Negative ion photoelectron spectroscopy of solvated electron cluster anions, (H2O) n − and (NH3) n −

The photodetachment spectra of (H₂O) _n ^=2?69/? and (NH₃) _n ^=41?1100/? have been recorded, and vertical detachment energies (VDEs) were obtained from the spectra. For both systems, the cluster anion VDEs increase smoothly with increasing sizes and most species plot linearly withn ^?1/3, extrapolating to a VDE (n=∞) value which is very close to the photoelectric threshold energy for the corresponding condensed phase solvated electron system. The linear extrapolation of this data to the analogous condensed phase property suggests that these cluster anions are gas phase counterparts to solvated electrons, i.e. they are embryonic forms of hydrated and ammoniated electrons which mature with increasing cluster size toward condensed phase solvated electrons.     

Single-molecule fluorescence spectroscopy of TOTO on poly-AT and poly-GC DNA

Excited state lifetime and amplitude measurements were made on thiazole orange dimer (TOTO), a dimeric DNA-intercalating fluorophore, at single-molecule concentrations. As expected from previous study, the excited state lifetime of TOTO intercalated in DNA is dependent on the sequence of the double-stranded DNA, having values of 2.2 ns in poly-GC DNA and 1.8 ns in poly-AT DNA. The distribution of excited state lifetimes of single molecules of TOTO intercalated into oligonucleotides having varying proportions of poly-GC sequences relative to poly-AT sequences were analyzed as a function of the fraction of poly-GC. By using excited state lifetime distributions from the purely GC and purely AT oligonucleotides as a basis set, it was possible to estimate the GC content of oligonucleotides with intermediate GC composition to within a few percent error. This serves as a model for the analysis of equilibrium binding distributions in DNA using single-molecule methods.     

Ruthenium bipyridyl compounds with two terminal alkynyl ligands

Compounds of the form Ru(X2bipy)(PPh3)2(-C triple bond CC6H4NO2-p)2(X2bipy = 4,4'-X(2)-2,2'-bipyridine, X = Me 3a, Br 3b, I 3c) have been synthesised from the mono-alkynyl precursors Ru(X2bipy)(PPh3)2(-C triple bond CC6H4NO2-p)Cl (X = Me 2a, Br 2b, I 2c); the former are the first ruthenium bis-alkynyl compounds that also contain a bipyridyl ligand. Spectroelectrochemical investigation of 3a shows that the metal is readily oxidised to form the ruthenium(III) compound 3a+, and will also undergo a single-electron reduction at each nitro group to form 3a2-. ESR and UV/visible spectra of these redox congeners are presented. We also report the synthesis of [Ru(Me2bipy)(PPh3)2(-C triple bond CBut)(N triple bond N)][PF6] during the attempted synthesis of Ru(Me2bipy)(PPh3)2(-C triple bond CBut)2, and report its X-ray crystal structure and IR spectrum. X-Ray crystal structures of 3b and 3c(as two different solvates) are presented, and the nature of the intermolecular interactions seen therein is discussed. Z-Scan measurements on Ru(Me2bipy)(PPh3)2(-C triple bond CR)Cl (R = C6H4NO2-p2a, But, Ph, C6H4Me) are also reported, and show that Ru(Me2bipy)(PPh3)2(-C triple bond CR)Cl (R = C6H4NO2-p2a, Ph) exhibit moderate third-order non-linearities.     

Molecular mechanics (MM3) parameterization of hydroxylamine and methyl derivatives

Based on results of electron diffraction, gas phase infrared spectroscopy (IR), and MP2/6-31 + G* ab initio calculations, a set of molecular mechanics (MM3) parameters was developed for molecules containing the N(sp³)—O(sp³) moiety. Using this set of parameters, MM3 is able to reproduce structures (bond lengths and bond angles) and vibrational spectra satisfactorily. © 1994 by John Wiley & Sons, Inc.     

Dipole-bound anions of highly polar molecules: ethylene carbonate and vinylene carbonate

