RESUMEN
We use differential holography to overcome the forward scattering problem in strong-field photoelectron holography. Our differential holograms of H_{2} and D_{2} molecules exhibit a fishbonelike structure, which arises from the backscattered part of the recolliding photoelectron wave packet. We demonstrate that the backscattering hologram can resolve the different nuclear dynamics between H_{2} and D_{2} with subangstrom spatial and subcycle temporal resolution. In addition, we show that attosecond electron dynamics can be resolved. These results open a new avenue for ultrafast studies of molecular dynamics in small molecules.
RESUMEN
In this work, the structures of cationic SinNb(+) (n = 4-12) clusters are determined using the combination of infrared multiple photon dissociation (IR-MPD) and density functional theory (DFT) calculations. The experimental IR-MPD spectra of the argon complexes of SinNb(+) are assigned by comparison to the calculated IR spectra of low-energy structures of SinNb(+) that are identified using the stochastic 'random kick' algorithm in conjunction with the BP86 GGA functional. It is found that the Nb dopant tends to bind in an apex position of the Sin framework for n = 4-9 and in surface positions with high coordination numbers for n = 10-12. For the larger doped clusters, it is suggested that multiple isomers coexist and contribute to the experimental spectra. The structural evolution of SinNb(+) clusters is similar to V-doped silicon clusters (J. Am. Chem. Soc., 2010, 132, 15589-15602), except for the largest size investigated (n = 12), since V takes an endohedral position in Si12V(+). The interaction with a Nb atom, with its partially unfilled 4d orbitals leads to a significant stability enhancement of the Sin framework as reflected, e.g. by high binding energies and large HOMO-LUMO gaps.
RESUMEN
The resonant multiple photon excitation of neutral niobium clusters using tunable infrared (IR) radiation leads to thermionic emission. By measuring the mass-resolved ionization yield as a function of IR wavenumber species selective IR spectra are obtained for Nb(n) (n = 5-20) over the 200-350 cm(-1) spectral range. The IR resonance-enhanced multiple photon ionization spectra obtained this way are in good agreement with those measured using IR photodissociation of neutral Nb(n)-Ar clusters. An investigation of the factors determining the applicability of this technique identifies the internal energy threshold towards thermionic emission in combination with a minimum required photon flux that rapidly grows as a function of excitation wavelength.
RESUMEN
We present a combined experimental and theoretical investigation of small neutral vanadium and manganese doped silicon clusters Si(n)X (n = 6-9, X = V, Mn). These species are studied by infrared multiple photon dissociation and mass spectrometry. Structural identification is achieved by comparison of the experimental data with computed infrared spectra of low-lying isomers using density functional theory at the B3P86∕6-311+G(d) level. The assigned structures of the neutral vanadium and manganese doped silicon clusters are compared with their cationic counterparts. In general, the neutral and cationic Si(n)V(0,+) and Si(n)Mn(0,+) clusters have similar structures, although the position of the capping atoms depends for certain sizes on the charge state. The influence of the charge state on the electronic properties of the clusters is also investigated by analysis of the density of states, the shapes of the molecular orbitals, and NBO charge analysis of the dopant atom.
RESUMEN
Structural information for neutral magnesium oxide clusters has been obtained by a comparison of their experimental vibrational spectra with predictions from theory. (MgO)(n) clusters with n = 3-16 have been studied in the gas phase with a tunable IR-UV two-color ionization scheme and size-selective infrared spectra have been measured. These IR spectra are compared to the calculated spectra of the global minimum structures predicted by a hybrid ab initio genetic algorithm. The comparison shows clear evidence that clusters of the composition (MgO)(3k) (k = 1-5) form hexagonal tubes, which confirm previous theoretical predictions. For the intermediate sizes (n≠ 3k) cage-like structures containing hexagonal (MgO)(3) rings are identified. Except for the cubic (MgO)(4) no evidence for bulk like structures is found.
