| 1. |
- Canton, Sophie, et al.
(författare)
-
Toward Highlighting the Ultrafast Electron Transfer Dynamics at the Optically Dark Sites of Photocatalysts
- 2013
-
Ingår i: The Journal of Physical Chemistry Letters. - : American Chemical Society (ACS). - 1948-7185. ; 4:11, s. 1972-1976
-
Tidskriftsartikel (refereegranskat)abstract
- Building a detailed understanding of the structure function relationship is a crucial step in the optimization of molecular photocatalysts employed in water splitting schemes. The optically dark nature of their active sites usually prevents a complete mapping of the photoinduced dynamics. In this work, transient X-ray absorption spectroscopy highlights the electronic and geometric changes that affect such a center in a bimetallic model complex. Upon selective excitation of the ruthenium chromophore, the cobalt moiety is reduced through intramolecular electron transfer and undergoes a spin flip accompanied by an average bond elongation of 0.20 +/- 0.03 angstrom. The analysis is supported by simulations based on density functional theory structures (B3LYP*/TZVP) and FEFF 9.0 multiple scattering calculations. More generally, these results exemplify the large potential of the technique for tracking elusive intermediates that impart unique functionalities in photochemical devices.
|
|
| 2. |
- Kjaer, Christina, et al.
(författare)
-
Luminescence Spectroscopy of Rhodamine Homodimer Dications in Vacuo Reveals Strong Dye-Dye Interactions
- 2019
-
Ingår i: ChemPhysChem. - : Wiley. - 1439-4235 .- 1439-7641. ; 20:4, s. 533-537
-
Tidskriftsartikel (refereegranskat)abstract
- Being alone or together makes a difference for the photophysics of dyes but for ionic dyes it is difficult to quantify the interactions due to solvent screening and nearby counter ions. Gas-phase luminescence experiments are desirable and now possible based on recent developments in mass spectrometry. Here we present results on tailor-made rhodamine homodimers where two dye cations are separated by methylene linkers, (CH2)(n). In solution the fluorescence is almost identical to that from the monomer whereas the emission from bare cation dimers redshifts with decreasing n. In the absence of screening, the electric field from the charge on one dye is strong enough to polarize the other dye, both in the ground state and in the excited state. An electrostatic model based on symmetric dye responses (equal induced-dipole moments in ground state) captures the underlying physics and demonstrates interaction even at large distances. Our results have possible implications for gas-phase Forster Resonance Energy Transfer.
|
|
| 3. |
- Vanko, Gyoergy, et al.
(författare)
-
Spin-state studies with XES and RIXS: From static to ultrafast
- 2013
-
Ingår i: Journal of Electron Spectroscopy and Related Phenomena. - : Elsevier BV. - 0368-2048. ; 188, s. 166-171
-
Tidskriftsartikel (refereegranskat)abstract
- We report on extending hard X-ray emission spectroscopy (XES) along with resonant inelastic X-ray scattering (RIXS) to study ultrafast phenomena in a pump-probe scheme at MHz repetition rates. The investigated systems include low-spin (LS) Fe-II complex compounds, where optical pulses induce a spin-state transition to their (sub)nanosecond-lived high-spin (HS) state. Time-resolved XES clearly reflects the spin-state variations with very high signal-to-noise ratio, in agreement with HS-LS difference spectra measured at thermal spin crossover, and reference HS-LS systems in static experiments, next to multiplet calculations. The 1s2p RIXS, measured at the Fe Is pre-edge region, shows variations after laser excitation, which are consistent with the formation of the HS state. Our results demonstrate that X-ray spectroscopy experiments with overall rather weak signals, such as RIXS, can now be reliably exploited to study chemical and physical transformations on ultrafast time scales. (C) 2012 Elsevier B.V. All rights reserved.
|
|
| 4. |
- Biasin, Elisa, et al.
(författare)
-
Femtosecond X-Ray Scattering Study of Ultrafast Photoinduced Structural Dynamics in Solvated[Co(terpy)2]2$
- 2016
-
Ingår i: Physical Review Letters. - : American Physical Society (APS). - 1079-7114 .- 0031-9007. ; 117:1
-
Tidskriftsartikel (refereegranskat)abstract
- 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 the high spin state is established on a single-picosecond time scale and that this state has a lifetime of ∼7 ps.
|
|
| 5. |
|
|
| 6. |
- Canton, Sophie, et al.
(författare)
-
Visualizing the non-equilibrium dynamics of photoinduced intramolecular electron transfer with femtosecond X-ray pulses.
