The site-specific hydrogen-atom elimination mechanism previously reported for photoexcited ethyl radicals (CHCH) [D. V. Chicharro , , 2019, , 6494] is interrogated in the photodissociation of the ethyl isotopologues CDCD, CHCD and CDCH through the velocity map imaging (VMI) detection of the produced hydrogen- and deuterium-atoms.
View Article and Find Full Text PDFPhotoelectron circular dichroism (PECD) is a highly sensitive enantiospecific spectroscopy for studying chiral molecules in the gas phase using either single-photon ionization or multiphoton ionization. In the short pulse limit investigated with femtosecond lasers, resonance-enhanced multiphoton ionization (REMPI) is rather instantaneous and typically occurs simultaneously via more than one vibrational or electronic intermediate state due to limited frequency resolution. In contrast, vibrational resolution in the REMPI spectrum can be achieved using nanosecond lasers.
View Article and Find Full Text PDFMass resolved REMPI spectra, as well as CHand I ion and photoelectron images, were recorded for two-photon resonant excitations of CHI via s, p and d Rydberg states (CHI**) in the excitation region of 55 700 to 70 000 cm. Photoelectron (PE) and ion kinetic energy release spectra (KERs) were derived from the images. The data revealed that after the two-photon resonant excitation, an additional photon is absorbed to form one or more superexcited state(s) (CHI), followed by branching into three pathways.
View Article and Find Full Text PDFTwo-color pump-probe experiments were performed to explore the multiphoton dynamics of CH3Br at high excitation energies of 8-10 eV, involving two-photon resonant excitations to a number of np and nd Rydberg states (pump) followed by REMPI detection (probe) of the Br, Br* and CH3(X) photoproducts. Slice images of Br+ and CH3+ ions were recorded in pump-only, probe-only and pump and probe experiments. Kinetic-energy release spectra (KERs), as well as spatial anisotropy parameters, were extracted from the images to identify the processes and the dynamics involved.
View Article and Find Full Text PDFThe multiphoton dynamics of CH3Br were probed by Mass Resolved MultiPhoton Ionization (MR-MPI), Slice Imaging and Photoelectron Imaging in the two-photon excitation region of 66 000 to 80 000 cm-1. Slice images of the CH3+ and Br+ photoproducts of ten two-photon resonant transitions to np and nd Rydberg states of the parent molecule were recorded. CH3+ ions dominate the mass spectra.
View Article and Find Full Text PDFWe report a novel highly spin-polarized deuterium (SPD) source, via the photodissociation of deuterium iodide at 270 nm. I(^{2}P_{3/2}) photofragments are ionized with m-state selectivity, and their velocity distribution measured via velocity-map slice imaging, from which the D polarization is determined. The process produces ∼100% electronically polarized D at the time of dissociation, which is then converted to ∼60% nuclear D polarization after ∼1.
View Article and Find Full Text PDFVelocity map imaging (VMI) data and mass resolved REMPI spectra are complementarily utilized to elucidate the involvement of homogeneous multistate interactions in excited state dynamics of HBr. The HΣ(v' = 0) and EΣ(v' = 1) Rydberg states and the VΣ(v'= m + 7) and VΣ(v'= m + 8) ion-pair states are explored as a function of rotational quantum number in the two-photon excitation region of 79 100-80 700 cm. H and Br images were recorded by one- as well as two-color excitation schemes.
View Article and Find Full Text PDFAnalysis of mass resolved spectra as well as velocity map images derived from resonance enhanced multiphoton ionization (REMPI) of HBr via resonance excitations to mixed Rydberg (6pπ Σ(v' = 0)) and valence (ion-pair) (V Σ(v' = m + 17)) states allows characterization of the effect of a triplet-to-singlet state interaction on further photoexcitation and photoionization processes. The analysis makes use of rotational spectra line shifts, line intensity alterations, kinetic energy release spectra as well as angular distributions. Energy-level-dependent state mixing of the resonance excited states is quantified and photoexcitation processes, leading to H formation, are characterized in terms of the states and fragmentation processes involved, depending on the state mixing.
View Article and Find Full Text PDFYttrium oxide cluster cations have been experimentally and theoretically studied. We produced small, oxygen-rich yttrium oxide clusters, YxOy+ (x = 1, 2, y = 1–13), by mixing the laser-produced yttrium plasma with a molecular oxygen jet. Mass spectrometry measurements showed that the most stable clusters are those consisting of one yttrium and an odd number of oxygen atoms of the form YO(+)(2k+1) (k = 0–6).
View Article and Find Full Text PDFPhotoexcitation dynamics of the E((1)Σ(+)) (v' = 0) Rydberg state and the V((1)Σ(+)) (v') ion-pair vibrational states of HBr are investigated by velocity map imaging (VMI). H(+) photoions, produced through a number of vibrational and rotational levels of the two states were imaged and kinetic energy release (KER) and angular distributions were extracted from the data. In agreement with previous work, we found the photodissociation channels forming H*(n = 2) + Br((2)P3/2)/Br*((2)P1/2) to be dominant.
View Article and Find Full Text PDFThe photodissociation of methyl bromide at 193 nm is studied using slice imaging. From the measured photofragment translational energy and angular distributions we were able to extract methyl-state-specific dissociation channel yields and crossing probabilities between (3)Q0 and (1)Q1 surfaces. The angular distributions for the Bromine photofragments show a strong dependence on the total translational energy release.
View Article and Find Full Text PDFWe present slice imaging data demonstrating the influence of clustering on the photodissociation dynamics of a diatomic molecule: iodine monochloride (ICl) was dissociated at 235 nm in He and Xe seed gasses, probing both Cl and I photofragment energy and angular distributions. We observe that the kinetic energy releases of both Cl and I fragments change from He to Xe seeding. For Cl fragments, the seeding in Xe increases the kinetic energy release of some Cl fragments with a narrow kinetic energy distribution, and leads to some fragments with rather broad statistical distribution falling off exponentially from near-zero energies up to about 2.
View Article and Find Full Text PDFIntroduction: This study was aimed at investigating the influence of certain cytotoxic drugs on the organ uptake of the following 9mTc-radiopharmaceuticals: 99mTc-2,3-dicarboxypropane-1, 1-diphosphonic acid, 99mTc-meso-2,3-dimercaptosuccinic acid, 9mTc-tin colloid and 99mTc-macraggregated albumin. Methotrexate sodium and cyclophosphamide were used as models to evaluate these effects.
Material And Methods: Two groups of healthy male Wistar rats were treated separately by oral application of the drugs for 7 days.