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13 pags., 7 figs., The site-specific hydrogen-atom elimination mechanism previously reported for photoexcited ethyl radicals (CH3CH2) [D. V. Chicharro et al., Chem. Sci., 2019, 10, 6494] is interrogated in the photodissociation of the ethyl isotopologues CD3CD2, CH3CD2 and CD3CH2 through the velocity map imaging (VMI) detection of the produced hydrogen- and deuterium-atoms. The radicals, generated in situ from photolysis of a precursor using the same laser pulse employed in their excitation to Rydberg states, decompose along the Cα-H/D and Cβ-H/D reaction coordinates through coexisting statistical and site-specific mechanisms. The experiments are carried out at two excitation wavelengths, 201 and 193 nm. The comparison between both sets of results provides accurate information regarding the primary role in the site-specific mechanism of the radical internal reservoir. Importantly, at 193 nm excitation, higher energy dissociation channels (not observed at 201 nm) producing low-recoil H/D-atoms become accessible. High-level ab initio calculations of potential energy curves and the corresponding non-adiabatic interactions allow us to rationalize the experimental results in terms of competitive non-adiabatic decomposition paths. Finally, the adiabatic behavior of the conical intersections in the face of several vibrational modes - the so-called vibrational promoting modes - is discussed., D. V. C. acknowledges financial support from the Spanish MINECO under the FPI predoctoral program. This work was financed by the grants PGC2018-096444-B-I00, PID2019-107115GB-C21, PID2021-122839NB-I00, PID2021-122549NB-C21 and PID2021-122796NB-I00 from the MCIN/AEI/10.13039/501100011033/FEDER, UE. A. G. V. acknowledges support from the COST Action CA21101 (COSY). The facilities provided by the Centro de Laseres Ultra-rrapidos at Universidad Complutense de Madrid are gratefully acknowledged. The Centro de Supercomputacion de Galicia (CESGA, Spain) and the Centro Tecnico de Informatica (CTI, CSIC) are acknowledged for the use of their resources. This work was performed in part at the Institute of Electronic Structure and Laser, Foundation for Research and Technology-Hellas (IESL- FORTH) and received financial support from LaserLab Europe through the ULF-FORTH002262 project (Grant agreement no. 654148)

Mass resolved REMPI spectra, as well as CH3+and I+ ion and photoelectron images, were recorded for two-photon resonant excitations of CH3I via s, p and d Rydberg states (CH3I**) in the excitation region of 55 700 to 70 000 cm−1. 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) (CH3I#), followed by branching into three pathways. The major one is the dissociation of CH3I# to form excited Rydberg states of iodine atoms (I**) along with CH3(X), a phenomenon not commonly observed in methyl halides. The second (minor) pathway involves autoionization of CH3I# towards CH3I+(X), which absorbs another photon to form CH3+ along with I/I* and the third one (minor) is CH3I# dissociation towards the ion pair, CH3+ + I−, prior to I− electron ejection. Furthermore, one-photon non-resonant dissociation of CH3I to form CH3(X) and I/I* prior to three-photon ionization of the fragments is also detected.

Photoelectron 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. In this work, we follow the high-resolution approach using a tunable narrow-band nanosecond laser to measure REMPI-PECD through distinct vibrational levels in the intermediate 3s and 3p Rydberg states of fenchone. We observe the PECD to be essentially independent of the vibrational level. This behaviour of the chiral sensitivity may pave the way for enantiomer specific molecular identification in multi-component mixtures: one can specifically excite a sharp, vibrationally resolved transition of a distinct molecule to distinguish different chiral species in mixtures.

Mass resolved REMPI spectra, as well as CH

The 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. Kinetic energy release spectra (KERs) were derived from slice and photoelectron images and anisotropy parameters were extracted from the angular distributions of the ions to identify the processes and the dynamics involved. At all wavelengths we observe three-photon excitations, via the two-photon resonant transitions to molecular Rydberg states, forming metastable, superexcited (CH3Br#) states which dissociate to form CH3 Rydberg states (CH3**) along with Br/Br*. A correlation between the parent Rydberg states excited and CH3** formed is evident. For the three highest excitation energies used, the CH3Br# metastable states also generate high kinetic energy fragments of CH3(X) and Br/Br*. In addition for two out of these three wavelengths we also measure one-photon photolysis of CH3Br in the A band forming CH3(X) in various vibrational modes and bromine atoms in the ground (Br) and spin–orbit excited (Br*) states.

Velocity 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 H1Σ+(v′ = 0) and E1Σ+(v′ = 1) Rydberg states and the V1Σ+(v′= m + 7) and V1Σ+(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−1. H+ and Br+ images were recorded by one- as well as two-color excitation schemes. Kinetic energy release (KER) spectra and angular distributions were extracted from the data. Strong-to-medium interactions between the E(1) and V(m + 8)/V(m + 7) states on one hand and the H(0) and V(m + 7)/V(m + 8) states on the other hand were quantified from peak shifts and intensity analysis of REMPI spectra. The effects of those interactions on subsequent photoionization and photolytic pathways of HBr were evaluated in one-color VMI experiments of the H+ and two-color VMI experiments of the Br+ photoproducts.

Two-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. Predissociation channels, following the two-photon resonant excitations and non-resonant photodissociation forming CH3(X) and Br/Br*, were identified and characterized. Furthermore, the probe excitations for CH3(X) involved near-resonant excitations to lower energy 5s Rydberg states of CH3Br. In three-photon excitation processes, a striking contrast is seen between excitations via the p/d and the s Rydberg states. Involvement of high-energy interactions between Rydberg and ion-pair states is identified.

Analysis 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 3Σ−(v′ = 0)) and valence (ion-pair) (V 1Σ+(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.

