Selection rules for rovibronic transitions in symmetric top molecules

A simple diagrammatic rule is presented for determining the rotational selection rules governing transitions between any pair of vibronic states in electric dipole spectra of symmetric top molecules. The rule is useful in cases where degenerate vibronic levels with first-order Coriolis splittings occur, because it gives immediately the selection rule for the (+l) and (-l) components in any degenerate state. The rule is also helpful in determining the symmetry species and the effective zeta constants in overtone and combination levels involving degenerate vibrations. Particular attention is devoted to the conventions concerning the signs of zeta constants.

Raman selection rules for vibration-rotation transitions in symmetric top molecules

Symmetry restrictions on Raman selection rules can be obtained, quite generally, by considering a Raman allowed transition as the result of two successive dipole allowed transitions, and imposing the usual symmetry restrictions on the dipole transitions. This leads to the same results as the more familiar polarizability theory, but the vibration-rotation selection rules are easier to obtain by this argument. The selection rules for symmetric top molecules involving the (+l) and (-l) components of a degenerate vibrational level with first-order Coriolis splitting are derived in this paper. It is shown that these selection rules depend on the order of the highest-fold symmetry axis Cn, being different for molecules with n=3, n=4, or n ≧ 5; moreover the selection rules are different again for molecules belonging to the point groups Dnd with n even, and Sm with 1/2m even, for which the highest-fold symmetry axes Cn and Sm are related by m=2n. Finally it is shown that an apparent anomaly between the observed Raman and infra-red vibration-rotation spectra of the allene molecule is resolved when the correct selection rules are used, and a value for the A rotational constant of allene is derived without making use of the zeta sum rule.

Argon predissociation spectroscopy of the OH-center dot H2O and Cl-center dot H2O complexes in the 1000-1900 cm(-1) region: Intramolecular bending transitions and the search for the shared-proton fundamental in the hydroxide monohydrate

We present argon predissociation vibrational spectra of the OH-.H2O and Cl-.H2O complexes in the 1000-1900 cm(-1) energy range, far below the OH stretching region reported in previous studies. This extension allows us to explore the fundamental transitions of the intramolecular bending vibrations associated with the water molecule, as well as that of the shared proton inferred from previous assignments of overtones in the higher energy region. Although the water bending fundamental in the Cl-.H2O spectrum is in very good agreement with expectations, the OH-.H2O spectrum is quite different than anticipated, being dominated by a strong feature at 1090 cm(-1). New full-diniensionality calculations of the OH-.H2O vibrational level structure using diffusion Monte Carlo and the VSCF/CI methods indicate this band arises from excitation of the shared proton.

Structure, and thermal, magnetic and chemical properties of copper(II)iodoacetate monohydrate

Reaction of iodoacetic acid with cupric carbonate in water in dimmed light yields green Cu(ICH2COO)(2 center dot)H2O (1). From X-ray crystallography, it is found to be a tetra-acetato bridged copper(II) dimer with the water molecules occupying the apical positions. In thermogravimetry, the coordinated water molecules are lost in the temperature range 50-100 degrees C. From magnetic susceptibility measurements in the temperature range 300-1.8 K, the exchange coupling constant J is found to be -142(1) cm(-1) and g = 2.18(2) with the spin Hamiltonian H = -2J{S-Cu1 center dot S-Cu2}. It reacts with 2,2'-bipyridine (bpy) to yield [Cu(bpy)(2)I]I. It oxidises thiophenol to Ph-S-S-Ph under dry N-2 atmosphere.

Chemical, physical and electrical properties of aged dodecylbenzene 3: thermal ageing of mixed isomers in nitrogen and under sealed conditions

Commercial dodecylbenzene cable fluid was aged at temperatures of 105 and 135 degrees C in dry oxygen-free nitrogen. In addition, selected samples were aged at 135 degrees C under sealed conditions where air was excluded from the headspace above the oil. A variety of analytical techniques, such as ultra-violet visible and infra-red spectroscopy, acid number and water content measurements, were then used to characterize the aged oils. In addition, their electrical properties were assessed by dielectric spectroscopy. Compared with ageing in air, the ageing rate was reduced significantly and, as expected, no major oxidation peaks were detected in the infrared spectrometer. Significantly, very little absorbance at 680 nm ("red absorbers") was detected in samples aged with copper and, consequentially, no large increases in dielectric loss were recorded within the ageing times considered here. This study compliments previous investigations on cable fluid and 1-phenyldodecane aged in air and show that the same ageing indicators are valid in oils aged under conditions which more closely resemble those found in high voltage plant.

