Ultrafast excited-state relaxation of a binuclear Ag(i) phosphine complex in gas phase and solution.

PubMed

Kruppa, S V; Bäppler, F; Klopper, W; Walg, S P; Thiel, W R; Diller, R; Riehn, C

2017-08-30

The binuclear complex [Ag 2 (dcpm) 2 ](PF 6 ) 2 (dcpm = bis(dicyclohexylphosphino)methane) exhibits a structure with a close silver-silver contact mediated by the bridging ligand and thus a weak argentophilic interaction. Upon electronic excitation this cooperative effect is strongly increased and determines the optical and luminescence properties of the compound. We have studied here the ultrafast electronic dynamics in parallel in gas phase by transient photodissociation and in solution by transient absorption. In particular, we report the diverse photofragmentation pathways of isolated [Ag 2 (dcpm) 2 ] 2+ in an ion trap and its gas phase UV photodissociation spectrum. By pump-probe fragmentation action spectroscopy (λ ex = 260 nm) in the gas phase, we have obtained fragment-specific transients which exhibit a common ultrafast multiexponential decay. This is fitted to four time constants (0.6/5.8/100/>1000 ps), highlighting complex intrinsic photophysical processes. Remarkably, multiexponential dynamics (0.9/8.5/73/604 ps) are as well found for the relaxation dynamics in acetonitrile solution. Ab initio calculations at the level of approximate coupled-cluster singles-doubles (CC2) theory of ground and electronically excited states of the reduced model system [Ag 2 (dmpm) 2 ] 2+ (dmpm = bis(dimethylphosphino)methane) indicate a shortening of the Ag-Ag distance upon excitation by 0.3-0.4 Å. In C 2 geometry two close-lying singlet states S 1 ( 1 MC(dσ*-pπ), 1 B, 4.13 eV) and S 2 ( 1 MC(dσ*-pσ), 1 A, 4.45 eV) are found. The nearly dark S 1 state has not been reported so far. The excitation of the S 2 state carries a large oscillator strength for the calculated vertical transition (266 nm). Two related triplets are calculated at T 1 (3.87 eV) and T 2 (3.90 eV). From these findings we suggest possible relaxation pathways with the two short time constants ascribed to ISC/IVR and propose from the obtained similar values in gas phase that the fast solution dynamics

Hard-X-Ray-Induced Multistep Ultrafast Dissociation

NASA Astrophysics Data System (ADS)

Travnikova, Oksana; Marchenko, Tatiana; Goldsztejn, Gildas; Jänkälä, Kari; Sisourat, Nicolas; Carniato, Stéphane; Guillemin, Renaud; Journel, Loïc; Céolin, Denis; Püttner, Ralph; Iwayama, Hiroshi; Shigemasa, Eiji; Piancastelli, Maria Novella; Simon, Marc

2016-05-01

Creation of deep core holes with very short (τ ≤1 fs ) lifetimes triggers a chain of relaxation events leading to extensive nuclear dynamics on a few-femtosecond time scale. Here we demonstrate a general multistep ultrafast dissociation on an example of HCl following Cl 1 s →σ* excitation. Intermediate states with one or multiple holes in the shallower core electron shells are generated in the course of the decay cascades. The repulsive character and large gradients of the potential energy surfaces of these intermediates enable ultrafast fragmentation after the absorption of a hard x-ray photon.

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).

Modelling ultrafast laser ablation

NASA Astrophysics Data System (ADS)

Rethfeld, Baerbel; Ivanov, Dmitriy S.; E Garcia, Martin; Anisimov, Sergei I.

2017-05-01

This review is devoted to the study of ultrafast laser ablation of solids and liquids. The ablation of condensed matter under exposure to subpicosecond laser pulses has a number of peculiar properties which distinguish this process from ablation induced by nanosecond and longer laser pulses. The process of ultrafast ablation includes light absorption by electrons in the skin layer, energy transfer from the skin layer to target interior by nonlinear electronic heat conduction, relaxation of the electron and ion temperatures, ultrafast melting, hydrodynamic expansion of heated matter accompanied by the formation of metastable states and subsequent formation of breaks in condensed matter. In case of ultrashort laser excitation, these processes are temporally separated and can thus be studied separately. As for energy absorption, we consider peculiarities of the case of metal irradiation in contrast to dielectrics and semiconductors. We discuss the energy dissipation processes of electronic thermal wave and lattice heating. Different types of phase transitions after ultrashort laser pulse irradiation as melting, vaporization or transitions to warm dense matter are discussed. Also nonthermal phase transitions, directly caused by the electronic excitation before considerable lattice heating, are considered. The final material removal occurs from the physical point of view as expansion of heated matter; here we discuss approaches of hydrodynamics, as well as molecular dynamic simulations directly following the atomic movements. Hybrid approaches tracing the dynamics of excited electrons, energy dissipation and structural dynamics in a combined simulation are reviewed as well.

Design of specially adapted reactive coordinates to economically compute potential and kinetic energy operators including geometry relaxation

NASA Astrophysics Data System (ADS)

Thallmair, Sebastian; Roos, Matthias K.; de Vivie-Riedle, Regina

2016-06-01

Quantum dynamics simulations require prior knowledge of the potential energy surface as well as the kinetic energy operator. Typically, they are evaluated in a low-dimensional subspace of the full configuration space of the molecule as its dimensionality increases proportional to the number of atoms. This entails the challenge to find the most suitable subspace. We present an approach to design specially adapted reactive coordinates spanning this subspace. In addition to the essential geometric changes, these coordinates take into account the relaxation of the non-reactive coordinates without the necessity of performing geometry optimizations at each grid point. The method is demonstrated for an ultrafast photoinduced bond cleavage in a commonly used organic precursor for the generation of electrophiles. The potential energy surfaces for the reaction as well as the Wilson G-matrix as part of the kinetic energy operator are shown for a complex chemical reaction, both including the relaxation of the non-reactive coordinates on equal footing. A microscopic interpretation of the shape of the G-matrix elements allows to analyze the impact of the non-reactive coordinates on the kinetic energy operator. Additionally, we compare quantum dynamics simulations with and without the relaxation of the non-reactive coordinates included in the kinetic energy operator to demonstrate its influence.

Design of specially adapted reactive coordinates to economically compute potential and kinetic energy operators including geometry relaxation.

PubMed

Thallmair, Sebastian; Roos, Matthias K; de Vivie-Riedle, Regina

2016-06-21

Quantum dynamics simulations require prior knowledge of the potential energy surface as well as the kinetic energy operator. Typically, they are evaluated in a low-dimensional subspace of the full configuration space of the molecule as its dimensionality increases proportional to the number of atoms. This entails the challenge to find the most suitable subspace. We present an approach to design specially adapted reactive coordinates spanning this subspace. In addition to the essential geometric changes, these coordinates take into account the relaxation of the non-reactive coordinates without the necessity of performing geometry optimizations at each grid point. The method is demonstrated for an ultrafast photoinduced bond cleavage in a commonly used organic precursor for the generation of electrophiles. The potential energy surfaces for the reaction as well as the Wilson G-matrix as part of the kinetic energy operator are shown for a complex chemical reaction, both including the relaxation of the non-reactive coordinates on equal footing. A microscopic interpretation of the shape of the G-matrix elements allows to analyze the impact of the non-reactive coordinates on the kinetic energy operator. Additionally, we compare quantum dynamics simulations with and without the relaxation of the non-reactive coordinates included in the kinetic energy operator to demonstrate its influence.

Probing the Ultrafast Energy Dissipation Mechanism of the Sunscreen Oxybenzone after UVA Irradiation.

PubMed

Baker, Lewis A; Horbury, Michael D; Greenough, Simon E; Coulter, Philip M; Karsili, Tolga N V; Roberts, Gareth M; Orr-Ewing, Andrew J; Ashfold, Michael N R; Stavros, Vasilios G

2015-04-16

Oxybenzone is a common constituent of many commercially available sunscreens providing photoprotection from ultraviolet light incident on the skin. Femtosecond transient electronic and vibrational absorption spectroscopies have been used to investigate the nonradiative relaxation pathways of oxybenzone in cyclohexane and methanol after excitation in the UVA region. The present data suggest that the photoprotective properties of oxybenzone can be understood in terms of an initial ultrafast excited state enol → keto tautomerization, followed by efficient internal conversion and subsequent vibrational relaxation to the ground state (enol) tautomer.

Femtosecond coherent nuclear dynamics of excited tetraphenylethylene: Ultrafast transient absorption and ultrafast Raman loss spectroscopic studies

NASA Astrophysics Data System (ADS)

Kayal, Surajit; Roy, Khokan; Umapathy, Siva

2018-01-01

Ultrafast torsional dynamics plays an important role in the photoinduced excited state dynamics. Tetraphenylethylene (TPE), a model system for the molecular motor, executes interesting torsional dynamics upon photoexcitation. The photoreaction of TPE involves ultrafast internal conversion via a nearly planar intermediate state (relaxed state) that further leads to a twisted zwitterionic state. Here, we report the photoinduced structural dynamics of excited TPE during the course of photoisomerization in the condensed phase by ultrafast Raman loss (URLS) and femtosecond transient absorption (TA) spectroscopy. TA measurements on the S1 state reveal step-wise population relaxation from the Franck-Condon (FC) state → relaxed state → twisted state, while the URLS study provides insights on the vibrational dynamics during the course of the reaction. The TA spectral dynamics and vibrational Raman amplitudes within 1 ps reveal vibrational wave packet propagating from the FC state to the relaxed state. Fourier transformation of this oscillation leads to a ˜130 cm-1 low-frequency phenyl torsional mode. Two vibrational marker bands, Cet=Cet stretching (˜1512 cm-1) and Cph=Cph stretching (˜1584 cm-1) modes, appear immediately after photoexcitation in the URLS spectra. The initial red-shift of the Cph=Cph stretching mode with a time constant of ˜400 fs (in butyronitrile) is assigned to the rate of planarization of excited TPE. In addition, the Cet=Cet stretching mode shows initial blue-shift within 1 ps followed by frequency red-shift, suggesting that on the sub-picosecond time scale, structural relaxation is dominated by phenyl torsion rather than the central Cet=Cet twist. Furthermore, the effect of the solvent on the structural dynamics is discussed in the context of ultrafast nuclear dynamics and solute-solvent coupling.

Femtosecond coherent nuclear dynamics of excited tetraphenylethylene: Ultrafast transient absorption and ultrafast Raman loss spectroscopic studies.

PubMed

Kayal, Surajit; Roy, Khokan; Umapathy, Siva

2018-01-14

Ultrafast torsional dynamics plays an important role in the photoinduced excited state dynamics. Tetraphenylethylene (TPE), a model system for the molecular motor, executes interesting torsional dynamics upon photoexcitation. The photoreaction of TPE involves ultrafast internal conversion via a nearly planar intermediate state (relaxed state) that further leads to a twisted zwitterionic state. Here, we report the photoinduced structural dynamics of excited TPE during the course of photoisomerization in the condensed phase by ultrafast Raman loss (URLS) and femtosecond transient absorption (TA) spectroscopy. TA measurements on the S 1 state reveal step-wise population relaxation from the Franck-Condon (FC) state → relaxed state → twisted state, while the URLS study provides insights on the vibrational dynamics during the course of the reaction. The TA spectral dynamics and vibrational Raman amplitudes within 1 ps reveal vibrational wave packet propagating from the FC state to the relaxed state. Fourier transformation of this oscillation leads to a ∼130 cm -1 low-frequency phenyl torsional mode. Two vibrational marker bands, C et =C et stretching (∼1512 cm -1 ) and C ph =C ph stretching (∼1584 cm -1 ) modes, appear immediately after photoexcitation in the URLS spectra. The initial red-shift of the C ph =C ph stretching mode with a time constant of ∼400 fs (in butyronitrile) is assigned to the rate of planarization of excited TPE. In addition, the C et =C et stretching mode shows initial blue-shift within 1 ps followed by frequency red-shift, suggesting that on the sub-picosecond time scale, structural relaxation is dominated by phenyl torsion rather than the central C et =C et twist. Furthermore, the effect of the solvent on the structural dynamics is discussed in the context of ultrafast nuclear dynamics and solute-solvent coupling.

Unifying ultrafast demagnetization and intrinsic Gilbert damping in Co/Ni bilayers with electronic relaxation near the Fermi surface

NASA Astrophysics Data System (ADS)

Zhang, Wei; He, Wei; Zhang, Xiang-Qun; Cheng, Zhao-Hua; Teng, Jiao; Fähnle, Manfred

2017-12-01

The ability to controllably manipulate the laser-induced ultrafast magnetic dynamics is a prerequisite for future high-speed spintronic devices. The optimization of devices requires the controllability of the ultrafast demagnetization time τM and intrinsic Gilbert damping αintr. In previous attempts to establish a relationship between τM and αintr, the rare-earth doping of a permalloy film with two different demagnetization mechanisms was not a suitable candidate. Here, we choose Co/Ni bilayers to investigate the relations between τM and αintr by means of the time-resolved magneto-optical Kerr effect (TR-MOKE) via adjusting the thickness of the Ni layers, and obtain an approximately proportional relation between these two parameters. The remarkable agreement between the TR-MOKE experiment and the prediction of a breathing Fermi-surface model confirms that a large Elliott-Yafet spin-mixing parameter b2 is relevant to the strong spin-orbital coupling at the Co/Ni interface. More importantly, a proportional relation between τM and αintr in such metallic films or heterostructures with electronic relaxation near the Fermi surface suggests the local spin-flip scattering dominates the mechanism of ultrafast demagnetization, otherwise the spin-current mechanism dominates. It is an effective method to distinguish the dominant contributions to ultrafast magnetic quenching in metallic heterostructures by simultaneously investigating both the ultrafast demagnetization time and Gilbert damping. Our work can open an avenue to manipulate the magnitude and efficiency of terahertz emission in metallic heterostructures such as perpendicular magnetic anisotropic Ta/Pt/Co/Ni/Pt/Ta multilayers, and then it has an immediate implication for the design of high-frequency spintronic devices.

Design of specially adapted reactive coordinates to economically compute potential and kinetic energy operators including geometry relaxation

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

Thallmair, Sebastian; Lehrstuhl für BioMolekulare Optik, Ludwig-Maximilians-Universität München, D-80538 München; Roos, Matthias K.

Quantum dynamics simulations require prior knowledge of the potential energy surface as well as the kinetic energy operator. Typically, they are evaluated in a low-dimensional subspace of the full configuration space of the molecule as its dimensionality increases proportional to the number of atoms. This entails the challenge to find the most suitable subspace. We present an approach to design specially adapted reactive coordinates spanning this subspace. In addition to the essential geometric changes, these coordinates take into account the relaxation of the non-reactive coordinates without the necessity of performing geometry optimizations at each grid point. The method is demonstratedmore » for an ultrafast photoinduced bond cleavage in a commonly used organic precursor for the generation of electrophiles. The potential energy surfaces for the reaction as well as the Wilson G-matrix as part of the kinetic energy operator are shown for a complex chemical reaction, both including the relaxation of the non-reactive coordinates on equal footing. A microscopic interpretation of the shape of the G-matrix elements allows to analyze the impact of the non-reactive coordinates on the kinetic energy operator. Additionally, we compare quantum dynamics simulations with and without the relaxation of the non-reactive coordinates included in the kinetic energy operator to demonstrate its influence.« less

Temperature dependence of the hydrated electron's excited-state relaxation. II. Elucidating the relaxation mechanism through ultrafast transient absorption and stimulated emission spectroscopy

NASA Astrophysics Data System (ADS)

Farr, Erik P.; Zho, Chen-Chen; Challa, Jagannadha R.; Schwartz, Benjamin J.

2017-08-01

The structure of the hydrated electron, particularly whether it exists primarily within a cavity or encompasses interior water molecules, has been the subject of much recent debate. In Paper I [C.-C. Zho et al., J. Chem. Phys. 147, 074503 (2017)], we found that mixed quantum/classical simulations with cavity and non-cavity pseudopotentials gave different predictions for the temperature dependence of the rate of the photoexcited hydrated electron's relaxation back to the ground state. In this paper, we measure the ultrafast transient absorption spectroscopy of the photoexcited hydrated electron as a function of temperature to confront the predictions of our simulations. The ultrafast spectroscopy clearly shows faster relaxation dynamics at higher temperatures. In particular, the transient absorption data show a clear excess bleach beyond that of the equilibrium hydrated electron's ground-state absorption that can only be explained by stimulated emission. This stimulated emission component, which is consistent with the experimentally known fluorescence spectrum of the hydrated electron, decreases in both amplitude and lifetime as the temperature is increased. We use a kinetic model to globally fit the temperature-dependent transient absorption data at multiple temperatures ranging from 0 to 45 °C. We find the room-temperature lifetime of the excited-state hydrated electron to be 137 ±40 fs, in close agreement with recent time-resolved photoelectron spectroscopy (TRPES) experiments and in strong support of the "non-adiabatic" picture of the hydrated electron's excited-state relaxation. Moreover, we find that the excited-state lifetime is strongly temperature dependent, changing by slightly more than a factor of two over the 45 °C temperature range explored. This temperature dependence of the lifetime, along with a faster rate of ground-state cooling with increasing bulk temperature, should be directly observable by future TRPES experiments. Our data also suggest

Ultrafast photophysics of transition metal complexes.

PubMed

Chergui, Majed

2015-03-17

The properties of transition metal complexes are interesting not only for their potential applications in solar energy conversion, OLEDs, molecular electronics, biology, photochemistry, etc. but also for their fascinating photophysical properties that call for a rethinking of fundamental concepts. With the advent of ultrafast spectroscopy over 25 years ago and, more particularly, with improvements in the past 10-15 years, a new area of study was opened that has led to insightful observations of the intramolecular relaxation processes such as internal conversion (IC), intersystem crossing (ISC), and intramolecular vibrational redistribution (IVR). Indeed, ultrafast optical spectroscopic tools, such as fluorescence up-conversion, show that in many cases, intramolecular relaxation processes can be extremely fast and even shorter than time scales of vibrations. In addition, more and more examples are appearing showing that ultrafast ISC rates do not scale with the magnitude of the metal spin-orbit coupling constant, that is, that there is no heavy-atom effect on ultrafast time scales. It appears that the structural dynamics of the system and the density of states play a crucial role therein. While optical spectroscopy delivers an insightful picture of electronic relaxation processes involving valence orbitals, the photophysics of metal complexes involves excitations that may be centered on the metal (called metal-centered or MC) or the ligand (called ligand-centered or LC) or involve a transition from one to the other or vice versa (called MLCT or LMCT). These excitations call for an element-specific probe of the photophysics, which is achieved by X-ray absorption spectroscopy. In this case, transitions from core orbitals to valence orbitals or higher allow probing the electronic structure changes induced by the optical excitation of the valence orbitals, while also delivering information about the geometrical rearrangement of the neighbor atoms around the atom of

Interpreting Quasi-Thermal Effects in Ultrafast Spectroscopy of Hydrogen-Bonded Systems.

PubMed

Stingel, Ashley M; Petersen, Poul B

2018-03-15

Vibrational excitation of molecules in the condensed phase relaxes through vibrational modes of decreasing energy to ultimately generate an equilibrium state in which the energy is distributed among low-frequency modes. In ultrafast vibrational spectroscopy, changes in the vibrational features of hydrogen-bonded NH and OH stretch modes are typically observed to persist long after these high-frequency vibrations have relaxed. Due to the resemblance to the spectral changes caused by heating the sample, these features are typically described as arising from a hot ground state. However, these spectral features appear on ultrafast time scales that are much too fast to result from a true thermal state, and significant differences between the thermal difference spectrum and the induced quasi-thermal changes in ultrafast spectroscopy are often observed. Here, we examine and directly compare the thermal and quasi-thermal responses of the hydrogen-bonded homodimer of 7-azaindole with temperature-dependent FTIR spectroscopy and ultrafast mid-IR continuum spectroscopy. We find that the thermal difference spectra contain contributions from both dissociation of the hydrogen bonds and from frequency shifts due to changes in the thermal population of low-frequency modes. The transient spectra in ultrafast vibrational spectroscopy are also found to contain two contributions: initial frequency shifts over 2.3 ± 0.11 ps associated with equilibration of the initial excitation, and frequency shifts associated with the excitation of several fingerprint modes, which decay over 21.8 ± 0.11 ps, giving rise to a quasi-thermal response caused by a distribution of fingerprint modes being excited within the sample ensemble. This resembles the thermal frequency shifts due to population changes of low-frequency modes, but not the overall thermal spectrum, which is dominated by features caused by dimer dissociation. These findings provide insight into the changes in the vibrational spectrum

Electron-lattice energy relaxation in laser-excited thin-film Au-insulator heterostructures studied by ultrafast MeV electron diffraction.

PubMed

Sokolowski-Tinten, K; Shen, X; Zheng, Q; Chase, T; Coffee, R; Jerman, M; Li, R K; Ligges, M; Makasyuk, I; Mo, M; Reid, A H; Rethfeld, B; Vecchione, T; Weathersby, S P; Dürr, H A; Wang, X J

2017-09-01

We apply time-resolved MeV electron diffraction to study the electron-lattice energy relaxation in thin film Au-insulator heterostructures. Through precise measurements of the transient Debye-Waller-factor, the mean-square atomic displacement is directly determined, which allows to quantitatively follow the temporal evolution of the lattice temperature after short pulse laser excitation. Data obtained over an extended range of laser fluences reveal an increased relaxation rate when the film thickness is reduced or the Au-film is capped with an additional insulator top-layer. This behavior is attributed to a cross-interfacial coupling of excited electrons in the Au film to phonons in the adjacent insulator layer(s). Analysis of the data using the two-temperature-model taking explicitly into account the additional energy loss at the interface(s) allows to deduce the relative strength of the two relaxation channels.

Ultrafast photoelectron spectroscopy of small molecule organic films

NASA Astrophysics Data System (ADS)

Read, Kendall Laine

As research in the field of ultrafast optics has produced shorter and shorter pulses, at an ever-widening range of frequencies, ultrafast spectroscopy has grown correspondingly. In particular, ultrafast photoelectron spectroscopy allows direct observation of electrons in transient or excited states, regardless of the eventual relaxation mechanisms. High-harmonic conversion of 800nm, femtosecond, Ti:sapphire laser pulses allows excite/probe spectroscopy down into atomic core level states. To this end, an ultrafast, X-UV photoelectron spectroscopic system is described, including design considerations for the high-harmonic generation line, the time of flight detector, and the subsequent data collection electronics. Using a similar experimental setup, I have performed several ultrafast, photoelectron excited state decay studies at the IBM, T. J. Watson Research Center. All of the observed materials were electroluminescent thin film organics, which have applications as the emitter layer in organic light emitting devices. The specific materials discussed are: Alq, BAlq, DPVBi, and Alq doped with DCM or DMQA. Alq:DCM is also known to lase at low photoexcitation thresholds. A detailed understanding of the involved relaxation mechanisms is beneficial to both applications. Using 3.14 eV excite, and 26.7 eV probe, 90 fs laser pulses, we have observed the lowest unoccupied molecular orbital (LUMO) decay rate over the first 200 picoseconds. During this time, diffusion is insignificant, and all dynamics occur in the absence of electron transport. With excitation intensities in the range of 100μJ/cm2, we have modeled the Alq, BAlq, and DPVBi decays via bimolecular singlet-singlet annihilation. At similar excitations, we have modeled the Alq:DCM decay via Förster transfer, stimulated emission, and excimeric formation. Furthermore, the Alq:DCM occupied to unoccupied molecular orbital energy gap was seen to shrink as a function of excite-to-probe delay, in accordance with the

Tin Oxide Nanowires: The Influence of Trap States on Ultrafast Carrier Relaxation

PubMed Central

2009-01-01

We have studied the optical properties and carrier dynamics in SnO2nanowires (NWs) with an average radius of 50 nm that were grown via the vapor–liquid solid method. Transient differential absorption measurements have been employed to investigate the ultrafast relaxation dynamics of photogenerated carriers in the SnO2NWs. Steady state transmission measurements revealed that the band gap of these NWs is 3.77 eV and contains two broad absorption bands. The first is located below the band edge (shallow traps) and the second near the center of the band gap (deep traps). Both of these absorption bands seem to play a crucial role in the relaxation of the photogenerated carriers. Time resolved measurements suggest that the photogenerated carriers take a few picoseconds to move into the shallow trap states whereas they take ~70 ps to move from the shallow to the deep trap states. Furthermore the recombination process of electrons in these trap states with holes in the valence band takes ~2 ns. Auger recombination appears to be important at the highest fluence used in this study (500 μJ/cm2); however, it has negligible effect for fluences below 50 μJ/cm2. The Auger coefficient for the SnO2NWs was estimated to be 7.5 ± 2.5 × 10−31 cm6/s. PMID:20596473

Ultrafast magnon generation in an Fe film on Cu(100).

PubMed

Schmidt, A B; Pickel, M; Donath, M; Buczek, P; Ernst, A; Zhukov, V P; Echenique, P M; Sandratskii, L M; Chulkov, E V; Weinelt, M

2010-11-05

We report on a combined experimental and theoretical study of the spin-dependent relaxation processes in the electron system of an iron film on Cu(100). Spin-, time-, energy- and angle-resolved two-photon photoemission shows a strong characteristic dependence of the lifetime of photoexcited electrons on their spin and energy. Ab initio calculations as well as a many-body treatment corroborate that the observed properties are determined by relaxation processes involving magnon emission. Thereby we demonstrate that magnon emission by hot electrons occurs on the femtosecond time scale and thus provides a significant source of ultrafast spin-flip processes. Furthermore, engineering of the magnon spectrum paves the way for tuning the dynamic properties of magnetic materials.

Ultrafast carrier dynamics in band edge and broad deep defect emission ZnSe nanowires

NASA Astrophysics Data System (ADS)

Othonos, Andreas; Lioudakis, Emmanouil; Philipose, U.; Ruda, Harry E.

2007-12-01

Ultrafast carrier dynamics of ZnSe nanowires grown under different growth conditions have been studied. Transient absorption measurements reveal the dependence of the competing effects of state filling and photoinduced absorption on the probed energy states. The relaxation of the photogenerated carriers occupying defect states in the stoichiometric and Se-rich samples are single exponentials with time constants of 3-4ps. State filling is the main contribution for probe energies below 1.85eV in the Zn-rich grown sample. This ultrafast carrier dynamics study provides an important insight into the role that intrinsic point defects play in the observed photoluminescence from ZnSe nanowires.

Electron-lattice energy relaxation in laser-excited thin-film Au-insulator heterostructures studied by ultrafast MeV electron diffraction

PubMed Central

Sokolowski-Tinten, K.; Shen, X.; Zheng, Q.; Chase, T.; Coffee, R.; Jerman, M.; Li, R. K.; Ligges, M.; Makasyuk, I.; Mo, M.; Reid, A. H.; Rethfeld, B.; Vecchione, T.; Weathersby, S. P.; Dürr, H. A.; Wang, X. J.

2017-01-01

We apply time-resolved MeV electron diffraction to study the electron-lattice energy relaxation in thin film Au-insulator heterostructures. Through precise measurements of the transient Debye-Waller-factor, the mean-square atomic displacement is directly determined, which allows to quantitatively follow the temporal evolution of the lattice temperature after short pulse laser excitation. Data obtained over an extended range of laser fluences reveal an increased relaxation rate when the film thickness is reduced or the Au-film is capped with an additional insulator top-layer. This behavior is attributed to a cross-interfacial coupling of excited electrons in the Au film to phonons in the adjacent insulator layer(s). Analysis of the data using the two-temperature-model taking explicitly into account the additional energy loss at the interface(s) allows to deduce the relative strength of the two relaxation channels. PMID:28795080

Ultrafast X-ray Auger probing of photoexcited molecular dynamics

DOE PAGES

McFarland, B. K.; Farrell, J. P.; Miyabe, S.; ...

2014-06-23

Here, molecules can efficiently and selectively convert light energy into other degrees of freedom. Disentangling the underlying ultrafast motion of electrons and nuclei of the photoexcited molecule presents a challenge to current spectroscopic approaches. Here we explore the photoexcited dynamics of molecules by an interaction with an ultrafast X-ray pulse creating a highly localized core hole that decays via Auger emission. We discover that the Auger spectrum as a function of photoexcitation—X-ray-probe delay contains valuable information about the nuclear and electronic degrees of freedom from an element-specific point of view. For the nucleobase thymine, the oxygen Auger spectrum shifts towardsmore » high kinetic energies, resulting from a particular C–O bond stretch in the ππ* photoexcited state. A subsequent shift of the Auger spectrum towards lower kinetic energies displays the electronic relaxation of the initial photoexcited state within 200 fs. Ab-initio simulations reinforce our interpretation and indicate an electronic decay to the nπ* state.« less

The dependence of the ultrafast relaxation kinetics of the S2 and S1 states in β-carotene homologs and lycopene on conjugation length studied by femtosecond time-resolved absorption and Kerr-gate fluorescence spectroscopies

NASA Astrophysics Data System (ADS)

Kosumi, Daisuke; Fujiwara, Masazumi; Fujii, Ritsuko; Cogdell, Richard J.; Hashimoto, Hideki; Yoshizawa, Masayuki

2009-06-01

The ultrafast relaxation kinetics of all-trans-β-carotene homologs with varying numbers of conjugated double bonds n(n =7-15) and lycopene (n =11) has been investigated using femtosecond time-resolved absorption and Kerr-gate fluorescence spectroscopies, both carried out under identical excitation conditions. The nonradiative relaxation rates of the optically allowed S2(1Bu+1) state were precisely determined by the time-resolved fluorescence. The kinetics of the optically forbidden S1(2Ag-1) state were observed by the time-resolved absorption measurements. The dependence of the S1 relaxation rates upon the conjugation length is adequately described by application of the energy gap law. In contrast to this, the nonradiative relaxation rates of S2 have a minimum at n =9 and show a reverse energy gap law dependence for values of n above 11. This anomalous behavior of the S2 relaxation rates can be explained by the presence of an intermediate state (here called the Sx state) located between the S2 and S1 states at large values of n (such as n =11). The presence of such an intermediate state would then result in the following sequential relaxation pathway S2→Sx→S1→S0. A model based on conical intersections between the potential energy curves of these excited singlet states can readily explain the measured relationships between the decay rates and the energy gaps.

Biexciton relaxation associated with dissociation into a surface polariton pair in semiconductor films

NASA Astrophysics Data System (ADS)

Mitsumori, Yasuyoshi; Matsuura, Shimpei; Uchiyama, Shoichi; Saito, Kentarao; Edamatsu, Keiichi; Nakayama, Masaaki; Ajiki, Hiroshi

2018-04-01

We study the biexciton relaxation process in CuCl films ranging from 6 to 200 nm. The relaxation time is measured as the dephasing time and the lifetime. We observe a unique thickness dependence of the biexciton relaxation time and also obtain an ultrafast relaxation time with a timescale as short as 100 fs, while the exciton lifetime monotonically decreases with increasing thickness. By analyzing the exciton-photon coupling energy for a surface polariton, we theoretically calculate the biexciton relaxation time as a function of the thickness. The calculated dependence qualitatively reproduces the observed relaxation time, indicating that the biexciton dissociation into a surface polariton pair is one of the major biexciton relaxation processes.

Ultrafast coherence transfer in DNA-templated silver nanoclusters

PubMed Central

Thyrhaug, Erling; Bogh, Sidsel Ammitzbøll; Carro-Temboury, Miguel R; Madsen, Charlotte Stahl; Vosch, Tom; Zigmantas, Donatas

2017-01-01

DNA-templated silver nanoclusters of a few tens of atoms or less have come into prominence over the last several years due to very strong absorption and efficient emission. Applications in microscopy and sensing have already been realized, however little is known about the excited-state structure and dynamics in these clusters. Here we report on a multidimensional spectroscopy investigation of the energy-level structure and the early-time relaxation cascade, which eventually results in the population of an emitting state. We find that the ultrafast intramolecular relaxation is strongly coupled to a specific vibrational mode, resulting in the concerted transfer of population and coherence between excited states on a sub-100 fs timescale. PMID:28548085

Relaxation dynamics and coherent energy exchange in coupled vibration-cavity polaritons (Conference Presentation)

NASA Astrophysics Data System (ADS)

Simpkins, Blake S.; Fears, Kenan P.; Dressick, Walter J.; Dunkelberger, Adam D.; Spann, Bryan T.; Owrutsky, Jeffrey C.

2016-09-01

Coherent coupling between an optical transition and confined optical mode have been investigated for electronic-state transitions, however, only very recently have vibrational transitions been considered. Here, we demonstrate both static and dynamic results for vibrational bands strongly coupled to optical cavities. We experimentally and numerically describe strong coupling between a Fabry-Pérot cavity and carbonyl stretch ( 1730 cm 1) in poly-methylmethacrylate and provide evidence that the mixed-states are immune to inhomogeneous broadening. We investigate strong and weak coupling regimes through examination of cavities loaded with varying concentrations of a urethane monomer. Rabi splittings are in excellent agreement with an analytical description using no fitting parameters. Ultrafast pump-probe measurements reveal transient absorption signals over a frequency range well-separated from the vibrational band, as well as drastically modified relaxation rates. We speculate these modified kinetics are a consequence of the energy proximity between the vibration-cavity polariton modes and excited state transitions and that polaritons offer an alternative relaxation path for vibrational excitations. Varying the polariton energies by angle-tuning yields transient results consistent with this hypothesis. Furthermore, Rabi oscillations, or quantum beats, are observed at early times and we see evidence that these coherent vibration-cavity polariton excitations impact excited state population through cavity losses. Together, these results indicate that cavity coupling may be used to influence both excitation and relaxation rates of vibrations. Opening the field of polaritonic coupling to vibrational species promises to be a rich arena amenable to a wide variety of infrared-active bonds that can be studied in steady state and dynamically.

Ultrafast Relaxation Dynamics of Au 38 (SC 2 H 4 Ph) 24 Nanoclusters and Effects of Structural Isomerism

DOE PAGES

Zhou, Meng; Tian, Shubo; Zeng, Chenjie; ...

2016-12-22

Structural isomerism in nanoparticles has recently emerged as a new topic and stimulated research interest because the atomic structures of ultrasmall nanoparticles may have great impact on their fundamental properties and applications. We report the correlation between ultrafast relaxation dynamics and atomic structures of two isomers of thiolate-protected Au 38(SC 2H 4Ph) 24. The bi-icosahedral Au 38 (denoted as Au 38Q) with a Au 23 inner core in its atomic structure shows rapid decay (1.5 ps) followed by nanosecond relaxation to the ground state, whereas its structural isomer (Au 38T) exhibits similar relaxation processes, but the rapid decay is acceleratedmore » by ~50% (1.0 ps). The picosecond relaxations in both cases can be assigned to core–shell charge transfer or electronic rearrangement within the metal core. The acceleration of the fast decay in Au38T is ascribed to its unique core structure, which is made up of a mono-icosahedral Au 13 capped by a Au 12 tri-tetrahedron by sharing two atoms. Interestingly, coherent phonon emissions (25 cm –1 for Au 38Q, 27 and 60 cm –1 for Au 38T) are observed in both isomers with pumping in the NIR region. These results illustrate for the first time the importance of atomic structures in the photophysics of same sized gold nanoclusters.« less

Ultrafast Relaxation Dynamics of Au 38 (SC 2 H 4 Ph) 24 Nanoclusters and Effects of Structural Isomerism

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

Zhou, Meng; Tian, Shubo; Zeng, Chenjie

Structural isomerism in nanoparticles has recently emerged as a new topic and stimulated research interest because the atomic structures of ultrasmall nanoparticles may have great impact on their fundamental properties and applications. We report the correlation between ultrafast relaxation dynamics and atomic structures of two isomers of thiolate-protected Au 38(SC 2H 4Ph) 24. The bi-icosahedral Au 38 (denoted as Au 38Q) with a Au 23 inner core in its atomic structure shows rapid decay (1.5 ps) followed by nanosecond relaxation to the ground state, whereas its structural isomer (Au 38T) exhibits similar relaxation processes, but the rapid decay is acceleratedmore » by ~50% (1.0 ps). The picosecond relaxations in both cases can be assigned to core–shell charge transfer or electronic rearrangement within the metal core. The acceleration of the fast decay in Au38T is ascribed to its unique core structure, which is made up of a mono-icosahedral Au 13 capped by a Au 12 tri-tetrahedron by sharing two atoms. Interestingly, coherent phonon emissions (25 cm –1 for Au 38Q, 27 and 60 cm –1 for Au 38T) are observed in both isomers with pumping in the NIR region. These results illustrate for the first time the importance of atomic structures in the photophysics of same sized gold nanoclusters.« less

Ultrafast collinear scattering and carrier multiplication in graphene.

PubMed

Brida, D; Tomadin, A; Manzoni, C; Kim, Y J; Lombardo, A; Milana, S; Nair, R R; Novoselov, K S; Ferrari, A C; Cerullo, G; Polini, M

2013-01-01

Graphene is emerging as a viable alternative to conventional optoelectronic, plasmonic and nanophotonic materials. The interaction of light with charge carriers creates an out-of-equilibrium distribution, which relaxes on an ultrafast timescale to a hot Fermi-Dirac distribution, that subsequently cools emitting phonons. Although the slower relaxation mechanisms have been extensively investigated, the initial stages still pose a challenge. Experimentally, they defy the resolution of most pump-probe setups, due to the extremely fast sub-100 fs carrier dynamics. Theoretically, massless Dirac fermions represent a novel many-body problem, fundamentally different from Schrödinger fermions. Here we combine pump-probe spectroscopy with a microscopic theory to investigate electron-electron interactions during the early stages of relaxation. We identify the mechanisms controlling the ultrafast dynamics, in particular the role of collinear scattering. This gives rise to Auger processes, including charge multiplication, which is key in photovoltage generation and photodetectors.

Early-Time Excited-State Relaxation Dynamics of Iridium Compounds: Distinct Roles of Electron and Hole Transfer.

PubMed

Liu, Xiang-Yang; Zhang, Ya-Hui; Fang, Wei-Hai; Cui, Ganglong

2018-06-28

Excited-state and photophysical properties of Ir-containing complexes have been extensively studied because of their potential applications as organic light-emitting diode emitting materials. However, their early time excited-state relaxation dynamics are less explored computationally. Herein we have employed our recently implemented TDDFT-based generalized surface-hopping dynamics method to simulate excited-state relaxation dynamics of three Ir(III) compounds having distinct ligands. According to our multistate dynamics simulations including five excited singlet states i.e., S n ( n = 1-5) and ten excited triplet states, i.e., T n ( n = 1-10), we have found that the intersystem crossing (ISC) processes from the S n to T n are very efficient and ultrafast in these three Ir(III) compounds. The corresponding ISC rates are estimated to be 65, 81, and 140 fs, which are reasonably close to the experimentally measured ca. 80, 80, and 110 fs. In addition, the internal conversion (IC) processes within respective singlet and triplet manifolds are also ultrafast. These ultrafast IC and ISC processes are caused by large nonadiabatic and spin-orbit couplings, respectively, as well as small energy gaps. Importantly, although these Ir(III) complexes share similar macroscopic phenomena, i.e., ultrafast IC and ISC, their microscopic excited-state relaxation mechanism and dynamics are qualitatively distinct. Specifically, the dynamical behaviors of electron and hole and their roles are variational in modulating the excited-state relaxation dynamics of these Ir(III) compounds. In other words, the electronic properties of the ligands that are coordinated with the central Ir(III) atom play important roles in regulating the microscopic excited-state relaxation dynamics. These gained insights could be useful for rationally designing Ir(III) compounds with excellent photoluminescence.

Broadband ultrafast photoprotection by oxybenzone across the UVB and UVC spectral regions.

PubMed

Baker, Lewis A; Horbury, Michael D; Greenough, Simon E; Ashfold, Michael N R; Stavros, Vasilios G

2015-10-01

Recent studies have shed light on the energy dissipation mechanism of oxybenzone, a common ingredient in commercial sunscreens. After UVA photoexcitation, the dissipation mechanism may be understood in terms of an initial ultrafast excited state enol → keto tautomerisation, followed by nonadiabatic transfer to the ground electronic state and subsequent collisional relaxation to the starting enol tautomer. We expand on these studies using femtosecond transient electronic absorption spectroscopy to understand the non-radiative relaxation pathways of oxybenzone in cyclohexane and in methanol after UVB and UVC excitation. We find that the relaxation pathway may be understood in the same way as when exciting in the UVA region, concluding that oxybenzone displays proficient broadband non-radiative photoprotection, and thus photophysically justifying its inclusion in sunscreen mixtures.

Ultrafast Microscopy of Energy and Charge Transport

NASA Astrophysics Data System (ADS)

Huang, Libai

The frontier in solar energy research now lies in learning how to integrate functional entities across multiple length scales to create optimal devices. Advancing the field requires transformative experimental tools that probe energy transfer processes from the nano to the meso lengthscales. To address this challenge, we aim to understand multi-scale energy transport across both multiple length and time scales, coupling simultaneous high spatial, structural, and temporal resolution. In my talk, I will focus on our recent progress on visualization of exciton and charge transport in solar energy harvesting materials from the nano to mesoscale employing ultrafast optical nanoscopy. With approaches that combine spatial and temporal resolutions, we have recently revealed a new singlet-mediated triplet transport mechanism in certain singlet fission materials. This work demonstrates a new triplet exciton transport mechanism leading to favorable long-range triplet exciton diffusion on the picosecond and nanosecond timescales for solar cell applications. We have also performed a direct measurement of carrier transport in space and in time by mapping carrier density with simultaneous ultrafast time resolution and 50 nm spatial precision in perovskite thin films using transient absorption microscopy. These results directly visualize long-range carrier transport of 220nm in 2 ns for solution-processed polycrystalline CH3NH3PbI3 thin films. The spatially and temporally resolved measurements reported here underscore the importance of the local morphology and establish an important first step towards discerning the underlying transport properties of perovskite materials.

Photon-assisted electron energy loss spectroscopy and ultrafast imaging.

PubMed

Howie, Archie

2009-08-01

A variety of ways is described in which photons can be used not only for ultrafast electron microscopy but also to enormously widen the energy range of spatially-resolved electron spectroscopy. Periodic chains of femtosecond laser pulses are a particularly important and accurately timed source for single-shot imaging and diffraction as well as for several forms of pump-probe microscopy at even higher spatial resolution and sub-picosecond timing. Many exciting new fields are opened up for study by these developments. Ultrafast, single shot diffraction with intense pulses of X-rays supplemented by phase retrieval techniques may eventually offer a challenging alternative and purely photon-based route to dynamic imaging at high spatial resolution.

Absorption spectrum and ultrafast response of monolayer and bilayer transition-metal dichalcogenides

NASA Astrophysics Data System (ADS)

Turkowski, Volodymyr; Ramirez-Torres, Alfredo; Rahman, Talat S.

2015-03-01

We apply a combined time-dependent density functional theory and many-body theory approach to examine the absorption spectrum and nonequilibrium response of monolayer and bilayer MoS2, MoSe2, WS2 and WSe2 systems. In particular, we evaluate the possibility of existence of bound states - excitons and trions in the undoped systems. In a previous work we have already demonstrated that the binding energies of these states in the monolayer systems are large which makes them available for room temperature applications. We analyze the possibility of ultrafast electron-hole separation in bilayer systems through inter-layer hole transfer, and show that such a possibility exists, in agreement with experimental observations. For doped systems we consider the possibility of Mahan excitonic states in monolayers and show that the binding energy for these states is of the order of 10 meV. We perform a detailed analysis of the relaxation of doped monolayers excited by ultrafast laser pulse by taking into account electron-phonon scattering effects, and demonstrate that ultrafast (10-100fs) processes, including luminescence, may be relevant for these materials. Work supported in part by DOE Grant No. DOE-DE-FG02-07ER46354.

Towards Direct Measurement of Ultrafast Vibrational Energy Flow in Proteins

NASA Astrophysics Data System (ADS)

Müller-Werkmeister, Henrike M.; Essig, Martin; Durkin, Patrick; Budisa, Nediljko; Bredenbeck, Jens

Vibrational energy transfer (VET) within a molecule can be investigated in great detail with ultrafast IR spectroscopy. We report on progress towards mapping of VET pathways in proteins using unnatural amino acids as site-specific probes.

Ultrafast relaxation dynamics in BiFeO 3/YBa 2Cu 3O 7 bilayers

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

Springer, D.; Nair, Saritha K.; He, Mi

The temperature dependence of the relaxation dynamics in the bilayer thin film heterostructure composed of multiferroic BiFeO 3 (BFO) and superconducting YBa 2Cu 3O 7 (YBCO) grown on (001) SrTiO 3 substrate is studied by time-resolved pump-probe technique, and compared with that of pure YBCO thin film grown under the same growth conditions. The superconductivity of YBCO is found to be retained in the heterostructure. We observe a speeding up of the YBCO recombination dynamics in the superconducting state of the heterostructure, and attribute it to the presence of weak ferromagnetism at the BFO/YBCOinterface as observed inmagnetization data. An extensionmore » of the Rothwarf-Taylor model is used to fit the ultrafast dynamics of BFO/YBCO, that models an increased quasiparticle occupation of the ferromagnetic interfacial layer in the superconducting state of YBCO.« less

Ultrafast relaxation dynamics in BiFeO 3/YBa 2Cu 3O 7 bilayers

DOE PAGES

Springer, D.; Nair, Saritha K.; He, Mi; ...

2016-02-12

The temperature dependence of the relaxation dynamics in the bilayer thin film heterostructure composed of multiferroic BiFeO 3 (BFO) and superconducting YBa 2Cu 3O 7 (YBCO) grown on (001) SrTiO 3 substrate is studied by time-resolved pump-probe technique, and compared with that of pure YBCO thin film grown under the same growth conditions. The superconductivity of YBCO is found to be retained in the heterostructure. We observe a speeding up of the YBCO recombination dynamics in the superconducting state of the heterostructure, and attribute it to the presence of weak ferromagnetism at the BFO/YBCOinterface as observed inmagnetization data. An extensionmore » of the Rothwarf-Taylor model is used to fit the ultrafast dynamics of BFO/YBCO, that models an increased quasiparticle occupation of the ferromagnetic interfacial layer in the superconducting state of YBCO.« less

Fusion of Ultraviolet-Visible and Infrared Transient Absorption Spectroscopy Data to Model Ultrafast Photoisomerization.

PubMed

Debus, Bruno; Orio, Maylis; Rehault, Julien; Burdzinski, Gotard; Ruckebusch, Cyril; Sliwa, Michel

2017-08-03

Ultrafast photoisomerization reactions generally start at a higher excited state with excess of internal vibrational energy and occur via conical intersections. This leads to ultrafast dynamics which are difficult to investigate with a single transient absorption spectroscopy technique, be it in the ultraviolet-visible (UV-vis) or infrared (IR) domain. On one hand, the information available in the UV-vis domain is limited as only slight spectral changes are observed for different isomers. On the other hand, the interpretation of vibrational spectra is strongly hindered by intramolecular relaxation and vibrational cooling. These limitations can be circumvented by fusing UV-vis and IR transient absorption spectroscopy data in a multiset multivariate curve resolution analysis. We apply this approach to describe the spectrodynamics of the ultrafast cis-trans photoisomerization around the C-N double bond observed for aromatic Schiff bases. Twisted intermediate states could be elucidated, and isomerization was shown to occur through a continuous complete rotation. More broadly, data fusion can be used to rationalize a vast range of ultrafast photoisomerization processes of interest in photochemistry.

Vibrational energy on surfaces: Ultrafast flash-thermal conductance of molecular monolayers

NASA Astrophysics Data System (ADS)

Dlott, Dana

2008-03-01

Vibrational energy flow through molecules remains a perennial problem in chemical physics. Usually vibrational energy dynamics are viewed through the lens of time-dependent level populations. This is natural because lasers naturally pump and probe vibrational transitions, but it is also useful to think of vibrational energy as being conducted from one location in a molecule to another. We have developed a new technique where energy is driven into a specific part of molecules adsorbed on a metal surface, and ultrafast nonlinear coherent vibrational spectroscopy is used to watch the energy arrive at another part. This technique is the analog of a flash thermal conductance apparatus, except it probes energy flow with angstrom spatial and femtosecond temporal resolution. Specific examples to be presented include energy flow along alkane chains, and energy flow into substituted benzenes. Ref: Z. Wang, J. A. Carter, A. Lagutchev, Y. K. Koh, N.-H. Seong, D. G. Cahill, and D. D. Dlott, Ultrafast flash thermal conductance of molecular chains, Science 317, 787-790 (2007). This material is based upon work supported by the National Science Foundation under award DMR 0504038 and the Air Force Office of Scientific Research under award FA9550-06-1-0235.

Weak nanoscale chaos and anomalous relaxation in DNA

NASA Astrophysics Data System (ADS)

Mazur, Alexey K.

2017-06-01

Anomalous nonexponential relaxation in hydrated biomolecules is commonly attributed to the complexity of the free-energy landscapes, similarly to polymers and glasses. It was found recently that the hydrogen-bond breathing of terminal DNA base pairs exhibits a slow power-law relaxation attributable to weak Hamiltonian chaos, with parameters similar to experimental data. Here, the relationship is studied between this motion and spectroscopic signals measured in DNA with a small molecular photoprobe inserted into the base-pair stack. To this end, the earlier computational approach in combination with an analytical theory is applied to the experimental DNA fragment. It is found that the intensity of breathing dynamics is strongly increased in the internal base pairs that flank the photoprobe, with anomalous relaxation quantitatively close to that in terminal base pairs. A physical mechanism is proposed to explain the coupling between the relaxation of base-pair breathing and the experimental response signal. It is concluded that the algebraic relaxation observed experimentally is very likely a manifestation of weakly chaotic dynamics of hydrogen-bond breathing in the base pairs stacked to the photoprobe and that the weak nanoscale chaos can represent an ubiquitous hidden source of nonexponential relaxation in ultrafast spectroscopy.

Weak nanoscale chaos and anomalous relaxation in DNA.

PubMed

Mazur, Alexey K

2017-06-01

Anomalous nonexponential relaxation in hydrated biomolecules is commonly attributed to the complexity of the free-energy landscapes, similarly to polymers and glasses. It was found recently that the hydrogen-bond breathing of terminal DNA base pairs exhibits a slow power-law relaxation attributable to weak Hamiltonian chaos, with parameters similar to experimental data. Here, the relationship is studied between this motion and spectroscopic signals measured in DNA with a small molecular photoprobe inserted into the base-pair stack. To this end, the earlier computational approach in combination with an analytical theory is applied to the experimental DNA fragment. It is found that the intensity of breathing dynamics is strongly increased in the internal base pairs that flank the photoprobe, with anomalous relaxation quantitatively close to that in terminal base pairs. A physical mechanism is proposed to explain the coupling between the relaxation of base-pair breathing and the experimental response signal. It is concluded that the algebraic relaxation observed experimentally is very likely a manifestation of weakly chaotic dynamics of hydrogen-bond breathing in the base pairs stacked to the photoprobe and that the weak nanoscale chaos can represent an ubiquitous hidden source of nonexponential relaxation in ultrafast spectroscopy.

Ultrafast hopping dynamics of 5f electrons in the Mott insulator UO₂ studied by femtosecond pump-probe spectroscopy.

PubMed

An, Yong Q; Taylor, Antoinette J; Conradson, Steven D; Trugman, Stuart A; Durakiewicz, Tomasz; Rodriguez, George

2011-05-20

We describe a femtosecond pump-probe study of ultrafast hopping dynamics of 5f electrons in the Mott insulator UO₂ following Mott-gap excitation at temperatures of 5-300 K. Hopping-induced response of the lattice and electrons is probed by transient reflectivity at mid- and above-gap photon energies, respectively. These measurements show an instantaneous hop, subsequent picosecond lattice deformation, followed by acoustic phonon emission and microsecond relaxation. Temperature-dependent studies indicate that the slow relaxation results from Hubbard excitons formed by U³⁺-U⁵⁺ pairs.

New Aspects of Photocurrent Generation at Graphene pn Junctions Revealed by Ultrafast Optical Measurements

NASA Astrophysics Data System (ADS)

Aivazian, Grant; Sun, Dong; Jones, Aaron; Ross, Jason; Yao, Wang; Cobden, David; Xu, Xiaodong

2012-02-01

The remarkable electrical and optical properties of graphene make it a promising material for new optoelectronic applications. However, one important, but so far unexplored, property is the role of hot carriers in charge and energy transport at graphene interfaces. Here we investigate the photocurrent (PC) dynamics at a tunable graphene pn junction using ultrafast scanning PC microscopy. Pump-probe measurements show a temperature dependent relaxation time of photogenerated carriers that increases from 1.5ps at 290K to 4ps at 20K; while the amplitude of the PC is independent of the lattice temperature. These observations imply that it is hot carriers, not phonons, which dominate ultrafast energy transport. Gate dependent measurements show many interesting features such as pump induced saturation, enhancement, and sign reversal of probe generated PC. These observations reveal that the underlying PC mechanism is a combination of the thermoelectric and built-in electric field effects. Our results enhance the understanding of non-equilibrium electron dynamics, electron-electron interactions, and electron-phonon interactions in graphene. They also determine fundamental limits on ultrafast device operation speeds (˜500 GHz) for graphene-based photodetectors.

Coherent energy scale revealed by ultrafast dynamics of UX3 (X = Al, Sn, Ga) single crystals

NASA Astrophysics Data System (ADS)

Nair, Saritha K.; Zhu, J.-X.; Sarrao, J. L.; Taylor, A. J.; Chia, Elbert E. M.

2012-09-01

The temperature dependence of relaxation dynamics of UX3 (X = Al, Ga, Sn) compounds is studied using the time-resolved pump-probe technique in reflectance geometry. For UGa3, our data are consistent with the formation of a spin density wave gap as evidenced from the quasidivergence of the relaxation time τ near the Néel temperature TN. For UAl3 and USn3, the relaxation dynamics shows a change from single-exponential to two-exponential behavior below a particular temperature, suggestive of coherence formation of the 5f electrons with the conduction band electrons. This particular temperature can be attributed to the spin fluctuation temperature Tsf, a measure of the strength of Kondo coherence. Our Tsf is consistent with other data such as resistivity and susceptibility measurements. The temperature dependence of the relaxation amplitude and time of UAl3 and USn3 were also fitted by the Rothwarf-Taylor model. Our results show that ultrafast optical spectroscopy is sensitive to c-f Kondo hybridization in the f-electron systems.

Carbon Nanotubes as an Ultrafast Emitter with a Narrow Energy Spread at Optical Frequency.

PubMed

Li, Chi; Zhou, Xu; Zhai, Feng; Li, Zhenjun; Yao, Fengrui; Qiao, Ruixi; Chen, Ke; Cole, Matthew Thomas; Yu, Dapeng; Sun, Zhipei; Liu, Kaihui; Dai, Qing

2017-08-01

Ultrafast electron pulses, combined with laser-pump and electron-probe technologies, allow ultrafast dynamics to be characterized in materials. However, the pursuit of simultaneous ultimate spatial and temporal resolution of microscopy and spectroscopy is largely subdued by the low monochromaticity of the electron pulses and their poor phase synchronization to the optical excitation pulses. Field-driven photoemission from metal tips provides high light-phase synchronization, but suffers large electron energy spreads (3-100 eV) as driven by a long wavelength laser (>800 nm). Here, ultrafast electron emission from carbon nanotubes (≈1 nm radius) excited by a 410 nm femtosecond laser is realized in the field-driven regime. In addition, the emitted electrons have great monochromaticity with energy spread as low as 0.25 eV. This great performance benefits from the extraordinarily high field enhancement and great stability of carbon nanotubes, superior to metal tips. The new nanotube-based ultrafast electron source opens exciting prospects for extending current characterization to sub-femtosecond temporal resolution as well as sub-nanometer spatial resolution. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Electron and hole relaxation pathways in semiconductor quantum dots

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

Klimov, V.I.; McBranch, D.W.; Leatherdale, C.A.

1999-11-01

Femtosecond (fs) broad-band transient absorption (TA) is used to study the intraband relaxation and depopulation dynamics of electron and hole quantized states in CdSe nanocrystals (NC{close_quote}s) with a range of surface properties. Instead of the drastic reduction in the energy relaxation rate expected due to a {open_quotes}phonon bottleneck,{close_quotes} we observe a fast subpicosecond 1P-to-1S electron relaxation, with the rate exceeding that due to phonon emission in bulk semiconductors. The energy relaxation is enhanced with reducing the NC{close_quote}s radius, and does not show any dependence on the NC surface properties (quality of the surface passivation). These data indicate that electron energymore » relaxation occurs by neither multiphonon emission nor by coupling to surface defects, but is likely meditated by Auger-type electron-hole energy transfer. We use fs infrared TA to probe electron and hole intraband transitions, which allows us to distinguish between electron and hole relaxation pathways leading to the depopulation of NC quantized states. In contrast to the electron relaxation, which is controlled by NC surface passivation, the depopulation of hole quantized states is extremely fast (sub-ps-to-ps time scales) in all types of samples, independent of NC surface treatment (including NC{close_quote}s overcoated with a ZnS layer). Our results indicate that ultrafast hole dynamics are not due to trapping at localized surface defects such as a vacancy, but rather arise from relaxation into intrinsic NC states or intrinsically unpassivated interface states. {copyright} {ital 1999} {ital The American Physical Society}« less

Ultrafast carrier dynamics in bilayer graphene studied by broadband infrared pump-probe spectroscopy

NASA Astrophysics Data System (ADS)

Limmer, Thomas; da Como, Enrico; Niggebaum, Alexander; Feldmann, Jochen

2010-03-01

Recently, bilayer graphene gained a large interest because of its electrically tunable gap appearing in the middle infrared part of the electromagnetic spectrum. This feature is expected to open a number of applications of bilayer graphene in optoelectronics. In this communication we report on the first pump-probe experiment on a single bilayer flake with an unprecedented probe photon energy interval (0.25 -- 1.3 eV). Single flakes were prepared by mechanical exfoliation of graphite and transferred to calcium fluoride substrates. When illuminated with 800 nm (1.5 eV) pump pulses the induced change in transmission shows an ultrafast saturation of the interband transitions from 1.3 to 0.5 eV. In this energy range the saturation recovery occurs within 3 ps and is consistent with an ultrafast relaxation of hot carriers. Interestingly, we report on the observation of a resonance at 0.4 eV characterized by a longer dynamics. The results are discussed considering many-body interactions.

Exciton Relaxation and Electron Transfer Dynamics of Semiconductor Quantum Dots

NASA Astrophysics Data System (ADS)

Liu, Cunming

Quantum dots (QDs), also referred to as colloidal semiconductor nanocrystals, exhibit unique electronic and optical properties arising from their three-dimensional confinement and strongly enhanced coulomb interactions. Developing a detailed understanding of the exciton relaxation dynamics within QDs is important not only for sake of exploring the fundamental physics of quantum confinement processes, but also for their applications. Ultrafast transient absorption (TA) spectroscopy, as a powerful tool to explore the relaxation dynamics of excitons, was employed to characterize the hot single/multiexciton relaxation dynamics at the first four exciton states of CdSe/CdZnS QDs. We observed for the first time that the hot hole can relax through two possible pathways: Intraband multiple phonon coupling and intrinsic defect trapping, with a lifetime of ˜7 ps. Additionally, an ultra-short component of ˜ 8 ps, directly associated with the Auger recombination of highly energetic exciton states, was discovered. After exploring the exciton relaxation inside QDs, ultrafast TA spectroscopy was further applied to study the electron transferring outside from QDs. By using a brand-new photocatalytic system consisting of CdSe QDs and Ni-dihydrolipoic acid (Ni-DHLA) catalyst, which has represented a robust photocatalysis of H2 from water, the photoinduced electron transfer (ET) dynamics between QD and the catalyst, one of most important steps during H2 generation, was studied. We found smaller bare CdSe QDs exhibit a better ET performance and CdS shelling on the bare QDs leads to worsen the ET. The calculations of effective mass approximation (EMA) and Marcus theory show the ET process is mainly dominated by driving force, electronic coupling strength and reorganization energy between QD and the catalyst.

Slow secondary relaxation in a free-energy landscape model for relaxation in glass-forming liquids

NASA Astrophysics Data System (ADS)

Diezemann, Gregor; Mohanty, Udayan; Oppenheim, Irwin

1999-02-01

Within the framework of a free-energy landscape model for the relaxation in supercooled liquids the primary (α) relaxation is modeled by transitions among different free-energy minima. The secondary (β) relaxation then corresponds to intraminima relaxation. We consider a simple model for the reorientational motions of the molecules associated with both processes and calculate the dielectric susceptibility as well as the spin-lattice relaxation times. The parameters of the model can be chosen in a way that both quantities show a behavior similar to that observed in experimental studies on supercooled liquids. In particular we find that it is not possible to obtain a crossing of the time scales associated with α and β relaxation. In our model these processes always merge at high temperatures and the α process remains above the merging temperature. The relation to other models is discussed.

Imaging Spatial Variations in the Dissipation and Transport of Thermal Energy within Individual Silicon Nanowires Using Ultrafast Microscopy.

PubMed

Cating, Emma E M; Pinion, Christopher W; Van Goethem, Erika M; Gabriel, Michelle M; Cahoon, James F; Papanikolas, John M

2016-01-13

Thermal management is an important consideration for most nanoelectronic devices, and an understanding of the thermal conductivity of individual device components is critical for the design of thermally efficient systems. However, it can be difficult to directly probe local changes in thermal conductivity within a nanoscale system. Here, we utilize the time-resolved and diffraction-limited imaging capabilities of ultrafast pump-probe microscopy to determine, in a contact-free configuration, the local thermal conductivity in individual Si nanowires (NWs). By suspending single NWs across microfabricated trenches in a quartz substrate, the properties of the same NW both on and off the substrate are directly compared. We find the substrate has no effect on the recombination lifetime or diffusion length of photogenerated charge carriers; however, it significantly impacts the thermal relaxation properties of the NW. In substrate-supported regions, thermal energy deposited into the lattice by the ultrafast laser pulse dissipates within ∼10 ns through thermal diffusion and coupling to the substrate. In suspended regions, the thermal energy persists for over 100 ns, and we directly image the time-resolved spatial motion of the thermal signal. Quantitative analysis of the transient images permits direct determination of the NW's local thermal conductivity, which we find to be a factor of ∼4 smaller than in bulk Si. Our results point to the strong potential of pump-probe microscopy to be used as an all-optical method to quantify the effects of localized environment and morphology on the thermal transport characteristics of individual nanostructured components.

Spin-controlled ultrafast vertical-cavity surface-emitting lasers

NASA Astrophysics Data System (ADS)

Höpfner, Henning; Lindemann, Markus; Gerhardt, Nils C.; Hofmann, Martin R.

2014-05-01

Spin-controlled semiconductor lasers are highly attractive spintronic devices providing characteristics superior to their conventional purely charge-based counterparts. In particular, spin-controlled vertical-cavity surface emitting lasers (spin-VCSELs) promise to offer lower thresholds, enhanced emission intensity, spin amplification, full polarization control, chirp control and ultrafast dynamics. Most important, the ability to control and modulate the polarization state of the laser emission with extraordinarily high frequencies is very attractive for many applications like broadband optical communication and ultrafast optical switches. We present a novel concept for ultrafast spin-VCSELs which has the potential to overcome the conventional speed limitation for directly modulated lasers by the relaxation oscillation frequency and to reach modulation frequencies significantly above 100 GHz. The concept is based on the coupled spin-photon dynamics in birefringent micro-cavity lasers. By injecting spin-polarized carriers in the VCSEL, oscillations of the coupled spin-photon system can by induced which lead to oscillations of the polarization state of the laser emission. These oscillations are decoupled from conventional relaxation oscillations of the carrier-photon system and can be much faster than these. Utilizing these polarization oscillations is thus a very promising approach to develop ultrafast spin-VCSELs for high speed optical data communication in the near future. Different aspects of the spin and polarization dynamics, its connection to birefringence and bistability in the cavity, controlled switching of the oscillations, and the limitations of this novel approach will be analysed theoretically and experimentally for spin-polarized VCSELs at room temperature.

Probing ultrafast proton induced dynamics in transparent dielectrics

NASA Astrophysics Data System (ADS)

Taylor, M.; Coughlan, M.; Nersisyan, G.; Senje, L.; Jung, D.; Currell, F.; Riley, D.; Lewis, C. L. S.; Zepf, M.; Dromey, B.

2018-05-01

A scheme has been developed permitting the spatial and temporal characterisation of ultrafast dynamics induced by laser driven proton bursts in transparent dielectrics. Advantage is taken of the high degree of synchronicity between the proton bursts generated during laser-foil target interactions and the probing laser to provide the basis for streaking of the dynamics. Relaxation times of electrons (<10‑12 s) are measured following swift excitation across the optical band gap for various glass samples. A temporal resolution of <500 fs is achieved demonstrating that these ultrafast dynamics can be characterized on a single-shot basis.

Laser selective cutting of biological tissues by impulsive heat deposition through ultrafast vibrational excitations.

PubMed

Franjic, Kresimir; Cowan, Michael L; Kraemer, Darren; Miller, R J Dwayne

2009-12-07

Mechanical and thermodynamic responses of biomaterials after impulsive heat deposition through vibrational excitations (IHDVE) are investigated and discussed. Specifically, we demonstrate highly efficient ablation of healthy tooth enamel using 55 ps infrared laser pulses tuned to the vibrational transition of interstitial water and hydroxyapatite around 2.95 microm. The peak intensity at 13 GW/cm(2) was well below the plasma generation threshold and the applied fluence 0.75 J/cm(2) was significantly smaller than the typical ablation thresholds observed with nanosecond and microsecond pulses from Er:YAG lasers operating at the same wavelength. The ablation was performed without adding any superficial water layer at the enamel surface. The total energy deposited per ablated volume was several times smaller than previously reported for non-resonant ultrafast plasma driven ablation with similar pulse durations. No micro-cracking of the ablated surface was observed with a scanning electron microscope. The highly efficient ablation is attributed to an enhanced photomechanical effect due to ultrafast vibrational relaxation into heat and the scattering of powerful ultrafast acoustic transients with random phases off the mesoscopic heterogeneous tissue structures.