The 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. Kinetic energy release spectra (KERs) were derived from slice and photoelectron images and anisotropy parameters were extracted from the angular distributions of the ions to identify the processes and the dynamics involved. At all wavelengths we observe three-photon excitations, via the two-photon resonant transitions to molecular Rydberg states, forming metastable, superexcited (CH3Br#) states which dissociate to form CH3 Rydberg states (CH3**) along with Br/Br*. A correlation between the parent Rydberg states excited and CH3** formed is evident. For the three highest excitation energies used, the CH3Br# metastable states also generate high kinetic energy fragments of CH3(X) and Br/Br*. In addition for two out of these three wavelengths we also measure one-photon photolysis of CH3Br in the A band forming CH3(X) in various vibrational modes and bromine atoms in the ground (Br) and spin-orbit excited (Br*) states.

Photoexcitation 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. Autoionization pathways leading to H(+) + Br((2)P3/2)/Br*((2)P1/2) via either HBr(+)((2)Π3/2) or HBr(+)*((2)Π1/2) formation were also present. The analysis of KER and angular distributions and comparison with rotationally and mass resolved resonance enhanced multiphoton ionization (REMPI) spectra revealed the excitation transition mechanisms and characteristics of states involved as well as the involvement of the E-V state interactions and their v' and J' dependence.

Oxygen-rich niobium oxide clusters are formed by mixing laser-produced Nb plasma with pure oxygen, and their stability is investigated by mass spectrometry and collision-induced dissociation. We use an experimental configuration recently developed by our group, where the cluster ions beam is crossed with a secondary beam of noble gas atoms, and the fragments are rejected by a retarding field energy analyzer. In this way, the relative collision cross sections of Nb x O + (x = 1, 2, y = 2–12) clusters have been measured and information about their fragmentation channels has been obtained.

Yttrium 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). Additionally, we performed collision induced dissociation experiments, which indicated that the loss of pairs of oxygen atoms down to a YO+ core is the preferred fragmentation channel for all clusters investigated. Furthermore, we conduct DFT calculations and we obtained two types of low-energy structures: one containing an yttrium cation core and the other composed of YO+ core and O2 ligands, being in agreement with the observed fragmentation pattern. Finally, from the fragmentation studies, total collision cross sections are obtained and these are compared with geometrical cross sections of the calculated structures.

The 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. Nonadiabatic transition probabilities from the (3)Q0 to (1)Q1 surface dominate the dynamics in this excitation energy region and for most of the methyl vibrational states probed.

ICl photolysis in the ultraviolet region of the spectrum (235-265 nm) is studied using the Slice Imaging technique. The Cl∗((2)P(1/2))/Cl((2)P(3/2)) and the I∗((2)P(1/2))/I((2)P(3/2)) branching ratio between the I((2)P(3/2)) + Cl((2)P(3/2))∕Cl∗((2)P(1/2)) and I∗((2)P(1/2)) + Cl((2)P(3∕/2))∕Cl∗((2)P(1/2)) channels is extracted from the respective iodine and chlorine photofragment images. We find that ground state chlorine atoms (Cl((2)P(3/2))) are formed nearly exclusively with excited state iodine atoms (I∗((2)P(1/2))), while excited spin-orbit chlorine atoms (Cl∗((2)P(1/2))) are concurrently produced only with ground state iodine atoms (I((2)P(3/2))). We conclude that photolysis of ICl in this UV region is a relatively "clean" source of spin-orbit excited chlorine atoms that can be used in crossed molecular beam experiments.

Two-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. Predissociation channels, following the two-photon resonant excitations and non-resonant photodissociation forming CH3(X) and Br/Br*, were identified and characterized. Furthermore, the probe excitations for CH3(X) involved near-resonant excitations to lower energy 5s Rydberg states of CH3Br. In three-photon excitation processes, a striking contrast is seen between excitations via the p/d and the s Rydberg states. Involvement of high-energy interactions between Rydberg and ion-pair states is identified.

Introduction. This study was aimed at investigating the influence of certain cytotoxic drugs on the organ uptake of the following 99mTc-radiopharma­ceuticals: 99mTc-2,3-dicarboxypropane-1,1-diphosphonic acid, 99mTc-meso-2,3-dimercaptosuccinic acid, 99mTc-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. On the eighth day, each of the 99mTc-radiopharmaceuticals was applied in a separate group of treated animals. They were sacrificed at different time intervals and the radioactivity in the organs of interest was measured. The organ uptake of the 99mTc-radiopharmaceuticals in an additional control group of animals was also studied. Results. The results obtained showed an alteration in the organ uptake of 99mTc-radiopharmaceuticals in animals treated with cytotoxic drugs. In the rats treated with methotrexate sodium, there was a higher up­take of 99mTc-meso-2,3-dimercaptosuccinic acid in the bones, stomach and intestine, a higher uptake of 99mTc-2,3-dicarboxypropane-1­,1-diphosphronic acid in the bones, intestine, blood and muscle, a lower uptake of 99mTc-tin colloid in the liver and a lower accumulation of 99mTc-macroaggregated albumin in the lungs. Cyclophospha­mide-treated animals showed enhanced uptake of 99mTc-meso-2,3-dimercaptosuccinic acid in the kidneys, a twofold enhanced uptake of 99mTc-2,3-dicarboxypropane-1,1-diphosphronic acid in all organs except the stomach, a decreased uptake of 99mTc-tin colloid in the lungs, spleen and kidneys and a significantly decreased uptake of 99mTc-macroaggregated albumin in the lungs. Conclusion. These results confirm that both methotrexate sodium and cyclophosphamide may alter the organ uptake of 99mTc-radiopharmaceuticals in experimental animals.