Coulomb excitation of the K π= 8⁻ isomeric band in 178Hf

DOE PAGES

Napiorkovsk, P. J.; Srebrny, J.; Czosnyka, T.; ...

2001-12-01

The Coulomb excitation experiment on the 178Hf was performed using 650 MeV beam of 136Xe. The first observation of discrete transitions in the K π = 8 - isomeric band. Coulomb excited from K π = 0+ ground state, is reported. The possible mechanisms of El coupling of the ground state band and the isomeric band is discussed.

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.

Modeling Photochemical Dynamics in Optically Active Energetic Materials

NASA Astrophysics Data System (ADS)

Nelson, Tammie; Bjorgaard, Josiah; Greenfield, Margo; Bolme, Cindy; Brown, Katie; McGrane, Shawn; Scharff, R. Jason; Tretiak, Sergei

Most high explosives (HEs) absorb in the UV range, making it difficult to develop HEs that can be excited with standard lasers. The conventional optical initiation mechanisms require high laser intensity and occur via indirect thermal or shock processes. A photochemical initiation mechanism could allow control over the chemistry contributing to decomposition leading to initiation. We combine UV femtosecond transient absorption (TA) spectroscopy and excited state femtosecond stimulated Raman spectroscopy (FSRS) with Nonadiabatic Excited State Molecular Dynamics (NA-ESMD) to model the photochemical pathways in nitromethane (NM), a low sensitivity HE known to undergo UV photolysis. We investigate the ultrafast photodecomposition of NM from the nπ* state excited at 266 nm. The FSRS photoproduct spectrum points to methyl nitrite formation as the dominant photoproduct. A total photolysis quantum yield of 0.27 and an nπ* state lifetime of 20 fs were predicted from simulations. Predicted time scales reveal that NO2 dissociation occurs in 81 +/-4 fs and methyl nitrite formation is much slower at 452 +/-9 fs corresponding to the absorption feature in the TA spectrum. The relative time scales are consistent with isomerization by NO2 dissociation and ONO rebinding.

Ultrafast dynamics of isolated model photoactive yellow protein chromophores: "Chemical perturbation theory" in the laboratory.

PubMed

Vengris, Mikas; Larsen, Delmar S; van der Horst, Michael A; Larsen, Olaf F A; Hellingwerf, Klaas J; van Grondelle, Rienk

2005-03-10

Pump-probe and pump-dump probe experiments have been performed on several isolated model chromophores of the photoactive yellow protein (PYP). The observed transient absorption spectra are discussed in terms of the spectral signatures ascribed to solvation, excited-state twisting, and vibrational relaxation. It is observed that the protonation state has a profound effect on the excited-state lifetime of p-coumaric acid. Pigments with ester groups on the coumaryl tail end and charged phenolic moieties show dynamics that are significantly different from those of other pigments. Here, an unrelaxed ground-state intermediate could be observed in pump-probe signals. A similar intermediate could be identified in the sinapinic acid and in isomerization-locked chromophores by means of pump-dump probe spectroscopy; however, in these compounds it is less pronounced and could be due to ground-state solvation and/or vibrational relaxation. Because of strong protonation-state dependencies and the effect of electron donor groups, it is argued that charge redistribution upon excitation determines the twisting reaction pathway, possibly through interaction with the environment. It is suggested that the same pathway may be responsible for the initiation of the photocycle in native PYP.

Nonadiabatic ab initio molecular dynamics with PME-ONIOM scheme of photoisomerization reaction between 1,3-cyclohexadiene and 1,3,5-cis-hexatriene in solution phase

NASA Astrophysics Data System (ADS)

Ohta, Ayumi; Kobayashi, Osamu; Danielache, Sebastian O.; Nanbu, Shinkoh

2017-03-01

The ultra-fast photoisomerization reactions between 1,3-cyclohexadiene (CHD) and 1,3,5-cis-hexatriene (HT) in both hexane and ethanol solvents were revealed by nonadiabatic ab initio molecular dynamics (AI-MD) with a particle-mesh Ewald summation method and our Own N-layered Integrated molecular Orbital and molecular Mechanics model (PME-ONIOM) scheme. Zhu-Nakamura version trajectory surface hopping method (ZN-TSH) was employed to treat the ultra-fast nonadiabatic decaying process. The results for hexane and ethanol simulations reasonably agree with experimental data. The high nonpolar-nonpolar affinity between CHD and the solvent was observed in hexane solvent, which definitely affected the excited state lifetimes, the product branching ratio of CHD:HT, and solute (CHD) dynamics. In ethanol solvent, however, the CHD solute was isomerized in the solvent cage caused by the first solvation shell. The photochemical dynamics in ethanol solvent results in the similar property to the process appeared in vacuo (isolated CHD dynamics).

Angular-split/temporal-delay approach to ultrafast protein dynamics at XFELs.

PubMed

Ren, Zhong; Yang, Xiaojing

2016-07-01

X-ray crystallography promises direct insights into electron-density changes that lead to and arise from structural changes such as electron and proton transfer and the formation, rupture and isomerization of chemical bonds. The ultrashort pulses of hard X-rays produced by free-electron lasers present an exciting opportunity for capturing ultrafast structural events in biological macromolecules within femtoseconds after photoexcitation. However, shot-to-shot fluctuations, which are inherent to the very process of self-amplified spontaneous emission (SASE) that generates the ultrashort X-ray pulses, are a major source of noise that may conceal signals from structural changes. Here, a new approach is proposed to angularly split a single SASE pulse and to produce a temporal delay of picoseconds between the split pulses. These split pulses will allow the probing of two distinct states before and after photoexcitation triggered by a laser pulse between the split X-ray pulses. The split pulses originate from a single SASE pulse and share many common properties; thus, noise arising from shot-to-shot fluctuations is self-canceling. The unambiguous interpretation of ultrafast structural changes would require diffraction data at atomic resolution, as these changes may or may not involve any atomic displacement. This approach, in combination with the strategy of serial crystallography, offers a solution to study ultrafast dynamics of light-initiated biochemical reactions or biological processes at atomic resolution.

Ultrafast 25-fs relaxation in highly excited states of methyl azide mediated by strong nonadiabatic coupling.

PubMed

Peters, William K; Couch, David E; Mignolet, Benoit; Shi, Xuetao; Nguyen, Quynh L; Fortenberry, Ryan C; Schlegel, H Bernhard; Remacle, Françoise; Kapteyn, Henry C; Murnane, Margaret M; Li, Wen

2017-12-26

Highly excited electronic states are challenging to explore experimentally and theoretically-due to the large density of states and the fact that small structural changes lead to large changes in electronic character with associated strong nonadiabatic dynamics. They can play a key role in astrophysical and ionospheric chemistry, as well as the detonation chemistry of high-energy density materials. Here, we implement ultrafast vacuum-UV (VUV)-driven electron-ion coincidence imaging spectroscopy to directly probe the reaction pathways of highly excited states of energetic molecules-in this case, methyl azide. Our data, combined with advanced theoretical simulations, show that photoexcitation of methyl azide by a 10-fs UV pulse at 8 eV drives fast structural changes and strong nonadiabatic coupling that leads to relaxation to other excited states on a surprisingly fast timescale of 25 fs. This ultrafast relaxation differs from dynamics occurring on lower excited states, where the timescale required for the wavepacket to reach a region of strong nonadiabatic coupling is typically much longer. Moreover, our theoretical calculations show that ultrafast relaxation of the wavepacket to a lower excited state occurs along one of the conical intersection seams before reaching the minimum energy conical intersection. These findings are important for understanding the unique strongly coupled non-Born-Oppenheimer molecular dynamics of VUV-excited energetic molecules. Although such observations have been predicted for many years, this study represents one of the few where such strongly coupled non-Born-Oppenheimer molecular dynamics of VUV-excited energetic molecules have been conclusively observed directly, making it possible to identify the ultrafast reaction pathways.

Ultrafast Photodissociation Dynamics of Nitromethane.

PubMed

Nelson, Tammie; Bjorgaard, Josiah; Greenfield, Margo; Bolme, Cindy; Brown, Katie; McGrane, Shawn; Scharff, R Jason; Tretiak, Sergei

2016-02-04

Nitromethane (NM), a high explosive (HE) with low sensitivity, is known to undergo photolysis upon ultraviolet (UV) irradiation. The optical transparency, homogeneity, and extensive study of NM make it an ideal system for studying photodissociation mechanisms in conventional HE materials. The photochemical processes involved in the decomposition of NM could be applied to the future design of controllable photoactive HE materials. In this study, the photodecomposition of NM from the nπ* state excited at 266 nm is being investigated on the femtosecond time scale. UV femtosecond transient absorption (TA) spectroscopy and excited state femtosecond stimulated Raman spectroscopy (FSRS) are combined with nonadiabatic excited state molecular dynamics (NA-ESMD) simulations to provide a unified picture of NM photodecomposition. The FSRS spectrum of the photoproduct exhibits peaks in the NO2 region and slightly shifted C-N vibrational peaks pointing to methyl nitrite formation as the dominant photoproduct. A total photolysis quantum yield of 0.27 and an nπ* state lifetime of ∼20 fs were predicted from NA-ESMD simulations. Predicted time scales revealed that NO2 dissociation occurs in 81 ± 4 fs and methyl nitrite formation is much slower having a time scale of 452 ± 9 fs corresponding to the excited state absorption feature with a decay of 480 ± 17 fs observed in the TA spectrum. Although simulations predict C-N bond cleavage as the primary photochemical process, the relative time scales are consistent with isomerization occurring via NO2 dissociation and subsequent rebinding of the methyl radical and nitrogen dioxide.

Intramolecular charge transfer and trans-cis isomerization of the DCM styrene dye in polar solvents. A CS INDO MRCI study

NASA Astrophysics Data System (ADS)

Marguet, S.; Mialocq, J. C.; Millie, P.; Berthier, G.; Momicchioli, F.

1992-03-01

The solvent-induced changes of trans-cis isomerization efficiency and electronic structure of the excited state of the DCM dye have been considered by means of CS INDO MRCI calculations. The potential energy curves, dipole moments and atomic charge densities as a function of two internal coordinates, namely the rotation angle about the central "double" bond and the twisting of the dimethylamino group, have been obtained for the ground state and the lowest excited states. The structural requirements for the existence of ICT (intramolecular charge transfer) excited states have been investigated by considering internal rotations about three single bonds. The reliability of the potential surfaces and of the solvation models has been discussed with reference to test-calculations on the DMABN molecule. In the first excited singlet state of DCM, the low-energy barrier for the trans-cis isomerization has been found unaffected by the solvent polarity. The only singlet excited state presenting a large ICT character has been found to be the S 2 state for a perpendicularly twisted conformation of the dimethylamino group (TICT state). The assumption of a deactivation of the trans-isomer in the locally excited state through the TICT funnel has been largely discussed with reference to the simplifications of the present theoretical approach.

One-way Z→E isomerization around the double bond of N-methoxy- 1- (2-anthryl) ethanimine in the excited triplet state. Direct observation of one-way isomerization from Z triplet to E triplet of the C dbnd N bond

NASA Astrophysics Data System (ADS)

Arai, Tatsuo; Furuya, Yasunori; Furuuchi, Hideo; Tokumaru, Katsumi

1993-09-01

On direct as well as benzil-sensitized irradiation in degassed benzene N-methoxy-1-(2-anthryl) ethanimine ( I), ArC (CH 3) dbnd N sbnd OCH 3 (Ar: 2-anthryl), underwent one-way Z→E isomerization through a quantum chain process. The barrier to Z→E isomerization of I in the excited triplet state was determined by directly observing the change of T—T absorption spectra from the Z triplet to the E triplet. Based on these results the potential energy surface of photoisomerization of I is discussed.

No Evidence of Isomerism for the First Excited State of {sup 93}Rb

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

Miernik, K., E-mail: kmiernik@fuw.edu.pl; Gross, C.J.; Grzywacz, R.

2014-06-15

The 253.3–keV excited state located in {sup 93}Rb was studied at the Holifield Radioactive Ion Beam Facility in Oak Ridge. This state, described as isomeric in databases, was populated in the decay of {sup 93}Kr produced by proton–induced fission of {sup 238}U and isolated using the isotope separation on–line technique. We report that the 253.3–keV level does not reveal isomerism and the upper limit of the half-life from our measurement is 4 ns. Our findings are supported by previously reported results that were not taken into account in the latest nuclear databases.

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 hypothesized to occur both due to enhanced acidity of the phenolic proton and enhanced basicity of the nitrogen in the excited state. We hope this study can provide insight for better understanding of the general class of excited state concerted electron-proton dynamics.

Identification of Excited States in the N=Z Nucleus 82Nb

NASA Astrophysics Data System (ADS)

Caceres, L. S.; Gorska, M.; Jungclaus, A.; Regan, P. H.; Garnsworthy, A. B.; Pietri, S.; Podolyak, Zs.; Rudolph, D.; Steer, S. J.; Grawe, H.; Balabanski, D. L.; Becker, F.; Bednarczyk, P.; Benzoni, G.; Blank, B.; Brandau, C.; Bruce, A. M.; Camera, F.; Catford, W. N.; Cullen, I. J.; Dombradi, Zs.; Doornenbal, P.; Estevez, E.; Geissel, H.; Gelletly, W.; Gerl, J.; Grebosz, J.; Heinz, A.; Hoischen, R.; Ilie, G.; Jolie, J.; Jones, G. A.; Kmiecik, M.; Kojouharov, I.; Kondev, F. G.; Kurtukian-Nieto, T.; Kurz, N.; Lalkowski, S.; Liu, L.; Maj, A.; Myalski, S.; Montes, F.; Pfuetzner, M.; Prokopowicz, W.; Saito, T.; Schaffner, H.; Schwertel, S.; Shizuma, T.; Simons, A. J.; Tashenov, S.; Walker, P. M.; Werner-Malento, E.; Wieland, O.; Wollersheim, H. J.

2007-04-01

Information on the first excited states in the N=Z=41 nucleus 82Nb sheds light on the competition of isospin T=0 and T=1 states in the A sim 80 region. The measurement was performed at the GSI laboratory using fragmentation of a 107Ag primary beam at 750 MeV/u on a 4 g/cm2 9Be target. The fragments were separated and identified unambiguously in the FRagment Separator. Three excited states were observed and the half-life estimate for the isomeric state was extracted. A tentative spin assignment based on the isobaric analogue states systematics in the Tz=1 nucleus 82Zr, and transition probabilities indicate T=1 character of the first two excited states, and T=0 for the isomeric state.

Time-resolved nanosecond fluorescence lifetime imaging and picosecond infrared spectroscopy of combretastatin A-4 in solution and in cellular systems

NASA Astrophysics Data System (ADS)

Bisby, Roger H.; Botchway, Stanley W.; Greetham, Greg M.; Hadfield, John A.; McGown, Alan T.; Parker, Anthony W.; Scherer, Kathrin M.; Towrie, Mike

2012-08-01

Fluorescence lifetime images of intrinsic fluorescence obtained with two-photon excitation at 630 nm are shown following uptake of a series of E-combretastatins into live cells, including human umbilical vein endothelial cells (HUVECs) that are the target for the anticancer activity of combretastatins. Images show distribution of the compounds within the cell cytoplasm and in structures identified as lipid droplets by comparison with images obtained following Nile red staining of the same cells. The intracellular fluorescent lifetimes are generally longer than in fluid solution as a consequence of the high viscosity of the cellular environment. Following incubation, the intracellular concentrations of a fluorinated derivative of E-combretastatin A-4 in HUVECs are between two and three orders of magnitude higher than the concentration in the surrounding medium. Evidence is presented to indicate that at moderate laser powers (up to 6 mW), it is possible to isomerize up to 25% of the combretastatin within the femtolitre focal volume of the femtosecond laser beam. This suggests that it may be possible to activate the E-combretastatin (with low cellular toxicity) to the Z-isomer with high anticancer drug activity using two-photon irradiation. The isomerization of Z- and E-combretastatins by 266 nm irradiation has been probed by ultrafast time-resolved infrared spectroscopy. Results for the E-isomer show a rapid loss of excess vibrational energy in the excited state with a lifetime of 7 ps, followed by a slower process with a lifetime of 500 ps corresponding to the return to the ground state as also determined from the fluorescence lifetime. In contrast, the Z-isomer, whilst also appearing to undergo a rapid cooling of the initial excited state, has a much shorter overall excited state lifetime of 14 ps. DedicationThis paper is dedicated to the memory of Professor Christopher G Morgan (1949-2011). He was a valued colleague and friend at the University of Salford and made significant contributions to the development and applications of fluorescence lifetime imaging.

Searching for high-K isomers in the proton-rich A ˜ 80 mass region

NASA Astrophysics Data System (ADS)

Bai, Zhi-Jun; Jiao, Chang-Feng; Gao, Yuan; Xu, Fu-Rong

2016-09-01

Configuration-constrained potential-energy-surface calculations have been performed to investigate the K isomerism in the proton-rich A ˜ 80 mass region. An abundance of high-K states are predicted. These high-K states arise from two and four-quasi-particle excitations, with Kπ = 8+ and Kπ = 16+, respectively. Their excitation energies are comparatively low, making them good candidates for long-lived isomers. Since most nuclei under study are prolate spheroids in their ground states, the oblate shapes of the predicted high-K states may indicate a combination of K isomerism and shape isomerism. Supported by National Key Basic Research Program of China (2013CB834402) and National Natural Science Foundation of China (11235001, 11320101004 and 11575007)

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.

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.

Photochromic ruthenium sulfoxide complexes: evidence for isomerization through a conical intersection.

PubMed

McClure, Beth Anne; Mockus, Nicholas V; Butcher, Dennis P; Lutterman, Daniel A; Turro, Claudia; Petersen, Jeffrey L; Rack, Jeffrey J

2009-09-07

The complexes [Ru(bpy)(2)(OS)](PF(6)) and [Ru(bpy)(2)(OSO)](PF(6)), where bpy is 2,2'-bipyridine, OS is 2-methylthiobenzoate, and OSO is 2-methylsulfinylbenzoate, have been studied. The electrochemical and photochemical reactivity of [Ru(bpy)(2)(OSO)](+) is consistent with an isomerization of the bound sulfoxide from S-bonded (S-) to O-bonded (O-) following irradiation or electrochemical oxidation. Charge transfer excitation of [Ru(bpy)(2)(OSO)](+) in MeOH results in the appearance of two new metal-to-ligand charge transfer (MLCT) maxima at 355 and 496 nm, while the peak at 396 nm diminishes in intensity. The isomerization is reversible at room temperature in alcohol or propylene carbonate solution. In the absence of light, solutions of O-[Ru(bpy)(2)(OSO)](+) revert to S-[Ru(bpy)(2)(OSO)](+). Kinetic analysis reveals a biexponential decay with rate constants of 5.66(3) x 10(-4) s(-1) and 3.1(1) x 10(-5) s(-1). Cyclic voltammograms of S-[Ru(bpy)(2)(OSO)](+) are consistent with electron-transfer-triggered isomerization of the sulfoxide. Analysis of these voltammograms reveal E(S)(o)' = 0.86 V and E(O)(o)' = 0.49 V versus Ag/Ag(+) for the S- and O-bonded Ru(3+/2+) couples, respectively, in propylene carbonate. We found k(S-->O) = 0.090(15) s(-1) in propylene carbonate and k(S-->O) = 0.11(3) s(-1) in acetonitrile on Ru(III), which is considerably slower than has been reported for other sulfoxide isomerizations on ruthenium polypyridyl complexes following oxidation. The photoisomerization quantum yield (Phi(S-->O) = 0.45, methanol) is quite large, indicating a rapid excited state isomerization rate constant. The kinetic trace at 500 nm is monoexponential with tau = 150 ps, which is assigned to the excited S-->O isomerization rate. There is no spectroscopic or kinetic evidence for an O-bonded (3)MLCT excited state in the spectral evolution of S-[Ru(bpy)(2)(OSO)](+) to O-[Ru(bpy)(2)(OSO)](+). Thus, isomerization occurs nonadiabatically from an S-bonded (or eta(2)-sulfoxide) (3)MLCT excited state to an O-bonded ground state. Density functional theory calculations support the assigned spectroscopy and provide insight into ruthenium ligand bonding.

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

DOE PAGES

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

2017-03-17

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

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

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

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

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

Dipole-resonance assisted isomerization in the electronic ground state using few-cycle infrared pulses.

PubMed

Skocek, Oliver; Uiberacker, Christoph; Jakubetz, Werner

2011-06-30

A computational investigation of HCN → HNC isomerization in the electronic ground state by one- and few-cycle infrared pulses is presented. Starting from a vibrationally pre-excited reagent state, isomerization yields of more than 50% are obtained using single one- to five-cycle pulses. The principal mechanism includes two steps of population transfer by dipole-resonance (DR), and hence, the success of the method is closely linked to the polarity of the system and, in particular, the stepwise change of the dipole moment from reactant to transition state and on to products. The yield drops massively if the diagonal dipole matrix elements are artificially set to zero. In detail, the mechanism includes DR-induced preparation of a delocalized vibrational wavepacket, which traverses the barrier region and is finally trapped in the product well by DR-dominated de-excitation. The excitation and de-excitation steps are triggered by pulse lobes of opposite field direction. As the number of optical cycles is increased, the leading field lobes prepare a vibrational superposition state by off-resonant ladder climbing, which is then subjected to the three steps of the principal isomerization mechanism. DR excitation is more efficient from a preformed vibrational wavepacket than from a molecular eigenstate. The entire process can be loosely described as Tannor-Kosloff-Rice type transfer mechanism on a single potential surface effected by a single pulse, individual field lobes assuming the roles of pump- and dump-pulses. Pre-excitation to a transient wavepacket can be enhanced by applying a separate, comparatively weak few-cycle prepulse, in which the prepulse prepares a vibrational wavepacket. The two-pulse setup corresponds to a double Tannor-Kosloff-Rice control scheme on a single potential surface.

Direct Measurement of the Photoelectric Response Time of Bacteriorhodopsin via Electro-Optic Sampling

PubMed Central

Xu, J.; Stickrath, A. B.; Bhattacharya, P.; Nees, J.; Váró, G.; Hillebrecht, J. R.; Ren, L.; Birge, R. R.

2003-01-01

The photovoltaic signal associated with the primary photochemical event in an oriented bacteriorhodopsin film is measured by directly probing the electric field in the bacteriorhodopsin film using an ultrafast electro-optic sampling technique. The inherent response time is limited only by the laser pulse width of 500 fs, and permits a measurement of the photovoltage with a bandwidth of better than 350 GHz. All previous published studies have been carried out with bandwidths of 50 GHz or lower. We observe a charge buildup with an exponential formation time of 1.68 ± 0.05 ps and an initial decay time of 31.7 ps. Deconvolution with a 500-fs Gaussian excitation pulse reduces the exponential formation time to 1.61 ± 0.04 ps. The photovoltaic signal continues to rise for 4.5 ps after excitation, and the voltage profile corresponds well with the population dynamics of the K state. The origin of the fast photovoltage is assigned to the partial isomerization of the chromophore and the coupled motion of the Arg-82 residue during the primary event. PMID:12885657

Excitation Localization/Delocalization Isomerism in a Strongly Coupled Covalent Dimer of 1,3-Diphenylisobenzofuran

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

Schrauben, Joel N.; Akdag, Akin; Wen, Jin

Two isomers of both the lowest excited singlet (S1) and triplet (T1) states of the directly para, para'-connected covalent dimer of the singlet-fission chromophore 1,3-diphenylisobenzofuran have been observed. In one isomer, excitation is delocalized over both halves of the dimer, and in the other, it is localized on one or the other half. For a covalent dimer in solution, such 'excitation isomerism' is extremely rare. The vibrationally relaxed isomers do not interconvert, and their photophysical properties, including singlet fission, differ significantly.

Short-lived isomers in 192Po and 194Po

NASA Astrophysics Data System (ADS)

Andel, B.; Andreyev, A. N.; Antalic, S.; Heßberger, F. P.; Ackermann, D.; Hofmann, S.; Huyse, M.; Kalaninová, Z.; Kindler, B.; Kojouharov, I.; Kuusiniemi, P.; Lommel, B.; Nishio, K.; Page, R. D.; Sulignano, B.; Van Duppen, P.

2016-06-01

Isomeric states in 194Po and 192Po were studied at the velocity filter SHIP. The isotopes were produced in the fusion-evaporation reactions 141Pr(56Fe, p 2 n )194Po and 144Sm(51V, p 2 n )192Po . Several new γ -ray transitions were attributed to the isomers and γ -γ coincidences for both isomers were studied for the first time. The 459-keV transition earlier, tentatively proposed as de-exciting the isomeric level in 194Po, was replaced by a new 248-keV transition, and the spin of this isomer was reassigned from (11-) to (10-). The de-excitation of the (11-) isomeric level in 192Po by the 154-keV transition was confirmed and a parallel de-excitation by a 733-keV (E 3 ) transition to (8+) level of the ground-state band was suggested. Moreover, side feeding to the (4+) level of the ground-state band was proposed. The paper also discusses strengths of transitions de-exciting 11- isomers in neighboring Po and Pb isotopes.

Anti-Stokes resonant x-ray Raman scattering for atom specific and excited state selective dynamics

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

Kunnus, Kristjan; Josefsson, Ida; Rajkovic, Ivan

Here, ultrafast electronic and structural dynamics of matter govern rate and selectivity of chemical reactions, as well as phase transitions and efficient switching in functional materials. Since x-rays determine electronic and structural properties with elemental, chemical, orbital and magnetic selectivity, short pulse x-ray sources have become central enablers of ultrafast science. Despite of these strengths, ultrafast x-rays have been poor at picking up excited state moieties from the unexcited ones. With time-resolved anti-Stokes resonant x-ray Raman scattering (AS-RXRS) performed at the LCLS, and ab initio theory we establish background free excited state selectivity in addition to the elemental, chemical, orbitalmore » and magnetic selectivity of x-rays. This unparalleled selectivity extracts low concentration excited state species along the pathway of photo induced ligand exchange of Fe(CO)5 in ethanol. Conceptually a full theoretical treatment of all accessible insights to excited state dynamics with AS-RXRS with transform-limited x-ray pulses is given—which will be covered experimentally by upcoming transform-limited x-ray sources.« less

Anti-Stokes resonant x-ray Raman scattering for atom specific and excited state selective dynamics

DOE PAGES

Kunnus, Kristjan; Josefsson, Ida; Rajkovic, Ivan; ...

2016-10-07

Here, ultrafast electronic and structural dynamics of matter govern rate and selectivity of chemical reactions, as well as phase transitions and efficient switching in functional materials. Since x-rays determine electronic and structural properties with elemental, chemical, orbital and magnetic selectivity, short pulse x-ray sources have become central enablers of ultrafast science. Despite of these strengths, ultrafast x-rays have been poor at picking up excited state moieties from the unexcited ones. With time-resolved anti-Stokes resonant x-ray Raman scattering (AS-RXRS) performed at the LCLS, and ab initio theory we establish background free excited state selectivity in addition to the elemental, chemical, orbitalmore » and magnetic selectivity of x-rays. This unparalleled selectivity extracts low concentration excited state species along the pathway of photo induced ligand exchange of Fe(CO)5 in ethanol. Conceptually a full theoretical treatment of all accessible insights to excited state dynamics with AS-RXRS with transform-limited x-ray pulses is given—which will be covered experimentally by upcoming transform-limited x-ray sources.« less

Excited state free energy calculations of Cy3 in different environments

NASA Astrophysics Data System (ADS)

Sawangsang, Pilailuk; Buranachai, Chittanon; Punwong, Chutintorn

2015-05-01

Cy3, a cyanine dye, is one of the most widely used dyes in investigating the structure and dynamics of biomolecules by means of fluorescence methods. However, Cy3 fluorescence emission is strongly competed by trans-cis isomerization, whose efficiency is dictated by the isomerization energy barrier and the environment of Cy3. The fluorescence quantum yield of Cy3 is very low when the dye is free in homogeneous solution but it is considerably enhanced in an environment that rigidifies the structure, e.g. when it is attached to a DNA strand. In this work, the barriers for isomerization on the excited state of free Cy3, and Cy3 attached to single- and double-stranded DNA in methanol, are presented. The free energy and subsequently the isomerization barrier calculations are performed using the umbrella sampling technique with the weighted histogram analysis method. The hybrid quantum mechanics/molecular mechanics (QM/MM) approach is employed to provide the potential energy surfaces for the excited state dynamics simulations in umbrella sampling. The semiempirical floating occupation molecular orbital configuration interaction method is used for electronic excited state calculations of the QM region (Cy3). From the free energy calculations, the barrier of Cy3 attached to the single-stranded DNA is highest, in agreement with previously reported experimental results. This is likely due to the stacking interaction between Cy3 and DNA. Such a stacking interaction is likely associated with steric hindrance that prevents the rotation around the conjugated bonds of Cy3. If Cy3 experiences high steric hindrance, it has a higher isomerization barrier and thus the efficiency of fluorescence emission increases.

Real-Time Time-Frequency Two-Dimensional Imaging of Ultrafast Transient Signals in Solid-State Organic Materials

PubMed Central

Takeda, Jun; Ishida, Akihiro; Makishima, Yoshinori; Katayama, Ikufumi

2010-01-01

In this review, we demonstrate a real-time time-frequency two-dimensional (2D) pump-probe imaging spectroscopy implemented on a single shot basis applicable to excited-state dynamics in solid-state organic and biological materials. Using this technique, we could successfully map ultrafast time-frequency 2D transient absorption signals of β-carotene in solid films with wide temporal and spectral ranges having very short accumulation time of 20 ms per unit frame. The results obtained indicate the high potential of this technique as a powerful and unique spectroscopic tool to observe ultrafast excited-state dynamics of organic and biological materials in solid-state, which undergo rapid photodegradation. PMID:22399879

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 expected relaxation within the excited states. Stable, shorter pulses allow finer temporal resolution and more efficient high-harmonic generation. This work therefore concludes by discussing a method for further shortening 25 femtosecond pulses via self-phase modulation, using filamentation in air and subsequent fiber channeling.

Benzil-tethered precipitons for controlling solubility: a round-trip energy-transfer mechanism in the isomerization of extended stilbene analogues.

PubMed

Ams, Mark R; Wilcox, Craig S

2007-04-04

We are investigating photoresponsive molecules called "precipitons" that undergo a solubility change co-incident with isomerization. Isomerization can be induced by light or by catalytic reagents. Previous work demonstrated that covalent attachment of a metal complex, Ru(II)(bpy)3, greatly accelerates photoisomerization and influences the photostationary state. In this paper, we describe precipitons (1,2-biphenylethenes; analogous to stilbenes) that are activated by a covalently attached organic sensitizer (benzil). We find that isomerization of these stilbene analogues is little effected by the presence of benzil in solution but that the intramolecular benzil effect is to increase the rate of isomerization and to significantly change the photostationary state. What is most interesting about these observations is that the precipiton is the primary chromophore in this bichromophoric system (precipiton absorbance is many times greater than benzil absorbance in the 300-400 nm range), yet the neighboring benzil has a significant effect on the rate and the photostationary state. The effect of unattached benzil on the rate was small, about a 24% increase in rate as compared with 4-6-fold changes for an attached benzil. We speculate that the isomerization process occurs by a "round-trip" energy-transfer mechanism. Initial excitation of the precipiton chromophore initiates a sequence that includes (1) formation of the precipiton singlet state, (2) singlet excitation transfer from the precipiton unit to the benzil, (3) benzil-centered intersystem crossing to the localized benzil triplet state, (4) triplet energy transfer from the benzil moiety back to the precipiton, and (5) isomerization.

Infrared-induced conformational isomerization and vibrational relaxation dynamics in melatonin and 5-methoxy-N-acetyl tryptophan methyl amide

NASA Astrophysics Data System (ADS)

Dian, Brian C.; Florio, Gina M.; Clarkson, Jasper R.; Longarte, Asier; Zwier, Timothy S.

2004-05-01

The conformational isomerization dynamics of melatonin and 5-methoxy N-acetyltryptophan methyl amide (5-methoxy NATMA) have been studied using the methods of IR-UV hole-filling spectroscopy and IR-induced population transfer spectroscopy. Using these techniques, single conformers of melatonin were excited via a well-defined NH stretch fundamental with an IR pump laser. This excess energy was used to drive conformational isomerization. By carrying out the infrared excitation early in a supersonic expansion, the excited molecules were re-cooled into their zero-point levels, partially re-filling the hole created in the ground state population of the excited conformer, and creating gains in population of the other conformers. These changes in population were detected using laser-induced fluorescence downstream in the expansion via an UV probe laser. The isomerization quantum yields for melatonin show some conformation specificity but no hint of vibrational mode specificity. In 5-methoxy NATMA, no isomerization was observed out of the single conformational well populated in the expansion in the absence of the infrared excitation. In order to study the dependence of the isomerization on the cooling rate, the experimental arrangement was modified so that faster cooling conditions could be studied. In this arrangement, the pump and probe lasers were overlapped in space in the high density region of the expansion, and the time dependence of the zero-point level populations of the conformers was probed following selective excitation of a single conformation. The analysis needed to extract isomerization quantum yields from the timing scans was developed and applied to the melatonin timing scans. Comparison between the frequency and time domain isomerization quantum yields under identical experimental conditions produced similar results. Under fast cooling conditions, the product quantum yields were shifted from their values under standard conditions. The results for melatonin are compared with those for N-acetyl tryptophan methyl amide.

Non-adiabatic dynamics investigation of the radiationless decay mechanism of trans-urocanic acid in the S{sub 2} state

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

Zhao, Li; University of the Chinese Academy of Sciences, Beijing 100049; Zhou, Pan-Wang, E-mail: pwzhou@dicp.ac.cn, E-mail: gjzhao@dicp.ac.cn

2016-07-28

The trans-urocanic acid, a UV chromophore in the epidermis of human skin, was found to exhibit a wavelength dependent isomerization property. The isomerization quantum yield to cis-urocanic is greatest when being excited to the S{sub 1} state, whereas exciting the molecule to the S{sub 2} state causes almost no isomerization. The comparative photochemical behavior of the trans-urocanic on the S{sub 1} and S{sub 2} states continues to be the subject of intense research effort. This study is concerned with the unique photo-behavior of this interesting molecule on the S{sub 2} state. Combining the on-the-fly surface hopping dynamics simulations and staticmore » electronic structure calculations, three decay channels were observed following excitation to the S{sub 2} state. An overwhelming majority of the molecules decay to the S{sub 1} state through a planar or pucker characterized minimum energy conical intersection (MECI), and then decay to the ground state along a relaxation coordinate driven by a pucker deformation of the ring. A very small fraction of molecules decay to the S{sub 1} state by a MECI characterized by a twisting motion around the CC double bond, which continues to drive the molecule to deactivate to the ground state. The latter channel is related with the photoisomerization process, whereas the former one will only generate the original trans-form products. The present work provides a novel S{sub 2} state decay mechanism of this molecule, which offers useful information to explain the wavelength dependent isomerization behavior.« less

Isomerization Intermediates In Solution Phase Photochemistry Of Stilbenes

NASA Astrophysics Data System (ADS)

Doany, F. E.; Hochstrasser, R. M.; Greene, B. I.

1985-04-01

Picosecond and subpicosecond spectroscopic studies have revealed evidence for an isomerization intermediate between cis and trans in the photoinduced isomerism of both stilbene and biindanyledene ("stiff" stilbene). In stiff stilbene, a transient absorption at 351 nm displays time evolution and viscosity dependence consistent with absorption by a twisted intermediate ("phantom" state) with a lOps lifetime. An analagous bottleneck state with a life-time of 4ps is also consistent with the ground state recovery dynamics of t-stilbene following excitation of c-stilbene when monitored with 0.1ps resolution.

Ultrafast Spin Crossover in [FeII (bpy)3 ]2+ : Revealing Two Competing Mechanisms by Extreme Ultraviolet Photoemission Spectroscopy.

PubMed

Moguilevski, Alexandre; Wilke, Martin; Grell, Gilbert; Bokarev, Sergey I; Aziz, Saadullah G; Engel, Nicholas; Raheem, Azhr A; Kühn, Oliver; Kiyan, Igor Yu; Aziz, Emad F

2017-03-03

Photoinduced spin-flip in Fe II complexes is an ultrafast phenomenon that has the potential to become an alternative to conventional processing and magnetic storage of information. Following the initial excitation by visible light into the singlet metal-to-ligand charge-transfer state, the electronic transition to the high-spin quintet state may undergo different pathways. Here we apply ultrafast XUV (extreme ultraviolet) photoemission spectroscopy to track the low-to-high spin dynamics in the aqueous iron tris-bipyridine complex, [Fe(bpy) 3 ] 2+ , by monitoring the transient electron density distribution among excited states with femtosecond time resolution. Aided by first-principles calculations, this approach enables us to reveal unambiguously both the sequential and direct de-excitation pathways from singlet to quintet state, with a branching ratio of 4.5:1. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

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.

Vibronic coupling in the excited-states of carotenoids

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

Miki, Takeshi; Buckup, Tiago; Krause, Marie S.

2016-01-01

The ultrafast femtochemistry of carotenoids is governed by the interaction between electronic excited states, which has been explained by the relaxation dynamics within a few hundred femtoseconds from the lowest optically allowed excited state S 2to the optically dark state S 1.

Vibronic coupling in the excited-states of carotenoids

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

Miki, Takeshi; Buckup, Tiago; Krause, Marie S.

The ultrafast femtochemistry of carotenoids is governed by the interaction between electronic excited states, which has been explained by the relaxation dynamics within a few hundred femtoseconds from the lowest optically allowed excited state S 2to the optically dark state S 1.

Polarization-controlled optimal scatter suppression in transient absorption spectroscopy

PubMed Central

Malý, Pavel; Ravensbergen, Janneke; Kennis, John T. M.; van Grondelle, Rienk; Croce, Roberta; Mančal, Tomáš; van Oort, Bart

2017-01-01

Ultrafast transient absorption spectroscopy is a powerful technique to study fast photo-induced processes, such as electron, proton and energy transfer, isomerization and molecular dynamics, in a diverse range of samples, including solid state materials and proteins. Many such experiments suffer from signal distortion by scattered excitation light, in particular close to the excitation (pump) frequency. Scattered light can be effectively suppressed by a polarizer oriented perpendicular to the excitation polarization and positioned behind the sample in the optical path of the probe beam. However, this introduces anisotropic polarization contributions into the recorded signal. We present an approach based on setting specific polarizations of the pump and probe pulses, combined with a polarizer behind the sample. Together, this controls the signal-to-scatter ratio (SSR), while maintaining isotropic signal. We present SSR for the full range of polarizations and analytically derive the optimal configuration at angles of 40.5° between probe and pump and of 66.9° between polarizer and pump polarizations. This improves SSR by (or compared to polarizer parallel to probe). The calculations are validated by transient absorption experiments on the common fluorescent dye Rhodamine B. This approach provides a simple method to considerably improve the SSR in transient absorption spectroscopy. PMID:28262765

Communication: An accurate calculation of the S{sub 1} C{sub 2}H{sub 2} cis-trans isomerization barrier height

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

Baraban, Joshua H.; Matthews, Devin A.; Stanton, John F.

2016-03-21

A high level ab initio calculation of the cis-trans isomerization barrier height in the first excited singlet electronic state of acetylene is found to agree very well with a recent experimental determination.

Communication: An accurate calculation of the S 1 C 2H 2 cis-trans isomerization barrier height

DOE PAGES

Baraban, Joshua H.; Matthews, Devin A.; Stanton, John F.

2016-03-16

In this study, a high level ab initio calculation of the cis-trans isomerization barrier height in the first excited singlet electronic state of acetylene is found to agree very well with a recent experimental determination.

Half-life measurements of isomeric states populated in projectile fragmentation

NASA Astrophysics Data System (ADS)

Bowry, M.; Podolyák, Zs.; Kurcewicz, J.; Pietri, S.; Bunce, M.; Regan, P. H.; Farinon, F.; Geissel, H.; Nociforo, C.; Prochazka, A.; Weick, H.; Allegro, P.; Benlliure, J.; Benzoni, G.; Boutachkov, P.; Gerl, J.; Gorska, M.; Gottardo, A.; Gregor, N.; Janik, R.; Knöbel, R.; Kojouharov, I.; Kubo, T.; Litvinov, Y. A.; Merchan, E.; Mukha, I.; Naqvi, F.; Pfeiffer, B.; Pfützner, M.; Plaß, W.; Pomorski, M.; Riese, B.; Ricciardi, M. V.; Schmidt, K.-H.; Schaffner, H.; Kurz, N.; Denis Bacelar, A. M.; Bruce, A. M.; Farrelly, G. F.; Alkhomashi, N.; Al-Dahan, N.; Scheidenberger, C.; Sitar, B.; Spiller, P.; Stadlmann, J.; Strmen, P.; Sun, B.; Takeda, H.; Tanihata, I.; Terashima, S.; Valiente Dobon, J. J.; Winfield, J. S.; Wollersheim, H.-J.; Woods, P. J.

2012-10-01

The half-lives of excited isomeric states observed in 195Au, 201Tl and 215Rn are reported for the first time. Delayed γ-rays were correlated with nuclei produced in the projectile fragmentation of relativistic 238U ions, unambiguously identified in terms of their atomic number (Z) and mass-to-charge ratio (A/Q) after traversing an in-flight separator. The observation of a long-lived isomeric state in 195Au with t1/2 = 16-4+8 μs is presented. Two shorter-lived isomeric states were detected in 201Tl and 215Rn with t1/2 = 95-21+39 and 57-12+21 ns respectively. In total 24 isomeric states were identified in different nuclei from Pt to Rn (A ˜ 200) during the current study, the majority of which were previously reported. The wealth of spectroscopic data provides the opportunity to determine the isomeric ratios over a wide range of Z, A and angular momentum (I ħ) of the reaction products. In particular, high-spin states with I ≳ 18 ħ provide a robust test of theoretical models of fragmentation.

Resolving Nonadiabatic Dynamics of Hydrated Electrons Using Ultrafast Photoemission Anisotropy.

PubMed

Karashima, Shutaro; Yamamoto, Yo-Ichi; Suzuki, Toshinori

2016-04-01

We have studied ultrafast nonadiabatic dynamics of excess electrons trapped in the band gap of liquid water using time- and angle-resolved photoemission spectroscopy. Anisotropic photoemission from the first excited state was discovered, which enabled unambiguous identification of nonadiabatic transition to the ground state in 60 fs in H_{2}O and 100 fs in D_{2}O. The photoelectron kinetic energy distribution exhibited a rapid spectral shift in ca. 20 fs, which is ascribed to the librational response of a hydration shell to electronic excitation. Photoemission anisotropy indicates that the electron orbital in the excited state is depolarized in less than 40 fs.

Ultrafast photodissociation dynamics of 1,4-diiodobenzene

NASA Astrophysics Data System (ADS)

Stankus, Brian; Zotev, Nikola; Rogers, David M.; Gao, Yan; Odate, Asami; Kirrander, Adam; Weber, Peter M.

2018-05-01

The photodissociation dynamics of 1,4-diiodobenzene is investigated using ultrafast time-resolved photoelectron spectroscopy. Following excitation by laser pulses at 271 nm, the excited-state dynamics is probed by resonance-enhanced multiphoton ionization with 405 nm probe pulses. A progression of Rydberg states, which come into resonance sequentially, provide a fingerprint of the dissociation dynamics of the molecule. The initial excitation decays with a lifetime of 33 ± 4 fs, in good agreement with a previous study. The spectrum is interpreted by reference to ab initio calculations at the CASPT2(18,14) level, including spin-orbit coupling. We propose that both the 5B1 and 6B1 states are excited initially, and based on the calculations, we identify diabatic spin-orbit coupled states corresponding to the main dissociation pathways.

Model studies on the photosensitized isomerization of bixin.

PubMed

Montenegro, Mariana A; Rios, Alessandro de O; Mercadante, Adriana Z; Nazareno, Mónica A; Borsarelli, Claudio D

2004-01-28

The photosensitized isomerization reaction of the natural cis carotenoid bixin (methyl hydrogen 9'-cis-6, 6'-diapocarotene-6, 6'-dioate) with rose bengal or methylene blue as the sensitizer in acetonitrile/methanol (1:1) solution was studied using UV-vis spectroscopy, high-performance liquid chromatography (HPLC), and time-resolved spectroscopic techniques, such as laser-flash photolysis and singlet oxygen phosphorescence detection. In both N(2)- and air-saturated solutions, the main product formed was all-trans-bixin. The observed isomerization rate constants, k(obs), decreased in the presence of air or with increase in the bixin concentration, suggesting the participation of the excited triplet state of bixin, (3)Bix, as precursor of the cis--> trans process. On the other hand, bixin solutions in the absence of sensitizer and/or light did not degrade, indicating that the ground state of bixin is stable to thermal isomerization at room temperature. Time-resolved spectroscopic experiments confirmed the formation of the excited triplet state of bixin and its deactivation by ground state bixin and molecular oxygen quenching processes. The primary isomerization products only degraded in the presence of air and under prolonged illumination conditions, probably due to the formation of oxidation products by reaction with singlet molecular oxygen. An energy-transfer mechanism was used to explain the observed results for the bixin transformations, and the consequences for food color are discussed.

Excited-State Dynamics of Biological Molecules in Solution: Photoinduced Charge Transfer in Oxidatively Damaged DNA and Deactivation of Violacein in Viscous Solvents

NASA Astrophysics Data System (ADS)

Beckstead, Ashley Ann

UV radiation from the sun is strongly absorbed by DNA, and the resulting electronic excited states can lead to the formation of mutagenic photoproducts. Decades of research have brought to light the excited-state dynamics of single RNA and DNA nucleobases, but questions remain about the nature of excited states accessed in DNA strands. In this thesis, I present ultrafast spectroscopic observations of photoinduced electron transfer from the oxidatively damaged bases, 8-oxo-7,8-dihydro-2'-deoxyguanosine, 5-hydroxy-2'-deoxycytidine and 5-hydroxy-2'-deoxyuridine, to adenine in three dinucleotides. The results reveal that charge transfer states are formed on a timescale faster than our instrumental resolution (<0.5 ps), and back electron transfer efficiently returns the excited-state population to the ground state on timescales from tens to hundreds of ps. In addition to recent spectroscopic observations of charge transfer state species in DNA by other groups, our results have augmented understanding of the long-lived transient signals observed in DNA strands. The observation of photoinduced electron transfer in these oxidatively damaged nucleobases also supports a recent proposal regarding the role of oxidative products in pre-RNA catalysis. I discuss these observations in the contexts of fundamental DNA excited-state dynamics and prebiotic chemical evolution. In this thesis, I also present the first ultrafast spectroscopic investigation of violacein, a pigment isolated from Antarctic bacteria. Despite claims for the photoprotective role of this pigment, there has never been a spectroscopic analysis of excited-state deactivation in violacein. Emission spectra, fluorescence quantum yields and excited-state lifetimes of violacein in various solvents were measured for the first time. Both the fluorescence quantum yield and excited-state lifetime of violacein increase in increasingly viscous solvents, suggesting a large-scale motion mediates excited-state deactivation. I compare these results to similar observations of viscosity-dependent excited-state decay rates in other molecules. I also consider the relevance of violacein's excited-state properties to the hypothesized sunscreening role of violacein. Overall, the studies presented in this dissertation illustrate how ultrafast spectroscopic techniques can be used to unravel complex biomolecular excited-state dynamics in solution.

Photochemistry of fac-[Re(CO)3(dcbH2)( trans-stpy)]+: New Insights on the Isomerization Mechanism of Coordinated Stilbene-like Ligands.

PubMed

Faustino, Leandro A; Hora Machado, Antonio Eduardo; Patrocinio, Antonio Otavio T

2018-03-05

In this work, a novel complex fac-[Re(CO) 3 (dcbH 2 )( trans-stpy)] + , (dcbH 2 = 4,4'-dicarboxylic acid-2,2'-bipyridine; trans-stpy = trans-4-styrylpyridine) was synthesized and characterized toward its spectroscopic, photochemical, and photophysical properties. The experimental data provide new insights on the mechanism of photochemical trans-to- cis isomerization of the stilbene-like ligand coordinated to Re(I) polypyridyl complexes. The new complex exhibits an unusual and strong dependence of the isomerization quantum yield (Φ t →c ) on the irradiation wavelength. Φ t →c was 0.81 ± 0.08 for irradiation at 365 nm and continuously decreased as the irradiation wavelength is shifted to the visible. At 405 nm irradiation Φ t →c is almost 2 orders of magnitude lower (0.010 ± 0.005) than that observed at 365 nm excitation. This behavior can be explained by the low-lying triplet metal-to-ligand charge-transfer excited state ( 3 MLCT) that hinders the triplet photoreaction mechanism under visible light absorption. Under UV irradiation, direct population of styrylpyridine-centered excited state ( 1 IL) leads to the occurrence of the photoisomerization via a singlet mechanism. Further experiments were performed with the complex immobilized on the surface of TiO 2 and Al 2 O 3 films. The nonoccurrence of isomerization at the oxide surfaces even under UV excitation evidences the role of energy gap between the 1 IL/ 1 MLCT states on the photochemical/photophysical processes. The results establish important relationships between the molecular structure and the photoelectrochemical behavior, which can further contribute to the development of solid-state molecular switches based on Re(I) polypyridyl complexes.

Photoionization and trans-to-cis isomerization of β-cyclodextrin-encapsulated azobenzene induced by two-color two-laser-pulse excitation.

PubMed

Takeshita, Tatsuya; Hara, Michihiro

2018-03-15

Azobenzene (1) and the complex resulting from the incorporation of 1 with cyclodextrin (1/CD) are attractive for light-driven applications such as micromachining and chemical biology tools. The highly sensitive photoresponse of 1 is crucial for light-driven applications containing both 1 and 1/CD to reach their full potential. In this study, we investigated the photoionization and trans-to-cis isomerization of 1/CD induced by one- and two-color two-laser pulse excitation. Photoionization of 1/CD, which was induced by stepwise two-photon absorption, was observed using laser pulse excitation at 266nm. Additionally, simultaneous irradiation with 266 and 532nm laser pulses increased the trans-to-cis isomerization yield (Υ t→c ) by 27%. It was concluded that the increase in Υ t→c was caused by the occurrence of trans-to-cis isomerization in the higher-energy singlet state (S n ), which was reached by S 1 →S n transition induced by laser pulse excitation at 532nm. The results of this study are potentially applicable in light-driven applications such as micromachining and chemical biology tools. Copyright © 2018 Elsevier B.V. All rights reserved.

Photoinduced electron-transfer in perylenediimide triphenylamine-based dendrimers: single photon timing and femtosecond transient absorption spectroscopy.

PubMed

Fron, Eduard; Pilot, Roberto; Schweitzer, Gerd; Qu, Jianqiang; Herrmann, Andreas; Müllen, Klaus; Hofkens, Johan; Van der Auweraer, Mark; De Schryver, Frans C

2008-05-01

The excited state dynamics of two generations perylenediimide chromophores substituted in the bay area with dendritic branches bearing triphenylamine units as well as those of the respective reference compounds are investigated. Using single photon timing and multi-pulse femtosecond transient absorption experiments a direct proof of a reversible charge transfer occurring from the peripheral triphenylamine to the electron acceptor perylenediimide core is revealed. Femtosecond pump-dump-probe experiments provide evidence for the ground state dynamics by populating excited vibronic levels. It is found by the means of both techniques that the rotational isomerization of the dendritic branches occurs on a time scale that ranges up to 1 ns. This time scale of the isomerization depends on the size of the dendritic arms and is similar both in the ground and excited state.

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 from different origins and are important for assigning, analyzing, and comparing features in thermal and ultrafast vibrational spectroscopy of hydrogen-bonded complexes.

Theoretical study on ultrafast intersystem crossing of chromium(III) acetylacetonate

NASA Astrophysics Data System (ADS)

Ando, Hideo; Iuchi, Satoru; Sato, Hirofumi

2012-05-01

In the relaxation process from the 4T2g state of chromium(III) acetylacetonate, CrIII(acac)3, ultrafast intersystem crossing (ISC) competes with vibrational relaxation (VR). This contradicts the conventional cascade model, where ISC rates are slower than VR ones. We hence investigate the relaxation process with quantum chemical calculations and excited-state wavepacket simulations to obtain clues about the origins of the ultrafast ISC. It is found that a potential energy curve of the 4T2g state crosses those of the 2T1g states near the Franck-Condon region and their spin-orbit couplings are strong. Consequently, ultrafast ISC between these states is observed in the wavepacket simulation.

Control of retinal isomerization in bacteriorhodopsin in the high-intensity regime

PubMed Central

Florean, Andrei C.; Cardoza, David; White, James L.; Lanyi, J. K.; Sension, Roseanne J.; Bucksbaum, Philip H.

2009-01-01

A learning algorithm was used to manipulate optical pulse shapes and optimize retinal isomerization in bacteriorhodopsin, for excitation levels up to 1.8 × 1016 photons per square centimeter. Below 1/3 the maximum excitation level, the yield was not sensitive to pulse shape. Above this level the learning algorithm found that a Fourier-transform-limited (TL) pulse maximized the 13-cis population. For this optimal pulse the yield increases linearly with intensity well beyond the saturation of the first excited state. To understand these results we performed systematic searches varying the chirp and energy of the pump pulses while monitoring the isomerization yield. The results are interpreted including the influence of 1-photon and multiphoton transitions. The population dynamics in each intermediate conformation and the final branching ratio between the all-trans and 13-cis isomers are modified by changes in the pulse energy and duration. PMID:19564608

Ultrafast Dynamics of 1,3-Cyclohexadiene in Highly Excited States

DOE PAGES

Bühler, Christine C.; Minitti, Michael P.; Deb, Sanghamitra; ...

2011-01-01

The ultrafast dynamics of 1,3-cyclohexadiene has been investigated via structurally sensitive Rydberg electron binding energies and shown to differ upon excitation to the 1B state and the 3p Rydberg state. Excitation of the molecule with 4.63 eV photons into the ultrashort-lived 1B state yields the well-known ring opening to 1,3,5-hexatriene, while a 5.99 eV photon lifts the molecule directly into the 3p-Rydberg state. Excitation to 3p does not induce ring opening. In both experiments, time-dependent shifts of the Rydberg electron binding energy reflect the structural dynamics of the molecular core. Structural distortions associated with 3p-excitation cause a dynamical shift in the -more » and -binding energies by 10 and 26 meV/ps, respectively, whereas after excitation into 1B, more severe structural transformations along the ring-opening coordinate produce shifts at a rate of 40 to 60 meV/ps. The experiment validates photoionization-photoelectron spectroscopy via Rydberg states as a powerful technique to observe structural dynamics of polyatomic molecules.« less

Ultrafast Photodetection in the Quantum Wells of Single AlGaAs/GaAs-Based Nanowires.

PubMed

Erhard, N; Zenger, S; Morkötter, S; Rudolph, D; Weiss, M; Krenner, H J; Karl, H; Abstreiter, G; Finley, J J; Koblmüller, G; Holleitner, A W

2015-10-14

We investigate the ultrafast optoelectronic properties of single Al0.3Ga0.7As/GaAs core-shell nanowires. The nanowires contain GaAs-based quantum wells. For a resonant excitation of the quantum wells, we find a picosecond photocurrent which is consistent with an ultrafast lateral expansion of the photogenerated charge carriers. This Dember-effect does not occur for an excitation of the GaAs-based core of the nanowires. Instead, the core exhibits an ultrafast displacement current and a photothermoelectric current at the metal Schottky contacts. Our results uncover the optoelectronic dynamics in semiconductor core-shell nanowires comprising quantum wells, and they demonstrate the possibility to use the low-dimensional quantum well states therein for ultrafast photoswitches and photodetectors.

Ultrafast X-Ray Spectroscopy of Conical Intersections

NASA Astrophysics Data System (ADS)

Neville, Simon P.; Chergui, Majed; Stolow, Albert; Schuurman, Michael S.

2018-06-01

Ongoing developments in ultrafast x-ray sources offer powerful new means of probing the complex nonadiabatically coupled structural and electronic dynamics of photoexcited molecules. These non-Born-Oppenheimer effects are governed by general electronic degeneracies termed conical intersections, which play a key role, analogous to that of a transition state, in the electronic-nuclear dynamics of excited molecules. Using high-level ab initio quantum dynamics simulations, we studied time-resolved x-ray absorption (TRXAS) and photoelectron spectroscopy (TRXPS) of the prototypical unsaturated organic chromophore, ethylene, following excitation to its S2(π π*) state. The TRXAS, in particular, is highly sensitive to all aspects of the ensuing dynamics. These x-ray spectroscopies provide a clear signature of the wave packet dynamics near conical intersections, related to charge localization effects driven by the nuclear dynamics. Given the ubiquity of charge localization in excited state dynamics, we believe that ultrafast x-ray spectroscopies offer a unique and powerful route to the direct observation of dynamics around conical intersections.

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

Carotenoids as electron or excited-state energy donors in artificial photosynthesis: an ultrafast investigation of a carotenoporphyrin and a carotenofullerene dyad.

PubMed

Pillai, Smitha; Ravensbergen, Janneke; Antoniuk-Pablant, Antaeres; Sherman, Benjamin D; van Grondelle, Rienk; Frese, Raoul N; Moore, Thomas A; Gust, Devens; Moore, Ana L; Kennis, John T M

2013-04-07

Photophysical investigations of molecular donor-acceptor systems have helped elucidate many details of natural photosynthesis and revealed design principles for artificial photosynthetic systems. To obtain insights into the factors that govern the partition between excited-state energy transfer (EET) and electron transfer (ET) processes among carotenoids and tetrapyrroles and fullerenes, we have designed artificial photosynthetic dyads that are thermodynamically poised to favor ET over EET processes. The dyads were studied using transient absorption spectroscopy with ∼100 femtosecond time resolution. For dyad , a carotenoporphyrin, excitation to the carotenoid S2 state induces ultrafast ET, competing with internal conversion (IC) to the carotenoid S1 state. In addition, the carotenoid S1 state gives rise to ET. In contrast with biological photosynthesis and many artificial photosynthetic systems, no EET at all was detected for this dyad upon carotenoid S2 excitation. Recombination of the charge separated state takes place in hundreds of picoseconds and yields a triplet state, which is interpreted as a triplet delocalized between the porphyrin and carotenoid moieties. In dyad , a carotenofullerene, excitation of the carotenoid in the S2 band results in internal conversion to the S1 state, ET and probably EET to fullerene on ultrafast timescales. From the carotenoid S1 state EET to fullerene occurs. Subsequently, the excited-state fullerene gives rise to ET from the carotenoid to the fullerene. Again, the charge separated state recombines in hundreds of picoseconds. The results illustrate that for a given rate of EET, the ratio of ET to EET can be controlled by adjusting the driving force for electron transfer.

Optical properties of transiently-excited semiconductor hyperbolic metamaterials

DOE PAGES

Campione, Salvatore; Luk, Ting S.; Liu, Sheng; ...

2015-10-02

Ultrafast optical excitation of photocarriers has the potential to transform undoped semiconductor superlattices into semiconductor hyperbolic metamaterials (SHMs). In this paper, we investigate the optical properties associated with such ultrafast topological transitions. We first show reflectance, transmittance, and absorption under TE and TM plane wave incidence. In the unpumped state, the superlattice exhibits a frequency region with high reflectance (>80%) and a region with low reflectance (<1%) for both TE and TM polarizations over a wide range of incidence angles. In contrast, in the photopumped state, the reflectance for both frequencies and polarizations is very low (<1%) for a similarmore » range of angles. Interestingly, this system can function as an all-optical reflection switch on ultrafast timescales. Furthermore, for TM incidence and close to the epsilon-near-zero point of the longitudinal permittivity, directional perfect absorption on ultrafast timescales may also be achieved. Lastly, we discuss the onset of negative refraction in the photopumped state.« less

Low-lying isomeric states in Ga80 from the β- decay of Zn80

NASA Astrophysics Data System (ADS)

Licǎ, R.; Mǎrginean, N.; GhiÅ£ǎ, D. G.; Mach, H.; Fraile, L. M.; Simpson, G. S.; Aprahamian, A.; Bernards, C.; Briz, J. A.; Bucher, B.; Chiara, C. J.; Dlouhý, Z.; Gheorghe, I.; Hoff, P.; Jolie, J.; Köster, U.; Kurcewicz, W.; Mǎrginean, R.; Olaizola, B.; Paziy, V.; Régis, J. M.; Rudigier, M.; Sava, T.; Stǎnoiu, M.; Stroe, L.; Walters, W. B.

2014-07-01

A new level scheme of Ga80 has been determined. This nucleus was populated following the β- decay of Zn80 at ISOLDE, CERN. The proposed level scheme is significantly different compared to the previously reported one and contains 26 levels up to 3.4 MeV in excitation energy. The present study establishes that the previously identified 1.9-s β--decaying 6- isomer is the ground state of Ga80 and the 1.3-s β--decaying 3- isomer lies at an excitation energy of 22.4 keV. A new isomeric level was identified at 707.8 keV and its half-life was measured to be 18.3(5) ns, allowing the 685.4-keV transition de-exciting this state to be assigned an M2 multipolarity. The newly measured spectroscopic observables are compared with shell-model calculations using the jj44bpn and JUN45 interactions.

Ultrafast Light-Driven Substrate Expulsion from the Active Site of a Photoswitchable Catalyst.