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.

Spatial and temporal laser pulse design for material processing on ultrafast scales

NASA Astrophysics Data System (ADS)

Stoian, R.; Colombier, J. P.; Mauclair, C.; Cheng, G.; Bhuyan, M. K.; Velpula, P. K.; Srisungsitthisunti, P.

2014-01-01

The spatio-temporal design of ultrafast laser excitation can have a determinant influence on the physical and engineering aspects of laser-matter interactions, with the potential of upgrading laser processing effects. Energy relaxation channels can be synergetically stimulated as the energy delivery rate is synchronized with the material response on ps timescales. Experimental and theoretical loops based on the temporal design of laser irradiation and rapid monitoring of irradiation effects are, therefore, able to predict and determine ideal optimal laser pulse forms for specific ablation objectives. We illustrate this with examples on manipulating the thermodynamic relaxation pathways impacting the ablation products and nanostructuring of bulk and surfaces using longer pulse envelopes. Some of the potential control factors will be pointed out. At the same time the spatial character can dramatically influence the development of laser interaction. We discuss spatial beam engineering examples such as parallel and non-diffractive approaches designed for high-throughput, high-accuracy processing events.

Ultrafast Multi-Level Logic Gates with Spin-Valley Coupled Polarization Anisotropy in Monolayer MoS2

PubMed Central

Wang, Yu-Ting; Luo, Chih-Wei; Yabushita, Atsushi; Wu, Kaung-Hsiung; Kobayashi, Takayoshi; Chen, Chang-Hsiao; Li, Lain-Jong

2015-01-01

The inherent valley-contrasting optical selection rules for interband transitions at the K and K′ valleys in monolayer MoS2 have attracted extensive interest. Carriers in these two valleys can be selectively excited by circularly polarized optical fields. The comprehensive dynamics of spin valley coupled polarization and polarized exciton are completely resolved in this work. Here, we present a systematic study of the ultrafast dynamics of monolayer MoS2 including spin randomization, exciton dissociation, free carrier relaxation, and electron-hole recombination by helicity- and photon energy-resolved transient spectroscopy. The time constants for these processes are 60 fs, 1 ps, 25 ps, and ~300 ps, respectively. The ultrafast dynamics of spin polarization, valley population, and exciton dissociation provides the desired information about the mechanism of radiationless transitions in various applications of 2D transition metal dichalcogenides. For example, spin valley coupled polarization provides a promising way to build optically selective-driven ultrafast valleytronics at room temperature. Therefore, a full understanding of the ultrafast dynamics in MoS2 is expected to provide important fundamental and technological perspectives. PMID:25656222

PREFACE: Ultrafast and nonlinear optics in carbon nanomaterials

NASA Astrophysics Data System (ADS)

Kono, Junichiro

2013-02-01

Journal of Physics: Condensed Matter staff for their help, patience and professionalism. Since this is a fast-moving field, there is absolutely no way of presenting definitive answers to all open questions, but we hope that this special section will provide an overview of the current state of knowledge regarding this topic. Furthermore, we hope that the exciting science and technology described in this section will attract and inspire other researchers and students working in related fields to enter into the study of ultrafast and nonlinear optical phenomena in carbon-based nanostructures. Ultrafast and nonlinear optics in carbon nanomaterials contents Ultrafast and nonlinear optics in carbon nanomaterialsJunichiro Kono The impact of pump fluence on carrier relaxation dynamics in optically excited grapheneT Winzer and E Malic Time-resolved spectroscopy on epitaxial graphene in the infrared spectral range: relaxation dynamics and saturation behaviorS Winnerl, F Göttfert, M Mittendorff, H Schneider, M Helm, T Winzer, E Malic, A Knorr, M Orlita, M Potemski, M Sprinkle, C Berger and W A de Heer Nonlinear optics of graphene in a strong magnetic fieldXianghan Yao and Alexey Belyanin Theory of coherent phonons in carbon nanotubes and graphene nanoribbonsG D Sanders, A R T Nugraha, K Sato, J-H Kim3, J Kono3, R Saito and C J Stanton Non-perturbative effects of laser illumination on the electrical properties of graphene nanoribbons Hernán L Calvo, Pablo M Perez-Piskunow, Horacio M Pastawski, Stephan Roche and Luis E F Foa Torres Transient absorption microscopy studies of energy relaxation in graphene oxide thin film Sean Murphy and Libai Huang Femtosecond dynamics of exciton localization: self-trapping from the small to the large polaron limit F X Morrissey, J G Mance, A D Van Pelt and S L Dexheimer

Ultrafast Solvation Dynamics and Vibrational Coherences of Halogenated Boron-Dipyrromethene Derivatives Revealed through Two-Dimensional Electronic Spectroscopy.

PubMed

Lee, Yumin; Das, Saptaparna; Malamakal, Roy M; Meloni, Stephen; Chenoweth, David M; Anna, Jessica M

2017-10-18

Boron-dipyrromethene (BODIPY) chromophores have a wide range of applications, spanning areas from biological imaging to solar energy conversion. Understanding the ultrafast dynamics of electronically excited BODIPY chromophores could lead to further advances in these areas. In this work, we characterize and compare the ultrafast dynamics of halogenated BODIPY chromophores through applying two-dimensional electronic spectroscopy (2DES). Through our studies, we demonstrate a new data analysis procedure for extracting the dynamic Stokes shift from 2DES spectra revealing an ultrafast solvent relaxation. In addition, we extract the frequency of the vibrational modes that are strongly coupled to the electronic excitation, and compare the results of structurally different BODIPY chromophores. We interpret our results with the aid of DFT calculations, finding that structural modifications lead to changes in the frequency, identity, and magnitude of Franck-Condon active vibrational modes. We attribute these changes to differences in the electron density of the electronic states of the structurally different BODIPY chromophores.

Picosecond absorption relaxation measured with nanosecond laser photoacoustics.

PubMed

Danielli, Amos; Favazza, Christopher P; Maslov, Konstantin; Wang, Lihong V

2010-10-18

Picosecond absorption relaxation-central to many disciplines-is typically measured by ultrafast (femtosecond or picosecond) pump-probe techniques, which however are restricted to optically thin and weakly scattering materials or require artificial sample preparation. Here, we developed a reflection-mode relaxation photoacoustic microscope based on a nanosecond laser and measured picosecond absorption relaxation times. The relaxation times of oxygenated and deoxygenated hemoglobin molecules, both possessing extremely low fluorescence quantum yields, were measured at 576 nm. The added advantages in dispersion susceptibility, laser-wavelength availability, reflection sensing, and expense foster the study of natural-including strongly scattering and nonfluorescent-materials.

Ultrafast Electron Dynamics in Solar Energy Conversion.

PubMed

Ponseca, Carlito S; Chábera, Pavel; Uhlig, Jens; Persson, Petter; Sundström, Villy

2017-08-23

Electrons are the workhorses of solar energy conversion. Conversion of the energy of light to electricity in photovoltaics, or to energy-rich molecules (solar fuel) through photocatalytic processes, invariably starts with photoinduced generation of energy-rich electrons. The harvesting of these electrons in practical devices rests on a series of electron transfer processes whose dynamics and efficiencies determine the function of materials and devices. To capture the energy of a photogenerated electron-hole pair in a solar cell material, charges of opposite sign have to be separated against electrostatic attractions, prevented from recombining and being transported through the active material to electrodes where they can be extracted. In photocatalytic solar fuel production, these electron processes are coupled to chemical reactions leading to storage of the energy of light in chemical bonds. With the focus on the ultrafast time scale, we here discuss the light-induced electron processes underlying the function of several molecular and hybrid materials currently under development for solar energy applications in dye or quantum dot-sensitized solar cells, polymer-fullerene polymer solar cells, organometal halide perovskite solar cells, and finally some photocatalytic systems.

Electron theory of fast and ultrafast dissipative magnetization dynamics.

PubMed

Fähnle, M; Illg, C

2011-12-14

For metallic magnets we review the experimental and electron-theoretical investigations of fast magnetization dynamics (on a timescale of ns to 100 ps) and of laser-pulse-induced ultrafast dynamics (few hundred fs). It is argued that for both situations the dominant contributions to the dissipative part of the dynamics arise from the excitation of electron-hole pairs and from the subsequent relaxation of these pairs by spin-dependent scattering processes, which transfer angular momentum to the lattice. By effective field theories (generalized breathing and bubbling Fermi-surface models) it is shown that the Gilbert equation of motion, which is often used to describe the fast dissipative magnetization dynamics, must be extended in several aspects. The basic assumptions of the Elliott-Yafet theory, which is often used to describe the ultrafast spin relaxation after laser-pulse irradiation, are discussed very critically. However, it is shown that for Ni this theory probably yields a value for the spin-relaxation time T(1) in good agreement with the experimental value. A relation between the quantity α characterizing the damping of the fast dynamics in simple situations and the time T(1) is derived. © 2011 IOP Publishing Ltd

Structural relaxation in the hydrogen-bonding liquids N-methylacetamide and water studied by optical Kerr effect spectroscopy.

PubMed

Turton, David A; Wynne, Klaas

2008-04-21

Structural relaxation in the peptide model N-methylacetamide (NMA) is studied experimentally by ultrafast optical Kerr effect spectroscopy over the normal-liquid temperature range and compared to the relaxation measured in water at room temperature. It is seen that in both hydrogen-bonding liquids, beta relaxation is present, and in each case, it is found that this can be described by the Cole-Cole function. For NMA in this temperature range, the alpha and beta relaxations are each found to have an Arrhenius temperature dependence with indistinguishable activation energies. It is known that the variations on the Debye function, including the Cole-Cole function, are unphysical, and we introduce two general modifications: One allows for the initial rise of the function, determined by the librational frequencies, and the second allows the function to be terminated in the alpha relaxation.

The ultrafast dynamics and conductivity of photoexcited graphene at different Fermi energies

PubMed Central

Turchinovich, Dmitry; Kläui, Mathias; Hendry, Euan; Polini, Marco

2018-01-01

For many of the envisioned optoelectronic applications of graphene, it is crucial to understand the subpicosecond carrier dynamics immediately following photoexcitation and the effect of photoexcitation on the electrical conductivity—the photoconductivity. Whereas these topics have been studied using various ultrafast experiments and theoretical approaches, controversial and incomplete explanations concerning the sign of the photoconductivity, the occurrence and significance of the creation of additional electron-hole pairs, and, in particular, how the relevant processes depend on Fermi energy have been put forward. We present a unified and intuitive physical picture of the ultrafast carrier dynamics and the photoconductivity, combining optical pump–terahertz probe measurements on a gate-tunable graphene device, with numerical calculations using the Boltzmann equation. We distinguish two types of ultrafast photo-induced carrier heating processes: At low (equilibrium) Fermi energy (EF ≲ 0.1 eV for our experiments), broadening of the carrier distribution involves interband transitions (interband heating). At higher Fermi energy (EF ≳ 0.15 eV), broadening of the carrier distribution involves intraband transitions (intraband heating). Under certain conditions, additional electron-hole pairs can be created [carrier multiplication (CM)] for low EF, and hot carriers (hot-CM) for higher EF. The resultant photoconductivity is positive (negative) for low (high) EF, which in our physical picture, is explained using solely electronic effects: It follows from the effect of the heated carrier distributions on the screening of impurities, consistent with the DC conductivity being mostly due to impurity scattering. The importance of these insights is highlighted by a discussion of the implications for graphene photodetector applications. PMID:29756035

Direct and simultaneous observation of ultrafast electron and hole dynamics in germanium.

PubMed

Zürch, Michael; Chang, Hung-Tzu; Borja, Lauren J; Kraus, Peter M; Cushing, Scott K; Gandman, Andrey; Kaplan, Christopher J; Oh, Myoung Hwan; Prell, James S; Prendergast, David; Pemmaraju, Chaitanya D; Neumark, Daniel M; Leone, Stephen R

2017-06-01

Understanding excited carrier dynamics in semiconductors is crucial for the development of photovoltaics and efficient photonic devices. However, overlapping spectral features in optical pump-probe spectroscopy often render assignments of separate electron and hole carrier dynamics ambiguous. Here, ultrafast electron and hole dynamics in germanium nanocrystalline thin films are directly and simultaneously observed by ultrafast transient absorption spectroscopy in the extreme ultraviolet at the germanium M 4,5 edge. We decompose the spectra into contributions of electronic state blocking and photo-induced band shifts at a carrier density of 8 × 10 20  cm -3 . Separate electron and hole relaxation times are observed as a function of hot carrier energies. A first-order electron and hole decay of ∼1 ps suggests a Shockley-Read-Hall recombination mechanism. The simultaneous observation of electrons and holes with extreme ultraviolet transient absorption spectroscopy paves the way for investigating few- to sub-femtosecond dynamics of both holes and electrons in complex semiconductor materials and across junctions.

Direct and simultaneous observation of ultrafast electron and hole dynamics in germanium

PubMed Central

Zürch, Michael; Chang, Hung-Tzu; Borja, Lauren J.; Kraus, Peter M.; Cushing, Scott K.; Gandman, Andrey; Kaplan, Christopher J.; Oh, Myoung Hwan; Prell, James S.; Prendergast, David; Pemmaraju, Chaitanya D.; Neumark, Daniel M.; Leone, Stephen R.

2017-01-01

Understanding excited carrier dynamics in semiconductors is crucial for the development of photovoltaics and efficient photonic devices. However, overlapping spectral features in optical pump-probe spectroscopy often render assignments of separate electron and hole carrier dynamics ambiguous. Here, ultrafast electron and hole dynamics in germanium nanocrystalline thin films are directly and simultaneously observed by ultrafast transient absorption spectroscopy in the extreme ultraviolet at the germanium M4,5 edge. We decompose the spectra into contributions of electronic state blocking and photo-induced band shifts at a carrier density of 8 × 1020 cm−3. Separate electron and hole relaxation times are observed as a function of hot carrier energies. A first-order electron and hole decay of ∼1 ps suggests a Shockley–Read–Hall recombination mechanism. The simultaneous observation of electrons and holes with extreme ultraviolet transient absorption spectroscopy paves the way for investigating few- to sub-femtosecond dynamics of both holes and electrons in complex semiconductor materials and across junctions. PMID:28569752

Tuning energy relaxation along quantum Hall channels.

PubMed

Altimiras, C; le Sueur, H; Gennser, U; Cavanna, A; Mailly, D; Pierre, F

2010-11-26

The chiral edge channels in the quantum Hall regime are considered ideal ballistic quantum channels, and have quantum information processing potentialities. Here, we demonstrate experimentally, at a filling factor of ν(L)=2, the efficient tuning of the energy relaxation that limits quantum coherence and permits the return toward equilibrium. Energy relaxation along an edge channel is controllably enhanced by increasing its transmission toward a floating Ohmic contact, in quantitative agreement with predictions. Moreover, by forming a closed inner edge channel loop, we freeze energy exchanges in the outer channel. This result also elucidates the inelastic mechanisms at work at ν(L)=2, informing us, in particular, that those within the outer edge channel are negligible.

Determination of hot carrier energy distributions from inversion of ultrafast pump-probe reflectivity measurements.

PubMed

Heilpern, Tal; Manjare, Manoj; Govorov, Alexander O; Wiederrecht, Gary P; Gray, Stephen K; Harutyunyan, Hayk

2018-05-10

Developing a fundamental understanding of ultrafast non-thermal processes in metallic nanosystems will lead to applications in photodetection, photochemistry and photonic circuitry. Typically, non-thermal and thermal carrier populations in plasmonic systems are inferred either by making assumptions about the functional form of the initial energy distribution or using indirect sensors like localized plasmon frequency shifts. Here we directly determine non-thermal and thermal distributions and dynamics in thin films by applying a double inversion procedure to optical pump-probe data that relates the reflectivity changes around Fermi energy to the changes in the dielectric function and in the single-electron energy band occupancies. When applied to normal incidence measurements our method uncovers the ultrafast excitation of a non-Fermi-Dirac distribution and its subsequent thermalization dynamics. Furthermore, when applied to the Kretschmann configuration, we show that the excitation of propagating plasmons leads to a broader energy distribution of electrons due to the enhanced Landau damping.

Ultrafast lattice dynamics in lead selenide quantum dot induced by laser excitation

DOE PAGES

Wang, Xuan; Rahmani, Hamidreza; Zhou, Jun; ...

2016-10-10

We directly monitored the lattice dynamics in PbSe quantum dots induced by laser excitation using ultrafast electron di raction. The energy relaxation between the carriers and the lattice took place within 10 ps, showing no evidence of any signi cant phonon bottleneck e ect. Meanwhile, the lattice dilation exhibited some unusual features that could not be explained by the available mechanisms of photon- induced acoustic vibrations in semiconductors alone. The heat transport between the QDs and the substrate deviates signi cantly from Fourier's Law, which opens questions about the heat transfer under nonequilibrium conditions in nanoscale materials.

Ultrafast lattice dynamics in lead selenide quantum dot induced by laser excitation

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

Wang, Xuan; Rahmani, Hamidreza; Zhou, Jun

We directly monitored the lattice dynamics in PbSe quantum dots induced by laser excitation using ultrafast electron di raction. The energy relaxation between the carriers and the lattice took place within 10 ps, showing no evidence of any signi cant phonon bottleneck e ect. Meanwhile, the lattice dilation exhibited some unusual features that could not be explained by the available mechanisms of photon- induced acoustic vibrations in semiconductors alone. The heat transport between the QDs and the substrate deviates signi cantly from Fourier's Law, which opens questions about the heat transfer under nonequilibrium conditions in nanoscale materials.

Universal binding energy relation for cleaved and structurally relaxed surfaces.

PubMed

Srirangarajan, Aarti; Datta, Aditi; Gandi, Appala Naidu; Ramamurty, U; Waghmare, U V

2014-02-05

The universal binding energy relation (UBER), derived earlier to describe the cohesion between two rigid atomic planes, does not accurately capture the cohesive properties when the cleaved surfaces are allowed to relax. We suggest a modified functional form of UBER that is analytical and at the same time accurately models the properties of surfaces relaxed during cleavage. We demonstrate the generality as well as the validity of this modified UBER through first-principles density functional theory calculations of cleavage in a number of crystal systems. Our results show that the total energies of all the relaxed surfaces lie on a single (universal) energy surface, that is given by the proposed functional form which contains an additional length-scale associated with structural relaxation. This functional form could be used in modelling the cohesive zones in crack growth simulation studies. We find that the cohesive law (stress-displacement relation) differs significantly in the case where cracked surfaces are allowed to relax, with lower peak stresses occurring at higher displacements.

Multilayer Relaxation and Surface Energies of Metallic Surfaces

NASA Technical Reports Server (NTRS)

Bozzolo, Guillermo; Rodriguez, Agustin M.; Ferrante, John

1994-01-01

The perpendicular and parallel multilayer relaxations of fcc (210) surfaces are studied using equivalent crystal theory (ECT). A comparison with experimental and theoretical results is made for AI(210). The effect of uncertainties in the input parameters on the magnitudes and ordering of surface relaxations for this semiempirical method is estimated. A new measure of surface roughness is proposed. Predictions for the multilayer relaxations and surface energies of the (210) face of Cu and Ni are also included.

Picosecond absorption relaxation measured with nanosecond laser photoacoustics

PubMed Central

Danielli, Amos; Favazza, Christopher P.; Maslov, Konstantin; Wang, Lihong V.

2010-01-01

Picosecond absorption relaxation—central to many disciplines—is typically measured by ultrafast (femtosecond or picosecond) pump-probe techniques, which however are restricted to optically thin and weakly scattering materials or require artificial sample preparation. Here, we developed a reflection-mode relaxation photoacoustic microscope based on a nanosecond laser and measured picosecond absorption relaxation times. The relaxation times of oxygenated and deoxygenated hemoglobin molecules, both possessing extremely low fluorescence quantum yields, were measured at 576 nm. The added advantages in dispersion susceptibility, laser-wavelength availability, reflection sensing, and expense foster the study of natural—including strongly scattering and nonfluorescent—materials. PMID:21079726

Excitation energy dependence of excited states dynamics in all- trans-carotenes determined by femtosecond absorption and fluorescence spectroscopy

NASA Astrophysics Data System (ADS)

Kosumi, Daisuke; Yanagi, Kazuhiro; Nishio, Tomohiro; Hashimoto, Hideki; Yoshizawa, Masayuki

2005-06-01

Ultrafast relaxation kinetics in β-carotene and lycopene has been investigated by femtosecond absorption and fluorescence spectroscopies using tunable excitation pulses. The transient signals induced by the photoexcitation with larger excess energy have broader bands and longer lifetimes both in the 11Bu+and21Ag- excited states. The excess vibrational energy remains longer than several picoseconds and slows the relaxation kinetics in carotenoids.

Ultrafast switching of valence and generation of coherent acoustic phonons in semiconducting rare-earth monosulfides

NASA Astrophysics Data System (ADS)

Punpongjareorn, Napat; He, Xing; Tang, Zhongjia; Guloy, Arnold M.; Yang, Ding-Shyue

2017-08-01

We report on the ultrafast carrier dynamics and generation of coherent acoustic phonons in YbS, a semiconducting rare-earth monochalcogenide, using two-color pump-probe reflectivity. Compared to the carrier relaxation processes and lifetimes of conventional semiconductors, recombination of photoexcited electrons with holes in localized f orbitals is found to take place rapidly with a density-independent time constant of <500 fs in YbS. Such carrier annihilation signifies the unique and ultrafast nature of valence restoration of ytterbium ions after femtosecond photoexcitation switching. Following transfer of the absorbed energy to the lattice, coherent acoustic phonons emerge on the picosecond timescale as a result of the thermal strain in the photoexcited region. By analyzing the electronic and structural dynamics, we obtain the physical properties of YbS including its two-photon absorption and thermooptic coefficients, the period and decay time of the coherent oscillation, and the sound velocity.

Probing energy transfer events in the light harvesting complex 2 (LH2) of Rhodobacter sphaeroides with two-dimensional spectroscopy.

PubMed

Fidler, Andrew F; Singh, Ved P; Long, Phillip D; Dahlberg, Peter D; Engel, Gregory S

2013-10-21

Excitation energy transfer events in the photosynthetic light harvesting complex 2 (LH2) of Rhodobacter sphaeroides are investigated with polarization controlled two-dimensional electronic spectroscopy. A spectrally broadened pulse allows simultaneous measurement of the energy transfer within and between the two absorption bands at 800 nm and 850 nm. The phased all-parallel polarization two-dimensional spectra resolve the initial events of energy transfer by separating the intra-band and inter-band relaxation processes across the two-dimensional map. The internal dynamics of the 800 nm region of the spectra are resolved as a cross peak that grows in on an ultrafast time scale, reflecting energy transfer between higher lying excitations of the B850 chromophores into the B800 states. We utilize a polarization sequence designed to highlight the initial excited state dynamics which uncovers an ultrafast transfer component between the two bands that was not observed in the all-parallel polarization data. We attribute the ultrafast transfer component to energy transfer from higher energy exciton states to lower energy states of the strongly coupled B850 chromophores. Connecting the spectroscopic signature to the molecular structure, we reveal multiple relaxation pathways including a cyclic transfer of energy between the two rings of the complex.

Mixed quantum-classical simulations of the vibrational relaxation of photolyzed carbon monoxide in a hemoprotein

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

Schubert, Alexander, E-mail: schubert@irsamc.ups-tlse.fr; Meier, Christoph; Falvo, Cyril

2016-08-07

We present mixed quantum-classical simulations on relaxation and dephasing of vibrationally excited carbon monoxide within a protein environment. The methodology is based on a vibrational surface hopping approach treating the vibrational states of CO quantum mechanically, while all remaining degrees of freedom are described by means of classical molecular dynamics. The CO vibrational states form the “surfaces” for the classical trajectories of protein and solvent atoms. In return, environmentally induced non-adiabatic couplings between these states cause transitions describing the vibrational relaxation from first principles. The molecular dynamics simulation yields a detailed atomistic picture of the energy relaxation pathways, taking themore » molecular structure and dynamics of the protein and its solvent fully into account. Using the ultrafast photolysis of CO in the hemoprotein FixL as an example, we study the relaxation of vibrationally excited CO and evaluate the role of each of the FixL residues forming the heme pocket.« less

Mixed quantum-classical simulations of the vibrational relaxation of photolyzed carbon monoxide in a hemoprotein

NASA Astrophysics Data System (ADS)

Schubert, Alexander; Falvo, Cyril; Meier, Christoph

2016-08-01

We present mixed quantum-classical simulations on relaxation and dephasing of vibrationally excited carbon monoxide within a protein environment. The methodology is based on a vibrational surface hopping approach treating the vibrational states of CO quantum mechanically, while all remaining degrees of freedom are described by means of classical molecular dynamics. The CO vibrational states form the "surfaces" for the classical trajectories of protein and solvent atoms. In return, environmentally induced non-adiabatic couplings between these states cause transitions describing the vibrational relaxation from first principles. The molecular dynamics simulation yields a detailed atomistic picture of the energy relaxation pathways, taking the molecular structure and dynamics of the protein and its solvent fully into account. Using the ultrafast photolysis of CO in the hemoprotein FixL as an example, we study the relaxation of vibrationally excited CO and evaluate the role of each of the FixL residues forming the heme pocket.

Normal-mode selectivity in ultrafast Raman excitations in C60

NASA Astrophysics Data System (ADS)

Zhang, G. P.; George, Thomas F.

2006-01-01

Ultrafast Raman spectra are a powerful tool to probe vibrational excitations, but inherently they are not normal-mode specific. For a system as complicated as C60 , there is no general rule to target a specific mode. A detailed study presented here aims to investigate normal-mode selectivity in C60 by an ultrafast laser. To accurately measure mode excitation, we formally introduce the kinetic-energy-based normal-mode analysis which overcomes the difficulty with the strong lattice anharmonicity and relaxation. We first investigate the resonant excitation and find that mode selectivity is normally difficult to achieve. However, for off-resonant excitations, it is possible to selectively excite a few modes in C60 by properly choosing an optimal laser pulse duration, which agrees with previous experimental and theoretical findings. Going beyond the phenomenological explanation, our study shines new light on the origin of the optimal duration: The phase matching between the laser field and mode vibration determines which mode is strongly excited or suppressed. This finding is very robust and should be a useful guide for future experimental and theoretical studies in more complicated systems.

Normal mode selectivity in ultrafast Raman excitations in C60

NASA Astrophysics Data System (ADS)

Zhang, Guoping; George, Thomas F.

2006-05-01

Ultrafast Raman spectra are a powerful tool to probe vibrational excitations, but inherently they are not normal-mode specific. For a system as complicated as C60, there is no general rule to target a specific mode. A detailed study presented here aims to investigate normal mode selectivity in C60 by an ultrafast laser. To accurately measure mode excitation, we formally introduce the kinetic energy-based normal mode analysis which overcomes the difficulty with the strong lattice anharmonicity and relaxation. We first investigate the resonant excitation and find that mode selectivity is normally difficult to achieve. However, for off-resonant excitations, it is possible to selectively excite a few modes in C60 by properly choosing an optimal laser pulse duration, which agrees with previous experimental and theoretical findings. Going beyond the phenomenological explanation, our study shines new light on the origin of the optimal duration: The phase matching between laser field and mode vibration determines which mode is strongly excited or suppressed. This finding is very robust and may be a useful guide for future experimental and theoretical studies in more complicated systems.

Direct and simultaneous observation of ultrafast electron and hole dynamics in germanium

DOE PAGES

Zurch, Michael; Chang, Hung -Tzu; Borja, Lauren J.; ...

2017-06-01

Understanding excited carrier dynamics in semiconductors is crucial for the development of photovoltaics and efficient photonic devices. However, overlapping spectral features in optical pump-probe spectroscopy often render assignments of separate electron and hole carrier dynamics ambiguous. Here, ultrafast electron and hole dynamics in germanium nanocrystalline thin films are directly and simultaneously observed by ultrafast transient absorption spectroscopy in the extreme ultraviolet at the germanium M 4,5 edge. We decompose the spectra into contributions of electronic state blocking and photo-induced band shifts at a carrier density of 8 × 10 20 cm –3. Separate electron and hole relaxation times are observedmore » as a function of hot carrier energies. A first-order electron and hole decay of ~1 ps suggests a Shockley–Read–Hall recombination mechanism. Furthermore, the simultaneous observation of electrons and holes with extreme ultraviolet transient absorption spectroscopy paves the way for investigating few- to sub-femtosecond dynamics of both holes and electrons in complex semiconductor materials and across junctions.« less

Direct and simultaneous observation of ultrafast electron and hole dynamics in germanium

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

Zurch, Michael; Chang, Hung -Tzu; Borja, Lauren J.

Understanding excited carrier dynamics in semiconductors is crucial for the development of photovoltaics and efficient photonic devices. However, overlapping spectral features in optical pump-probe spectroscopy often render assignments of separate electron and hole carrier dynamics ambiguous. Here, ultrafast electron and hole dynamics in germanium nanocrystalline thin films are directly and simultaneously observed by ultrafast transient absorption spectroscopy in the extreme ultraviolet at the germanium M 4,5 edge. We decompose the spectra into contributions of electronic state blocking and photo-induced band shifts at a carrier density of 8 × 10 20 cm –3. Separate electron and hole relaxation times are observedmore » as a function of hot carrier energies. A first-order electron and hole decay of ~1 ps suggests a Shockley–Read–Hall recombination mechanism. Furthermore, the simultaneous observation of electrons and holes with extreme ultraviolet transient absorption spectroscopy paves the way for investigating few- to sub-femtosecond dynamics of both holes and electrons in complex semiconductor materials and across junctions.« less

Vibronic coupling explains the ultrafast carotenoid-to-bacteriochlorophyll energy transfer in natural and artificial light harvesters

NASA Astrophysics Data System (ADS)

Perlík, Václav; Seibt, Joachim; Cranston, Laura J.; Cogdell, Richard J.; Lincoln, Craig N.; Savolainen, Janne; Šanda, František; Mančal, Tomáš; Hauer, Jürgen

2015-06-01

The initial energy transfer steps in photosynthesis occur on ultrafast timescales. We analyze the carotenoid to bacteriochlorophyll energy transfer in LH2 Marichromatium purpuratum as well as in an artificial light-harvesting dyad system by using transient grating and two-dimensional electronic spectroscopy with 10 fs time resolution. We find that Förster-type models reproduce the experimentally observed 60 fs transfer times, but overestimate coupling constants, which lead to a disagreement with both linear absorption and electronic 2D-spectra. We show that a vibronic model, which treats carotenoid vibrations on both electronic ground and excited states as part of the system's Hamiltonian, reproduces all measured quantities. Importantly, the vibronic model presented here can explain the fast energy transfer rates with only moderate coupling constants, which are in agreement with structure based calculations. Counterintuitively, the vibrational levels on the carotenoid electronic ground state play the central role in the excited state population transfer to bacteriochlorophyll; resonance between the donor-acceptor energy gap and the vibrational ground state energies is the physical basis of the ultrafast energy transfer rates in these systems.

Energy relaxation mechanisms in capacitively shunted flux qubits

NASA Astrophysics Data System (ADS)

Corcoles, Antonio; Rozen, Jim; Rothwell, Mary Beth; Keefe, George; di Vincenzo, David; Ketchen, Mark; Chow, Jerry; Rigetti, Chad; Rohrs, Jack; Borstelmann, Mark; Steffen, Matthias; IBM Quantum Computing Group Team

2011-03-01

Energy losses in superconducting qubits remain a major object of study in the road towards scalable, highly coherent qubit devices. The current understanding of the loss mechanisms in these devices is far from being complete and it is sometimes difficult to experimentally separate the different contributions to decoherence. Here we compare a traditional three Josephson-junction flux qubit to the recently implemented capacitively shunted flux qubit, whose energy decay is thought to be limited by dielectric losses arising from native oxides in the shunting capacitor. Keeping all parameters identical except for the shunting capacitance, we obtain energy relaxation times that are comparable for both types of qubit. This suggests that the energy relaxation time is not limited by junction losses in capacitively shunted flux qubits. We discuss some other possible loss mechanisms present in these devices.

Optically detecting the edge-state of a three-dimensional topological insulator under ambient conditions by ultrafast infrared photoluminescence spectroscopy

PubMed Central

Maezawa, Shun-ya; Watanabe, Hiroshi; Takeda, Masahiro; Kuroda, Kenta; Someya, Takashi; Matsuda, Iwao; Suemoto, Tohru

2015-01-01

Ultrafast infrared photoluminescence spectroscopy was applied to a three-dimensional topological insulator TlBiSe2 under ambient conditions. The dynamics of the luminescence exhibited bulk-insulating and gapless characteristics bounded by the bulk band gap energy. The existence of the topologically protected surface state and the picosecond-order relaxation time of the surface carriers, which was distinguishable from the bulk response, were observed. Our results provide a practical method applicable to topological insulators under ambient conditions for device applications. PMID:26552784

Energy thresholds of discrete breathers in thermal equilibrium and relaxation processes.

PubMed

Ming, Yi; Ling, Dong-Bo; Li, Hui-Min; Ding, Ze-Jun

2017-06-01

So far, only the energy thresholds of single discrete breathers in nonlinear Hamiltonian systems have been analytically obtained. In this work, the energy thresholds of discrete breathers in thermal equilibrium and the energy thresholds of long-lived discrete breathers which can remain after a long time relaxation are analytically estimated for nonlinear chains. These energy thresholds are size dependent. The energy thresholds of discrete breathers in thermal equilibrium are the same as the previous analytical results for single discrete breathers. The energy thresholds of long-lived discrete breathers in relaxation processes are different from the previous results for single discrete breathers but agree well with the published numerical results known to us. Because real systems are either in thermal equilibrium or in relaxation processes, the obtained results could be important for experimental detection of discrete breathers.

Fast responses from slowly relaxing'' liquids: A comparative study of the femtosecond dynamics of triacetin, ethylene glycol, and water

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

Chang, Y.J.; Castner, E.W. Jr.

1993-11-15

We have measured the ultrafast solvent relaxation of liquid ethylene glycol, triacetin, and water by means of femtosecond polarization spectroscopy, using optical-heterodyne-detected Raman-induced Kerr-effect spectroscopy. In the viscous liquids triacetin and ethylene glycol, femtosecond relaxation processes were resolved. Not surprisingly, the femtosecond nonlinear optical response of ethylene glycol is quite similar to that of water. Using the theory of Maroncelli, Kumar, and Papazyan, we transform the pure-nuclear solvent response into a dipolar-solvation correlation function for comparison with ultrafast electron-transfer reaction rates.

Fast responses from ``slowly relaxing'' liquids: A comparative study of the femtosecond dynamics of triacetin, ethylene glycol, and water

NASA Astrophysics Data System (ADS)

Chang, Yong Joon; Castner, Edward W., Jr.

1993-11-01

We have measured the ultrafast solvent relaxation of liquid ethylene glycol, triacetin, and water by means of femtosecond polarization spectroscopy, using optical-heterodyne-detected Raman-induced Kerr-effect spectroscopy. In the viscous liquids triacetin and ethylene glycol, femtosecond relaxation processes were resolved. Not surprisingly, the femtosecond nonlinear optical response of ethylene glycol is quite similar to that of water. Using the theory of Maroncelli, Kumar, and Papazyan, we transform the pure-nuclear solvent response into a dipolar-solvation correlation function for comparison with ultrafast electron-transfer reaction rates.

Transient absorption microscopy studies of energy relaxation in graphene oxide thin film.

PubMed

Murphy, Sean; Huang, Libai

2013-04-10

Spatial mapping of energy relaxation in graphene oxide (GO) thin films has been imaged using transient absorption microscopy (TAM). Correlated AFM images allow us to accurately determine the thickness of the GO films. In contrast to previous studies, correlated TAM-AFM allows determination of the effect of interactions of GO with the substrate and between stacked GO layers on the relaxation dynamics. Our results show that energy relaxation in GO flakes has little dependence on the substrate, number of stacked layers, and excitation intensity. This is in direct contrast to pristine graphene, where these factors have great consequences in energy relaxation. This suggests intrinsic factors rather than extrinsic ones dominate the excited state dynamics of GO films.

Ultrafast formation of the benzoic acid triplet upon ultraviolet photolysis and its sequential photodissociation in solution

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

Yang Chunfan; Su Hongmei; Sun Xuezhong

2012-05-28

Time-resolved infrared (TR-IR) absorption spectroscopy in both the femtosecond and nanosecond time domain has been applied to examine the photolysis of benzoic acid in acetonitrile solution following either 267 nm or 193 nm excitation. By combining the ultrafast and nanosecond TR-IR measurements, both the excited states and the photofragments have been detected and key mechanistic insights were obtained. We show that the solvent interaction modifies the excited state relaxation pathways and thus the population dynamics, leading to different photolysis behavior in solution from that observed in the gas phase. Vibrational energy transfer to solvents dissipates excitation energy efficiently, suppressing themore » photodissociation and depopulating the excited S{sub 2} or S{sub 3} state molecules to the lowest T{sub 1} state with a rate of {approx}2.5 ps after a delayed onset of {approx}3.7 ps. Photolysis of benzoic acid using 267 nm excitation is dominated by the formation of the T{sub 1} excited state and no photofragments could be detected. The results from TR-IR experiments using higher energy of 193 nm indicate that photodissociation proceeds more rapidly than the vibrational energy transfer to solvents and C-C bond fission becomes the dominant relaxation pathway in these experiments as featured by the prominent observation of the COOH photofragments and negligible yield of the T{sub 1} excited state. The measured ultrafast formation of T{sub 1} excited state supports the existence of the surface intersections of S{sub 2}/S{sub 1}, S{sub 2}/T{sub 2}, and S{sub 1}/T{sub 1}/T{sub 2}, and the large T{sub 1} quantum yield of {approx}0.65 indicates the importance of the excited state depopulation to triplet manifold as the key factor affecting the photophysical and photochemical behavior of the monomeric benzoic acid.« less

Ultrafast Science Opportunities with Electron Microscopy

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

Durr, Hermann

X-rays and electrons are two of the most fundamental probes of matter. When the Linac Coherent Light Source (LCLS), the world’s first x-ray free electron laser, began operation in 2009, it transformed ultrafast science with the ability to generate laser-like x-ray pulses from the manipulation of relativistic electron beams. This document describes a similar future transformation. In Transmission Electron Microscopy, ultrafast relativistic (MeV energy) electron pulses can achieve unsurpassed spatial and temporal resolution. Ultrafast temporal resolution will be the next frontier in electron microscopy and can ideally complement ultrafast x-ray science done with free electron lasers. This document describes themore » Grand Challenge science opportunities in chemistry, material science, physics and biology that arise from an MeV ultrafast electron diffraction & microscopy facility, especially when coupled with linac-based intense THz and X-ray pump capabilities.« less

Mapping momentum-dependent electron-phonon coupling and nonequilibrium phonon dynamics with ultrafast electron diffuse scattering

NASA Astrophysics Data System (ADS)

Stern, Mark J.; René de Cotret, Laurent P.; Otto, Martin R.; Chatelain, Robert P.; Boisvert, Jean-Philippe; Sutton, Mark; Siwick, Bradley J.

2018-04-01

Despite their fundamental role in determining material properties, detailed momentum-dependent information on the strength of electron-phonon and phonon-phonon coupling (EPC and PPC, respectively) across the entire Brillouin zone has remained elusive. Here we demonstrate that ultrafast electron diffuse scattering (UEDS) directly provides such information. By exploiting symmetry-based selection rules and time resolution, scattering from different phonon branches can be distinguished even without energy resolution. Using graphite as a model system, we show that UEDS patterns map the relative EPC and PPC strength through their profound sensitivity to photoinduced changes in phonon populations. We measure strong EPC to the K -point TO phonon of A1' symmetry (K -A1' ) and along the entire TO branch between Γ -K , not only to the Γ -E2 g phonon. We also determine that the subsequent phonon relaxation of these strongly coupled optical phonons involve three stages: decay via several identifiable channels to TA and LA phonons (1 -2 ps), intraband thermalization of the non-equilibrium TA/LA phonon populations (30 -40 ps) and interband relaxation of the TA/LA modes (115 ps). Combining UEDS with ultrafast angle-resolved photoelectron spectroscopy will yield a complete picture of the dynamics within and between electron and phonon subsystems, helping to unravel complex phases in which the intertwined nature of these systems has a strong influence on emergent properties.

A Static Picture of the Relaxation and Intersystem Crossing Mechanisms of Photoexcited 2-Thiouracil

PubMed Central

2015-01-01

Accurate excited-state quantum chemical calculations on 2-thiouracil, employing large active spaces and up to quadruple-ζ quality basis sets in multistate complete active space perturbation theory calculations, are reported. The results suggest that the main relaxation path for 2-thiouracil after photoexcitation should be S2 → S1 → T2 → T1, and that this relaxation occurs on a subpicosecond time scale. There are two deactivation pathways from the initially excited bright S2 state to S1, one of which is nearly barrierless and should promote ultrafast internal conversion. After relaxation to the S1 minimum, small singlet–triplet energy gaps and spin–orbit couplings of about 130 cm–1 are expected to facilitate intersystem crossing to T2, from where very fast internal conversion to T1 occurs. An important finding is that 2-thiouracil shows strong pyramidalization at the carbon atom of the thiocarbonyl group in several excited states. PMID:26284285

Ultrafast dynamics of electrons in ammonia.

PubMed

Vöhringer, Peter

2015-04-01

Solvated electrons were first discovered in solutions of metals in liquid ammonia. The physical and chemical properties of these species have been studied extensively for many decades using an arsenal of electrochemical, spectroscopic, and theoretical techniques. Yet, in contrast to their hydrated counterpart, the ultrafast dynamics of ammoniated electrons remained completely unexplored until quite recently. Femtosecond pump-probe spectroscopy on metal-ammonia solutions and femtosecond multiphoton ionization spectroscopy on the neat ammonia solvent have provided new insights into the optical properties and the reactivities of this fascinating species. This article reviews the nature of the optical transition, which gives the metal-ammonia solutions their characteristic blue appearance, in terms of ultrafast relaxation processes involving bound and continuum excited states. The recombination processes following the injection of an electron via photoionization of the solvent are discussed in the context of the electronic structure of the liquid and the anionic defect associated with the solvated electron.

Simulating Energy Relaxation in Pump-Probe Vibrational Spectroscopy of Hydrogen-Bonded Liquids.

PubMed

Dettori, Riccardo; Ceriotti, Michele; Hunger, Johannes; Melis, Claudio; Colombo, Luciano; Donadio, Davide

2017-03-14

We introduce a nonequilibrium molecular dynamics simulation approach, based on the generalized Langevin equation, to study vibrational energy relaxation in pump-probe spectroscopy. A colored noise thermostat is used to selectively excite a set of vibrational modes, leaving the other modes nearly unperturbed, to mimic the effect of a monochromatic laser pump. Energy relaxation is probed by analyzing the evolution of the system after excitation in the microcanonical ensemble, thus providing direct information about the energy redistribution paths at the molecular level and their time scale. The method is applied to hydrogen-bonded molecular liquids, specifically deuterated methanol and water, providing a robust picture of energy relaxation at the molecular scale.

Vibronic coupling explains the ultrafast carotenoid-to-bacteriochlorophyll energy transfer in natural and artificial light harvesters

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

Perlík, Václav; Seibt, Joachim; Šanda, František

The initial energy transfer steps in photosynthesis occur on ultrafast timescales. We analyze the carotenoid to bacteriochlorophyll energy transfer in LH2 Marichromatium purpuratum as well as in an artificial light-harvesting dyad system by using transient grating and two-dimensional electronic spectroscopy with 10 fs time resolution. We find that Förster-type models reproduce the experimentally observed 60 fs transfer times, but overestimate coupling constants, which lead to a disagreement with both linear absorption and electronic 2D-spectra. We show that a vibronic model, which treats carotenoid vibrations on both electronic ground and excited states as part of the system’s Hamiltonian, reproduces all measuredmore » quantities. Importantly, the vibronic model presented here can explain the fast energy transfer rates with only moderate coupling constants, which are in agreement with structure based calculations. Counterintuitively, the vibrational levels on the carotenoid electronic ground state play the central role in the excited state population transfer to bacteriochlorophyll; resonance between the donor-acceptor energy gap and the vibrational ground state energies is the physical basis of the ultrafast energy transfer rates in these systems.« less

Rippling ultrafast dynamics of suspended 2D monolayers, graphene.

PubMed

Hu, Jianbo; Vanacore, Giovanni M; Cepellotti, Andrea; Marzari, Nicola; Zewail, Ahmed H

2016-10-25

Here, using ultrafast electron crystallography (UEC), we report the observation of rippling dynamics in suspended monolayer graphene, the prototypical and most-studied 2D material. The high scattering cross-section for electron/matter interaction, the atomic-scale spatial resolution, and the ultrafast temporal resolution of UEC represent the key elements that make this technique a unique tool for the dynamic investigation of 2D materials, and nanostructures in general. We find that, at early time after the ultrafast optical excitation, graphene undergoes a lattice expansion on a time scale of 5 ps, which is due to the excitation of short-wavelength in-plane acoustic phonon modes that stretch the graphene plane. On a longer time scale, a slower thermal contraction with a time constant of 50 ps is observed and associated with the excitation of out-of-plane phonon modes, which drive the lattice toward thermal equilibrium with the well-known negative thermal expansion coefficient of graphene. From our results and first-principles lattice dynamics and out-of-equilibrium relaxation calculations, we quantitatively elucidate the deformation dynamics of the graphene unit cell.

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.

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

Transverse Mode Dynamics and Ultrafast Modulation of Vertical-Cavity Surface-Emitting Lasers

NASA Technical Reports Server (NTRS)

Ning, Cun-Zheng; Biegel, Bryan A. (Technical Monitor)

2002-01-01

We show that multiple transverse mode dynamics of VCSELs (Vertical-Cavity Surface-Emitting Lasers) can be utilized to generate ultrafast intensity modulation at a frequency over 100 GHz, much higher than the relaxation oscillation frequency. Such multimode beating can be greatly enhanced by taking laser output from part of the output facet.

Redox Conditions Affect Ultrafast Exciton Transport in Photosynthetic Pigment-Protein Complexes.

PubMed

Allodi, Marco A; Otto, John P; Sohail, Sara H; Saer, Rafael G; Wood, Ryan E; Rolczynski, Brian S; Massey, Sara C; Ting, Po-Chieh; Blankenship, Robert E; Engel, Gregory S

2018-01-04

Pigment-protein complexes in photosynthetic antennae can suffer oxidative damage from reactive oxygen species generated during solar light harvesting. How the redox environment of a pigment-protein complex affects energy transport on the ultrafast light-harvesting time scale remains poorly understood. Using two-dimensional electronic spectroscopy, we observe differences in femtosecond energy-transfer processes in the Fenna-Matthews-Olson (FMO) antenna complex under different redox conditions. We attribute these differences in the ultrafast dynamics to changes to the system-bath coupling around specific chromophores, and we identify a highly conserved tyrosine/tryptophan chain near the chromophores showing the largest changes. We discuss how the mechanism of tyrosine/tryptophan chain oxidation may contribute to these differences in ultrafast dynamics that can moderate energy transfer to downstream complexes where reactive oxygen species are formed. These results highlight the importance of redox conditions on the ultrafast transport of energy in photosynthesis. Tailoring the redox environment may enable energy transport engineering in synthetic light-harvesting systems.

Distinctive Spectral Features of Exciton and Excimer States in the Ultrafast Electronic Deactivation of the Adenine Dinucleotide

NASA Astrophysics Data System (ADS)

Stuhldreier, Mayra C.; Röttger, Katharina; Temps, Friedrich

We report the observation by transient absorption spectroscopy of distinctive spectro-temporal signatures of delocalized exciton versus relaxed, weakly bound excimer states in the ultrafast electronic deactivation after UV photoexcitation of the adenine dinucleotide.

Enhanced ultrafast relaxation rate in the Weyl semimetal phase of MoTe2 measured by time- and angle-resolved photoelectron spectroscopy

NASA Astrophysics Data System (ADS)

Crepaldi, A.; Autès, G.; Gatti, G.; Roth, S.; Sterzi, A.; Manzoni, G.; Zacchigna, M.; Cacho, C.; Chapman, R. T.; Springate, E.; Seddon, E. A.; Bugnon, Ph.; Magrez, A.; Berger, H.; Vobornik, I.; Kalläne, M.; Quer, A.; Rossnagel, K.; Parmigiani, F.; Yazyev, O. V.; Grioni, M.

2017-12-01

MoTe2 has recently been shown to realize in its low-temperature phase the type-II Weyl semimetal (WSM). We investigated by time- and angle- resolved photoelectron spectroscopy (tr-ARPES) the possible influence of the Weyl points on the electron dynamics above the Fermi level EF, by comparing the ultrafast response of MoTe2 in the trivial and topological phases. In the low-temperature WSM phase, we report an enhanced relaxation rate of electrons optically excited to the conduction band, which we interpret as a fingerprint of the local gap closure when Weyl points form. By contrast, we find that the electron dynamics of the related compound WTe2 is slower and temperature independent, consistent with a topologically trivial nature of this material. Our results shows that tr-ARPES is sensitive to the small modifications of the unoccupied band structure accompanying the structural and topological phase transition of MoTe2.

Microscopic origins of the terahertz carrier relaxation and cooling dynamics in graphene

PubMed Central

Mihnev, Momchil T.; Kadi, Faris; Divin, Charles J.; Winzer, Torben; Lee, Seunghyun; Liu, Che-Hung; Zhong, Zhaohui; Berger, Claire; de Heer, Walt A.; Malic, Ermin; Knorr, Andreas; Norris, Theodore B.

2016-01-01

The ultrafast dynamics of hot carriers in graphene are key to both understanding of fundamental carrier–carrier interactions and carrier–phonon relaxation processes in two-dimensional materials, and understanding of the physics underlying novel high-speed electronic and optoelectronic devices. Many recent experiments on hot carriers using terahertz spectroscopy and related techniques have interpreted the variety of observed signals within phenomenological frameworks, and sometimes invoke extrinsic effects such as disorder. Here, we present an integrated experimental and theoretical programme, using ultrafast time-resolved terahertz spectroscopy combined with microscopic modelling, to systematically investigate the hot-carrier dynamics in a wide array of graphene samples having varying amounts of disorder and with either high or low doping levels. The theory reproduces the observed dynamics quantitatively without the need to invoke any fitting parameters, phenomenological models or extrinsic effects such as disorder. We demonstrate that the dynamics are dominated by the combined effect of efficient carrier–carrier scattering, which maintains a thermalized carrier distribution, and carrier–optical–phonon scattering, which removes energy from the carrier liquid. PMID:27221060

Exchange and relaxation effects in low-energy radiationless transitions

NASA Technical Reports Server (NTRS)

Chen, M. H.; Crasemann, B.; Aoyagi, M.; Mark, H.

1978-01-01

The effect on low-energy atomic inner-shell Coster-Kronig and super Coster-Kronig transitions that is produced by relaxation and by exchange between the continuum electron and bound electrons was examined and illustrated by specific calculations for transitions that deexcite the 3p vacancy state of Zn. Taking exchange and relaxation into account is found to reduce, but not to eliminate, the discrepancies between theoretical rates and measurements.

Ultrafast exciton fine structure relaxation dynamics in lead chalcogenide nanocrystals.

PubMed

Johnson, Justin C; Gerth, Kathrine A; Song, Qing; Murphy, James E; Nozik, Arthur J; Scholes, Gregory D

2008-05-01

The rates of fine structure relaxation in PbS, PbSe, and PbTe nanocrystals were measured on a femtosecond time scale as a function of temperature with no applied magnetic field by cross-polarized transient grating spectroscopy (CPTG) and circularly polarized pump-probe spectroscopy. The relaxation rates among exciton fine structure states follow trends with nanocrystal composition and size that are consistent with the expected influence of material dependent spin-orbit coupling, confinement enhanced electron-hole exchange interaction, and splitting between L valleys that are degenerate in the bulk. The size dependence of the fine structure relaxation rate is considerably different from what is observed for small CdSe nanocrystals, which appears to result from the unique material properties of the highly confined lead chalcogenide quantum dots. Modeling and qualitative considerations lead to conclusions about the fine structure of the lowest exciton absorption band, which has a potentially significant bearing on photophysical processes that make these materials attractive for practical purposes.

Hot carrier and hot phonon coupling during ultrafast relaxation of photoexcited electrons in graphene

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

Iglesias, J. M.; Martín, M. J.; Pascual, E.

2016-01-25

We study, by means of a Monte Carlo simulator, the hot phonon effect on the relaxation dynamics in photoexcited graphene and its quantitative impact as compared with considering an equilibrium phonon distribution. Our multi-particle approach indicates that neglecting the hot phonon effect significantly underestimates the relaxation times in photoexcited graphene. The hot phonon effect is more important for a higher energy of the excitation pulse and photocarrier densities between 1 and 3 × 10{sup 12 }cm{sup −2}. Acoustic intervalley phonons play a non-negligible role, and emitted phonons with wavelengths limited up by a maximum (determined by the carrier concentration) induce a slower carriermore » cooling rate. Intrinsic phonon heating is damped in graphene on a substrate due to the additional cooling pathways, with the hot phonon effect showing a strong inverse dependence with the carrier density.« less

Harmonium: An Ultrafast Vacuum Ultraviolet Facility.

PubMed

Arrell, Christopher A; Ojeda, José; Longetti, Luca; Crepaldi, Alberto; Roth, Silvan; Gatti, Gianmarco; Clark, Andrew; van Mourik, Frank; Drabbels, Marcel; Grioni, Marco; Chergui, Majed

2017-05-31

Harmonium is a vacuum ultraviolet (VUV) photon source built within the Lausanne Centre for Ultrafast Science (LACUS). Utilising high harmonic generation, photons from 20-110 eV are available to conduct steady-state or ultrafast photoelectron and photoion spectroscopies (PES and PIS). A pulse preserving monochromator provides either high energy resolution (70 meV) or high temporal resolution (40 fs). Three endstations have been commissioned for: a) PES of liquids; b) angular resolved PES (ARPES) of solids and; c) coincidence PES and PIS of gas phase molecules or clusters. The source has several key advantages: high repetition rate (up to 15 kHz) and high photon flux (1011 photons per second at 38 eV). The capabilities of the facility complement the Swiss ultrafast and X-ray community (SwissFEL, SLS, NCCR MUST, etc.) helping to maintain Switzerland's leading role in ultrafast science in the world.

Ultrafast Phenomena XIV

NASA Astrophysics Data System (ADS)

Kobayashi, Takayoshi; Okada, Tadashi; Kobayashi, Tetsuro; Nelson, Keith A.; de Silvestri, Sandro

Ultrafast Phenomena XIV presents the latest advances in ultrafast science, including ultrafast laser and measurement technology as well as studies of ultrafast phenomena. Pico-, femto-, and atosecond processes relevant in physics, chemistry, biology, and engineering are presented. Ultrafast technology is now having a profound impact within a wide range of applications, among them imaging, material diagnostics, and transformation and high-speed optoelectronics . This book summarizes results presented at the 14th Ultrafast Phenomena Conference and reviews the state of the art in this important and rapidly advancing field.

Rippling ultrafast dynamics of suspended 2D monolayers, graphene

PubMed Central

Hu, Jianbo; Vanacore, Giovanni M.; Cepellotti, Andrea; Marzari, Nicola; Zewail, Ahmed H.

2016-01-01

Here, using ultrafast electron crystallography (UEC), we report the observation of rippling dynamics in suspended monolayer graphene, the prototypical and most-studied 2D material. The high scattering cross-section for electron/matter interaction, the atomic-scale spatial resolution, and the ultrafast temporal resolution of UEC represent the key elements that make this technique a unique tool for the dynamic investigation of 2D materials, and nanostructures in general. We find that, at early time after the ultrafast optical excitation, graphene undergoes a lattice expansion on a time scale of 5 ps, which is due to the excitation of short-wavelength in-plane acoustic phonon modes that stretch the graphene plane. On a longer time scale, a slower thermal contraction with a time constant of 50 ps is observed and associated with the excitation of out-of-plane phonon modes, which drive the lattice toward thermal equilibrium with the well-known negative thermal expansion coefficient of graphene. From our results and first-principles lattice dynamics and out-of-equilibrium relaxation calculations, we quantitatively elucidate the deformation dynamics of the graphene unit cell. PMID:27791028

Origin of the Ultrafast Response of the Lateral Photovoltaic Effect in Amorphous MoS2/Si Junctions.

PubMed

Hu, Chang; Wang, Xianjie; Miao, Peng; Zhang, Lingli; Song, Bingqian; Liu, Weilong; Lv, Zhe; Zhang, Yu; Sui, Yu; Tang, Jinke; Yang, Yanqiang; Song, Bo; Xu, Ping

2017-05-31

The lateral photovoltaic (LPV) effect has attracted much attention for a long time because of its application in position-sensitive detectors (PSD). Here, we report the ultrafast response of the LPV in amorphous MoS 2 /Si (a-MoS 2 /Si) junctions prepared by the pulsed laser deposition (PLD) technique. Different orientations of the built-in field and the breakover voltages are observed for a-MoS 2 films deposited on p- and n-type Si wafers, resulting in the induction of positive and negative voltages in the a-MoS 2 /n-Si and a-MoS 2 /p-Si junctions upon laser illumination, respectively. The dependence of the LPV on the position of the illumination shows very high sensitivity (183 mV mm -1 ) and good linearity. The optical relaxation time of LPV with a positive voltage was about 5.8 μs in a-MoS 2 /n-Si junction, whereas the optical relaxation time of LPV with a negative voltage was about 2.1 μs in a-MoS 2 /p-Si junction. Our results clearly suggested that the inversion layer at the a-MoS 2 /Si interface made a good contribution to the ultrafast response of the LPV in a-MoS 2 /Si junctions. The large positional sensitivity and ultrafast relaxation of LPV may promise the a-MoS 2 /Si junction's applications in fast position-sensitive detectors.

Ultrafast time-resolved carotenoid to-bacteriochlorophyll energy transfer in LH2 complexes from photosynthetic bacteria.

PubMed

Cong, Hong; Niedzwiedzki, Dariusz M; Gibson, George N; LaFountain, Amy M; Kelsh, Rhiannon M; Gardiner, Alastair T; Cogdell, Richard J; Frank, Harry A

2008-08-28

Steady-state and ultrafast time-resolved optical spectroscopic investigations have been carried out at 293 and 10 K on LH2 pigment-protein complexes isolated from three different strains of photosynthetic bacteria: Rhodobacter (Rb.) sphaeroides G1C, Rb. sphaeroides 2.4.1 (anaerobically and aerobically grown), and Rps. acidophila 10050. The LH2 complexes obtained from these strains contain the carotenoids, neurosporene, spheroidene, spheroidenone, and rhodopin glucoside, respectively. These molecules have a systematically increasing number of pi-electron conjugated carbon-carbon double bonds. Steady-state absorption and fluorescence excitation experiments have revealed that the total efficiency of energy transfer from the carotenoids to bacteriochlorophyll is independent of temperature and nearly constant at approximately 90% for the LH2 complexes containing neurosporene, spheroidene, spheroidenone, but drops to approximately 53% for the complex containing rhodopin glucoside. Ultrafast transient absorption spectra in the near-infrared (NIR) region of the purified carotenoids in solution have revealed the energies of the S1 (2(1)Ag-)-->S2 (1(1)Bu+) excited-state transitions which, when subtracted from the energies of the S0 (1(1)Ag-)-->S2 (1(1)Bu+) transitions determined by steady-state absorption measurements, give precise values for the positions of the S1 (2(1)Ag-) states of the carotenoids. Global fitting of the ultrafast spectral and temporal data sets have revealed the dynamics of the pathways of de-excitation of the carotenoid excited states. The pathways include energy transfer to bacteriochlorophyll, population of the so-called S* state of the carotenoids, and formation of carotenoid radical cations (Car*+). The investigation has found that excitation energy transfer to bacteriochlorophyll is partitioned through the S1 (1(1)Ag-), S2 (1(1)Bu+), and S* states of the different carotenoids to varying degrees. This is understood through a consideration of the

Ultrafast dynamics of localized magnetic moments in the unconventional Mott insulator Sr 2IrO 4

DOE PAGES

Krupin, O.; Dakovski, G. L.; Kim, B. J.; ...

2016-06-16

Here, we report a time-resolved study of the ultrafast dynamics of the magnetic moments formed by themore » $${{J}_{\\text{eff}}}=1/2$$ states in Sr 2IrO 4 by directly probing the localized iridium 5d magnetic state through resonant x-ray diffraction. Using optical pump–hard x-ray probe measurements, two relaxation time scales were determined: a fast fluence-independent relaxation is found to take place on a time scale of 1.5 ps, followed by a slower relaxation on a time scale of 500 ps–1.5 ns.« less

Charge and spin control of ultrafast electron and hole dynamics in single CdSe/ZnSe quantum dots

NASA Astrophysics Data System (ADS)

Hinz, C.; Gumbsheimer, P.; Traum, C.; Holtkemper, M.; Bauer, B.; Haase, J.; Mahapatra, S.; Frey, A.; Brunner, K.; Reiter, D. E.; Kuhn, T.; Seletskiy, D. V.; Leitenstorfer, A.

2018-01-01

We study the dynamics of photoexcited electrons and holes in single negatively charged CdSe/ZnSe quantum dots with two-color femtosecond pump-probe spectroscopy. An initial characterization of the energy level structure is performed at low temperatures and magnetic fields of up to 5 T. Emission and absorption resonances are assigned to specific transitions between few-fermion states by a theoretical model based on a configuration interaction approach. To analyze the dynamics of individual charge carriers, we initialize the quantum system into excited trion states with defined energy and spin. Subsequently, the time-dependent occupation of the trion ground state is monitored by spectrally resolved differential transmission measurements. We observe subpicosecond dynamics for a hole excited to the D shell. The energy dependence of this D -to-S shell intraband transition is investigated in quantum dots of varying size. Excitation of an electron-hole pair in the respective p shells leads to the formation of singlet and triplet spin configurations. Relaxation of the p -shell singlet is observed to occur on a time scale of a few picoseconds. Pumping of p -shell triplet transitions opens up two pathways with distinctly different scattering times. These processes are shown to be governed by the mixing of singlet and triplet states due to exchange interactions enabling simultaneous electron and hole spin flips. To isolate the relaxation channels, we align the spin of the residual electron by a magnetic field and employ laser pulses of defined helicity. This step provides ultrafast preparation of a fully inverted trion ground state of the quantum dot with near unity probability, enabling deterministic addition of a single photon to the probe pulse. Therefore our experiments represent a significant step towards using single quantum emitters with well-controled inversion to manipulate the photon statistics of ultrafast light pulses.

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

Self-phase modulation enabled, wavelength-tunable ultrafast fiber laser sources: an energy scalable approach.

PubMed

Liu, Wei; Li, Chen; Zhang, Zhigang; Kärtner, Franz X; Chang, Guoqing

2016-07-11

We propose and demonstrate a new approach to implement a wavelength-tunable ultrafast fiber laser source suitable for multiphoton microscopy. We employ fiber-optic nonlinearities to broaden a narrowband optical spectrum generated by an Yb-fiber laser system and then use optical bandpass filters to select the leftmost or rightmost spectral lobes from the broadened spectrum. Detailed numerical modeling shows that self-phase modulation dominates the spectral broadening, self-steepening tends to blue shift the broadened spectrum, and stimulated Raman scattering is minimal. We also find that optical wave breaking caused by fiber dispersion slows down the shift of the leftmost/rightmost spectral lobes and therefore limits the wavelength tuning range of the filtered spectra. We show both numerically and experimentally that shortening the fiber used for spectral broadening while increasing the input pulse energy can overcome this dispersion-induced limitation; as a result, the filtered spectral lobes have higher power, constituting a powerful and practical approach for energy scaling the resulting femtosecond sources. We use two commercially available photonic crystal fibers to verify the simulation results. More specific, use of 20-mm fiber NL-1050-ZERO-2 enables us to implement an Yb-fiber laser based ultrafast source, delivering femtosecond (70-120 fs) pulses tunable from 825 nm to 1210 nm with >1 nJ pulse energy.

Photovoltaic Properties and Ultrafast Plasmon Relaxation Dynamics of Diamond-Like Carbon Nanocomposite Films with Embedded Ag Nanoparticles.

PubMed

Meškinis, Šarūnas; Peckus, Domantas; Vasiliauskas, Andrius; Čiegis, Arvydas; Gudaitis, Rimantas; Tamulevičius, Tomas; Yaremchuk, Iryna; Tamulevičius, Sigitas

2017-12-01

Ultrafast relaxation dynamics of diamond-like carbon (DLC) films with embedded Ag nanoparticles (DLC:Ag) and photovoltaic properties of heterojunctions consisting of DLC:Ag and crystalline silicon (DLC:Ag/Si) were investigated by means of transient absorption (TAS) spectroscopy and photovoltaic measurements. The heterojunctions using both p type and n type silicon were studied. It was found that TAS spectra of DLC:Ag films were dependent on the used excitation wavelength. At wavelengths where Ag nanoparticles absorbed light most intensively, only DLC signal was registered. This result is in good accordance with an increase of the DLC:Ag/Si heterojunction short circuit current and open circuit voltage with the excitation wavelength in the photovoltaic measurements. The dependence of the TAS spectra of DLC:Ag films and photovoltaic properties of DLC:Ag/Si heterostructures on the excitation wavelength was explained as a result of trapping of the photoexcited hot charge carriers in DLC matrix. The negative photovoltaic effect was observed for DLC:Ag/p-Si heterostructures and positive ("conventional") for DLC:Ag/n-Si ones. It was explained by the excitation of hot plasmonic holes in the Ag nanoparticles embedded into DLC matrix. Some decrease of DLC:Ag/Si heterostructures photovoltage as well as photocurrent with DLC:Ag film thickness was observed, indicating role of the interface in the charge transfer process of photocarriers excited in Ag nanoparticles.

