate the size distribution of electron localization in the plane of a metal-adsorbate interface is discussed. It is shown that the width of angular distribution of the photoelectric current is inversely proportional to the electron localization size within the most common approximations in the description of image potential states. The localization of the n=1 image potential state for two monolayers of butyronitrile on Ag(111) is used as an example. For the delocalized n=1 state, the shape of the signal amplitude as a function of momentum parallel to the surface changes rapidly with time, indicating efficient intraband relaxation on a 100 fs time scale. For the localized state, little change was observed. The latter is related to the constant size distribution of electron localization, which is estimated to be a Gaussian with a 15±4 Å full width at half maximum in the plane of the interface. A simple model was used to study the effect of a weak localization potential on the overall width of the angular distribution of the photoemitted electrons, which exhibited little sensitivity to the details of the potential. This substantiates the validity of the localization size estimate.

Reassessment of MxiH subunit orientation and fold within native Shigella T3SS needles using surface labelling and solid-state NMR.

PubMed

Verasdonck, Joeri; Shen, Da-Kang; Treadgold, Alexander; Arthur, Christopher; Böckmann, Anja; Meier, Beat H; Blocker, Ariel J

2015-12-01

T3SSs are essential virulence determinants of many Gram-negative bacteria, used to inject bacterial effectors of virulence into eukaryotic host cells. Their major extracellular portion, a ∼50 nm hollow, needle-like structure, is essential to host cell sensing and the conduit for effector secretion. It is formed of a small, conserved subunit arranged as a helical polymer. The structure of the subunit has been studied by electron cryomicroscopy within native polymers and by solid-state NMR in recombinant polymers, yielding two incompatible atomic models. To resolve this controversy, we re-examined the native polymer used for electron cryomicroscopy via surface labelling and solid-state NMR. Our data show the orientation and overall fold of the subunit within this polymer is as established by solid-state NMR for recombinant polymers. Copyright © 2015 The Authors. Published by Elsevier Inc. All rights reserved.

Organic semiconductor density of states controls the energy level alignment at electrode interfaces

PubMed Central

Oehzelt, Martin; Koch, Norbert; Heimel, Georg

2014-01-01

Minimizing charge carrier injection barriers and extraction losses at interfaces between organic semiconductors and metallic electrodes is critical for optimizing the performance of organic (opto-) electronic devices. Here, we implement a detailed electrostatic model, capable of reproducing the alignment between the electrode Fermi energy and the transport states in the organic semiconductor both qualitatively and quantitatively. Covering the full phenomenological range of interfacial energy level alignment regimes within a single, consistent framework and continuously connecting the limiting cases described by previously proposed models allows us to resolve conflicting views in the literature. Our results highlight the density of states in the organic semiconductor as a key factor. Its shape and, in particular, the energy distribution of electronic states tailing into the fundamental gap is found to determine both the minimum value of practically achievable injection barriers as well as their spatial profile, ranging from abrupt interface dipoles to extended band-bending regions. PMID:24938867

``New'' energy states lead to phonon-less optoelectronic properties in nanostructured silicon

NASA Astrophysics Data System (ADS)

Singh, Vivek; Yu, Yixuan; Korgel, Brian; Nagpal, Prashant

2014-03-01

Silicon is arguably one of the most important technological material for electronic applications. However, indirect bandgap of silicon semiconductor has prevented optoelectronic applications due to phonon assistance required for photon light absorption/emission. Here we show, that previously unexplored surface states in nanostructured silicon can couple with quantum-confined energy levels, leading to phonon-less exciton-recombination and photoluminescence. We demonstrate size dependence (2.4 - 8.3 nm) of this coupling observed in small uniform silicon nanocrystallites, or quantum-dots, by direct measurements of their electronic density of states and low temperature measurements. To enhance the optical absorption of the these silicon quantum-dots, we utilize generation of resonant surface plasmon polariton waves, which leads to several fold increase in observed spectrally-resolved photocurrent near the quantum-confined bandedge states. Therefore, these enhanced light emission and absorption enhancement can have important implications for applications of nanostructured silicon for optoelectronic applications in photovoltaics and LEDs.

Storage of charge carriers on emitter molecules in organic light-emitting diodes

NASA Astrophysics Data System (ADS)

Weichsel, Caroline; Burtone, Lorenzo; Reineke, Sebastian; Hintschich, Susanne I.; Gather, Malte C.; Leo, Karl; Lüssem, Björn

2012-08-01

Organic light-emitting diodes (OLEDs) using the red phosphorescent emitter iridium(III)bis(2-methyldibenzo[f,h]quinoxaline) (acetylacetonate) [Ir(MDQ)2(acac)] are studied by time-resolved electroluminescence measurements. A transient overshoot after voltage turn-off is found, which is attributed to electron accumulation on Ir(MDQ)2(acac) molecules. The mechanism is verified via impedance spectroscopy and by application of positive and negative off-voltages. We calculate the density of accumulated electrons and find that it scales linearly with the doping concentration of the emitter. Using thin quenching layers, we locate the position of the emission zone during normal OLED operation and after voltage turn-off. In addition, the transient overshoot is also observed in three-color white-emitting OLEDs. By time- and spectrally resolved measurements using a streak camera, we directly attribute the overshoot to electron accumulation on Ir(MDQ)2(acac). We propose that similar processes are present in many state-of-the-art OLEDs and believe that the quantification of charge carrier storage will help to improve the efficiency of OLEDs.

CuPc/Au(1 1 0): Determination of the azimuthal alignment by a combination of angle-resolved photoemission and density functional theory

PubMed Central

Lüftner, Daniel; Milko, Matus; Huppmann, Sophia; Scholz, Markus; Ngyuen, Nam; Wießner, Michael; Schöll, Achim; Reinert, Friedrich; Puschnig, Peter

2014-01-01

Here we report on a combined experimental and theoretical study on the structural and electronic properties of a monolayer of Copper-Phthalocyanine (CuPc) on the Au(1 1 0) surface. Low-energy electron diffraction reveals a commensurate overlayer unit cell containing one adsorbate species. The azimuthal alignment of the CuPc molecule is revealed by comparing experimental constant binding energy (kxky)-maps using angle-resolved photoelectron spectroscopy with theoretical momentum maps of the free molecule's highest occupied molecular orbital (HOMO). This structural information is confirmed by total energy calculations within the framework of van-der-Waals corrected density functional theory. The electronic structure is further analyzed by computing the molecule-projected density of states, using both a semi-local and a hybrid exchange-correlation functional. In agreement with experiment, the HOMO is located about 1.2 eV below the Fermi-level, while there is no significant charge transfer into the molecule and the CuPc LUMO remains unoccupied on the Au(1 1 0) surface. PMID:25284953

X-ray phase-contrast imaging: the quantum perspective

NASA Astrophysics Data System (ADS)

Slowik, J. M.; Santra, R.

2013-08-01

Time-resolved phase-contrast imaging using ultrafast x-ray sources is an emerging method to investigate ultrafast dynamical processes in matter. Schemes to generate attosecond x-ray pulses have been proposed, bringing electronic timescales into reach and emphasizing the demand for a quantum description. In this paper, we present a method to describe propagation-based x-ray phase-contrast imaging in nonrelativistic quantum electrodynamics. We explain why the standard scattering treatment via Fermi’s golden rule cannot be applied. Instead, the quantum electrodynamical treatment of phase-contrast imaging must be based on a different approach. It turns out that it is essential to select a suitable observable. Here, we choose the quantum-mechanical Poynting operator. We determine the expectation value of our observable and demonstrate that the leading order term describes phase-contrast imaging. It recovers the classical expression of phase-contrast imaging. Thus, it makes the instantaneous electron density of non-stationary electronic states accessible to time-resolved imaging. Interestingly, inelastic (Compton) scattering does automatically not contribute in leading order, explaining the success of the semiclassical description.

Developing DIII-D To Prepare For ITER And The Path To Fusion Energy

NASA Astrophysics Data System (ADS)

Buttery, Richard; Hill, David; Solomon, Wayne; Guo, Houyang; DIII-D Team

2017-10-01

DIII-D pursues the advancement of fusion energy through scientific understanding and discovery of solutions. Research targets two key goals. First, to prepare for ITER we must resolve how to use its flexible control tools to rapidly reach Q =10, and develop the scientific basis to interpret results from ITER for fusion projection. Second, we must determine how to sustain a high performance fusion core in steady state conditions, with minimal actuators and a plasma exhaust solution. DIII-D will target these missions with: (i) increased electron heating and balanced torque neutral beams to simulate burning plasma conditions (ii) new 3D coil arrays to resolve control of transients (iii) off axis current drive to study physics in steady state regimes (iv) divertors configurations to promote detachment with low upstream density (v) a reactor relevant wall to qualify materials and resolve physics in reactor-like conditions. With new diagnostics and leading edge simulation, this will position the US for success in ITER and a unique knowledge to accelerate the approach to fusion energy. Supported by the US DOE under DE-FC02-04ER54698.

Chromophore twisting in the excited state of a photoswitchable fluorescent protein captured by time-resolved serial femtosecond crystallography

NASA Astrophysics Data System (ADS)

Coquelle, Nicolas; Sliwa, Michel; Woodhouse, Joyce; Schirò, Giorgio; Adam, Virgile; Aquila, Andrew; Barends, Thomas R. M.; Boutet, Sébastien; Byrdin, Martin; Carbajo, Sergio; de La Mora, Eugenio; Doak, R. Bruce; Feliks, Mikolaj; Fieschi, Franck; Foucar, Lutz; Guillon, Virginia; Hilpert, Mario; Hunter, Mark S.; Jakobs, Stefan; Koglin, Jason E.; Kovacsova, Gabriela; Lane, Thomas J.; Lévy, Bernard; Liang, Mengning; Nass, Karol; Ridard, Jacqueline; Robinson, Joseph S.; Roome, Christopher M.; Ruckebusch, Cyril; Seaberg, Matthew; Thepaut, Michel; Cammarata, Marco; Demachy, Isabelle; Field, Martin; Shoeman, Robert L.; Bourgeois, Dominique; Colletier, Jacques-Philippe; Schlichting, Ilme; Weik, Martin

2018-01-01

Chromophores absorb light in photosensitive proteins and thereby initiate fundamental biological processes such as photosynthesis, vision and biofluorescence. An important goal in their understanding is the provision of detailed structural descriptions of the ultrafast photochemical events that they undergo, in particular of the excited states that connect chemistry to biological function. Here we report on the structures of two excited states in the reversibly photoswitchable fluorescent protein rsEGFP2. We populated the states through femtosecond illumination of rsEGFP2 in its non-fluorescent off state and observed their build-up (within less than one picosecond) and decay (on the several picosecond timescale). Using an X-ray free-electron laser, we performed picosecond time-resolved crystallography and show that the hydroxybenzylidene imidazolinone chromophore in one of the excited states assumes a near-canonical twisted configuration halfway between the trans and cis isomers. This is in line with excited-state quantum mechanics/molecular mechanics and classical molecular dynamics simulations. Our new understanding of the structure around the twisted chromophore enabled the design of a mutant that displays a twofold increase in its off-to-on photoswitching quantum yield.

Chromophore twisting in the excited state of a photoswitchable fluorescent protein captured by time-resolved serial femtosecond crystallography

DOE PAGES

Coquelle, Nicolas; Sliwa, Michel; Woodhouse, Joyce; ...

2017-09-11

Chromophores absorb light in photosensitive proteins and thereby initiate fundamental biological processes such as photosynthesis, vision and biofluorescence. An important goal in their understanding is the provision of detailed structural descriptions of the ultrafast photochemical events that they undergo, in particular of the excited states that connect chemistry to biological function. Here in this paper we report on the structures of two excited states in the reversibly photoswitchable fluorescent protein rsEGFP2. We populated the states through femtosecond illumination of rsEGFP2 in its non-fluorescent off state and observed their build-up (within less than one picosecond) and decay (on the several picosecondmore » timescale). Using an X-ray free-electron laser, we performed picosecond time-resolved crystallography and show that the hydroxybenzylidene imidazolinone chromophore in one of the excited states assumes a near-canonical twisted configuration halfway between the trans and cis isomers. This is in line with excited-state quantum mechanics/molecular mechanics and classical molecular dynamics simulations. Our new understanding of the structure around the twisted chromophore enabled the design of a mutant that displays a twofold increase in its off-to-on photoswitching quantum yield.« less

Chromophore twisting in the excited state of a photoswitchable fluorescent protein captured by time-resolved serial femtosecond crystallography

DOE Office of Scientific and Technical Information (OSTI.GOV)

Coquelle, Nicolas; Sliwa, Michel; Woodhouse, Joyce

Chromophores absorb light in photosensitive proteins and thereby initiate fundamental biological processes such as photosynthesis, vision and biofluorescence. An important goal in their understanding is the provision of detailed structural descriptions of the ultrafast photochemical events that they undergo, in particular of the excited states that connect chemistry to biological function. Here in this paper we report on the structures of two excited states in the reversibly photoswitchable fluorescent protein rsEGFP2. We populated the states through femtosecond illumination of rsEGFP2 in its non-fluorescent off state and observed their build-up (within less than one picosecond) and decay (on the several picosecondmore » timescale). Using an X-ray free-electron laser, we performed picosecond time-resolved crystallography and show that the hydroxybenzylidene imidazolinone chromophore in one of the excited states assumes a near-canonical twisted configuration halfway between the trans and cis isomers. This is in line with excited-state quantum mechanics/molecular mechanics and classical molecular dynamics simulations. Our new understanding of the structure around the twisted chromophore enabled the design of a mutant that displays a twofold increase in its off-to-on photoswitching quantum yield.« less

Numerical Study of Current Driven Instabilities and Anomalous Electron Transport in Hall-effect Thrusters

NASA Astrophysics Data System (ADS)

Tran, Jonathan

Plasma turbulence and the resulting anomalous electron transport due to azimuthal current driven instabilities in Hall-effect thrusters is a promising candidate for developing predictive models for the observed anomalous transport. A theory for anomalous electron transport and current driven instabilities has been recently studied by [Lafluer et al., 2016a]. Due to the extreme cost of fully resolving the Debye length and plasma frequency, hybrid plasma simulations utilizing kinetic ions and quasi-steady state fluid electrons have long been the principle workhorse methodology for Hall-effect thruster modeling. Using a reduced dimension particle in cell simulation implemented in the Thermophysics Universal Research Framework developed by the Air Force Research Lab, we show collective electron-wave scattering due to large amplitude azimuthal fluctuations of the electric field and the plasma density. These high-frequency and short wavelength fluctuations can lead to an effective cross-field mobility many orders of magnitude larger than what is expected from classical electron-neutral momentum collisions in the low neutral density regime. We further adapt the previous study by [Lampe et al., 1971] and [Stringer, 1964] for related current driven instabilities to electric propulsion relevant mass ratios and conditions. Finally, we conduct a preliminary study of resolving this instability with a modified hybrid simulation with the hope of integration with established hybrid Hall-effect thruster simulations.

X-Ray Sum Frequency Diffraction for Direct Imaging of Ultrafast Electron Dynamics

NASA Astrophysics Data System (ADS)

Rouxel, Jérémy R.; Kowalewski, Markus; Bennett, Kochise; Mukamel, Shaul

2018-06-01

X-ray diffraction from molecules in the ground state produces an image of their charge density, and time-resolved x-ray diffraction can thus monitor the motion of the nuclei. However, the density change of excited valence electrons upon optical excitation can barely be monitored with regular diffraction techniques due to the overwhelming background contribution of the core electrons. We present a nonlinear x-ray technique made possible by novel free electron laser sources, which provides a spatial electron density image of valence electron excitations. The technique, sum frequency generation carried out with a visible pump and a broadband x-ray diffraction pulse, yields snapshots of the transition charge densities, which represent the electron density variations upon optical excitation. The technique is illustrated by ab initio simulations of transition charge density imaging for the optically induced electronic dynamics in a donor or acceptor substituted stilbene.

Spatial potential ripples of azimuthal surface modes in topological insulator Bi2Te3 nanowires

PubMed Central

Muñoz Rojo, Miguel; Zhang, Yingjie; Manzano, Cristina V.; Alvaro, Raquel; Gooth, Johannes; Salmeron, Miquel; Martin-Gonzalez, Marisol

2016-01-01

Topological insulators (TI) nanowires (NW) are an emerging class of structures, promising both novel quantum effects and potential applications in low-power electronics, thermoelectrics and spintronics. However, investigating the electronic states of TI NWs is complicated, due to their small lateral size, especially at room temperature. Here, we perform scanning probe based nanoscale imaging to resolve the local surface potential landscapes of Bi2Te3 nanowires (NWs) at 300 K. We found equipotential rings around the NWs perimeter that we attribute to azimuthal 1D modes. Along the NW axis, these modes are altered, forming potential ripples in the local density of states, due to intrinsic disturbances. Potential mapping of electrically biased NWs enabled us to accurately determine their conductivity which was found to increase with the decrease of NW diameter, consistent with surface dominated transport. Our results demonstrate that TI NWs can pave the way to both exotic quantum states and novel electronic devices. PMID:26751282

Spatial potential ripples of azimuthal surface modes in topological insulator Bi2Te3 nanowires.

PubMed

Muñoz Rojo, Miguel; Zhang, Yingjie; Manzano, Cristina V; Alvaro, Raquel; Gooth, Johannes; Salmeron, Miquel; Martin-Gonzalez, Marisol

2016-01-11

Topological insulators (TI) nanowires (NW) are an emerging class of structures, promising both novel quantum effects and potential applications in low-power electronics, thermoelectrics and spintronics. However, investigating the electronic states of TI NWs is complicated, due to their small lateral size, especially at room temperature. Here, we perform scanning probe based nanoscale imaging to resolve the local surface potential landscapes of Bi2Te3 nanowires (NWs) at 300 K. We found equipotential rings around the NWs perimeter that we attribute to azimuthal 1D modes. Along the NW axis, these modes are altered, forming potential ripples in the local density of states, due to intrinsic disturbances. Potential mapping of electrically biased NWs enabled us to accurately determine their conductivity which was found to increase with the decrease of NW diameter, consistent with surface dominated transport. Our results demonstrate that TI NWs can pave the way to both exotic quantum states and novel electronic devices.

Molecular Polygons Probe the Role of Intramolecular Strain in the Photophysics of π-Conjugated Chromophores.

PubMed

Wilhelm, Philipp; Vogelsang, Jan; Poluektov, Georgiy; Schönfelder, Nina; Keller, Tristan J; Jester, Stefan-Sven; Höger, Sigurd; Lupton, John M

2017-01-24

π-Conjugated segments, chromophores, are the electronically active units of polymer materials used in organic electronics. To elucidate the effect of the bending of these linear moieties on elementary electronic properties, such as luminescence color and radiative rate, we introduce a series of molecular polygons. The π-system in these molecules becomes so distorted in bichromophores (digons) that these absorb and emit light of arbitrary polarization: any part of the chain absorbs and emits radiation with equal probability. Bending leads to a cancellation of transition dipole moment (TDM), increasing excited-state lifetime. Simultaneously, fluorescence shifts to the red as radiative transitions require mixing of the excited state with vibrational modes. However, strain can become so large that excited-state localization on shorter units of the chain occurs, compensating TDM cancellation. The underlying correlations between shape and photophysics can only be resolved in single molecules. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Interfacing the Ab initio multiple spawning method with electronic structure methods in GAMESS: Photodecay of trans-Azomethane

DOE PAGES

Gaenko, Alexander; DeFusco, Albert; Varganov, Sergey A.; ...

2014-10-20

This work presents a nonadiabatic molecular dynamics study of the nonradiative decay of photoexcited trans-azomethane, using the ab initio multiple spawning (AIMS) program that has been interfaced with the General Atomic and Molecular Electronic Structure System (GAMESS) quantum chemistry package for on-the-fly electronic structure evaluation. The interface strategy is discussed, and the capabilities of the combined programs are demonstrated with a nonadiabatic molecular dynamics study of the nonradiative decay of photoexcited trans-azomethane. Energies, gradients, and nonadiabatic coupling matrix elements were obtained with the state-averaged complete active space self-consistent field method, as implemented in GAMESS. The influence of initial vibrational excitationmore » on the outcome of the photoinduced isomerization is explored. Increased vibrational excitation in the CNNC torsional mode shortens the excited state lifetime. Depending on the degree of vibrational excitation, the excited state lifetime varies from ~60–200 fs. As a result, these short lifetimes are in agreement with time-resolved photoionization mass spectroscopy experiments.« less

Ultrafast dynamics of an unoccupied surface resonance state in B i2T e2Se

NASA Astrophysics Data System (ADS)

Munisa, Nurmamat; Krasovskii, E. E.; Ishida, Y.; Sumida, K.; Chen, Jiahua; Yoshikawa, T.; Chulkov, E. V.; Kokh, K. A.; Tereshchenko, O. E.; Shin, S.; Kimura, Akio

2018-03-01

Electronic structure and electron dynamics in the ternary topological insulator B i2T e2Se are studied with time- and angle-resolved photoemission spectroscopy using optical pumping. An unoccupied surface resonance split off from the bulk conduction band previously indirectly observed in scanning tunneling measurements is spectroscopically identified. Furthermore, an unoccupied topological surface state (TSS) is found, which is serendipitously located at about 1.5 eV above the occupied TSS, thereby facilitating direct optical transitions between the two surface states at ℏ ω =1.5 eV in an n -type topological insulator. An appreciable nonequilibrium population of the bottom of the bulk conduction band is observed for longer than 15 ps after the pump pulse. This leads to a long recovery time of the lower TSS, which is constantly populated by the electrons coming from the bulk conduction band. Our results demonstrate B i2T e2Se to be an ideal platform for designing future optoelectronic devices based on topological insulators.