PubMed

Pescher, Manuel D; van Wilderen, Luuk J G W; Grützner, Susanne; Slavov, Chavdar; Wachtveitl, Josef; Hecht, Stefan; Bredenbeck, Jens

2017-09-25

The photoswitchable piperidine general base catalyst is a prototype structure for light control of catalysis. Its azobenzene moiety moves sterically shielding groups to either protect or expose the active site, thereby changing the basicity and hydrogen-bonding affinity of the compound. The reversible switching dynamics of the catalyst is probed in the infrared spectral range by monitoring hydrogen bond (HB) formation between its active site and methanol (MeOH) as HB donor. Steady-state infrared (IR) and ultrafast IR and UV/Vis spectroscopies are used to uncover ultrafast expulsion of MeOH from the active site within a few picoseconds. Thus, the force generated by the azobenzene moiety even in the final phase of its isomerization is sufficient to break a strong HB within 3 ps and to shut down access to the active site. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Ultrafast electronic and vibrational dynamics of stabilized A state mutants of the green fluorescent protein (GFP): Snipping the proton wire

NASA Astrophysics Data System (ADS)

Stoner-Ma, Deborah; Jaye, Andrew A.; Ronayne, Kate L.; Nappa, Jérôme; Tonge, Peter J.; Meech, Stephen R.

2008-06-01

Two blue absorbing and emitting mutants (S65G/T203V/E222Q and S65T at pH 5.5) of the green fluorescent protein (GFP) have been investigated through ultrafast time resolved infra-red (TRIR) and fluorescence spectroscopy. In these mutants, in which the excited state proton transfer reaction observed in wild-type GFP has been blocked, the photophysics are dominated by the neutral A state. It was found that the A∗ excited state lifetime is short, indicating that it is relatively less stabilised in the protein matrix than the anionic form. However, the lifetime of the A state can be increased through modifications to the protein structure. The TRIR spectra show that a large shifts in protein vibrational modes on excitation of the A state occurs in both these GFP mutants. This is ascribed to a change in H-bonding interactions between the protein matrix and the excited state.

Excited state dynamics & optical control of molecular motors

NASA Astrophysics Data System (ADS)

Wiley, Ted; Sension, Roseanne

2014-03-01

Chiral overcrowded alkenes are likely candidates for light driven rotary molecular motors. At their core, these molecular motors are based on the chromophore stilbene, undergoing ultrafast cis/trans photoisomerization about their central double bond. Unlike stilbene, the photochemistry of molecular motors proceeds in one direction only. This unidirectional rotation is a result of helicity in the molecule induced by steric hindrance. However, the steric hindrance which ensures unidirectional excited state rotation, has the unfortunate consequence of producing large ground state barriers which dramatically decrease the overall rate of rotation. These molecular scale ultrafast motors have only recently been studied by ultrafast spectroscopy. Our lab has studied the photochemistry and photophysics of a ``first generation'' molecular motor with UV-visible transient absorption spectroscopy. We hope to use optical pulse shaping to enhance the efficiency and turnover rate of these molecular motors.

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.

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.

Excited-state structure and isomerization dynamics of the retinal chromophore in rhodopsin from resonance Raman intensities.

PubMed Central

Loppnow, G R; Mathies, R A

1988-01-01

Resonance Raman excitation profiles have been measured for the bovine visual pigment rhodopsin using excitation wavelengths ranging from 457.9 to 647.1 nm. A complete Franck-Condon analysis of the absorption spectrum and resonance Raman excitation profiles has been performed using an excited-state, time-dependent wavepacket propagation technique. This has enabled us to determine the change in geometry upon electronic excitation of rhodopsin's 11-cis-retinal protonated Schiff base chromophore along 25 normal coordinates. Intense low-frequency Raman lines are observed at 98, 135, 249, 336, and 461 cm-1 whose intensities provide quantitative, mode-specific information about the excited-state torsional deformations that lead to isomerization. The dominant contribution to the width of the absorption band in rhodopsin results from Franck-Condon progressions in the 1,549 cm-1 ethylenic normal mode. The lack of vibronic structure in the absorption spectrum is shown to be caused by extensive progressions in low-frequency torsional modes and a large homogeneous linewidth (170 cm-1 half-width) together with thermal population of low-frequency modes and inhomogeneous site distribution effects. The resonance Raman cross-sections of rhodopsin are unusually weak because the excited-state wavepacket moves rapidly (approximately 35 fs) and permanently away from the Franck-Condon geometry along skeletal stretching and torsional coordinates. PMID:3416032

Photoinduced molecular chirality probed by ultrafast resonant X-ray spectroscopy

DOE PAGES

Rouxel, Jérémy R.; Kowalewski, Markus; Mukamel, Shaul

2017-07-01

Recently developed circularly polarized X-ray light sources can probe the ultrafast chiral electronic and nuclear dynamics through spatially localized resonant core transitions. Here, we present simulations of time-resolved circular dichroism signals given by the difference of left and right circularly polarized X-ray probe transmission following an excitation by a circularly polarized optical pump with the variable time delay. Application is made to formamide which is achiral in the ground state and assumes two chiral geometries upon optical excitation to the first valence excited state. Probes resonant with various K-edges (C, N, and O) provide different local windows onto the paritymore » breaking geometry change thus revealing the enantiomer asymmetry.« less

Photoinduced molecular chirality probed by ultrafast resonant X-ray spectroscopy

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

Rouxel, Jérémy R.; Kowalewski, Markus; Mukamel, Shaul

Recently developed circularly polarized X-ray light sources can probe the ultrafast chiral electronic and nuclear dynamics through spatially localized resonant core transitions. Here, we present simulations of time-resolved circular dichroism signals given by the difference of left and right circularly polarized X-ray probe transmission following an excitation by a circularly polarized optical pump with the variable time delay. Application is made to formamide which is achiral in the ground state and assumes two chiral geometries upon optical excitation to the first valence excited state. Probes resonant with various K-edges (C, N, and O) provide different local windows onto the paritymore » breaking geometry change thus revealing the enantiomer asymmetry.« less

Nonadiabatic nuclear dynamics of the ammonia cation studied by surface hopping classical trajectory calculations

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

Belyaev, Andrey K., E-mail: belyaev@herzen.spb.ru; Domcke, Wolfgang, E-mail: wolfgang.domcke@ch.tum.de; Lasser, Caroline, E-mail: classer@ma.tum.de

The Landau–Zener (LZ) type classical-trajectory surface-hopping algorithm is applied to the nonadiabatic nuclear dynamics of the ammonia cation after photoionization of the ground-state neutral molecule to the excited states of the cation. The algorithm employs a recently proposed formula for nonadiabatic LZ transition probabilities derived from the adiabatic potential energy surfaces. The evolution of the populations of the ground state and the two lowest excited adiabatic states is calculated up to 200 fs. The results agree well with quantum simulations available for the first 100 fs based on the same potential energy surfaces. Three different time scales are detected formore » the nuclear dynamics: Ultrafast Jahn–Teller dynamics between the excited states on a 5 fs time scale; fast transitions between the excited state and the ground state within a time scale of 20 fs; and relatively slow partial conversion of a first-excited-state population to the ground state within a time scale of 100 fs. Beyond 100 fs, the adiabatic electronic populations are nearly constant due to a dynamic equilibrium between the three states. The ultrafast nonradiative decay of the excited-state populations provides a qualitative explanation of the experimental evidence that the ammonia cation is nonfluorescent.« less

Existence of a new emitting singlet state of proflavine: femtosecond dynamics of the excited state processes and quantum chemical studies in different solvents.

PubMed

Kumar, Karuppannan Senthil; Selvaraju, Chellappan; Malar, Ezekiel Joy Padma; Natarajan, Paramasivam

2012-01-12

Proflavine (3,6-diaminoacridine) shows fluorescence emission with lifetime, 4.6 ± 0.2 ns, in all the solvents irrespective of the solvent polarity. To understand this unusual photophysical property, investigations were carried out using steady state and time-resolved fluorescence spectroscopy in the pico- and femtosecond time domain. Molecular geometries in the ground and low-lying excited states of proflavine were examined by complete structural optimization using ab initio quantum chemical computations at HF/6-311++G** and CIS/6-311++G** levels. Time dependent density functional theory (TDDFT) calculations were performed to study the excitation energies in the low-lying excited states. The steady state absorption and emission spectral details of proflavine are found to be influenced by solvents. The femtosecond fluorescence decay of the proflavine in all the solvents follows triexponential function with two ultrafast decay components (τ(1) and τ(2)) in addition to the nanosecond component. The ultrafast decay component, τ(1), is attributed to the solvation dynamics of the particular solvent used. The second ultrafast decay component, τ(2), is found to vary from 50 to 215 ps depending upon the solvent. The amplitudes of the ultrafast decay components vary with the wavelength and show time dependent spectral shift in the emission maximum. The observation is interpreted that the time dependent spectral shift is not only due to solvation dynamics but also due to the existence of more than one emitting state of proflavine in the solvent used. Time resolved area normalized emission spectral (TRANES) analysis shows an isoemissive point, indicating the presence of two emitting states in homogeneous solution. Detailed femtosecond fluorescence decay analysis allows us to isolate the two independent emitting components of the close lying singlet states. The CIS and TDDFT calculations also support the existence of the close lying emitting states. The near constant lifetime observed for proflavine in different solvents is suggested to be due to the similar dipole moments of the ground and the evolved emitting singlet state of the dye from the Franck-Condon excited state.

Excited-state dynamics of pentacene derivatives with stable radical substituents.

PubMed

Ito, Akitaka; Shimizu, Akihiro; Kishida, Noriaki; Kawanaka, Yusuke; Kosumi, Daisuke; Hashimoto, Hideki; Teki, Yoshio

2014-06-23

The excited-state dynamics of pentacene derivatives with stable radical substituents were evaluated in detail through transient absorption measurements. The derivatives showed ultrafast formation of triplet excited state(s) in the pentacene moiety from a photoexcited singlet state through the contributions of enhanced intersystem crossing and singlet fission. Detailed kinetic analyses for the transient absorption data were conducted to quantify the excited-state characteristics of the derivatives. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

New insights into mechanistic photoisomerization of ethylene-bridged azobenzene from ab initio multiple spawning simulation.

PubMed

Liu, Lihong; Wang, Yating; Fang, Qiu

2017-02-14

Ethylene-bridged azobenzene (br-AB) has aroused broad interests due to its unique photoswitching properties. Numerous dynamical simulations have been performed for the br-AB photoisomerization, which focused mainly on the conformational effect and the funnel role of minimum-energy conical intersection (MECI) on the mechanism. In the present work, we use the "full quantum" ab initio multiple spawning method to simulate the br-AB photoisomerization, which provides new insights into the mechanism. Upon irradiation of br-AB to the first excited singlet state (S 1 ), most of the excess energies are trapped in the azo-moiety. Since the intramolecular vibrational energy redistribution is slower than the S 1 relaxation processes, the nonadiabatic transition from S 1 to the ground state (S 0 ) occurs in the vicinity of high-energy crossing seam and even the largest probabilities of the S 1 → S 0 transition are not distributed in the MECI regions. Once decaying to the S 0 state through the high-energy region, the subsequent isomerization and re-formation of the initial isomer are ultrafast processes in the S 0 state. It is the nonergodic behavior of the S 1 and S 0 dynamics that is mainly responsible for the unique photoswitching properties of the ethylene-bridged azobenzene, which will be discussed in detail.

A VUV detection system for the direct photonic identification of the first excited isomeric state of 229Th

NASA Astrophysics Data System (ADS)

Seiferle, Benedict; von der Wense, Lars; Laatiaoui, Mustapha; Thirolf, Peter G.

2016-03-01

With an expected energy of 7.6(5) eV, 229Th possesses the lowest excited nuclear state in the landscape of all presently known nuclei. The energy corresponds to a wavelength of about 160 nm and would conceptually allow for an optical laser excitation of a nuclear transition. We report on a VUV optical detection system that was designed for the direct detection of the isomeric ground-state transition of 229Th. 229(m)Th ions originating from a 233U α-recoil source are collected on a micro electrode that is placed in the focus of an annular parabolic mirror. The latter is used to parallelize the UV fluorescence that may emerge from the isomeric ground-state transition of 229Th. The parallelized light is then focused by a second annular parabolic mirror onto a CsI-coated position-sensitive MCP detector behind the mirror exit. To achieve a high signal-to-background ratio, a small spot size on the MCP detector needs to be achieved. Besides extensive ray-tracing simulations of the optical setup, we present a procedure for its alignment, as well as test measurements using a D2 lamp, where a focal-spot size of ≈100 μm has been achieved. Assuming a purely photonic decay, a signal-to-background ratio of ≈7000:1 could be achieved.

Ultrafast quantum control of ionization dynamics in krypton.

PubMed

Hütten, Konrad; Mittermair, Michael; Stock, Sebastian O; Beerwerth, Randolf; Shirvanyan, Vahe; Riemensberger, Johann; Duensing, Andreas; Heider, Rupert; Wagner, Martin S; Guggenmos, Alexander; Fritzsche, Stephan; Kabachnik, Nikolay M; Kienberger, Reinhard; Bernhardt, Birgitta

2018-02-19

Ultrafast spectroscopy with attosecond resolution has enabled the real time observation of ultrafast electron dynamics in atoms, molecules and solids. These experiments employ attosecond pulses or pulse trains and explore dynamical processes in a pump-probe scheme that is selectively sensitive to electronic state of matter via photoelectron or XUV absorption spectroscopy or that includes changes of the ionic state detected via photo-ion mass spectrometry. Here, we demonstrate how the implementation of combined photo-ion and absorption spectroscopy with attosecond resolution enables tracking the complex multidimensional excitation and decay cascade of an Auger auto-ionization process of a few femtoseconds in highly excited krypton. In tandem with theory, our study reveals the role of intermediate electronic states in the formation of multiply charged ions. Amplitude tuning of a dressing laser field addresses different groups of decay channels and allows exerting temporal and quantitative control over the ionization dynamics in rare gas atoms.

Temperature dependent of IVR investigated by steady-state and time-frequency resolved CARS for liquid nitrobenzene and nitromethane

NASA Astrophysics Data System (ADS)

Yang, Yanqiang; Zhu, Gangbei; Yan, Lin; Liu, Xiaosong; Yang's Ultrafast Spectroscopy Group Team

2017-06-01

Intramolecular vibrational energy redistribution (IVR) is important process in thermal decomposition, shock chemistry and photochemistry. Anti-Stokes Raman scattering is sensitive to the vibrational population in excited states because only vibrational excited states are responsible to the anti-Stokes Raman scattering, does not vibrational ground states. In this report, steady-state anti-Stokes Raman spectroscopy and broad band ultrafast coherent anti-Stokes Raman scattering (CARS) are performed. The steady-state anti-Stokes Raman spectroscopy shows temperature dependent of vibrational energy redistribution in vibrational excited-state molecule, and reveal that, in liquid nitrobenzene, with temperature increasing, vibrational energy is mainly redistributed in NO2 symmetric stretching mode, and phenyl ring stretching mode of νCC. For liquid nitromethane, it is found that, with temperature increasing, vibrational energy concentrate in CN stretching mode and methyl umbrella vibrational mode. In the broad band ultrafast CARS experiment, multiple vibrational modes are coherently excited to vibrational excited states, and the time-frequency resolved CARS spectra show the coincident IVR processes. This work is supported by the National Natural Science Foundation of China (Grant Numbers 21673211 and 11372053), and the Science Challenging Program (Grant Number JCKY2016212A501).

Alternative Electron-Transfer Channels Ensure Ultrafast Deactivation of Light-Induced Excited States in Riboflavin Binding Protein.

PubMed

Zanetti-Polzi, Laura; Aschi, Massimiliano; Amadei, Andrea; Daidone, Isabella

2017-07-20

Flavoproteins, containing flavin chromophores, are enzymes capable of transferring electrons at very high speeds. The ultrafast photoinduced electron-transfer (ET) kinetics of riboflavin binding protein to the excited riboflavin was studied by femtosecond spectroscopy and found to occur within a few hundred femtoseconds [ Zhong and Zewail, Proc. Natl. Acad. Sci. U.S.A. 2001, 98, 11867-11872 ]. This ultrafast kinetics was attributed to the presence of two aromatic rings that could transfer the electron to riboflavin: the side chains of tryptophan 156 and tyrosine 75. However, the underlying ET mechanism remained unclear. Here, using a hybrid quantum mechanical-molecular dynamics approach, we perform ET dynamics simulations taking into account the motion of the protein and the solvent upon ET. This approach reveals that ET occurs via a major reaction channel involving tyrosine 75 (83%) and a minor one involving tryptophan 156 (17%). We also show that the protein environment is designed to ensure the fast quenching of the riboflavin excited state.

Mean-field studies of time reversal breaking states in super-heavy nuclei with the Gogny force

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

Robledo, L. M., E-mail: luis.robledo@uam.es

2015-10-15

Recent progress on the description of time reversal breaking (odd mass and multi-quasiparticle excitation) states in super-heavy nuclei within a mean field framework and using several flavors of the Gogny interaction is reported. The study includes ground and excited states in selected odd mass isotopes of nobelium and mendelevium as well as high K isomeric states in {sup 254}No. These are two and four-quasiparticle excitations that are treated in the same self-consistent HFB plus blocking framework as the odd mass states.

Configurations and decay hindrances of high- K states in Hf 180

DOE PAGES

Tandel, S. K.; Chowdhury, P.; Kondev, F. G.; ...

2016-12-02

Multi-quasiparticle high-K states, several of which are isomeric, were observed in Hf-180 with the Gammasphere array. We determined the lifetimes in the ns-μs range using centroid-shift and decay measurements within a mu s coincidence time window. The configurations of high-K states involve two and four quasiparticles, with states up to K π = (18 -) established. High-K excitations are found to be progressively more favored with increasing excitation energy. The K quantum number is quite robust up to the highest spins observed, as evidenced by the large values of the reduced hindrance for isomeric decays. Furthermore, rotational bands built onmore » three high-K states are identified, and the measured branching ratios in these sequences enable the assignment of underlying configurations. Multi-quasiparticle calculations using the Lipkin-Nogami approach for pairing, with blocking included, reproduce the observed high-K energies quite well.« less

Configurations and decay hindrances of high-K states in 180Hf

NASA Astrophysics Data System (ADS)

Tandel, S. K.; Chowdhury, P.; Kondev, F. G.; Janssens, R. V. F.; Khoo, T. L.; Carpenter, M. P.; Lauritsen, T.; Lister, C. J.; Seweryniak, D.; Zhu, S.; Deacon, A.; Freeman, S. J.; Hammond, N. J.; Jones, G. D.; Moore, E. F.; Smith, J. F.

2016-12-01

Multi-quasiparticle high-K states, several of which are isomeric, were observed in 180Hf with the Gammasphere array. Lifetimes in the ns-μ s range were determined using centroid-shift and decay measurements within a μ s coincidence time window. The configurations of high-K states involve two and four quasiparticles, with states up to Kπ=(18-) established. High-K excitations are found to be progressively more favored with increasing excitation energy. The K quantum number is quite robust up to the highest spins observed, as evidenced by the large values of the reduced hindrance for isomeric decays. Rotational bands built on three high-K states are identified, and the measured branching ratios in these sequences enable the assignment of underlying configurations. Multi-quasiparticle calculations using the Lipkin-Nogami approach for pairing, with blocking included, reproduce the observed high-K energies quite well.

Configurations and decay hindrances of high- K states in Hf 180

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

Tandel, S. K.; Chowdhury, P.; Kondev, F. G.

Multi-quasiparticle high-K states, several of which are isomeric, were observed in Hf-180 with the Gammasphere array. We determined the lifetimes in the ns-μs range using centroid-shift and decay measurements within a mu s coincidence time window. The configurations of high-K states involve two and four quasiparticles, with states up to K π = (18 -) established. High-K excitations are found to be progressively more favored with increasing excitation energy. The K quantum number is quite robust up to the highest spins observed, as evidenced by the large values of the reduced hindrance for isomeric decays. Furthermore, rotational bands built onmore » three high-K states are identified, and the measured branching ratios in these sequences enable the assignment of underlying configurations. Multi-quasiparticle calculations using the Lipkin-Nogami approach for pairing, with blocking included, reproduce the observed high-K energies quite well.« less

Improved measurement of the half-life of the J π = 8 - nuclear isomer 152m2 Eu

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

Humby, Peter; Simon, Anna; Beausang, C. W.

2015-02-23

The standard γ-ray energy calibration source 152Eu is well known based on the 13.5 y decay of its ground state. Nevertheless, in addition to this decay 152Eu also has two relatively long-lived isomeric states: a 9 h J π=0 - state at E *=46 keV and a 96 min J π=8 - state at E *=148 keV. Here we report a new measurement of the half-lives of both of these isomeric states. Excited states in 152Eu were populated following the 154Sm (p,3n) reaction using a 25 MeV proton beam from the K-150 cyclotron at the Cyclotron Institute of Texas A&Mmore » University. Post irradiation, γ rays from the de-excitation of the long lived isomeric states were measured using the six BGO shielded high-purity germanium (HPGe) clover detectors that are part of the STARLiTeR array. The half-life of the J π=8 - isomer 152m2Eu was obtained by measuring the decrease in intensity of the 90 keV γ ray from the cascade to the ground state. The half-life of this state was measured to be 95.8(4) min which is in agreement with and significantly more precise than the previously measured value of 96(1) min. In a manner similar to the ground state the second long-lived isomer 151m1Eu, the J π=0 - state at 46 keV, β decays to excited states in 152Gd and 152Sm. Also, the half-life of this state was measured to be 9.39(7) h using five γ-ray transitions.« less

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

PubMed

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

2013-08-01

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

Toward spectroscopically accurate global ab initio potential energy surface for the acetylene-vinylidene isomerization

NASA Astrophysics Data System (ADS)

Han, Huixian; Li, Anyang; Guo, Hua

2014-12-01

A new full-dimensional global potential energy surface (PES) for the acetylene-vinylidene isomerization on the ground (S0) electronic state has been constructed by fitting ˜37 000 high-level ab initio points using the permutation invariant polynomial-neural network method with a root mean square error of 9.54 cm-1. The geometries and harmonic vibrational frequencies of acetylene, vinylidene, and all other stationary points (two distinct transition states and one secondary minimum in between) have been determined on this PES. Furthermore, acetylene vibrational energy levels have been calculated using the Lanczos algorithm with an exact (J = 0) Hamiltonian. The vibrational energies up to 12 700 cm-1 above the zero-point energy are in excellent agreement with the experimentally derived effective Hamiltonians, suggesting that the PES is approaching spectroscopic accuracy. In addition, analyses of the wavefunctions confirm the experimentally observed emergence of the local bending and counter-rotational modes in the highly excited bending vibrational states. The reproduction of the experimentally derived effective Hamiltonians for highly excited bending states signals the coming of age for the ab initio based PES, which can now be trusted for studying the isomerization reaction.

Ultrafast excited-state dynamics of 2,5-dimethylpyrrole.

PubMed

Yang, Dongyuan; Min, Yanjun; Chen, Zhichao; He, Zhigang; Yuan, Kaijun; Dai, Dongxu; Yang, Xueming; Wu, Guorong

2018-04-17

The ultrafast excited-state dynamics of 2,5-dimethylpyrrole following excitation at wavelengths in the range of 265.7-216.7 nm is studied using the time-resolved photoelectron imaging method. It is found that excitation at longer wavelengths (265.7-250.2 nm) results in the population of the S1(1πσ*) state, which decays out of the photoionization window in about 90 fs. At shorter pump wavelengths (242.1-216.7 nm), the assignments are less clear-cut. We tentatively assign the initially photoexcited state(s) to the 1π3p Rydberg state(s) which has lifetimes of 159 ± 20, 125 ± 15, 102 ± 10 and 88 ± 10 fs for the pump wavelengths of 242.1, 238.1, 232.6 and 216.7 nm, respectively. Internal conversion to the S1(1πσ*) state represents at most a minor decay channel. The methyl substitution effects on the decay dynamics of the excited states of pyrrole are also discussed. Methyl substitution on the pyrrole ring seems to enhance the direct internal conversion from the 1π3p Rydberg state to the ground state, while methyl substitution on the N atom has less influence and the internal conversion to the S1(πσ*) state represents a main channel.

Structural Properties and UV-Visible Absorption Spectroscopy of Retinal-pyridyl-CN Re(I) Carbonyl Bipyridine Complex: A Theoretical Study.

PubMed

Eng, Julien; Daniel, Chantal

2015-10-29

The structural, electronic, and optical properties of the all-trans and five cis conformers of [Re(CO)3(bpy)(ret-pyr-CN)](+) (bpy = 2,2'-bipyridine; ret-pyr-CN = pyridyl-CN-3,7-dimethyl-9-(2,6,6-trimethylcyclohex-2-n)-none-(2,4,6,8-tetraen) were studied in solvent by means of density functional theory (DFT) and time-dependent DFT. The isolated retinal-like chromophore ret-pyr-CN was investigated as well for comparison. By coordination to the complex the two lowest intraligand (IL) states localized on the retinal group are slightly red-shifted from 627 to 690 nm and from 415 to 450 nm, respectively. Several isomerization pathways are open upon irradiation of the Re(I) complex by visible light (400-450 nm), especially to two cis conformers corresponding to the isomerization of the two double bonds of the retinal-like ligand close to the pyridyl group linked to the Re(I) fragment. The metal-to-ligand charge transfer states localized either on the retinal group or on the bpy ligand should play a minor role in the isomerization process itself but could improve its efficiency via ultra-fast intersystem crossing.

Ultrafast excited-state deactivation of 9-methylhypoxanthine in aqueous solution: A QM/MM MD study.

PubMed

Guo, Xugeng; Yuan, Huijuan; An, Beibei; Zhu, Qiuling; Zhang, Jinglai

2016-04-21

Photoinduced ultrafast non-adiabatic decay of 9-methylhypoxanthine (9MHPX) in aqueous solution was investigated by ab initio surface-hopping dynamics calculations using a combined quantum mechanical/molecular mechanical approach. The absorption spectra of 9MHPX in aqueous solution were also explored by the hybrid cluster-continuum model at the level of time-dependent density functional theory along with the polarizable continuum model (PCM). The static electronic-structure calculations indicate that the absorption spectra of 9MHPX simulated by TD-B3LYP/PCM and TD-X3LYP/PCM can reproduce very well the experimental findings, with the accuracy of about 0.20 eV. According to dynamics simulations, irradiation of 9MHPX populates the bright excited singlet S1 state, which may undergo an ultrafast non-radiative deactivation to the S0 state. The lifetime of the S1 state of 9MHPX in aqueous solution is predicted to be 115.6 fs, slightly longer than that in the gas phase (88.8 fs), suggesting that the solventwater has no significant influence on the excited-state lifetime of 9MHPX. Such a behavior in 9MHPX is distinctly different from its parent hypoxanthine keto-N9H tautomer in which the excited-state lifetime of the latter in watersolution was remarkably enhanced as compared to the gas phase. The significant difference of the photodynamical behaviors between 9MHPX and keto-N9H can be ascribed to their different hydrogen bond environment in aqueous solution.

{gamma}-vibrational states in superheavy nuclei

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

Sun Yang; Institute of Modern Physics, Chinese Academy of Sciences, Lanzhou 730000; Joint Institute for Nuclear Astrophysics, University of Notre Dame, Notre Dame, Indiana 46556

2008-04-15

Recent experimental advances have made it possible to study excited structure in superheavy nuclei. The observed states have often been interpreted as quasiparticle excitations. We show that in superheavy nuclei collective vibrations systematically appear as low-energy excitation modes. By using the microscopic Triaxial Projected Shell Model, we make a detailed prediction on {gamma}-vibrational states and their E2 transition probabilities to the ground state band in fermium and nobelium isotopes where active structure research is going on, and in {sup 270}Ds, the heaviest isotope where decay data have been obtained for the ground-state and for an isomeric state.

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

The molecular mechanism of excitation in visual transduction and bacteriorhodopsin

PubMed Central

Lewis, Aaron

1978-01-01

An electronic theory of excitation is proposed and described in terms of a three-dimensional excited/ground-state energy surface which elucidates the photochemical and excited-state dynamics of rhodopsins. In this theory the primary action of light is to produce significant electron redistribution in the retinal, thereby generating new interactions that vibrationally excite and perturb the ground-state protein conformation. Thus, light energy causes charge redistribution in the retinal and induces transient charge-density assisted bond rearrangements (such as proton translocation) in the protein structure which is stabilized by subsequent retinal structural alteration. In this theory the isoprenoid chain of the retinal is considered a structurally pliable molecular entity that can generate charge redistributions and can be subsequently achieve intermediate conformations or various isomeric states to minimize the energy of the new protein structure generated by light. Thus, the 11-cis to all trans isomerization of the retinylidene chromophore is not considered a primary mechanism of excitation. An alternate biological role for this molecular process (which is eventually completed in all photoreceptors but not in bacterial rhodopsins) is to provide the irreversibility needed for effective quantum detection on the time scale of a neural response. Finally, it will be demonstrated that this mechanism, which readily accounts for the photophysical and photochemical data, can also be restated in terms of the Monod, Wyman, and Changeux terminology suggesting that aggregates of these pigments may function allosterically. PMID:273216

Quantum optimal control pathways of ozone isomerization dynamics subject to competing dissociation: A two-state one-dimensional model

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

Kurosaki, Yuzuru, E-mail: kurosaki.yuzuru@jaea.go.jp; Ho, Tak-San, E-mail: tsho@Princeton.EDU; Rabitz, Herschel, E-mail: hrabitz@Princeton.EDU

We construct a two-state one-dimensional reaction-path model for ozone open → cyclic isomerization dynamics. The model is based on the intrinsic reaction coordinate connecting the cyclic and open isomers with the O{sub 2} + O asymptote on the ground-state {sup 1}A{sup ′} potential energy surface obtained with the high-level ab initio method. Using this two-state model time-dependent wave packet optimal control simulations are carried out. Two possible pathways are identified along with their respective band-limited optimal control fields; for pathway 1 the wave packet initially associated with the open isomer is first pumped into a shallow well on the excitedmore » electronic state potential curve and then driven back to the ground electronic state to form the cyclic isomer, whereas for pathway 2 the corresponding wave packet is excited directly to the primary well of the excited state potential curve. The simulations reveal that the optimal field for pathway 1 produces a final yield of nearly 100% with substantially smaller intensity than that obtained in a previous study [Y. Kurosaki, M. Artamonov, T.-S. Ho, and H. Rabitz, J. Chem. Phys. 131, 044306 (2009)] using a single-state one-dimensional model. Pathway 2, due to its strong coupling to the dissociation channel, is less effective than pathway 1. The simulations also show that nonlinear field effects due to molecular polarizability and hyperpolarizability are small for pathway 1 but could become significant for pathway 2 because much higher field intensity is involved in the latter. The results suggest that a practical control may be feasible with the aid of a few lowly excited electronic states for ozone isomerization.« less

Spectroscopic Studies of Carotenoid-to-Bacteriochlorophyll Energy Transfer in LHRC Photosynthetic Complex from Roseiflexus castenholzii

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

Niedzwiedzki, Dariusz; Collins, Aaron M.; LaFountain, Amy M.

Carotenoids present in the photosynthetic light-harvesting reaction center (LHRC) complex from chlorosome lacking filamentous anoxygenic phototroph, Roseiflexus castenholzii were purified and characterized for their photochemical properties. The LHRC from anaerobically grown cells contains five different carotenoids, methoxy-keto-myxocoxanthin, γ-carotene, and its three derivatives, whereas the LHRC from aerobically grown cells contains only three carotenoid pigments with methoxy-keto-myxocoxanthin being the dominant one. The spectroscopic properties and dynamics of excited singlet states of the carotenoids were studied by steady-state absorption, fluorescence and ultrafast time-resolved optical spectroscopy in organic solvent and in the intact LHRC complex. Time-resolved transient absorption spectroscopy performed in the near-infraredmore » (NIR) on purified carotenoids combined with steady-state absorption spectroscopy led to the precise determination of values of the energies of the S 1(2 1A g -) excited state. Global and single wavelength fitting of the ultrafast spectral and temporal data sets of the carotenoids in solvents and in the LHRC revealed the pathways of de-excitation of the carotenoid excited states.« less

Femtosecond Structural Dynamics Drives the Trans/Cis Isomerization in Photoactive Yellow Protein

PubMed Central

Pande, Kanupriya; Hutchison, Christopher D. M.; Groenhof, Gerrit; Aquila, Andy; Robinson, Josef S.; Tenboer, Jason; Basu, Shibom; Boutet, Sébastien; DePonte, Daniel P.; Liang, Mengning; White, Thomas A.; Zatsepin, Nadia A.; Yefanov, Oleksandr; Morozov, Dmitry; Oberthuer, Dominik; Gati, Cornelius; Subramanian, Ganesh; James, Daniel; Zhao, Yun; Koralek, Jake; Brayshaw, Jennifer; Kupitz, Christopher; Conrad, Chelsie; Roy-Chowdhury, Shatabdi; Coe, Jesse D.; Metz, Markus; Xavier, Paulraj Lourdu; Grant, Thomas D.; Koglin, Jason E.; Ketawala, Gihan; Fromme, Raimund; Šrajer, Vukica; Henning, Robert; Spence, John C. H.; Ourmazd, Abbas; Schwander, Peter; Weierstall, Uwe; Frank, Matthias; Fromme, Petra; Barty, Anton; Chapman, Henry N.; Moffat, Keith; van Thor, Jasper J.; Schmidt, Marius

2017-01-01

A variety of organisms have evolved mechanisms to detect and respond to light, in which the response is mediated by protein structural changes following photon absorption. The initial step is often the photo-isomerization of a conjugated chromophore. Isomerization occurs on ultrafast timescales, and is substantially influenced by the chromophore environment. Here we identify structural changes associated with the earliest steps in the trans to cis isomerization of the chromophore in photoactive yellow protein. Femtosecond, hard X-ray pulses emitted by the Linac Coherent Light Source were used to conduct time-resolved serial femtosecond crystallography on PYP microcrystals over the time range from 100 femtoseconds to 3 picoseconds to determine the structural dynamics of the photoisomerization reaction. PMID:27151871

Spectroscopic Identification of Isomeric Trimethylbenzyl Radicals Generated in Corona Discharge of Tetramethylbenzene

NASA Astrophysics Data System (ADS)

Yoon, Young Wook; Lee, Sang Kuk; Lee, Gi Woo

2011-06-01

The visible vibronic emission spectra were recorded from the corona discharge of precursor tetramethylbenzene with a large amount of inert carrier gas helium using a pinhole-type glass nozzle coupled with corona excited supersonic expansion (CESE) well developed in this laboratory. The spectra showed a series of vibronic bands in the D_1 → D_0 electronic transition of jet-cooled benzyl-type radicals formed from the precursor in a corona excitation. The analysis confirmed that two isomeric radicals, 2,3,4- and 2,3,6-trimethylbenzyl radicals and three isomeric radicals, 3,4,5-, 2,3,5- and 2,4,6-trimethylbenzyl radicals were produced, respectively, from 1,2,3,4- and 1,2,3,5-tetramethylbenzenes as a result of removal of a hydrogen atom from the methyl group at different substitution position. For each isomeric trimethylbenzyl radical generated in the corona discharge of precursor, the electronic transition and a few vibrational mode frequencies were determined in the ground electronic state by comparing with those from both ab initio calculations and the known vibrational data of the precursor. The substitution effect that states the shift of electronic transition depends on the nature, the number, and the position of substituents on the ring has been qualitatively proved for the case of benzyl-type radicals.

Special features of isomeric ratios in nuclear reactions induced by various projectile particles

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

Danagulyan, A. S.; Hovhannisyan, G. H., E-mail: hov-gohar@ysu.am; Bakhshiyan, T. M.

2016-05-15

Calculations for (p, n) and (α, p3n) reactions were performed with the aid of the TALYS-1.4 code. Reactions in which the mass numbers of target and product nuclei were identical were examined in the range of A = 44–124. Excitation functions were obtained for product nuclei in ground and isomeric states, and isomeric ratios were calculated. The calculated data reflect well the dependence of the isomeric ratios on the projectile type. A comparison of the calculated and experimental data reveals, that, for some nuclei in a high-spin state, the calculated data fall greatly short of their experimental counterparts. These discrepanciesmore » may be due to the presence of high-spin yrast states and rotational bands in these nuclei. Calculations involving various level-density models included in the TALYS-1.4 code with allowance for the enhancement of collective effects do not remove the discrepancies in the majority of cases.« less

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.

Ultrafast Charge Transfer in Nickel Phthalocyanine Probed by Femtosecond Raman-Induced Kerr Effect Spectroscopy

PubMed Central

2015-01-01

The recently developed technique of femtosecond stimulated Raman spectroscopy, and its variant, femtosecond Raman-induced Kerr effect spectroscopy (FRIKES), offer access to ultrafast excited-state dynamics via structurally specific vibrational spectra. We have used FRIKES to study the photoexcitation dynamics of nickel(II) phthalocyanine with eight butoxy substituents, NiPc(OBu)8. NiPc(OBu)8 is reported to have a relatively long-lived ligand-to-metal charge-transfer (LMCT) state, an essential characteristic for efficient electron transfer in photocatalysis. Following photoexcitation, vibrational transitions in the FRIKES spectra, assignable to phthalocyanine ring modes, evolve on the femtosecond to picosecond time scales. Correlation of ring core size with the frequency of the ν10 (asymmetric C–N stretching) mode confirms the identity of the LMCT state, which has a ∼500 ps lifetime, as well as that of a precursor d-d excited state. An even earlier (∼0.2 ps) transient is observed and tentatively assigned to a higher-lying Jahn–Teller-active LMCT state. This study illustrates the power of FRIKES spectroscopy in elucidating ultrafast molecular dynamics. PMID:24841906

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.

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 coherent excitation of a trapped ion qubit for fast gates and photon frequency qubits.

PubMed

Madsen, M J; Moehring, D L; Maunz, P; Kohn, R N; Duan, L-M; Monroe, C

2006-07-28

We demonstrate ultrafast coherent excitation of an atomic qubit stored in the hyperfine levels of a single trapped cadmium ion. Such ultrafast excitation is crucial for entangling networks of remotely located trapped ions through the interference of photon frequency qubits, and is also a key component for realizing ultrafast quantum gates between Coulomb-coupled ions.

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.

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.

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).

Geometrical Optimization Approach to Isomerization: Models and Limitations.

PubMed

Chang, Bo Y; Shin, Seokmin; Engel, Volker; Sola, Ignacio R

2017-11-02

We study laser-driven isomerization reactions through an excited electronic state using the recently developed Geometrical Optimization procedure. Our goal is to analyze whether an initial wave packet in the ground state, with optimized amplitudes and phases, can be used to enhance the yield of the reaction at faster rates, driven by a single picosecond pulse or a pair of femtosecond pulses resonant with the electronic transition. We show that the symmetry of the system imposes limitations in the optimization procedure, such that the method rediscovers the pump-dump mechanism.

Room-temperature ultrafast nonlinear spectroscopy of a single molecule

NASA Astrophysics Data System (ADS)

Liebel, Matz; Toninelli, Costanza; van Hulst, Niek F.

2018-01-01

Single-molecule spectroscopy aims to unveil often hidden but potentially very important contributions of single entities to a system's ensemble response. Albeit contributing tremendously to our ever growing understanding of molecular processes, the fundamental question of temporal evolution, or change, has thus far been inaccessible, thus painting a static picture of a dynamic world. Here, we finally resolve this dilemma by performing ultrafast time-resolved transient spectroscopy on a single molecule. By tracing the femtosecond evolution of excited electronic state spectra of single molecules over hundreds of nanometres of bandwidth at room temperature, we reveal their nonlinear ultrafast response in an effective three-pulse scheme with fluorescence detection. A first excitation pulse is followed by a phase-locked de-excitation pulse pair, providing spectral encoding with 25 fs temporal resolution. This experimental realization of true single-molecule transient spectroscopy demonstrates that two-dimensional electronic spectroscopy of single molecules is experimentally within reach.

Self-amplified photo-induced gap quenching in a correlated electron material

PubMed Central

Mathias, S.; Eich, S.; Urbancic, J.; Michael, S.; Carr, A. V.; Emmerich, S.; Stange, A.; Popmintchev, T.; Rohwer, T.; Wiesenmayer, M.; Ruffing, A.; Jakobs, S.; Hellmann, S.; Matyba, P.; Chen, C.; Kipp, L.; Bauer, M.; Kapteyn, H. C.; Schneider, H. C.; Rossnagel, K.; Murnane, M. M.; Aeschlimann, M.

2016-01-01

Capturing the dynamic electronic band structure of a correlated material presents a powerful capability for uncovering the complex couplings between the electronic and structural degrees of freedom. When combined with ultrafast laser excitation, new phases of matter can result, since far-from-equilibrium excited states are instantaneously populated. Here, we elucidate a general relation between ultrafast non-equilibrium electron dynamics and the size of the characteristic energy gap in a correlated electron material. We show that carrier multiplication via impact ionization can be one of the most important processes in a gapped material, and that the speed of carrier multiplication critically depends on the size of the energy gap. In the case of the charge-density wave material 1T-TiSe2, our data indicate that carrier multiplication and gap dynamics mutually amplify each other, which explains—on a microscopic level—the extremely fast response of this material to ultrafast optical excitation. PMID:27698341

Direct measurement of the energy thresholds to conformational isomerization in tryptamine: experiment and theory.

PubMed

Clarkson, Jasper R; Dian, Brian C; Moriggi, Loïck; DeFusco, Albert; McCarthy, Valerie; Jordan, Kenneth D; Zwier, Timothy S

2005-06-01

The methods of stimulated emission pumping-hole filling spectroscopy (SEP-HFS) and stimulated emission pumping population transfer spectroscopy (SEP-PTS) were applied to the conformation-specific study of conformational isomerization in tryptamine [TRA, 3-(2-aminoethyl)indole]. These experimental methods employ stimulated emission pumping to selectively excite a fraction of the population of a single conformation of TRA to well-defined ground-state vibrational levels. This produces single conformations with well-defined internal energy, tunable over a range of energies from near the zero-point level to well above the lowest barriers to conformational isomerization. When the SEP step overcomes a barrier to isomerization, a fraction of the excited population isomerizes to form that product. By carrying out SEP excitation early in a supersonic expansion, these product molecules are subsequently cooled to their zero-point vibrational levels, where they can be detected downstream with a third tunable laser that probes the ground-state population of a particular product conformer via a unique ultraviolet transition using laser-induced fluorescence. The population transfer spectra (recorded by tuning the SEP dump laser while holding the pump and probe lasers fixed) exhibit sharp onsets that directly determine the energy thresholds for conformational isomerization in a given reactant-product conformer pair. In the absence of tunneling effects, the first observed transition in a given X-Y PTS constitutes an upper bound to the energy barrier to conformational isomerization, while the last transition not observed constitutes a lower bound. The bounds for isomerizing conformer A of tryptamine to B(688-748 cm(-1)), C(1)(860-1000 cm(-1)), C(2)(1219-1316 cm(-1)), D(1219-1282 cm(-1)), E(1219-1316 cm(-1)), and F(688-748 cm(-1)) are determined. In addition, thresholds for isomerizing from B to A(<1562 cm(-1)), B to F(562-688 cm(-1)), and out of C(2) to B(<747 cm(-1)) are also determined. The A-->B and B-->A transitions are used to place bounds on the relative energies of minima B relative to A, with B lying at least 126 cm(-1) above A. The corresponding barriers have been computed using both density functional and second-order many-body perturbation theory methods in order to establish the level of theory needed to reproduce experimental results. While most of the computed barriers match experiment well, the barriers for the A-F and B-F transitions are too high by almost a factor of 2. Possible reasons for this discrepancy are discussed.

Capturing local structure modulations of photoexcited BiVO4 by ultrafast transient XAFS.

PubMed

Uemura, Yohei; Kido, Daiki; Koide, Akihiro; Wakisaka, Yuki; Niwa, Yasuhiro; Nozawa, Shunsuke; Ichiyanagi, Kohei; Fukaya, Ryo; Adachi, Shin-Ichi; Katayama, Tetsuo; Togashi, Tadashi; Owada, Shigeki; Yabashi, Makina; Hatada, Keisuke; Iwase, Akihide; Kudo, Akihiko; Takakusagi, Satoru; Yokoyama, Toshihiko; Asakura, Kiyotaka

2017-06-29

Ultrafast excitation of photocatalytically active BiVO 4 was characterized by femto- and picosecond transient X-ray absorption fine structure spectroscopy. An initial photoexcited state (≪500 fs) changed to a metastable state accompanied by a structural change with a time constant of ∼14 ps. The structural change might stabilize holes on oxygen atoms since the interaction between Bi and O increases.

Ultrafast excited-state deactivation of 9-methylhypoxanthine in aqueous solution: A QM/MM MD study

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

Guo, Xugeng, E-mail: xgguo@henu.edu.cn, E-mail: zhangjinglai@henu.edu.cn; Yuan, Huijuan; An, Beibei

Photoinduced ultrafast non-adiabatic decay of 9-methylhypoxanthine (9MHPX) in aqueous solution was investigated by ab initio surface-hopping dynamics calculations using a combined quantum mechanical/molecular mechanical approach. The absorption spectra of 9MHPX in aqueous solution were also explored by the hybrid cluster-continuum model at the level of time-dependent density functional theory along with the polarizable continuum model (PCM). The static electronic-structure calculations indicate that the absorption spectra of 9MHPX simulated by TD-B3LYP/PCM and TD-X3LYP/PCM can reproduce very well the experimental findings, with the accuracy of about 0.20 eV. According to dynamics simulations, irradiation of 9MHPX populates the bright excited singlet S{sub 1}more » state, which may undergo an ultrafast non-radiative deactivation to the S{sub 0} state. The lifetime of the S{sub 1} state of 9MHPX in aqueous solution is predicted to be 115.6 fs, slightly longer than that in the gas phase (88.8 fs), suggesting that the solvent water has no significant influence on the excited-state lifetime of 9MHPX. Such a behavior in 9MHPX is distinctly different from its parent hypoxanthine keto-N9H tautomer in which the excited-state lifetime of the latter in water solution was remarkably enhanced as compared to the gas phase. The significant difference of the photodynamical behaviors between 9MHPX and keto-N9H can be ascribed to their different hydrogen bond environment in aqueous solution.« less

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.

Ultrafast dynamics of the lowest-lying neutral states in carbon dioxide

DOE PAGES

Wright, Travis W.; Champenois, Elio G.; Cryan, James P.; ...

2017-02-17

Here, we present a study of the ultrafast dissociation dynamics of the lowest-lying electronic excited states in CO 2 by using ultraviolet (UV) and extreme-ultraviolet (XUV) pulses from high-order harmonic generation. We observe two primary dissociation channels: a direct dissociation channel along the 1Π g electronically excited manifold, and a second channel which results from the mixing of electronic states. The direct dissociation channel is found to have a lifetime which is shorter than our experimental resolution, whereas the second channel has a significantly longer lifetime of nearly 200 fs. In this long-lived channel we observe a beating of themore » vibrational populations with a period of ~133 fs.« less

Toward spectroscopically accurate global ab initio potential energy surface for the acetylene-vinylidene isomerization

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

Han, Huixian; School of Physics, Northwest University, Xi’an, Shaanxi 710069; Li, Anyang

2014-12-28

A new full-dimensional global potential energy surface (PES) for the acetylene-vinylidene isomerization on the ground (S{sub 0}) electronic state has been constructed by fitting ∼37 000 high-level ab initio points using the permutation invariant polynomial-neural network method with a root mean square error of 9.54 cm{sup −1}. The geometries and harmonic vibrational frequencies of acetylene, vinylidene, and all other stationary points (two distinct transition states and one secondary minimum in between) have been determined on this PES. Furthermore, acetylene vibrational energy levels have been calculated using the Lanczos algorithm with an exact (J = 0) Hamiltonian. The vibrational energies upmore » to 12 700 cm{sup −1} above the zero-point energy are in excellent agreement with the experimentally derived effective Hamiltonians, suggesting that the PES is approaching spectroscopic accuracy. In addition, analyses of the wavefunctions confirm the experimentally observed emergence of the local bending and counter-rotational modes in the highly excited bending vibrational states. The reproduction of the experimentally derived effective Hamiltonians for highly excited bending states signals the coming of age for the ab initio based PES, which can now be trusted for studying the isomerization reaction.« less

Evolution of Excited-State Dynamics in Periodic Au 28, Au 36, Au 44, and Au 52 Nanoclusters

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

Zhou, Meng; Zeng, Chenjie; Sfeir, Matthew Y.

An understanding of the correlation between the atomic structure and optical properties of gold nanoclusters is essential for exploration of their functionalities and applications involving light harvesting and electron transfer. We report the femto-nanosecond excited state dynamics of a periodic series of face-centered cubic (FCC) gold nanoclusters (including Au 28, Au 36, Au 44, and Au 52), which exhibit a set of unique features compared with other similar sized clusters. Molecular-like ultrafast S n → S 1 internal conversions (i.e., radiationless electronic transitions) are observed in the relaxation dynamics of FCC periodic series. Excited-state dynamics with near-HOMO–LUMO gap excitation lacksmore » ultrafast decay component, and only the structural relaxation dominates in the dynamical process, which proves the absence of core–shell relaxation. Interestingly, both the relaxation of the hot carriers and the band-edge carrier recombination become slower as the size increases. The evolution in excited-state properties of this FCC series offers new insight into the structure-dependent properties of metal nanoclusters, which will benefit their optical energy harvesting and photocatalytic applications.« less

Evolution of Excited-State Dynamics in Periodic Au 28, Au 36, Au 44, and Au 52 Nanoclusters

DOE PAGES

Zhou, Meng; Zeng, Chenjie; Sfeir, Matthew Y.; ...

2017-08-10

An understanding of the correlation between the atomic structure and optical properties of gold nanoclusters is essential for exploration of their functionalities and applications involving light harvesting and electron transfer. We report the femto-nanosecond excited state dynamics of a periodic series of face-centered cubic (FCC) gold nanoclusters (including Au 28, Au 36, Au 44, and Au 52), which exhibit a set of unique features compared with other similar sized clusters. Molecular-like ultrafast S n → S 1 internal conversions (i.e., radiationless electronic transitions) are observed in the relaxation dynamics of FCC periodic series. Excited-state dynamics with near-HOMO–LUMO gap excitation lacksmore » ultrafast decay component, and only the structural relaxation dominates in the dynamical process, which proves the absence of core–shell relaxation. Interestingly, both the relaxation of the hot carriers and the band-edge carrier recombination become slower as the size increases. The evolution in excited-state properties of this FCC series offers new insight into the structure-dependent properties of metal nanoclusters, which will benefit their optical energy harvesting and photocatalytic applications.« less

The separation of vibrational coherence from ground- and excited-electronic states in P3HT film

NASA Astrophysics Data System (ADS)

Song, Yin; Hellmann, Christoph; Stingelin, Natalie; Scholes, Gregory D.

2015-06-01

Concurrence of the vibrational coherence and ultrafast electron transfer has been observed in polymer/fullerene blends. However, it is difficult to experimentally investigate the role that the excited-state vibrational coherence plays during the electron transfer process since vibrational coherence from the ground- and excited-electronic states is usually temporally and spectrally overlapped. Here, we performed 2-dimensional electronic spectroscopy (2D ES) measurements on poly(3-hexylthiophene) (P3HT) films. By Fourier transforming the whole 2D ES datasets ( S ( λ 1 , T ˜ 2 , λ 3 ) ) along the population time ( T ˜ 2 ) axis, we develop and propose a protocol capable of separating vibrational coherence from the ground- and excited-electronic states in 3D rephasing and nonrephasing beating maps ( S ( λ 1 , ν ˜ 2 , λ 3 ) ). We found that the vibrational coherence from pure excited electronic states appears at positive frequency ( + ν ˜ 2 ) in the rephasing beating map and at negative frequency ( - ν ˜ 2 ) in the nonrephasing beating map. Furthermore, we also found that vibrational coherence from excited electronic state had a long dephasing time of 244 fs. The long-lived excited-state vibrational coherence indicates that coherence may be involved in the electron transfer process. Our findings not only shed light on the mechanism of ultrafast electron transfer in organic photovoltaics but also are beneficial for the study of the coherence effect on photoexcited dynamics in other systems.

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.

Selective ultrafast probing of transient hot chemisorbed and precursor states of CO on Ru(0001).

PubMed

Beye, M; Anniyev, T; Coffee, R; Dell'Angela, M; Föhlisch, A; Gladh, J; Katayama, T; Kaya, S; Krupin, O; Møgelhøj, A; Nilsson, A; Nordlund, D; Nørskov, J K; Öberg, H; Ogasawara, H; Pettersson, L G M; Schlotter, W F; Sellberg, J A; Sorgenfrei, F; Turner, J J; Wolf, M; Wurth, W; Oström, H

2013-05-03

We have studied the femtosecond dynamics following optical laser excitation of CO adsorbed on a Ru surface by monitoring changes in the occupied and unoccupied electronic structure using ultrafast soft x-ray absorption and emission. We recently reported [M. Dell'Angela et al. Science 339, 1302 (2013)] a phonon-mediated transition into a weakly adsorbed precursor state occurring on a time scale of >2 ps prior to desorption. Here we focus on processes within the first picosecond after laser excitation and show that the metal-adsorbate coordination is initially increased due to hot-electron-driven vibrational excitations. This process is faster than, but occurs in parallel with, the transition into the precursor state. With resonant x-ray emission spectroscopy, we probe each of these states selectively and determine the respective transient populations depending on optical laser fluence. Ab initio molecular dynamics simulations of CO adsorbed on Ru(0001) were performed at 1500 and 3000 K providing insight into the desorption process.

Activation energy of light induced isomerization of resveratrol.

PubMed

Figueiras, Teresa Sofia; Neves-Petersen, Maria Teresa; Petersen, Steffen B

2011-09-01

Isomerization of trans-stilbenes is known to be induced by light. The two isomers have distinct absorption, fluorescence excitation and emission spectra. Resveratrol, 3,4',5-trihydroxystilbene, is a member of the stilbene family. The interest of the scientific community in resveratrol has increased over the last years due to its biomedical properties. Whereas there is a growing confidence that trans-resveratrol is non-toxic, very little is known about the pharmacology of cis-resveratrol. Of this very reason there is considerable interest in knowing the energetics of the trans-cis conversion. Cis-resveratrol is characterized by a large fluorescence quantum yield when compared to trans-resveratrol. In the present paper we report a detailed analysis of the spectral changes induced in trans-resveratrol upon 260 nm excitation for different time periods. Spectral changes have been monitored with UV-visible absorption and steady-state fluorescence spectroscopy at pH 4 at 20, 25, 30, 35, 40, 45 and 50 °C. Continuous 260 nm excitation induces a blue shift in the absorption and fluorescence excitation spectra of resveratrol and a 14 nm blue shift in its fluorescence emission. The photoisomerization yield is reported as a function of 260 nm excitation time. 330 min continuous excitation led to ~60% isomerization yield. The kinetics of trans-cis isomerization has been monitored following the increase in fluorescence quantum yield upon continuous 260 nm excitation of trans-resveratrol. The study was carried out at the above mentioned temperatures in order to obtain the Arrhenius activation energy of photoisomerization. Activation energy and pre-exponential factor were 3.7 ± 0.3 kcal.mol(-1) and 10.6 ± 1.6 s(-1), respectively. The activation energy is comparable with previously reported values for the photoisomerization of other stilbenes.

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. Counterintuitively, singlet excited-state lifetime increases on going from Cl (85 fs) to Br (128 fs) and to I (152 fs). Moreover, correlation between the Re-X stretching mode and the rate of ISC is observed. In this Account, we emphasize on the role of spin-vibronic coupling on the mechanism of ultrafast ISC put in evidence in [Re(Br)(CO)3(bpy)]. For this purpose, we have developed a model Hamiltonian for solving an 11 electronic excited states multimode problem including vibronic and SO coupling within the linear vibronic coupling (LVC) approximation and the assumption of harmonic potentials. The presence of a central metal atom coupled to rigid ligands, such as α-diimine, ensures nuclear motion of small amplitudes and a priori justifies the use of the LVC model. The simulation of the ultrafast dynamics by wavepacket propagations using the multiconfiguration time-dependent Hartree (MCTDH) method is based on density functional theory (DFT), and its time-dependent extension to excited states (TD-DFT) electronic structure data. We believe that the interplay between time-resolved experiments and these pioneering simulations covering the first picoseconds and including spin-vibronic coupling will promote a number of quantum dynamical studies that will contribute to a better understanding of ultrafast processes in a wide range of organic and inorganic chromophores easily incorporated in biosystems or supramolecular devices for specific functions.

Investigating the large deformation of the 5 /2+ isomeric state in 73Zn: An indicator for triaxiality

NASA Astrophysics Data System (ADS)

Yang, X. F.; Tsunoda, Y.; Babcock, C.; Billowes, J.; Bissell, M. L.; Blaum, K.; Cheal, B.; Flanagan, K. T.; Garcia Ruiz, R. F.; Gins, W.; Gorges, C.; Grob, L. K.; Heylen, H.; Kaufmann, S.; Kowalska, M.; Krämer, J.; Malbrunot-Ettenauer, S.; Neugart, R.; Neyens, G.; Nörtershäuser, W.; Otsuka, T.; Papuga, J.; Sánchez, R.; Wraith, C.; Xie, L.; Yordanov, D. T.

2018-04-01

Recently reported nuclear spins and moments of neutron-rich Zn isotopes measured at ISOLDE-CERN [C. Wraith et al., Phys. Lett. B 771, 385 (2017), 10.1016/j.physletb.2017.05.085] show an uncommon behavior of the isomeric state in 73Zn. Additional details relating to the measurement and analysis of the Znm73 hyperfine structure are addressed here to further support its spin-parity assignment 5 /2+ and to estimate its half-life. A systematic investigation of this 5 /2+ isomer indicates that significant collectivity appears due to proton/neutron E 2 excitations across the proton Z = 28 and neutron N = 50 shell gaps. This is confirmed by the good agreement of the observed quadrupole moments with large scale Monte Carlo shell model calculations. In addition, potential energy surface calculations in combination with T plots reveal a triaxial shape for this isomeric state.

Nudat 2

Science.gov Websites

modes), gamma rays (energy, intensity, multipolarity, coinc.) Nuclear Wallet Cards Search Latest Ground NuDat 2.7 Levels and Gammas Search Ground and excited states (energy, T1/2, spin/parity, decay and isomeric states properties Decay Radiation Search Radiation type, energy, intensity and dose

Femtosecond stimulated Raman evidence for charge-transfer character in pentacene singlet fission.

PubMed

Hart, Stephanie M; Silva, W Ruchira; Frontiera, Renee R

2018-02-07

Singlet fission is a spin-allowed process in which an excited singlet state evolves into two triplet states. We use femtosecond stimulated Raman spectroscopy, an ultrafast vibrational technique, to follow the molecular structural evolution during singlet fission in order to determine the mechanism of this process. In crystalline pentacene, we observe the formation of an intermediate characterized by pairs of excited state peaks that are red- and blue-shifted relative to the ground state features. We hypothesize that these features arise from the formation of cationic and anionic species due to partial transfer of electron density from one pentacene molecule to a neighboring molecule. These observations provide experimental evidence for the role of states with significant charge-transfer character which facilitate the singlet fission process in pentacene. Our work both provides new insight into the singlet fission mechanism in pentacene and demonstrates the utility of structurally-sensitive time-resolved spectroscopic techniques in monitoring ultrafast processes.

Using Vibrations to Probe and Control Photoisomerization in Liquids

DTIC Science & Technology

2014-08-07

Aniline in Supercritical CO2 The influence that different solvent environments have on the reaction dynamics of molecules in solution is a long...vibrationally excited stilbene, of a biomimetic switch, an N- alkylated indanylidene pyrroline Schiff base (NAIP), and of a model com- pound for excited...supercritical carbon dioxide, scCO2. Monitor- ing the excited-state isomerization of salicylidene aniline has shown the role of viscosity on the course of

Light, Molecules, Action: Using Ultrafast Uv-Visible and X-Ray Spectroscopy to Probe Excited State Dynamics in Photoactive Molecules

NASA Astrophysics Data System (ADS)

Sension, R. J.

2017-06-01

Light provides a versatile energy source capable of precise manipulation of material systems on size scales ranging from molecular to macroscopic. Photochemistry provides the means for transforming light energy from photon to process via movement of charge, a change in shape, a change in size, or the cleavage of a bond. Photochemistry produces action. In the work to be presented here ultrafast UV-Visible pump-probe, and pump-repump-probe methods have been used to probe the excited state dynamics of stilbene-based molecular motors, cyclohexadiene-based switches, and polyene-based photoacids. Both ultrafast UV-Visible and X-ray absorption spectroscopies have been applied to the study of cobalamin (vitamin B_{12}) based compounds. Optical measurements provide precise characterization of spectroscopic signatures of the intermediate species on the S_{1} surface, while time-resolved XANES spectra at the Co K-edge probe the structural changes that accompany these transformations.

Self-amplified photo-induced gap quenching in a correlated electron material

DOE PAGES

Mathias, S.; Eich, S.; Urbancic, J.; ...

2016-10-04

Capturing the dynamic electronic band structure of a correlated material presents a powerful capability for uncovering the complex couplings between the electronic and structural degrees of freedom. When combined with ultrafast laser excitation, new phases of matter can result, since far-from-equilibrium excited states are instantaneously populated. Here, we elucidate a general relation between ultrafast non-equilibrium electron dynamics and the size of the characteristic energy gap in a correlated electron material. Here, we show that carrier multiplication via impact ionization can be one of the most important processes in a gapped material, and that the speed of carrier multiplication critically dependsmore » on the size of the energy gap. In the case of the charge-density wave material 1T-TiSe 2, our data indicate that carrier multiplication and gap dynamics mutually amplify each other, which explains—on a microscopic level—the extremely fast response of this material to ultrafast optical excitation.« less

Transient ultrafast coherent spectroscopy of 2-propanol

NASA Astrophysics Data System (ADS)

Meiselman, Seth; Decamp, Matthew; Lorenz, Virginia

We use transient coherent spontaneous Raman spectroscopy to measure the coherence lifetimes of vibrational states in liquid propanol. By creating single-photon-level collective excitations of the vibrational states in the system we observe coherence oscillations due to simultaneous excitation of the 2885 cm-1, 2938 cm-1, and 2976 cm-1 modes. These lifetimes and oscillation frequencies agree with frequency-domain lineshape measurements.