Photovoltaic Properties and Ultrafast Plasmon Relaxation Dynamics of Diamond-Like Carbon Nanocomposite Films with Embedded Ag Nanoparticles

NASA Astrophysics Data System (ADS)

Meškinis, Šarūnas; Peckus, Domantas; Vasiliauskas, Andrius; Čiegis, Arvydas; Gudaitis, Rimantas; Tamulevičius, Tomas; Yaremchuk, Iryna; Tamulevičius, Sigitas

2017-04-01

Ultrafast relaxation dynamics of diamond-like carbon (DLC) films with embedded Ag nanoparticles (DLC:Ag) and photovoltaic properties of heterojunctions consisting of DLC:Ag and crystalline silicon (DLC:Ag/Si) were investigated by means of transient absorption (TAS) spectroscopy and photovoltaic measurements. The heterojunctions using both p type and n type silicon were studied. It was found that TAS spectra of DLC:Ag films were dependent on the used excitation wavelength. At wavelengths where Ag nanoparticles absorbed light most intensively, only DLC signal was registered. This result is in good accordance with an increase of the DLC:Ag/Si heterojunction short circuit current and open circuit voltage with the excitation wavelength in the photovoltaic measurements. The dependence of the TAS spectra of DLC:Ag films and photovoltaic properties of DLC:Ag/Si heterostructures on the excitation wavelength was explained as a result of trapping of the photoexcited hot charge carriers in DLC matrix. The negative photovoltaic effect was observed for DLC:Ag/p-Si heterostructures and positive ("conventional") for DLC:Ag/n-Si ones. It was explained by the excitation of hot plasmonic holes in the Ag nanoparticles embedded into DLC matrix. Some decrease of DLC:Ag/Si heterostructures photovoltage as well as photocurrent with DLC:Ag film thickness was observed, indicating role of the interface in the charge transfer process of photocarriers excited in Ag nanoparticles.

Surface hopping investigation of the relaxation dynamics in radical cations

DOE PAGES

Assmann, Mariana; Weinacht, Thomas; Matsika, Spiridoula

2016-01-19

Ionization processes can lead to the formation of radical cations with population in several ionic states. In this study, we examine the dynamics of three radical cations starting from an excited ionic state using trajectory surface hopping dynamics in combination with multiconfigurational electronic structure methods. The efficiency of relaxation to the ground state is examined in an effort to understand better whether fragmentation of cations is likely to occur directly on excited states or after relaxation to the ground state. The results on cyclohexadiene, hexatriene, and uracil indicate that relaxation to the ground ionic state is very fast in thesemore » systems, while fragmentation before relaxation is rare. Ultrafast relaxation is facilitated by the close proximity of electronic states and the presence of two- and three-state conical intersections. Furthermore, examining the properties of the systems in the Franck-Condon region can give some insight into the subsequent dynamics.« less

Density and energy relaxation in an open one-dimensional system

NASA Astrophysics Data System (ADS)

Jose, Prasanth P.; Bagchi, Biman

2004-05-01

A new master equation to mimic the dynamics of a collection of interacting random walkers in an open system is proposed and solved numerically. In this model, the random walkers interact through excluded volume interaction (single-file system); and the total number of walkers in the lattice can fluctuate because of exchange with a bath. In addition, the movement of the random walkers is biased by an external perturbation. Two models for the latter are considered: (1) an inverse potential (V∝1/r), where r is the distance between the center of the perturbation and the random walker and (2) an inverse of sixth power potential (V∝1/r6). The calculated density of the walkers and the total energy show interesting dynamics. When the size of the system is comparable to the range of the perturbing field, the energy relaxation is found to be highly nonexponential. In this range, the system can show stretched exponential (e-(t/τs)β) and even logarithmic time dependence of energy relaxation over a limited range of time. Introduction of density exchange in the lattice markedly weakens this nonexponentiality of the relaxation function, irrespective of the nature of perturbation.

Ultrafast photophysical studies of a multicomponent sunscreen: Oxybenzone-titanium dioxide mixtures

NASA Astrophysics Data System (ADS)

Baker, Lewis A.; Grosvenor, Lucy C.; Ashfold, Michael N. R.; Stavros, Vasilios G.

2016-11-01

Recent studies of the sunscreen constituent oxybenzone have suggested that the dominant mechanism underlying the efficient photoprotection it offers relies on an initial ultrafast enol → keto tautomerisation, followed by nonadiabatic transfer to the ground electronic state. Subsequent collisions with the solvent bath then reform the original enol-tautomer. Utilising femtosecond transient electronic absorption spectroscopy we explore the dissipation of electronic excitation energy in oxybenzone in the presence of titanium dioxide, a widely used, and complementary sunscreen component. We find the relaxation dynamics of this popular organic filter are unaltered by the presence of this favoured inorganic scatterer and the overall dynamics can be described by the additive contribution of the individual constituents. The combination of the two components provides broadband photoprotective properties justifying the widely used organic filter and inorganic scatterer mixtures in commercial sunscreen products.

Ultrafast fiber lasers: practical applications

NASA Astrophysics Data System (ADS)

Pastirk, Igor; Sell, Alexander; Herda, Robert; Brodschelm, Andreas; Zach, Armin

2015-05-01

Over past three decades ultrafast lasers have come a long way from the bulky, demanding and very sensitive scientific research projects to widely available commercial products. For the majority of this period the titanium-sapphire-based ultrafast systems were the workhorse for scientific and emerging industrial and biomedical applications. However the complexity and intrinsic bulkiness of solid state lasers have prevented even larger penetration into wider array of practical applications. With emergence of femtosecond fiber lasers, based primarily on Er-doped and Yb-doped fibers that provide compact, inexpensive and dependable fs and ps pulses, new practical applications have become a reality. The overview of current state of the art ultrafast fiber sources, their basic principles and most prominent applications will be presented, including micromachining and biomedical implementations (ophthalmology) on one end of the pulse energy spectrum and 3D lithography and THz applications on the other.

Non-radiative relaxation of photoexcited chlorophylls: Theoretical and experimental study

DOE PAGES

Bricker, William P.; Shenai, Prathamesh M.; Ghosh, Avishek; ...

2015-09-08

Nonradiative relaxation of high-energy excited states to the lowest excited state in chlorophylls marks the first step in the process of photosynthesis. We perform ultrafast transient absorption spectroscopy measurements, that reveal this internal conversion dynamics to be slightly slower in chlorophyll B than in chlorophyll A. With modeling this process, non-adiabatic excited state molecular dynamics simulations uncovers a critical role played by the different side groups in the two molecules in governing the intramolecular redistribution of excited state wavefunction, leading, in turn, to different time-scales. Even given smaller electron-vibrational couplings compared to common organic conjugated chromophores, these molecules are ablemore » to efficiently dissipate about 1 eV of electronic energy into heat on the timescale of around 200 fs. This is achieved via selective participation of specific atomic groups and complex global migration of the wavefunction from the outer to inner ring, which may have important implications for biological light-harvesting function.« less

Photoinduced Ultrafast Intramolecular Excited-State Energy Transfer in the Silylene-Bridged Biphenyl and Stilbene (SBS) System: A Nonadiabatic Dynamics Point of View.

PubMed

Wang, Jun; Huang, Jing; Du, Likai; Lan, Zhenggang

2015-07-09

The photoinduced intramolecular excited-state energy-transfer (EET) process in conjugated polymers has received a great deal of research interest because of its important role in the light harvesting and energy transport of organic photovoltaic materials in photoelectric devices. In this work, the silylene-bridged biphenyl and stilbene (SBS) system was chosen as a simplified model system to obtain physical insight into the photoinduced intramolecular energy transfer between the different building units of the SBS copolymer. In the SBS system, the vinylbiphenyl and vinylstilbene moieties serve as the donor (D) unit and the acceptor (A) unit, respectively. The ultrafast excited-state dynamics of the SBS system was investigated from the point of view of nonadiabatic dynamics with the surface-hopping method at the TDDFT level. The first two excited states (S1 and S2) are characterized by local excitations at the acceptor (vinylstilbene) and donor (vinylbiphenyl) units, respectively. Ultrafast S2-S1 decay is responsible for the intramolecular D-A excitonic energy transfer. The geometric distortion of the D moiety play an essential role in this EET process, whereas the A moiety remains unchanged during the nonadiabatic dynamics simulation. The present work provides a direct dynamical approach to understand the ultrafast intramolecular energy-transfer dynamics in SBS copolymers and other similar organic photovoltaic copolymers.

Femtosecond tracking of carrier relaxation in germanium with extreme ultraviolet transient reflectivity

NASA Astrophysics Data System (ADS)

Kaplan, Christopher J.; Kraus, Peter M.; Ross, Andrew D.; Zürch, Michael; Cushing, Scott K.; Jager, Marieke F.; Chang, Hung-Tzu; Gullikson, Eric M.; Neumark, Daniel M.; Leone, Stephen R.

2018-05-01

Extreme ultraviolet (XUV) transient reflectivity around the germanium M4 ,5 edge (3 d core-level to valence transition) at 30 eV is advanced to obtain the transient dielectric function of crystalline germanium [100] on femtosecond to picosecond time scales following photoexcitation by broadband visible-to-infrared (VIS/NIR) pulses. By fitting the transient dielectric function, carrier-phonon induced relaxations are extracted for the excited carrier distribution. The measurements reveal a hot electron relaxation rate of 3.2 ±0.2 ps attributed to the X -L intervalley scattering and a hot hole relaxation rate of 600 ±300 fs ascribed to intravalley scattering within the heavy hole (HH) band, both in good agreement with previous work. An overall energy shift of the XUV dielectric function is assigned to a thermally induced band gap shrinkage by formation of acoustic phonons, which is observed to be on a timescale of 4-5 ps, in agreement with previously measured optical phonon lifetimes. The results reveal that the transient reflectivity signal at an angle of 66∘ with respect to the surface normal is dominated by changes to the real part of the dielectric function, due to the near critical angle of incidence of the experiment (66∘-70∘) for the range of XUV energies used. This work provides a methodology for interpreting XUV transient reflectivity near core-level transitions, and it demonstrates the power of the XUV spectral region for measuring ultrafast excitation dynamics in solids.

Shift in Chemical Potential of Superconducting Bi2212 Measured by Ultrafast Photoemission Spectroscopy

NASA Astrophysics Data System (ADS)

Miller, Tristan; Smallwood, Chris; Zhang, Wentao; Eisaki, Hiroshi; Lee, Dung-Hai; Lanzara, Alessandra

2015-03-01

Time- and Angle-resolved photoemission spectroscopy (tr-ARPES) has been used to directly measure the dynamics of many different properties of high-temperature superconductors, including the quasiparticle relaxation, cooper pair recombination, and many-body interactions. There have also been several intriguing results on several materials showing how laser pulses can manipulate their chemical potential on ultrafast timescales, and it's been suggested that these effects could find applications in optoelectronic devices. Studies on GaAs have also found that laser pulses may induce a surface voltage effect. Here, we extend these studies for the first time to a Bi2212 sample in the superconducting state, and disentangle the shift in chemical potential from surface voltage effects. This work was supported by Berkeley Lab's program on Quantum Materials, funded by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, Materials Sciences and Engineering Division, under Contract No. DE-AC02-05CH11231.

Ultrafast electron-optical phonon scattering and quasiparticle lifetime in CVD-grown graphene.

PubMed

Shang, Jingzhi; Yu, Ting; Lin, Jianyi; Gurzadyan, Gagik G

2011-04-26

Ultrafast quasiparticle dynamics in graphene grown by chemical vapor deposition (CVD) has been studied by UV pump/white-light probe spectroscopy. Transient differential transmission spectra of monolayer graphene are observed in the visible probe range (400-650 nm). Kinetics of the quasiparticle (i.e., low-energy single-particle excitation with renormalized energy due to electron-electron Coulomb, electron-optical phonon (e-op), and optical phonon-acoustic phonon (op-ap) interactions) was monitored with 50 fs resolution. Extending the probe range to near-infrared, we find the evolution of quasiparticle relaxation channels from monoexponential e-op scattering to double exponential decay due to e-op and op-ap scattering. Moreover, quasiparticle lifetimes of mono- and randomly stacked graphene films are obtained for the probe photon energies continuously from 1.9 to 2.3 eV. Dependence of quasiparticle decay rate on the probe energy is linear for 10-layer stacked graphene films. This is due to the dominant e-op intervalley scattering and the linear density of states in the probed electronic band. A dimensionless coupling constant W is derived, which characterizes the scattering strength of quasiparticles by lattice points in graphene.

Relaxation of a High-Energy Quasiparticle in a One-Dimensional Bose Gas

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

Tan, Shina; Glazman, Leonid I.; Pustilnik, Michael

2010-08-27

We evaluate the relaxation rate of high-energy quasiparticles in a weakly interacting one-dimensional Bose gas. Unlike in higher dimensions, the rate is a nonmonotonic function of temperature, with a maximum at the crossover to the state of suppressed density fluctuations. At the maximum, the relaxation rate may significantly exceed its zero-temperature value. We also find the dependence of the differential inelastic scattering rate on the transferred energy. This rate yields information about temperature dependence of local pair correlations.

PREFACE: Ultrafast biophotonics Ultrafast biophotonics

NASA Astrophysics Data System (ADS)

Gu, Min; Reid, Derryck; Ben-Yakar, Adela

2010-08-01

The use of light to explore biology can be traced to the first observations of tissue made with early microscopes in the mid-seventeenth century, and has today evolved into the discipline which we now know as biophotonics. This field encompasses a diverse range of activities, each of which shares the common theme of exploiting the interaction of light with biological material. With the rapid advancement of ultrafast optical technologies over the last few decades, ultrafast lasers have increasingly found applications in biophotonics, to the extent that the distinctive new field of ultrafast biophotonics has now emerged, where robust turnkey ultrafast laser systems are facilitating cutting-edge studies in the life sciences to take place in everyday laboratories. The broad spectral bandwidths, precision timing resolution, low coherence and high peak powers of ultrafast optical pulses provide unique opportunities for imaging and manipulating biological systems. Time-resolved studies of bio-molecular dynamics exploit the short pulse durations from such lasers, while other applications such as optical coherence tomography benefit from the broad optical bandwidths possible by using super-continuum generation and additionally allowing for high speed imaging with speeds as high as 47 000 scans per second. Continuing progress in laser-system technology is accelerating the adoption of ultrafast techniques across the life sciences, both in research laboratories and in clinical applications, such as laser-assisted in situ keratomileusis (LASIK) eye surgery. Revolutionizing the field of optical microscopy, two-photon excitation fluorescence (TPEF) microscopy has enabled higher spatial resolution with improved depth penetration into biological specimens. Advantages of this nonlinear optical process include: reduced photo-interactions, allowing for extensive imaging time periods; simultaneously exciting multiple fluorescent molecules with only one excitation wavelength; and

Ultrafast vibrational dynamics of BH{sub 4}{sup −} ions in liquid and crystalline environments

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

Tyborski, Tobias, E-mail: tyborski@mbi-berlin.de; Costard, Rene; Woerner, Michael

2014-07-21

Ultrafast vibrational dynamics of BH{sub 4}{sup −} ions, the key units in boron hydride materials for hydrogen storage, are studied in diluted polar liquid solution and in NaBH{sub 4} crystallites by femtosecond infrared spectroscopy. Two-color pump-probe experiments reveal v = 1 lifetimes of 3 ps for the asymmetric BH{sub 4}{sup −} stretching mode ν{sub 3} and of 3.6 ps for the asymmetric bending mode ν{sub 4} in the solvent isopropylamine. We provide direct evidence for the BH{sub 4}{sup −} stretching relaxation pathway via the asymmetric bending mode ν{sub 4} by probing the latter after femtosecond excitation of ν{sub 3}. Pump-probemore » traces measured in the crystalline phase show signatures of radiative coupling between the densely packed BH{sub 4}{sup −} oscillators, most clearly manifested in an accelerated subpicosecond depopulation of the v = 1 state of the ν{sub 4} mode. The radiative decay is followed by incoherent vibrational relaxation similar to the liquid phase. The excess energy released in the relaxation processes of the BH{sub 4}{sup −} intramolecular modes is transferred into the environment with thermal pump-probe signals being much more pronounced in the dense solid than in the diluted solution.« less

Spin relaxation dynamics of holes in intrinsic GaAs quantum wells studied by transient circular dichromatic absorption spectroscopy at room temperature.

PubMed

Fang, Shaoyin; Zhu, Ruidan; Lai, Tianshu

2017-03-21

Spin relaxation dynamics of holes in intrinsic GaAs quantum wells is studied using time-resolved circular dichromatic absorption spectroscopy at room temperature. It is found that ultrafast dynamics is dominated by the cooperative contributions of band filling and many-body effects. The relative contribution of the two effects is opposite in strength for electrons and holes. As a result, transient circular dichromatic differential transmission (TCD-DT) with co- and cross-circularly polarized pump and probe presents different strength at several picosecond delay time. Ultrafast spin relaxation dynamics of excited holes is sensitively reflected in TCD-DT with cross-circularly polarized pump and probe. A model, including coherent artifact, thermalization of nonthermal carriers and the cooperative contribution of band filling and many-body effects, is developed, and used to fit TCD-DT with cross-circularly polarized pump and probe. Spin relaxation time of holes is achieved as a function of excited hole density for the first time at room temperature, and increases with hole density, which disagrees with a theoretical prediction based on EY spin relaxation mechanism, implying that EY mechanism may be not dominant hole spin relaxation mechanism at room temperature, but DP mechanism is dominant possibly.

Ultrafast carrier dynamics in GaN/InGaN multiple quantum wells nanorods

NASA Astrophysics Data System (ADS)

Chen, Weijian; Wen, Xiaoming; Latzel, Michael; Yang, Jianfeng; Huang, Shujuan; Shrestha, Santosh; Patterson, Robert; Christiansen, Silke; Conibeer, Gavin

2018-01-01

GaN/InGaN multiple quantum wells (MQW) is a promising material for high-efficiency solid-state lighting. Ultrafast optical pump-probe spectroscopy is an important characterization technique for examining fundamental phenomena in semiconductor nanostructure with sub-picosecond resolution. In this study, ultrafast exciton and charge carrier dynamics in GaN/InGaN MQW planar layer and nanorod are investigated using femtosecond transient absorption (TA) techniques at room temperature. Here nanorods are fabricated by etching the GaN/InGaN MQW planar layers using nanosphere lithography and reactive ion etching. Photoluminescence efficiency of the nanorods have been proved to be much higher than that of the planar layers, but the mechanism of the nanorod structure improvement of PL efficiency is not adequately studied. By comparing the TA profile of the GaN/InGaN MQW planar layers and nanorods, the impact of surface states and nanorods lateral confinement in the ultrafast carrier dynamics of GaN/InGaN MQW is revealed. The nanorod sidewall surface states have a strong influence on the InGaN quantum well carrier dynamics. The ultrafast relaxation processes studied in this GaN/InGaN MQW nanostructure is essential for further optimization of device application.

Ultrafast laser ablation for targeted atherosclerotic plaque removal

NASA Astrophysics Data System (ADS)

Lanvin, Thomas; Conkey, Donald B.; Descloux, Laurent; Frobert, Aurelien; Valentin, Jeremy; Goy, Jean-Jacques; Cook, Stéphane; Giraud, Marie-Noelle; Psaltis, Demetri

2015-07-01

Coronary artery disease, the main cause of heart disease, develops as immune cells and lipids accumulate into plaques within the coronary arterial wall. As a plaque grows, the tissue layer (fibrous cap) separating it from the blood flow becomes thinner and increasingly susceptible to rupturing and causing a potentially lethal thrombosis. The stabilization and/or treatment of atherosclerotic plaque is required to prevent rupturing and remains an unsolved medical problem. Here we show for the first time targeted, subsurface ablation of atherosclerotic plaque using ultrafast laser pulses. Excised atherosclerotic mouse aortas were ablated with ultrafast near-infrared (NIR) laser pulses. The physical damage was characterized with histological sections of the ablated atherosclerotic arteries from six different mice. The ultrafast ablation system was integrated with optical coherence tomography (OCT) imaging for plaque-specific targeting and monitoring of the resulting ablation volume. We find that ultrafast ablation of plaque just below the surface is possible without causing damage to the fibrous cap, which indicates the potential use of ultrafast ablation for subsurface atherosclerotic plaque removal. We further demonstrate ex vivo subsurface ablation of a plaque volume through a catheter device with the high-energy ultrafast pulse delivered via hollow-core photonic crystal fiber.

The effect of a broad activation energy distribution on deuteron spin-lattice relaxation.

PubMed

Ylinen, E E; Punkkinen, M; Birczyński, A; Lalowicz, Z T

2015-10-01

Deuteron NMR spectra and spin-lattice relaxation were studied experimentally in zeolite NaY(2.4) samples containing 100% or 200% of CD3OH or CD3OD molecules of the total coverage of Na atoms in the temperature range 20-150K. The activation energies describing the methyl and hydroxyl motions show broad distributions. The relaxation data were interpreted by improving a recent model (Stoch et al., 2013 [16]) in which the nonexponential relaxation curves are at first described by a sum of three exponentials with adjustable relaxation rates and weights. Then a broad distribution of activation energies (the mean activation energy A0 and the width σ) was assumed for each essentially different methyl and hydroxyl position. The correlation times were calculated from the Arrhenius equation (containing the pre-exponential factor τ0), individual relaxation rates computed and classified into three classes, and finally initial relaxation rates and weights for each class formed. These were compared with experimental data, motional parameters changed slightly and new improved rates and weights for each class calculated, etc. This method was improved by deriving for the deuterons of the A and E species methyl groups relaxation rates, which depend explicitly on the tunnel frequency ωt. The temperature dependence of ωt and of the low-temperature correlation time were obtained by using the solutions of the Mathieu equation for a threefold potential. These dependencies were included in the simulations and as the result sets of A0, σ and τ0 obtained, which describe the methyl and hydroxyl motions in different positions in zeolite. Copyright © 2015 Elsevier Inc. All rights reserved.

Ultrafast Manipulation of Magnetic Order with Electrical Pulses

NASA Astrophysics Data System (ADS)

Yang, Yang

During the last 30 years spintronics has been a very rapidly expanding field leading to lots of new interesting physics and applications. As with most technology-oriented fields, spintronics strives to control devices with very low energy consumption and high speed. The combination of spin and electronics inherent to spintronics directly tackles energy efficiency, due to the non-volatility of magnetism. However, speed of operation of spintronic devices is still rather limited ( nanoseconds), due to slow magnetization precessional frequencies. Ultrafast magnetism (or opto-magnetism) is a relatively new field that has been very active in the last 20 years. The main idea is that intense femtosecond laser pulses can be used in order to manipulate the magnetization at very fast time-scales ( 100 femtoseconds). However, the use of femtosecond lasers poses great application challenges such as diffraction limited optical spot sizes which hinders device density, and bulky and expensive integration of femtosecond lasers into devices. In this thesis, our efforts to combine ultrafast magnetism and spintronics are presented. First, we show that the magnetization of ferrimagnetic GdFeCo films can be switched by picosecond electronic heat current pulses. This result shows that a non-thermal distribution of electrons directly excited by laser is not necessary for inducing ultrafast magnetic dynamics. Then, we fabricate photoconductive switch devices on a LT-GaAs substrate, to generate picosecond electrical pulses. Intense electrical pulses with 10ps (FWHM) duration and peak current up to 3A can be generated and delivered into magnetic films. Distinct magnetic dynamics in CoPt films are found between direct optical heating and electrical heating. More importantly, by delivering picosecond electrical pulses into GdFeCo films, we are able to deterministically reverse the magnetization of GdFeCo within 10ps. This is more than one order of magnitude faster than any other electrically

Space charge effects in ultrafast electron diffraction and imaging

NASA Astrophysics Data System (ADS)

Tao, Zhensheng; Zhang, He; Duxbury, P. M.; Berz, Martin; Ruan, Chong-Yu

2012-02-01

Understanding space charge effects is central for the development of high-brightness ultrafast electron diffraction and microscopy techniques for imaging material transformation with atomic scale detail at the fs to ps timescales. We present methods and results for direct ultrafast photoelectron beam characterization employing a shadow projection imaging technique to investigate the generation of ultrafast, non-uniform, intense photoelectron pulses in a dc photo-gun geometry. Combined with N-particle simulations and an analytical Gaussian model, we elucidate three essential space-charge-led features: the pulse lengthening following a power-law scaling, the broadening of the initial energy distribution, and the virtual cathode threshold. The impacts of these space charge effects on the performance of the next generation high-brightness ultrafast electron diffraction and imaging systems are evaluated.

Nonequilibrium dynamics of the phonon gas in ultrafast-excited antimony

NASA Astrophysics Data System (ADS)

Krylow, Sergej; Zijlstra, Eeuwe S.; Kabeer, Fairoja Cheenicode; Zier, Tobias; Bauerhenne, Bernd; Garcia, Martin E.

2017-12-01

The ultrafast relaxation dynamics of a nonequilibrium phonon gas towards thermal equilibrium involves many-body collisions that cannot be properly described by perturbative approaches. Here, we develop a nonperturbative method to elucidate the microscopic mechanisms underlying the decay of laser-excited coherent phonons in the presence of electron-hole pairs, which so far are not fully understood. Our theory relies on ab initio molecular dynamics simulations on laser-excited potential-energy surfaces. Those simulations are compared with runs in which the laser-excited coherent phonon is artificially deoccupied. We apply this method to antimony and show that the decay of the A1 g phonon mode at low laser fluences can be accounted mainly to three-body down-conversion processes of an A1 g phonon into acoustic phonons. For higher excitation strengths, however, we see a crossover to a four-phonon process, in which two A1 g phonons decay into two optical phonons.

Ultrafast Electron Diffraction: How It Works

ScienceCinema

None

2018-01-16

A new technology at SLAC uses high-energy electrons to unravel motions in materials that are faster than a tenth of a trillionth of a second, opening up new research opportunities in ultrafast science.

Ultrafast Electron Diffraction: How It Works

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

None

2015-08-05

A new technology at SLAC uses high-energy electrons to unravel motions in materials that are faster than a tenth of a trillionth of a second, opening up new research opportunities in ultrafast science.

Ultrafast Hot Carrier Dynamics in GaN and Its Impact on the Efficiency Droop.

PubMed

Jhalani, Vatsal A; Zhou, Jin-Jian; Bernardi, Marco

2017-08-09

GaN is a key material for lighting technology. Yet, the carrier transport and ultrafast dynamics that are central in GaN light-emitting devices are not completely understood. We present first-principles calculations of carrier dynamics in GaN, focusing on electron-phonon (e-ph) scattering and the cooling and nanoscale dynamics of hot carriers. We find that e-ph scattering is significantly faster for holes compared to electrons and that for hot carriers with an initial 0.5-1 eV excess energy, holes take a significantly shorter time (∼0.1 ps) to relax to the band edge compared to electrons, which take ∼1 ps. The asymmetry in the hot carrier dynamics is shown to originate from the valence band degeneracy, the heavier effective mass of holes compared to electrons, and the details of the coupling to different phonon modes in the valence and conduction bands. We show that the slow cooling of hot electrons and their long ballistic mean free paths (over 3 nm at room temperature) are a possible cause of efficiency droop in GaN light-emitting diodes. Taken together, our work sheds light on the ultrafast dynamics of hot carriers in GaN and the nanoscale origin of efficiency droop.

Single-shot Monitoring of Ultrafast Processes via X-ray Streaking at a Free Electron Laser.

PubMed

Buzzi, Michele; Makita, Mikako; Howald, Ludovic; Kleibert, Armin; Vodungbo, Boris; Maldonado, Pablo; Raabe, Jörg; Jaouen, Nicolas; Redlin, Harald; Tiedtke, Kai; Oppeneer, Peter M; David, Christian; Nolting, Frithjof; Lüning, Jan

2017-08-03

The advent of x-ray free electron lasers has extended the unique capabilities of resonant x-ray spectroscopy techniques to ultrafast time scales. Here, we report on a novel experimental method that allows retrieving with a single x-ray pulse the time evolution of an ultrafast process, not only at a few discrete time delays, but continuously over an extended time window. We used a single x-ray pulse to resolve the laser-induced ultrafast demagnetisation dynamics in a thin cobalt film over a time window of about 1.6 ps with an excellent signal to noise ratio. From one representative single shot measurement we extract a spin relaxation time of (130 ± 30) fs with an average value, based on 193 single shot events of (113 ± 20) fs. These results are limited by the achieved experimental time resolution of 120 fs, and both values are in excellent agreement with previous results and theoretical modelling. More generally, this new experimental approach to ultrafast x-ray spectroscopy paves the way to the study of non-repetitive processes that cannot be investigated using traditional repetitive pump-probe schemes.

Quantum modeling of ultrafast photoinduced charge separation

NASA Astrophysics Data System (ADS)

Rozzi, Carlo Andrea; Troiani, Filippo; Tavernelli, Ivano

2018-01-01

Phenomena involving electron transfer are ubiquitous in nature, photosynthesis and enzymes or protein activity being prominent examples. Their deep understanding thus represents a mandatory scientific goal. Moreover, controlling the separation of photogenerated charges is a crucial prerequisite in many applicative contexts, including quantum electronics, photo-electrochemical water splitting, photocatalytic dye degradation, and energy conversion. In particular, photoinduced charge separation is the pivotal step driving the storage of sun light into electrical or chemical energy. If properly mastered, these processes may also allow us to achieve a better command of information storage at the nanoscale, as required for the development of molecular electronics, optical switching, or quantum technologies, amongst others. In this Topical Review we survey recent progress in the understanding of ultrafast charge separation from photoexcited states. We report the state-of-the-art of the observation and theoretical description of charge separation phenomena in the ultrafast regime mainly focusing on molecular- and nano-sized solar energy conversion systems. In particular, we examine different proposed mechanisms driving ultrafast charge dynamics, with particular regard to the role of quantum coherence and electron-nuclear coupling, and link experimental observations to theoretical approaches based either on model Hamiltonians or on first principles simulations.

Orbital relaxation effects on Kohn–Sham frontier orbital energies in density functional theory

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

Zhang, DaDi; Zheng, Xiao, E-mail: xz58@ustc.edu.cn; Synergetic Innovation Center of Quantum Information and Quantum Physics, University of Science and Technology of China, Hefei, Anhui 230026

2015-04-21

We explore effects of orbital relaxation on Kohn–Sham frontier orbital energies in density functional theory by using a nonempirical scaling correction approach developed in Zheng et al. [J. Chem. Phys. 138, 174105 (2013)]. Relaxation of Kohn–Sham orbitals upon addition/removal of a fractional number of electrons to/from a finite system is determined by a systematic perturbative treatment. The information of orbital relaxation is then used to improve the accuracy of predicted Kohn–Sham frontier orbital energies by Hartree–Fock, local density approximation, and generalized gradient approximation methods. The results clearly highlight the significance of capturing the orbital relaxation effects. Moreover, the proposed scalingmore » correction approach provides a useful way of computing derivative gaps and Fukui quantities of N-electron finite systems (N is an integer), without the need to perform self-consistent-field calculations for (N ± 1)-electron systems.« less

Analysis of energy relaxation kinetics for control of the electron energy distributions in capacitively coupled RF discharges

NASA Astrophysics Data System (ADS)

Lee, Jung Yeol; Verboncoeur, John P.; Lee, Hae June

2018-04-01

The transition of electron energy probability functions (EEPFs) through the change of heating mode is an important issue in plasma science. A well-known example is that the increase of gas pressure, which was analyzed in terms of the ratio of the energy relaxation mean free path to the electrode gap distance, changes the EEPF from bi-Maxwellian to Maxwellian or Druyvesteyn. In this study, a new aspect of the temporal decay of kinetic energy during the energy relaxation time is theoretically analyzed and compared with a particle-in-cell Monte Carlo collision simulation of capacitively coupled plasmas. A fully kinetic description of electron transport and collisions shows drastic changes of EEPFs with the variation of the driving frequency due to the heating mode transition.

A study of internal energy relaxation in shocks using molecular dynamics based models

NASA Astrophysics Data System (ADS)

Li, Zheng; Parsons, Neal; Levin, Deborah A.

2015-10-01

Recent potential energy surfaces (PESs) for the N2 + N and N2 + N2 systems are used in molecular dynamics (MD) to simulate rates of vibrational and rotational relaxations for conditions that occur in hypersonic flows. For both chemical systems, it is found that the rotational relaxation number increases with the translational temperature and decreases as the rotational temperature approaches the translational temperature. The vibrational relaxation number is observed to decrease with translational temperature and approaches the rotational relaxation number in the high temperature region. The rotational and vibrational relaxation numbers are generally larger in the N2 + N2 system. MD-quasi-classical trajectory (QCT) with the PESs is also used to calculate the V-T transition cross sections, the collision cross section, and the dissociation cross section for each collision pair. Direct simulation Monte Carlo (DSMC) results for hypersonic flow over a blunt body with the total collision cross section from MD/QCT simulations, Larsen-Borgnakke with new relaxation numbers, and the N2 dissociation rate from MD/QCT show a profile with a decreased translational temperature and a rotational temperature close to vibrational temperature. The results demonstrate that many of the physical models employed in DSMC should be revised as fundamental potential energy surfaces suitable for high temperature conditions become available.

Ultrafast optical pulse convertor caused by oscillations of the energy level structure in the conjugated polymer poly(p-phenylenevinylene).

PubMed

Zhang, Yusong; Chen, Weikang; Lin, Zhe; Li, Sheng; George, Thomas F

2017-08-21

For a conjugated polymer irradiated by two optical pulses, the whole process of excitation, involving lattice oscillations, oscillations of the energy level structure, and evolution of the electron cloud, is investigated. Localization of the electron cloud appears in the first 100 fs of irradiation, which in turn induces vibrations of lattice of the polymer chain as well as oscillations of the band gap. These oscillations filter the absorption of the external optical field inversely and convert the original optical field to an ultrafast light field whose intensity varies with a certain period. Based on the mechanism, oscillations of the energy level structure, induced by the external excitation, can be designed as an ultrafast response optical convertor that is able to change the external optical pulse into a new effective light field with a certain oscillation period. This helps provide new insight into designing nanostructures for polymeric optoelectronics.

Size and structure dependent ultrafast dynamics of plasmonic gold nanosphere heterostructures on poly (ethylene glycol) brushes

NASA Astrophysics Data System (ADS)

Karatay, Ahmet; Küçüköz, Betül; Pekdemir, Sami; Onses, Mustafa Serdar; Elmali, Ayhan

2017-11-01

We have investigated the plasmonic properties of heterostructures that consist of gold nanosphere (NSs) with average diameters of 60 nm, 40 nm and 20 nm on poly (ethylene glycol) (PEG) brushes by using ultrafast pump-probe spectroscopy experiments. Gold NSs start to behave like gold nanorods with increasing number of immobilization cycles due to the close proximity. Gold NSs immobilized by 3 and 5 deposition cycles show longitudinal modes of plasmon bands at long wavelengths which are characteristic behaviors for gold nanorods. Increasing the number of immobilization cycle also increase relaxation times of samples due to the close proximity. Linear absorption spectra and scanning electron microscopy images show that there are close packing assemblies for heterostructures containing 20 nm gold NSs as the small particle. Ultrafast electron transfer (<100 fs) occurs between transverse and longitudinal modes by exciting the samples at both 520 nm and 650 nm. Further, experimental results indicate that, heterostructures with the small particles have faster relaxation times than other heterostructures due to closed packing of 20 nm gold NSs.

Ultrafast surface carrier dynamics in the topological insulator Bi₂Te₃.

PubMed

Hajlaoui, M; Papalazarou, E; Mauchain, J; Lantz, G; Moisan, N; Boschetto, D; Jiang, Z; Miotkowski, I; Chen, Y P; Taleb-Ibrahimi, A; Perfetti, L; Marsi, M

2012-07-11

We discuss the ultrafast evolution of the surface electronic structure of the topological insulator Bi(2)Te(3) following a femtosecond laser excitation. Using time and angle-resolved photoelectron spectroscopy, we provide a direct real-time visualization of the transient carrier population of both the surface states and the bulk conduction band. We find that the thermalization of the surface states is initially determined by interband scattering from the bulk conduction band, lasting for about 0.5 ps; subsequently, few picoseconds are necessary for the Dirac cone nonequilibrium electrons to recover a Fermi-Dirac distribution, while their relaxation extends over more than 10 ps. The surface sensitivity of our measurements makes it possible to estimate the range of the bulk-surface interband scattering channel, indicating that the process is effective over a distance of 5 nm or less. This establishes a correlation between the nanoscale thickness of the bulk charge reservoir and the evolution of the ultrafast carrier dynamics in the surface Dirac cone.

Broadband nonlinear optical response of monolayer MoSe2 under ultrafast excitation

NASA Astrophysics Data System (ADS)

Nie, Zhonghui; Trovatello, Chiara; Pogna, Eva A. A.; Dal Conte, Stefano; Miranda, Paulo B.; Kelleher, Edmund; Zhu, Chunhui; Turcu, Ion Crisitan Edmond; Xu, Yongbing; Liu, Kaihui; Cerullo, Giulio; Wang, Fengqiu

2018-01-01

Due to their strong light-matter interaction, monolayer transition metal dichalcogenides (TMDs) have proven to be promising candidates for nonlinear optics and optoelectronics. Here, we characterize the nonlinear absorption of chemical vapour deposition (CVD)-grown monolayer MoSe2 in the 720-810 nm wavelength range. Surprisingly, despite the presence of strong exciton resonances, monolayer MoSe2 exhibits a uniform modulation depth of ˜80 ± 3% and a saturation intensity of ˜2.5 ± 0.4 MW/cm2. In addition, pump-probe spectroscopy is performed to confirm the saturable absorption and reveal the photocarrier relaxation dynamics over hundreds of picoseconds. Our results unravel the unique broadband nonlinear absorptive behavior of monolayer MoSe2 under ultrafast excitation and highlight the potential of using monolayer TMDs as broadband ultrafast optical switches with customizable saturable absorption characteristics.

Time-resolved fluorescence and ultrafast energy transfer in a zinc (hydr)oxide-graphite oxide mesoporous composite

NASA Astrophysics Data System (ADS)

Secor, Jeff; Narinesingh, Veeshan; Seredych, Mykola; Giannakoudakis, Dimitrios A.; Bandosz, Teresa; Alfano, Robert R.

2015-01-01

Ultrafast energy decay kinetics of a zinc (hydr)oxide-graphite oxide (GO) composite is studied via time-resolved fluorescence spectroscopy. The time-resolved emission is spectrally decomposed into emission regions originating from the zinc (hydr)oxide optical gap, surface, and defect states of the composite material. The radiative lifetime of deep red emission becomes an order of magnitude longer than that of GO alone while the radiative lifetime of the zinc optical gap is shortened in the composite. An energy transfer scheme from the zinc (hydr)oxide to GO is considered.

Model of ultrafast demagnetization driven by spin-orbit coupling in a photoexcited antiferromagnetic insulator Cr2O3

NASA Astrophysics Data System (ADS)

Guo, Feng; Zhang, Na; Jin, Wei; Chang, Jun

2017-06-01

We theoretically study the dynamic time evolution following laser pulse pumping in an antiferromagnetic insulator Cr2O3. From the photoexcited high-spin quartet states to the long-lived low-spin doublet states, the ultrafast demagnetization processes are investigated by solving the dissipative Schrödinger equation. We find that the demagnetization times are of the order of hundreds of femtoseconds, in good agreement with recent experiments. The switching times could be strongly reduced by properly tuning the energy gaps between the multiplet energy levels of Cr3+. Furthermore, the relaxation times also depend on the hybridization of atomic orbitals in the first photoexcited state. Our results suggest that the selective manipulation of the electronic structure by engineering stress-strain or chemical substitution allows effective control of the magnetic state switching in photoexcited insulating transition-metal oxides.

Quasiperiodic energy dependence of exciton relaxation kinetics in the sexithiophene crystal.

PubMed

Petelenz, Piotr; Zak, Emil

2014-10-16

Femtosecond kinetics of fluorescence rise in the sexithiophene crystal is studied on a microscopic model of intraband relaxation, where exciton energy is assumed to be dissipated by phonon-accompanied scattering, with the rates calculated earlier. The temporal evolution of the exciton population is described by a set of kinetic equations, solved numerically to yield the population buildup at the band bottom. Not only the time scale but also the shape of the rise curves is found to be unusually sensitive to excitation energy, exhibiting unique quasiperiodic dependence thereon, which is rationalized in terms of the underlying model. Further simulations demonstrate that the main conclusions are robust with respect to experimental factors such as finite temperature and inherent spectral broadening of the exciting pulse, while the calculated fluorescence rise times are found to be in excellent agreement with experimental data available to date. As the rise profiles are composed of a number of exponential contributions, which varies with excitation energy, the common practice of characterizing the population buildup in the emitting state by a single value of relaxation time turns out to be an oversimplification. New experiments giving further insight into the kinetics and mechanism of intraband exciton relaxation are suggested.

Quantifying the Energy Landscape Statistics in Proteins - a Relaxation Mode Analysis

NASA Astrophysics Data System (ADS)

Cai, Zhikun; Zhang, Yang

Energy landscape, the hypersurface in the configurational space, has been a useful concept in describing complex processes that occur over a very long time scale, such as the multistep slow relaxations of supercooled liquids and folding of polypeptide chains into structured proteins. Despite extensive simulation studies, its experimental characterization still remains a challenge. To address this challenge, we developed a relaxation mode analysis (RMA) for liquids under a framework analogous to the normal mode analysis for solids. Using RMA, important statistics of the activation barriers of the energy landscape becomes accessible from experimentally measurable two-point correlation functions, e.g. using quasi-elastic and inelastic scattering experiments. We observed a prominent coarsening effect of the energy landscape. The results were further confirmed by direct sampling of the energy landscape using a metadynamics-like adaptive autonomous basin climbing computation. We first demonstrate RMA in a supercooled liquid when dynamical cooperativity emerges in the landscape-influenced regime. Then we show this framework reveals encouraging energy landscape statistics when applied to proteins.

Quasiparticle dynamics across the full Brillouin zone of Bi 2Sr 2CaCu 2O 8+δ traced with ultrafast time and angle-resolved photoemission spectroscopy

DOE PAGES

Dakovski, Georgi L.; Durakiewicz, Tomasz; Zhu, Jian-Xin; ...

2015-10-12

A hallmark in the cuprate family of high-temperature superconductors is the nodal-antinodal dichotomy. In this regard, angle-resolved photoemission spectroscopy (ARPES) has proven especially powerful, providing band structure information directly in energy-momentum space. Time-resolved ARPES (trARPES) holds great promise of adding ultrafast temporal information, in an attempt to identify different interaction channels in the time domain. Previous studies of the cuprates using trARPES were handicapped by the low probing energy which significantly limits the accessible momentum space. Using 20.15eV, 12 fs pulses we show for the first time the evolution of quasiparticles in the antinodal region of Bi 2Sr 2CaCu 2Omore » 8+δ and demonstrate that nonmonotonic relaxation dynamics dominates above a certain fluence threshold. The dynamics is heavily influenced by transient modification of the electron-phonon interaction and phase space restrictions, in severe contrast to the monotonic relaxation in the nodal and off-nodal regions.« less

Ultrafast photochemistry of polyatomic molecules containing labile halogen atoms in solution

NASA Astrophysics Data System (ADS)

Mereshchenko, Andrey S.

Because breaking and making of chemical bonds lies at the heart of chemistry, this thesis focuses on dynamic studies of labile molecules in solutions using ultrafast transient absorption spectroscopy. Specifically, my interest is two-fold: (i) novel reaction intermediates of polyhalogenated carbon, boron and phosphorus compounds; (ii) photophysics and photochemistry of labile copper(II) halide complexes. Excitation of CH2Br2, CHBr3, BBr 3, and PBr3 into n(Br)sigma*(X-Br) states, where X=C, B, or P, leads to direct photoisomerization with formation of isomers having Br-Br bonds as well as rupture of one of X-Br bonds with the formation of a Br atom and a polyatomic radical fragment, which subsequently recombine to form similar isomer products. Nonpolar solvation stabilizes the isomers, consistent with intrinsic reaction coordinate calculations of the isomer ground state potential energy surfaces at the density functional level of theory, and consequently, the involvement of these highly energetic species on chemically-relevant time scales needs to be taken into account. Monochlorocomplexes in methanol solutions promoted to the ligand-to-metal charge transfer (LMCT) excited state predominantly undergo internal conversion via back electron transfer, giving rise to vibrationally hot ground-state parent complexes. Copper-chloride homolitical bond dissociation yielding the solvated copper(I) and Cl- atom/solvent CT complexes constitutes a minor pathway. Insights into ligand substitution mechanisms were acquired by monitoring the recovery of monochloro complexes at the expense of two unexcited dichloro- and unsubstituted forms of Cu(II) complexes also present in the solution. Detailed description of ultrafast excited-state dynamics of CuCl 42- complexes in acetonitrile upon excitation into all possible Ligand Field (LF) excited states and two most intense LMCT transitions is reported. The LF states were found to be nonreactive with lifetimes remarkably longer than those

Watching proton transfer in real time: Ultrafast photoionization-induced proton transfer in phenol-ammonia complex cation.

PubMed

Shen, Ching-Chi; Tsai, Tsung-Ting; Wu, Jun-Yi; Ho, Jr-Wei; Chen, Yi-Wei; Cheng, Po-Yuan

2017-10-28

In this paper, we give a full account of our previous work [C. C. Shen et al., J. Chem. Phys. 141, 171103 (2014)] on the study of an ultrafast photoionization-induced proton transfer (PT) reaction in the phenol-ammonia (PhOH-NH 3 ) complex using ultrafast time-resolved ion photofragmentation spectroscopy implemented by the photoionization-photofragmentation pump-probe detection scheme. Neutral PhOH-NH 3 complexes prepared in a free jet are photoionized by femtosecond 1 + 1 resonance-enhanced multiphoton ionization via the S 1 state. The evolving cations are then probed by delayed pulses that result in ion fragmentation, and the ionic dynamics is followed by measuring the parent-ion depletion as a function of the pump-probe delay time. By comparing with systems in which PT is not feasible and the steady-state ion photofragmentation spectra, we concluded that the observed temporal evolutions of the transient ion photofragmentation spectra are consistent with an intracomplex PT reaction after photoionization from the initial non-PT to the final PT structures. Our experiments revealed that PT in [PhOH-NH 3 ] + cation proceeds in two distinct steps: an initial impulsive wave-packet motion in ∼70 fs followed by a slower relaxation of about 1 ps that stabilizes the system into the final PT configuration. These results indicate that for a barrierless PT system, even though the initial PT motions are impulsive and ultrafast, the time scale to complete the reaction can be much slower and is determined by the rate of energy dissipation into other modes.

Watching proton transfer in real time: Ultrafast photoionization-induced proton transfer in phenol-ammonia complex cation

NASA Astrophysics Data System (ADS)

Shen, Ching-Chi; Tsai, Tsung-Ting; Wu, Jun-Yi; Ho-Wei, Jr.; Chen, Yi-Wei; Cheng, Po-Yuan

2017-10-01

In this paper, we give a full account of our previous work [C. C. Shen et al., J. Chem. Phys. 141, 171103 (2014)] on the study of an ultrafast photoionization-induced proton transfer (PT) reaction in the phenol-ammonia (PhOH-NH3) complex using ultrafast time-resolved ion photofragmentation spectroscopy implemented by the photoionization-photofragmentation pump-probe detection scheme. Neutral PhOH-NH3 complexes prepared in a free jet are photoionized by femtosecond 1 + 1 resonance-enhanced multiphoton ionization via the S1 state. The evolving cations are then probed by delayed pulses that result in ion fragmentation, and the ionic dynamics is followed by measuring the parent-ion depletion as a function of the pump-probe delay time. By comparing with systems in which PT is not feasible and the steady-state ion photofragmentation spectra, we concluded that the observed temporal evolutions of the transient ion photofragmentation spectra are consistent with an intracomplex PT reaction after photoionization from the initial non-PT to the final PT structures. Our experiments revealed that PT in [PhOH-NH3]+ cation proceeds in two distinct steps: an initial impulsive wave-packet motion in ˜70 fs followed by a slower relaxation of about 1 ps that stabilizes the system into the final PT configuration. These results indicate that for a barrierless PT system, even though the initial PT motions are impulsive and ultrafast, the time scale to complete the reaction can be much slower and is determined by the rate of energy dissipation into other modes.

Bright and ultra-fast scintillation from a semiconductor?

PubMed Central

Derenzo, Stephen E.; Bourret-Courshesne, Edith; Bizarri, Gregory; Canning, Andrew

2015-01-01

Semiconductor scintillators are worth studying because they include both the highest luminosities and shortest decay times of all known scintillators. Moreover, many semiconductors have the heaviest stable elements (Tl, Hg, Pb, Bi) as a major constituent and a high ion pair yield that is proportional to the energy deposited. We review the scintillation properties of semiconductors activated by native defects, isoelectronic impurities, donors and acceptors with special emphasis on those that have exceptionally high luminosities (e.g. ZnO:Zn, ZnS:Ag,Cl, CdS:Ag,Cl) and those that have ultra-fast decay times (e.g. ZnO:Ga; CdS:In). We discuss underlying mechanisms that are consistent with these properties and the possibilities for achieving (1) 200,000 photons/MeV and 1% fwhm energy resolution for 662 keV gamma rays, (2) ultra-fast (ns) decay times and coincident resolving times of 30 ps fwhm for time-of-flight positron emission tomography, and (3) both a high luminosity and an ultra-fast decay time from the same scintillator at cryogenic temperatures. PMID:26855462

Ultrafast carrier dynamics in the large-magnetoresistance material WTe 2

DOE PAGES

Dai, Y. M.; Bowlan, J.; Li, H.; ...

2015-10-07

In this study, ultrafast optical pump-probe spectroscopy is used to track carrier dynamics in the large-magnetoresistance material WTe 2. Our experiments reveal a fast relaxation process occurring on a subpicosecond time scale that is caused by electron-phonon thermalization, allowing us to extract the electron-phonon coupling constant. An additional slower relaxation process, occurring on a time scale of ~5–15 ps, is attributed to phonon-assisted electron-hole recombination. As the temperature decreases from 300 K, the time scale governing this process increases due to the reduction of the phonon population. However, below ~50 K, an unusual decrease of the recombination time sets in,more » most likely due to a change in the electronic structure that has been linked to the large magnetoresistance observed in this material.« less

Transient thermal and nonthermal electron and phonon relaxation after short-pulsed laser heating of metals

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

Giri, Ashutosh; Hopkins, Patrick E., E-mail: phopkins@virginia.edu

2015-12-07

Several dynamic thermal and nonthermal scattering processes affect ultrafast heat transfer in metals after short-pulsed laser heating. Even with decades of measurements of electron-phonon relaxation, the role of thermal vs. nonthermal electron and phonon scattering on overall electron energy transfer to the phonons remains unclear. In this work, we derive an analytical expression for the electron-phonon coupling factor in a metal that includes contributions from equilibrium and nonequilibrium distributions of electrons. While the contribution from the nonthermal electrons to electron-phonon coupling is non-negligible, the increase in the electron relaxation rates with increasing laser fluence measured by thermoreflectance techniques cannot bemore » accounted for by only considering electron-phonon relaxations. We conclude that electron-electron scattering along with electron-phonon scattering have to be considered simultaneously to correctly predict the transient nature of electron relaxation during and after short-pulsed heating of metals at elevated electron temperatures. Furthermore, for high electron temperature perturbations achieved at high absorbed laser fluences, we show good agreement between our model, which accounts for d-band excitations, and previous experimental data. Our model can be extended to other free electron metals with the knowledge of the density of states of electrons in the metals and considering electronic excitations from non-Fermi surface states.« less

Ultrafast Optical Microscopy of Single Monolayer Molybdenum Disulfide Flakes

DOE PAGES

Seo, Minah; Yamaguchi, Hisato; Mohite, Aditya D.; ...

2016-02-15

We performed ultrafast optical microscopy on single flakes of atomically thin CVD-grown molybdenum disulfide, using non-degenerate femtosecond pump-probe spectroscopy to excite and probe carriers above and below the indirect and direct band gaps. These measurements reveal the influence of layer thickness on carrier dynamics when probing near the band gap. Furthermore, fluence-dependent measurements indicate that carrier relaxation is primarily influenced by surface-related defect and trap states after above-bandgap photoexcitation. Furthermore, the ability to probe femtosecond carrier dynamics in individual flakes can thus give much insight into light-matter interactions in these two-dimensional nanosystems.

A simple model of entropy relaxation for explaining effective activation energy behavior below the glass transition temperature.

PubMed

Bisquert, Juan; Henn, François; Giuntini, Jean-Charles

2005-03-01

Strong changes in relaxation rates observed at the glass transition region are frequently explained in terms of a physical singularity of the molecular motions. We show that the unexpected trends and values for activation energy and preexponential factor of the relaxation time tau, obtained at the glass transition from the analysis of the thermally stimulated current signal, result from the use of the Arrhenius law for treating the experimental data obtained in nonstationary experimental conditions. We then demonstrate that a simple model of structural relaxation based on a time dependent configurational entropy and Adam-Gibbs relaxation time is sufficient to explain the experimental behavior, without invoking a kinetic singularity at the glass transition region. The pronounced variation of the effective activation energy appears as a dynamic signature of entropy relaxation that governs the change of relaxation time in nonstationary conditions. A connection is demonstrated between the peak of apparent activation energy measured in nonequilibrium dielectric techniques, with the overshoot of the dynamic specific heat that is obtained in calorimetry techniques.

Terahertz radiation from accelerating charge carriers in graphene under ultrafast photoexcitation

NASA Astrophysics Data System (ADS)

Rustagi, Avinash; Stanton, C. J.

2016-11-01

We study the generation of terahertz (THz) radiation from the acceleration of ultrafast photoexcited charge carriers in graphene in the presence of a dc electric field. Our model is based on calculating the transient current density from the time-dependent distribution function which is determined using the Boltzmann transport equation (BTE) within a relaxation time approximation. We include the time-dependent generation of carriers by the pump pulse by solving for the carrier generation rate using the optical Bloch equations in the rotating wave approximation (RWA). The linearly polarized pump pulse generates an anisotropic distribution of photoexcited carriers in the kx-ky plane. The collision integral in the Boltzmann equation includes a term that leads to the thermalization of carriers via carrier-carrier scattering to an effective temperature above the lattice temperature, as well as a cooling term, which leads to energy relaxation via inelastic carrier-phonon scattering. The radiated signal is proportional to the time derivative of the transient current density. In spite of the fact that the magnitude of the velocity is the same for all the carriers in graphene, there is still emitted radiation from the photoexcited charge carriers with frequency components in the THz range due to a change in the direction of velocity of the photoexcited carriers in the external electric field as well as cooling of the photoexcited carriers on a subpicosecond time scale.

Dielectric Relaxation of the Ionic Liquid 1-Ethyl-3-methylimidazolium Ethyl Sulfate: Microwave and Far-IR Properties.

PubMed

Dhumal, Nilesh R; Kiefer, Johannes; Turton, David; Wynne, Klaas; Kim, Hyung J

2017-05-11

Dielectric relaxation of the ionic liquid, 1-ethyl-3-methylimidazolium ethyl sulfate (EMI + ETS - ), is studied using molecular dynamics (MD) simulations. The collective dynamics of polarization arising from cations and anions are examined. Characteristics of the rovibrational and translational components of polarization dynamics are analyzed to understand their respective roles in the microwave and terahertz regions of dielectric relaxation. The MD results are compared with the experimental low-frequency spectrum of EMI + ETS - , obtained via ultrafast optical Kerr effect (OKE) measurements.

Effects of single atom doping on the ultrafast electron dynamics of M1Au24(SR)18 (M = Pd, Pt) nanoclusters

NASA Astrophysics Data System (ADS)

Zhou, Meng; Qian, Huifeng; Sfeir, Matthew Y.; Nobusada, Katsuyuki; Jin, Rongchao

2016-03-01

Atomically precise, doped metal clusters are receiving wide research interest due to their synergistic properties dependent on the metal composition. To understand the electronic properties of doped clusters, it is highly desirable to probe the excited state behavior. Here, we report the ultrafast relaxation dynamics of doped M1@Au24(SR)18 (M = Pd, Pt; R = CH2CH2Ph) clusters using femtosecond visible and near infrared transient absorption spectroscopy. Three relaxation components are identified for both mono-doped clusters: (1) sub-picosecond relaxation within the M1Au12 core states; (2) core to shell relaxation in a few picoseconds; and (3) relaxation back to the ground state in more than one nanosecond. Despite similar relaxation pathways for the two doped nanoclusters, the coupling between the metal core and surface ligands is accelerated by over 30% in the case of the Pt dopant compared with the Pd dopant. Compared to Pd doping, the case of Pt doping leads to much more drastic changes in the steady state and transient absorption of the clusters, which indicates that the 5d orbitals of the Pt atom are more strongly mixed with Au 5d and 6s orbitals than the 4d orbitals of the Pd dopant. These results demonstrate that a single foreign atom can lead to entirely different excited state spectral features of the whole cluster compared to the parent Au25(SR)18 cluster. The detailed excited state dynamics of atomically precise Pd/Pt doped gold clusters help further understand their properties and benefit the development of energy-related applications.Atomically precise, doped metal clusters are receiving wide research interest due to their synergistic properties dependent on the metal composition. To understand the electronic properties of doped clusters, it is highly desirable to probe the excited state behavior. Here, we report the ultrafast relaxation dynamics of doped M1@Au24(SR)18 (M = Pd, Pt; R = CH2CH2Ph) clusters using femtosecond visible and near infrared

Direct diode pumped Ti:sapphire ultrafast regenerative amplifier system

DOE PAGES

Backus, Sterling; Durfee, Charles; Lemons, Randy; ...

2017-02-10

Here, we report on a direct diode-pumped Ti:sapphire ultrafast regenerative amplifier laser system producing multi-uJ energies with repetition rate from 50 to 250 kHz. By combining cryogenic cooling of Ti:sapphire with high brightness fiber-coupled 450nm laser diodes, we for the first time demonstrate a power-scalable CW-pumped architecture that can be directly applied to demanding ultrafast applications such as coherent high-harmonic EUV generation without any complex post-amplification pulse compression. Initial results promise a new era for Ti:sapphire amplifiers not only for ultrafast laser applications, but also for tunable CW sources. We discuss the unique challenges to implementation, as well as themore » solutions to these challenges.« less

Direct diode pumped Ti:sapphire ultrafast regenerative amplifier system

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

Backus, Sterling; Durfee, Charles; Lemons, Randy

Here, we report on a direct diode-pumped Ti:sapphire ultrafast regenerative amplifier laser system producing multi-uJ energies with repetition rate from 50 to 250 kHz. By combining cryogenic cooling of Ti:sapphire with high brightness fiber-coupled 450nm laser diodes, we for the first time demonstrate a power-scalable CW-pumped architecture that can be directly applied to demanding ultrafast applications such as coherent high-harmonic EUV generation without any complex post-amplification pulse compression. Initial results promise a new era for Ti:sapphire amplifiers not only for ultrafast laser applications, but also for tunable CW sources. We discuss the unique challenges to implementation, as well as themore » solutions to these challenges.« less

Ultrafast magnetization reversal by picosecond electrical pulses

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

Yang, Yang; Wilson, Richard B.; Gorchon, Jon

The field of spintronics involves the study of both spin and charge transport in solid-state devices. Ultrafast magnetism involves the use of femtosecond laser pulses to manipulate magnetic order on subpicosecond time scales. Here, we unite these phenomena by using picosecond charge current pulses to rapidly excite conduction electrons in magnetic metals. We observe deterministic, repeatable ultrafast reversal of the magnetization of a GdFeCo thin film with a single sub–10-ps electrical pulse. The magnetization reverses in ~10 ps, which is more than one order of magnitude faster than any other electrically controlled magnetic switching, and demonstrates a fundamentally new electricalmore » switching mechanism that does not require spin-polarized currents or spin-transfer/orbit torques. The energy density required for switching is low, projecting to only 4 fJ needed to switch a (20 nm) 3 cell. This discovery introduces a new field of research into ultrafast charge current–driven spintronic phenomena and devices.« less

Ultrafast magnetization reversal by picosecond electrical pulses

DOE PAGES

Yang, Yang; Wilson, Richard B.; Gorchon, Jon; ...

2017-11-03

The field of spintronics involves the study of both spin and charge transport in solid-state devices. Ultrafast magnetism involves the use of femtosecond laser pulses to manipulate magnetic order on subpicosecond time scales. Here, we unite these phenomena by using picosecond charge current pulses to rapidly excite conduction electrons in magnetic metals. We observe deterministic, repeatable ultrafast reversal of the magnetization of a GdFeCo thin film with a single sub–10-ps electrical pulse. The magnetization reverses in ~10 ps, which is more than one order of magnitude faster than any other electrically controlled magnetic switching, and demonstrates a fundamentally new electricalmore » switching mechanism that does not require spin-polarized currents or spin-transfer/orbit torques. The energy density required for switching is low, projecting to only 4 fJ needed to switch a (20 nm) 3 cell. This discovery introduces a new field of research into ultrafast charge current–driven spintronic phenomena and devices.« less

Semiclassical study of quantum coherence and isotope effects in ultrafast electron transfer reactions coupled to a proton and a phonon bath.

PubMed

Venkataraman, Charulatha

2011-11-28

The linearized semiclassical initial value representation is employed to describe ultrafast electron transfer processes coupled to a phonon bath and weakly coupled to a proton mode. The goal of our theoretical investigation is to understand the influence of the proton on the electronic dynamics in various bath relaxation regimes. More specifically, we study the impact of the proton on coherences and analyze if the coupling to the proton is revealed in the form of an isotope effect. This will be important in distinguishing reactions in which the proton does not undergo significant rearrangement from those in which the electron transfer is accompanied by proton transfer. Unlike other methodologies widely employed to describe nonadiabatic electron transfer, this approach treats the electronic and nuclear degrees of freedom consistently. However, due to the linearized approximation, quantum interference effects are not captured accurately. Our study shows that at small phonon bath reorganization energies, coherent oscillations and isotope effect are observed in both slow and fast bath regimes. The coherences are more substantially damped by deuterium in comparison to the proton. Further, in contrast to the dynamics of the spin-boson model, the coherences are not long-lived. At large bath reorganization energies, the decay is incoherent in the slow and fast bath regimes. In this case, the extent of the isotope effect depends on the relative relaxation timescales of the proton mode and the phonon bath. The isotope effect is magnified for baths that relax on picosecond timescales in contrast to baths that relax in femtoseconds.

Excitation and doping dependence of hole-spin relaxation in bulk GaAs

NASA Astrophysics Data System (ADS)

Krauss, Michael; Hilton, David; Schneider, Hans Christian

2009-03-01

We present theoretical and experimental results on ultrafast hole-spin dynamics in bulk GaAs. By combining a sufficiently realistic bandstructure at the level of an 8x8 k .p theory and a dynamical treatment of the relevant scattering mechanisms [1], we obtain quantitative agreement between the microscopic theoretical results and differential transmission measurements [2] for different excitation conditions. In particular, we examine the dependence of the hole-spin relaxation time on the optically excited carrier density, lattice temperature, and doping concentration. Although the spin relaxation is rather insensitive to changes in the optically excited density and temperature, strong p-doping causes a significantly faster relaxation. [1] M. Krauss, M. Aeschlimann, and H. C. Schneider, Phys.Rev.Lett. 100, 256601 (2008)[2] D. J. Hilton and C. L. Tang, Phys. Rev. Lett. 89, 146601 (2002)

Structural Relaxation of Vit4Amorphous Alloy by the Enthalpy Relaxation

NASA Astrophysics Data System (ADS)

O'Reilly, James; Hammond, Vincent

2002-03-01

The structural relaxation of an amorphous alloy designated Vit4 has been investigated as a function of thermal history using differential scanning calorimetry. Results indicate that the width of the glass transition region is approximately 30 °C, which is broader than molecular or polymeric glasses but similar to inorganic glasses. The broad transition implies a large distribution of relaxation times, a low activation energy, or a combination of these effects. The Tool-Narayanaswamy model for structural relaxation has been used to analyze the change in fictive temperature that occurs for a series of cooling rates. The activation energy calculated from these data the is 187 kJ/mol, a value that is low compared to other glasses. Using optimization programs, the other relaxation parameters, the characteristic relaxation time, the non-linearity parameter, x, and the fractional exponent of distribution of relaxation times, b, were determined from the experimental specific heat curves. Although the parameters were in good agreement with values typical of other glassy materials, there appears to be less correlation between them than is observed in molecular and polymeric glasses. The results obtained in this study indicate that the structural relaxation of Vit 4 is similar to other glasses except for a low activation energy with high glass transition. This could be due to a low free volume or configurational entropy. The width of the glass transition could result from a large distribution of relaxation times or a low activation energy. The exponent of the distribution of relaxation times, b, is 0.45±0.1 and the non-linearity parameter, x =0.5±0.2. The structural relaxation of Vit 4 is dominated by a low activation energy which is related to the atomic jump motion of hard spheres. The DCp at Tg should be 11.7 J/mol. deg per bead according to Wunderlich’s rule. This means that the change in Cp at Tg in Vit4 can be accounted for by one bead although there are five metal

Interatomic Coulombic Decay Mediated by Ultrafast Superexchange Energy Transfer.