Sub-nanometre resolution of atomic motion during electronic excitation in phase-change materials.

PubMed

Mitrofanov, Kirill V; Fons, Paul; Makino, Kotaro; Terashima, Ryo; Shimada, Toru; Kolobov, Alexander V; Tominaga, Junji; Bragaglia, Valeria; Giussani, Alessandro; Calarco, Raffaella; Riechert, Henning; Sato, Takahiro; Katayama, Tetsuo; Ogawa, Kanade; Togashi, Tadashi; Yabashi, Makina; Wall, Simon; Brewe, Dale; Hase, Muneaki

2016-02-12

Phase-change materials based on Ge-Sb-Te alloys are widely used in industrial applications such as nonvolatile memories, but reaction pathways for crystalline-to-amorphous phase-change on picosecond timescales remain unknown. Femtosecond laser excitation and an ultrashort x-ray probe is used to show the temporal separation of electronic and thermal effects in a long-lived (>100 ps) transient metastable state of Ge2Sb2Te5 with muted interatomic interaction induced by a weakening of resonant bonding. Due to a specific electronic state, the lattice undergoes a reversible nondestructive modification over a nanoscale region, remaining cold for 4 ps. An independent time-resolved x-ray absorption fine structure experiment confirms the existence of an intermediate state with disordered bonds. This newly unveiled effect allows the utilization of non-thermal ultra-fast pathways enabling artificial manipulation of the switching process, ultimately leading to a redefined speed limit, and improved energy efficiency and reliability of phase-change memory technologies.

Sub-nanometre resolution of atomic motion during electronic excitation in phase-change materials

DOE PAGES

Mitrofanov, Kirill V.; Fons, Paul; Makino, Kotaro; ...

2016-02-12

Phase-change materials based on Ge-Sb-Te alloys are widely used in industrial applications such as nonvolatile memories, but reaction pathways for crystalline-to-amorphous phase-change on picosecond timescales remain unknown. Femtosecond laser excitation and an ultrashort x-ray probe is used to show the temporal separation of electronic and thermal effects in a long-lived (>100 ps) transient metastable state of Ge 2Sb 2Te 5 with muted interatomic interaction induced by a weakening of resonant bonding. Due to a specific electronic state, the lattice undergoes a reversible nondestructive modification over a nanoscale region, remaining cold for 4 ps. An independent time-resolved x-ray absorption fine structuremore » experiment confirms the existence of an intermediate state with disordered bonds. Furthermore, this newly unveiled effect allows the utilization of non-thermal ultra-fast pathways enabling artificial manipulation of the switching process, ultimately leading to a redefined speed limit, and improved energy efficiency and reliability of phase-change memory technologies.« less

Femtosecond time-resolved optical and Raman spectroscopy of photoinduced spin crossover: temporal resolution of low-to-high spin optical switching.

PubMed

Smeigh, Amanda L; Creelman, Mark; Mathies, Richard A; McCusker, James K

2008-10-29

A combination of femtosecond electronic absorption and stimulated Raman spectroscopies has been employed to determine the kinetics associated with low-spin to high-spin conversion following charge-transfer excitation of a FeII spin-crossover system in solution. A time constant of tau = 190 +/- 50 fs for the formation of the 5T2 ligand-field state was assigned based on the establishment of two isosbestic points in the ultraviolet in conjunction with changes in ligand stretching frequencies and Raman scattering amplitudes; additional dynamics observed in both the electronic and vibrational spectra further indicate that vibrational relaxation in the high-spin state occurs with a time constant of ca. 10 ps. The results set an important precedent for extremely rapid, formally forbidden (DeltaS = 2) nonradiative relaxation as well as defining the time scale for intramolecular optical switching between two electronic states possessing vastly different spectroscopic, geometric, and magnetic properties.

Ultrafast X-Ray Spectroscopy of Conical Intersections

NASA Astrophysics Data System (ADS)

Neville, Simon P.; Chergui, Majed; Stolow, Albert; Schuurman, Michael S.

2018-06-01

Ongoing developments in ultrafast x-ray sources offer powerful new means of probing the complex nonadiabatically coupled structural and electronic dynamics of photoexcited molecules. These non-Born-Oppenheimer effects are governed by general electronic degeneracies termed conical intersections, which play a key role, analogous to that of a transition state, in the electronic-nuclear dynamics of excited molecules. Using high-level ab initio quantum dynamics simulations, we studied time-resolved x-ray absorption (TRXAS) and photoelectron spectroscopy (TRXPS) of the prototypical unsaturated organic chromophore, ethylene, following excitation to its S2(π π*) state. The TRXAS, in particular, is highly sensitive to all aspects of the ensuing dynamics. These x-ray spectroscopies provide a clear signature of the wave packet dynamics near conical intersections, related to charge localization effects driven by the nuclear dynamics. Given the ubiquity of charge localization in excited state dynamics, we believe that ultrafast x-ray spectroscopies offer a unique and powerful route to the direct observation of dynamics around conical intersections.

Spatial potential ripples of azimuthal surface modes in topological insulator Bi 2Te 3 nanowires

DOE PAGES

Muñoz Rojo, Miguel; Zhang, Yingjie; Manzano, Cristina V.; ...

2016-01-11

Topological insulators (TI) nanowires (NW) are an emerging class of structures, promising both novel quantum effects and potential applications in low-power electronics, thermoelectrics and spintronics. However, investigating the electronic states of TI NWs is complicated, due to their small lateral size, especially at room temperature. Here, we perform scanning probe based nanoscale imaging to resolve the local surface potential landscapes of Bi 2Te 3 nanowires (NWs) at 300 K. We found equipotential rings around the NWs perimeter that we attribute to azimuthal 1D modes. Along the NW axis, these modes are altered, forming potential ripples in the local density ofmore » states, due to intrinsic disturbances. Potential mapping of electrically biased NWs enabled us to accurately determine their conductivity which was found to increase with the decrease of NW diameter, consistent with surface dominated transport. Finally, our results demonstrate that TI NWs can pave the way to both exotic quantum states and novel electronic devices.« less

Ultrafast Time-Resolved Hard X-Ray Emission Spectroscopy on a Tabletop

NASA Astrophysics Data System (ADS)

Miaja-Avila, Luis; O'Neil, Galen C.; Joe, Young I.; Alpert, Bradley K.; Damrauer, Niels H.; Doriese, William B.; Fatur, Steven M.; Fowler, Joseph W.; Hilton, Gene C.; Jimenez, Ralph; Reintsema, Carl D.; Schmidt, Daniel R.; Silverman, Kevin L.; Swetz, Daniel S.; Tatsuno, Hideyuki; Ullom, Joel N.

2016-07-01

Experimental tools capable of monitoring both atomic and electronic structure on ultrafast (femtosecond to picosecond) time scales are needed for investigating photophysical processes fundamental to light harvesting, photocatalysis, energy and data storage, and optical display technologies. Time-resolved hard x-ray (>3 keV ) spectroscopies have proven valuable for these measurements due to their elemental specificity and sensitivity to geometric and electronic structures. Here, we present the first tabletop apparatus capable of performing time-resolved x-ray emission spectroscopy. The time resolution of the apparatus is better than 6 ps. By combining a compact laser-driven plasma source with a highly efficient array of microcalorimeter x-ray detectors, we are able to observe photoinduced spin changes in an archetypal polypyridyl iron complex [Fe (2 ,2'-bipyridine)3]2 + and accurately measure the lifetime of the quintet spin state. Our results demonstrate that ultrafast hard x-ray emission spectroscopy is no longer confined to large facilities and now can be performed in conventional laboratories with 10 times better time resolution than at synchrotrons. Our results are enabled, in part, by a 100- to 1000-fold increase in x-ray collection efficiency compared to current techniques.

Lipidic cubic phase injector is a viable crystal delivery system for time-resolved serial crystallography

DOE PAGES

Nogly, Przemyslaw; Panneels, Valerie; Nelson, Garrett; ...

2016-08-22

Serial femtosecond crystallography (SFX) using X-ray free-electron laser sources is an emerging method with considerable potential for time-resolved pump-probe experiments. Here we present a lipidic cubic phase SFX structure of the light-driven proton pump bacteriorhodopsin (bR) to 2.3 Å resolution and a method to investigate protein dynamics with modest sample requirement. Time-resolved SFX (TR-SFX) with a pump-probe delay of 1 ms yields difference Fourier maps compatible with the dark to M state transition of bR. Importantly, the method is very sample efficient and reduces sample consumption to about 1 mg per collected time point. Accumulation of M intermediate within themore » crystal lattice is confirmed by time-resolved visible absorption spectroscopy. Furthermore, this study provides an important step towards characterizing the complete photocycle dynamics of retinal proteins and demonstrates the feasibility of a sample efficient viscous medium jet for TR-SFX.« less

Lipidic cubic phase injector is a viable crystal delivery system for time-resolved serial crystallography

DOE Office of Scientific and Technical Information (OSTI.GOV)

Nogly, Przemyslaw; Panneels, Valerie; Nelson, Garrett

Serial femtosecond crystallography (SFX) using X-ray free-electron laser sources is an emerging method with considerable potential for time-resolved pump-probe experiments. Here we present a lipidic cubic phase SFX structure of the light-driven proton pump bacteriorhodopsin (bR) to 2.3 Å resolution and a method to investigate protein dynamics with modest sample requirement. Time-resolved SFX (TR-SFX) with a pump-probe delay of 1 ms yields difference Fourier maps compatible with the dark to M state transition of bR. Importantly, the method is very sample efficient and reduces sample consumption to about 1 mg per collected time point. Accumulation of M intermediate within themore » crystal lattice is confirmed by time-resolved visible absorption spectroscopy. Furthermore, this study provides an important step towards characterizing the complete photocycle dynamics of retinal proteins and demonstrates the feasibility of a sample efficient viscous medium jet for TR-SFX.« less

Lipidic cubic phase injector is a viable crystal delivery system for time-resolved serial crystallography

PubMed Central

Nogly, Przemyslaw; Panneels, Valerie; Nelson, Garrett; Gati, Cornelius; Kimura, Tetsunari; Milne, Christopher; Milathianaki, Despina; Kubo, Minoru; Wu, Wenting; Conrad, Chelsie; Coe, Jesse; Bean, Richard; Zhao, Yun; Båth, Petra; Dods, Robert; Harimoorthy, Rajiv; Beyerlein, Kenneth R.; Rheinberger, Jan; James, Daniel; DePonte, Daniel; Li, Chufeng; Sala, Leonardo; Williams, Garth J.; Hunter, Mark S.; Koglin, Jason E.; Berntsen, Peter; Nango, Eriko; Iwata, So; Chapman, Henry N.; Fromme, Petra; Frank, Matthias; Abela, Rafael; Boutet, Sébastien; Barty, Anton; White, Thomas A.; Weierstall, Uwe; Spence, John; Neutze, Richard; Schertler, Gebhard; Standfuss, Jörg

2016-01-01

Serial femtosecond crystallography (SFX) using X-ray free-electron laser sources is an emerging method with considerable potential for time-resolved pump-probe experiments. Here we present a lipidic cubic phase SFX structure of the light-driven proton pump bacteriorhodopsin (bR) to 2.3 Å resolution and a method to investigate protein dynamics with modest sample requirement. Time-resolved SFX (TR-SFX) with a pump-probe delay of 1 ms yields difference Fourier maps compatible with the dark to M state transition of bR. Importantly, the method is very sample efficient and reduces sample consumption to about 1 mg per collected time point. Accumulation of M intermediate within the crystal lattice is confirmed by time-resolved visible absorption spectroscopy. This study provides an important step towards characterizing the complete photocycle dynamics of retinal proteins and demonstrates the feasibility of a sample efficient viscous medium jet for TR-SFX. PMID:27545823

Real-Space Mapping of Surface Trap States in CIGSe Nanocrystals Using 4D Electron Microscopy.

PubMed

Bose, Riya; Bera, Ashok; Parida, Manas R; Adhikari, Aniruddha; Shaheen, Basamat S; Alarousu, Erkki; Sun, Jingya; Wu, Tom; Bakr, Osman M; Mohammed, Omar F

2016-07-13

Surface trap states in copper indium gallium selenide semiconductor nanocrystals (NCs), which serve as undesirable channels for nonradiative carrier recombination, remain a great challenge impeding the development of solar and optoelectronics devices based on these NCs. In order to design efficient passivation techniques to minimize these trap states, a precise knowledge about the charge carrier dynamics on the NCs surface is essential. However, selective mapping of surface traps requires capabilities beyond the reach of conventional laser spectroscopy and static electron microscopy; it can only be accessed by using a one-of-a-kind, second-generation four-dimensional scanning ultrafast electron microscope (4D S-UEM) with subpicosecond temporal and nanometer spatial resolutions. Here, we precisely map the collective surface charge carrier dynamics of copper indium gallium selenide NCs as a function of the surface trap states before and after surface passivation in real space and time using S-UEM. The time-resolved snapshots clearly demonstrate that the density of the trap states is significantly reduced after zinc sulfide (ZnS) shelling. Furthermore, the removal of trap states and elongation of carrier lifetime are confirmed by the increased photocurrent of the self-biased photodetector fabricated using the shelled NCs.

Spectroscopic evidence for a type II Weyl semimetallic state in MoTe2

NASA Astrophysics Data System (ADS)

Huang, Lunan; McCormick, Timothy M.; Ochi, Masayuki; Zhao, Zhiying; Suzuki, Michi-To; Arita, Ryotaro; Wu, Yun; Mou, Daixiang; Cao, Huibo; Yan, Jiaqiang; Trivedi, Nandini; Kaminski, Adam

2016-11-01

In a type I Dirac or Weyl semimetal, the low-energy states are squeezed to a single point in momentum space when the chemical potential μ is tuned precisely to the Dirac/Weyl point. Recently, a type II Weyl semimetal was predicted to exist, where the Weyl states connect hole and electron bands, separated by an indirect gap. This leads to unusual energy states, where hole and electron pockets touch at the Weyl point. Here we present the discovery of a type II topological Weyl semimetal state in pure MoTe2, where two sets of Weyl points (, ) exist at the touching points of electron and hole pockets and are located at different binding energies above EF. Using angle-resolved photoemission spectroscopy, modelling, density functional theory and calculations of Berry curvature, we identify the Weyl points and demonstrate that they are connected by different sets of Fermi arcs for each of the two surface terminations. We also find new surface `track states' that form closed loops and are unique to type II Weyl semimetals. This material provides an exciting, new platform to study the properties of Weyl fermions.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tayebjee, Murad J. Y.; Sanders, Samuel N.; Kumarasamy, Elango

Singlet fission, in which two triplet excitons are generated from a single absorbed photon, is a key third-generation solar cell concept. Conservation of angular momentum requires that singlet fission populates correlated multiexciton states, which can subsequently dissociate to generate free triplets. However, little is known about electronic and spin correlations in these systems since, due to its typically short lifetime, the multiexciton state is challenging to isolate and study. Here, we use bridged pentacene dimers, which undergo intramolecular singlet fission while isolated in solution and in solid matrices, as a unimolecular model system that can trap long-lived multiexciton states. Wemore » also combine transient absorption and time-resolved electron spin resonance spectroscopies to show that spin correlations in the multiexciton state persist for hundreds of nanoseconds. Furthermore, we confirm long-standing predictions that singlet fission produces triplet pair states of quintet character. Finally, we compare two different pentacene–bridge–pentacene chromophores, systematically tuning the coupling between the pentacenes to understand how differences in molecular structure affect the population and dissociation of multiexciton quintet states.« less

ROVIBRATIONALLY RESOLVED DIRECT PHOTODISSOCIATION THROUGH THE LYMAN AND WERNER TRANSITIONS OF H{sub 2} FOR FUV/X-RAY-IRRADIATED ENVIRONMENTS

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gay, C. D.; Porter, R. L.; Stancil, P. C.

Using ab initio potential curves and dipole transition moments, cross-section calculations were performed for the direct continuum photodissociation of H{sub 2} through the B{sup 1}{Sigma}{sup +}{sub u} <- X{sup 1}{Sigma}{sup +}{sub g} (Lyman) and C{sup 1}{Pi}{sub u} <- X{sup 1}{Sigma}{sup +}{sub g} (Werner) transitions. Partial cross-sections were obtained for wavelengths from 100 A to the dissociation threshold between the upper electronic state and each of the 301 bound rovibrational levels v''J'' within the ground electronic state. The resulting cross-sections are incorporated into three representative classes of interstellar gas models: diffuse clouds, photon-dominated regions, and X-ray-dominated regions (XDRs). The models, whichmore » used the CLOUDY plasma/molecular spectra simulation code, demonstrate that direct photodissociation is comparable to fluorescent dissociation (or spontaneous radiative dissociation, the Solomon process) as an H{sub 2} destruction mechanism in intense far-ultraviolet or X-ray-irradiated gas. In particular, changes in H{sub 2} rotational column densities are found to be as large as 20% in the XDR model with the inclusion of direct photodissociation. The photodestruction rate from some high-lying rovibrational levels can be enhanced by pumping from H Ly{beta} due to a wavelength coincidence with cross-section resonances resulting from quasi-bound levels of the upper electronic states. Given the relatively large size of the photodissociation data set, a strategy is described to create truncated, but reliable, cross-section data consistent with the wavelength resolving power of typical observations.« less

Tunneling-Electron-Induced Light Emission from Single Gold Nanoclusters.

PubMed

Yu, Arthur; Li, Shaowei; Czap, Gregory; Ho, W

2016-09-14

The coupling of tunneling electrons with the tip-nanocluster-substrate junction plasmon was investigated by monitoring light emission in a scanning tunneling microscope (STM). Gold atoms were evaporated onto the ∼5 Å thick Al2O3 thin film grown on the NiAl (110) surface where they formed nanoclusters 3-7 nm wide. Scanning tunneling spectroscopy (STS) of these nanoclusters revealed quantum-confined electronic states. Spatially resolved photon imaging showed localized emission hot spots. Size dependent study and light emission from nanocluster dimers further support the viewpoint that coupling of tunneling electrons to the junction plasmon is the main radiative mechanism. These results showed the potential of the STM to reveal the electronic and optical properties of nanoscale metallic systems in the confined geometry of the tunnel junction.

Julius Edgar Lilienfeld Prize Talk: Quantum spintronics: abandoning perfection for new technologies

NASA Astrophysics Data System (ADS)

Awschalom, David D.

2015-03-01

There is a growing interest in exploiting the quantum properties of electronic and nuclear spins for the manipulation and storage of information in the solid state. Such schemes offer qualitatively new scientific and technological opportunities by leveraging elements of standard electronics to precisely control coherent interactions between electrons, nuclei, and electromagnetic fields. We provide an overview of the field, including a discussion of temporally- and spatially-resolved magneto-optical measurements designed for probing local moment dynamics in electrically and magnetically doped semiconductor nanostructures. These early studies provided a surprising proof-of-concept that quantum spin states can be created and controlled with high-speed optoelectronic techniques. However, as electronic structures approach the atomic scale, small amounts of disorder begin to have outsized negative effects. An intriguing solution to this conundrum is emerging from recent efforts to embrace semiconductor defects themselves as a route towards quantum machines. Individual defects in carbon-based materials possess an electronic spin state that can be employed as a solid state quantum bit at and above room temperature. Developments at the frontier of this field include gigahertz coherent control, nanofabricated spin arrays, nuclear spin quantum memories, and nanometer-scale sensing. We will describe advances towards quantum information processing driven by both physics and materials science to explore electronic, photonic, and magnetic control of spin. Work supported by the AFOSR, ARO, DARPA, NSF, and ONR.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Godfrey, T. J.; Yu, Hui; Ullrich, Susanne, E-mail: ullrich@physast.uga.edu

The studies herein investigate the involvement of the low-lying {sup 1}L{sub a} and {sup 1}L{sub b} states with {sup 1}ππ{sup *} character and the {sup 1}πσ{sup *} state in the deactivation process of indole following photoexcitation at 201 nm. Three gas-phase, pump-probe spectroscopic techniques are employed: (1) Time-resolved photoelectron spectroscopy (TR-PES), (2) hydrogen atom (H-atom) time-resolved kinetic energy release (TR-KER), and (3) time-resolved ion yield (TR-IY). Each technique provides complementary information specific to the photophysical processes in the indole molecule. In conjunction, a thorough examination of the electronically excited states in the relaxation process, with particular focus on the involvement ofmore » the {sup 1}πσ{sup *} state, is afforded. Through an extensive analysis of the TR-PES data presented here, it is deduced that the initial excitation of the {sup 1}B{sub b} state decays to the {sup 1}L{sub a} state on a timescale beyond the resolution of the current experimental setup. Relaxation proceeds on the {sup 1}L{sub a} state with an ultrafast decay constant (<100 femtoseconds (fs)) to the lower-lying {sup 1}L{sub b} state, which is found to possess a relatively long lifetime of 23 ± 5 picoseconds (ps) before regressing to the ground state. These studies also manifest an additional component with a relaxation time of 405 ± 76 fs, which is correlated with activity along the {sup 1}πσ{sup *} state. TR-KER and TR-IY experiments, both specifically probing {sup 1}πσ{sup *} dynamics, exhibit similar decay constants, further validating these observations.« less

Observation of topological surface states and strong electron/hole imbalance in extreme magnetoresistance compound LaBi

NASA Astrophysics Data System (ADS)

Jiang, J.; Schröter, N. B. M.; Wu, S.-C.; Kumar, N.; Shekhar, C.; Peng, H.; Xu, X.; Chen, C.; Yang, H. F.; Hwang, C.-C.; Mo, S.-K.; Felser, C.; Yan, B. H.; Liu, Z. K.; Yang, L. X.; Chen, Y. L.

