Transition dipole matrix elements for 14NH3 from the line intensities of the 2ν2 and ν4 bands

Line intensities as well as self- and nitrogen-broadening coefficients have been determined for 20 transitions in the 2ν₂ and ν₄ bands of ¹⁴NH₃ using a diode laser spectrometer. Vibrational-inversional transition moments have been determined for transitions from the ground state to the ν₂, 2ν₂ and ν₄ states by a least-squares fit to the line intensities, taking into account Coriolis and l-type interactions between the nν₂ (n = 1, 2, 3), ν₄ and ν₂ + ν₄ states [?. Urban, V. ?pirko, D. Papou?ek, R. S. McDowell, N. G. Nereson, S. P. Belov, L. I. Gershtein, A. V. Maslovskij, A. F. Krupnov, J. Curtis, and K. Narahari Rao, J. Mol. Spectrosc.79, 455–495 (1980)]. The values of these transition moments have been combined with the previously obtained transition moments for NH₃ and its isotopomers to obtain an improved fit to the μ_z component of the electric dipole moment function of ammonia [cf. V. ?pirko, J. Mol. Spectrosc.74, 456–464 (1979)].     

Dielectric Relaxation and Quasielastic Neutron Scattering Study of Molecular Reorientation in the Nematic and Solid Phases of 4,4'-Di-N-Butyloxyazoxybenzene

Dielectric relaxation measurements carried out in the nematic phae of 4,4'-di-n-butyloxyazoxybenzene (BOAOB) reveal fast reorientational motions of the whole molecule around the long axis (τ₁ ∼ 60 ps) as well as slow reorientational motions of the whole molecule around the short axis (τ₁ ∼ 10^-8 s). Incoherent quasielastic neutron scattering spectra obtained for nematic BOAOB, with normal and deuteriated alkoxy terminals, are interpreted as dominated by reorientation (around the C-N bonds) of moieties consisting of benzene rings coupled with alkoxy terminal chains (τ₁ ∼ 4ps). In addition fast conformational changes occur in these chains. Dielectric relaxation measurements reveal librations of the whole molecule in the crystal phases CI and CII accompanied by reorientation of the terminal chains in these phases. The reorientations occur on the time scale amounting to 10^-8 s. Incoherent quasielastic neutron scattering spectra obtained for the CI and CII phases of BOAOB are interpreted as being dominated by overdamped librational motions of the moieties accompanied by fast conformational changes in the alkyl chains. The CIII phase corresponds to a normal molecular crystal.     

Search for narrow baryons in π−p total cross section between 2 and 14 GeV/c

A high-statistics search for resonances in the π^?p total cross section has been carried out over the incident momentum region from 2 to 14 GeV/c. The measurements were performed with a transmission technique using multiwire proportional chambers in place of the conventional counter arrays. A microprocessor unit was used for the on-line analysis of the data, allowing a total of ≈ 50 000 events to be examined in a 300 ms burst. The search aimed at detecting the possible formation in π^?p collisions of narrow non-strange baryon resonances. The momentum region was uniformly scanned with a total of ≈4500 mmeasurements in fixed fractional momentum steps of dP/P = 5 × 10^?4. The relative statistical precision of each measurement was dσ/σ = ±0.3%. Within these limits no significant structure was detected.     

Polarizabilities of confined two-electron systems: the 2-electron quantum dot,the hydrogen anion,the helium atom and the lithium cation

The static dipole polarizabilities of two-electron systems confined by a spherical harmonic-oscillator potential?ω?have been calculated by the coupled-cluster CCSD method. The combined effect of the confining potential?ω?and the central electrostatic field on the polarizabilities of the quantum dot, and the confined systems, H^?, He and Li⁺, respectively, have been investigated. The polarizabilities of the quantum dot can be calculated analytically. The polarizability?α?of the 2-electron quantum dot for ω?=?0.01 is calculated to be 19?996?au, in perfect agreement with the exact value, 20?000?au. Already medium confinement, ω?=?1.0, reduces?α?to 2.00?au. The decrease of the polarizability is smaller for H^? (α?=?216.1?au for ω?=?0.0 and 0.985 au for ω?=?1.0), and much smaller for He and Li⁺ (1.3819 and 0.3813?au for He for ω?=?0.0 and ω?=?1.0, respectively, and 0.1921 and 0.128?au for Li⁺). The theoretical polarizabilities for unconfined (ω?=?0.0) H^?, He and the Li⁺ cation are in very good agreement with the best published theoretical and/or experimental data. Our final polarizability for H^?, 216.0±0.5?au, appears to be one of the most accurate values published so far. The optimization procedures of basis sets applicable to calculations of polarizabilities of systems confined by a spherical harmonic-oscillator potential are presented.     

Singlet excited-state interactions in naphthalene-thymine dyads.

Two thymidine-derived nucleosides 1 and 2 were prepared by attaching a chiral naphthalene to the positions 5' and 3' of the sugar. The resulting dyads, which contain key substructures present in drugs and nucleic acids, exhibit different spatial arrangements (transoid or cisoid) of the fluorophore relative to the thymine unit. Emission measurements on these compounds in the presence of ROH molecules revealed a remarkable intramolecular prescence quenching for dyad 1. The obtained results are consistent with quenching of the singlet excited state of 1 by hydrogen-bond donor solvents. Thus, a physical deactivation process (vibronically induced internal conversion) would be the pathway responsible for the accelerated decay of 1*, favorably competing with fluorescence and intersystem crossing to the triplet. This effect appears to be strongly dependent on the relative spatial arrangement between the naphthalene and thymine units, together with the hydrogen-bonding ability of the employed ROH.     

Polarization functions for gaussian basis sets for the first row atoms

Exponent optimization was performed for a single set ofd-type Gaussians on the first row atoms C, N, and O in fifteen small molecules. The hydrogenp-exponents were kept at the fixed value of 1.0. For the underlying valence shell basis sets, Dunning's double zeta basis sets were used. Standard exponents of polarization functions are suggested for the most common valence states of the C, N, and O atoms.