Time-of-flight two-photon photoemission spectromicroscopy with femtosecond laser radiation

Time-of-flight photoemission spectromicroscopy was used to measure and compare the two-photon photoemission (2PPE) spectra of Cu and Ag nanoparticles with linear dimensions ranging between 40 nm and several 100 nm, with those of the corresponding homogeneous surfaces. 2PPE was induced employing femtosecond laser radiation from a frequency-doubled Ti:sapphire laser in the spectral range between 375 nm and 425 nm with a pulse width of 200 fs and a repetition rate of 80 MHz. The use of a pulsed radiation source allowed us to use a high-resolution photoemission electron microscope as imaging time-of-flight spectrometer, and thus to obtain spectroscopic information about the laterally resolved electron signal. Ag nanoparticle films have been deposited on Si(111) by electron-beam evaporation, a technique leading to hemispherically-shaped Ag clusters. Isolated Cu nanoparticles have been generated by prolonged heating of a polycrystalline Cu sample. If compared to the spectra of the corresponding homogeneous surfaces, the Cu and Ag nanoparticle spectra are characterized by a strongly enhanced total 2PPE yield (enhancement factor up to 70), by a shift (about 0.1 eV) of the Fermi level onset towards lower final state energies, by a reduction of the work function (typically by 0.2 eV) and by a much steeper increase of the 2PPE yield towards lower final state energies. The shift of the Fermi level onset in the nanoparticle spectra has been explained by a positive unit charge (localized photohole) residing on the particle during the time-scale relevant for the 2PPE process (few femtoseconds). The total 2PPE yield enhancement and the different overall shape of the spectra have been explained by considering that the laser frequency was close to the localized surface plasmon resonance of the Cu and Ag nanoparticles. The synchronous oscillations induced by the laser in the metal electrons enhance the near-zone (NZ) field, defined as the linear superposition of the laser field and the field produced in the vicinity of the particles by the forced charge oscillations. From the present measurements it is clear that the NZ field behavior is responsible for the 2PPE enhancement and affects the 2PPE spatial and energy distribution and its dynamics. In particular, its strong spatial dependence allows indirect transitions through real intermediate states to take place in the metal clusters. Such transitions are forbidden by momentum conservation arguments and are thus experimentally much less probable on homogeneous surfaces. Further, we investigated specially tailored moon-shaped small metal nanostructures, whose NZ field was theoretically predicted, and compared the calculation with the laterally resolved 2PPE signal. We could show that the 2PPE signal gives a clear fingerprint of the theoretically predicted spatial dependence of the NZ field. This potential of our method is highly attractive in the novel field of plasmonics.

Measurement of volatile organic compounds and total OH reactivity in the atmosphere

