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The deconvolution of low-resolution time-of-flight data has numerous advantages, including the ability to extract additional information from the experimental data. We augment the well-known Lucy-Richardson deconvolution algorithm using various Bayesian prior distributions and show that a prior of second-differences of the signal outperforms the standard Lucy-Richardson algorithm, accelerating the rate of convergence by more than a factor of four, while preserving the peak amplitude ratios of a similar fraction of the total peaks. A novel stopping criterion and boosting mechanism are implemented to ensure that these methods converge to a similar final entropy and local minima are avoided. Improvement by a factor of two in mass resolution allows more accurate quantification of the spectra. The general method is demonstrated in this paper through the deconvolution of fragmentation peaks of the 2,5-dihydroxybenzoic acid matrix and the benzyltriphenylphosphonium thermometer ion, following femtosecond ultraviolet laser desorption. [ABSTRACT FROM AUTHOR]

The development of electron sources capable of temporal resolution on the order of 1 ps or less raises a number of questions associated with the estimation of the physical meaning and accuracy of the dynamic parameters based on the analysis of time-dependent scattering intensity. The use of low brightness ultrashort pulses with few electrons leads to the necessity for increasing the total exposure time and lengthening the time of data acquisition, with attendant problems with the limited sample. The sample restrictions can be mitigated by increasing the charge per pulse, i.e., by going to high brightness sources. Increasing in the number of electrons, however, is limited by the Coulomb repulsion between them, which leads on one hand to distortion of the diffraction pattern and on the other hand to an increase in the duration of the pulse. An analytical technique for estimating the deformation of the diffraction pattern caused by the Coulomb repulsion of the electrons in electron bunches with duration of less than 10 ps and the influence of this effect on the accuracy of determination of the interatomic distances is developed for the non-relativistic and relativistic regimes for electron energies. [ABSTRACT FROM AUTHOR]

We have employed ultrafast transient-grating and two- dimensional electronic spectroscopy to probe dynamics of photo-excited CH3NH3PbI3 thin films with 16-fs temporal resolution. We distinctly capture the 30-fs decay of excitons, weakly coupled to the phonons.

Femtosecond electron diffraction is used to resolve structural dynamics in single-crystal (EDO-TTF)2XF6 (X = P, Sb). The retarded and lower-dimensional dynamics of the latter illustrate the dominant role of counterion motion in stabilizing electron transfer.

The photochemistry of the triiodide anion has been investigated by femtosecond electron diffraction. The time-resolved signal indicates the presence of reaction products and large-amplitude coherent motion produced by participating species. To reconstruct the atomic detail of the reaction and identify the major contributors to the detected signal, we outline the approach for atomic-level reconstruction.

Femtosecond spectroscopy and electron diffraction are used to characterize spin crossover in single crystal iron(II)-tris(bipyridine)-bis(hexafluorophosphate). The high-spin lifetime is reduced compared to in solution. Preliminary electron diffraction experiments show evidence of ultrafast Fe-N bond elongation associated with spin crossover and the subsequent molecular reorganization resulting from vibrational cooling.

Photoinduced spin transitions are studied by femtosecond electron diffraction to understand ultrafast structural dynamics associated with intersystem crossing. The results indicate the structural reorganization occurs within 2.3 ps, as the metal-ligand bond distribution narrows during intramolecular vibrational energy redistribution.

The wave guiding feature of the optical fibre optical fibres is specifically exploited to construct a novel type of electron gun to realize single-shot low-energy electron diffraction experiments with the sub-picosecond resolution for studying irreversible samples.

We have studied the FMO, LHCII and PSII reaction center complex by electronic 2D spectroscopy. At ambient temperature the electronic coherences are too short lived to play any functional role in the natural energy transfer.

Material ablation and evaporation using pulsed infrared lasers pose promising approaches for matrix-free laser desorption ionization and in laser surgery. For the best results, key parameters such as laser wavelength, pulse duration, and pulse energy need to be carefully adjusted to the application. We characterize the dynamics at the water-air interface induced by a 10 ps infrared laser tuned to the water absorption band at 3 μ m , a parameter set facilitating stress confined desorption for typical absorption depths in biological samples and tissue. By driving the ablation faster than nucleation growth, cavitation induced sample damage during the ablation process can be mitigated. The resultant explosive ablation process leads to a shock front expansion and material ejection which we capture using off-axis digital interference microscopy, an interference technique particularly useful for detecting the phase shift caused by transparent objects. It is demonstrated that the method can yield local density information of the observed shock front with a single image acquisition as compared to the usually performed fit of the velocity extracted from several consecutive snapshots. We determine the ablation threshold to be (0.5 ± 0.2) J cm − 2 and observe a significant distortion of the central parts of the primary shock wave above approximately 2.5 J cm − 2 . The differences in plume shape observed for higher fluences are reflected in an analysis based on shock wave theory, which shows a very fast initial expansion. [ABSTRACT FROM AUTHOR]

This work treats the impact of vibrational coherence on the quantum efficiency of a dissipative electronic wave packet in the vicinity of a conical intersection by monitoring the time-dependent wave packet projection onto the tuning and the coupling mode. The vibrational coherence of the wave packet is tuned by varying the strength of the dissipative vibrational coupling of the tuning and the coupling modes to their thermal baths. We observe that the most coherent wave packet yields a quantum efficiency of 93%, but with a large transfer time constant. The quantum yield is dramatically decreased to 50% for a strongly damped incoherentwave packet, but the associated transfer time of the strongly localized wave packet is short. In addition, we find for the strongly damped wave packet that the transfer occurs via tunneling of the wave packet between the potential energy surfaces before the seam of the conical intersection is reached and a direct passage takes over. Our results provide direct evidence that vibrational coherence of the electronicwave packet is a decisive factor which determines the dynamical behavior of a wave packet in the vicinity of the conical intersection. [ABSTRACT FROM AUTHOR]