2018-02-01

The recent discovery of the extreme magnetoresistance (XMR) in the nonmagnetic rare-earth monopnictides La X (X = P, As, Sb, Bi,), a recently proposed new topological semimetal family, has inspired intensive research effort in the exploration of the correlation between the XMR and their electronic structures. In this work, using angle-resolved photoemission spectroscopy to investigate the three-dimensional band structure of LaBi, we unraveled its topologically nontrivial nature with the observation of multiple topological surface Dirac fermions, as supported by our ab initio calculations. Furthermore, we observed substantial imbalance between the volume of electron and hole pockets, which rules out the electron-hole compensation as the primary cause of the XMR in LaBi.

Adsorbate-induced shifts of electronic surface states: Cs on the (100) faces of tungsten, molybdenum, and tantalum

DOE Office of Scientific and Technical Information (OSTI.GOV)

Soukiassian, P.; Riwan, R.; Lecante, J.

1985-04-15

The adsorption of cesium on the (100) faces of W, Mo, and Ta for coverages between 0 and 1 monolayer is studied by angle-resolved ultraviolet photoemission spectroscopy with use of synchro- tron radiation, by electron-energy-loss spectroscopy, and by low-energy electron diffraction. With increasing cesiation, the W(100) surface state at Gamma-bar located 0.3 eV below the Fermi level is shifted by up to 1.0 eV to larger binding energies while remaining sharp and intense. A similar behavior is observed on Ta(100), whereas on Mo(100) the shift of 0.9 eV of this surface state is accompanied by a pronounced attenuation of itsmore » intensity. These experimental shifts are shown to be in excellent agreement with all-electron local-density-functional results obtained with the full-potential linearized augmented-plane-wave method for Cs monolayers on the W(100) and Mo(100) surfaces. Based on these ab initio results, the electronic origin of the shifts is understood by the formation of strongly polarized covalent bonds between the d-like surface states and the Cs 6s--derived valence states. It is argued that even at high Cs coverages, the main electron-energy-loss peaks, which are observed between 1 and 2 eV, could be interpreted as Cs 6s..-->..6p--like interband transitions rather than as surface-plasmon peaks.« less

Delocalization Drives Free Charge Generation in Conjugated Polymer Films

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pace, Natalie A.; Reid, Obadiah G.; Rumbles, Garry

We demonstrate that the product of photoinduced electron transfer between a conjugated polymer host and a dilute molecular sensitizer is controlled by the structural state of the polymer. Ordered semicrystalline solids exhibit free charge generation, while disordered polymers in the melt phase do not. We use photoluminescence (PL) and time-resolved microwave conductivity (TRMC) measurements to sweep through polymer melt transitions in situ. Free charge generation measured by TRMC turns off upon melting, whereas PL quenching of the molecular sensitizers remains constant, implying unchanged electron transfer efficiency. The key difference is the intermolecular order of the polymer host in the solidmore » state compared to the melt. We propose that this order-disorder transition modulates the localization length of the initial charge-transfer state, which controls the probability of free charge formation.« less

Delocalization Drives Free Charge Generation in Conjugated Polymer Films

DOE PAGES

Pace, Natalie A.; Reid, Obadiah G.; Rumbles, Garry

2018-02-19

We demonstrate that the product of photoinduced electron transfer between a conjugated polymer host and a dilute molecular sensitizer is controlled by the structural state of the polymer. Ordered semicrystalline solids exhibit free charge generation, while disordered polymers in the melt phase do not. We use photoluminescence (PL) and time-resolved microwave conductivity (TRMC) measurements to sweep through polymer melt transitions in situ. Free charge generation measured by TRMC turns off upon melting, whereas PL quenching of the molecular sensitizers remains constant, implying unchanged electron transfer efficiency. The key difference is the intermolecular order of the polymer host in the solidmore » state compared to the melt. We propose that this order-disorder transition modulates the localization length of the initial charge-transfer state, which controls the probability of free charge formation.« less

Theory of hydrodynamic transport in fluctuating electronic charge density wave states

NASA Astrophysics Data System (ADS)

Delacrétaz, Luca V.; Goutéraux, Blaise; Hartnoll, Sean A.; Karlsson, Anna

2017-11-01

We describe the collective hydrodynamic motion of an incommensurate charge density wave state in a clean electronic system. Our description simultaneously incorporates the effects of both pinning due to weak disorder and also phase relaxation due to proliferating dislocations. We show that the interplay between these two phenomena has important consequences for charge and momentum transport. For instance, it can lead to metal-insulator transitions. We furthermore identify signatures of fluctuating density waves in frequency and spatially resolved conductivities. Phase disordering is well known to lead to a large viscosity. We derive a precise formula for the phase relaxation rate in terms of the viscosity in the dislocation cores. We thereby determine the viscosity of the superconducting state of BSCCO from the observed melting dynamics of Abrikosov lattices and show that the result is consistent with dissipation into Bogoliubov quasiparticles.

Creation of Rydberg Polarons in a Bose Gas

NASA Astrophysics Data System (ADS)

Camargo, F.; Schmidt, R.; Whalen, J. D.; Ding, R.; Woehl, G.; Yoshida, S.; Burgdörfer, J.; Dunning, F. B.; Sadeghpour, H. R.; Demler, E.; Killian, T. C.

2018-02-01

We report spectroscopic observation of Rydberg polarons in an atomic Bose gas. Polarons are created by excitation of Rydberg atoms as impurities in a strontium Bose-Einstein condensate. They are distinguished from previously studied polarons by macroscopic occupation of bound molecular states that arise from scattering of the weakly bound Rydberg electron from ground-state atoms. The absence of a p -wave resonance in the low-energy electron-atom scattering in Sr introduces a universal behavior in the Rydberg spectral line shape and in scaling of the spectral width (narrowing) with the Rydberg principal quantum number, n . Spectral features are described with a functional determinant approach (FDA) that solves an extended Fröhlich Hamiltonian for a mobile impurity in a Bose gas. Excited states of polyatomic Rydberg molecules (trimers, tetrameters, and pentamers) are experimentally resolved and accurately reproduced with a FDA.

Attaching naphthalene derivatives onto BODIPY for generating excited triplet state and singlet oxygen: Tuning PET-based photosensitizer by electron donors

NASA Astrophysics Data System (ADS)

Zhang, Xian-Fu; Feng, Nan

2018-01-01

meso-Naphthalene substituted BODIPY compounds were prepared in a facile one pot reaction. The naphthalene functionalization of BODIPY leads up to a 5-fold increase in the formation efficiency of excited triplet state and singlet oxygen in polar solvents. Steady state and time resolved fluorescence, laser flash photolysis, and quantum chemistry methods were used to reveal the mechanism. All measured data and quantum chemical results suggest that these systems can be viewed as electron donor-acceptor (D-A) pair (BODIPY acts as the acceptor), photoinduced charge transfer (PCT) or photoinduced electron transfer (PET) occurs upon photo excitation (D-A + hν → Dδ +-Aδ -, 0 < δ ≤ 1), and the charge recombination induced the formation of triplet state (Dδ +-Aδ - → D-A (T1). These novel PCT- or PET-based photosensitizers (PSs) show different features from traditional PSs, such as the strong tunability by facile structural modification and good selectivity upon medium polarity. The new character for this type of PSs can lead to important applications in organic oxygenation reactions and photodynamic therapy of tumors.

Layer speciation and electronic structure investigation of freestanding hexagonal boron nitride nanosheets

NASA Astrophysics Data System (ADS)

WangEqual Contribution To This Work., Jian; Wang, Zhiqiang; Cho, Hyunjin; Kim, Myung Jong; Sham, T. K.; Sun, Xuhui

2015-01-01

Chemical imaging, thickness mapping, layer speciation and polarization dependence have been performed on single and multilayered (up to three layers and trilayered nanosheets overlapping to form 6 and 9 layers) hexagonal boron nitride (hBN) nanosheets by scanning transmission X-ray microscopy. Spatially-resolved XANES directly from freestanding regions of different layers has been extracted and compared with sample normal and 30° tilted configurations. Notably a double feature σ* excitonic state and a stable high energy σ* state were observed at the boron site in addition to the intense π* excitonic state. The boron projected σ* DOS, especially the first σ* exciton, is sensitive to surface modification, particularly in the single layered hBN nanosheet which shows more significant detectable contaminants and defects such as tri-coordinated boron/nitrogen oxide. The nitrogen site has shown very weak or no excitonic character. The distinct excitonic effect on boron and nitrogen was interpreted to the partly ionic state of hBN. Bulk XANES of hBN nanosheets was also measured to confirm the spectro-microscopic STXM result. Finally, the unoccupied electronic structures of hBN and graphene were compared.Chemical imaging, thickness mapping, layer speciation and polarization dependence have been performed on single and multilayered (up to three layers and trilayered nanosheets overlapping to form 6 and 9 layers) hexagonal boron nitride (hBN) nanosheets by scanning transmission X-ray microscopy. Spatially-resolved XANES directly from freestanding regions of different layers has been extracted and compared with sample normal and 30° tilted configurations. Notably a double feature σ* excitonic state and a stable high energy σ* state were observed at the boron site in addition to the intense π* excitonic state. The boron projected σ* DOS, especially the first σ* exciton, is sensitive to surface modification, particularly in the single layered hBN nanosheet which shows more significant detectable contaminants and defects such as tri-coordinated boron/nitrogen oxide. The nitrogen site has shown very weak or no excitonic character. The distinct excitonic effect on boron and nitrogen was interpreted to the partly ionic state of hBN. Bulk XANES of hBN nanosheets was also measured to confirm the spectro-microscopic STXM result. Finally, the unoccupied electronic structures of hBN and graphene were compared. Electronic supplementary information (ESI) available. See DOI: 10.1039/c4nr04445b

Evidence for unnatural-parity contributions to electron-impact ionization of laser-aligned atoms

DOE PAGES

Armstrong, Gregory S. J.; Colgan, James Patrick; Pindzola, M. S.; ...

2015-09-11

Recent measurements have examined the electron-impact ionization of excited-state laser-aligned Mg atoms. In this paper we show that the ionization cross section arising from the geometry where the aligned atom is perpendicular to the scattering plane directly probes the unnatural parity contributions to the ionization amplitude. The contributions from natural parity partial waves cancel exactly in this geometry. Our calculations resolve the discrepancy between the nonzero measured cross sections in this plane and the zero cross section predicted by distorted-wave approaches. Finally, we demonstrate that this is a general feature of ionization from p-state targets by additional studies of ionizationmore » from excited Ca and Na atoms.« less

Photodissociation spectroscopy and ab initio calculations for the Sr +-N 2 complex

NASA Astrophysics Data System (ADS)

Massaouti, Maria; Fanourgakis, George S.; Velegrakis, Michalis

2010-04-01

Electronic vibrationally resolved spectra of the Sr +-N 2 complex have been recorded in two energy regions 20 284-22 988 cm -1 and 15 576-16 380 cm -1. In the high energy region, two progressions are present and they are attributed to the (2) 2Π 3/2,1/2 ← X2Σ+ transitions assuming a linear molecule. This linear configuration is supported from the observed spin-orbit splitting of these excited states as well as from electronic structure calculations. The lower energy spectrum shows a structure, which ends up to a continuum. Considering the complex as an anharmonic oscillator, the spectroscopic constants and the dissociation energies of the corresponding states are determined.

Vibrationally-resolved Photoelectron Spectroscopy of the Model GFP Chromophore Anion Revealing the Photoexcited S-1 State being both Vertically and Adiabatically Bound against the Photodetached D-0 Continuum

DOE Office of Scientific and Technical Information (OSTI.GOV)

Deng, Shihu; Kong, Xiangyu; Zhang, GuanXin

2014-06-19

The first excited state of the model green fluorescence protein (GFP) chromophore anion (S1) and its energy level against the electron-detached neutral radical, D0 state are crucial in determining the photophysics and the photo-induced dynamics of GFP. Extensive experimental and theoretical studies, particularly several very recent gas phase investigations concluded that S1 is a bound state in the Franck-Condon vertical region with respect to D0. However, what remains unknown and challenging is if S1 is bound adiabatically, primarily due to lack of accurate experimental measurements, as well as due to close proximity in energy for these two states that evenmore » sophisticated high-level ab initio calculations can’t reliably predict. Here, we report a negative ion photoelectron spectroscopy study on the model GFP chromophore anion, the deprotonated p-hydroxybenzylidene-2,3-dimethylimidazolinone anion (HBDI–). Despite the considerable size and low symmetry of the molecule, well resolved vibrational structures were obtained with the 0–0 transition being the most intense peak. The adiabatic (ADE) and vertical detachment energy (VDE) therefore are determined, both to be 2.73 ± 0.01 eV, indicating the detached D0 state is 0.16 eV higher in energy than the photon excited S1 state. The accurate ADE and VDE values and the well-resolved photoelectron spectra reported here provide much needed, robust benchmarks for future theoretical investigations.« less

Layer-dependent quantum cooperation of electron and hole states in the anomalous semimetal WTe 2

DOE PAGES

Das, Pranab Kumar; Di Sante, D.; Vobornik, I.; ...

2016-02-29

The behaviour of electrons and holes in a crystal lattice is a fundamental quantum phenomenon, accounting for a rich variety of material properties. Boosted by the remarkable electronic and physical properties of two-dimensional materials such as graphene and topological insulators, transition metal dichalcogenides have recently received renewed attention. In this context, the anomalous bulk properties of semimetallic WTe 2 have attracted considerable interest. We report angle- and spin-resolved photoemission spectroscopy of WTe 2 single crystals, through which we disentangle the role of W and Te atoms in the formation of the band structure and identify the interplay of charge, spinmore » and orbital degrees of freedom. Supported by first-principles calculations and high-resolution surface topography, we also reveal the existence of a layer-dependent behaviour. The balance of electron and hole states is found only when considering at least three Te–W–Te layers, showing that the behaviour of WTe 2 is not strictly two dimensional.« less

Observation of Fermi arcs in the type-II Weyl semimetal candidate WTe 2

DOE PAGES

Wu, Yun; Mou, Daixiang; Jo, Na Hyun; ...

2016-09-14

We use ultrahigh resolution, tunable, vacuum ultraviolet laser angle-resolved photoemission spectroscopy (ARPES) to study the electronic properties of WTe 2, a material that was predicted to be a type-II Weyl semimetal. The Weyl fermion states in WTe 2 were proposed to emerge at the crossing points of electron and hole pockets, and Fermi arcs connecting electron and hole pockets would be visible in the spectral function on (001) surface. Here we report the observation of such Fermi arcs in WTe 2 confirming the theoretical predictions. This provides strong evidence for type-II Weyl semimetallic states in WTe 2. Here, we alsomore » find that trivial and topological domains coexist on the same surface of the sample due to the presence of inhomogeneous strain detected by scanning electron microscopy data. This is in agreement with the theoretical prediction that strain can drive this system from topological Weyl to trivial semimetal. WTe 2 therefore provides a tunable playground for studying exotic topological quantum effects.« less

Observation of Fermi arcs in the type-II Weyl semimetal candidate WTe 2

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wu, Yun; Mou, Daixiang; Jo, Na Hyun

We use ultrahigh resolution, tunable, vacuum ultraviolet laser angle-resolved photoemission spectroscopy (ARPES) to study the electronic properties of WTe 2, a material that was predicted to be a type-II Weyl semimetal. The Weyl fermion states in WTe 2 were proposed to emerge at the crossing points of electron and hole pockets, and Fermi arcs connecting electron and hole pockets would be visible in the spectral function on (001) surface. Here we report the observation of such Fermi arcs in WTe 2 confirming the theoretical predictions. This provides strong evidence for type-II Weyl semimetallic states in WTe 2. Here, we alsomore » find that trivial and topological domains coexist on the same surface of the sample due to the presence of inhomogeneous strain detected by scanning electron microscopy data. This is in agreement with the theoretical prediction that strain can drive this system from topological Weyl to trivial semimetal. WTe 2 therefore provides a tunable playground for studying exotic topological quantum effects.« less

Materials Properties and Solvated Electron Dynamics of Isolated Nanoparticles and Nanodroplets Probed with Ultrafast Extreme Ultraviolet Beams.

PubMed

Ellis, Jennifer L; Hickstein, Daniel D; Xiong, Wei; Dollar, Franklin; Palm, Brett B; Keister, K Ellen; Dorney, Kevin M; Ding, Chengyuan; Fan, Tingting; Wilker, Molly B; Schnitzenbaumer, Kyle J; Dukovic, Gordana; Jimenez, Jose L; Kapteyn, Henry C; Murnane, Margaret M

2016-02-18

We present ultrafast photoemission measurements of isolated nanoparticles in vacuum using extreme ultraviolet (EUV) light produced through high harmonic generation. Surface-selective static EUV photoemission measurements were performed on nanoparticles with a wide array of compositions, ranging from ionic crystals to nanodroplets of organic material. We find that the total photoelectron yield varies greatly with nanoparticle composition and provides insight into material properties such as the electron mean free path and effective mass. Additionally, we conduct time-resolved photoelectron yield measurements of isolated oleylamine nanodroplets, observing that EUV photons can create solvated electrons in liquid nanodroplets. Using photoemission from a time-delayed 790 nm pulse, we observe that a solvated electron is produced in an excited state and subsequently relaxes to its ground state with a lifetime of 151 ± 31 fs. This work demonstrates that femotosecond EUV photoemission is a versatile surface-sensitive probe of the properties and ultrafast dynamics of isolated nanoparticles.

Near UV bands of jet-cooled CaO

NASA Astrophysics Data System (ADS)

Stewart, Jacob T.; Sullivan, Michael N.; Heaven, Michael C.

2016-04-01

The electronic spectrum of CaO has been recorded for the 29,800-33,150 cm-1 energy range. Jet cooling was used to obtain relatively uncongested spectra. Rotationally resolved bands have been assigned to the C1Σ+-X1Σ+ and F1∏-X transitions. These data extend the range of vibronic levels characterized for the upper states. Three additional vibronic states were observed as a short progression. One of these levels, which are of 0+ symmetry, interacts strongly with the C1Σ+, v‧ = 7 level. Possible assignments for the perturbing state are considered.

Effect of spin fluctuations on the electronic structure in iron-based superconductors

NASA Astrophysics Data System (ADS)

Heimes, Andreas; Grein, Roland; Eschrig, Matthias

2012-08-01

Magnetic inelastic neutron scattering studies of iron-based superconductors reveal a strongly temperature-dependent spin-fluctuation spectrum in the normal conducting state, which develops a prominent low-energy resonance feature when entering the superconducting state. Angle-resolved photoemission spectroscopy (ARPES) and scanning tunneling spectroscopy (STS) allow us to study the fingerprints of fluctuation modes via their interactions with electronic quasiparticles. We calculate such fingerprints in 122 iron pnictides using an experimentally motivated spin-fluctuation spectrum and make a number of predictions that can be tested in ARPES and STS experiments. This includes discussions of the quasiparticle scattering rate and the superconducting order parameter. In quantitative agreement with experiment we reproduce the quasiparticle dispersions obtained from momentum distribution curves as well as energy distribution curves. We discuss the relevance of the coupling between spin fluctuations and electronic excitations for the superconducting mechanism.

Non-Adiabatic Effects on Excited States of Vinylidene Observed with Slow Photoelectron Velocity-Map Imaging.

PubMed

DeVine, Jessalyn A; Weichman, Marissa L; Zhou, Xueyao; Ma, Jianyi; Jiang, Bin; Guo, Hua; Neumark, Daniel M

2016-12-21

High-resolution slow photoelectron velocity-map imaging spectra of cryogenically cooled X̃ 2 B 2 H 2 CC - and D 2 CC - in the region of the vinylidene triplet excited states are reported. Three electronic bands are observed and, with the assistance of electronic structure calculations and quantum dynamics on ab initio-based near-equilibrium potential energy surfaces, are assigned as detachment to the [Formula: see text] 3 B 2 (T 1 ), b̃ 3 A 2 (T 2 ), and à 1 A 2 (S 1 ) excited states of neutral vinylidene. This work provides the first experimental observation of the à singlet excited state of H 2 CC. While regular vibrational structure is observed for the ã and à electronic bands, a number of irregular features are resolved in the vicinity of the b̃ band vibrational origin. High-level ab initio calculations suggest that this anomalous structure arises from a conical intersection between the ã and b̃ triplet states near the b̃ state minimum, which strongly perturbs the vibrational levels in the two electronic states through nonadiabatic coupling. Using the adiabatic electron affinity of H 2 CC previously measured to be 0.490(6) eV by Ervin and co-workers [J. Chem. Phys. 1989, 91, 5974], term energies for the excited neutral states of H 2 CC are found to be T 0 (ã 3 B 2 ) = 2.064(6), T 0 (b̃ 3 A 2 ) = 2.738(6), and T 0 (à 1 A 2 ) = 2.991(6) eV.

