RESUMO
Site-selective probing of iodine 4d orbitals at 13.1 nm was used to characterize the photolysis of CH2I2 and CH2BrI initiated at 202.5 nm. Time-dependent fragment ion momenta were recorded using Coulomb explosion imaging mass spectrometry and used to determine the structural dynamics of the dissociating molecules. Correlations between these fragment momenta, as well as the onset times of electron transfer reactions between them, indicate that each molecule can undergo neutral three-body photolysis. For CH2I2, the structural evolution of the neutral molecule was simultaneously characterized along the C-I and I-C-I coordinates, demonstrating the sensitivity of these measurements to nuclear motion along multiple degrees of freedom.
RESUMO
Polycyclic aromatic hydrocarbons (PAHs) play an important role in interstellar chemistry and are subject to high energy photons that can induce excitation, ionization, and fragmentation. Previous studies have demonstrated electronic relaxation of parent PAH monocations over 10-100 femtoseconds as a result of beyond-Born-Oppenheimer coupling between the electronic and nuclear dynamics. Here, we investigate three PAH molecules: fluorene, phenanthrene, and pyrene, using ultrafast XUV and IR laser pulses. Simultaneous measurements of the ion yields, ion momenta, and electron momenta as a function of laser pulse delay allow a detailed insight into the various molecular processes. We report relaxation times for the electronically excited PAH*, PAH+* and PAH2+* states, and show the time-dependent conversion between fragmentation pathways. Additionally, using recoil-frame covariance analysis between ion images, we demonstrate that the dissociation of the PAH2+ ions favors reaction pathways involving two-body breakup and/or loss of neutral fragments totaling an even number of carbon atoms.
RESUMO
We report the results of a time-resolved coincident ion momentum imaging experiment probing nuclear wave packet dynamics in the strong-field ionization and dissociation of iodomethane (CH3I), a prototypical polyatomic system for photochemistry and ultrafast laser science. By measuring yields, kinetic energies, and angular distributions of CH3+ + I+ and CH3+ + I++ ion pairs as a function of the delay between two 25 fs, 790 nm pump and probe pulses, we map both, bound and dissociating nuclear wave packets in intermediate cationic states, thereby tracking different ionization and dissociation pathways. In both channels, we find oscillatory features with a 130 fs periodicity resulting from vibrational motion (C-I symmetric stretch mode) in the first electronically excited state of CH3I+. This vibrational wave packet dephases within 1 ps, in good agreement with a simple wave packet propagation model. Our results indicate that the first excited cationic state plays a key role in the dissociative ionization of CH3I and that it represents an important intermediate in the sequential double and multiple ionization at moderate intensities.
RESUMO
A series of novel self-crosslinkable and biodegradable polymers; poly(hexamethylene carbonate-fumarate), poly(hexamethylene carbonate) diacrylate and their amphiphilic copolymers with polyethylene glycol, poly(ethylene glycol fumarate-co-hexamethylene carbonate-fumarate) (PEGF-co-PHMCF) were developed for tissue engineering using novel synthesis approach. These novel polymers were fully characterized using nuclear magnetic resonance spectroscopy, Fourier transform infrared spectroscopy, gel permeation chromatography, differential scanning calorimetry, rheometry and shrinkage strain measurement. The cytocompatibility of macromers and their networks were evaluated by [3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide] MTT assay. The synthetic macromers were light colored with self-crosslinking ability via both photocrosslinking and chemical crosslinking. These polymers can be used as precursors to prepare polymer networks and scaffolds with controlled hydrophilicity, biodegradability and mechanical characteristics for application in cell delivery, tissue engineering and controlled release of biologically active agents.
