Molecular fragmentation into three products poses an analytical challenge to theory and experiment alike. We used translational spectroscopy and high-level ab initio calculations to explore the highly debated three-body dissociation of sym-triazine to three hydrogen cyanide molecules. Dissociation was induced by charge exchange between the sym-triazine radical cation and cesium. Calculated state energies and electronic couplings suggest that reduction initially produces a population of sym-triazine partitioned between the 3s Rydberg and pi* <-- n electronically excited manifolds. Analysis of the topology of these manifolds, along with momentum correlation in the dissociation products, suggests that a conical intersection of two potential energy surfaces in the 3s Rydberg manifold leads to stepwise dissociation, whereas a four-fold glancing intersection in the pi* <-- n manifold leads to a symmetric concerted reaction.
Dissociative charge exchange of CH5+ with Cs, coupled with quasiclassical trajectory calculations on an ab initio PES for CH5, has been used to probe the structure of the CH5+ cation. Product kinetic energy release distributions and branching ratios for CH5 --> CH4 + H and CH5 --> CH3 + H2 have been compared. The agreement of the product branching ratios provides evidence for the fluxional nature of CH5+.
The greater information depth provided in Hard X-ray Photoelectron Spectroscopy (HAXPES) enables non-destructive analyses of the chemistry and electronic structure of buried interfaces. Moreover, for industrially relevant elements like Al, Si and Ti, the combined access to the Al 1s, Si 1s or Ti 1s photoelectron line and its associated Al KLL, Si KLL or Ti KLL Auger transition, as required for local chemical state analysis on the basis of the Auger parameter, is only possible with hard X-rays. Until now, such photoemission studies were only possible at synchrotron facilities. Recently however, the first commercial XPS/HAXPES systems, equipped with both soft and hard X-ray sources, have entered the market, providing unique opportunities for monitoring the local chemical state of all constituent ions in functional oxides at different probing depths, in a routine laboratory environment. Bulksensitive shallow core-levels can be excited using either the hard or soft X-ray source, whereas more surface-sensitive deep core-level photoelectron lines and associated Auger transitions can be measured using the hard X-ray source. As demonstrated for thin Al2O3, SiO2 and TiO2 films, the local chemical state of the constituting ions in the oxide may even be probed at near constant probing depth by careful selection of sets of photoelectron and Auger lines, as excited with the combined soft and hard X-ray sources. We highlight the potential of lab-based HAXPES for the research on functional oxides and also discuss relevant technical details regarding the calibration of the kinetic binding energy scale. Supporting information:Advanced chemical state studies of oxide films by lab-based HAXPES combining soft and hard X-ray sources
Molecular hydrogen (H2) is an excellent alternative fuel. It can be produced from the abundantly present water on earth. Transition-metal oxides are widely used in the environmentally benign photocatalytic generation of H2 from water, thus actively driving scientific research on the mechanisms for this process. In this study, we investigate the chemical reactions of W3O5(-) and Mo3O5(-) clusters with water that shed light on a variety of key factors central to H2 generation. Our computational results explain why experimentally Mo3O5(-) forms a unique kinetic trap in its reaction while W3O5(-) undergoes a facile oxidation to form the lowest-energy isomer of W3O6(-) and liberates H2. Mechanistic insights on the reaction pathways that occur, as well as the reaction pathways that do not occur, are found to be of immense assistance to comprehend the hitherto poorly understood pivotal roles of (a) differing metal-oxygen and metal-hydrogen bond strengths, (b) the initial electrostatic complex formed, (c) the loss of entropy when these TMO clusters react with water, and (d) the geometric factors involved in the liberation of H2.
