Beyond the Born-Oppenheimer approximation: high-resolution overtone spectroscopy of H2D+ and D2H+

Transitions to overtone 2v2 and 2v3, and combination v2 + v3 vibrations in jet-cooled H2D+ and D2H+ molecular ions have been measured for the first time by high-resolution IR spectroscopy. The source of these ions is a pulsed slit jet supersonic discharge, which allows for efficient generation, rotational cooling, and high frequency (100 KHz) concentration modulation for detection via sensitive lock-in detection methods. Isotopic substitution and high-resolution overtone spectroscopy in this fundamental molecular ion permit a systematic, first principles investigation of Born–Oppenheimer "breakdown" effects due to large amplitude vibrational motion as well as provide rigorous tests of approximate theoretical methods beyond the Born–Oppenheimer level. The observed overtone transitions are in remarkably good agreement (<0.1 cm–1) with non-Born–Oppenheimer ab initio theoretical predictions, with small but systematic deviations for 2v2, 2v + 3v, and 2v3 excited states indicating directions for further improvement in such treatments. Spectroscopic assignment and analysis of the isotopomeric transitions reveals strong Coriolis mixing between near resonant 2v3 and 2v + 3v vibrations in D2H+. Population-independent line intensity ratios for transitions from common lower states indicate excellent overall agreement with theoretical predictions for D2H+, but with statistically significant discrepancies noted for H2D+. Finally, H2D+ versus D2H+ isotopomer populations are analyzed as a function of D2/H2 mixing ratio and can be well described by steady state kinetics in the slit discharge expansion

The taxonomy and anatomy of rauisuchian archosaurs from the Late Triassic of Germany and Poland

The German Late Triassic archosaur Teratosaurus suevicus is a historically important taxon, being the first described rauisuchian. Unfortunately the holotype is a single element, a maxilla, which is poorly preserved and incomplete. We redescribe this maxilla and identify a single potential autapomorphy. The fragmentary type specimen complicates attempts to refer additional material to this taxon, and other unassociated archosaur and rauisuchian specimens from the Mittlerer Stubensandstein of Germany cannot be referred to T. suevicus with any degree of confidence. The stratigraphically older T. silesiacus, from the upper Carnian of Poland, is represented by a much more complete and better preserved specimen. Comparison of the maxillae of T. suevicus and T. silesiacus reveals that the two are distinct taxa, contra recent suggestions, but also that they do not share any synapomorphies or a unique combination of characters relative to Postosuchus kirkpatricki and other rauisuchians. Thus, the Polish material must be transferred to a new genus, Polonosuchus gen. nov. Both Polonosuchus and Teratosaurus are very similar to Postosuchus kirkpatricki, and the three taxa are likely closely related

Rovibrational states of the h(2)o-h(2) complex: An ab initio calculation

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A new archosauriform (Reptilia: Diapsida) from the Manda Beds (Middle Triassic) of southwestern Tanzania

BackgroundArchosauria and their closest relatives, the non-archosaurian archosauriforms, diversified in the Early and Middle Triassic, soon after the end-Permian extinction. This diversification is poorly documented in most Lower and Middle Triassic rock sequences because fossils of early groups of archosauriforms are relatively rare compared to those of other amniotes. The early Middle Triassic (? late Anisian) Manda beds of southwestern Tanzania form an exception, with early archosaur skeletons being relatively common and preserved as articulated or associated specimens. The Manda archosaur assemblage is exceptionally diverse for the Middle Triassic. However, to date, no non-archosaurian archosauriforms have been reported from these rocks.Methodology/principal findingsHere, we name a new taxon, Asperoris mnyama gen. et sp. nov., from the Manda beds and thoroughly describe the only known specimen. The specimen consists of a well-preserved partial skull including tooth-bearing elements (premaxilla, maxilla), the nasal, partial skull roof, and several incomplete elements. All skull elements are covered in an autapomorphic highly rugose sculpturing. A unique combination of character states indicates that A. mnyama lies just outside Archosauria as a stem archosaur within Archosauriformes, but more precise relationships of A. mnyama relative to other early archosauriform clades (e.g., Erythrosuchidae) cannot be determined currently.Conclusions/significanceAsperoris mnyama is the first confirmed non-archosaurian archosauriform from the Manda beds and increases the morphological and taxonomic diversity of early archosauriforms known from the Middle Triassic. The direct association of A. mnyama with species referable to Archosauria demonstrates that non-archosaurian archosauriforms were present during the rise and early diversification of Archosauria. Non-archosaurian archosauriforms and archosaurs co-occur in fossil reptile assemblages across Pangaea from the late Early Triassic to the end of the Late Triassic

Overtone vibrational spectroscopy in h-2-h2o complexes: A combined high level theoretical ab initio, dynamical and experimental study

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Evidence for a high Mg andesitic parental magma to the East and West satellite dykes of the Great Dyke, Zimbabwe: a comparison with the continental tholeiitic Mashonaland sills

One of the most significant mafic intrusive events in the Zimbabwe Craton was the emplacement of the Great Dyke layered ultramafic-mafic complex and its two parallel ‘satellite’ dykes at the end of the Archæan (?2.6 Ga). The two satellite dykes, the East Dyke and the West (Umvimeela) Dyke, were far less affected by crystal accumulation and layering processes than the Great Dyke, and therefore may provide a clearer picture of parental magma compositions of the Great Dyke event. The geochemical character of this major episode of mafic magmatism is markedly different to that of more typical continental tholeiites, such as the ?1.9 Ga Mashonaland sills, and reflects significant contrasts in petrogenetic influences. Despite its mid-continental setting, the parental magma of the satellite dykes had geochemical characteristics more often associated with magmas generated at destructive plate margins, suggesting that the nature of this magma was perhaps more similar to high Mg andesitic, rather than continental tholeiitic magmatism. Fine-grained samples with ?14% MgO perhaps most closely approximate to the parental magma composition. Certain major and trace element concentrations (high MgO, SiO2, LREE and LILE, and low Nb, Ta and Ti) and the lack of an Fe enrichment trend, suggest that the mafic magma had either suffered severe crustal contamination or had been derived from a metasomatised harzburgitic mantle source