RESUMEN
We have been studying the thermionic emission of negatively charged molecules and small clusters for more than a decade. The kinetic energy released distribution (KERD) of mass-selected negative ions has been measured with a velocity map imaging spectrometer. A comparison of the experimental KERD to detailed balance models provided information on the reverse process, namely, the electron attachment to the parent. The electron attachment to neutral systems (reverse process of the electron emission from anions) is usually described in a simplified way as a single electron capture in the framework of the classical Langevin model. Our measurements show that this approach is insufficient and that, in addition to the capture step, an intramolecular vibrational redistribution (IVR) step should be included. As far as multiply charged anions are concerned, the electron attachment to anions (reverse process of the electron emission from dianions) is strongly affected by the repulsive Coulomb barrier (RCB). Previous studies assumed a pure over-the-barrier process, which is in disagreement with our study. Indeed, electron emission is measured below the RCB, revealing significant thermal tunneling. In the present review, we summarize these works on singly and doubly charged anions in an attempt to present a unified view of the involved processes. It is worth noting that the detailed measurements of KERDs in the very low kinetic energy region (typically around 0.1 eV) have been made possible thanks to electron imaging methods, without which all of this work could never have been done, with time-resolution capabilities allowing the disentangling of direct and delayed electron emission.
RESUMEN
The kinetic energy release distribution (KERD) in the vibrational autodetachment (VAD) from sulfur hexafluoride anion SF6 - has been measured in a velocity map imaging spectrometer for delays in the range of a few tens of microseconds. The experimental KERD is analyzed within the framework of the detailed-balance: first using the standard Langevin model and subsequently using a more refined and realistic model based on the experimental attachment cross section. A discussion on the processes involved in the attachment and the VAD is presented based on an empirical fit of the attachment cross section. The lifetime derived from the model is in good agreement with the experimental time window, strengthening this theoretical approach for this model system.
RESUMEN
Understanding optical properties of molecular dyes is required to drive progress in molecular photonics. This requires a fundamental comprehension of the role of electronic structure, geometry, and interactions with the environment in order to guide molecular engineering strategies. In this context, we studied charged cyanine dye molecules in the gas phase with a controlled microenvironment to unravel the origin of the spectral tuning of this class of molecules. This was performed using a new approach combining femtosecond multiple-photon action spectroscopy of on-the-fly mass-selected molecular ions and high-level quantum calculations. While arguments based on molecular geometry are often used to design new polymethine dyes, we provide experimental evidence that electronic structure is of primary importance and hence the decisive criterion as suggested by recent theoretical investigations.
RESUMEN
A detailed-balance model for thermionic emission from polyanions has been developed and applied to fullerene dianions. The specificity of this delayed decay process is electron tunneling through the repulsive Coulomb barrier (RCB). An analytical expression of the RCB is derived from electrostatic modeling of the fullerene cage. The reverse process, namely, electron attachment to the singly charged anion, is described by a hard sphere cross section weighted by the Wentzel-Kramers-Brillouin tunneling probability. This simple expression leads to a very good agreement with a measured time-resolved kinetic energy distribution of C842-. Electron binding energy is reduced when the fullerene cage size decreases, leading to an almost zero one for C702- and a negative one for C602-. Extension of the model to these systems of interest is discussed, and model outputs are compared with the experimental data from the literature.
RESUMEN
An instrument combining an electrospray ionization source and a velocity-map imaging (VMI) spectrometer has been developed in order to study the delayed electron emission of molecular anions and especially of polyanions. It operates at a high repetition rate (kHz) in order to increase the acquisition speed. The VMI spectrometer has been upgraded for nanosecond time resolution by gating the voltages applied on the position-sensitive detector. Kinetic energy release distribution of thermionic emission (without any contribution from direct detachment) can be recorded for well-defined delays after the nanosecond laser excitation. The capability of the instrument is demonstrated by recording photodetachment spectra of the benchmark C60(-) anion and C84(2-) dianion.
RESUMEN
The delayed electron emission from small mass-selected anionic tungsten clusters W(n)(-) has been studied for sizes in the range 9 < or = n < or = 21. Kinetic energy spectra have been measured for delays of about 100 ns after laser excitation by a velocity-map imaging spectrometer. They are analyzed in the framework of microreversible statistical theories. The low-energy behavior shows some significant deviations with respect to the classical Langevin capture model, which we interpret as possibly due to the influence of quantum dynamical effects such as tunneling through the centrifugal barrier, rather than shape effects. The cluster temperature has been extracted from both the experimental kinetic energy spectrum and the absolute decay rate. Discrepancies between the two approaches suggest that the sticking probability can be as low as a few percent for the smallest clusters.
RESUMEN
Electron detachment from fullerene dianions Cm2- (m=76,84) stored in a room temperature Penning trap was probed upon pulsed laser excitation at wavelengths of 355 and 532 nm. The fraction of Cm(2-) surviving trapping times exceeding tens of milliseconds under UHV conditions, as well as the fraction of singly charged anions Cm(-) generated were recorded as a function of the laser fluence. Analysis by means of Poisson statistics yields absolute absorption cross sections and the number of photons necessary to induce the detachment. The cross sections obtained are in good agreement with the literature values. By describing the electron detachment as a statistical unimolecular process, we deduce effective activation energies from the number of photons required. These energies are compared to the sum of the second electron affinity and the Coulomb barrier height as calculated from an electrostatic charging model.