Income drawdown option with minimum guarantee

This paper deals with a constrained investment problem for a defined contribution (DC) pension fund where retirees are allowed to defer the purchase of the annuity at some future time after retirement.     

Mechanical stabilization effect of water on a membrane-like system

The penetration resistance of a prototypical model-membrane system (HS-(CH2)11-OH self-assembled monolayer (SAM) on Au(111)) to the tip of an atomic force microscope (AFM) is investigated in the presence of different solvents. The compressibility (i.e., height vs tip load) of the HS-(CH2)11-OH SAM is studied differentially, with respect to a reference structure. The reference consists of hydrophobic alkylthiol molecules (HS-(CH2)17-CH3) embedded as nanosized patches into the hydrophilic SAM by nanografting, an AFM-assisted nanolithography technique. We find that the penetration resistance of the hydrophilic SAM depends on the nature of the solvent and is much higher in the presence of water than in 2-butanol. In contrast, no solvent-dependent effect is observed in the case of hydrophobic SAMs. We argue that the mechanical resistance of the hydroxyl-terminated SAM is a consequence of the structural order of the solvent-SAM interface, as suggested by our molecular dynamics simulations. The simulations show that in the presence of 2-butanol the polar head groups of the HS-(CH2)11-OH SAM, which bind only weakly to the solvent molecules, try to bind to each other, disrupting the local order at the interface. On the contrary, in the presence of water the polar head groups bind preferentially to the solvent that, in turn, mediates the release of the surface strain, leading to a more ordered interface. We suggest that the mechanical stabilization effect induced by water may be responsible for the stability of even more complex, real membrane systems.     

Highly efficient synchronous amplification of a picosecond dye laser at a kHz repetition rate

A short pulse, high energy, high repetition rate dye amplifier with superior conversion efficiency is reported. The dye amplifier is composed of three single-pass dye cells, longitudinally pumped by a frequency doubled 1 kHz Nd: YLF regenerative amplifier. The dye amplifier yields 3.5 ps, 150 J pulses at 595 nm, corresponding to a 12% conversion efficiency. The ASE is 1% or less, and the transverse mode quality is near-Gaussian.In absentia from the Department of Chemistry, Princeton University, Princeton, NJ 08544, USA     

Supersonic molecular beams production and temperature distribution in free expanding jets

Summary A supersonic molecular beam production system is described in which a continuous flux of Argon molecules can be produced as high as4 · 10 ¹⁸ molecules sterad^–1 sec^–1 in a vessel where the background pressure can be kept below10 ^–6 mmHg using relatively little cryo and diffusion pumping facilities. The beam intensity is measured at different stagnation pressures as a function of nozzle-skimmer separation and skimmer diameter. The results are compared with the existing theories, and information is obtained on the radial temperature distribution in the free expanding jet.

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Sommario Si descrive un apparecchio per la produzione di fasci molecolari supersonici nel quale, facendo uso di stazioni di pompaggio, a diffusione e criogenico, relativamente modeste, si può produrre un flusso continuo di molecole di Argon di4 · 10 ¹⁸ molecole sterad^–1 sec^–1 in un ambiente in cui la pressione di fondo è mantenuta inferiore a10 ^–6 mmHg. Vengono riportate misure di intensità del fascio, a diversi valori della pressione nell'ugello, in funzione della distanza ugello-primo collimatore e del diametro del primo collimatore. I risultati vengono confrontati con le teorie esistenti e dal confronto si ottiene informazioni sulla distribuzione della temperatura radiale nei getti in espansione libera.

     

The Reaction Pathway of Cellulose Pyrolysis to a Multifunctional Chiral Building Block: The Role of Water Unveiled by a DFT Computational Investigation

LAC (hydroxylactone (1R,5S)‐1‐hydroxy‐3,6‐dioxabicyclo[3.2.1]octan‐2‐one) is one of the most interesting products of the pyrolysis of cellulose and represents a useful chiral building block in organic synthesis. A computational investigation at the DFT level on the mechanism of formation of LAC shows that this species can be obtained following two reaction paths, path A and path B , starting from a well‐known pyrolysis product (ascopyrone P). A series of internal rearrangements involving in all cases a proton transfer leads directly to LAC ( path B ). An alternative path ( path A ) can be also followed. From this path, via a “gate” connecting the two reaction channels, it is possible to reach path B and form LAC. In both cases, the rate‐determining step of the process is the initial keto‐enol isomerization. We found that water, which is present in the reaction mixture, “catalyzes” the reaction by assisting the proton transfers present in all the steps of the process. In particular, water lowers the barrier of the rate‐determining step that becomes 40.9 kcal mol^?1 (79.4 kcal mol^?1 in the absence of water). The corresponding computed rate constant is 4.3×10 s^?1 at 500 °C, a value which is consistent with the presence of LAC in the absence of metal catalysts. The results of this study on the non‐catalyzed process underpin the important role played by water in the formation of pyrolysis products of cellulose where proton transfer is a key mechanistic step.     

Electronic spectroscopy of biphenylene inside helium nanodroplets

We have recorded the S1 <-- S0 electronic spectra of Biphenylene and its Ar and O2 van der Waals complexes inside helium nanodroplets using beam depletion detection. In general, the spectrum is similar to the previously reported high-resolution REMPI spectrum. The zero phonon lines, however, are split similar to the previously reported tetracene case. The calculated potential energy surface predicts that helium atoms can simultaneously occupy all equivalent global minima positions. Therefore, it appears that the splitting cannot be explained either by different isomers or by tunneling. Furthermore, surprisingly the splitting is retained for the Ar van der Waals complexes (and possibly for the O2 complex as well). This case suggests that the current models of the origin of zero phonon line splitting and the helium solvation are incomplete.     

Thermal detection laser spectroscopy of molecular beams

We describe the experimental methods used in carrying out high resolution infrared spectroscopy of molecular beams using bolometric thermal detection. The main applications of this technique are also described and include: studies on molecular internal vibrational relaxation, radiationless transition after “visible” excitation, photodissociation spectroscopy of van der Waals molecules, the study of coherent excitation of molecules in the infrared, multiphoton infrared spectroscopy, overtone spectroscopy and the study of large molecular clusters.