The syntheses of C6CH2.– and the corresponding carbenoid cumulene C6CH2 in the gas phase

The ion (C6CH2)(.-) is formed in the gas phase by the process -C=C-C=C-C=CH2OEt --> (C6CH2)(.-) + EtO., and charge stripping of the product radical anion yields the carbenoid neutral C6CH2; this can be either a singlet (the ground state), which is best represented as the carbene :C=C=C=C=C=C=CH2, or a triplet; the adiabatic electron affinity and the dipole moment of the carbenoid neutral are calculated to be 2.82 eV and 7.33 D respectively.

Potential interstellar molecules : Formation of neutral C6CO from C6CO- in the gas phase

Computations at the RCCSD(T)/aug-cc-pVDZ//B3LYP/6-31G* level of theory indicate that neutral C6CO is a stable species. The ground state of this neutral is the singlet cumulene oxide :C=C=C=C=C=C=C=O. The adiabatic electron affinity and dipole moment of singlet C6CO are 2.47 eV and 4.13 D, respectively, at this level of theory. The anion (C6CO)(-.) should be a possible precursor to this neutral. It has been formed by an unequivocal synthesis in the ion source of a mass spectrometer by the S(N)2(Si) reaction between (CH3)(3)Si-C=C-C=C-C=C-CO-CMe3 and F- to form C-=C-C=C-C=C-CO-CMe3 which loses Me3C in the source to form C6CO-.. Charge stripping of this anion by vertical Franck-Condon oxidation forms C6CO, characterised by the neutralisation-reionisation spectrum (-NR+) of C6CO-., which is stable during the timeframe of this experiment (10(-6) s), Copyright (C) 2000 John Wiley & Sons, Ltd.

Generation and characterization of ionic and neutral dihydroxy boron B(OH)(2)(+/0) in the gas phase

The dicoordinated borinium ion, dihydroxyborinium, B(OH)(2)(+) is generated from methyl boronic acid CH3B(OH)(2) by dissociative electron ionization and its connectivity confirmed by collisional activation. Neutralization-reionization (NR) experiments on this ion indicate that the neutral B(OH)(2) radical is a viable species in the gas phase. Both vertical neutralization of B(OH)(2)(+) and reionization of B(OH)(2) in the NR experiment are, however, associated with particularly unfavorable Franck-Condon factors. The differences in adiabatic and vertical electron transfer behavior can be traced back to a particular pi stabilization of the cationic species compared to the sp(2)-type neutral radical. Thermochemical data on several neutral and cationic boron compounds are presented based on calculations performed at the G2 level of theory.

The lowest singlet and triplet states of the oxyallyl diradical

Small S-T splitting : The photoelectron spectrum of the oxyallyl radical anion (see picture) reveals that the electronic ground state of oxyallyl is singlet, and the lowest triplet state is separated from the singlet state by only (55 ± 2) meV in adiabatic energy.

Negative-ion photoelectron spectroscopy, gas-phase acidity, and thermochemistry of the peroxyl radicals CH3OO and CH3CH2OO

Methyl, methyl-d(3), and ethyl hydroperoxide anions (CH3OO-, CD3OO-, and CH3CH2OO-) have been prepared by deprotonation of their respective hydroperoxides in a stream of helium buffer, gas. Photodetachment with 364 nm (3.408 eV) radiation was used to measure the adiabatic electron affinities: EA[CH3OO, (X) over tilde (2)A"] = 1.161 +/- 0.005 eV, EA[CD3OO, (X) over tilde (2)A"] = 1.154 +/- 0.004 eV, and EA[CH3CH2OO, (X) over tilde (2)A"] = 1.186 +/- 0.004 eV. The photoelectron spectra yield values for the term energies: DeltaE((X) over tilde 2A"-(A) over tilde 2A')[CH3OO] = 0.914 +/- 0.005 eV, DeltaE((X) over tilde (2)A"-(A) over tilde 2A') [CD3OO] = 0.913 +/- 0.004 eV, and DeltaE((X) over tilde (2)A"-(A) over tilde (2)A')[CH3CH2OO] = 0.938 +/- 0.004 eV. A localized RO-O stretching mode was observed near 1100 cm(-1) for the ground state of all three radicals, and low-frequency R-O-O bending modes are also reported. Proton-transfer kinetics of the hydroperoxides have been measured in a tandem flowing afterglow-selected ion flow tube k(FA-SIFT) to determine the gas-phase acidity of the parent hydroperoxides: Delta (acid)G(298)(CH3OOH) = 367.6 +/- 0.7 kcal mol(-1), Delta (acid)G(298)(CD3OOH) = 367.9 +/- 0.9 kcal mol(-1), and Delta (acid)G(298)(CH3CH2OOH) = 363.9 +/- 2.0 kcal mol(-1). From these acidities we have derived the enthalpies of deprotonation: Delta H-acid(298)(CH3OOH) = 374.6 +/- 1.0 kcal mol(-1), Delta H-acid(298)(CD3OOH) = 374.9 +/- 1.1 kcal mol(-1), and Delta H-acid(298)(CH2CH3OOH) = 371.0 +/- 2.2 kcal mol(-1). Use of the negative-ion acidity/EA cycle provides the ROO-H bond enthalpies: DH298(CH3OO-H) 87.8 +/- 1.0 kcal mol(-1), DH298(CD3OO-H) = 87.9 +/- 1.1 kcal mol(-1), and DH298(CH3CH2OO-H) = 84.8 +/- 2.2 kcal mol(-1). We review the thermochemistry of the peroxyl radicals, CH3OO and CH3CH2OO. Using experimental bond enthalpies, DH298(ROO-H), and CBS/APNO ab initio electronic structure calculations for the energies of the corresponding hydroperoxides, we derive the heats of formation of the peroxyl radicals. The "electron affinity/acidity/CBS" cycle yields Delta H-f(298)[CH3OO] = 4.8 +/- 1.2 kcal mol(-1) and Delta H-f(298)[CH3CH2OO] = -6.8 +/- 2.3 kcal mol(-1).