Chemical, physical and electrical properties of aged dodecylbenzene: thermal ageing of mixed isomers in air

A commercial dodecylbenzene (DDB) cable oil was aged at temperatures between 90 and 135 degrees C in air and was analyzed using various analytical techniques including optical and infra-red spectroscopy and dielectric analysis. On ageing, the oil darkened, significant oxidation features were found by infra-red spectroscopy and the acid number, water content and dielectric loss all increased. Ageing in the presence of paper or aluminum did not affect the ageing process, whereas ageing was significantly modified by the presence of copper. An absorption at 680 nm ("red absorbers") was detected by ultra-violet/visible spectroscopy followed by the production of an opaque precipitate. A reaction between copper and the acid generated on ageing is thought to produce copper carboxylates, and X-ray fluorescence confirmed that copper was indeed present in both the aged oil and the precipitate. Significantly, once red absorbers were detected, the dielectric loss increased to catastrophically high values and, therefore, the appearance of these compounds may serve as a useful diagnostic indicator. The development of acidity on ageing appears to be key in initiating the destructive copper conversion reaction and hence the control of oil acidity may be key to prolonging the life of DDB cable oils.

Chemical, physical and electrical properties of aged dodecylbenzene 2: thermal ageing of single isomers in air

The linear isomer of dodecylbenzene (DDB), 1-phenyldodecane, was aged at temperatures of 105 and 135 degrees C in air and the resultant products were analyzed using a range of analytical techniques. On ageing, the 1-phenyldodecane darkened, the acid number, dielectric loss and water content increased and significant oxidation peaks were detected in the infrared spectrum. When aged in the presence of copper, a characteristic peak at 680 nm was also detected by UV/visible spectroscopy but, compared with previous studies of a cable-grade DDB, the strength of this peak was much increased and no appreciable precipitate formation occurred. At the same time, very high values of dielectric loss were recorded. On ageing in the absence of copper, an unusually strong infrared carbonyl band was seen, which correlates well with the detection of dodecanophenone by gas chromatography / mass spectrometry and nuclear magnetic resonance spectroscopy. It was therefore concluded that the ageing process proceeds via the initial production of aromatic ketones, which may then be further oxidized to carboxylic acids. In the presence of copper, these oxidation products are present in lower quantities, most of these oxidation products being combined with the copper present in the oil to give copper carboxylates. The behavior is described in terms of a complex autoxidation mechanism, in which copper acts as both an oxidizing and a reducing agent, depending on its oxidation state and, in particular, promotes elimination via the oxidation of intermediate alkyl radical species to carbocations.

Synthesis, crystal structure, magnetic behavior and thermal property of three polynuclear complexes: [M(dca)(2)(H2O)2](n)center dot(hmt)(n) [M = Mn(II), Co(II)] and [Co(dca)(2)(bpds)](n) [dca, dicyanamide; hint, hexamethylenetetramine; bpds, 4,4 '-bipyridyl disulfide]