Isomer-delayed γ -ray spectroscopy of A =159 -164 midshell nuclei and the variation of K -forbidden E 1 transition hindrance factors

NASA Astrophysics Data System (ADS)

Patel, Z.; Walker, P. M.; Podolyák, Zs.; Regan, P. H.; Berry, T. A.; Söderström, P.-A.; Watanabe, H.; Ideguchi, E.; Simpson, G. S.; Nishimura, S.; Wu, Q.; Xu, F. R.; Browne, F.; Doornenbal, P.; Lorusso, G.; Rice, S.; Sinclair, L.; Sumikama, T.; Wu, J.; Xu, Z. Y.; Aoi, N.; Baba, H.; Bello Garrote, F. L.; Benzoni, G.; Daido, R.; Dombrádi, Zs.; Fang, Y.; Fukuda, N.; Gey, G.; Go, S.; Gottardo, A.; Inabe, N.; Isobe, T.; Kameda, D.; Kobayashi, K.; Kobayashi, M.; Komatsubara, T.; Kojouharov, I.; Kubo, T.; Kurz, N.; Kuti, I.; Li, Z.; Matsushita, M.; Michimasa, S.; Moon, C.-B.; Nishibata, H.; Nishizuka, I.; Odahara, A.; Şahin, E.; Sakurai, H.; Schaffner, H.; Suzuki, H.; Takeda, H.; Tanaka, M.; Taprogge, J.; Vajta, Zs.; Yagi, A.; Yokoyama, R.

2017-09-01

Excited states have been studied in 159Sm, 161Sm, 162Sm (Z =62 ), 163Eu (Z =63 ), and 164Gd (Z =64 ), populated by isomeric decay following 238U projectile fission at RIBF, RIKEN. The isomer half-lives range from 50 ns to 2.6 μ s . In comparison with other published data, revised interpretations are proposed for 159Sm and 163Eu. The first data for excited states in 161Sm are presented, where a 2.6-μ s isomer is assigned a three-quasiparticle, Kπ=17 /2- structure. The interpretation is supported by multi-quasiparticle Nilsson-BCS calculations, including the blocking of pairing correlations. A consistent set of reduced E 1 hindrance factors is obtained. Limited evidence is also reported for isomeric decay in 163Sm, 164Eu, and 165Eu.

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 energies of the states and the spectral profiles of the molecules. A significant finding is that, due to the low S1 (2(1)Ag-) energy of rhodopin glucoside, energy transfer from this state to the bacteriochlorophylls is significantly less probable compared to the other complexes. This work resolves a long-standing question regarding the cause of the precipitous drop in energy transfer efficiency when the extent of pi-electron conjugation of the carotenoid is extended from ten to eleven conjugated carbon-carbon double bonds in LH2 complexes from purple photosynthetic bacteria.

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 for copper(II) complexes studied so far, in particular, copper blue proteins. The highest 2A1 and lowest 2E LF states relax directly to the ground electronic state whereas the intermediate 2B1 LF state relaxes stepwise through the 2E state. The LMCT excited states are short-lived undergoing either ionic dissociation (CuCl3- + Cl-) or cascading relaxation through the manifold of vibrationally hot LF states to the ground state.

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.

Multiphoton manipulations of enzymatic photoactivity in aspartate aminotransferase.

PubMed

Hill, Melissa P; Freer, Lucy H; Vang, Mai C; Carroll, Elizabeth C; Larsen, Delmar S

2011-04-21

The aspartate aminotransferase (AAT) enzyme utilizes the chromophoric pyridoxal 5'-phosphate (PLP) cofactor to facilitate the transamination of amino acids. Recently, we demonstrated that, upon exposure to blue light, PLP forms a reactive triplet state that rapidly (in microseconds) generates the high-energy quinonoid intermediate when bound to PLP-dependent enzymes [J. Am. Chem. Soc.2010, 132 (47), 16953-16961]. This increases the net catalytic activity (k(cat)) of AAT, since formation of the quinonoid is partially rate limiting via the thermally activated enzymatic pathway. The magnitude of observed photoenhancement initially scales linearly with pump fluence; however when a critical threshold is exceeded, the photoactivity saturates and is even suppressed at greater excitation fluences. The photodynamic mechanisms associated with this suppression behavior are characterized with the use of ultrafast multipulse pump-dump-probe and pump-repump-probe transient absorption techniques in combination with complementary two-color, steady-state excitation assays. Via multistate kinetic modeling of the transient ultrafast data and the steady-state assay data, the nonmonotonic incident power dependence of the photoactivty in AAT is decomposed into contributions from high-intensity dumping of the excited singlet state and repumping of the excited triplet state with induces the repopulation of the ground state via rapid intersystem crossing in the higher-lying triplet electronic manifold.

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.

Multifaceted Quadruplet of Low-Lying Spin-Zero States in 66Ni: Emergence of Shape Isomerism in Light Nuclei

NASA Astrophysics Data System (ADS)

Leoni, S.; Fornal, B.; Mǎrginean, N.; Sferrazza, M.; Tsunoda, Y.; Otsuka, T.; Bocchi, G.; Crespi, F. C. L.; Bracco, A.; Aydin, S.; Boromiza, M.; Bucurescu, D.; Cieplicka-Oryǹczak, N.; Costache, C.; Cǎlinescu, S.; Florea, N.; GhiÅ£ǎ, D. G.; Glodariu, T.; Ionescu, A.; Iskra, Ł. W.; Krzysiek, M.; Mǎrginean, R.; Mihai, C.; Mihai, R. E.; Mitu, A.; NegreÅ£, A.; NiÅ£ǎ, C. R.; Olǎcel, A.; Oprea, A.; Pascu, S.; Petkov, P.; Petrone, C.; Porzio, G.; Şerban, A.; Sotty, C.; Stan, L.; Ştiru, I.; Stroe, L.; Şuvǎilǎ, R.; Toma, S.; Turturicǎ, A.; Ujeniuc, S.; Ur, C. A.

2017-04-01

A search for shape isomers in the 66Ni nucleus was performed, following old suggestions of various mean-field models and recent ones, based on state-of-the-art Monte Carlo shell model (MCSM), all considering 66Ni as the lightest nuclear system with shape isomerism. By employing the two-neutron transfer reaction induced by an 18O beam on a 64Ni target, at the sub-Coulomb barrier energy of 39 MeV, all three lowest-excited 0+ states in 66Ni were populated and their γ decay was observed by γ -coincidence technique. The 0+ states lifetimes were assessed with the plunger method, yielding for the 02+, 03+, and 04+ decay to the 21+ state the B (E 2 ) values of 4.3, 0.1, and 0.2 Weisskopf units (W.u.), respectively. MCSM calculations correctly predict the existence of all three excited 0+ states, pointing to the oblate, spherical, and prolate nature of the consecutive excitations. In addition, they account for the hindrance of the E 2 decay from the prolate 04+ to the spherical 21+ state, although overestimating its value. This result makes 66Ni a unique nuclear system, apart from U,238236 , in which a retarded γ transition from a 0+ deformed state to a spherical configuration is observed, resembling a shape-isomerlike behavior.

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

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.

A QM/MM study of the initial excited state dynamics of green-absorbing proteorhodopsin.

PubMed

Borin, Veniamin A; Wiebeler, Christian; Schapiro, Igor

2018-04-17

The primary photochemical reaction of the green-absorbing proteorhodopsin is studied by means of a hybrid quantum mechanics/molecular mechanics (QM/MM) approach. The simulations are based on a homology model derived from the blue-absorbing proteorhodopsin crystal structure. The geometry of retinal and the surrounding sidechains in the protein binding pocket were optimized using the QM/MM method. Starting from this geometry the isomerization was studied with a relaxed scan along the C13[double bond, length as m-dash]C14 dihedral. It revealed an "aborted bicycle pedal" mechanism of isomerization that was originally proposed by Warshel for bovine rhodopsin and bacteriorhodopsin. However, the isomerization involved the concerted rotation about C13[double bond, length as m-dash]C14 and C15[double bond, length as m-dash]N, with the latter being highly twisted but not isomerized. Further, the simulation showed an increased steric interaction between the hydrogen at the C14 of the isomerizing bond and the hydroxyl group at the neighbouring tyrosine 200. In addition, we have simulated a nonadiabatic trajectory which showed the timing of the isomerization. In the first 20 fs upon excitation the order of the conjugated double and single bonds is inverted, consecutively the C13[double bond, length as m-dash]C14 rotation is activated for 200 fs until the S1-S0 transition is detected. However, the isomerization is reverted due to the specific interaction with the tyrosine as observed along the relaxed scan calculation. Our simulations indicate that the retinal - tyrosine 200 interaction plays an important role in the outcome of the photoisomerization.

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 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.

Simultaneous monitoring of oxidation, deamidation, isomerization, and glycosylation of monoclonal antibodies by liquid chromatography-mass spectrometry method with ultrafast tryptic digestion.

PubMed

Wang, Yi; Li, Xiaojuan; Liu, Yan-Hui; Richardson, Daisy; Li, Huijuan; Shameem, Mohammed; Yang, Xiaoyu

Monoclonal antibodies are subjected to a wide variety of post-translational modifications (PTMs) that cause structural heterogeneity. Characterization and control of these modifications or quality attributes are critical to ensure antibody quality and to define any potential effects on the ultimate safety and potency of antibody therapeutics. The biopharmaceutical industry currently uses numerous tools to analyze these quality attributes individually, which requires substantial time and resources. Here, we report a simple and ultrafast bottom-up liquid chromatography-mass spectrometry (uLC-MS) method with 5 min tryptic digestion to simultaneously analyze multiple modifications, including oxidation, deamidation, isomerization, glycation, glycosylation, and N-terminal pyro-glutamate formation, which can occur during antibody production in mammalian cell culture, during purification and/or on storage. Compared to commonly used preparation procedures, this uLC-MS method eliminates assay artifacts of falsely-increased Met oxidation, Asp isomerization, and Asn deamidation, a problem associated with long digestion times in conventional LC-MS methods. This simple, low artifact multi-attribute uLC-MS method can be used to quickly and accurately analyze samples at any stage of antibody drug development, in particular for clone and media selection during cell culture development.

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

Gurgi, L. A.; Regan, P. H.; Söderström, P. -A.

In-flight fission of a 345 MeV per nucleon 238U primary beam on a 2 mm thick 9Be target has been used to produce and study the decays of a range of neutron-rich nuclei centred around the doubly mid-shell nucleus 170Dy at the RIBF Facility, RIKEN, Japan. The produced secondary fragments of interest were identified event-by-event using the BigRIPS separator. The fragments were implanted into the WAS3ABI position sensitive silicon active stopper which allowed pixelated correlations between implants and their subsequent β-decay. Discrete γ-ray transitions emitted following decays from either metastable states or excited states populated following beta decay were identifiedmore » using the 84 coaxial high-purity germanium (HPGe) detectors of the EURICA spectrometer, which was complemented by 18 additional cerium-doped lanthanum bromide (LaBr3) fast-timing scintillation detectors from the FATIMA collaboration. This paper presents the internal decay of a metastable isomeric excited state in the odd-odd nucleus 168Tb, which corresponds to a single proton-neutron hole configuration in the valence maximum nucleus 170Dy. These data represent the first information on excited states in this nucleus, which is the most neutron-rich odd-odd isotope of terbium (Z=65) studied to date. Nilsson configurations associated with an axially symmetric, prolate-deformed nucleus are proposed for the 168Tb ground state the observed isomeric state by comparison with Blocked BCS-Nilsson calculations.« less

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

Gurgi, L. A.; Regan, P. H.; Söderström, P. -A.

In-flight fission of a 345 MeV per nucleon 238U primary beam on a 2 mm thick 9Be target has been used to produce and study the decays of a range of neutron-rich nuclei centred around the doubly mid-shell nucleus 170Dy at the RIBF Facility, RIKEN, Japan. The produced secondary fragments of interest were identified event-by-event using the BigRIPS separator. The fragments were implanted into the WAS3ABI position sensitive silicon active stopper which allowed pixelated correlations between implants and their subsequent β-decay. Discrete γ-ray transitions emitted following decays from either metastable states or excited states populated following beta decay were identifiedmore » using the 84 coaxial high-purity germanium (HPGe) detectors of the EURICA spectrometer, which was complemented by 18 additional cerium-doped lanthanum bromide (LaBr 3) fast-timing scintillation detectors from the FATIMA collaboration. This paper presents the internal decay of a metastable isomeric excited state in the odd-odd nucleus 168Tb, which corresponds to a single proton-neutron hole configuration in the valence maximum nucleus 170Dy. These data represent the first information on excited states in this nucleus, which is the most neutron-rich odd-odd isotope of terbium (Z = 65) studied to date. Here, Nilsson configurations associated with an axially symmetric, prolate-deformed nucleus are proposed for the 168Tb ground state the observed isomeric state by comparison with Blocked BCS-Nilsson calculations.« less

Survival of nature's rarest isotope {sup 180}Ta under stellar conditions

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

Mohr, P.; Kaeppeler, F.; Gallino, R.

2007-01-15

The nucleosynthesis of nature's rarest isotope {sup 180}Ta depends sensitively on the temperature of the astrophysical environment because of depopulation of the long-living isomeric state via intermediate states to the short-living ground state by thermal photons. Reaction rates for this transition have been measured in the laboratory. These ground state rates underestimate the stellar rates dramatically because under stellar conditions intermediate states are mainly populated by excitations from thermally excited states in {sup 180m}Ta. Full thermalization of {sup 180}Ta is already achieved for typical s-process temperatures around kT=25 keV. Consequently, for the survival of {sup 180}Ta in the s-process fastmore » convective mixing is required which has to transport freshly synthesized {sup 180}Ta to cooler regions. In supernova explosions {sup 180}Ta is synthesized by photon- or neutrino-induced reactions at temperatures above T{sub 9}=1 in thermal equilibrium; independent of the production mechanism, freeze-out from thermal equilibrium occurs at kT{approx_equal}40 keV, and only 35{+-}4% of the synthesized {sup 180}Ta survive in the isomeric state.« less

First spatial separation of a heavy ion isomeric beam with a multiple-reflection time-of-flight mass spectrometer

NASA Astrophysics Data System (ADS)

Dickel, T.; Plaß, W. R.; Ayet San Andres, S.; Ebert, J.; Geissel, H.; Haettner, E.; Hornung, C.; Miskun, I.; Pietri, S.; Purushothaman, S.; Reiter, M. P.; Rink, A.-K.; Scheidenberger, C.; Weick, H.; Dendooven, P.; Diwisch, M.; Greiner, F.; Heiße, F.; Knöbel, R.; Lippert, W.; Moore, I. D.; Pohjalainen, I.; Prochazka, A.; Ranjan, M.; Takechi, M.; Winfield, J. S.; Xu, X.

2015-05-01

211Po ions in the ground and isomeric states were produced via 238U projectile fragmentation at 1000 MeV/u. The 211Po ions were spatially separated in flight from the primary beam and other reaction products by the fragment separator FRS. The ions were energy-bunched, slowed-down and thermalized in a gas-filled cryogenic stopping cell (CSC). They were then extracted from the CSC and injected into a high-resolution multiple-reflection time-of-flight mass spectrometer (MR-TOF-MS). The excitation energy of the isomer and, for the first time, the isomeric-to-ground state ratio were determined from the measured mass spectrum. In the subsequent experimental step, the isomers were spatially separated from the ions in the ground state by an ion deflector and finally collected with a silicon detector for decay spectroscopy. This pioneering experimental result opens up unique perspectives for isomer-resolved studies. With this versatile experimental method new isomers with half-lives longer than a few milliseconds can be discovered and their decay properties can be measured with highest sensitivity and selectivity. These experiments can be extended to studies with isomeric beams in nuclear reactions.

Ultrafast Excited-State Dynamics of Cytosine Aza-Derivative and Analogues.

PubMed

Zhou, Zhongneng; Zhou, Xueyao; Wang, Xueli; Jiang, Bin; Li, Yongle; Chen, Jinquan; Xu, Jianhua

2017-04-13

Excited state dynamics of 5-azacytosine (5-AC), 2,4-diamino-1,3,5-triazine (2,4-DT), and 2-amino-1,3,5-triazine (2-AT) were comprehensively investigated by steady state absorption, fluorescence, and femtosecond transient absorption measurements. Time-dependent density functional theory (TDDFT) calculations were performed to help assign the absorption bands and understand the excited state decay mechanisms. The experimental results of excited singlet state dynamics for 5-AC, 2,4-DT, and 2-AT with femtosecond time resolution were reported for the first time. Two distinct decay pathways, with ∼1 ps and tens of picosecond lifetimes, were observed in 5-AC. Only one decay pathway with 17 ps lifetime was observed in 2,4-DT while an emissive state was found in 2-AT. TDDFT calculations suggest that 5-AC has a dark nπ* (S 1 ) state below the first allowed ππ* (S 2 ) state, which leads to the ultrafast decay of the ππ* state. In 2,4-DT, there is no dark nπ* state below the bright ππ* (S 1 ) state and the 17 ps lifetime is assigned to the relaxation from the ππ* (S 1 ) state to ground state. Two dark nπ* states (S 1 and S 2 ) were found in 2-AT, which exhibits much more complex excited state dynamics compared with the other two. Photoluminescence in 2-AT has been confirmed to be fluorescence emission from its bright ππ* (S 3 ) state. Our results strongly suggest that electronic structures are very sensitive to the substitution on the triazine ring and that the photophysical properties of nucleic acid analogues depend highly on their molecular structures.

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

Many of the spectroscopic features and photophysical properties of carotenoids are explained using a three-state model in which the strong visible absorption of the molecules is associated with an S0 (1(1)Ag-) --> S2 (1(1)Bu+) transition, and the lowest lying singlet state, S1 (2(1)Ag-), is a state into which absorption from the ground state is forbidden by symmetry. However, semiempirical and ab initio quantum calculations have suggested additional excited singlet states may lie either between or in the vicinity of S1 (2(1)Ag-) and S2 (1(1)Bu+), and some ultrafast spectroscopic studies have reported evidence for these states. One such state, denoted S*, has been implicated as an intermediate in the depopulation of S2 (1(1)Bu+) and as a pathway for the formation of carotenoid triplet states in light-harvesting complexes. In this work, we present the results of an ultrafast, time-resolved spectroscopic investigation of a series of open-chain carotenoids derived from photosynthetic bacteria and systematically increasing in their number of pi-electron carbon-carbon double bonds (n). The molecules are neurosporene (n = 9), spheroidene (n = 10), rhodopin glucoside (n = 11), rhodovibrin (n = 12), and spirilloxanthin (n = 13). The molecules were studied in acetone and CS2 solvents at room temperature. These experiments explore the effect of solvent polarity and polarizability on the spectroscopic and kinetic behavior of the molecules. The molecules were also studied in ether/isopentane/ethanol (EPA) glasses at 77 K, in which the spectral resolution is greatly enhanced. Analysis of the data using global fitting techniques has revealed the ultrafast dynamics of the excited states and spectral changes associated with their decay, including spectroscopic features not previously reported. The data are consistent with S* being identified with a twisted conformational structure, the yield of which is increased in molecules having longer pi-electron conjugations. In particular, 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 photo-initiated molecular quantum dynamics in the DNA dinucleotide d(ApG) revealed by broadband transient absorption spectroscopy.

PubMed

Stuhldreier, Mayra C; Temps, Friedrich

2013-01-01

The ultrafast photo-initiated quantum dynamics of the adenine-guanine dinucleotide d(ApG) in aqueous solution (pH 7) has been studied by femtosecond time-resolved spectroscopy after excitation at lambda = 260 nm. The results reveal a hierarchy of processes on time scales from tau < 100 fs to tau > 100 ps. Characteristic spectro-temporal signatures are observed indicating the transformation of the molecules in the electronic relaxation from the photo-excited state to a long-lived exciplex. In particular, broadband UV/VIS excited-state absorption (ESA) measurements detected a distinctive absorption by the excited dinucleotide around lambda = 335 nm, approximately 0.5 eV to the blue compared to the maximum of the broad and unstructured ESA spectrum after excitation of an equimolar mixture of the mononucleotides dAMP and dGMP. A similar feature has been identified as signature of the excimer in the dynamics of the adenine dinucleotide d(ApA). The lifetime of the d(ApG) exciplex was found to be tau = 124 +/- 4 ps both from the ESA decay time and from the ground-state recovery time, far longer than the sub-picosecond lifetimes of excited dAMP or dGMP. Fluorescence-time profiles measured by the up-conversion technique indicate that the exciplex state is reached around approximately 6 ps after excitation. Very weak residual fluorescence at longer times red-shifted to the emission from the photo-excited state shows that the exciplex is almost optically dark, but still has enough oscillator strength to give rise to the dual fluorescence of the dinucleotide in the static fluorescence spectrum.

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.

Dynamics of liquids, molecules, and proteins measured with ultrafast 2D IR vibrational echo chemical exchange spectroscopy.

PubMed

Fayer, M D

2009-01-01

A wide variety of molecular systems undergo fast structural changes under thermal equilibrium conditions. Such transformations are involved in a vast array of chemical problems. Experimentally measuring equilibrium dynamics is a challenging problem that is at the forefront of chemical research. This review describes ultrafast 2D IR vibrational echo chemical exchange experiments and applies them to several types of molecular systems. The formation and dissociation of organic solute-solvent complexes are directly observed. The dissociation times of 13 complexes, ranging from 4 ps to 140 ps, are shown to obey a relationship that depends on the complex's formation enthalpy. The rate of rotational gauche-trans isomerization around a carbon-carbon single bond is determined for a substituted ethane at room temperature in a low viscosity solvent. The results are used to obtain an approximate isomerization rate for ethane. Finally, the time dependence of a well-defined single structural transformation of a protein is measured.

Laser pulse induced multi-exciton dynamics in molecular systems

NASA Astrophysics Data System (ADS)

Wang, Luxia; May, Volkhard

2018-03-01

Ultrafast optical excitation of an arrangement of identical molecules is analyzed theoretically. The computations are particularly dedicated to molecules where the excitation energy into the second excited singlet state E(S 2) - E(S 0) is larger than twice the excitation energy into the first excited singlet state E(S 1) - E(S 0). Then, exciton-exciton annihilation is diminished and resonant and intensive excitation may simultaneously move different molecules into their first excited singlet state | {S}1> . To describe the temporal evolution of the thus created multi-exciton state a direct computation of the related wave function is circumvented. Instead, we derive equations of motion for expectation values formed by different arrangements of single-molecule transition operators | {S}1> < {S}0| . First simulation results are presented and the approximate treatment suggested recently in 2016 Phys. Rev. B 94 195413 is evaluated.

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

Ultrafast internal conversion dynamics of highly excited pyrrole studied with VUV/UV pump probe spectroscopy.

PubMed

Horton, Spencer L; Liu, Yusong; Chakraborty, Pratip; Matsika, Spiridoula; Weinacht, Thomas

2017-02-14

We study the relaxation dynamics of pyrrole after excitation with an 8 eV pump pulse to a state just 0.2 eV below the ionization potential using vacuum ultraviolet/ultraviolet pump probe spectroscopy. Our measurements in conjunction with electronic structure calculations indicate that pyrrole undergoes rapid internal conversion to the ground state in less than 300 fs. We find that internal conversion to the ground state dominates over dissociation.

Vibrational motions associated with primary processes in bacteriorhodopsin studied by coherent infrared emission spectroscopy.

PubMed

Groma, Géza I; Colonna, Anne; Martin, Jean-Louis; Vos, Marten H

2011-03-16

The primary energetic processes driving the functional proton pump of bacteriorhodopsin take place in the form of complex molecular dynamic events after excitation of the retinal chromophore into the Franck-Condon state. These early events include a strong electronic polarization, skeletal stretching, and all-trans-to-13-cis isomerization upon formation of the J intermediate. The effectiveness of the photoreaction is ensured by a conical intersection between the electronic excited and ground states, providing highly nonadiabatic coupling to nuclear motions. Here, we study real-time vibrational coherences associated with these motions by analyzing light-induced infrared emission from oriented purple membranes in the 750-1400 cm(-)(1) region. The experimental technique applied is based on second-order femtosecond difference frequency generation on macroscopically ordered samples that also yield information on phase and direction of the underlying motions. Concerted use of several analysis methods resulted in the isolation and characterization of seven different vibrational modes, assigned as C-C stretches, out-of-plane methyl rocks, and hydrogen out-of-plane wags, whereas no in-plane H rock was found. Based on their lifetimes and several other criteria, we deduce that the majority of the observed modes take place on the potential energy surface of the excited electronic state. In particular, the direction sensitivity provides experimental evidence for large intermediate distortions of the retinal plane during the excited-state isomerization process. Copyright © 2011 Biophysical Society. Published by Elsevier Inc. All rights reserved.

Molecular and excited state properties of isomeric scarlet disperse dyes

NASA Astrophysics Data System (ADS)

Lim, Jihye; Szymczyk, Malgorzata; Mehraban, Nahid; Ding, Yi; Parrillo-Chapman, Lisa; El-Shafei, Ahmed; Freeman, Harold S.

2018-06-01

This work was part of an investigation aimed at characterizing the molecular and excited state properties of currently available disperse dyes developed to provide stability to extensive sunlight exposures when adsorbed on poly(ethylene terephthalate) (PET) fibers. Having completed the characterization of yellow, magenta, and cyan disperse dyes for PET-based fabrics used outdoors, our attention turned to the colors designed to enhance the color gamut of a standard 4-member (cyan/yellow/magenta/black) color set. The present study pertained specifically to the characterization of commercially available scarlet dyes. In this regard, HPLC analysis showed that a scarlet product used for PET coloration was mainly a 70/30 mixture of dyes, and the use of HRMS and single crystal X-ray diffraction analyses indicated that these two dyes were azo compounds derived from isomeric pyridine-based couplers which differed in the location of the primary amino (sbnd NH2) and anilino (sbnd NHPh) groups attached to the pyridine ring. One dye structure has the sbnd NHPh group para to the azo group (Sc2), while the other has that group in the ortho position (Sc3). The presence of either ortho substituent provides photostabilization through intramolecular H-bonding with the azo moiety. Further, results from molecular modeling studies showed that the lower excited state oxidation potential of Sc3 relative to that of Sc2 allows Sc3 to function as an energy quencher for the excited state of Sc2 - through thermodynamically favorable electron transfer.

Complete coherent control of silicon vacancies in diamond nanopillars containing single defect centers

DOE PAGES

Zhang, Jingyuan Linda; Lagoudakis, Konstantinos G.; Tzeng, Yan -Kai; ...

2017-10-23

Arrays of identical and individually addressable qubits lay the foundation for the creation of scalable quantum hardware such as quantum processors and repeaters. Silicon-vacancy (SiV) centers in diamond offer excellent physical properties such as low inhomogeneous broadening, fast photon emission, and a large Debye–Waller factor. The possibility for all-optical ultrafast manipulation and techniques to extend the spin coherence times makes them promising candidates for qubits. Here, we have developed arrays of nanopillars containing single (SiV) centers with high yield, and we demonstrate ultrafast all-optical complete coherent control of the excited state population of a single SiV center at the opticalmore » transition frequency. The high quality of the chemical vapor deposition (CVD) grown SiV centers provides excellent spectral stability, which allows us to coherently manipulate and quasi-resonantly read out the excited state population of individual SiV centers on picosecond timescales using ultrafast optical pulses. Furthermore, this work opens new opportunities to create a scalable on-chip diamond platform for quantum information processing and scalable nanophotonics applications.« less

Complete coherent control of silicon vacancies in diamond nanopillars containing single defect centers

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

Zhang, Jingyuan Linda; Lagoudakis, Konstantinos G.; Tzeng, Yan -Kai

Arrays of identical and individually addressable qubits lay the foundation for the creation of scalable quantum hardware such as quantum processors and repeaters. Silicon-vacancy (SiV) centers in diamond offer excellent physical properties such as low inhomogeneous broadening, fast photon emission, and a large Debye–Waller factor. The possibility for all-optical ultrafast manipulation and techniques to extend the spin coherence times makes them promising candidates for qubits. Here, we have developed arrays of nanopillars containing single (SiV) centers with high yield, and we demonstrate ultrafast all-optical complete coherent control of the excited state population of a single SiV center at the opticalmore » transition frequency. The high quality of the chemical vapor deposition (CVD) grown SiV centers provides excellent spectral stability, which allows us to coherently manipulate and quasi-resonantly read out the excited state population of individual SiV centers on picosecond timescales using ultrafast optical pulses. Furthermore, this work opens new opportunities to create a scalable on-chip diamond platform for quantum information processing and scalable nanophotonics applications.« less

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.

Properties of the anion-binding site of pharaonis Halorhodopsin studied by ultrafast pump-probe spectroscopy and low-temperature FTIR spectroscopy.

PubMed

Nakashima, Keisuke; Nakamura, Takumi; Takeuchi, Satoshi; Shibata, Mikihiro; Demura, Makoto; Tahara, Tahei; Kandori, Hideki

2009-06-18

Halorhodopsin (HR) is a light-driven chloride pump. Cl(-) is bound in the Schiff base region of the retinal chromophore, and unidirectional Cl(-) transport is probably enforced by the specific hydrogen-bonding interaction with the protonated Schiff base and internal water molecules. It is known that HR from Natronobacterium pharaonis (pHR) also pumps NO(3)(-) with similar efficiency, suggesting that NO(3)(-) binds to the Cl(-)-binding site. In the present study, we investigated the properties of the anion-binding site by means of ultrafast pump-probe spectroscopy and low-temperature FTIR spectroscopy. The obtained data were surprisingly similar between pHR-NO(3)(-) and pHR-Cl(-), even though the shapes and sizes of the two anions are quite different. Femtosecond pump-probe spectroscopy showed very similar excited-state dynamics between pHR-NO(3)(-) and pHR-Cl(-). Low-temperature FTIR spectroscopy of unlabeled and [zeta-(15)N]Lys-labeled pHR revealed almost identical hydrogen-bonding strengths of the protonated retinal Schiff base between pHR-NO(3)(-) and pHR-Cl(-), which is similarly strengthened after retinal isomerization. There were spectral variations for water stretching vibrations between pHR-NO(3)(-) and pHR-Cl(-), suggesting that the water molecules hydrate each anion. Nevertheless, the overall spectral features were similar for the two species. These observations strongly suggest that the anion-binding site has a flexible structure and that the interaction between retinal and the anions is weak, despite the presence of an electrostatic interaction. Such a flexible hydrogen-bonding network in the Schiff base region in HR appears to be in remarkable contrast to that in light-driven proton-pumping proteins.

The use of dendrimers as high-performance shells for round-trip energy transfer: efficient trans-cis photoisomerization from an excited triplet state produced within a dendrimer shell.

PubMed

Miura, Yousuke; Momotake, Atsuya; Takeuchi, Keiichirou; Arai, Tatsuo

2011-01-01

A series of stilbene-cored poly(benzyl ether) dendrimers with benzophenone peripheries were synthesized and their photophysical and photochemical properties were studied. Fluorescence studies revealed that singlet-singlet energy transfer (SSET) from the stilbene core to the benzophenone units took place efficiently in dendrimers of all generations. Similarly, phosphorescence and time-resolved spectroscopic measurements indicated efficient triplet-triplet energy transfer (TTET) from the benzophenone periphery to the stilbene core. Upon excitation at 310 nm, the stilbene core isomerizes via an energy round trip within the dendrimer shell. The quantum yields for the energy round trip (Φ(ERT)), defined as the product of the quantum yields of SSET, intersystem crossing, and TTET (Φ(ERT) = Φ(SS)Φ(isc)Φ(TT)), were extremely high for all generations--99%, 95% and 94% for G1, G2, and G3, respectively--which means that the excitation energy of the dendrimer core was transferred to the dendrimer periphery and back to the core almost quantitatively. The quantum yield for photoisomerization of G1-G3 via an energy round trip was higher than for other stilbene-cored dendrimers, which mainly isomerize from the excited singlet state. Photostability in the dendrimers was also demonstrated and discussed.

Ultrafast non-adiabatic dynamics of methyl substituted ethylenes: the π3s Rydberg state.

PubMed

Wu, Guorong; Boguslavskiy, Andrey E; Schalk, Oliver; Schuurman, Michael S; Stolow, Albert

2011-10-28

Excited state unimolecular reactions of some polyenes exhibit localization of their dynamics at a single ethylenic double bond. Here we present studies of the fundamental photophysical processes in the ethylene unit itself. Combined femtosecond time-resolved photoelectron spectroscopy (TRPES) and ab initio quantum chemical calculations was applied to the study of excited state dynamics in cis-butene, trans-butene, trimethylethylene, and tetramethylethylene, following initial excitation to their respective π3s Rydberg states. The wavelength dependence of the π3s Rydberg state dynamics of tetramethylethylene was investigated in more detail. The π3s Rydberg to ππ(∗) valence state decay rate varies greatly with substituent: the 1,2-di- and tri-methyl substituted ethylenes (cis-butene, trans-butene, and trimethylethylene) show an ultrafast decay (∼20 fs), whereas the fully methylated tetramethylethylene shows a decay rate of 2 to 4 orders of magnitude slower. These observations are rationalized in terms of topographical trends in the relevant potential energy surfaces, as found from ab initio calculations: (1) the barrier between the π3s state and the ππ∗ state increases with increasing methylation, and (2) the π3s∕ππ∗ minimum energy conical intersection displaces monotonically away from the π3s Franck-Condon region with increasing methylation. The use of systematic methylation in combination with TRPES and ab initio computation is emerging as an important tool in discerning the excited state dynamics of unsaturated hydrocarbons.

Ultrafast non-adiabatic dynamics of methyl substituted ethylenes: The π3s Rydberg state

NASA Astrophysics Data System (ADS)

Wu, Guorong; Boguslavskiy, Andrey E.; Schalk, Oliver; Schuurman, Michael S.; Stolow, Albert

2011-10-01

Excited state unimolecular reactions of some polyenes exhibit localization of their dynamics at a single ethylenic double bond. Here we present studies of the fundamental photophysical processes in the ethylene unit itself. Combined femtosecond time-resolved photoelectron spectroscopy (TRPES) and ab initio quantum chemical calculations was applied to the study of excited state dynamics in cis-butene, trans-butene, trimethylethylene, and tetramethylethylene, following initial excitation to their respective π3s Rydberg states. The wavelength dependence of the π3s Rydberg state dynamics of tetramethylethylene was investigated in more detail. The π3s Rydberg to ππ* valence state decay rate varies greatly with substituent: the 1,2-di- and tri-methyl substituted ethylenes (cis-butene, trans-butene, and trimethylethylene) show an ultrafast decay (˜20 fs), whereas the fully methylated tetramethylethylene shows a decay rate of 2 to 4 orders of magnitude slower. These observations are rationalized in terms of topographical trends in the relevant potential energy surfaces, as found from ab initio calculations: (1) the barrier between the π3s state and the ππ* state increases with increasing methylation, and (2) the π3s/ππ* minimum energy conical intersection displaces monotonically away from the π3s Franck-Condon region with increasing methylation. The use of systematic methylation in combination with TRPES and ab initio computation is emerging as an important tool in discerning the excited state dynamics of unsaturated hydrocarbons.

A new twist in the photophysics of the GFP chromophore: a volume-conserving molecular torsion couple† †Electronic supplementary information (ESI) available: Synthetic methods and characterization; fluorescence up-conversion data; additional computational details; Cartesian coordinates of key structures; photochemical isomerization data; data for the anion of I. See DOI: 10.1039/c7sc04091a

PubMed Central

Conyard, Jamie; Heisler, Ismael A.; Chan, Yohan; Bulman Page, Philip C.

2018-01-01

The simple structure of the chromophore of the green fluorescent protein (GFP), a phenol and an imidazolone ring linked by a methyne bridge, supports an exceptionally diverse range of excited state phenomena. Here we describe experimentally and theoretically the photochemistry of a novel sterically crowded nonplanar derivative of the GFP chromophore. It undergoes an excited state isomerization reaction accompanied by an exceptionally fast (sub 100 fs) excited state decay. The decay dynamics are essentially independent of solvent polarity and viscosity. Excited state structural dynamics are probed by high level quantum chemical calculations revealing that the fast decay is due to a conical intersection characterized by a twist of the rings and pyramidalization of the methyne bridge carbon. The intersection can be accessed without a barrier from the pre-twisted Franck–Condon structure, and the lack of viscosity dependence is due to the fact that the rings twist in the same direction, giving rise to a volume-conserving decay coordinate. Moreover, the rotation of the phenyl, methyl and imidazolone groups is coupled in the sterically crowded structure, with the methyl group translating the rotation of one ring to the next. As a consequence, the excited state dynamics can be viewed as a torsional couple, where the absorbed photon energy leads to conversion of the out-of-plane orientation from one ring to the other in a volume conserving fashion. A similar modification of the range of methyne dyes may provide a new family of devices for molecular machines, specifically torsional couples. PMID:29675225

Effect of wetting-layer density of states on the gain and phase recovery dynamics of quantum-dot semiconductor optical amplifiers

NASA Astrophysics Data System (ADS)

Kim, Jungho; Yu, Bong-Ahn

2015-03-01

We numerically investigate the effect of the wetting-layer (WL) density of states on the gain and phase recovery dynamics of quantum-dot semiconductor optical amplifiers in both electrical and optical pumping schemes by solving 1088 coupled rate equations. The temporal variations of the ultrafast gain and phase recovery responses at the ground state (GS) are calculated as a function of the WL density of states. The ultrafast gain recovery responses do not significantly depend on the WL density of states in the electrical pumping scheme and the three optical pumping schemes such as the optical pumping to the WL, the optical pumping to the excited state ensemble, and the optical pumping to the GS ensemble. The ultrafast phase recovery responses are also not significantly affected by the WL density of states except the optical pumping to the WL, where the phase recovery component caused by the WL becomes slowed down as the WL density of states increases.

Exciton Splitting of Adsorbed and Free 4-Nitroazobenzene Dimers: A Quantum Chemical Study.

PubMed

Titov, Evgenii; Saalfrank, Peter

2016-05-19

Molecular photoswitches such as azobenzenes, which undergo photochemical trans ↔ cis isomerizations, are often mounted for possible applications on a surface and/or surrounded by other switches, for example, in self-assembled monolayers. This may suppress the isomerization cross section due to possible steric reasons, or, as recently speculated, by exciton coupling to neighboring switches, leading to ultrafast electronic quenching (Gahl et al., J. Am. Chem. Soc. 2010, 132, 1831). The presence of exciton coupling has been anticipated from a blue shift of the optical absorption band, compared to molecules in solution. From the theory side the need arises to properly analyze and quantify the change of absorption spectra of interacting and adsorbed switches. In particular, suitable methods should be identified, and effects of intermolecule and molecule-surface interactions on spectra should be disentangled. In this paper by means of time-dependent Hartree-Fock (TD-HF), various flavors of time-dependent density functional theory (TD-DFT), and the correlated wave function based coupled-cluster (CC2) method we investigated the 4-nitroazobenzene molecule as an example: The low-lying singlet excited states in the isolated trans monomer and dimer as well as their composites with a silicon pentamantane nanocluster, which serves also as a crude model for a silicon surface, were determined. As most important results we found that (i) HF, CC2, range-separated density functionals, or global hybrids with large amount of exact exchange are able to describe exciton (Davydov) splitting properly, while hybrids with small amount of exact exchange fail producing spurious charge transfer. (ii) The exciton splitting in a free dimer would lead to a blue shift of the absorption signal; however, this effect is almost nullified or even overcompensated by the shift arising from van der Waals interactions between the two molecules. (iii) Adsorption on the Si "surface" leads to a further, strong red shift for the present system. (iv) At a next-nearest neighbor distance (of ∼3.6 Å), the exciton splitting is ∼0.3 eV, with or without "surface", suggesting a rapid quenching of the molecular π → π* excitation. At larger distances, exciton splitting decreases rapidly.

Ultrafast re-structuring of the electronic landscape of transparent dielectrics: new material states (Die-Met)

NASA Astrophysics Data System (ADS)

Gamaly, E. G.; Rode, A. V.

2018-03-01

Swift excitation of transparent dielectrics by ultrashort and highly intense laser pulse leads to ultra-fast re-structuring of the electronic landscape and generates many transient material states, which are continuously reshaped in accord with the changing pulse intensity. These unconventional transient material states, which exhibit simultaneously both dielectric and metallic properties, we termed here as the `Die-Met' states. The excited material is transparent and conductive at the same time. The real part of permittivity of the excited material changes from positive to negative values with the increase of excitation, which affects strongly the interaction process during the laser pulse. When the incident field has a component along the permittivity gradient, the amplitude of the field increases resonantly near the point of zero permittivity, which dramatically changes the interaction mode and increases absorption in a way that is similar to the resonant absorption in plasma. The complex 3D structure of the permittivity makes a transparent part of the excited dielectric (at ɛ 0 > ɛ re > 0) optically active. The electro-magnetic wave gets a twisted trajectory and accrues the geometric phase while passing through such a medium. Both the phase and the rotation of the polarisation plane depend on the 3D permittivity structure. Measuring the transmission, polarisation and the phase of the probe beam allows one to quantitatively identify these new transient states. We discuss the revelations of this effect in different experimental situations and their possible applications.

Energy cascades, excited state dynamics, and photochemistry in cob(III)alamins and ferric porphyrins.

PubMed

Rury, Aaron S; Wiley, Theodore E; Sension, Roseanne J

2015-03-17

Porphyrins and the related chlorins and corrins contain a cyclic tetrapyrrole with the ability to coordinate an active metal center and to perform a variety of functions exploiting the oxidation state, reactivity, and axial ligation of the metal center. These compounds are used in optically activated applications ranging from light harvesting and energy conversion to medical therapeutics and photodynamic therapy to molecular electronics, spintronics, optoelectronic thin films, and optomagnetics. Cobalt containing corrin rings extend the range of applications through photolytic cleavage of a unique axial carbon-cobalt bond, permitting spatiotemporal control of drug delivery. The photochemistry and photophysics of cyclic tetrapyrroles are controlled by electronic relaxation dynamics including internal conversion and intersystem crossing. Typically the electronic excitation cascades through ring centered ππ* states, ligand to metal charge transfer (LMCT) states, metal to ligand charge transfer (MLCT) states, and metal centered states. Ultrafast transient absorption spectroscopy provides a powerful tool for the investigation of the electronic state dynamics in metal containing tetrapyrroles. The UV-visible spectrum is sensitive to the oxidation state, electronic configuration, spin state, and axial ligation of the central metal atom. Ultrashort broadband white light probes spanning the range from 270 to 800 nm, combined with tunable excitation pulses, permit the detailed unravelling of the time scales involved in the electronic energy cascade. State-of-the-art theoretical calculations provide additional insight required for precise assignment of the states. In this Account, we focus on recent ultrafast transient absorption studies of ferric porphyrins and corrin containing cob(III)alamins elucidating the electronic states responsible for ultrafast energy cascades, excited state dynamics, and the resulting photoreactivity or photostability of these compounds. Iron tetraphenyl porphyrin chloride (Fe((III))TPPCl) exhibits picosecond decay to a metal centered d → d* (4)T state. This state decays on a ca. 16 ps time scale in room temperature solution but persists for much longer in a cryogenic glass. The photoreactivity of the (4)T state may lead to novel future applications for these compounds. In contrast, the nonplanar cob(III)alamins contain two axial ligands to the central cobalt atom. The upper axial ligand can be an alkyl group as in the two biologically active coenzymes or a nonalkyl ligand such as -CN in cyanocobalamin (vitamin B12) or -OH in hydroxocobalamin. The electronic structure, energy cascade, and bond cleavage of these compounds is sensitive to the details of the axial ligand. Nonalkylcobalamins exhibit ultrafast internal conversion to a low-lying state of metal to ligand or ligand to metal charge transfer character. The compounds are generally photostable with ground state recovery complete on a time scale of 2-7 ps in room temperature aqueous solution. Alkylcobalamins exhibit ultrafast internal conversion to an S1 state of d/π → π* character. Most compounds undergo bond cleavage from this state with near unit quantum yield within ∼100 ps. Recent theoretical calculations provide a potential energy surface accounting for these observations. Conformation dependent mixing of the corrin π and cobalt d orbitals plays a significant role in the observed photochemistry and photophysics.

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 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

Fluorescence of carotenoids. Effect of oxygenation and cis/trans isomerization

NASA Astrophysics Data System (ADS)

Jørgensen, Kevin; Stapelfeldt, Henrik; Skibsted, Leif H.

1992-03-01

C 40 carotenoids fall, with respect to fluorescence in homogeneous solution, into two distinct groups depending on the presence of a CO group in the molecule. Excitation spectra agree with absorption spectra for the carbonyl derivatives astaxanthin and canthaxanthin. In contrast, zeaxanthin and isomers of β-carotene have a twentyfold increase in fluorescence quantum yield for excitation around 350 nm compared to excitation near the absorption maximum (at approximatively 430 nm). These differences are interpreted in terms of the role of non-emitting 1(n, π*) states related to the CO group in facilitating non-radiative deactivation of higher 1(π, π*) states.

Electronic and Structural Elements That Regulate the Excited-State Dynamics in Purine Nucleobase Derivatives

PubMed Central

2015-01-01

The excited-state dynamics of the purine free base and 9-methylpurine are investigated using experimental and theoretical methods. Femtosecond broadband transient absorption experiments reveal that excitation of these purine derivatives in aqueous solution at 266 nm results primarily in ultrafast conversion of the S2(ππ*) state to the vibrationally excited 1nπ* state. Following vibrational and conformational relaxation, the 1nπ* state acts as a doorway state in the efficient population of the triplet manifold with an intersystem crossing lifetime of hundreds of picoseconds. Experiments show an almost 2-fold increase in the intersystem crossing rate on going from polar aprotic to nonpolar solvents, suggesting that a solvent-dependent energy barrier must be surmounted to access the singlet-to-triplet crossing region. Ab initio static and surface-hopping dynamics simulations lend strong support to the proposed relaxation mechanism. Collectively, the experimental and computational results demonstrate that the accessibility of the nπ* states and the topology of the potential energy surfaces in the vicinity of conical intersections are key elements in controlling the excited-state dynamics of the purine derivatives. From a structural perspective, it is shown that the purine chromophore is not responsible for the ultrafast internal conversion in the adenine and guanine monomers. Instead, C6 functionalization plays an important role in regulating the rates of radiative and nonradiative relaxation. C6 functionalization inhibits access to the 1nπ* state while simultaneously facilitating access to the 1ππ*(La)/S0 conical intersection, such that population of the 1nπ* state cannot compete with the relaxation pathways to the ground state involving ring puckering at the C2 position. PMID:25763596

Identification of four rotamers of m-methoxystyrene by resonant two-photon ionization and mass analyzed threshold ionization spectroscopy

NASA Astrophysics Data System (ADS)

Xu, Yanqi; Tzeng, Sheng Yuan; Shivatare, Vidya; Takahashi, Kaito; Zhang, Bing; Tzeng, Wen Bih

2015-03-01

We report the vibronic and cation spectra of four rotamers of m-methoxystyrene, recorded by using the two-color resonant two-photon ionization and mass-analyzed threshold ionization techniques. The excitation energies of the S1← S0 electronic transition are found to be 32 767, 32 907, 33 222, and 33 281 cm-1, and the corresponding adiabatic ionization energies are 65 391, 64 977, 65 114, and 64 525 cm-1 for these isomeric species. Most of the observed active vibrations in the electronically excited S1 and cationic ground D0 states involve in-plane ring deformation and substituent-sensitive bending motions. It is found that the relative orientation of the methoxyl with respect to the vinyl group does not influence the vibrational frequencies of the ring-substituent bending modes. The two dimensional potential energy surface calculations support our experimental finding that the isomerization is restricted in the S1 and D0 states.

Cooperative photoinduced metastable phase control in strained manganite films

NASA Astrophysics Data System (ADS)

Zhang, Jingdi; Tan, Xuelian; Liu, Mengkun; Teitelbaum, S. W.; Post, K. W.; Jin, Feng; Nelson, K. A.; Basov, D. N.; Wu, Wenbin; Averitt, R. D.

2016-09-01

A major challenge in condensed-matter physics is active control of quantum phases. Dynamic control with pulsed electromagnetic fields can overcome energetic barriers, enabling access to transient or metastable states that are not thermally accessible. Here we demonstrate strain-engineered tuning of La2/3Ca1/3MnO3 into an emergent charge-ordered insulating phase with extreme photo-susceptibility, where even a single optical pulse can initiate a transition to a long-lived metastable hidden metallic phase. Comprehensive single-shot pulsed excitation measurements demonstrate that the transition is cooperative and ultrafast, requiring a critical absorbed photon density to activate local charge excitations that mediate magnetic-lattice coupling that, in turn, stabilize the metallic phase. These results reveal that strain engineering can tune emergent functionality towards proximal macroscopic states to enable dynamic ultrafast optical phase switching and control.

Initial decomposition mechanism for the energy release from electronically excited energetic materials: FOX-7 (1,1-diamino-2,2-dinitroethene, C{sub 2}H{sub 4}N{sub 4}O{sub 4})

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

Yuan, Bing; Yu, Zijun; Bernstein, Elliot R., E-mail: erb@lamar.Colostate.edu

Decomposition of the energetic material FOX-7 (1,1-diamino-2,2-dinitroethylene, C{sub 2}H{sub 4}N{sub 4}O{sub 4}) is investigated both theoretically and experimentally. The NO molecule is observed as an initial decomposition product subsequent to electronic excitation. The observed NO product is rotationally cold (<35 K) and vibrationally hot (2800 K). The initial decomposition mechanism is explored at the complete active space self-consistent field (CASSCF) level. Potential energy surface calculations at the CASSCF(12,8)/6-31G(d) level illustrate that conical intersections play an essential role in the decomposition mechanism. Electronically excited S{sub 2} FOX-7 can radiationlessly relax to lower electronic states through (S{sub 2}/S{sub 1}){sub CI} and (S{submore » 1}/S{sub 0}){sub CI} conical intersections and undergo a nitro-nitrite isomerization to generate NO product on the S{sub 0} state. The theoretically predicted mechanism is consistent with the experimental results. As FOX-7 decomposes on the ground electronic state, thus, the vibrational energy of the NO product from FOX-7 is high. The observed rotational energy distribution for NO is consistent with the final transition state structure on the S{sub 0} state. Ground state FOX-7 decomposition agrees with previous work: the nitro-nitrite isomerization has the lowest average energy barrier, the C–NH{sub 2} bond cleavage is unlikely under the given excitation conditions, and HONO formation on the ground state surface is energy accessible but not the main process.« less

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

PubMed

Adachi, Shunsuke; Kohguchi, Hiroshi; Suzuki, Toshinori

2018-01-18

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

Conformational Control of Ultrafast Molecular Rotor Property: Tuning Viscosity Sensing Efficiency by Twist Angle Variation.

PubMed

Ghosh, Rajib; Kushwaha, Archana; Das, Dipanwita

2017-09-21

Fluorescent molecular rotors find widespread application in sensing and imaging of microscopic viscosity in complex chemical and biological media. Development of viscosity-sensitive ultrafast molecular rotor (UMR) relies upon the understanding of the excited-state dynamics and their implications for viscosity-dependent fluorescence signaling. Unraveling the structure-property relationship of UMR behavior is of significance toward development of an ultrasensitive fluorescence microviscosity sensor. Herein we show that the ground-state equilibrium conformation has an important role in the ultrafast twisting dynamics of UMRs and consequent viscosity sensing efficiency. Synthesis, photophysics, and ultrafast spectroscopic experiments in conjunction with quantum chemical calculation of a series of UMRs based on dimethylaniline donor and benzimidazolium acceptor with predefined ground-state torsion angle led us to unravel that the ultrafast torsional dynamics around the bond connecting donor and acceptor groups profoundly influences the molecular rotor efficiency. This is the first experimental demonstration of conformational control of small-molecule-based UMR efficiencies which can have wider implication toward development of fluorescence sensors based on the UMR principle. Conformation-controlled UMR efficiency has been shown to exhibit commensurate fluorescence enhancement upon DNA binding.

Isomer spectroscopy of neutron-rich 168Tb 103

DOE PAGES

Gurgi, L. A.; Regan, P. H.; Söderström, P. -A.; ...

2016-12-29

In-flight fission of a 345 MeV per nucleon 238U primary beam on a 2 mm thick 9Be target has been used to produce and study the decays of a range of neutron-rich nuclei centred around the doubly mid-shell nucleus 170Dy at the RIBF Facility, RIKEN, Japan. The produced secondary fragments of interest were identified event-by-event using the BigRIPS separator. The fragments were implanted into the WAS3ABI position sensitive silicon active stopper which allowed pixelated correlations between implants and their subsequent β-decay. Discrete γ-ray transitions emitted following decays from either metastable states or excited states populated following beta decay were identifiedmore » using the 84 coaxial high-purity germanium (HPGe) detectors of the EURICA spectrometer, which was complemented by 18 additional cerium-doped lanthanum bromide (LaBr 3) fast-timing scintillation detectors from the FATIMA collaboration. This paper presents the internal decay of a metastable isomeric excited state in the odd-odd nucleus 168Tb, which corresponds to a single proton-neutron hole configuration in the valence maximum nucleus 170Dy. These data represent the first information on excited states in this nucleus, which is the most neutron-rich odd-odd isotope of terbium (Z = 65) studied to date. Here, Nilsson configurations associated with an axially symmetric, prolate-deformed nucleus are proposed for the 168Tb ground state the observed isomeric state by comparison with Blocked BCS-Nilsson calculations.« less

Isomer spectroscopy of neutron-rich 168Tb103

NASA Astrophysics Data System (ADS)

Gurgi, L. A.; Regan, P. H.; Söderström, P.-A.; Watanabe, H.; Walker, P. M.; Podolyák, Zs.; Nishimura, S.; Berry, T. A.; Doornenbal, P.; Lorusso, G.; Isobe, T.; Baba, H.; Xu, Z. Y.; Sakurai, H.; Sumikama, T.; Catford, W. N.; Bruce, A. M.; Browne, F.; Lane, G. J.; Kondev, F. G.; Odahara, A.; Wu, J.; Liu, H. L.; Xu, F. R.; Korkulu, Z.; Lee, P.; Liu, J. J.; Phong, V. H.; Yag, A.; Zhang, G. X.; Alharbi, T.; Carroll, R. J.; Chae, K. Y.; Dombradi, Zs.; Estrade, A.; Fukuda, N.; Griffin, C.; Ideguchi, E.; Inabe, N.; Kanaoka, H.; Kojouharov, I.; Kubo, T.; Kubono, S.; Kurz, N.; Kuti, I.; Lalkovski, S.; Lee, E. J.; Lee, C. S.; Lotay, G.; Moon, C.-B.; Nishizuka, I.; Nita, C. R.; Patel, Z.; Roberts, O. J.; Schaffner, H.; Shand, C. M.; Suzuki, H.; Takeda, H.; Terashima, S.; Vajta, Zs.; Yoshida, S.; Valiente-Dòbon, J. J.

2017-11-01

In-flight fission of a 345 MeV per nucleon 238U primary beam on a 2 mm thick 9Be target has been used to produce and study the decays of a range of neutron-rich nuclei centred around the doubly mid-shell nucleus 170Dy at the RIBF Facility, RIKEN, Japan. The produced secondary fragments of interest were identified event-by-event using the BigRIPS separator. The fragments were implanted into the WAS3ABI position sensitive silicon active stopper which allowed pixelated correlations between implants and their subsequent β-decay. Discrete γ-ray transitions emitted following decays from either metastable states or excited states populated following beta decay were identified using the 84 coaxial high-purity germanium (HPGe) detectors of the EURICA spectrometer, which was complemented by 18 additional cerium-doped lanthanum bromide (LaBr3) fast-timing scintillation detectors from the FATIMA collaboration. This paper presents the internal decay of a metastable isomeric excited state in the odd-odd nucleus 168Tb, which corresponds to a single proton-neutron hole configuration in the valence maximum nucleus 170Dy. These data represent the first information on excited states in this nucleus, which is the most neutron-rich odd-odd isotope of terbium (Z=65) studied to date. Nilsson configurations associated with an axially symmetric, prolate-deformed nucleus are proposed for the 168Tb ground state the observed isomeric state by comparison with Blocked BCS-Nilsson calculations.

Excited state non-adiabatic dynamics of the smallest polyene, trans 1,3-butadiene. II. Ab initio multiple spawning simulations

NASA Astrophysics Data System (ADS)

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

2018-04-01

The excited state non-adiabatic dynamics of the smallest polyene, trans 1,3-butadiene (BD), has long been the subject of controversy due to its strong coupling, ultrafast time scales and the difficulties that theory faces in describing the relevant electronic states in a balanced fashion. Here we apply Ab Initio Multiple Spawning (AIMS) using state-averaged complete active space multistate second order perturbation theory [SA-3-CAS(4/4)-MSPT2] which describes both static and dynamic electron correlation effects, providing a balanced description of both the initially prepared bright 11Bu (ππ*) state and non-adiabatically coupled dark 21Ag state of BD. Importantly, AIMS allows for on-the-fly calculations of experimental observables. We validate our approach by directly simulating the time resolved photoelectron-photoion coincidence spectroscopy results presented in Paper I [A. E. Boguslavskiy et al., J. Chem. Phys. 148, 164302 (2018)], demonstrating excellent agreement with experiment. Our simulations reveal that the initial excitation to the 11Bu state rapidly evolves via wavepacket dynamics that follow both bright- and dark-state pathways as well as mixtures of these. In order to test the sensitivity of the AIMS results to the relative ordering of states, we considered two hypothetical scenarios biased toward either the bright 1Bu or the dark 21Ag state. In contrast with AIMS/SA-3-CAS(4/4)-MSPT2 simulations, neither of these scenarios yields favorable agreement with experiment. Thus, we conclude that the excited state non-adiabatic dynamics in BD involves both of these ultrafast pathways.

Ultrafast non-radiative dynamics of atomically thin MoSe 2

DOE PAGES

Lin, Ming -Fu; Kochat, Vidya; Krishnamoorthy, Aravind; ...

2017-10-17

Non-radiative energy dissipation in photoexcited materials and resulting atomic dynamics provide a promising pathway to induce structural phase transitions in two-dimensional materials. However, these dynamics have not been explored in detail thus far because of incomplete understanding of interaction between the electronic and atomic degrees of freedom, and a lack of direct experimental methods to quantify real-time atomic motion and lattice temperature. Here, we explore the ultrafast conversion of photoenergy to lattice vibrations in a model bi-layered semiconductor, molybdenum diselenide, MoSe 2. Specifically, we characterize sub-picosecond lattice dynamics initiated by the optical excitation of electronic charge carriers in the highmore » electron-hole plasma density regime. Our results focuses on the first ten picosecond dynamics subsequent to photoexcitation before the onset of heat transfer to the substrate, which occurs on a ~100 picosecond time scale. Photoinduced atomic motion is probed by measuring the time dependent Bragg diffraction of a delayed mega-electronvolt femtosecond electron beam. Transient lattice temperatures are characterized through measurement of Bragg peak intensities and calculation of the Debye-Waller factor (DWF). These measurements show a sub-picosecond decay of Bragg diffraction and a correspondingly rapid rise in lattice temperatures. We estimate a high quantum yield for the conversion of excited charge carrier energy to lattice motion under our experimental conditions, indicative of a strong electron-phonon interaction. First principles nonadiabatic quantum molecular dynamics simulations (NAQMD) on electronically excited MoSe 2 bilayers reproduce the observed picosecond-scale increase in lattice temperature and ultrafast conversion of photoenergy to lattice vibrations. Calculation of excited-state phonon dispersion curves suggests that softened vibrational modes in the excited state are involved in efficient and rapid energy transfer between the electronic system and the lattice.« less

Ultrafast non-radiative dynamics of atomically thin MoSe 2

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

Lin, Ming -Fu; Kochat, Vidya; Krishnamoorthy, Aravind

Non-radiative energy dissipation in photoexcited materials and resulting atomic dynamics provide a promising pathway to induce structural phase transitions in two-dimensional materials. However, these dynamics have not been explored in detail thus far because of incomplete understanding of interaction between the electronic and atomic degrees of freedom, and a lack of direct experimental methods to quantify real-time atomic motion and lattice temperature. Here, we explore the ultrafast conversion of photoenergy to lattice vibrations in a model bi-layered semiconductor, molybdenum diselenide, MoSe 2. Specifically, we characterize sub-picosecond lattice dynamics initiated by the optical excitation of electronic charge carriers in the highmore » electron-hole plasma density regime. Our results focuses on the first ten picosecond dynamics subsequent to photoexcitation before the onset of heat transfer to the substrate, which occurs on a ~100 picosecond time scale. Photoinduced atomic motion is probed by measuring the time dependent Bragg diffraction of a delayed mega-electronvolt femtosecond electron beam. Transient lattice temperatures are characterized through measurement of Bragg peak intensities and calculation of the Debye-Waller factor (DWF). These measurements show a sub-picosecond decay of Bragg diffraction and a correspondingly rapid rise in lattice temperatures. We estimate a high quantum yield for the conversion of excited charge carrier energy to lattice motion under our experimental conditions, indicative of a strong electron-phonon interaction. First principles nonadiabatic quantum molecular dynamics simulations (NAQMD) on electronically excited MoSe 2 bilayers reproduce the observed picosecond-scale increase in lattice temperature and ultrafast conversion of photoenergy to lattice vibrations. Calculation of excited-state phonon dispersion curves suggests that softened vibrational modes in the excited state are involved in efficient and rapid energy transfer between the electronic system and the lattice.« less

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.