PubMed

Miteva, Tsveta; Kazandjian, Sévan; Kolorenč, Přemysl; Votavová, Petra; Sisourat, Nicolas

2017-08-25

Inner-valence ionized states of atoms and molecules live shorter if these species are embedded in an environment due to the possibility for ultrafast deexcitation known as interatomic Coulombic decay (ICD). In this Letter we show that the lifetime of these ICD active states decreases further when a bridge atom is in proximity to the two interacting monomers. This novel mechanism, termed superexchange ICD, is an electronic correlation effect driven by the efficient energy transfer via virtual states of the bridge atom. The superexchange ICD is discussed in detail on the example of the NeHeNe trimer. We demonstrate that the decay width of the Ne^{+}(2s^{-1})  ^{2}Σ_{g}^{+} resonance increases 6 times in the presence of the He atom at a distance of 4 Å between the two Ne atoms. Using a simple model, we provide a qualitative explanation of the superexchange ICD and we derive analytical expressions for the dependence of the decay width on the distance between the neon atoms.

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

Heterogeneous to homogeneous melting transition visualized with ultrafast electron diffraction

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

None

The ultrafast laser excitation of matters leads to non-equilibrium states with complex solid-liquid phase transition dynamics. We used electron diffraction at mega-electronvolt energies to visualize the ultrafast melting of gold on the atomic scale length. For energy densities approaching the irreversible melting regime, we first observed heterogeneous melting on time scales of 100 ps to 1000 ps, transitioning to homogeneous melting that occurs catastrophically within 10-20 ps at higher energy densities. We showed evidence for the heterogeneous coexistence of solid and liquid. We determined the ion and electron temperature evolution and found superheated conditions. Our results constrain the electron-ion couplingmore » rate, determine the Debye temperature and reveal the melting sensitivity to nucleation seeds.« less

Direct Imaging of Frenkel Exciton Transport by Ultrafast Microscopy.

PubMed

Zhu, Tong; Wan, Yan; Huang, Libai

2017-07-18

Long-range transport of Frenkel excitons is crucial for achieving efficient molecular-based solar energy harvesting. Understanding of exciton transport mechanisms is important for designing materials for solar energy applications. One major bottleneck in unraveling of exciton transport mechanisms is the lack of direct measurements to provide information in both spatial and temporal domains, imposed by the combination of fast energy transfer (typically ≤1 ps) and short exciton diffusion lengths (typically ≤100 nm). This challenge requires developing experimental tools to directly characterize excitation energy transport, and thus facilitate the elucidation of mechanisms. To address this challenge, we have employed ultrafast transient absorption microscopy (TAM) as a means to directly image exciton transport with ∼200 fs time resolution and ∼50 nm spatial precision. By mapping population in spatial and temporal domains, such approach has unraveled otherwise obscured information and provided important parameters for testing exciton transport models. In this Account, we discuss the recent progress in imaging Frenkel exciton migration in molecular crystals and aggregates by ultrafast microscopy. First, we establish the validity of the TAM methods by imaging singlet and triplet exciton transport in a series of polyacene single crystals that undergo singlet fission. A new singlet-mediated triplet transport pathway has been revealed by TAM, resulting from the equilibrium between triplet and singlet exciton populations. Such enhancement of triplet exciton transport enables triplet excitons to migrate as singlet excitons and leads to orders of magnitude faster apparent triplet exciton diffusion rate in the picosecond and nanosecond time scales, favorable for solar cell applications. Next we discuss how information obtained by ultrafast microscopy can evaluate coherent effects in exciton transport. We use tubular molecular aggregates that could support large exciton

Rational material design for ultrafast rechargeable lithium-ion batteries.

PubMed

Tang, Yuxin; Zhang, Yanyan; Li, Wenlong; Ma, Bing; Chen, Xiaodong

2015-10-07

Rechargeable lithium-ion batteries (LIBs) are important electrochemical energy storage devices for consumer electronics and emerging electrical/hybrid vehicles. However, one of the formidable challenges is to develop ultrafast charging LIBs with the rate capability at least one order of magnitude (>10 C) higher than that of the currently commercialized LIBs. This tutorial review presents the state-of-the-art developments in ultrafast charging LIBs by the rational design of materials. First of all, fundamental electrochemistry and related ionic/electronic conduction theories identify that the rate capability of LIBs is kinetically limited by the sluggish solid-state diffusion process in electrode materials. Then, several aspects of the intrinsic materials, materials engineering and processing, and electrode materials architecture design towards maximizing both ionic and electronic conductivity in the electrode with a short diffusion length are deliberated. Finally, the future trends and perspectives for the ultrafast rechargeable LIBs are discussed. Continuous rapid progress in this area is essential and urgent to endow LIBs with ultrafast charging capability to meet huge demands in the near future.

Ultrafast Ultrasound Imaging With Cascaded Dual-Polarity Waves.

PubMed

Zhang, Yang; Guo, Yuexin; Lee, Wei-Ning

2018-04-01

Ultrafast ultrasound imaging using plane or diverging waves, instead of focused beams, has advanced greatly the development of novel ultrasound imaging methods for evaluating tissue functions beyond anatomical information. However, the sonographic signal-to-noise ratio (SNR) of ultrafast imaging remains limited due to the lack of transmission focusing, and thus insufficient acoustic energy delivery. We hereby propose a new ultrafast ultrasound imaging methodology with cascaded dual-polarity waves (CDWs), which consists of a pulse train with positive and negative polarities. A new coding scheme and a corresponding linear decoding process were thereby designed to obtain the recovered signals with increased amplitude, thus increasing the SNR without sacrificing the frame rate. The newly designed CDW ultrafast ultrasound imaging technique achieved higher quality B-mode images than coherent plane-wave compounding (CPWC) and multiplane wave (MW) imaging in a calibration phantom, ex vivo pork belly, and in vivo human back muscle. CDW imaging shows a significant improvement in the SNR (10.71 dB versus CPWC and 7.62 dB versus MW), penetration depth (36.94% versus CPWC and 35.14% versus MW), and contrast ratio in deep regions (5.97 dB versus CPWC and 5.05 dB versus MW) without compromising other image quality metrics, such as spatial resolution and frame rate. The enhanced image qualities and ultrafast frame rates offered by CDW imaging beget great potential for various novel imaging applications.

Ultrafast and nonlinear spectroscopy of brilliant green-based nanoGUMBOS with enhanced near-infrared emission

NASA Astrophysics Data System (ADS)

Karam, Tony E.; Siraj, Noureen; Zhang, Zhenyu; Ezzir, Abdulrahman F.; Warner, Isiah M.; Haber, Louis H.

2017-10-01

The synthesis, characterization, ultrafast dynamics, and nonlinear spectroscopy of 30 nm nanospheres of brilliant green-bis(pentafluoroethylsulfonyl)imide ([BG][BETI]) in water are reported. These thermally stable nanoparticles are derived from a group of uniform materials based on organic salts (nanoGUMBOS) that exhibit enhanced near-infrared emission compared with the molecular dye in water. The examination of ultrafast transient absorption spectroscopy results reveals that the overall excited-state relaxation lifetimes of [BG][BETI] nanoGUMBOS are longer than the brilliant green molecular dye in water due to steric hindrance of the torsional degrees of freedom of the phenyl rings around the central carbon. Furthermore, the second harmonic generation signal of [BG][BETI] nanoGUMBOS is enhanced by approximately 7 times and 23 times as compared with colloidal gold nanoparticles of the same size and the brilliant green molecular dye in water, respectively. A very clear third harmonic generation signal is observed from the [BG][BETI] nanoGUMBOS but not from either the molecular dye or the gold nanoparticles. Overall, these results show that [BG][BETI] nanoGUMBOS exhibit altered ultrafast and nonlinear spectroscopy that is beneficial for various applications including nonlinear imaging probes, biomedical imaging, and molecular sensing.

Photon gating in four-dimensional ultrafast electron microscopy.

PubMed

Hassan, Mohammed T; Liu, Haihua; Baskin, John Spencer; Zewail, Ahmed H

2015-10-20

Ultrafast electron microscopy (UEM) is a pivotal tool for imaging of nanoscale structural dynamics with subparticle resolution on the time scale of atomic motion. Photon-induced near-field electron microscopy (PINEM), a key UEM technique, involves the detection of electrons that have gained energy from a femtosecond optical pulse via photon-electron coupling on nanostructures. PINEM has been applied in various fields of study, from materials science to biological imaging, exploiting the unique spatial, energy, and temporal characteristics of the PINEM electrons gained by interaction with a "single" light pulse. The further potential of photon-gated PINEM electrons in probing ultrafast dynamics of matter and the optical gating of electrons by invoking a "second" optical pulse has previously been proposed and examined theoretically in our group. Here, we experimentally demonstrate this photon-gating technique, and, through diffraction, visualize the phase transition dynamics in vanadium dioxide nanoparticles. With optical gating of PINEM electrons, imaging temporal resolution was improved by a factor of 3 or better, being limited only by the optical pulse widths. This work enables the combination of the high spatial resolution of electron microscopy and the ultrafast temporal response of the optical pulses, which provides a promising approach to attain the resolution of few femtoseconds and attoseconds in UEM.

Photon gating in four-dimensional ultrafast electron microscopy

PubMed Central

Hassan, Mohammed T.; Liu, Haihua; Baskin, John Spencer; Zewail, Ahmed H.

2015-01-01

Ultrafast electron microscopy (UEM) is a pivotal tool for imaging of nanoscale structural dynamics with subparticle resolution on the time scale of atomic motion. Photon-induced near-field electron microscopy (PINEM), a key UEM technique, involves the detection of electrons that have gained energy from a femtosecond optical pulse via photon–electron coupling on nanostructures. PINEM has been applied in various fields of study, from materials science to biological imaging, exploiting the unique spatial, energy, and temporal characteristics of the PINEM electrons gained by interaction with a “single” light pulse. The further potential of photon-gated PINEM electrons in probing ultrafast dynamics of matter and the optical gating of electrons by invoking a “second” optical pulse has previously been proposed and examined theoretically in our group. Here, we experimentally demonstrate this photon-gating technique, and, through diffraction, visualize the phase transition dynamics in vanadium dioxide nanoparticles. With optical gating of PINEM electrons, imaging temporal resolution was improved by a factor of 3 or better, being limited only by the optical pulse widths. This work enables the combination of the high spatial resolution of electron microscopy and the ultrafast temporal response of the optical pulses, which provides a promising approach to attain the resolution of few femtoseconds and attoseconds in UEM. PMID:26438835

The Behavior of Hydrogen Under Extreme Conditions on Ultrafast Timescales (A "Life at the Frontiers of Energy Research" contest entry from the 2011 Energy Frontier Research Centers (EFRCs) Summit and Forum)

ScienceCinema

Mao, Ho-kwang (Director, Center for Energy Frontier Research in Extreme Environments); EFree Staff

2017-12-09

'The Behavior of Hydrogen Under Extreme Conditions on Ultrafast Timescales ' was submitted by the Center for Energy Frontier Research in Extreme Environments (EFree) to the 'Life at the Frontiers of Energy Research' video contest at the 2011 Science for Our Nation's Energy Future: Energy Frontier Research Centers (EFRCs) Summit and Forum. Twenty-six EFRCs created short videos to highlight their mission and their work. EFree is directed by Ho-kwang Mao at the Carnegie Institute of Washington and is a partnership of scientists from thirteen institutions.The Office of Basic Energy Sciences in the U.S. Department of Energy's Office of Science established the 46 Energy Frontier Research Centers (EFRCs) in 2009. These collaboratively-organized centers conduct fundamental research focused on 'grand challenges' and use-inspired 'basic research needs' recently identified in major strategic planning efforts by the scientific community. The overall purpose is to accelerate scientific progress toward meeting the nation's critical energy challenges. The mission of Energy Frontier Research in Extreme Environments is 'to accelerate the discovery and creation of energy-relevant materials using extreme pressures and temperatures.' Research topics are: catalysis (CO{sub 2}, water), photocatalysis, solid state lighting, optics, thermelectric, phonons, thermal conductivity, solar electrodes, fuel cells, superconductivity, extreme environment, radiation effects, defects, spin dynamics, CO{sub 2} (capture, convert, store), greenhouse gas, hydrogen (fuel, storage), ultrafast physics, novel materials synthesis, and defect tolerant materials.

Single-electron pulses for ultrafast diffraction

PubMed Central

Aidelsburger, M.; Kirchner, F. O.; Krausz, F.; Baum, P.

2010-01-01

Visualization of atomic-scale structural motion by ultrafast electron diffraction and microscopy requires electron packets of shortest duration and highest coherence. We report on the generation and application of single-electron pulses for this purpose. Photoelectric emission from metal surfaces is studied with tunable ultraviolet pulses in the femtosecond regime. The bandwidth, efficiency, coherence, and electron pulse duration are investigated in dependence on excitation wavelength, intensity, and laser bandwidth. At photon energies close to the cathode’s work function, the electron pulse duration shortens significantly and approaches a threshold that is determined by interplay of the optical pulse width and the acceleration field. An optimized choice of laser wavelength and bandwidth results in sub-100-fs electron pulses. We demonstrate single-electron diffraction from polycrystalline diamond films and reveal the favorable influences of matched photon energies on the coherence volume of single-electron wave packets. We discuss the consequences of our findings for the physics of the photoelectric effect and for applications of single-electron pulses in ultrafast 4D imaging of structural dynamics. PMID:21041681

Design and commissioning of an aberration-corrected ultrafast spin-polarized low energy electron microscope with multiple electron sources.

PubMed

Wan, Weishi; Yu, Lei; Zhu, Lin; Yang, Xiaodong; Wei, Zheng; Liu, Jefferson Zhe; Feng, Jun; Kunze, Kai; Schaff, Oliver; Tromp, Ruud; Tang, Wen-Xin

2017-03-01

We describe the design and commissioning of a novel aberration-corrected low energy electron microscope (AC-LEEM). A third magnetic prism array (MPA) is added to the standard AC-LEEM with two prism arrays, allowing the incorporation of an ultrafast spin-polarized electron source alongside the standard cold field emission electron source, without degrading spatial resolution. The high degree of symmetries of the AC-LEEM are utilized while we design the electron optics of the ultrafast spin-polarized electron source, so as to minimize the deleterious effect of time broadening, while maintaining full control of electron spin. A spatial resolution of 2nm and temporal resolution of 10ps (ps) are expected in the future time resolved aberration-corrected spin-polarized LEEM (TR-AC-SPLEEM). The commissioning of the three-prism AC-LEEM has been successfully finished with the cold field emission source, with a spatial resolution below 2nm. Copyright © 2017 Elsevier B.V. All rights reserved.

Ultrafast Dynamics of Energetic Materials

DTIC Science & Technology

2014-01-23

redistributed in condensed-phase materials. In this subproject we developed a technique termed three-dimensional IR- Raman spectroscopy that allowed us to...Fang, 2011, “The distribution of local enhancement factors in surface enhanced Raman -active substrates and the vibrational dynamics in the liquid phase...3. (invited) “Vibrational energy and molecular thermometers in liquids: Ultrafast IR- Raman spectroscopy”, Brandt C. Pein and Dana D. Dlott, To

Indirect excitation of ultrafast demagnetization

DOE PAGES

Vodungbo, Boris; Tudu, Bahrati; Perron, Jonathan; ...

2016-01-06

Does the excitation of ultrafast magnetization require direct interaction between the photons of the optical pump pulse and the magnetic layer? Here, we demonstrate unambiguously that this is not the case. For this we have studied the magnetization dynamics of a ferromagnetic cobalt/palladium multilayer capped by an IR-opaque aluminum layer. Upon excitation with an intense femtosecond-short IR laser pulse, the film exhibits the classical ultrafast demagnetization phenomenon although only a negligible number of IR photons penetrate the aluminum layer. In comparison with an uncapped cobalt/palladium reference film, the initial demagnetization of the capped film occurs with a delayed onset andmore » at a slower rate. Both observations are qualitatively in line with energy transport from the aluminum layer into the underlying magnetic film by the excited, hot electrons of the aluminum film. As a result, our data thus confirm recent theoretical predictions.« less

Indirect excitation of ultrafast demagnetization

PubMed Central

Vodungbo, Boris; Tudu, Bahrati; Perron, Jonathan; Delaunay, Renaud; Müller, Leonard; Berntsen, Magnus H.; Grübel, Gerhard; Malinowski, Grégory; Weier, Christian; Gautier, Julien; Lambert, Guillaume; Zeitoun, Philippe; Gutt, Christian; Jal, Emmanuelle; Reid, Alexander H.; Granitzka, Patrick W.; Jaouen, Nicolas; Dakovski, Georgi L.; Moeller, Stefan; Minitti, Michael P.; Mitra, Ankush; Carron, Sebastian; Pfau, Bastian; von Korff Schmising, Clemens; Schneider, Michael; Eisebitt, Stefan; Lüning, Jan

2016-01-01

Does the excitation of ultrafast magnetization require direct interaction between the photons of the optical pump pulse and the magnetic layer? Here, we demonstrate unambiguously that this is not the case. For this we have studied the magnetization dynamics of a ferromagnetic cobalt/palladium multilayer capped by an IR-opaque aluminum layer. Upon excitation with an intense femtosecond-short IR laser pulse, the film exhibits the classical ultrafast demagnetization phenomenon although only a negligible number of IR photons penetrate the aluminum layer. In comparison with an uncapped cobalt/palladium reference film, the initial demagnetization of the capped film occurs with a delayed onset and at a slower rate. Both observations are qualitatively in line with energy transport from the aluminum layer into the underlying magnetic film by the excited, hot electrons of the aluminum film. Our data thus confirm recent theoretical predictions. PMID:26733106

Ultrafast Spectroscopy of Mid-Infrared Semiconductors Using the Signal and Idler Beams of a Synchronous Optical Parametric Oscillator

DTIC Science & Technology

2008-03-01

then used to fit theoretical models describing radiative and non-radiative relaxation processes. 3.2 Experimental Setup This thesis uses a mode...Russian Efforts. Master’s thesis, Naval Postgraduate School, 2005. 5. Chirsto, Farid C. “Thermochemistry and Kinetics Models for MagnesiumTe- flon/Viton...Coherent Mira Model 900-F Laser. 7. Cooley, William T. Measurement of Ultrafast Carrier Recombination Dynamics in Mid-Infrared Semiconductor Laser Material

Ultrafast Absorption Spectroscopy of Aluminum Plasmas Created by LCLS using Betatron X-Ray Radiation

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

Albert, Felicie

2016-10-12

This document summarizes the goals and accomplishments of a six month-long LDRD project, awarded through the LLNL director Early and Mid Career Recognition (EMCR) program. This project allowed us to support beamtime awarded at the Matter under Extreme Conditions (MEC) end station of the Linac Coherent Light Source (LCLS). The goal of the experiment was to heat metallic samples with the bright x-rays from the LCLS free electron laser. Then, we studied how they relaxed back to equilibrium by probing them with ultrafast x-ray absorption spectroscopy using laser-based betatron radiation. Our work enabled large collaborations between LLNL, SLAC, LBNL, andmore » institutions in France and in the UK, while providing training to undergraduate and graduate students during the experiment. Following this LDRD project, the PI was awarded a 5-year DOE early career research grant to further develop applications of laser-driven x-ray sources for high energy density science experiments and warm dense matter states.« less

Energy Transfer Between Coherently Delocalized States in Thin Films of the Explosive Pentaerythritol Tetranitrate (PETN) Revealed by Two-Dimensional Infrared Spectroscopy

NASA Astrophysics Data System (ADS)

Ostrander, Joshua; Knepper, Robert; Tappan, Alexander; Kay, Jeffery; Zanni, Martin; Farrow, Darcie

2017-06-01

Pentaerythritol tetranitrate (PETN) is a common secondary explosive and has been used extensively to study shock initiation and energy propagation in energetic materials. We report 2D IR measurements of PETN thin films that resolve vibrational energy transfer and relaxation mechanisms. Ultrafast anisotropy measurements reveal a sub-500 fs reorientation of transition dipoles in thin films of vapor-deposited PETN that is absent in solution measurements, consistent with intermolecular energy transfer. The anisotropy is frequency dependent, suggesting spectrally heterogeneous vibrational relaxation. Cross peaks are observed in 2D IR spectra that resolve a specific energy transfer pathway with a 2 ps time scale. Measurements of the transition dipole strength indicate that these vibrational modes are coherently delocalized over at least 15-30 molecules. We discuss the implications of vibrational relaxation between coherently delocalized eigenstates for mechanisms relevant to explosives. Sandia National Laboratories is a multi-program laboratory managed and operated by Sandia Corporation, a wholly owned subsidiary of Lockheed Martin Corporation, for the U.S. Department of Energy's National Nuclear Security Administration under contract DE-AC04-94AL85000.

Generalized GW+Boltzmann Approach for the Description of Ultrafast Electron Dynamics in Topological Insulators

PubMed Central

Battiato, Marco; Sánchez-Barriga, Jaime

2017-01-01

Quantum-phase transitions between trivial insulators and topological insulators differ from ordinary metal-insulator transitions in that they arise from the inversion of the bulk band structure due to strong spin–orbit coupling. Such topological phase transitions are unique in nature as they lead to the emergence of topological surface states which are characterized by a peculiar spin texture that is believed to play a central role in the generation and manipulation of dissipationless surface spin currents on ultrafast timescales. Here, we provide a generalized GW+Boltzmann approach for the description of ultrafast dynamics in topological insulators driven by electron–electron and electron–phonon scatterings. Taking the prototypical insulator Bi2Te3 as an example, we test the robustness of our approach by comparing the theoretical prediction to results of time- and angle-resolved photoemission experiments. From this comparison, we are able to demonstrate the crucial role of the excited spin texture in the subpicosecond relaxation of transient electrons, as well as to accurately obtain the magnitude and strength of electron–electron and electron–phonon couplings. Our approach could be used as a generalized theory for three-dimensional topological insulators in the bulk-conducting transport regime, paving the way for the realization of a unified theory of ultrafast dynamics in topological materials. PMID:28773171

Generalized GW+Boltzmann Approach for the Description of Ultrafast Electron Dynamics in Topological Insulators.

PubMed

Battiato, Marco; Aguilera, Irene; Sánchez-Barriga, Jaime

2017-07-17

Quantum-phase transitions between trivial insulators and topological insulators differ from ordinary metal-insulator transitions in that they arise from the inversion of the bulk band structure due to strong spin-orbit coupling. Such topological phase transitions are unique in nature as they lead to the emergence of topological surface states which are characterized by a peculiar spin texture that is believed to play a central role in the generation and manipulation of dissipationless surface spin currents on ultrafast timescales. Here, we provide a generalized G W +Boltzmann approach for the description of ultrafast dynamics in topological insulators driven by electron-electron and electron-phonon scatterings. Taking the prototypical insulator Bi 2 Te 3 as an example, we test the robustness of our approach by comparing the theoretical prediction to results of time- and angle-resolved photoemission experiments. From this comparison, we are able to demonstrate the crucial role of the excited spin texture in the subpicosecond relaxation of transient electrons, as well as to accurately obtain the magnitude and strength of electron-electron and electron-phonon couplings. Our approach could be used as a generalized theory for three-dimensional topological insulators in the bulk-conducting transport regime, paving the way for the realization of a unified theory of ultrafast dynamics in topological materials.

Selective resolution of photocurrent generating pathways in transition metal dichalcogenides by ultrafast microscopy (Conference Presentation)

NASA Astrophysics Data System (ADS)

Graham, Matthew W.

2017-02-01

Presently, there exists no reliable in-situ time-resolved method that selectively isolates both the recombination and escape times relevant to photocurrent generation in the ultrafast regime. Transport based measurements lack the required time resolution, while purely optical measurement give a convoluted weighted-average of all electronic dynamics, offering no selectivity for photocurrent generating pathways. Recently, the ultrafast photocurrent (U-PC) autocorrelation method has successfully measured the rate limiting electronic relaxation processes in materials such as graphene, carbon nanotubes, and transition metal dichalcogenide (TMD) materials. Here, we unambiguously derive and experimentally confirm a generic U-PC response function by simultaneously resolving the transient absorption (TA) and U-PC response for highly-efficient (48% IQE at 0 bias) WSe2 devices and twisted bilayer graphene. Surprisingly, both optical TA and electrical U-PC responses give the same E-field-dependent electronic escape and recombination rates. These rates further accurately quantify a material's intrinsic PC generation efficiency. We demonstrate that the chirality of the incident light impacts the U-PC kinetics, suggesting such measurements directly access the ultrafast dynamics need to complex electronic physics such as the valley-Hall effect. By combining E-field dependent ultrafast photocurrent with transient absorption microscopy, we have selectively imaged the dominant kinetic bottlenecks that inhibit photocurrent production in devices made from stacked few-layer TMD materials. This provides a new methodology to intelligently select materials that intrinsically avoid recombination bottlenecks and maximize photocurrent yield.

Ultrafast Growth of High-Quality Monolayer WSe2 on Au.

PubMed

Gao, Yang; Hong, Yi-Lun; Yin, Li-Chang; Wu, Zhangting; Yang, Zhiqing; Chen, Mao-Lin; Liu, Zhibo; Ma, Teng; Sun, Dong-Ming; Ni, Zhenhua; Ma, Xiu-Liang; Cheng, Hui-Ming; Ren, Wencai

2017-08-01

The ultrafast growth of high-quality uniform monolayer WSe 2 is reported with a growth rate of ≈26 µm s -1 by chemical vapor deposition on reusable Au substrate, which is ≈2-3 orders of magnitude faster than those of most 2D transition metal dichalcogenides grown on nonmetal substrates. Such ultrafast growth allows for the fabrication of millimeter-size single-crystal WSe 2 domains in ≈30 s and large-area continuous films in ≈60 s. Importantly, the ultrafast grown WSe 2 shows excellent crystal quality and extraordinary electrical performance comparable to those of the mechanically exfoliated samples, with a high mobility up to ≈143 cm 2 V -1 s -1 and ON/OFF ratio up to 9 × 10 6 at room temperature. Density functional theory calculations reveal that the ultrafast growth of WSe 2 is due to the small energy barriers and exothermic characteristic for the diffusion and attachment of W and Se on the edges of WSe 2 on Au substrate. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Electrically-driven GHz range ultrafast graphene light emitter (Conference Presentation)

NASA Astrophysics Data System (ADS)

Kim, Youngduck; Gao, Yuanda; Shiue, Ren-Jye; Wang, Lei; Aslan, Ozgur Burak; Kim, Hyungsik; Nemilentsau, Andrei M.; Low, Tony; Taniguchi, Takashi; Watanabe, Kenji; Bae, Myung-Ho; Heinz, Tony F.; Englund, Dirk R.; Hone, James

2017-02-01

Ultrafast electrically driven light emitter is a critical component in the development of the high bandwidth free-space and on-chip optical communications. Traditional semiconductor based light sources for integration to photonic platform have therefore been heavily studied over the past decades. However, there are still challenges such as absence of monolithic on-chip light sources with high bandwidth density, large-scale integration, low-cost, small foot print, and complementary metal-oxide-semiconductor (CMOS) technology compatibility. Here, we demonstrate the first electrically driven ultrafast graphene light emitter that operate up to 10 GHz bandwidth and broadband range (400 1600 nm), which are possible due to the strong coupling of charge carriers in graphene and surface optical phonons in hBN allow the ultrafast energy and heat transfer. In addition, incorporation of atomically thin hexagonal boron nitride (hBN) encapsulation layers enable the stable and practical high performance even under the ambient condition. Therefore, electrically driven ultrafast graphene light emitters paves the way towards the realization of ultrahigh bandwidth density photonic integrated circuits and efficient optical communications networks.

Ultrafast control and monitoring of material properties using terahertz pulses

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

Bowlan, Pamela Renee

These are a set of slides on ultrafast control and monitoring of material properties using terahertz pulses. A few of the topics covered in these slides are: How fast is a femtosecond (fs), Different frequencies probe different properties of molecules or solids, What can a THz pulse do to a material, Ultrafast spectroscopy, Generating and measuring ultrashort THz pulses, Tracking ultrafast spin dynamics in antiferromagnets through spin wave resonances, Coherent two-dimensional THz spectroscopy, and Probing vibrational dynamics at a surface. Conclusions are: Coherent two-dimensional THz spectroscopy: a powerful approach for studying coherence and dynamics of low energy resonances. Applying thismore » to graphene we investigated the very strong THz light mater interaction which dominates over scattering. Useful for studying coupled excitations in multiferroics and monitoring chemical reactions. Also, THz-pump, SHG-probe spectoscopy: an ultrafast, surface sensitive probe of atomic-scale symmetry changes and nonlinear phonon dymanics. We are using this in Bi 2Se 3 to investigate the nonlinear surface phonon dynamics. This is potentially very useful for studying catalysis.« less

Ultrafast structural and electronic dynamics of the metallic phase in a layered manganite

PubMed Central

Piazza, L.; Ma, C.; Yang, H. X.; Mann, A.; Zhu, Y.; Li, J. Q.; Carbone, F.

2013-01-01

The transition between different states in manganites can be driven by various external stimuli. Controlling these transitions with light opens the possibility to investigate the microscopic path through which they evolve. We performed femtosecond (fs) transmission electron microscopy on a bi-layered manganite to study its response to ultrafast photoexcitation. We show that a photoinduced temperature jump launches a pressure wave that provokes coherent oscillations of the lattice parameters, detected via ultrafast electron diffraction. Their impact on the electronic structure are monitored via ultrafast electron energy loss spectroscopy, revealing the dynamics of the different orbitals in response to specific structural distortions. PMID:26913564

Ultrafast exciton dynamics in cadmium selenide nanocrystals determined by femtosecond fluorescence upconversion spectroscopy

NASA Astrophysics Data System (ADS)

Underwood, David Frederick

Femtosecond fluorescence upconversion spectroscopy is a technique that allows the unambiguous determination of the excited state dynamics of an analyte. Combining this method with the use of tunable laser excitation, the exciton dynamics in semiconducting nanocrystals (NC's) of cadmium selenide (CdSe) have been determined, devoid of the complications arising from more common spectroscopic methods such as pump-probe. The results of this investigation were used to construct a model to fully describe the three-level system comprising of the valence and conduction bands and surface states, which have been calculated by others to lie mid-gap in energy. Smaller NC's showed faster decay components due to increased interaction between the exciton and surface states. The deep trap emission, which has never before been measured by ultrafast fluorescence techniques, shows a rapid rise time (˜2 ps), which is attributed to surface selenium dangling bonds relaxing to the valence band and radiatively combining with the photo-generated hole. The band edge fluorescence decays as the deep trap emission grows in, inherently coupling the two processes. An experiment which measured the dependence of the excitation energy showed that increased energy imparted to the NC's resulted in increased rise times, yielding the timescales for exciton relaxation through the valence and conduction band states to the lowest emitting state. Surface-oxidized and normally-passivated NC's display the same decay dynamics in time but differ in relative amplitude; the latter point agrees with steady-state measurements. The rotational anisotrophy of the NC's was measured and agrees with previous pump-probe data. Upconversion on the red and blue sides of the static fluorescence spectrum showed no discernable differences, which is either and inherent limitation of the experimental apparatus, or the possibility that lower-lying triplet states are populated on a timescale below the instrument resolution.

Effects of single atom doping on the ultrafast electron dynamics of M1Au24(SR)18 (M = Pd, Pt) nanoclusters.

PubMed

Zhou, Meng; Qian, Huifeng; Sfeir, Matthew Y; Nobusada, Katsuyuki; Jin, Rongchao

2016-04-07

Atomically precise, doped metal clusters are receiving wide research interest due to their synergistic properties dependent on the metal composition. To understand the electronic properties of doped clusters, it is highly desirable to probe the excited state behavior. Here, we report the ultrafast relaxation dynamics of doped M1@Au24(SR)18 (M = Pd, Pt; R = CH2CH2Ph) clusters using femtosecond visible and near infrared transient absorption spectroscopy. Three relaxation components are identified for both mono-doped clusters: (1) sub-picosecond relaxation within the M1Au12 core states; (2) core to shell relaxation in a few picoseconds; and (3) relaxation back to the ground state in more than one nanosecond. Despite similar relaxation pathways for the two doped nanoclusters, the coupling between the metal core and surface ligands is accelerated by over 30% in the case of the Pt dopant compared with the Pd dopant. Compared to Pd doping, the case of Pt doping leads to much more drastic changes in the steady state and transient absorption of the clusters, which indicates that the 5d orbitals of the Pt atom are more strongly mixed with Au 5d and 6s orbitals than the 4d orbitals of the Pd dopant. These results demonstrate that a single foreign atom can lead to entirely different excited state spectral features of the whole cluster compared to the parent Au25(SR)18 cluster. The detailed excited state dynamics of atomically precise Pd/Pt doped gold clusters help further understand their properties and benefit the development of energy-related applications.

Effects of single atom doping on the ultrafast electron dynamics of M 1Au 24(SR) 18 (M = Pd, Pt) nanoclusters

DOE PAGES

Zhou, Meng; Qian, Huifeng; Sfeir, Matthew Y.; ...

2016-02-29

Atomically precise, doped metal clusters are receiving wide research interest due to their synergistic properties dependent on the metal composition. To understand the electronic properties of doped clusters, it is highly desirable to probe the excited state behavior. Here, we report the ultrafast relaxation dynamics of doped M 1@Au 24(SR) 18 (M = Pd, Pt; R = CH 2CH 2Ph) clusters using femtosecond visible and near infrared transient absorption spectroscopy. Three relaxation components are identified for both mono-doped clusters: (1) sub-picosecond relaxation within the M 1Au 12 core states; (2) core to shell relaxation in a few picoseconds; and (3)more » relaxation back to the ground state in more than one nanosecond. Despite similar relaxation pathways for the two doped nanoclusters, the coupling between the metal core and surface ligands is accelerated by over 30% in the case of the Pt dopant compared with the Pd dopant. Compared to Pd doping, the case of Pt doping leads to much more drastic changes in the steady state and transient absorption of the clusters, which indicates that the 5d orbitals of the Pt atom are more strongly mixed with Au 5d and 6s orbitals than the 4d orbitals of the Pd dopant. These results demonstrate that a single foreign atom can lead to entirely different excited state spectral features of the whole cluster compared to the parent Au 25(SR) 18 cluster. As a result, the detailed excited state dynamics of atomically precise Pd/Pt doped gold clusters help further understand their properties and benefit the development of energy-related applications.« less

Ultrafast investigation of photoinduced charge transfer in aminoanthraquinone pharmaceutical product

NASA Astrophysics Data System (ADS)

Zhang, Song; Sun, Simei; Zhou, Miaomiao; Wang, Lian; Zhang, Bing

2017-02-01

We investigated the mechanism of intramolecular charge transfer and the following radiationless dynamics of the excited states of 1-aminoanthraquinone using steady state and time-resolved absorption spectroscopy combined with quantum chemical calculations. Following photoexcitation with 460 nm, conformational relaxation via twisting of the amino group, charge transfer and the intersystem crossing (ISC) processes have been established to be the major relaxation pathways responsible for the ultrafast nonradiative of the excited S1 state. Intramolecular proton transfer, which could be induced by intramolecular hydrogen bonding is inspected and excluded. Time-dependent density functional theory (TDDFT) calculations reveal the change of the dipole moments of the S0 and S1 states along the twisted coordinate of the amino group, indicating the mechanism of twisted intra-molecular charge transfer (TICT). The timescale of TICT is measured to be 5 ps due to the conformational relaxation and a barrier on the S1 potential surface. The ISC from the S1 state to the triplet manifold is a main deactivation pathway with the decay time of 28 ps. Our results observed here have yield a physically intuitive and complete picture of the photoinduced charge transfer and radiationless dynamics in anthraquinone pharmaceutial products.

Vibrational energy flow in photoactive yellow protein revealed by infrared pump-visible probe spectroscopy.

PubMed

Nakamura, Ryosuke; Hamada, Norio

2015-05-14

Vibrational energy flow in the electronic ground state of photoactive yellow protein (PYP) is studied by ultrafast infrared (IR) pump-visible probe spectroscopy. Vibrational modes of the chromophore and the surrounding protein are excited with a femtosecond IR pump pulse, and the subsequent vibrational dynamics in the chromophore are selectively probed with a visible probe pulse through changes in the absorption spectrum of the chromophore. We thus obtain the vibrational energy flow with four characteristic time constants. The vibrational excitation with an IR pulse at 1340, 1420, 1500, or 1670 cm(-1) results in ultrafast intramolecular vibrational redistribution (IVR) with a time constant of 0.2 ps. The vibrational modes excited through the IVR process relax to the initial ground state with a time constant of 6-8 ps in parallel with vibrational cooling with a time constant of 14 ps. In addition, upon excitation with an IR pulse at 1670 cm(-1), we observe the energy flow from the protein backbone to the chromophore that occurs with a time constant of 4.2 ps.

Ultrafast vibrational energy flow in water monomers in acetonitrile

NASA Astrophysics Data System (ADS)

Dahms, Fabian; Costard, Rene; Nibbering, Erik T. J.; Elsaesser, Thomas

2016-05-01

Vibrational relaxation of the OH stretching and bending modes of water monomers in acetonitrile is studied by two-color pump-probe experiments in a frequency range from 1400 to 3800 cm-1. Measurements with resonant infrared excitation reveal vibrational lifetimes of 6.4 ± 1.0 ps of the OH stretching modes and 4.0 ± 0.5 ps of the OH bending mode. After OH stretching excitation, the OH bending mode shows an instantaneous response, a hallmark of the anharmonic coupling of stretching and bending modes, and a delayed population buildup by relaxation of the stretching via the bending mode. The relaxation steps are discussed within the framework of current theoretical pictures of water's vibrational relaxation.

Ultrafast spatiotemporal relaxation dynamics of excited electrons in a metal nanostructure detected by femtosecond-SNOM.

PubMed

Li, Zhi; Yue, Song; Chen, Jianjun; Gong, Qihuang

2010-06-21

Ultrahigh spatiotemporal resolved pump-probe signal near a gold nano-slit is detected by femtosecond-SNOM. By employing two-color pump-probe configuration and probing at the interband transition wavelength of the gold, signal contributed by surface plasmon polariton is avoided and spatiotemporal evolvement of excited electrons is successfully observed. From the contrast decaying of the periodical distribution of the pump-probe signal, ultrafast diffusion of excited electrons with a time scale of a few hundred femtoseconds is clearly identified. For comparison, such phenomenon cannot be observed by the one-color pump-probe configuration.

Imaging ultrafast excited state pathways in transition metal complexes by X-ray transient absorption and scattering using X-ray free electron laser source

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

Chen, Lin X.; Shelby, Megan L.; Lestrange, Patrick J.

2016-01-01

This report will describe our recent studies of transition metal complex structural dynamics on the fs and ps time scales using an X-ray free electron laser source, Linac Coherent Light Source (LCLS). Ultrafast XANES spectra at the Ni K-edge of nickel(II) tetramesitylporphyrin (NiTMP) were successfully measured for optically excited state at a timescale from 100 fs to 50 ps, providing insight into its sub-ps electronic and structural relaxation processes. Importantly, a transient reduced state Ni(I) (π, 3dx2-y2) electronic state is captured through the interpretation of a short-lived excited state absorption on the low-energy shoulder of the edge, which is aidedmore » by the computation of X-ray transitions for postulated excited electronic states. The observed and computed inner shell to valence orbital transition energies demonstrate and quantify the influence of electronic configuration on specific metal orbital energies. A strong influence of the valence orbital occupation on the inner shell orbital energies indicates that one should not use the transition energy from 1s to other orbitals to draw conclusions about the d-orbital energies. For photocatalysis, a transient electronic configuration could influence d-orbital energies up to a few eV and any attempt to steer the reaction pathway should account for this to ensure that external energies can be used optimally in driving desirable processes. NiTMP structural evolution and the influence of the porphyrin macrocycle conformation on relaxation kinetics can be likewise inferred from this study.« less

The Behavior of Hydrogen Under Extreme Conditions on Ultrafast Timescales (A "Life at the Frontiers of Energy Research" contest entry from the 2011 Energy Frontier Research Centers (EFRCs) Summit and Forum)

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

None

"The Behavior of Hydrogen Under Extreme Conditions on Ultrafast Timescales" was submitted by the Center for Energy Frontier Research in Extreme Environments (EFree) to the "Life at the Frontiers of Energy Research" video contest at the 2011 Science for Our Nation's Energy Future: Energy Frontier Research Centers (EFRCs) Summit and Forum. Twenty-six EFRCs created short videos to highlight their mission and their work. EFree is directed by Ho-kwang Mao at the Carnegie Institute of Science in Washington, DC and is a partnership of scientists from thirteen institutions.The Office of Basic Energy Sciences in the U.S. Department of Energy's Office ofmore » Science established the 46 Energy Frontier Research Centers (EFRCs) in 2009. These collaboratively-organized centers conduct fundamental research focused on 'grand challenges' and use-inspired 'basic research needs' recently identified in major strategic planning efforts by the scientific community. The overall purpose is to accelerate scientific progress toward meeting the nation's critical energy challenges. The mission of Energy Frontier Research in Extreme Environments is 'to accelerate the discovery and creation of energy-relevant materials using extreme pressures and temperatures.' Research topics are: catalysis (CO2, water), photocatalysis, solid state lighting, optics, thermelectric, phonons, thermal conductivity, solar electrodes, fuel cells, superconductivity, extreme environment, radiation effects, defects, spin dynamics, CO2 (capture, convert, store), greenhouse gas, hydrogen (fuel, storage), ultrafast physics, novel materials synthesis, and defect tolerant materials.« less

Ablation experiment and threshold calculation of titanium alloy irradiated by ultra-fast pulse laser

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

Zheng, Buxiang; Jiang, Gedong; Wang, Wenjun, E-mail: wenjunwang@mail.xjtu.edu.cn

The interaction between an ultra-fast pulse laser and a material's surface has become a research hotspot in recent years. Micromachining of titanium alloy with an ultra-fast pulse laser is a very important research direction, and it has very important theoretical significance and application value in investigating the ablation threshold of titanium alloy irradiated by ultra-fast pulse lasers. Irradiated by a picosecond pulse laser with wavelengths of 1064 nm and 532 nm, the surface morphology and feature sizes, including ablation crater width (i.e. diameter), ablation depth, ablation area, ablation volume, single pulse ablation rate, and so forth, of the titanium alloymore » were studied, and their ablation distributions were obtained. The experimental results show that titanium alloy irradiated by a picosecond pulse infrared laser with a 1064 nm wavelength has better ablation morphology than that of the green picosecond pulse laser with a 532 nm wavelength. The feature sizes are approximately linearly dependent on the laser pulse energy density at low energy density and the monotonic increase in laser pulse energy density. With the increase in energy density, the ablation feature sizes are increased. The rate of increase in the feature sizes slows down gradually once the energy density reaches a certain value, and gradually saturated trends occur at a relatively high energy density. Based on the linear relation between the laser pulse energy density and the crater area of the titanium alloy surface, and the Gaussian distribution of the laser intensity on the cross section, the ablation threshold of titanium alloy irradiated by an ultra-fast pulse laser was calculated to be about 0.109 J/cm{sup 2}.« less

Engineering model for ultrafast laser microprocessing

NASA Astrophysics Data System (ADS)

Audouard, E.; Mottay, E.

2016-03-01

Ultrafast laser micro-machining relies on complex laser-matter interaction processes, leading to a virtually athermal laser ablation. The development of industrial ultrafast laser applications benefits from a better understanding of these processes. To this end, a number of sophisticated scientific models have been developed, providing valuable insights in the physics of the interaction. Yet, from an engineering point of view, they are often difficult to use, and require a number of adjustable parameters. We present a simple engineering model for ultrafast laser processing, applied in various real life applications: percussion drilling, line engraving, and non normal incidence trepanning. The model requires only two global parameters. Analytical results are derived for single pulse percussion drilling or simple pass engraving. Simple assumptions allow to predict the effect of non normal incident beams to obtain key parameters for trepanning drilling. The model is compared to experimental data on stainless steel with a wide range of laser characteristics (time duration, repetition rate, pulse energy) and machining conditions (sample or beam speed). Ablation depth and volume ablation rate are modeled for pulse durations from 100 fs to 1 ps. Trepanning time of 5.4 s with a conicity of 0.15° is obtained for a hole of 900 μm depth and 100 μm diameter.

Tuning ultrafast electron injection dynamics at organic-graphene/metal interfaces.

PubMed

Ravikumar, Abhilash; Kladnik, Gregor; Müller, Moritz; Cossaro, Albano; Bavdek, Gregor; Patera, Laerte L; Sánchez-Portal, Daniel; Venkataraman, Latha; Morgante, Alberto; Brivio, Gian Paolo; Cvetko, Dean; Fratesi, Guido

2018-05-03

We compare the ultrafast charge transfer dynamics of molecules on epitaxial graphene and bilayer graphene grown on Ni(111) interfaces through first principles calculations and X-ray resonant photoemission spectroscopy. We use 4,4'-bipyridine as a prototypical molecule for these explorations as the energy level alignment of core-excited molecular orbitals allows ultrafast injection of electrons from a substrate to a molecule on a femtosecond timescale. We show that the ultrafast injection of electrons from the substrate to the molecule is ∼4 times slower on weakly coupled bilayer graphene than on epitaxial graphene. Through our experiments and calculations, we can attribute this to a difference in the density of states close to the Fermi level between graphene and bilayer graphene. We therefore show how graphene coupling with the substrate influences charge transfer dynamics between organic molecules and graphene interfaces.

Ultrafast laser-induced modifications of energy bands of non-metal crystals

NASA Astrophysics Data System (ADS)

Gruzdev, Vitaly

2009-10-01

Ultrafast laser-induced variations of electron energy bands of transparent solids significantly influence ionization and conduction-band electron absorption driving the initial stage of laser-induced damage (LID). The mechanisms of the variations are attributed to changing electron functions from bonding to anti-bonding configuration via laser-induced ionization; laser-driven electron oscillations in quasi-momentum space; and direct distortion of the inter-atomic potential by electric field of laser radiation. The ionization results in the band-structure modification via accumulation of broken chemical bonds between atoms and provides significant contribution to the overall modification only when enough excited electrons are accumulated in the conduction band. The oscillations are associated with modification of electron energy by pondermotive potential of the oscillations. The direct action of radiation's electric field leads to specific high-frequency Franz-Keldysh effect (FKE) spreading the allowed electron states into the bands of forbidden energy. Those processes determine the effective band gap that is a laser-driven energy gap between the modified electron energy bands. Among those mechanisms, the latter two provide reversible band-structure modification that takes place from the beginning of the ionization and are, therefore, of special interest due to their strong influence on the initial stage of the ionization. The pondermotive potential results either in monotonous increase or oscillatory variations of the effective band gap that has been taken into account in some ionization models. The classical FKE provides decrease of the band gap. We analyzing the competition between those two opposite trends of the effective-band-gap variations and discuss applications of those effects for considerations of the laser-induced damage and its threshold in transparent solids.

Ab initio nonadiabatic molecular dynamics of the ultrafast electron injection from a PbSe quantum dot into the TiO2 surface.

PubMed

Long, Run; Prezhdo, Oleg V

2011-11-30

Following recent experiments [Science 2010, 328, 1543; PNAS 2011, 108, 965], we report an ab initio nonadiabatic molecular dynamics (NAMD) simulation of the ultrafast photoinduced electron transfer (ET) from a PbSe quantum dot (QD) into the rutile TiO(2) (110) surface. The system forms the basis for QD-sensitized semiconductor solar cells and demonstrates that ultrafast interfacial ET is instrumental for achieving high efficiencies in solar-to-electrical energy conversion. The simulation supports the observation that the ET successfully competes with energy losses due to electron-phonon relaxation. The ET proceeds by the adiabatic mechanism because of strong donor-acceptor coupling. High frequency polar vibrations of both QD and TiO(2) promote the ET, since these modes can rapidly influence the donor-acceptor state energies and coupling. Low frequency vibrations generate a distribution of initial conditions for ET, which shows a broad variety of scenarios at the single-molecule level. Compared to the molecule-TiO(2) interfaces, the QD-TiO(2) system exhibits pronounced differences that arise due to the larger size and higher rigidity of QDs relative to molecules. Both donor and acceptor states are more delocalized in the QD system, and the ET is promoted by optical phonons, which have relatively low frequencies in the QD materials composed of heavy elements. In contrast, in molecular systems, optical phonons are not thermally accessible under ambient conditions. Meanwhile, TiO(2) acceptor states resemble surface impurities due to the local influence of molecular chromophores. At the same time, the photoinduced ET at both QD-TiO(2) and molecule-TiO(2) interfaces is ultrafast and occurs by the adiabatic mechanism, as a result of strong donor-acceptor coupling. The reported state-of-the-art simulation generates a detailed time-domain atomistic description of the interfacial ET process that is fundamental to a wide variety of applications.

Ultrafast Graphene Light Emitters.

PubMed

Kim, Young Duck; Gao, Yuanda; Shiue, Ren-Jye; Wang, Lei; Aslan, Ozgur Burak; Bae, Myung-Ho; Kim, Hyungsik; Seo, Dongjea; Choi, Heon-Jin; Kim, Suk Hyun; Nemilentsau, Andrei; Low, Tony; Tan, Cheng; Efetov, Dmitri K; Taniguchi, Takashi; Watanabe, Kenji; Shepard, Kenneth L; Heinz, Tony F; Englund, Dirk; Hone, James

2018-02-14

Ultrafast electrically driven nanoscale light sources are critical components in nanophotonics. Compound semiconductor-based light sources for the nanophotonic platforms have been extensively investigated over the past decades. However, monolithic ultrafast light sources with a small footprint remain a challenge. Here, we demonstrate electrically driven ultrafast graphene light emitters that achieve light pulse generation with up to 10 GHz bandwidth across a broad spectral range from the visible to the near-infrared. The fast response results from ultrafast charge-carrier dynamics in graphene and weak electron-acoustic phonon-mediated coupling between the electronic and lattice degrees of freedom. We also find that encapsulating graphene with hexagonal boron nitride (hBN) layers strongly modifies the emission spectrum by changing the local optical density of states, thus providing up to 460% enhancement compared to the gray-body thermal radiation for a broad peak centered at 720 nm. Furthermore, the hBN encapsulation layers permit stable and bright visible thermal radiation with electronic temperatures up to 2000 K under ambient conditions as well as efficient ultrafast electronic cooling via near-field coupling to hybrid polaritonic modes under electrical excitation. These high-speed graphene light emitters provide a promising path for on-chip light sources for optical communications and other optoelectronic applications.

Correlating Nanoscopic Energy Transfer and Far-Field Emission to Unravel Lasing Dynamics in Plasmonic Nanocavity Arrays

DOE PAGES

Deeb, Claire; Guo, Zhi; Yang, Ankun; ...

2018-01-25

Excited-state interactions between nanoscale cavities and photoactive molecules are critical in plasmonic nanolasing, although the underlying details are less-resolved. This paper reports direct visualization of the energy-transfer dynamics between two-dimensional arrays of plasmonic gold bowtie nanocavities and dye molecules. Transient absorption microscopy measurements of single bowties within the array surrounded by gain molecules showed fast excited-state quenching (2.6 ± 1 ps) characteristic of individual nanocavities. Upon optical pumping at powers above threshold, lasing action emerged depending on the spacing of the array. By correlating ultrafast microscopy and far-field light emission characteristics, we found that bowtie nanoparticles acted as isolated cavitiesmore » when the diffractive modes of the array did not couple to the plasmonic gap mode. These results demonstrate how ultrafast microscopy can provide insight into energy relaxation pathways and, specifically, how nanocavities in arrays can show single-unit nanolaser properties.« less

Correlating Nanoscopic Energy Transfer and Far-Field Emission to Unravel Lasing Dynamics in Plasmonic Nanocavity Arrays

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

Deeb, Claire; Guo, Zhi; Yang, Ankun

Excited-state interactions between nanoscale cavities and photoactive molecules are critical in plasmonic nanolasing, although the underlying details are less-resolved. This paper reports direct visualization of the energy-transfer dynamics between two-dimensional arrays of plasmonic gold bowtie nanocavities and dye molecules. Transient absorption microscopy measurements of single bowties within the array surrounded by gain molecules showed fast excited-state quenching (2.6 ± 1 ps) characteristic of individual nanocavities. Upon optical pumping at powers above threshold, lasing action emerged depending on the spacing of the array. By correlating ultrafast microscopy and far-field light emission characteristics, we found that bowtie nanoparticles acted as isolated cavitiesmore » when the diffractive modes of the array did not couple to the plasmonic gap mode. These results demonstrate how ultrafast microscopy can provide insight into energy relaxation pathways and, specifically, how nanocavities in arrays can show single-unit nanolaser properties.« less

Ultrafast intersystem crossings in Fe-Co Prussian blue analogues

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

van Veenendaal, Michel

Ultrafast spincrossover is studied in Fe-Co Prussian blue analogues using a dissipative quantum-mechanical model of a cobalt ion coupled to a breathing mode. All electronic interactions are treated on an equal footing. It is theoretically demonstrated that the divalent cobalt ion reaches 90% of the S = 3/2 value within 20 fs after photoexciting a low-spin Co 3+ ion by an iron-to-cobalt charge transfer. The doublet-to-quartet spin crossover is significantly faster than the oscillation period of the breathing mode. The system relaxes to the lowest manifold of divalent cobalt ( 4T 1) in 150-200 fs. In conclusion, strong oscillations inmore » spin-orbit coupling and the involvement of higher-lying quartets are found.« less

Ultrafast intersystem crossings in Fe-Co Prussian blue analogues

DOE PAGES

van Veenendaal, Michel

2017-07-27

Ultrafast spincrossover is studied in Fe-Co Prussian blue analogues using a dissipative quantum-mechanical model of a cobalt ion coupled to a breathing mode. All electronic interactions are treated on an equal footing. It is theoretically demonstrated that the divalent cobalt ion reaches 90% of the S = 3/2 value within 20 fs after photoexciting a low-spin Co 3+ ion by an iron-to-cobalt charge transfer. The doublet-to-quartet spin crossover is significantly faster than the oscillation period of the breathing mode. The system relaxes to the lowest manifold of divalent cobalt ( 4T 1) in 150-200 fs. In conclusion, strong oscillations inmore » spin-orbit coupling and the involvement of higher-lying quartets are found.« less

Sensing Atomic Motion from the Zero Point to Room Temperature with Ultrafast Atom Interferometry.

PubMed

Johnson, K G; Neyenhuis, B; Mizrahi, J; Wong-Campos, J D; Monroe, C

2015-11-20

We sense the motion of a trapped atomic ion using a sequence of state-dependent ultrafast momentum kicks. We use this atom interferometer to characterize a nearly pure quantum state with n=1 phonon and accurately measure thermal states ranging from near the zero-point energy to n[over ¯]~10^{4}, with the possibility of extending at least 100 times higher in energy. The complete energy range of this method spans from the ground state to far outside of the Lamb-Dicke regime, where atomic motion is greater than the optical wavelength. Apart from thermometry, these interferometric techniques are useful for characterizing ultrafast entangling gates between multiple trapped ions.

Distributed ultrafast fibre laser

PubMed Central

Liu, Xueming; Cui, Yudong; Han, Dongdong; Yao, Xiankun; Sun, Zhipei

2015-01-01

A traditional ultrafast fibre laser has a constant cavity length that is independent of the pulse wavelength. The investigation of distributed ultrafast (DUF) lasers is conceptually and technically challenging and of great interest because the laser cavity length and fundamental cavity frequency are changeable based on the wavelength. Here, we propose and demonstrate a DUF fibre laser based on a linearly chirped fibre Bragg grating, where the total cavity length is linearly changeable as a function of the pulse wavelength. The spectral sidebands in DUF lasers are enhanced greatly, including the continuous-wave (CW) and pulse components. We observe that all sidebands of the pulse experience the same round-trip time although they have different round-trip distances and refractive indices. The pulse-shaping of the DUF laser is dominated by the dissipative processes in addition to the phase modulations, which makes our ultrafast laser simple and stable. This laser provides a simple, stable, low-cost, ultrafast-pulsed source with controllable and changeable cavity frequency. PMID:25765454

Ultrafast dynamics of ligand and substrate interaction in endothelial nitric oxide synthase under Soret excitation.

PubMed

Hung, Chih-Chang; Yabushita, Atsushi; Kobayashi, Takayoshi; Chen, Pei-Feng; Liang, Keng S

2016-01-01

Ultrafast transient absorption spectroscopy of endothelial NOS oxygenase domain (eNOS-oxy) was performed to study dynamics of ligand or substrate interaction under Soret band excitation. Photo-excitation dissociates imidazole ligand in <300fs, then followed by vibrational cooling and recombination within 2ps. Such impulsive bond breaking and late rebinding generate proteinquakes, which relaxes in several tens of picoseconds. The photo excited dynamics of eNOS-oxy with L-arginine substrate mainly occurs at the local site of heme, including ultrafast internal conversion within 400fs, vibrational cooling, charge transfer, and complete ground-state recovery within 1.4ps. The eNOS-oxy without additive is partially bound with water molecule, thus its photoexcited dynamics also shows ligand dissociation in <800fs. Then it followed by vibrational cooling coupled with charge transfer in 4.8ps, and recombination of ligand to distal side of heme in 12ps. Copyright © 2016 Elsevier B.V. All rights reserved.

Linear and ultrafast nonlinear plasmonics of single nano-objects

NASA Astrophysics Data System (ADS)

Crut, Aurélien; Maioli, Paolo; Vallée, Fabrice; Del Fatti, Natalia

2017-03-01

Single-particle optical investigations have greatly improved our understanding of the fundamental properties of nano-objects, avoiding the spurious inhomogeneous effects that affect ensemble experiments. Correlation with high-resolution imaging techniques providing morphological information (e.g. electron microscopy) allows a quantitative interpretation of the optical measurements by means of analytical models and numerical simulations. In this topical review, we first briefly recall the principles underlying some of the most commonly used single-particle optical techniques: near-field, dark-field, spatial modulation and photothermal microscopies/spectroscopies. We then focus on the quantitative investigation of the surface plasmon resonance (SPR) of metallic nano-objects using linear and ultrafast optical techniques. While measured SPR positions and spectral areas are found in good agreement with predictions based on Maxwell’s equations, SPR widths are strongly influenced by quantum confinement (or, from a classical standpoint, surface-induced electron scattering) and, for small nano-objects, cannot be reproduced using the dielectric functions of bulk materials. Linear measurements on single nano-objects (silver nanospheres and gold nanorods) allow a quantification of the size and geometry dependences of these effects in confined metals. Addressing the ultrafast response of an individual nano-object is also a powerful tool to elucidate the physical mechanisms at the origin of their optical nonlinearities, and their electronic, vibrational and thermal relaxation processes. Experimental investigations of the dynamical response of gold nanorods are shown to be quantitatively modeled in terms of modifications of the metal dielectric function enhanced by plasmonic effects. Ultrafast spectroscopy can also be exploited to unveil hidden physical properties of more complex nanosystems. In this context, two-color femtosecond pump-probe experiments performed on individual

Practical Design and Applications of Ultrafast Semiconductor Disk Lasers

NASA Astrophysics Data System (ADS)

Baker, Caleb W.

Vertical External Cavity Surface Emitting Lasers (VECSELs) have become well established in recent years for their design flexibility and promising power scalability. Recent efforts in VECSEL development have focused heavily on expanding the medium into the ultrafast regime of modelocked operation. Presented in this thesis is a detailed discussion regarding the development of ultrafast VECSEL devices. Achievements in continuous wave (CW) operation will be highlighted, followed by several chapters detailing the engineering challenges and design solutions which enable modelocked operation of VECSELs in the ultrafast regime, including the design of the saturable absorbers used to enforce modelocking, management of the net group delay dispersion (GDD) inside the cavity, and the design of the active region to support pulse durations on the order of 100 fs. Work involving specific applications - VECSELs emitting on multiple wavelengths simultaneously and the use of VECSEL seed oscillators for amplification and spectral broadening - will also be presented. Key experimental results will include a novel multi-fold cavity design that produced record-setting peak powers of 6.3 kW from a modelocked VECSEL, an octave-spanning supercontinuum with an average power of 2 W generated using a VECSEL seed and a 2-stage Yb fiber amplifier, and two separate experiments where a VECSEL was made to emit on multiple wavelengths simultaneously in modelocked and highly stable CW operation, respectively. Further, many diagnostic and characterization measurements will be presented, most notably the in-situ probing of a VECSEL gain medium during stable modelocked operation with temporal resolution on the order of 100 fs, but also including characterization of the relaxation rates in different saturable absorber designs and the effectiveness of different methods for managing the net GDD of a device.

Modified relaxation dynamics and coherent energy exchange in coupled vibration-cavity polaritons

PubMed Central

Dunkelberger, A. D.; Spann, B. T.; Fears, K. P.; Simpkins, B. S.; Owrutsky, J. C.

2016-01-01

Coupling vibrational transitions to resonant optical modes creates vibrational polaritons shifted from the uncoupled molecular resonances and provides a convenient way to modify the energetics of molecular vibrations. This approach is a viable method to explore controlling chemical reactivity. In this work, we report pump–probe infrared spectroscopy of the cavity-coupled C–O stretching band of W(CO)6 and the direct measurement of the lifetime of a vibration-cavity polariton. The upper polariton relaxes 10 times more quickly than the uncoupled vibrational mode. Tuning the polariton energy changes the polariton transient spectra and relaxation times. We also observe quantum beats, so-called vacuum Rabi oscillations, between the upper and lower vibration-cavity polaritons. In addition to establishing that coupling to an optical cavity modifies the energy-transfer dynamics of the coupled molecules, this work points out the possibility of systematic and predictive modification of the excited-state kinetics of vibration-cavity polariton systems. PMID:27874010

Roadmap on ultrafast optics

NASA Astrophysics Data System (ADS)

Reid, Derryck T.; Heyl, Christoph M.; Thomson, Robert R.; Trebino, Rick; Steinmeyer, Günter; Fielding, Helen H.; Holzwarth, Ronald; Zhang, Zhigang; Del'Haye, Pascal; Südmeyer, Thomas; Mourou, Gérard; Tajima, Toshiki; Faccio, Daniele; Harren, Frans J. M.; Cerullo, Giulio

2016-09-01

The year 2015 marked the 25th anniversary of modern ultrafast optics, since the demonstration of the first Kerr lens modelocked Ti:sapphire laser in 1990 (Spence et al 1990 Conf. on Lasers and Electro-Optics, CLEO, pp 619-20) heralded an explosion of scientific and engineering innovation. The impact of this disruptive technology extended well beyond the previous discipline boundaries of lasers, reaching into biology labs, manufacturing facilities, and even consumer healthcare and electronics. In recognition of such a milestone, this roadmap on Ultrafast Optics draws together articles from some of the key opinion leaders in the field to provide a freeze-frame of the state-of-the-art, while also attempting to forecast the technical and scientific paradigms which will define the field over the next 25 years. While no roadmap can be fully comprehensive, the thirteen articles here reflect the most exciting technical opportunities presented at the current time in Ultrafast Optics. Several articles examine the future landscape for ultrafast light sources, from practical solid-state/fiber lasers and Raman microresonators to exotic attosecond extreme ultraviolet and possibly even zeptosecond x-ray pulses. Others address the control and measurement challenges, requiring radical approaches to harness nonlinear effects such as filamentation and parametric generation, coupled with the question of how to most accurately characterise the field of ultrafast pulses simultaneously in space and time. Applications of ultrafast sources in materials processing, spectroscopy and time-resolved chemistry are also discussed, highlighting the improvements in performance possible by using lasers of higher peak power and repetition rate, or by exploiting the phase stability of emerging new frequency comb sources.

Ultrafast dynamics and excited state spectra of open-chain carotenoids at room and low temperatures.

PubMed

Niedzwiedzki, Dariusz; Koscielecki, Jeremy F; Cong, Hong; Sullivan, James O; Gibson, George N; Birge, Robert R; Frank, Harry A

2007-05-31

, for the longest molecule in the series, spirilloxanthin, the experiments and a detailed quantum computational analysis reveal the presence of two S* states associated with relaxed S1 (2(1)Ag-) conformations involving nearly planar 6-s-cis and 6-s-trans geometries. We propose that in polar solvents, the ground state of spirilloxanthin takes on a corkscrew conformation that generates a net solute dipole moment while decreasing the cavity formation energy. Upon excitation and relaxation into the S1 (2(1)Ag-) state, the polyene unravels and flattens into a more planar geometry with comparable populations of 6-s-trans and 6-s-cis conformations.

Ultrafast and nonlinear surface-enhanced Raman spectroscopy.