Volatile organic compounds play a critical role in ozone formation and drive the chemistry of the atmosphere, together with OH radicals. The simplest volatile organic compound methane is a climatologically important greenhouse gas, and plays a key role in regulating water vapour in the stratosphere and hydroxyl radicals in the troposphere. The OH radical is the most important atmospheric oxidant and knowledge of the atmospheric OH sink, together with the OH source and ambient OH concentrations is essential for understanding the oxidative capacity of the atmosphere. Oceanic emission and / or uptake of methanol, acetone, acetaldehyde, isoprene and dimethyl sulphide (DMS) was characterized as a function of photosynthetically active radiation (PAR) and a suite of biological parameters, in a mesocosm experiment conducted in the Norwegian fjord. High frequency (ca. 1 minute-1) methane measurements were performed using a gas chromatograph - flame ionization detector (GC-FID) in the boreal forests of Finland and the tropical forests of Suriname. A new on-line method (Comparative Reactivity Method - CRM) was developed to directly measure the total OH reactivity (sink) of ambient air. It was observed that under conditions of high biological activity and a PAR of ~ 450 μmol photons m-2 s-1, the ocean acted as a net source of acetone. However, if either of these criteria was not fulfilled then the ocean acted as a net sink of acetone. This new insight into the biogeochemical cycling of acetone at the ocean-air interface has helped to resolve discrepancies from earlier works such as Jacob et al. (2002) who reported the ocean to be a net acetone source (27 Tg yr-1) and Marandino et al. (2005) who reported the ocean to be a net sink of acetone (- 48 Tg yr-1). The ocean acted as net source of isoprene, DMS and acetaldehyde but net sink of methanol. Based on these findings, it is recommended that compound specific PAR and biological dependency be used for estimating the influence of the global ocean on atmospheric VOC budgets. Methane was observed to accumulate within the nocturnal boundary layer, clearly indicating emissions from the forest ecosystems. There was a remarkable similarity in the time series of the boreal and tropical forest ecosystem. The average of the median mixing ratios during a typical diel cycle were 1.83 μmol mol-1 and 1.74 μmol mol-1 for the boreal forest ecosystem and tropical forest ecosystem respectively. A flux value of (3.62 ± 0.87) x 1011 molecules cm-2 s-1 (or 45.5 ± 11 Tg CH4 yr-1 for global boreal forest area) was derived, which highlights the importance of the boreal forest ecosystem for the global budget of methane (~ 600 Tg yr-1). The newly developed CRM technique has a dynamic range of ~ 4 s-1 to 300 s-1 and accuracy of ± 25 %. The system has been tested and calibrated with several single and mixed hydrocarbon standards showing excellent linearity and accountability with the reactivity of the standards. Field tests at an urban and forest site illustrate the promise of the new method. The results from this study have improved current understanding about VOC emissions and uptake from ocean and forest ecosystems. Moreover, a new technique for directly measuring the total OH reactivity of ambient air has been developed and validated, which will be a valuable addition to the existing suite of atmospheric measurement techniques.

Measurement of the e + e - pi + pi - pi + pi - cross section using initial state radiation at BABAR

One of the most precisely measured quantities in particle physics is the magnetic moment of the muon, which describes its coupling to an external magnetic field. It is expressed in form of the anomalous magnetic moment of the muon a_mu=(g_mu-2)/2 and has been determined experimentally with a precision of 0.5 parts per million. The current direct measurement and the theoretical prediction of the standard model differ by more than 3.5 standard deviations. Concerning theory, the contribution of the QED and weak interaction to a_mu can be calculated with very high precision in a perturbative approach.rnAt low energies, however, perturbation theory cannot be used to determine the hadronic contribution a^had_mu. On the other hand, a^had_mu may be derived via a dispersion relation from the sum of measured cross sections of exclusive hadronic reactions. Decreasing the experimental uncertainty on these hadronic cross sections is of utmost importance for an improved standard model prediction of a_mu.rnrnIn addition to traditional energy scan experiments, the method of Initial State Radiation (ISR) is used to measure hadronic cross sections. This approach allows experiments at colliders running at a fixed centre-of-mass energy to access smaller effective energies by studying events which contain a high-energetic photon emitted from the initial electron or positron. Using the technique of ISR, the energy range from threshold up to 4.5GeV can be accessed at Babar.rnrnThe cross section e+e- -> pi+pi- contributes with approximately 70% to the hadronic part of the anomalous magnetic moment of the muon a_mu^had. This important channel has been measured with a precision of better than 1%. Therefore, the leading contribution to the uncertainty of a_mu^had at present stems from the invariant mass region between 1GeV and 2GeV. In this energy range, the channels e+e- -> pi+pi-pi+pi- and e+e- -> pi+pi-pi0pi0 dominate the inclusive hadronic cross section. The measurement of the process e+e- -> pi+pi-pi+pi- will be presented in this thesis. This channel has been previously measured by Babar based on 25% of the total dataset. The new analysis includes a more detailed study of the background contamination from other ISR and non-radiative background reactions. In addition, sophisticated studies of the track reconstruction as well as the photon efficiency difference between the data and the simulation of the Babar detector are performed. With these auxiliary studies, a reduction of the systematic uncertainty from 5.0% to 2.4% in the peak region was achieved.rnrnThe pi+pi-pi+pi- final state has a rich internal structure. Hints are seen for the intermediate states rho(770)^0 f_2(1270), rho(770)^0 f_0(980), as well as a_1(1260)pi. In addition, the branching ratios BR(jpsi -> pi+pi-pi+pi-) and BR(psitwos -> jpsi pi+pi-) are extracted.rn