Mass-selective threshold photoelectron spectroscopy in the gas phase was employed to characterize the dialkynyl triplet carbenes pentadiynylidene (HC5H), methylpentadiynylidene (MeC5H) and dimethylpentadiynylidene (MeC5Me). Diazo compounds were employed as precursors to generate the carbenes by flash pyrolysis. The R1-C5-R2 carbon chains were photoionized by vacuum ultraviolet (VUV) synchrotron radiation in photoelectron photoion coincidence (PEPICO) experiments. High-level ab initio computations were carried out to support the interpretation of the experiments. For the unsubstituted pentadiynylidene (R1= R2= H) the recorded spectrum yields an adiabatic ionization energy (IEad) of 8.36 ± 0.03 eV. In addition, a second carbene isomer, 3-(didehydrovinylidene)cyclopropane, with a singlet electronic ground state, was identified in the spectrum based on the IEad of 8.60 ± 0.03 eV and Franck Condon simulations. We found that multireference computations are required to reliably calculate the IEad for this molecule. CASPT2 computations predicted an IEad =8.55 eV, while coupled-cluster computations significantly overestimate the IE. The cyclic isomer is most likely formed from another isomer of the precursor present in the sample. Stepwise methyl-substitution of the carbene leads to a reduction of the IE to 7.77 ± 0.04 eV for methylpentadiynylidene and 7.27 ± 0.06 eV for dimethylpentadiynylidene. The photoionization and dissociative photoionization of the precursors is investigated as well.
Postbuckling analysis of composite laminates representative of wind turbine blade substructures, utilizing the commercial finite element software ANSYS, is presented in this paper. The procedure was validated against an existing postbuckling analysis. Three shell element formulations, SHELL91, SHELL99, and SHELL181, were examined. It was found that the SHELL181 element with reduced integration should be used to avoid shear locking. The validated procedure was used to examine the variation of the buckling behavior, including postbuckling, with lamination schedule of a laminate representative of a wind turbine blade shear web. This analysis was correlated with data from a static test. A 100% postbuckling reserve in a composite structure representative of a shear web was quantified through test and analysis. The buckling behavior of the shear web was improved by modifying the lamination schedule to increase the web bending stiffness. Modifications that improved the buckling load of the structure did not always equate to improvements in the postbuckling reserve.
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