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.

Towards a Reconstruction of Thermal Properties of Light Nuclei from Fusion - Evaporation reactions

This thesis work has been developed in the framework of a new experimental campaign, proposed by the NUCL-EX Collaboration (INFN III Group), in order to progress in the understanding of the statistical properties of light nuclei, at excitation energies above particle emission threshold, by measuring exclusive data from fusion-evaporation reactions. The determination of the nuclear level density in the A~20 region, the understanding of the statistical behavior of light nuclei with excitation energies ~3 A.MeV, and the measurement of observables linked to the presence of cluster structures of nuclear excited levels are the main physics goals of this work. On the theory side, the contribution to this project given by this work lies in the development of a dedicated Monte-Carlo Hauser-Feshbach code for the evaporation of the compound nucleus. The experimental part of this thesis has consisted in the participation to the measurement 12C+12C at 95 MeV beam energy, at Laboratori Nazionali di Legnaro - INFN, using the GARFIELD+Ring Counter(RCo) set-up, from the beam-time request to the data taking, data reduction, detector calibrations and data analysis. Different results of the data analysis are presented in this thesis, together with a theoretical study of the system, performed with the new statistical decay code. As a result of this work, constraints on the nuclear level density at high excitation energy for light systems ranging from C up to Mg are given. Moreover, pre-equilibrium effects, tentatively interpreted as alpha-clustering effects, are put in evidence, both in the entrance channel of the reaction and in the dissipative dynamics on the path towards thermalisation.

Implementation of a phenomenological evaporation model into a porous network simulation for water management in low temperature fuel cells

A phenomenological transition film evaporation model was introduced to a pore network model with the consideration of pore radius, contact angle, non-isothermal interface temperature, microscale fluid flows and heat and mass transfers. This was achieved by modeling the transition film region of the menisci in each pore throughout the porous transport layer of a half-cell polymer electrolyte membrane (PEM) fuel cell. The model presented in this research is compared with the standard diffusive fuel cell modeling approach to evaporation and shown to surpass the conventional modeling approach in terms of predicting the evaporation rates in porous media. The current diffusive evaporation models used in many fuel cell transport models assumes a constant evaporation rate across the entire liquid-air interface. The transition film model was implemented into the pore network model to address this issue and create a pore size dependency on the evaporation rates. This is accomplished by evaluating the transition film evaporation rates determined by the kinetic model for every pore containing liquid water in the porous transport layer (PTL). The comparison of a transition film and diffusive evaporation model shows an increase in predicted evaporation rates for smaller pore sizes with the transition film model. This is an important parameter when considering the micro-scaled pore sizes seen in the PTL and becomes even more substantial when considering transport in fuel cells containing an MPL, or a large variance in pore size. Experimentation was performed to validate the transition film model by monitoring evaporation rates from a non-zero contact angle water droplet on a heated substrate. The substrate was a glass plate with a hydrophobic coating to reduce wettability. The tests were performed at a constant substrate temperature and relative humidity. The transition film model was able to accurately predict the drop volume as time elapsed. By implementing the transition film model to a pore network model the evaporation rates present in the PTL can be more accurately modeled. This improves the ability of a pore network model to predict the distribution of liquid water and ultimately the level of flooding exhibited in a PTL for various operating conditions.

(Table 1) Deuterium excess record during different time periods in Lomonosovfonna ice core

In this paper we present a deuterium excess (d) record from an ice core drilled on a small ice cap in Svalbard in 1997. The core site is located at Lomonosovfonna at 1255 m asl, and the analyzed time series spans the period 1400-1990 A.D. The record shows pronounced multidecadal to centennial-scale variations coherent with sea surface temperature changes registered in the subtropical to southern middle-latitude North Atlantic during the instrumental period. We interpret the negative trend in the deuterium excess during the 1400s and 1500s as an indication of cooling in the North Atlantic associated with the onset of the Little Ice Age. Consistently positive anomalies of d after 1900, peaking at about 1950, correspond with well-documented contemporary warming. Yet the maximum values of deuterium excess during 1900-1990 are not as high as in the early part of the record (pre-1550). This suggests that the sea surface temperatures during this earlier period of time in the North Atlantic to the south of approximately 45°N were at least comparable with those registered in the 20th century before the end of the 1980s. We examine the potential for a cold bias to exist in the deuterium excess record due to increased evaporation from the local colder sources of moisture having isotopically cold signature. It is argued that despite a recent oceanic warming, the contribution from this local moisture to the Lomonosovfonna precipitation budget is still insufficient to interfere with the isotopic signal from the primary moisture region in the midlatitude North Atlantic.

Table 2: Evaporation from individual shoots of antarctic mosses

Experimental observations on pathways of water movement are discussed in relation to anatomical and micromorphological features of five moss species from Signy Island, South Orkney Islands. Significant internal uptake of water was recorded only in the mesic species Polytrichum alpinum (internal=>60% of total) and Bartramia patens (internal=c.30% of total), in experiments in which uptake by cut shoots was compared in individuals with the external pathway blocked, and others with both external and internal pathways open. Internal uptake maintained shoot water content close to full turgor in P. alpinun and at 30% of full tugor in B. patens, whereas water content fell to 12-15% dry wt. in the lithophytes Andreaea gainii and Schistidium antarctici and in the mesic/hydric species Drepanocladus uncinatus, with the external pathway blocked. Where both pathways were open water uptake from below maintained water content at or above full turgor in shoots of all five species. External water uptake by capillarity occurred most rapidly in the lithophytes, and was slower in initially air-dry than in hydrated shoots of the other species. The spreading limbs of leaves in B. patens and P. alpinum are water-repellent, as are the bright green leaves in the apical 1-2 mm of dry shoots of the lithophytes. A central strand of hydroids is well-developed only in B. patens and P. alpinum. These two species have deposits of surface wax on parts of the leaves, and surface wax also occurs on the green apical leaves in some specimens of S. antarcticum and other lithophytes from Signy Island.

Temperature time series and physical properties of snow samples of a high-arctic permafrost site on Svalbard, Norway

Independent measurements of radiation, sensible and latent heat fluxes and the ground heat flux are used to describe the annual cycle of the surface energy budget at a high-arctic permafrost site on Svalbard. During summer, the net short-wave radiation is the dominant energy source, while well developed turbulent processes and the heat flux in the ground lead to a cooling of the surface. About 15% of the net radiation is consumed by the seasonal thawing of the active layer in July and August. The Bowen ratio is found to vary between 0.25 and 2, depending on water content of the uppermost soil layer. During the polar night in winter, the net long-wave radiation is the dominant energy loss channel for the surface, which is mainly compensated by the sensible heat flux and, to a lesser extent, by the ground heat flux, which originates from the refreezing of the active layer. The average annual sensible heat flux of -6.9 W/m**2 is composed of strong positive fluxes in July and August, while negative fluxes dominate during the rest of the year. With 6.8 W/m**2, the latent heat flux more or less compensates the sensible heat flux in the annual average. Strong evaporation occurs during the snow melt period and particularly during the snow-free period in summer and fall. When the ground is covered by snow, latent heat fluxes through sublimation of snow are recorded, but are insignificant for the average surface energy budget. The near-surface atmospheric stratification is found to be predominantly unstable to neutral, when the ground is snow-free, and stable to neutral for snow-covered ground. Due to long-lasting near-surface inversions in winter, an average temperature difference of approximately 3 K exists between the air temperature at 10 m height and the surface temperature of the snow.