Polycyclopentane Als Steroid-Analoga

Polycyclopentanes as Steroid Analoga The synthesis of linearly annellated pentaquinanes from a readily available triquinane is reported.     

Dynamics and stability of a laser system with second-order nonlinearity

We use a multimode rate-equation model to investigate the stability of a laser system with second-order nonlinearity and compare the results with the literature on intracavity frequency-doubled lasers. The emphasis is on the Hopf bifurcation between the asymptotically stable state and the stable oscillation that occurs with variation of the conversion efficiency from the fundamental frequencies to their sum. This bifurcation results in two simple expressions that describe the stability curve, depending on material and cavity parameters. We also report on an experimental confirmation of the predicted temporal behavior of sum-frequency generation.     

Synthesis and Structure of [4.5.5.5]Fenestranes ( = tetracyclo[5.4.1.04, 12.09, 12]dodecanes)

The preparation and the X-ray structure analysis of cis, trans, cis, cis-10-hydroxy-[4.5.5.5]fenestrane-1-methanol ( 8b ) is reported. The measured bond angles and bond lengths of the central C(C)₄ fragment are better reproduced by calculations with the AM 1 than by the MNDO method.     

Ab initio calculation of the vibrational and electronic spectra of trans- and cis-azobenzene

We report accurate geometries and harmonic force fields for trans- and cis-azobenzene determined by second-order M?ller-Plesset perturbation theory. For the trans isomer, the planar structure with C(2h) symmetry, found in a recent gas electron diffraction experiment, is verified. The calculated vibrational spectra are compared with experimental data and density functional calculations. Important vibrational frequencies are localized and discussed. For both isomers, we report UV spectra calculated using the second-order approximate coupled-cluster singles-and-doubles model CC2 with accurate basis sets. Vertical excitation energies and oscillator strengths have been determined for the lowest singlet n(pi)* and (pi)(pi)* transitions. The results are compared with the available experimental data and second-order polarization propagator (SOPPA) and density functional (DFT) calculations. For both isomers, the CC2 results for the excitation energies into the S(1) and S(2) states agree within 0.1 eV with experimental gas-phase measurements.     

Synthesis and Structure of Functionalized Cyclododecadiynes and -dienes

The cyclododecadiynes 3b–d, 8b–d , and 10b–c with functionalities in two propargylic positions, as well as the monofunctionalized diyne 13b have been prepared from simple open-chain building blocks. In the DMPU ( = N,N'-dimethylpropyleneurea)-assisted ring-closing alkylation of 1,7-diynes, the twelve-membered ring compounds have been prepared in yields of 16–55%. The preparation of the diene-diyne 15 and the cyclododeca-5,11-diyne-1,4-dione 18 are described.     

Auxiliary basis sets for main row atoms and transition metals and their use to approximate Coulomb potentials

We present auxilliary basis sets for the atoms H to At – excluding the Lanthanides – optimized for an efficient treatment of molecular electronic Coulomb interactions. For atoms beyond Kr our approach is based on effective core potentials to describe core electrons. The approximate representation of the electron density in terms of the auxilliary basis has virtually no effect on computed structures and affects the energy by less than 10⁻⁴ a.u. per atom. Efficiency is demonstrated in applications for molecules with up to 300 atoms and 2500 basis functions. Received: 17 December 1996 / Accepted: 8 May 1997     

Millimeter/submillimeter nonlinear spectroscopy

The techniques of coherent transient spectroscopy have been successfully applied to the microwave and optical regions of the spectrum, but lack of suitable sources has prevented convenient extension to the millimeter/submillimeter region where several strong molecular transitions occur. Analysis of the experimental requirements and theory for such experiments considering several molecules including H₂O and CH₃Cl indicates how such experiments can be performed employing recently developed oscillators with increased power.