Study of poly(N,N-dimethylacrylamide)/CdS nanocomposite organic/inorganic gels.

PubMed

Bekiari, Vlasoula; Pagonis, Konstantinos; Bokias, Georgios; Lianos, Panagiotis

2004-09-14

CdS nanoparticles have been synthesized and stabilized in poly(N,N-dimethylacrylamide) hydrogels. The properties of the composite material have been characterized by UV-vis spectroscopy, scanning electron microscopy, X-ray diffraction, thermogravimetric analysis, and steady-state and time-resolved luminescence spectroscopy. This material can be obtained in three different states: swollen, shrunk, and freeze-dried. The swollen and the freeze-dried states correspond to a nanocomposite organic/inorganic (wet or dry) gel containing CdS nanoparticles of approximately 50 nm diameter while the shrunk state is a two-phase system containing CdS crystals, which precipitate forming interesting geometrical shapes.

Genuine binding energy of the hydrated electron

PubMed Central

Luckhaus, David; Yamamoto, Yo-ichi; Suzuki, Toshinori; Signorell, Ruth

2017-01-01

The unknown influence of inelastic and elastic scattering of slow electrons in water has made it difficult to clarify the role of the solvated electron in radiation chemistry and biology. We combine accurate scattering simulations with experimental photoemission spectroscopy of the hydrated electron in a liquid water microjet, with the aim of resolving ambiguities regarding the influence of electron scattering on binding energy spectra, photoelectron angular distributions, and probing depths. The scattering parameters used in the simulations are retrieved from independent photoemission experiments of water droplets. For the ground-state hydrated electron, we report genuine values devoid of scattering contributions for the vertical binding energy and the anisotropy parameter of 3.7 ± 0.1 eV and 0.6 ± 0.2, respectively. Our probing depths suggest that even vacuum ultraviolet probing is not particularly surface-selective. Our work demonstrates the importance of quantitative scattering simulations for a detailed analysis of key properties of the hydrated electron. PMID:28508051

Electrically-Generated Spin Polarization in Non-Magnetic Semiconductors

DTIC Science & Technology

2016-03-31

resolved Faraday rotation data due to electron spin polarization from previous pump pulses was characterized, and an analytic solution for this phase...electron spin polarization was shown to produce nuclear hyperpolarization through dynamic nuclear polarization. Time-resolved Faraday rotation...Distribution approved for public release. 3    Figure 3. Total magnetic field measured using time-resolved Faraday rotation with the electrically

Femtosecond electron diffraction and spectroscopic studies of a solid state organic chemical reaction

NASA Astrophysics Data System (ADS)

Jean-Ruel, Hubert

Photochromic diarylethene molecules are excellent model systems for studying electrocyclic reactions, in addition to having important technological applications in optoelectronics. The photoinduced ring-closing reaction in a crystalline photochromic diarylethene derivative was fully resolved using the complementary techniques of transient absorption spectroscopy and femtosecond electron crystallography. These studies are detailed in this thesis, together with the associated technical developments which enabled them. Importantly, the time-resolved crystallographic investigation reported here represents a highly significant proof-of-principle experiment. It constitutes the first study directly probing the molecular structural changes associated with an organic chemical reaction with sub-picosecond temporal and atomic spatial resolution---to follow the primary motions directing chemistry. In terms of technological development, the most important advance reported is the implementation of a radio frequency rebunching system capable of producing femtosecond electron pulses of exceptional brightness. The temporal resolution of this newly developed electron source was fully characterized using laser ponderomotive scattering, confirming a 435 +/- 75 fs instrument response time with 0.20 pC bunches. The ultrafast spectroscopic and crystallographic measurements were both achieved by exploiting the photoreversibility of diarylethene. The transient absorption study was first performed, after developing a novel robust acquisition scheme for thermally irreversible reactions in the solid state. It revealed the formation of an open-ring excited state intermediate, following photoexcitation of the open-ring isomer with an ultraviolet laser pulse, with a time constant of approximately 200 fs. The actual ring closing was found to occur from this intermediate with a time constant of 5.3 +/- 0.3 ps. The femtosecond diffraction measurements were then performed using multiple crystal orientations and a large number of different samples. To analyse the results, an innovative method was developed in which the apparently complex ring-closing reaction is distilled down to a small number of basic rotations. Immediately following photoexcitation, sub-picosecond structural changes associated with the formation of the intermediate are observed. The rotation of the thiophene rings is identified as the key motion. Subsequently, on the few picosecond time scale, the time-resolved diffraction patterns are observed to converge towards those associated with the closed-ring photoproduct. The formation of the closed-ring molecule is thus unambiguously witnessed.

Time-resolved vibrational spectroscopy detects protein-based intermediates in the photosynthetic oxygen-evolving cycle.

PubMed

Barry, Bridgette A; Cooper, Ian B; De Riso, Antonio; Brewer, Scott H; Vu, Dung M; Dyer, R Brian

2006-05-09

Photosynthetic oxygen production by photosystem II (PSII) is responsible for the maintenance of aerobic life on earth. The production of oxygen occurs at the PSII oxygen-evolving complex (OEC), which contains a tetranuclear manganese (Mn) cluster. Photo-induced electron transfer events in the reaction center lead to the accumulation of oxidizing equivalents on the OEC. Four sequential photooxidation reactions are required for oxygen production. The oxidizing complex cycles among five oxidation states, called the S(n) states, where n refers to the number of oxidizing equivalents stored. Oxygen release occurs during the S(3)-to-S(0) transition from an unstable intermediate, known as the S(4) state. In this report, we present data providing evidence for the production of an intermediate during each S state transition. These protein-derived intermediates are produced on the microsecond to millisecond time scale and are detected by time-resolved vibrational spectroscopy on the microsecond time scale. Our results suggest that a protein-derived conformational change or proton transfer reaction precedes Mn redox reactions during the S(2)-to-S(3) and S(3)-to-S(0) transitions.

Analysis of Rotationally Resolved Spectra to Non-Degenerate (a''_1) Upper-State Vibronic Levels in the tilde{A} ^2E''-tilde{X}^2A^'_2 Electronic Transition of NO_3

NASA Astrophysics Data System (ADS)

Roudjane, Mourad; Codd, Terrance Joseph; Chen, Ming-Wei; Tran, Henry; Melnik, Dmitry G.; Miller, Terry A.; Stanton, John F.

2015-06-01

The vibronic structure of the tilde{A}-tilde{X} electronic spectrum of NO_3 has been observed using both room-temperature and jet-cooled samples. A recent analysis of this structure is consistent with the Jahn-Teller effect (JTE) in the e^' ν_3 vibrational mode (N-O stretch) being quite strong while the JTE in the e^' ν_4 mode (O-N-O) bend) is rather weak. Electronic structure calculations qualitatively predict these results but the calculated magnitude of the JTE is quantitatively inconsistent with the spectral analysis. Rotationally resolved spectra have been obtained for over a dozen vibronic bands of the tilde{A}-tilde{X} electronic transition in NO_3. An analysis of these spectra should provide considerably more experimental information about the JTE in the tilde{A} state of NO_3 as the rotational structure should be quite sensitive to the geometric distortion of the molecule due to the JTE. This talk will focus upon the parallel bands, which terminate on tilde{A} state levels of a''_1 vibronic symmetry, which were the subject of a preliminary analysis reported at this meeting in 2014. We have now recorded the rotational structure of over a half-dozen parallel bands and have completed analysis on the 3^1_0 and 3^1_0 4^1_0 transitions with several other bands being reasonably well understood. Two general conclusions emerge from this work. (i) All the spectral bands show evidence of perturbations which can reasonably be assumed to result from interactions of the observed tilde{A} state levels with high vibrational levels of the tilde{X} state. The perturbations range from severe in some bands to quite modest in others. (ii) Analyses of observed spectra, insofar as the perturbations permit, have all been performed with an oblate symmetric top model including only additional spin-rotation effects. This result is, of course, consistent with an effective, undistorted geometry for NO_3 of D3h symmetry on the rotational timescale.

Quadratic Fermi node in a 3D strongly correlated semimetal

PubMed Central

Kondo, Takeshi; Nakayama, M.; Chen, R.; Ishikawa, J. J.; Moon, E.-G.; Yamamoto, T.; Ota, Y.; Malaeb, W.; Kanai, H.; Nakashima, Y.; Ishida, Y.; Yoshida, R.; Yamamoto, H.; Matsunami, M.; Kimura, S.; Inami, N.; Ono, K.; Kumigashira, H.; Nakatsuji, S.; Balents, L.; Shin, S.

2015-01-01

Strong spin–orbit coupling fosters exotic electronic states such as topological insulators and superconductors, but the combination of strong spin–orbit and strong electron–electron interactions is just beginning to be understood. Central to this emerging area are the 5d transition metal iridium oxides. Here, in the pyrochlore iridate Pr2Ir2O7, we identify a non-trivial state with a single-point Fermi node protected by cubic and time-reversal symmetries, using a combination of angle-resolved photoemission spectroscopy and first-principles calculations. Owing to its quadratic dispersion, the unique coincidence of four degenerate states at the Fermi energy, and strong Coulomb interactions, non-Fermi liquid behaviour is predicted, for which we observe some evidence. Our discovery implies that Pr2Ir2O7 is a parent state that can be manipulated to produce other strongly correlated topological phases, such as topological Mott insulator, Weyl semimetal, and quantum spin and anomalous Hall states. PMID:26640114

Ubiquitous formation of bulk Dirac cones and topological surface states from a single orbital manifold in transition-metal dichalcogenides

NASA Astrophysics Data System (ADS)

Bahramy, M. S.; Clark, O. J.; Yang, B.-J.; Feng, J.; Bawden, L.; Riley, J. M.; Marković, I.; Mazzola, F.; Sunko, V.; Biswas, D.; Cooil, S. P.; Jorge, M.; Wells, J. W.; Leandersson, M.; Balasubramanian, T.; Fujii, J.; Vobornik, I.; Rault, J. E.; Kim, T. K.; Hoesch, M.; Okawa, K.; Asakawa, M.; Sasagawa, T.; Eknapakul, T.; Meevasana, W.; King, P. D. C.

2018-01-01

Transition-metal dichalcogenides (TMDs) are renowned for their rich and varied bulk properties, while their single-layer variants have become one of the most prominent examples of two-dimensional materials beyond graphene. Their disparate ground states largely depend on transition metal d-electron-derived electronic states, on which the vast majority of attention has been concentrated to date. Here, we focus on the chalcogen-derived states. From density-functional theory calculations together with spin- and angle-resolved photoemission, we find that these generically host a co-existence of type-I and type-II three-dimensional bulk Dirac fermions as well as ladders of topological surface states and surface resonances. We demonstrate how these naturally arise within a single p-orbital manifold as a general consequence of a trigonal crystal field, and as such can be expected across a large number of compounds. Already, we demonstrate their existence in six separate TMDs, opening routes to tune, and ultimately exploit, their topological physics.

Fermiology of the strongly spin-orbit coupled superconductor Sn(1-x)In(x)Te: implications for topological superconductivity.

PubMed

Sato, T; Tanaka, Y; Nakayama, K; Souma, S; Takahashi, T; Sasaki, S; Ren, Z; Taskin, A A; Segawa, Kouji; Ando, Yoichi

2013-05-17

We have performed angle-resolved photoemission spectroscopy on the strongly spin-orbit coupled low-carrier density superconductor Sn(1-x)In(x)Te (x = 0.045) to elucidate the electronic states relevant to the possible occurrence of topological superconductivity, as recently reported for this compound based on point-contact spectroscopy. The obtained energy-band structure reveals a small holelike Fermi surface centered at the L point of the bulk Brillouin zone, together with a signature of a topological surface state, indicating that this material is a doped topological crystalline insulator characterized by band inversion and mirror symmetry. A comparison of the electronic states with a band-noninverted superconductor possessing a similar Fermi surface structure, Pb(1-x)Tl(x)Te, suggests that the anomalous behavior in the superconducting state of Sn(1-x)In(x)Te is related to the peculiar orbital characteristics of the bulk valence band and/or the presence of a topological surface state.

Femtosecond Photoelectron Imaging of Dissociating and Autoionizing States in Oxygen

NASA Astrophysics Data System (ADS)

Plunkett, Alexander; Sandhu, Arvinder

2017-04-01

Time-resolved photoelectron spectra from molecular oxygen have been recorded with high energy and time resolution using a velocity map imaging (VMI) spectrometer. High harmonics were used to prepare neutral Rydberg states converging to the c4Σu- ionic state. These states display both autoionization and predissociation. A femtosecond laser pulse centered at 780 nm was used to probe the system, ionizing both the excited molecular states and the predissociated neutral atomic fragments. Electrons were collected in the 0-3 eV range using a VMI spectrometer and their spectra were reconstructed using a Fast Onion-peeling algorithm. By looking at IR modification to the electron spectrum, new features are observed which could originate from long-range columbic interactions or previously unobserved molecular decay channels. Ongoing studies extend this technique to other systems exhibiting non-adiabatic dynamics. This work was supported by the U. S. Army Research Laboratory and the U. S. Army Research Office under Grant No. W911NF-14-1-0383.

Sn-doped Bi 1.1Sb 0.9Te 2S bulk crystal topological insulator with excellent properties

DOE PAGES

S. K. Kushwaha; Pletikosic, I.; Liang, T.; ...

2016-04-27

A long-standing issue in topological insulator research has been to find a bulk single crystal material that provides a high quality platform for characterizing topological surface states without interference from bulk electronic states. This material would ideally be a bulk insulator, have a surface state Dirac point energy well isolated from the bulk valence and conduction bands, display quantum oscillations from the surface state electrons, and be growable as large, high quality bulk single crystals. Here we show that this materials obstacle is overcome by bulk crystals of lightly Sn-doped Bi 1.1Sb 0.9Te 2S grown by the Vertical Bridgeman method.more » We characterize Sn-BSTS via angle-resolved photoemission spectroscopy, scanning tunneling microscopy, transport studies, X-ray diffraction, and Raman scattering. We present this material as a high quality topological insulator that can be reliably grown as bulk single crystals and thus studied by many researchers interested in topological surface states.« less

Quadratic Fermi node in a 3D strongly correlated semimetal

DOE PAGES

Kondo, Takeshi; Nakayama, M.; Chen, R.; ...

2015-12-07

We report that strong spin–orbit coupling fosters exotic electronic states such as topological insulators and superconductors, but the combination of strong spin–orbit and strong electron–electron interactions is just beginning to be understood. Central to this emerging area are the 5d transition metal iridium oxides. Here, in the pyrochlore iridate Pr 2Ir 2O 7, we identify a non-trivial state with a single-point Fermi node protected by cubic and time-reversal symmetries, using a combination of angle-resolved photoemission spectroscopy and first-principles calculations. Owing to its quadratic dispersion, the unique coincidence of four degenerate states at the Fermi energy, and strong Coulomb interactions, non-Fermimore » liquid behaviour is predicted, for which we observe some evidence. Lastly, our discovery implies that Pr 2Ir 2O 7 is a parent state that can be manipulated to produce other strongly correlated topological phases, such as topological Mott insulator, Weyl semimetal, and quantum spin and anomalous Hall states.« less

The electronically excited states of LH2 complexes from Rhodopseudomonas acidophila strain 10050 studied by time-resolved spectroscopy and dynamic Monte Carlo simulations. I. Isolated, non-interacting LH2 complexes.

PubMed

Pflock, Tobias J; Oellerich, Silke; Southall, June; Cogdell, Richard J; Ullmann, G Matthias; Köhler, Jürgen

2011-07-21

We have employed time-resolved spectroscopy on the picosecond time scale in combination with dynamic Monte Carlo simulations to investigate the photophysical properties of light-harvesting 2 (LH2) complexes from the purple photosynthetic bacterium Rhodopseudomonas acidophila. The variations of the fluorescence transients were studied as a function of the excitation fluence, the repetition rate of the excitation and the sample preparation conditions. Here we present the results obtained on detergent solubilized LH2 complexes, i.e., avoiding intercomplex interactions, and show that a simple four-state model is sufficient to grasp the experimental observations quantitatively without the need for any free parameters. This approach allows us to obtain a quantitative measure for the singlet-triplet annihilation rate in isolated, noninteracting LH2 complexes.

Spatially resolved multicolor CsPbX 3 nanowire heterojunctions via anion exchange

DOE PAGES

Dou, Letian; Lai, Minliang; Kley, Christopher S.; ...

2017-06-26

Halide perovskites are promising semiconductor materials for solution-processed optoelectronic devices. Their strong ionic bonding nature results in highly dynamic crystal lattices, inherently allowing rapid ion exchange at the solid–vapor and solid–liquid interface. In this paper, we show that the anion-exchange chemistry can be precisely controlled in single-crystalline halide perovskite nanomaterials when combined with nanofabrication techniques. We demonstrate spatially resolved multicolor CsPbX 3 (X = Cl, Br, I, or alloy of two halides) nanowire heterojunctions with a pixel size down to 500 nm with the photoluminescence tunable over the entire visible spectrum. In addition, the heterojunctions show distinct electronic states acrossmore » the interface, as revealed by Kelvin probe force microscopy. Finally, these perovskite heterojunctions represent key building blocks for high-resolution multicolor displays beyond current state-of-the-art technology as well as high-density diode/transistor arrays.« less

Dynamics of the time-resolved stimulated Raman scattering spectrum in presence of transient vibronic inversion of population on the example of optically excited trans-β-apo-8{sup ′}-carotenal

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kardaś, T. M., E-mail: kardas@chem.uw.edu.pl; Ratajska-Gadomska, B.; Gadomski, W.

2014-05-28

We have studied the effect of transient vibrational inversion of population in trans-β-apo-8{sup ′}-carotenal on the time-resolved femtosecond stimulated Raman scattering (TR-FSRS) signal. The experimental data are interpreted by applying a quantum mechanical approach, using the formalism of projection operators for constructing the theoretical model of TR-FSRS. Within this theoretical frame we explain the presence of transient Raman losses on the Stokes side of the TR-FSRS spectrum as the effect of vibrational inversion of population. In view of the obtained experimental and theoretical results, we conclude that the excited S{sub 2} electronic level of trans-β-apo-8{sup ′}-carotenal relaxes towards the S{submore » 0} ground state through a set of four vibrational sublevels of S{sub 1} state.« less

Investigation of the optical property and photocatalytic activity of mixed phase nanocrystalline titania

NASA Astrophysics Data System (ADS)

Paul, Susmita; Choudhury, Amarjyoti

2014-10-01

Mixed phase nanocrystalline titania are prepared by simple sol-gel method. The physico-chemical characteristics of the prepared nanoparticles are studied with X-ray diffraction, high-resolution transmission electron microscopy, RAMAN, BET, UV-Vis, steady state and time resolved photoluminescence. X-ray diffraction and Raman spectra clearly demarcate the anatase and rutile phase as both the phases give different diffraction patterns and Raman peaks. A comparison in the band gap indicates that pure anatase and rutile phase have band gap in the UV region, whereas a mixture of these phases has lower band gap and corresponds to the visible region. Steady state and time resolved photoluminescence are employed to understand the emissivity and carrier lifetime. The photocatalytic activity is evaluated by monitoring the degradation of phenol under visible light illumination. Due to the synergistic effect of mixed anatase and rutile phases, mixed phase nanocrystalline titania exhibit superior photocatalytic activity.

Spectroscopic evidence for a type II Weyl semimetallic state in MoTe 2

DOE PAGES

Huang, Lunan; McCormick, Timothy M.; Ochi, Masayuki; ...

2016-07-11

In a type I Dirac or Weyl semimetal, the low-energy states are squeezed to a single point in momentum space when the chemical potential μ is tuned precisely to the Dirac/Weyl point. Recently, a type II Weyl semimetal was predicted to exist, where the Weyl states connect hole and electron bands, separated by an indirect gap. This leads to unusual energy states, where hole and electron pockets touch at the Weyl point. Here we present the discovery of a type II topological Weyl semimetal state in pure MoTe 2, where two sets of Weyl points ( W±2 , W±3) existmore » at the touching points of electron and hole pockets and are located at different binding energies above E F. Using angle-resolved photoemission spectroscopy, modelling, density functional theory and calculations of Berry curvature, we identify the Weyl points and demonstrate that they are connected by different sets of Fermi arcs for each of the two surface terminations. We also find new surface ‘track states’ that form closed loops and are unique to type II Weyl semimetals. Lastly, this material provides an exciting, new platform to study the properties of Weyl fermions.« less

The Spectroscopy and Photophysics of Aniline, 2-AMINOPYRIDINE, and 3-AMINOPYRIDINE

NASA Astrophysics Data System (ADS)

Kim, Byungjoo

1995-01-01

Two-photon ionization photoelectron spectroscopic techniques have been employed in concert with a picosecond laser system and molecular beam machine to study the vibrational structure of molecular ions and the intramolecular dynamics of optically prepared intermediate states. From photoelectron spectra of 2-aminopyridine via various S_1 vibronic resonances, the frequencies of several vibrations in the ionic state are assigned. The ionization potential of the molecule is found to be 8.099 +/- 0.003 eV. Using two-color ionization techniques, the electronic overlap effects in the photoionization of excited molecules have been studied, on the example of 2-aminopyridine, 3-aminopyridine, and aniline. The molecules are excited to their S_1 states, and ionized by a 200 nm laser pulse within 50 ps. The spectra of the aminopyridines show a striking absence of transitions to excited electronic states of the ions, indicating small electronic overlap factors in the ionization transitions and very little configuration interaction in the S _1 states. The spectra of aniline show the vibrationally resolved first excited electronic state band of the ion, which is very weak compared to the ground electronic state band, indicating a small amount of orbital mixing in the S_1 state. The vibrational peaks in the band were assigned by comparison of the spectra via two different vibronic resonances. The observations demonstrate that electronic overlap effects play a very general role in the ionization of polyatomic molecules in electronically excited states, and that orbital mixing patterns of the excited electronic states may become observable by projecting molecular electronic wavefunctions onto the ion states. In the time-delayed experiments for these molecules, all spectra reveal only one product of the nonradiative relaxation process. Careful considerations of electronic and vibrational overlap propensity rules for the ionization step lead to the conclusion that the dominant nonradiative decay mechanism in these molecules is the intersystem crossing to excited vibrational states of the T_1 state. This technique has been applied to study the predissociation process of CS_2 in the S_3 vibronic levels near 200 nm. The spectra show extensive vibrational structure, with unusual activity in the antisymmetric vibrations, indicating the possibility of level mixing in the intermediate state by the IVR couplings.