PubMed

Gruenke, Natalie L; Cardinal, M Fernanda; McAnally, Michael O; Frontiera, Renee R; Schatz, George C; Van Duyne, Richard P

2016-04-21

Ultrafast surface-enhanced Raman spectroscopy (SERS) has the potential to study molecular dynamics near plasmonic surfaces to better understand plasmon-mediated chemical reactions such as plasmonically-enhanced photocatalytic or photovoltaic processes. This review discusses the combination of ultrafast Raman spectroscopic techniques with plasmonic substrates for high temporal resolution, high sensitivity, and high spatial resolution vibrational spectroscopy. First, we introduce background information relevant to ultrafast SERS: the mechanisms of surface enhancement in Raman scattering, the characterization of plasmonic materials with ultrafast techniques, and early complementary techniques to study molecule-plasmon interactions. We then discuss recent advances in surface-enhanced Raman spectroscopies with ultrafast pulses with a focus on the study of molecule-plasmon coupling and molecular dynamics with high sensitivity. We also highlight the challenges faced by this field by the potential damage caused by concentrated, highly energetic pulsed fields in plasmonic hotspots, and finally the potential for future ultrafast SERS studies.

Ultrafast pre-breakdown dynamics in Al₂O₃SiO₂ reflector by femtosecond UV laser spectroscopy.

PubMed

Du, Juan; Li, Zehan; Xue, Bing; Kobayashi, Takayoshi; Han, Dongjia; Zhao, Yuanan; Leng, Yuxin

2015-06-29

Ultrafast carrier dynamics in Al2O3/SiO2 high reflectors has been investigated by UV femtosecond laser. It is identified by laser spectroscopy that, the carrier dynamics contributed from the front few layers of Al2O3 play a dominating role in the initial laser-induced damage of the UV reflector. Time-resolved reflection decrease after the UV excitation is observed, and conduction electrons is found to relaxed to a mid-gap defect state locating about one photon below the conduction band . To interpret the laser induced carrier dynamics further, a theoretical model including electrons relaxation to a mid-gap state is built, and agrees very well with the experimental results.. To the best of our knowledge, this is the first study on the pre-damage dynamics in UV high reflector induced by femtosecond UV laser.

Direct observation of a photochemical activation energy: a case study of acetone photodissociation

NASA Astrophysics Data System (ADS)

Koch, Markus; Heim, Pascal; Thaler, Bernhard; Kitzler, Markus; Ernst, Wolfgang E.

2017-06-01

The ability to observe and quantify the conversion of electronic potential energy to vibrational kinetic energy in a molecule after photoexcitation is essential to understand and control the outcome of photoinduced molecular fragmentation. We exploit the high selectivity of photoelectron-photoion coincidence detection to distinguish different relaxation channels and observe the fragmentation behavior of each channel. We demonstrate the concept by investigating the fragmentation of gas-phase acetone molecules initiated by three-photon excitation to high lying Rydberg states between 9.0 and 9.5 eV above the ground state. By applying variations of the photon energy, pulse duration (100-200 fs) and pulse energy, we are able to fully characterize the fragmentation process. Rydberg states between 5s and 8s are populated, which undergo ultrafast internal conversion to lower states. The corresponding non-adiabatic dynamics in the neutral molecule cause the conversion of electronic to vibrational energy, leading to fragmentation. Our scheme allows us to directly measure the activation energy for fragmentation of acetone to an acetyl ion and a methyl radical, which we determine to be (0.79 ± 0.04) eV. Longer laser pulses result in an increased fragment-to-parent ratio, representing a higher probability for relaxation because the relaxation time constants are comparable to the pulse duration. Upon excitation to Rydberg states at 9.5 eV we surprisingly observe reduced fragmentation, although ˜2 eV are coupled into vibrational energy, indicating that different relaxation pathways become active, which results in a change of the redistribution of vibrational energy within the molecule. Fragmentation due to subsequent excitation of the cation is found to play a minor role.

Electron heating and thermal relaxation of gold nanorods revealed by two-dimensional electronic spectroscopy.

PubMed

Lietard, Aude; Hsieh, Cho-Shuen; Rhee, Hanju; Cho, Minhaeng

2018-03-01

To elucidate the complex interplay between the size and shape of gold nanorods and their electronic, photothermal, and optical properties for molecular imaging, photothermal therapy, and optoelectronic devices, it is a prerequisite to characterize ultrafast electron dynamics in gold nanorods. Time-resolved transient absorption (TA) studies of plasmonic electrons in various nanostructures have revealed the time scales for electron heating, lattice vibrational excitation, and phonon relaxation processes in condensed phases. However, because linear spectroscopic and time-resolved TA signals are vulnerable to inhomogeneous line-broadening, pure dephasing and direct electron heating effects are difficult to observe. Here we show that femtosecond two-dimensional electronic spectroscopy, with its unprecedented time resolution and phase sensitivity, can be used to collect direct experimental evidence for ultrafast electron heating, anomalously strong coherent and transient electronic plasmonic responses, and homogenous dephasing processes resulting from electron-vibration couplings even for polydisperse gold nanorods.

Coherent fifth-order visible-infrared spectroscopies: ultrafast nonequilibrium vibrational dynamics in solution.

PubMed

Lynch, Michael S; Slenkamp, Karla M; Cheng, Mark; Khalil, Munira

2012-07-05

Obtaining a detailed description of photochemical reactions in solution requires measuring time-evolving structural dynamics of transient chemical species on ultrafast time scales. Time-resolved vibrational spectroscopies are sensitive probes of molecular structure and dynamics in solution. In this work, we develop doubly resonant fifth-order nonlinear visible-infrared spectroscopies to probe nonequilibrium vibrational dynamics among coupled high-frequency vibrations during an ultrafast charge transfer process using a heterodyne detection scheme. The method enables the simultaneous collection of third- and fifth-order signals, which respectively measure vibrational dynamics occurring on electronic ground and excited states on a femtosecond time scale. Our data collection and analysis strategy allows transient dispersed vibrational echo (t-DVE) and dispersed pump-probe (t-DPP) spectra to be extracted as a function of electronic and vibrational population periods with high signal-to-noise ratio (S/N > 25). We discuss how fifth-order experiments can measure (i) time-dependent anharmonic vibrational couplings, (ii) nonequilibrium frequency-frequency correlation functions, (iii) incoherent and coherent vibrational relaxation and transfer dynamics, and (iv) coherent vibrational and electronic (vibronic) coupling as a function of a photochemical reaction.

Theoretical ultra-fast spectroscopy in transition metal dichalcogenides

NASA Astrophysics Data System (ADS)

Molina-Sanchez, Alejandro; Sangalli, Davide; Marini, Andrea; Wirtz, Ludger

Semiconducting 2D-materials like the transition metal dichalcogenides (TMDs) MoS2, MoSe2, WS2, WSe2 are promising alternatives to graphene for designing novel opto-electronic devices. The strong spin-orbit interaction along with the breaking of inversion symmetry in single-layer TMDs allow using the valley-index as a new quantum number. The practical use of valley physics depends on the lifetimes of valley-polarized excitons which are affected by scattering at phonons, impurities and by carrier-carrier interactions. The carrier dynamics can be monitored using ultra-fast spectroscopies such as pump-probe experiments. The carrier dynamics is simulated using non-equilibrium Green's function theory in an ab-initio framework. We include carrier relaxation through electron-phonon interaction. We obtain the transient absorption spectra of single-layer TMD and compare our simulations with recent pump-probe experiments

Energy Distribution among Reaction Products. III: The Method of Measured Relaxation Applied to H + Cl2

NASA Technical Reports Server (NTRS)

Pacey, P. D.; Polyani, J. C.

1971-01-01

The method of measured relaxation is described for the determination of initial vibrational energy distribution in the products of exothermic reaction. Hydrogen atoms coming from an orifice were diffused into flowing chlorine gas. Measurements were made of the resultant ir chemiluminescence at successive points along the line of flow. The concurrent processes of reaction, diffusion, flow, radiation, and deactivation were analyzed in some detail on a computer. A variety of relaxation models were used in an attempt to place limits on k(nu prime), the rate constant for reaction to form HCl in specified vibrational energy levels: H+Cl2 yields (sup K(nu prime) HCl(sub nu prime) + Cl. The set of k(?) obtained from this work is in satisfactory agreement with those obtained by another experimental method (the method of arrested relaxation described in Parts IV and V of the present series.

Real Gas Computation Using an Energy Relaxation Method and High-Order WENO Schemes

NASA Technical Reports Server (NTRS)

Montarnal, Philippe; Shu, Chi-Wang

1998-01-01

In this paper, we use a recently developed energy relaxation theory by Coquel and Perthame and high order weighted essentially non-oscillatory (WENO) schemes to simulate the Euler equations of real gas. The main idea is an energy decomposition into two parts: one part is associated with a simpler pressure law and the other part (the nonlinear deviation) is convected with the flow. A relaxation process is performed for each time step to ensure that the original pressure law is satisfied. The necessary characteristic decomposition for the high order WENO schemes is performed on the characteristic fields based on the first part. The algorithm only calls for the original pressure law once per grid point per time step, without the need to compute its derivatives or any Riemann solvers. Both one and two dimensional numerical examples are shown to illustrate the effectiveness of this approach.

Novel Electron-Phonon Relaxation Pathway in Graphite Revealed by Time-Resolved Raman Scattering and Angle-Resolved Photoemission Spectroscopy.

PubMed

Yang, Jhih-An; Parham, Stephen; Dessau, Daniel; Reznik, Dmitry

2017-01-19

Time dynamics of photoexcited electron-hole pairs is important for a number of technologies, in particular solar cells. We combined ultrafast pump-probe Raman scattering and photoemission to directly follow electron-hole excitations as well as the G-phonon in graphite after an excitation by an intense laser pulse. This phonon is known to couple relatively strongly to electrons. Cross-correlating effective electronic and phonon temperatures places new constraints on model-based fits. The accepted two-temperature model predicts that G-phonon population should start to increase as soon as excited electron-hole pairs are created and that the rate of increase should not depend strongly on the pump fluence. Instead we found that the increase of the G-phonon population occurs with a delay of ~65 fs. This time-delay is also evidenced by the absence of the so-called self-pumping for G phonons. It decreases with increased pump fluence. We show that these observations imply a new relaxation pathway: Instead of hot carriers transferring energy to G-phonons directly, the energy is first transferred to optical phonons near the zone boundary K-points, which then decay into G-phonons via phonon-phonon scattering. Our work demonstrates that phonon-phonon interactions must be included in any calculations of hot carrier relaxation in optical absorbers even when only short timescales are considered.

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.

Relaxation mode analysis and Markov state relaxation mode analysis for chignolin in aqueous solution near a transition temperature

NASA Astrophysics Data System (ADS)

Mitsutake, Ayori; Takano, Hiroshi

2015-09-01

It is important to extract reaction coordinates or order parameters from protein simulations in order to investigate the local minimum-energy states and the transitions between them. The most popular method to obtain such data is principal component analysis, which extracts modes of large conformational fluctuations around an average structure. We recently applied relaxation mode analysis for protein systems, which approximately estimates the slow relaxation modes and times from a simulation and enables investigations of the dynamic properties underlying the structural fluctuations of proteins. In this study, we apply this relaxation mode analysis to extract reaction coordinates for a system in which there are large conformational changes such as those commonly observed in protein folding/unfolding. We performed a 750-ns simulation of chignolin protein near its folding transition temperature and observed many transitions between the most stable, misfolded, intermediate, and unfolded states. We then applied principal component analysis and relaxation mode analysis to the system. In the relaxation mode analysis, we could automatically extract good reaction coordinates. The free-energy surfaces provide a clearer understanding of the transitions not only between local minimum-energy states but also between the folded and unfolded states, even though the simulation involved large conformational changes. Moreover, we propose a new analysis method called Markov state relaxation mode analysis. We applied the new method to states with slow relaxation, which are defined by the free-energy surface obtained in the relaxation mode analysis. Finally, the relaxation times of the states obtained with a simple Markov state model and the proposed Markov state relaxation mode analysis are compared and discussed.

rf streak camera based ultrafast relativistic electron diffraction.

PubMed

Musumeci, P; Moody, J T; Scoby, C M; Gutierrez, M S; Tran, T

2009-01-01

We theoretically and experimentally investigate the possibility of using a rf streak camera to time resolve in a single shot structural changes at the sub-100 fs time scale via relativistic electron diffraction. We experimentally tested this novel concept at the UCLA Pegasus rf photoinjector. Time-resolved diffraction patterns from thin Al foil are recorded. Averaging over 50 shots is required in order to get statistics sufficient to uncover a variation in time of the diffraction patterns. In the absence of an external pump laser, this is explained as due to the energy chirp on the beam out of the electron gun. With further improvements to the electron source, rf streak camera based ultrafast electron diffraction has the potential to yield truly single shot measurements of ultrafast processes.

Ultrafast dynamics during the photoinduced phase transition in VO2

NASA Astrophysics Data System (ADS)

Wegkamp, Daniel; Stähler, Julia

2015-12-01

The phase transition of VO2 from a monoclinic insulator to a rutile metal, which occurs thermally at TC = 340 K, can also be driven by strong photoexcitation. The ultrafast dynamics during this photoinduced phase transition (PIPT) have attracted great scientific attention for decades, as this approach promises to answer the question of whether the insulator-to-metal (IMT) transition is caused by electronic or crystallographic processes through disentanglement of the different contributions in the time domain. We review our recent results achieved by femtosecond time-resolved photoelectron, optical, and coherent phonon spectroscopy and discuss them within the framework of a selection of latest, complementary studies of the ultrafast PIPT in VO2. We show that the population change of electrons and holes caused by photoexcitation launches a highly non-equilibrium plasma phase characterized by enhanced screening due to quasi-free carriers and followed by two branches of non-equilibrium dynamics: (i) an instantaneous (within the time resolution) collapse of the insulating gap that precedes charge carrier relaxation and significant ionic motion and (ii) an instantaneous lattice potential symmetry change that represents the onset of the crystallographic phase transition through ionic motion on longer timescales. We discuss the interconnection between these two non-thermal pathways with particular focus on the meaning of the critical fluence of the PIPT in different types of experiments. Based on this, we conclude that the PIPT threshold identified in optical experiments is most probably determined by the excitation density required to drive the lattice potential change rather than the IMT. These considerations suggest that the IMT can be driven by weaker excitation, predicting a transiently metallic, monoclinic state of VO2 that is not stabilized by the non-thermal structural transition and, thus, decays on ultrafast timescales.

Carotenoid-to-bacteriochlorophyll energy transfer through vibronic coupling in LH2 from Phaeosprillum molischianum.

PubMed

Thyrhaug, Erling; Lincoln, Craig N; Branchi, Federico; Cerullo, Giulio; Perlík, Václav; Šanda, František; Lokstein, Heiko; Hauer, Jürgen

2018-03-01

The peripheral light-harvesting antenna complex (LH2) of purple photosynthetic bacteria is an ideal testing ground for models of structure-function relationships due to its well-determined molecular structure and ultrafast energy deactivation. It has been the target for numerous studies in both theory and ultrafast spectroscopy; nevertheless, certain aspects of the convoluted relaxation network of LH2 lack a satisfactory explanation by conventional theories. For example, the initial carotenoid-to-bacteriochlorophyll energy transfer step necessary on visible light excitation was long considered to follow the Förster mechanism, even though transfer times as short as 40 femtoseconds (fs) have been observed. Such transfer times are hard to accommodate by Förster theory, as the moderate coupling strengths found in LH2 suggest much slower transfer within this framework. In this study, we investigate LH2 from Phaeospirillum (Ph.) molischianum in two types of transient absorption experiments-with narrowband pump and white-light probe resulting in 100 fs time resolution, and with degenerate broadband 10 fs pump and probe pulses. With regard to the split Q x band in this system, we show that vibronically mediated transfer explains both the ultrafast carotenoid-to-B850 transfer, and the almost complete lack of transfer to B800. These results are beyond Förster theory, which predicts an almost equal partition between the two channels.

Visualization of carrier dynamics in p(n)-type GaAs by scanning ultrafast electron microscopy

PubMed Central

Cho, Jongweon; Hwang, Taek Yong; Zewail, Ahmed H.

2014-01-01

Four-dimensional scanning ultrafast electron microscopy is used to investigate doping- and carrier-concentration-dependent ultrafast carrier dynamics of the in situ cleaved single-crystalline GaAs(110) substrates. We observed marked changes in the measured time-resolved secondary electrons depending on the induced alterations in the electronic structure. The enhancement of secondary electrons at positive times, when the electron pulse follows the optical pulse, is primarily due to an energy gain involving the photoexcited charge carriers that are transiently populated in the conduction band and further promoted by the electron pulse, consistent with a band structure that is dependent on chemical doping and carrier concentration. When electrons undergo sufficient energy loss on their journey to the surface, dark contrast becomes dominant in the image. At negative times, however, when the electron pulse precedes the optical pulse (electron impact), the dynamical behavior of carriers manifests itself in a dark contrast which indicates the suppression of secondary electrons upon the arrival of the optical pulse. In this case, the loss of energy of material’s electrons is by collisions with the excited carriers. These results for carrier dynamics in GaAs(110) suggest strong carrier–carrier scatterings which are mirrored in the energy of material’s secondary electrons during their migration to the surface. The approach presented here provides a fundamental understanding of materials probed by four-dimensional scanning ultrafast electron microscopy, and offers possibilities for use of this imaging technique in the study of ultrafast charge carrier dynamics in heterogeneously patterned micro- and nanostructured material surfaces and interfaces. PMID:24469803

Visualization of carrier dynamics in p(n)-type GaAs by scanning ultrafast electron microscopy.

PubMed

Cho, Jongweon; Hwang, Taek Yong; Zewail, Ahmed H

2014-02-11

Four-dimensional scanning ultrafast electron microscopy is used to investigate doping- and carrier-concentration-dependent ultrafast carrier dynamics of the in situ cleaved single-crystalline GaAs(110) substrates. We observed marked changes in the measured time-resolved secondary electrons depending on the induced alterations in the electronic structure. The enhancement of secondary electrons at positive times, when the electron pulse follows the optical pulse, is primarily due to an energy gain involving the photoexcited charge carriers that are transiently populated in the conduction band and further promoted by the electron pulse, consistent with a band structure that is dependent on chemical doping and carrier concentration. When electrons undergo sufficient energy loss on their journey to the surface, dark contrast becomes dominant in the image. At negative times, however, when the electron pulse precedes the optical pulse (electron impact), the dynamical behavior of carriers manifests itself in a dark contrast which indicates the suppression of secondary electrons upon the arrival of the optical pulse. In this case, the loss of energy of material's electrons is by collisions with the excited carriers. These results for carrier dynamics in GaAs(110) suggest strong carrier-carrier scatterings which are mirrored in the energy of material's secondary electrons during their migration to the surface. The approach presented here provides a fundamental understanding of materials probed by four-dimensional scanning ultrafast electron microscopy, and offers possibilities for use of this imaging technique in the study of ultrafast charge carrier dynamics in heterogeneously patterned micro- and nanostructured material surfaces and interfaces.

Mechanism of vibrational energy dissipation of free OH groups at the air-water interface.

PubMed

Hsieh, Cho-Shuen; Campen, R Kramer; Okuno, Masanari; Backus, Ellen H G; Nagata, Yuki; Bonn, Mischa

2013-11-19

Interfaces of liquid water play a critical role in a wide variety of processes that occur in biology, a variety of technologies, and the environment. Many macroscopic observations clarify that the properties of liquid water interfaces significantly differ from those of the bulk liquid. In addition to interfacial molecular structure, knowledge of the rates and mechanisms of the relaxation of excess vibrational energy is indispensable to fully understand physical and chemical processes of water and aqueous solutions, such as chemical reaction rates and pathways, proton transfer, and hydrogen bond dynamics. Here we elucidate the rate and mechanism of vibrational energy dissipation of water molecules at the air-water interface using femtosecond two-color IR-pump/vibrational sum-frequency probe spectroscopy. Vibrational relaxation of nonhydrogen-bonded OH groups occurs at a subpicosecond timescale in a manner fundamentally different from hydrogen-bonded OH groups in bulk, through two competing mechanisms: intramolecular energy transfer and ultrafast reorientational motion that leads to free OH groups becoming hydrogen bonded. Both pathways effectively lead to the transfer of the excited vibrational modes from free to hydrogen-bonded OH groups, from which relaxation readily occurs. Of the overall relaxation rate of interfacial free OH groups at the air-H2O interface, two-thirds are accounted for by intramolecular energy transfer, whereas the remaining one-third is dominated by the reorientational motion. These findings not only shed light on vibrational energy dynamics of interfacial water, but also contribute to our understanding of the impact of structural and vibrational dynamics on the vibrational sum-frequency line shapes of aqueous interfaces.

Temporal-spatial measurement of electron relaxation time in femtosecond laser induced plasma using two-color pump-probe imaging technique

NASA Astrophysics Data System (ADS)

Pan, Changji; Jiang, Lan; Wang, Qingsong; Sun, Jingya; Wang, Guoyan; Lu, Yongfeng

2018-05-01

The femtosecond (fs) laser is a powerful tool to study ultrafast plasma dynamics, especially electron relaxation in strong ionization of dielectrics. Herein, temporal-spatial evolution of femtosecond laser induced plasma in fused silica was investigated using a two-color pump-probe technique (i.e., 400 nm and 800 nm, respectively). We demonstrated that when ionized electron density is lower than the critical density, free electron relaxation time is inversely proportional to electron density, which can be explained by the electron-ion scattering regime. In addition, electron density evolution within plasma was analyzed in an early stage (first 800 fs) of the laser-material interaction.

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.

Quantitative ultra-fast MRI of HPMC swelling and dissolution.

PubMed

Chen, Ya Ying; Hughes, L P; Gladden, L F; Mantle, M D

2010-08-01

For the first time quantitative Rapid Acquisition with Relaxation Enhancement (RARE) based ultra-fast two-dimensional magnetic resonance imaging has been used to follow the dissolution of hydroxypropylmethyl cellulose (HPMC) in water. Quantitative maps of absolute water concentration, spin-spin relaxation times and water self-diffusion coefficient are obtained at a spatial resolution of 469 microm in less than 3 min each. These maps allow the dynamic development of the medium release rate HPMC/water system to be followed. It is demonstrated that the evolution of the gel layer and, in particular, the gradient in water concentration across it, is significantly different when comparing the quantitative RARE sequence with a standard (nonquantitative) implementation of RARE. The total gel thickness in the axial direction grows faster than that in the radial direction and that the dry core initially expands anisotropically. Additionally, while HPMC absorbs a large amount of water during the dissolution process, the concentration gradient of water within the gel layer is relatively small. For the first time MRI evidence is presented for a transition swollen glassy layer which resides between the outer edge of the dry tablet core and the inner edge of the gel layer. (c) 2010 Wiley-Liss, Inc. and the American Pharmacists Association

Ultrafast Three-Dimensional X-ray Imaging of Deformation Modes in ZnO Nanocrystals.

PubMed

Cherukara, Mathew J; Sasikumar, Kiran; Cha, Wonsuk; Narayanan, Badri; Leake, Steven J; Dufresne, Eric M; Peterka, Tom; McNulty, Ian; Wen, Haidan; Sankaranarayanan, Subramanian K R S; Harder, Ross J

2017-02-08

Imaging the dynamical response of materials following ultrafast excitation can reveal energy transduction mechanisms and their dissipation pathways, as well as material stability under conditions far from equilibrium. Such dynamical behavior is challenging to characterize, especially operando at nanoscopic spatiotemporal scales. In this letter, we use X-ray coherent diffractive imaging to show that ultrafast laser excitation of a ZnO nanocrystal induces a rich set of deformation dynamics including characteristic "hard" or inhomogeneous and "soft" or homogeneous modes at different time scales, corresponding respectively to the propagation of acoustic phonons and resonant oscillation of the crystal. By integrating the 3D nanocrystal structure obtained from the ultrafast X-ray measurements with a continuum thermo-electro-mechanical finite element model, we elucidate the deformation mechanisms following laser excitation, in particular, a torsional mode that generates a 50% greater electric potential gradient than that resulting from the flexural mode. Understanding of the time-dependence of these mechanisms on ultrafast scales has significant implications for development of new materials for nanoscale power generation.

Ultrafast Three-Dimensional X-ray Imaging of Deformation Modes in ZnO Nanocrystals

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

Cherukara, Mathew J.; Sasikumar, Kiran; Cha, Wonsuk

Imaging the dynamical response of materials following ultrafast excitation can reveal energy transduction mechanisms and their dissipation pathways, as well as material stability under conditions far from equilibrium. Such dynamical behaviour is challenging to characterize, especially operando at nanoscopic spatiotemporal scales. In this letter, we use x-ray coherent diffractive imaging to show that ultrafast laser excitation of a ZnO nanocrystal induces a rich set of deformation dynamics including characteristic ‘hard’ or inhomogeneous and ‘soft’ or homogeneous modes at different time scales, corresponding respectively to the propagation of acoustic phonons and resonant oscillation of the crystal. By integrating the 3D nanocrystalmore » structure obtained from the ultrafast x-ray measurements with a continuum thermo-electro-mechanical finite element model, we elucidate the deformation mechanisms following laser excitation, in particular, a torsional mode that generates a 50% greater electric potential gradient than that resulting from the flexural mode. Furthermore, understanding of the time-dependence of these mechanisms on ultrafast scales has significant implications for development of new materials for nanoscale power generation.« less

Ultrafast Three-Dimensional X-ray Imaging of Deformation Modes in ZnO Nanocrystals

DOE PAGES

Cherukara, Mathew J.; Sasikumar, Kiran; Cha, Wonsuk; ...

2016-12-27

Imaging the dynamical response of materials following ultrafast excitation can reveal energy transduction mechanisms and their dissipation pathways, as well as material stability under conditions far from equilibrium. Such dynamical behaviour is challenging to characterize, especially operando at nanoscopic spatiotemporal scales. In this letter, we use x-ray coherent diffractive imaging to show that ultrafast laser excitation of a ZnO nanocrystal induces a rich set of deformation dynamics including characteristic ‘hard’ or inhomogeneous and ‘soft’ or homogeneous modes at different time scales, corresponding respectively to the propagation of acoustic phonons and resonant oscillation of the crystal. By integrating the 3D nanocrystalmore » structure obtained from the ultrafast x-ray measurements with a continuum thermo-electro-mechanical finite element model, we elucidate the deformation mechanisms following laser excitation, in particular, a torsional mode that generates a 50% greater electric potential gradient than that resulting from the flexural mode. Furthermore, understanding of the time-dependence of these mechanisms on ultrafast scales has significant implications for development of new materials for nanoscale power generation.« less

Effects of Energy Relaxation via Quantum Coupling Among Three-Dimensional Motion on the Tunneling Current of Graphene Field-Effect Transistors.

PubMed

Mao, Ling-Feng; Ning, Huansheng; Li, Xijun

2015-12-01

We report theoretical study of the effects of energy relaxation on the tunneling current through the oxide layer of a two-dimensional graphene field-effect transistor. In the channel, when three-dimensional electron thermal motion is considered in the Schrödinger equation, the gate leakage current at a given oxide field largely increases with the channel electric field, electron mobility, and energy relaxation time of electrons. Such an increase can be especially significant when the channel electric field is larger than 1 kV/cm. Numerical calculations show that the relative increment of the tunneling current through the gate oxide will decrease with increasing the thickness of oxide layer when the oxide is a few nanometers thick. This highlights that energy relaxation effect needs to be considered in modeling graphene transistors.

Ultrafast carrier dynamics in a GaN/Al 0.18Ga0.82N superlattice

NASA Astrophysics Data System (ADS)

Mahler, Felix; Tomm, Jens W.; Reimann, Klaus; Woerner, Michael; Elsaesser, Thomas; Flytzanis, Christos; Hoffmann, Veit; Weyers, Markus

2018-04-01

Relaxation processes of photoexcited carriers in a GaN /Al0.18Ga0.82N superlattice are studied in femtosecond spectrally resolved reflectivity measurements at ambient temperature. The transient reflectivity reveals electron trapping into defect states close to the conduction-band minimum with a 150-200 fs time constant, followed by few-picosecond carrier cooling. A second slower trapping process into a different manifold of defect states is observed on a time scale of approximately 10 ps. Our results establish the prominent role of structural defects and disorder for ultrafast carrier dynamics in nitride semiconductor structures.

Ultrafast visualization of the structural evolution of dense hydrogen towards warm dense matter

NASA Astrophysics Data System (ADS)

Fletcher, Luke

2016-10-01

Hot dense hydrogen far from equilibrium is ubiquitous in nature occurring during some of the most violent and least understood events in our universe such as during star formation, supernova explosions, and the creation of cosmic rays. It is also a state of matter important for applications in inertial confinement fusion research and in laser particle acceleration. Rapid progress occurred in recent years characterizing the high-pressure structural properties of dense hydrogen under static or dynamic compression. Here, we show that spectrally and angularly resolved x-ray scattering measure the thermodynamic properties of dense hydrogen and resolve the ultrafast evolution and relaxation towards thermodynamic equilibrium. These studies apply ultra-bright x-ray pulses from the Linac Coherent Light (LCLS) source. The interaction of rapidly heated cryogenic hydrogen with a high-peak power optical laser is visualized with intense LCLS x-ray pulses in a high-repetition rate pump-probe setting. We demonstrate that electron-ion coupling is affected by the small number of particles in the Debye screening cloud resulting in much slower ion temperature equilibration than predicted by standard theory. This work was supported by the DOE Office of Science, Fusion Energy Science under FWP 100182.

Quasiparticle relaxation in superconducting nanostructures

NASA Astrophysics Data System (ADS)

Savich, Yahor; Glazman, Leonid; Kamenev, Alex

2017-09-01

We examine energy relaxation of nonequilibrium quasiparticles in "dirty" superconductors with the electron mean free path much shorter than the superconducting coherence length. Relaxation of low-energy nonequilibrium quasiparticles is dominated by phonon emission. We derive the corresponding collision integral and find the quasiparticle relaxation rate. The latter is sensitive to the breaking of time reversal symmetry (TRS) by a magnetic field (or magnetic impurities). As a concrete application of the developed theory, we address quasiparticle trapping by a vortex and a current-biased constriction. We show that trapping of hot quasiparticles may predominantly occur at distances from the vortex core, or the constriction, significantly exceeding the superconducting coherence length.

Magnetic relaxation pathways in lanthanide single-molecule magnets.

PubMed

Blagg, Robin J; Ungur, Liviu; Tuna, Floriana; Speak, James; Comar, Priyanka; Collison, David; Wernsdorfer, Wolfgang; McInnes, Eric J L; Chibotaru, Liviu F; Winpenny, Richard E P

2013-08-01

Single-molecule magnets are compounds that exhibit magnetic bistability caused by an energy barrier for the reversal of magnetization (relaxation). Lanthanide compounds are proving promising as single-molecule magnets: recent studies show that terbium phthalocyanine complexes possess large energy barriers, and dysprosium and terbium complexes bridged by an N2(3-) radical ligand exhibit magnetic hysteresis up to 13 K. Magnetic relaxation is typically controlled by single-ion factors rather than magnetic exchange (whether one or more 4f ions are present) and proceeds through thermal relaxation of the lowest excited states. Here we report polylanthanide alkoxide cage complexes, and their doped diamagnetic yttrium analogues, in which competing relaxation pathways are observed and relaxation through the first excited state can be quenched. This leads to energy barriers for relaxation of magnetization that exceed 800 K. We investigated the factors at the lanthanide sites that govern this behaviour.

Electron and lattice dynamics of transition metal thin films observed by ultrafast electron diffraction and transient optical measurements.

PubMed

Nakamura, A; Shimojima, T; Nakano, M; Iwasa, Y; Ishizaka, K

2016-11-01

We report the ultrafast dynamics of electrons and lattice in transition metal thin films (Au, Cu, and Mo) investigated by a combination of ultrafast electron diffraction (UED) and pump-probe optical methods. For a single-crystalline Au thin film, we observe the suppression of the diffraction intensity occuring in 10 ps, which direcly reflects the lattice thermalization via the electron-phonon interaction. By using the two-temperature model, the electron-phonon coupling constant ( g ) and the electron and lattice temperatures ( T e , T l ) are evaluated from UED, with which we simulate the transient optical transmittance. The simulation well agrees with the experimentally obtained transmittance data, except for the slight deviations at the initial photoexcitation and the relaxed quasi-equilibrium state. We also present the results similarly obtained for polycrystalline Au, Cu, and Mo thin films and demonstrate the electron and lattice dynamics occurring in metals with different electron-phonon coupling strengths.

The Current Collapse in AlGaN/GaN High-Electron Mobility Transistors Can Originate from the Energy Relaxation of Channel Electrons?

PubMed Central

Mao, Ling-Feng; Ning, Huan-Sheng; Wang, Jin-Yan

2015-01-01

Influence of the energy relaxation of the channel electrons on the performance of AlGaN/GaN high-electron mobility transistors (HEMTs) has been investigated using self-consistent solution to the coupled Schrödinger equation and Poisson equation. The first quantized energy level in the inversion layer rises and the average channel electron density decreases when the channel electric field increases from 20 kV/cm to 120 kV/cm. This research also demonstrates that the energy relaxation of the channel electrons can lead to current collapse and suggests that the energy relaxation should be considered in modeling the performance of AlGaN/GaN HEMTs such as, the gate leakage current, threshold voltage, source-drain current, capacitance-voltage curve, etc. PMID:26039589

The Current Collapse in AlGaN/GaN High-Electron Mobility Transistors Can Originate from the Energy Relaxation of Channel Electrons?

PubMed

Mao, Ling-Feng; Ning, Huan-Sheng; Wang, Jin-Yan

2015-01-01

Influence of the energy relaxation of the channel electrons on the performance of AlGaN/GaN high-electron mobility transistors (HEMTs) has been investigated using self-consistent solution to the coupled Schrödinger equation and Poisson equation. The first quantized energy level in the inversion layer rises and the average channel electron density decreases when the channel electric field increases from 20 kV/cm to 120 kV/cm. This research also demonstrates that the energy relaxation of the channel electrons can lead to current collapse and suggests that the energy relaxation should be considered in modeling the performance of AlGaN/GaN HEMTs such as, the gate leakage current, threshold voltage, source-drain current, capacitance-voltage curve, etc.

Spin-vibronic quantum dynamics for ultrafast excited-state processes.

PubMed

Eng, Julien; Gourlaouen, Christophe; Gindensperger, Etienne; Daniel, Chantal

2015-03-17

Ultrafast intersystem crossing (ISC) processes coupled to nuclear relaxation and solvation dynamics play a central role in the photophysics and photochemistry of a wide range of transition metal complexes. These phenomena occurring within a few hundred femtoseconds are investigated experimentally by ultrafast picosecond and femtosecond transient absorption or luminescence spectroscopies, and optical laser pump-X-ray probe techniques using picosecond and femtosecond X-ray pulses. The interpretation of ultrafast structural changes, time-resolved spectra, quantum yields, and time scales of elementary processes or transient lifetimes needs robust theoretical tools combining state-of-the-art quantum chemistry and developments in quantum dynamics for solving the electronic and nuclear problems. Multimode molecular dynamics beyond the Born-Oppenheimer approximation has been successfully applied to many small polyatomic systems. Its application to large molecules containing a transition metal atom is still a challenge because of the nuclear dimensionality of the problem, the high density of electronic excited states, and the spin-orbit coupling effects. Rhenium(I) α-diimine carbonyl complexes, [Re(L)(CO)3(N,N)](n+) are thermally and photochemically robust and highly flexible synthetically. Structural variations of the N,N and L ligands affect the spectroscopy, the photophysics, and the photochemistry of these chromophores easily incorporated into a complex environment. Visible light absorption opens the route to a wide range of applications such as sensors, probes, or emissive labels for imaging biomolecules. Halide complexes [Re(X)(CO)3(bpy)] (X = Cl, Br, or I; bpy = 2,2'-bipyridine) exhibit complex electronic structure and large spin-orbit effects that do not correlate with the heavy atom effects. Indeed, the (1)MLCT → (3)MLCT intersystem crossing (ISC) kinetics is slower than in [Ru(bpy)3](2+) or [Fe(bpy)3](2+) despite the presence of a third-row transition metal

Strain relaxation of CdTe on Ge studied by medium energy ion scattering

NASA Astrophysics Data System (ADS)

Pillet, J. C.; Pierre, F.; Jalabert, D.

2016-10-01

We have used the medium energy ion scattering (MEIS) technique to assess the strain relaxation in molecular-beam epitaxial (MBE) grown CdTe (2 1 1)/Ge (2 1 1) system. A previous X-ray diffraction study, on 10 samples of the same heterostructure having thicknesses ranging from 25 nm to 10 μm has allowed the measurement of the strain relaxation on a large scale. However, the X-ray diffraction measurements cannot achieve a stress measurement in close proximity to the CdTe/Ge interface at the nanometer scale. Due to the huge lattice misfit between the CdTe and Ge, a high degree of disorder is expected at the interface. The MEIS in channeling mode is a good alternative in order to profile defects with a high depth resolution. For a 21 nm thick CdTe layer, we observed, at the interface, a high density of Cd and/or Te atoms moved from their expected crystallographic positions followed by a rapid recombination of defects. Strain relaxation mechanisms in the vicinity of the interface are discussed

Ultrafast spectroscopic investigation of a fullerene poly(3-hexylthiophene) dyad

NASA Astrophysics Data System (ADS)

Banerji, Natalie; Seifter, Jason; Wang, Mingfeng; Vauthey, Eric; Wudl, Fred; Heeger, Alan J.

2011-08-01

We present the femtosecond spectroscopic investigation of a covalently linked dyad, PCB-P3HT, formed by a segment of the conjugated polymer P3HT (regioregular poly(3-hexylthiophene)) that is end capped with the fullerene derivative PCB ([6,6]-phenyl-C61-butyric acid ester), adapted from PCBM. The fluorescence of the P3HT segment in tetrahydrofuran (THF) solution is reduced by 64% in the dyad compared to a control compound without attached fullerene (P3HT-OH). Fluorescence upconversion measurements reveal that the partial fluorescence quenching of PCB-P3HT in THF is multiphasic and occurs on an average time scale of 100 ps, in parallel to excited-state relaxation processes. Judging from ultrafast transient absorption experiments, the origin of the quenching is excitation energy transfer from the P3HT donor to the PCB acceptor. Due to the much higher solubility of P3HT compared to PCB in THF, the PCB-P3HT dyad molecules self-assemble into micelles. When pure C60 is added to the solution, it is incorporated into the fullerene-rich center of the micelles. This dramatically increases the solubility of C60 but does not lead to significant additional quenching of the P3HT fluorescence by the C60 contained in the micelles. In PCB-P3HT thin films drop-cast from THF, the micelle structure is conserved. In contrast to solution, quantitative and ultrafast (<150 fs) charge separation occurs in the solid-state films and leads to the formation of long-lived mobile charge carriers with characteristic transient absorption signatures similar to those that have been observed in P3HT:PCBM bulk heterojunction blends. While π-stacking interactions between neighboring P3HT chains are weak in the micelles, they are strong in thin films drop-cast from ortho-dichlorobenzene. Here, PCB-P3HT self-assembles into a network of long fibers, clearly seen in atomic force microscopy images. Ultrafast charge separation occurs also for the fibrous morphology, but the transient absorption experiments

Ultrafast Intramolecular Electron and Proton Transfer in Bis(imino)isoindole Derivatives.

PubMed

Driscoll, Eric; Sorenson, Shayne; Dawlaty, Jahan M

2015-06-04

Concerted motion of electrons and protons in the excited state is pertinent to a wide range of chemical phenomena, including those relevant for solar-to-fuel light harvesting. The excited state dynamics of small proton-bearing molecules are expected to serve as models for better understanding such phenomena. In particular, for designing the next generation of multielectron and multiproton redox catalysts, understanding the dynamics of more than one proton in the excited state is important. Toward this goal, we have measured the ultrafast dynamics of intramolecular excited state proton transfer in a recently synthesized dye with two equivalent transferable protons. We have used a visible ultrafast pump to initiate the proton transfer in the excited state, and have probed the transient absorption of the molecule over a wide bandwidth in the visible range. The measurement shows that the signal which is characteristic of proton transfer emerges within ∼710 fs. To identify whether both protons were transferred in the excited state, we have measured the ultrafast dynamics of a related derivative, where only a single proton was available for transfer. The measured proton transfer time in that molecule was ∼427 fs. The observed dynamics in both cases were reasonably fit with single exponentials. Supported by the ultrafast observations, steady-state fluorescence, and preliminary computations of the relaxed excited states, we argue that the doubly protonated derivative most likely transfers only one of its two protons in the excited state. We have performed calculations of the frontier molecular orbitals in the Franck-Condon region. The calculations show that in both derivatives, the excitation is primarily from the HOMO to LUMO causing a large rearrangement of the electronic charge density immediately after photoexcitation. In particular, charge density is shifted away from the phenolic protons and toward the proton acceptor nitrogens. The proton transfer is

Ultrafast Laser-Based Spectroscopy and Sensing: Applications in LIBS, CARS, and THz Spectroscopy

PubMed Central

Leahy-Hoppa, Megan R.; Miragliotta, Joseph; Osiander, Robert; Burnett, Jennifer; Dikmelik, Yamac; McEnnis, Caroline; Spicer, James B.

2010-01-01

Ultrafast pulsed lasers find application in a range of spectroscopy and sensing techniques including laser induced breakdown spectroscopy (LIBS), coherent Raman spectroscopy, and terahertz (THz) spectroscopy. Whether based on absorption or emission processes, the characteristics of these techniques are heavily influenced by the use of ultrafast pulses in the signal generation process. Depending on the energy of the pulses used, the essential laser interaction process can primarily involve lattice vibrations, molecular rotations, or a combination of excited states produced by laser heating. While some of these techniques are currently confined to sensing at close ranges, others can be implemented for remote spectroscopic sensing owing principally to the laser pulse duration. We present a review of ultrafast laser-based spectroscopy techniques and discuss the use of these techniques to current and potential chemical and environmental sensing applications. PMID:22399883

Neutral-atom electron binding energies from relaxed-orbital relativistic Hartree-Fock-Slater calculations for Z between 2 and 106

NASA Technical Reports Server (NTRS)

Huang, K.-N.; Aoyagi, M.; Mark, H.; Chen, M. H.; Crasemann, B.

1976-01-01

Electron binding energies in neutral atoms have been calculated relativistically, with the requirement of complete relaxation. Hartree-Fock-Slater wave functions served as zeroth-order eigenfunctions to compute the expectation of the total Hamiltonian. A first-order correction to the local approximation was thus included. Quantum-electrodynamic corrections were made. For all elements with atomic numbers ranging from 2 to 106, the following quantities are listed: total energies, electron kinetic energies, electron-nucleus potential energies, electron-electron potential energies consisting of electrostatic and Breit interaction (magnetic and retardation) terms, and vacuum polarization energies. Binding energies including relaxation are listed for all electrons in all atoms over the indicated range of atomic numbers. A self-energy correction is included for the 1s, 2s, and 2p(1/2) levels. Results for selected atoms are compared with energies calculated by other methods and with experimental values.

Ultrafast selective transport of alkali metal ions in metal organic frameworks with subnanometer pores

PubMed Central

Zhang, Huacheng; Hou, Jue; Hu, Yaoxin; Wang, Peiyao; Ou, Ranwen; Jiang, Lei; Liu, Jefferson Zhe; Freeman, Benny D.; Hill, Anita J.; Wang, Huanting

2018-01-01

Porous membranes with ultrafast ion permeation and high ion selectivity are highly desirable for efficient mineral separation, water purification, and energy conversion, but it is still a huge challenge to efficiently separate monatomic ions of the same valence and similar sizes using synthetic membranes. We report metal organic framework (MOF) membranes, including ZIF-8 and UiO-66 membranes with uniform subnanometer pores consisting of angstrom-sized windows and nanometer-sized cavities for ultrafast selective transport of alkali metal ions. The angstrom-sized windows acted as ion selectivity filters for selection of alkali metal ions, whereas the nanometer-sized cavities functioned as ion conductive pores for ultrafast ion transport. The ZIF-8 and UiO-66 membranes showed a LiCl/RbCl selectivity of ~4.6 and ~1.8, respectively, which are much greater than the LiCl/RbCl selectivity of 0.6 to 0.8 measured in traditional porous membranes. Molecular dynamics simulations suggested that ultrafast and selective ion transport in ZIF-8 was associated with partial dehydration effects. This study reveals ultrafast and selective transport of monovalent ions in subnanometer MOF pores and opens up a new avenue to develop unique MOF platforms for efficient ion separations in the future. PMID:29487910

Ultrafast selective transport of alkali metal ions in metal organic frameworks with subnanometer pores.

PubMed

Zhang, Huacheng; Hou, Jue; Hu, Yaoxin; Wang, Peiyao; Ou, Ranwen; Jiang, Lei; Liu, Jefferson Zhe; Freeman, Benny D; Hill, Anita J; Wang, Huanting

2018-02-01

Porous membranes with ultrafast ion permeation and high ion selectivity are highly desirable for efficient mineral separation, water purification, and energy conversion, but it is still a huge challenge to efficiently separate monatomic ions of the same valence and similar sizes using synthetic membranes. We report metal organic framework (MOF) membranes, including ZIF-8 and UiO-66 membranes with uniform subnanometer pores consisting of angstrom-sized windows and nanometer-sized cavities for ultrafast selective transport of alkali metal ions. The angstrom-sized windows acted as ion selectivity filters for selection of alkali metal ions, whereas the nanometer-sized cavities functioned as ion conductive pores for ultrafast ion transport. The ZIF-8 and UiO-66 membranes showed a LiCl/RbCl selectivity of ~4.6 and ~1.8, respectively, which are much greater than the LiCl/RbCl selectivity of 0.6 to 0.8 measured in traditional porous membranes. Molecular dynamics simulations suggested that ultrafast and selective ion transport in ZIF-8 was associated with partial dehydration effects. This study reveals ultrafast and selective transport of monovalent ions in subnanometer MOF pores and opens up a new avenue to develop unique MOF platforms for efficient ion separations in the future.

Monitoring Ultrafast Chemical Dynamics by Time-Domain X-ray Photo- and Auger-Electron Spectroscopy.

PubMed

Gessner, Oliver; Gühr, Markus

2016-01-19

The directed flow of charge and energy is at the heart of all chemical processes. Extraordinary efforts are underway to monitor and understand the concerted motion of electrons and nuclei with ever increasing spatial and temporal sensitivity. The element specificity, chemical sensitivity, and temporal resolution of ultrafast X-ray spectroscopy techniques hold great promise to provide new insight into the fundamental interactions underlying chemical dynamics in systems ranging from isolated molecules to application-like devices. Here, we focus on the potential of ultrafast X-ray spectroscopy techniques based on the detection of photo- and Auger electrons to provide new fundamental insight into photochemical processes of systems with various degrees of complexity. Isolated nucleobases provide an excellent testing ground for our most fundamental understanding of intramolecular coupling between electrons and nuclei beyond the traditionally applied Born-Oppenheimer approximation. Ultrafast electronic relaxation dynamics enabled by the breakdown of this approximation is the major component of the nucleobase photoprotection mechanisms. Transient X-ray induced Auger electron spectroscopy on photoexcited thymine molecules provides atomic-site specific details of the extremely efficient coupling that converts potentially bond changing ultraviolet photon energy into benign heat. In particular, the time-dependent spectral shift of a specific Auger band is sensitive to the length of a single bond within the molecule. The X-ray induced Auger transients show evidence for an electronic transition out of the initially excited state within only ∼200 fs in contrast to theoretically predicted picosecond population trapping behind a reaction barrier. Photoinduced charge transfer dynamics between transition metal complexes and semiconductor nanostructures are of central importance for many emerging energy and climate relevant technologies. Numerous demonstrations of photovoltaic and

Ultrafast Photo-Carrier Dynamics and Coherent Phonon Excitations in Topological Dirac Semimetal Cd3As2

NASA Astrophysics Data System (ADS)

Sun, Fei; Wu, Qiong; Wu, Yanling; Tian, Yichao; Shi, Youguo; Zhao, Jimin

Three dimensional (3D) topological Dirac semimetal has attracted growing research interest owing to its intriguing quantum properties such as high bulk carrier mobility and quantum spin Hall effects. However, so far, the ultrafast dynamics of a typical 3D topological Dirac semimetal, Cd3As2, as well as its coherent phonon has not been thoroughly investigated. Here we report the ultrafast dynamics of Cd3As2 by using femtosecond pump-probe spectroscopy. Two distinct relaxation processes was observed, with the lifetimes (at 5 K) of 2.4 ps and 18.6 ps, respectively. Variable temperature experiment from 5 K to 295 K also reveals signatures of phase transitions. Furthermore, coherent optical (8.1 meV) and acoustic (0.036 THz) phonon modes were generated and detected, respectively, with signatures of hybrid-excitation of the two modes. The National Basic Research Program of China (2012CB821402), the National Natural Science Foundation of China (11274372), and the External Cooperation Program of the Chinese Academy of Sciences (GJHZ1403).

Excited-state relaxation in PbSe quantum dots

NASA Astrophysics Data System (ADS)

An, Joonhee M.; Califano, Marco; Franceschetti, Alberto; Zunger, Alex

2008-04-01

In solids the phonon-assisted, nonradiative decay from high-energy electronic excited states to low-energy electronic excited states is picosecond fast. It was hoped that electron and hole relaxation could be slowed down in quantum dots, due to the unavailability of phonons energy matched to the large energy-level spacings ("phonon-bottleneck"). However, excited-state relaxation was observed to be rather fast (⩽1ps) in InP, CdSe, and ZnO dots, and explained by an efficient Auger mechanism, whereby the excess energy of electrons is nonradiatively transferred to holes, which can then rapidly decay by phonon emission, by virtue of the densely spaced valence-band levels. The recent emergence of PbSe as a novel quantum-dot material has rekindled the hope for a slow down of excited-state relaxation because hole relaxation was deemed to be ineffective on account of the widely spaced hole levels. The assumption of sparse hole energy levels in PbSe was based on an effective-mass argument based on the light effective mass of the hole. Surprisingly, fast intraband relaxation times of 1-7ps were observed in PbSe quantum dots and have been considered contradictory with the Auger cooling mechanism because of the assumed sparsity of the hole energy levels. Our pseudopotential calculations, however, do not support the scenario of sparse hole levels in PbSe: Because of the existence of three valence-band maxima in the bulk PbSe band structure, hole energy levels are densely spaced, in contradiction with simple effective-mass models. The remaining question is whether the Auger decay channel is sufficiently fast to account for the fast intraband relaxation. Using the atomistic pseudopotential wave functions of Pb2046Se2117 and Pb260Se249 quantum dots, we explicitly calculated the electron-hole Coulomb integrals and the P →S electron Auger relaxation rate. We find that the Auger mechanism can explain the experimentally observed P →S intraband decay time scale without the need to

Controlling the metal-to-insulator relaxation of the metastable hidden quantum state in 1T-TaS2.

PubMed

Vaskivskyi, Igor; Gospodaric, Jan; Brazovskii, Serguei; Svetin, Damjan; Sutar, Petra; Goreshnik, Evgeny; Mihailovic, Ian A; Mertelj, Tomaz; Mihailovic, Dragan

2015-07-01

Controllable switching between metastable macroscopic quantum states under nonequilibrium conditions induced either by light or with an external electric field is rapidly becoming of great fundamental interest. We investigate the relaxation properties of a "hidden" (H) charge density wave (CDW) state in thin single crystals of the layered dichalcogenide 1T-TaS2, which can be reached by either a single 35-fs optical laser pulse or an ~30-ps electrical pulse. From measurements of the temperature dependence of the resistivity under different excitation conditions, we find that the metallic H state relaxes to the insulating Mott ground state through a sequence of intermediate metastable states via discrete jumps over a "Devil's staircase." In between the discrete steps, an underlying glassy relaxation process is observed, which arises because of reciprocal-space commensurability frustration between the CDW and the underlying lattice. We show that the metastable state relaxation rate may be externally stabilized by substrate strain, thus opening the way to the design of nonvolatile ultrafast high-temperature memory devices based on switching between CDW states with large intrinsic differences in electrical resistance.

Ultrafast Extreme Ultraviolet Spectroscopy of Methylammonium Lead Iodide Perovskite for Carrier Specific Photophysics

NASA Astrophysics Data System (ADS)

Verkamp, Max A.; Lin, Ming-Fu; Ryland, Elizabeth S.; Benke, Kristin; Vura-Weis, Josh

2017-06-01

Methyl ammonium lead iodide (perovskite) is a leading candidate for next-generation solar cell devices. However, the fundamental photophysics responsible for its strong photovoltaic qualities are not fully understood. Ultrafast extreme ultraviolet (XUV) spectroscopy was used to investigate relaxation dynamics in perovskite with carrier specific signals arising from transitions from the common inner-shell level (I 4d) to the valence and conduction bands. Ultrashort (30 fs) pulses of XUV radiation in a broad spectrum (40-70 eV) were obtained using high-harmonic generation in a tabletop instrument. Transient absorption measurements with visible pump and XUV probe directly observed the dynamics of charge carriers after above-band and band-edge excitation.

Mechanism of vibrational energy dissipation of free OH groups at the air–water interface

PubMed Central

Hsieh, Cho-Shuen; Campen, R. Kramer; Okuno, Masanari; Backus, Ellen H. G.; Nagata, Yuki; Bonn, Mischa

2013-01-01

Interfaces of liquid water play a critical role in a wide variety of processes that occur in biology, a variety of technologies, and the environment. Many macroscopic observations clarify that the properties of liquid water interfaces significantly differ from those of the bulk liquid. In addition to interfacial molecular structure, knowledge of the rates and mechanisms of the relaxation of excess vibrational energy is indispensable to fully understand physical and chemical processes of water and aqueous solutions, such as chemical reaction rates and pathways, proton transfer, and hydrogen bond dynamics. Here we elucidate the rate and mechanism of vibrational energy dissipation of water molecules at the air–water interface using femtosecond two-color IR-pump/vibrational sum-frequency probe spectroscopy. Vibrational relaxation of nonhydrogen-bonded OH groups occurs at a subpicosecond timescale in a manner fundamentally different from hydrogen-bonded OH groups in bulk, through two competing mechanisms: intramolecular energy transfer and ultrafast reorientational motion that leads to free OH groups becoming hydrogen bonded. Both pathways effectively lead to the transfer of the excited vibrational modes from free to hydrogen-bonded OH groups, from which relaxation readily occurs. Of the overall relaxation rate of interfacial free OH groups at the air–H2O interface, two-thirds are accounted for by intramolecular energy transfer, whereas the remaining one-third is dominated by the reorientational motion. These findings not only shed light on vibrational energy dynamics of interfacial water, but also contribute to our understanding of the impact of structural and vibrational dynamics on the vibrational sum-frequency line shapes of aqueous interfaces. PMID:24191016

Elastic strain relaxation in interfacial dislocation patterns: I. A parametric energy-based framework

NASA Astrophysics Data System (ADS)

Vattré, A.

2017-08-01

A parametric energy-based framework is developed to describe the elastic strain relaxation of interface dislocations. By means of the Stroh sextic formalism with a Fourier series technique, the proposed approach couples the classical anisotropic elasticity theory with surface/interface stress and elasticity properties in heterogeneous interface-dominated materials. For any semicoherent interface of interest, the strain energy landscape is computed using the persistent elastic fields produced by infinitely periodic hexagonal-shaped dislocation configurations with planar three-fold nodes. A finite element based procedure combined with the conjugate gradient and nudged elastic band methods is applied to determine the minimum-energy paths for which the pre-computed energy landscapes yield to elastically favorable dislocation reactions. Several applications on the Au/Cu heterosystems are given. The simple and limiting case of a single set of infinitely periodic dislocations is introduced to determine exact closed-form expressions for stresses. The second limiting case of the pure (010) Au/Cu heterophase interfaces containing two crossing sets of straight dislocations investigates the effects due to the non-classical boundary conditions on the stress distributions, including separate and appropriate constitutive relations at semicoherent interfaces and free surfaces. Using the quantized Frank-Bilby equation, it is shown that the elastic strain landscape exhibits intrinsic dislocation configurations for which the junction formation is energetically unfavorable. On the other hand, the mismatched (111) Au/Cu system gives rise to the existence of a minimum-energy path where the fully strain-relaxed equilibrium and non-regular intrinsic hexagonal-shaped dislocation rearrangement is accompanied by a significant removal of the short-range elastic energy.

Scanning ultrafast electron microscopy.

PubMed

Yang, Ding-Shyue; Mohammed, Omar F; Zewail, Ahmed H

2010-08-24

Progress has been made in the development of four-dimensional ultrafast electron microscopy, which enables space-time imaging of structural dynamics in the condensed phase. In ultrafast electron microscopy, the electrons are accelerated, typically to 200 keV, and the microscope operates in the transmission mode. Here, we report the development of scanning ultrafast electron microscopy using a field-emission-source configuration. Scanning of pulses is made in the single-electron mode, for which the pulse contains at most one or a few electrons, thus achieving imaging without the space-charge effect between electrons, and still in ten(s) of seconds. For imaging, the secondary electrons from surface structures are detected, as demonstrated here for material surfaces and biological specimens. By recording backscattered electrons, diffraction patterns from single crystals were also obtained. Scanning pulsed-electron microscopy with the acquired spatiotemporal resolutions, and its efficient heat-dissipation feature, is now poised to provide in situ 4D imaging and with environmental capability.

Scanning ultrafast electron microscopy

PubMed Central

Yang, Ding-Shyue; Mohammed, Omar F.; Zewail, Ahmed H.

2010-01-01

Progress has been made in the development of four-dimensional ultrafast electron microscopy, which enables space-time imaging of structural dynamics in the condensed phase. In ultrafast electron microscopy, the electrons are accelerated, typically to 200 keV, and the microscope operates in the transmission mode. Here, we report the development of scanning ultrafast electron microscopy using a field-emission-source configuration. Scanning of pulses is made in the single-electron mode, for which the pulse contains at most one or a few electrons, thus achieving imaging without the space-charge effect between electrons, and still in ten(s) of seconds. For imaging, the secondary electrons from surface structures are detected, as demonstrated here for material surfaces and biological specimens. By recording backscattered electrons, diffraction patterns from single crystals were also obtained. Scanning pulsed-electron microscopy with the acquired spatiotemporal resolutions, and its efficient heat-dissipation feature, is now poised to provide in situ 4D imaging and with environmental capability. PMID:20696933

Spatially and temporally resolved exciton dynamics and transport in single nanostructures and assemblies

NASA Astrophysics Data System (ADS)

Huang, Libai

2015-03-01

The frontier in solar energy conversion now lies in learning how to integrate functional entities across multiple length scales to create optimal devices. To address this new frontier, I will discuss our recent efforts on elucidating multi-scale energy transfer, migration, and dissipation processes with simultaneous femtosecond temporal resolution and nanometer spatial resolution. We have developed ultrafast microscopy that combines ultrafast spectroscopy with optical microscopy to map exciton dynamics and transport with simultaneous ultrafast time resolution and diffraction-limited spatial resolution. We have employed pump-probe transient absorption microscopy to elucidate morphology and structure dependent exciton dynamics and transport in single nanostructures and molecular assemblies. More specifically, (1) We have applied transient absorption microscopy (TAM) to probe environmental and structure dependent exciton relaxation pathways in sing-walled carbon nanotubes (SWNTs) by mapping dynamics in individual pristine SWNTs with known structures. (2) We have systematically measured and modeled the optical properties of the Frenkel excitons in self-assembled porphyrin tubular aggregates that represent an analog to natural photosynthetic antennae. Using a combination of ultrafast optical microscopy and stochastic exciton modeling, we address exciton transport and relaxation pathways, especially those related to disorder.

Probing Structural and Electronic Dynamics with Ultrafast Electron Microscopy

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

Plemmons, DA; Suri, PK; Flannigan, DJ

In this Perspective, we provide an overview,of the field of ultrafast electron microscopy (UEM). We begin by briefly discussing the emergence of methods for probing ultrafast structural dynamics and the information that can be obtained. Distinctions are drawn between the two main types a probes for femtosecond (fs) dynamics fast electrons and X-ray photons and emphasis is placed on hour the nature of charged particles is exploited in ultrafast electron-based' experiments:. Following this, we describe the versatility enabled by the ease with which electron trajectories and velocities can be manipulated with transmission electron microscopy (TEM): hardware configurations, and we emphasizemore » how this is translated to the ability to measure scattering intensities in real, reciprocal, and energy space from presurveyed and selected rianoscale volumes. Owing to decades of ongoing research and development into TEM instrumentation combined with advances in specimen holder technology, comprehensive experiments can be conducted on a wide range of materials in various phases via in situ methods. Next, we describe the basic operating concepts, of UEM, and we emphasize that its development has led to extension of several of the formidable capabilities of TEM into the fs domain, dins increasing the accessible temporal parameter spade by several orders of magnitude. We then divide UEM studies into those conducted in real (imaging), reciprocal (diffraction), and energy (spectroscopy) spate. We begin each of these sections by providing a brief description of the basic operating principles and the types of information that can be gathered followed by descriptions of how these approaches are applied in UM, the type of specimen parameter space that can be probed, and an example of the types of dynamics that can be resolved. We conclude with an Outlook section, wherein we share our perspective on some future directions of the field pertaining to continued instrument development

Thermally Driven Transport and Relaxation Switching Self-Powered Electromagnetic Energy Conversion.

PubMed

Cao, Maosheng; Wang, Xixi; Cao, Wenqiang; Fang, Xiaoyong; Wen, Bo; Yuan, Jie

2018-06-07

Electromagnetic energy radiation is becoming a "health-killer" of living bodies, especially around industrial transformer substation and electricity pylon. Harvesting, converting, and storing waste energy for recycling are considered the ideal ways to control electromagnetic radiation. However, heat-generation and temperature-rising with performance degradation remain big problems. Herein, graphene-silica xerogel is dissected hierarchically from functions to "genes," thermally driven relaxation and charge transport, experimentally and theoretically, demonstrating a competitive synergy on energy conversion. A generic approach of "material genes sequencing" is proposed, tactfully transforming the negative effects of heat energy to superiority for switching self-powered and self-circulated electromagnetic devices, beneficial for waste energy harvesting, conversion, and storage. Graphene networks with "well-sequencing genes" (w = P c /P p > 0.2) can serve as nanogenerators, thermally promoting electromagnetic wave absorption by 250%, with broadened bandwidth covering the whole investigated frequency. This finding of nonionic energy conversion opens up an unexpected horizon for converting, storing, and reusing waste electromagnetic energy, providing the most promising way for governing electromagnetic pollution with self-powered and self-circulated electromagnetic devices. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Ultrafast and nanoscale diodes

NASA Astrophysics Data System (ADS)

Zhang, Peng; Lau, Y. Y.

2016-10-01

Charge carrier transport across interfaces of dissimilar materials (including vacuum) is the essence of all electronic devices. Ultrafast charge transport across a nanometre length scale is of fundamental importance in the miniaturization of vacuum and plasma electronics. With the combination of recent advances in electronics, photonics and nanotechnology, these miniature devices may integrate with solid-state platforms, achieving superior performance. This paper reviews recent modelling efforts on quantum tunnelling, ultrafast electron emission and transport, and electrical contact resistance. Unsolved problems and challenges in these areas are addressed.

Four-Dimensional Ultrafast Electron Microscopy: Insights into an Emerging Technique.

PubMed

Adhikari, Aniruddha; Eliason, Jeffrey K; Sun, Jingya; Bose, Riya; Flannigan, David J; Mohammed, Omar F

2017-01-11

Four-dimensional ultrafast electron microscopy (4D-UEM) is a novel analytical technique that aims to fulfill the long-held dream of researchers to investigate materials at extremely short spatial and temporal resolutions by integrating the excellent spatial resolution of electron microscopes with the temporal resolution of ultrafast femtosecond laser-based spectroscopy. The ingenious use of pulsed photoelectrons to probe surfaces and volumes of materials enables time-resolved snapshots of the dynamics to be captured in a way hitherto impossible by other conventional techniques. The flexibility of 4D-UEM lies in the fact that it can be used in both the scanning (S-UEM) and transmission (UEM) modes depending upon the type of electron microscope involved. While UEM can be employed to monitor elementary structural changes and phase transitions in samples using real-space mapping, diffraction, electron energy-loss spectroscopy, and tomography, S-UEM is well suited to map ultrafast dynamical events on materials surfaces in space and time. This review provides an overview of the unique features that distinguish these techniques and also illustrates the applications of both S-UEM and UEM to a multitude of problems relevant to materials science and chemistry.

Unravelling the mechanisms of vibrational relaxation in solution.

PubMed

Grubb, Michael P; Coulter, Philip M; Marroux, Hugo J B; Orr-Ewing, Andrew J; Ashfold, Michael N R

2017-04-01

We present a systematic study of the mode-specific vibrational relaxation of NO 2 in six weakly-interacting solvents (perfluorohexane, perfluoromethylcyclohexane, perfluorodecalin, carbon tetrachloride, chloroform, and d-chloroform), chosen to elucidate the dominant energy transfer mechanisms in the solution phase. Broadband transient vibrational absorption spectroscopy has allowed us to extract quantum state-resolved relaxation dynamics of the two distinct NO 2 fragments produced from the 340 nm photolysis of N 2 O 4 → NO 2 (X) + NO 2 (A) and their separate paths to thermal equilibrium. Distinct relaxation pathways are observed for the NO 2 bending and stretching modes, even at energies as high as 7000 cm -1 above the potential minimum. Vibrational energy transfer is governed by different interaction mechanisms in the various solvent environments, and proceeds with timescales ranging from 20-1100 ps. NO 2 relaxation rates in the perfluorocarbon solvents are identical despite differences in acceptor mode state densities, infrared absorption cross sections, and local solvent structure. Vibrational energy is shown to be transferred to non-vibrational solvent degrees of freedom (V-T) through impulsive collisions with the perfluorocarbon molecules. Conversely, NO 2 relaxation in chlorinated solvents is reliant on vibrational resonances (V-V) while V-T energy transfer is inefficient and thermal excitation of the surrounding solvent molecules inhibits faster vibrational relaxation through direct complexation. Intramolecular vibrational redistribution allows the symmetric stretch of NO 2 to act as a gateway for antisymmetric stretch energy to exit the molecule. This study establishes an unprecedented level of detail for the cooling dynamics of a solvated small molecule, and provides a benchmark system for future theoretical studies of vibrational relaxation processes in solution.

