Femtosecond real-time probing of reactions. IX. Hydrogen-atom transfer

The real-time dynamics of hydrogen-atom-transfer processes under collisionless conditions are studied using femtosecond depletion techniques. The experiments focus on the methyl salicylate system, which exhibits ultrafast hydrogen motion between two oxygen atoms due to molecular tautomerization, loosely referred to as intramolecular ''proton'' transfer. To test for tunneling and mass effects on the excited potential surface, we also studied deuterium and methyl-group substitutions. We observe that the motion of the hydrogen, under collisionless conditions, takes place within 60 fs. At longer times, on the picosecond time scale, the hydrogen-transferred form decays with a threshold of 15.5 kJ/mol; this decay behavior was observed up to a total vibrational energy of approximately 7200 cm-1. The observed dynamics provide the global nature of the motion, which takes into account bonding before and after the motion, and the evolution of the wave packet from the initial nonequilibrium state to the transferred form along the O-H-O reaction coordinate. The vibrational periods (2pi/omega) of the relevant modes range from 13 fs (the OH stretch) to 190 fs (the low-frequency distortion) and the motion involves (in part) these coordinates. The intramolecular vibrational-energy redistribution dynamics at longer times are important to the hydrogen-bond dissociation and to the nonradiative decay of the hydrogen-transferred form

Femtosecond multichannel photodissociation dynamics of CH3I from the A band by velocity map imaging

4 pages, 3 figures, 1 table.The reaction times of several well-defined channels of the C–I bond rupture of methyl iodide from the A band, which involves nonadiabatic dynamics yielding ground state I(2P3/2) and spin-orbit excited I*(2P1/2) and ground and vibrationally excited CH3 fragments, have been measured by a combination of a femtosecond laser pump-probe scheme and velocity map imaging techniques using resonant detection of ground state CH3 fragments. The reaction times found for the different channels studied are directly related with the nonadiabatic nature of this multidimensional photodissociation reaction.Two of the authors (J. G. I. and J. D.) gratefully acknowledge financial support from the FPI program and the CSIC-Unidades Asociadas program, respectively, of the Spanish Ministry of Education and Science (MEC). This work has been financed by the Spanish MEC through Grant No. CTQ2005-08493- C02-01.Peer reviewe

A femtosecond velocity map imaging study on B-band predissociation in CH 3I. II. the 2 0 1 and 3 0 1 vibronic levels

Femtosecond time-resolved velocity map imaging experiments are reported on several vibronic levels of the second absorption band (B-band) of CH 3I, including vibrational excitation in the 2 and 3 modes of the bound 3R 1(E) Rydberg state. Specific predissociation lifetimes have been determined for the 201 and 301 vibronic levels from measurements of time-resolved I*( 2P 12) and CH 3 fragment images, parent decay, and photoelectron images obtained through both resonant and non-resonant multiphoton ionization. The results are compared with our previously reported predissociation lifetime measurements for the band origin 000 [Gitzinger, J. Chem. Phys. 132, 234313 (2010)10.1063/1.3455207]. The result, previously reported in the literature, where vibrational excitation to the C-I stretching mode ( 3) of the CH 3I 3R 1(E) Rydberg state yields a predissociation lifetime about four times slower than that corresponding to the vibrationless state, whereas predissociation is twice faster if the vibrational excitation is to the umbrella mode ( 2), is confirmed in the present experiments. In addition to the specific vibrational state lifetimes, which were found to be 0.85 0.04 ps and 4.34 0.13 ps for the 201 and 301 vibronic levels, respectively, the time evolution of the fragment anisotropy and the vibrational activity of the CH 3 fragment are presented. Additional striking results found in the present work are the evidence of ground state I( 2P 32) fragment production when excitation is produced specifically to the 301 vibronic level, which is attributed to predissociation via the A-band 1Q 1 potential energy surface, and the indication of a fast adiabatic photodissociation process through the repulsive A-band 3A 1(4E) state, after direct absorption to this state, competing with absorption to the 301 vibronic level of the 3R 1(E) Rydberg state of the B-band.Peer Reviewe

Insights into the room temperature magnetism of ZnO/Co3O4 mixtures

The origin of room temperature (RT) ferromagneticlike behavior in ZnO-based diluted magnetic semiconductors is still an unclear topic. The present work concentrates on the appearance of RT magnetic moments in just mixed ZnO/Co3O4 mixtures without thermal treatment. In this study, it is shown that the magnetism seems to be related to surface reduction of the Co3O4 nanoparticles, in which, an antiferromagnetic Co3O4 nanoparticle (core) is surrounded by a CoO-like shell. This singular superficial magnetism has also been found in other mixtures with semiconductors such as TiO2 and insulators such as Al2O3

Femtosecond XUV induced dynamics of the methyl iodide cation

Ultrashort XUV wavelength-selected pulses obtained with high harmonic generation are used to study the dynamics of molecular cations with state-to-state resolution. We demonstrate this by XUV pump - IR probe experiments on CH3I+ cations and identify both resonant and non-resonant dynamics

Femtosecond pulsed laser deposition of nanostructured CdS films

In this work, we report an investigation of the properties of nanostructured deposits obtained from femtosecond pulsed laser deposition of CdS sintered targets. Specifically, we address the effects of laser irradiation wavelength, laser fluence, and substrate temperature (from 25 to 450 °C). The composition of the deposits was characterized using X-ray photoelectron spectroscopy (XPS), their crystallinity by X-ray diffraction (XRD), and the surface morphology was studied by environmental scanning electron microscopy (ESEM) and atomic force microscopy (AFM). It has been found that the smallest nanoparticles, with an average diameter of 25 nm and a narrow size distribution, together with particulates in the range of 80-120 nm, are obtained at the shortest laser wavelength of 266 nm on room-temperature substrates. Deposits do not contain microscopic droplets in any of the explored conditions. © 2010 American Chemical Society.Peer Reviewe

A detailed experimental and theoretical study of the femtosecond A -band photodissociation of C H3I

The real time photodissociation dynamics of C H3I from the A band has been studied experimentally and theoretically. Femtosecond pump-probe experiments in combination with velocity map imaging have been carried out to measure the reaction times (clocking) of the different (nonadiabatic) channels of this photodissociation reaction yielding ground and spin-orbit excited states of the I fragment and vibrationless and vibrationally excited (symmetric stretch and umbrella modes) C H3 fragments. The measured reaction times have been rationalized by means of a wave packet calculation on the available ab initio potential energy surfaces for the system using a reduced dimensionality model. A 40 fs delay time has been found experimentally between the channels yielding vibrationless CH3(ν=0) and I(2P3/2) and I*(2P1/2) that is well reproduced by the calculations. However, the observed reduction in delay time between the I and I* channels when the C H3 fragment appears with one or two quanta of vibrational excitation in the umbrella mode is not well accounted for by the theoretical model. © 2008 American Institute of Physics.This work has been financed by the Spanish MEC through Grant Nos. CTQ2005-08493-C02-01, FIS-2007- 62002, and Consolider program “Science and Applications of Ultrafast Ultraintense Lasers” No. CSD2007-00013.Peer Reviewe