Photoinduced electron transfer at the tetrapyrrole-TiO2 interface: Effect of the energy alignment

NASA Astrophysics Data System (ADS)

Nieto-Pescador, Jesus S.

Photoinduced electron transfer is a ubiquitous process behind several physical, chemical, and biological processes. Its potential applications, ranging from solar cell technologies to photodynamic cancer therapy, require a thorough understanding of the basics of the reaction. This dissertation addresses open questions for a particular case of electron transfer processes: Heterogeneous Electron Transfer (HET). In this process, an electron is transferred between a localized donor and a multitude of delocalized acceptor states. HET between photoexcited tetrapyrroles and colloidal TiO2 has been investigated using femtosecond transient absorption spectroscopy. Specifically, this work explores the not well-understood influence of the availability of states on the HET reaction. This problem is addressed by measuring electron injection times as a function of the energy difference between the LUMO and the conduction band of TiO2. The change in the energy alignment was done using two experimental strategies. The first one employs a recently synthesized phlorin with two different excited states above the conduction band of TiO2. This molecule allows comparing HET rates from two different excited states. The second strategy measures the electron injection rates after exciting the same electronic state of a set of specially designed porphyrins. The novelty of the approach is that the difference in energy alignment is attained by the introduction of dipole groups within the bridge group of the molecule. This strategy generates a difference in energy alignment of up to 200 meV. The reported measurements were carried in a high vacuum environment with an apparatus capable of resolving sub 30 fs processes. Disentanglement of the electron transfer processes was done, after careful study of the relaxation dynamics of the molecules in solution, by monitoring the decay of the excited state absorption and the rise of the cation spectral signatures. Within our time resolution, our results show that the increase in the availability of acceptor states does not influence the electron injection dynamics. The results suggest that the injection process takes place into a spectrum of states different from those obtained by steady state calculations.

Hunting for Snarks in Quantum Mechanics

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hestenes, David

2009-12-08

A long-standing debate over the interpretation of quantum mechanics has centered on the meaning of Schroedinger's wave function {psi} for an electron. Broadly speaking, there are two major opposing schools. On the one side, the Copenhagen school(led by Bohr, Heisenberg and Pauli) holds that {psi} provides a complete description of a single electron state; hence the probability interpretation of {psi}{psi}* expresses an irreducible uncertainty in electron behavior that is intrinsic in nature. On the other side, the realist school(led by Einstein, de Broglie, Bohm and Jaynes) holds that {psi} represents a statistical ensemble of possible electron states; hence it ismore » an incomplete description of a single electron state. I contend that the debaters have overlooked crucial facts about the electron revealed by Dirac theory. In particular, analysis of electron zitterbewegung(first noticed by Schroedinger) opens a window to particle substructure in quantum mechanics that explains the physical significance of the complex phase factor in {psi}. This led to a testable model for particle substructure with surprising support by recent experimental evidence. If the explanation is upheld by further research, it will resolve the debate in favor of the realist school. I give details. The perils of research on the foundations of quantum mechanics have been foreseen by Lewis Carroll in The Hunting of the Snark{exclamation_point}.« less

New developments in laser-based photoemission spectroscopy and its scientific applications: a key issues review

NASA Astrophysics Data System (ADS)

Zhou, Xingjiang; He, Shaolong; Liu, Guodong; Zhao, Lin; Yu, Li; Zhang, Wentao

2018-06-01

The significant progress in angle-resolved photoemission spectroscopy (ARPES) in last three decades has elevated it from a traditional band mapping tool to a precise probe of many-body interactions and dynamics of quasiparticles in complex quantum systems. The recent developments of deep ultraviolet (DUV, including ultraviolet and vacuum ultraviolet) laser-based ARPES have further pushed this technique to a new level. In this paper, we review some latest developments in DUV laser-based photoemission systems, including the super-high energy and momentum resolution ARPES, the spin-resolved ARPES, the time-of-flight ARPES, and the time-resolved ARPES. We also highlight some scientific applications in the study of electronic structure in unconventional superconductors and topological materials using these state-of-the-art DUV laser-based ARPES. Finally we provide our perspectives on the future directions in the development of laser-based photoemission systems.

Ab initio study of excited state electronic circular dichroism. Two prototype cases: methyl oxirane and R-(+)-1,1'-bi(2-naphthol).

PubMed

Rizzo, Antonio; Vahtras, Olav

2011-06-28

A computational approach to the calculation of excited state electronic circular dichroism (ESECD) spectra of chiral molecules is discussed. Frequency dependent quadratic response theory is employed to compute the rotatory strength for transitions between excited electronic states, by employing both a magnetic gauge dependent and a (velocity-based) magnetic gauge independent approach. Application is made to the lowest excited states of two prototypical chiral molecules, propylene oxide, also known as 1,2-epoxypropane or methyl oxirane, and R-(+)-1,1'-bi(2-naphthol), or BINOL. The dependence of the rotatory strength for transitions between the lowest three excited states of methyl oxirane upon the quality and extension of the basis set is analyzed, by employing a hierarchy of correlation consistent basis sets. Once established that basis sets of at least triple zeta quality, and at least doubly augmented, are sufficient to ensure sufficiently converged results, at least at the Hartree-Fock self-consistent field (HF-SCF) level, the rotatory strengths for all transitions between the lowest excited electronic states of methyl oxirane are computed and analyzed, employing HF-SCF, and density functional theory (DFT) electronic structure models. For DFT, both the popular B3LYP and its recently highly successful CAM-B3LYP extension are exploited. The strong dependence of the spectra upon electron correlation is highlighted. A HF-SCF and DFT study is carried out also for BINOL, a system where excited states show the typical pairing structure arising from the interaction of the two monomeric moieties, and whose conformational changes following photoexcitation were studied recently with via time-resolved CD.

Unusually large chemical potential shift in a degenerate semiconductor: Angle-resolved photoemission study of SnSe and Na-doped SnSe

NASA Astrophysics Data System (ADS)

Maeda, M.; Yamamoto, K.; Mizokawa, T.; Saini, N. L.; Arita, M.; Namatame, H.; Taniguchi, M.; Tan, G.; Zhao, L. D.; Kanatzidis, M. G.

2018-03-01

We have studied the electronic structure of SnSe and Na-doped SnSe by means of angle-resolved photoemission spectroscopy. The valence-band top reaches the Fermi level by the Na doping, indicating that Na-doped SnSe can be viewed as a degenerate semiconductor. However, in the Na-doped system, the chemical potential shift with temperature is unexpectedly large and is apparently inconsistent with the degenerate semiconductor picture. The large chemical potential shift and anomalous spectral shape are key ingredients for an understanding of the novel metallic state with the large thermoelectric performance in Na-doped SnSe.

Unusually large chemical potential shift in a degenerate semiconductor: Angle-resolved photoemission study of SnSe and Na-doped SnSe

DOE Office of Scientific and Technical Information (OSTI.GOV)

Maeda, M.; Yamamoto, K.; Mizokawa, T.

In this work, we have studied the electronic structure of SnSe and Na-doped SnSe by means of angle-resolved photoemission spectroscopy. The valence-band top reaches the Fermi level by the Na doping, indicating that Na-doped SnSe can be viewed as a degenerate semiconductor. However, in the Na-doped system, the chemical potential shift with temperature is unexpectedly large and is apparently inconsistent with the degenerate semiconductor picture. Lastly, the large chemical potential shift and anomalous spectral shape are key ingredients for an understanding of the novel metallic state with the large thermoelectric performance in Na-doped SnSe.

Unusually large chemical potential shift in a degenerate semiconductor: Angle-resolved photoemission study of SnSe and Na-doped SnSe

DOE PAGES

Maeda, M.; Yamamoto, K.; Mizokawa, T.; ...

2018-03-23

In this work, we have studied the electronic structure of SnSe and Na-doped SnSe by means of angle-resolved photoemission spectroscopy. The valence-band top reaches the Fermi level by the Na doping, indicating that Na-doped SnSe can be viewed as a degenerate semiconductor. However, in the Na-doped system, the chemical potential shift with temperature is unexpectedly large and is apparently inconsistent with the degenerate semiconductor picture. Lastly, the large chemical potential shift and anomalous spectral shape are key ingredients for an understanding of the novel metallic state with the large thermoelectric performance in Na-doped SnSe.

Transport limited interfacial carrier relaxation in a double-layer device investigated by time-resolved second harmonic generation and impedance spectroscopy

NASA Astrophysics Data System (ADS)

Zhang, Le; Taguchi, Dai; Li, Jun; Manaka, Takaaki; Iwamoto, Mitsumasa

2011-02-01

The interfacial carrier relaxation in an indium tin oxide/polyimide/pentacene/Au double-layer device was studied in both time and frequency domains by using time-resolved second harmonic generation (TR-SHG) and impedance spectroscopy (IS), respectively. Although both hole and electron injection into the pentacene layer and their accumulation at the pentacene/polyimide interface were revealed in TR-SHG, it was only observed in IS under the hole injection condition. The "contradiction" between the two methods for the same carrier relaxation process was explained on the basis of a model, transport limited interfacial carrier relaxation, in which the quasistatic state governs the one-directional carrier transport.

Photoelectron imaging using an ellipsoidal display analyzer

NASA Astrophysics Data System (ADS)

Dütemeyer, T.; Quitmann, C.; Kitz, M.; Dörnemann, K.; Johansson, L. S. O.; Reihl, B.

2001-06-01

We have built an ellipsoidal display analyzer (EDA) for angle-resolved photoelectron spectroscopy and related techniques. The instrument is an improved version of a design by Eastman et al. [Nucl. Instrum. Methods 172, 327 (1980)] and measures the angle-resolved intensity distribution of photoelectrons at fixed energy I(θ,φ)|E=const.. Such two-dimensional cuts through the Brillouin zone are recorded using a position-sensitive detector. The large acceptance angle (Δθ=43° in the polar direction and Δφ=360° in the azimuthal direction) leads to a collection efficiency which exceeds that of conventional hemispherical analyzers by a factor of about 3000. Using ray-tracing calculations we analyze the electron optical properties of the various analyzer components and optimize their arrangement. This minimizes distortions and aberrations in the recorded images and greatly improves the performance compared to previous realizations of this analyzer. We present examples demonstrating the performance of the analyzer and its versatility. Using a commercial He-discharge lamp we are able to measure complete angular distribution patterns in less than 5 s. The energy and angular resolution are ΔEEDA=85 meV and Δθ=1.2°, respectively. Complete stacks of such cuts through the Brillouin zone at different kinetic energies E can be acquired automatically using custom software. The raw data are processed leading to a three-dimensional set (I(EB,k∥) of photoelectron intensity versus binding energy E and wave vector k∥. From this all relevant information, like the dispersion relations EB(k∥) along arbitrary directions of the Brillouin zone or Fermi-surface maps, can then be computed. An additional electron gun enables low-energy electron diffraction, Auger electron spectroscopy, and electron energy-loss spectroscopy. Switching between electrons and photons as the excitation source is possible without any movement of the sample or analyzer. Because of the high acquisition speed it is possible to study the electronic structure of solids as a function of an external parameter (i.e., temperature) or to make animated movies showing, for example, the evolution of electronic states in reciprocal space. After installation of this EDA at a synchrotron providing tunable photon energy, the full power of the instrument will come into play by adding techniques like constant final state or constant initial state spectroscopy, and x-ray photoelectron diffraction.

The effect of vibrational autoionization on the H2+ X 2Σg+ state rotationally resolved photoionization dynamics

NASA Astrophysics Data System (ADS)

Holland, D. M. P.; Shaw, D. A.

2014-01-01

The effect of vibrational autoionization on the H2+ X 2Σg+ v+ = 3, N+ state rotationally resolved photoelectron angular distributions and branching ratios has been investigated with a velocity map imaging spectrometer and synchrotron radiation. In photon excitation regions free from the influence of autoionizing Rydberg states, where direct ionization dominates, the photoelectron anisotropy parameter associated with the X 1Σg+ v″ = 0, N″ = 1 → X 2Σg+ v+ = 3, N+ = 1 transition has a value close to the theoretical maximum. However, in the vicinity of a Rydberg state, vibrational autoionization leads to a substantial reduction in anisotropy. The value of the anisotropy parameter associated with the S-branch of the photoelectron spectrum is found to be considerably higher than that predicted under the assumption that the outgoing electron can be represented solely as a p-wave. This suggests that the f-wave contribution must be taken into account to obtain a proper description of the photoionization dynamics. The observed variations in the rotationally resolved branching ratios, in the vicinity of an autoionizing resonance, depend upon the rotational level of the Rydberg state. The rotationally averaged photoelectron anisotropy parameters have been compared with the corresponding, previously calculated, theoretical results and reasonable agreement has been found. The influence of vibrational autoionization on the H2+ X 2Σg+ v+ = 0, 1, 2, 3 vibrational branching ratios has also been investigated, and the experimental results show that, in energy regions encompassing Rydberg states, these ratios deviate strongly from the Franck-Condon factors for direct ionization.

Open-Circuit Voltage Losses in Selenium-Substituted Organic Photovoltaic Devices from Increased Density of Charge-Transfer States

DOE PAGES

Sulas, Dana B.; Yao, Kai; Intemann, Jeremy J.; ...

2015-09-12

Using an analysis based on Marcus theory, we characterize losses in open-circuit voltage (V OC) due to changes in charge-transfer state energy, electronic coupling, and spatial density of charge-transfer states in a series of polymer/fullerene solar cells. Here, we use a series of indacenodithiophene polymers and their selenium-substituted analogs as electron donor materials and fullerenes as the acceptors. By combining device measurements and spectroscopic studies (including subgap photocurrent, electroluminescence, and, importantly, time-resolved photoluminescence of the charge-transfer state) we are able to isolate the values for electronic coupling and the density of charge-transfer states (NCT), rather than the more commonly measuredmore » product of these values. We find values for NCT that are surprisingly large (~4.5 × 10 21–6.2 × 10 22 cm -3), and we find that a significant increase in N CT upon selenium substitution in donor polymers correlates with lower VOC for bulk heterojunction photovoltaic devices. The increase in N CT upon selenium substitution is also consistent with nanoscale morphological characterization. Using transmission electron microscopy, selected area electron diffraction, and grazing incidence wide-angle X-ray scattering, we find evidence of more intermixed polymer and fullerene domains in the selenophene blends, which have higher densities of polymer/fullerene interfacial charge-transfer states. Our results provide an important step toward understanding the spatial nature of charge-transfer states and their effect on the open-circuit voltage of polymer/fullerene solar cells« less

Superconductivity across Lifshitz transition and anomalous insulating state in surface K-dosed (Li0.8Fe0.2OH)FeSe.

PubMed

Ren, Mingqiang; Yan, Yajun; Niu, Xiaohai; Tao, Ran; Hu, Die; Peng, Rui; Xie, Binping; Zhao, Jun; Zhang, Tong; Feng, Dong-Lai

2017-07-01

In iron-based superconductors, understanding the relation between superconductivity and electronic structure upon doping is crucial for exploring the pairing mechanism. Recently, it was found that, in iron selenide (FeSe), enhanced superconductivity ( T c of more than 40 K) can be achieved via electron doping, with the Fermi surface only comprising M-centered electron pockets. By using surface K dosing, scanning tunneling microscopy/spectroscopy, and angle-resolved photoemission spectroscopy, we studied the electronic structure and superconductivity of (Li 0.8 Fe 0.2 OH)FeSe in the deep electron-doped regime. We find that a Γ-centered electron band, which originally lies above the Fermi level ( E F ), can be continuously tuned to cross E F and contribute a new electron pocket at Γ. When this Lifshitz transition occurs, the superconductivity in the M-centered electron pocket is slightly suppressed, and a possible superconducting gap with a small size (up to ~5 meV) and a dome-like doping dependence is observed on the new Γ electron pocket. Upon further K dosing, the system eventually evolves into an insulating state. Our findings provide new clues to understand superconductivity versus Fermi surface topology and the correlation effect in FeSe-based superconductors.

Superconductivity across Lifshitz transition and anomalous insulating state in surface K–dosed (Li0.8Fe0.2OH)FeSe

PubMed Central

Ren, Mingqiang; Yan, Yajun; Niu, Xiaohai; Tao, Ran; Hu, Die; Peng, Rui; Xie, Binping; Zhao, Jun; Zhang, Tong; Feng, Dong-Lai

2017-01-01

In iron-based superconductors, understanding the relation between superconductivity and electronic structure upon doping is crucial for exploring the pairing mechanism. Recently, it was found that, in iron selenide (FeSe), enhanced superconductivity (Tc of more than 40 K) can be achieved via electron doping, with the Fermi surface only comprising M-centered electron pockets. By using surface K dosing, scanning tunneling microscopy/spectroscopy, and angle-resolved photoemission spectroscopy, we studied the electronic structure and superconductivity of (Li0.8Fe0.2OH)FeSe in the deep electron-doped regime. We find that a Γ-centered electron band, which originally lies above the Fermi level (EF), can be continuously tuned to cross EF and contribute a new electron pocket at Γ. When this Lifshitz transition occurs, the superconductivity in the M-centered electron pocket is slightly suppressed, and a possible superconducting gap with a small size (up to ~5 meV) and a dome-like doping dependence is observed on the new Γ electron pocket. Upon further K dosing, the system eventually evolves into an insulating state. Our findings provide new clues to understand superconductivity versus Fermi surface topology and the correlation effect in FeSe-based superconductors. PMID:28740865

Resolving runaway electron distributions in space, time, and energy

NASA Astrophysics Data System (ADS)

Paz-Soldan, C.; Cooper, C. M.; Aleynikov, P.; Eidietis, N. W.; Lvovskiy, A.; Pace, D. C.; Brennan, D. P.; Hollmann, E. M.; Liu, C.; Moyer, R. A.; Shiraki, D.

2018-05-01

Areas of agreement and disagreement with present-day models of runaway electron (RE) evolution are revealed by measuring MeV-level bremsstrahlung radiation from runaway electrons (REs) with a pinhole camera. Spatially resolved measurements localize the RE beam, reveal energy-dependent RE transport, and can be used to perform full two-dimensional (energy and pitch-angle) inversions of the RE phase-space distribution. Energy-resolved measurements find qualitative agreement with modeling on the role of collisional and synchrotron damping in modifying the RE distribution shape. Measurements are consistent with predictions of phase-space attractors that accumulate REs, with non-monotonic features observed in the distribution. Temporally resolved measurements find qualitative agreement with modeling on the impact of collisional and synchrotron damping in varying the RE growth and decay rate. Anomalous RE loss is observed and found to be largest at low energy. Possible roles for kinetic instability or spatial transport to resolve these anomalies are discussed.

Time-Resolved Tandem Faraday Cup Development for High Energy TNSA Particles

NASA Astrophysics Data System (ADS)

Padalino, S.; Simone, A.; Turner, E.; Ginnane, M. K.; Glisic, M.; Kousar, B.; Smith, A.; Sangster, C.; Regan, S.

2015-11-01

MTW and OMEGA EP Lasers at LLE utilize ultra-intense laser light to produce high-energy ion pulses through Target Normal Sheath Acceleration (TNSA). A Time Resolved Tandem Faraday Cup (TRTF) was designed and built to collect and differentiate protons from heavy ions (HI) produced during TNSA. The TRTF includes a replaceable thickness absorber capable of stopping a range of user-selectable HI emitted from TNSA plasma. HI stop within the primary cup, while less massive particles continue through and deposit their remaining charge in the secondary cup, releasing secondary electrons in the process. The time-resolved beam current generated in each cup will be measured on a fast storage scope in multiple channels. A charge-exchange foil at the TRTF entrance modifies the charge state distribution of HI to a known distribution. Using this distribution and the time of flight of the HI, the total HI current can be determined. Initial tests of the TRTF have been made using a proton beam produced by SUNY Geneseo's 1.7 MV Pelletron accelerator. A substantial reduction in secondary electron production, from 70% of the proton beam current at 2MeV down to 0.7%, was achieved by installing a pair of dipole magnet deflectors which successfully returned the electrons to the cups in the TRTF. Ultimately the TRTF will be used to normalize a variety of nuclear physics cross sections and stopping power measurements. Based in part upon work supported by a DOE NNSA Award#DE-NA0001944.