Ultrafast dynamics of multi-exciton state coupled to coherent vibration in zinc chlorin aggregates for artificial photosynthesis.

PubMed

Shi, Tongchao; Liu, Zhengzheng; Miyatake, Tomohiro; Tamiaki, Hitoshi; Kobayashi, Takayoshi; Zhang, Zeyu; Du, Juan; Leng, Yuxin

2017-11-27

Ultrafast vibronic dynamics induced by the interaction of the Frenkel exciton with the coherent molecular vibrations in a layer-structured zinc chlorin aggregates prepared for artificial photosynthesis have been studied by 7.1 fs real-time vibrational spectroscopy with multi-spectrum detection. The fast decay of 100 ± 5fs is ascribed to the relaxation from the higher multi-exciton state (MES) to the one-exciton state, and the slow one of 863 ± 70fs is assigned to the relaxation from Q-exciton state to the dark nonfluorescent charge-transfer (CT) state, respectively. In addition, the wavelength dependences of the exciton-vibration coupling strength are found to follow the zeroth derivative of the transient absorption spectra of the exciton. It could be explained in term of the transition dipole moment modulated by dynamic intensity borrowing between the B transition and the Q transition through the vibronic interactions.

R&D 100, 2016: Ultrafast X-ray Imager

ScienceCinema

Porter, John; Claus, Liam; Sanchez, Marcos; Robertson, Gideon; Riley, Nathan; Rochau, Greg

2018-06-13

The Ultrafast X-ray Imager is a solid-state camera capable of capturing a sequence of images with user-selectable exposure times as short as 2 billionths of a second. Using 3D semiconductor integration techniques to form a hybrid chip, this camera was developed to enable scientists to study the heating and compression of fusion targets in the quest to harness the energy process that powers the stars.

R&D 100, 2016: Ultrafast X-ray Imager

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

Porter, John; Claus, Liam; Sanchez, Marcos

The Ultrafast X-ray Imager is a solid-state camera capable of capturing a sequence of images with user-selectable exposure times as short as 2 billionths of a second. Using 3D semiconductor integration techniques to form a hybrid chip, this camera was developed to enable scientists to study the heating and compression of fusion targets in the quest to harness the energy process that powers the stars.

Periodic surface structure bifurcation induced by ultrafast laser generated point defect diffusion in GaAs

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

Abere, Michael J.; Yalisove, Steven M.; Torralva, Ben

2016-04-11

The formation of high spatial frequency laser induced periodic surface structures (HSFL) with period <0.3 λ in GaAs after irradiation with femtosecond laser pulses in air is studied. We have identified a point defect generation mechanism that operates in a specific range of fluences in semiconductors between the band-gap closure and ultrafast-melt thresholds that produces vacancy/interstitial pairs. Stress relaxation, via diffusing defects, forms the 350–400 nm tall and ∼90 nm wide structures through a bifurcation process of lower spatial frequency surface structures. The resulting HSFL are predominately epitaxial single crystals and retain the original GaAs stoichiometry.

Fiber Based Seed Laser for CO 2 Ultrafast Laser Systems

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

Chen, Yuchuan

A compact and effective 10-micron femtosecond laser with pulse duration <500fs and repetition rate of >100Hz or smaller is desirable by DOE for seeding CO 2 ultrafast laser systems to improve the stability, reliability and efficiency in generating 10-micron laser from GW up to 100TW peak power, which is irreplaceable in driving an accelerator for particle beam generation due to the efficiency proportional to the square of the laser wavelength. Agiltron proposes a fiber based ultrafast 10-micron seed laser that can provide the required specifications and high performance. Its success will directly benefit DOE’s compact proton and ion sources. Themore » innovative technology can be used for ultrafast laser generation over the whole mid-IR range, and speed up the development of mid-IR laser applications. Agiltron, Inc. has successfully completed all tasks and demonstrated the feasibility of a fiber based 10-micron ultrafast laser in Phase I of the Program. We built a mode-locked fiber laser that generated < 400fs ultrafast laser pulses and successfully controlled the repetition rate to be the required 100Hz. Using this mode-locked laser, we demonstrated the feasibility of parametric femtosecond laser generation based on frequency down conversion. The experimental results agree with our simulation results. The investigation results of Phase I will be used to optimize the design of the laser system and build a fully functional prototype for delivery to the DOE in the Phase II program. The prototype development in Phase II program will be in the collaboration with Professor Chandrashekhar Joshi, the leader of UCLA Laser-Plasma group. Prof. Joshi discovered a new mechanism for generation of monoenergetic proton/ion beams: Shock Wave Acceleration in a near critical density plasma and demonstrated that high-energy proton beams using CO 2 laser driven collisionless shocks in a gas jet plasma, which opened an opportunity to develop a rather compact high-repetition rate

Ultrafast demagnetization at high temperatures

NASA Astrophysics Data System (ADS)

Hoveyda, F.; Hohenstein, E.; Judge, R.; Smadici, S.

2018-05-01

Time-resolved pump-probe measurements were made at variable heat accumulation in Co/Pd superlattices. Heat accumulation increases the baseline temperature and decreases the equilibrium magnetization. Transient ultrafast demagnetization first develops with higher fluence in parallel with strong equilibrium thermal spin fluctuations. The ultrafast demagnetization is then gradually removed as the equilibrium temperature approaches the Curie temperature. The transient magnetization time-dependence is well fit with the spin-flip scattering model.

Staggered Multiple-PRF Ultrafast Color Doppler.

PubMed

Posada, Daniel; Poree, Jonathan; Pellissier, Arnaud; Chayer, Boris; Tournoux, Francois; Cloutier, Guy; Garcia, Damien

2016-06-01

Color Doppler imaging is an established pulsed ultrasound technique to visualize blood flow non-invasively. High-frame-rate (ultrafast) color Doppler, by emissions of plane or circular wavefronts, allows severalfold increase in frame rates. Conventional and ultrafast color Doppler are both limited by the range-velocity dilemma, which may result in velocity folding (aliasing) for large depths and/or large velocities. We investigated multiple pulse-repetition-frequency (PRF) emissions arranged in a series of staggered intervals to remove aliasing in ultrafast color Doppler. Staggered PRF is an emission process where time delays between successive pulse transmissions change in an alternating way. We tested staggered dual- and triple-PRF ultrafast color Doppler, 1) in vitro in a spinning disc and a free jet flow, and 2) in vivo in a human left ventricle. The in vitro results showed that the Nyquist velocity could be extended to up to 6 times the conventional limit. We found coefficients of determination r(2) ≥ 0.98 between the de-aliased and ground-truth velocities. Consistent de-aliased Doppler images were also obtained in the human left heart. Our results demonstrate that staggered multiple-PRF ultrafast color Doppler is efficient for high-velocity high-frame-rate blood flow imaging. This is particularly relevant for new developments in ultrasound imaging relying on accurate velocity measurements.

Kagome fiber based ultrafast laser microsurgery probe delivering micro-Joule pulse energies

PubMed Central

Subramanian, Kaushik; Gabay, Ilan; Ferhanoğlu, Onur; Shadfan, Adam; Pawlowski, Michal; Wang, Ye; Tkaczyk, Tomasz; Ben-Yakar, Adela

2016-01-01

We present the development of a 5 mm, piezo-actuated, ultrafast laser scalpel for fast tissue microsurgery. Delivery of micro-Joules level energies to the tissue was made possible by a large, 31 μm, air-cored inhibited-coupling Kagome fiber. We overcome the fiber’s low NA by using lenses made of high refractive index ZnS, which produced an optimal focusing condition with 0.23 NA objective. The optical design achieved a focused laser spot size of 4.5 μm diameter covering a 75 × 75 μm2 scan area in a miniaturized setting. The probe could deliver the maximum available laser power, achieving an average fluence of 7.8 J/cm2 on the tissue surface at 62% transmission efficiency. Such fluences could produce uninterrupted, 40 μm deep cuts at translational speeds of up to 5 mm/s along the tissue. We predicted that the best combination of speed and coverage exists at 8 mm/s for our conditions. The onset of nonlinear absorption in ZnS, however, limited the probe’s energy delivery capabilities to 1.4 μJ for linear operation at 1.5 picosecond pulse-widths of our fiber laser. Alternatives like broadband CaF2 crystals should mitigate such nonlinear limiting behavior. Improved opto-mechanical design and appropriate material selection should allow substantially higher fluence delivery and propel such Kagome fiber-based scalpels towards clinical translation. PMID:27896003

Kagome fiber based ultrafast laser microsurgery probe delivering micro-Joule pulse energies.

PubMed

Subramanian, Kaushik; Gabay, Ilan; Ferhanoğlu, Onur; Shadfan, Adam; Pawlowski, Michal; Wang, Ye; Tkaczyk, Tomasz; Ben-Yakar, Adela

2016-11-01

We present the development of a 5 mm, piezo-actuated, ultrafast laser scalpel for fast tissue microsurgery. Delivery of micro-Joules level energies to the tissue was made possible by a large, 31 μm, air-cored inhibited-coupling Kagome fiber. We overcome the fiber's low NA by using lenses made of high refractive index ZnS, which produced an optimal focusing condition with 0.23 NA objective. The optical design achieved a focused laser spot size of 4.5 μm diameter covering a 75 × 75 μm 2 scan area in a miniaturized setting. The probe could deliver the maximum available laser power, achieving an average fluence of 7.8 J/cm 2 on the tissue surface at 62% transmission efficiency. Such fluences could produce uninterrupted, 40 μm deep cuts at translational speeds of up to 5 mm/s along the tissue. We predicted that the best combination of speed and coverage exists at 8 mm/s for our conditions. The onset of nonlinear absorption in ZnS, however, limited the probe's energy delivery capabilities to 1.4 μJ for linear operation at 1.5 picosecond pulse-widths of our fiber laser. Alternatives like broadband CaF 2 crystals should mitigate such nonlinear limiting behavior. Improved opto-mechanical design and appropriate material selection should allow substantially higher fluence delivery and propel such Kagome fiber-based scalpels towards clinical translation.

Energy and momentum relaxation of electrons in bulk and 2D GaN

NASA Astrophysics Data System (ADS)

Zanato, D.; Balkan, N.; Hill, G.; Schaff, W. J.

2004-10-01

We present our experimental and theoretical studies regarding the energy and momentum relaxation of hot electrons in n-type bulk GaN and AlGaN/GaN HEMT structures. We determine the non-equilibrium temperatures and the energy relaxation rates in the steady state using the mobility mapping technique together with the power balance conditions as described by us elsewhere [N. Balkan, M.C. Arikan, S. Gokden, V. Tilak, B. Schaff, R.J. Shealy, J. Phys.: Condens. Matter 14 (2002) 3457]. We obtain the e-LO phonon scattering time of 8 fs and show that the power loss of electrons due to optical phonon emission agrees with the theoretical prediction. The drift velocity-field curves at high electric fields indicate that the drift velocity saturates at approximately 3×10 6 cm/s for the two-dimensional structure and 4×10 6 cm/s for the bulk material at 77 K. These values are much lower than those predicted by the existing theories. A critical analysis of the observations is given with a model taking into account of the non-drifting non-equilibrium phonon production.

Ultrafast dynamics in multifunctional Ru(II)-loaded polymers for solar energy conversion.

PubMed

Morseth, Zachary A; Wang, Li; Puodziukynaite, Egle; Leem, Gyu; Gilligan, Alexander T; Meyer, Thomas J; Schanze, Kirk S; Reynolds, John R; Papanikolas, John M

2015-03-17

The use of sunlight to make chemical fuels (i.e., solar fuels) is an attractive approach in the quest to develop sustainable energy sources. Using nature as a guide, assemblies for artificial photosynthesis will need to perform multiple functions. They will need to be able to harvest light across a broad region of the solar spectrum, transport excited-state energy to charge-separation sites, and then transport and store redox equivalents for use in the catalytic reactions that produce chemical fuels. This multifunctional behavior will require the assimilation of multiple components into a single macromolecular system. A wide variety of different architectures including porphyrin arrays, peptides, dendrimers, and polymers have been explored, with each design posing unique challenges. Polymer assemblies are attractive due to their relative ease of production and facile synthetic modification. However, their disordered nature gives rise to stochastic dynamics not present in more ordered assemblies. The rational design of assemblies requires a detailed understanding of the energy and electron transfer events that follow light absorption, which can occur on time scales ranging from femtoseconds to hundreds of microseconds, necessitating the use of sophisticated techniques. We have used a combination of time-resolved absorption and emission spectroscopies with observation times that span 9 orders of magnitude to follow the excited-state evolution within polymer-based molecular assemblies. We complement experimental observations with molecular dynamics simulations to develop a microscopic view of these dynamics. This Account provides an overview of our work on polymers decorated with pendant Ru(II) chromophores, both in solution and on surfaces. We have examined site-to-site energy transport among the Ru(II) complexes, and in systems incorporating π-conjugated polymers, we have observed ultrafast formation of a long-lived charge-separated state. When attached to TiO2

Deuteron spin-lattice relaxation in the presence of an activation energy distribution: application to methanols in zeolite NaX.

PubMed

Stoch, G; Ylinen, E E; Birczynski, A; Lalowicz, Z T; Góra-Marek, K; Punkkinen, M

2013-02-01

A new method is introduced for analyzing deuteron spin-lattice relaxation in molecular systems with a broad distribution of activation energies and correlation times. In such samples the magnetization recovery is strongly non-exponential but can be fitted quite accurately by three exponentials. The considered system may consist of molecular groups with different mobility. For each group a Gaussian distribution of the activation energy is introduced. By assuming for every subsystem three parameters: the mean activation energy E(0), the distribution width σ and the pre-exponential factor τ(0) for the Arrhenius equation defining the correlation time, the relaxation rate is calculated for every part of the distribution. Experiment-based limiting values allow the grouping of the rates into three classes. For each class the relaxation rate and weight is calculated and compared with experiment. The parameters E(0), σ and τ(0) are determined iteratively by repeating the whole cycle many times. The temperature dependence of the deuteron relaxation was observed in three samples containing CD(3)OH (200% and 100% loading) and CD(3)OD (200%) in NaX zeolite and analyzed by the described method between 20K and 170K. The obtained parameters, equal for all the three samples, characterize the methyl and hydroxyl mobilities of the methanol molecules at two different locations. Copyright © 2012 Elsevier Inc. All rights reserved.

Electron-impact vibrational relaxation in high-temperature nitrogen

NASA Technical Reports Server (NTRS)

Lee, Jong-Hun

1992-01-01

Vibrational relaxation process of N2 molecules by electron-impact is examined for the future planetary entry environments. Multiple-quantum transitions from excited states to higher/lower states are considered for the electronic ground state of the nitrogen molecule N2 (X 1Sigma-g(+)). Vibrational excitation and deexcitation rate coefficients obtained by computational quantum chemistry are incorporated into the 'diffusion model' to evaluate the time variations of vibrational number densities of each energy state and total vibrational energy. Results show a non-Boltzmann distribution of number densities at the earlier stage of relaxation, which in turn suppresses the equilibrium process but affects little the time variation of total vibrational energy. An approximate rate equation and a corresponding relaxation time from the excited states, compatible with the system of flow conservation equations, are derived. The relaxation time from the excited states indicates the weak dependency of the initial vibrational temperature. The empirical curve-fit formula for the improved e-V relaxation time is obtained.

MCNP6.1 simulations for low-energy atomic relaxation: Code-to-code comparison with GATEv7.2, PENELOPE2014, and EGSnrc

NASA Astrophysics Data System (ADS)

Jung, Seongmoon; Sung, Wonmo; Lee, Jaegi; Ye, Sung-Joon

2018-01-01

Emerging radiological applications of gold nanoparticles demand low-energy electron/photon transport calculations including details of an atomic relaxation process. Recently, MCNP® version 6.1 (MCNP6.1) has been released with extended cross-sections for low-energy electron/photon, subshell photoelectric cross-sections, and more detailed atomic relaxation data than the previous versions. With this new feature, the atomic relaxation process of MCNP6.1 has not been fully tested yet with its new physics library (eprdata12) that is based on the Evaluated Atomic Data Library (EADL). In this study, MCNP6.1 was compared with GATEv7.2, PENELOPE2014, and EGSnrc that have been often used to simulate low-energy atomic relaxation processes. The simulations were performed to acquire both photon and electron spectra produced by interactions of 15 keV electrons or photons with a 10-nm-thick gold nano-slab. The photon-induced fluorescence X-rays from MCNP6.1 fairly agreed with those from GATEv7.2 and PENELOPE2014, while the electron-induced fluorescence X-rays of the four codes showed more or less discrepancies. A coincidence was observed in the photon-induced Auger electrons simulated by MCNP6.1 and GATEv7.2. A recent release of MCNP6.1 with eprdata12 can be used to simulate the photon-induced atomic relaxation.

Visible-Light-Mediated Excited State Relaxation in Semi-Synthetic Genetic Alphabet: d5SICS and dNaM.

PubMed

Bhattacharyya, Kalishankar; Datta, Ayan

2017-08-25

The excited state dynamics of an unnatural base pair (UBP) d5SICS/dNaM were investigated by accurate ab-initio calculations. Time-dependent density functional and high-level multireference calculations (MS-CASPT2) were performed to elucidate the excitation of this UBP and its excited state relaxation mechanism. After excitation to the bright state S 2 (ππ*), it decays to the S 1 state and then undergoes efficient intersystem crossing to the triplet manifold. The presence of sulfur atom in d5SICS leads to strong spin-orbit coupling (SOC) and a small energy gap that facilitates intersystem crossing from S 1 (n s π*) to T 2 (ππ*) followed by internal conversion to T 1 state. Similarly in dNaM, the deactivation pathway follows analogous trends. CASPT2 calculations suggest that the S 1 (ππ*) state is a dark state below the accessible S 2 (ππ*) bright state. During the ultrafast deactivation, it exhibits bond length inversion. From S 1 state, significant SOC leads the population transfer to T 3 due to a smaller energy gap. Henceforth, fast internal conversion occurs from T 3 to T 2 followed by T 1 . From time-dependent trajectory surface hopping dynamics, it is found that excited state relaxation occurs on a sub-picosecond timescale in d5SICS and dNaM. Our findings strongly suggest that there is enough energy available in triplet state of UBP to generate reactive oxygen species and induce phototoxicity with respect to cellular DNA. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Surface modified CF x cathode material for ultrafast discharge and high energy density

DOE PAGES

Dai, Yang; Zhu, Yimei; Cai, Sendan; ...

2014-11-10

Li/CF x primary possesses the highest energy density of 2180 W h kg⁻¹ among all primary lithium batteries. However, a key limitation for the utility of this type of battery is in its poor rate capability because the cathode material, CF x, is an intrinsically poor electronic conductor. Here, we report on our development of a controlled process of surface de-fluorination under mild hydrothermal conditions to modify the highly fluorinated CF x. The modified CF x, consisting of an in situ generated shell component of F-graphene layers, possesses good electronic conductivity and removes the transporting barrier for lithium ions, yieldingmore » a high-capacity performance and an excellent rate-capability. Indeed, a capacity of 500 mA h g⁻¹ and a maximum power density of 44 800 W kg⁻¹ can be realized at the ultrafast rate of 30 C (24 A g⁻¹), which is over one order of magnitude higher than that of the state-of-the-art primary lithium-ion batteries.« less

Relation between magnetization and Faraday angles produced by ultrafast spin-flip processes within the three-level Λ-type system

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

Hinschberger, Y.; Lavoine, J. P.

2015-08-07

Ultrafast magneto-optical (MO) experiments constitute a powerful tool to explore the magnetization dynamics of diverse materials. Over the last decade, there have been many theoretical and experimental developments on this subject. However, the relation between the magnetization dynamics and the transient MO response still remains unclear. In this work, we calculate the magnetization of a material, as well as the magneto-optical rotation and ellipticity angles measured in a single-beam experiment. Then, we compare the magnetization to the MO response. The magnetic material is modeled by a three-level Λ-type system, which represents a simple model to describe MO effects induced bymore » an ultrafast laser pulse. Our calculations use the density matrix formalism, while the dynamics of the system is obtained by solving the Lindblad equation taking into account population relaxation and dephasing processes. Furthermore, we consider the Faraday rotation of the optical waves that simultaneously causes spin-flip. We show that the Faraday angles remain proportional to the magnetization only if the system has reached the equilibrium-state, and that this proportionality is directly related to the population and coherence decay rates. For the non-equilibrium situation, the previous proportionality relation is no longer valid. We show that our model is able to interpret some recent experimental results obtained in a single-pulse experiment. We further show that, after a critical pulse duration, the decrease of the ellipticity as a function of the absorbed energy is a characteristic of the system.« less

4-D ultrafast shear-wave imaging.

PubMed

Gennisson, Jean-Luc; Provost, Jean; Deffieux, Thomas; Papadacci, Clément; Imbault, Marion; Pernot, Mathieu; Tanter, Mickael

2015-06-01

Over the last ten years, shear wave elastography (SWE) has seen considerable development and is now routinely used in clinics to provide mechanical characterization of tissues to improve diagnosis. The most advanced technique relies on the use of an ultrafast scanner to generate and image shear waves in real time in a 2-D plane at several thousands of frames per second. We have recently introduced 3-D ultrafast ultrasound imaging to acquire with matrix probes the 3-D propagation of shear waves generated by a dedicated radiation pressure transducer in a single acquisition. In this study, we demonstrate 3-D SWE based on ultrafast volumetric imaging in a clinically applicable configuration. A 32 × 32 matrix phased array driven by a customized, programmable, 1024-channel ultrasound system was designed to perform 4-D shear-wave imaging. A matrix phased array was used to generate and control in 3-D the shear waves inside the medium using the acoustic radiation force. The same matrix array was used with 3-D coherent plane wave compounding to perform high-quality ultrafast imaging of the shear wave propagation. Volumetric ultrafast acquisitions were then beamformed in 3-D using a delay-and-sum algorithm. 3-D volumetric maps of the shear modulus were reconstructed using a time-of-flight algorithm based on local multiscale cross-correlation of shear wave profiles in the three main directions using directional filters. Results are first presented in an isotropic homogeneous and elastic breast phantom. Then, a full 3-D stiffness reconstruction of the breast was performed in vivo on healthy volunteers. This new full 3-D ultrafast ultrasound system paves the way toward real-time 3-D SWE.

Extended MHD Modeling of Tearing-Driven Magnetic Relaxation

NASA Astrophysics Data System (ADS)

Sauppe, Joshua

2016-10-01

Driven plasma pinch configurations are characterized by the gradual accumulation and episodic release of free energy in discrete relaxation events. The hallmark of this relaxation in a reversed-field pinch (RFP) plasma is flattening of the parallel current density profile effected by a fluctuation-induced dynamo emf in Ohm's law. Nonlinear two-fluid modeling of macroscopic RFP dynamics has shown appreciable coupling of magnetic relaxation and the evolution of plasma flow. Accurate modeling of RFP dynamics requires the Hall effect in Ohm's law as well as first order ion finite Larmor radius (FLR) effects, represented by the Braginskii ion gyroviscous stress tensor. New results find that the Hall dynamo effect from < J × B > / ne can counter the MHD effect from - < V × B > in some of the relaxation events. The MHD effect dominates these events and relaxes the current profile toward the Taylor state, but the opposition of the two dynamos generates plasma flow in the direction of equilibrium current density, consistent with experimental measurements. Detailed experimental measurements of the MHD and Hall emf terms are compared to these extended MHD predictions. Tracking the evolution of magnetic energy, helicity, and hybrid helicity during relaxation identifies the most important contributions in single-fluid and two-fluid models. Magnetic helicity is well conserved relative to the magnetic energy during relaxation. The hybrid helicity is dominated by magnetic helicity in realistic low-beta pinch conditions and is also well conserved. Differences of less than 1 % between magnetic helicity and hybrid helicity are observed with two-fluid modeling and result from cross helicity evolution through ion FLR effects, which have not been included in contemporary relaxation theories. The kinetic energy driven by relaxation in the computations is dominated by velocity components perpendicular to the magnetic field, an effect that had not been predicted. Work performed at

Ultrafast photoconductivity of undoped cuprates

NASA Astrophysics Data System (ADS)

Dodge, J. Steven; Farahani, Amir; Petersen, Jesse; Liang, Ruixing; Bozovic, Ivan

2010-03-01

Using a visible pump-THz probe technique, we studied the ultrafast transient photoconductivity of the insulating cuprate La2CuO4, and compared it with earlier measurements of Sr2CuO2Cl2 and YBa2Cu3O6. In all these compounds, we observe a rapid onset of photoconductivity that is followed by a non-exponential relaxation on a picosecond time scales, the dynamics of which are independent of photocarrier concentration ranging from 0.2 to 1.5 percent. The photoconductivity decay is qualitatively similar to the decay of the photoinduced gap absorption in Sr2CuO2Cl2,footnotetextJ. S. Dodge, arXiv:0910.5048 indicating a common origin for the two effects. Assuming a quantum efficiency of unity, the estimated peak mobility for all three compounds is within 0.1-0.4 cm^2/V.s; this is lower than the Hall mobility in chemically doped systems with similar carrier concentrations,footnotetext Ando et al, Phys. Rev. Lett. 87, 017001 (2001) but orders of magnitude larger than earlier DC photoconductivity results.footnotetextThio et al, Phys. Rev. B 42, 10800 (1990) The similarity of the peak photoconductivity across three different compounds indicates that it is an intrinsic feature of the copper oxide plane.

Accurate determination of the binding energy of the formic acid dimer: The importance of geometry relaxation

NASA Astrophysics Data System (ADS)

Kalescky, Robert; Kraka, Elfi; Cremer, Dieter

2014-02-01

The formic acid dimer in its C2h-symmetrical cyclic form is stabilized by two equivalent H-bonds. The currently accepted interaction energy is 18.75 kcal/mol whereas the experimental binding energy D0 value is only 14.22 ±0.12 kcal/mol [F. Kollipost, R. W. Larsen, A. V. Domanskaya, M. Nörenberg, and M. A. Suhm, J. Chem. Phys. 136, 151101 (2012)]. Calculation of the binding energies De and D0 at the CCSD(T) (Coupled Cluster with Single and Double excitations and perturbative Triple excitations)/CBS (Complete Basis Set) level of theory, utilizing CCSD(T)/CBS geometries and the frequencies of the dimer and monomer, reveals that there is a 3.2 kcal/mol difference between interaction energy and binding energy De, which results from (i) not relaxing the geometry of the monomers upon dissociation of the dimer and (ii) approximating CCSD(T) correlation effects with MP2. The most accurate CCSD(T)/CBS values obtained in this work are De = 15.55 and D0 = 14.32 kcal/mol where the latter binding energy differs from the experimental value by 0.1 kcal/mol. The necessity of employing augmented VQZ and VPZ calculations and relaxing monomer geometries of H-bonded complexes upon dissociation to obtain reliable binding energies is emphasized.

Ultrafast Electric Field Pulse Control of Giant Temperature Change in Ferroelectrics

NASA Astrophysics Data System (ADS)

Qi, Y.; Liu, S.; Lindenberg, A. M.; Rappe, A. M.

2018-01-01

There is a surge of interest in developing environmentally friendly solid-state-based cooling technology. Here, we point out that a fast cooling rate (≈1011 K /s ) can be achieved by driving solid crystals to a high-temperature phase with a properly designed electric field pulse. Specifically, we predict that an ultrafast electric field pulse can cause a giant temperature decrease up to 32 K in PbTiO3 occurring on few picosecond time scales. We explain the underlying physics of this giant electric field pulse-induced temperature change with the concept of internal energy redistribution: the electric field does work on a ferroelectric crystal and redistributes its internal energy, and the way the kinetic energy is redistributed determines the temperature change and strongly depends on the electric field temporal profile. This concept is supported by our all-atom molecular dynamics simulations of PbTiO3 and BaTiO3 . Moreover, this internal energy redistribution concept can also be applied to understand electrocaloric effect. We further propose new strategies for inducing giant cooling effect with ultrafast electric field pulse. This Letter offers a general framework to understand electric-field-induced temperature change and highlights the opportunities of electric field engineering for controlled design of fast and efficient cooling technology.

Distinguishing between relaxation pathways by combining dissociative ionization pump probe spectroscopy and ab initio calculations: a case study of cytosine.

PubMed

Kotur, Marija; Weinacht, Thomas C; Zhou, Congyi; Kistler, Kurt A; Matsika, Spiridoula

2011-05-14

We present a general method for tracking molecular relaxation along different pathways from an excited state down to the ground state. We follow the excited state dynamics of cytosine pumped near the S(0)-S(1) resonance using ultrafast laser pulses in the deep ultraviolet and probed with strong field near infrared pulses which ionize and dissociate the molecules. The fragment ions are detected via time of flight mass spectroscopy as a function of pump probe delay and probe pulse intensity. Our measurements reveal that different molecular fragments show different timescales, indicating that there are multiple relaxation pathways down to the ground state. We interpret our measurements with the help of ab initio electronic structure calculations of both the neutral molecule and the molecular cation for different conformations en route to relaxation back down to the ground state. Our measurements and calculations show passage through two seams of conical intersections between ground and excited states and demonstrate the ability of dissociative ionization pump probe measurements in conjunction with ab initio electronic structure calculations to track molecular relaxation through multiple pathways.

Ultrafast transmission electron microscopy using a laser-driven field emitter: Femtosecond resolution with a high coherence electron beam.

PubMed

Feist, Armin; Bach, Nora; Rubiano da Silva, Nara; Danz, Thomas; Möller, Marcel; Priebe, Katharina E; Domröse, Till; Gatzmann, J Gregor; Rost, Stefan; Schauss, Jakob; Strauch, Stefanie; Bormann, Reiner; Sivis, Murat; Schäfer, Sascha; Ropers, Claus

2017-05-01

We present the development of the first ultrafast transmission electron microscope (UTEM) driven by localized photoemission from a field emitter cathode. We describe the implementation of the instrument, the photoemitter concept and the quantitative electron beam parameters achieved. Establishing a new source for ultrafast TEM, the Göttingen UTEM employs nano-localized linear photoemission from a Schottky emitter, which enables operation with freely tunable temporal structure, from continuous wave to femtosecond pulsed mode. Using this emission mechanism, we achieve record pulse properties in ultrafast electron microscopy of 9Å focused beam diameter, 200fs pulse duration and 0.6eV energy width. We illustrate the possibility to conduct ultrafast imaging, diffraction, holography and spectroscopy with this instrument and also discuss opportunities to harness quantum coherent interactions between intense laser fields and free-electron beams. Copyright © 2016 The Authors. Published by Elsevier B.V. All rights reserved.

Electron beam dynamics in an ultrafast transmission electron microscope with Wehnelt electrode.

PubMed

Bücker, K; Picher, M; Crégut, O; LaGrange, T; Reed, B W; Park, S T; Masiel, D J; Banhart, F

2016-12-01

High temporal resolution transmission electron microscopy techniques have shown significant progress in recent years. Using photoelectron pulses induced by ultrashort laser pulses on the cathode, these methods can probe ultrafast materials processes and have revealed numerous dynamic phenomena at the nanoscale. Most recently, the technique has been implemented in standard thermionic electron microscopes that provide a flexible platform for studying material's dynamics over a wide range of spatial and temporal scales. In this study, the electron pulses in such an ultrafast transmission electron microscope are characterized in detail. The microscope is based on a thermionic gun with a Wehnelt electrode and is operated in a stroboscopic photoelectron mode. It is shown that the Wehnelt bias has a decisive influence on the temporal and energy spread of the picosecond electron pulses. Depending on the shape of the cathode and the cathode-Wehnelt distance, different emission patterns with different pulse parameters are obtained. The energy spread of the pulses is determined by space charge and Boersch effects, given by the number of electrons in a pulse. However, filtering effects due to the chromatic aberrations of the Wehnelt electrode allow the extraction of pulses with narrow energy spreads. The temporal spread is governed by electron trajectories of different length and in different electrostatic potentials. High temporal resolution is obtained by excluding shank emission from the cathode and aberration-induced halos in the emission pattern. By varying the cathode-Wehnelt gap, the Wehnelt bias, and the number of photoelectrons in a pulse, tradeoffs between energy and temporal resolution as well as beam intensity can be made as needed for experiments. Based on the characterization of the electron pulses, the optimal conditions for the operation of ultrafast TEMs with thermionic gun assembly are elaborated. Copyright © 2016 Elsevier B.V. All rights reserved.

Mode-specific vibrational excitation and energy redistribution after ultrafast intramolecular electron transfer

NASA Astrophysics Data System (ADS)

Hogiu, S.; Werncke, W.; Pfeiffer, M.; Dreyer, J.; Elsaesser, T.

2000-07-01

Vibrational relaxation in the electronic ground state initiated by intramolecular back-electron transfer (b-ET) of betaine-30 (B-30) is studied by picosecond time-resolved anti-Stokes Raman spectroscopy. Measurements were carried out with B-30 dissolved in slowly as well as in rapidly relaxing solvents. We observed a risetime of the Raman band with the highest frequency near 1600 cm-1 which is close to the b-ET time τb-ET of B-30. For B-30 dissolved in propylene carbonate (τb-ET˜1 ps), the population of this mode exhibits a rise time of 1 ps whereas vibrational populations between 400 and 1400 cm-1 increase substantially slower. In contrast, in glycerol triacetin (τb-ET˜3.5 ps) and in ethanol (τb-ET˜6 ps) rise times of all modes are close to the respective b-ET times. Within the first few picoseconds, direct vibrational excitation through b-ET is favored for modes with the highest frequencies and high Franck-Condon factors. Later on, indirect channels of population due to vibrational energy redistribution (IVR) become effective. Thermal equilibrium populations of the Raman active modes are established within 10 to 15 ps after optical excitation.

Breaking resolution limits in ultrafast electron diffraction and microscopy.

PubMed

Baum, Peter; Zewail, Ahmed H

2006-10-31

Ultrafast electron microscopy and diffraction are powerful techniques for the study of the time-resolved structures of molecules, materials, and biological systems. Central to these approaches is the use of ultrafast coherent electron packets. The electron pulses typically have an energy of 30 keV for diffraction and 100-200 keV for microscopy, corresponding to speeds of 33-70% of the speed of light. Although the spatial resolution can reach the atomic scale, the temporal resolution is limited by the pulse width and by the difference in group velocities of electrons and the light used to initiate the dynamical change. In this contribution, we introduce the concept of tilted optical pulses into diffraction and imaging techniques and demonstrate the methodology experimentally. These advances allow us to reach limits of time resolution down to regimes of a few femtoseconds and, possibly, attoseconds. With tilted pulses, every part of the sample is excited at precisely the same time as when the electrons arrive at the specimen. Here, this approach is demonstrated for the most unfavorable case of ultrafast crystallography. We also present a method for measuring the duration of electron packets by autocorrelating electron pulses in free space and without streaking, and we discuss the potential of tilting the electron pulses themselves for applications in domains involving nuclear and electron motions.

Breaking resolution limits in ultrafast electron diffraction and microscopy

PubMed Central

Baum, Peter; Zewail, Ahmed H.

2006-01-01

Ultrafast electron microscopy and diffraction are powerful techniques for the study of the time-resolved structures of molecules, materials, and biological systems. Central to these approaches is the use of ultrafast coherent electron packets. The electron pulses typically have an energy of 30 keV for diffraction and 100–200 keV for microscopy, corresponding to speeds of 33–70% of the speed of light. Although the spatial resolution can reach the atomic scale, the temporal resolution is limited by the pulse width and by the difference in group velocities of electrons and the light used to initiate the dynamical change. In this contribution, we introduce the concept of tilted optical pulses into diffraction and imaging techniques and demonstrate the methodology experimentally. These advances allow us to reach limits of time resolution down to regimes of a few femtoseconds and, possibly, attoseconds. With tilted pulses, every part of the sample is excited at precisely the same time as when the electrons arrive at the specimen. Here, this approach is demonstrated for the most unfavorable case of ultrafast crystallography. We also present a method for measuring the duration of electron packets by autocorrelating electron pulses in free space and without streaking, and we discuss the potential of tilting the electron pulses themselves for applications in domains involving nuclear and electron motions. PMID:17056711

Ultrafast core-loss spectroscopy in four-dimensional electron microscopy

PubMed Central

van der Veen, Renske M.; Penfold, Thomas J.; Zewail, Ahmed H.

2015-01-01

We demonstrate ultrafast core-electron energy-loss spectroscopy in four-dimensional electron microscopy as an element-specific probe of nanoscale dynamics. We apply it to the study of photoexcited graphite with femtosecond and nanosecond resolutions. The transient core-loss spectra, in combination with ab initio molecular dynamics simulations, reveal the elongation of the carbon-carbon bonds, even though the overall behavior is a contraction of the crystal lattice. A prompt energy-gap shrinkage is observed on the picosecond time scale, which is caused by local bond length elongation and the direct renormalization of band energies due to temperature-dependent electron–phonon interactions. PMID:26798793

Controlling the metal-to-insulator relaxation of the metastable hidden quantum state in 1T-TaS2

PubMed Central

Vaskivskyi, Igor; Gospodaric, Jan; Brazovskii, Serguei; Svetin, Damjan; Sutar, Petra; Goreshnik, Evgeny; Mihailovic, Ian A.; Mertelj, Tomaz; Mihailovic, Dragan

2015-01-01

Controllable switching between metastable macroscopic quantum states under nonequilibrium conditions induced either by light or with an external electric field is rapidly becoming of great fundamental interest. We investigate the relaxation properties of a “hidden” (H) charge density wave (CDW) state in thin single crystals of the layered dichalcogenide 1T-TaS2, which can be reached by either a single 35-fs optical laser pulse or an ~30-ps electrical pulse. From measurements of the temperature dependence of the resistivity under different excitation conditions, we find that the metallic H state relaxes to the insulating Mott ground state through a sequence of intermediate metastable states via discrete jumps over a “Devil’s staircase.” In between the discrete steps, an underlying glassy relaxation process is observed, which arises because of reciprocal-space commensurability frustration between the CDW and the underlying lattice. We show that the metastable state relaxation rate may be externally stabilized by substrate strain, thus opening the way to the design of nonvolatile ultrafast high-temperature memory devices based on switching between CDW states with large intrinsic differences in electrical resistance. PMID:26601218

A general strategy for the ultrafast surface modification of metals.

PubMed

Shen, Mingli; Zhu, Shenglong; Wang, Fuhui

2016-12-07

Surface modification is an essential step in engineering materials that can withstand the increasingly aggressive environments encountered in various modern energy-conversion systems and chemical processing industries. However, most traditional technologies exhibit disadvantages such as slow diffusion kinetics, processing difficulties or compatibility issues. Here, we present a general strategy for the ultrafast surface modification of metals inspired by electromigration, using aluminizing austenitic stainless steel as an example. Our strategy facilitates the rapid formation of a favourable ductile surface layer composed of FeCrAl or β-FeAl within only 10 min compared with several hours in conventional processes. This result indicates that electromigration can be used to achieve the ultrafast surface modification of metals and can overcome the limitations of traditional technologies. This strategy could be used to aluminize ultra-supercritical steam tubing to withstand aggressive oxidizing environments.

A general strategy for the ultrafast surface modification of metals

PubMed Central

Shen, Mingli; Zhu, Shenglong; Wang, Fuhui

2016-01-01

Surface modification is an essential step in engineering materials that can withstand the increasingly aggressive environments encountered in various modern energy-conversion systems and chemical processing industries. However, most traditional technologies exhibit disadvantages such as slow diffusion kinetics, processing difficulties or compatibility issues. Here, we present a general strategy for the ultrafast surface modification of metals inspired by electromigration, using aluminizing austenitic stainless steel as an example. Our strategy facilitates the rapid formation of a favourable ductile surface layer composed of FeCrAl or β-FeAl within only 10 min compared with several hours in conventional processes. This result indicates that electromigration can be used to achieve the ultrafast surface modification of metals and can overcome the limitations of traditional technologies. This strategy could be used to aluminize ultra-supercritical steam tubing to withstand aggressive oxidizing environments. PMID:27924909

Plasmonic antennas as design elements for coherent ultrafast nanophotonics.

PubMed

Brinks, Daan; Castro-Lopez, Marta; Hildner, Richard; van Hulst, Niek F

2013-11-12

Broadband excitation of plasmons allows control of light-matter interaction with nanometric precision at femtosecond timescales. Research in the field has spiked in the past decade in an effort to turn ultrafast plasmonics into a diagnostic, microscopy, computational, and engineering tool for this novel nanometric-femtosecond regime. Despite great developments, this goal has yet to materialize. Previous work failed to provide the ability to engineer and control the ultrafast response of a plasmonic system at will, needed to fully realize the potential of ultrafast nanophotonics in physical, biological, and chemical applications. Here, we perform systematic measurements of the coherent response of plasmonic nanoantennas at femtosecond timescales and use them as building blocks in ultrafast plasmonic structures. We determine the coherent response of individual nanoantennas to femtosecond excitation. By mixing localized resonances of characterized antennas, we design coupled plasmonic structures to achieve well-defined ultrafast and phase-stable field dynamics in a predetermined nanoscale hotspot. We present two examples of the application of such structures: control of the spectral amplitude and phase of a pulse in the near field, and ultrafast switching of mutually coherent hotspots. This simple, reproducible and scalable approach transforms ultrafast plasmonics into a straightforward tool for use in fields as diverse as room temperature quantum optics, nanoscale solid-state physics, and quantum biology.

Intense Plasma Waveguide Terahertz Sources for High-Field THz Probe Science with Ultrafast Lasers for Solid State Physics

DTIC Science & Technology

2016-08-25

AFRL-AFOSR-UK-TR-2016-0029 Intense Plasma-Waveguide Terahertz Sources for High-Field THz probe science with ultrafast lasers for Solid State Physics...Plasma-Waveguide Terahertz Sources for High-Field THz probe science with ultrafast lasers for Solid State Physics, 5a.  CONTRACT NUMBER 5b.  GRANT...an existing high energy laser system, has been applied to the study of intense terahertz radiation generated in gaseous plasmas in purpose

Dynamics of Carotenoids Probed by Femtosecond Absorption, Fluorescence, and Raman Spectroscopy

NASA Astrophysics Data System (ADS)

Yoshizawa, M.; Kosumi, D.; Komukai, M.; Yanagi, K.; Hashimoto, H.

Ultrafast optical responses in β-carotene and lycopene depend on the pump wavelength. Excess vibrational energy induced by the photoexcitation remains longer than several picoseconds in the excited states and slows down the relaxation kinetics.

Ultrafast dynamics of non-equilibrium electrons and strain generation under femtosecond laser irradiation of Nickel

NASA Astrophysics Data System (ADS)

Tsibidis, George D.

2018-04-01

We present a theoretical study of the ultrafast electron dynamics in transition metals of large electron-phonon coupling constant using ultrashort pulsed laser beams. The significant influence of the dynamics of produced nonthermal electrons to electron thermalisation and electron-phonon interaction is thoroughly investigated for various values of the pulse duration (i.e., from 10 fs to 2.3 ps). The model correlates the role of nonthermal electrons, relaxation processes and induced stress-strain fields. Simulations are presented by choosing Nickel (Ni) as a test material to compute electron-phonon relaxation time due to its large electron-phonon coupling constant. We demonstrate that the consideration of the aforementioned factors leads to significant changes compared to the results the traditional two-temperature model provides. The proposed model predicts a substantially ( 33%) smaller damage threshold and a large increase of the stress ( 20%, at early times) which first underlines the role of the nonthermal electron interactions and second enhances its importance with respect to the precise determination of laser specifications in material micromachining techniques.

Material processing with fiber based ultrafast pulse delivery

NASA Astrophysics Data System (ADS)

Baumbach, S.; Stockburger, R.; Führa, B.; Zoller, S.; Thum, S.; Moosmann, J.; Maier, D.; Kanal, F.; Russ, S.; Kaiser, E.; Budnicki, A.; Sutter, D. H.; Pricking, S.; Killi, A.

2018-02-01

We report on TRUMPF's ultrafast laser systems equipped with industrialized hollow core fiber laser light cables. Beam guidance in general by means of optical fibers, e.g. for multi kilowatt cw laser systems, has become an integral part of laser-based material processing. One advantage of fiber delivery, among others, is the mechanical separation between laser and processing head. An equally important benefit is given by the fact that the fiber end acts as an opto-mechanical fix-point close to successive optical elements in the processing head. Components like lenses, diffractive optical elements etc. can thus be designed towards higher efficiency which results in better material processing. These aspects gain increasing significance when the laser system operates in fundamental mode which is usually the case for ultrafast lasers. Through the last years beam guidance of ultrafast laser pulses by means of hollow core fiber technology established very rapidly. The combination of TRUMPF's long-term stable ultrafast laser sources, passive fiber coupling, connector and packaging forms a flexible and powerful system for laser based material processing well suited for an industrial environment. In this article we demonstrate common material processing applications with ultrafast lasers realized with TRUMPF's hollow core fiber delivery. The experimental results are contrasted and evaluated against conventional free space propagation in order to illustrate the performance of flexible ultrafast beam delivery.

Ultrafast energy transfer with competing channels: Non-equilibrium Förster and Modified Redfield theories

NASA Astrophysics Data System (ADS)

Seibt, Joachim; Mančal, Tomáš

2017-05-01

We derive equations of motion for the reduced density matrix of a molecular system which undergoes energy transfer dynamics competing with fast internal conversion channels. Environmental degrees of freedom of such a system have no time to relax to quasi-equilibrium in the electronic excited state of the donor molecule, and thus the conditions of validity of Förster and Modified Redfield theories in their standard formulations do not apply. We derive non-equilibrium versions of the two well-known rate theories and apply them to the case of carotenoid-chlorophyll energy transfer. Although our reduced density matrix approach does not account for the formation of vibronic excitons, it still confirms the important role of the donor ground-state vibrational states in establishing the resonance energy transfer conditions. We show that it is essential to work with a theory valid in a strong system-bath interaction regime to obtain correct dependence of the rates on donor-acceptor energy gap.

Magnetic-field sensing with quantum error detection under the effect of energy relaxation

NASA Astrophysics Data System (ADS)

Matsuzaki, Yuichiro; Benjamin, Simon

2017-03-01

A solid state spin is an attractive system with which to realize an ultrasensitive magnetic field sensor. A spin superposition state will acquire a phase induced by the target field, and we can estimate the field strength from this phase. Recent studies have aimed at improving sensitivity through the use of quantum error correction (QEC) to detect and correct any bit-flip errors that may occur during the sensing period. Here we investigate the performance of a two-qubit sensor employing QEC and under the effect of energy relaxation. Surprisingly, we find that the standard QEC technique to detect and recover from an error does not improve the sensitivity compared with the single-qubit sensors. This is a consequence of the fact that the energy relaxation induces both a phase-flip and a bit-flip noise where the former noise cannot be distinguished from the relative phase induced from the target fields. However, we have found that we can improve the sensitivity if we adopt postselection to discard the state when error is detected. Even when quantum error detection is moderately noisy, and allowing for the cost of the postselection technique, we find that this two-qubit system shows an advantage in sensing over a single qubit in the same conditions.

Ultrafast studies of coexisting electronic order in cuprate superconductors

NASA Astrophysics Data System (ADS)

Hinton, James; Thewalt, Eric; Alpichshev, Zhanybek; Sternbach, Aaron; McLeod, Alex; Ji, L.; Veit, Mike; Dorrow, Chelsey; Koralek, Jake; Xhao, Xudong; Barisic, Neven; Kemper, Alexander; Gedik, Nuh; Greven, Martin; Basov, Dimitri; Orenstein, Joe

The cuprate family of high temperature superconductors displays a variety of electronic phases which emerge when charge carriers are added to the antiferromagnetic parent compound. These electronic phases are characterized by subtle differences in the low energy electronic excitations. Ultrafast time-resolved reflectivity (TRR) provides an ideal tool for investigating the cuprate phase diagram, as small changes in the electronic structure can produce significant contrast in the non-equilibrium reflectivity. Here we present TRR measurements of cuprate superconductors, focusing on the model single-layer cuprate HgBa2CuO4+δ. We observe a cusp-like feature in the quasiparticle lifetime near the superconducting transition temperature Tc. This feature can be understood using a model of coherently-mixed charge-density wave and superconducting pairing. We propose extending this technique to the nanoscale using ultrafast scattering scanning near-field microscopy (u-SNOM). This will allow us to explore how these electronic phases coexist and compete in real-space.

Precision machining of pig intestine using ultrafast laser pulses

NASA Astrophysics Data System (ADS)

Beck, Rainer J.; Góra, Wojciech S.; Carter, Richard M.; Gunadi, Sonny; Jayne, David; Hand, Duncan P.; Shephard, Jonathan D.

2015-07-01

Endoluminal surgery for the treatment of early stage colorectal cancer is typically based on electrocautery tools which imply restrictions on precision and the risk of harm through collateral thermal damage to the healthy tissue. As a potential alternative to mitigate these drawbacks we present laser machining of pig intestine by means of picosecond laser pulses. The high intensities of an ultrafast laser enable nonlinear absorption processes and a predominantly nonthermal ablation regime. Laser ablation results of square cavities with comparable thickness to early stage colorectal cancers are presented for a wavelength of 1030 nm using an industrial picosecond laser. The corresponding histology sections exhibit only minimal collateral damage to the surrounding tissue. The depth of the ablation can be controlled precisely by means of the pulse energy. Overall, the application of ultrafast lasers to ablate pig intestine enables significantly improved precision and reduced thermal damage to the surrounding tissue compared to conventional techniques.

Laser-driven ultrafast antiproton beam

NASA Astrophysics Data System (ADS)

Li, Shun; Pei, Zhikun; Shen, Baifei; Xu, Jiancai; Zhang, Lingang; Zhang, Xiaomei; Xu, Tongjun; Yu, Yong; Bu, Zhigang

2018-02-01

Antiproton beam generation is investigated based on the ultra-intense femtosecond laser pulse by using two-dimensional particle-in-cell and Geant4 simulations. A high-flux proton beam with an energy of tens of GeV is generated in sequential radiation pressure and bubble regime and then shoots into a high-Z target for producing antiprotons. Both yield and energy of the antiproton beam increase almost linearly with the laser intensity. The generated antiproton beam has a short pulse duration of about 5 ps and its flux reaches 2 × 10 20 s - 1 at the laser intensity of 2.14 × 10 23 W / cm 2 . Compared to conventional methods, this new method based on the ultra-intense laser pulse is able to provide a compact, tunable, and ultrafast antiproton source, which is potentially useful for quark-gluon plasma study, all-optical antihydrogen generation, and so on.

Calculating Interaction Energies Using First Principle Theories: Consideration of Basis Set Superposition Error and Fragment Relaxation

ERIC Educational Resources Information Center

Bowen, J. Philip; Sorensen, Jennifer B.; Kirschner, Karl N.

2007-01-01

The analysis explains the basis set superposition error (BSSE) and fragment relaxation involved in calculating the interaction energies using various first principle theories. Interacting the correlated fragment and increasing the size of the basis set can help in decreasing the BSSE to a great extent.

Ultrafast electronic dynamics driven by nuclear motion

NASA Astrophysics Data System (ADS)

Vendrell, Oriol

2016-05-01

The transfer of electrical charge on a microscopic scale plays a fundamental role in chemistry, in biology, and in technological applications. In this contribution, we will discuss situations in which nuclear motion plays a central role in driving the electronic dynamics of photo-excited or photo-ionized molecular systems. In particular, we will explore theoretically the ultrafast transfer of a double electron hole between the functional groups of glycine after K-shell ionization and subsequent Auger decay. Although a large energy gap of about 15 eV initially exists between the two electronic states involved and coherent electronic dynamics play no role in the hole transfer, we will illustrate how the double hole can be transferred within 3 to 4 fs between both functional ends of the glycine molecule driven solely by specific nuclear displacements and non-Born-Oppenheimer effects. This finding challenges the common wisdom that nuclear dynamics of the molecular skeleton are unimportant for charge transfer processes at the few-femtosecond time scale and shows that they can even play a prominent role. We thank the Hamburg Centre for Ultrafast Imaging and the Volkswagen Foundation for financial support.

Ultrafast Terahertz Nonlinear Optics of Landau Level Transitions in a Monolayer Graphene

NASA Astrophysics Data System (ADS)

Yumoto, Go; Matsunaga, Ryusuke; Hibino, Hiroki; Shimano, Ryo

2018-03-01

We investigated the ultrafast terahertz (THz) nonlinearity in a monolayer graphene under the strong magnetic field using THz pump-THz probe spectroscopy. An ultrafast suppression of the Faraday rotation associated with inter-Landau level (LL) transitions is observed, reflecting the Dirac electron character of nonequidistant LLs with large transition dipole moments. A drastic modulation of electron distribution in LLs is induced by far off-resonant THz pulse excitation in the transparent region. Numerical simulation based on the density matrix formalism without rotating-wave approximation reproduces the experimental results. Our results indicate that the strong light-matter coupling regime is realized in graphene, with the Rabi frequency exceeding the carrier wave frequency and even the relevant energy scale of the inter-LL transition.

Ultrafast carrier capture and Auger recombination in single GaN/InGaN multiple quantum well nanowires

DOE PAGES

Boubanga-Tombet, Stephane; Wright, Jeremy B.; Lu, Ping; ...

2016-11-04

Ultrafast optical microscopy is an important tool for examining fundamental phenomena in semiconductor nanowires with high temporal and spatial resolution. In this paper, we used this technique to study carrier dynamics in single GaN/InGaN core–shell nonpolar multiple quantum well nanowires. We find that intraband carrier–carrier scattering is the main channel governing carrier capture, while subsequent carrier relaxation is dominated by three-carrier Auger recombination at higher densities and bimolecular recombination at lower densities. Finally, the Auger constants in these nanowires are approximately 2 orders of magnitude lower than in planar InGaN multiple quantum wells, highlighting their potential for future light-emitting devices.

Quantum simulation of ultrafast dynamics using trapped ultracold atoms.

PubMed

Senaratne, Ruwan; Rajagopal, Shankari V; Shimasaki, Toshihiko; Dotti, Peter E; Fujiwara, Kurt M; Singh, Kevin; Geiger, Zachary A; Weld, David M

2018-05-25

Ultrafast electronic dynamics are typically studied using pulsed lasers. Here we demonstrate a complementary experimental approach: quantum simulation of ultrafast dynamics using trapped ultracold atoms. Counter-intuitively, this technique emulates some of the fastest processes in atomic physics with some of the slowest, leading to a temporal magnification factor of up to 12 orders of magnitude. In these experiments, time-varying forces on neutral atoms in the ground state of a tunable optical trap emulate the electric fields of a pulsed laser acting on bound charged particles. We demonstrate the correspondence with ultrafast science by a sequence of experiments: nonlinear spectroscopy of a many-body bound state, control of the excitation spectrum by potential shaping, observation of sub-cycle unbinding dynamics during strong few-cycle pulses, and direct measurement of carrier-envelope phase dependence of the response to an ultrafast-equivalent pulse. These results establish cold-atom quantum simulation as a complementary tool for studying ultrafast dynamics.

Ultrafast Electric Field Pulse Control of Giant Temperature Change in Ferroelectrics

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

Qi, Y.; Liu, S.; Lindenberg, A. M.

There is a surge of interest in developing environmentally friendly solid-state-based cooling technology. Here, we point out that a fast cooling rate (≈ 10 11 K/s) can be achieved by driving solid crystals to a high-temperature phase with a properly designed electric field pulse. Specifically, we predict that an ultrafast electric field pulse can cause a giant temperature decrease up to 32 K in PbTiO 3 occurring on few picosecond time scales. Here, we explain the underlying physics of this giant electric field pulse-induced temperature change with the concept of internal energy redistribution: the electric field does work on amore » ferroelectric crystal and redistributes its internal energy, and the way the kinetic energy is redistributed determines the temperature change and strongly depends on the electric field temporal profile. This concept is supported by our all-atom molecular dynamics simulations of PbTiO 3 and BaTiO 3. Moreover, this internal energy redistribution concept can also be applied to understand electrocaloric effect. We further propose new strategies for inducing giant cooling effect with ultrafast electric field pulse. This Letter offers a general framework to understand electric-field-induced temperature change and highlights the opportunities of electric field engineering for controlled design of fast and efficient cooling technology.« less

Ultrafast Electric Field Pulse Control of Giant Temperature Change in Ferroelectrics

DOE PAGES

Qi, Y.; Liu, S.; Lindenberg, A. M.; ...

2018-01-30

There is a surge of interest in developing environmentally friendly solid-state-based cooling technology. Here, we point out that a fast cooling rate (≈ 10 11 K/s) can be achieved by driving solid crystals to a high-temperature phase with a properly designed electric field pulse. Specifically, we predict that an ultrafast electric field pulse can cause a giant temperature decrease up to 32 K in PbTiO 3 occurring on few picosecond time scales. Here, we explain the underlying physics of this giant electric field pulse-induced temperature change with the concept of internal energy redistribution: the electric field does work on amore » ferroelectric crystal and redistributes its internal energy, and the way the kinetic energy is redistributed determines the temperature change and strongly depends on the electric field temporal profile. This concept is supported by our all-atom molecular dynamics simulations of PbTiO 3 and BaTiO 3. Moreover, this internal energy redistribution concept can also be applied to understand electrocaloric effect. We further propose new strategies for inducing giant cooling effect with ultrafast electric field pulse. This Letter offers a general framework to understand electric-field-induced temperature change and highlights the opportunities of electric field engineering for controlled design of fast and efficient cooling technology.« less

Ultra-fast Object Recognition from Few Spikes

DTIC Science & Technology

2005-07-06

Computer Science and Artificial Intelligence Laboratory Ultra-fast Object Recognition from Few Spikes Chou Hung, Gabriel Kreiman , Tomaso Poggio...neural code for different kinds of object-related information. *The authors, Chou Hung and Gabriel Kreiman , contributed equally to this work...Supplementary Material is available at http://ramonycajal.mit.edu/ kreiman /resources/ultrafast

Progress in ultrafast laser processing and future prospects

NASA Astrophysics Data System (ADS)

Sugioka, Koji

2017-03-01

The unique characteristics of ultrafast lasers have rapidly revolutionized materials processing after their first demonstration in 1987. The ultrashort pulse width of the laser suppresses heat diffusion to the surroundings of the processed region, which minimizes the formation of a heat-affected zone and thereby enables ultrahigh precision micro- and nanofabrication of various materials. In addition, the extremely high peak intensity can induce nonlinear multiphoton absorption, which extends the diversity of materials that can be processed to transparent materials such as glass. Nonlinear multiphoton absorption enables three-dimensional (3D) micro- and nanofabrication by irradiation with tightly focused femtosecond laser pulses inside transparent materials. Thus, ultrafast lasers are currently widely used for both fundamental research and practical applications. This review presents progress in ultrafast laser processing, including micromachining, surface micro- and nanostructuring, nanoablation, and 3D and volume processing. Advanced technologies that promise to enhance the performance of ultrafast laser processing, such as hybrid additive and subtractive processing, and shaped beam processing are discussed. Commercial and industrial applications of ultrafast laser processing are also introduced. Finally, future prospects of the technology are given with a summary.

Ultrafast dynamics of the photo-excited hemes b and cn in the cytochrome b6f complex.

PubMed

Agarwal, Rachna; Chauvet, Adrien A P

2017-01-25

The dynamics of hemes b and c n within the cytochrome b 6 f complex are investigated by means of ultrafast broad-band transient absorption spectroscopy. On the one hand, the data reveal that, subsequent to visible light excitation, part of the b hemes undergoes pulse-limited photo-oxidation, with the liberated electron supposedly being transferred to one of the adjacent aromatic amino acids. Photo-oxidation is followed by charge recombination in about 8.2 ps. Subsequent to charge recombination, heme b is promoted to a vibrationally excited ground state that relaxes in about 4.6 ps. On the other hand, heme c n undergoes ultrafast ground state recovery in about 140 fs. Interestingly, the data also show that, in contrast to previous beliefs, Chl a is involved in the photochemistry of hemes. Indeed, subsequent to heme excitation, Chl a bleaches and recovers to its ground state in 90 fs and 650 fs, respectively. Chl a bleaching allegedly corresponds to the formation of a short lived Chl a anion. Beyond the previously suggested structural role, this study provides unique evidence that Chl a is directly involved in the photochemistry of the hemes.

State-to-State Internal Energy Relaxation Following the Quantum-Kinetic Model in DSMC

NASA Technical Reports Server (NTRS)

Liechty, Derek S.

2014-01-01

A new model for chemical reactions, the Quantum-Kinetic (Q-K) model of Bird, has recently been introduced that does not depend on macroscopic rate equations or values of local flow field data. Subsequently, the Q-K model has been extended to include reactions involving charged species and electronic energy level transitions. Although this is a phenomenological model, it has been shown to accurately reproduce both equilibrium and non-equilibrium reaction rates. The usefulness of this model becomes clear as local flow conditions either exceed the conditions used to build previous models or when they depart from an equilibrium distribution. Presently, the applicability of the relaxation technique is investigated for the vibrational internal energy mode. The Forced Harmonic Oscillator (FHO) theory for vibrational energy level transitions is combined with the Q-K energy level transition model to accurately reproduce energy level transitions at a reduced computational cost compared to the older FHO models.

Ab initio study of potential ultrafast internal conversion routes in oxybenzone, caffeic acid, and ferulic acid: implications for sunscreens.

PubMed

Karsili, Tolga N V; Marchetti, Barbara; Ashfold, Michael N R; Domcke, Wolfgang

2014-12-26

Oxybenzone (OB) and ferulic acid (FA) both find use in commercial sunscreens; caffeic acid (CA) differs from FA by virtue of an -OH group in place of a -OCH3 group on the aromatic ring. We report the results of ab initio calculations designed to explore the excited state nonradiative relaxation pathways that provide photostability to these molecules and the photoprotection they offer toward UV-A and UV-B radiation. In the case of OB, internal conversion (IC) is deduced to occur on ultrafast time scales, via a barrierless electron-driven H atom transfer pathway from the S1(1(1)nπ*) state to a conical intersection (CI) with the ground (S0) state potential energy surface (PES). The situation with respect to CA and FA is somewhat less clear-cut, with low energy CIs identified by linking excited states to the S0 state following photoexcitation and subsequent evolution along (i) a ring centered out-of-plane deformation coordinate, (ii) the E/Z isomerism coordinate and, in the case of CA, (iii) an O-H stretch coordinate. Analogy with catechol suggests that the last of these processes (if active) would lead to radical formation (and thus potential phototoxicity), encouraging a suggestion that FA might be superior to CA as a sunscreen ingredient.

Ultrafast High Harmonic, Soft X-Ray Probing of Molecular Dynamics

DTIC Science & Technology

2013-04-30

590 L/s scroll pump and a titanium sublimation pump . A TOF-PES has been designed and constructed to analyze the energy of the photoelectrons...are studied using the quasi-continuous vacuum ultraviolet light of the Advanced Light Source at Lawrence Berkeley National Laboratory. The molecular...34), the method of high order harmonic generation of ultrashort vacuum ultraviolet pulses was used to investigate molecular photodissociation, ultrafast

Monte Carlo solution of Boltzmann equation for a simple model of highly nonequilibrium diatomic gases: Translational rotational energy relaxation

NASA Technical Reports Server (NTRS)

Yoshikawa, K. K.

1978-01-01

The semiclassical transition probability was incorporated in the simulation for energy exchange between rotational and translational energy. The results provide details on the fundamental mechanisms of gas kinetics where analytical methods were impractical. The validity of the local Maxwellian assumption and relaxation time, rotational-translational energy transition, and a velocity analysis of the inelastic collision were discussed in detail.

3D ultrafast ultrasound imaging in vivo.

PubMed

Provost, Jean; Papadacci, Clement; Arango, Juan Esteban; Imbault, Marion; Fink, Mathias; Gennisson, Jean-Luc; Tanter, Mickael; Pernot, Mathieu

2014-10-07

Very high frame rate ultrasound imaging has recently allowed for the extension of the applications of echography to new fields of study such as the functional imaging of the brain, cardiac electrophysiology, and the quantitative imaging of the intrinsic mechanical properties of tumors, to name a few, non-invasively and in real time. In this study, we present the first implementation of Ultrafast Ultrasound Imaging in 3D based on the use of either diverging or plane waves emanating from a sparse virtual array located behind the probe. It achieves high contrast and resolution while maintaining imaging rates of thousands of volumes per second. A customized portable ultrasound system was developed to sample 1024 independent channels and to drive a 32  ×  32 matrix-array probe. Its ability to track in 3D transient phenomena occurring in the millisecond range within a single ultrafast acquisition was demonstrated for 3D Shear-Wave Imaging, 3D Ultrafast Doppler Imaging, and, finally, 3D Ultrafast combined Tissue and Flow Doppler Imaging. The propagation of shear waves was tracked in a phantom and used to characterize its stiffness. 3D Ultrafast Doppler was used to obtain 3D maps of Pulsed Doppler, Color Doppler, and Power Doppler quantities in a single acquisition and revealed, at thousands of volumes per second, the complex 3D flow patterns occurring in the ventricles of the human heart during an entire cardiac cycle, as well as the 3D in vivo interaction of blood flow and wall motion during the pulse wave in the carotid at the bifurcation. This study demonstrates the potential of 3D Ultrafast Ultrasound Imaging for the 3D mapping of stiffness, tissue motion, and flow in humans in vivo and promises new clinical applications of ultrasound with reduced intra--and inter-observer variability.

