Photoionization mass spectrometry of ω-phenylalkylamines: Role of radical cation-π interaction

Linear ω-phenylalkylamines of increasing alkyl chain length have been investigated employing synchrotron radiation in the photon energy range from 7 to 15 eV. These molecules have received considerable interest because they bear the skeleton of biologically relevant compounds including neurotransmitters and because of the possible interaction between the amino moiety and the phenyl ring. Recently, the contribution of this interaction has been assayed in both neutral and protonated species, pointing to a role of the polymethylene chain length. In this work, the ionization energy (IE) values of benzylamine (BA), 2-phenylethylamine (2-PEA), 3-phenylpropylamine (3-PPA), and 4-phenylbutylamine (4-PBA) were investigated in order to ascertain the impact of the different alkyl chain lengths and to verify an amino radical cation-π interaction. The IEs obtained experimentally, 8.54, 8.37, 8.29, and 8.31 eV for BA, 2-PEA, 3-PPA and 4-PBA, respectively, show a decreasing trend that is discussed employing calculations at the CBS-QB3 level. Moreover, the appearance energy values for major fragments produced by the photofragmentation process are reported

Time-resolved optical studies, heat dissipation and melting of Ag and Au nanoparticle systems and arrays

Transient absorption spectroscopy has been extensively used in recent years to examine the temporal response of isolated nanoparticles (NPs) to the absorption of light [1]. These studies are largely based on the use of the surface plasmon resonance (SPR) to monitor characteristics of the NP such as electronic and lattice temperature, shape and morphology as a function of time. In the case of extended Au/Ag NP structures the plasmon resonance is strongly distorted due to the inter-particle coupling effects. For example, we have observed this effect in Rhodamine dye functionalized Au nanoparticles which undergo self-assembly to form nanostructures due to the interactions between the dye molecules attached to the surfaces of the nanoparticles. Indeed the SPR splits into two with one resonance remaining in the vicinity of that of the isolated AuNPs and is generally called the transverse SPR while a second resonance due to an extended excitation spanning across multiple particles appears to the lower energies. The precise spectral energy and shape of the extended plasmon resonance depends on the inter-particle distance, the particle disposition and the number of particles involved. When the plasmon band or interband spectral region of the NP is excited by an intense pulse the photon energy absorbed by the electrons is transferred to the lattice of the NP as heat through electron-phonon coupling. Depending on the intensity of the light pulse and thus the initial electron temperature a number of outcomes are possible. The first aim of this work is to use low intensity pump pulses to study the wavelength dependence of the sub 10 ps dynamics which reflects the electron-photon scattering within the nanoparticle structure. On the other hand, the interaction of more intense light with the NPs can modify the morphology of NP systems, for example by reshaping gold nanorods into nanospheres or, in general, mediate the synthesis of metallic nanostructures. At medium intensities the initial temperature is sufficient to induce melting of the NPs which can lead to morphological changes of the NP structure. Higher intensities can cause other effects such as photofragmentation of the NPs, release of stabiliser molecules from the surface of the NPs or even Coulomb explosion due to multiple ionisation events. The second aim of this work is to concentrate on the effects of medium intensity laser excitation of a self-assembled Au/Ag NP systems. The NP system is excited by a femtosecond laser pulse of different wavelengths allowing selective deposition of energy and the subsequent heat dissipation through phonon-phonon coupling and morphological changes are monitored in time by recording transient absorption spectra in the visible range. This wavelength range makes it possible to follow the phonon-phonon coupling effects on the recovery of the bleaching of both the transverse and extended plasmon resonances of the NP system. As the intensity of the pump pulse is increased it can be seen that the NPs are no longer able to dissipate all of the heat before arrival of subsequent laser pulses thus leading to melting of the NP structure and strong changes in the plasmon response of the system. The overall aim of this study is to fully understand the delocalized electron-phonon coupling in the extended plasmon region of the NP structures and to use this knowledge to control the melting in nanostructures. The methods developed can be useful for plasmon mediated nano-engineerin

Double photoionization of propylene oxide: a coincidence study of the ejection of a pair of valence-shell electrons