Demonstration of Two-Atom Entanglement with Ultrafast Optical Pulses

NASA Astrophysics Data System (ADS)

Wong-Campos, J. D.; Moses, S. A.; Johnson, K. G.; Monroe, C.

2017-12-01

We demonstrate quantum entanglement of two trapped atomic ion qubits using a sequence of ultrafast laser pulses. Unlike previous demonstrations of entanglement mediated by the Coulomb interaction, this scheme does not require confinement to the Lamb-Dicke regime and can be less sensitive to ambient noise due to its speed. To elucidate the physics of an ultrafast phase gate, we generate a high entanglement rate using just ten pulses, each of ˜20 ps duration, and demonstrate an entangled Bell state with (76 ±1 )% fidelity. These results pave the way for entanglement operations within a large collection of qubits by exciting only local modes of motion.

Demonstration of Two-Atom Entanglement with Ultrafast Optical Pulses.

PubMed

Wong-Campos, J D; Moses, S A; Johnson, K G; Monroe, C

2017-12-08

We demonstrate quantum entanglement of two trapped atomic ion qubits using a sequence of ultrafast laser pulses. Unlike previous demonstrations of entanglement mediated by the Coulomb interaction, this scheme does not require confinement to the Lamb-Dicke regime and can be less sensitive to ambient noise due to its speed. To elucidate the physics of an ultrafast phase gate, we generate a high entanglement rate using just ten pulses, each of ∼20  ps duration, and demonstrate an entangled Bell state with (76±1)% fidelity. These results pave the way for entanglement operations within a large collection of qubits by exciting only local modes of motion.

Ultrafast electronic relaxation in superheated bismuth

NASA Astrophysics Data System (ADS)

Gamaly, E. G.; Rode, A. V.

2013-01-01

Interaction of moving electrons with vibrating ions in the lattice forms the basis for many physical properties from electrical resistivity and electronic heat capacity to superconductivity. In ultrafast laser interaction with matter the electrons are heated much faster than the electron-ion energy equilibration, leading to a two-temperature state with electron temperature far above that of the lattice. The rate of temperature equilibration is governed by the strength of electron-phonon energy coupling, which is conventionally described by a coupling constant, neglecting the dependence on the electron and lattice temperature. The application of this constant to the observations of fast relaxation rate led to a controversial notion of ‘ultra-fast non-thermal melting’ under extreme electronic excitation. Here we provide theoretical grounds for a strong dependence of the electron-phonon relaxation time on the lattice temperature. We show, by taking proper account of temperature dependence, that the heating and restructuring of the lattice occurs much faster than were predicted on the assumption of a constant, temperature independent energy coupling. We applied the temperature-dependent momentum and energy transfer time to experiments on fs-laser excited bismuth to demonstrate that all the observed ultra-fast transformations of the transient state of bismuth are purely thermal in nature. The developed theory, when applied to ultrafast experiments on bismuth, provides interpretation of the whole variety of transient phase relaxation without the non-thermal melting conjecture.

Preferential Charge Generation at Aggregate Sites in Narrow Band Gap Infrared Photoresponsive Polymer Semiconductors

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

Sulas, Dana B.; London, Alexander E.; Huang, Lifeng

Infrared organic photodetector materials are investigated using transient absorption spectroscopy, demonstrating that ultrafast charge generation assisted by polymer aggregation is essential to compensate for the energy gap law, which dictates that excited state lifetimes decrease as the band gap narrows. Short sub–picosecond singlet exciton lifetimes are measured in a structurally related series of infrared–absorbing copolymers that consist of alternating cyclopentadithiophene electron–rich “push” units and strong electron–deficient “pull” units, including benzothiadiazole, benzoselenadiazole, pyridalselenadiazole, or thiadiazoloquinoxaline. While the ultrafast lifetimes of excitons localized on individual polymer chains suggest that charge carrier generation will be inefficient, high detectivity for polymer:PC 71BM infrared photodetectorsmore » is measured in the 0.6 < λ < 1.5 µm range. The photophysical processes leading to charge generation are investigated by performing a global analysis on transient absorption data of blended polymer:PC 71BM films. In these blends, charge carriers form primarily at polymer aggregate sites on the ultrafast time scale (within our instrument response), leaving quickly decaying single–chain excitons unquenched. Lastly, the results have important implications for the further development of organic infrared optoelectronic devices, where targeting processes such as excited state delocalization over aggregates may be necessary to mitigate losses to ultrafast exciton decay as materials with even lower band gaps are developed.« less

Preferential Charge Generation at Aggregate Sites in Narrow Band Gap Infrared Photoresponsive Polymer Semiconductors

DOE PAGES

Sulas, Dana B.; London, Alexander E.; Huang, Lifeng; ...

2018-02-13

Infrared organic photodetector materials are investigated using transient absorption spectroscopy, demonstrating that ultrafast charge generation assisted by polymer aggregation is essential to compensate for the energy gap law, which dictates that excited state lifetimes decrease as the band gap narrows. Short sub–picosecond singlet exciton lifetimes are measured in a structurally related series of infrared–absorbing copolymers that consist of alternating cyclopentadithiophene electron–rich “push” units and strong electron–deficient “pull” units, including benzothiadiazole, benzoselenadiazole, pyridalselenadiazole, or thiadiazoloquinoxaline. While the ultrafast lifetimes of excitons localized on individual polymer chains suggest that charge carrier generation will be inefficient, high detectivity for polymer:PC 71BM infrared photodetectorsmore » is measured in the 0.6 < λ < 1.5 µm range. The photophysical processes leading to charge generation are investigated by performing a global analysis on transient absorption data of blended polymer:PC 71BM films. In these blends, charge carriers form primarily at polymer aggregate sites on the ultrafast time scale (within our instrument response), leaving quickly decaying single–chain excitons unquenched. Lastly, the results have important implications for the further development of organic infrared optoelectronic devices, where targeting processes such as excited state delocalization over aggregates may be necessary to mitigate losses to ultrafast exciton decay as materials with even lower band gaps are developed.« less

Isomer-delayed gamma-ray spectroscopy of neutron-rich 166Tb

DOE PAGES

Gurgi, L. A.; Regan, P. H.; Söderström, P. -A.; ...

2017-09-13

Here, this short paper presents the identification of a metastable, isomeric-state decay in the neutron-rich odd-odd, prolate-deformed nucleus 166Tb. The nucleus of interest was formed using the in-flight fission of a 345 MeV per nucleon 238U primary beam at the RIBF facility, RIKEN, Japan. Gamma-ray transitions decaying from the observed isomeric states in 166Tb were identified using the EURICA gamma-ray spectrometer, positioned at the final focus of the BigRIPS fragments separator. The current work identifies a single discrete gamma-ray transition of energy 119 keV which de-excites an isomeric state in 166Tb with a measured half-life of 3.5(4) μs. The multipolaritymore » assignment for this transition is an electric dipole and is made on the basis internal conversion and decay lifetime arguments. Possible two quasi-particle Nilsson configurations for the initial and final states which are linked by this transition in 166Tb are made on the basis of comparison with Blocked BCS Nilsson calculations, with the predicted ground state configuration for this nucleus arising from the coupling of the v(1-/2)[521] and π(3+/2) Nilsson orbitals.« less

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

Gurgi, L. A.; Regan, P. H.; Söderström, P. -A.

Here, this short paper presents the identification of a metastable, isomeric-state decay in the neutron-rich odd-odd, prolate-deformed nucleus 166Tb. The nucleus of interest was formed using the in-flight fission of a 345 MeV per nucleon 238U primary beam at the RIBF facility, RIKEN, Japan. Gamma-ray transitions decaying from the observed isomeric states in 166Tb were identified using the EURICA gamma-ray spectrometer, positioned at the final focus of the BigRIPS fragments separator. The current work identifies a single discrete gamma-ray transition of energy 119 keV which de-excites an isomeric state in 166Tb with a measured half-life of 3.5(4) μs. The multipolaritymore » assignment for this transition is an electric dipole and is made on the basis internal conversion and decay lifetime arguments. Possible two quasi-particle Nilsson configurations for the initial and final states which are linked by this transition in 166Tb are made on the basis of comparison with Blocked BCS Nilsson calculations, with the predicted ground state configuration for this nucleus arising from the coupling of the v(1-/2)[521] and π(3+/2) Nilsson orbitals.« less

Isomer-delayed gamma-ray spectroscopy of neutron-rich 166Tb

NASA Astrophysics Data System (ADS)

Gurgi, L. A.; Regan, P. H.; Söderström, P.-A.; Watanabe, H.; Walker, P. M.; Podolyák, Zs.; Nishimura, S.; Berry, T. A.; Doornenbal, P.; Lorusso, G.; Isobe, T.; Baba, H.; Xu, Z. Y.; Sakurai, H.; Sumikama, T.; Catford, W. N.; Bruce, A. M.; Browne, F.; Lane, G. J.; Kondev, F. G.; Odahara, A.; Wu, J.; Liu, H. L.; Xu, F. R.; Korkulu, Z.; Lee, P.; Liu, J. J.; Phong, V. H.; Yagi, A.; Zhang, G. X.; Alharbi, T.; Carroll, R. J.; Chae, K. Y.; Dombradi, Zs.; Estrade, A.; Fukuda, N.; Griffin, C.; Ideguchi, E.; Inabe, N.; Kanaoka, H.; Kojouharov, I.; Kubo, T.; Kubono, S.; Kurz, N.; Kuti, I.; Lalkovski, S.; Lee, E. J.; Lee, C. S.; Lotay, G.; Moon, C. B.; Nishizuka, I.; Nita, C. R.; Patel, Z.; Roberts, O. J.; Schaffner, H.; Shand, C. M.; Suzuki, H.; Takeda, H.; Terashima, S.; Vajta, Zs.; Kanaya, S.; Valiente-Dobòn, J. J.

2017-09-01

This short paper presents the identification of a metastable, isomeric-state decay in the neutron-rich odd-odd, prolate-deformed nucleus 166Tb. The nucleus of interest was formed using the in-flight fission of a 345 MeV per nucleon 238U primary beam at the RIBF facility, RIKEN, Japan. Gamma-ray transitions decaying from the observed isomeric states in 166Tb were identified using the EURICA gamma-ray spectrometer, positioned at the final focus of the BigRIPS fragments separator. The current work identifies a single discrete gamma-ray transition of energy 119 keV which de-excites an isomeric state in 166Tb with a measured half-life of 3.5(4) μs. The multipolarity assignment for this transition is an electric dipole and is made on the basis internal conversion and decay lifetime arguments. Possible two quasi-particle Nilsson configurations for the initial and final states which are linked by this transition in 166Tb are made on the basis of comparison with Blocked BCS Nilsson calculations, with the predicted ground state configuration for this nucleus arising from the coupling of the v(1-/2)?[521] and ? π(3+/2) Nilsson orbitals.

Free electron laser-driven ultrafast rearrangement of the electronic structure in Ti

PubMed Central

Principi, E.; Giangrisostomi, E.; Cucini, R.; Bencivenga, F.; Battistoni, A.; Gessini, A.; Mincigrucci, R.; Saito, M.; Di Fonzo, S.; D'Amico, F.; Di Cicco, A.; Gunnella, R.; Filipponi, A.; Giglia, A.; Nannarone, S.; Masciovecchio, C.

2015-01-01

High-energy density extreme ultraviolet radiation delivered by the FERMI seeded free-electron laser has been used to create an exotic nonequilibrium state of matter in a titanium sample characterized by a highly excited electron subsystem at temperatures in excess of 10 eV and a cold solid-density ion lattice. The obtained transient state has been investigated through ultrafast absorption spectroscopy across the Ti M2,3-edge revealing a drastic rearrangement of the sample electronic structure around the Fermi level occurring on a time scale of about 100 fs. PMID:26798835

Pump-shaped dump optimal control reveals the nuclear reaction pathway of isomerization of a photoexcited cyanine dye.

PubMed

Dietzek, Benjamin; Brüggemann, Ben; Pascher, Torbjörn; Yartsev, Arkady

2007-10-31

Using optimal control as a spectroscopic tool we decipher the details of the molecular dynamics of the essential multidimensional excited-state photoisomerization - a fundamental chemical reaction of key importance in biology. Two distinct nuclear motions are identified in addition to the overall bond-twisting motion: Initially, the reaction is dominated by motion perpendicular to the torsion coordinate. At later times, a second optically active vibration drives the system along the reaction path to the bottom of the excited-state potential. The time scales of the wavepacket motion on a different part of the excited-state potential are detailed by pump-shaped dump optimal control. This technique offers new means to control a chemical reaction far from the Franck-Condon point of absorption and to map details of excited-state reaction pathways revealing unique insights into the underlying reaction mechanism.

Optical and Nonlinear Optical Response of Light Sensor Thin Films

PubMed Central

Liu, Huimin; Rua, Armando; Vasquez, Omar; Vikhnin, Valentin S.; Fernandez, Felix E.; Fonseca, Luis F.; Resto, Oscar; Weisz, Svi Z.

2005-01-01

For potential ultrafast optical sensor application, both VO2 thin films and nanocomposite crystal-Si enriched SiO2 thin films grown on fused quartz substrates were successfully prepared using pulsed laser deposition (PLD) and RF co-sputtering techniques. In photoluminescence (PL) measurement c-Si/SiO2 film contains nanoparticles of crystal Si exhibits strong red emission with the band maximum ranging from 580 to 750 nm. With ultrashort pulsed laser excitation all films show extremely intense and ultrafast nonlinear optical (NLO) response. The recorded holography from all these thin films in a degenerate-four-wave-mixing configuration shows extremely large third-order response. For VO2 thin films, an optically induced semiconductor-to-metal phase transition (PT) immediately occurred upon laser excitation. it accompanied. It turns out that the fast excited state dynamics was responsible to the induced PT. For c-Si/SiO2 film, its NLO response comes from the contribution of charge carriers created by laser excitation in conduction band of the c-Si nanoparticles. It was verified by introducing Eu3+ which is often used as a probe sensing the environment variations. It turns out that the entire excited state dynamical process associated with the creation, movement and trapping of the charge carriers has a characteristic 500 ps duration.

Overtone-induced dissociation and isomerization dynamics of the hydroxymethyl radical (CH2OH and CD2OH). I. A theoretical study

NASA Astrophysics Data System (ADS)

Kamarchik, E.; Rodrigo, C.; Bowman, J. M.; Reisler, H.; Krylov, A. I.

2012-02-01

The dissociation of the hydroxymethyl radical, CH2OH, and its isotopolog, CD2OH, following the excitation of high OH stretch overtones is studied by quasi-classical molecular dynamics calculations using a global potential energy surface (PES) fitted to ab initio calculations. The PES includes CH2OH and CH3O minima, dissociation products, and all relevant barriers. Its analysis shows that the transition states for OH bond fission and isomerization are both very close in energy to the excited vibrational levels reached in recent experiments and involve significant geometry changes relative to the CH2OH equilibrium structure. The energies of key stationary points are refined using high-level electronic structure calculations. Vibrational energies and wavefunctions are computed by coupled anharmonic vibrational calculations. They show that high OH-stretch overtones are mixed with other modes. Consequently, trajectory calculations carried out at energies about ˜3000 cm-1 above the barriers reveal that despite initial excitation of the OH stretch, the direct OH bond fission is relatively slow (10 ps) and a considerable fraction of the radicals undergoes isomerization to the methoxy radical. The computed dissociation energies are: D0(CH2OH → CH2O + H) = 10 188 cm-1, D0(CD2OH → CD2O + H) = 10 167 cm-1, D0(CD2OH → CHDO + D) = 10 787 cm-1. All are in excellent agreement with the experimental results. For CH2OH, the barriers for the direct OH bond fission and isomerization are: 14 205 and 13 839 cm-1, respectively.

Role of Electron-Driven Proton-Transfer Processes in the Ultrafast Deactivation of Photoexcited Anionic 8-oxoGuanine-Adenine and 8-oxoGuanine-Cytosine Base Pairs.

PubMed

Wu, Xiuxiu; Karsili, Tolga N V; Domcke, Wolfgang

2017-01-14

It has been reported that 8-oxo-7,8-dihydro-guanosine (8-oxo-G), which is the main product of oxidative damage of DNA, can repair cyclobutane pyrimidine dimer (CPD) lesions when incorporated into DNA or RNA strands in proximity to such lesions. It has therefore been suggested that the 8-oxo-G nucleoside may have been a primordial precursor of present-day flavins in DNA or RNA repair. Because the electron transfer leading to the splitting of a thymine-thymine pair in a CPD lesion occurs in the photoexcited state, a reasonably long excited-state lifetime of 8-oxo-G is required. The neutral (protonated) form of 8-oxo-G exhibits a very short (sub-picosecond) intrinsic excited-state lifetime which is unfavorable for repair. It has therefore been argued that the anionic (deprotonated) form of 8-oxo-G, which exhibits a much longer excited-state lifetime, is more likely to be a suitable cofactor for DNA repair. Herein, we have investigated the exited-state quenching mechanisms in the hydrogen-bonded complexes of deprotonated 8-oxo-G - with adenine (A) and cytosine (C) using ab initio wave-function-based electronic-structure calculations. The calculated reaction paths and potential-energy profiles reveal the existence of barrierless electron-driven inter-base proton-transfer reactions which lead to low-lying S₁/S₀ conical intersections. The latter can promote ultrafast excited-state deactivation of the anionic base pairs. While the isolated deprotonated 8-oxo-G - nucleoside may have been an efficient primordial repair cofactor, the excited states of the 8-oxo-G - -A and 8-oxo-G - -C base pairs are likely too short-lived to be efficient electron-transfer repair agents.

β-γ and isomeric decay spectroscopy of 168Dy

NASA Astrophysics Data System (ADS)

Zhang, G. X.; Watanabe, H.; Kondev, F. G.; Lane, G. J.; Regan, P. H.; Söderström, P.-A.; Walker, P. M.; Kanaoka, H.; Korkulu, Z.; Lee, P. S.; Liu, J. J.; Nishimura, S.; Wu, J.; Yagi, A.; Ahn, D. S.; Alharbi, T.; Baba, H.; Browne, F.; Bruce, A. M.; Carroll, R. J.; Chae, K. Y.; Dombradi, Zs.; Doornenbal, P.; Estrade, A.; Fukuda, N.; Griffin, C.; Ideguchi, E.; Inabe, N.; Isobe, T.; Kanaya, S.; Kojouharov, I.; Kubo, T.; Kubono, S.; Kurz, N.; Kuti, I.; Lalkovski, S.; Lee, C. S.; Lee, E. J.; Lorusso, G.; Lotay, G.; Moon, C.-B.; Nishizuka, I.; Nita, C. R.; Odahara, A.; Patel, Z.; Phong, V. H.; Podolyák, Zs.; Roberts, O. J.; Sakurai, H.; Schaffner, H.; Shand, C. M.; Shimizu, Y.; Sumikama, T.; Suzuki, H.; Takeda, H.; Terashima, S.; Vajta, Zs.; Valiente-Dóbon, J. J.; Xu, Z. Y.

2018-05-01

This contribution will report on the experimental work on the level structure of 168Dy. The experimental data have been taken as part of the EURICA decay spectroscopy campaign at RIBF, RIKEN in November 2014. In the experiment, a 238U primary beam is accelerated up to 345 MeV/u with an average intensity of 12 pnA. The nuclei of interest are produced by in-flight fission of 238U impinging on Be target with a thickness of 5 mm. The excited states of 168Dy have been populated through the decay from a newly identified isomeric state and via the β decay from 168Tb. In this contribution, scientific motivations, experimental procedure and some preliminary results for this study are presented.

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

PubMed

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

2011-10-01

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

Ultrafast Relaxation Dynamics of Photoexcited Zinc-Porphyrin: Electronic-Vibrational Coupling

DOE PAGES

Abraham, Baxter; Nieto-Pescador, Jesus; Gundlach, Lars

2016-08-02

Cyclic tetrapyrroles are the active core of compounds with crucial roles in living systems, such as hemoglobin and chlorophyll, and in technology as photocatalysts and light absorbers for solar energy conversion. Zinc-tetraphenylporphyrin (Zn-TPP) is a prototypical cyclic tetrapyrrole that has been intensely studied in past decades. Because of its importance for photochemical processes the optical properties are of particular interest, and, accordingly, numerous studies have focused on light absorption and excited-state dynamics of Zn-TPP. Relaxation after photoexcitation in the Soret band involves internal conversion that is preceded by an ultrafast process. This relaxation process has been observed by several groups.more » Until now, it has not been established if it involves a higher lying ”dark” state or vibrational relaxation in the excited S 2 state. Here we combine high time resolution electronic and vibrational spectroscopy to show that this process constitutes vibrational relaxation in the anharmonic 2 potential.« less

Ultrafast Relaxation Dynamics of Photoexcited Zinc-Porphyrin: Electronic-Vibrational Coupling

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

Abraham, Baxter; Nieto-Pescador, Jesus; Gundlach, Lars

Cyclic tetrapyrroles are the active core of compounds with crucial roles in living systems, such as hemoglobin and chlorophyll, and in technology as photocatalysts and light absorbers for solar energy conversion. Zinc-tetraphenylporphyrin (Zn-TPP) is a prototypical cyclic tetrapyrrole that has been intensely studied in past decades. Because of its importance for photochemical processes the optical properties are of particular interest, and, accordingly, numerous studies have focused on light absorption and excited-state dynamics of Zn-TPP. Relaxation after photoexcitation in the Soret band involves internal conversion that is preceded by an ultrafast process. This relaxation process has been observed by several groups.more » Until now, it has not been established if it involves a higher lying ”dark” state or vibrational relaxation in the excited S 2 state. Here we combine high time resolution electronic and vibrational spectroscopy to show that this process constitutes vibrational relaxation in the anharmonic 2 potential.« less

Ultrafast decoherence dynamics govern photocarrier generation efficiencies in polymer solar cells

PubMed Central

Vella, Eleonora; Li, Hao; Grégoire, Pascal; Tuladhar, Sachetan M.; Vezie, Michelle S.; Few, Sheridan; Bazán, Claudia M.; Nelson, Jenny; Silva-Acuña, Carlos; Bittner, Eric R.

2016-01-01

All-organic-based photovoltaic solar cells have attracted considerable attention because of their low-cost processing and short energy payback time. In such systems the primary dissociation of an optical excitation into a pair of photocarriers has been recently shown to be extremely rapid and efficient, but the physical reason for this remains unclear. Here, two-dimensional photocurrent excitation spectroscopy, a novel non-linear optical spectroscopy, is used to probe the ultrafast coherent decay of photoexcitations into charge-producing states in a polymer:fullerene based solar cell. The two-dimensional photocurrent spectra are interpreted by introducing a theoretical model for the description of the coupling of the electronic states of the system to an external environment and to the applied laser fields. The experimental data show no cross-peaks in the twodimensional photocurrent spectra, as predicted by the model for coherence times between the exciton and the photocurrent producing states of 20 fs or less. PMID:27412119

Femtosecond two-photon Rabi oscillations in excited He driven by ultrashort intense laser fields

NASA Astrophysics Data System (ADS)

Fushitani, M.; Liu, C.-N.; Matsuda, A.; Endo, T.; Toida, Y.; Nagasono, M.; Togashi, T.; Yabashi, M.; Ishikawa, T.; Hikosaka, Y.; Morishita, T.; Hishikawa, A.

2016-02-01

Coherent light-matter interaction provides powerful methods for manipulating quantum systems. Rabi oscillation is one such process. As it enables complete population transfer to a target state, it is thus routinely exploited in a variety of applications in photonics, notably quantum information processing. The extension of coherent control techniques to the multiphoton regime offers wider applicability, and access to highly excited or dipole-forbidden transition states. However, the multiphoton Rabi process is often disrupted by other competing nonlinear effects such as the a.c. Stark shift, especially at the high laser-field intensities necessary to achieve ultrafast Rabi oscillations. Here we demonstrate a new route to drive two-photon Rabi oscillations on timescales as short as tens of femtoseconds, by utilizing the strong-field phenomenon known as Freeman resonance. The scenario is not specific to atomic helium as investigated in the present study, but broadly applicable to other systems, thus opening new prospects for the ultrafast manipulation of Rydberg states.

Ultrafast studies of the excited-state dynamics of copper and nickel phthalocyanine tetrasulfonates: potential sensitizers for the two-photon photodynamic therapy of tumors.

PubMed

Fournier, Michel; Pépin, Claude; Houde, Daniel; Ouellet, René; van Lier, Johan E

2004-01-01

In order to evaluate the potential of copper and nickel phthalocyanine tetrasulfonates as sensitizers for two-photon photodynamic therapy, we conducted kinetic femtosecond measurements of transient absorption and bleaching of their excited state dynamics in aqueous solution. Samples were pumped with 620 nm and 310 nm laser light, which allowed us to study relaxation processes from both the first and second singlet (or doublet for the copper phthalocyanine) excited states. A second excitation from the first excited triplet state, approximately 685 and 105 ps after the first excitation for copper and nickel phthalocyanine tetrasulfonate respectively, was the most efficient way to bring the molecules to an upper triplet state. Presumably this highest triplet state can inflict molecular damage on adjacent biomolecules int eh absence of oxygen, resulting in the desired cytotoxic cellular response. Transient absorption spectra at different fixed delays indicate that optimum efficiency would require that the second photon has a wavelength of approximately 750 nm.

Thermally and vibrationally induced conformational isomerizations, infrared spectra, and photochemistry of gallic acid in low-temperature matrices

NASA Astrophysics Data System (ADS)

Justino, Licínia L. G.; Reva, Igor; Fausto, Rui

2016-07-01

Near-infrared (near-IR) narrowband selective vibrational excitation and annealing of gallic acid (3,4,5-trihydroxybenzoic acid) isolated in cryogenic matrices were used to induce interconversions between its most stable conformers. The isomerizations were probed by infrared spectroscopy. An extensive set of quantum chemical calculations, carried out at the DFT(B3LYP)/6-311++G(d,p) level of approximation, was used to undertake a detailed analysis of the ground state potential energy surface of the molecule. This investigation of the molecule conformational space allowed extracting mechanistic insights into the observed annealing- or near-IR-induced isomerization processes. The infrared spectra of the two most stable conformers of gallic acid in N2, Xe, and Ar matrices were fully assigned. Finally, the UV-induced photochemistry of the matrix isolated compound was investigated.

Excited-state thermionic emission in III-antimonides: Low emittance ultrafast photocathodes

NASA Astrophysics Data System (ADS)

Berger, Joel A.; Rickman, B. L.; Li, T.; Nicholls, A. W.; Andreas Schroeder, W.

2012-11-01

The normalized rms transverse emittance of an electron source is shown to be proportional to √m* , where m* is the effective mass of the state from which the electron is emitted, by direct observation of the transverse momentum distribution for excited-state thermionic emission from two III-V semiconductor photocathodes, GaSb and InSb, together with a control experiment employing two-photon emission from gold. Simulations of the experiment using an extended analytical Gaussian model of electron pulse propagation are in close agreement with the data.

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.

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.

Excited state non-adiabatic dynamics of the smallest polyene, trans 1,3-butadiene. II. Ab initio multiple spawning simulations

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

Glover, William J.; Mori, Toshifumi; Schuurman, Michael S.

The excited state non-adiabatic dynamics of the smallest polyene, trans 1,3-butadiene (BD), has long been the subject of controversy due to its strong coupling, ultrafast time scales and the difficulties that theory faces in describing the relevant electronic states in a balanced fashion. Here we apply Ab Initio Multiple Spawning (AIMS) using state-averaged complete active space multistate second order perturbation theory [SA-3-CAS(4/4)-MSPT2] which describes both static and dynamic electron correlation effects, providing a balanced description of both the initially prepared bright 1 1B u (ππ*) state and non-adiabatically coupled dark 2 1A g state of BD. Importantly, AIMS allows formore » on-the-fly calculations of experimental observables. We validate our approach by directly simulating the time resolved photoelectron-photoion coincidence spectroscopy results presented in Paper I [A. E. Boguslavskiy et al., J. Chem. Phys. 148, 164302 (2018)], demonstrating excellent agreement with experiment. Our simulations reveal that the initial excitation to the 1 1B u state rapidly evolves via wavepacket dynamics that follow both bright- and dark-state pathways as well as mixtures of these. In order to test the sensitivity of the AIMS results to the relative ordering of states, we considered two hypothetical scenarios biased toward either the bright 1B u or the dark 2 1A g state. In contrast with AIMS/SA-3-CAS(4/4)-MSPT2 simulations, neither of these scenarios yields favorable agreement with experiment. Thus, we conclude that the excited state non-adiabatic dynamics in BD involves both of these ultrafast pathways.« less

Excited state non-adiabatic dynamics of the smallest polyene, trans 1,3-butadiene. II. Ab initio multiple spawning simulations.

PubMed

Glover, William J; Mori, Toshifumi; Schuurman, Michael S; Boguslavskiy, Andrey E; Schalk, Oliver; Stolow, Albert; Martínez, Todd J

2018-04-28

The excited state non-adiabatic dynamics of the smallest polyene, trans 1,3-butadiene (BD), has long been the subject of controversy due to its strong coupling, ultrafast time scales and the difficulties that theory faces in describing the relevant electronic states in a balanced fashion. Here we apply Ab Initio Multiple Spawning (AIMS) using state-averaged complete active space multistate second order perturbation theory [SA-3-CAS(4/4)-MSPT2] which describes both static and dynamic electron correlation effects, providing a balanced description of both the initially prepared bright 1 1 B u (ππ*) state and non-adiabatically coupled dark 2 1 A g state of BD. Importantly, AIMS allows for on-the-fly calculations of experimental observables. We validate our approach by directly simulating the time resolved photoelectron-photoion coincidence spectroscopy results presented in Paper I [A. E. Boguslavskiy et al., J. Chem. Phys. 148, 164302 (2018)], demonstrating excellent agreement with experiment. Our simulations reveal that the initial excitation to the 1 1 B u state rapidly evolves via wavepacket dynamics that follow both bright- and dark-state pathways as well as mixtures of these. In order to test the sensitivity of the AIMS results to the relative ordering of states, we considered two hypothetical scenarios biased toward either the bright 1 B u or the dark 2 1 A g state. In contrast with AIMS/SA-3-CAS(4/4)-MSPT2 simulations, neither of these scenarios yields favorable agreement with experiment. Thus, we conclude that the excited state non-adiabatic dynamics in BD involves both of these ultrafast pathways.

Excited state non-adiabatic dynamics of the smallest polyene, trans 1,3-butadiene. II. Ab initio multiple spawning simulations

DOE PAGES

Glover, William J.; Mori, Toshifumi; Schuurman, Michael S.; ...

2018-04-28

The excited state non-adiabatic dynamics of the smallest polyene, trans 1,3-butadiene (BD), has long been the subject of controversy due to its strong coupling, ultrafast time scales and the difficulties that theory faces in describing the relevant electronic states in a balanced fashion. Here we apply Ab Initio Multiple Spawning (AIMS) using state-averaged complete active space multistate second order perturbation theory [SA-3-CAS(4/4)-MSPT2] which describes both static and dynamic electron correlation effects, providing a balanced description of both the initially prepared bright 1 1B u (ππ*) state and non-adiabatically coupled dark 2 1A g state of BD. Importantly, AIMS allows formore » on-the-fly calculations of experimental observables. We validate our approach by directly simulating the time resolved photoelectron-photoion coincidence spectroscopy results presented in Paper I [A. E. Boguslavskiy et al., J. Chem. Phys. 148, 164302 (2018)], demonstrating excellent agreement with experiment. Our simulations reveal that the initial excitation to the 1 1B u state rapidly evolves via wavepacket dynamics that follow both bright- and dark-state pathways as well as mixtures of these. In order to test the sensitivity of the AIMS results to the relative ordering of states, we considered two hypothetical scenarios biased toward either the bright 1B u or the dark 2 1A g state. In contrast with AIMS/SA-3-CAS(4/4)-MSPT2 simulations, neither of these scenarios yields favorable agreement with experiment. Thus, we conclude that the excited state non-adiabatic dynamics in BD involves both of these ultrafast pathways.« less

Ultrafast Excited-state Deactivation of Flavins Bound to Dodecin*

PubMed Central

Staudt, Heike; Oesterhelt, Dieter; Grininger, Martin; Wachtveitl, Josef

2012-01-01

Dodecins, a group of flavin-binding proteins with a dodecameric quaternary structure, are able to incorporate two flavins within each of their six identical binding pockets building an aromatic tetrade with two tryptophan residues. Dodecin from the archaeal Halobacterium salinarum is a riboflavin storage device. We demonstrate that unwanted side reactions induced by reactive riboflavin species and degradation of riboflavin are avoided by ultrafast depopulation of the reactive excited state of riboflavin. Intriguingly, in this process, the staggered riboflavin dimers do not interact in ground and photoexcited states. Rather, within the tetrade assembly, each riboflavin is kept under the control of the respective adjacent tryptophan, which suggests that the stacked arrangement is a matter of optimizing the flavin load. We further identify an electron transfer in combination with a proton transfer as a central element of the effective excited state depopulation mechanism. Structural and functional comparisons of the archaeal dodecin with bacterial homologs reveal diverging evolution. Bacterial dodecins bind the flavin FMN instead of riboflavin and exhibit a clearly different binding pocket design with inverse incorporations of flavin dimers. The different adoption of flavin changes photochemical properties, making bacterial dodecin a comparably less efficient quencher of flavins. This supports a functional role different for bacterial and archaeal dodecins. PMID:22451648

Ultrafast photocarrier dynamics related to defect states of Si1-xGex nanowires measured by optical pump-THz probe spectroscopy.

PubMed

Bae, Jung Min; Lee, Woo-Jung; Jung, Seonghoon; Ma, Jin Won; Jeong, Kwang-Sik; Oh, Seung Hoon; Kim, Seongsin M; Suh, Dongchan; Song, Woobin; Kim, Sunjung; Park, Jaehun; Cho, Mann-Ho

2017-06-14

Slightly tapered Si 1-x Ge x nanowires (NWs) (x = 0.29-0.84) were synthesized via a vapor-liquid-solid procedure using Au as a catalyst. We measured the optically excited carrier dynamics of Si 1-x Ge x NWs as a function of Ge content using optical pump-THz probe spectroscopy. The measured -ΔT/T 0 signals of Si 1-x Ge x NWs were converted into conductivity in the THz region. We developed a fitting formula to apply to indirect semiconductors such as Si 1-x Ge x , which explains the temporal population of photo-excited carriers in the band structure and the relationship between the trapping time and the defect states on an ultrafast time scale. From the fitting results, we extracted intra- and inter-valley transition times and trapping times of electrons and holes of Si 1-x Ge x NWs as a function of Ge content. On the basis of theoretical reports, we suggest a physical model to interpret the trapping times related to the species of interface defect states located at the oxide/NW: substoichiometric oxide states of Si(Ge) 0+,1+,2+ , but not Si(Ge) 3+ , could function as defect states capturing photo-excited electrons or holes and could determine the different trapping times of electrons and holes depending on negatively or neutrally charged states.

Activation of coherent lattice phonon following ultrafast molecular spin-state photo-switching: A molecule-to-lattice energy transfer

PubMed Central

Marino, A.; Cammarata, M.; Matar, S. F.; Létard, J.-F.; Chastanet, G.; Chollet, M.; Glownia, J. M.; Lemke, H. T.; Collet, E.

2015-01-01

We combine ultrafast optical spectroscopy with femtosecond X-ray absorption to study the photo-switching dynamics of the [Fe(PM-AzA)2(NCS)2] spin-crossover molecular solid. The light-induced excited spin-state trapping process switches the molecules from low spin to high spin (HS) states on the sub-picosecond timescale. The change of the electronic state (<50 fs) induces a structural reorganization of the molecule within 160 fs. This transformation is accompanied by coherent molecular vibrations in the HS potential and especially a rapidly damped Fe-ligand breathing mode. The time-resolved studies evidence a delayed activation of coherent optical phonons of the lattice surrounding the photoexcited molecules. PMID:26798836

Interrogating ultrafast dynamics of a salicylideneaniline derivative within faujasite zeolites

NASA Astrophysics Data System (ADS)

Alarcos, Noemí; Sánchez, Félix; Douhal, Abderrazzak

2017-09-01

We report on femtosecond (fs) studies of (E)-2-(2-hydroxybenzyliden) amino-4-nitrophenol (HBA-4NP) in dichloromethane (DCM) and triacetin (TAC) solutions, and within NaX and NaY zeolites. In solution, an ultrafast (≤80 fs) excited-state intramolecular proton-transfer (ESIPT) reaction produces a keto (K) tautomer, which undergoes a rotational process in ∼4 (DCM) and ∼7 ps (TAC) toward the formation of non-emitting structures. Within NaX and NaY, where monomers and aggregates are formed, host-guest and guest-guest interactions play an important role in the ultrafast behaviour of these complexes. These results clearly reflect how nanoconfinement and zeolite composition affect the encapsulated dye photodynamics.

Femtochemistry of confined water

NASA Astrophysics Data System (ADS)

Douhal, A.; Carranza, M. A.; Sanz, M.; Organero, J. A.; Santos, L.

In this contribution, we applied ultrafast spectroscopy to study the H-bond network of water confined in nanostructures (Cyclodextrins and Micelles). We examine the effect of caging on ultrafast reaction dynamics and discuss the related processes under different experimental conditions. The results show an ultrafast dynamic giving birth to intermediates of the probe, which show femtosecond and picosecond dynamics leading to the final structure at the excited state. The results show the high sensitivity of the used technique in detecting small of water. This work was supported by the Ministry of Science and Technology (MCYT, Spain) and ``Conserjería de Ciencia y Tecnologia de la JCCM, Spain'' through projects MAT2002-01829 and PAI-02-004.

Enhanced coherent oscillations in the superconducting state of underdoped YB a 2 C u 3 O 6 + x induced via ultrafast terahertz excitation

DOE PAGES

Dakovski, Georgi L.; Lee, Wei -Sheng; Hawthorn, David G.; ...

2015-06-24

We utilize intense, single-cycle terahertz pulses to induce collective excitations in the charge-density-wave-ordered underdoped cuprate YBa 2Cu 3O 6+x. These excitations manifest themselves as pronounced coherent oscillations of the optical reflectivity in the transient state, accompanied by minimal incoherent quasiparticle relaxation dynamics. The oscillations occur at frequencies consistent with soft phonon energies associated with the charge-density-wave, but vanish above the superconducting transition temperature rather than that at the charge-density-wave transition. These results indicate an intimate relationship of the terahertz excitation with the underlying charge-density-wave and the superconducting condensate itself.

Nonradiative inter- and intramolecular energy transfer from the aromatic donor anisole to a synthesized photoswitchable acceptor system.

PubMed

Bardhan, Munmun; Bhattacharya, Sudeshna; Misra, Tapas; Mukhopadhyay, Rupa; De, Asish; Chowdhury, Joydeep; Ganguly, Tapan

2010-02-01

We report steady state and time resolved fluorescence measurements on acetonitrile (ACN) solutions of the model compounds, energy donor anisole (A) and a photoswitchable acceptor N,N'-1,2-phenylene di-p-tosylamide (B) and the multichromophore (M) where A and B are connected by a spacer containing both rigid triple (acetylenic) and flexible methylene bonds. Both steady state and time correlated single photon counting measurements demonstrate that though intermolecular energy transfer, of Forster type, between the donor and acceptor moieties occurs with rate 10(8)s(-1) but when these two reacting components are linked by a spacer (multichromophore, M) the observed transfer rate ( approximately 10(11)s(-1)) enhances. This seemingly indicates that the imposition of the spacer by inserting a triple bond may facilitate in the propagation of electronic excitation energy through bond. The time resolved fluorescence measurements along with the theoretical predictions using Configuration interaction singles (CIS) method by using 6-31G (d,p) basis set, implemented in the Gaussian package indicate the formations of the two excited conformers of B. The experimental findings made from the steady state and time resolved fluorescence measurements demonstrate that, though two different isomeric species of the acceptor B are formed in the excited singlet states, the prevailing singlet-singlet nonradiative energy transfer route was found from the donor A to the relatively longer-lived isomeric species of B. Copyright (c) 2009 Elsevier B.V. All rights reserved.

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

PubMed

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

2018-03-06

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

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

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.

Characterization of the X~ 2A1, A~ 2B1, and X~ 2Π electronic states of the Ga2H molecule and the X~ 2A' and A~ 2A'' isomerization transition states connecting the three minima

NASA Astrophysics Data System (ADS)

Wang, Hongyan; Wang, Suyun; Yan, Ge; Yamaguchi, Yukio; Schaefer, Henry F.

2006-01-01

A wide range of highly correlated ab initio methods has been used to predict the geometrical parameters of the linear (X˜Π2) and H-bridged (X˜A12 and ÃB12) Ga2H isomers and two isomerization transition states (X˜A'2 and ÃA″2) connecting the three minima. Dipole moments and vibrational frequencies are also obtained. The global minimum X˜A12 ground state of the H-bridged GaHGa isomer is predicted to lie only 1.6 [1.9 with the zero-point vibrational energy (ZPVE) corrections] kcalmol-1 below the ÃB12 state. The X˜A12 state lies 5.4kcalmol-1 below the X˜Π2 ground state of the linear GaGaH isomer at the coupled-cluster with single, double, and perturbative triple excitations [CCSD(T)] level of theory with the augmented correlation-consistent polarized valence quadruple-zeta (aug-cc-pVQZ) basis set. The full triples coupled-cluster method is found to alter these CCSD(T) predictions by as much as 0.3kcalmol-1. The forward isomerization barriers from the linear ground state to the X˜A'2 and ÃA″2 transition states are determined to be 3.3 and 5.3kcalmol-1, respectively. The reverse isomerization barrier between the X˜A12 GaHGa structure and the X˜Π2 GaGaH structure is predicted to be 8.6 (8.2 with the ZPVE corrections) kcalmol-1 at the aug-cc-pVQZ CCSD(T) level of theory.

Vibrational relaxation in liquid chloroform following ultrafast excitation of the CH stretch fundamental

NASA Astrophysics Data System (ADS)

Sibert, Edwin L.; Rey, Rossend

2002-01-01

Vibrational energy flow in liquid chloroform that follows the ultrafast excitation of the CH stretch fundamental is modeled using semiclassical methods. Relaxation rates are calculated using Landau-Teller theory and a time-dependent method both of which consider a quantum mechanical CHCl3 solute molecule coupled to a classical bath of CHCl3 solvent molecules. Probability flow is examined for several potentials to determine the sensitivity of calculated relaxation rates to the parameters that describe the model potentials. Three stages of relaxation are obtained. Probability is calculated to decay initially to a single acceptor state, a combination state of the solute molecule with two quanta of excitation in the CH bend and one in the CCl stretch, in 13-23 ps depending on the potential model employed. This is followed by rapid and complex intramolecular energy flow into the remaining vibrational degrees of freedom. During this second stage the lowest frequency Cl-C-Cl bend is found to serve as a conduit for energy loss to the solvent. The bottleneck for relaxation back to the ground state is predicted to be the slow 100-200 ps relaxation of the CH bend and CCl stretch fundamentals. Several aspects of the incoherent anti-Stokes scattering that follows strong infrared excitation of the CH fundamental as observed by Graener, Zürl, and Hoffman [J. Phys. Chem. B 101, 1745 (1997)] are elucidated in the present study.

Population branching in the conical intersection of the retinal chromophore revealed by multipulse ultrafast optical spectroscopy.

PubMed

Zgrablić, Goran; Novello, Anna Maria; Parmigiani, Fulvio

2012-01-18

The branching ratio of the excited-state population at the conical intersection between the S(1) and S(0) energy surfaces (Φ(CI)) of a protonated Schiff base of all-trans retinal in protic and aprotic solvents was studied by multipulse ultrafast transient absorption spectroscopy. In particular, pump-dump-probe experiments allowed to isolate the S(1) reactive state and to measure the photoisomerization time constant with unprecedented precision. Starting from these results, we demonstrate that the polarity of the solvent is the key factor influencing the Φ(CI) and the photoisomerization yield. © 2011 American Chemical Society

Intrinsic subpicosecond magnetization reversal driven by femtosecond laser pulses in GdFeCo amorphous films

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

Li, Shufa; Gao, Ruixin; Cheng, Chuyuan

2013-12-09

Ultrafast magnetization dynamics in GdFeCo films triggered by femtosecond laser pulses with and without an external field applied is studied experimentally for different excitation fluence. It is found that subpicosecond magnetization reversal occurs simultaneously in the ultrafast dynamics of both saturation and remnant magnetization states and almost identical within 13 ps, whereas relatively slow magnetization reversal across compensation point appears only in the dynamics of saturation magnetization state. It shows the subpicosecond magnetization reversal is external field independent, and originates from intrinsic magnetic evolution in ferrimagnetic system. The intrinsic subpicosecond reversal is qualitatively explained by linear reversal.

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 effect of solvent relaxation time constants on free energy gap law for ultrafast charge recombination following photoinduced charge separation.

PubMed

Mikhailova, Valentina A; Malykhin, Roman E; Ivanov, Anatoly I

2018-05-16

To elucidate the regularities inherent in the kinetics of ultrafast charge recombination following photoinduced charge separation in donor-acceptor dyads in solutions, the simulations of the kinetics have been performed within the stochastic multichannel point-transition model. Increasing the solvent relaxation time scales has been shown to strongly vary the dependence of the charge recombination rate constant on the free energy gap. In slow relaxing solvents the non-equilibrium charge recombination occurring in parallel with solvent relaxation is very effective so that the charge recombination terminates at the non-equilibrium stage. This results in a crucial difference between the free energy gap laws for the ultrafast charge recombination and the thermal charge transfer. For the thermal reactions the well-known Marcus bell-shaped dependence of the rate constant on the free energy gap is realized while for the ultrafast charge recombination only a descending branch is predicted in the whole area of the free energy gap exceeding 0.2 eV. From the available experimental data on the population kinetics of the second and first excited states for a series of Zn-porphyrin-imide dyads in toluene and tetrahydrofuran solutions, an effective rate constant of the charge recombination into the first excited state has been calculated. The obtained rate constant being very high is nearly invariable in the area of the charge recombination free energy gap from 0.2 to 0.6 eV that supports the theoretical prediction.

Delocalized versus localized excitations in the photoisomerization of azobenzene-functionalized alkanethiolate SAMs

NASA Astrophysics Data System (ADS)

Bronsch, Wibke; Moldt, Thomas; Boie, Larissa; Gahl, Cornelius; Weinelt, Martin

2017-12-01

Self-assembled monolayers of azobenzene-functionalized alkanethiolates form molecular ensembles with preferential orientation and significant excitonic coupling among the azobenzene chromophores. We have studied their optical switching with differential reflectance and two-photon-photoemission spectroscopy tuning the excitation wavelength through the excitonically broadened S2 absorption band. While the effective isomerization cross-section increases towards shorter wavelengths, the fraction of cis molecules in the photostationary state decreases. We attribute this observation to the absorption of the cis isomer in the SAM. The photoisomerization in the SAM thereby follows the behavior of non-interacting chromophores in solution, despite the formation of H-aggregates. Our study thus reveals that photoswitching occurs via localized excitations while strongly excitonically coupled, delocalized states do not contribute significantly.

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

PubMed

Kim, So Young; Joo, Taiha

2015-08-06

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

Molecular symmetry determines the mechanism of a very efficient ultrafast excitation-to-heat conversion in Ni-substituted chlorophylls.

PubMed

Pilch, Mariusz; Dudkowiak, Alina; Jurzyk, Barbara; Lukasiewicz, Jędrzej; Susz, Anna; Stochel, Grażyna; Fiedor, Leszek

2013-01-01

In the Ni-substituted chlorophylls, an ultrafast (<60 fs) deactivation channel is created, which is not present in Ni-porphyrins. This observation prompted us to investigate in detail the mechanism of excitation-to-heat conversion in Ni-substituted chlorophylls, experimentally, using time-resolved laser-induced optoacoustic spectroscopy, and theoretically, using group theory approach. The Ni-substituted chlorophylls show exceptional photostability and the optoacoustic measurements confirm the prompt and very efficient (100%) excitation-into-heat conversion in these complexes. Considering their excellent spectral properties and the loss-free excitation-into-heat conversion they are likely to become a new class of versatile photocalorimetric references. The curious features of the Ni-substituted chlorophylls originate from the symmetry of a ligand field created in the central cavity. The central N-Ni(2+) bonds, formed via the donation of two electrons from each of the sp(2) orbitals of two central nitrogens to an empty [Formula: see text] hybrid centered on Ni(2+), have a considerable covalent character. The extreme rate of excited state relaxation is then not due to a ladder of the metal centered d-states, often invoked in metalloporphyrins, but seems to result from a peculiar topology of the potential energy surface (a saddle-shaped crossing) due to the covalent character of the N-Ni(2+) bonds. This is confirmed by a strong 0→0 character of electronic transitions in these complexes indicating a similarity of their equilibrium geometries in the ground (S(0)) and the excited states (both Q(X) and Q(Y)). The excitation energy is very efficiently converted into molecular vibrations and dissipated as heat, involving the central Ni(2+). These Ni-substituted pigments pose a fine exemplification of symmetry control over properties of excited states of transition metal complexes. Copyright © 2012. Published by Elsevier B.V.

An ultrafast spectroscopic and quantum mechanical investigation of multiple emissions in push-pull pyridinium derivatives bearing different electron donors.

PubMed

Carlotti, B; Benassi, E; Cesaretti, A; Fortuna, C G; Spalletti, A; Barone, V; Elisei, F

2015-08-28

A joint experimental and theoretical approach, involving state-of-the-art femtosecond fluorescence up-conversion measurements and quantum mechanical computations including vibronic effects, was employed to get a deep insight into the excited state dynamics of two cationic dipolar chromophores (Donor-π-Acceptor(+)) where the electron deficient portion is a N-methyl pyridinium and the electron donor a trimethoxyphenyl or a pyrene, respectively. The ultrafast spectroscopic investigation, and the time resolved area normalised emission spectra in particular, revealed a peculiar multiple emissive behaviour and allowed the distinct emitting states to be remarkably distinguished from solvation dynamics, occurring in water in a similar timescale. The two and three emissions experimentally detected for the trimethoxyphenyl and pyrene derivatives, respectively, were associated with specific local emissive minima in the potential energy surface of S1 on the ground of quantum-mechanical calculations. A low polar and planar Locally Excited (LE) state together with a highly polar and Twisted Intramolecular Charge Transfer (TICT) state is identified to be responsible for the dual emission of the trimethoxyphenyl compound. Interestingly, the more complex photobehaviour of the pyrenyl derivative was explained considering the contribution to the fluorescence coming not only from the LE and TICT states but also from a nearly Planar Intramolecular Charge Transfer (PICT) state, with both the TICT and the PICT generated from LE by progressive torsion around the quasi-single bond between the methylpyridinium and the ethene bridge. These findings point to an interconversion between rotamers for the pyrene compound taking place in its excited state against the Non-equilibrated Excited Rotamers (NEER) principle.

QM/MM nonadiabatic dynamics simulations on photoinduced Wolff rearrangements of 1,2,3-thiadiazole

NASA Astrophysics Data System (ADS)

Liu, Xiang-Yang; Fang, Ye-Guang; Xie, Bin-Bin; Fang, Wei-Hai; Cui, Ganglong

2017-06-01

The photoinduced rearrangement reaction mechanism of 1,2,3-thiadiazole remains experimentally elusive. Two possible mechanisms have been proposed to date. The first is a stepwise mechanism via a thiocarbene intermediate; the second is an excited-state concerted rearrangement mechanism. Herein we have adopted both the electronic structure calculations and nonadiabatic dynamics simulations to study the photoinduced rearrangement reactions of 1,2,3-thiadiazole in the S2, S1, and S0 states in solution. On the basis of QM(CASPT2)/MM [quantum mechanics(complete active space self-consistent field second-order perturbation theory)/molecular mechanics] calculations, we have found that (1) the thiocarbene intermediate is not stable; thus, the stepwise mechanism should be unfavorable; (2) the excited-state decay from the S2 via S1 to S0 state is ultrafast and completed within ca. 200 fs; therefore, both the S2 and S1 states should not have a long enough time for the excited-state rearrangements. Instead, we have computationally proposed a modified photoinduced rearrangement mechanism. Upon irradiation, the S2 state is first populated (114.0 kcal/mol), followed by an ultrafast S2 → S1 → S0 excited-state decay along the S-N bond fission, which eventually leads to a very "hot" intermediate with the S-N bond broken (18.3 kcal/mol). Then, thermal rearrangements to thioketene, thiirene, and ethynethiol occur in a concerted asynchronous way. This mechanistic scenario has been verified by full-dimensional trajectory-based nonadiabatic dynamics simulations at the QM(CASPT2)/MM level. Finally, our present computational work provides experimentally interesting mechanistic insights into the photoinduced rearrangement reactions of cyclic and acyclic diazo compounds.

Thermally and vibrationally induced conformational isomerizations, infrared spectra, and photochemistry of gallic acid in low-temperature matrices

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

Justino, Licínia L. G., E-mail: liciniaj@ci.uc.pt; Reva, Igor; Fausto, Rui

2016-07-07

Near-infrared (near-IR) narrowband selective vibrational excitation and annealing of gallic acid (3,4,5-trihydroxybenzoic acid) isolated in cryogenic matrices were used to induce interconversions between its most stable conformers. The isomerizations were probed by infrared spectroscopy. An extensive set of quantum chemical calculations, carried out at the DFT(B3LYP)/6-311++G(d,p) level of approximation, was used to undertake a detailed analysis of the ground state potential energy surface of the molecule. This investigation of the molecule conformational space allowed extracting mechanistic insights into the observed annealing- or near-IR-induced isomerization processes. The infrared spectra of the two most stable conformers of gallic acid in N{sub 2},more » Xe, and Ar matrices were fully assigned. Finally, the UV-induced photochemistry of the matrix isolated compound was investigated.« less

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 interest. With the emergence of new instruments such as X-ray free electron lasers (XFELs), it is now possible to perform ultrafast laser pump/X-ray emission probe experiments. In this case, one probes the density of occupied states. These core-level spectroscopies and other emerging ones, such as photoelectron spectroscopy of solutions, are delivering a hitherto unseen degree of detail into the photophysics of metal-based molecular complexes. In this Account, we will give examples of applications of the various methods listed above to address specific photophysical processes.

Ultrafast hole carrier relaxation dynamics in p-type CuO nanowires

PubMed Central

2011-01-01

Ultrafast hole carrier relaxation dynamics in CuO nanowires have been investigated using transient absorption spectroscopy. Following femtosecond pulse excitation in a non-collinear pump-probe configuration, a combination of non-degenerate transmission and reflection measurements reveal initial ultrafast state filling dynamics independent of the probing photon energy. This behavior is attributed to the occupation of states by photo-generated carriers in the intrinsic hole region of the p-type CuO nanowires located near the top of the valence band. Intensity measurements indicate an upper fluence threshold of 40 μJ/cm2 where carrier relaxation is mainly governed by the hole dynamics. The fast relaxation of the photo-generated carriers was determined to follow a double exponential decay with time constants of 0.4 ps and 2.1 ps. Furthermore, time-correlated single photon counting measurements provide evidence of three exponential relaxation channels on the nanosecond timescale. PMID:22151927

Exploring coherent electron excitation and migration dynamics by electron diffraction with ultrashort X-ray pulses.

PubMed

Yuan, Kai-Jun; Bandrauk, André D

2017-10-04

Exploring ultrafast charge migration is of great importance in biological and chemical reactions. We present a scheme to monitor attosecond charge migration in molecules by electron diffraction with spatial and temporal resolutions from ab initio numerical simulations. An ultraviolet pulse creates a coherent superposition of electronic states, after which a time-delayed attosecond X-ray pulse is used to ionize the molecule. It is found that diffraction patterns in the X-ray photoelectron spectra show an asymmetric structure, which is dependent on the time delay between the pump-probe pulses, encoding the information of molecular orbital symmetry and chemical bonding. We describe these phenomena by developing an electronic time-dependent ultrafast molecular photoionization model of a coherent superposition state. The periodical distortion of electron diffraction patterns illustrates the evolution of the electronic coherence, providing a tool for attosecond imaging of ultrafast molecular reaction processes.

Spatial Temperature Mapping within Polymer Nanocomposites Undergoing Ultrafast Photothermal Heating via Gold Nanorods

PubMed Central

Maity, Somsubhra; Wu, Wei-Chen; Xu, Chao; Tracy, Joseph B.; Gundogdu, Kenan; Bochinski, Jason R.; Clarke, Laura I.

2015-01-01

Heat emanates from gold nanorods (GNRs) under ultrafast optical excitation of the localized surface plasmon resonance. The steady state nanoscale temperature distribution formed within a polymer matrix embedded with GNRs undergoing pulsed femtosecond photothermal heating is determined experimentally using two independent ensemble optical techniques. Physical rotation of the nanorods reveals the average local temperature of the polymer melt in the immediate spatial volume surrounding them while fluorescence of homogeneously-distributed perylene molecules monitors temperature over sample regions at larger distances from the GNRs. Polarization-sensitive fluorescence measurements of the perylene probes provide an estimate of the average size of the quasi-molten region surrounding each nanorod (that is, the boundary between softened polymer and solid material as the temperature decreases radially away from each particle) and distinguishes the steady state temperature in the solid and melt regions. Combining these separate methods enables nanoscale spatial mapping of the average steady state temperature distribution caused by ultrafast excitation of the GNRs. These observations definitively demonstrate the presence of a steady-state temperature gradient and indicate that localized heating via the photothermal effect within materials enables nanoscale thermal manipulations without significantly altering the bulk sample temperature in these systems. These quantitative results are further verified by reorienting nanorods within a solid polymer nanofiber without inducing any morphological changes to the highly temperature-sensitive nanofiber surface. Temperature differences of 70 – 90 °C were observed over a distances of ~100 nm. PMID:25379775

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 state is accompanied by the formation of an ICT character and dynamic exciton localization, which controls the mechanism of excitation energy transfer to chlorophyll a acceptors in the peridinin-chlorophyll a protein.

Nuclear Data Sheets for A = 26

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

Basunia, M.S.; Hurst, A.M.

2016-05-15

Evaluated spectroscopic data and level schemes from radioactive decay and nuclear reaction studies are presented for {sup 26}O, {sup 26}F, {sup 26}Ne, {sup 26}Na, {sup 26}Mg, {sup 26}Al, {sup 26}Si, {sup 26}P, and {sup 26}S. This evaluation for A = 26 supersedes the earlier one by P. M. Endt (1998En04) and updates for some nuclides in ENSDF. Highlights of this evaluation are the following: This evaluation includes search results for {sup 26}S nuclide and its proton–decay mode (2011Fo08). An isomeric state (2.2 ms) in {sup 26}F has been discovered by 2013Le03. The state is proposed at 643.4 keV 1 frommore » γ–ray measurements. Internal-transition and beta-decay branches for the state are also determined. New excited levels in {sup 26}Ne have been identified from {sup 26}F β{sup −} decay (2.2 ms). For some {sup 26}Si resonance states conflicting spin-parity assignments exist in the literature. These are identified by footnotes. 2015Do07 ({sup 3}He,nγ) propose the first 0+ state above proton separation energy at an excitation energy of 5890 keV and suggested for additional independent measurements to confirm or refute the existence of 5946 keV 4. 2016Ch09 consider 5946 keV level as a distinct excited state in their reanalysis of the literature data with possible spin-parity assignment of 0+ or 4+ This evaluation also includes discovery of an isomeric state, at 164.1 keV 1, in {sup 26}P by 2014NiZZ.« less

Transient and stationary spectroscopy of cytochrome c: ultrafast internal conversion controls photoreduction.

PubMed

Löwenich, Dennis; Kleinermanns, Karl; Karunakaran, Venugopal; Kovalenko, Sergey Alexander

2008-01-01

Photoreduction of cytochrome c (Cyt c) has been reinvestigated using femtosecond-to-nanosecond transient absorption and stationary spectroscopy. Femtosecond spectra of oxidized Cyt c, recorded in the probe range 270-1000 nm, demonstrate similar evolution upon 266 or 403 nm excitation: an ultrafast 0.3 ps internal conversion followed by a 4 ps vibrational cooling. Late transient spectra after 20 ps, from the cold ground-state chromophore, reveal a small but measurable signal from reduced Cyt c. The yield phi for Fe3+-->Fe2+ photoreduction is measured to be phi(403) = 0.016 and phi(266) = 0.08 for 403 and 266 nm excitation. These yields lead to a guess of the barrier E(f)(A) = 55 kJ mol(-1) for thermal ground-state electron transfer (ET). Nanosecond spectra initially show the typical absorption from reduced Cyt c and then exhibit temperature-dependent sub-microsecond decays (0.5 micros at 297 K), corresponding to a barrier E(A)(b) = 33 kJ mol(-1) for the back ET reaction and a reaction energy DeltaE = 22 kJ mol(-1). The nanosecond transients do not decay to zero on a second time scale, demonstrating the stability of some of the reduced Cyt c. The yields calculated from this stable reduced form agree with quasistationary reduction yields. Modest heating of Cyt c leads to its efficient thermal reduction as demonstrated by differential stationary absorption spectroscopy. In summary, our results point to ultrafast internal conversion of oxidized Cyt c upon UV or visible excitation, followed by Fe-porphyrin reduction due to thermal ground-state ET as the prevailing mechanism.

Measurement of excitation functions and analysis of isomeric population in some reactions induced by proton on natural indium at low energy

NASA Astrophysics Data System (ADS)

Muhammed Shan, P. T.; Musthafa, M. M.; Najmunnisa, T.; Mohamed Aslam, P.; Rajesh, K. K.; Hajara, K.; Surendran, P.; Nair, J. P.; Shanbagh, Anil; Ghugre, S.