Three mu(1.5)-dicyanamide bridged Mn(II) and Co(II) complexes having molecular formula [Mn(dca)(2)(H2O)(2)](n)center dot(hmt)(n) (1), [Co(dca)(2) (H2O)(2)](n)center dot(hmt)(n) (2) and [Co(dca)(2)(bpds)](n) (3) [dca = dicyanamide; hmt = hexamethylenetetramine; bpds = 4,4'-bipyridyl disulfide] have been synthesized and characterized by single crystal X-ray diffraction study, low temperature (300-2 K) magnetic measurement and thermal behavior. The X-ray diffraction analysis of 1 and 2 reveals that they are isostructural, comprising of 1D coordination polymers [M(dca)(2)(H2O)(2)](n) [M = Mn(II), Co(II) for 1 and 2. respectively] with uncoordinated hmt molecules located among the chains. The [M(dca)(2)(H2O)(2)](n) chains and the lattice hint molecules are connected through H-bonds resulting in a 3D supramolecular architecture. The octahedral N4O2 chromophore surrounding the metal ion forms via two trans located water oxygens and four nitrogens from four nitrile dca. Complex 3 is a 1D chain formed by two mu(1.5)-dca and one bridging bpds. The octahedral N-6 coordination sphere surrounding the cobalt ions comprises four nitrogens from dca and two from bpds. Low temperature magnetic study indicates small antiferromagnetic coupling for all the complexes. Best fit parameters for 1: J = -0.17 cm(-1), g = -2.03 with R = 6.1 x 10(-4), for 2, J = -0.50 cm(-1), and for 3, J = -0.95 cm(-1). (c) 2005 Elsevier B.V. All rights reserved.

Synthesis, crystal structure and thermal studies of catena(L-glutamato)-aqua copper(II) monohydrate

The synthesis. crystal structure and thermal study of the blue catena-(L-glutamato)-aqua copper(II) monohydrate have been reported. The compound crystallizes in P2(1)2(1)2(1) space group and consists of a polymeric three-dimensional network of copper(II) which is coordinated with the amino nitrogen and the carboxylate oxygen Of L-glutamate, the side chain carboxylate oxygen of a neighbouring L-glutamate and the oxygen of a water molecule in the equatorial position. Weak coordination of two additional glutamate oxygen atoms to both the axial positions Completes a distorted octahedron. The crystal structure shows that the lattice water is stabilized by the formation of strong H-bonding network with the coordinated water molecule. Removal and reabsorption of the water molecule have been studied by thermal analysis.

The thermal transformations of bicyclopropylidene and methylenespiropentane revisited

The overall and the individual rate constants of the unimolecular thermal isomerization of methylenespiropentane (4) to 1,2- and 1,3-dimethylenecyclobutanes (7 and 8) have been determined to be lg (k(-4)/s(-1)) = (13.78 +/- 0.06) - (49.7 +/- 0.2) kcal mol(-1)/RT.ln 10, lg(k(7)/s(-1)) = (13.03 +/- 0.19) - (48.0 +/- 0.6) kcal mol(-1)/RT.ln 10 and lg(k(8)/s(-1)) = (14.15 +/- 0.19) - (52.4 +/- 0.5) kcal mol(-1)/RT.ln 10, respectively. The activation energies are significantly lower than that for the rearrangement of the parent spiropentane. ((c) Wiley-VCH Verlag GmbH & Co.

Pressure-jump X-ray studies of liquid crystal transitions in lipids

In this paper, we give an overview of our studies by static and time-resolved X-ray diffraction of inverse cubic phases and phase transitions in lipids. In 1, we briefly discuss the lyotropic phase behaviour of lipids, focusing attention on non-lamellar structures, and their geometric/topological relationship to fusion processes in lipid membranes. Possible pathways for transitions between different cubic phases are also outlined. In 2, we discuss the effects of hydrostatic pressure on lipid membranes and lipid phase transitions, and describe how the parameters required to predict the pressure dependence of lipid phase transition temperatures can be conveniently measured. We review some earlier results of inverse bicontinuous cubic phases from our laboratory, showing effects such as pressure-induced formation and swelling. In 3, we describe the technique of pressure-jump synchrotron X-ray diffraction. We present results that have been obtained from the lipid system 1:2 dilauroylphosphatidylcholine/lauric acid for cubic-inverse hexagonal, cubic-cubic and lamellar-cubic transitions. The rate of transition was found to increase with the amplitude of the pressure-jump and with increasing temperature. Evidence for intermediate structures occurring transiently during the transitions was also obtained. In 4, we describe an IDL-based 'AXCESS' software package being developed in our laboratory to permit batch processing and analysis of the large X-ray datasets produced by pressure-jump synchrotron experiments. In 5, we present some recent results on the fluid lamellar-Pn3m cubic phase transition of the single-chain lipid 1-monoelaidin, which we have studied both by pressure-jump and temperature-jump X-ray diffraction. Finally, in 6, we give a few indicators of future directions of this research. We anticipate that the most useful technical advance will be the development of pressure-jump apparatus on the microsecond time-scale, which will involve the use of a stack of piezoelectric pressure actuators. The pressure-jump technique is not restricted to lipid phase transitions, but can be used to study a wide range of soft matter transitions, ranging from protein unfolding and DNA unwinding and transitions, to phase transitions in thermotropic liquid crystals, surfactants and block copolymers.