Perspective: Ultrafast magnetism and THz spintronics

NASA Astrophysics Data System (ADS)

Walowski, Jakob; Münzenberg, Markus

2016-10-01

This year the discovery of femtosecond demagnetization by laser pulses is 20 years old. For the first time, this milestone work by Bigot and coworkers gave insight directly into the time scales of microscopic interactions that connect the spin and electron system. While intense discussions in the field were fueled by the complexity of the processes in the past, it now became evident that it is a puzzle of many different parts. Rather than providing an overview that has been presented in previous reviews on ultrafast processes in ferromagnets, this perspective will show that with our current depth of knowledge the first applications are developed: THz spintronics and all-optical spin manipulation are becoming more and more feasible. The aim of this perspective is to point out where we can connect the different puzzle pieces of understanding gathered over 20 years to develop novel applications. Based on many observations in a large number of experiments. Differences in the theoretical models arise from the localized and delocalized nature of ferromagnetism. Transport effects are intrinsically non-local in spintronic devices and at interfaces. We review the need for multiscale modeling to address the processes starting from electronic excitation of the spin system on the picometer length scale and sub-femtosecond time scale, to spin wave generation, and towards the modeling of ultrafast phase transitions that altogether determine the response time of the ferromagnetic system. Today, our current understanding gives rise to the first usage of ultrafast spin physics for ultrafast magnetism control: THz spintronic devices. This makes the field of ultrafast spin-dynamics an emerging topic open for many researchers right now.

Perspective: Ultrafast magnetism and THz spintronics

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

Walowski, Jakob; Münzenberg, Markus

This year the discovery of femtosecond demagnetization by laser pulses is 20 years old. For the first time, this milestone work by Bigot and coworkers gave insight directly into the time scales of microscopic interactions that connect the spin and electron system. While intense discussions in the field were fueled by the complexity of the processes in the past, it now became evident that it is a puzzle of many different parts. Rather than providing an overview that has been presented in previous reviews on ultrafast processes in ferromagnets, this perspective will show that with our current depth of knowledgemore » the first applications are developed: THz spintronics and all-optical spin manipulation are becoming more and more feasible. The aim of this perspective is to point out where we can connect the different puzzle pieces of understanding gathered over 20 years to develop novel applications. Based on many observations in a large number of experiments. Differences in the theoretical models arise from the localized and delocalized nature of ferromagnetism. Transport effects are intrinsically non-local in spintronic devices and at interfaces. We review the need for multiscale modeling to address the processes starting from electronic excitation of the spin system on the picometer length scale and sub-femtosecond time scale, to spin wave generation, and towards the modeling of ultrafast phase transitions that altogether determine the response time of the ferromagnetic system. Today, our current understanding gives rise to the first usage of ultrafast spin physics for ultrafast magnetism control: THz spintronic devices. This makes the field of ultrafast spin-dynamics an emerging topic open for many researchers right now.« less

Ultrafast FADC multiplexer

NASA Astrophysics Data System (ADS)

Mirzoyan, R.; Cortina, J.; Lorenz, E.; Martinez, M.; Ostankov, A.; Paneque, D.

2002-10-01

Ultrafast Flash amplitude-to-digital converters (FADCs) are still very expensive. Here we propose a multiplexing scheme allowing one in common trigger mode to read out multiple signal sources by using a single FADC channel. Usual coaxial cables can be used in the multiplexer as analog signal delay elements. The limited bandwidth of the coaxial cable, depending on its type and length will set an upper limit to the number of multiplexed channels. Better bandwidth and the correspondingly higher number of multiplexed channels one can obtain when using the technique of transmission of analog signals via optical fibers. Low-cost vertical cavity surface emitting laser (VCSEL) diodes can be used as converters of fast electrical signals into near infrared light. Multiplexing can be an economically priced solution when one needs ultrafast digitization of hundreds of fast signal channels.

4D multiple-cathode ultrafast electron microscopy

PubMed Central

Baskin, John Spencer; Liu, Haihua; Zewail, Ahmed H.

2014-01-01

Four-dimensional multiple-cathode ultrafast electron microscopy is developed to enable the capture of multiple images at ultrashort time intervals for a single microscopic dynamic process. The dynamic process is initiated in the specimen by one femtosecond light pulse and probed by multiple packets of electrons generated by one UV laser pulse impinging on multiple, spatially distinct, cathode surfaces. Each packet is distinctly recorded, with timing and detector location controlled by the cathode configuration. In the first demonstration, two packets of electrons on each image frame (of the CCD) probe different times, separated by 19 picoseconds, in the evolution of the diffraction of a gold film following femtosecond heating. Future elaborations of this concept to extend its capabilities and expand the range of applications of 4D ultrafast electron microscopy are discussed. The proof-of-principle demonstration reported here provides a path toward the imaging of irreversible ultrafast phenomena of materials, and opens the door to studies involving the single-frame capture of ultrafast dynamics using single-pump/multiple-probe, embedded stroboscopic imaging. PMID:25006261

4D multiple-cathode ultrafast electron microscopy.

PubMed

Baskin, John Spencer; Liu, Haihua; Zewail, Ahmed H

2014-07-22

Four-dimensional multiple-cathode ultrafast electron microscopy is developed to enable the capture of multiple images at ultrashort time intervals for a single microscopic dynamic process. The dynamic process is initiated in the specimen by one femtosecond light pulse and probed by multiple packets of electrons generated by one UV laser pulse impinging on multiple, spatially distinct, cathode surfaces. Each packet is distinctly recorded, with timing and detector location controlled by the cathode configuration. In the first demonstration, two packets of electrons on each image frame (of the CCD) probe different times, separated by 19 picoseconds, in the evolution of the diffraction of a gold film following femtosecond heating. Future elaborations of this concept to extend its capabilities and expand the range of applications of 4D ultrafast electron microscopy are discussed. The proof-of-principle demonstration reported here provides a path toward the imaging of irreversible ultrafast phenomena of materials, and opens the door to studies involving the single-frame capture of ultrafast dynamics using single-pump/multiple-probe, embedded stroboscopic imaging.

Idiosyncratic reality claims, relaxation dispositions, and ABC relaxation theory: happiness, literal christianity, miraculous powers, metaphysics, and the paranormal.

PubMed

Smith, Jonathan C; Karmin, Aaron D

2002-12-01

This study examined idiosyncratic reality claims, that is, irrational or paranormal beliefs often claimed to enhance relaxation and happiness and reduce stress. The Smith Idiosyncratic Reality Claims Inventory and the Smith Relaxation Dispositions Inventory (which measures relaxation and stress dispositions, or enduring states of mind frequently associated with relaxation or stress) were given to 310 junior college student volunteers. Principal components factor analysis with varimax rotation identified five idiosyncratic reality claim factors: belief in Literal Christianity; Magic; Space Aliens: After Death experiences; and Miraculous Powers of Meditation, Prayer, and Belief. No factor correlated with increased relaxation dispositions Peace, Energy, or Joy, or reduced dispositional somatic stress, worry, or negative emotion on the Smith Relaxation Dispositions Inventory. It was concluded that idiosyncratic reality claims may not be associated with reported relaxation, happiness, or stress. In contrast, previous research strongly supported self-affirming beliefs with few paranormal assumptions display such an association.

Ultrafast exciton migration in an HJ-aggregate: Potential surfaces and quantum dynamics

NASA Astrophysics Data System (ADS)

Binder, Robert; Polkehn, Matthias; Ma, Tianji; Burghardt, Irene

2017-01-01

Quantum dynamical and electronic structure calculations are combined to investigate the mechanism of exciton migration in an oligothiophene HJ aggregate, i.e., a combination of oligomer chains (J-type aggregates) and stacked aggregates of such chains (H-type aggregates). To this end, a Frenkel exciton model is parametrized by a recently introduced procedure [Binder et al., J. Chem. Phys. 141, 014101 (2014)] which uses oligomer excited-state calculations to perform an exact, point-wise mapping of coupled potential energy surfaces to an effective Frenkel model. Based upon this parametrization, the Multi-Layer Multi-Configuration Time-Dependent Hartree (ML-MCTDH) method is employed to investigate ultrafast dynamics of exciton transfer in a small, asymmetric HJ aggregate model composed of 30 sites and 30 active modes. For a partially delocalized initial condition, it is shown that a torsional defect confines the trapped initial exciton, and planarization induces an ultrafast resonant transition between an HJ-aggregated segment and a covalently bound "dangling chain" end. This model is a minimal realization of experimentally investigated mixed systems exhibiting ultrafast exciton transfer between aggregated, highly planarized chains and neighboring disordered segments.

Ultrafast Adiabatic Photodehydration of 2-Hydroxymethylphenol and the Formation of Quinone Methide.

PubMed

Škalamera, Đani; Antol, Ivana; Mlinarić-Majerski, Kata; Vančik, Hrvoj; Phillips, David Lee; Ma, Jiani; Basarić, Nikola

2018-04-20

The photochemical reactivity of 2-hydroxymethylphenol (1) was investigated experimentally by photochemistry under cryogenic conditions, by detecting reactive intermediates by IR spectroscopy, and by using nanosecond and femtosecond transient absorption spectroscopic methods in solution at room temperature. In addition, theoretical studies were performed to facilitate the interpretation of the experimental results and also to simulate the reaction pathway to obtain a better understanding of the reaction mechanism. The main finding of this work is that photodehydration of 1 takes place in an ultrafast adiabatic photochemical reaction without any clear intermediate, delivering quinone methide (QM) in the excited state. Upon photoexcitation to a higher vibrational level of the singlet excited state, 1 undergoes vibrational relaxation leading to two photochemical pathways, one by which synchronous elimination of H 2 O gives QM 2 in its S 1 state and the other by which homolytic cleavage of the phenolic O-H bond produces a phenoxyl radical (S 0 ). Both are ultrafast processes that occur within a picosecond. The excited state of QM 2 (S 1 ) probably deactivates to S 0 through a conical intersection to give QM 2 (S 0 ), which subsequently delivers benzoxete 4. Elucidation of the reaction mechanisms for the photodehydration of phenols by which QMs are formed is important to tune the reactivity of QMs with DNA and proteins for the potential application of QMs in medicine as therapeutic agents. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Anomalous ultrafast dynamics of hot plasmonic electrons in nanostructures with hot spots

DOE PAGES

Harutyunyan, Hayk; Martinson, Alex B. F.; Rosenmann, Daniel; ...

2015-08-03

The interaction of light and matter in metallic nanosystems is mediated by the collective oscillation of surface electrons, called plasmons. After excitation, plasmons are absorbed by the metal electrons through inter- and intraband transitions, creating a highly non-thermal distribution of electrons. The electron population then decays through electron-electron interactions, creating a hot electron distribution within a few hundred femtoseconds, followed by a further relaxation via electron-phonon scattering on the timescale of a few pico-seconds. In the spectral domain, hot plasmonic electrons induce changes to the plasmonic resonance of the nanostructure by modifying the dielectric constant of the metal. Here, wemore » report on the observation of anomalously strong changes to the ultrafast temporal and spectral responses of these excited hot plasmonic electrons in hybrid metal/oxide nanostructures as a result of varying the geometry and composition of the nanostructure and the excitation wavelength. In particular, we show a large ultrafast, pulsewidth-limited contribution to the excited electron decay signal in hybrid nanostructures containing hot spots. The intensity of this contribution correlates with the efficiency of the generation of highly excited surface electrons. Using theoretical models, we attribute this effect to the generation of hot plasmonic electrons from hot spots. Finally, we then develop general principles to enhance the generation of energetic electrons through specifically designed plasmonic nanostructures that could be used in applications where hot electron generation is beneficial, such as in solar photocatalysis, photodetectors and nonlinear devices.« less

Anomalous ultrafast dynamics of hot plasmonic electrons in nanostructures with hot spots.

PubMed

Harutyunyan, Hayk; Martinson, Alex B F; Rosenmann, Daniel; Khorashad, Larousse Khosravi; Besteiro, Lucas V; Govorov, Alexander O; Wiederrecht, Gary P

2015-09-01

The interaction of light and matter in metallic nanosystems is mediated by the collective oscillation of surface electrons, called plasmons. After excitation, plasmons are absorbed by the metal electrons through inter- and intraband transitions, creating a highly non-thermal distribution of electrons. The electron population then decays through electron-electron interactions, creating a hot electron distribution within a few hundred femtoseconds, followed by a further relaxation via electron-phonon scattering on the timescale of a few picoseconds. In the spectral domain, hot plasmonic electrons induce changes to the plasmonic resonance of the nanostructure by modifying the dielectric constant of the metal. Here, we report on the observation of anomalously strong changes to the ultrafast temporal and spectral responses of these excited hot plasmonic electrons in hybrid metal/oxide nanostructures as a result of varying the geometry and composition of the nanostructure and the excitation wavelength. In particular, we show a large ultrafast, pulsewidth-limited contribution to the excited electron decay signal in hybrid nanostructures containing hot spots. The intensity of this contribution correlates with the efficiency of the generation of highly excited surface electrons. Using theoretical models, we attribute this effect to the generation of hot plasmonic electrons from hot spots. We then develop general principles to enhance the generation of energetic electrons through specifically designed plasmonic nanostructures that could be used in applications where hot electron generation is beneficial, such as in solar photocatalysis, photodetectors and nonlinear devices.

Ultrafast Two-Dimensional Infrared Spectroscopy of a Quasifree Rotor: J Scrambling and Perfectly Anticorrelated Cross Peaks

NASA Astrophysics Data System (ADS)

Mandal, Aritra; Ng Pack, Greg; Shah, Parth P.; Erramilli, Shyamsunder; Ziegler, L. D.

2018-03-01

Ultrafast two-dimensional infrared (2DIR) spectra of the N2O ν3 mode in moderately dense SF6 gas exhibit complex line shapes with diagonal and antidiagonal features in contrast to condensed phase vibrational 2DIR spectroscopy. Observed spectra for this quasifree rotor system are well captured by a model that includes all 36 possible rovibrational pathways and treats P (Δ J =-1 ) and R (Δ J =+1 ) branch resonances as distinct Kubo line shape features. Transition frequency correlation decay is due to J scrambling within one to two gas collisions at each density. Studies of supercritical solvation and relaxation at high pressure and temperature are enabled by this methodology.

Time scales of relaxation dynamics during transient conditions in two-phase flow: RELAXATION DYNAMICS

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

Schlüter, Steffen; Berg, Steffen; Li, Tianyi

2017-06-01

The relaxation dynamics toward a hydrostatic equilibrium after a change in phase saturation in porous media is governed by fluid reconfiguration at the pore scale. Little is known whether a hydrostatic equilibrium in which all interfaces come to rest is ever reached and which microscopic processes govern the time scales of relaxation. Here we apply fast synchrotron-based X-ray tomography (X-ray CT) to measure the slow relaxation dynamics of fluid interfaces in a glass bead pack after fast drainage of the sample. The relaxation of interfaces triggers internal redistribution of fluids, reduces the surface energy stored in the fluid interfaces, andmore » relaxes the contact angle toward the equilibrium value while the fluid topology remains unchanged. The equilibration of capillary pressures occurs in two stages: (i) a quick relaxation within seconds in which most of the pressure drop that built up during drainage is dissipated, a process that is to fast to be captured with fast X-ray CT, and (ii) a slow relaxation with characteristic time scales of 1–4 h which manifests itself as a spontaneous imbibition process that is well described by the Washburn equation for capillary rise in porous media. The slow relaxation implies that a hydrostatic equilibrium is hardly ever attained in practice when conducting two-phase experiments in which a flux boundary condition is changed from flow to no-flow. Implications for experiments with pressure boundary conditions are discussed.« less

Graphene-clad microfibre saturable absorber for ultrafast fibre lasers.

PubMed

Liu, X M; Yang, H R; Cui, Y D; Chen, G W; Yang, Y; Wu, X Q; Yao, X K; Han, D D; Han, X X; Zeng, C; Guo, J; Li, W L; Cheng, G; Tong, L M

2016-05-16

Graphene, whose absorbance is approximately independent of wavelength, allows broadband light-matter interactions with ultrafast responses. The interband optical absorption of graphene can be saturated readily under strong excitation, thereby enabling scientists to exploit the photonic properties of graphene to realize ultrafast lasers. The evanescent field interaction scheme of the propagating light with graphene covered on a D-shaped fibre or microfibre has been employed extensively because of the nonblocking configuration. Obviously, most of the fibre surface is unused in these techniques. Here, we exploit a graphene-clad microfibre (GCM) saturable absorber in a mode-locked fibre laser for the generation of ultrafast pulses. The proposed all-surface technique can guarantee a higher efficiency of light-graphene interactions than the aforementioned techniques. Our GCM-based saturable absorber can generate ultrafast optical pulses within 1.5 μm. This saturable absorber is compatible with current fibre lasers and has many merits such as low saturation intensities, ultrafast recovery times, and wide wavelength ranges. The proposed saturable absorber will pave the way for graphene-based wideband photonics.

Graphene-clad microfibre saturable absorber for ultrafast fibre lasers

PubMed Central

Liu, X. M.; Yang, H. R.; Cui, Y. D.; Chen, G. W.; Yang, Y.; Wu, X. Q.; Yao, X. K.; Han, D. D.; Han, X. X.; Zeng, C.; Guo, J.; Li, W. L.; Cheng, G.; Tong, L. M.

2016-01-01

Graphene, whose absorbance is approximately independent of wavelength, allows broadband light–matter interactions with ultrafast responses. The interband optical absorption of graphene can be saturated readily under strong excitation, thereby enabling scientists to exploit the photonic properties of graphene to realize ultrafast lasers. The evanescent field interaction scheme of the propagating light with graphene covered on a D-shaped fibre or microfibre has been employed extensively because of the nonblocking configuration. Obviously, most of the fibre surface is unused in these techniques. Here, we exploit a graphene-clad microfibre (GCM) saturable absorber in a mode-locked fibre laser for the generation of ultrafast pulses. The proposed all-surface technique can guarantee a higher efficiency of light–graphene interactions than the aforementioned techniques. Our GCM-based saturable absorber can generate ultrafast optical pulses within 1.5 μm. This saturable absorber is compatible with current fibre lasers and has many merits such as low saturation intensities, ultrafast recovery times, and wide wavelength ranges. The proposed saturable absorber will pave the way for graphene-based wideband photonics. PMID:27181419

Long-period fiber gratings as ultrafast optical differentiators.

PubMed

Kulishov, Mykola; Azaña, José

2005-10-15

It is demonstrated that a single, uniform long-period fiber grating (LPFG) working in the linear regime inherently behaves as an ultrafast optical temporal differentiator. Specifically, we show that the output temporal waveform in the core mode of a LPFG providing full energy coupling into the cladding mode is proportional to the first derivative of the optical temporal signal (e.g., optical pulse) launched at the input of the LPFG. Moreover, a LPFG providing full energy recoupling back from the cladding mode into the core mode inherently implements second-order temporal differentiation. Our numerical results have confirmed the feasibility of this simple, all-fiber approach to processing optical signals with temporal features in the picosecond and subpicosecond ranges.

Dynamic absorption and scattering of water and hydrogel during high-repetition-rate (>100 MHz) burst-mode ultrafast-pulse laser ablation.

PubMed

Qian, Zuoming; Covarrubias, Andrés; Grindal, Alexander W; Akens, Margarete K; Lilge, Lothar; Marjoribanks, Robin S

2016-06-01

High-repetition-rate burst-mode ultrafast-laser ablation and disruption of biological tissues depends on interaction of each pulse with the sample, but under those particular conditions which persist from previous pulses. This work characterizes and compares the dynamics of absorption and scattering of a 133-MHz repetition-rate, burst-mode ultrafast-pulse laser, in agar hydrogel targets and distilled water. The differences in energy partition are quantified, pulse-by-pulse, using a time-resolving integrating-sphere-based device. These measurements reveal that high-repetition-rate burst-mode ultrafast-laser ablation is a highly dynamical process affected by the persistence of ionization, dissipation of plasma plume, neutral material flow, tissue tensile strength, and the hydrodynamic oscillation of cavitation bubbles.

Several new directions for ultrafast fiber lasers [Invited].

PubMed

Fu, Walter; Wright, Logan G; Sidorenko, Pavel; Backus, Sterling; Wise, Frank W

2018-04-16

Ultrafast fiber lasers have the potential to make applications of ultrashort pulses widespread - techniques not only for scientists, but also for doctors, manufacturing engineers, and more. Today, this potential is only realized in refractive surgery and some femtosecond micromachining. The existing market for ultrafast lasers remains dominated by solid-state lasers, primarily Ti:sapphire, due to their superior performance. Recent advances show routes to ultrafast fiber sources that provide performance and capabilities equal to, and in some cases beyond, those of Ti:sapphire, in compact, versatile, low-cost devices. In this paper, we discuss the prospects for future ultrafast fiber lasers built on new kinds of pulse generation that capitalize on nonlinear dynamics. We focus primarily on three promising directions: mode-locked oscillators that use nonlinearity to enhance performance; systems that use nonlinear pulse propagation to achieve ultrashort pulses without a mode-locked oscillator; and multimode fiber lasers that exploit nonlinearities in space and time to obtain unparalleled control over an electric field.

Low-power, ultrafast, and dynamic all-optical tunable plasmon induced transparency in two stub resonators side-coupled with a plasmonic waveguide system

NASA Astrophysics Data System (ADS)

Wang, Boyun; Zeng, Qingdong; Xiao, Shuyuan; Xu, Chen; Xiong, Liangbin; Lv, Hao; Du, Jun; Yu, Huaqing

2017-11-01

We theoretically and numerically investigate a low-power, ultrafast, and dynamic all-optical tunable plasmon induced transparency (PIT) in two stub resonators side-coupled with a metal-dielectric-metal (MDM) plasmonic waveguide system. The optical Kerr effect is enhanced by the local electromagnetic field of surface plasmon polaritons (SPPs) and the plasmonic waveguide based on graphene-Ag composite material structures with large effective Kerr nonlinear coefficient. An ultrafast response time of the order of 1 ps is reached because of ultrafast carrier relaxation dynamics of graphene. With dynamically tuning the propagation phase of the plasmonic waveguide, π-phase shift of the transmission spectrum in the PIT system is achieved under excitation of a pump light with an intensity as low as 5.8 MW cm-2. The group delay is controlled between 0.14 and 0.67 ps. Moreover, the tunable bandwidth of about 42 nm is obtained. For the indirect coupling between two stub cavities or the phase coupling scheme, the phase shift multiplication effect of the PIT effect is found. All observed schemes are analyzed rigorously through finite-difference time-domain simulations and coupled-mode formalism. This work not only paves the way towards the realization of on-chip integrated nanophotonic devices but also opens the possibility of the construction of ultrahigh-speed information processing chips based on plasmonic circuits.

Reversible ultrafast melting in bulk CdSe

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

Wu, Wenzhi; Department of Mechanical Engineering, The University of Texas at Austin, Austin, Texas 78712; He, Feng

2016-02-07

In this work, transient reflectivity changes in bulk CdSe have been measured with two-color femtosecond pump-probe spectroscopy under a wide range of pump fluences. Three regions of reflectivity change with pump fluences have been consistently revealed for excited carrier density, coherent phonon amplitude, and lattice temperature. For laser fluences from 13 to 19.3 mJ/cm{sup 2}, ultrafast melting happens in first several picoseconds. This melting process is purely thermal and reversible. A complete phase transformation in bulk CdSe may be reached when the absorbed laser energy is localized long enough, as observed in nanocrystalline CdSe.

Modeling 2D and 3D periodic nanostructuring of materials with ultrafast laser pulses (Conference Presentation)

NASA Astrophysics Data System (ADS)

Colombier, Jean-Philippe; Rudenko, Anton; Bévillon, Emile; Zhang, Hao; Itina, Tatiana E.; Stoian, Razvan

2017-03-01

Generation of periodic arrangements of matter on materials irradiated by laser fields of uniform and isotropic energy distribution is a key issue in controlling laser structuring processes below the diffractive limit. Using three-dimensional finite-difference time-domain methods, we evaluate energy deposition patterns below a material's rough surface [1] and in bulk dielectric materials containing randomly distributed nano-inhomogeneities [2]. We show that both surface and volume patterns can be attributed to spatially ordered electromagnetic solutions of linear and nonlinear Maxwell equations. In particular, simulations revealed that anisotropic energy deposition results from the coherent superposition of the incident and the inhomogeneity-scattered light waves. Transient electronic response is also analyzed by kinetic equations of free electron excitation/relaxation processes for dielectrics and by ab initio calculations for metals. They show that for nonplasmonic metals, ultrafast carrier excitation can drastically affect electronic structures, driving a transient surface plasmonic state with high consequences for optical resonances generation [3]. Comparing condition formations of 2D laser-induced periodic surface structures (LIPSS) and 3D self-organized nanogratings, we will discuss the role of collective scattering of nanoroughness and the feedback-driven growth of the nanostructures. [1] H. Zhang, J.P. Colombier, C. Li, N. Faure, G. Cheng, and R. Stoian, Physical Review B 92, 174109 (2015). [2] A. Rudenko, J.P. Colombier, and T.E. Itina, Physical Review B 93 (7), 075427 (2016). [3] E. Bévillon, J.P. Colombier, V. Recoules, H. Zhang, C. Li and R. Stoian, Physical Review B 93 (16), 165416 (2016).

Ultrafast Bessel beams: advanced tools for laser materials processing

NASA Astrophysics Data System (ADS)

Stoian, Razvan; Bhuyan, Manoj K.; Zhang, Guodong; Cheng, Guanghua; Meyer, Remy; Courvoisier, Francois

2018-05-01

Ultrafast Bessel beams demonstrate a significant capacity of structuring transparent materials with a high degree of accuracy and exceptional aspect ratio. The ability to localize energy on the nanometer scale (bypassing the 100-nm milestone) makes them ideal tools for advanced laser nanoscale processing on surfaces and in the bulk. This allows to generate and combine micron and nano-sized features into hybrid structures that show novel functionalities. Their high aspect ratio and the accurate location can equally drive an efficient material modification and processing strategy on large dimensions. We review, here, the main concepts of generating and using Bessel non-diffractive beams and their remarkable features, discuss general characteristics of their interaction with matter in ablation and material modification regimes, and advocate their use for obtaining hybrid micro and nanoscale structures in two and three dimensions (2D and 3D) performing complex functions. High-throughput applications are indicated. The example list ranges from surface nanostructuring and laser cutting to ultrafast laser welding and the fabrication of 3D photonic systems embedded in the volume.

Ultrafast band-gap oscillations in iron pyrite

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

Kolb, B; Kolpak, AM

2013-12-20

With its combination of favorable band gap, high absorption coefficient, material abundance, and low cost, iron pyrite, FeS2, has received a great deal of attention over the past decades as a promising material for photovoltaic applications such as solar cells and photoelectrochemical cells. Devices made from pyrite, however, exhibit open circuit voltages significantly lower than predicted, and despite a recent resurgence of interest in the material, there currently exists no widely accepted explanation for this disappointing behavior. In this paper, we show that phonons, which have been largely overlooked in previous efforts, may play a significant role. Using fully self-consistentmore » GW calculations, we demonstrate that a phonon mode related to the oscillation of the sulfur-sulfur bond distance in the pyrite structure is strongly coupled to the energy of the conduction-band minimum, leading to an ultrafast (approximate to 100 fs) oscillation in the band gap. Depending on the coherency of the phonons, we predict that this effect can cause changes of up to +/- 0.3 eV relative to the accepted FeS2 band gap at room temperature. Harnessing this effect via temperature or irradiation with infrared light could open up numerous possibilities for novel devices such as ultrafast switches and adaptive solar absorbers.« less

Ultrafast control of strong light-matter coupling

NASA Astrophysics Data System (ADS)

Lange, Christoph; Cancellieri, Emiliano; Panna, Dmitry; Whittaker, David M.; Steger, Mark; Snoke, David W.; Pfeiffer, Loren N.; West, Kenneth W.; Hayat, Alex

2018-01-01

We dynamically modulate strong light-matter coupling in a GaAs/AlGaAs microcavity using intense ultrashort laser pulses tuned below the interband exciton energy, which induce a transient Stark shift of the cavity polaritons. For 225-fs pulses, shorter than the cavity Rabi cycle period of 1000 fs, this shift decouples excitons and cavity photons for the duration of the pulse, interrupting the periodic energy exchange between photonic and electronic states. For 1500-fs pulses, longer than the Rabi cycle period, however, the Stark shift does not affect the strong coupling. The two regimes are marked by distinctly different line shapes in ultrafast reflectivity measurements—regardless of the Stark field intensity. The crossover marks the transition from adiabatic to diabatic switching of strong light-matter coupling.

Nuclear spin relaxation of methane in solid xenon

NASA Astrophysics Data System (ADS)

Sugimoto, Takeru; Arakawa, Ichiro; Yamakawa, Koichiro

2018-03-01

Nuclear spin relaxation of methane in solid xenon has been studied by infrared spectroscopy. From the analysis of the temporal changes of the rovibrational peaks, the rates of the nuclear spin relaxation of I = 2 ← 1 correlated to the rotational relaxation of J = 0 ← 1 were obtained at temperatures of 5.1-11.5 K. On the basis of the temperature dependence of the relaxation rate, the activation energy of the indirect two-phonon process was determined to be 50 ± 6 K, which is in good agreement with the rotational transition energies of J = 2 ← 1 and J = 3 ← 1. Taking into account this result and the spin degeneracy, we argue that the lowest J = 3 level in which the I = 1 and I = 2 states are degenerate acts as the intermediate point of the indirect process.

Ultrafast Spectroscopy of Proton-Coupled Electron Transfer (PCET) in Photocatalysis

DTIC Science & Technology

2016-07-08

AFRL-AFOSR-VA-TR-2016-0244 Ultrafast Spectroscopy of Proton-Coupled Electron Transfer (PCET) in Photocatalysis Jahan Dawlaty UNIVERSITY OF SOUTHERN...TITLE AND SUBTITLE Ultrafast Spectroscopy of Proton-Coupled Electron Transfer (PCET) in Photocatalysis 5a. CONTRACT NUMBER 5b. GRANT NUMBER FA9550...298 Back (Rev. 8/98) DISTRIBUTION A: Distribution approved for public release. Final Report: AFOSR YIP Grant FA9550-13-1-0128: Ultrafast Spectroscopy

Polarization and Thickness Dependent Absorption Properties of Black Phosphorus: New Saturable Absorber for Ultrafast Pulse Generation

PubMed Central

Li, Diao; Jussila, Henri; Karvonen, Lasse; Ye, Guojun; Lipsanen, Harri; Chen, Xianhui; Sun, Zhipei

2015-01-01

Black phosphorus (BP) has recently been rediscovered as a new and interesting two-dimensional material due to its unique electronic and optical properties. Here, we study the linear and nonlinear optical properties of BP flakes. We observe that both the linear and nonlinear optical properties are anisotropic and can be tuned by the film thickness in BP, completely different from other typical two-dimensional layered materials (e.g., graphene and the most studied transition metal dichalcogenides). We then use the nonlinear optical properties of BP for ultrafast (pulse duration down to ~786 fs in mode-locking) and large-energy (pulse energy up to >18 nJ in Q-switching) pulse generation in fiber lasers at the near-infrared telecommunication band ~1.5 μm. We observe that the output of our BP based pulsed lasers is linearly polarized (with a degree-of-polarization ~98% in mode-locking, >99% in Q-switching, respectively) due to the anisotropic optical property of BP. Our results underscore the relatively large optical nonlinearity of BP with unique polarization and thickness dependence, and its potential for polarized optical pulse generation, paving the way to BP based nonlinear and ultrafast photonic applications (e.g., ultrafast all-optical polarization switches/modulators, frequency converters etc.). PMID:26514090

Ultrafast dynamics induced by the interaction of molecules with electromagnetic fields: Several quantum, semiclassical, and classical approaches.

PubMed

Antipov, Sergey V; Bhattacharyya, Swarnendu; El Hage, Krystel; Xu, Zhen-Hao; Meuwly, Markus; Rothlisberger, Ursula; Vaníček, Jiří

2017-11-01

Several strategies for simulating the ultrafast dynamics of molecules induced by interactions with electromagnetic fields are presented. After a brief overview of the theory of molecule-field interaction, we present several representative examples of quantum, semiclassical, and classical approaches to describe the ultrafast molecular dynamics, including the multiconfiguration time-dependent Hartree method, Bohmian dynamics, local control theory, semiclassical thawed Gaussian approximation, phase averaging, dephasing representation, molecular mechanics with proton transfer, and multipolar force fields. In addition to the general overview, some focus is given to the description of nuclear quantum effects and to the direct dynamics, in which the ab initio energies and forces acting on the nuclei are evaluated on the fly. Several practical applications, performed within the framework of the Swiss National Center of Competence in Research "Molecular Ultrafast Science and Technology," are presented: These include Bohmian dynamics description of the collision of H with H 2 , local control theory applied to the photoinduced ultrafast intramolecular proton transfer, semiclassical evaluation of vibrationally resolved electronic absorption, emission, photoelectron, and time-resolved stimulated emission spectra, infrared spectroscopy of H-bonding systems, and multipolar force fields applications in the condensed phase.

Ultrafast dynamics induced by the interaction of molecules with electromagnetic fields: Several quantum, semiclassical, and classical approaches

PubMed Central

Antipov, Sergey V.; Bhattacharyya, Swarnendu; El Hage, Krystel; Xu, Zhen-Hao; Meuwly, Markus; Rothlisberger, Ursula; Vaníček, Jiří

2018-01-01

Several strategies for simulating the ultrafast dynamics of molecules induced by interactions with electromagnetic fields are presented. After a brief overview of the theory of molecule-field interaction, we present several representative examples of quantum, semiclassical, and classical approaches to describe the ultrafast molecular dynamics, including the multiconfiguration time-dependent Hartree method, Bohmian dynamics, local control theory, semiclassical thawed Gaussian approximation, phase averaging, dephasing representation, molecular mechanics with proton transfer, and multipolar force fields. In addition to the general overview, some focus is given to the description of nuclear quantum effects and to the direct dynamics, in which the ab initio energies and forces acting on the nuclei are evaluated on the fly. Several practical applications, performed within the framework of the Swiss National Center of Competence in Research “Molecular Ultrafast Science and Technology,” are presented: These include Bohmian dynamics description of the collision of H with H2, local control theory applied to the photoinduced ultrafast intramolecular proton transfer, semiclassical evaluation of vibrationally resolved electronic absorption, emission, photoelectron, and time-resolved stimulated emission spectra, infrared spectroscopy of H-bonding systems, and multipolar force fields applications in the condensed phase. PMID:29376107

Chirality effect on electron phonon relaxation, energy loss, and thermopower in single and bilayer graphene in BG regime

NASA Astrophysics Data System (ADS)

Ansari, Meenhaz; Ashraf, S. S. Z.

2017-10-01

We investigate the energy dependent electron-phonon relaxation rate, energy loss rate, and phonon drag thermopower in single layer graphene (SLG) and bilayer graphene (BLG) under the Bloch-Gruneisen (BG) regime through coupling to acoustic phonons interacting via the Deformation potential in the Boltzmann transport equation approach. We find that the consideration of the chiral nature of electrons alters the temperature dependencies in two-dimensional structures of SLG and BLG from that shown by other conventional 2DEG system. Our investigations indicate that the BG analytical results are valid for temperatures far below the BG limit (˜TBG/4) which is in conformity with a recent experimental investigation for SLG [C. B. McKitterick et al., Phys. Rev. B 93, 075410 (2016)]. For temperatures above this renewed limit (˜TBG/4), there is observed a suppression in energy loss rate and thermo power in SLG, but enhancement is observed in relaxation rate and thermopower in BLG, while a suppression in the energy loss rate is observed in BLG. This strong nonmonotonic temperature dependence in SLG has also been experimentally observed within the BG limit [Q. Ma et al., Phys. Rev. Lett. 112, 247401 (2014)].

Dielectric relaxation of gamma irradiated muscovite mica

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

Kaur, Navjeet; Singh, Mohan, E-mail: mohansinghphysics@gmail.com; Singh, Lakhwant

2015-03-15

Highlights: • The present article reports the effect of gamma irradiation on the dielectric relaxation characteristics of muscovite mica. • Dielectric and electrical relaxations have been analyzed in the framework of dielectric permittivity, electric modulus and Cole–Cole formalisms. • The frequency dependent electrical conductivity has been rationalized using Johnsher’s universal power law. • The experimentally measured electric modulus and conductivity data have been fitted using Havriliak–Negami dielectric relaxation function. - Abstract: In the present research, the dielectric relaxation of gamma irradiated muscovite mica was studied in the frequency range of 0.1 Hz–10 MHz and temperature range of 653–853 K, usingmore » the dielectric permittivity, electric modulus and conductivity formalisms. The dielectric constants (ϵ′ and ϵ′′) are found to be high for gamma irradiated muscovite mica as compared to the pristine sample. The frequency dependence of the imaginary part of complex electric modulus (M′′) and dc conductivity data conforms Arrhenius law with single value of activation energy for pristine sample and two values of activation energy for gamma irradiated mica sample. The experimentally assessed electric modulus and conductivity information have been interpreted by the Havriliak–Negami dielectric relaxation explanation. Using the Cole–Cole framework, an analysis of real and imaginary characters of the electric modulus for pristine and gamma irradiated sample was executed which reflects the non-Debye relaxation mechanism.« less

Steric hindrance inhibits excited-state relaxation and lowers the extent of intramolecular charge transfer in two-photon absorbing dyes.

PubMed

Stewart, David J; Dalton, Matthew J; Long, Stephanie L; Kannan, Ramamurthi; Yu, Zhenning; Cooper, Thomas M; Haley, Joy E; Tan, Loon-Seng

2016-02-21

The two-photon absorbing dye AF240 [1, (7-benzothiazol-2-yl-9,9-diethylfluoren-2-yl)diphenylamine] is modified by adding bulky alkyl groups to the diphenylamino moiety. Three new compounds are synthesized which have ethyl groups in both ortho positions of each phenyl ring (2), t-butyl groups in one ortho position of each phenyl ring (3), and t-butyl groups in the para position of each phenyl ring (4). The dyes are examined in several aprotic solvents with varying polarity to observe the effects of the sterically hindering bulky groups on the ground and excited-state photophysical properties. While the ground state shows minimal solvent dependence, there is significant dependence on the fluorescence quantum yield and lifetime, as well as the excited-state energy levels. This effect is caused by the formation of an intramolecular charge-transfer (ICT) state, which is observed in the solvents more polar than n-hexane and supported by TD-DFT calculations. Electronic effects of ortho or para alkyl substitution should be similar, yet drastic differences are observed. A red shift in the fluorescence maximum is observed in 4 relative to 1, yet a blue shift occurs in 2 and 3 because the substituents at the sterically sensitive ortho-positions inhibit excited-state geometric relaxation and result in less ICT character than 1. Coupled with theoretical calculations, the data support a planar ICT (PICT) excited state where the diphenylamino nitrogen in an sp(2)-like geometry is integral with the plane containing the fluorene and benzothiazole moieties. Ultrafast transient absorption experiments show that ICT occurs rapidly (<150 fs) followed by geometric and solvent relaxation in ∼ 1-4 ps to form the PICT or solvent-stabilized ICT (SSICT) state. This relaxation is not observed in non-polar n-hexane because the solvent dependent ICT state energy lies higher than the locally-excited (LE) state. Finally, formation of a triplet state (T1) is only efficiently observed in n

Giant ultrafast Kerr effect in superconductors

NASA Astrophysics Data System (ADS)

Robson, Charles W.; Fraser, Kieran A.; Biancalana, Fabio

2017-06-01

We study the ultrafast Kerr effect and high-harmonic generation in superconductors by formulating a model for a time-varying electromagnetic pulse normally incident on a thin-film superconductor. It is found that superconductors exhibit exceptionally large χ(3 ) due to the progressive destruction of Cooper pairs, and display high-harmonic generation at low incident intensities, and the highest nonlinear susceptibility of all known materials in the THz regime. Our theory opens up avenues for accessible analytical and numerical studies of the ultrafast dynamics of superconductors.

Diagnostic Performance of Ultrafast Brain MRI for Evaluation of Abusive Head Trauma.

PubMed

Kralik, S F; Yasrebi, M; Supakul, N; Lin, C; Netter, L G; Hicks, R A; Hibbard, R A; Ackerman, L L; Harris, M L; Ho, C Y

2017-04-01

MR imaging with sedation is commonly used to detect intracranial traumatic pathology in the pediatric population. Our purpose was to compare nonsedated ultrafast MR imaging, noncontrast head CT, and standard MR imaging for the detection of intracranial trauma in patients with potential abusive head trauma. A prospective study was performed in 24 pediatric patients who were evaluated for potential abusive head trauma. All patients received noncontrast head CT, ultrafast brain MR imaging without sedation, and standard MR imaging with general anesthesia or an immobilizer, sequentially. Two pediatric neuroradiologists independently reviewed each technique blinded to other modalities for intracranial trauma. We performed interreader agreement and consensus interpretation for standard MR imaging as the criterion standard. Diagnostic accuracy was calculated for ultrafast MR imaging, noncontrast head CT, and combined ultrafast MR imaging and noncontrast head CT. Interreader agreement was moderate for ultrafast MR imaging (κ = 0.42), substantial for noncontrast head CT (κ = 0.63), and nearly perfect for standard MR imaging (κ = 0.86). Forty-two percent of patients had discrepancies between ultrafast MR imaging and standard MR imaging, which included detection of subarachnoid hemorrhage and subdural hemorrhage. Sensitivity, specificity, and positive and negative predictive values were obtained for any traumatic pathology for each examination: ultrafast MR imaging (50%, 100%, 100%, 31%), noncontrast head CT (25%, 100%, 100%, 21%), and a combination of ultrafast MR imaging and noncontrast head CT (60%, 100%, 100%, 33%). Ultrafast MR imaging was more sensitive than noncontrast head CT for the detection of intraparenchymal hemorrhage ( P = .03), and the combination of ultrafast MR imaging and noncontrast head CT was more sensitive than noncontrast head CT alone for intracranial trauma ( P = .02). In abusive head trauma, ultrafast MR imaging, even combined with noncontrast

Ultrafast Nonradiative Decay and Excitation Energy Transfer by Carotenoids in Photosynthetic Light-Harvesting Proteins

NASA Astrophysics Data System (ADS)

Ghosh, Soumen

This dissertation investigates the photophysical and structural dynamics that allow carotenoids to serve as efficient excitation energy transfer donor to chlorophyll acceptors in photosynthetic light harvesting proteins. Femtosecond transient grating spectroscopy with optical heterodyne detection has been employed to follow the nonradiative decay pathways of carotenoids and excitation energy transfer to chlorophylls. It was found that the optically prepared S2 (11Bu+) state of beta-carotene decays in 12 fs fs to populate an intermediate electronic state, Sx, which then decays nonradiatively to the S 1 state. The ultrafast rise of the dispersion component of the heterodyne transient grating signal reports the formation of Sx intermediate since the rise of the dispersion signal is controlled by the loss of stimulated emission from the S2 state. These findings were extended to studies of peridinin, a carbonyl substituted carotenoid that serves as a photosynthetic light-harvesting chromophore in dinoflagellates. Numerical simulations using nonlinear response formalism and the multimode Brownian oscillator model assigned the Sx intermediate to a torsionally distorted structure evolving on the S2 potential surface. The decay of the Sx state is promoted by large amplitude out-of-plane torsional motions and is significantly retarded by solvent friction owing to the development of an intramolecular charge transfer character in peridinin. The slowing of the nonradiative decay allows the Sx state to transfer significant portion of the excitation energy to chlorophyll a acceptors in the peridinin-chlorophyll a protein. The results of heterodyne transient grating study on peridinin-chlorophyll a protein suggests two distinct energy transfer channels from peridinin to chlorophyll a: a 30 fs process involving quantum coherence and delocalized peridinin-Chl states and an incoherent, 2.5 ps process involving the distorted S2 state of peridinin. The torsional evolution on the S2

Synchronous Measurement of Ultrafast Anisotropy Decay of the B850 in Bacterial LH2 Complex

NASA Astrophysics Data System (ADS)

Wang, Yun-Peng; Du, Lu-Chao; Zhu, Gang-Bei; Wang, Zhuan; Weng, Yu-Xiang

2015-02-01

Ultrafast anisotropic decay is a prominent parameter revealing ultrafast energy and electron transfer; however, it is difficult to be determined reliably owing to the requirement of a simultaneous availability of the parallel and perpendicular polarized decay kinetics. Nowadays, any measurement of anisotropic decay is a kind of approach to the exact simultaneity. Here we report a novel method for a synchronous ultrafast anisotropy decay measurement, which can well determine the anisotropy, even at a very early time, as the rising phase of the excitation laser pulse. The anisotropic decay of the B850 in bacterial light harvesting antenna complex LH2 of Rhodobacter sphaeroides in solution at room temperature with coherent excitation is detected by this method, which shows a polarization response time of 30 fs, and the energy transfer from the initial excitation to the bacteriochlorophylls in B850 ring takes about 70 fs. The anisotropic decay that is probed at the red side of the absorption spectrum, such as 880 nm, has an initial value of 0.4, corresponding to simulated emission, while the blue side with an anisotropy of 0.1 contributes to the ground-state bleaching. Our results show that the coherent excitation covering the whole ring might not be realized owing to the symmetry breaking of LH2: from C9 symmetry in membrane to C2 symmetry in solution.

Electrode Reactions in Slowly Relaxing Media

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

Matyushov, Dmitry V.; Newton, Marshall D.

Here, standard models of reaction kinetics in condensed materials rely on the Boltzmann-Gibbs distribution for the population of reactants at the top of the free energy barrier separating them from the products. While energy dissipation and quantum effects at the barrier top can potentially affect the transmission coefficient entering the rate preexponential factor, much stronger dynamical effects on the reaction barrier are caused by the breakdown of ergodicity for populating the reaction barrier (violation of the Boltzmann-Gibbs statistics). When the spectrum of medium modes coupled to the reaction coordinate includes fluctuations slower than the reaction rate, such nuclear motions dynamicallymore » freeze on the reaction time-scale and do not contribute to the activation barrier. In this paper, we consider the consequences of this scenario for electrode reactions in slowly relaxing media. Changing electrode overpotential speeds electrode electron transfer up, potentially cutting through the spectrum of nuclear modes coupled to the reaction coordinate. The reorganization energy of electrochemical electron transfer becomes a function of the electrode overpotential, switching between the thermodynamic value at low rates to the nonergodic limit at higher rates. The sharpness of this transition depends of the relaxation spectrum of the medium. The reorganization energy experiences a sudden drop with increasing overpotential for a medium with a Debye relaxation, but becomes a much shallower function of the overpotential for media with stretched exponential dynamics. The latter scenario characterizes electron transfer in ionic liquids. The analysis of electrode reactions in room-temperature ionic liquids shows that the magnitude of the free energy of nuclear solvation is significantly below its thermodynamic limit. Finally, this result applies to reaction times faster than microseconds and is currently limited by the available dielectric relaxation data.« less

Electrode Reactions in Slowly Relaxing Media

DOE PAGES

Matyushov, Dmitry V.; Newton, Marshall D.

2017-11-17

Here, standard models of reaction kinetics in condensed materials rely on the Boltzmann-Gibbs distribution for the population of reactants at the top of the free energy barrier separating them from the products. While energy dissipation and quantum effects at the barrier top can potentially affect the transmission coefficient entering the rate preexponential factor, much stronger dynamical effects on the reaction barrier are caused by the breakdown of ergodicity for populating the reaction barrier (violation of the Boltzmann-Gibbs statistics). When the spectrum of medium modes coupled to the reaction coordinate includes fluctuations slower than the reaction rate, such nuclear motions dynamicallymore » freeze on the reaction time-scale and do not contribute to the activation barrier. In this paper, we consider the consequences of this scenario for electrode reactions in slowly relaxing media. Changing electrode overpotential speeds electrode electron transfer up, potentially cutting through the spectrum of nuclear modes coupled to the reaction coordinate. The reorganization energy of electrochemical electron transfer becomes a function of the electrode overpotential, switching between the thermodynamic value at low rates to the nonergodic limit at higher rates. The sharpness of this transition depends of the relaxation spectrum of the medium. The reorganization energy experiences a sudden drop with increasing overpotential for a medium with a Debye relaxation, but becomes a much shallower function of the overpotential for media with stretched exponential dynamics. The latter scenario characterizes electron transfer in ionic liquids. The analysis of electrode reactions in room-temperature ionic liquids shows that the magnitude of the free energy of nuclear solvation is significantly below its thermodynamic limit. Finally, this result applies to reaction times faster than microseconds and is currently limited by the available dielectric relaxation data.« less

Photoinduced relaxation dynamics of nitrogen-capped silicon nanoclusters: a TD-DFT study

NASA Astrophysics Data System (ADS)

Liu, Xiang-Yang; Xie, Xiao-Ying; Fang, Wei-Hai; Cui, Ganglong

2018-04-01

Herein we have developed and implemented a TD-DFT-based surface-hopping dynamics simulation method with a recently proposed numerical algorithm capable of efficiently computing nonadiabatic couplings, a semiclassical spectrum simulation method, and an excited-state character analysis method based on one-electron transition density matrix. With the use of these developed methods, we have studied the spectroscopic properties, excited-state characters, and photoinduced relaxation dynamics of three silicon nanoclusters capped with different chromophores (Cl@SiQD, Car@SiQD, Azo@SiQD). Spectroscopically, the main absorption peak is visibly red-shifted from Cl@SiQD via Car@SiQD to Azo@SiQD. In contrast to Cl@SiQD and Car@SiQD, there are two peaks observed in Azo@SiQD. Mechanistically, the excited-state relaxation to the lowest S1 excited singlet state is ultrafast in Cl@SiQD, which is less than 190 fs and without involving excited-state trapping. In comparison, there are clear excited-state trappings in Car@SiQD and Azo@SiQD. In the former, the S2 state is trapped more than 300 fs; in the latter, the S3 excited-state trapping is more than 615 fs. These results demonstrate that the interfacial interaction has significant influences on the spectroscopic properties and excited-state relaxation dynamics. The knowledge gained in this work could be helpful for the design of silicon nanoclusters with better photoluminescence performance.

Vibrational energy transfer dynamics in ruthenium polypyridine transition metal complexes.

PubMed

Fedoseeva, Marina; Delor, Milan; Parker, Simon C; Sazanovich, Igor V; Towrie, Michael; Parker, Anthony W; Weinstein, Julia A

2015-01-21

Understanding the dynamics of the initial stages of vibrational energy transfer in transition metal complexes is a challenging fundamental question which is also of crucial importance for many applications, such as improving the performance of solar devices or photocatalysis. The present study investigates vibrational energy transport in the ground and the electronic excited state of Ru(4,4'-(COOEt)2-2,2-bpy)2(NCS)2, a close relative of the efficient "N3" dye used in dye-sensitized solar cells. Using the emerging technique of ultrafast two-dimensional infrared spectroscopy, we show that, similarly to other transition-metal complexes, the central Ru heavy atom acts as a "bottleneck" making the energy transfer from small ligands with high energy vibrational stretching frequencies less favorable and thereby affecting the efficiency of vibrational energy flow in the complex. Comparison of the vibrational relaxation times in the electronic ground and excited state of Ru(4,4'-(COOEt)2-2,2-bpy)2(NCS)2 shows that it is dramatically faster in the latter. We propose to explain this observation by the intramolecular electrostatic interactions between the thiocyanate group and partially oxidised Ru metal center, which increase the degree of vibrational coupling between CN and Ru-N modes in the excited state thus reducing structural and thermodynamic barriers that slow down vibrational relaxation and energy transport in the electronic ground state. As a very similar behavior was earlier observed in another transition-metal complex, Re(4,4'-(COOEt)2-2,2'-bpy)(CO)3Cl, we suggest that this effect in vibrational energy dynamics might be common for transition-metal complexes with heavy central atoms.

Unraveling shock-induced chemistry using ultrafast lasers

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

Moore, David Steven

The exquisite time synchronicity between shock and diagnostics needed to unravel chemical events occurring in picoseconds has been achieved using a shaped ultrafast laser pulse to both drive the shocks and interrogate the sample via a multiplicity of optical diagnostics. The shaped laser drive pulse can produce well-controlled shock states of sub-ns duration with sub-10 ps risetimes, sufficient for investigation offast reactions or phase transformations in a thin layer with picosecond time resolution. The shock state is characterized using ultrafast dynamic ellipsometry (UDE) in either planar or Gaussian spatial geometries, the latter allowing measurements of the equation of state ofmore » materials at a range of stresses in a single laser pulse. Time-resolved processes in materials are being interrogated using UDE, ultrafast infrared absorption, ultrafast UV/visible absorption, and femtosecond stimulated Raman spectroscopy. Using these tools we showed that chemistry in an energetic thin film starts only after an induction time of a few tens of ps, an observation that allows differentiation between proposed shock-induced reaction mechanisms. These tools are presently being applied to a variety of energetic and reactive sample systems, from nitromethane and carbon disulfide, to microengineered interfaces in tunable energetic mixtures. Recent results will be presented, and future trends outlined.« less

Spatially resolved nuclear spin relaxation, electron spin relaxation and light absorption in swift heavy ion irradiated LiF crystals.

PubMed

Stork, H; Dinse, K-P; Ditter, M; Fujara, F; Masierak, W; Neumann, R; Schuster, B; Schwartz, K; Trautmann, C

2010-05-12

Spatially resolved (19)F and (7)Li spin-lattice relaxation rates are measured for LiF single crystals after irradiation with two kinds of swift heavy ions ((12)C of 133 MeV and (208)Pb of 1.78 GeV incident energy). Like in earlier studies on (130)Xe and (238)U irradiated LiF crystals, we found a strong enhancement of the nuclear spin-lattice relaxation rate within the ion penetration depth and a slight--but still significant--enhancement beyond. By evaluating the nuclear relaxation rate enhancement within the ion range after irradiation with different projectiles, a universal relationship between the spin-lattice relaxation rate and the dose is deduced. The results of accompanying X-band electron paramagnetic resonance relaxation measurements and optical absorption spectroscopy are included in a physical interpretation of this relationship. Also the reason for the enhanced relaxation rate beyond the ion range is further discussed.

Concept and design of a beam blanker with integrated photoconductive switch for ultrafast electron microscopy.

PubMed

Weppelman, I G C; Moerland, R J; Hoogenboom, J P; Kruit, P

2018-01-01

We present a new method to create ultrashort electron pulses by integrating a photoconductive switch with an electrostatic deflector. This paper discusses the feasibility of such a system by analytical and numerical calculations. We argue that ultrafast electron pulses can be achieved for micrometer scale dimensions of the blanker, which are feasible with MEMS-based fabrication technology. According to basic models, the design presented in this paper is capable of generating 100 fs electron pulses with spatial resolutions of less than 10 nm. Our concept for an ultrafast beam blanker (UFB) may provide an attractive alternative to perform ultrafast electron microscopy, as it does not require modification of the microscope nor realignment between DC and pulsed mode of operation. Moreover, only low laser pulse energies are required. Due to its small dimensions the UFB can be inserted in the beam line of a commercial microscope via standard entry ports for blankers or variable apertures. The use of a photoconductive switch ensures minimal jitter between laser and electron pulses. Copyright © 2017 Elsevier B.V. All rights reserved.

Proposed imaging of the ultrafast electronic motion in samples using x-ray phase contrast.

PubMed

Dixit, Gopal; Slowik, Jan Malte; Santra, Robin

2013-03-29

Tracing the motion of electrons has enormous relevance to understanding ubiquitous phenomena in ultrafast science, such as the dynamical evolution of the electron density during complex chemical and biological processes. Scattering of ultrashort x-ray pulses from an electronic wave packet would appear to be the most obvious approach to image the electronic motion in real time and real space with the notion that such scattering patterns, in the far-field regime, encode the instantaneous electron density of the wave packet. However, recent results by Dixit et al. [Proc. Natl. Acad. Sci. U.S.A. 109, 11636 (2012)] have put this notion into question and have shown that the scattering in the far-field regime probes spatiotemporal density-density correlations. Here, we propose a possible way to image the instantaneous electron density of the wave packet via ultrafast x-ray phase contrast imaging. Moreover, we show that inelastic scattering processes, which plague ultrafast scattering in the far-field regime, do not contribute in ultrafast x-ray phase contrast imaging as a consequence of an interference effect. We illustrate our general findings by means of a wave packet that lies in the time and energy range of the dynamics of valence electrons in complex molecular and biological systems. This present work offers a potential to image not only instantaneous snapshots of nonstationary electron dynamics, but also the laplacian of these snapshots which provide information about the complex bonding and topology of the charge distributions in the systems.

Proposed Imaging of the Ultrafast Electronic Motion in Samples using X-Ray Phase Contrast

NASA Astrophysics Data System (ADS)

Dixit, Gopal; Slowik, Jan Malte; Santra, Robin

2013-03-01

Tracing the motion of electrons has enormous relevance to understanding ubiquitous phenomena in ultrafast science, such as the dynamical evolution of the electron density during complex chemical and biological processes. Scattering of ultrashort x-ray pulses from an electronic wave packet would appear to be the most obvious approach to image the electronic motion in real time and real space with the notion that such scattering patterns, in the far-field regime, encode the instantaneous electron density of the wave packet. However, recent results by Dixit et al. [Proc. Natl. Acad. Sci. U.S.A. 109, 11 636 (2012)] have put this notion into question and have shown that the scattering in the far-field regime probes spatiotemporal density-density correlations. Here, we propose a possible way to image the instantaneous electron density of the wave packet via ultrafast x-ray phase contrast imaging. Moreover, we show that inelastic scattering processes, which plague ultrafast scattering in the far-field regime, do not contribute in ultrafast x-ray phase contrast imaging as a consequence of an interference effect. We illustrate our general findings by means of a wave packet that lies in the time and energy range of the dynamics of valence electrons in complex molecular and biological systems. This present work offers a potential to image not only instantaneous snapshots of nonstationary electron dynamics, but also the Laplacian of these snapshots which provide information about the complex bonding and topology of the charge distributions in the systems.

Role of the Heat Sink Layer Ta for Ultrafast Spin Dynamic Process in Amorphous TbFeCo Thin Films

NASA Astrophysics Data System (ADS)

Ren, Y.; Zhang, Z. Z.; Min, T.; Jin, Q. Y.

The ultrafast demagnetization processes (UDP) in Ta (t nm)/TbFeCo (20 nm) films have been studied using the time-resolved magneto-optical Kerr effect (TRMOKE). With a fixed pump fluence of 2 mJ/cm2, for the sample without a Ta underlayer (t=0nm), we observed the UDP showing a two-step decay behavior, with a relatively longer decay time (τ2) around 3.0 ps in the second step due to the equilibrium of spin-lattice relaxation following the 4f occupation. As a 10nm Ta layer is deposited, the two-step demagnetization still exists while τ2 decreases to ˜1.9ps. Nevertheless, the second-step decay (τ2=0ps) disappears as the Ta layer thickness is increased up to 20 nm, only the first-step UDP occurs within 500 fs, followed by a fast recovery process. The rapid magnetization recovery rate strongly depends on the pump fluence. We infer that the Ta layer provides conduction electrons involving the thermal equilibrium of spin-lattice interaction and serves as heat bath taking away energy from spins of TbFeCo alloy film in UDP.

RELAX: detecting relaxed selection in a phylogenetic framework.

PubMed

Wertheim, Joel O; Murrell, Ben; Smith, Martin D; Kosakovsky Pond, Sergei L; Scheffler, Konrad

2015-03-01

Relaxation of selective strength, manifested as a reduction in the efficiency or intensity of natural selection, can drive evolutionary innovation and presage lineage extinction or loss of function. Mechanisms through which selection can be relaxed range from the removal of an existing selective constraint to a reduction in effective population size. Standard methods for estimating the strength and extent of purifying or positive selection from molecular sequence data are not suitable for detecting relaxed selection, because they lack power and can mistake an increase in the intensity of positive selection for relaxation of both purifying and positive selection. Here, we present a general hypothesis testing framework (RELAX) for detecting relaxed selection in a codon-based phylogenetic framework. Given two subsets of branches in a phylogeny, RELAX can determine whether selective strength was relaxed or intensified in one of these subsets relative to the other. We establish the validity of our test via simulations and show that it can distinguish between increased positive selection and a relaxation of selective strength. We also demonstrate the power of RELAX in a variety of biological scenarios where relaxation of selection has been hypothesized or demonstrated previously. We find that obligate and facultative γ-proteobacteria endosymbionts of insects are under relaxed selection compared with their free-living relatives and obligate endosymbionts are under relaxed selection compared with facultative endosymbionts. Selective strength is also relaxed in asexual Daphnia pulex lineages, compared with sexual lineages. Endogenous, nonfunctional, bornavirus-like elements are found to be under relaxed selection compared with exogenous Borna viruses. Finally, selection on the short-wavelength sensitive, SWS1, opsin genes in echolocating and nonecholocating bats is relaxed only in lineages in which this gene underwent pseudogenization; however, selection on the functional

Adlayer structure dependent ultrafast desorption dynamics in carbon monoxide adsorbed on Pd (111)

NASA Astrophysics Data System (ADS)

Hong, Sung-Young; Xu, Pan; Camillone, Nina R.; White, Michael G.; Camillone, Nicholas

2016-07-01

We report our ultrafast photoinduced desorption investigation of the coverage dependence of substrate-adsorbate energy transfer in carbon monoxide adlayers on the (111) surface of palladium. As the CO coverage is increased, the adsorption site population shifts from all threefold hollows (up to 0.33 ML), to bridge and near bridge (>0.5 to 0.6 ML) and finally to mixed threefold hollow plus top site (at saturation at 0.75 ML). We show that between 0.24 and 0.75 ML this progression of binding site motifs is accompanied by two remarkable features in the ultrafast photoinduced desorption of the adsorbates: (i) the desorption probability increases roughly two orders magnitude, and (ii) the adsorbate-substrate energy transfer rate observed in two-pulse correlation experiments varies nonmonotonically, having a minimum at intermediate coverages. Simulations using a phenomenological model to describe the adsorbate-substrate energy transfer in terms of frictional coupling indicate that these features are consistent with an adsorption-site dependent electron-mediated energy coupling strength, ηel, that decreases with binding site in the order: three-fold hollow > bridge and near bridge > top site. This weakening of ηel largely counterbalances the decrease in the desorption activation energy that accompanies this progression of adsorption site motifs, moderating what would otherwise be a rise of several orders of magnitude in the desorption probability. Within this framework, the observed energy transfer rate enhancement at saturation coverage is due to interadsorbate energy transfer from the copopulation of molecules bound in three-fold hollows to their top-site neighbors.

Adlayer structure dependent ultrafast desorption dynamics in carbon monoxide adsorbed on Pd (111)

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

Hong, Sung -Young; Xu, Pan; Camillone, Nina R.

Here, we report our ultrafast photoinduced desorption investigation of the coverage dependence of substrate–adsorbate energy transfer in carbon monoxide adlayers on the (111) surface of palladium. As the CO coverage is increased, the adsorption site population shifts from all threefold hollows (up to 0.33 ML), to bridge and near bridge (>0.5 to 0.6 ML) and finally to mixed threefold hollow plus top site (at saturation at 0.75 ML). We show that between 0.24 and 0.75 ML this progression of binding site motifs is accompanied by two remarkable features in the ultrafast photoinduced desorption of the adsorbates: (i) the desorption probabilitymore » increases roughly two orders magnitude, and (ii) the adsorbate–substrate energy transfer rate observed in two-pulse correlation experiments varies nonmonotonically, having a minimum at intermediate coverages. Simulations using a phenomenological model to describe the adsorbate–substrate energy transfer in terms of frictional coupling indicate that these features are consistent with an adsorption-site dependent electron-mediated energy coupling strength, η el, that decreases with binding site in the order: three-fold hollow > bridge and near bridge > top site. This weakening of η el largely counterbalances the decrease in the desorption activation energy that accompanies this progression of adsorption site motifs, moderating what would otherwise be a rise of several orders of magnitude in the desorption probability. Within this framework, the observed energy transfer rate enhancement at saturation coverage is due to interadsorbate energy transfer from the copopulation of molecules bound in three-fold hollows to their top-site neighbors.« less

Adlayer structure dependent ultrafast desorption dynamics in carbon monoxide adsorbed on Pd (111)

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

Hong, Sung-Young; Camillone, Nina R.; Camillone, Nicholas, E-mail: nicholas@bnl.gov

We report our ultrafast photoinduced desorption investigation of the coverage dependence of substrate–adsorbate energy transfer in carbon monoxide adlayers on the (111) surface of palladium. As the CO coverage is increased, the adsorption site population shifts from all threefold hollows (up to 0.33 ML), to bridge and near bridge (>0.5 to 0.6 ML) and finally to mixed threefold hollow plus top site (at saturation at 0.75 ML). We show that between 0.24 and 0.75 ML this progression of binding site motifs is accompanied by two remarkable features in the ultrafast photoinduced desorption of the adsorbates: (i) the desorption probability increasesmore » roughly two orders magnitude, and (ii) the adsorbate–substrate energy transfer rate observed in two-pulse correlation experiments varies nonmonotonically, having a minimum at intermediate coverages. Simulations using a phenomenological model to describe the adsorbate–substrate energy transfer in terms of frictional coupling indicate that these features are consistent with an adsorption-site dependent electron-mediated energy coupling strength, η{sub el}, that decreases with binding site in the order: three-fold hollow > bridge and near bridge > top site. This weakening of η{sub el} largely counterbalances the decrease in the desorption activation energy that accompanies this progression of adsorption site motifs, moderating what would otherwise be a rise of several orders of magnitude in the desorption probability. Within this framework, the observed energy transfer rate enhancement at saturation coverage is due to interadsorbate energy transfer from the copopulation of molecules bound in three-fold hollows to their top-site neighbors.« less

Adlayer structure dependent ultrafast desorption dynamics in carbon monoxide adsorbed on Pd (111)

DOE PAGES

Hong, Sung -Young; Xu, Pan; Camillone, Nina R.; ...

