A series of model transition-metal complexes, CrF6, ferrocene, Cr(CO)6, ferrous porphin, cobalt corrole, and FeO/FeO(-), have been studied using second-order perturbation theory based on a restricted active space self-consistent field reference wave function (RASPT2). Several important properties (structures, relative energies of different structural minima, binding energies, spin state energetics, and electronic excitation energies) were investigated. A systematic investigation was performed on the effect of: (a) the size and composition of the global RAS space, (b) different (RAS1/RAS2/RAS3) subpartitions of the global RAS space, and (c) different excitation levels (out of RAS1/into RAS3) within the RAS space. Calculations with active spaces, including up to 35 orbitals, are presented. The results obtained with smaller active spaces (up to 16 orbitals) were compared to previous and current results obtained with a complete active space self-consistent field reference wave function (CASPT2). Higly accurate RASPT2 results were obtained for the heterolytic binding energy of ferrocene and for the electronic spectrum of Cr(CO)6, with errors within chemical accuracy. For ferrous porphyrin the intermediate spin (3)A2g ground state is (for the first time with a wave function-based method) correctly predicted, while its high magnetic moment (4.4 μB) is attributed to spin-orbit coupling with very close-lying (5)A1g and (3)Eg states. The toughest case met in this work is cobalt corrole, for which we studied the relative energy of several low-lying Co(II)-corrole π radical states with respect to the Co(III) ground state. Very large RAS spaces (25-33 orbitals) are required for this system, making compromises on the size of RAS2 and/or the excitation level unavoidable, thus increasing the uncertainty of the RASPT2 results by 0.1-0.2 eV. Still, also for this system, the RASPT2 method is shown to provide distinct improvements over CASPT2, by overcoming the strict limitations in the size of the active space inherent to the latter method.

The accuracy of the relative spin-state energetics of three small Fe(II) or Fe(III) heme models from multiconfigurational perturbation theory (CASPT2) and density functional theory with selected functionals (including the recently developed M06 and M06-L functionals) was assessed by comparing with recently available coupled cluster results. While the CASPT2 calculations of spin-state energetics were found to be very accurate for the studied Fe(III) complexes (including FeP(SH), a model of the active site of cytochrome P450 in its resting state), there is a strong indication of a systematic error (around 5 kcal/mol) in favor of the high-spin state for the studied Fe(II) complexes (including FeP(Im), a model of the active site of myoglobin). A larger overstabilization of the high-spin states was observed for the M06 and M06-L functionals, up to 22 and 11 kcal/mol, respectively. None of the tested density functionals consistently provides a better accuracy than CASPT2 for all model complexes.

growing public concern, some vehicle architecture changes may be needed to offset issues surroundingThe automotive industry is facing demands the relationship between vehicle weight and safety, simultaneously to increase its fleet average fuel economy and to reduce the emission of with increasing use of spaceframes, or spaceframe greenhouse gases by its products. In order to meet subassemblies expected. Increased use of technologies these new standards, the industry is increasingly such as hydroforming that can be used to produce aiming to decrease the weight of vehicles through complex single piece sections, further decreasing the use of new materials, especially lightweight weight, while enhancing structural strength and stiffaluminium alloys. Laser welding is a critical ness, will also be seen. All of these technologies are enabling technology in reducing the weight of the likely to be implemented in aluminium as well as in body structure through increased use of steel, as the weight of the body structure drops.aluminium and tailor welded blanks. In this reviewInevitably, this will lead to needs for new jointhe available research on the laser welding of ing technologies for automotive aluminium alloys. 5xxx, 6xxx, and some 2xxx series automotive aluminium alloys is critically examined and Resistance spot welding (RSW) is the most important interpreted from different perspectives. First, the welding process now used in autobody construction. current understanding of the important physical While RSW is a nearly ideal process for the assembly processes occurring during laser welding of these of stamped steel body structures, offering robustness alloys such as energy absorption, fluid flow and and low cost, it is more costly and less robust when heat transfer in the weld pool, and alloying used on aluminium structures. Further, increased use element vaporisation are examined. Second, the of closed sections made via hydroforming will require structure and properties of these weldments are processes other than RSW. Introducing tailor welded critically evaluated. Third, commonly encountered blanks in aluminium will also require new joining defects found in laser welded automotive grade aluminium alloys and their science based capability to support high volume production. remedies are discussed. Finally, several important Laser welding is a particularly interesting approach unanswered questions related to laser welding are to the construction of advanced automotive body identified and an outlook on future trends in the structures because of its high speed, low heat input, laser welding of automotive grade aluminium and flexibility. Among laser welding's potential benalloys is presented. The review is written for efits are thinner flanges, the ability to produce tailor scientists and materials engineers who are not welded blanks, and reduced distortion in hydroformed specialists in welding, practising engineers in the frame structures. New developments in laser techautomotive industry, welding engineers, and nology, su...