Quantitative model for the kinetics of lyotropic phase transitions involving changes in monolayer curvature

We present a kinetic model for transformations between different self-assembled lipid structures. The model shows how data on the rates of phase transitions between mesophases of different geometries can be used to provide information on the mechanisms of the transformations and the transition states involved. This can be used, for example, to gain an insight into intermediate structures in cell membrane fission or fusion. In cases where the monolayer curvature changes on going from the initial to the final mesophase, we consider the phase transition to be driven primarily by the change in the relaxed curvature with pressure or temperature, which alters the relative curvature elastic energies of the two mesophase structures. Using this model, we have analyzed previously published kinetic data on the inter-conversion of inverse bicontinuous cubic phases in the 1-monoolein-30 wt% water system. The data are for a transition between QII(G) and QII(D) phases, and our analysis indicates that the transition state more closely resembles the QII(D) than the QII(G) phase. Using estimated values for the monolayer mean curvatures of the QII(G) and QII(D) phases of -0.123 nm(-1) and -0.133 nm(-1), respectively, gives values for the monolayer mean curvature of the transition state of between -0.131 nm(-1) and -0.132 nm(-1). Furthermore, we estimate that several thousand molecules undergo the phase transition cooperatively within one "cooperative unit", equivalent to 1-2 unit cells of QII(G) or 4-10 unit cells of QII(D).

Thermal Fractionation and isothermal crystallization of polyethylene nanocomposites prepared by in situ polymerization

Nanocomposites of high-density polyethylene (HDPE) and carbon nanotubes (CNT) of different geometries (single wall, double wall, and multiwall; SWNT, DWNT, and MWNT) were prepared by in situ polymerization of ethylene on CNT whose surface had been previously treated with a metallocene catalytic system. In this work, we have studied the effects of applying the successive self-nucleation and annealing thermal fractionation technique (SSA) to the nanocomposites and have also determined the influence of composition and type of CNT on the isothermal crystallization behavior of the HDPE. SSA results indicate that all types of CNT induce the formation of a population of thicker lamellar crystals that melt at higher temperatures as compared to the crystals formed in neat HDPE prepared under the same catalytic and polymerization conditions and subjected to the same SSA treatment. Furthermore, the peculiar morphology induced by the CNT on the HDPE matrix allows the resolution of thermal fractionation to be much better. The isothermal crystallization results indicated that the strong nucleation effect caused by CNT reduced the supercooling needed for crystallization. The interaction between the HDPE chains and the surface of the CNT is probably very strong as judged by the results obtained, even though it is only physical in nature. When the total crystallinity achieved during isothermal crystallization is considered as a function of CNT content, it was found that a competition between nucleation and topological confinement could account for the results. At low CNT content the crystallinity increases (because of the nucleating effect of CNT on HDPE), however, at higher CNT content there is a dramatic reduction in crystallinity reflecting the increased confinement experienced by the HDPE chains at the interfaces which are extremely large in these nanocomposites. Another consequence of these strong interactions is the remarkable decrease in Avrami index as CNT content increases. When the Avrami index reduces to I or lower, nucleation dominates the overall kinetics as a consequence of confinement effects. Wide-angle X-ray experiments were performed at a high-energy synchrotron source and demonstrated that no change in the orthorhombic unit cell of HDPE occurred during crystallization with or without CNT.