Angle-resolved photoelectron spectroscopy of randomly oriented 3-hydroxytetrahydrofuran enantiomers.

Circular dichroism in the angular distribution of valence photoelectrons emitted from randomly oriented 3-hydroxytetrahydrofuran enantiomers (ThS and ThR) has been observed in gas-phase experiments using circularly polarized vacuum ultraviolet (VUV) light. The measured dichroism for both ThS and ThR, acquired at the single magic angle theta=234.73 degrees and at photon energies of 22, 19, 16, and 14 eV, points to an asymmetric forward-backward scattering of the photoelectrons from their highest occupied molecular orbitals (HOMO) HOMO-1 and HOMO-2, of up to 5%, depending on the photon energy. The asymmetry reverses on exchange of either the helicity of the radiation or the configuration of Th. The photoionization dichroic D parameters of ThS and ThR have been measured and their values discussed in the light of LCAO B-spline density functional theory (DFT) predictions. While an acceptable agreement is found between the dichroic parameter measured and calculated at the highest photon energy for the HOMO and HOMO-2 orbitals of Th, a significant discrepancy is observed for the HOMO-1 state which is attributed to the floppiness of Th, in particular to the comparatively large sensitivity of the size and shape of its HOMO-1 on nuclear vibrational motion.     

Conformational studies by dynamic NMR. 91. Conformational stereodynamics of tetraethylmethane and analogous C(CH2X)4 compounds

Variable-temperature NMR studies of tetraethylmethane (1a), tetrapropylmethane (1b), tetrachloromethylmethane (1c), tetrabromomethylmethane (1d), tetracyclopropylmethylmethane (1e), and tetrabenzylmethane (1f) show a range of dynamic behavior. Separate signals for two types of conformation are observed for 1a, 1c, and 1d at low temperatures, with more than 95% of the molecules in a time-averaged D2d conformation, and the S4 conformation as the minor populated alternative. Compound 1e populates only S4-type conformations but equilibrates slowly between degenerate versions of these at low temperatures. Compounds 1b and 1f show a temperature-dependent spectrum but the low-temperature limit spectrum could not be observed. Ab initio calculations agree well with experiment on the conformational equilibria and suggest in particular that compounds 1b and 1f behave similarly to compounds 1a and 1e, respectively. A crystal structure of compound 1f is reported.     

Materials and technological aspects of gilded buckles from a North Eastern Medieval Italian context

This study concerns the archaeometric characterization of two artefacts from the medieval site of San Rocco (Castelfranco Veneto, Italy). Both of them belong to a larger set of metallic objects, some being part of tomb ornaments belonging to two very well distinct periods of frequentation of the site. Both items are buckles and they have been selected as representative of two very well-known and established typologies. The older one, at the end of the sixth—beginning of the seventh century AD, is made of silver, although relicts of gold have been found. A number of relevant counterparts of this item have been found in different sites of the Longobard Italy. The main body of the second artefact (second half of the fourteenth century AD) consists of a bent strip of a copper rich alloy, coated on one side with a nearly continuous, decorated, gold layer. This is a so-called lyre-buckle, with a widespread diffusion not only in Italian, but also North European contexts. From the results of the analyses carried out using low-vacuum scanning electron microscopy, energy dispersive X-ray spectroscopy, and X-ray diffractometry, information on manufacturing, gilding technology and materials have been obtained that will be an useful benchmark for the archaeometric characterization of similar items from selected collections. In this way, the already established typological affinity of these two classes of items will be extended to technological and materials aspects, also.     

Direct optimization of orbitals for multiconfiguration self-consistent field theory by unitary transformations

In this paper the orbital variations which make stationary the MCSCF energy are generated by unitary transformations worked out directly from the null-gradient condition. A number of iterative procedures are given, compared with other recent proposals and tested numerically on LiH for SCF and geminal theory. A satisfactory convergence rate is found, particularly for the MCSCF case.