Resonator Optical Designs For Free Electron Lasers

NASA Astrophysics Data System (ADS)

Viswanathan, V. K.; Saxman, A.; Woodfin, G.

1985-11-01

The output beam from free-electron lasers tends to be a thin, pencil-like beam because of the nature of the gain volume. For moderate power devices, mirror damage considerations imply that the beam has to travel many meters before it can expand enough to allow retro-reflection from state-of-the-art mirrors. However, use of grazing incidence optics can resolve the problem of damage to the optical elements and result in a cavity of reasonable dimensions. The optical design considerations for such resonators are addressed in this paper. A few of the practical resonator designs approaching diffraction limited performance are presented.

Resonator optical designs for free electron lasers

NASA Astrophysics Data System (ADS)

Viswanathan, V. K.; Saxman, A.; Woodfin, G.

1985-03-01

The output beam from free-electron lasers tends to be a thin, pencil-like beam because of the nature of the gain volume. For moderate power devices, mirror damage considerations imply that the beam has to travel many meters before it can expand enough to allow retro-reflection from state-of-the-art mirrors. However, use of grazing incidence optics can resolve the problem of damage to the optical elements and result in a cavity of reasonable dimensions. The optical design considerations for such resonators are discussed. A few of the practical resonator designs approaching diffraction limited performance are presented.

Laser-Induced Skyrmion Writing and Erasing in an Ultrafast Cryo-Lorentz Transmission Electron Microscope

NASA Astrophysics Data System (ADS)

Berruto, G.; Madan, I.; Murooka, Y.; Vanacore, G. M.; Pomarico, E.; Rajeswari, J.; Lamb, R.; Huang, P.; Kruchkov, A. J.; Togawa, Y.; LaGrange, T.; McGrouther, D.; Rønnow, H. M.; Carbone, F.

2018-03-01

We demonstrate that light-induced heat pulses of different duration and energy can write Skyrmions in a broad range of temperatures and magnetic field in FeGe. Using a combination of camera-rate and pump-probe cryo-Lorentz transmission electron microscopy, we directly resolve the spatiotemporal evolution of the magnetization ensuing optical excitation. The Skyrmion lattice was found to maintain its structural properties during the laser-induced demagnetization, and its recovery to the initial state happened in the sub-μ s to μ s range, depending on the cooling rate of the system.

Direct correlations of structural and optical properties of three-dimensional GaN/InGaN core/shell micro-light emitting diodes

NASA Astrophysics Data System (ADS)

Sadat Mohajerani, Matin; Müller, Marcus; Hartmann, Jana; Zhou, Hao; Wehmann, Hergo-H.; Veit, Peter; Bertram, Frank; Christen, Jürgen; Waag, Andreas

2016-05-01

Three-dimensional (3D) InGaN/GaN quantum-well (QW) core-shell light emitting diodes (LEDs) are a promising candidate for the future solid state lighting. In this contribution, we study direct correlations of structural and optical properties of the core-shell LEDs using highly spatially-resolved cathodoluminescence spectroscopy (CL) in combination with scanning electron microscopy (SEM) and scanning transmission electron microscopy (STEM). Temperature-dependent resonant photoluminescence (PL) spectroscopy has been performed to understand recombination mechanisms and to estimate the internal quantum efficiency (IQE).

Damage-free vibrational spectroscopy of biological materials in the electron microscope

PubMed Central

Rez, Peter; Aoki, Toshihiro; March, Katia; Gur, Dvir; Krivanek, Ondrej L.; Dellby, Niklas; Lovejoy, Tracy C.; Wolf, Sharon G.; Cohen, Hagai

2016-01-01

Vibrational spectroscopy in the electron microscope would be transformative in the study of biological samples, provided that radiation damage could be prevented. However, electron beams typically create high-energy excitations that severely accelerate sample degradation. Here this major difficulty is overcome using an ‘aloof' electron beam, positioned tens of nanometres away from the sample: high-energy excitations are suppressed, while vibrational modes of energies <1 eV can be ‘safely' investigated. To demonstrate the potential of aloof spectroscopy, we record electron energy loss spectra from biogenic guanine crystals in their native state, resolving their characteristic C–H, N–H and C=O vibrational signatures with no observable radiation damage. The technique opens up the possibility of non-damaging compositional analyses of organic functional groups, including non-crystalline biological materials, at a spatial resolution of ∼10 nm, simultaneously combined with imaging in the electron microscope. PMID:26961578

Damage-free vibrational spectroscopy of biological materials in the electron microscope.

PubMed

Rez, Peter; Aoki, Toshihiro; March, Katia; Gur, Dvir; Krivanek, Ondrej L; Dellby, Niklas; Lovejoy, Tracy C; Wolf, Sharon G; Cohen, Hagai

2016-03-10

Vibrational spectroscopy in the electron microscope would be transformative in the study of biological samples, provided that radiation damage could be prevented. However, electron beams typically create high-energy excitations that severely accelerate sample degradation. Here this major difficulty is overcome using an 'aloof' electron beam, positioned tens of nanometres away from the sample: high-energy excitations are suppressed, while vibrational modes of energies <1 eV can be 'safely' investigated. To demonstrate the potential of aloof spectroscopy, we record electron energy loss spectra from biogenic guanine crystals in their native state, resolving their characteristic C-H, N-H and C=O vibrational signatures with no observable radiation damage. The technique opens up the possibility of non-damaging compositional analyses of organic functional groups, including non-crystalline biological materials, at a spatial resolution of ∼10 nm, simultaneously combined with imaging in the electron microscope.

Damage-free vibrational spectroscopy of biological materials in the electron microscope

DOE PAGES

Rez, Peter; Aoki, Toshihiro; March, Katia; ...

2016-03-10

Vibrational spectroscopy in the electron microscope would be transformative in the study of biological samples, provided that radiation damage could be prevented. However, electron beams typically create high-energy excitations that severely accelerate sample degradation. Here this major difficulty is overcome using an ‘aloof’ electron beam, positioned tens of nanometres away from the sample: high-energy excitations are suppressed, while vibrational modes of energies o1 eV can be ‘safely’ investigated. To demonstrate the potential of aloof spectroscopy, we record electron energy loss spectra from biogenic guanine crystals in their native state, resolving their characteristic C–H, N–H and C=O vibrational signatures with nomore » observable radiation damage. Furthermore, the technique opens up the possibility of non-damaging compositional analyses of organic functional groups, including non-crystalline biological materials, at a spatial resolution of ~10nm, simultaneously combined with imaging in the electron microscope.« less

Damage-free vibrational spectroscopy of biological materials in the electron microscope

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rez, Peter; Aoki, Toshihiro; March, Katia

Vibrational spectroscopy in the electron microscope would be transformative in the study of biological samples, provided that radiation damage could be prevented. However, electron beams typically create high-energy excitations that severely accelerate sample degradation. Here this major difficulty is overcome using an ‘aloof’ electron beam, positioned tens of nanometres away from the sample: high-energy excitations are suppressed, while vibrational modes of energies o1 eV can be ‘safely’ investigated. To demonstrate the potential of aloof spectroscopy, we record electron energy loss spectra from biogenic guanine crystals in their native state, resolving their characteristic C–H, N–H and C=O vibrational signatures with nomore » observable radiation damage. Furthermore, the technique opens up the possibility of non-damaging compositional analyses of organic functional groups, including non-crystalline biological materials, at a spatial resolution of ~10nm, simultaneously combined with imaging in the electron microscope.« less

Resolving the Spatial Structures of Bound Hole States in Black Phosphorus.

PubMed

Qiu, Zhizhan; Fang, Hanyan; Carvalho, Alexandra; Rodin, A S; Liu, Yanpeng; Tan, Sherman J R; Telychko, Mykola; Lv, Pin; Su, Jie; Wang, Yewu; Castro Neto, A H; Lu, Jiong

2017-11-08

Understanding the local electronic properties of individual defects and dopants in black phosphorus (BP) is of great importance for both fundamental research and technological applications. Here, we employ low-temperature scanning tunnelling microscope (LT-STM) to probe the local electronic structures of single acceptors in BP. We demonstrate that the charge state of individual acceptors can be reversibly switched by controlling the tip-induced band bending. In addition, acceptor-related resonance features in the tunnelling spectra can be attributed to the formation of Rydberg-like bound hole states. The spatial mapping of the quantum bound states shows two distinct shapes evolving from an extended ellipse shape for the 1s ground state to a dumbbell shape for the 2p x excited state. The wave functions of bound hole states can be well-described using the hydrogen-like model with anisotropic effective mass, corroborated by our theoretical calculations. Our findings not only provide new insight into the many-body interactions around single dopants in this anisotropic two-dimensional material but also pave the way to the design of novel quantum devices.

Ultrafast Physics Behind the Nonradiative Relaxation Process of Chromium Ions in Forsterite Crystals.

NASA Astrophysics Data System (ADS)

Demos, Stavros Gregorios

The nonradiative relaxation following photoexcitation has been studied in Cr^{4+} -doped forsterite (Mg_2SiO _4) using picosecond laser excitation and ultrasensitive photon counting detection. The experimental techniques utilized were time resolved antiStokes Raman scattering and up-converted hot and ordinary luminescence. The up-converted hot luminescence technique allowed the investigation of the upper state nonradiative relaxation of the excited state manifold of Cr^{4+ }-doped forsterite. The excitation involves the absorption of two photons per photoexcited ion in a two-step absorption. Discrete peaks are observed in the hot up-converted luminescence spectrum and are attributed to the population of nonequilibrium vibronic levels during the deexcitation of the ions by phonon emission. This work reveals that the phonon modes participating in the initial steps of the nonradiative relaxation of the photoexcited ions have energies 218 +/- 20, 325 +/- 20, 365 +/- 20 and 513 +/- 12 cm^ {-1}. The shape of the luminescence spectral envelope suggests two electronic bottlenecks at ~2.1 and ~2.45 eV associated with slower rates of vibrational relaxation at different parts of the excited state manifold. Time resolved measurements indicated that the average time for phonon emission is of the order of hundreds of fs. Information on the nonequilibrium phonon dynamics of the 225, 335 and 370 cm^{-1} modes of forsterite has been obtained using time resolved Raman scattering. Laser pulses of 450 fs in duration and 590 nm in wavelength were used to excite the Cr ions 2.1 eV above the ground state. The probe pulses (obtained from the same laser) are monitoring the nonequilibrium phonon population through the intensity of the antiStokes Raman lines at various pump-probe delay times. Experiments were performed at room and liquid nitrogen temperatures. The observed nonequilibrium phonon populations are associated with the overall complex nonradiative decay following the excitation of the impurity Cr^{4+} ions. Using rate equations to describe the electron -lattice system, the nonradiative relaxation time and the phonon lifetimes were estimated by fitting to the experimental data. The nonradiative relaxation time is estimated to be in the order of few ps while the phonon lifetimes are of the order of 10 ps. Best fit suggests the presence of an electronic bottleneck immediately after photoexcitation with an estimated lifetime of 3 ps at room temperature.

Energy transfer in a mechanically trapped exciplex.

PubMed

Klosterman, Jeremy K; Iwamura, Munetaka; Tahara, Tahei; Fujita, Makoto

2009-07-15

Host-guest complexes involving M(6)L(4) coordination cages can display unusual photoreactivity, and enclathration of the very large fluorophore bisanthracene resulted in an emissive, mechanically trapped intramolecular exciplex. Mechanically linked intramolecular exciplexes are important for understanding the dependence of energy transfer on donor-acceptor distance, orientation, and electronic coupling but are relatively unexplored. Steady-state and picosecond time-resolved fluorescence measurements have revealed that selective excitation of the encapsulated guest fluorophore results in efficient energy transfer from the excited guest to an emissive host-guest exciplex state.

Evidence for strong Breit interaction in dielectronic recombination of highly charged heavy ions.

PubMed

Nakamura, Nobuyuki; Kavanagh, Anthony P; Watanabe, Hirofumi; Sakaue, Hiroyuki A; Li, Yueming; Kato, Daiji; Currell, Fred J; Ohtani, Shunsuke

2008-02-22

Resonant strengths have been measured for dielectronic recombination of Li-like iodine, holmium, and bismuth using an electron beam ion trap. By observing the atomic number dependence of the state-resolved resonant strength, clear experimental evidence has been obtained that the importance of the generalized Breit interaction (GBI) effect on dielectronic recombination increases as the atomic number increases. In particular, it has been shown that the GBI effect is exceptionally strong for the recombination through the resonant state [1s2s(2)2p(1/2)](1).

Magnetoelectroluminescence of organic heterostructures: Analytical theory and spectrally resolved measurements

NASA Astrophysics Data System (ADS)

Liu, Feilong; Kelley, Megan R.; Crooker, Scott A.; Nie, Wanyi; Mohite, Aditya D.; Ruden, P. Paul; Smith, Darryl L.

2014-12-01

The effect of a magnetic field on the electroluminescence of organic light emitting devices originates from the hyperfine interaction between the electron/hole polarons and the hydrogen nuclei of the host molecules. In this paper, we present an analytical theory of magnetoelectroluminescence for organic semiconductors. To be specific, we focus on bilayer heterostructure devices. In the case we are considering, light generation at the interface of the donor and acceptor layers results from the formation and recombination of exciplexes. The spin physics is described by a stochastic Liouville equation for the electron/hole spin density matrix. By finding the steady-state analytical solution using Bloch-Wangsness-Redfield theory, we explore how the singlet/triplet exciplex ratio is affected by the hyperfine interaction strength and by the external magnetic field. To validate the theory, spectrally resolved electroluminescence experiments on BPhen/m-MTDATA devices are analyzed. With increasing emission wavelength, the width of the magnetic field modulation curve of the electroluminescence increases while its depth decreases. These observations are consistent with the model.

Effect of magnetic coupling on non-radiative relaxation time of Fe3+ sites on LaAl1-xFexO3 pigments

NASA Astrophysics Data System (ADS)

Novatski, A.; Somer, A.; Maranha, F. G.; de Souza, E. C. F.; Andrade, A. V. C.; Antunes, S. R. M.; Borges, C. P. F.; Dias, D. T.; Medina, A. N.; Astrath, N. G. C.

2018-02-01

Inorganic pigments of the system LaAl1-xFexO3 were prepared by the Pechini and the Solid State Reaction (SSR) methods. Magnetic interactions and non-radiative relaxation time were analyzed by means of phase-resolved photoacoustic spectroscopy and electron paramagnetic resonance (EPR) techniques. EPR results show a change in the magnetic behavior from paramagnetic (x = 0.2 and 0.4) to antiferromagnetic (x = 1.0), which is believed to be a result of the SSR preparation method. Trends in the optical absorption bands of the Fe3+ are attributed to their electronic transitions, and the increase in the band's intensity at 480 and 550 nm was assigned to the increase in the magnetic coupling between Fe-Fe. The phase-resolved method is capable of distinguishing between the two preparation methods, and it is possible to infer that SSR modifies the magnetic coupling of Fe-Fe with x.

Fluorescence of acridinic dyes in anionic surfactant solution

NASA Astrophysics Data System (ADS)

Pereira, Robson Valentim; Gehlen, Marcelo Henrique

2005-10-01

The interaction of the cationic dyes acridine, 9-aminoacridine (9AA), and proflavine, with sodium dodecyl sulfate (SDS) was studied by electronic absorption, steady-state and time-resolved fluorescence spectroscopies. The dyes interact with SDS in the pre-micellar region leading in two cases to dimerization in dye-surfactant aggregates, but with distinct molecular arrangements. For proflavine, the observed red shift of the electronic absorption band indicates the presence of J-aggregate, which are nonfluorescent. In the case of 9AA, the aggregates were characterized as nonspecific (neither J- nor H-type is spectroscopically observed). The time-resolved emission spectra gives evidences of the presence of weakly bound dimers by the recovery of three defined decay times by global analysis: dye monomer ( τ1 = 16.4 ns), dimer ( τ2 = 7.1 ns), and a faster component ( τ3 = 2.1 ns) ascribed to intracluster energy migration between monomer and dimer. Acridine has a weak interaction with SDS forming only an ion pair without further self-aggregation of the dye.

Fluorescence of acridinic dyes in anionic surfactant solution.

PubMed

Pereira, Robson Valentim; Gehlen, Marcelo Henrique

2005-10-01

The interaction of the cationic dyes acridine, 9-aminoacridine (9AA), and proflavine, with sodium dodecyl sulfate (SDS) was studied by electronic absorption, steady-state and time-resolved fluorescence spectroscopies. The dyes interact with SDS in the pre-micellar region leading in two cases to dimerization in dye-surfactant aggregates, but with distinct molecular arrangements. For proflavine, the observed red shift of the electronic absorption band indicates the presence of J-aggregate, which are nonfluorescent. In the case of 9AA, the aggregates were characterized as nonspecific (neither J- nor H-type is spectroscopically observed). The time-resolved emission spectra gives evidences of the presence of weakly bound dimers by the recovery of three defined decay times by global analysis: dye monomer (tau1 = 16.4 ns), dimer (tau2 = 7.1 ns), and a faster component (tau3 = 2.1 ns) ascribed to intracluster energy migration between monomer and dimer. Acridine has a weak interaction with SDS forming only an ion pair without further self-aggregation of the dye.

Ribosome dynamics and tRNA movement by time-resolved electron cryomicroscopy.

PubMed

Fischer, Niels; Konevega, Andrey L; Wintermeyer, Wolfgang; Rodnina, Marina V; Stark, Holger

2010-07-15

The translocation step of protein synthesis entails large-scale rearrangements of the ribosome-transfer RNA (tRNA) complex. Here we have followed tRNA movement through the ribosome during translocation by time-resolved single-particle electron cryomicroscopy (cryo-EM). Unbiased computational sorting of cryo-EM images yielded 50 distinct three-dimensional reconstructions, showing the tRNAs in classical, hybrid and various novel intermediate states that provide trajectories and kinetic information about tRNA movement through the ribosome. The structures indicate how tRNA movement is coupled with global and local conformational changes of the ribosome, in particular of the head and body of the small ribosomal subunit, and show that dynamic interactions between tRNAs and ribosomal residues confine the path of the tRNAs through the ribosome. The temperature dependence of ribosome dynamics reveals a surprisingly flat energy landscape of conformational variations at physiological temperature. The ribosome functions as a Brownian machine that couples spontaneous conformational changes driven by thermal energy to directed movement.

Delayed entanglement echo for individual control of a large number of nuclear spins

PubMed Central

Wang, Zhen-Yu; Casanova, Jorge; Plenio, Martin B.

2017-01-01

Methods to selectively detect and manipulate nuclear spins by single electrons of solid-state defects play a central role for quantum information processing and nanoscale nuclear magnetic resonance (NMR). However, with standard techniques, no more than eight nuclear spins have been resolved by a single defect centre. Here we develop a method that improves significantly the ability to detect, address and manipulate nuclear spins unambiguously and individually in a broad frequency band by using a nitrogen-vacancy (NV) centre as model system. On the basis of delayed entanglement control, a technique combining microwave and radio frequency fields, our method allows to selectively perform robust high-fidelity entangling gates between hardly resolved nuclear spins and the NV electron. Long-lived qubit memories can be naturally incorporated to our method for improved performance. The application of our ideas will increase the number of useful register qubits accessible to a defect centre and improve the signal of nanoscale NMR. PMID:28256508

Delayed entanglement echo for individual control of a large number of nuclear spins.

PubMed

Wang, Zhen-Yu; Casanova, Jorge; Plenio, Martin B

2017-03-03

Methods to selectively detect and manipulate nuclear spins by single electrons of solid-state defects play a central role for quantum information processing and nanoscale nuclear magnetic resonance (NMR). However, with standard techniques, no more than eight nuclear spins have been resolved by a single defect centre. Here we develop a method that improves significantly the ability to detect, address and manipulate nuclear spins unambiguously and individually in a broad frequency band by using a nitrogen-vacancy (NV) centre as model system. On the basis of delayed entanglement control, a technique combining microwave and radio frequency fields, our method allows to selectively perform robust high-fidelity entangling gates between hardly resolved nuclear spins and the NV electron. Long-lived qubit memories can be naturally incorporated to our method for improved performance. The application of our ideas will increase the number of useful register qubits accessible to a defect centre and improve the signal of nanoscale NMR.

Electron scattering, charge order, and pseudogap physics in La 1.6–xNd 0.4Sr xCuO 4: An angle-resolved photoemission spectroscopy study

DOE PAGES

Matt, C. E.; Fatuzzo, C. G.; Sassa, Y.; ...

2015-10-27

We report an angle-resolved photoemission study of the charge stripe ordered La 1.6–xNd 0.4Sr xCuO 4 (Nd-LSCO) system. A comparative and quantitative line-shape analysis is presented as the system evolves from the overdoped regime into the charge ordered phase. On the overdoped side (x = 0.20), a normal-state antinodal spectral gap opens upon cooling below 80 K. In this process, spectral weight is preserved but redistributed to larger energies. A correlation between this spectral gap and electron scattering is found. A different line shape is observed in the antinodal region of charge ordered Nd-LSCO x = 1/8. Significant low-energy spectralmore » weight appears to be lost. As a result, these observations are discussed in terms of spectral-weight redistribution and gapping originating from charge stripe ordering.« less

Magneto-optical properties and recombination dynamics of isoelectronic bound excitons in ZnO

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chen, S. L.; Chen, W. M.; Buyanova, I. A.

