Activation energies of pericyclic reactions: performance of DFT, MP2, and CBS-QB3 methods for the prediction of activation barriers and reaction energetics of 1,3-dipolar cycloadditions, and revised activation enthalpies for a standard set of hydrocarbon pericyclic reactions

Activation barriers and reaction energetics for the three main classes of 1,3-dipolar cycloadditions, including nine different reactions, were evaluated with the MPW1K and B3LYP density functional methods, MP2, and the multicomponent CBS-QB3 method. The CBS-QB3 values were used as standards for 1,3-dipolar cycloaddition activation barriers and reaction energetics, and the density functional theory (DFT) and MP2 methods were benchmarked against these values. The MPW1K/6-31G* method and basis set performs best for activation barriers, with a mean absolute deviation (MAD) value of 1.1 kcal/mol. The B3LYP/6-31G* method and basis set performs best for reaction enthalpies, with a MAD value of 2.4 kcal/mol, while the MPW1K method shows large errors for reaction energetics. The MP2 method gives the expected systematic underestimation of barriers. Concerted and nearly synchronous transition structures are predicted by all DFT and MP2 methods. Also reported are revised estimated 0 K experimental activation enthalpies for a standard set of hydrocarbon pericyclic reactions and updated comparisons to experiment for DFT, ab initio, and multicomponent methods. B3LYP and MPW1K methods with MAD values of 1.5 and 2.1 kcal/mol, respectively, fortuitously outperform the multicomponent CBS-QB3 method, which has a MAD value of 2.3. The MAD value of the O3LYP functional improves to 2.4 kcal/mol from the previously reported 3.0 kcal/mol.     

Coloring arcs of convex sets

In this note we consider Ramsey-type problems on graphs whose vertices are represented by the vertices of a convex polygon in the Euclidean plane. The edges of the graph are represented by the segments between the points of the polygon. The edges are arbitrarily colored by a fixed number of colors and the problem is to decide whether there exist monochromatic subgraphs of certain types satisfying some geometric conditions. We will give lower and upper bounds for these geometric Ramsey numbers for certain paths and cycles and also some exact values. It turns out that the particular type of the embedding is crucial for the growth rate of the corresponding geometric Ramsey numbers. In particular, the Ramsey numbers for crossing 4-cycles and t colors grow quadratically in t, while for convex 4-cycles they grow at least exponentially.     

Comparison of water isotope-ratio determinations using two cavity ring-down instruments and classical mass spectrometry in continuous ice-core analysis

We present a detailed comparison between subsequent versions of commercially available wavelength-scanned cavity ring-down water isotope analysers (L2120-i and L2130-i, Picarro Inc.). The analysers are used in parallel in a continuous mode by adaption of a low-volume flash evaporation module. Application of the analysers to ice-core analysis is assessed by comparison between continuous water isotope measurements of a glacial ice-core from Severnaya Zemlya with discrete isotope-ratio mass spectrometry measurements performed on parallel samples from the same ice-core. The great advances between instrument versions, particularly in the measurement of δ²H, allow the continuous technique to achieve the same high level of accuracy and precision obtained using traditional isotope spectrometry techniques in a fraction of the experiment time. However, when applied to continuous ice-core measurements, increased integration times result in a compromise of the achievable depth resolution of the ice-core records.     

Scattering Theory for Quantum Fields¶with Indefinite Metric

In this work, we discuss the scattering theory of local, relativistic quantum fields with indefinite metric. Since the results of Haag–Ruelle theory do not carry over to the case of indefinite metric [4], we propose an axiomatic framework for the construction of in- and out-states, such that the LSZ asymptotic condition can be derived from the assumptions. The central mathematical object for this construction is the collection of mixed vacuum expectation values of local, in- and out-fields, called the “form factor functional”, which is required to fulfill a Hilbert space structure condition. Given a scattering matrix with polynomial transfer functions, we then construct interpolating, local, relativistic quantum fields with indefinite metric, which fit into the given scattering framework. Received: 13 September 1999/ Accepted: 1 August 2000     

Synthesis and Reactivity of a Neutral,Three‐Coordinate Platinum(II) Complex Featuring Terminal Amido Ligation

A crystallographically characterized three‐coordinate, formally 14 electron Pt^II complex 1 featuring terminal amido ligation is reported. Computational analysis revealed relatively weak π donation from the amide lone pair to platinum and supports a 14‐electron assignment for 1 . Stoichiometric reactivity studies confirmed the viability of net O? H and C? H addition across, as well as isonitrile insertion into, the terminal platinum–amido linkage of 1 .