In this paper, the results are presented from a comparative study of the electronic and geometric structure of copper corroles by means of either density functional theory (DFT, using both pure and hybrid functionals) and multiconfigurational ab initio methods, starting from either a complete active space (CASSCF) or restricted active space (RASSCF) reference wave function and including dynamic correlation by means of second-order perturbation theory (CASPT2/RASPT2). DFT geometry optimizations were performed for the lowest singlet and triplet states of copper corrole, both unsubstituted and meso-substituted with three phenyl groups. The effect of saddling on the electronic structure was investigated by comparing the results obtained for planar (C(2v)) and saddled (C(2)) structures. With DFT, the origin of the saddling distortion is found to be dependent on the applied functional: covalent Cu 3d-corrole π interactions with pure functionals (BP86, OLYP), antiferromagnetic exchange coupling between an electron in the corrolate (C(2)) b type π orbital, and an unpaired Cu(II) 3d electron with hybrid functionals (B3LYP, PBE0). The CASPT2 results essentially confirm the suggestion from the hybrid functionals that copper corroles are noninnocent, although the contribution of diradical character to the copper-corrole bond is found to be limited to 50% or less. The lowest triplet state is calculated at 0-10 kcal/mol and conform with the experimental observation (variable temperature NMR) that this state should be thermally accessible.

Selective vaporization of volatile elements during laser welding of automotive aluminum alloys affects weld metal composition and properties. An experimental and theoretical study was carried out to seek a quantitative understanding of the influences of various welding variables on vaporization and composition change during conduction mode laser welding of aluminum alloy 5182. A comprehensive model for the calculation of vaporization rate and weld metal composition change was developed based on the principles of transport phenomena, kinetics, and thermodynamics. The calculations showed that the vaporization was concentrated in a small high-temperature region under the laser beam where the local vapor pressure exceeded the ambient pressure. The convective vapor flux driven by the pressure gradient was much higher than the diffusive vapor flux driven by the concentration gradient. The computed weld pool geometry, vaporization rates, and composition changes for different welding conditions agreed well with the corresponding experimental data. The good agreement demonstrates that the comprehensive model can serve as a basis for the quantitative understanding of the influences of various welding variables on the heat transfer, fluid flow, and vaporization occurring during conduction mode laser welding of automotive aluminum alloys.

A transport phenomena-based numerical model is developed to predict the keyhole geometry and temperature profiles in the weldment during laser welding. The model can be used to prevent macroporosity formation during laser welding of aluminum alloys. The experimental results show that the weld metal contains large pores when the welding mode changes from conduction to keyhole mode or vice versa due to changes in welding variables. Based on this observation, the mathematical model predicts macroporosity formation when welding is conducted under conditions where small changes in welding parameters lead to a change in the welding mode. The model has been used to predict the geometry of the keyhole and the fusion zone, and the weldment temperature field for laser beam welding of aluminum alloys 5182 and 5754. The calculated weld pool depth, width, and shape for different welding speeds agreed well with the experimental results. The calculations showed that the keyhole profiles for high-speed welding were asymmetric. Negative beam defocusing resulted in a deeper keyhole than that obtained with positive beam defocusing. The transition from keyhole to conduction mode was more abrupt for negative beam defocusing. The model could predict the formation of macroporosity during laser welding of aluminum alloys 5182 and 5754. The results provide hope that transport phenomena-based models can be useful to prevent the formation of macroporosity during keyhole mode laser welding of aluminum alloys.

This study shows that the formation of macroporosity and overfill in the weld pool were the most pronounced problems during continuous wave Nd:yttrium-aluminum-garnet laser welding of AM60B die cast magnesium alloy. The influences of various welding parameters on the formation of porosity and overfill were investigated with particular emphasis on the mechanism and prevention of porosity formation. It was found that the macro pores in the weld pool were mainly formed by the expansion and coalescence of the preexisting pores in the base metal. The amount of macroporosity in the weld pool could be reduced to approximately that in the base metal by reducing heat input, i.e., by increasing welding speed and decreasing laser power. Increasing the beam defocusing did not reduce porosity in the weld metal until the beam was highly defocused and a shallow weld pool, characteristic of conduction mode welding was obtained. Overfill was observed for deep penetration autogenous welds and its formation could be attributed to porosity formation and the resulting displacement of the liquid metal over the top surface of the workpiece.

Abstract:The annulation reaction between various indoles and 2-alkoxycyclopropanoate esters is reported. Both high efficiency and complete stereochemical control was observed in some cases with this annulation process. A single stereocenter on the cyclopropane controls the diastereoselective formation of up to four new stereocenters. A different reaction course was observed with 3-substituted indole substrates, and an intervening C-3 to C-2-migration process arose that gives synthetically useful C-2 alkylation indole products.