2018-06-01

The excitation functions for reaction residues populated via 115In(p , p) 115 mIn, 115In(p , pn) 114 mIn, 115In(p , p 2 n) 113 mIn, 113In(p , p) 113 mIn, 115In(p , nα) 111 mCd, 115In(p , 3 n) 113Sn and 113In(p , n) 113Sn channels were measured over the proton energy range of 8-22 MeV using stacked foil activation technique. Theoretical analysis of the data were performed within the framework of two statistical model codes EMPIRE-3.2 and TALYS-1.8. Isomeric cross section ratio for isomeric pairs m,g 115In, m,g 114In, m,g 113In, 113Sn m,g and m,g 111Cd were determined for the first time. The dependence of isomeric cross section ratio on various factors are analysed.

Ultrafast Independent N-H and N-C Bond Deformation Investigated with Resonant Inelastic X-Ray Scattering

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

Eckert, Sebastian; Norell, Jesper; Miedema, Piter S.

Here, the femtosecond excited-state dynamics following resonant photoexcitation enable the selective deformation of N-H and N-C chemical bonds in 2-thiopyridone in aqueous solution with optical or X-ray pulses. In combination with multiconfigurational quantum-chemical calculations, the orbital-specific electronic structure and its ultrafast dynamics accessed with resonant inelastic X-ray scattering at the N 1s level using synchrotron radiation and the soft X-ray free-electron laser LCLS provide direct evidence for this controlled photoinduced molecular deformation and its ultrashort timescale.

Ultrafast Independent N-H and N-C Bond Deformation Investigated with Resonant Inelastic X-Ray Scattering

DOE PAGES

Eckert, Sebastian; Norell, Jesper; Miedema, Piter S.; ...

2017-04-04

Here, the femtosecond excited-state dynamics following resonant photoexcitation enable the selective deformation of N-H and N-C chemical bonds in 2-thiopyridone in aqueous solution with optical or X-ray pulses. In combination with multiconfigurational quantum-chemical calculations, the orbital-specific electronic structure and its ultrafast dynamics accessed with resonant inelastic X-ray scattering at the N 1s level using synchrotron radiation and the soft X-ray free-electron laser LCLS provide direct evidence for this controlled photoinduced molecular deformation and its ultrashort timescale.

Ultrafast hydrogen bond dynamics and partial electron transfer after photoexcitation of diethyl ester of 7-(diethylamino)-coumarin-3-phosphonic acid and its benzoxaphosphorin analog.

PubMed

Wagner, M S; Ilieva, E D; Petkov, P St; Nikolova, R D; Kienberger, R; Iglev, H

2015-04-21

The solvation dynamics after optical excitation of two phosphono-substituted coumarin derivatives dissolved in various solutions are studied by fluorescence up-conversion spectroscopy and quantum chemical simulations. The Kamlet-Taft analysis of the conventional absorption and emission spectra suggests weakening of the solvent-solute H-bonds upon optical excitation, which is in contrast to the results gained by the quantum simulations and earlier studies reported for coumarin derivatives without phosphono groups. The simulations give evidence that the solvent reorganisation around the excited fluorophore leads to partial electron transfer to the first solvation shell. The process occurs on a timescale between 1 and 10 ps depending on the solvent polarity and leads to a fast decay of the time-resolved emission signal. Using the ultrafast spectral shift of the time-dependent fluorescence we estimated the relaxation time of the H-bonds in the electronically excited state to be about 0.6 ps in water, 1.5 ps in ethanol and 2.8 ps in formamide.

Photodissociation dynamics of nitromethane and methyl nitrite by infrared multiphoton dissociation imaging with quasiclassical trajectory calculations: signatures of the roaming pathway.

PubMed

Dey, Arghya; Fernando, Ravin; Abeysekera, Chamara; Homayoon, Zahra; Bowman, Joel M; Suits, Arthur G

2014-02-07

We combine the techniques of infrared multiphoton dissociation (IRMPD) with state selective ion imaging to probe roaming dynamics in the unimolecular dissociation of nitromethane and methyl nitrite. Recent theoretical calculations suggest a "roaming-mediated isomerization" pathway of nitromethane to methyl nitrite prior to decomposition. State-resolved imaging of the NO product coupled with infrared multiphoton dissociation was carried out to examine this unimolecular decomposition near threshold. The IRMPD images for the NO product from nitromethane are consistent with the earlier IRMPD studies that first suggested the importance of an isomerization pathway. A significant Λ-doublet propensity is seen in nitromethane IRMPD but not methyl nitrite. The experimental observations are augmented by quasiclassical trajectory calculations for nitromethane and methyl nitrite near threshold for each dissociation pathway. The observation of distinct methoxy vibrational excitation for trajectories from nitromethane and methyl nitrite dissociation at the same total energy show that the nitromethane dissociation bears a nonstatistical signature of the roaming isomerization pathway, and this is possibly responsible for the nitromethane Λ-doublet propensity as well.

Rotational band on a three-quasineutron isomer in 127Xe

NASA Astrophysics Data System (ADS)

Chakraborty, S.; Sharma, H. P.; Tiwary, S. S.; Majumder, C.; Banerjee, P.; Ganguly, S.; Rai, S.; Pragati, Modi, Swati; Arumugam, P.; Mayank, Kumar, S.; Palit, R.; Kumar, A.; Bhattacharjee, S. S.; Singh, R. P.; Muralithar, S.

2018-05-01

Excited states in 127Xe were populated via 122Sn(9Be,4 n γ ) fusion-evaporation reaction at Ebeam=48 MeV. A rotational band above an isomeric state at 2730.3 keV has been established. Jπ=23 /2+ has been assigned unambiguously to the bandhead. Structural features, configuration, and reduced hindrance factor per degree of K -forbiddenness (fν) have been discussed in the context of neighboring nuclei. Half-lives of 7 /2+ (t1 /2=37 ±1 ns) and 23 /2+ (t1 /2=28 ±1 ns) isomeric states have also been estimated and found to be consistent with the earlier reported values. The experimentally observed energy levels of the rotational band have been reproduced successfully by theoretical calculations carried out using the modified particle rotor model (MPRM) with β2˜0.22 and 15∘≲γ ≲22∘ .

A single-shot spatial chirp method for measuring initial AC conductivity evolution of femtosecond laser pulse excited warm dense matter

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

Chen, Z.; Hering, P.; Brown, S. B.

To study the rapid evolution of AC conductivity from ultrafast laser excited warm dense matter (WDM), a spatial chirp single-shot method is developed utilizing a crossing angle pump-probe configuration. The pump beam is shaped individually in two spatial dimensions so that it can provide both sufficient laser intensity to excite the material to warm dense matter state and a uniform time window of up to 1 ps with sub-100 fs FWHM temporal resolution. Here, temporal evolution of AC conductivity in laser excited warm dense gold was also measured.

A single-shot spatial chirp method for measuring initial AC conductivity evolution of femtosecond laser pulse excited warm dense matter

DOE PAGES

Chen, Z.; Hering, P.; Brown, S. B.; ...

2016-09-19

To study the rapid evolution of AC conductivity from ultrafast laser excited warm dense matter (WDM), a spatial chirp single-shot method is developed utilizing a crossing angle pump-probe configuration. The pump beam is shaped individually in two spatial dimensions so that it can provide both sufficient laser intensity to excite the material to warm dense matter state and a uniform time window of up to 1 ps with sub-100 fs FWHM temporal resolution. Here, temporal evolution of AC conductivity in laser excited warm dense gold was also measured.

Lifetime Measurement of the 229Th nuclear isomer

NASA Astrophysics Data System (ADS)

Seiferle, Benedict; von der Wense, Lars; Thirolf, Peter G.

2017-01-01

The first excited isomeric state of 229Th possesses the lowest energy among all known excited nuclear states. The expected energy is accessible with today's laser technology and in principle allows for a direct optical laser excitation of the nucleus. The isomer decays via three channels to its ground state (internal conversion, γ decay, and bound internal conversion), whose strengths depend on the charge state of Thm229 . We report on the measurement of the internal-conversion decay half-life of neutral Thm229 . A half-life of 7 ±1 μ s has been measured, which is in the range of theoretical predictions and, based on the theoretically expected lifetime of ≈1 04 s of the photonic decay channel, gives further support for an internal conversion coefficient of ≈1 09, thus constraining the strength of a radiative branch in the presence of internal conversion.

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.

Measurements of ultrafast spin-profiles and spin-diffusion properties in the domain wall area at a metal/ferromagnetic film interface.

PubMed

Sant, T; Ksenzov, D; Capotondi, F; Pedersoli, E; Manfredda, M; Kiskinova, M; Zabel, H; Kläui, M; Lüning, J; Pietsch, U; Gutt, C

2017-11-08

Exciting a ferromagnetic material with an ultrashort IR laser pulse is known to induce spin dynamics by heating the spin system and by ultrafast spin diffusion processes. Here, we report on measurements of spin-profiles and spin diffusion properties in the vicinity of domain walls in the interface region between a metallic Al layer and a ferromagnetic Co/Pd thin film upon IR excitation. We followed the ultrafast temporal evolution by means of an ultrafast resonant magnetic scattering experiment in surface scattering geometry, which enables us to exploit the evolution of the domain network within a 1/e distance of 3 nm to 5 nm from the Al/FM film interface. We observe a magnetization-reversal close to the domain wall boundaries that becomes more pronounced closer to the Al/FM film interface. This magnetization-reversal is driven by the different transport properties of majority and minority carriers through a magnetically disordered domain network. Its finite lateral extension has allowed us to measure the ultrafast spin-diffusion coefficients and ultrafast spin velocities for majority and minority carriers upon IR excitation.

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

An efficient implementation of semiempirical quantum-chemical orthogonalization-corrected methods for excited-state dynamics

NASA Astrophysics Data System (ADS)

Liu, Jie; Thiel, Walter

2018-04-01

We present an efficient implementation of configuration interaction with single excitations (CIS) for semiempirical orthogonalization-corrected OMx methods and standard modified neglect of diatomic overlap (MNDO)-type methods for the computation of vertical excitation energies as well as analytical gradients and nonadiabatic couplings. This CIS implementation is combined with Tully's fewest switches algorithm to enable surface hopping simulations of excited-state nonadiabatic dynamics. We introduce an accurate and efficient expression for the semiempirical evaluation of nonadiabatic couplings, which offers a significant speedup for medium-size molecules and is suitable for use in long nonadiabatic dynamics runs. As a pilot application, the semiempirical CIS implementation is employed to investigate ultrafast energy transfer processes in a phenylene ethynylene dendrimer model.

An efficient implementation of semiempirical quantum-chemical orthogonalization-corrected methods for excited-state dynamics.

PubMed

Liu, Jie; Thiel, Walter

2018-04-21

We present an efficient implementation of configuration interaction with single excitations (CIS) for semiempirical orthogonalization-corrected OMx methods and standard modified neglect of diatomic overlap (MNDO)-type methods for the computation of vertical excitation energies as well as analytical gradients and nonadiabatic couplings. This CIS implementation is combined with Tully's fewest switches algorithm to enable surface hopping simulations of excited-state nonadiabatic dynamics. We introduce an accurate and efficient expression for the semiempirical evaluation of nonadiabatic couplings, which offers a significant speedup for medium-size molecules and is suitable for use in long nonadiabatic dynamics runs. As a pilot application, the semiempirical CIS implementation is employed to investigate ultrafast energy transfer processes in a phenylene ethynylene dendrimer model.

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 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.

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 dynamics of exciton fission in polycrystalline pentacene.

PubMed

Wilson, Mark W B; Rao, Akshay; Clark, Jenny; Kumar, R Sai Santosh; Brida, Daniele; Cerullo, Giulio; Friend, Richard H

2011-08-10

We use ultrafast transient absorption spectroscopy with sub-20 fs time resolution and broad spectral coverage to directly probe the process of exciton fission in polycrystalline thin films of pentacene. We observe that the overwhelming majority of initially photogenerated singlet excitons evolve into triplet excitons on an ∼80 fs time scale independent of the excitation wavelength. This implies that exciton fission occurs at a rate comparable to phonon-mediated exciton localization processes and may proceed directly from the initial, delocalized, state. The singlet population is identified due to the brief presence of stimulated emission, which is emitted at wavelengths which vary with the photon energy of the excitation pulse, a violation of Kasha's Rule that confirms that the lowest-lying singlet state is extremely short-lived. This direct demonstration that triplet generation is both rapid and efficient establishes multiple exciton generation by exciton fission as an attractive route to increased efficiency in organic solar cells. © 2011 American Chemical Society

The origin of absorptive features in the two-dimensional electronic spectra of rhodopsin.

PubMed

Farag, Marwa H; Jansen, Thomas L C; Knoester, Jasper

2018-05-09

In rhodopsin, the absorption of a photon causes the isomerization of the 11-cis isomer of the retinal chromophore to its all-trans isomer. This isomerization is known to occur through a conical intersection (CI) and the internal conversion through the CI is known to be vibrationally coherent. Recently measured two-dimensional electronic spectra (2DES) showed dramatic absorptive spectral features at early waiting times associated with the transition through the CI. The common two-state two-mode model Hamiltonian was unable to elucidate the origin of these features. To rationalize the source of these features, we employ a three-state three-mode model Hamiltonian where the hydrogen out-of plane (HOOP) mode and a higher-lying electronic state are included. The 2DES of the retinal chromophore in rhodopsin are calculated and compared with the experiment. Our analysis shows that the source of the observed features in the measured 2DES is the excited state absorption to a higher-lying electronic state and not the HOOP mode.

High-seniority states in spherical nuclei: Triple pair breaking in tin isotopes

NASA Astrophysics Data System (ADS)

Astier, Alain

2013-03-01

The 119-126Sn nuclei have been produced as fission fragments in two reactions induced by heavy ions: 12C+238U at 90 MeV bombarding energy, 18O+208Pb at 85 MeV. Their level schemes have been built from gamma rays detected using the Euroball array. High-spin states located above the long-lived isomeric states of the even- A and odd-A 120-126Sn nuclei have been identified. Moreover isomeric states lying around 4.5 MeV have been established in the even-A 120-126Sn from the delayed coincidences between the fission fragment detector SAPhIR and the Euroball array. All the states located above 3-MeV excitation energy are ascribed to several broken pairs of neutrons occupying the h11/2 orbit. The maximum value of angular momentum available in such a high-j shell, i.e. for mid-occupation and the breaking of the three neutron pairs (seniority v=6), has been identified.

Effect of nuclear-reaction mechanisms on the population of excited nuclear states and isomeric ratios

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

Skobelev, N. K., E-mail: skobelev@jinr.ru

2016-07-15

Experimental data on the cross sections for channels of fusion and transfer reactions induced by beams of radioactive halo nuclei and clustered and stable loosely bound nuclei were analyzed, and the results of this analysis were summarized. The interplay of the excitation of single-particle states in reaction-product nuclei and direct reaction channels was established for transfer reactions. Respective experiments were performed in stable ({sup 6}Li) and radioactive ({sup 6}He) beams of the DRIBs accelerator complex at the Flerov Laboratory of Nuclear Reactions, Joint Institute for Nuclear Research, and in deuteron and {sup 3}He beams of the U-120M cyclotron at themore » Nuclear Physics Institute, Academy Sciences of Czech Republic (Řež and Prague, Czech Republic). Data on subbarrier and near-barrier fusion reactions involving clustered and loosely bound light nuclei ({sup 6}Li and {sup 3}He) can be described quite reliably within simple evaporation models with allowance for different reaction Q-values and couple channels. In reactions involving halo nuclei, their structure manifests itself most strongly in the region of energies below the Coulomb barrier. Neutron transfer occurs with a high probability in the interactions of all loosely bound nuclei with light and heavy stable nuclei at positive Q-values. The cross sections for such reactions and the respective isomeric ratios differ drastically for nucleon stripping and nucleon pickup mechanisms. This is due to the difference in the population probabilities for excited single-particle states.« less

Mechanisms of ultrafast laser-induced deep-subwavelength gratings on graphite and diamond

NASA Astrophysics Data System (ADS)

Huang, Min; Zhao, Fuli; Cheng, Ya; Xu, Ningsheg; Xu, Zhizhan

2009-03-01

Deep-subwavelength gratings with periodicities of 170, 120, and 70 nm can be observed on highly oriented pyrolytic graphite irradiated by a femtosecond (fs) laser at 800 nm. Under picosecond laser irradiation, such gratings likewise can be produced. Interestingly, the 170-nm grating is also observed on single-crystal diamond irradiated by the 800-nm fs laser. In our opinion, the optical properties of the high-excited state of material surface play a key role for the formation of the deep-subwavelength gratings. The numerical simulations of the graphite deep-subwavelength grating at normal and high-excited states confirm that in the groove the light intensity can be extraordinarily enhanced via cavity-mode excitation in the condition of transverse-magnetic wave irradiation with near-ablation-threshold fluences. This field enhancement of polarization sensitiveness in deep-subwavelength apertures acts as an important feedback mechanism for the growth and polarization dependence of the deep-subwavelength gratings. In addition, we suggest that surface plasmons are responsible for the formation of seed deep-subwavelength apertures with a particular periodicity and the initial polarization dependence. Finally, we propose that the nanoscale Coulomb explosion occurring in the groove is responsible for the ultrafast nonthermal ablation mechanism.

Ultrafast dynamics in atomic clusters: Analysis and control

PubMed Central

Bonačić-Koutecký, Vlasta; Mitrić, Roland; Werner, Ute; Wöste, Ludger; Berry, R. Stephen

2006-01-01

We present a study of dynamics and ultrafast observables in the frame of pump–probe negative-to-neutral-to-positive ion (NeNePo) spectroscopy illustrated by the examples of bimetallic trimers Ag2Au−/Ag2Au/Ag2Au+ and silver oxides Ag3O2−/Ag3O2/Ag3O2+ in the context of cluster reactivity. First principle multistate adiabatic dynamics allows us to determine time scales of different ultrafast processes and conditions under which these processes can be experimentally observed. Furthermore, we present a strategy for optimal pump–dump control in complex systems based on the ab initio Wigner distribution approach and apply it to tailor laser fields for selective control of the isomerization process in Na3F2. The shapes of pulses can be assigned to underlying processes, and therefore control can be used as a tool for analysis. PMID:16740664

Ultrafast dynamics in atomic clusters: analysis and control.

PubMed

Bonacić-Koutecký, Vlasta; Mitrić, Roland; Werner, Ute; Wöste, Ludger; Berry, R Stephen

2006-07-11

We present a study of dynamics and ultrafast observables in the frame of pump-probe negative-to-neutral-to-positive ion (NeNePo) spectroscopy illustrated by the examples of bimetallic trimers Ag2Au-/Ag2Au/Ag2Au+ and silver oxides Ag3O2-/Ag3O2/Ag3O2+ in the context of cluster reactivity. First principle multistate adiabatic dynamics allows us to determine time scales of different ultrafast processes and conditions under which these processes can be experimentally observed. Furthermore, we present a strategy for optimal pump-dump control in complex systems based on the ab initio Wigner distribution approach and apply it to tailor laser fields for selective control of the isomerization process in Na3F2. The shapes of pulses can be assigned to underlying processes, and therefore control can be used as a tool for analysis.

Qualitative assessment of ultra-fast non-Grotthuss proton dynamics in S1 excited state of liquid H2O from ab initio time-dependent density functional theory★

NASA Astrophysics Data System (ADS)

Ziaei, Vafa; Bredow, Thomas

2017-11-01

We study qualitatively ultra-fast proton transfer (PT) in the first singlet (S1) state of liquid water (absorption onset) through excited-state dynamics by means of time-dependent density functional theory and ab initio Born-Oppenheimer molecular dynamics. We find that after the initial excitation, a PT occurs in S1 in form of a rapid jump to a neighboring water molecule, on which the proton either may rest for a relatively long period of time (as a consequence of possible defect in the hydrogen bond network) followed by back and forth hops to its neighboring water molecule or from which it further moves to the next water molecule accompanied by back and forth movements. In this way, the proton may become delocalized over a long water wire branch, followed again by back and forth jumps or short localization on a water molecule for some femtoseconds. As a result, the mechanism of PT in S1 is in most cases highly non-Grotthuss-like, delayed and discrete. Furthermore, upon PT an excess charge is ejected to the solvent trap, the so-called solvated electron. The spatial extent of the ejected solvated electron is mainly localized within one solvent shell with overlappings on the nearest neighbor water molecules and delocalizing (diffuse) tails extending beyond the first solvent sphere. During the entire ultra-short excited-state dynamics the remaining OH radical from the initially excited water molecule exhibits an extremely low mobility and is non-reactive. Supplementary material in the form of one pdf file available from the Journal web page at http://https://doi.org/10.1140/epjb/e2017-80329-7.

Super-diffusion of excited carriers in semiconductors

PubMed Central

Najafi, Ebrahim; Ivanov, Vsevolod; Zewail, Ahmed; Bernardi, Marco

2017-01-01

The ultrafast spatial and temporal dynamics of excited carriers are important to understanding the response of materials to laser pulses. Here we use scanning ultrafast electron microscopy to image the dynamics of electrons and holes in silicon after excitation with a short laser pulse. We find that the carriers exhibit a diffusive dynamics at times shorter than 200 ps, with a transient diffusivity up to 1,000 times higher than the room temperature value, D0≈30 cm2s−1. The diffusivity then decreases rapidly, reaching a value of D0 roughly 500 ps after the excitation pulse. We attribute the transient super-diffusive behaviour to the rapid expansion of the excited carrier gas, which equilibrates with the environment in 100−150 ps. Numerical solution of the diffusion equation, as well as ab initio calculations, support our interpretation. Our findings provide new insight into the ultrafast spatial dynamics of excited carriers in materials. PMID:28492283

Phase diagram of the ultrafast photoinduced insulator-metal transition in vanadium dioxide

NASA Astrophysics Data System (ADS)

Cocker, T. L.; Titova, L. V.; Fourmaux, S.; Holloway, G.; Bandulet, H.-C.; Brassard, D.; Kieffer, J.-C.; El Khakani, M. A.; Hegmann, F. A.

2012-04-01

We use time-resolved terahertz spectroscopy to probe the ultrafast dynamics of the insulator-metal phase transition induced by femtosecond laser pulses in a nanogranular vanadium dioxide (VO2) film. Based on the observed thresholds for characteristic transient terahertz dynamics, a phase diagram of critical pump fluence versus temperature for the insulator-metal phase transition in VO2 is established for the first time over a broad range of temperatures down to 17 K. We find that both Mott and Peierls mechanisms are present in the insulating state and that the photoinduced transition is nonthermal. We propose a critical-threshold model for the ultrafast photoinduced transition based on a critical density of electrons and a critical density of coherently excited phonons necessary for the structural transition to the metallic state. As a result, evidence is found at low temperatures for an intermediate metallic state wherein the Mott state is melted but the Peierls distortion remains intact, consistent with recent theoretical predictions. Finally, the observed terahertz conductivity dynamics above the photoinduced transition threshold reveal nucleation and growth of metallic nanodomains over picosecond time scales.

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 that the red side of the hydrated electron's fluorescence spectrum should significantly decrease with increasing temperature. Overall, our results are not consistent with the nearly complete lack of temperature dependence predicted by traditional cavity models of the hydrated electron but instead agree qualitatively and nearly quantitatively with the temperature-dependent structural changes predicted by the non-cavity hydrated electron model.

How does the trans-cis photoisomerization of azobenzene take place in organic solvents?

PubMed

Tiberio, Giustiniano; Muccioli, Luca; Berardi, Roberto; Zannoni, Claudio

2010-04-06

The trans-cis photoisomerization of azobenzene-containing materials is key to a number of photomechanical applications, but the actual conversion mechanism in condensed phases is still largely unknown. Herein, we study the n, pi* isomerization in a vacuum and in various solvents via a modified molecular dynamics simulation adopting an ab initio torsion-inversion force field in the ground and excited states, while allowing for electronic transitions and a stochastic decay to the fundamental state. We determine the trans-cis photoisomerization quantum yield and decay times in various solvents (n-hexane, anisole, toluene, ethanol, and ethylene glycol), and obtain results comparable with experimental ones where available. A profound difference between the isomerization mechanism in vacuum and in solution is found, with the often neglected mixed torsional-inversion pathway being the most important in solvents.

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.

Ligand manipulation of charge transfer excited state relaxation and spin crossover in [Fe(2,2'-bipyridine) 2(CN) 2

DOE PAGES

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

2017-07-06

Here, we have used femtosecond resolution UV-visible and Kβ x-ray emission spectroscopy to characterize the electronic excited state dynamics of [Fe(bpy) 2(CN) 2], where bpy=2,2'-bipyridine, initiated by metal-to-ligand charge transfer (MLCT) excitation. The excited-state absorption in the transient UV-visible spectra, associated with the 2,2'-bipyridine radical anion, provides a robust marker for the MLCT excited state, while the transient Kβ x-ray emission spectra provide a clear measure of intermediate and high spin metal-centered excited states. From these measurements, we conclude that the MLCT state of [Fe(bpy) 2(CN) 2] undergoes ultrafast spin crossover to a metal-centered quintet excited state through a shortmore » lived metal-centered triplet transient species. These measurements of [Fe(bpy) 2(CN) 2] complement prior measurement performed on [Fe(bpy) 3] 2+ and [Fe(bpy)(CN) 4] 2– in dimethylsulfoxide solution and help complete the chemical series [Fe(bpy) N(CN) 6–2N] 2N-4, where N = 1–3. The measurements confirm that simple ligand modifications can significantly change the relaxation pathways and excited state lifetimes and support the further investigation of light harvesting and photocatalytic applications of 3 d transition metal complexes.« less

Ligand manipulation of charge transfer excited state relaxation and spin crossover in [Fe(2,2'-bipyridine) 2(CN) 2

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

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

Here, we have used femtosecond resolution UV-visible and Kβ x-ray emission spectroscopy to characterize the electronic excited state dynamics of [Fe(bpy) 2(CN) 2], where bpy=2,2'-bipyridine, initiated by metal-to-ligand charge transfer (MLCT) excitation. The excited-state absorption in the transient UV-visible spectra, associated with the 2,2'-bipyridine radical anion, provides a robust marker for the MLCT excited state, while the transient Kβ x-ray emission spectra provide a clear measure of intermediate and high spin metal-centered excited states. From these measurements, we conclude that the MLCT state of [Fe(bpy) 2(CN) 2] undergoes ultrafast spin crossover to a metal-centered quintet excited state through a shortmore » lived metal-centered triplet transient species. These measurements of [Fe(bpy) 2(CN) 2] complement prior measurement performed on [Fe(bpy) 3] 2+ and [Fe(bpy)(CN) 4] 2– in dimethylsulfoxide solution and help complete the chemical series [Fe(bpy) N(CN) 6–2N] 2N-4, where N = 1–3. The measurements confirm that simple ligand modifications can significantly change the relaxation pathways and excited state lifetimes and support the further investigation of light harvesting and photocatalytic applications of 3 d transition metal complexes.« less

Ligand manipulation of charge transfer excited state relaxation and spin crossover in [Fe(2,2′-bipyridine)2(CN)2

PubMed Central

Kjær, Kasper S.; Zhang, Wenkai; Alonso-Mori, Roberto; Bergmann, Uwe; Chollet, Matthieu; Hadt, Ryan G.; Hartsock, Robert W.; Harlang, Tobias; Kroll, Thomas; Kubiček, Katharina; Lemke, Henrik T.; Liang, Huiyang W.; Liu, Yizhu; Nielsen, Martin M.; Robinson, Joseph S.; Solomon, Edward I.; Sokaras, Dimosthenis; van Driel, Tim B.; Weng, Tsu-Chien; Zhu, Diling; Persson, Petter; Wärnmark, Kenneth; Sundström, Villy; Gaffney, Kelly J.

2017-01-01

We have used femtosecond resolution UV-visible and Kβ x-ray emission spectroscopy to characterize the electronic excited state dynamics of [Fe(bpy)2(CN)2], where bpy=2,2′-bipyridine, initiated by metal-to-ligand charge transfer (MLCT) excitation. The excited-state absorption in the transient UV-visible spectra, associated with the 2,2′-bipyridine radical anion, provides a robust marker for the MLCT excited state, while the transient Kβ x-ray emission spectra provide a clear measure of intermediate and high spin metal-centered excited states. From these measurements, we conclude that the MLCT state of [Fe(bpy)2(CN)2] undergoes ultrafast spin crossover to a metal-centered quintet excited state through a short lived metal-centered triplet transient species. These measurements of [Fe(bpy)2(CN)2] complement prior measurement performed on [Fe(bpy)3]2+ and [Fe(bpy)(CN)4]2− in dimethylsulfoxide solution and help complete the chemical series [Fe(bpy)N(CN)6–2N]2N-4, where N = 1–3. The measurements confirm that simple ligand modifications can significantly change the relaxation pathways and excited state lifetimes and support the further investigation of light harvesting and photocatalytic applications of 3d transition metal complexes. PMID:28653021

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

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.

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

Unveiling the excited state energy transfer pathways in peridinin-chlorophyll a-protein by ultrafast multi-pulse transient absorption spectroscopy.

PubMed

Redeckas, Kipras; Voiciuk, Vladislava; Zigmantas, Donatas; Hiller, Roger G; Vengris, Mikas

2017-04-01

Time-resolved multi-pulse methods were applied to investigate the excited state dynamics, the interstate couplings, and the excited state energy transfer pathways between the light-harvesting pigments in peridinin-chlorophyll a-protein (PCP). The utilized pump-dump-probe techniques are based on perturbation of the regular PCP energy transfer pathway. The PCP complexes were initially excited with an ultrashort pulse, resonant to the S 0 →S 2 transition of the carotenoid peridinin. A portion of the peridinin-based emissive intramolecular charge transfer (ICT) state was then depopulated by applying an ultrashort NIR pulse that perturbed the interaction between S 1 and ICT states and the energy flow from the carotenoids to the chlorophylls. The presented data indicate that the peridinin S 1 and ICT states are spectrally distinct and coexist in an excited state equilibrium in the PCP complex. Moreover, numeric analysis of the experimental data asserts ICT→Chl-a as the main energy transfer pathway in the photoexcited PCP systems. Copyright © 2017 Elsevier B.V. All rights reserved.

Sub-500 fs electronically nonadiabatic chemical dynamics of energetic molecules from the S1 excited state: Ab initio multiple spawning study

NASA Astrophysics Data System (ADS)

Ghosh, Jayanta; Gajapathy, Harshad; Konar, Arindam; Narasimhaiah, Gowrav M.; Bhattacharya, Atanu

2017-11-01

Energetic materials store a large amount of chemical energy. Different ignition processes, including laser ignition and shock or compression wave, initiate the energy release process by first promoting energetic molecules to the electronically excited states. This is why a full understanding of initial steps of the chemical dynamics of energetic molecules from the excited electronic states is highly desirable. In general, conical intersection (CI), which is the crossing point of multidimensional electronic potential energy surfaces, is well established as a controlling factor in the initial steps of chemical dynamics of energetic molecules following their electronic excitations. In this article, we have presented different aspects of the ultrafast unimolecular relaxation dynamics of energetic molecules through CIs. For this task, we have employed ab initio multiple spawning (AIMS) simulation using the complete active space self-consistent field (CASSCF) electronic wavefunction and frozen Gaussian-based nuclear wavefunction. The AIMS simulation results collectively reveal that the ultrafast relaxation step of the best energetic molecules (which are known to exhibit very good detonation properties) is completed in less than 500 fs. Many, however, exhibit sub-50 fs dynamics. For example, nitro-containing molecules (including C-NO2, N-NO2, and O-NO2 active moieties) relax back to the ground state in approximately 40 fs through similar (S1/S0)CI conical intersections. The N3-based energetic molecule undergoes the N2 elimination process in 40 fs through the (S1/S0)CI conical intersection. Nitramine-Fe complexes exhibit sub-50 fs Fe-O and N-O bond dissociation through the respective (S1/S0)CI conical intersection. On the other hand, tetrazine-N-oxides, which are known to exhibit better detonation properties than tetrazines, undergo internal conversion in a 400-fs time scale, while the relaxation time of tetrazine is very long (about 100 ns). Many other characteristics of sub-500 fs nonadiabatic decay of energetic molecules are discussed. In the end, many unresolved issues associated with the ultrafast nonadiabatic chemical dynamics of energetic molecules are presented.

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.

Multiphoton-gated cycloreversion reaction of a fluorescent diarylethene derivative as revealed by transient absorption spectroscopy.

PubMed

Nagasaka, Tatsuhiro; Kunishi, Tomohiro; Sotome, Hikaru; Koga, Masafumi; Morimoto, Masakazu; Irie, Masahiro; Miyasaka, Hiroshi

2018-06-07

The one- and two-photon cycloreversion reactions of a fluorescent diarylethene derivative with oxidized benzothiophene moieties were investigated by means of ultrafast laser spectroscopy. Femtosecond transient absorption spectroscopy under the one-photon excitation condition revealed that the excited closed-ring isomer is simply deactivated into the initial ground state with a time constant of 2.6 ns without remarkable cycloreversion, the results of which are consistent with the very low cycloreversion reaction yield (<10-5) under steady-state light irradiation. On the other hand, an efficient cycloreversion reaction was observed under irradiation with a picosecond laser pulse at 532 nm. The excitation intensity dependence of the cycloreversion reaction indicates that a highly excited state attained by the stepwise two-photon absorption is responsible for the marked increase of the cycloreversion reaction, and the quantum yield at the highly excited state was estimated to be 0.018 from quantitative analysis, indicating that the reaction is enhanced by a factor of >1800.

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

NUBASE2012 Evaluation of Nuclear Properties

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

Wang, M., E-mail: wangm@impcas.ac.cn; CSNSM-Orsay, MPI-K, D-69117 Heidelberg; Audi, G.

NUBASE is a database containing the recommended values for the main properties of all known nuclides in their ground and excited isomeric states. Since the publication of the first version in 1997, NUBASE has been widely used in the nuclear science community. The latest version (NUBASE2012) was published in December 2012. Two specific examples are given to illustrate the evaluation policy of NUBASE2012.

Interfacing the Ab initio multiple spawning method with electronic structure methods in GAMESS: Photodecay of trans-Azomethane

DOE PAGES

Gaenko, Alexander; DeFusco, Albert; Varganov, Sergey A.; ...

2014-10-20

This work presents a nonadiabatic molecular dynamics study of the nonradiative decay of photoexcited trans-azomethane, using the ab initio multiple spawning (AIMS) program that has been interfaced with the General Atomic and Molecular Electronic Structure System (GAMESS) quantum chemistry package for on-the-fly electronic structure evaluation. The interface strategy is discussed, and the capabilities of the combined programs are demonstrated with a nonadiabatic molecular dynamics study of the nonradiative decay of photoexcited trans-azomethane. Energies, gradients, and nonadiabatic coupling matrix elements were obtained with the state-averaged complete active space self-consistent field method, as implemented in GAMESS. The influence of initial vibrational excitationmore » on the outcome of the photoinduced isomerization is explored. Increased vibrational excitation in the CNNC torsional mode shortens the excited state lifetime. Depending on the degree of vibrational excitation, the excited state lifetime varies from ~60–200 fs. As a result, these short lifetimes are in agreement with time-resolved photoionization mass spectroscopy experiments.« less

Femtosecond stimulated Raman evidence for charge-transfer character in pentacene singlet fission† †Electronic supplementary information (ESI) available: Actinic pump spectrum, discussion on ground state addition process, peak fitting procedure, transient absorption data, power dependence measurements, etalon pulse shaping, TIPS-pentacene FSRS data, and optimized geometry and frequency calculation results. See DOI: 10.1039/c7sc03496b

PubMed Central

Hart, Stephanie M.; Silva, W. Ruchira

2017-01-01

Singlet fission is a spin-allowed process in which an excited singlet state evolves into two triplet states. We use femtosecond stimulated Raman spectroscopy, an ultrafast vibrational technique, to follow the molecular structural evolution during singlet fission in order to determine the mechanism of this process. In crystalline pentacene, we observe the formation of an intermediate characterized by pairs of excited state peaks that are red- and blue-shifted relative to the ground state features. We hypothesize that these features arise from the formation of cationic and anionic species due to partial transfer of electron density from one pentacene molecule to a neighboring molecule. These observations provide experimental evidence for the role of states with significant charge-transfer character which facilitate the singlet fission process in pentacene. Our work both provides new insight into the singlet fission mechanism in pentacene and demonstrates the utility of structurally-sensitive time-resolved spectroscopic techniques in monitoring ultrafast processes. PMID:29675170

Molecular isomerization induced by ultrashort infrared pulses. I. Few-cycle to sub-one-cycle Gaussian pulses and the role of the carrier-envelope phase.

PubMed

Uiberacker, Christoph; Jakubetz, Werner

2004-06-22

Using 550 previously calculated vibrational energy levels and dipole moments we performed simulations of the HCN-->HNC isomerization dynamics induced by sub-one-cycle and few-cycle IR pulses, which we represent as Gaussian pulses with 0.25-2 optical cycles in the pulse width. Starting from vibrationally pre-excited states, isomerization probabilities of up to 50% are obtained for optimized pulses. With decreasing number of optical cycles a strong dependence on the carrier-envelope phase (CEP) emerges. Although the optimized pulse parameters change significantly with the number of optical cycles, the distortion by the Gaussian envelope produces nearly equal fields, with a positive lobe followed by a negative one. The positions and areas of the lobes are also almost unchanged, irrespective of the number of cycles in the half-width. Isomerization proceeds via a pump-dumplike mechanism induced by the sequential lobes. The first lobe prepares a wave packet incorporating many delocalized states above the barrier. It is the motion of this wave packet across the barrier, which determines the timing of the pump and dump lobes. The role of the pulse parameters, and in particular of the CEP, is to produce the correct lobe sequence, size and timing within a continuous pulse. (c) 2004 American Institute of Physics.

Molecular isomerization induced by ultrashort infrared pulses. II. Pump-dump isomerization using pairs of time-delayed half-cycle pulses.

PubMed

Uiberacker, Christoph; Jakubetz, Werner

2004-06-22

We investigate population transfer across the barrier in a double-well potential, induced by a pair of time-delayed single-lobe half-cycle pulses. We apply this setup both to a one-dimensional (1D) quartic model potential and to a three-dimensional potential representing HCN-->HNC isomerization. Overall the results for the two systems are similar, although in the 3D system some additional features appear not seen in the 1D case. The generic mechanism of population transfer is the preparation by the pump pulse of a wave packet involving delocalized states above the barrier, followed by the essentially 1D motion of the delocalized part of wave packet across the barrier, and the eventual de-excitation by the dump pulse to localized states in the other well. The correct timing is given by the well-to-well passage time of the wave packet and its recurrence properties, and by the signs of the field lobes which determine the direction and acceleration or deceleration of the wave packet motion. In the 3D system an additional pump-pump-dump mechanism linked to wave packet motion in the reagent well can mediate isomerization. Since the transfer time and the pulse durations are of the same order of magnitude, there is also a marked dependence of the dynamics and the transfer yield on the pulse duration. Our analysis also sheds light on the pronounced carrier envelope phase dependence previously observed for isomerization and molecular dissociation with one-cycle and sub-one-cycle pulses. (c) 2004 American Institute of Physics.

The observation of ultrafast excited-state dynamical evolution in B800- partially or completely released LH2 of Rhodobacter sphaeroides 601 at room temperature.

PubMed

Liu, Weimin; Liu, Yuan; Yan, Yongli; Liu, Kangjun; Guo, Lijun; Xu, Chunhe; Qian, Shixiong

2006-04-01

Photodynamics of two kinds of peripheral antenna complexes (LH2 of Rhodobacter sphaeroides, native LH2 (RS601) and B800-released LH2 where B800-BChls were partially or completely removed with different pH treatments), were studied using femtosecond pump-probe technique at different laser wavelengths. The obtained results for these samples with different B800/B850 ratios demonstrated that under the excitation around B800 nm, the photoabsorption and photobleaching dynamics were caused by the direct excitation of upper excitonic levels of B850 and excited state of B800 pigments, respectively. Furthermore, the removal of B800 pigments had little effect on the energy transfer processes of B850 interband/intraband transfer.

XUV-induced reactions in benzene on sub-10 fs timescale: nonadiabatic relaxation and proton migration.

PubMed

Galbraith, M C E; Smeenk, C T L; Reitsma, G; Marciniak, A; Despré, V; Mikosch, J; Zhavoronkov, N; Vrakking, M J J; Kornilov, O; Lépine, F

2017-08-02

Unraveling ultrafast dynamical processes in highly excited molecular species has an impact on our understanding of chemical processes such as combustion or the chemical composition of molecular clouds in the universe. In this article we use short (<7 fs) XUV pulses to produce excited cationic states of benzene molecules and probe their dynamics using few-cycle VIS/NIR laser pulses. The excited states produced by the XUV pulses lie in an especially complex spectral region where multi-electronic effects play a dominant role. We show that very fast τ ≈ 20 fs nonadiabatic processes dominate the relaxation of these states, in agreement with the timescale expected for most excited cationic states in benzene. In the CH 3 + fragmentation channel of the doubly ionized benzene cation we identify pathways that involve structural rearrangement and proton migration to a specific carbon atom. Further, we observe non-trivial transient behavior in this fragment channel, which can be interpreted either in terms of propagation of the nuclear wavepacket in the initially excited electronic state of the cation or as a two-step electronic relaxation via an intermediate state.

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.

Recent advances in multidimensional ultrafast spectroscopy

NASA Astrophysics Data System (ADS)

Oliver, Thomas A. A.

2018-01-01

Multidimensional ultrafast spectroscopies are one of the premier tools to investigate condensed phase dynamics of biological, chemical and functional nanomaterial systems. As they reach maturity, the variety of frequency domains that can be explored has vastly increased, with experimental techniques capable of correlating excitation and emission frequencies from the terahertz through to the ultraviolet. Some of the most recent innovations also include extreme cross-peak spectroscopies that directly correlate the dynamics of electronic and vibrational states. This review article summarizes the key technological advances that have permitted these recent advances, and the insights gained from new multidimensional spectroscopic probes.

Recent advances in multidimensional ultrafast spectroscopy

PubMed Central

2018-01-01

Multidimensional ultrafast spectroscopies are one of the premier tools to investigate condensed phase dynamics of biological, chemical and functional nanomaterial systems. As they reach maturity, the variety of frequency domains that can be explored has vastly increased, with experimental techniques capable of correlating excitation and emission frequencies from the terahertz through to the ultraviolet. Some of the most recent innovations also include extreme cross-peak spectroscopies that directly correlate the dynamics of electronic and vibrational states. This review article summarizes the key technological advances that have permitted these recent advances, and the insights gained from new multidimensional spectroscopic probes. PMID:29410844

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.

Ultrafast energy relaxation in single light-harvesting complexes

DOE PAGES

Maly, Pavel; Gruber, J. Michael; Cogdell, Richard J.; ...

2016-02-22

Energy relaxation in light-harvesting complexes has been extensively studied by various ultrafast spectroscopic techniques, the fastest processes being in the sub–100-fs range. At the same time, much slower dynamics have been observed in individual complexes by single-molecule fluorescence spectroscopy (SMS). In this work, we use a pump–probe-type SMS technique to observe the ultrafast energy relaxation in single light-harvesting complexes LH2 of purple bacteria. After excitation at 800 nm, the measured relaxation time distribution of multiple complexes has a peak at 95 fs and is asymmetric, with a tail at slower relaxation times. When tuning the excitation wavelength, the distribution changesmore » in both its shape and position. The observed behavior agrees with what is to be expected from the LH2 excited states structure. As we show by a Redfield theory calculation of the relaxation times, the distribution shape corresponds to the expected effect of Gaussian disorder of the pigment transition energies. By repeatedly measuring few individual complexes for minutes, we find that complexes sample the relaxation time distribution on a timescale of seconds. Furthermore, by comparing the distribution from a single long-lived complex with the whole ensemble, we demonstrate that, regarding the relaxation times, the ensemble can be considered ergodic. Lastly, our findings thus agree with the commonly used notion of an ensemble of identical LH2 complexes experiencing slow random fluctuations.« less

Ultrafast energy relaxation in single light-harvesting complexes.

PubMed

Malý, Pavel; Gruber, J Michael; Cogdell, Richard J; Mančal, Tomáš; van Grondelle, Rienk

2016-03-15

Energy relaxation in light-harvesting complexes has been extensively studied by various ultrafast spectroscopic techniques, the fastest processes being in the sub-100-fs range. At the same time, much slower dynamics have been observed in individual complexes by single-molecule fluorescence spectroscopy (SMS). In this work, we use a pump-probe-type SMS technique to observe the ultrafast energy relaxation in single light-harvesting complexes LH2 of purple bacteria. After excitation at 800 nm, the measured relaxation time distribution of multiple complexes has a peak at 95 fs and is asymmetric, with a tail at slower relaxation times. When tuning the excitation wavelength, the distribution changes in both its shape and position. The observed behavior agrees with what is to be expected from the LH2 excited states structure. As we show by a Redfield theory calculation of the relaxation times, the distribution shape corresponds to the expected effect of Gaussian disorder of the pigment transition energies. By repeatedly measuring few individual complexes for minutes, we find that complexes sample the relaxation time distribution on a timescale of seconds. Furthermore, by comparing the distribution from a single long-lived complex with the whole ensemble, we demonstrate that, regarding the relaxation times, the ensemble can be considered ergodic. Our findings thus agree with the commonly used notion of an ensemble of identical LH2 complexes experiencing slow random fluctuations.

Ultrafast energy relaxation in single light-harvesting complexes

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

Maly, Pavel; Gruber, J. Michael; Cogdell, Richard J.

Energy relaxation in light-harvesting complexes has been extensively studied by various ultrafast spectroscopic techniques, the fastest processes being in the sub–100-fs range. At the same time, much slower dynamics have been observed in individual complexes by single-molecule fluorescence spectroscopy (SMS). In this work, we use a pump–probe-type SMS technique to observe the ultrafast energy relaxation in single light-harvesting complexes LH2 of purple bacteria. After excitation at 800 nm, the measured relaxation time distribution of multiple complexes has a peak at 95 fs and is asymmetric, with a tail at slower relaxation times. When tuning the excitation wavelength, the distribution changesmore » in both its shape and position. The observed behavior agrees with what is to be expected from the LH2 excited states structure. As we show by a Redfield theory calculation of the relaxation times, the distribution shape corresponds to the expected effect of Gaussian disorder of the pigment transition energies. By repeatedly measuring few individual complexes for minutes, we find that complexes sample the relaxation time distribution on a timescale of seconds. Furthermore, by comparing the distribution from a single long-lived complex with the whole ensemble, we demonstrate that, regarding the relaxation times, the ensemble can be considered ergodic. Lastly, our findings thus agree with the commonly used notion of an ensemble of identical LH2 complexes experiencing slow random fluctuations.« less

Time of flight emission spectroscopy of laser produced nickel plasma: Short-pulse and ultrafast excitations

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

Smijesh, N.; Chandrasekharan, K.; Joshi, Jagdish C.

2014-07-07

We report the experimental investigation and comparison of the temporal features of short-pulse (7 ns) and ultrafast (100 fs) laser produced plasmas generated from a solid nickel target, expanding into a nitrogen background. When the ambient pressure is varied in a large range of 10⁻⁶Torr to 10²Torr, the plume intensity is found to increase rapidly as the pressure crosses 1 Torr. Time of flight (TOF) spectroscopy of emission from neutral nickel (Ni I) at 361.9 nm (3d⁹(²D) 4p → 3d⁹(²D) 4s transition) reveals two peaks (fast and slow species) in short-pulse excitation and a single peak in ultrafast excitation. Themore » fast and slow peaks represent recombined neutrals and un-ionized neutrals, respectively. TOF emission from singly ionized nickel (Ni II) studied using the 428.5 nm (3p⁶3d⁸(³P) 4s→ 3p⁶3d⁹ 4s) transition shows only a single peak for either excitation. Velocities of the neutral and ionic species are determined from TOF measurements carried out at different positions (i.e., at distances of 2 mm and 4 mm, respectively, from the target surface) on the plume axis. Measured velocities indicate acceleration of neutrals and ions, which is caused by the Coulomb pull of the electrons enveloping the plume front in the case of ultrafast excitation. Both Coulomb pull and laser-plasma interaction contribute to the acceleration in the case of short-pulse excitation. These investigations provide new information on the pressure dependent temporal behavior of nickel plasmas produced by short-pulse and ultrafast laser pulses, which have potential uses in applications such as pulsed laser deposition and laser-induced nanoparticle generation.« less

Entanglement of two, three, or four plasmonically coupled quantum dots

NASA Astrophysics Data System (ADS)

Otten, Matthew; Shah, Raman A.; Scherer, Norbert F.; Min, Misun; Pelton, Matthew; Gray, Stephen K.

2015-09-01

We model the quantum dynamics of two, three, or four quantum dots (QDs) in proximity to a plasmonic system such as a metal nanoparticle or an array of metal nanoparticles. For all systems, an initial state with only one QD in its excited state evolves spontaneously into a state with entanglement between all pairs of QDs. The entanglement arises from the couplings of the QDs to the dissipative, plasmonic environment. Moreover, we predict that similarly entangled states can be generated in systems with appropriate geometries, starting in their ground states, by exciting the entire system with a single, ultrafast laser pulse. By using a series of repeated pulses, the system can also be prepared in an entangled state at an arbitrary time.

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

PubMed

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

2007-01-01

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

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.

Theory of multiexciton dynamics in molecular chains

NASA Astrophysics Data System (ADS)

Wang, Luxia; May, Volkhard

2016-11-01

Ultrafast and strong optical excitation of a molecular system is considered which is formed by a regular one-dimensional arrangement of identical molecules. As it is typical for zinc chlorine-type molecules the transition energy from the ground state to the first excited singlet state is assumed to be smaller than the energy difference between the first excited state and the following one. This enables the creation of many excitons without their immediate quenching due to exciton-exciton annihilation. As a first step into the field of dense Frenkel-exciton systems the present approach stays at a mean-field type of description and ignores vibrational contributions. The resulting nonlinear kinetic equations mix Rabi-type oscillations with those caused by energy transfer and suggest an excitation-dependent narrowing of the exciton band. The indication of this effect in the framework of a two-color pump-probe experiment and of the detection of photon emission is discussed.

Strong-Field Control of Laser Filamentation Mechanisms

NASA Astrophysics Data System (ADS)

Levis, Robert; Romanov, Dmitri; Filin, Aleskey; Compton, Ryan

2008-05-01

The propagation of short strong-file laser pulses in gas and solution phases often result in formation of filaments. This phenomenon involves many nonlinear processes including Kerr lensing, group velocity dispersion, multi-photon ionization, plasma defocusing, intensity clamping, and self-steepening. Of these, formation and dynamics of pencil-shape plasma areas plays a crucial role. The fundamental understanding of these laser-induced plasmas requires additional effort, because the process is highly nonlinear and complex. We studied the ultrafast laser-generated plasma dynamics both experimentally and theoretically. Ultrafast plasma dynamics was probed using Coherent Anti-Stokes Raman Scattering. The measurements were made in a room temperature gas maintained at 1 atm in a flowing cell. The time dependent scattering was measured by delaying the CARS probe with respect to the intense laser excitation pulse. A general trend is observed between the spacing of the ground state and the first allowed excited state with the rise time for the noble gas series and the molecular gases. This trend is consistent with our theoretical model, which considers the ultrafast dynamics of the strong field generated plasma as a three-step process; (i) strong-field ionization followed by the electron gaining considerable kinetic energy during the pulse; (ii) immediate post-pulse dynamics: fast thermalization, impact-ionization-driven electron multiplication and cooling; (iii) ensuing relaxation: evolution to electron-ion equilibrium and eventual recombination.

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

Nonadiabatic excited-state molecular dynamics: modeling photophysics in organic conjugated materials.

PubMed

Nelson, Tammie; Fernandez-Alberti, Sebastian; Roitberg, Adrian E; Tretiak, Sergei

2014-04-15

To design functional photoactive materials for a variety of technological applications, researchers need to understand their electronic properties in detail and have ways to control their photoinduced pathways. When excited by photons of light, organic conjugated materials (OCMs) show dynamics that are often characterized by large nonadiabatic (NA) couplings between multiple excited states through a breakdown of the Born-Oppenheimer (BO) approximation. Following photoexcitation, various nonradiative intraband relaxation pathways can lead to a number of complex processes. Therefore, computational simulation of nonadiabatic molecular dynamics is an indispensable tool for understanding complex photoinduced processes such as internal conversion, energy transfer, charge separation, and spatial localization of excitons. Over the years, we have developed a nonadiabatic excited-state molecular dynamics (NA-ESMD) framework that efficiently and accurately describes photoinduced phenomena in extended conjugated molecular systems. We use the fewest-switches surface hopping (FSSH) algorithm to treat quantum transitions among multiple adiabatic excited state potential energy surfaces (PESs). Extended molecular systems often contain hundreds of atoms and involve large densities of excited states that participate in the photoinduced dynamics. We can achieve an accurate description of the multiple excited states using the configuration interaction single (CIS) formalism with a semiempirical model Hamiltonian. Analytical techniques allow the trajectory to be propagated "on the fly" using the complete set of NA coupling terms and remove computational bottlenecks in the evaluation of excited-state gradients and NA couplings. Furthermore, the use of state-specific gradients for propagation of nuclei on the native excited-state PES eliminates the need for simplifications such as the classical path approximation (CPA), which only uses ground-state gradients. Thus, the NA-ESMD methodology offers a computationally tractable route for simulating hundreds of atoms on ~10 ps time scales where multiple coupled excited states are involved. In this Account, we review recent developments in the NA-ESMD modeling of photoinduced dynamics in extended conjugated molecules involving multiple coupled electronic states. We have successfully applied the outlined NA-ESMD framework to study ultrafast conformational planarization in polyfluorenes where the rate of torsional relaxation can be controlled based on the initial excitation. With the addition of the state reassignment algorithm to identify instances of unavoided crossings between noninteracting PESs, NA-ESMD can now be used to study systems in which these so-called trivial unavoided crossings are expected to predominate. We employ this technique to analyze the energy transfer between poly(phenylene vinylene) (PPV) segments where conformational fluctuations give rise to numerous instances of unavoided crossings leading to multiple pathways and complex energy transfer dynamics that cannot be described using a simple Förster model. In addition, we have investigated the mechanism of ultrafast unidirectional energy transfer in dendrimers composed of poly(phenylene ethynylene) (PPE) chromophores and have demonstrated that differential nuclear motion favors downhill energy transfer in dendrimers. The use of native excited-state gradients allows us to observe this feature.

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.

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.

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.

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.

Confirmed assignments of isomeric dimethylbenzyl radicals generated by corona discharge.

PubMed

Yoon, Young Wook; Lee, Sang Kuk

2011-12-07

The controversial vibronic assignments of isomeric dimethylbenzyl radicals were clearly resolved by using different precursors. By employing corresponding dimethylbenzyl chlorides as precursors, we identified the origins of the vibronic bands of the dimethylbenzyl radicals generated by corona discharge of 1,2,4-trimethylbenzene. From the analysis of the spectra observed from the dimethylbenzyl chlorides in a corona excited supersonic expansion, we revised previous assignments of the 3,4-, 2,4-, and 2,5-dimethylbenzyl radicals. Spectroscopic data of electronic transition and vibrational mode frequencies in the ground electronic state of each isomer were accurately determined by comparing them with those obtained by an ab initio calculation and with the known vibrational data of 1,2,4-trimethylbenzene. © 2011 American Institute of Physics

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.

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

NASA Astrophysics Data System (ADS)

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

2015-10-01

Optical control of spin is of central importance in the research of ultrafast spintronic devices utilizing spin dynamics at short time scales. Recently developed optical approaches such as ultrafast demagnetization, spin-transfer and spin-orbit torques open new pathways to manipulate spin through its interaction with photon, orbit, charge or phonon. However, these processes are limited by either the long thermal recovery time or the low-temperature requirement. Here we experimentally demonstrate ultrafast coherent spin precession via optical charge-transfer processes in the exchange-coupled Fe/CoO system at room temperature. The efficiency of spin precession excitation is significantly higher and the recovery time of the exchange-coupling torque is much shorter than for the demagnetization procedure, which is desirable for fast switching. The exchange coupling is a key issue in spin valves and tunnelling junctions, and hence our findings will help promote the development of exchange-coupled device concepts for ultrafast coherent spin manipulation.

Polarization-dependent force driving the Eg mode in bismuth under optical excitation: comparison of first-principles theory with ultra-fast x-ray experiments

NASA Astrophysics Data System (ADS)

Fahy, Stephen; Murray, Eamonn

2015-03-01

Using first principles electronic structure methods, we calculate the induced force on the Eg (zone centre transverse optical) phonon mode in bismuth immediately after absorption of a ultrafast pulse of polarized light. To compare the results with recent ultra-fast, time-resolved x-ray diffraction experiments, we include the decay of the force due to carrier scattering, as measured in optical Raman scattering experiments, and simulate the optical absorption process, depth-dependent atomic driving forces, and x-ray diffraction in the experimental geometry. We find excellent agreement between the theoretical predictions and the observed oscillations of the x-ray diffraction signal, indicating that first-principles theory of optical absorption is well suited to the calculation of initial atomic driving forces in photo-excited materials following ultrafast excitation. This work is supported by Science Foundation Ireland (Grant No. 12/IA/1601) and EU Commission under the Marie Curie Incoming International Fellowships (Grant No. PIIF-GA-2012-329695).

Following the dynamics of matter with femtosecond precision using the X-ray streaking method

DOE PAGES

David, C.; Karvinen, P.; Sikorski, M.; ...

2015-01-06

X-ray Free Electron Lasers (FELs) can produce extremely intense and very short pulses, down to below 10 femtoseconds (fs). Among the key applications are ultrafast time-resolved studies of dynamics of matter by observing responses to fast excitation pulses in a pump-probe manner. Detectors with sufficient time resolution for observing these processes are not available. Therefore, such experiments typically measure a sample's full dynamics by repeating multiple pump-probe cycles at different delay times. This conventional method assumes that the sample returns to an identical or very similar state after each cycle. Here we describe a novel approach that can provide amore » time trace of responses following a single excitation pulse, jitter-free, with fs timing precision. We demonstrate, in an X-ray diffraction experiment, how it can be applied to the investigation of ultrafast irreversible processes.« less

Carrier-Specific Femtosecond XUV Transient Absorption of PbI 2 Reveals Ultrafast Nonradiative Recombination

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

Lin, Ming-Fu; Verkamp, Max A.; Leveillee, Joshua

Femtosecond carrier recombination in PbI 2 is measured using tabletop high-harmonic extreme ultraviolet (XUV) transient absorption spectroscopy and ultrafast electron diffraction. XUV absorption from 45 eV to 62 eV measures transitions from the iodine 4d core level to the conduction band density of states. Photoexcitation at 400 nm creates separate and distinct transient absorption signals for holes and electrons, separated in energy by the 2.4 eV band gap of the semiconductor. The shape of the conduction band and therefore the XUV absorption spectrum is temperature dependent, and nonradiative recombination converts the initial electronic excitation to thermal excitation within picoseconds. Ultrafastmore » electron diffraction (UED) is used to measure the lattice temperature and confirm the recombination mechanism. Lastly, the XUV and UED results support a 2nd-order recombination model with a rate constant of 2.5x10 -9 cm 3/s.« less

Carrier-Specific Femtosecond XUV Transient Absorption of PbI 2 Reveals Ultrafast Nonradiative Recombination

DOE PAGES

Lin, Ming-Fu; Verkamp, Max A.; Leveillee, Joshua; ...

2017-11-30

Femtosecond carrier recombination in PbI 2 is measured using tabletop high-harmonic extreme ultraviolet (XUV) transient absorption spectroscopy and ultrafast electron diffraction. XUV absorption from 45 eV to 62 eV measures transitions from the iodine 4d core level to the conduction band density of states. Photoexcitation at 400 nm creates separate and distinct transient absorption signals for holes and electrons, separated in energy by the 2.4 eV band gap of the semiconductor. The shape of the conduction band and therefore the XUV absorption spectrum is temperature dependent, and nonradiative recombination converts the initial electronic excitation to thermal excitation within picoseconds. Ultrafastmore » electron diffraction (UED) is used to measure the lattice temperature and confirm the recombination mechanism. Lastly, the XUV and UED results support a 2nd-order recombination model with a rate constant of 2.5x10 -9 cm 3/s.« less

Nonadiabatic dynamics simulation of photoisomerization mechanism of the second stablest isomer of N-salicilydenemethylfurylamine

NASA Astrophysics Data System (ADS)

Gao, Aihua; Li, Jianpeng; Wang, Dehua; Ma, Xiaoguang; Wang, Meishan

2018-02-01

The photoisomerization processes of the second stablest isomer in the aromatic Schiff base, N-salicilydenemethylfurylamine, in the gas phase have been studied by static electronic structure calculations and surface-hopping dynamics simulations based on the Zhu-Nakamura theory. Various stable structures are obtained in the optimization because of different orientations of methyl-furyl part with respect to the salicylaldimine part and different orientations of hydroxy group with respect to the benzene ring. Upon photoexcitation into the first excited state, bond isomerization in the salicylaldimine part is completely suppressed until the strong excited-state hydrogen bond is broken. The decay pathway involves two excited-state minima, one in cis-enol form and the other in cis-keto form. After the excited-state proton transfer, twists of bonds lead to a conical intersection between the ground and excited states. After internal conversion around a conical intersection, the molecule is stabilized in cis- or trans-keto form. If the reverse hydrogen transfer process occurs in the ground state, the molecule will finally end up in the cis-enol region. The cis-keto and trans-keto isomers are observed as photoproducts. According to our full-dimensional nonadiabatic dynamics simulations, we find the excited-state intramolecular proton transfer and torsions of three single bonds in the chain to be responsible for photoisomerization of the second stablest isomer of N-salicilydenemethylfurylamine.