Propylene oxide, a favorite target of experimental and theoretical studies of circular dichroism, was recently discovered in interstellar space, further amplifying the attention to its role in the current debate on protobiological homochirality. In the present work, a photoelectron-photoion-photoion coincidence technique, using an ion-imaging detector and tunable synchrotron radiation in the 18.0-37.0 eV energy range, permits us (i) to observe six double ionization fragmentation channels, their relative yields being accounted for about two-thirds by the couple (C2H4+, CH2O+) and one-fifth by (C2H3+, CH3O+); (ii) to measure thresholds for their openings as a function of photon energy; and (iii) to unravel a pronounced bimodality for a kinetic-energy-released distribution, fingerprint of competitive non-adiabatic mechanisms

Carbon nanotube film/silicon heterojunction photodetector for new cutting-edge technological devices

Photodetector (PD) devices based on carbon nanotube/n-silicon heterojunction (NSH) have been realized, with a linear response in a large optical power range, proving competitive performances with respect to a recent nanostructure-based detector and those currently available on the market. The core of these devices is a thin semi-transparent and conductive single-walled carbon nanotubes film with a multitask role: junction element, light absorber and transmitter, photocarrier transporting layer, and charge collector. The PD exhibits rise times of some nanoseconds, detecting light from ultraviolet (240 nm) to infrared (1600 nm), and external quantum efficiency reaching 300% in the VIS spectra region

Ultrafast Charge Carrier Dynamics in Vanadium-Modified TiO2 Thin Films and Its Relation to Their Photoelectrocatalytic Efficiency for Water Splitting

Light absorption and charge transport in oxide semiconductors can be tuned by the introduction, during deposition, of a small quantity of foreign elements, leading to the improvement of the photoelectrocatalytic performance. In this work, both unmodified and vanadium-modified TiO2 thin films deposited by radio-frequency magnetron sputtering are investigated as photoanodes for photoelectrochemical water splitting. Following a structural characterization by X-ray diffraction, atomic force microscopy, Raman spectroscopy, and X-ray photoelectron spectroscopy, photoelectrocatalysis is discussed based on ultrafast transient absorbance spectroscopy measurements. In particular, three different pump wavelengths from UV to the visible range are used (300, 390, and 530 nm) in order to cover the relevant photoactive spectral range of modified TiO2. Incident photon-to-current conversion efficiency spectra show that incorporation of vanadium in TiO2 extends water splitting in the visible range up to approximate to 530 nm, a significant improvement compared to unmodified TiO2 that is active only in the UV range less than or similar to 390 nm. However, transient absorbance spectroscopy clearly reveals that vanadium accelerates electron-hole recombination upon UV irradiation, resulting in a lower photon-to-current conversion efficiency in the UV spectral range with respect to unmodified TiO2. The new photoelectrocatalytic activity in the visible range is attributed to a V-induced introduction of intragap levels at approximate to 2.2 eV below the bottom of the conduction band. This is confirmed by long-living transient signals due to electrons photoexcited into the conduction band after visible light (530 nm) pulses. The remaining holes migrate to the semiconductor-electrolyte interface where they are captured by long-lived traps and eventually promote water oxidation under visible light

Effects of crystal morphology on the hot-carrier dynamics in mixed-cation hybrid lead halide perovskites

Ultrafast pump-probe spectroscopies have proved to be an important tool for the investigation of charge carriers dynamics in perovskite materials providing crucial information on the dynamics of the excited carriers, and fundamental in the development of new devices with tailored photovoltaic properties. Fast transient absorbance spectroscopy on mixed-cation hybrid lead halide perovskite samples was used to investigate how the dimensions and the morphology of the per-ovskite crystals embedded in the capping (large crystals) and mesoporous (small crystals) layers affect the hot-carrier dynamics in the first hundreds of femtoseconds as a function of the excitation energy. The comparative study between samples with perovskite deposited on substrates with and without the mesoporous layer has shown how the small crystals preserve the temperature of the carriers for a longer period after the excitation than the large crystals. This study showed how the high sensitivity of the time-resolved spectroscopies in discriminating the transient response due to the different morphology of the crystals embedded in the layers of the same sample can be applied in the general characterization of materials to be used in solar cell devices and large area modules, providing further and valuable information for the optimization and enhancement of stability and efficiency in the power conversion of new perovskite-based devices