On natures of sub-gap photoelectric and optical spectra in nitrogen-contaminated nanocrystalline diamond

Experimentally observed optical and photoelectrical spectra of nitrogen-contaminated (unintentionally doped) nano-crystalline CVD diamond films are simulated using semi-empirical adiabatic General Skettrup Model (GSM), which presumes dominant contributions of defect states from sp 3-coordinated intra-granular carbon atoms to intra-band single electron spectrum N(E) of the material. This picture disagrees with a common viewpoint that the N(E) spectrum of the gap states in diamond powders and polycrystalline CVD films mainly originates from π and π* bonds of sp2-coordinated carbon atoms, which are distributed nearly uniformly over outer surfaces and/or interfaces of the diamond grains. The GSM predicts as well strong effect of granular morphology on the density of intra-band defect states in polycrystalline diamonds.

Natural convection heat transfer in a baffled triangular enclosure

To reduce the natural convection heat loss from enclosures many researchers used convection suppression devices in the past. In this study a single baffle is used under the top tip to investigate numerically the natural convection heat loss in an attic shaped enclosure which is a cost effective approach. The case considered here is one inclined wall of the enclosure is uniformly heated while the other inclined wall is uniformly cooled with adiabatic bottom wall. The finite volume method has been used to discretize the governing equations, with the QUICK scheme approximating the advection term. The diffusion terms are discretized using central-differencing with second order accuracy. A wide range of governing parameters are studied (Rayleigh number, aspect ratio, baffle length etc.). It is observed that the heat transfer due to natural convection in the enclosure reduces when the baffle length is increased. Effects of other parameters on heat transfer and flow field are described in this study.

Natural convection due to differential heating of inclined walls and heat source placed on bottom wall of an attic shaped space

Numerical investigation of free convection heat transfer in an attic shaped enclosure with differentially heated two inclined walls and filled with air is performed in this study. The left inclined surface is uniformly heated whereas the right inclined surface is uniformly cooled. There is a heat source placed on the right side of the bottom surface. Rest of the bottom surface is kept as adiabatic. Finite volume based commercial software ANSYS 15 (Fluent) is used to solve the governing equations. Dependency of various flow parameters of fluid flow and heat transfer is analyzed including Rayleigh number, Ra ranging from 103 to 106, heater size from 0.2 to 0.6, heater position from 0.3 to 0.7 and aspect ratio from 0.2 to 1.0 with a fixed Prandtl number of 0.72. Outcomes have been reported in terms of temperature and stream function contours and local Nusselt number for various Ra, heater size, heater position, and aspect ratio. Grid sensitivity analysis is performed and numerically obtained results have been compared with those results available in the literature and found good agreement.

Transition to an unsteady flow induced by a fin on the sidewall of a differentially heated air-filled square cavity and heat transfer

The transition from a steady to an unsteady flow induced by an adiabatic fin on the sidewall of a differentially heated air-filled cavity is numerically investigated. Numerical simulations have been performed over the range of Rayleigh numbers from Ra = 105–109. The temporal development and spatial structures of natural convection flows in the cavity with a fin are described. It has been demonstrated that the fin may induce the transition to an unsteady flow and the critical Rayleigh number for the occurrence of the transition is between 3.72 × 106 and 3.73 × 106. Furthermore, the peak frequencies of the oscillations triggered by different mechanisms are obtained through spectral analysis. It has been found that the flow rate through the cavity with a fin is larger than that without a fin under the unsteady flow, indicating that the fin may improve the unsteady flow in the cavity.

Plasmon nanofocusing with negative refraction in a high-index dielectric wedge

Here, we describe a metal-insulator-insulator nanofocusing structure formed by a high-permittivity dielectric wedge on a metal substrate. The structure is shown to produce nanofocusing of surface plasmon polaritons (SPPs) in the direction opposite to the taper of the wedge, including a range of nanoplasmonic effects such as nanofocusing of SPPs with negative refraction, formation of plasmonic caustics within a nanoscale distance from the wedge tip, mutual transformation of SPP modes, and significant local field enhancements in the adiabatic and strongly nonadiabatic regimes. A combination of approximate analytical and rigorous numerical approaches is used to analyze the strength and position of caustics in the structure. In particular, it is demonstrated that strong SPP localization within spatial regions as small as a few tens of nanometers near the caustic is achievable in the considered structures. Contrary to other nanofocusing configurations, efficient nanofocusing is shown to occur in the strongly nonadiabatic regime with taper angles of the dielectric wedge as large as ∼40° and within uniquely short distances (as small as a few dozens of nanometers) from the tip of the wedge. Physical interpretations of the obtained results are also presented and discussed.