Role of excited state solvent fluctuations on time-dependent fluorescence Stokes shift

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

Li, Tanping, E-mail: tanping@lsu.edu, E-mail: revatik@lsu.edu; Kumar, Revati, E-mail: tanping@lsu.edu, E-mail: revatik@lsu.edu

2015-11-07

We explore the connection between the solvation dynamics of a chromophore upon photon excitation and equilibrium fluctuations of the solvent. Using molecular dynamics simulations, fluorescence Stokes shift for the tryptophan in Staphylococcus nuclease was examined using both nonequilibrium calculations and linear response theory. When the perturbed and unperturbed surfaces exhibit different solvent equilibrium fluctuations, the linear response approach on the former surface shows agreement with the nonequilibrium process. This agreement is excellent when the perturbed surface exhibits Gaussian statistics and qualitative in the case of an isomerization induced non-Gaussian statistics. However, the linear response theory on the unperturbed surface breaksmore » down even in the presence of Gaussian fluctuations. Experiments also provide evidence of the connection between the excited state solvent fluctuations and the total fluorescence shift. These observations indicate that the equilibrium statistics on the excited state surface characterize the relaxation dynamics of the fluorescence Stokes shift. Our studies specifically analyze the Gaussian fluctuations of the solvent in the complex protein environment and further confirm the role of solvent fluctuations on the excited state surface. The results are consistent with previous investigations, found in the literature, of solutes dissolved in liquids.« 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

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 is dominated by intramolecular processes. A further relaxation by IC/IVR in the triplet manifold is likely to account for the observed intermediate time constants. For the acetonitrile relaxation dynamics additional modifications are invoked based on solvent-induced shifts of the energy levels and the possible formation of solvent and counterion exciplexes on a longer timescale.

Ultrafast dynamics and decoherence of quasiparticles in surface bands: Development of the formalism

NASA Astrophysics Data System (ADS)

Gumhalter, Branko

2005-10-01

We describe a formalism suitable for studying the ultrafast dynamics and nonadiabatic effects associated with propagation of a single electron injected into an empty band. Within the band the electron is coupled to vibrational or electronic excitations that can be modeled by bosons. The formalism is based on the application of cumulant expansion to calculations of diagonal single particle propagators that are used in the interpretations of time resolved measurements of the surface electronic structure. Second and fourth order cumulants which arise from linear coupling to bosonic excitations and give leading contributions to the renormalization of propagators are explicitly calculated in the real time domain and their properties analyzed. This approach enables the assessment of transient effects and energy transfer associated with nonadiabatic response of the system to promotion of electrons into unoccupied bands, as well as of higher order corrections to the lifetimes and energy shifts of the initial electronic states that in the adiabatic regime are obtained from Fermi’s golden rule approach or its improvements such as the GW approximation. In the form presented the formalism is particularly suitable for studying the non-Markovian evolution and ultrafast decoherence of electronic states encountered in electron spectroscopies of quasi-two-dimensional bands on metal surfaces whose descriptions are inaccessible to the approaches based on the adiabatic hypothesis. The fast convergence of the results obtained by this procedure is demonstrated for a simple model system relevant to surface problems. On the basis of this and some general properties of cumulants it is argued that in the majority of surface problems involving electron-boson interactions the ultrafast dynamics of quasiparticles is accurately described by the second order cumulant, which can be calculated with the effort not exceeding those encountered in the standard GW approximation calculations.

The roles of the solute and solvent cavities in charge-transfer-to-solvent dynamics: Ultrafast studies of potasside and sodide in diethyl ether

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

Cavanagh, Molly C.; Young, Ryan M.; Schwartz, Benjamin J.

2008-10-07

Although electron transfer reactions are among the most fundamental in chemistry, it is still not clear how to isolate the roles of the solute and solvent in moving charge between reactants in solution. In this paper, we address this question by comparing the ultrafast charge-transfer-to-solvent (CTTS) dynamics of potasside (K{sup -}) in diethyl ether (DEE) to those of sodide (Na{sup -}) in both DEE and tetrahydrofuran (THF). We find that for sodide in both DEE and THF, CTTS excitation leads to delayed ejection of a solvated electron that appears with its equilibrium absorption spectrum. This indicates that the ejected electronsmore » are localized in pre-existing solvent traps, suggesting that the structure of liquid DEE is characterized by cavities that are favorably polarized to localize an excess electron, as has been previously shown is the case for liquid THF. We also find that the geminate recombination dynamics following CTTS excitation of sodide in THF and DEE are similar, suggesting that the nature of the CTTS excited states and their coupling to the electronic states supported by the naturally occurring solvent cavities are similar in the two solvents. In contrast, the geminate recombination dynamics of potasside and sodide in DEE are different, with red-edge excitation of the K{sup -} CTTS band producing a greater number of long-lived electrons than is seen following the corresponding red-edge excitation of the Na{sup -} CTTS band. This indicates that the CTTS excited states of K{sup -} are better able to couple to the electronic states supported by the naturally occurring solvent cavities, allowing us to compare the energetic positions of the potasside and sodide ground and CTTS excited states on a common absolute scale. Finally, we also observe a strong transient absorption following the CTTS excitation of potasside in DEE that correlates well with the 766 nm position of the gas-phase potassium D-line. The data indicate that CTTS excitation of alkali metal anions essentially instantaneously produces a gas-phase-like neutral alkali metal atom, which then spontaneously undergoes partial ejection of the remaining valence electron to form a neutral alkali metal cation:solvated electron tight-contact pair.« less

Sensitivity of the nuclear deformability and fission barriers to the equation of state

NASA Astrophysics Data System (ADS)

Seif, W. M.; Anwer, Hisham

2018-07-01

The model-dependent analysis of the fission data impacts the extracted fission-related quantities, which are not directly observables, such as the super- and hyperdeformed isomeric states and their energies. We investigated the model dependence of the deformability of a nucleus and its fission barriers on the nuclear equation of state. Within the microscopic-macroscopic model based on a large number of Skyrme nucleon-nucleon interactions, the total energy surfaces and the double-humped fission barrier of 230Th are calculated in a multidimensional deformation space. In addition to the ground-state (GS) and the superdeformed (SD) minima, all the investigated forces yielded a hyperdeformed (HD) minimum. The contour map of the shell-plus-pairing energy clearly displayed the three minima. We found that the GS binding energy and the deformation energy of the different deformation modes along the fission path increase with the incompressibility coefficient K0, while the fission barrier heights and the excitation energies of the SD and HD modes decrease with it. Conversely, the surface-energy coefficient asurf, the symmetry-energy, and its density-slope parameter decrease the GS energy and the deformation energies, but increase the fission barrier heights and the excitation energies. The obtained deformation parameters of the different deformation modes exhibit almost independence on K0, and on the symmetry-energy and its density-slope. The principle deformation parameters of the SD and HD isomeric states tend to decrease with asurf.

Recovery of photoinduced reversible dark States utilized for molecular diffusion measurements.

PubMed

Chmyrov, Andriy; Sandén, Tor; Widengren, Jerker

2010-12-15

For a spatially restricted excitation volume, the effective modulation of the excitation in time is influenced by the passage times of the molecules through the excitation volume. By applying an additional time-modulated excitation, the buildup of photoinduced reversible dark states in fluorescent molecules can be made to vary significantly with their passage times through the excitation volume. The variations in the dark state populations are reflected by the time-averaged fluorescence intensity, which thus can be used to characterize the mobilities of the molecules. The concept was experimentally verified by measuring the fluorescence response of freely diffusing cyanine fluorophores (Cy5), undergoing trans-cis isomerization when subject to time-modulated excitation in a focused laser beam. From the fluorescence response, and by applying a simple photodynamic model, the transition times of the Cy5 molecules could be well reproduced when applying different laminar flow speeds through the detection volume. The presented approach puts no constraints on sample concentration, no requirements for high time resolution or sensitivity in the detection, nor requires a high fluorescence brightness of the characterized molecules. This can make the concept useful for a broad range of biomolecular mobility studies.

Ultrafast energy- and momentum-resolved dynamics of magnetic correlations in the photo-doped Mott insulator Sr2IrO4.

PubMed

Dean, M P M; Cao, Y; Liu, X; Wall, S; Zhu, D; Mankowsky, R; Thampy, V; Chen, X M; Vale, J G; Casa, D; Kim, Jungho; Said, A H; Juhas, P; Alonso-Mori, R; Glownia, J M; Robert, A; Robinson, J; Sikorski, M; Song, S; Kozina, M; Lemke, H; Patthey, L; Owada, S; Katayama, T; Yabashi, M; Tanaka, Yoshikazu; Togashi, T; Liu, J; Rayan Serrao, C; Kim, B J; Huber, L; Chang, C-L; McMorrow, D F; Först, M; Hill, J P

2016-06-01

Measuring how the magnetic correlations evolve in doped Mott insulators has greatly improved our understanding of the pseudogap, non-Fermi liquids and high-temperature superconductivity. Recently, photo-excitation has been used to induce similarly exotic states transiently. However, the lack of available probes of magnetic correlations in the time domain hinders our understanding of these photo-induced states and how they could be controlled. Here, we implement magnetic resonant inelastic X-ray scattering at a free-electron laser to directly determine the magnetic dynamics after photo-doping the Mott insulator Sr2IrO4. We find that the non-equilibrium state, 2 ps after the excitation, exhibits strongly suppressed long-range magnetic order, but hosts photo-carriers that induce strong, non-thermal magnetic correlations. These two-dimensional (2D) in-plane Néel correlations recover within a few picoseconds, whereas the three-dimensional (3D) long-range magnetic order restores on a fluence-dependent timescale of a few hundred picoseconds. The marked difference in these two timescales implies that the dimensionality of magnetic correlations is vital for our understanding of ultrafast magnetic dynamics.

Quantum Nuclear Dynamics Pumped and Probed by Ultrafast Polarization Controlled Steering of a Coherent Electronic State in LiH.

PubMed

Nikodem, Astrid; Levine, R D; Remacle, F

2016-05-19

The quantum wave packet dynamics following a coherent electronic excitation of LiH by an ultrashort, polarized, strong one-cycle infrared optical pulse is computed on several electronic states using a grid method. The coupling to the strong field of the pump and the probe pulses is included in the Hamiltonian used to solve the time-dependent Schrodinger equation. The polarization of the pump pulse allows us to control the localization in time and in space of the nonequilibrium coherent electronic motion and the subsequent nuclear dynamics. We show that transient absorption, resulting from the interaction of the total molecular dipole with the electric fields of the pump and the probe, is a very versatile probe of the different time scales of the vibronic dynamics. It allows probing both the ultrashort, femtosecond time scale of the electronic coherences as well as the longer dozens of femtoseconds time scales of the nuclear motion on the excited electronic states. The ultrafast beatings of the electronic coherences in space and in time are shown to be modulated by the different periods of the nuclear motion.

Applications of Second Harmonic and Sum Frequency Generation to Graphite and Silica Type Interfaces.

DTIC Science & Technology

1994-08-01

investigated. The ultrafast barrierless isomerization of an organic dye, Malachite Green, has also been probed with femtosecond time resolution, enabling the... Malachite Green, has also been probed with femtosecond time resolution, enabling the structure of water at various aqueous interfaces to be probed. In...6G at air/aqueous interface ....................................... 7 6. Time-resolved SHG of Malachite Green at air and silica/aqueous interfaces

Hot electron dynamics at semiconductor surfaces: Implications for quantum dot photovoltaics

NASA Astrophysics Data System (ADS)

Tisdale, William A., III

Finding a viable supply of clean, renewable energy is one of the most daunting challenges facing the world today. Solar cells have had limited impact in meeting this challenge because of their high cost and low power conversion efficiencies. Semiconductor nanocrystals, or quantum dots, are promising materials for use in novel solar cells because they can be processed with potentially inexpensive solution-based techniques and because they are predicted to have novel optoelectronic properties that could enable the realization of ultra-efficient solar power converters. However, there is a lack of fundamental understanding regarding the behavior of highly-excited, or "hot," charge carriers near quantum-dot and semiconductor interfaces, which is of paramount importance to the rational design of high-efficiency devices. The elucidation of these ultrafast hot electron dynamics is the central aim of this Dissertation. I present a theoretical framework for treating the electronic interactions between quantum dots and bulk semiconductor surfaces and propose a novel experimental technique, time-resolved surface second harmonic generation (TR-SHG), for probing these interactions. I then describe a series of experimental investigations into hot electron dynamics in specific quantum-dot/semiconductor systems. A two-photon photoelectron spectroscopy (2PPE) study of the technologically-relevant ZnO(1010) surface reveals ultrafast (sub-30fs) cooling of hot electrons in the bulk conduction band, which is due to strong electron-phonon coupling in this highly polar material. The presence of a continuum of defect states near the conduction band edge results in Fermi-level pinning and upward (n-type) band-bending at the (1010) surface and provides an alternate route for electronic relaxation. In monolayer films of colloidal PbSe quantum dots, chemical treatment with either hydrazine or 1,2-ethanedithiol results in strong and tunable electronic coupling between neighboring quantum dots. A TR-SHG study of these electronically-coupled quantum-dot films reveals temperature-activated cooling of hot charge carriers and coherent excitation of a previously-unidentified surface optical phonon. Finally, I report the first experimental observation of ultrafast electron transfer from the higher excited states of a colloidal quantum dot (PbSe) to delocalized conduction band states of a widely-used electron acceptor (TiO2). The electric field resulting from ultrafast (<50fs) separation of charge carriers across the PbSe/TiO2(110) interface excites coherent vibration of the TiO2 surface atoms, whose collective motions can be followed in real time.

Photophysical properties and photoisomerization processes of Methyl Red embedded in rigid polymer

NASA Astrophysics Data System (ADS)

Lee, Geon Joon; Kim, Dongho; Lee, Minyung

1995-01-01

The photophysical properties of Methyl Red molecules embedded in a poly(methyl methacrylate) (PMMA) matrix were investigated with photoinduced absorption, absorption kinetics, steady-state, and time-resolved luminescence spectroscopy. The excited singlet (S1) state lifetimes for trans and cis isomers of Methyl Red in PMMA at room temperature have been measured as 35 and 420 ps, respectively. The excited triplet (T1) state energy level and its lifetime at 77 K were also obtained. A slow trans-cis isomerization process having a time constant of a few hundred seconds was observed for the illuminated Methyl Red in rigid polymer. Based on measured photophysical properties and dynamic processes, an energy-level diagram for Methyl Red molecules in rigid polymer is introduced to explain these observations.

Protonation-induced ultrafast torsional dynamics in 9-anthrylbenzimidazole: a pH activated molecular rotor.

PubMed

Nandi, Amitabha; Kushwaha, Archana; Das, Dipanwita; Ghosh, Rajib

2018-03-07

We report the photophysical properties and excited state dynamics of 9-anthrylbenzimidazole (ANBI) which exhibits protonation-induced molecular rotor properties. In contrast to the highly emissive behavior of neutral ANBI, protonation of the benzimidazole group of ANBI induces efficient nonradiative deactivation by ultrafast torsional motion around the bond connecting the anthracene and benzimidazole units, as revealed by ultrafast transient absorption and fluorescence spectroscopy. Contrary to viscosity-independent fluorescence of neutral dyes, protonated ANBI is shown to display linear variation of emission yield and lifetime with solvent viscosity. The protonation-induced molecular rotor properties in the studied system are shown to be driven by enhanced charge transfer and are corroborated by quantum chemical calculations. Potential application as a microviscosity sensor of acidic regions in a heterogeneous environment by these proton-activated molecular rotor properties of ANBI is discussed.

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

Chromophore twisting in the excited state of a photoswitchable fluorescent protein captured by time-resolved serial femtosecond crystallography

NASA Astrophysics Data System (ADS)

Coquelle, Nicolas; Sliwa, Michel; Woodhouse, Joyce; Schirò, Giorgio; Adam, Virgile; Aquila, Andrew; Barends, Thomas R. M.; Boutet, Sébastien; Byrdin, Martin; Carbajo, Sergio; de La Mora, Eugenio; Doak, R. Bruce; Feliks, Mikolaj; Fieschi, Franck; Foucar, Lutz; Guillon, Virginia; Hilpert, Mario; Hunter, Mark S.; Jakobs, Stefan; Koglin, Jason E.; Kovacsova, Gabriela; Lane, Thomas J.; Lévy, Bernard; Liang, Mengning; Nass, Karol; Ridard, Jacqueline; Robinson, Joseph S.; Roome, Christopher M.; Ruckebusch, Cyril; Seaberg, Matthew; Thepaut, Michel; Cammarata, Marco; Demachy, Isabelle; Field, Martin; Shoeman, Robert L.; Bourgeois, Dominique; Colletier, Jacques-Philippe; Schlichting, Ilme; Weik, Martin

2018-01-01

Chromophores absorb light in photosensitive proteins and thereby initiate fundamental biological processes such as photosynthesis, vision and biofluorescence. An important goal in their understanding is the provision of detailed structural descriptions of the ultrafast photochemical events that they undergo, in particular of the excited states that connect chemistry to biological function. Here we report on the structures of two excited states in the reversibly photoswitchable fluorescent protein rsEGFP2. We populated the states through femtosecond illumination of rsEGFP2 in its non-fluorescent off state and observed their build-up (within less than one picosecond) and decay (on the several picosecond timescale). Using an X-ray free-electron laser, we performed picosecond time-resolved crystallography and show that the hydroxybenzylidene imidazolinone chromophore in one of the excited states assumes a near-canonical twisted configuration halfway between the trans and cis isomers. This is in line with excited-state quantum mechanics/molecular mechanics and classical molecular dynamics simulations. Our new understanding of the structure around the twisted chromophore enabled the design of a mutant that displays a twofold increase in its off-to-on photoswitching quantum yield.

Chromophore twisting in the excited state of a photoswitchable fluorescent protein captured by time-resolved serial femtosecond crystallography

DOE PAGES

Coquelle, Nicolas; Sliwa, Michel; Woodhouse, Joyce; ...

2017-09-11

Chromophores absorb light in photosensitive proteins and thereby initiate fundamental biological processes such as photosynthesis, vision and biofluorescence. An important goal in their understanding is the provision of detailed structural descriptions of the ultrafast photochemical events that they undergo, in particular of the excited states that connect chemistry to biological function. Here in this paper we report on the structures of two excited states in the reversibly photoswitchable fluorescent protein rsEGFP2. We populated the states through femtosecond illumination of rsEGFP2 in its non-fluorescent off state and observed their build-up (within less than one picosecond) and decay (on the several picosecondmore » timescale). Using an X-ray free-electron laser, we performed picosecond time-resolved crystallography and show that the hydroxybenzylidene imidazolinone chromophore in one of the excited states assumes a near-canonical twisted configuration halfway between the trans and cis isomers. This is in line with excited-state quantum mechanics/molecular mechanics and classical molecular dynamics simulations. Our new understanding of the structure around the twisted chromophore enabled the design of a mutant that displays a twofold increase in its off-to-on photoswitching quantum yield.« less

Chromophore twisting in the excited state of a photoswitchable fluorescent protein captured by time-resolved serial femtosecond crystallography

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

Coquelle, Nicolas; Sliwa, Michel; Woodhouse, Joyce

Chromophores absorb light in photosensitive proteins and thereby initiate fundamental biological processes such as photosynthesis, vision and biofluorescence. An important goal in their understanding is the provision of detailed structural descriptions of the ultrafast photochemical events that they undergo, in particular of the excited states that connect chemistry to biological function. Here in this paper we report on the structures of two excited states in the reversibly photoswitchable fluorescent protein rsEGFP2. We populated the states through femtosecond illumination of rsEGFP2 in its non-fluorescent off state and observed their build-up (within less than one picosecond) and decay (on the several picosecondmore » timescale). Using an X-ray free-electron laser, we performed picosecond time-resolved crystallography and show that the hydroxybenzylidene imidazolinone chromophore in one of the excited states assumes a near-canonical twisted configuration halfway between the trans and cis isomers. This is in line with excited-state quantum mechanics/molecular mechanics and classical molecular dynamics simulations. Our new understanding of the structure around the twisted chromophore enabled the design of a mutant that displays a twofold increase in its off-to-on photoswitching quantum yield.« less

Monte Carlo wave-packet approach to trace nuclear dynamics in molecular excited states by XUV-pump-IR-probe spectroscopy

NASA Astrophysics Data System (ADS)

Jing, Qingli; Bello, Roger Y.; Martín, Fernando; Palacios, Alicia; Madsen, Lars Bojer

2018-04-01

Recent research interests have been raised in uncovering and controlling ultrafast dynamics in excited neutral molecules. In this work we generalize the Monte Carlo wave packet (MCWP) approach to XUV-pump-IR-probe schemes to simulate the process of dissociative double ionization of H2 where singly excited states in H2 are involved. The XUV pulse is chosen to resonantly excite the initial ground state of H2 to the lowest excited electronic state of 1Σu + symmetry in H2 within the Franck-Condon region. The delayed intense IR pulse couples the excited states of 1Σu + symmetry with the nearby excited states of 1Σg + symmetry. It also induces the first ionization from H2 to H2 + and the second ionization from H2 + to H++H+. To reduce the computational costs in the MCWP approach, a sampling method is proposed to determine in time the dominant ionization events from H2 to H2+. By conducting a trajectory analysis, which is a unique possibility within the MCWP approach, the origins of the characteristic features in the nuclear kinetic energy release spectra are identified for delays ranging from 0 to 140 fs and the nuclear dynamics in the singly excited states in H2 is mapped out.

Laser pulse control of ultrafast heterogeneous electron transfer: a computational study.

PubMed

Wang, Luxia; May, Volkhard

2004-10-22

Laser pulse control of the photoinduced 90 fs charge injection from perylene into the conduction band of TiO2 is studied theoretically. The approach accounts for the electronic-ground state of the dye, the first excited state, the ionized state formed after charge injection, and the continuum of the electronic states in the conduction band, all defined vs a single reaction coordinate. To address different control tasks optimal control theory is combined with a full quantum dynamical description of the electron-vibrational motion accompanying the charge injection process. First it is proved in which way the charge injection time can be changed by tailored laser pulses. In a second step a pump-dump scheme from the perylene ground state to the first excited electronic state and back to the ground state is discussed. Because of the strong coupling of the excited perylene state to the band continuum of TiO2 this control task is more suited to an experimental test than the direct control of the charge injection.

Multistate photo-induced relaxation and photoisomerization ability of fumaramide threads: a computational and experimental study.

PubMed

Altoè, Piero; Haraszkiewicz, Natalia; Gatti, Francesco G; Wiering, Piet G; Frochot, Céline; Brouwer, Albert M; Balkowski, Grzegorz; Shaw, Daniel; Woutersen, Sander; Buma, Wybren Jan; Zerbetto, Francesco; Orlandi, Giorgio; Leigh, David A; Garavelli, Marco

2009-01-14

Fumaric and maleic amides are the photoactive units of an important and widely investigated class of photocontrollable rotaxanes as they trigger ring shuttling via a cis-trans photoisomerization. Here, ultrafast decay and photoinduced isomerization in isolated fumaramide and solvated nitrogen-substituted fumaramides (that are employed as threads in those rotaxanes) have been investigated by means of CASPT2//CASSCF computational and time-resolved spectroscopic techniques, respectively. A complex multistate network of competitive deactivation channels, involving both internal conversion and intersystem crossing (ISC) processes, has been detected and characterized that accounts for the picosecond decay and photochemical/photophysical properties observed in the singlet as well as triplet (photosensitized) photochemistry of fumaramides threads. Interestingly, singlet photochemistry appears to follow a non-Kasha rule model, where nonequilibrium dynamical factors control the outcome of the photochemical process: accessible high energy portions of extended crossing seams turn out to drive the deactivation process and ground-state recovery. Concurrently, extended singlet/triplet degenerate regions of twisted molecular structures with significant spin-orbit-coupling values account for ultrafast (picosecond time scale) ISC processes that lead to higher photoisomerization efficiencies. This model discloses the principles behind the intrinsic photochemical reactivity of fumaramide and its control.

Selective excitation enables assignment of proton resonances and (1)H-(1)H distance measurement in ultrafast magic angle spinning solid state NMR spectroscopy.

PubMed

Zhang, Rongchun; Ramamoorthy, Ayyalusamy

2015-07-21

Remarkable developments in ultrafast magic angle spinning (MAS) solid-state NMR spectroscopy enabled proton-based high-resolution multidimensional experiments on solids. To fully utilize the benefits rendered by proton-based ultrafast MAS experiments, assignment of (1)H resonances becomes absolutely necessary. Herein, we propose an approach to identify different proton peaks by using dipolar-coupled heteronuclei such as (13)C or (15)N. In this method, after the initial preparation of proton magnetization and cross-polarization to (13)C nuclei, transverse magnetization of desired (13)C nuclei is selectively prepared by using DANTE (Delays Alternating with Nutations for Tailored Excitation) sequence and then, it is transferred to bonded protons with a short-contact-time cross polarization. Our experimental results demonstrate that protons bonded to specific (13)C atoms can be identified and overlapping proton peaks can also be assigned. In contrast to the regular 2D HETCOR experiment, only a few 1D experiments are required for the complete assignment of peaks in the proton spectrum. Furthermore, the finite-pulse radio frequency driven recoupling sequence could be incorporated right after the selection of specific proton signals to monitor the intensity buildup for other proton signals. This enables the extraction of (1)H-(1)H distances between different pairs of protons. Therefore, we believe that the proposed method will greatly aid in fast assignment of peaks in proton spectra and will be useful in the development of proton-based multi-dimensional solid-state NMR experiments to study atomic-level resolution structure and dynamics of solids.

Ultrafast Energy Transfer Dynamics Between a Polypyridyl Ru(II) Chromophore and a Covalently Attached Acceptor

NASA Astrophysics Data System (ADS)

Styers-Barnett, David; Gannon, Erika; Papanikolas, John; Meyer, Thomas

2003-03-01

The energy transfer dynamics between the ^3MLCT excited state of a polypyridyl Ru(II) chromophore and a ligand-bound anthracene has been studied using femtosecond transient absorption spectroscopy. Photoexcitation of the metal complex at 450 nm promotes an electron from a d-orbital on the metal to a π* orbital on the bipyridine, forming a metal-to-ligand charge-transfer (MLCT) excited state. Energy transfer to the covalently appended anthracene is followed by the growth of the anthracene excited state absorption at 425 nm, and the simultaneous decay of the ^3MLCT absorption at 380 nm. The observed growth is biexponential, with the fast component attributed to energy transfer (19 ps), and the slow component arising from a combination of interligand electron transfer between the polypyridyl ligands and energy transfer (75 ps).

Inverting pump-probe spectroscopy for state tomography of excitonic systems.

PubMed

Hoyer, Stephan; Whaley, K Birgitta

2013-04-28

We propose a two-step protocol for inverting ultrafast spectroscopy experiments on a molecular aggregate to extract the time-evolution of the excited state density matrix. The first step is a deconvolution of the experimental signal to determine a pump-dependent response function. The second step inverts this response function to obtain the quantum state of the system, given a model for how the system evolves following the probe interaction. We demonstrate this inversion analytically and numerically for a dimer model system, and evaluate the feasibility of scaling it to larger molecular aggregates such as photosynthetic protein-pigment complexes. Our scheme provides a direct alternative to the approach of determining all Hamiltonian parameters and then simulating excited state dynamics.

Single-order laser high harmonics in XUV for ultrafast photoelectron spectroscopy of molecular wavepacket dynamics.

PubMed

Fushitani, Mizuho; Hishikawa, Akiyoshi

2016-11-01

We present applications of extreme ultraviolet (XUV) single-order laser harmonics to gas-phase ultrafast photoelectron spectroscopy. Ultrashort XUV pulses at 80 nm are obtained as the 5th order harmonics of the fundamental laser at 400 nm by using Xe or Kr as the nonlinear medium and separated from other harmonic orders by using an indium foil. The single-order laser harmonics is applied for real-time probing of vibrational wavepacket dynamics of I 2 molecules in the bound and dissociating low-lying electronic states and electronic-vibrational wavepacket dynamics of highly excited Rydberg N 2 molecules.

Excited state dynamics of the astaxanthin radical cation

NASA Astrophysics Data System (ADS)

Amarie, Sergiu; Förster, Ute; Gildenhoff, Nina; Dreuw, Andreas; Wachtveitl, Josef

2010-07-01

Femtosecond transient absorption spectroscopy in the visible and NIR and ultrafast fluorescence spectroscopy were used to examine the excited state dynamics of astaxanthin and its radical cation. For neutral astaxanthin, two kinetic components corresponding to time constants of 130 fs (decay of the S 2 excited state) and 5.2 ps (nonradiative decay of the S 1 excited state) were sufficient to describe the data. The dynamics of the radical cation proved to be more complex. The main absorption band was shifted to 880 nm (D 0 → D 3 transition), showing a weak additional band at 1320 nm (D 0 → D 1 transition). We found, that D 3 decays to the lower-lying D 2 within 100 fs, followed by a decay to D 1 with a time constant of 0.9 ps. The D 1 state itself exhibited a dual behavior, the majority of the population is transferred to the ground state in 4.9 ps, while a small population decays on a longer timescale of 40 ps. Both transitions from D 1 were found to be fluorescent.

Modeling ultrafast exciton migration within the electron donor domains of bulk heterojunction organic photovoltaics

DOE PAGES

Bednarz, Mateusz; Lapin, Joel; McGillicuddy, Ryan; ...

2017-02-21

Recent experimental studies revealed that charge carriers harvested by bulk heterojunction organic photovoltaics can be collected on ultrafast time scales. To investigate ultrafast exciton mobility, we construct simple, nonatomistic models of a common polymeric electron donor material. We first explore the relationship between the magnitude of energetic noise in the model Hamiltonian and the spatial extent of resulting eigenstates. We then employ a quantum master equation approach to simulate migration of chromophore-localized initial excited states. Excitons initially localized on a single chromophore at the center of the model delocalize down polymer chains and across pi-stacked chromophores through a coherent, wavelikemore » mechanism during the first few tens of femtoseconds. We explore the dependence of this coherent delocalization on coupling strength and on the magnitude of energetic noise. At longer times we observe continued migration toward a uniform population distribution that proceeds through an incoherent, diffusive mechanism. A series of simulations modeling exciton harvesting in domains of varying size demonstrates that smaller domains enhance ultrafast exciton harvesting yield. Finally, our nonatomistic model falls short of quantitative accuracy but demonstrates that excitons are mobile within electron donor domains on ultrafast time scales and that coherent exciton transport can enhance ultrafast exciton harvesting.« less

Modeling ultrafast exciton migration within the electron donor domains of bulk heterojunction organic photovoltaics

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

Bednarz, Mateusz; Lapin, Joel; McGillicuddy, Ryan

Recent experimental studies revealed that charge carriers harvested by bulk heterojunction organic photovoltaics can be collected on ultrafast time scales. To investigate ultrafast exciton mobility, we construct simple, nonatomistic models of a common polymeric electron donor material. We first explore the relationship between the magnitude of energetic noise in the model Hamiltonian and the spatial extent of resulting eigenstates. We then employ a quantum master equation approach to simulate migration of chromophore-localized initial excited states. Excitons initially localized on a single chromophore at the center of the model delocalize down polymer chains and across pi-stacked chromophores through a coherent, wavelikemore » mechanism during the first few tens of femtoseconds. We explore the dependence of this coherent delocalization on coupling strength and on the magnitude of energetic noise. At longer times we observe continued migration toward a uniform population distribution that proceeds through an incoherent, diffusive mechanism. A series of simulations modeling exciton harvesting in domains of varying size demonstrates that smaller domains enhance ultrafast exciton harvesting yield. Finally, our nonatomistic model falls short of quantitative accuracy but demonstrates that excitons are mobile within electron donor domains on ultrafast time scales and that coherent exciton transport can enhance ultrafast exciton harvesting.« less

Competing 1πσ* mediated dynamics in mequinol: O-H versus O-CH3 photodissociation pathways.

PubMed

Hadden, David J; Roberts, Gareth M; Karsili, Tolga N V; Ashfold, Michael N R; Stavros, Vasilios G

2012-10-14

Deactivation of excited electronic states through coupling to dissociative (1)πσ* states in heteroaromatic systems has received considerable attention in recent years, particularly as a mechanism that contributes to the ultraviolet (UV) photostability of numerous aromatic biomolecules and their chromophores. Recent studies have expanded upon this work to look at more complex species, which involves understanding competing dynamics on two different (1)πσ* potential energy surfaces (PESs) localized on different heteroatom hydride coordinates (O-H and N-H bonds) within the same molecule. In a similar spirit, the work presented here utilizes ultrafast time-resolved velocity map ion imaging to study competing dissociation pathways along (1)πσ* PESs in mequinol (p-methoxyphenol), localized at O-H and O-CH(3) bonds yielding H atoms or CH(3) radicals, respectively, over an excitation wavelength range of 298-238 nm and at 200 nm. H atom elimination is found to be operative via either tunneling under a conical intersection (CI) (298 ≥ λ ≥ 280 nm) or ultrafast internal conversion through appropriate CIs (λ ≤ 245 nm), both of which provide mechanisms for coupling onto the dissociative state associated with the O-H bond. In the intermediate wavelength range of 280 ≥ λ ≥ 245 nm, mediated H atom elimination is not observed. In contrast, we find that state driven CH(3) radical elimination is only observed in the excitation range 264 ≥ λ ≥ 238 nm. Interpretation of these experimental results is guided by: (i) high level complete active space with second order perturbation theory (CASPT2) calculations, which provide 1-D potential energy cuts of the ground and low lying singlet excited electronic states along the O-H and O-CH(3) bond coordinates; and (ii) calculated excitation energies using CASPT2 and the equation-of-motion coupled cluster with singles and doubles excitations (EOM-CCSD) formalism. From these comprehensive studies, we find that the dynamics along the O-H coordinate generally mimic H atom elimination previously observed in phenol, whereas O-CH(3) bond fission in mequinol appears to present notably different behavior to the CH(3) elimination dynamics previously observed in anisole (methoxybenzene).

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

NASA Astrophysics Data System (ADS)

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

2018-04-01

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

Nonlinear performance of asymmetric coupler based on dual-core photonic crystal fiber: Towards sub-nanojoule solitonic ultrafast all-optical switching

NASA Astrophysics Data System (ADS)

Curilla, L.; Astrauskas, I.; Pugzlys, A.; Stajanca, P.; Pysz, D.; Uherek, F.; Baltuska, A.; Bugar, I.

2018-05-01

We demonstrate ultrafast soliton-based nonlinear balancing of dual-core asymmetry in highly nonlinear photonic crystal fiber at sub-nanojoule pulse energy level. The effect of fiber asymmetry was studied experimentally by selective excitation and monitoring of individual fiber cores at different wavelengths between 1500 nm and 1800 nm. Higher energy transfer rate to non-excited core was observed in the case of fast core excitation due to nonlinear asymmetry balancing of temporal solitons, which was confirmed by the dedicated numerical simulations based on the coupled generalized nonlinear Schrödinger equations. Moreover, the simulation results correspond qualitatively with the experimentally acquired dependences of the output dual-core extinction ratio on excitation energy and wavelength. In the case of 1800 nm fast core excitation, narrow band spectral intensity switching between the output channels was registered with contrast of 23 dB. The switching was achieved by the change of the excitation pulse energy in sub-nanojoule region. The performed detailed analysis of the nonlinear balancing of dual-core asymmetry in solitonic propagation regime opens new perspectives for the development of ultrafast nonlinear all-optical switching devices.

Nonadiabatic excited-state molecular dynamics modeling of photoinduced dynamics in conjugated molecules.

PubMed

Nelson, Tammie; Fernandez-Alberti, Sebastian; Chernyak, Vladimir; Roitberg, Adrian E; Tretiak, Sergei

2011-05-12

Nonadiabatic dynamics generally defines the entire evolution of electronic excitations in optically active molecular materials. It is commonly associated with a number of fundamental and complex processes such as intraband relaxation, energy transfer, and light harvesting influenced by the spatial evolution of excitations and transformation of photoexcitation energy into electrical energy via charge separation (e.g., charge injection at interfaces). To treat ultrafast excited-state dynamics and exciton/charge transport we have developed a nonadiabatic excited-state molecular dynamics (NA-ESMD) framework incorporating quantum transitions. Our calculations rely on the use of the Collective Electronic Oscillator (CEO) package accounting for many-body effects and actual potential energy surfaces of the excited states combined with Tully's fewest switches algorithm for surface hopping for probing nonadiabatic processes. This method is applied to model the photoinduced dynamics of distyrylbenzene (a small oligomer of polyphenylene vinylene, PPV). Our analysis shows intricate details of photoinduced vibronic relaxation and identifies specific slow and fast nuclear motions that are strongly coupled to the electronic degrees of freedom, namely, torsion and bond length alternation, respectively. Nonadiabatic relaxation of the highly excited mA(g) state is predicted to occur on a femtosecond time scale at room temperature and on a picosecond time scale at low temperature.

Use of ultrafast dispersed pump-dump-probe and pump-repump-probe spectroscopies to explore the light-induced dynamics of peridinin in solution.

PubMed

Papagiannakis, Emmanouil; Vengris, Mikas; Larsen, Delmar S; van Stokkum, Ivo H M; Hiller, Roger G; van Grondelle, Rienk

2006-01-12

Optical pump-induced dynamics of the highly asymmetric carotenoid peridinin in methanol was studied by dispersed pump-probe, pump-dump-probe, and pump-repump-probe transient absorption spectroscopy in the visible region. Dispersed pump-probe measurements show that the decay of the initially excited S2 state populates two excited states, the S1 and the intramolecular charge-transfer (ICT) state, at a ratio determined by the excitation wavelength. The ensuing spectral evolution occurs on the time scale of a few picoseconds and suggests the equilibration of these states. Dumping the stimulated emission of the ICT state with an additional 800-nm pulse after 400- and 530-nm excitation preferentially removes the ICT state contribution from the broad excited-state absorption, allowing for its spectral characterization. At the same time, an unrelaxed ground-state species, which has a subpicosecond lifetime, is populated. The application of the 800-nm pulse at early times, when the S2 state is still populated, led to direct generation of the peridinin cation, observed for the first time in a transient absorption experiment. The excited and ground electronic states manifold of peridinin has been reconstructed using target analysis; this approach combined with the measured multipulse spectroscopic data allows us to estimate the spectra and time scales of the corresponding transient states.

Electronic structure and photochemistry of squaraine dyes: basic theoretical analysis and direct detection of the photoisomer of a symmetrical squarylium cyanine.

PubMed

Momicchioli, Fabio; Tatikolov, Aleksandr S; Vanossi, Davide; Ponterini, Glauco

2004-04-01

The photoisomerization kinetics of a squaraine dye has been the object both of experimental investigation and of interpretation in the framework of a qualitative theoretical model formulated by the aid of simple HMO calculations and orbital symmetry considerations. Such a model has first confirmed that the electronic structure and the spectroscopic properties of symmetrical squaraines are related to those of the parent cyanines, with ketocyanines as intermediate systems. Extension of the approach to structures twisted by 90[degree] about a polymethine bond has then provided insight into the electronic aspects and the mechanism of the photoisomerization of the squaraine under study. The reaction, previously indirectly investigated by fluorescence analysis, has been directly monitored by laser flash photolysis. These experiments indicate that, while photoisomerization is likely the main radiationless decay route from the spectroscopic minimum of the lowest excited singlet state (S(1)), the cis photoisomer is produced with only a 1% yield, likely because of an unfavourable cis/trans branching ratio from the perpendicular minimum of the S(1)-state potential energy surface. In contrast with what found for symmetrical cyanines, an increase in the solvent polarity was found to accelerate both the direct, excited-state reaction and, to a much larger extent, the ground-state back-isomerization. Such observations are consistent with predictions of the theoretical model and provide a clue for the identification of the isomerization coordinate.

Evidence for carrier localization in the pseudogap state of cuprate superconductors from coherent quench experiments

PubMed Central

Madan, I.; Kurosawa, T.; Toda, Y.; Oda, M.; Mertelj, T.; Mihailovic, D.

2015-01-01

A ‘pseudogap' was introduced by Mott to describe a state of matter that has a minimum in the density of states at the Fermi level, deep enough for states to become localized. It can arise either from Coulomb repulsion between electrons, and/or incipient charge or spin order. Here we employ ultrafast spectroscopy to study dynamical properties of the normal to pseudogap state transition in the prototype high-temperature superconductor Bi2Sr2CaCu2O8+δ. We perform a systematic temperature and doping dependence study of the pseudogap photodestruction and recovery in coherent quench experiments, revealing marked absence of critical behaviour of the elementary excitations, which implies an absence of collective electronic ordering beyond a few coherence lengths on short timescales. The data imply ultrafast carrier localization into a textured polaronic state arising from a competing Coulomb interaction and lattice strain, enhanced by a Fermi surface instability. PMID:25891310

Multi-state nonadiabatic deactivation mechanism of coumarin revealed by ab initio on-the-fly trajectory surface hopping dynamic simulation.

PubMed

Gan, Yanzhen; Yue, Ling; Guo, Xugeng; Zhu, Chaoyuan; Cao, Zexing

2017-05-17

An on-the-fly trajectory surface hopping dynamic simulation has been performed for revealing the multi-state nonadiabatic deactivation mechanism of coumarin. The mechanism involves three adiabatic excited states, S 3 (ππ*L b ), S 2 (nπ*, ππ*L a ) and S 1 (ππ*L a , nπ*), and the ground state S 0 at the four state-averaged complete active space self-consistent field, SA4-CASSCF(12,10)/6-31G* level of theory. Upon photoexcitation to the third excited state S 3 (ππ*L b ) in the Franck-Condon region, 80% sampling trajectories decay to the dark S 2 (nπ*) state within an average of 5 fs via the conical intersection S 3 (ππ*L b )/S 2 (nπ*), while 20% decay to the S 2 (ππ*L a ) state within an average of 11 fs via the conical intersection S 3 (ππ*L b )/S 2 (ππ*L a ). Then, sampling trajectories via S 2 (nπ*)/S 1 (ππ*L a ) continue with ultrafast decay processes to give a final distribution of quantum yields as follows: 42% stay on the dark S 1 (nπ*) state, 43.3% go back to the ground S 0 state, 12% undergo a ring-opening reaction to the Z-form S 0 (Z) state, and 2.7% go to the E-form S 0 (E) state. The lifetimes of the excited states are estimated as follows: the S 3 state is about 12 fs on average, the S 2 state is about 80 fs, and the S 1 state has a fast component of about 160 fs and a slow component of 15 ps. The simulated ultrafast radiationless deactivation pathways of photoexcited coumarin immediately interpret the experimentally observed weak fluorescence emission.

Ultrafast Photoinduced Electron Transfer in a π-Conjugated Oligomer/Porphyrin Complex.

PubMed

Aly, Shawkat M; Goswami, Subhadip; Alsulami, Qana A; Schanze, Kirk S; Mohammed, Omar F

2014-10-02

Controlling charge transfer (CT), charge separation (CS), and charge recombination (CR) at the donor-acceptor interface is extremely important to optimize the conversion efficiency in solar cell devices. In general, ultrafast CT and slow CR are desirable for optimal device performance. In this Letter, the ultrafast excited-state CT between platinum oligomer (DPP-Pt(acac)) as a new electron donor and porphyrin as an electron acceptor is monitored for the first time using femtosecond (fs) transient absorption (TA) spectroscopy with broad-band capability and 120 fs temporal resolution. Turning the CT on/off has been shown to be possible either by switching from an organometallic oligomer to a metal-free oligomer or by controlling the charge density on the nitrogen atom of the porphyrin meso unit. Our time-resolved data show that the CT and CS between DPP-Pt(acac) and cationic porphyrin are ultrafast (approximately 1.5 ps), and the CR is slow (ns time scale), as inferred from the formation and the decay of the cationic and anionic species. We also found that the metallic center in the DPP-Pt(acac) oligomer and the positive charge on the porphyrin are the keys to switching on/off the ultrafast CT process.

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

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.

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

DOE PAGES

Ma, X.; Fang, F.; Li, Q.; ...

2015-10-28

In this study, optical control of spin is of central importance in the research of ultrafast spintronic devices utilizing spin dynamics at short time scales. Recently developed optical approaches such as ultrafast demagnetization, spin-transfer and spin-orbit torques open new pathways to manipulate spin through its interaction with photon, orbit, charge or phonon. However, these processes are limited by either the long thermal recovery time or the low-temperature requirement. Here we experimentally demonstrate ultrafast coherent spin precession via optical charge-transfer processes in the exchange-coupled Fe/CoO system at room temperature. The efficiency of spin precession excitation is significantly higher and the recoverymore » time of the exchange-coupling torque is much shorter than for the demagnetization procedure, which is desirable for fast switching. The exchange coupling is a key issue in spin valves and tunnelling junctions, and hence our findings will help promote the development of exchange-coupled device concepts for ultrafast coherent spin manipulation.« less

Ultrafast Nanoimaging of the Photoinduced Phase Transition Dynamics in VO2.

PubMed

Dönges, Sven A; Khatib, Omar; O'Callahan, Brian T; Atkin, Joanna M; Park, Jae Hyung; Cobden, David; Raschke, Markus B

2016-05-11

Many phase transitions in correlated matter exhibit spatial inhomogeneities with expected yet unexplored effects on the associated ultrafast dynamics. Here we demonstrate the combination of ultrafast nondegenerate pump-probe spectroscopy with far from equilibrium excitation, and scattering scanning near-field optical microscopy (s-SNOM) for ultrafast nanoimaging. In a femtosecond near-field near-IR (NIR) pump and mid-IR (MIR) probe study, we investigate the photoinduced insulator-to-metal (IMT) transition in nominally homogeneous VO2 microcrystals. With pump fluences as high as 5 mJ/cm(2), we can reach three distinct excitation regimes. We observe a spatial heterogeneity on ∼50-100 nm length scales in the fluence-dependent IMT dynamics ranging from <100 fs to ∼1 ps. These results suggest a high sensitivity of the IMT with respect to small local variations in strain, doping, or defects that are difficult to discern microscopically. We provide a perspective with the distinct requirements and considerations of ultrafast spatiotemporal nanoimaging of phase transitions in quantum materials.

Phonon-coupled ultrafast interlayer charge oscillation at van der Waals heterostructure interfaces

NASA Astrophysics Data System (ADS)

Zheng, Qijing; Xie, Yu; Lan, Zhenggang; Prezhdo, Oleg V.; Saidi, Wissam A.; Zhao, Jin

2018-05-01

Van der Waals (vdW) heterostructures of transition-metal dichalcogenide (TMD) semiconductors are central not only for fundamental science, but also for electro- and optical-device technologies where the interfacial charge transfer is a key factor. Ultrafast interfacial charge dynamics has been intensively studied, however, the atomic scale insights into the effects of the electron-phonon (e-p) coupling are still lacking. In this paper, using time dependent ab initio nonadiabatic molecular dynamics, we study the ultrafast interfacial charge transfer dynamics of two different TMD heterostructures MoS2/WS2 and MoSe2/WSe2 , which have similar band structures but different phonon frequencies. We found that MoSe2/WSe2 has softer phonon modes compared to MoS2/WS2 , and thus phonon-coupled charge oscillation can be excited with sufficient phonon excitations at room temperature. In contrast, for MoS2/WS2 , phonon-coupled interlayer charge oscillations are not easily excitable. Our study provides an atomic level understanding on how the phonon excitation and e-p coupling affect the interlayer charge transfer dynamics, which is valuable for both the fundamental understanding of ultrafast dynamics at vdW hetero-interfaces and the design of novel quasi-two-dimensional devices for optoelectronic and photovoltaic applications.

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.

Ultrafast photoinduced dynamics of the 3,6-diaminoacridinium derivative ATTO 465 in solution.

PubMed

Arden-Jacob, Jutta; Drexhage, Karl-Heinz; Druzhinin, Sergey I; Ekimova, Maria; Flender, Oliver; Lenzer, Thomas; Oum, Kawon; Scholz, Mirko

2013-02-14

The excited state dynamics of the dye ATTO 465, a well-known fluorescence marker for biological applications, have been characterized in various solvents including THF, ethanol, methanol, water and the highly polar protic ionic liquid 2-hydroxyethylammonium formate (2-OH-EAF) by combining results from time-correlated single-photon counting (TCSPC) and ultrafast pump-supercontinuum probe (PSCP) spectroscopy as well as steady-state absorption and fluorescence. In water, 2-OH-EAF and two fluorinated alcohols, there is a pronounced blue-shift and broadening of the S(0) → S(1) absorption band and also a larger Stokes shift than in the other solvents, indicating a particular influence of hydrogen-bonding interactions. S(1) lifetimes from TCSPC at 25 °C range from 3.3 ns to 5.6 ns. An unusual increase in the S(1) lifetime with temperature is observed for ethanol and methanol, however water behaves in the opposite way. The behavior can be tentatively explained by a solvent- and temperature-dependent "proximity effect", where coupling of the close-lying S(1) and S(2) states influences the intramolecular relaxation rate of the dye. In addition, temperature-dependent complex equilibria of ATTO 465 with solvent molecules may influence the measured lifetimes. Several excited-state absorption (ESA) transitions are identified in the PSCP spectra, which are in good agreement with the position of the UV bands in the steady-state absorption spectra. Small shifts of the stimulated emission and ESA bands are consistent with solvation dynamics in the excited electronic state. An additional ~16 ps component in water, visible over the entire spectral range, is tentatively ascribed to a fast IC channel which is accessed by a fraction of ATTO 465 molecules.

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

Dynamics of Functionalized Surface Molecular Monolayers Studied with Ultrafast Infrared Vibrational Spectroscopy

PubMed Central

Rosenfeld, Daniel E.; Nishida, Jun; Yan, Chang; Gengeliczki, Zsolt; Smith, Brian J.; Fayer, Michael D.

2012-01-01

The structural dynamics of thin films consisting of tricarbonyl (1,10-phenanthroline)rhenium chloride (RePhen(CO)3Cl) linked to an alkyl silane monolayer through a triazole linker synthesized on silica-on-calcium-fluoride substrates are investigated using ultrafast infrared (IR) techniques. Ultrafast 2D IR vibrational echo experiments and polarization selective heterodyne detected transient grating (HDTG) measurements, as well as polarization dependent FT-IR and AFM experiments are employed to study the samples. The vibrational echo experiments measure spectral diffusion, while the HDTG experiments measure the vibrational excited state population relaxation and investigate the vibrational transition dipole orientational anisotropy decay. To investigate the anticipated impact of vibrational excitation transfer, which can be caused by the high concentration of RePhen(CO)3Cl in the monolayer, a concentration dependence of the spectral diffusion is measured. To generate a range of concentrations, mixed monolayers consisting of both hydrogen terminated and triazole/RePhen(CO)3Cl terminated alkyl silanes are synthesized. It is found that the measured rate of spectral diffusion is independent of concentration, with all samples showing spectral diffusion of 37 ± 6 ps. To definitively test for vibrational excitation transfer, polarization selective HDTG experiments are conducted. Excitation transfer will cause anisotropy decay. Polarization resolved heterodyne detected transient grating spectroscopy is sensitive to anisotropy decay (depolarization) caused by excitation transfer and molecular reorientation. The HDTG experiments show no evidence of anisotropy decay on the appropriate time scale, demonstrating the absence of excitation transfer the RePhen(CO)3Cl. Therefore the influence of excitation transfer on spectral diffusion is inconsequential in these samples, and the vibrational echo measurements of spectral diffusion report solely on structural dynamics. A small amount of very fast (~2 ps time scale) anisotropy decay is observed. The decay is concentration independent, and is assigned to wobbling-in-a-cone orientational motions of the RePhen(CO)3Cl. Theoretical calculations reported previously for experiments on a single concentration of the same type of sample suggested the presence of some vibrational excitation transfer and excitation transfer induced spectral diffusion. Possible reasons for the experimentally observed lack of excitation transfer in these high concentration samples are discussed. PMID:23259027

Nonadiabatic Photo-Process Involving the πσ* State in Intramolecular Charge Transfer: a Concerted Spectroscopic and Computational Study 4-(DIMETHYLAMINO)BENZETHYNE and 4-(DIMETHYLAMINO)BENZONITRILE.

NASA Astrophysics Data System (ADS)

Fujiwara, Takashige; Segarra-Martí, Javier; Coto, Pedro B.

2014-06-01

The ubiquitous nature of the low-lying πσ* state in the photo-excited aromatic molecules or biomolecules is widely recognized to play an important role in nonadiabatic photo-process such as photodissociation or intramolecular charge transfer (ICT). For instance, the O--H elimination channel in phenol is attributed to the state-cross of the repulsive πσ* state that exhibits a conical intersection with the lowest bright ππ* state and with the ground state, leading to ultrafast electronic deactivation. A similar decay pathway has been found in the ICT formation of 4-(dialkylamino)benzonitriles in a polar environment, where an initially photoexcited Frank-Condon state bifurcates in the presence of a dark intermediate πσ* state that crosses the fluorescent ππ* state, followed by a conical intersection with the twisted intramolecular charge transfer (TICT) state. We proposed such a two-fold decay mechanism that πσ*-state highly mediates intramolecular charge transfer in 4-(dialkylamino)benzonitriles, which is supported from both our high-level ab initio calculations and ultrafast laser spectroscopies in the previous study. 4-(Dimethylamino)benzethyne (DMABE) is isoelectronic with 4-(dimethylamino)benzonitrile (DMABN), and the electronic structures and electronic spectra of the two molecules bear very close resemblance. However, DMABN does show the ICT formation in a polar environment, whereas DMABE does not. To probe the photophysical differences among the low-lying excited-state configurations, we performed concerted time-resolved laser spectroscopies and high level ab initio multireference perturbation theory quantum-chemical (CASPT2//CASSCF) computations on the two molecules. In this paper we demonstrate the importance of the bound excited-state of a πσ* configuration that induce highly πσ*-state mediated intramolecular charge transfer in 4-(dialkylamino)benzonitriles.

Ultrafast optical excitation of magnetic skyrmions

NASA Astrophysics Data System (ADS)

Ogawa, N.; Seki, S.; Tokura, Y.

2015-04-01

Magnetic skyrmions in an insulating chiral magnet Cu2OSeO3 were studied by all-optical spin wave spectroscopy. The spins in the conical and skyrmion phases were excited by the impulsive magnetic field from the inverse-Faraday effect, and resultant spin dynamics were detected by using time-resolved magneto-optics. Clear dispersions of the helimagnon were observed, which is accompanied by a distinct transition into the skyrmion phase, by sweeping temperature and magnetic field. In addition to the collective excitations of skyrmions, i.e., rotation and breathing modes, several spin precession modes were identified, which would be specific to optical excitation. The ultrafast, nonthermal, and local excitation of the spin systems by photons would lead to the efficient manipulation of nano-magnetic structures.

Concerted electron-proton transfer in the optical excitation of hydrogen-bonded dyes

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

Westlake, Brittany C.; Brennaman, Kyle M.; Concepcion, Javier J.

2011-05-24

The simultaneous, concerted transfer of electrons and protons—electron-proton transfer (EPT)—is an important mechanism utilized in chemistry and biology to avoid high energy intermediates. There are many examples of thermally activated EPT in ground-state reactions and in excited states following photoexcitation and thermal relaxation. Here we report application of ultrafast excitation with absorption and Raman monitoring to detect a photochemically driven EPT process (photo-EPT). In this process, both electrons and protons are transferred during the absorption of a photon. Photo-EPT is induced by intramolecular charge-transfer (ICT) excitation of hydrogen-bonded-base adducts with either a coumarin dye or 4-nitro-4'-biphenylphenol. Femtosecond transient absorption spectralmore » measurements following ICT excitation reveal the appearance of two spectroscopically distinct states having different dynamical signatures. One of these states corresponds to a conventional ICT excited state in which the transferring H⁺ is initially associated with the proton donor. Proton transfer to the base (B) then occurs on the picosecond time scale. The other state is an ICT-EPT photoproduct. Upon excitation it forms initially in the nuclear configuration of the ground state by application of the Franck–Condon principle. However, due to the change in electronic configuration induced by the transition, excitation is accompanied by proton transfer with the protonated base formed with a highly elongated ⁺H–B bond. Coherent Raman spectroscopy confirms the presence of a vibrational mode corresponding to the protonated base in the optically prepared state.« less

Concerted electron-proton transfer in the optical excitation of hydrogen-bonded dyes.

PubMed

Westlake, Brittany C; Brennaman, M Kyle; Concepcion, Javier J; Paul, Jared J; Bettis, Stephanie E; Hampton, Shaun D; Miller, Stephen A; Lebedeva, Natalia V; Forbes, Malcolm D E; Moran, Andrew M; Meyer, Thomas J; Papanikolas, John M

2011-05-24

The simultaneous, concerted transfer of electrons and protons--electron-proton transfer (EPT)--is an important mechanism utilized in chemistry and biology to avoid high energy intermediates. There are many examples of thermally activated EPT in ground-state reactions and in excited states following photoexcitation and thermal relaxation. Here we report application of ultrafast excitation with absorption and Raman monitoring to detect a photochemically driven EPT process (photo-EPT). In this process, both electrons and protons are transferred during the absorption of a photon. Photo-EPT is induced by intramolecular charge-transfer (ICT) excitation of hydrogen-bonded-base adducts with either a coumarin dye or 4-nitro-4'-biphenylphenol. Femtosecond transient absorption spectral measurements following ICT excitation reveal the appearance of two spectroscopically distinct states having different dynamical signatures. One of these states corresponds to a conventional ICT excited state in which the transferring H(+) is initially associated with the proton donor. Proton transfer to the base (B) then occurs on the picosecond time scale. The other state is an ICT-EPT photoproduct. Upon excitation it forms initially in the nuclear configuration of the ground state by application of the Franck-Condon principle. However, due to the change in electronic configuration induced by the transition, excitation is accompanied by proton transfer with the protonated base formed with a highly elongated (+)H ─ B bond. Coherent Raman spectroscopy confirms the presence of a vibrational mode corresponding to the protonated base in the optically prepared state.

How to manipulate magnetic states of antiferromagnets

NASA Astrophysics Data System (ADS)

Song, Cheng; You, Yunfeng; Chen, Xianzhe; Zhou, Xiaofeng; Wang, Yuyan; Pan, Feng

2018-03-01

Antiferromagnetic materials, which have drawn considerable attention recently, have fascinating features: they are robust against perturbation, produce no stray fields, and exhibit ultrafast dynamics. Discerning how to efficiently manipulate the magnetic state of an antiferromagnet is key to the development of antiferromagnetic spintronics. In this review, we introduce four main methods (magnetic, strain, electrical, and optical) to mediate the magnetic states and elaborate on intrinsic origins of different antiferromagnetic materials. Magnetic control includes a strong magnetic field, exchange bias, and field cooling, which are traditional and basic. Strain control involves the magnetic anisotropy effect or metamagnetic transition. Electrical control can be divided into two parts, electric field and electric current, both of which are convenient for practical applications. Optical control includes thermal and electronic excitation, an inertia-driven mechanism, and terahertz laser control, with the potential for ultrafast antiferromagnetic manipulation. This review sheds light on effective usage of antiferromagnets and provides a new perspective on antiferromagnetic spintronics.

Controlling competing orders via nonequilibrium acoustic phonons: Emergence of anisotropic effective electronic temperature

NASA Astrophysics Data System (ADS)

Schütt, Michael; Orth, Peter P.; Levchenko, Alex; Fernandes, Rafael M.

2018-01-01

Ultrafast perturbations offer a unique tool to manipulate correlated systems due to their ability to promote transient behaviors with no equilibrium counterpart. A widely employed strategy is the excitation of coherent optical phonons, as they can cause significant changes in the electronic structure and interactions on short time scales. One of the issues, however, is the inevitable heating that accompanies these resonant excitations. Here, we explore a promising alternative route: the nonequilibrium excitation of acoustic phonons, which, due to their low excitation energies, generally lead to less heating. We demonstrate that driving acoustic phonons leads to the remarkable phenomenon of a momentum-dependent effective temperature, by which electronic states at different regions of the Fermi surface are subject to distinct local temperatures. Such an anisotropic effective electronic temperature can have a profound effect on the delicate balance between competing ordered states in unconventional superconductors, opening a so far unexplored avenue to control correlated phases.

Imaging Molecular Motion: Femtosecond X-Ray Scattering of an Electrocyclic Chemical Reaction

NASA Astrophysics Data System (ADS)

Minitti, M. P.; Budarz, J. M.; Kirrander, A.; Robinson, J. S.; Ratner, D.; Lane, T. J.; Zhu, D.; Glownia, J. M.; Kozina, M.; Lemke, H. T.; Sikorski, M.; Feng, Y.; Nelson, S.; Saita, K.; Stankus, B.; Northey, T.; Hastings, J. B.; Weber, P. M.

2015-06-01

Structural rearrangements within single molecules occur on ultrafast time scales. Many aspects of molecular dynamics, such as the energy flow through excited states, have been studied using spectroscopic techniques, yet the goal to watch molecules evolve their geometrical structure in real time remains challenging. By mapping nuclear motions using femtosecond x-ray pulses, we have created real-space representations of the evolving dynamics during a well-known chemical reaction and show a series of time-sorted structural snapshots produced by ultrafast time-resolved hard x-ray scattering. A computational analysis optimally matches the series of scattering patterns produced by the x rays to a multitude of potential reaction paths. In so doing, we have made a critical step toward the goal of viewing chemical reactions on femtosecond time scales, opening a new direction in studies of ultrafast chemical reactions in the gas phase.

Imaging Molecular Motion: Femtosecond X-Ray Scattering of an Electrocyclic Chemical Reaction.