Reactions between molybdenum suboxide cluster anions, Mo(x)O(y)(-) (x=1-4; y < or = 3x), and water (H(2)O and D(2)O) have been studied using mass spectrometric analysis of products formed in a high-pressure, fast-flow reactor. Product distributions vary with the number of metal atoms in the cluster. Within the MoO(y)(-) oxide series, product masses correspond to the addition of one water molecule, as well as a H/D exchange with MoO(4)H(-). Within the Mo(2)O(y)(-) oxide series, product evolution and distribution suggest sequential oxidation via Mo(2)O(y)(-)+H(2)O/D(2)O-->Mo(2)O(y+1)(-)+H(2)/D(2) reactions for y<5, while for Mo(2)O(5)(-), Mo(2)O(6)H(2)/D(2)(-) is produced. Mo(2)O(6)(-) does not appear to be reactive toward water. For the Mo(3)O(y)(-) oxide series, sequential oxidation similarly is suggested for y<5, while Mo(3)O(5)(-) reactions result in Mo(3)O(6)H(2)/D(2)(-) formation. Mo(3)O(6)(-) appears uniquely unreactive. Mo(3)O(7)(-) and Mo(3)O(8)(-) react to form Mo(3)O(8)H(2)/D(2)(-) and Mo(3)O(9)H(2)/D(2)(-), respectively. Lower mass resolution in the Mo(4)O(y)(-) mass range prevents unambiguous mass analysis, but intensity changes in the mass spectra do suggest that sequential oxidation with H(2)/D(2) evolution occurs for y<6, while Mo(4)O(y+1)H(2)/D(2)(-) addition products are formed in Mo(4)O(6)(-) and Mo(4)O(7)(-) reactions with water. The relative rate constants for sequential oxidation and H(2)O/D(2)O addition for the x=2 series were determined. There is no evidence of a kinetic isotope effect when comparing reaction rates of H(2)O with D(2)O, suggesting that the H(2) and D(2) losses from the lower-oxide/hydroxide intermediates are very fast relative to initial reaction complex formation with H(2)O or D(2)O. The rate constants determined here are two times higher than those determined in identical reactions between W(2)O(y)(-)+H(2)O/D(2)O.
The highly debated three-body dissociation of sym-triazine to three HCN products has been investigated by translational spectroscopy and high-level ab initio calculations. Dissociation was induced by charge exchange between the sym-triazine radical cation and cesium. Calculated state energies and electronic couplings suggest that sym-triazine is produced in the 3s Rydberg and pi* <-- n manifolds. Analysis of the topology of these manifolds along with momentum correlation in the dissociation products suggest that the 3s Rydberg manifold characterized by a conical intersection of two potential energy surfaces leads to stepwise dissociation, while the pi* <-- n manifold consisting of a four-fold glancing intersection leads to a symmetric concerted reaction.
Purpose The immune checkpoint inhibitors (ICIs) have resulted in subgroups of patients with metastatic melanoma achieving high-quality durable responses. Metastatic melanoma survivors are a new population in the era of cancer survivorship. The aim of this study was to evaluate metastatic melanoma survivors in terms of health-related quality of life (HRQoL), immune-related adverse events (irAEs) and exposure to immunosuppressive agents in a large single centre in the UK. Methods We defined the survivor population as patients with a diagnosis of metastatic melanoma who achieved a durable response to an ICI and had been followed-up for a minimum of 12 months from initiation of ICI without disease progression. HRQoL was assessed using SF-36. Electronic health records were accessed to collect data on demographics, treatments, irAEs and survival. HRQoL data was compared with two norm-based datasets. Results Eighty-four metastatic melanoma survivors were eligible and 87% (N = 73) completed the SF-36. ICI-related toxicity of any grade occurred in 92% of patients and 43% had experienced a grade 3 or 4 toxicity. Almost half (49%) of the patients required steroids for the treatment of ICI-related toxicity, whilst 14% required treatment with an immunosuppressive agent beyond steroids. Melanoma survivors had statistically significant lower HRQoL scores with regard to physical, social and physical role functioning and general health compared with the normative population. There was a trend towards inferior scores in patients with previous exposure to ipilimumab compared with those never exposed to ipilimumab. Conclusions Our results show that metastatic melanoma survivors have potentially experienced significant ICI-related toxicity and experience significant impairments in specific HRQoL domains. Future service planning is required to meet this population's unique survivorship needs.
The anion photoelectron imaging spectra of O·VOC and O·VOC (VOC = hexane, isoprene, benzene, and benzene-d) complexes measured using 3.49 eV photon energy, along with the results of ab initio and density functional theory results are reported and analyzed. Photodetachment of these anionic complexes accesses neutrals that model collision complexes, offering a probe of the effects of symmetry-breaking collision events on the electronic structure of normally transparent neutral molecules. The energies of O·VOC spectral features compared to the bare O indicate that photodetachment of the anion accesses a modestly repulsive region of the O-VOC potential energy surface, with subtle VOC dependence on the relative energies of the O (X Σ)·VOC ground state and O (a Δ)·VOC excited state. In contrast, a significantly higher intensity of the transition to the O (a Δ)·VOC excited state relative to the O (X Σ)·VOC ground state is observed for VOC = benzene, with a less pronounced effect observed for VOC = isoprene. Similar spectral effects are observed in the O·benzene and O·isoprene PE spectra. Several explanations are considered, with involvement of a temporary anion state emerging as the most plausible.
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