Femtosecond real-time probing of reactions. 13. Multiphoton dynamics of IHgI

Real-time studies of the dynamics were performed on the reaction of HgI_2 in a molecular beam. Excitation was by either one or multi pump photons (311 nm), leading to two separate sets of dynamics, each of which could be investigated by a time-delayed probe laser (622 nm) that ionized the parent molecule and the fragments by REMPI processes. These dynamics were distinguished by combining the information from transients taken at each mass (HgI_2, HgI, I_2, Hg, and I) with the results of pump (and probe) power dependence studies on each mass. A method of plotting the slope of the intensity dependence against the pump-probe time delay proved essential. In the preceding publication, we detailed the dynamics of the reaction initiated by a one photon excitation to the A-continuum. Here, we present studies of higher-energy states. Multiphoton excitation accesses predissociative states of HgI_2, for which there are crossings into the symmetric and asymmetric stretch coordinates. The dynamics of these channels, which lead to atomic (I or Hg) and diatomic (HgI) fragments, are discussed and related to the nature of the intermediates along the reaction pathway.

Femtosecond real-time probing of reactions

Femtosecond reaction dynamics of OClO in a supersonic molecular beam are reported. The system is excited to the A^2A_2 state with a femtosecond pulse, covering a range of excitation in the symmetric stretch between v_1 = 17 to v_1 = 11 (308-352 nm). A time-delayed femtosecond probe pulse ionizes the OClO, and OClO^+ is detected. This ion has not been observed in previous experiments because of its ultrafast fragmentation. Transients are reported for the mass of the parent OClO as well as the mass of the ClO. Apparent biexponential decays are observed and related to the fragmentation dynamics: OClO+hv \rightarrow (OClO)^{(++)*} \rightarrow ClO+O \rightarrow Cl+O_2. Clusters of OClO with water (OClO)_n (H_2 0)_m with n from 1 to 3 and m from 0 to 3 are also observed. The dynamics of the fragmentation reveal the nuclear motions and the electronic coupling between surfaces. The time scale for bond breakage is in the range of 300-500 fs, depending on v_1; surface crossing to form new intermediates is a pathway for the two channels of fragmentation: ClO+O (primary) and Cl+O_2 (minor). Comparisons with results of ab initio calculations are made.

Das Einzugsgebiet der Fulda - Untersuchung der Methoden der Hochwasserstatistik im Zeichen des Klimawandels

Numerous studies have proven an effect of a probable climate change on the hydrosphere’s different subsystems. In the 21st century global and regional redistribution of water has to be expected and it is very likely that extreme weather phenomenon will occur more frequently. From a global view the flood situation will exacerbate. In contrast to these discoveries the classical approach of flood frequency analysis provides terms like “mean flood recurrence interval”. But for this analysis to be valid there is a need for the precondition of stationary distribution parameters which implies that the flood frequencies are constant in time. Newer approaches take into account extreme value distributions with time-dependent parameters. But the latter implies a discard of the mentioned old terminology that has been used up-to-date in engineering hydrology. On the regional scale climate change affects the hydrosphere in various ways. So, the question appears to be whether in central Europe the classical approach of flood frequency analysis is not usable anymore and whether the traditional terminology should be renewed. In the present case study hydro-meteorological time series of the Fulda catchment area (6930 km²), upstream of the gauging station Bonaforth, are analyzed for the time period 1960 to 2100. At first a distributed catchment area model (SWAT2005) is build up, calibrated and finally validated. The Edertal reservoir is regulated as well by a feedback control of the catchments output in case of low water. Due to this intricacy a special modeling strategy has been necessary: The study area is divided into three SWAT basin models and an additional physically-based reservoir model is developed. To further improve the streamflow predictions of the SWAT model, a correction by an artificial neural network (ANN) has been tested successfully which opens a new way to improve hydrological models. With this extension the calibration and validation of the SWAT model for the Fulda catchment area is improved significantly. After calibration of the model for the past 20th century observed streamflow, the SWAT model is driven by high resolution climate data of the regional model REMO using the IPCC scenarios A1B, A2, and B1, to generate future runoff time series for the 21th century for the various sub-basins in the study area. In a second step flood time series HQ(a) are derived from the 21st century runoff time series (scenarios A1B, A2, and B1). Then these flood projections are extensively tested with regard to stationarity, homogeneity and statistical independence. All these tests indicate that the SWAT-predicted 21st-century trends in the flood regime are not significant. Within the projected time the members of the flood time series are proven to be stationary and independent events. Hence, the classical stationary approach of flood frequency analysis can still be used within the Fulda catchment area, notwithstanding the fact that some regional climate change has been predicted using the IPCC scenarios. It should be noted, however, that the present results are not transferable to other catchment areas. Finally a new method is presented that enables the calculation of extreme flood statistics, even if the flood time series is non-stationary and also if the latter exhibits short- and longterm persistence. This method, which is called Flood Series Maximum Analysis here, enables the calculation of maximum design floods for a given risk- or safety level and time period.

Femtosecond wavepacket interferometry using the rotational dynamics of a trapped cold molecular ion

A Ramsey-type interferometer is suggested, employing a cold trapped ion and two time-delayed offresonant femtosecond laser pulses. The laser light couples to the molecular polarization anisotropy, inducing rotational wavepacket dynamics. An interferogram is obtained from the delay dependent populations of the final field-free rotational states. Current experimental capabilities for cooling and preparation of the initial state are found to yield an interferogram visibility of more than 80%. The interferograms can be used to determine the polarizability anisotropy with an accuracy of about ±2%, respectively ±5%, provided the uncertainty in the initial populations and measurement errors are confined to within the same limits.

Efficient Characterisation and Optimal Control of Open Quantum Systems - Mathematical Foundations and Physical Applications

Since no physical system can ever be completely isolated from its environment, the study of open quantum systems is pivotal to reliably and accurately control complex quantum systems. In practice, reliability of the control field needs to be confirmed via certification of the target evolution while accuracy requires the derivation of high-fidelity control schemes in the presence of decoherence. In the first part of this thesis an algebraic framework is presented that allows to determine the minimal requirements on the unique characterisation of arbitrary unitary gates in open quantum systems, independent on the particular physical implementation of the employed quantum device. To this end, a set of theorems is devised that can be used to assess whether a given set of input states on a quantum channel is sufficient to judge whether a desired unitary gate is realised. This allows to determine the minimal input for such a task, which proves to be, quite remarkably, independent of system size. These results allow to elucidate the fundamental limits regarding certification and tomography of open quantum systems. The combination of these insights with state-of-the-art Monte Carlo process certification techniques permits a significant improvement of the scaling when certifying arbitrary unitary gates. This improvement is not only restricted to quantum information devices where the basic information carrier is the qubit but it also extends to systems where the fundamental informational entities can be of arbitary dimensionality, the so-called qudits. The second part of this thesis concerns the impact of these findings from the point of view of Optimal Control Theory (OCT). OCT for quantum systems utilises concepts from engineering such as feedback and optimisation to engineer constructive and destructive interferences in order to steer a physical process in a desired direction. It turns out that the aforementioned mathematical findings allow to deduce novel optimisation functionals that significantly reduce not only the required memory for numerical control algorithms but also the total CPU time required to obtain a certain fidelity for the optimised process. The thesis concludes by discussing two problems of fundamental interest in quantum information processing from the point of view of optimal control - the preparation of pure states and the implementation of unitary gates in open quantum systems. For both cases specific physical examples are considered: for the former the vibrational cooling of molecules via optical pumping and for the latter a superconducting phase qudit implementation. In particular, it is illustrated how features of the environment can be exploited to reach the desired targets.