PubMed

Minitti, M P; Budarz, J M; Kirrander, A; Robinson, J S; Ratner, D; Lane, T J; Zhu, D; Glownia, J M; Kozina, M; Lemke, H T; Sikorski, M; Feng, Y; Nelson, S; Saita, K; Stankus, B; Northey, T; Hastings, J B; Weber, P M

2015-06-26

Structural rearrangements within single molecules occur on ultrafast time scales. Many aspects of molecular dynamics, such as the energy flow through excited states, have been studied using spectroscopic techniques, yet the goal to watch molecules evolve their geometrical structure in real time remains challenging. By mapping nuclear motions using femtosecond x-ray pulses, we have created real-space representations of the evolving dynamics during a well-known chemical reaction and show a series of time-sorted structural snapshots produced by ultrafast time-resolved hard x-ray scattering. A computational analysis optimally matches the series of scattering patterns produced by the x rays to a multitude of potential reaction paths. In so doing, we have made a critical step toward the goal of viewing chemical reactions on femtosecond time scales, opening a new direction in studies of ultrafast chemical reactions in the gas phase.

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.

Early events associated with the excited state proton transfer in 2-(2{sup '}-pyridyl)benzimidazole

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

Burai, Tarak Nath; Mukherjee, Tushar Kanti; Lahiri, Priyanka

2009-07-21

2-(2{sup '}-pyridyl)benzimidazole (2PBI) undergoes excited state proton transfer (ESPT) in acidic solutions, leading to a tautomer emission at 460 nm. This photoprocess has been studied using ultrafast fluorescence spectroscopic techniques in acidic neat aqueous solutions, in viscous mixtures of glycerol with water, as well as in sucrose solutions. The tautomer is found to be stabilized in the more viscous medium, leading to a greater relative quantum yield as well as lifetime. The long rise time in tautomer emission is not affected by viscosity though. Rather, it appears to have the same value as the long component of the decay ofmore » the cationic excited state (C*). In addition to the subnanosecond lifetime reported earlier, C* is found to exhibit a decay time of 2 ps. This is assigned to its protonation to form the nonfluorescent dication in its excited state (D*) considering the ground and excited state pK{sub a} values reported earlier. An additional rising component of 100 ps is observed in the region of C* emission. This is likely to arise from a structural change or charge redistribution in C* immediately after its creation and before the phototautomerization.« less

UV excitation of single DNA and RNA strands produces high yields of exciplex states between two stacked bases

PubMed Central

Takaya, Tomohisa; Su, Charlene; de La Harpe, Kimberly; Crespo-Hernández, Carlos E.; Kohler, Bern

2008-01-01

Excited electronic states created by UV excitation of the diribonucleoside monophosphates ApA, ApG, ApC, ApU, and CpG were studied by the femtosecond transient-absorption technique. Bleach recovery signals recorded at 252 nm show that long-lived excited states are formed in all five dinucleosides. The lifetimes of these states exceed those measured in equimolar mixtures of the constituent mononucleotides by one to two orders of magnitude, indicating that electronic coupling between proximal nucleobases dramatically slows the relaxation of excess electronic energy. The decay rates of the long-lived states decrease with increasing energy of the charge-transfer state produced by transferring an electron from one base to another. The charge-transfer character of the long-lived states revealed by this analysis supports their assignment to excimer or exciplex states. Identical bleach recovery signals were seen for ApA, (A)4, and poly(A) at delay times >10 ps after photoexcitation. This indicates that excited states localized on a stack of just two bases are the common trap states independent of the number of stacked nucleotides. The fraction of initial excitations that decay to long-lived exciplex states is approximately equal to the fraction of stacked bases determined by NMR measurements. This supports a model in which excitations associated with two stacked bases decay to exciplex states, whereas excitations in unstacked bases decay via ultrafast internal conversion. These results establish the importance of charge transfer-quenching pathways for UV-irradiated RNA and DNA in room-temperature solution. PMID:18647840

UV excitation of single DNA and RNA strands produces high yields of exciplex states between two stacked bases.

PubMed

Takaya, Tomohisa; Su, Charlene; de La Harpe, Kimberly; Crespo-Hernández, Carlos E; Kohler, Bern

2008-07-29

Excited electronic states created by UV excitation of the diribonucleoside monophosphates ApA, ApG, ApC, ApU, and CpG were studied by the femtosecond transient-absorption technique. Bleach recovery signals recorded at 252 nm show that long-lived excited states are formed in all five dinucleosides. The lifetimes of these states exceed those measured in equimolar mixtures of the constituent mononucleotides by one to two orders of magnitude, indicating that electronic coupling between proximal nucleobases dramatically slows the relaxation of excess electronic energy. The decay rates of the long-lived states decrease with increasing energy of the charge-transfer state produced by transferring an electron from one base to another. The charge-transfer character of the long-lived states revealed by this analysis supports their assignment to excimer or exciplex states. Identical bleach recovery signals were seen for ApA, (A)(4), and poly(A) at delay times >10 ps after photoexcitation. This indicates that excited states localized on a stack of just two bases are the common trap states independent of the number of stacked nucleotides. The fraction of initial excitations that decay to long-lived exciplex states is approximately equal to the fraction of stacked bases determined by NMR measurements. This supports a model in which excitations associated with two stacked bases decay to exciplex states, whereas excitations in unstacked bases decay via ultrafast internal conversion. These results establish the importance of charge transfer-quenching pathways for UV-irradiated RNA and DNA in room-temperature solution.

Dewar Lesion Formation in Single- and Double-Stranded DNA is Quenched by Neighboring Bases.

PubMed

Bucher, Dominik B; Pilles, Bert M; Carell, Thomas; Zinth, Wolfgang

2015-07-16

UV-induced Dewar lesion formation is investigated in single- and double-stranded oligonucleotides with ultrafast vibrational spectroscopy. The quantum yield for the conversion of the (6-4) lesion to the Dewar isomer in DNA strands is reduced by a factor of 4 in comparison to model dinucleotides. Time resolved spectroscopy reveals a fast process in the excited state with spectral characteristics of bases which are adjacent to the excited (6-4) lesion. These kinetic components have large amplitudes and indicate that an additional quenching channel acts in the stranded DNA systems and reduces the Dewar formation yield. Presumably relaxation evolves via a charge transfer to the neighboring guanine and the paired cytosine participates in a double-stranded oligomer. Changes in the decay of the relaxed excited electronic state of the (6-4) chromophore point to modifications in the excited state energy landscape which may lead to an additional reduction of the Dewar formation yield.

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

NASA Astrophysics Data System (ADS)

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

2009-11-01

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

Toroidal high-spin isomers in the nucleus 304120

NASA Astrophysics Data System (ADS)

Staszczak, A.; Wong, Cheuk-Yin; Kosior, A.

2017-05-01

Background: Strongly deformed oblate superheavy nuclei form an intriguing region where the toroidal nuclear structures may bifurcate from the oblate spheroidal shape. The bifurcation may be facilitated when the nucleus is endowed with a large angular moment about the symmetry axis with I =Iz . The toroidal high-K isomeric states at their local energy minima can be theoretically predicted using the cranked self-consistent Skyrme-Hartree-Fock method. Purpose: We use the cranked Skyrme-Hartree-Fock method to predict the properties of the toroidal high-spin isomers in the superheavy nucleus 120304184. Method: Our method consists of three steps: First, we use the deformation-constrained Skyrme-Hartree-Fock-Bogoliubov approach to search for the nuclear density distributions with toroidal shapes. Next, using these toroidal distributions as starting configurations, we apply an additional cranking constraint of a large angular momentum I =Iz about the symmetry z axis and search for the energy minima of the system as a function of the deformation. In the last step, if a local energy minimum with I =Iz is found, we perform at this point the cranked symmetry- and deformation-unconstrained Skyrme-Hartree-Fock calculations to locate a stable toroidal high-spin isomeric state in free convergence. Results: We have theoretically located two toroidal high-spin isomeric states of 120304184 with an angular momentum I =Iz=81 ℏ (proton 2p-2h, neutron 4p-4h excitation) and I =Iz=208 ℏ (proton 5p-5h, neutron 8p-8h) at the quadrupole moment deformations Q20=-297.7 b and Q20=-300.8 b with energies 79.2 and 101.6 MeV above the spherical ground state, respectively. The nuclear density distributions of the toroidal high-spin isomers 120304184(Iz=81 ℏ and 208 ℏ ) have the maximum density close to the nuclear matter density, 0.16 fm-3, and a torus major to minor radius aspect ratio R /d =3.25 . Conclusions: We demonstrate that aligned angular momenta of Iz=81 ℏ and 208 ℏ arising from multiparticle-multihole excitations in the toroidal system of 120304184 can lead to high-spin isomeric states, even though the toroidal shape of 120304184 without spin is unstable. Toroidal energy minima without spin may be possible for superheavy nuclei with higher atomic numbers, Z ≳122 , as reported previously [7 A. Staszczak and C. Y. Wong, Acta Phys. Pol. B 40, 753 (2008)].

Toroidal high-spin isomers in the nucleus 120 304

DOE PAGES

Staszczak, A.; Wong, Cheuk-Yin; Kosior, A.

2017-05-22

Strongly deformed oblate superheavy nuclei form an intriguing region where the toroidal nuclear structures may bifurcate from the oblate spheroidal shape. The bifurcation may be facilitated when the nucleus is endowed with a large angular moment about the symmetry axis withmore » $$I=I_{z}$$. The toroidal high-$K$ isomeric states at their local energy minima can be theoretically predicted using the cranked self-consistent Skyrme-Hartree-Fock method. We use the cranked Skyrme-Hartree-Fock method to predict the properties of the toroidal high-spin isomers in the superheavy nucleus $$^{304}{120}_{184}$$. This method consists of three steps: first, we use the deformation-constrained Skyrme-Hartree-Fock-Bogoliubov approach to search for the nuclear density distributions with toroidal shapes. Next, using these toroidal distributions as starting configurations we apply an additional cranking constraint of a large angular momentum $$I=I_{z}$$ about the symmetry $z$-axis and search for the energy minima of the system as a function of the deformation. In the last step, if a local energy minimum with $$I=I_{z}$$ is found, we perform at this point the cranked symmetry- and deformation-unconstrained Skyrme-Hartree-Fock calculations to locate a stable toroidal high-spin isomeric state in free convergence. Furthemore, we have theoretically located two toroidal high-spin isomeric states of $$^{304}{120}_{184}$$ with an angular momentum $I$=$$I_z$$=81$$\\hbar$$ (proton 2p-2h, neutron 4p-4h excitation) and $I$=$$I_z$$=208$$\\hbar$$ (proton 5p-5h, neutron 8p-8h) at the quadrupole moment deformations $$Q_{20}=-297.7$$~b and $$Q_{20}=-300.8$$~b with energies 79.2 MeV and 101.6 MeV above the spherical ground state, respectively. The nuclear density distributions of the toroidal high-spin isomers $$^{304}{120}_{184}(I_z$$=81$$\\hbar$$ and 208$$\\hbar$$) have the maximum density close to the nuclear matter density, 0.16 fm$$^{-3}$$, and a torus major to minor radius aspect ratio $R/d=3.25$. Here, we demonstrate that aligned angular momenta of $$I_z$$=81$$\\hbar$$ and 208$$\\hbar$$ arising from multi-particle-multi-hole excitations in the toroidal system of $$^{304}{120}_{184}$$ can lead to high-spin isomeric states, even though the toroidal shape of $$^{304}120_{184}$$ without spin is unstable. Toroidal energy minima without spin may be possible for superheavy nuclei with higher atomic numbers, $$Z\\gtrsim$$122, as reported previously [A. Staszczak and C. Y. Wong,Acta Phys. Pol. B 40 , 753 (2008)].« less

Intermolecular electron transfer from intramolecular excitation and coherent acoustic phonon generation in a hydrogen-bonded charge-transfer solid

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

Rury, Aaron S., E-mail: arury@usc.edu; Sorenson, Shayne; Dawlaty, Jahan M.

2016-03-14

Organic materials that produce coherent lattice phonon excitations in response to external stimuli may provide next generation solutions in a wide range of applications. However, for these materials to lead to functional devices in technology, a full understanding of the possible driving forces of coherent lattice phonon generation must be attained. To facilitate the achievement of this goal, we have undertaken an optical spectroscopic study of an organic charge-transfer material formed from the ubiquitous reduction-oxidation pair hydroquinone and p-benzoquinone. Upon pumping this material, known as quinhydrone, on its intermolecular charge transfer resonance as well as an intramolecular resonance of p-benzoquinone,more » we find sub-cm{sup −1} oscillations whose dispersion with probe energy resembles that of a coherent acoustic phonon that we argue is coherently excited following changes in the electron density of quinhydrone. Using the dynamical information from these ultrafast pump-probe measurements, we find that the fastest process we can resolve does not change whether we pump quinhydrone at either energy. Electron-phonon coupling from both ultrafast coherent vibrational and steady-state resonance Raman spectroscopies allows us to determine that intramolecular electronic excitation of p-benzoquinone also drives the electron transfer process in quinhydrone. These results demonstrate the wide range of electronic excitations of the parent of molecules found in many functional organic materials that can drive coherent lattice phonon excitations useful for applications in electronics, photonics, and information technology.« less

Intermolecular electron transfer from intramolecular excitation and coherent acoustic phonon generation in a hydrogen-bonded charge-transfer solid

NASA Astrophysics Data System (ADS)

Rury, Aaron S.; Sorenson, Shayne; Dawlaty, Jahan M.

2016-03-01

Organic materials that produce coherent lattice phonon excitations in response to external stimuli may provide next generation solutions in a wide range of applications. However, for these materials to lead to functional devices in technology, a full understanding of the possible driving forces of coherent lattice phonon generation must be attained. To facilitate the achievement of this goal, we have undertaken an optical spectroscopic study of an organic charge-transfer material formed from the ubiquitous reduction-oxidation pair hydroquinone and p-benzoquinone. Upon pumping this material, known as quinhydrone, on its intermolecular charge transfer resonance as well as an intramolecular resonance of p-benzoquinone, we find sub-cm-1 oscillations whose dispersion with probe energy resembles that of a coherent acoustic phonon that we argue is coherently excited following changes in the electron density of quinhydrone. Using the dynamical information from these ultrafast pump-probe measurements, we find that the fastest process we can resolve does not change whether we pump quinhydrone at either energy. Electron-phonon coupling from both ultrafast coherent vibrational and steady-state resonance Raman spectroscopies allows us to determine that intramolecular electronic excitation of p-benzoquinone also drives the electron transfer process in quinhydrone. These results demonstrate the wide range of electronic excitations of the parent of molecules found in many functional organic materials that can drive coherent lattice phonon excitations useful for applications in electronics, photonics, and information technology.

Photophysics of Zinc Porphyrin Aggregates in Dilute Water-Ethanol Solutions.

PubMed

Stevens, Amy L; Joshi, Neeraj K; Paige, Matthew F; Steer, Ronald P

2017-12-14

Dimeric and multimeric aggregates of a model metalloporphyrin, zinc tetraphenylporphyrin (ZnTPP), have been produced in a controlled manner by incrementally increasing the water content of dilute aqueous ethanol solutions. Steady state absorption, fluorescence emission, and fluorescence excitation spectra have been measured to identify the aggregates present as a function of solvent composition. The dynamics of the excited states of the aggregates produced initially by excitation in the Soret region have been measured by ultrafast fluorescence upconversion techniques. Only the monomer produces measurable emission from S 2 with a picosecond lifetime; all Soret-excited aggregates, including the dimer, decay radiationlessly on a femtosecond time scale. The S 1 state is the only significant product of the radiationless decay of the S 2 state of the excited monomer, and the aggregates also produce substantial quantum yields of S 1 fluorescence when initially excited in the Soret region. The resulting fluorescent aggregates all decay on a subnanosecond time scale, likely by a mechanism that involves dissociation of the excited monomer from the excitonic multimer. The ZnTPP dimers excited at their ground state geometries in the Soret region exhibit a dynamic behavior that is quite different from those produced following noncoherent triplet-triplet annihilation under the same conditions. The important implications of these observations in determining the aggregation conditions promoting efficient photon upconversion by excitonic annihilation in a variety of media are thoroughly discussed.

New information on medium-spin structure of {sup 133}Sb

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

Urban, W.; Faculty of Physics, University of Warsaw, ul. Hoza 69, PL-00-681 Warsaw; Zlomaniec, A.

2009-03-15

Excited states in the nucleus {sup 133}Sb, populated in the fission of {sup 235}U induced by thermal neutrons were studied using the Lohengrin fission-fragment separator. A new 4191.8 keV level in {sup 133}Sb, populated in the decay of the 16.6 {mu}s isomer, was observed. The level is interpreted as the 11/2{sup +} member of the {pi}g{sub 7/2} x core configuration, predicted by the shell model at 4095 keV. Levels corresponding to octupole excitation of the {sup 132}Sn core, identified previously in prompt-{gamma} measurement, were now observed in the isomeric decay.

Spectroscopy of Isolated Prebiotic Nucleobases

NASA Technical Reports Server (NTRS)

Svadlenak, Nathan; Callahan, Michael P.; Ligare, Marshall; Gulian, Lisa; Gengeliczki, Zsolt; Nachtigallova, Dana; Hobza, Pavel; deVries, Mattanjah

2011-01-01

We use multiphoton ionization and double resonance spectroscopy to study the excited state dynamics of biologically relevant molecules as well as prebiotic nucleobases, isolated in the gas phase. Molecules that are biologically relevant to life today tend to exhibit short excited state lifetimes compared to similar but non-biologically relevant analogs. The mechanism is internal conversion, which may help protect the biologically active molecules from UV damage. This process is governed by conical intersections that depend very strongly on molecular structure. Therefore we have studied purines and pyrimidines with systematic variations of structure, including substitutions, tautomeric forms, and cluster structures that represent different base pair binding motifs. These structural variations also include possible alternate base pairs that may shed light on prebiotic chemistry. With this in mind we have begun to probe the ultrafast dynamics of molecules that exhibit very short excited states and search for evidence of internal conversions.

Singlet-to-triplet intermediates and triplet exciton dynamics in pentacene thinfilms

NASA Astrophysics Data System (ADS)

Thorsmolle, Verner; Korber, Michael; Obergfell, Emanuel; Kuhlman, Thomas; Campbell, Ian; Crone, Brian; Taylor, Antoinette; Averitt, Richard; Demsar, Jure

Singlet-to-triplet fission in organic semiconductors is a spin-conserving multiexciton process in which one spin-zero singlet excitation is converted into two spin-one triplet excitations on an ultrafast timescale. Current scientific interest into this carrier multiplication process is largely driven by prospects of enhancing the efficiency in photovoltaic applications by generating two long-lived triplet excitons by one photon. The fission process is known to involve intermediate states, known as correlated triplet pairs, with an overall singlet character, before being interchanged into uncorrelated triplets. Here we use broadband femtosecond real-time spectroscopy to study the excited state dynamics in pentacene thin films, elucidating the fission process and the role of intermediate triplet states. VKT and AJT acknowledge support by the LDRD program at Los Alamos National Laboratory and the Department of Energy, Grant No. DE-FG02-04ER118. MK, MO and JD acknowledge support by the Alexander von Humboldt Foundation.

Ab Initio Multiple Spawning Photochemical Dynamics of DMABN Using GPUs

DOE PAGES

Curchod, Basile F. E.; Sisto, Aaron; Martinez, Todd J.

2016-12-15

The ultrafast decay dynamics of 4-( N,N-dimethylamino)benzonitrile (DMABN) following photoexcitation was studied with the ab initio multiple spawning (AIMS) method, combined with GPU-accelerated linear-response time-dependent density functional theory (LR-TDDFT). We validate the LR-TDDFT method for this case and then present a detailed analysis of the first ≈200 fs of DMABN excited-state dynamics. Almost complete nonadiabatic population transfer from S 2 (the initially populated bright state) to S 1 takes place in less than 50 fs, without significant torsion of the dimethylamino (DMA) group. Significant torsion of the DMA group is only observed after the nuclear wavepacket reaches S 1 andmore » acquires locally excited electronic character. Here, our results show that torsion of the DMA group is not prerequisite for nonadiabatic transitions in DMABN, although such motion is indeed relevant on the lowest excited state (S 1).« less

Emerging Low-Dimensional Materials for Nonlinear Optics and Ultrafast Photonics.

PubMed

Liu, Xiaofeng; Guo, Qiangbing; Qiu, Jianrong

2017-04-01

Low-dimensional (LD) materials demonstrate intriguing optical properties, which lead to applications in diverse fields, such as photonics, biomedicine and energy. Due to modulation of electronic structure by the reduced structural dimensionality, LD versions of metal, semiconductor and topological insulators (TIs) at the same time bear distinct nonlinear optical (NLO) properties as compared with their bulk counterparts. Their interaction with short pulse laser excitation exhibits a strong nonlinear character manifested by NLO absorption, giving rise to optical limiting or saturated absorption associated with excited state absorption and Pauli blocking in different materials. In particular, the saturable absorption of these emerging LD materials including two-dimensional semiconductors as well as colloidal TI nanoparticles has recently been utilized for Q-switching and mode-locking ultra-short pulse generation across the visible, near infrared and middle infrared wavelength regions. Beside the large operation bandwidth, these ultrafast photonics applications are especially benefit from the high recovery rate as well as the facile processibility of these LD materials. The prominent NLO response of these LD materials have also provided new avenues for the development of novel NLO and photonics devices for all-optical control as well as optical circuits beyond ultrafast lasers. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

Jay, Raphael M.; Norell, Jesper; Eckert, Sebastian

Soft X-ray spectroscopies are ideal probes of the local valence electronic structure of photocatalytically active metal sites. Here, we apply the selectivity of time-resolved resonant inelastic X-ray scattering at the iron L-edge to the transient charge distribution of an optically excited charge-transfer state in aqueous ferricyanide. Through comparison to steady-state spectra and quantum chemical calculations, the coupled effects of valence-shell closing and ligand-hole creation are experimentally and theoretically disentangled and described in terms of orbital occupancy, metal–ligand covalency, and ligand field splitting, thereby extending established steady-state concepts to the excited-state domain. π-Back-donation is found to be mainly determined by themore » metal site occupation, whereas the ligand hole instead influences σ-donation. Here, our results demonstrate how ultrafast resonant inelastic X-ray scattering can help characterize local charge distributions around catalytic metal centers in short-lived charge-transfer excited states, as a step toward future rationalization and tailoring of photocatalytic capabilities of transition-metal complexes.« less

Two-color vibrational, femtosecond, fully resonant electronically enhanced CARS (FREE-CARS) of gas-phase nitric oxide.

PubMed

Stauffer, Hans U; Roy, Sukesh; Schmidt, Jacob B; Wrzesinski, Paul J; Gord, James R

2016-09-28

A resonantly enhanced, two-color, femtosecond time-resolved coherent anti-Stokes Raman scattering (CARS) approach is demonstrated and used to explore the nature of the frequency- and time-dependent signals produced by gas-phase nitric oxide (NO). Through careful selection of the input pulse wavelengths, this fully resonant electronically enhanced CARS (FREE-CARS) scheme allows rovibronic-state-resolved observation of time-dependent rovibrational wavepackets propagating on the vibrationally excited ground-state potential energy surface of this diatomic species. Despite the use of broadband, ultrafast time-resolved input pulses, high spectral resolution of gas-phase rovibronic transitions is observed in the FREE-CARS signal, dictated by the electronic dephasing timescales of these states. Analysis and computational simulation of the time-dependent spectra observed as a function of pump-Stokes and Stokes-probe delays provide insight into the rotationally resolved wavepacket motion observed on the excited-state and vibrationally excited ground-state potential energy surfaces of NO, respectively.

Theory of spin and lattice wave dynamics excited by focused laser pulses

NASA Astrophysics Data System (ADS)

Shen, Ka; Bauer, Gerrit E. W.

2018-06-01

We develop a theory of spin wave dynamics excited by ultrafast focused laser pulses in a magnetic film. We take into account both the volume and surface spin wave modes in the presence of applied, dipolar and magnetic anisotropy fields and include the dependence on laser spot exposure size and magnetic damping. We show that the sound waves generated by local heating by an ultrafast focused laser pulse can excite a wide spectrum of spin waves (on top of a dominant magnon–phonon contribution). Good agreement with recent experiments supports the validity of the model.

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.

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.

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 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. Electronic supplementary information (ESI) available: The pump dependent transient absorption spectra and the corresponding global analysis results. See DOI: 10.1039/c6nr01008c

Ultrafast energy- and momentum-resolved dynamics of magnetic correlations in the photo-doped Mott insulator Sr 2IrO 4

DOE PAGES

Dean, M. P. M.; Cao, Y.; Liu, X.; ...

2016-05-09

Measuring how the magnetic correlations evolve in doped Mott insulators has greatly improved our understanding of the pseudogap, non-Fermi liquids and high-temperature superconductivity 1, 2, 3, 4. Recently, photo-excitation has been used to induce similarly exotic states transiently 5, 6, 7. However, the lack of available probes of magnetic correlations in the time domain hinders our understanding of these photo-induced states and how they could be controlled. Here, we implement magnetic resonant inelastic X-ray scattering at a free-electron laser to directly determine the magnetic dynamics after photo-doping the Mott insulator Sr 2IrO 4. We find that the non-equilibrium state, 2more » ps after the excitation, exhibits strongly suppressed long-range magnetic order, but hosts photo-carriers that induce strong, non-thermal magnetic correlations. These two-dimensional (2D) in-plane Néel correlations recover within a few picoseconds, whereas the three-dimensional (3D) long-range magnetic order restores on a fluence-dependent timescale of a few hundred picoseconds. In conclusion, the marked difference in these two timescales implies that the dimensionality of magnetic correlations is vital for our understanding of ultrafast magnetic dynamics.« less

Ultrafast excited-state dynamics of RNA and DNA C tracts

NASA Astrophysics Data System (ADS)

Cohen, Boiko; Larson, Matthew H.; Kohler, Bern

2008-06-01

The excited-state dynamics of the RNA homopolymer of cytosine and of the 18-mer (dC) 18 were studied by steady-state and time-resolved absorption and emission spectroscopy. At pH 6.8, excitation of poly(rC) by a femtosecond UV pump pulse produces excited states that decay up to one order of magnitude more slowly than the excited states formed in the mononucleotide cytidine 5'-monophosphate under the same conditions. Even slower relaxation is observed for the hemiprotonated, self-associated form of poly(rC), which is stable at acidic pH. Transient absorption and time-resolved fluorescence signals for (dC) 18 at pH 6.8 are similar to ones observed for poly(rC) near pH 4, indicating that hemiprotonated structures are found in DNA C tracts at neutral pH. In both systems, there is evidence for two kinds of emitting states with lifetimes of ˜100 ps and slightly more than 1 ns. The former states are responsible for the bulk of emission from the hemiprotonated structures. Evidence suggests that slow electronic relaxation in these self-complexes is the result of vertical base stacking. The similar signals from RNA and DNA C tracts suggest a common base-stacked structure, which may be identical with that of i-motif DNA.

Spin-orbit torque-driven skyrmion dynamics revealed by time-resolved X-ray microscopy

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

Woo, Seonghoon; Song, Kyung Mee; Han, Hee-Sung

Magnetic skyrmions are topologically protected spin textures with attractive properties suitable for high-density and low-power spintronic device applications. Much effort has been dedicated to understanding the dynamical behaviours of the magnetic skyrmions. However, experimental observation of the ultrafast dynamics of this chiral magnetic texture in real space, which is the hallmark of its quasiparticle nature, has so far remained elusive. Here, we report nanosecond-dynamics of a 100nm-diameter magnetic skyrmion during a current pulse application, using a time-resolved pump-probe soft X-ray imaging technique. We demonstrate that distinct dynamic excitation states of magnetic skyrmions, triggered by current-induced spin-orbit torques, can be reliablymore » tuned by changing the magnitude of spin-orbit torques. Our findings show that the dynamics of magnetic skyrmions can be controlled by the spin-orbit torque on the nanosecond time scale, which points to exciting opportunities for ultrafast and novel skyrmionic appl ications in the future.« less

Direct observation of multistep energy transfer in LHCII with fifth-order 3D electronic spectroscopy.

PubMed

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

2015-07-31

During photosynthesis, sunlight is efficiently captured by light-harvesting complexes, and the excitation energy is then funneled towards the reaction centre. These photosynthetic excitation energy transfer (EET) pathways are complex and proceed in a multistep fashion. Ultrafast two-dimensional electronic spectroscopy (2DES) is an important tool to study EET processes in photosynthetic complexes. However, the multistep EET processes can only be indirectly inferred by correlating different cross peaks from a series of 2DES spectra. Here we directly observe multistep EET processes in LHCII using ultrafast fifth-order three-dimensional electronic spectroscopy (3DES). We measure cross peaks in 3DES spectra of LHCII that directly indicate energy transfer from excitons in the chlorophyll b (Chl b) manifold to the low-energy level chlorophyll a (Chl a) via mid-level Chl a energy states. This new spectroscopic technique allows scientists to move a step towards mapping the complete complex EET processes in photosynthetic systems.

Spin-orbit torque-driven skyrmion dynamics revealed by time-resolved X-ray microscopy

DOE PAGES

Woo, Seonghoon; Song, Kyung Mee; Han, Hee-Sung; ...

2017-05-24

Magnetic skyrmions are topologically protected spin textures with attractive properties suitable for high-density and low-power spintronic device applications. Much effort has been dedicated to understanding the dynamical behaviours of the magnetic skyrmions. However, experimental observation of the ultrafast dynamics of this chiral magnetic texture in real space, which is the hallmark of its quasiparticle nature, has so far remained elusive. Here, we report nanosecond-dynamics of a 100nm-diameter magnetic skyrmion during a current pulse application, using a time-resolved pump-probe soft X-ray imaging technique. We demonstrate that distinct dynamic excitation states of magnetic skyrmions, triggered by current-induced spin-orbit torques, can be reliablymore » tuned by changing the magnitude of spin-orbit torques. Our findings show that the dynamics of magnetic skyrmions can be controlled by the spin-orbit torque on the nanosecond time scale, which points to exciting opportunities for ultrafast and novel skyrmionic appl ications in the future.« less

The Ultrafast Wolff Rearrangement in the Gas Phase

NASA Astrophysics Data System (ADS)

Steinbacher, Andreas; Roeding, Sebastian; Brixner, Tobias; Nuernberger, Patrick

The Wolff rearrangement of gas-phase 5-diazo Meldrum's acid is disclosed with femtosecond ion spectroscopy. Distinct differences are found for 267 nm and 200 nm excitation, the latter leading to even two ultrafast rearrangement reactions.

Selective excitation enables assignment of proton resonances and {sup 1}H-{sup 1}H distance measurement in ultrafast magic angle spinning solid state NMR spectroscopy

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

Zhang, Rongchun; Ramamoorthy, Ayyalusamy, E-mail: ramamoor@umich.edu

2015-07-21

Remarkable developments in ultrafast magic angle spinning (MAS) solid-state NMR spectroscopy enabled proton-based high-resolution multidimensional experiments on solids. To fully utilize the benefits rendered by proton-based ultrafast MAS experiments, assignment of {sup 1}H resonances becomes absolutely necessary. Herein, we propose an approach to identify different proton peaks by using dipolar-coupled heteronuclei such as {sup 13}C or {sup 15}N. In this method, after the initial preparation of proton magnetization and cross-polarization to {sup 13}C nuclei, transverse magnetization of desired {sup 13}C nuclei is selectively prepared by using DANTE (Delays Alternating with Nutations for Tailored Excitation) sequence and then, it is transferredmore » to bonded protons with a short-contact-time cross polarization. Our experimental results demonstrate that protons bonded to specific {sup 13}C atoms can be identified and overlapping proton peaks can also be assigned. In contrast to the regular 2D HETCOR experiment, only a few 1D experiments are required for the complete assignment of peaks in the proton spectrum. Furthermore, the finite-pulse radio frequency driven recoupling sequence could be incorporated right after the selection of specific proton signals to monitor the intensity buildup for other proton signals. This enables the extraction of {sup 1}H-{sup 1}H distances between different pairs of protons. Therefore, we believe that the proposed method will greatly aid in fast assignment of peaks in proton spectra and will be useful in the development of proton-based multi-dimensional solid-state NMR experiments to study atomic-level resolution structure and dynamics of solids.« less

Double Molecular Photoswitch Driven by Light and Collisions

NASA Astrophysics Data System (ADS)

Bull, James N.; Scholz, Michael S.; Carrascosa, Eduardo; da Silva, Gabriel; Bieske, Evan J.

2018-06-01

The shapes of many molecules can be transformed by light or heat. Here we investigate collision- and photon-induced interconversions of E E , E Z , and Z Z isomers of the isolated Congo red (CR) dianion, a double molecular switch containing two - N ═ N - azo groups, each of which can have the E or Z configuration. We find that collisional activation of CR dianions drives a one-way Z Z →E Z →E E cascade towards the lowest-energy isomer, whereas the absorption of a single photon over the 270-600 nm range can switch either azo group from E to Z or Z to E , driving the CR dianion to lower- or higher-energy forms. The experimental results, which are interpreted with the aid of calculated statistical isomerization rates, indicate that photoisomerization of CR in the gas phase involves a passage through conical intersection seams linking the excited and ground state potential energy surfaces rather than through isomerization on the ground state potential energy surface following internal conversion.

Femtosecond x-ray scattering study of ultrafast photoinduced structural dynamics in solvated [ Co ( terpy ) 2 ] 2 +

DOE PAGES

Biasin, Elisa; van Driel, Tim Brandt; Kjær, Kasper S.; ...

2016-06-30

Here, we study the structural dynamics of photoexcited [Co(terpy) 2] 2+ in an aqueous solution with ultrafast x-ray diffuse scattering experiments conducted at the Linac Coherent Light Source. Through direct comparisons with density functional theory calculations, our analysis shows that the photoexcitation event leads to elongation of the Co-N bonds, followed by coherent Co-N bond length oscillations arising from the impulsive excitation of a vibrational mode dominated by the symmetrical stretch of all six Co-N bonds. This mode has a period of 0.33 ps and decays on a subpicosecond time scale. We find that the equilibrium bond-elongated structure of themore » high spin state is established on a single-picosecond time scale and that this state has a lifetime of ~7 ps.« less

Influence of optical pumping wavelength on the ultrafast gain and phase recovery acceleration of quantum-dot semiconductor optical amplifiers

NASA Astrophysics Data System (ADS)

Kim, Jungho

2013-10-01

We numerically investigate the influence of the optical pumping wavelength on the ultrafast gain and phase recovery acceleration of quantum-dot (QD) semiconductor optical amplifiers (SOAs) by solving 1088 coupled rate equations. The temporal variations of the gain and phase recovery response at the ground state (GS) of QDs are calculated at various signal wavelengths when the optical pumping wavelengths at the excited state (ES) of QDs are varied. The phase recovery response is fastest when the wavelength of the signal and pumping beams corresponds to the respective emission wavelength of the GS and the ES in the same size of QDs. The absorption efficiency of the optical pumping beam at the ES is determined by the Lorentzian line shape function of the homogeneous broadening.

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

Probing cis-trans isomerization in the S{sub 1} state of C{sub 2}H{sub 2} via H-atom action and hot band-pumped IR-UV double resonance spectroscopies

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

Changala, P. Bryan; Baraban, Joshua H.; Field, Robert W., E-mail: rwfield@mit.edu

2015-08-28

We report novel experimental strategies that should prove instrumental in extending the vibrational and rotational assignments of the S{sub 1} state of acetylene, C{sub 2}H{sub 2}, in the region of the cis-trans isomerization barrier. At present, the assignments are essentially complete up to ∼500 cm{sup −1} below the barrier. Two difficulties arise when the assignments are continued to higher energies. One is that predissociation into C{sub 2}H + H sets in roughly 1100 cm{sup −1} below the barrier; the resulting quenching of laser-induced fluorescence (LIF) reduces its value for recording spectra in this region. The other difficulty is that tunnelingmore » through the barrier causes a staggering in the K-rotational structure of isomerizing vibrational levels. The assignment of these levels requires data for K values up to at least 3. Given the rotational selection rule K′ − ℓ{sup ′′} = ± 1, such data must be obtained via excited vibrational levels of the ground state with ℓ{sup ′′} > 0. In this paper, high resolution H-atom resonance-enhanced multiphoton ionization spectra are demonstrated to contain predissociated bands which are almost invisible in LIF spectra, while preliminary data using a hyperthermal pulsed nozzle show that ℓ{sup ′′} = 2 states can be selectively populated in a jet, giving access to K′ = 3 states in IR-UV double resonance.« less

Ultrafast all-optical control of the magnetization in magnetic dielectrics

NASA Astrophysics Data System (ADS)

Kirilyuk, Andrei; Kimel, Alexey; Hansteen, Fredrik; Rasing, Theo; Pisarev, Roman V.

2006-08-01

The purpose of this review is to summarize the recent progress on laser-induced magnetization dynamics in magnetic dielectrics. Due to the slow phonon-magnon interaction in these materials, direct thermal effects of the laser excitation can only be seen on the time scale of almost a nanosecond and thus are clearly distinguished from the ultrafast nonthermal effects. However, laser pulses are shown to indirectly modify the magnetic anisotropy in rare-earth orthoferrites via the crystal field, and to bring about spin reorientation within a few picoseconds. More interesting, however, are the direct nonthermal effects of light on spin systems. We demonstrate coherent optical control of the magnetization in ferrimagnetic garnet films on a 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. In addition, circularly polarized pulses are shown to act as strong transient magnetic field pulses originating from the nonabsorptive inverse Faraday effect. An all-optical scheme of excitation and detection of different antiferromagnetic resonance modes with frequencies of up to 500GHz will be discussed as well. The reported effects open new and exciting possibilities for ultrafast manipulation of spins by light and provide new insight into the physics of magnetism on ultrafast time scales.

Ultrafast dynamics of hard tissue ablation using fs-lasers.

PubMed

Domke, Matthias; Wick, Sebastian; Laible, Maike; Rapp, Stephan; Huber, Heinz P; Sroka, Ronald

2018-05-29

Several studies on hard tissue laser ablation demonstrated that ultrafast lasers enable precise material removal without thermal side effects. Although the principle ablation mechanisms have been thoroughly investigated, there are still open questions regarding the influence of material properties on transient dynamics. In this investigation, we applied pump-probe microscopy to record ablation dynamics of biomaterials with different tensile strengths (dentin, chicken bone, gallstone, kidney stones) at delay times between 1 ps and 10 μs. Transient reflectivity changes, pressure and shock wave velocities, and elastic constants were determined. The result revealed that absorption and excitation show the typical well-known transient behaviour of dielectric materials. We observed for all samples a photomechanical laser ablation process, where ultrafast expansion of the excited volume generates pressure waves leading to fragmentation around the excited region. Additionally, we identified tensile-strength-related differences in the size of ablated craters and ejected particles. The elastic constants derived were in agreement with literature values. In conclusion, pressure-wave-assisted material removal seems to be a general mechanism for hard tissue ablation with ultrafast lasers. This photomechanical process increases ablation efficiency and removes heated material, thus ultrafast laser ablation is of interest for clinical application where heating of the tissue must be avoided. This article is protected by copyright. All rights reserved. This article is protected by copyright. All rights reserved.

Evidence for excited state intramolecular charge transfer in benzazole-based pseudo-stilbenes.

PubMed

Santos, Fabiano da Silveira; Descalzo, Rodrigo Roceti; Gonçalves, Paulo Fernando Bruno; Benvenutti, Edilson Valmir; Rodembusch, Fabiano Severo

2012-08-21

Two azo compounds were obtained through the diazotization reaction of aminobenzazole derivatives and N,N-dimethylaniline using clay montmorillonite KSF as catalyst. The synthesized dyes were characterized using elemental analysis, Fourier transform infrared spectroscopy, and (13)C and (1)H NMR spectroscopy in solution. Their photophysical behavior was studied using UV-vis and steady-state fluorescence in solution. These dyes present intense absorption in the blue region. The spectral features of the azo compounds can be related to the pseudo-stilbene type as well as the E isomer of the dyes. Excitation at the absorption maxima does not produce emissive species in the excited state. However, excitation around 350 nm allowed dual emission of fluorescence, from both a locally excited (LE, short wavelength) and an intramolecular charge transfer (ICT, long wavelength) state, which was corroborated by a linear relation of the fluorescence maximum (ν(max)) versus the solvent polarity function (Δf) from the Lippert-Mataga correlation. Evidence of TICT in these dyes was discussed from the viscosity dependence of the fluorescence intensity in the ICT emission band. Theoretical calculations were also performed in order to study the geometry and charge distribution of the dyes in their ground and excited electronic states. Using DFT methods at the theoretical levels BLYP/Aug-cc-pVDZ, for geometry optimizations and frequency calculations, and B3LYP/6-311+G(2d), for single-point energy evaluations, the calculations revealed that the least energetic and most intense photon absorption leads to a very polar excited state that relaxes non-radioactively, which can be associated with photochemical isomerization.

Laser spectroscopy of CaNC and SrNC

NASA Astrophysics Data System (ADS)

Douay, M.; Bernath, P. F.

1990-11-01

Low-resolution laser excitation and dispersed laser-induced fluorescence spectra of CaNC and SrNC were recorded. The laser excitation spectra of the overlineB2Σ+-overlineX2Σ+ and overlineA2Π-overlineX2Σ+ transitions of SrNC are consistent with a linear,isocyanide structure. For both CaNC and SrNC, additional strong, non-resonant features occur to the red of the overlineB2Σ+-overlineX2Σ+ and overlineA2Π-overlineX2Σ+ transitions in the dispersed fluorescence spectra. Although these features remain unassigned, they might be due to emission from the isomeric,linear cyanides, CaCN and SrCN. In this case, the excited state potential curves need to have a small barrier between the cyanide and the isocyanide forms.

The 11/2{sup -}[505] neutron extruder orbital in {sup 159}Sm

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

Urban, W.; Faculty of Physics, University of Warsaw, ul. Hoza 69, PL-00-681 Warsaw; Pinston, J. A.

Excited states in {sup 159}Sm, populated following the spontaneous fission of {sup 252}Cf have been studied by means of {gamma} spectroscopy, using the Gammasphere array. In {sup 159}Sm we have identified an isomeric level with a half-life of T{sub 1/2}=116(8) ns at an excitation energy of 1276.8 keV and observed a rotational band on top of this isomer. On the basis of the observed properties of the isomer and the band on top of it we propose that the 1276.8-keV level in {sup 159}Sm corresponds to the 11/2{sup -}[505] neutron extruder configuration. The new excitation scheme of {sup 159}Sm ismore » compared to quasiparticle rotor model calculations.« less

Roaming Reactions and Roaming-Mediated Isomerization in the Decomposition of Energetic Materials

DTIC Science & Technology

2015-12-02

not   permit   effective   competition   between   isomerization  and  SBF  as  had  been  seen   for  nitromethane   in...vinylidene   is   formed   with   only   modest  rotational  excitation,  precluding   Coriolis -­‐induced  mixing  among  the

Electronic energy transfer in bimetallic Ru-Os complexes containing the 3,5-bis(pyridin-2-yl)-1,2,4-triazolate bridging ligand

NASA Astrophysics Data System (ADS)

De Cola, Luisa; Barigelletti, Francesco; Balzani, Vincenzo; Hage, Ronald; Haasnoot, Jaap G.; Reedijk, Jan; Vos, Johannes G.

1991-04-01

The luminescence and photochemical properties of the two isomeric heterobimetallic [(bpy) 2Ru(bpt)Os(bpy) 2] 3+ and [(bpy) 2Os(bpt)Ru(bpy) 2] 3+ complexes have been investigated (bpy=2,2'-pyridine; bpt -=3,5-bis(pyridin-2-yl)-1,2,4-triazolate ion). The properties of the two isomeric compounds are compared with those of the corresponding dinuclear homometallic inert and exhibit luminescence only from the Os-based component. Excitation in the Ru-based component is followed by ≈ 100% efficient energy transfer to the Os-based component. The energy-transfer mechanism is briefly discussed. The one-electron oxidation products (which contain Os in the 3+ oxidation state) are not luminescent because of the presence of a low-energy intervalence transfer level.

Carbon nanorings with inserted acenes: Breaking symmetry in excited state dynamics

DOE PAGES

Franklin-Mergarejo, R.; Alvarez, D. Ondarse; Tretiak, S.; ...

2016-08-10

Conjugated cycloparaphenylene rings have unique electronic properties being the smallest segments of carbon nanotubes. Their conjugated backbones support delocalized electronic excitations, which dynamics is strongly influenced by cyclic geometry. Here we present a comparative theoretical study of the electronic and vibrational energy relaxation and redistribution in photoexcited cycloparaphenylene carbon nanorings with inserted naphthalene, anthracene, and tetracene units using non-adiabatic excited-state molecular dynamics simulations. Calculated excited state structures reflect modifications of optical selection rules and appearance of low-energy electronic states localized on the acenes due to gradual departure from a perfect circular symmetry. After photoexcitation, an ultrafast electronic energy relaxation tomore » the lowest excited state is observed on the time scale of hundreds of femtoseconds in all molecules studied. Concomitantly, the efficiency of the exciton trapping in the acene raises when moving from naphthalene to anthracene and to tetracene, being negligible in naphthalene, and ~60% and 70% in anthracene and tetracene within the first 500 fs after photoexcitation. Observed photoinduced dynamics is further analyzed in details using induced molecular distortions, delocatization properties of participating electronic states and non-adiabatic coupling strengths. Lastly, our results provide a number of insights into design of cyclic molecular systems for electronic and light-harvesting applications.« less

Carbene based photochemical molecular assemblies for solar driven hydrogen generation.

PubMed

Peuntinger, Katrin; Pilz, T David; Staehle, Robert; Schaub, Markus; Kaufhold, Simon; Petermann, Lydia; Wunderlin, Markus; Görls, Helmar; Heinemann, Frank W; Li, Jing; Drewello, Thomas; Vos, Johannes G; Guldi, Dirk M; Rau, Sven

2014-09-28

Novel photocatalysts based on ruthenium complexes with NHC (N-heterocyclic carbene)-type bridging ligands have been prepared and structurally and photophysically characterised. The identity of the NHC-unit of the bridging ligand was established unambiguously by means of X-ray structural analysis of a heterodinuclear ruthenium-silver complex. The photophysical data indicate ultrafast intersystem crossing into an emissive and a non-emissive triplet excited state after excitation of the ruthenium centre. Exceptionally high luminescence quantum yields of up to 39% and long lifetimes of up to 2 μs are some of the triplet excited state characteristics. Preliminary studies into the visible light driven photocatalytic hydrogen formation show no induction phase and constant turnover frequencies that are independent on the concentration of the photocatalyst. In conclusion this supports the notion of a stable assembly under photocatalytic conditions.

‘Horror vacui’ or topological in-out isomerism in perhydrogenated fullerenes: C60H60 and monoalkylated perhydrogenated fullerenes

NASA Astrophysics Data System (ADS)

Dodziuk, Helena; Nowinski, Krzysztof

1996-02-01

In endohedral chemistry, one of the exciting prospects offered by the cage-like structure of fullerenes, several aspects of the calculations on in-out isomerism of perhydrogenated fullerene and their consequences went unnoticed, e.g. the topological character of the isomerism, the instability of C 60F 60, which was thought to revolutionize industry as an ideal lubricant, as well as the possibility of in-out isomerism in alkylated fulleranes. Molecular mechanics calculations indicate that for smaller alkyl groups the 'in' isomer is significantly more stable extending the possibility of endohedral fullerene chemistry. C 60H 60 and its derivatives can be considered as examples of a manifestation of the ancient 'horror vacui' concept.

Photophysics of self-assembled zinc porphyrin-bidentate diamine ligand complexes.

PubMed

Danger, Brook R; Bedient, Krysta; Maiti, Manisankar; Burgess, Ian J; Steer, Ronald P

2010-10-21

The effects of complexation--by bidentate nitrogen-containing ligands such as pyrazine and 4,4'-bipyridine commonly used for porphyrin self-assembly--on the photophysics of the model metalloporphyrin, ZnTPP, are reported. Ligation to form the 5-coordinate species introduces an intramolecular charge transfer (ITC) state that, depending on the oxidation and reduction potentials of the electron donor and acceptor, can become involved in the excited state relaxation processes. For ZnTPP, ligation with pyridine has little effect on excited state relaxation following either Q-band or Soret band excitation. However, coordination of ZnTPP with pyrazine and bipyridine causes the S(2) (Soret) state of the ligated species to decay almost exclusively via an S(2)-ICT-S(1) pathway, while affecting the S(1) decay route only slightly. In these 5-coordinate species the S(2)-ICT-S(1) decay route is ultrafast and nearly quantitative. Literature redox data for other bidentate ligands such as DABCO and multidentate ligands commonly used for pophyrin assembly suggest that the ITC states introduced by them could also modify the excited state relaxation dynamics of a wide variety of multiporphyrin arrays.

Effect of charged and excited states on the decomposition of 1,1-diamino-2,2-dinitroethylene molecules

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

Kimmel, Anna V.; Sushko, Peter V.; Shluger, Alexander L.

The authors have calculated the electronic structure of individual 1,1-diamino-2,2-dinitroethylene molecules (FOX-7) in the gas phase by means of density functional theory with the hybrid B3LYP functional and 6-31+G(d,p) basis set and considered their dissociation pathways. Positively and negatively charged states as well as the lowest excited states of the molecule were simulated. They found that charging and excitation can not only reduce the activation barriers for decomposition reactions but also change the dominating chemistry from endo- to exothermic type. In particular, they found that there are two competing primary initiation mechanisms of FOX-7 decomposition: C-NO{sub 2} bond fission andmore » C-NO{sub 2} to CONO isomerization. Electronic excitation or charging of FOX-7 disfavors CONO formation and, thus, terminates this channel of decomposition. However, if CONO is formed from the neutral FOX-7 molecule, charge trapping and/or excitation results in spontaneous splitting of an NO group accompanied by the energy release. Intramolecular hydrogen transfer is found to be a rare event in FOX-7 unless free electrons are available in the vicinity of the molecule, in which case HONO formation is a feasible exothermic reaction with a relatively low energy barrier. The effect of charged and excited states on other possible reactions is also studied. Implications of the obtained results to FOX-7 decomposition in condensed state are discussed.« less

a Study of the Role of Large-Amplitude Motions in Unimolecular Energy Transfer Using Molecular Beam Optothermal Spectroscopy.

NASA Astrophysics Data System (ADS)

Miller, Carl Cameron

1995-01-01

The role of molecular structure in energy transfer reactions in the ground and excited electronic states was explored using optothermal spectroscopy. In the ground state, the relationship between intramolecular van der Waals interactions and vibrational mode coupling was explored in a homologous series of disubstituted ethanes, including Gg^' -2-fluoroethanol, g-1,2-difluoroethane, g-1-chloro-2-fluoroethane, t-1-chloro-2-fluoroethane, and 1,1,2-trifluoroethane. This series of substituted ethanes varies in degree of van der Waals interactions that hinder internal rotation about the C-C bond. High resolution infrared molecular beam spectroscopy was used to determine the extent of vibrational mode coupling. Perturbations in the rotational structure of these molecules provided a measure of vibrational mode coupling. We have observed that the degree of intramolecular interaction, which is dependent on the van der Waals separation of the substituents and the shape of the potential well, correlates with the extent of vibrational mode coupling. The extent of vibrational mode coupling in this series of molecules did not correlate with the density of states available for coupling. Therefore, density of states alone is insufficient to explain the observed trend. In the excited electronic state, optothermal detection has been used to observe non-radiative relaxation channels in aniline, p-bromoaniline and trans-stilbene. p-Bromoaniline has no detectable fluorescence due to a heavy atom effect which increases the rate of intersystem crossing to the triplet state. An optothermal spectrum of p-bromoaniline was observed with the origin at 32625 cm^ {-1}. For trans-stilbene the differences between the laser excitation spectrum and the optothermal spectrum of the S_1 state clearly show the onset of isomerization at ~1250 cm^{-1} above the origin. Absolute quantum yields of fluorescence, Frank-Condon factors, non -radiative rates, and radiative rates have been obtained for a series of vibronic transitions. For low energy vibrational states there is good agreement between the current study and previous work. For vibrational energies above the barrier of isomerization predicted quantum yields do not agree with our experimental results.

Unified Time and Frequency Picture of Ultrafast Atomic Excitation in Strong Laser Fields

NASA Astrophysics Data System (ADS)

Zimmermann, H.; Patchkovskii, S.; Ivanov, M.; Eichmann, U.

2017-01-01

Excitation and ionization in strong laser fields lies at the heart of such diverse research directions as high-harmonic generation and spectroscopy, laser-induced diffraction imaging, emission of femtosecond electron bunches from nanotips, self-guiding, filamentation and mirrorless lasing during propagation of light in atmospheres. While extensive quantum mechanical and semiclassical calculations on strong-field ionization are well backed by sophisticated experiments, the existing scattered theoretical work aiming at a full quantitative understanding of strong-field excitation lacks experimental confirmation. Here we present experiments on strong-field excitation in both the tunneling and multiphoton regimes and their rigorous interpretation by time dependent Schrödinger equation calculations, which finally consolidates the seemingly opposing strong-field regimes with their complementary pictures. Most strikingly, we observe an unprecedented enhancement of excitation yields, which opens new possibilities in ultrafast strong-field control of Rydberg wave packet excitation and laser intensity characterization.

Spectroscopy of 50Sc and ab initio calculations of B (M 3 ) strengths

NASA Astrophysics Data System (ADS)

Garnsworthy, A. B.; Bowry, M.; Olaizola, B.; Holt, J. D.; Stroberg, S. R.; Cruz, S.; Georges, S.; Hackman, G.; MacLean, A. D.; Measures, J.; Patel, H. P.; Pearson, C. J.; Svensson, C. E.

2017-10-01

The GRIFFIN spectrometer at TRIUMF-ISAC has been used to study excited states and transitions in 50Sc following the β decay of 50Ca. Branching ratios were determined from the measured γ -ray intensities, and angular correlations of γ rays have been used to firmly assign the spins of excited states. The presence of an isomeric state that decays by an M 3 transition with a B (M 3 ) strength of 13.6(7) W.u. has been confirmed. We compare the first ab initio calculations of B (M 3 ) strengths in light- and medium-mass nuclei from the valence-space in-medium similarity renormalization group approach, using consistently derived effective Hamiltonians and effective M 3 operator. The experimental data are well reproduced for isoscalar M 3 transitions when using bare g factors, but the strength of isovector M 3 transitions are found to be underestimated by an order of magnitude.

Higgs amplitude mode in the BCS superconductors Nb1-xTi(x)N induced by terahertz pulse excitation.

PubMed

Matsunaga, Ryusuke; Hamada, Yuki I; Makise, Kazumasa; Uzawa, Yoshinori; Terai, Hirotaka; Wang, Zhen; Shimano, Ryo

2013-08-02

Ultrafast responses of BCS superconductor Nb(1-x)Ti(x)N films in a nonadiabatic excitation regime were investigated by using terahertz (THz) pump-THz probe spectroscopy. After an instantaneous excitation with the monocycle THz pump pulse, a transient oscillation emerges in the electromagnetic response in the BCS gap energy region. The oscillation frequency coincides with the asymptotic value of the BCS gap energy, indicating the appearance of the theoretically anticipated collective amplitude mode of the order parameter, namely the Higgs amplitude mode. Our result opens a new pathway to the ultrafast manipulation of the superconducting order parameter by optical means.

Identification of the dominant photochemical pathways and mechanistic insights to the ultrafast ligand exchange of Fe(CO) 5 to Fe(CO) 4EtOH

DOE PAGES

Kunnus, K.; Josefsson, I.; Rajkovic, I.; ...

2016-02-09

We utilized femtosecond time-resolved resonant inelastic X-ray scattering and ab initio theory to study the transient electronic structure and the photoinduced molecular dynamics of a model metal carbonyl photocatalyst Fe(CO) 5 in ethanol solution. We propose mechanistic explanation for the parallel ultrafast intra-molecular spin crossover and ligation of the Fe(CO) 4 which are observed following a charge transfer photoexcitation of Fe(CO) 5 as reported in our previous study [Wernet et al., Nature 520, 78 (2015)]. We find that branching of the reaction pathway likely happens in the 1A 1 state of Fe(CO) 4. A sub-picosecond time constant of themore » spin crossover from 1B 2 to 3B 2 is rationalized by the proposed 1B 2 → 1A 1 → 3B 2 mechanism. Ultrafast ligation of the 1B 2 Fe(CO) 4 state is significantly faster than the spin-forbidden and diffusion limited ligation process occurring from the 3B 2 Fe(CO) 4 ground state that has been observed in the previous studies. We propose that the ultrafast ligation occurs via 1B 2 → 1A 1 → 1A' Fe(CO) 4EtOH pathway and the time scale of the 1A 1 Fe(CO) 4 state ligation is governed by the solute-solvent collision frequency. In conclusion, our study emphasizes the importance of understanding the interaction of molecular excited states with the surrounding environment to explain the relaxation pathways of photoexcited metal carbonyls in solution.« less

Excitation laser energy dependence of surface-enhanced fluorescence showing plasmon-induced ultrafast electronic dynamics in dye molecules

NASA Astrophysics Data System (ADS)

Itoh, Tamitake; Yamamoto, Yuko S.; Tamaru, Hiroharu; Biju, Vasudevanpillai; Murase, Norio; Ozaki, Yukihiro

2013-06-01

We find unique properties accompanying surface-enhanced fluorescence (SEF) from dye molecules adsorbed on Ag nanoparticle aggregates, which generate surface-enhanced Raman scattering. The properties are observed in excitation laser energy dependence of SEF after excluding plasmonic spectral modulation in SEF. The unique properties are large blue shifts of fluorescence spectra, deviation of ratios between anti-Stokes SEF intensity and Stokes from those of normal fluorescence, super-broadening of Stokes spectra, and returning to original fluorescence by lower energy excitation. We elucidate that these properties are induced by electromagnetic enhancement of radiative decay rates exceeding the vibrational relaxation rates within an electronic excited state, which suggests that molecular electronic dynamics in strong plasmonic fields can be largely deviated from that in free space.

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.

Ultrafast isomerization initiated by X-ray core ionization

NASA Astrophysics Data System (ADS)

Liekhus-Schmaltz, Chelsea E.; Tenney, Ian; Osipov, Timur; Sanchez-Gonzalez, Alvaro; Berrah, Nora; Boll, Rebecca; Bomme, Cedric; Bostedt, Christoph; Bozek, John D.; Carron, Sebastian; Coffee, Ryan; Devin, Julien; Erk, Benjamin; Ferguson, Ken R.; Field, Robert W.; Foucar, Lutz; Frasinski, Leszek J.; Glownia, James M.; Gühr, Markus; Kamalov, Andrei; Krzywinski, Jacek; Li, Heng; Marangos, Jonathan P.; Martinez, Todd J.; McFarland, Brian K.; Miyabe, Shungo; Murphy, Brendan; Natan, Adi; Rolles, Daniel; Rudenko, Artem; Siano, Marco; Simpson, Emma R.; Spector, Limor; Swiggers, Michele; Walke, Daniel; Wang, Song; Weber, Thorsten; Bucksbaum, Philip H.; Petrovic, Vladimir S.

2015-09-01

Rapid proton migration is a key process in hydrocarbon photochemistry. Charge migration and subsequent proton motion can mitigate radiation damage when heavier atoms absorb X-rays. If rapid enough, this can improve the fidelity of diffract-before-destroy measurements of biomolecular structure at X-ray-free electron lasers. Here we study X-ray-initiated isomerization of acetylene, a model for proton dynamics in hydrocarbons. Our time-resolved measurements capture the transient motion of protons following X-ray ionization of carbon K-shell electrons. We Coulomb-explode the molecule with a second precisely delayed X-ray pulse and then record all the fragment momenta. These snapshots at different delays are combined into a `molecular movie' of the evolving molecule, which shows substantial proton redistribution within the first 12 fs. We conclude that significant proton motion occurs on a timescale comparable to the Auger relaxation that refills the K-shell vacancy.

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

NASA Astrophysics Data System (ADS)

Joo, Taiha

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

Pump-probe study of the formation of rubidium molecules by ultrafast photoassociation of ultracold atoms

NASA Astrophysics Data System (ADS)

McCabe, David J.; England, Duncan G.; Martay, Hugo E. L.; Friedman, Melissa E.; Petrovic, Jovana; Dimova, Emiliya; Chatel, Béatrice; Walmsley, Ian A.

2009-09-01

An experimental pump-probe study of the photoassociative creation of translationally ultracold rubidium molecules is presented together with numerical simulations of the process. The formation of loosely bound excited-state dimers is observed as a first step toward a fully coherent pump-dump approach to the stabilization of Rb2 into its lowest ground vibrational states. The population that contributes to the pump-probe process is characterized and found to be distinct from a background population of preassociated molecules.

Ultrafast time-resolved spectroscopy of lead halide perovskite films

NASA Astrophysics Data System (ADS)

Idowu, Mopelola A.; Yau, Sung H.; Varnavski, Oleg; Goodson, Theodore

2015-09-01

Recently, lead halide perovskites which are organic-inorganic hybrid structures, have been discovered to be highly efficient as light absorbers. Herein, we show the investigation of the excited state dynamics and emission properties of non-stoichiometric precursor formed lead halide perovskites grown by interdiffusion method using steady-state and time-resolved spectroscopic measurements. The influence of the different ratios of the non-stoichiometric precursor solution was examined. The observed photoluminescence properties were correlated with the femtosecond transient absorption measurements.

Tracking of the nuclear wavepacket motion in cyanine photoisomerization by ultrafast pump-dump-probe spectroscopy.