2014-02-21

Magneto-optical and time-resolved photoluminescence (PL) spectroscopies are employed to evaluate electronic structure of a bound exciton (BX) responsible for the 3.364 eV line (labeled as I{sub 1}{sup *}) in bulk ZnO. From time-resolved PL spectroscopy, I{sub 1}{sup *} is concluded to originate from the exciton ground state. Based on performed magneto-PL studies, the g-factors of the involved electron and hole are determined as being g{sub e} = 1.98 and g{sub h}{sup ∥}(g{sub h}{sup ⊥}) = 1.2(1.62), respectively. These values are nearly identical to the reported g-factors for the I{sup *} line in ZnO (Phys. Rev. B 86, 235205 (2012)), which proves thatmore » I{sub 1}{sup *} should have a similar origin as I{sup *} and should arise from an exciton bound to an isoelectronic center with a hole-attractive potential.« less

π-Electron-system-layered polymer: through-space conjugation and properties as a single molecular wire.

PubMed

Morisaki, Yasuhiro; Ueno, Shizue; Saeki, Akinori; Asano, Atsushi; Seki, Shu; Chujo, Yoshiki

2012-04-02

[2.2]Paracyclophane-based through-space conjugated oligomers and polymers were prepared, in which poly(p-arylene-ethynylene) (PAE) units were partially π-stacked and layered, and their properties in the ground state and excited state were investigated in detail. Electronic interactions among PAE units were effective through at least ten units in the ground state. Photoexcited energy transfer occurred from the stacked PAE units to the end-capping PAE moieties. The electrical conductivity of the polymers was estimated using the flash-photolysis time-resolved microwave conductivity (FP-TRMC) method and investigated together with time-dependent density functional theory (TD-DFT) calculations, showing that intramolecular charge carrier mobility through the stacked PAE units was a few tens of percentage larger than through the twisted PAE units. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

The ground state infrared spectrum of the MnH radical ( 7Σ) from diode laser spectroscopy

NASA Astrophysics Data System (ADS)

Urban, Rolf-Dieter; Jones, Harold

1989-11-01

The infrared spectrum of the manganese hydride radical ( 55MnH) in its ground electronic state ( 7Σ) has been observed using a diode laser spectrometer. The wavenumbers of twelve transitions of the v=1→0 band, five of the v=2→1 band and seven of the v=3→2 band have been measured with a nominal accuracy of ±0.001 cm -1. Coupling between the electronic spin ( S=3) and the overall molecular rotation causes each ro-vibrational transition with N>3 to be split (γ splitting) into seven components each separated by a few hundredths of a wavenumber. In most cases the complete structure was resolved. Correction terms arising from spin-spin coupling had to be included in the analysis. This work has produced the most accurate set of ground-state parameters available for MnH.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Xiao, Kai; Ma, Ying -Zhong; Simpson, Mary Jane

Charge carrier trapping degrades the performance of organometallic halide perovskite solar cells. To characterize the locations of electronic trap states in a heterogeneous photoactive layer, a spatially resolved approach is essential. Here, we report a comparative study on methylammonium lead tri-iodide perovskite thin films subject to different thermal annealing times using a combined photoluminescence (PL) and femtosecond transient absorption microscopy (TAM) approach to spatially map trap states. This approach coregisters the initially populated electronic excited states with the regions that recombine radiatively. Although the TAM images are relatively homogeneous for both samples, the corresponding PL images are highly structured. Themore » remarkable variation in the PL intensities as compared to transient absorption signal amplitude suggests spatially dependent PL quantum efficiency, indicative of trapping events. Furthermore, detailed analysis enables identification of two trapping regimes: a densely packed trapping region and a sparse trapping area that appear as unique spatial features in scaled PL maps.« less

Nanoclusters as a new family of high temperature superconductors (Conference Presentation)

NASA Astrophysics Data System (ADS)

Halder, Avik; Kresin, Vitaly V.

2017-03-01

Electrons in metal clusters organize into quantum shells, akin to atomic shells in the periodic table. Such nanoparticles are referred to as "superatoms". The electronic shell levels are highly degenerate giving rise to sharp peaks in the density of states, which can enable exceptionally strong electron pairing in certain clusters containing tens to hundreds of atoms. A spectroscopic investigation of size - resolved aluminum nanoclusters has revealed a sharp rise in the density of states near the Fermi level as the temperature decreases towards 100 K. The effect is especially prominent in the closed-shell "magic" cluster Al66 [1, 2]. The characteristics of this behavior are fully consistent with a pairing transition, implying a high temperature superconducting state with Tc < 100K. This value exceeds that of bulk aluminum by two orders of magnitude. As a new class of high-temperature superconductors, such metal nanocluster particles are promising building blocks for high-Tc materials, devices, and networks. ---------- 1. Halder, A., Liang, A., Kresin, V. V. A novel feature in aluminum cluster photoionization spectra and possibility of electron pairing at T 100K. Nano Lett 15, 1410 - 1413 (2015) 2. Halder, A., Kresin, V. V. A transition in the density of states of metal "superatom" nanoclusters and evidence for superconducting pairing at T 100K. Phys. Rev. B 92, 214506 (2015).

Investigation of carrier dynamics in InAs/GaAsSb quantum dots with different silicon delta-doping levels

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ban, Keun-Yong; Kim, Yeongho; Kuciauskas, Darius

2016-11-10

The optical properties of InAs quantum dots (QDs) embedded in a GaAsSb matrix with different delta (d)-doping levels of 0, 2, 4, and 6 electrons per dot (e-/dot), incorporated to control the occupation of QD electronic states, are studied by photoluminescence (PL) spectroscopy. The time-resolved PL data taken at 10 K reveal that the increase of δ-doping density from 2 to 6 e -/dot decreases the recombination lifetime of carriers at ground states of the QDs from 996 ± 36 to 792 ± 19 ps, respectively. Furthermore, the carrier lifetime of the sample with 4 e -/dot is found tomore » increase at a slower rate than that of the undoped sample as temperature increases above 70 K. An Arrhenius plot of the temperature dependent PL intensity indicates that the thermal activation energy of electrons in the QDs, required for carrier escape from the dot ground state to continuum state, is increased when the d-doping density is high enough (>4 e -/dot). These results are attributed to the enhanced Coulomb interaction of electrons provided by the d-doping, leading to reduced thermal quenching of the PL.« less

Photoinduced electron transfer (PET) versus excimer formation in supramolecular p/n-heterojunctions of perylene bisimide dyes and implications for organic photovoltaics.

PubMed

Nowak-Król, Agnieszka; Fimmel, Benjamin; Son, Minjung; Kim, Dongho; Würthner, Frank

2015-01-01

Foldamer systems comprised of two perylene bisimide (PBI) dyes attached to the conjugated backbones of 1,2-bis(phenylethynyl)benzene and phenylethynyl-bis(phenylene)indane, respectively, were synthesized and investigated with regard to their solvent-dependent properties. UV/Vis absorption and steady-state fluorescence spectra show that both foldamers exist predominantly in a folded H-aggregated state consisting of π-π-stacked PBIs in THF and in more random conformations with weaker excitonic coupling between the PBIs in chloroform. Time-resolved fluorescence spectroscopy and transient absorption spectroscopy reveal entirely different relaxation pathways for the photoexcited molecules in the given solvents, i.e. photoinduced electron transfer leading to charge separated states for the open conformations (in chloroform) and relaxation into excimer states with red-shifted emission for the stacked conformations (in THF). Supported by redox data from cyclic voltammetry and Rehm-Weller analysis we could relate the processes occurring in these solution-phase model systems to the elementary processes in organic solar cells. Accordingly, only if relaxation pathways such as excimer formation are strictly avoided in molecular semiconductor materials, excitons may diffuse over larger distances to the heterojunction interface and produce photocurrent via the formation of electron/hole pairs by photoinduced electron transfer.

Long-lived coherence in carotenoids

NASA Astrophysics Data System (ADS)

Davis, J. A.; Cannon, E.; Van Dao, L.; Hannaford, P.; Quiney, H. M.; Nugent, K. A.

2010-08-01

We use two-colour vibronic coherence spectroscopy to observe long-lived vibrational coherences in the ground electronic state of carotenoid molecules, with decoherence times in excess of 1 ps. Lycopene and spheroidene were studied isolated in solution, and within the LH2 light-harvesting complex extracted from purple bacteria. The vibrational coherence time is shown to increase significantly for the carotenoid in the complex, providing further support to previous assertions that long-lived electronic coherences in light-harvesting complexes are facilitated by in-phase motion of the chromophores and surrounding proteins. Using this technique, we are also able to follow the evolution of excited state coherences and find that for carotenoids in the light-harvesting complex the langS2|S0rang superposition remains coherent for more than 70 fs. In addition to the implications of this long electronic decoherence time, the extended coherence allows us to observe the evolution of the excited state wavepacket. These experiments reveal an enhancement of the vibronic coupling to the first vibrational level of the C-C stretching mode and/or methyl-rocking mode in the ground electronic state 70 fs after the initial excitation. These observations open the door to future experiments and modelling that may be able to resolve the relaxation dynamics of carotenoids in solution and in natural light-harvesting systems.

Direct detection of a transport-blocking trap in a nanoscaled silicon single-electron transistor by radio-frequency reflectometry

DOE Office of Scientific and Technical Information (OSTI.GOV)

Villis, B. J.; Sanquer, M.; Jehl, X.

2014-06-09

The continuous downscaling of transistors results in nanoscale devices which require fewer and fewer charged carriers for their operation. The ultimate charge controlled device, the single-electron transistor (SET), controls the transfer of individual electrons. It is also the most sensitive electrometer, and as a result the electron transport through it can be dramatically affected by nearby charges. Standard direct-current characterization techniques, however, are often unable to unambiguously detect and resolve the origin of the observed changes in SET behavior arising from changes in the charge state of a capacitively coupled trap. Using a radio-frequency (RF) reflectometry technique, we are ablemore » to unequivocally detect this process, in very close agreement with modeling of the trap's occupation probability.« less

Millimeter-Wave Time Resolved Studies of the Formation and Decay of CO^+

NASA Astrophysics Data System (ADS)

Oesterling, Lee; Herbst, Eric; de Lucia, Frank

1998-04-01

Since the rate constants for ion-molecule interactions are typically much larger than neutral-neutral interactions, understanding ion-molecule interactions is essential to interpreting radio astronomical spectra from interstellar clouds and modeling the processes which lead to the formation of stars in these regions. We have developed a cell which allows us to study ion-molecule interactions in gases at low temperatures and pressures by using an electron gun technique to create ions. By centering our millimeter-wave source on a rotational resonance and gating the electron beam on and off, we are able to study the time-dependent rotational state distribution of the ion during its formation and decay, and so learn about excitation and relaxation processes as functions of temperature, pressure, electron beam energy, and electron beam current.

Coupled sensitizer-catalyst dyads: electron-transfer reactions in a perylene-polyoxometalate conjugate.

PubMed

Odobel, Fabrice; Séverac, Marjorie; Pellegrin, Yann; Blart, Errol; Fosse, Céline; Cannizzo, Caroline; Mayer, Cédric R; Elliott, Kristopher J; Harriman, Anthony

2009-01-01

Ultrafast discharge of a single-electron capacitor: A variety of intramolecular electron-transfer reactions are apparent for polyoxometalates functionalized with covalently attached perylene monoimide chromophores, but these are restricted to single-electron events. (et=electron transfer, cr=charge recombination, csr=charge-shift reaction, PER=perylene, POM=polyoxometalate).A new strategy is introduced that permits covalent attachment of an organic chromophore to a polyoxometalate (POM) cluster. Two examples are reported that differ according to the nature of the anchoring group and the flexibility of the linker. Both POMs are functionalized with perylene monoimide units, which function as photon collectors and form a relatively long-lived charge-transfer state under illumination. They are reduced to a stable pi-radical anion by electrolysis or to a protonated dianion under photolysis in the presence of aqueous triethanolamine. The presence of the POM opens up an intramolecular electron-transfer route by which the charge-transfer state reduces the POM. The rate of this process depends on the molecular conformation and appears to involve through-space interactions. Prior reduction of the POM leads to efficient fluorescence quenching, again due to intramolecular electron transfer. In most cases, it is difficult to resolve the electron-transfer products because of relatively fast reverse charge shift that occurs within a closed conformer. Although the POM can store multiple electrons, it has not proved possible to use these systems as molecular-scale capacitors because of efficient electron transfer from the one-electron-reduced POM to the excited singlet state of the perylene monoimide.

High resolution in-operando microimaging of solar cells with pulsed electrically-detected magnetic resonance

NASA Astrophysics Data System (ADS)

Katz, Itai; Fehr, Matthias; Schnegg, Alexander; Lips, Klaus; Blank, Aharon

2015-02-01

The in-operando detection and high resolution spatial imaging of paramagnetic defects, impurities, and states becomes increasingly important for understanding loss mechanisms in solid-state electronic devices. Electron spin resonance (ESR), commonly employed for observing these species, cannot meet this challenge since it suffers from limited sensitivity and spatial resolution. An alternative and much more sensitive method, called electrically-detected magnetic resonance (EDMR), detects the species through their magnetic fingerprint, which can be traced in the device's electrical current. However, until now it could not obtain high resolution images in operating electronic devices. In this work, the first spatially-resolved electrically-detected magnetic resonance images (EDMRI) of paramagnetic states in an operating real-world electronic device are provided. The presented method is based on a novel microwave pulse sequence allowing for the coherent electrical detection of spin echoes in combination with powerful pulsed magnetic-field gradients. The applicability of the method is demonstrated on a device-grade 1-μm-thick amorphous silicon (a-Si:H) solar cell and an identical device that was degraded locally by an electron beam. The degraded areas with increased concentrations of paramagnetic defects lead to a local increase in recombination that is mapped by EDMRI with ∼20-μm-scale pixel resolution. The novel approach presented here can be widely used in the nondestructive in-operando three-dimensional characterization of solid-state electronic devices with a resolution potential of less than 100 nm.

High-resolution studies of tropolone in the S0 and S1 electronic states: isotope driven dynamics in the zero-point energy levels.

PubMed

Keske, John C; Lin, Wei; Pringle, Wallace C; Novick, Stewart E; Blake, Thomas A; Plusquellic, David F

2006-02-21

Rotationally resolved microwave (MW) and ultraviolet (UV) spectra of jet-cooled tropolone have been obtained in S(0) and S(1) electronic states using Fourier-transform microwave and UV-laser/molecular-beam spectrometers. In the ground electronic state, the MW spectra of all heavy-atom isotopomers including one (18)O and four (13)C isotopomers were observed in natural abundance. The OD isotopomer was obtained from isotopically enriched samples. The two lowest tunneling states of each isotopomer except (18)O have been assigned. The observed inversion splitting for the OD isotopomer is 1523.227(5) MHz. For the asymmetric (13)C structures, the magnitudes of tunneling-rotation interactions are found to diminish with decreasing distance between the heavy atom and the tunneling proton. In the limit of closest approach, the 0(+) state of (18)O was well fitted to an asymmetric rotor Hamiltonian, reflecting significant changes in the tautomerization dynamics. Comparisons of the substituted atom coordinates with theoretical predictions at the MP2/aug-cc-pVTZ level of theory suggest the localized 0(+) and 0(-) wave functions of the heavier isotopes favor the C-OH and C=O forms of tropolone, respectively. The only exception occurs for the (13)C-OH and (13)C[Double Bond]O structures which correlate to the 0(-) and 0(+) states, respectively. These preferences reflect kinetic isotope effects as quantitatively verified by the calculated zero-point energy differences between members of the asymmetric atom pairs. From rotationally resolved data of the 0(+) <--0(+) and 0(-) <--0(-) bands in S(1), line-shape fits have yielded Lorentzian linewidths that differ by 12.2(16) MHz over the 19.88(4) cm(-1) interval in S(1). The fluorescence decay rates together with previously reported quantum yield data give nonradiative decay rates of 7.7(5) x 10(8) and 8.5(5) x 10(8) s(-1) for the 0(+) and 0(-) levels of the S(1) state of tropolone.

Evaluating the Nature of So-Called S*-State Feature in Transient Absorption of Carotenoids in Light-Harvesting Complex 2 (LH2) from Purple Photosynthetic Bacteria.

PubMed

Niedzwiedzki, Dariusz M; Hunter, C Neil; Blankenship, Robert E

2016-11-03

Carotenoids are a class of natural pigments present in all phototrophic organisms, mainly in their light-harvesting proteins in which they play roles of accessory light absorbers and photoprotectors. Extensive time-resolved spectroscopic studies of these pigments have revealed unexpectedly complex photophysical properties, particularly for carotenoids in light-harvesting LH2 complexes from purple bacteria. An ambiguous, optically forbidden electronic excited state designated as S* has been postulated to be involved in carotenoid excitation relaxation and in an alternative carotenoid-to-bacteriochlorophyll energy transfer pathway, as well as being a precursor of the carotenoid triplet state. However, no definitive and satisfactory origin of the carotenoid S* state in these complexes has been established, despite a wide-ranging series of studies. Here, we resolve the ambiguous origin of the carotenoid S* state in LH2 complex from Rba. sphaeroides by showing that the S* feature can be seen as a combination of ground state absorption bleaching of the carotenoid pool converted to cations and the Stark spectrum of neighbor neutral carotenoids, induced by temporal electric field brought by the carotenoid cation-bacteriochlorophyll anion pair. These findings remove the need to assign an S* state, and thereby significantly simplify the photochemistry of carotenoids in these photosynthetic antenna complexes.

Ultrafast excited-state dynamics of RNA and DNA C tracts

NASA Astrophysics Data System (ADS)

Cohen, Boiko; Larson, Matthew H.; Kohler, Bern

2008-06-01

The excited-state dynamics of the RNA homopolymer of cytosine and of the 18-mer (dC) 18 were studied by steady-state and time-resolved absorption and emission spectroscopy. At pH 6.8, excitation of poly(rC) by a femtosecond UV pump pulse produces excited states that decay up to one order of magnitude more slowly than the excited states formed in the mononucleotide cytidine 5'-monophosphate under the same conditions. Even slower relaxation is observed for the hemiprotonated, self-associated form of poly(rC), which is stable at acidic pH. Transient absorption and time-resolved fluorescence signals for (dC) 18 at pH 6.8 are similar to ones observed for poly(rC) near pH 4, indicating that hemiprotonated structures are found in DNA C tracts at neutral pH. In both systems, there is evidence for two kinds of emitting states with lifetimes of ˜100 ps and slightly more than 1 ns. The former states are responsible for the bulk of emission from the hemiprotonated structures. Evidence suggests that slow electronic relaxation in these self-complexes is the result of vertical base stacking. The similar signals from RNA and DNA C tracts suggest a common base-stacked structure, which may be identical with that of i-motif DNA.

Low-lying vibronic level structure of the ground state of the methoxy radical: Slow electron velocity-map imaging (SEVI) spectra and Köppel-Domcke-Cederbaum (KDC) vibronic Hamiltonian calculations

DOE Office of Scientific and Technical Information (OSTI.GOV)

Weichman, Marissa L.; Cheng, Lan; Kim, Jongjin B.

A joint experimental and theoretical study is reported on the low-lying vibronic level structure of the ground state of the methoxy radical using slow photoelectron velocity-map imaging spectroscopy of cryogenically cooled, mass-selected anions (cryo-SEVI) and Köppel-Domcke-Cederbaum (KDC) vibronic Hamiltonian calculations. The KDC vibronic model Hamiltonian in the present study was parametrized using high-level quantum chemistry, allowing the assignment of the cryo-SEVI spectra for vibronic levels of CH 3O up to 2000 cm –1 and of CD 3O up to 1500 cm –1 above the vibrational origin, using calculated vibronic wave functions. The adiabatic electron affinities of CH 3O and CDmore » 3O are determined from the cryo-SEVI spectra to be 1.5689 ± 0.0007 eV and 1.5548 ± 0.0007 eV, respectively, demonstrating improved precision compared to previous work. Experimental peak splittings of <10 cm –1 are resolved between the e 1/2 and e 3/2 components of the 6 1 and 5 1 vibronic levels. A pair of spin-vibronic levels at 1638 and 1677 cm –1 were predicted in the calculation as the e 1/2 and e 3/2 components of 6 2 levels and experimentally resolved for the first time. The strong variation of the spin-orbit splittings with a vibrational quantum number is in excellent agreement between theory and experiment. In conclusion, the observation of signals from nominally forbidden a 1 vibronic levels in the cryo-SEVI spectra also provides direct evidence of vibronic coupling between ground and electronically excited states of methoxy.« less

Low-lying vibronic level structure of the ground state of the methoxy radical: Slow electron velocity-map imaging (SEVI) spectra and Köppel-Domcke-Cederbaum (KDC) vibronic Hamiltonian calculations

DOE PAGES

Weichman, Marissa L.; Cheng, Lan; Kim, Jongjin B.; ...