- 2015
-
Ingår i: Nature Communications. - : Springer Science and Business Media LLC. - 2041-1723. ; 6
-
Tidskriftsartikel (refereegranskat)abstract
- Ultrafast photoinduced electron transfer preceding energy equilibration still poses many experimental and conceptual challenges to the optimization of photoconversion since an atomic-scale description has so far been beyond reach. Here we combine femtosecond transient optical absorption spectroscopy with ultrafast X-ray emission spectroscopy and diffuse X-ray scattering at the SACLA facility to track the non-equilibrated electronic and structural dynamics within a bimetallic donor-acceptor complex that contains an optically dark centre. Exploiting the 100-fold increase in temporal resolution as compared with storage ring facilities, these measurements constitute the first X-ray-based visualization of a non-equilibrated intramolecular electron transfer process over large interatomic distances. Experimental and theoretical results establish that mediation through electronically excited molecular states is a key mechanistic feature. The present study demonstrates the extensive potential of femtosecond X-ray techniques as diagnostics of non-adiabatic electron transfer processes in synthetic and biological systems, and some directions for future studies, are outlined.
|
|
| 7. |
- Abdallah, J, et al.
(författare)
-
Rapidity-alignment and p(T) compensation of particle pairs in hadronic Z(0) decays
- 2002
-
Ingår i: Physics Letters. Section B: Nuclear, Elementary Particle and High-Energy Physics. - 0370-2693. ; 533:3-4, s. 243-252
-
Tidskriftsartikel (refereegranskat)abstract
- Observation is made of rapidity-alignment of K+K- and (p) over barp pairs which results from their asymmetric orientation in rapidity, with respect to the direction from primary quark to antiquark. The K+K- and (p) over barp data are consistent with predictions from the fragmentation string model. However, the (p) over barp data strongly disagree with the conventional implementation of the cluster model. The non-perturbative process of 'gluon splitting to diquarks' has to be incorporated into the cluster model for it to agree with the data. Local conservation of PT between particles nearby in rapidity (i.e., p(T) compensation) is analysed with respect to the thrust direction for pi(+)pi(-), K+K-, and (p) over barp pairs. In this case, the string model provides fair agreement with the data. The cluster model is incompatible with the data for all three particle pairs. The model with its central premiss of isotropically-decaying clusters predicts a p(T) correlation not seen in the data. (C) 2002 Elsevier Science B.V. All rights reserved.
|
|
| 8. |
- Abdallah, J, et al.
(författare)
-
Search for charged Higgs bosons in e(+)e(-) collisions root s=189-202 GeV
- 2002
-
Ingår i: Physics Letters. Section B: Nuclear, Elementary Particle and High-Energy Physics. - 0370-2693. ; 525:1-2, s. 17-28
-
Tidskriftsartikel (refereegranskat)abstract
- A search for pair-produced charged Higgs bosons was performed in the high energy data collected by the DELPHI detector at LEP II at centre-of-mass energies from 189 GeV to 202 GeV. The three different final states, taunutaunu, c (s) over bar(c) over bars and c (s) over bar taunu were considered. New methods were applied to reject wrong hadronic jet pairings and for the tau identification, where a discriminator based on tau polarisation and polar angles was used. No excess of data compared to the expected Standard Model processes was observed and the existence of a charged Higgs boson with mass lower than 71.5 GeV/c(2) is excluded at the 95% confidence level. (C) 2002 Published by Elsevier Science B.V.
|
|
| 9. |
- Abdallah, J, et al.
(författare)
-
Searches for neutral Higgs bosons in e(+)e(-), collisions from root s=191.6 to 201.7 GeV
- 2002
-
Ingår i: European Physical Journal C. Particles and Fields. - : Springer Science and Business Media LLC. - 1434-6044. ; 23:3, s. 409-435
-
Tidskriftsartikel (refereegranskat)abstract
- Neutral Higgs bosons of the Standard Model (SM) and the Minimal Supersymmetric Standard Model (MSSM) were searched for in the data collected in 1999 by the DELPHI experiment at centre-of-mass energies between 191.6 and 201.7 GeV with a total integrated luminosity of 228 pb(-1). These analyses, in combination with our results at lower energies, set 95% confidence level lower mass bounds on the Standard Model Higgs boson (107.3 GeV/c(2)) and on the lightest neutral scalar (85.9 GeV/c(2)) and neutral pseudoscalar (86.5 GeV/c(2)) Higgs bosons in representative scans of the MSSM parameter space. An extended scan of the MSSM parameter space was also performed to test the robustness of these limits.
|
|
| 10. |
- Abreu, P, et al.
(författare)
-
b-tagging in DELPHI at LEP
- 2004
-
Ingår i: European Physical Journal C. Particles and Fields. - : Springer Science and Business Media LLC. - 1434-6044. ; 32:2, s. 185-208
-
Tidskriftsartikel (refereegranskat)abstract
- The standard method used for tagging b-hadrons in the DELPHI experiment at the CERN LEP Collider is discussed in detail. The main ingredient of b-tagging is the impact parameters of tracks, which relies mostly on the vertex detector. Additional information, such as the mass of particles associated to a secondary vertex, significantly improves the selection efficiency and the background suppression. The paper describes various discriminating variables used for the tagging and the procedure of their combination. In addition, applications of b-tagging to some physics analyses, which depend crucially on the performance and reliability of b-tagging, are described briefly.
|
|