2016-07-01

Here, we report our ultrafast photoinduced desorption investigation of the coverage dependence of substrate–adsorbate energy transfer in carbon monoxide adlayers on the (111) surface of palladium. As the CO coverage is increased, the adsorption site population shifts from all threefold hollows (up to 0.33 ML), to bridge and near bridge (>0.5 to 0.6 ML) and finally to mixed threefold hollow plus top site (at saturation at 0.75 ML). We show that between 0.24 and 0.75 ML this progression of binding site motifs is accompanied by two remarkable features in the ultrafast photoinduced desorption of the adsorbates: (i) the desorption probabilitymore » increases roughly two orders magnitude, and (ii) the adsorbate–substrate energy transfer rate observed in two-pulse correlation experiments varies nonmonotonically, having a minimum at intermediate coverages. Simulations using a phenomenological model to describe the adsorbate–substrate energy transfer in terms of frictional coupling indicate that these features are consistent with an adsorption-site dependent electron-mediated energy coupling strength, η el, that decreases with binding site in the order: three-fold hollow > bridge and near bridge > top site. This weakening of η el largely counterbalances the decrease in the desorption activation energy that accompanies this progression of adsorption site motifs, moderating what would otherwise be a rise of several orders of magnitude in the desorption probability. Within this framework, the observed energy transfer rate enhancement at saturation coverage is due to interadsorbate energy transfer from the copopulation of molecules bound in three-fold hollows to their top-site neighbors.« less

Realizing Ultrafast Electron Pulse Self-Compression by Femtosecond Pulse Shaping Technique.

PubMed

Qi, Yingpeng; Pei, Minjie; Qi, Dalong; Yang, Yan; Jia, Tianqing; Zhang, Shian; Sun, Zhenrong

2015-10-01

Uncorrelated position and velocity distribution of the electron bunch at the photocathode from the residual energy greatly limit the transverse coherent length and the recompression ability. Here we first propose a femtosecond pulse-shaping method to realize the electron pulse self-compression in ultrafast electron diffraction system based on a point-to-point space-charge model. The positively chirped femtosecond laser pulse can correspondingly create the positively chirped electron bunch at the photocathode (such as metal-insulator heterojunction), and such a shaped electron pulse can realize the self-compression in the subsequent propagation process. The greatest advantage for our proposed scheme is that no additional components are introduced into the ultrafast electron diffraction system, which therefore does not affect the electron bunch shape. More importantly, this scheme can break the limitation that the electron pulse via postphotocathode static compression schemes is not shorter than the excitation laser pulse due to the uncorrelated position and velocity distribution of the initial electron bunch.

EDITORIAL: Ultrafast magnetization processes

NASA Astrophysics Data System (ADS)

Hillebrands, Burkard

2008-09-01

This Cluster Issue of Journal of Physics D: Applied Physics is devoted to ultrafast magnetization processes. It reports on the scientific yield of the Priority Programme 1133 'Ultrafast Magnetization Processes' which was funded by the Deutsche Forschungsgemeinschaft in the period 2002-2008 in three successive two-year funding periods, supporting research of 17-18 groups in Germany. Now, at the end of this Priority Programme, the members feel that the achievements made in the course of the programme merit communication to the international scientific community in a concerted way. Therefore, each of the projects of the last funding period presents a key result in a published contribution to this Cluster Issue. The purpose of the funding by a Priority Programme is to advance knowledge in an emerging field of research through collaborative networked support over several locations. Priority Programmes are characterized by their enhanced quality of research through the use of new methods and forms of collaboration in emerging fields, by added value through interdisciplinary cooperation, and by networking. The aim of the Priority Programme 1133 'Ultrafast Magnetization Processes' may be well characterized by the call for projects in June 2001 after the programme was approved by the Deutsche Forschungsgemeinschaft: 'The aim of the priority programme is the achievement of a basic understanding of the temporal evolution of fast magnetization processes in magnetically ordered films, multilayers and micro-structured systems. The challenge lies in the advancement of the field of ultrafast magnetization processes into the regime of a few femtoseconds to nanoseconds, a topic not yet well explored. A general aim is to understand the fundamental mechanisms needed for applications in ultrafast magneto-electronic devices. The fundamental topic to be addressed is the response of the magnetization of small structures upon the application of pulsed magnetic fields, laser pulses or

Ultrafast optical excitations in supramolecular metallacycles with charge transfer properties.

PubMed

Flynn, Daniel C; Ramakrishna, Guda; Yang, Hai-Bo; Northrop, Brian H; Stang, Peter J; Goodson, Theodore

2010-02-03

New organometallic materials such as two-dimensional metallacycles and three-dimensional metallacages are important for the development of novel optical, electronic, and energy related applications. In this article, the ultrafast dynamics of two different platinum-containing metallacycles have been investigated by femtosecond fluorescence upconversion and transient absorption. These measurements were carried out in an effort to probe the charge transfer dynamics and the rate of intersystem crossing in metallacycles of different geometries and dimensions. The processes of ultrafast intersystem crossing and charge transfer vary between the two different classes of metallacyclic systems studied. For rectangular anthracene-containing metallacycles, the electronic coupling between adjacent ligands was relatively weak, whereas for the triangular phenanthrene-containing structures, there was a clear interaction between the conjugated ligand and the metal complex center. The transient lifetimes increased with increasing conjugation in that case. The results show that differences in the dimensionality and structure of metallacycles result in different optical properties, which may be utilized in the design of nonlinear optical materials and potential new, longer-lived excited state materials for further electronic applications.

Escape time, relaxation, and sticky states of a softened Henon-Heiles model: Low-frequency vibrational mode effects and glass relaxation

NASA Astrophysics Data System (ADS)

Toledo-Marín, J. Quetzalcóatl; Naumis, Gerardo G.

2018-04-01

Here we study the relaxation of a chain consisting of three masses joined by nonlinear springs and periodic conditions when the stiffness is weakened. This system, when expressed in their normal coordinates, yields a softened Henon-Heiles system. By reducing the stiffness of one low-frequency vibrational mode, a faster relaxation is enabled. This is due to a reduction of the energy barrier heights along the softened normal mode as well as for a widening of the opening channels of the energy landscape in configurational space. The relaxation is for the most part exponential, and can be explained by a simple flux equation. Yet, for some initial conditions the relaxation follows as a power law, and in many cases there is a regime change from exponential to power-law decay. We pinpoint the initial conditions for the power-law decay, finding two regions of sticky states. For such states, quasiperiodic orbits are found since almost for all components of the initial momentum orientation, the system is trapped inside two pockets of configurational space. The softened Henon-Heiles model presented here is intended as the simplest model in order to understand the interplay of rigidity, nonlinear interactions and relaxation for nonequilibrium systems such as glass-forming melts or soft matter. Our softened system can be applied to model β relaxation in glasses and suggest that local reorientational jumps can have an exponential and a nonexponential contribution for relaxation, the latter due to asymmetric molecules sticking in cages for certain orientations.

Large-area tungsten disulfide for ultrafast photonics.

PubMed

Yan, Peiguang; Chen, Hao; Yin, Jinde; Xu, Zihan; Li, Jiarong; Jiang, Zike; Zhang, Wenfei; Wang, Jinzhang; Li, Irene Ling; Sun, Zhipei; Ruan, Shuangchen

2017-02-02

Two-dimensional (2D) layered transition metal dichalcogenides (TMDs) have attracted significant interest in various optoelectronic applications due to their excellent nonlinear optical properties. One of the most important applications of TMDs is to be employed as an extraordinary optical modulation material (e.g., the saturable absorber (SA)) in ultrafast photonics. The main challenge arises while embedding TMDs into fiber laser systems to generate ultrafast pulse trains and thus constraints their practical applications. Herein, few-layered WS 2 with a large-area was directly transferred on the facet of the pigtail and acted as a SA for erbium-doped fiber laser (EDFL) systems. In our study, WS 2 SA exhibited remarkable nonlinear optical properties (e.g., modulation depth of 15.1% and saturable intensity of 157.6 MW cm -2 ) and was used for ultrafast pulse generation. The soliton pulses with remarkable performances (e.g., ultrashort pulse duration of 1.49 ps, high stability of 71.8 dB, and large pulse average output power of 62.5 mW) could be obtained in a telecommunication band. To the best of our knowledge, the average output power of the mode-locked pulse trains is the highest by employing TMD materials in fiber laser systems. These results indicate that atomically large-area WS 2 could be used as excellent optical modulation materials in ultrafast photonics.

On the ultrafast charge migration and subsequent charge directed reactivity in Cl⋯N halogen-bonded clusters following vertical ionization

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

Chandra, Sankhabrata; Bhattacharya, Atanu, E-mail: atanub@ipc.iisc.ernet.in; Periyasamy, Ganga

2015-06-28

In this article, we have presented ultrafast charge transfer dynamics through halogen bonds following vertical ionization of representative halogen bonded clusters. Subsequent hole directed reactivity of the radical cations of halogen bonded clusters is also discussed. Furthermore, we have examined effect of the halogen bond strength on the electron-electron correlation- and relaxation-driven charge migration in halogen bonded complexes. For this study, we have selected A-Cl (A represents F, OH, CN, NH{sub 2}, CF{sub 3}, and COOH substituents) molecules paired with NH{sub 3} (referred as ACl:NH{sub 3} complex): these complexes exhibit halogen bonds. To the best of our knowledge, this ismore » the first report on purely electron correlation- and relaxation-driven ultrafast (attosecond) charge migration dynamics through halogen bonds. Both density functional theory and complete active space self-consistent field theory with 6-31 + G(d, p) basis set are employed for this work. Upon vertical ionization of NCCl⋯NH{sub 3} complex, the hole is predicted to migrate from the NH{sub 3}-end to the ClCN-end of the NCCl⋯NH{sub 3} complex in approximately 0.5 fs on the D{sub 0} cationic surface. This hole migration leads to structural rearrangement of the halogen bonded complex, yielding hydrogen bonding interaction stronger than the halogen bonding interaction on the same cationic surface. Other halogen bonded complexes, such as H{sub 2}NCl:NH{sub 3}, F{sub 3}CCl:NH{sub 3}, and HOOCCl:NH{sub 3}, exhibit similar charge migration following vertical ionization. On the contrary, FCl:NH{sub 3} and HOCl:NH{sub 3} complexes do not exhibit any charge migration following vertical ionization to the D{sub 0} cation state, pointing to interesting halogen bond strength-dependent charge migration.« less

Ultrafast dynamics of quasiparticles and coherent acoustic phonons in slightly underdoped (BaK)Fe2As2

PubMed Central

Lin, Kung-Hsuan; Wang, Kuan-Jen; Chang, Chung-Chieh; Wen, Yu-Chieh; Lv, Bing; Chu, Ching-Wu; Wu, Maw-Kuen

2016-01-01

We have utilized ultrafast optical spectroscopy to study carrier dynamics in slightly underdoped (BaK)Fe2As2 crystals without magnetic transition. The photoelastic signals due to coherent acoustic phonons have been quantitatively investigated. According to our temperature-dependent results, we found that the relaxation component of superconducting quasiparticles persisted from the superconducting state up to at least 70 K in the normal state. Our findings suggest that the pseudogaplike feature in the normal state is possibly the precursor of superconductivity. We also highlight that the pseudogap feature of K-doped BaFe2As2 is different from that of other iron-based superconductors, including Co-doped or P-doped BaFe2As2. PMID:27180873

In vivo studies of ultrafast near-infrared laser tissue bonding and wound healing

NASA Astrophysics Data System (ADS)

Sriramoju, Vidyasagar; Alfano, Robert R.

2015-10-01

Femtosecond (fs) pulse lasers in the near-infrared (NIR) range exhibit very distinct properties upon their interaction with biomolecules compared to the corresponding continuous wave (CW) lasers. Ultrafast NIR laser tissue bonding (LTB) was used to fuse edges of two opposing animal tissue segments in vivo using fs laser photoexcitation of the native vibrations of chomophores. The fusion of the incised tissues was achieved in vivo at the molecular level as the result of the energy-matter interactions of NIR laser radiation with water and the structural proteins like collagen in the target tissues. Nonthermal vibrational excitation from the fs laser absorption by water and collagen induced the formation of cross-links between tissue proteins on either sides of the weld line resulting in tissue bonding. No extrinsic agents were used to facilitate tissue bonding in the fs LTB. These studies were pursued for the understanding and evaluation of the role of ultrafast NIR fs laser radiation in the LTB and consequent wound healing. The fs LTB can be used for difficult to suture structures such as blood vessels, nerves, gallbladder, liver, intestines, and other viscera. Ultrafast NIR LTB yields promising outcomes and benefits in terms of wound closure and wound healing under optimal conditions.

Carotid Artery Stiffness Assessment by Ultrafast Ultrasound Imaging: Feasibility and Potential Influencing Factors.

PubMed

Pan, Fu-Shun; Yu, Liang; Luo, Jia; Wu, Ri-Dong; Xu, Ming; Liang, Jin-Yu; Zheng, Yan-Ling; Xie, Xiao-Yan

2018-04-19

To evaluate the feasibility of the ultrafast ultrasound pulsed wave velocity (PWV) for carotid stiffness assessment and potential influencing factors. Ultrafast PWV measurements of 442 carotid arteries in 162 consecutive patients (patient group) and 66 healthy volunteers (control group) were performed. High- and very high-frequency transducers were used in 110 carotid segments. The ultrafast PWVs at the beginning and end of systole were automatically measured. The correlations between the intima-media thickness (IMT) and ultrafast PWV and the equipment and carotid factors influencing the utility of ultrafast PWV were analyzed. Each ultrafast PWV acquisition was completed within 1 minute. The intraobserver variability showed mean differences ± SD of 0.12 ± 1.28 m/s for the PWV before systole and 0.06 ± 1.30 m/s for the PWV at the end of systole. Ultrafast PWV measurements were more likely obtained with the very high- frequency transducer when the IMT was less than 1.5 mm (P < .05). A generalized linear mixed-effects model analysis showed that the very high-frequency transducer had a greater ability to obtain a valid carotid ultrafast PWV measurement with an IMT of less than 1.5 mm (P < .05). The IMT was positively correlated with the PWV before systole and at the end of systole (r = 0.207-0.771; all P < .05) in the control group, patient group, and carotid subgroup with an IMT of less than 1.5 mm. A multiple regression analysis showed that the IMT and plaque were important independent factors in predicting failure of the ultrafast PWV (P < .001). The ultrafast PWV is an effective and user-friendly method for evaluating carotid stiffness. The IMT and transducer type are factors influencing the ability to obtain an ultrafast PWV measurement. © 2018 by the American Institute of Ultrasound in Medicine.

Relaxation mechanisms, structure and properties of semi-coherent interfaces

DOE PAGES

Shao, Shuai; Wang, Jian

2015-10-15

In this work, using the Cu–Ni (111) semi-coherent interface as a model system, we combine atomistic simulations and defect theory to reveal the relaxation mechanisms, structure, and properties of semi-coherent interfaces. By calculating the generalized stacking fault energy (GSFE) profile of the interface, two stable structures and a high-energy structure are located. During the relaxation, the regions that possess the stable structures expand and develop into coherent regions; the regions with high-energy structure shrink into the intersection of misfit dislocations (nodes). This process reduces the interface excess potential energy but increases the core energy of the misfit dislocations and nodes.more » The core width is dependent on the GSFE of the interface. The high-energy structure relaxes by relative rotation and dilatation between the crystals. The relative rotation is responsible for the spiral pattern at nodes. The relative dilatation is responsible for the creation of free volume at nodes, which facilitates the nodes’ structural transformation. Several node structures have been observed and analyzed. In conclusion, the various structures have significant impact on the plastic deformation in terms of lattice dislocation nucleation, as well as the point defect formation energies.« less

Feed-forward motor control of ultrafast, ballistic movements.

PubMed

Kagaya, K; Patek, S N

2016-02-01

To circumvent the limits of muscle, ultrafast movements achieve high power through the use of springs and latches. The time scale of these movements is too short for control through typical neuromuscular mechanisms, thus ultrafast movements are either invariant or controlled prior to movement. We tested whether mantis shrimp (Stomatopoda: Neogonodactylus bredini) vary their ultrafast smashing strikes and, if so, how this control is achieved prior to movement. We collected high-speed images of strike mechanics and electromyograms of the extensor and flexor muscles that control spring compression and latch release. During spring compression, lateral extensor and flexor units were co-activated. The strike initiated several milliseconds after the flexor units ceased, suggesting that flexor activity prevents spring release and determines the timing of strike initiation. We used linear mixed models and Akaike's information criterion to serially evaluate multiple hypotheses for control mechanisms. We found that variation in spring compression and strike angular velocity were statistically explained by spike activity of the extensor muscle. The results show that mantis shrimp can generate kinematically variable strikes and that their kinematics can be changed through adjustments to motor activity prior to the movement, thus supporting an upstream, central-nervous-system-based control of ultrafast movement. Based on these and other findings, we present a shishiodoshi model that illustrates alternative models of control in biological ballistic systems. The discovery of feed-forward control in mantis shrimp sets the stage for the assessment of targets, strategic variation in kinematics and the role of learning in ultrafast animals. © 2016. Published by The Company of Biologists Ltd.

Imaging CF3I conical intersection and photodissociation dynamics by ultrafast electron diffraction

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

Yang, Jie

Conical intersections play a critical role in excited state dynamics of polyatomic molecules, as they govern the reaction pathways of many nonadiabatic processes. However, ultrafast probes have lacked sufficient spatial resolution to image wavepacket trajectories through these intersections directly. Here we present the simultaneous experimental characterization of one-photon and two-photon excitation channels in isolated CF3I molecules using ultrafast gas phase electron diffraction. In the two-photon channel, we have mapped out the real space trajectories of a coherent nuclear wavepacket, which bifurcates onto two potential energy surfaces when passing through a conical intersection. In the one-photon channel, we have resolved excitationmore » of both the umbrella and the breathing vibrational modes in the CF3 fragment in multiple nuclear dimensions. These findings benchmark and validate ab-initio nonadiabatic dynamics calculations.« less

Effect of pressure on β relaxation in La60Ni15Al25 metallic glass

NASA Astrophysics Data System (ADS)

Xu, H. Y.; Sheng, H. W.; Li, M. Z.

2018-03-01

The effect of pressure on β relaxation in La60Ni15Al25 metallic glass (MG) was investigated by activation-relaxation technique in combination with molecular dynamics simulation. It is found that the β relaxation behavior and the potential energy landscape are significantly modulated by pressure. With increasing pressure, the atomic motion in β relaxation in La60Ni15Al25 MG changes from hopping-dominated to the string-like-dominated motion with increased activation energy. Moreover, while the hopping motion is gradually suppressed as pressure is increased, the cooperative rearrangements with more atoms involved but very low activation energies are significantly enhanced by pressure. It is further found that the "subbasins" in the potential energy landscape in La60Ni15Al25 MG become deeper and steeper with increasing pressure, leading to the increase of activation energy. Meanwhile, some neighboring "subbasins" merge under pressure accompanied by the disappearance of energy barriers in-between, leading to events with very low activation energies in the β relaxation. The atomic structure analysis reveals that the transformation of atomic motions in β relaxation in La60Ni15Al25 MG under pressure is strongly correlated with the decrease of pentagon-rich atomic clusters and the increase of clusters with fewer pentagons. These findings provide a new understanding of the β relaxation mechanism and some clues for tuning β relaxation in MGs.

Relaxation dynamics of C60

NASA Astrophysics Data System (ADS)

Walsh, Tiffany R.; Wales, David J.

1998-10-01

The relaxation dynamics of C60 from high-energy isomers to Buckminsterfullerene is examined using a master equation approach. An exhaustive catalog of the C60 fullerene isomers containing only five- and six-membered rings is combined with knowledge of the Stone-Wales rearrangements that connect all such isomers. Full geometry optimizations have been performed for all the minima and the transition states which connect them up to six Stone-Wales steps away from the global minimum. A density-functional tight-binding potential was employed to provide a quantum mechanical description of the bonding. The resulting picture of the potential energy landscape reveals a "weeping willow" structure which offers a clear explanation for the relatively long relaxation times observed experimentally. We also predict the most important transient local minima on the annealing pathway.

Applications of ultrafast laser direct writing: from polarization control to data storage

NASA Astrophysics Data System (ADS)

Donko, A.; Gertus, T.; Brambilla, G.; Beresna, M.

2018-02-01

Ultrafast laser direct writing is a fascinating technology which emerged more than two decades from fundamental studies of material resistance to high-intensity optical fields. Its development saw the discovery of many puzzling phenomena and demonstration of useful applications. Today, ultrafast laser writing is seen as a technology with great potential and is rapidly entering the industrial environment. Whereas, less than 10 years ago, ultrafast lasers were still confined within the research labs. This talk will overview some of the unique features of ultrafast lasers and give examples of its applications in optical data storage, polarization control and optical fibers.

Ultrafast Plasmon-Enhanced Hot Electron Generation at Ag Nanocluster/Graphite Heterojunctions.

PubMed

Tan, Shijing; Liu, Liming; Dai, Yanan; Ren, Jindong; Zhao, Jin; Petek, Hrvoje

2017-05-03

Hot electron processes at metallic heterojunctions are central to optical-to-chemical or electrical energy transduction. Ultrafast nonlinear photoexcitation of graphite (Gr) has been shown to create hot thermalized electrons at temperatures corresponding to the solar photosphere in less than 25 fs. Plasmonic resonances in metallic nanoparticles are also known to efficiently generate hot electrons. Here we deposit Ag nanoclusters (NC) on Gr to study the ultrafast hot electron generation and dynamics in their plasmonic heterojunctions by means of time-resolved two-photon photoemission (2PP) spectroscopy. By tuning the wavelength of p-polarized femtosecond excitation pulses, we find an enhancement of 2PP yields by 2 orders of magnitude, which we attribute to excitation of a surface-normal Mie plasmon mode of Ag/Gr heterojunctions at 3.6 eV. The 2PP spectra include contributions from (i) coherent two-photon absorption of an occupied interface state (IFS) 0.2 eV below the Fermi level, which electronic structure calculations assign to chemisorption-induced charge transfer, and (ii) hot electrons in the π*-band of Gr, which are excited through the coherent screening response of the substrate. Ultrafast pump-probe measurements show that the IFS photoemission occurs via virtual intermediate states, whereas the characteristic lifetimes attribute the hot electrons to population of the π*-band of Gr via the plasmon dephasing. Our study directly probes the mechanisms for enhanced hot electron generation and decay in a model plasmonic heterojunction.

Ultrafast transient photocarrier dynamics of the bulk-insulating topological insulator B i1.5S b0.5T e1.7S e1.3

NASA Astrophysics Data System (ADS)

Choi, Young Gwan; Zhung, Chan June; Park, Sun-Hee; Park, Joonbum; Kim, Jun Sung; Kim, Seongheun; Park, Jaehun; Lee, J. S.

2018-02-01

Using optical-pump terahertz-probe spectroscopy, we investigated an ultrafast photocarrier relaxation behavior in a B i1.5S b0.5T e1.7S e1.3 (BSTS) single crystal, which is one of the most bulk-insulating topological insulators. Compared to n -type bulk-metallic B i2S e3 , we found that BSTS endows distinct behaviors in its photocarrier dynamics; the relaxation time turns out to be an order of magnitude longer, and the transient conductance spectrum exhibits a nonlinear increase as a function of the pumping power. Also, we observed an abrupt reduction of the photocarrier scattering rate in several picoseconds after the initial photoexcitation. We discuss these intriguing experimental observations based on a bulk-to-surface carrier injection assisted by the built-in electric field near the surface and electron-phonon scattering.

Entropic multi-relaxation free-energy lattice Boltzmann model for two-phase flows

NASA Astrophysics Data System (ADS)

Bösch, F.; Dorschner, B.; Karlin, I.

2018-04-01

The entropic multi-relaxation lattice Boltzmann method is extended to two-phase systems following the free-energy approach. Gain in stability is achieved by incorporating the force term due to Korteweg's stress into the redefined entropic stabilizer, which allows simulation of higher Weber and Reynolds numbers with an efficient and explicit algorithm. Results for head-on droplet collisions and droplet impact on super-hydrophobic substrates are matching experimental data accurately. Furthermore, it is demonstrated that the entropic stabilization leads to smaller spurious currents without affecting the interface thickness. The present findings demonstrate the universality of the simple and explicit entropic lattice Boltzmann models and provide a viable and robust alternative to existing methods.

Ultrafast Exciton Delocalization, Localization, and Excimer Formation Dynamics in a Highly Defined Perylene Bisimide Quadruple π-Stack.

PubMed

Kaufmann, Christina; Kim, Woojae; Nowak-Król, Agnieszka; Hong, Yongseok; Kim, Dongho; Würthner, Frank

2018-03-28

An adequately designed, bay-tethered perylene bisimide (PBI) dimer Bis-PBI was synthesized by Pd/Cu-catalyzed Glaser-type oxidative homocoupling of the respective PBI building block. This newly synthesized PBI dimer self-assembles exclusively and with high binding constants of up to 10 6 M -1 into a discrete π-stack of four chromophores. Steady-state absorption and emission spectra show the signatures of H-type excitonic coupling among the dye units. Broadband fluorescence upconversion spectroscopy (FLUPS) reveals an ultrafast dynamics in the optically excited state. An initially coherent Frenkel exciton state that is delocalized over the whole quadruple stack rapidly (τ = ∼200 fs) loses its coherence and relaxes into an excimer state. Comparison with Frenkel exciton dynamics in PBI dimeric and oligomeric H-aggregates demonstrates that in the quadruple stack coherent exciton propagation is absent due to its short length of aggregates, thereby it has only one relaxation pathway to the excimer state. Furthermore, the absence of pump-power dependence in transient absorption experiments suggests that multiexciton cannot be generated in the quadruple stack, which is in line with time-resolved fluorescence measurements.

Measurement of Nanoplasmonic Field Enhancement with Ultrafast Photoemission.

PubMed

Rácz, Péter; Pápa, Zsuzsanna; Márton, István; Budai, Judit; Wróbel, Piotr; Stefaniuk, Tomasz; Prietl, Christine; Krenn, Joachim R; Dombi, Péter

2017-02-08

Probing nanooptical near-fields is a major challenge in plasmonics. Here, we demonstrate an experimental method utilizing ultrafast photoemission from plasmonic nanostructures that is capable of probing the maximum nanoplasmonic field enhancement in any metallic surface environment. Directly measured field enhancement values for various samples are in good agreement with detailed finite-difference time-domain simulations. These results establish ultrafast plasmonic photoelectrons as versatile probes for nanoplasmonic near-fields.

Nonthermal ultrafast optical control of the magnetization in garnet films

NASA Astrophysics Data System (ADS)

Hansteen, Fredrik; Kimel, Alexey; Kirilyuk, Andrei; Rasing, Theo

2006-01-01

We demonstrate coherent optical control of the magnetization in ferrimagnetic garnet films on the femtosecond time scale through a combination of two different ultrafast and nonthermal photomagnetic effects and by employing multiple pump pulses. Linearly polarized laser pulses are shown to create a long-lived modification of the magnetocrystalline anisotropy via optically induced electron transfer between nonequivalent ion sites while circularly polarized pulses additionally act as strong transient magnetic field pulses originating from the nonabsorptive inverse Faraday effect. Due to the slow phonon-magnon interaction in these dielectrics, thermal effects of the laser excitation are clearly distinguished from the ultrafast nonthermal effects and can be seen only on the time scale of nanoseconds for sample temperatures near the Curie point. The reported effects open exciting possibilities for ultrafast manipulation of spins by light, and provide insight into the physics of magnetism on ultrafast time scales.

Relaxation Dynamics in Heme Proteins.

NASA Astrophysics Data System (ADS)

Scholl, Reinhard Wilhelm

A protein molecule possesses many conformational substates that are likely arranged in a hierarchy consisting of a number of tiers. A hierarchical organization of conformational substates is expected to give rise to a multitude of nonequilibrium relaxation phenomena. If the temperature is lowered, transitions between substates of higher tiers are frozen out, and relaxation processes characteristic of lower tiers will dominate the observational time scale. This thesis addresses the following questions: (i) What is the energy landscape of a protein? How does the landscape depend on the environment such as pH and viscosity, and how can it be connected to specific structural parts? (ii) What relaxation phenomena can be observed in a protein? Which are protein specific, and which occur in other proteins? How does the environment influence relaxations? (iii) What functional form best describes relaxation functions? (iv) Can we connect the motions to specific structural parts of the protein molecule, and are these motions important for the function of the protein?. To this purpose, relaxation processes after a pressure change are studied in carbonmonoxy (CO) heme proteins (myoglobin-CO, substrate-bound and substrate-free cytochrome P450cam-CO, chloroperoxidase-CO, horseradish peroxidase -CO) between 150 K and 250 K using FTIR spectroscopy to monitor the CO bound to the heme iron. Two types of p -relaxation experiments are performed: p-release (200 to ~eq40 MPa) and p-jump (~eq40 to 200 MPa) experiments. Most of the relaxations fall into one of three groups and are characterized by (i) nonexponential time dependence and non-Arrhenius temperature dependence (FIM1( nu), FIM1(Gamma)); (ii) exponential time dependence and non-Arrhenius temperature dependence (FIM0(A_{i}to A_{j})); exponential time dependence and Arrhenius temperature dependence (FIMX( nu)). The influence of pH is studied in myoglobin-CO and shown to have a strong influence on the substate population of the

Ultrafast Spectral Diffusion of the First Subband Exciton in Single-Wall Carbon Nanotubes

NASA Astrophysics Data System (ADS)

Schilling, Daniel; Hertel, Tobias

2013-03-01

The width of optical transitions in semiconductors is determined by homogeneous and inhomogeneous contributions. Here, we report on the determination of homogeneous linewidths for the first exciton subband transition and the dynamics of spectral diffusion in single-wall carbon nanotubes (SWNTs) using one- and two-dimensional time resolved spectral hole burning spectroscopy. Our investigation of highly purified semiconducting (6,5)-SWNTs suggests that room temperature homogeneous linewidths are on the order of 4 meV and are rapidly broadened by an ultrafast sub-ps spectral diffusion process. These findings are supported by our off-resonant excitation experiments where we observe sub-ps population transfer reflecting the thermal distribution of energy levels around the first subband exciton transition. The results of temperature-dependent spectral hole burning experiments between 17 K and 293 K suggest that homogeneous linewidths are due to exciton interaction with low energy optical phonons, most likely of the radial breathing mode type. In contrast, we find that inhomogeneous broadening is determined by an electronic degree of freedom such as ultrafast intra-tube exciton diffusion which is characteristic and unique for excitons in these one-dimensional semiconductors.

Relaxation Assessment with Varied Structured Milieu (RELAX).

ERIC Educational Resources Information Center

Cassel, Russell N.; Cassel, Susie L.

1983-01-01

Describes Relaxation Assessment with Varied Structured Milieu (RELAX), a clinical program designed to assess the degree to which an individual is able to demonstrate self-control for overall general relaxation. The program is designed for use with the Cassel Biosensors biofeedback equipment. (JAC)

Advanced optic fabrication using ultrafast laser radiation

NASA Astrophysics Data System (ADS)

Taylor, Lauren L.; Qiao, Jun; Qiao, Jie

2016-03-01

Advanced fabrication and finishing techniques are desired for freeform optics and integrated photonics. Methods including grinding, polishing and magnetorheological finishing used for final figuring and polishing of such optics are time consuming, expensive, and may be unsuitable for complex surface features while common photonics fabrication techniques often limit devices to planar geometries. Laser processing has been investigated as an alternative method for optic forming, surface polishing, structure writing, and welding, as direct tuning of laser parameters and flexible beam delivery are advantageous for complex freeform or photonics elements and material-specific processing. Continuous wave and pulsed laser radiation down to the nanosecond regime have been implemented to achieve nanoscale surface finishes through localized material melting, but the temporal extent of the laser-material interaction often results in the formation of a sub-surface heat affected zone. The temporal brevity of ultrafast laser radiation can allow for the direct vaporization of rough surface asperities with minimal melting, offering the potential for smooth, final surface quality with negligible heat affected material. High intensities achieved in focused ultrafast laser radiation can easily induce phase changes in the bulk of materials for processing applications. We have experimentally tested the effectiveness of ultrafast laser radiation as an alternative laser source for surface processing of monocrystalline silicon. Simulation of material heating associated with ultrafast laser-material interaction has been performed and used to investigate optimized processing parameters including repetition rate. The parameter optimization process and results of experimental processing will be presented.

Ultrafast Microwave Nano-manufacturing of Fullerene-Like Metal Chalcogenides

PubMed Central

Liu, Zhen; Zhang, Lin; Wang, Ruigang; Poyraz, Selcuk; Cook, Jonathan; Bozack, Michael J.; Das, Siddhartha; Zhang, Xinyu; Hu, Liangbing

2016-01-01

Metal Chalcogenides (MCs) have emerged as an extremely important class of nanomaterials with applications ranging from lubrication to energy storage devices. Here we report our discovery of a universal, ultrafast (60 seconds), energy-efficient, and facile technique of synthesizing MC nanoparticles and nanostructures, using microwave-assisted heating. A suitable combination of chemicals was selected for reactions on Polypyrrole nanofibers (PPy-NF) in presence of microwave irradiation. The PPy-NF serves as the conducting medium to absorb microwave energy to heat the chemicals that provide the metal and the chalcogenide constituents separately. The MCs are formed as nanoparticles that eventually undergo a size-dependent, multi-stage aggregation process to yield different kinds of MC nanostructures. Most importantly, this is a single-step metal chalcogenide formation process that is much faster and much more energy-efficient than all the other existing methods and can be universally employed to produce different kinds of MCs (e.g., MoS2, and WS2). PMID:26931353

Ultrafast Microwave Nano-manufacturing of Fullerene-Like Metal Chalcogenides

NASA Astrophysics Data System (ADS)

Liu, Zhen; Zhang, Lin; Wang, Ruigang; Poyraz, Selcuk; Cook, Jonathan; Bozack, Michael J.; Das, Siddhartha; Zhang, Xinyu; Hu, Liangbing

2016-03-01

Metal Chalcogenides (MCs) have emerged as an extremely important class of nanomaterials with applications ranging from lubrication to energy storage devices. Here we report our discovery of a universal, ultrafast (60 seconds), energy-efficient, and facile technique of synthesizing MC nanoparticles and nanostructures, using microwave-assisted heating. A suitable combination of chemicals was selected for reactions on Polypyrrole nanofibers (PPy-NF) in presence of microwave irradiation. The PPy-NF serves as the conducting medium to absorb microwave energy to heat the chemicals that provide the metal and the chalcogenide constituents separately. The MCs are formed as nanoparticles that eventually undergo a size-dependent, multi-stage aggregation process to yield different kinds of MC nanostructures. Most importantly, this is a single-step metal chalcogenide formation process that is much faster and much more energy-efficient than all the other existing methods and can be universally employed to produce different kinds of MCs (e.g., MoS2, and WS2).

Ultrafast Microwave Nano-manufacturing of Fullerene-Like Metal Chalcogenides.

PubMed

Liu, Zhen; Zhang, Lin; Wang, Ruigang; Poyraz, Selcuk; Cook, Jonathan; Bozack, Michael J; Das, Siddhartha; Zhang, Xinyu; Hu, Liangbing

2016-03-02

Metal Chalcogenides (MCs) have emerged as an extremely important class of nanomaterials with applications ranging from lubrication to energy storage devices. Here we report our discovery of a universal, ultrafast (60 seconds), energy-efficient, and facile technique of synthesizing MC nanoparticles and nanostructures, using microwave-assisted heating. A suitable combination of chemicals was selected for reactions on Polypyrrole nanofibers (PPy-NF) in presence of microwave irradiation. The PPy-NF serves as the conducting medium to absorb microwave energy to heat the chemicals that provide the metal and the chalcogenide constituents separately. The MCs are formed as nanoparticles that eventually undergo a size-dependent, multi-stage aggregation process to yield different kinds of MC nanostructures. Most importantly, this is a single-step metal chalcogenide formation process that is much faster and much more energy-efficient than all the other existing methods and can be universally employed to produce different kinds of MCs (e.g., MoS2, and WS2).

Intramolecular and intermolecular vibrational energy relaxation of CH 2I 2 dissolved in supercritical fluid

NASA Astrophysics Data System (ADS)

Sekiguchi, K.; Shimojima, A.; Kajimoto, O.

2002-04-01

A pump-probe experiment was performed to examine vibrational population relaxation of diiodomethane (CH 2I 2) molecule dissolved in supercritical CO 2. Using an apparatus with femtosecond time resolution, we observed the contributions of intramolecular vibrational energy redistribution (IVR) and intermolecular vibrational energy transfer (VET) separately. IVR and VET rates were measured with varying solvent densities at a constant temperature. It is shown that the IVR rate is not density dependent while the VET rate increases with increasing density from 0.4 to 0.8 g cm-3. This observation suggests that the rate of the VET process is determined by solute-solvent collisions whereas the IVR rate is not much affected by solute-solvent interaction.

Ultrafast carrier thermalization and trapping in silicon-germanium alloy probed by extreme ultraviolet transient absorption spectroscopy

PubMed Central

Zürch, Michael; Chang, Hung-Tzu; Kraus, Peter M.; Cushing, Scott K.; Borja, Lauren J.; Gandman, Andrey; Kaplan, Christopher J.; Oh, Myoung Hwan; Prell, James S.; Prendergast, David; Pemmaraju, Chaitanya D.; Neumark, Daniel M.; Leone, Stephen R.

2017-01-01

Semiconductor alloys containing silicon and germanium are of growing importance for compact and highly efficient photonic devices due to their favorable properties for direct integration into silicon platforms and wide tunability of optical parameters. Here, we report the simultaneous direct and energy-resolved probing of ultrafast electron and hole dynamics in a silicon-germanium alloy with the stoichiometry Si0.25Ge0.75 by extreme ultraviolet transient absorption spectroscopy. Probing the photoinduced dynamics of charge carriers at the germanium M4,5-edge (∼30 eV) allows the germanium atoms to be used as reporter atoms for carrier dynamics in the alloy. The photoexcitation of electrons across the direct and indirect band gap into conduction band (CB) valleys and their subsequent hot carrier relaxation are observed and compared to pure germanium, where the Ge direct (ΔEgap,Ge,direct=0.8 eV) and Si0.25Ge0.75 indirect gaps (ΔEgap,Si0.25Ge0.75,indirect=0.95 eV) are comparable in energy. In the alloy, comparable carrier lifetimes are observed for the X, L, and Γ valleys in the conduction band. A midgap feature associated with electrons accumulating in trap states near the CB edge following intraband thermalization is observed in the Si0.25Ge0.75 alloy. The successful implementation of the reporter atom concept for capturing the dynamics of the electronic bands by site-specific probing in solids opens a route to study carrier dynamics in more complex materials with femtosecond and sub-femtosecond temporal resolution. PMID:28653020

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.

Fast and ultrafast endocytosis.

PubMed

Watanabe, Shigeki; Boucrot, Emmanuel

2017-08-01

Clathrin-mediated endocytosis (CME) is the main endocytic pathway supporting housekeeping functions in cells. However, CME may be too slow to internalize proteins from the cell surface during certain physiological processes such as reaction to stress hormones ('fight-or-flight' reaction), chemotaxis or compensatory endocytosis following exocytosis of synaptic vesicles or hormone-containing vesicles. These processes take place on a millisecond to second timescale and thus require very rapid cellular reaction to prevent overstimulation or exhaustion of the response. There are several fast endocytic processes identified so far: macropinocytosis, activity-dependent bulk endocytosis (ABDE), fast-endophilin-mediated endocytosis (FEME), kiss-and-run and ultrafast endocytosis. All are clathrin-independent and are not constitutively active but may use different molecular mechanisms to rapidly remove receptors and proteins from the cell surface. Here, we review our current understanding of fast and ultrafast endocytosis, their functions, and molecular mechanisms. Copyright © 2017 Elsevier Ltd. All rights reserved.

Relaxation processes in a low-order three-dimensional magnetohydrodynamics model

NASA Technical Reports Server (NTRS)

Stribling, Troy; Matthaeus, William H.

1991-01-01

The time asymptotic behavior of a Galerkin model of 3D magnetohydrodynamics (MHD) has been interpreted using the selective decay and dynamic alignment relaxation theories. A large number of simulations has been performed that scan a parameter space defined by the rugged ideal invariants, including energy, cross helicity, and magnetic helicity. It is concluded that time asymptotic state can be interpreted as a relaxation to minimum energy. A simple decay model, based on absolute equilibrium theory, is found to predict a mapping of initial onto time asymptotic states, and to accurately describe the long time behavior of the runs when magnetic helicity is present. Attention is also given to two processes, operating on time scales shorter than selective decay and dynamic alignment, in which the ratio of kinetic to magnetic energy relaxes to values 0(1). The faster of the two processes takes states initially dominant in magnetic energy to a state of near-equipartition between kinetic and magnetic energy through power law growth of kinetic energy. The other process takes states initially dominant in kinetic energy to the near-equipartitioned state through exponential growth of magnetic energy.

Mega-electron-volt ultrafast electron diffraction at SLAC National Accelerator Laboratory.

PubMed

Weathersby, S P; Brown, G; Centurion, M; Chase, T F; Coffee, R; Corbett, J; Eichner, J P; Frisch, J C; Fry, A R; Gühr, M; Hartmann, N; Hast, C; Hettel, R; Jobe, R K; Jongewaard, E N; Lewandowski, J R; Li, R K; Lindenberg, A M; Makasyuk, I; May, J E; McCormick, D; Nguyen, M N; Reid, A H; Shen, X; Sokolowski-Tinten, K; Vecchione, T; Vetter, S L; Wu, J; Yang, J; Dürr, H A; Wang, X J

2015-07-01

Ultrafast electron probes are powerful tools, complementary to x-ray free-electron lasers, used to study structural dynamics in material, chemical, and biological sciences. High brightness, relativistic electron beams with femtosecond pulse duration can resolve details of the dynamic processes on atomic time and length scales. SLAC National Accelerator Laboratory recently launched the Ultrafast Electron Diffraction (UED) and microscopy Initiative aiming at developing the next generation ultrafast electron scattering instruments. As the first stage of the Initiative, a mega-electron-volt (MeV) UED system has been constructed and commissioned to serve ultrafast science experiments and instrumentation development. The system operates at 120-Hz repetition rate with outstanding performance. In this paper, we report on the SLAC MeV UED system and its performance, including the reciprocal space resolution, temporal resolution, and machine stability.

Ultrafast electron microscopy in materials science, biology, and chemistry

NASA Astrophysics Data System (ADS)

King, Wayne E.; Campbell, Geoffrey H.; Frank, Alan; Reed, Bryan; Schmerge, John F.; Siwick, Bradley J.; Stuart, Brent C.; Weber, Peter M.

2005-06-01

The use of pump-probe experiments to study complex transient events has been an area of significant interest in materials science, biology, and chemistry. While the emphasis has been on laser pump with laser probe and laser pump with x-ray probe experiments, there is a significant and growing interest in using electrons as probes. Early experiments used electrons for gas-phase diffraction of photostimulated chemical reactions. More recently, scientists are beginning to explore phenomena in the solid state such as phase transformations, twinning, solid-state chemical reactions, radiation damage, and shock propagation. This review focuses on the emerging area of ultrafast electron microscopy (UEM), which comprises ultrafast electron diffraction (UED) and dynamic transmission electron microscopy (DTEM). The topics that are treated include the following: (1) The physics of electrons as an ultrafast probe. This encompasses the propagation dynamics of the electrons (space-charge effect, Child's law, Boersch effect) and extends to relativistic effects. (2) The anatomy of UED and DTEM instruments. This includes discussions of the photoactivated electron gun (also known as photogun or photoelectron gun) at conventional energies (60-200 keV) and extends to MeV beams generated by rf guns. Another critical aspect of the systems is the electron detector. Charge-coupled device cameras and microchannel-plate-based cameras are compared and contrasted. The effect of various physical phenomena on detective quantum efficiency is discussed. (3) Practical aspects of operation. This includes determination of time zero, measurement of pulse-length, and strategies for pulse compression. (4) Current and potential applications in materials science, biology, and chemistry. UEM has the potential to make a significant impact in future science and technology. Understanding of reaction pathways of complex transient phenomena in materials science, biology, and chemistry will provide fundamental

High Harmonic Generation XUV Spectroscopy for Studying Ultrafast Photophysics of Coordination Complexes

NASA Astrophysics Data System (ADS)

Ryland, Elizabeth S.; Lin, Ming-Fu; Benke, Kristin; Verkamp, Max A.; Zhang, Kaili; Vura-Weis, Josh

2017-06-01

Extreme ultraviolet (XUV) spectroscopy is an inner shell technique that probes the M_{2,3}-edge excitation of atoms. Absorption of the XUV photon causes a 3p→3d transition, the energy and shape of which is directly related to the element and ligand environment. This technique is thus element-, oxidation state-, spin state-, and ligand field specific. A process called high-harmonic generation (HHG) enables the production of ultrashort (˜20fs) pulses of collimated XUV photons in a tabletop instrument. This allows transient XUV spectroscopy to be conducted as an in-lab experiment, where it was previously only possible at accelerator-based light sources. Additionally, ultrashort pulses provide the capability for unprecedented time resolution (˜50fs IRF). This technique has the capacity to serve a pivotal role in the study of electron and energy transfer processes in materials and chemical biology. I will present the XUV transient absorption instrument we have built, along with ultrafast transient M_{2,3}-edge absorption data of a series of small inorganic molecules in order to demonstrate the high specificity and time resolution of this tabletop technique as well as how our group is applying it to the study of ultrafast electronic dynamics of coordination complexes.

Transthoracic Ultrafast Doppler Imaging of Human Left Ventricular Hemodynamic Function

PubMed Central

Osmanski, Bruno-Félix; Maresca, David; Messas, Emmanuel; Tanter, Mickael; Pernot, Mathieu

2016-01-01

Heart diseases can affect intraventricular blood flow patterns. Real-time imaging of blood flow patterns is challenging because it requires both a high frame rate and a large field of view. To date, standard Doppler techniques can only perform blood flow estimation with high temporal resolution within small regions of interest. In this work, we used ultrafast imaging to map in 2D human left ventricular blood flow patterns during the whole cardiac cycle. Cylindrical waves were transmitted at 4800 Hz with a transthoracic phased array probe to achieve ultrafast Doppler imaging of the left ventricle. The high spatio-temporal sampling of ultrafast imaging permits to rely on a much more effective wall filtering and to increase sensitivity when mapping blood flow patterns during the pre-ejection, ejection, early diastole, diastasis and late diastole phases of the heart cycle. The superior sensitivity and temporal resolution of ultrafast Doppler imaging makes it a promising tool for the noninvasive study of intraventricular hemodynamic function. PMID:25073134

The effect of the polymer relaxation time on the nonlinear energy cas- cade and dissipation of statistically steady and decaying homogeneous isotropic turbulence

NASA Astrophysics Data System (ADS)

Valente, Pedro C.; da Silva, Carlos B.; Pinho, Fernando T.

2013-11-01

We report a numerical study of statistically steady and decaying turbulence of FENE-P fluids for varying polymer relaxation times ranging from the Kolmogorov dissipation time-scale to the eddy turnover time. The total turbulent kinetic energy dissipation is shown to increase with the polymer relaxation time in both steady and decaying turbulence, implying a ``drag increase.'' If the total power input in the statistically steady case is kept equal in the Newtonian and the viscoelastic simulations the increase in the turbulence-polymer energy transfer naturally lead to the previously reported depletion of the Newtonian, but not the overall, kinetic energy dissipation. The modifications to the nonlinear energy cascade with varying Deborah/Weissenberg numbers are quantified and their origins investigated. The authors acknowledge the financial support from Fundação para a Ciência e a Tecnologia under grant PTDC/EME-MFE/113589/2009.

Conformationally controlled ultrafast intersystem crossing in bithiophene systems.

PubMed

Skov, Anders B; Larsen, Martin A B; Liisberg, Mikkel B; Hansen, Thorsten; Sølling, Theis I

2018-05-16

Bithiophenes serve as model systems for larger polythiophenes used in solar cell applications and molecular electronics. We report a study of ultrafast dynamics of two bithiophene systems measured with femtosecond time-resolved photoelectron spectroscopy, and show that their intersystem crossing takes place within the first few picoseconds after excitation, in line with previous studies. We show that the intersystem crossing rate can be explained in terms of arguments based on symmetry of the S1 minimum energy geometry, which depends on the specific conformation of bithiophene. Furthermore, this work shows that the minor cis-conformer contributes to an even higher intersystem crossing rate than the major trans conformer. The work presented here can provide guiding principles towards the design of solar cell components with even faster formation of long-lived excited states for solar energy harvesting.

Mapping carrier diffusion in single silicon core-shell nanowires with ultrafast optical microscopy.

PubMed

Seo, M A; Yoo, J; Dayeh, S A; Picraux, S T; Taylor, A J; Prasankumar, R P

2012-12-12

Recent success in the fabrication of axial and radial core-shell heterostructures, composed of one or more layers with different properties, on semiconductor nanowires (NWs) has enabled greater control of NW-based device operation for various applications. (1-3) However, further progress toward significant performance enhancements in a given application is hindered by the limited knowledge of carrier dynamics in these structures. In particular, the strong influence of interfaces between different layers in NWs on transport makes it especially important to understand carrier dynamics in these quasi-one-dimensional systems. Here, we use ultrafast optical microscopy (4) to directly examine carrier relaxation and diffusion in single silicon core-only and Si/SiO(2) core-shell NWs with high temporal and spatial resolution in a noncontact manner. This enables us to reveal strong coherent phonon oscillations and experimentally map electron and hole diffusion currents in individual semiconductor NWs for the first time.

Strong field acceleration and steering of ultrafast electron pulses from a sharp metallic nanotip.

PubMed

Park, Doo Jae; Piglosiewicz, Bjoern; Schmidt, Slawa; Kollmann, Heiko; Mascheck, Manfred; Lienau, Christoph

2012-12-14

We report a strong, laser-field induced modification of the propagation direction of ultrashort electron pulses emitted from nanometer-sized gold tapers. Angle-resolved kinetic energy spectra of electrons emitted from such tips are recorded using ultrafast near-infrared light pulses of variable wavelength and intensity for excitation. For sufficiently long wavelengths, we observe a pronounced strong-field acceleration of electrons within the field gradient at the taper apex. We find a distinct narrowing of the emission cone angle of the fastest electrons. We ascribe this to the field-induced steering of subcycle electrons as opposed to the diverging emission of quiver electrons. Our findings are corroborated by simulations based on a modified Simpleman model incorporating the curved, vectorial field gradient in the vicinity of the tip. Our results indicate new pathways for designing highly directional nanometer-sized ultrafast electron sources.

Capturing ultrafast photoinduced local structural distortions of BiFeO3

PubMed Central

Wen, Haidan; Sassi, Michel; Luo, Zhenlin; Adamo, Carolina; Schlom, Darrell G.; Rosso, Kevin M.; Zhang, Xiaoyi

2015-01-01

The interaction of light with materials is an intensively studied research forefront, in which the coupling of radiation energy to selective degrees of freedom offers contact-free tuning of functionalities on ultrafast time scales. Capturing the fundamental processes and understanding the mechanism of photoinduced structural rearrangement are essential to applications such as photo-active actuators and efficient photovoltaic devices. Using ultrafast x-ray absorption spectroscopy aided by density functional theory calculations, we reveal the local structural arrangement around the transition metal atom in a unit cell of the photoferroelectric archetype BiFeO3 film. The out-of-plane elongation of the unit cell is accompanied by the in-plane shrinkage with minimal change of interaxial lattice angles upon photoexcitation. This anisotropic elastic deformation of the unit cell is driven by localized electric field as a result of photoinduced charge separation, in contrast to a global lattice constant increase and lattice angle variations as a result of heating. The finding of a photoinduced elastic unit cell deformation elucidates a microscopic picture of photocarrier-mediated non-equilibrium processes in polar materials. PMID:26463128

Capturing ultrafast photoinduced local structural distortions of BiFeO3.

PubMed

Wen, Haidan; Sassi, Michel; Luo, Zhenlin; Adamo, Carolina; Schlom, Darrell G; Rosso, Kevin M; Zhang, Xiaoyi

2015-10-14

The interaction of light with materials is an intensively studied research forefront, in which the coupling of radiation energy to selective degrees of freedom offers contact-free tuning of functionalities on ultrafast time scales. Capturing the fundamental processes and understanding the mechanism of photoinduced structural rearrangement are essential to applications such as photo-active actuators and efficient photovoltaic devices. Using ultrafast x-ray absorption spectroscopy aided by density functional theory calculations, we reveal the local structural arrangement around the transition metal atom in a unit cell of the photoferroelectric archetype BiFeO3 film. The out-of-plane elongation of the unit cell is accompanied by the in-plane shrinkage with minimal change of interaxial lattice angles upon photoexcitation. This anisotropic elastic deformation of the unit cell is driven by localized electric field as a result of photoinduced charge separation, in contrast to a global lattice constant increase and lattice angle variations as a result of heating. The finding of a photoinduced elastic unit cell deformation elucidates a microscopic picture of photocarrier-mediated non-equilibrium processes in polar materials.

Capturing ultrafast photoinduced local structural distortions of BiFeO3

NASA Astrophysics Data System (ADS)

Wen, Haidan; Sassi, Michel; Luo, Zhenlin; Adamo, Carolina; Schlom, Darrell G.; Rosso, Kevin M.; Zhang, Xiaoyi

2015-10-01

The interaction of light with materials is an intensively studied research forefront, in which the coupling of radiation energy to selective degrees of freedom offers contact-free tuning of functionalities on ultrafast time scales. Capturing the fundamental processes and understanding the mechanism of photoinduced structural rearrangement are essential to applications such as photo-active actuators and efficient photovoltaic devices. Using ultrafast x-ray absorption spectroscopy aided by density functional theory calculations, we reveal the local structural arrangement around the transition metal atom in a unit cell of the photoferroelectric archetype BiFeO3 film. The out-of-plane elongation of the unit cell is accompanied by the in-plane shrinkage with minimal change of interaxial lattice angles upon photoexcitation. This anisotropic elastic deformation of the unit cell is driven by localized electric field as a result of photoinduced charge separation, in contrast to a global lattice constant increase and lattice angle variations as a result of heating. The finding of a photoinduced elastic unit cell deformation elucidates a microscopic picture of photocarrier-mediated non-equilibrium processes in polar materials.

A 5-mm piezo-scanning fiber device for high speed ultrafast laser microsurgery

PubMed Central

Ferhanoglu, Onur; Yildirim, Murat; Subramanian, Kaushik; Ben-Yakar, Adela

2014-01-01

Towards developing precise microsurgery tools for the clinic, we previously developed image-guided miniaturized devices using low repetition rate amplified ultrafast lasers for surgery. To improve the speed of tissue removal while reducing device diameter, here we present a new 5-mm diameter device that delivers high-repetition rate laser pulses for high speed ultrafast laser microsurgery. The device consists of an air-core photonic bandgap fiber (PBF) for the delivery of high energy pulses, a piezoelectric tube actuator for fiber scanning, and two aspheric lenses for focusing the light. Its inline optical architecture provides easy alignment and substantial size reduction to 5 mm diameter as compared to our previous MEMS-scanning devices while realizing improved intensity squared (two-photon) lateral and axial resolutions of 1.16 μm and 11.46 μm, respectively. Our study also sheds light on the maximum pulse energies that can be delivered through the air-core PBF and identifies cladding damage at the input facet of the fiber as the limiting factor. We have achieved a maximum energy delivery larger than 700 nJ at 92% coupling efficiency. An in depth analysis reveals how this value is greatly affected by possible slight misalignments of the beam during coupling and the measured small beam pointing fluctuations. In the absence of these imperfections, self-phase modulation becomes the limiting factor for the maximum energy delivery, setting the theoretical upper bound to near 2 μJ for a 1-m long, 7-μm, air-core PBF. Finally, the use of a 300 kHz repetition rate fiber laser enabled rapid ablation of 150 µm x 150 µm area within only 50 ms. Such ablation speeds can now allow the surgeons to translate the surgery device as fast as ~4 mm/s to continuously remove a thin layer of a 150 µm wide tissue. Thanks to a high optical transmission efficiency of the in-line optical architecture of the device and improved resolution, we could successfully perform ablation of

Broadband ultrafast nonlinear absorption and ultra-long exciton relaxation time of black phosphorus quantum dots.

PubMed

Chen, Runze; Zheng, Xin; Jiang, Tian

2017-04-03

Black phosphorus (BP) has recently attracted significant attention for its brilliant physical and chemical features. The remarkable strong light-matter interaction and tunable direct wide range band-gap make it an ideal candidate in various application regions, especially saturable absorbers. In this paper, ultrasmall black phosphorus quantum dots (BPQDs), a unique form of phosphorus nanostructures, with average size of 5.7 ± 0.8 nm are synthesized. Compared with BP nanosheets (BPNs) with similar thickness, the ultrafast nonlinear optical (NLO) absorption properties and excited carrier dynamics are investigated in wide spectra. Beyond the saturation absorption (SA), giant two photon absorption (TPA) is observed in BPQDs. BPQDs exhibit quite different excitation intensity and wavelength dependent nonlinear optical (NLO) response from BPNs, which is attributed to the quantum confinement and edge effects. The BPQDs show broadband photon-induced absorption (PIA) under the probe wavelength from 470 nm to 850 nm and a fast and a slow decay time are obtained as long as 92 ± 10 ps and 1100 ± 100 ps, respectively. The substantial independence for ultra-long time scales of pump intensity and temperature reveals that the carrier recombination mechanism may be attributed to a defect-assisted Auger capture process. These findings will help to develop optoelectronic and photonic devices operating in the infrared and visible wavelength region.

Efficient Relaxation of Protein-Protein Interfaces by Discrete Molecular Dynamics Simulations.

PubMed

Emperador, Agusti; Solernou, Albert; Sfriso, Pedro; Pons, Carles; Gelpi, Josep Lluis; Fernandez-Recio, Juan; Orozco, Modesto

2013-02-12

Protein-protein interactions are responsible for the transfer of information inside the cell and represent one of the most interesting research fields in structural biology. Unfortunately, after decades of intense research, experimental approaches still have difficulties in providing 3D structures for the hundreds of thousands of interactions formed between the different proteins in a living organism. The use of theoretical approaches like docking aims to complement experimental efforts to represent the structure of the protein interactome. However, we cannot ignore that current methods have limitations due to problems of sampling of the protein-protein conformational space and the lack of accuracy of available force fields. Cases that are especially difficult for prediction are those in which complex formation implies a non-negligible change in the conformation of the interacting proteins, i.e., those cases where protein flexibility plays a key role in protein-protein docking. In this work, we present a new approach to treat flexibility in docking by global structural relaxation based on ultrafast discrete molecular dynamics. On a standard benchmark of protein complexes, the method provides a general improvement over the results obtained by rigid docking. The method is especially efficient in cases with large conformational changes upon binding, in which structure relaxation with discrete molecular dynamics leads to a predictive success rate double that obtained with state-of-the-art rigid-body docking.

Ultrafast Electronic Relaxation through a Conical Intersection: Nonadiabatic Dynamics Disentangled through an Oscillator Strength-Based Diabatization Framework

DOE PAGES

Medders, Gregory R.; Alguire, Ethan C.; Jain, Amber; ...

2017-01-18

Here, we employ surface hopping trajectories to model the short-time dynamics of gas-phase and partially solvated 4-(N,N-dimethylamino)benzonitrile (DMABN), a dual fluorescent molecule that is known to undergo a nonadiabatic transition through a conical intersection. To compare theory vs time-resolved fluorescence measurements, we calculate the mixed quantum–classical density matrix and the ensemble averaged transition dipole moment. We introduce a diabatization scheme based on the oscillator strength to convert the TDDFT adiabatic states into diabatic states of L a and L b character. Somewhat surprisingly, we find that the rate of relaxation reported by emission to the ground state is almost 50%more » slower than the adiabatic population relaxation. Although our calculated adiabatic rates are largely consistent with previous theoretical calculations and no obvious effects of decoherence are seen, the diabatization procedure introduced here enables an explicit picture of dynamics in the branching plane, raising tantalizing questions about geometric phase effects in systems with dozens of atoms.« less

Unlocking the Constraints of Cyanobacterial Productivity: Acclimations Enabling Ultrafast Growth

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

Bernstein, Hans C.; McClure, Ryan S.; Hill, Eric A.

ABSTRACT Harnessing the metabolic potential of photosynthetic microbes for next-generation biotechnology objectives requires detailed scientific understanding of the physiological constraints and regulatory controls affecting carbon partitioning between biomass, metabolite storage pools, and bioproduct synthesis. We dissected the cellular mechanisms underlying the remarkable physiological robustness of the euryhaline unicellular cyanobacteriumSynechococcussp. strain PCC 7002 (Synechococcus7002) and identify key mechanisms that allow cyanobacteria to achieve unprecedented photoautotrophic productivities (~2.5-h doubling time). Ultrafast growth ofSynechococcus7002 was supported by high rates of photosynthetic electron transfer and linked to significantly elevated transcription of precursor biosynthesis and protein translation machinery. Notably, no growth or photosynthesis inhibition signaturesmore » were observed under any of the tested experimental conditions. Finally, the ultrafast growth inSynechococcus7002 was also linked to a 300% expansion of average cell volume. We hypothesize that this cellular adaptation is required at high irradiances to support higher cell division rates and reduce deleterious effects, corresponding to high light, through increased carbon and reductant sequestration. IMPORTANCEEfficient coupling between photosynthesis and productivity is central to the development of biotechnology based on solar energy. Therefore, understanding the factors constraining maximum rates of carbon processing is necessary to identify regulatory mechanisms and devise strategies to overcome productivity constraints. Here, we interrogate the molecular mechanisms that operate at a systems level to allow cyanobacteria to achieve ultrafast growth. This was done by considering growth and photosynthetic kinetics with global transcription patterns. We have delineated putative biological principles that allow unicellular cyanobacteria to achieve ultrahigh growth rates

Probing Ultrafast Electron Dynamics at Surfaces Using Soft X-Ray Transient Reflectivity Spectroscopy

NASA Astrophysics Data System (ADS)

Baker, L. Robert; Husek, Jakub; Biswas, Somnath; Cirri, Anthony

The ability to probe electron dynamics with surface sensitivity on the ultrafast time scale is critical for understanding processes such as charge separation, injection, and surface trapping that mediate efficiency in catalytic and energy conversion materials. Toward this goal, we have developed a high harmonic generation (HHG) light source for femtosecond soft x-ray reflectivity. Using this light source we investigated the ultrafast carrier dynamics at the surface of single crystalline α-Fe2O3, polycrystalline α-Fe2O3, and the mixed metal oxide, CuFeO2. We have recently demonstrated that CuFeO2 in particular is a selective catalyst for photo-electrochemical CO2 reduction to acetate; however, the role of electronic structure and charge carrier dynamics in mediating catalytic selectivity has not been well understood. Soft x-ray reflectivity measurements probe the M2,3, edges of the 3d transition metals, which provide oxidation and spin state resolution with element specificity. In addition to chemical state specificity, these measurements are also surface sensitive, and by independently simulating the contributions of the real and imaginary components of the complex refractive index, we can differentiate between surface and sub-surface contributions to the excited state spectrum. Accordingly, this work demonstrates the ability to probe ultrafast carrier dynamics in catalytic materials with element and chemical state specificity and with surface sensitivity.

Ultrafast Spreading Effect Induced Rapid Cell Trapping into Porous Scaffold with Superhydrophilic Surface.

PubMed

Wang, Chenmiao; Qiao, Chunyan; Song, Wenlong; Sun, Hongchen

2015-08-19

In this contribution, superhydrophilic chitosan-based scaffolds with ultrafast spreading property were fabricated and used to improve the trapped efficiency of cells. The ultrafast spreading property allowed cells to be trapped into the internal 3D porous structures of the prepared scaffolds more quickly and effectively. Cell adhesion, growth, and proliferation were also improved, which could be attributed to the combination of UV irradiation and ultrafast spreading property. The construction of ultrafast spreading property on the scaffold surface will offer a novel way to design more effective scaffold in tissue engineering that could largely shorten the therapeutic time for patients.

Ultrafast electric phase control of a single exciton qubit

NASA Astrophysics Data System (ADS)

Widhalm, Alex; Mukherjee, Amlan; Krehs, Sebastian; Sharma, Nandlal; Kölling, Peter; Thiede, Andreas; Reuter, Dirk; Förstner, Jens; Zrenner, Artur

2018-03-01

We report on the coherent phase manipulation of quantum dot excitons by electric means. For our experiments, we use a low capacitance single quantum dot photodiode which is electrically controlled by a custom designed SiGe:C BiCMOS chip. The phase manipulation is performed and quantified in a Ramsey experiment, where ultrafast transient detuning of the exciton energy is performed synchronous to double pulse π/2 ps laser excitation. We are able to demonstrate electrically controlled phase manipulations with magnitudes up to 3π within 100 ps which is below the dephasing time of the quantum dot exciton.

High Contrast Ultrafast Imaging of the Human Heart

PubMed Central