PubMed

Wei, Zhengrong; Nakamura, Takumi; Takeuchi, Satoshi; Tahara, Tahei

2011-06-01

Understanding ultrafast reactions, which proceed on a time scale of nuclear motions, requires a quantitative characterization of the structural dynamics. To track such structural changes with time, we studied a nuclear wavepacket motion in photoisomerization of a prototype cyanine dye, 1,1'-diethyl-4,4'-cyanine, by ultrafast pump-dump-probe measurements in solution. The temporal evolution of wavepacket motion was examined by monitoring the efficiency of stimulated emission dumping, which was obtained from the recovery of a ground-state bleaching signal. The dump efficiency versus pump-dump delay exhibited a finite rise time, and it became longer (97 fs → 330 fs → 390 fs) as the dump pulse was tuned to longer wavelengths (690 nm → 950 nm → 1200 nm). This result demonstrates a continuous migration of the leading edge of the wavepacket on the excited-state potential from the Franck-Condon region toward the potential minimum. A slowly decaying feature of the dump efficiency indicated a considerable broadening of the wavepacket over a wide range of the potential, which results in the spread of a population distribution on the flat S(1) potential energy surface. The rapid migration as well as broadening of the wavepacket manifests a continuous nature of the structural dynamics and provides an intuitive visualization of this ultrafast reaction. We also discussed experimental strategies to evaluate reliable dump efficiencies separately from other ultrafast processes and showed a high capability and possibility of the pump-dump-probe method for spectroscopic investigation of unexplored potential regions such as conical intersections. © 2011 American Chemical Society

Cyclohexane isomerization. Unimolecular dynamics of the twist-boat intermediate.

PubMed

Kakhiani, Khatuna; Lourderaj, Upakarasamy; Hu, Wenfang; Birney, David; Hase, William L

2009-04-23

Direct dynamics simulations were performed at the HF/6-31G level of theory to investigate the intramolecular and unimolecuar dynamics of the twist-boat (TB) intermediate on the cyclohexane potential energy surface (PES). Additional calculations were performed at the MP2/aug-cc-pVDZ level of theory to further characterize the PES's stationary points. The trajectories were initiated at the C(1) and C(2) half-chair transition states (TSs) connecting a chair conformer with a TB intermediate, via an intrinsic reaction coordinate (IRC). Energy was added in accord with a microcanonical ensemble at the average energy for experiments at 263 K. Important nontransition state theory (TST), non-IRC, and non-RRKM dynamics were observed in the simulations. Trajectories initially directed toward the chair conformer had a high probability of recrossing the TS, with approximately 30% forming a TB intermediate instead of accessing the potential energy well for the conformer. The TB intermediate initially formed was not necessarily the one connected to the TS via the IRC. Of the trajectories initiated at the C(2) half-chair TS and initially directed toward the chair conformer, 35% formed a TB intermediate instead of the chair conformer. Also, of the trajectories forming a TB intermediate, only 16% formed the TB intermediate connected with the C(2) TS via the IRC. Up to eight consecutive TB --> TB isomerizations were followed, and non-RRKM behavior was observed in their dynamics. A TB can isomerize to two different TBs, one by a clockwise rotation of C-C-C-C dihedral angles and the other by a counterclockwise rotation. In contrast to RRKM theory, which predicts equivalent probabilities for these rotations, the trajectory dynamics show they are not equivalent and depend on whether the C(1) or C(2) half-chair TS is initially excited. Non-RRKM dynamics is also observed in the isomerization of the TB intermediates to the chair conformers. RRKM theory assumes equivalent probabilities for isomerizing to the two chair conformers. In contrast, for the first and following TB intermediate formed, there is a preference to isomerize to the chair conformer connected to the TS at which the trajectories were initiated. For the first TB intermediate formed, approximately 30% of the isomerization is to a chair conformer, but this fraction decreases for the later formed TB intermediates and becomes approximately 10% for the eighth consecutive TB intermediate formed.

Observation of the 2+ isomer in 52Co

NASA Astrophysics Data System (ADS)

Orrigo, S. E. A.; Rubio, B.; Gelletly, W.; Blank, B.; Fujita, Y.; Giovinazzo, J.; Agramunt, J.; Algora, A.; Ascher, P.; Bilgier, B.; Cáceres, L.; Cakirli, R. B.; de France, G.; Ganioǧlu, E.; Gerbaux, M.; Grévy, S.; Kamalou, O.; Kozer, H. C.; Kucuk, L.; Kurtukian-Nieto, T.; Molina, F.; Popescu, L.; Rogers, A. M.; Susoy, G.; Stodel, C.; Suzuki, T.; Tamii, A.; Thomas, J. C.

2016-10-01

We report the first observation of the 2+ isomer in 52Co, produced in the β decay of the 0+, 52Ni ground state. We have observed three γ rays at 849, 1910, and 5185 keV characterizing the β de-excitation of the isomer. We have measured a half-life of 102(6) ms for the isomeric state. The Fermi and Gamow-Teller transition strengths for the β decay of Com52 to 52Fe have been determined. We also add new information on the β decay of the 6+, 52Co ground state, for which we have measured a half-life of 112(3) ms.

Excited-state potential-energy surfaces of metal-adsorbed organic molecules from linear expansion Δ-self-consistent field density-functional theory (ΔSCF-DFT).

PubMed

Maurer, Reinhard J; Reuter, Karsten

2013-07-07

Accurate and efficient simulation of excited state properties is an important and much aspired cornerstone in the study of adsorbate dynamics on metal surfaces. To this end, the recently proposed linear expansion Δ-self-consistent field method by Gavnholt et al. [Phys. Rev. B 78, 075441 (2008)] presents an efficient alternative to time consuming quasi-particle calculations. In this method, the standard Kohn-Sham equations of density-functional theory are solved with the constraint of a non-equilibrium occupation in a region of Hilbert-space resembling gas-phase orbitals of the adsorbate. In this work, we discuss the applicability of this method for the excited-state dynamics of metal-surface mounted organic adsorbates, specifically in the context of molecular switching. We present necessary advancements to allow for a consistent quality description of excited-state potential-energy surfaces (PESs), and illustrate the concept with the application to Azobenzene adsorbed on Ag(111) and Au(111) surfaces. We find that the explicit inclusion of substrate electronic states modifies the topologies of intra-molecular excited-state PESs of the molecule due to image charge and hybridization effects. While the molecule in gas phase shows a clear energetic separation of resonances that induce isomerization and backreaction, the surface-adsorbed molecule does not. The concomitant possibly simultaneous induction of both processes would lead to a significantly reduced switching efficiency of such a mechanism.

Direct growth of graphene on quartz substrate as saturable absorber for femtosecond solid-state laser

NASA Astrophysics Data System (ADS)

Xu, S. C.; Man, B. Y.; Jiang, S. Z.; Chen, C. S.; Liu, M.; Yang, C.; Gao, S. B.; Feng, D. J.; Hu, G. D.; Huang, Q. J.; Chen, X. F.; Zhang, C.

2014-08-01

We present a novel method for the direct metal-free growth of graphene on quartz substrate. The direct-grown graphene yields excellent nonlinear saturable absorption properties and is demonstrated to be suitable as a saturable absorber (SA) for an ultrafast solid-state laser. Nearly Fourier-limited 367 fs was obtained at a central wavelength of 1048 nm with a repetition rate of 105.7 MHz. At a pump power of 7.95 W, the average output power was 1.93 W and the highest pulse energy reached 18.3 nJ, with a peak power of 49.8 kW. Our work opens an easy route for making a reliable graphene SA with a mode-locking technique and also displays an exciting prospect in making low-cost and ultrafast lasers.

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.

Understanding the features in the ultrafast transient absorption spectra of CdSe quantum dots

NASA Astrophysics Data System (ADS)

Zhang, Cheng; Do, Thanh Nhut; Ong, Xuanwei; Chan, Yinthai; Tan, Howe-Siang

2016-12-01

We describe a model to explain the features of the ultrafast transient absorption (TA) spectra of CdSe core type quantum dots (QDs). The measured TA spectrum consists of contributions by the ground state bleach (GSB), stimulated emission (SE) and excited state absorption (ESA) processes associated with the three lowest energy transition of the QDs. We model the shapes of the GSB, SE and ESA spectral components after fits to the linear absorption. The spectral positions of the ESA components take into account the biexcitonic binding energy. In order to obtain the correct weightage of the GSB, SE and ESA components to the TA spectrum, we enumerate the set of coherence transfer pathways associated with these processes. From our fits of the experimental TA spectra of 65 Å diameter QDs, biexcitonic binding energies for the three lowest energy transitions are obtained.

Ultrafast atomic-scale visualization of acoustic phonons generated by optically excited quantum dots

PubMed Central

Vanacore, Giovanni M.; Hu, Jianbo; Liang, Wenxi; Bietti, Sergio; Sanguinetti, Stefano; Carbone, Fabrizio; Zewail, Ahmed H.

2017-01-01

Understanding the dynamics of atomic vibrations confined in quasi-zero dimensional systems is crucial from both a fundamental point-of-view and a technological perspective. Using ultrafast electron diffraction, we monitored the lattice dynamics of GaAs quantum dots—grown by Droplet Epitaxy on AlGaAs—with sub-picosecond and sub-picometer resolutions. An ultrafast laser pulse nearly resonantly excites a confined exciton, which efficiently couples to high-energy acoustic phonons through the deformation potential mechanism. The transient behavior of the measured diffraction pattern reveals the nonequilibrium phonon dynamics both within the dots and in the region surrounding them. The experimental results are interpreted within the theoretical framework of a non-Markovian decoherence, according to which the optical excitation creates a localized polaron within the dot and a travelling phonon wavepacket that leaves the dot at the speed of sound. These findings indicate that integration of a phononic emitter in opto-electronic devices based on quantum dots for controlled communication processes can be fundamentally feasible. PMID:28852685

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.

Ultrafast proton shuttling in Psammocora cyan fluorescent protein.

PubMed

Kennis, John T M; van Stokkum, Ivo H M; Peterson, Dayna S; Pandit, Anjali; Wachter, Rebekka M

2013-09-26

Cyan, green, yellow, and red fluorescent proteins (FPs) homologous to green fluorescent protein (GFP) are used extensively as model systems to study fundamental processes in photobiology, such as the capture of light energy by protein-embedded chromophores, color tuning by the protein matrix, energy conversion by Förster resonance energy transfer (FRET), and excited-state proton transfer (ESPT) reactions. Recently, a novel cyan fluorescent protein (CFP) termed psamFP488 was isolated from the genus Psammocora of reef building corals. Within the cyan color class, psamFP488 is unusual because it exhibits a significantly extended Stokes shift. Here, we applied ultrafast transient absorption and pump-dump-probe spectroscopy to investigate the mechanistic basis of psamFP488 fluorescence, complemented with fluorescence quantum yield and dynamic light scattering measurements. Transient absorption spectroscopy indicated that, upon excitation at 410 nm, the stimulated cyan emission rises in 170 fs. With pump-dump-probe spectroscopy, we observe a very short-lived (110 fs) ground-state intermediate that we assign to the deprotonated, anionic chromophore. In addition, a minor fraction (14%) decays with 3.5 ps to the ground state. Structural analysis of homologous proteins indicates that Glu-167 is likely positioned in sufficiently close vicinity to the chromophore to act as a proton acceptor. Our findings support a model where unusually fast ESPT from the neutral chromophore to Glu-167 with a time constant of 170 fs and resulting emission from the anionic chromophore forms the basis of the large psamFP488 Stokes shift. When dumped to the ground state, the proton on neutral Glu is very rapidly shuttled back to the anionic chromophore in 110 fs. Proton shuttling in excited and ground states is a factor of 20-4000 faster than in GFP, which probably results from a favorable hydrogen-bonding geometry between the chromophore phenolic oxygen and the glutamate acceptor, possibly involving a short hydrogen bond. At any time in the reaction, the proton is localized on either the chromophore or Glu-167, which implies that most likely no low-barrier hydrogen bond exists between these molecular groups. This work supports the notion that proton transfer in biological systems, be it in an electronic excited or ground state, can be an intrinsically fast process that occurs on a 100 fs time scale. PsamFP488 represents an attractive model system that poses an ultrafast proton transfer regime in discrete steps. It constitutes a valuable model system in addition to wild type GFP, where proton transfer is relatively slow, and the S65T/H148D GFP mutant, where the effects of low-barrier hydrogen bonds dominate.

Regio- and conformational isomerization critical to design of efficient thermally-activated delayed fluorescence emitters

PubMed Central

Etherington, Marc K.; Franchello, Flavio; Gibson, Jamie; Northey, Thomas; Santos, Jose; Ward, Jonathan S.; Higginbotham, Heather F.; Data, Przemyslaw; Kurowska, Aleksandra; Dos Santos, Paloma Lays; Graves, David R.; Batsanov, Andrei S.; Dias, Fernando B.; Bryce, Martin R.; Penfold, Thomas J.; Monkman, Andrew P.

2017-01-01

Regio- and conformational isomerization are fundamental in chemistry, with profound effects upon physical properties, however their role in excited state properties is less developed. Here two regioisomers of bis(10H-phenothiazin-10-yl)dibenzo[b,d]thiophene-S,S-dioxide, a donor–acceptor–donor (D–A–D) thermally-activated delayed fluorescence (TADF) emitter, are studied. 2,8-bis(10H-phenothiazin-10-yl)dibenzo[b,d]thiophene-S,S-dioxide exhibits only one quasi-equatorial conformer on both donor sites, with charge-transfer (CT) emission close to the local triplet state leading to efficient TADF via spin-vibronic coupling. However, 3,7-bis(10H-phenothiazin-10-yl)dibenzo[b,d]thiophene-S,S-dioxide displays both a quasi-equatorial CT state and a higher-energy quasi-axial CT state. No TADF is observed in the quasi-axial CT emission. These two CT states link directly to the two folded conformers of phenothiazine. The presence of the low-lying local triplet state of the axial conformer also means that this quasi-axial CT is an effective loss pathway both photophysically and in devices. Importantly, donors or acceptors with more than one conformer have negative repercussions for TADF in organic light-emitting diodes. PMID:28406153

A system to measure isomeric state half-lives in the 10 ns to 10 μs range

NASA Astrophysics Data System (ADS)

Toufen, D. L.; Allegro, P. R. P.; Medina, N. H.; Oliveira, J. R. B.; Cybulska, E. W.; Seale, W. A.; Linares, R.; Silveira, M. A. G.; Ribas, R. V.

2014-07-01

The Isomeric State Measurement System (SISMEI) was developed to search for isomeric nuclear states produced by fusion-evaporation reactions. The SISMEI consists of 10 plastic phoswich telescopes, two lead shields, one NaI(Tl) scintillation detector, two Compton suppressed HPGe γ-ray detectors, and a cone with a recoil product catcher. The new system was tested at the 8 UD Pelletron tandem accelerator of the University of São Paulo with the measurement of two known isomeric states: 54Fe, 10+ state (E = 6527.1 (11) keV, T1/2 = 364(7) ns) and the 5/2+ state of 19F (E = 197.143 (4) keV, T1/2 = 89.3 (10) ns). The results indicate that the system is capable of identifying delayed transitions, of measuring isomeric state lifetimes, and of identifying the feeding transitions of the isomeric state through the delayed γ-γ coincidence method. The measured half-life for the 10+ state was T1/2 = 365(14) ns and for the 5/2+ state, 100(36) ns.

A system to measure isomeric state half-lives in the 10 ns to 10 μs range.

PubMed

Toufen, D L; Allegro, P R P; Medina, N H; Oliveira, J R B; Cybulska, E W; Seale, W A; Linares, R; Silveira, M A G; Ribas, R V

2014-07-01

The Isomeric State Measurement System (SISMEI) was developed to search for isomeric nuclear states produced by fusion-evaporation reactions. The SISMEI consists of 10 plastic phoswich telescopes, two lead shields, one NaI(Tl) scintillation detector, two Compton suppressed HPGe γ-ray detectors, and a cone with a recoil product catcher. The new system was tested at the 8 UD Pelletron tandem accelerator of the University of São Paulo with the measurement of two known isomeric states: (54)Fe, 10(+) state (E = 6527.1 (11) keV, T(1/2) = 364(7) ns) and the 5/2(+) state of (19)F (E = 197.143 (4) keV, T(1/2) = 89.3 (10) ns). The results indicate that the system is capable of identifying delayed transitions, of measuring isomeric state lifetimes, and of identifying the feeding transitions of the isomeric state through the delayed γ-γ coincidence method. The measured half-life for the 10(+) state was T(1/2) = 365(14) ns and for the 5/2(+) state, 100(36) ns.

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

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

Ultrafast Photoinduced Symmetry-Breaking Charge Separation and Electron Sharing in Perylenediimide Molecular Triangles.

PubMed

Wu, Yilei; Young, Ryan M; Frasconi, Marco; Schneebeli, Severin T; Spenst, Peter; Gardner, Daniel M; Brown, Kristen E; Würthner, Frank; Stoddart, J Fraser; Wasielewski, Michael R

2015-10-21

We report on a visible-light-absorbing chiral molecular triangle composed of three covalently linked 1,6,7,12-tetra(phenoxy)perylene-3,4:9,10-bis(dicarboximide) (PDI) units. The rigid triangular architecture reduces the electronic coupling between the PDIs, so ultrafast symmetry-breaking charge separation is kinetically favored over intramolecular excimer formation, as revealed by femtosecond transient absorption spectroscopy. Photoexcitation of the PDI triangle dissolved in CH2Cl2 gives PDI(+•)-PDI(-•) in τCS = 12.0 ± 0.2 ps. Fast subsequent intramolecular electron/hole hopping can equilibrate the six possible energetically degenerate ion-pair states, as suggested by electron paramagnetic resonance/electron-nuclear double resonance spectroscopy, which shows that one-electron reduction of the PDI triangle results in complete electron sharing among the three PDIs. Charge recombination of PDI(+•)-PDI(-•) to the ground state occurs in τCR = 1.12 ± 0.01 ns with no evidence of triplet excited state formation.

Two-magnon bound state causes ultrafast thermally induced magnetisation switching

PubMed Central

Barker, J.; Atxitia, U.; Ostler, T. A.; Hovorka, O.; Chubykalo-Fesenko, O.; Chantrell, R. W.

2013-01-01

There has been much interest recently in the discovery of thermally induced magnetisation switching using femtosecond laser excitation, where a ferrimagnetic system can be switched deterministically without an applied magnetic field. Experimental results suggest that the reversal occurs due to intrinsic material properties, but so far the microscopic mechanism responsible for reversal has not been identified. Using computational and analytic methods we show that the switching is caused by the excitation of two-magnon bound states, the properties of which are dependent on material factors. This discovery allows us to accurately predict the onset of switching and the identification of this mechanism will allow new classes of materials to be identified or designed for memory devices in the THz regime. PMID:24253110

Femtosecond dynamics of a non-steroidal anti-inflammatory drug (piroxicam) in solution: The involvement of twisting motion

NASA Astrophysics Data System (ADS)

Gil, Michał; Douhal, Abderrazzak

2008-06-01

In this contribution, we report on fast and ultrafast dynamics of a non-steroidal anti-inflammatory drug, piroxicam (PX), in methyl acetate (MAC) and triacetin (TAC), two solvents of different viscosities. The enol form of PX undergoes a femtosecond (shorter than 100 fs) electronically excited state intramolecular proton-transfer reaction to produce keto tautomers. These structures exhibit an internal twisting motion to generate keto rotamers in ˜2-5 ps, a time being longer in TAC. The transient absorption/emission spectrum is very broad indicating that the potential-energy surface at the electronically excited state is very flat, and reflecting the involvement of several coordinates along which the wavepacket of the fs-produced structures evolve.

Excited state dynamics of thiophene and bithiophene: new insights into theoretically challenging systems.

PubMed

Prlj, Antonio; Curchod, Basile F E; Corminboeuf, Clémence

2015-06-14

The computational elucidation and proper description of the ultrafast deactivation mechanisms of simple organic electronic units, such as thiophene and its oligomers, is as challenging as it is contentious. A comprehensive excited state dynamics analysis of these systems utilizing reliable electronic structure approaches is currently lacking, with earlier pictures of the photochemistry of these systems being conceived based upon high-level static computations or lower level dynamic trajectories. Here a detailed surface hopping molecular dynamics of thiophene and bithiophene using the algebraic diagrammatic construction to second order (ADC(2)) method is presented. Our findings illustrate that ring puckering plays an important role in thiophene photochemistry and that the photostability increases when going upon dimerization into bithiophene.

Broad-Band Pump-Probe Spectroscopy Quantifies Ultrafast Solvation Dynamics of Proteins and Molecules.

PubMed

Jumper, Chanelle C; Arpin, Paul C; Turner, Daniel B; McClure, Scott D; Rafiq, Shahnawaz; Dean, Jacob C; Cina, Jeffrey A; Kovac, Philip A; Mirkovic, Tihana; Scholes, Gregory D

2016-11-17

In this work, we demonstrate the use of broad-band pump-probe spectroscopy to measure femtosecond solvation dynamics. We report studies of a rhodamine dye in methanol and cryptophyte algae light-harvesting proteins in aqueous suspension. Broad-band impulsive excitation generates a vibrational wavepacket that oscillates on the excited-state potential energy surface, destructively interfering with itself at the minimum of the surface. This destructive interference gives rise to a node at a certain probe wavelength that varies with time. This reveals the Gibbs free-energy changes of the excited-state potential energy surface, which equates to the solvation time correlation function. This method captures the inertial solvent response of water (∼40 fs) and the bimodal inertial response of methanol (∼40 and ∼150 fs) and reveals how protein-buried chromophores are sensitive to the solvent dynamics inside and outside of the protein environment.

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.

Excited state electron and energy relays in supramolecular dinuclear complexes revealed by ultrafast optical and X-ray transient absorption spectroscopy.

PubMed

Hayes, Dugan; Kohler, Lars; Hadt, Ryan G; Zhang, Xiaoyi; Liu, Cunming; Mulfort, Karen L; Chen, Lin X

2018-01-28

The kinetics of photoinduced electron and energy transfer in a family of tetrapyridophenazine-bridged heteroleptic homo- and heterodinuclear copper(i) bis(phenanthroline)/ruthenium(ii) polypyridyl complexes were studied using ultrafast optical and multi-edge X-ray transient absorption spectroscopies. This work combines the synthesis of heterodinuclear Cu(i)-Ru(ii) analogs of the homodinuclear Cu(i)-Cu(i) targets with spectroscopic analysis and electronic structure calculations to first disentangle the dynamics at individual metal sites by taking advantage of the element and site specificity of X-ray absorption and theoretical methods. The excited state dynamical models developed for the heterodinuclear complexes are then applied to model the more challenging homodinuclear complexes. These results suggest that both intermetallic charge and energy transfer can be observed in an asymmetric dinuclear copper complex in which the ground state redox potentials of the copper sites are offset by only 310 meV. We also demonstrate the ability of several of these complexes to effectively and unidirectionally shuttle energy between different metal centers, a property that could be of great use in the design of broadly absorbing and multifunctional multimetallic photocatalysts. This work provides an important step toward developing both a fundamental conceptual picture and a practical experimental handle with which synthetic chemists, spectroscopists, and theoreticians may collaborate to engineer cheap and efficient photocatalytic materials capable of performing coulombically demanding chemical transformations.

Possible Demonstration of a Polaronic Bose-Einstein(-Mott) Condensate in UO 2(+x) by Ultrafast THz Spectroscopy and Microwave Dissipation

DOE PAGES

Conradson, Steven D.; Gilbertson, Steven M.; Daifuku, Stephanie L.; ...

2015-10-16

Bose-Einstein condensates (BECs) composed of polarons would be an advance because they would combine coherently charge, spin, and a crystal lattice. Following our earlier report of unique structural and spectroscopic properties, we now identify potentially definitive evidence for polaronic BECs in photo- and chemically doped UO 2(+x) on the basis of exceptional coherence in the ultrafast time dependent terahertz absorption and microwave spectroscopy results that show collective behavior including dissipation patterns whose precedents are condensate vortex and defect disorder and condensate excitations. Furthermore, that some of these signatures of coherence in an atom-based system extend to ambient temperature suggests amore » novel mechanism that could be a synchronized, dynamical, disproportionation excitation, possibly via the solid state analog of a Feshbach resonance that promotes the coherence. Such a mechanism would demonstrate that the use of ultra-low temperatures to establish the BEC energy distribution is a convenience rather than a necessity, with the actual requirement for the particles being in the same state that is not necessarily the ground state attainable by other means. Interestingly, a macroscopic quantum object created by chemical doping that can persist to ambient temperature and resides in a bulk solid would be revolutionary in a number of scientific and technological fields.« less

Possible Demonstration of a Polaronic Bose-Einstein(-Mott) Condensate in UO 2(+x) by Ultrafast THz Spectroscopy and Microwave Dissipation

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

Conradson, Steven D.; Gilbertson, Steven M.; Daifuku, Stephanie L.

Bose-Einstein condensates (BECs) composed of polarons would be an advance because they would combine coherently charge, spin, and a crystal lattice. Following our earlier report of unique structural and spectroscopic properties, we now identify potentially definitive evidence for polaronic BECs in photo- and chemically doped UO 2(+x) on the basis of exceptional coherence in the ultrafast time dependent terahertz absorption and microwave spectroscopy results that show collective behavior including dissipation patterns whose precedents are condensate vortex and defect disorder and condensate excitations. Furthermore, that some of these signatures of coherence in an atom-based system extend to ambient temperature suggests amore » novel mechanism that could be a synchronized, dynamical, disproportionation excitation, possibly via the solid state analog of a Feshbach resonance that promotes the coherence. Such a mechanism would demonstrate that the use of ultra-low temperatures to establish the BEC energy distribution is a convenience rather than a necessity, with the actual requirement for the particles being in the same state that is not necessarily the ground state attainable by other means. Interestingly, a macroscopic quantum object created by chemical doping that can persist to ambient temperature and resides in a bulk solid would be revolutionary in a number of scientific and technological fields.« less

Disentangling Transient Charge Density and Metal–Ligand Covalency in Photoexcited Ferricyanide with Femtosecond Resonant Inelastic Soft X-ray Scattering

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

Jay, Raphael M.; Norell, Jesper; Eckert, Sebastian

Soft X-ray spectroscopies are ideal probes of the local valence electronic structure of photocatalytically active metal sites. Here, we apply the selectivity of time-resolved resonant inelastic X-ray scattering at the iron L-edge to the transient charge distribution of an optically excited charge-transfer state in aqueous ferricyanide. Through comparison to steady-state spectra and quantum chemical calculations, the coupled effects of valence-shell closing and ligand-hole creation are experimentally and theoretically disentangled and described in terms of orbital occupancy, metal–ligand covalency, and ligand field splitting, thereby extending established steady-state concepts to the excited-state domain. π-Back-donation is found to be mainly determined by themore » metal site occupation, whereas the ligand hole instead influences σ-donation. Here, our results demonstrate how ultrafast resonant inelastic X-ray scattering can help characterize local charge distributions around catalytic metal centers in short-lived charge-transfer excited states, as a step toward future rationalization and tailoring of photocatalytic capabilities of transition-metal complexes.« less

Disentangling Transient Charge Density and Metal–Ligand Covalency in Photoexcited Ferricyanide with Femtosecond Resonant Inelastic Soft X-ray Scattering

DOE PAGES

Jay, Raphael M.; Norell, Jesper; Eckert, Sebastian; ...

2018-06-11

Soft X-ray spectroscopies are ideal probes of the local valence electronic structure of photocatalytically active metal sites. Here, we apply the selectivity of time-resolved resonant inelastic X-ray scattering at the iron L-edge to the transient charge distribution of an optically excited charge-transfer state in aqueous ferricyanide. Through comparison to steady-state spectra and quantum chemical calculations, the coupled effects of valence-shell closing and ligand-hole creation are experimentally and theoretically disentangled and described in terms of orbital occupancy, metal–ligand covalency, and ligand field splitting, thereby extending established steady-state concepts to the excited-state domain. π-Back-donation is found to be mainly determined by themore » metal site occupation, whereas the ligand hole instead influences σ-donation. Here, our results demonstrate how ultrafast resonant inelastic X-ray scattering can help characterize local charge distributions around catalytic metal centers in short-lived charge-transfer excited states, as a step toward future rationalization and tailoring of photocatalytic capabilities of transition-metal complexes.« less

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.

THz-circuits driven by photo-thermoelectric, gate-tunable graphene-junctions

NASA Astrophysics Data System (ADS)

Brenneis, Andreas; Schade, Felix; Drieschner, Simon; Heimbach, Florian; Karl, Helmut; Garrido, Jose A.; Holleitner, Alexander W.

2016-10-01

For future on-chip communication schemes, it is essential to integrate nanoscale materials with an ultrafast optoelectronic functionality into high-frequency circuits. The atomically thin graphene has been widely demonstrated to be suitable for photovoltaic and optoelectronic devices because of its broadband optical absorption and its high electron mobility. Moreover, the ultrafast relaxation of photogenerated charge carriers has been verified in graphene. Here, we show that dual-gated graphene junctions can be functional parts of THz-circuits. As the underlying optoelectronic process, we exploit ultrafast photo-thermoelectric currents. We describe an immediate photo-thermoelectric current of the unbiased device following a femtosecond laser excitation. For a picosecond time-scale after the optical excitation, an additional photo-thermoelectric contribution shows up, which exhibits the fingerprint of a spatially inverted temperature profile. The latter can be understood by the different time-constants and thermal coupling mechanisms of the electron and phonon baths within graphene to the substrate and the metal contacts. The interplay of the processes gives rise to ultrafast electromagnetic transients in high-frequency circuits, and it is equally important for a fundamental understanding of graphene-based ultrafast photodetectors and switches.

THz-circuits driven by photo-thermoelectric, gate-tunable graphene-junctions

PubMed Central

Brenneis, Andreas; Schade, Felix; Drieschner, Simon; Heimbach, Florian; Karl, Helmut; Garrido, Jose A.; Holleitner, Alexander W.

2016-01-01

For future on-chip communication schemes, it is essential to integrate nanoscale materials with an ultrafast optoelectronic functionality into high-frequency circuits. The atomically thin graphene has been widely demonstrated to be suitable for photovoltaic and optoelectronic devices because of its broadband optical absorption and its high electron mobility. Moreover, the ultrafast relaxation of photogenerated charge carriers has been verified in graphene. Here, we show that dual-gated graphene junctions can be functional parts of THz-circuits. As the underlying optoelectronic process, we exploit ultrafast photo-thermoelectric currents. We describe an immediate photo-thermoelectric current of the unbiased device following a femtosecond laser excitation. For a picosecond time-scale after the optical excitation, an additional photo-thermoelectric contribution shows up, which exhibits the fingerprint of a spatially inverted temperature profile. The latter can be understood by the different time-constants and thermal coupling mechanisms of the electron and phonon baths within graphene to the substrate and the metal contacts. The interplay of the processes gives rise to ultrafast electromagnetic transients in high-frequency circuits, and it is equally important for a fundamental understanding of graphene-based ultrafast photodetectors and switches. PMID:27762291

THz-circuits driven by photo-thermoelectric, gate-tunable graphene-junctions.

PubMed

Brenneis, Andreas; Schade, Felix; Drieschner, Simon; Heimbach, Florian; Karl, Helmut; Garrido, Jose A; Holleitner, Alexander W

2016-10-20

For future on-chip communication schemes, it is essential to integrate nanoscale materials with an ultrafast optoelectronic functionality into high-frequency circuits. The atomically thin graphene has been widely demonstrated to be suitable for photovoltaic and optoelectronic devices because of its broadband optical absorption and its high electron mobility. Moreover, the ultrafast relaxation of photogenerated charge carriers has been verified in graphene. Here, we show that dual-gated graphene junctions can be functional parts of THz-circuits. As the underlying optoelectronic process, we exploit ultrafast photo-thermoelectric currents. We describe an immediate photo-thermoelectric current of the unbiased device following a femtosecond laser excitation. For a picosecond time-scale after the optical excitation, an additional photo-thermoelectric contribution shows up, which exhibits the fingerprint of a spatially inverted temperature profile. The latter can be understood by the different time-constants and thermal coupling mechanisms of the electron and phonon baths within graphene to the substrate and the metal contacts. The interplay of the processes gives rise to ultrafast electromagnetic transients in high-frequency circuits, and it is equally important for a fundamental understanding of graphene-based ultrafast photodetectors and switches.

Electronic-structure and quantum dynamical study of the photochromism of the aromatic Schiff base salicylideneaniline

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

Ortiz-Sanchez, Juan Manuel; Gelabert, Ricard; Moreno, Miquel

2008-12-07

The ultrafast proton transfer dynamics of salicylideneaniline has been theoretically analyzed in the ground and first singlet excited electronic states using density functional theory (DFT) and time-dependent DFT calculations, which predict a ({pi},{pi}*) barrierless excited state intramolecular proton transfer (ESIPT). In addition to this, the photochemistry of salicylideneaniline is experimentally known to present fast depopulation processes of the photoexcited species before and after the proton transfer reaction. Such processes are explained by means of conical intersections between the ground and first singlet ({pi},{pi}*) excited electronic states. The electronic energies obtained by the time-dependent density functional theory formalism have been fittedmore » to a monodimensional potential energy surface in order to perform quantum dynamics study of the processes. Our results show that the proton transfer and deactivation of the photoexcited species before the ESIPT processes are completed within 49.6 and 37.7 fs, respectively, which is in remarkable good agreement with experiments.« less

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

Solvent effects on the ultrafast nonradiative deactivation mechanisms of thymine in aqueous solution: Excited-state QM/MM molecular dynamics simulations

NASA Astrophysics Data System (ADS)

Nakayama, Akira; Arai, Gaku; Yamazaki, Shohei; Taketsugu, Tetsuya

2013-12-01

On-the-fly excited-state quantum mechanics/molecular mechanics molecular dynamics (QM/MM-MD) simulations of thymine in aqueous solution are performed to investigate the role of solvent water molecules on the nonradiative deactivation process. The complete active space second-order perturbation theory (CASPT2) method is employed for a thymine molecule as the QM part in order to provide a reliable description of the excited-state potential energies. It is found that, in addition to the previously reported deactivation pathway involving the twisting of the C-C double bond in the pyrimidine ring, another efficient deactivation pathway leading to conical intersections that accompanies the out-of-plane displacement of the carbonyl group is observed in aqueous solution. Decay through this pathway is not observed in the gas phase simulations, and our analysis indicates that the hydrogen bonds with solvent water molecules play a key role in stabilizing the potential energies of thymine in this additional decay pathway.

Electronic and nuclear contributions to time-resolved optical and X-ray absorption spectra of hematite and insights into photoelectrochemical performance

DOE PAGES

Hayes, Dugan; Hadt, Ryan G.; Emery, Jonathan D.; ...

2016-11-02

Ultrafast time-resolved studies of photocatalytic thin films can provide a wealth of information crucial for understanding and thereby improving the performance of these materials by directly probing electronic structure, reaction intermediates, and charge carrier dynamics. The interpretation of transient spectra, however, can be complicated by thermally induced structural distortions, which appear within the first few picoseconds following excitation due to carrier–phonon scattering. Here we present a comparison of ex situ steady-state thermal difference spectra and transient absorption spectra spanning from NIR to hard X-ray energies of hematite thin films grown by atomic layer deposition. We find that beyond the firstmore » 100 picoseconds, the transient spectra measured for all excitation wavelengths and probe energies are almost entirely due to thermal effects as the lattice expands in response to the ultrafast temperature jump and then cools to room temperature on the microsecond timescale. At earlier times, a broad excited state absorption band that is assigned to free carriers appears at 675 nm, and the lifetime and shape of this feature also appear to be mostly independent of excitation wavelength. The combined spectroscopic data, which are modeled with density functional theory and full multiple scattering calculations, support an assignment of the optical absorption spectrum of hematite that involves two LMCT bands that nearly span the visible spectrum. Lastly, our results also suggest a framework for shifting the ligand-to-metal charge transfer absorption bands of ferric oxide films from the near-UV further into the visible part of the solar spectrum to improve solar conversion efficiency.« less

Elucidating ultrafast electron dynamics at surfaces using extreme ultraviolet (XUV) reflection-absorption spectroscopy.

PubMed

Biswas, Somnath; Husek, Jakub; Baker, L Robert

2018-04-24

Here we review the recent development of extreme ultraviolet reflection-absorption (XUV-RA) spectroscopy. This method combines the benefits of X-ray absorption spectroscopy, such as element, oxidation, and spin state specificity, with surface sensitivity and ultrafast time resolution, having a probe depth of only a few nm and an instrument response less than 100 fs. Using this technique we investigated the ultrafast electron dynamics at a hematite (α-Fe2O3) surface. Surface electron trapping and small polaron formation both occur in 660 fs following photoexcitation. These kinetics are independent of surface morphology indicating that electron trapping is not mediated by defects. Instead, small polaron formation is proposed as the likely driving force for surface electron trapping. We also show that in Fe2O3, Co3O4, and NiO, band gap excitation promotes electron transfer from O 2p valence band states to metal 3d conduction band states. In addition to detecting the photoexcited electron at the metal M2,3-edge, the valence band hole is directly observed as transient signal at the O L1-edge. The size of the resulting charge transfer exciton is on the order of a single metal-oxygen bond length. Spectral shifts at the O L1-edge correlate with metal-oxygen bond covalency, confirming the relationship between valence band hybridization and the overpotential for water oxidation. These examples demonstrate the unique ability to measure ultrafast electron dynamics with element and chemical state resolution using XUV-RA spectroscopy. Accordingly, this method is poised to play an important role to reveal chemical details of previously unseen surface electron dynamics.

Evidence for a vibrational phase-dependent isotope effect on the photochemistry of vision.

PubMed

Schnedermann, C; Yang, X; Liebel, M; Spillane, K M; Lugtenburg, J; Fernández, I; Valentini, A; Schapiro, I; Olivucci, M; Kukura, P; Mathies, R A

2018-04-01

Vibronic coupling is key to efficient energy flow in molecular systems and a critical component of most mechanisms invoking quantum effects in biological processes. Despite increasing evidence for coherent coupling of electronic states being mediated by vibrational motion, it is not clear how and to what degree properties associated with vibrational coherence such as phase and coupling of atomic motion can impact the efficiency of light-induced processes under natural, incoherent illumination. Here, we show that deuteration of the H 11 -C 11 =C 12 -H 12 double-bond of the 11-cis retinal chromophore in the visual pigment rhodopsin significantly and unexpectedly alters the photoisomerization yield while inducing smaller changes in the ultrafast isomerization dynamics assignable to known isotope effects. Combination of these results with non-adiabatic molecular dynamics simulations reveals a vibrational phase-dependent isotope effect that we suggest is an intrinsic attribute of vibronically coherent photochemical 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.

Time-resolved fluorescence polarization spectroscopy of visible and near infrared dyes in picosecond dynamics

NASA Astrophysics Data System (ADS)

Pu, Yang; Alfano, Robert R.

2015-03-01

Near-infrared (NIR) dyes absorb and emit light within the range from 700 to 900 nm have several benefits in biological studies for one- and/or two-photon excitation for deeper penetration of tissues. These molecules undergo vibrational and rotational motion in the relaxation of the excited electronic states, Due to the less than ideal anisotropy behavior of NIR dyes stemming from the fluorophores elongated structures and short fluorescence lifetime in picosecond range, no significant efforts have been made to recognize the theory of these dyes in time-resolved polarization dynamics. In this study, the depolarization of the fluorescence due to emission from rotational deactivation in solution will be measured with the excitation of a linearly polarized femtosecond laser pulse and a streak camera. The theory, experiment and application of the ultrafast fluorescence polarization dynamics and anisotropy are illustrated with examples of two of the most important medical based dyes. One is NIR dye, namely Indocyanine Green (ICG) and is compared with Fluorescein which is in visible range with much longer lifetime. A set of first-order linear differential equations was developed to model fluorescence polarization dynamics of NIR dye in picosecond range. Using this model, the important parameters of ultrafast polarization spectroscopy were identified: risetime, initial time, fluorescence lifetime, and rotation times.

Unveiling Singlet Fission Mediating States in TIPS-pentacene and its Aza Derivatives.

PubMed

Herz, Julia; Buckup, Tiago; Paulus, Fabian; Engelhart, Jens U; Bunz, Uwe H F; Motzkus, Marcus

2015-06-25

Femtosecond pump-depletion-probe experiments were carried out in order to shed light on the ultrafast excited-state dynamics of triisopropylsilylethynyl (TIPS)-pentacene and two nitrogen-containing derivatives, namely, diaza-TIPS-pentacene and tetraaza-TIPS-pentacene. Measurements performed in the visible and near-infrared spectral range in combination with rate model simulations reveal that singlet fission proceeds via the extremely short-lived intermediate (1)TT state, which absorbs in the near-infrared spectral region only. The T1 → T3 transition probed in the visible region shows a rise time that comprises two components according to a consecutive reaction (S1 → (1)TT → T1). The incorporation of nitrogen atoms into the acene structure leads to shorter dynamics, but the overall triplet formation follows the same kinetic model. This is of particular importance, since experiments on tetraaza-TIPS-pentacene allow for investigation of the triplet state in the visible range without an overlapping singlet contribution. In addition, the pump-depletion-probe experiments show that the triplet absorption in the visible (T1 → T3) and near-infrared (T1 → T2) regions occurs from the same initial state, which was questioned in previous studies. Furthermore, an additional ultrafast transfer between the excited triplet states (T3 → T2) is identified, which is also in agreement with the rate model simulation. By applying depletion pulses, which are resonant with higher vibrational levels, we gain insight into internal vibrational energy redistribution processes within the triplet manifold. This additional information is of great relevance regarding the study of loss channels within these materials.

Mechanism of resonant electron emission from the deprotonated GFP chromophore and its biomimetics.

PubMed

Bochenkova, Anastasia V; Mooney, Ciarán R S; Parkes, Michael A; Woodhouse, Joanne L; Zhang, Lijuan; Lewin, Ross; Ward, John M; Hailes, Helen C; Andersen, Lars H; Fielding, Helen H

2017-04-01

The Green Fluorescent Protein (GFP), which is widely used in bioimaging, is known to undergo light-induced redox transformations. Electron transfer is thought to occur resonantly through excited states of its chromophore; however, a detailed understanding of the electron gateway states of the chromophore is still missing. Here, we use photoelectron spectroscopy and high-level quantum chemistry calculations to show that following UV excitation, the ultrafast electron dynamics in the chromophore anion proceeds via an excited shape resonance strongly coupled to the open continuum. The impact of this state is found across the entire 355-315 nm excitation range, from above the first bound-bound transition to below the opening of higher-lying continua. By disentangling the electron dynamics in the photodetachment channels, we provide an important reference for the adiabatic position of the electron gateway state, which is located at 348 nm, and discover the source of the curiously large widths of the photoelectron spectra that have been reported in the literature. By introducing chemical modifications to the GFP chromophore, we show that the detachment threshold and the position of the gateway state, and hence the underlying excited-state dynamics, can be changed systematically. This enables a fine tuning of the intrinsic electron emission properties of the GFP chromophore and has significant implications for its function, suggesting that the biomimetic GFP chromophores are more stable to photooxidation.

Excited-State Charge Separation in the Photochemical Mechanism of the Light-Driven Enzyme Protochlorophyllide Oxidoreductase**

PubMed Central

Heyes, Derren J; Hardman, Samantha J O; Hedison, Tobias M; Hoeven, Robin; Greetham, Greg M; Towrie, Michael; Scrutton, Nigel S

2015-01-01

The unique light-driven enzyme protochlorophyllide oxidoreductase (POR) is an important model system for understanding how light energy can be harnessed to power enzyme reactions. The ultrafast photochemical processes, essential for capturing the excitation energy to drive the subsequent hydride- and proton-transfer chemistry, have so far proven difficult to detect. We have used a combination of time-resolved visible and IR spectroscopy, providing complete temporal resolution over the picosecond–microsecond time range, to propose a new mechanism for the photochemistry. Excited-state interactions between active site residues and a carboxyl group on the Pchlide molecule result in a polarized and highly reactive double bond. This so-called “reactive” intramolecular charge-transfer state creates an electron-deficient site across the double bond to trigger the subsequent nucleophilic attack of NADPH, by the negatively charged hydride from nicotinamide adenine dinucleotide phosphate. This work provides the crucial, missing link between excited-state processes and chemistry in POR. Moreover, it provides important insight into how light energy can be harnessed to drive enzyme catalysis with implications for the design of light-activated chemical and biological catalysts. PMID:25488797

Excited-state charge separation in the photochemical mechanism of the light-driven enzyme protochlorophyllide oxidoreductase.

PubMed

Heyes, Derren J; Hardman, Samantha J O; Hedison, Tobias M; Hoeven, Robin; Greetham, Greg M; Towrie, Michael; Scrutton, Nigel S

2015-01-26

The unique light-driven enzyme protochlorophyllide oxidoreductase (POR) is an important model system for understanding how light energy can be harnessed to power enzyme reactions. The ultrafast photochemical processes, essential for capturing the excitation energy to drive the subsequent hydride- and proton-transfer chemistry, have so far proven difficult to detect. We have used a combination of time-resolved visible and IR spectroscopy, providing complete temporal resolution over the picosecond-microsecond time range, to propose a new mechanism for the photochemistry. Excited-state interactions between active site residues and a carboxyl group on the Pchlide molecule result in a polarized and highly reactive double bond. This so-called "reactive" intramolecular charge-transfer state creates an electron-deficient site across the double bond to trigger the subsequent nucleophilic attack of NADPH, by the negatively charged hydride from nicotinamide adenine dinucleotide phosphate. This work provides the crucial, missing link between excited-state processes and chemistry in POR. Moreover, it provides important insight into how light energy can be harnessed to drive enzyme catalysis with implications for the design of light-activated chemical and biological catalysts. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Observation of ultrafast temporal evolution of symmetry in short-pulsed laser induced transient states of matter (Conference Presentation)

NASA Astrophysics Data System (ADS)

Garnett, Joy; Krzyzanowska, Halina; Baydin, Andrey; Tolk, Norman H.

2017-02-01

In condensed matter physics, ultrafast photoexcitation has been shown to result in modification of macroscopic material properties, sometimes involving phase changes, on a subpicosecond time scale. In semiconductors, irreversible non-thermal solid-to-liquid structural transitions have been demonstrated at high laser fluences. In the pump-probe experiments reported here, we observe a striking continuously varying low-fluence pump-induced time-dependent structural symmetry modification in intrinsic gallium arsenide (GaAs) using a probe that produces femtosecond polarization-resolved second harmonic generation (f-PRSHG) data. SHG spectroscopy is particularly suited to monitor symmetry changes since its magnitude is governed by the nonlinear optical susceptibility tensor whose elements are determined by the underlying material symmetry. Conceptually, these experiments seek to provide insight into the details of the time evolution of symmetry arising from laser induced transient states of matter in GaAs. Overall, the basic explanation of these experimental observations is that as a result of the photoinduced electronic excitation, many electrons, including bond electrons are excited to higher states. This results in subpicosecond changes in the local anharmonic potential and produces a changing nonlinear polarization response thus accounting for the nonthermal time dependent symmetry changes. Clearly, our approach may be easily extended to many different crystalline materials with different levels of defects, dopants and stresses to fully characterize the time dependent behavior of laser induced transient states in material systems.

Visualization of the ultrafast structural phase transitions in warm dense matter

NASA Astrophysics Data System (ADS)

Mo, Mianzhen

2017-10-01

It is still a great challenge to obtain real-time atomistic-scale information on the structural phase transitions that lead to warm dense matter state. Recent advances in ultrafast electron diffraction (UED) techniques have opened up exciting prospects to unravel the mechanisms of solid-liquid phase transitions under these extreme non-equilibrium conditions. Here we report on precise measurements of melt time dependency on laser excitation energy density that resolve for the first time the transition from heterogeneous to homogeneous melting. This transition appears in both polycrystalline and single-crystal gold nanofilms with distinct measurable differences. These results test predictions from molecular-dynamics simulations with different interatomic potential models. These data further deliver accurate structure factor data to large wavenumbers that allow us to constrain electron-ion equilibration constants. Our results demonstrate electron-phonon coupling strength much weaker than DFT calculations, and contrary to previous results, provide evidence for bond softening. This work is supported by DOE Office of Science, Fusion Energy Science under FWP 100182, and the DOE BES Accelerator and Detector R&D program.

Exciton versus free carrier photogeneration in organometal trihalide perovskites probed by broadband ultrafast polarization memory dynamics.

PubMed

Sheng, ChuanXiang; Zhang, Chuang; Zhai, Yaxin; Mielczarek, Kamil; Wang, Weiwei; Ma, Wanli; Zakhidov, Anvar; Vardeny, Z Valy

2015-03-20

We studied the ultrafast transient response of photoexcitations in two hybrid organic-inorganic perovskite films used for high efficiency photovoltaic cells, namely, CH(3)NH(3)PbI(3) and CH(3)NH(3)PbI(1.1)Br(1.9) using polarized broadband pump-probe spectroscopy in the spectral range of 0.3-2.7 eV with 300 fs time resolution. For CH(3)NH(3)PbI(3) with above-gap excitation we found both photogenerated carriers and excitons, but only carriers are photogenerated with below-gap excitation. In contrast, mainly excitons are photogenerated in CH(3)NH(3)PbI(1.1)Br(1.9). Surprisingly, we also discovered in CH(3)NH(3)PbI(3), but not in CH(3)NH(3)PbI(1.1)Br(1.9), transient photoinduced polarization memory for both excitons and photocarriers, which is also reflected in the steady state photoluminescence. From the polarization memory dynamics we obtained the excitons diffusion constant in CH(3)NH(3)PbI(3), D≈0.01  cm(2) s(-1).

Exciton versus Free Carrier Photogeneration in Organometal Trihalide Perovskites Probed by Broadband Ultrafast Polarization Memory Dynamics

NASA Astrophysics Data System (ADS)

Sheng, ChuanXiang; Zhang, Chuang; Zhai, Yaxin; Mielczarek, Kamil; Wang, Weiwei; Ma, Wanli; Zakhidov, Anvar; Vardeny, Z. Valy

2015-03-01

We studied the ultrafast transient response of photoexcitations in two hybrid organic-inorganic perovskite films used for high efficiency photovoltaic cells, namely, CH3NH3PbI3 and CH3NH3PbI1.1Br1.9 using polarized broadband pump-probe spectroscopy in the spectral range of 0.3-2.7 eV with 300 fs time resolution. For CH3NH3PbI3 with above-gap excitation we found both photogenerated carriers and excitons, but only carriers are photogenerated with below-gap excitation. In contrast, mainly excitons are photogenerated in CH3NH3PbI1.1Br1.9 . Surprisingly, we also discovered in CH3NH3PbI3 , but not in CH3NH3PbI1.1Br1.9 , transient photoinduced polarization memory for both excitons and photocarriers, which is also reflected in the steady state photoluminescence. From the polarization memory dynamics we obtained the excitons diffusion constant in CH3NH3PbI3 , D ≈0.01 cm2 s-1 .

Spatially confined low-power optically pumped ultrafast synchrotron x-ray nanodiffraction

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

Park, Joonkyu; Zhang, Qingteng; Chen, Pice

2015-08-27

The combination of ultrafast optical excitation and time-resolved synchrotron x-ray nanodiffraction provides unique insight into the photoinduced dynamics of materials, with the spatial resolution required to probe individual nanostructures or small volumes within heterogeneous materials. Optically excited x-ray nanobeam experiments are challenging because the high total optical power required for experimentally relevant optical fluences leads to mechanical instability due to heating. For a given fluence, tightly focusing the optical excitation reduces the average optical power by more than three orders of magnitude and thus ensures sufficient thermal stability for x-ray nanobeam studies. Delivering optical pulses via a scannable fiber-coupled opticalmore » objective provides a well-defined excitation geometry during rotation and translation of the sample and allows the selective excitation of isolated areas within the sample. Finally, experimental studies of the photoinduced lattice dynamics of a 35 nm BiFeO 3 thin film on a SrTiO 3 substrate demonstrate the potential to excite and probe nanoscale volumes.« less

Analysis of isomeric ratios for medium-mass nuclei

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

Danagulyan, A. S.; Hovhannisyan, G. H., E-mail: hov-gohar@ysu.am; Bakhshiyan, T. M.

Values of the isomeric ratios for product nuclei originating from simple charge-exchange reactions were analyzed. The cross sections for the formation of product nuclei in ground and isomeric states were calculated with the aid of the TALYS 1.4 and EMPIRE 3.2 codes. The calculated values of the isomeric ratios were compared with their experimental counterparts taken from the EXFOR database. For the {sup 86,87}Y, {sup 94,95,96,99}Tc, and {sup 44}Sc nuclei, the experimental values of the isomeric ratios exceed the respective calculated values. The nuclei in question feature weak deformations and have high-spin yrast lines and rotational bands. The possible reasonmore » behind the discrepancy between theoretical and experimental isomeric ratios is that the decay of yrast states leads with a high probability to the formation of isomeric states of detected product nuclei.« less

A system to measure isomeric state half-lives in the 10 ns to 10 μs range

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

Toufen, D. L., E-mail: dennis@if.usp.br; Federal Institute of Education, Science and Technology of São Paulo - IFSP, 07115-000 Guarulhos, São Paulo; Allegro, P. R. P.

2014-07-15

The Isomeric State Measurement System (SISMEI) was developed to search for isomeric nuclear states produced by fusion-evaporation reactions. The SISMEI consists of 10 plastic phoswich telescopes, two lead shields, one NaI(Tl) scintillation detector, two Compton suppressed HPGe γ-ray detectors, and a cone with a recoil product catcher. The new system was tested at the 8 UD Pelletron tandem accelerator of the University of São Paulo with the measurement of two known isomeric states: {sup 54}Fe, 10{sup +} state (E = 6527.1 (11) keV, T{sub 1/2} = 364(7) ns) and the 5/2{sup +} state of {sup 19}F (E = 197.143 (4)more » keV, T{sub 1/2} = 89.3 (10) ns). The results indicate that the system is capable of identifying delayed transitions, of measuring isomeric state lifetimes, and of identifying the feeding transitions of the isomeric state through the delayed γ-γ coincidence method. The measured half-life for the 10{sup +} state was T{sub 1/2} = 365(14) ns and for the 5/2{sup +} state, 100(36) ns.« less

New low-spin states of 122Xe observed via high-statistics β-decay of 122Cs

NASA Astrophysics Data System (ADS)

Jigmeddorj, B.; Garrett, P. E.; Andreoiu, C.; Ball, G. C.; Bruhn, T.; Cross, D. S.; Garnsworthy, A. B.; Hadinia, B.; Moukaddam, M.; Park, J.; Pore, J. L.; Radich, A. J.; Rajabali, M. M.; Rand, E. T.; Rizwan, U.; Svensson, C. E.; Voss, P.; Wang, Z. M.; Wood, J. L.; Yates, S. W.

2018-05-01

Excited states of 122Xe were studied via the β+/EC decay of 122Cs with the 8π γ-ray spectrometer at the TRIUMF-ISAC facility. Compton-suppressed HPGe detectors were used for measurements of γ-ray intensities, γγ coincidences, and γ-γ angular correlations. Two sets of data were collected to optimize the decays of the ground (21.2 s) and isomeric (3.7 min) states of 122Cs. The data collected have enabled the observation of about 505 new transitions and about 250 new levels, including 51 new low-spin states. Spin assignments have been made for 58 low-spin states based on the deduced β-decay feeding and γ-γ angular correlation analyses.

Chromophore Protonation State Controls Photoswitching of the Fluoroprotein asFP595

PubMed Central

Schäfer, Lars V.; Groenhof, Gerrit; Boggio-Pasqua, Martial; Robb, Michael A.; Grubmüller, Helmut

2008-01-01

Fluorescent proteins have been widely used as genetically encodable fusion tags for biological imaging. Recently, a new class of fluorescent proteins was discovered that can be reversibly light-switched between a fluorescent and a non-fluorescent state. Such proteins can not only provide nanoscale resolution in far-field fluorescence optical microscopy much below the diffraction limit, but also hold promise for other nanotechnological applications, such as optical data storage. To systematically exploit the potential of such photoswitchable proteins and to enable rational improvements to their properties requires a detailed understanding of the molecular switching mechanism, which is currently unknown. Here, we have studied the photoswitching mechanism of the reversibly switchable fluoroprotein asFP595 at the atomic level by multiconfigurational ab initio (CASSCF) calculations and QM/MM excited state molecular dynamics simulations with explicit surface hopping. Our simulations explain measured quantum yields and excited state lifetimes, and also predict the structures of the hitherto unknown intermediates and of the irreversibly fluorescent state. Further, we find that the proton distribution in the active site of the asFP595 controls the photochemical conversion pathways of the chromophore in the protein matrix. Accordingly, changes in the protonation state of the chromophore and some proximal amino acids lead to different photochemical states, which all turn out to be essential for the photoswitching mechanism. These photochemical states are (i) a neutral chromophore, which can trans-cis photoisomerize, (ii) an anionic chromophore, which rapidly undergoes radiationless decay after excitation, and (iii) a putative fluorescent zwitterionic chromophore. The overall stability of the different protonation states is controlled by the isomeric state of the chromophore. We finally propose that radiation-induced decarboxylation of the glutamic acid Glu215 blocks the proton transfer pathways that enable the deactivation of the zwitterionic chromophore and thus leads to irreversible fluorescence. We have identified the tight coupling of trans-cis isomerization and proton transfers in photoswitchable proteins to be essential for their function and propose a detailed underlying mechanism, which provides a comprehensive picture that explains the available experimental data. The structural similarity between asFP595 and other fluoroproteins of interest for imaging suggests that this coupling is a quite general mechanism for photoswitchable proteins. These insights can guide the rational design and optimization of photoswitchable proteins. PMID:18369426

Stimulated Raman scattering: old physics, new applications.

PubMed

Yakovlev, Vladislav V; Petrov, Georgi I; Zhang, Hao F; Noojin, Gary D; Denton, Michael L; Thomas, Robert J; Scully, Marlan O

2009-10-01

Stimulated Raman scattering as a promising way of expanding the tunability of ultrafast lasers and as an exciting new biomedical imaging modality capable of selective excitation and chemically-specific diagnostics of molecular species.

Ultrafast photo-induced hidden phases in strained manganite thin films

NASA Astrophysics Data System (ADS)

Zhang, Jingdi; McLeod, A. S.; Zhang, Gu-Feng; Stoica, Vladimir; Jin, Feng; Gu, Mingqiang; Gopalan, Venkatraman; Freeland, John W.; Wu, Wenbin; Rondinelli, James; Wen, Haidan; Basov, D. N.; Averitt, R. D.

Correlated transition metal oxides (TMOs) are particularly sensitive to external control because of energy degeneracy in a complex energy landscape that promote a plethora of metastable states. However, it remains a grand challenge to actively control and fully explore the rich landscape of TMOs. Dynamic control with pulsed photons can overcome energetic barriers, enabling access to transient or metastable states that are not thermally accessible. In the past, we have demonstrated that mode-selective single-laser-pulse excitation of a strained manganite thin film La2/3Ca1/3MnO3 initiates a persistent phase transition from an emergent antiferromagnetic insulating ground state to a ferromagnetic metallic metastable state. Beyond the photo-induced insulator to metal transition, we recently discovered a new peculiar photo-induced hidden phase, identified by an experimental approach that combines ultrafast pump-probe spectroscopy, THz spectroscopy, X-ray diffraction, cryogenic near-field spectroscopy and SHG probe. This work is funded by the DOE, Office of Science, Office of Basic Energy Science under Award Numbers DE-SC0012375 and DE-SC0012592.

Patterns of Broken Patterns

NASA Astrophysics Data System (ADS)

Field, R. W.; Park, G. B.; Changala, P. B.; Baraban, J. H.; Stanton, J. F.; Merer, A. J.

2013-06-01

Spectroscopy - it is all about patterns. Some patterns look so indescribably complicated that, unlike pornography, you do not know one when you see one. It is tempting to say that, at high vibrational excitation, interactions among normal mode basis states are so strong and widespread that all patterns are obliterated. But this is not true. When normal mode frequencies are in near integer multiple ratios, polyads emerge. A polyad is a robust pattern often comprising many vibrational eigenstates. Each such pattern might span many hundreds of cm^{-1}, and it is inevitable that several unrelated polyad patterns overlap. When polyads overlap, it might seem impossible to disentangle them. However, the key to disentanglement is that polyads come in families in which successive generations are related by harmonic oscillator matrix element selection and scaling rules. Families of polyads are described by families of scaling-based effective Hamiltonian matrices, {H}^{{eff}}. No matter how complex and overlapped, the polyad {H}^{{eff}} serves as a magic decoder for picking out the polyad pattern. Sometimes the polyad patterns are systematically broken (a meta-pattern), owing to proximity to an isomerization barrier, as occurs in highly excited bending levels of the S_{1} state of HCCH, which encode the trans-cis minimum energy isomerization path. Quantum Chemists often dismiss {H}^{{eff}} models, precisely because they are models that do not express the full dimensionality of the complete Hamiltonian. But an {H}^{{eff}} explains rather than describes. Shunning {H}^{{eff}}s is like throwing out the baby with the bath water. Don't do it!

Probing ultrafast ππ*/nπ* internal conversion in organic chromophores via K-edge resonant absorption

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

Wolf, T. J. A.; Myhre, R. H.; Cryan, J. P.

Many photoinduced processes including photosynthesis and human vision happen in organic molecules and involve coupled femtosecond dynamics of nuclei and electrons. Organic molecules with heteroatoms often possess an important excited-state relaxation channel from an optically allowed ππ* to a dark nπ* state. The ππ*/nπ* internal conversion is difficult to investigate, as most spectroscopic methods are not exclusively sensitive to changes in the excited-state electronic structure. Here, we report achieving the required sensitivity by exploiting the element and site specificity of near-edge soft X-ray absorption spectroscopy. As a hole forms in the n orbital during ππ*/nπ* internal conversion, the absorption spectrummore » at the heteroatom K-edge exhibits an additional resonance. We demonstrate the concept using the nucleobase thymine at the oxygen K-edge, and unambiguously show that ππ*/nπ* internal conversion takes place within (60 ± 30) fs. Furthermore, high-level-coupled cluster calculations confirm the method’s impressive electronic structure sensitivity for excited-state investigations.« less