RESUMEN
Vibrational spectra of neutral silicon clusters Si(n), in the size range of n = 6-10 and for n = 15, have been measured in the gas phase by two fundamentally different IR spectroscopic methods. Silicon clusters composed of 8, 9, and 15 atoms have been studied by IR multiple photon dissociation spectroscopy of a cluster-xenon complex, while clusters containing 6, 7, 9, and 10 atoms have been studied by a tunable IR-UV two-color ionization scheme. Comparison of both methods is possible for the Si(9) cluster. By using density functional theory, an identification of the experimentally observed neutral cluster structures is possible, and the effect of charge on the structure of neutrals and cations, which have been previously studied via IR multiple photon dissociation, can be investigated. Whereas the structures of small clusters are based on bipyramidal motifs, a trigonal prism as central unit is found in larger clusters. Bond weakening due to the loss of an electron leads to a major structural change between neutral and cationic Si(8).
RESUMEN
Far- and mid-infrared multiple photon dissociation spectroscopy has been employed to study both the structure and surface reactivity of isolated cationic rhodium clusters with surface-adsorbed nitrous oxide, Rh(n)N(2)O(+) (n = 4-8). Comparison of experimental spectra recorded using the argon atom tagging method with those calculated using density functional theory (DFT) reveals that the nitrous oxide is molecularly bound on the rhodium cluster via the terminal N-atom. Binding is thought to occur exclusively on atop sites with the rhodium clusters adopting close-packed structures. In related, but conceptually different experiments, infrared pumping of the vibrational modes corresponding with the normal modes of the adsorbed N(2)O has been observed to result in the decomposition of the N(2)O moiety and the production of oxide clusters. This cluster surface chemistry is observed for all cluster sizes studied except for n = 5. Plausible N(2)O decomposition mechanisms are given based on DFT calculations using exchange-correlation functionals. Similar experiments pumping the Rh-O stretch in Rh(n)ON(2)O(+) complexes, on which the same chemistry is observed, confirm the thermal nature of this reaction.
RESUMEN
Multiple photon infrared excitation of size-selected Rh(6)N(2)O(+) clusters drives surface chemistry resulting in partially oxidized clusters.
RESUMEN
The binding of isolated oxygen atoms to small tantalum clusters is investigated using vibrational spectroscopy. Infrared spectra of Ta(n)O(0,1,2)(+) (n = 6-11) are reported in the range of 90-1100 cm(-1), comprising both the internal cluster modes and the adatom's vibrations. The vibrational spectra are compared to the results of DFT calculations for n = 6-8, which show that the oxygen atoms bind preferentially as 2-fold bridging adatoms. Addition of one or two O atoms induces only minor distortions of the underlying metal cluster core.
RESUMEN
We report on the development of thermoelectrically cooled (TE-cooled) InAs/GaSb type-II superlattice (T2SL) single element infrared (IR) photodetectors and exemplify their applicability for real-time IR spectroscopy in the mid-infrared in a possible application. As the European Union's Restriction of Hazardous Substances (RoHS) threatens the usage of the state-of-the-art detector material mercury cadmium telluride (MCT), RoHS-compatible alternatives to MCT have to be established for IR detection. We use bandgap engineered InAs/GaSb T2SLs to tailor the temperature-dependent bandgap energy for detection throughout the required spectral range. Molecular beam epitaxy of superlattice samples is performed on GaAs substrates with a metamorphic GaAsSb buffer layer. Photolithographic processing yields laterally-operated T2SL photodetectors. Integrated in a TE-cooled IR detector module, such T2SL photodetectors can be an alternative to MCT photodetectors for spectroscopy applications. Here, we exemplify this by exchanging a commercially available MCT-based IR detector module with our T2SL-based IR detector module in a real-time mid-infrared backscattering spectroscopy system for substance identification. The key detector requirements imposed by the spectroscopy system are a MHz-bandwidth, a broad spectral response, and a high signal-to-noise ratio, all of which are covered by the reported T2SL-based IR detector module. Hence, in this paper, we demonstrate the versatility of TE-cooled InAs/GaSb T2SL photodetectors and their applicability in an IR spectroscopy system.
RESUMEN
Tunable far-infrared-vacuum-ultraviolet two color ionization is used to obtain vibrational spectra of neutral silicon clusters in the gas phase. Upon excitation with tunable infrared light prior to irradiation with UV photons we observe strong enhancements in the mass spectrometric signal of specific cluster sizes. This allowed the recording of the infrared absorption spectra of Si(6), Si(7), and Si(10). Structural assignments were made by comparison with calculated linear absorption spectra from quantum chemical theory.