Results of experimental and theoretical studies of dipole-bound negative ions of the highly polar molecules ethylene carbonate (EC, C3H4O3, mu=5.35 D) and vinylene carbonate (VC, C3H2O3, mu=4.55 D) are presented. These negative ions are prepared in Rydberg electron transfer (RET) reactions in which rubidium (Rb) atoms, excited to ns or nd Rydberg states, collide with EC or VC molecules to produce EC- or VC- ions. In both cases ions are produced only when the Rb atoms are excited to states described by a relatively narrow range of effective principal quantum numbers, n*; the greatest yields of EC- and VC- are obtained for n*(max)=9.0+/-0.5 and 11.6+/-0.5, respectively. Charge transfer from low-lying Rydberg states of Rb is characteristic of a large excess electron binding energy (Eb) of the neutral parent; employing the previously derived empirical relationship Eb=23/n*(max)(2.8) eV, the electron binding energies are estimated to be 49+/-8 meV for EC and 24+/-3 meV for VC. Electron photodetachment studies of EC- show that the excess electron is bound by 49+/-5 meV, in excellent agreement with the RET results, lending credibility to the empirical relationship between Eb and n*(max). Vertical electron affinities for EC and VC are computed employing aug-cc-pVDZ atom-centered basis sets supplemented with a (5s5p) set of diffuse Gaussian primitives to support the dipole-bound electron; at the CCSD(T) level of theory the computed electron affinities are 40.9 and 20.1 meV for EC and VC, respectively.     

On some contact problems for composite half-spaces PMM vol. 31, no. 6, 1967, pp. 1001–1008

Solutions are presented herein of some contact problems connected with the torsion of a composite half-space. In the general case the problem of the torsion of a composite elastic half-space is examined by means of the rotation of a stiff finite cylinder welded into a vertical recess of this half-space. Moreover, the following particular problems on the torsion of such a half-space are considered.

1. 1) A composite half-space with a vertical elastic infinite core, twisted by means of the rotation of a stiff stamp affixed to the upper endplate of the elastic core.

2. 2) A half-space with a vertical cylindrical infinite hole, twisted by means of the rotation of a stiff finite cylinder welded into the upper part of this hole.

In the general case the solution of the problem reduces to the solution of an integral equation of the second kind on a half-line. The question of the solvability of this fundamental integral equation is investigated, and it is shown that its solution may be constructed by successive approximations.

Let us note that the problem of the torsion of a homogeneous half space and of an elastic layer by means of rotation of a stiff stamp has been considered by Rostovtsev [1], Reissner and Sagoci [2], Ufliand [3], Florence [4], Grilitskii [5] and others.

The problem of the torsion of a circular cylindrical rod and the half-space welded to it which are subject to a torque applied to the free endface of the rod has been considered by Grilitskii and Kizyma[6].

The torsion of an elastic half-space with a vertical cylindrical inclusion of some other material by the rotation of a stiff stamp on the surface of this half-space has been considered in [7], wherein it has been assumed that the stamp is symmetrically disposed relative to the axis of the inclusion and lies simultaneously on both materials.     

A multi-color and white-light emissive cucurbituril/ terpyridine/ lanthanide supramolecular nanofiber

The enhanced lanthanide white-emission in solid by cucurbituril-based supramolecular assembly may provide a new strategy for smart light-emitting materials.     

An investigation of catalytic activity in mixed metal oxide nanophase materials

We present preliminary evidence for catalytic activity by unsupported mixed metal oxide nanocrystalline materials. The results of this study show that a nanophase form of Li-MgO has begun to exhibit catalytic activity by 300 °C. This is at least 200 degrees below the temperature at which conventional Li-MgO catalysts exhibit comparable activity. Furthermore, at higher temperatures, the same nanophase composition shows enhanced activities and somewhat improved hydrocarbon selectivities over conventional Li-MgO catalysts.     

Crystal Structures of Hydrochlorides of 2,3-Pentamethylene-3, 4-dihydroquinazolin-4-one

The crystal structures of hydrate (1) and anhydrate (2) forms of 2,3-pentamethylene-3,4-dihydroquinazolin-4-one hydrochloride have been determined by X-ray structure analysis. Crystal data of 1 are 2(C₁₃H₁₄N₂O)*3(HCl)*4.5 (H₂O), triclinic P?1, Z=2, a=8.004(5), b=13.129(7), c=15.725(7) Å, α=106.45(4), β=92.61(4), γ=97.98(5), R=0.0652 and 2 are C₁₃H₁₄N₂O*HCl, monoclinic C2/c, Z=8, a=21.360(4), b=5.954(1), c=21.263(4), β=117.89(3), R=0.0556. The crystal of the hydrate form 1is unstable. This form collapses easily with evaporation of H₂O and part of HCl molecules from crystals. By recrystallizing destroyed form has been obtained stable crystal form 2.     

Low energy,low temperature mass spectra: I—selected derivatives of n-octane

The low voltage, low temperature mass spectra of a series of octane derivatives n-C₈H₁₇X with X=CH₃, OH, OCH₃, NH₂, NHCH₃, N(CH₃)₂, CO₂H, CO₂CH₃, CO₂C₂H₅, CHO and COCH₃ are reported and discussed, using arguments involving thermochemistry where appropriate. The structures of these compounds can be uniquely assigned on the basis of such mass spectra.