2017-06-12

A joint experimental and theoretical study is reported on the low-lying vibronic level structure of the ground state of the methoxy radical using slow photoelectron velocity-map imaging spectroscopy of cryogenically cooled, mass-selected anions (cryo-SEVI) and Köppel-Domcke-Cederbaum (KDC) vibronic Hamiltonian calculations. The KDC vibronic model Hamiltonian in the present study was parametrized using high-level quantum chemistry, allowing the assignment of the cryo-SEVI spectra for vibronic levels of CH 3O up to 2000 cm –1 and of CD 3O up to 1500 cm –1 above the vibrational origin, using calculated vibronic wave functions. The adiabatic electron affinities of CH 3O and CDmore » 3O are determined from the cryo-SEVI spectra to be 1.5689 ± 0.0007 eV and 1.5548 ± 0.0007 eV, respectively, demonstrating improved precision compared to previous work. Experimental peak splittings of <10 cm –1 are resolved between the e 1/2 and e 3/2 components of the 6 1 and 5 1 vibronic levels. A pair of spin-vibronic levels at 1638 and 1677 cm –1 were predicted in the calculation as the e 1/2 and e 3/2 components of 6 2 levels and experimentally resolved for the first time. The strong variation of the spin-orbit splittings with a vibrational quantum number is in excellent agreement between theory and experiment. In conclusion, the observation of signals from nominally forbidden a 1 vibronic levels in the cryo-SEVI spectra also provides direct evidence of vibronic coupling between ground and electronically excited states of methoxy.« less

Vibrational cooling dynamics of a [FeFe]-hydrogenase mimic probed by time-resolved infrared spectroscopy.

PubMed

Caplins, Benjamin W; Lomont, Justin P; Nguyen, Son C; Harris, Charles B

2014-12-11

Picosecond time-resolved infrared spectroscopy (TRIR) was performed for the first time on a dithiolate bridged binuclear iron(I) hexacarbonyl complex ([Fe₂(μ-bdt)(CO)₆], bdt = benzene-1,2-dithiolate) which is a structural mimic of the active site of the [FeFe]-hydrogenase enzyme. As these model active sites are increasingly being studied for their potential in photocatalytic systems for hydrogen production, understanding their excited and ground state dynamics is critical. In n-heptane, absorption of 400 nm light causes carbonyl loss with low quantum yield (<10%), while the majority (ca. 90%) of the parent complex is regenerated with biexponential kinetics (τ₁ = 21 ps and τ₂ = 134 ps). In order to understand the mechanism of picosecond bleach recovery, a series of UV-pump TRIR experiments were performed in different solvents. The long time decay (τ₂) of the transient spectra is seen to change substantially as a function of solvent, from 95 ps in THF to 262 ps in CCl₄. Broadband IR-pump TRIR experiments were performed for comparison. The measured vibrational lifetimes (T₁(avg)) of the carbonyl stretches were found to be in excellent correspondence to the observed τ₂ decays in the UV-pump experiments, signifying that vibrationally excited carbonyl stretches are responsible for the observed longtime decays. The fast spectral evolution (τ₁) was determined to be due to vibrational cooling of low frequency modes anharmonically coupled to the carbonyl stretches that were excited after electronic internal conversion. The results show that cooling of both low and high frequency vibrational modes on the electronic ground state give rise to the observed picosecond TRIR transient spectra of this compound, without the need to invoke electronically excited states.

Detection of local chemical states of lithium and their spatial mapping by scanning transmission electron microscopy, electron energy-loss spectroscopy and hyperspectral image analysis.

PubMed

Muto, Shunsuke; Tatsumi, Kazuyoshi

2017-02-08

Advancements in the field of renewable energy resources have led to a growing demand for the analysis of light elements at the nanometer scale. Detection of lithium is one of the key issues to be resolved for providing guiding principles for the synthesis of cathode active materials, and degradation analysis after repeated use of those materials. We have reviewed the different techniques currently used for the characterization of light elements such as high-resolution transmission electron microscopy, scanning transmission electron microscopy (STEM) and electron energy-loss spectroscopy (EELS). In the present study, we have introduced a methodology to detect lithium in solid materials, particularly for cathode active materials used in lithium-ion battery. The chemical states of lithium were isolated and analyzed from the overlapping multiple spectral profiles, using a suite of STEM, EELS and hyperspectral image analysis. The method was successfully applied in the chemical state analyses of hetero-phases near the surface and grain boundary regions of the active material particles formed by chemical reactions between the electrolyte and the active materials. © The Author 2016. Published by Oxford University Press on behalf of The Japanese Society of Microscopy. All rights reserved. For permissions, please e-mail: journals.permissions@oup.com.

Ab initio study on rare-earth iron-pnictides RFeAsO (R = Pr, Nd, Sm, Gd) in low-temperature Cmma phase

NASA Astrophysics Data System (ADS)

Eryigit, Resul; Gurel, Tanju; Erturk, Esra; Lukoyanov, A. V.; Akcay, Guven; Anisimov, V. I.

2014-03-01

We present density functional theory calculations on iron-based pnictides RFeAsO (R = Pr, Nd, Sm, Gd). The calculations have been carried out using plane-waves and projector augmented wave (PAW) pseudopotential approach. Structural, magnetic and electronic properties are studied within generalized gradient approximation (GGA) and also within GGA+U in order to investigate the influence of electron correlation effects. Low-temperature Cmma structure is fully optimized by GGA considering both non-magnetic and magnetic cells. We have found that spin-polarized structure improves the agreement with experiments on equilibrium lattice parameters, particularly c lattice parameter and Fe-As bond-lengths. Electronic band structure, total density of states, and spin-dependent orbital-resolved density of states are also analyzed in the frameworks of GGA and GGA+U and discussed. For all materials, by including on-site Coulomb correction, rare earth 4f states move away from the Fermi level and the Fermi level features of the systems are found to be mostly defined by the 3d electron-electron correlations in Fe. This work was supported by the Scientific and Technological Research Council of Turkey (TUBITAK Project No. TBAG-111T796) and the Russian Foundation for Basic Research (Project No. 12-02-91371-CT_a).

Rare-gas-cluster explosions under irradiation by intense short XUV pulses

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hoffmann, K.; Murphy, B.; Kandadai, N.

High-intensity, extreme-ultraviolet (XUV) femtosecond interactions with large rare-gas clusters of xenon and argon have been studied at a wavelength of 38 nm. Pulses of XUV radiation with nJ energy are produced by high-order harmonic conversion from a 35-fs, near-infrared, terawatt laser. Mass resolved ion spectra show charge states up to Xe{sup 8+} and Ar{sup 4+}. Kinetic-energy measurements of ions and electrons indicate that a nanoplasma is formed and a hydrodynamic cluster explosion ensues after heating by the short wavelength pulse. It appears that the observed charge states and electron temperatures are consistent with sequential, single-photon ionization and collisional ionization ofmore » ions that have had their ionization potential depressed by plasma continuum lowering in the cluster nanoplasma.« less

Photophysical properties of fullerene-dendron-pyropheophorbide supramolecules

NASA Astrophysics Data System (ADS)

Ermilov, E. A.; Al-Omari, S.; Helmreich, M.; Jux, N.; Hirsch, A.; Röder, B.

2004-05-01

Two novel monofullerene-bis(pyropheophorbide a) complexes were synthesized and their photophysical properties were studied by using both steady-state and time-resolved techniques. It was revealed that in the pyropheophorbide a (pyroPheo)-C 60 molecular system (FP1) strong quenching of the first excited singlet state of the pyroPheo and, as result, dramatically decreasing of photosensitized singlet oxygen generation occurs by efficient photoinduced electron transfer to the fullerene molecule with a rate constant of 2.5 × 10 9 s -1. In contrast, the fullerene hexaadduct-bis(pyroPheo) system (FHP1), which possesses five diethyl malonate addends in the remaining octahedral positions, shows a high singlet oxygen quantum yield which is due to the reduced fullerene chromophore which is not a good electron acceptor anymore.

Electronic structure of negative charge transfer CaFeO3 across the metal-insulator transition

NASA Astrophysics Data System (ADS)

Rogge, Paul C.; Chandrasena, Ravini U.; Cammarata, Antonio; Green, Robert J.; Shafer, Padraic; Lefler, Benjamin M.; Huon, Amanda; Arab, Arian; Arenholz, Elke; Lee, Ho Nyung; Lee, Tien-Lin; Nemšák, Slavomír; Rondinelli, James M.; Gray, Alexander X.; May, Steven J.

2018-01-01

We investigated the metal-insulator transition for epitaxial thin films of the perovskite CaFeO3, a material with a significant oxygen ligand hole contribution to its electronic structure. We find that biaxial tensile and compressive strain suppress the metal-insulator transition temperature. By combining hard x-ray photoelectron spectroscopy, soft x-ray absorption spectroscopy, and density functional calculations, we resolve the element-specific changes to the electronic structure across the metal-insulator transition. We demonstrate that the Fe sites undergo no observable spectroscopic change between the metallic and insulating states, whereas the O electronic configuration undergoes significant changes. This strongly supports the bond-disproportionation model of the metal-insulator transition for CaFeO3 and highlights the importance of ligand holes in its electronic structure. By sensitively measuring the ligand hole density, however, we find that it increases by ˜5 -10 % in the insulating state, which we ascribe to a further localization of electron charge on the Fe sites. These results provide detailed insight into the metal-insulator transition of negative charge transfer compounds and should prove instructive for understanding metal-insulator transitions in other late transition metal compounds such as the nickelates.

Resolving the role of femtosecond heated electrons in ultrafast spin dynamics.

PubMed

Mendil, J; Nieves, P; Chubykalo-Fesenko, O; Walowski, J; Santos, T; Pisana, S; Münzenberg, M

2014-02-05

Magnetization manipulation is essential for basic research and applications. A fundamental question is, how fast can the magnetization be reversed in nanoscale magnetic storage media. When subject to an ultrafast laser pulse, the speed of the magnetization dynamics depends on the nature of the energy transfer pathway. The order of the spin system can be effectively influenced through spin-flip processes mediated by hot electrons. It has been predicted that as electrons drive spins into the regime close to almost total demagnetization, characterized by a loss of ferromagnetic correlations near criticality, a second slower demagnetization process takes place after the initial fast drop of magnetization. By studying FePt, we unravel the fundamental role of the electronic structure. As the ferromagnet Fe becomes more noble in the FePt compound, the electronic structure is changed and the density of states around the Fermi level is reduced, thereby driving the spin correlations into the limit of critical fluctuations. We demonstrate the impact of the electrons and the ferromagnetic interactions, which allows a general insight into the mechanisms of spin dynamics when the ferromagnetic state is highly excited, and identifies possible recording speed limits in heat-assisted magnetization reversal.

Nuclear quantum effects in electronically adiabatic quantum time correlation functions: Application to the absorption spectrum of a hydrated electron

NASA Astrophysics Data System (ADS)

Turi, László; Hantal, György; Rossky, Peter J.; Borgis, Daniel

2009-07-01

A general formalism for introducing nuclear quantum effects in the expression of the quantum time correlation function of an operator in a multilevel electronic system is presented in the adiabatic limit. The final formula includes the nuclear quantum time correlation functions of the operator matrix elements, of the energy gap, and their cross terms. These quantities can be inferred and evaluated from their classical analogs obtained by mixed quantum-classical molecular dynamics simulations. The formalism is applied to the absorption spectrum of a hydrated electron, expressed in terms of the time correlation function of the dipole operator in the ground electronic state. We find that both static and dynamic nuclear quantum effects distinctly influence the shape of the absorption spectrum, especially its high energy tail related to transitions to delocalized electron states. Their inclusion does improve significantly the agreement between theory and experiment for both the low and high frequency edges of the spectrum. It does not appear sufficient, however, to resolve persistent deviations in the slow Lorentzian-like decay part of the spectrum in the intermediate 2-3 eV region.

Formation, stability and dissociation dynamics of {{\\rm{N}}}_{2}{}^{{\\rm{n}}+} cations (n = 1 - 2) in 3.5 keV e - -N2 collisions studied using the energy resolved electron-ion coincidence technique

NASA Astrophysics Data System (ADS)

Kumar, S.; Prajapati, S.; Singh, B.; Singh, B. K.; Shanker, R.

2018-04-01

Coincidences between energy selected electrons and ions produced in the decay of a core hole ionized (excited) state in a free nitrogen molecule have been measured at three specified energies of emitted electrons to reveal the individual pathways produced in 3.5 keV electron-induced fragmentation processes. From these measurements, it has been possible to show, for the first time, that in addition to the normal Auger decay, the resonant Auger excitation channels also share their appreciable contributions in producing singly charged parent ions in an electron-induced collision system. The correlations between ion fragmentation products and electronic structures with a hole configuration in singly-, doubly- and possibly in triply charged molecular electronic states populated in the electronic decay of the initial core hole have been studied and discussed. KER values obtained from our experiments are found to be consistent with the previous results of photo absorption experiments for fragmentation channel {{{{N}}}2}2+ → N+ + N+ however, N2+ fragment ions are found to arise mainly from the fragmentation channel {{{{N}}}2}2+ → N2+ + N and to possess relatively low kinetic energies in the considered region of binding energies.

The time-resolved photoelectron spectrum of toluene using a perturbation theory approach

DOE Office of Scientific and Technical Information (OSTI.GOV)

Richings, Gareth W.; Worth, Graham A., E-mail: g.a.worth@bham.ac.uk

A theoretical study of the intra-molecular vibrational-energy redistribution of toluene using time-resolved photo-electron spectra calculated using nuclear quantum dynamics and a simple, two-mode model is presented. Calculations have been carried out using the multi-configuration time-dependent Hartree method, using three levels of approximation for the calculation of the spectra. The first is a full quantum dynamics simulation with a discretisation of the continuum wavefunction of the ejected electron, whilst the second uses first-order perturbation theory to calculate the wavefunction of the ion. Both methods rely on the explicit inclusion of both the pump and probe laser pulses. The third method includesmore » only the pump pulse and generates the photo-electron spectrum by projection of the pumped wavepacket onto the ion potential energy surface, followed by evaluation of the Fourier transform of the autocorrelation function of the subsequently propagated wavepacket. The calculations performed have been used to study the periodic population flow between the 6a and 10b16b modes in the S{sub 1} excited state, and compared to recent experimental data. We obtain results in excellent agreement with the experiment and note the efficiency of the perturbation method.« less

Walking peptide on Au(110) surface: Origin and nature of interfacial process

NASA Astrophysics Data System (ADS)

Humblot, V.; Tejeda, A.; Landoulsi, J.; Vallée, A.; Naitabdi, A.; Taleb, A.; Pradier, C.-M.

2014-10-01

IGF tri-peptide adsorption on Au(110)-(1 × 2) under Ultra High Vacuum (UHV) conditions has been investigated using surface science techniques such as synchrotron based Angle Resolved X-ray Photoemission Spectroscopy (AR-PES or AR-XPS), Low Energy Electron Diffraction (LEED) and Scanning Tunnelling Microscopy (STM). The behaviour of IGF molecules has been revealed to be coverage dependent; at low coverage, there is formation of islands presenting a chiral self-organised molecular network with a (4 2, - 3 2) symmetry as shown by Low Energy Electron Diffraction (LEED) and Scanning Tunnelling Microscopy (STM) on the unaltered Au(110)-(1 × 2) reconstruction, suggesting significant intermolecular interactions. When the coverage is increased, the islands grow bigger, and one can observe the disappearance of the self-organised network, along with a remarkable destruction of the (1 × 2) substrate reconstruction, as shown by STM. The effect of IGF on the surface gold atoms has been further confirmed by angle-resolved photoemission measurements which suggest a modification of the electronic states with the (1 × 2) symmetry. The resulting molecular organisation, and overall the gold surface disorganisation, prove a strong surface-molecule interaction, which may be probably be explained by a covalent bonding.

Element-resolved atomic structure imaging of rocksalt Ge{sub 2}Sb{sub 2}Te{sub 5} phase-change material

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhang, Bin; Chen, Yongjin; Han, Xiaodong, E-mail: wzhang0@mail.xjtu.edu.cn, E-mail: ema@jhu.edu, E-mail: xdhan@bjut.edu.cn

Disorder-induced electron localization and metal-insulator transitions (MITs) have been a very active research field starting from the seminal paper by Anderson half a century ago. However, pure Anderson insulators are very difficult to identify due to ubiquitous electron-correlation effects. Recently, an MIT has been observed in electrical transport measurements on the crystalline state of phase-change GeSbTe compounds, which appears to be exclusively disorder driven. Subsequent density functional theory simulations have identified vacancy disorder to localize electrons at the Fermi level. Here, we report a direct atomic scale chemical identification experiment on the rocksalt structure obtained upon crystallization of amorphous Ge{submore » 2}Sb{sub 2}Te{sub 5}. Our results confirm the two-sublattice structure resolving the distribution of chemical species and demonstrate the existence of atomic disorder on the Ge/Sb/vacancy sublattice. Moreover, we identify a gradual vacancy ordering process upon further annealing. These findings not only provide a structural underpinning of the observed Anderson localization but also have implications for the development of novel multi-level data storage within the crystalline phases.« less

Direct observation of how the heavy-fermion state develops in CeCoIn5

NASA Astrophysics Data System (ADS)

Chen, Q. Y.; Xu, D. F.; Niu, X. H.; Jiang, J.; Peng, R.; Xu, H. C.; Wen, C. H. P.; Ding, Z. F.; Huang, K.; Shu, L.; Zhang, Y. J.; Lee, H.; Strocov, V. N.; Shi, M.; Bisti, F.; Schmitt, T.; Huang, Y. B.; Dudin, P.; Lai, X. C.; Kirchner, S.; Yuan, H. Q.; Feng, D. L.

2017-07-01

Heavy-fermion systems share some of the strange metal phenomenology seen in other unconventional superconductors, providing a unique opportunity to set strange metals in a broader context. Central to understanding heavy-fermion systems is the interplay of localization and itinerancy. These materials acquire high electronic masses and a concomitant Fermi volume increase as the f electrons delocalize at low temperatures. However, despite the wide-spread acceptance of this view, a direct microscopic verification has been lacking. Here we report high-resolution angle-resolved photoemission measurements on CeCoIn5, a prototypical heavy-fermion compound, which spectroscopically resolve the development of band hybridization and the Fermi surface expansion over a wide temperature region. Unexpectedly, the localized-to-itinerant transition occurs at surprisingly high temperatures, yet f electrons are still largely localized even at the lowest temperature. These findings point to an unanticipated role played by crystal-field excitations in the strange metal behavior of CeCoIn5. Our results offer a comprehensive experimental picture of the heavy-fermion formation, setting the stage for understanding the emergent properties, including unconventional superconductivity, in this and related materials.

Ultrafast nuclear dynamics in halomethanes studied with time-resolved Coulomb explosion imaging and channel-selective Fourier spectroscopy

NASA Astrophysics Data System (ADS)

Malakar, Y.; Kaderiya, B.; Pearson, W. L.; Ziaee, F.; Kanaka Raju, P.; Zohrabi, M.; Jensen, K.; Rajput, J.; Ben-Itzhak, I.; Rolles, D.; Rudenko, A.

2016-05-01

Halomethanes have recently attracted considerable attention since they often serve as prototype systems for laser-controlled chemistry (e.g., selective bond breaking or concerted elimination reactions), and are important molecules in atmospheric chemistry. Here we combine a femtosecond laser pump-probe setup with coincident 3D ion momentum imaging apparatus to study strong-field induced nuclear dynamics in methane and several of its halogenated derivatives (CH3 I, CH2 I2, CH2 ICl). We apply a time-resolved Coulomb explosion imaging technique to map the nuclear motion on both, bound and continuum potential surfaces, disentangle different fragmentation pathways and, for halogenated molecules, observe clear signatures of vibrational wave packets in neutral or ionized states. Channel-selective and kinetic-energy resolved Fourier analysis of these data allows for unique identification of different electronic states and vibrational modes responsible for a particular structure. Supported by the Chemical Sciences, Geosciences, and Biosciences Division, Office of Basic Energy Sciences, Office of Science, U. S. DOE. K. R. P. and W. L. P. supported by NSF Award No. IIA-143049. K.J. supported by the NSF-REU Grant No. PHYS-1461251.

Symmetry properties of the electron density and following from it limits on the KS-DFT applications

NASA Astrophysics Data System (ADS)

Kaplan, Ilya G.

2018-03-01

At present, the Density Functional Theory (DFT) approach elaborated by Kohn with co-authors more than 50 years ago became the most widely used method for study molecules and solids. Using modern computation facilities, it can be applied to systems with million atoms. In the atmosphere of such great popularity, it is particularly important to know the limits of the applicability of DFT methods. In this report, I will discuss two cases when the conventional DFT approaches, using only electron density ρ and its gradients, cannot be applied (I will not consider the Ψ-versions of DFT). The first case is quite evident. In the degenerated states, the electron density may not be defined, since electronic and nuclear motions cannot be separated, the vibronic interaction mixed them. The second case is related to the spin of the state. As it was rigorously proved by group theoretical methods at the theorem level, the electron density does not depend on the total spin S of the arbitrary N-electron state. It means that the Kohn-Sham equations have the same form for states with different S. The critical survey of elaborated DFT procedures, taking into account spin, shows that they modified only exchange functionals, the correlation functionals do not correspond to the spin of the state. The point is that the conception of spin cannot be defined in the framework of the electron density formalism, which corresponds to the one-particle reduced density matrix. This is the main reason of the problems arising in the study by DFT of magnetic properties of the transition metals. The possible way of resolving these problems can be found in the two-particle reduced density matrix formulation of DFT.