We have developed a facile method for the construction of liquid-phase eutectic gallium-indium (EGaIn) alloy nanoparticles. Particle formation is directed by molecular self-assembly and assisted by sonication. As the bulk liquid alloy is ultrasonically dispersed, fast thiolate self-assembly at the EGaIn interface protects the material against oxidation. The choice of self-assembled monolayer ligand directs the ultimate size reduction in the material; strongly interacting molecules induce surface strain and assist particle cleavage to the nanoscale. Transmission electron microscopy images and diffraction analyses reveal that the nanoscale particles are in an amorphous or liquid phase, with no observed faceting. The particles exhibit strong absorption in the ultraviolet (∼200 nm), consistent with the gallium surface plasmon resonance, but dependent on the nature of the particle ligand shell.
Effective oscillator strength distributions are systematically generated and tabulated for the alkali atoms, the alkaline-earth atoms, the alkaline-earth ions, the rare gases and some miscellaneous atoms. These effective distributions are used to compute the dipole, quadrupole and octupole static polarizabilities, and are then applied to the calculation of the dynamic polarizabilities at imaginary frequencies. These polarizabilities can be used to determine the long-range C 6 , C 8 and C 10 atom-atom interactions for the dimers formed from any of these atoms and ions, and we present tables covering all of these combinations.
Dibenzo-7-phosphanorbornadiene Ph3PC(H)PA (1, A = C14H10, anthracene) is reported here as a molecular precursor to phosphaethyne (HC≡P), produced together with anthracene and triphenylphosphine. HCP generated by thermolysis of 1 has been observed by molecular beam mass spectrometry, laser-induced fluorescence, microwave spectroscopy, and nuclear magnetic resonance (NMR) spectroscopy. In toluene, fragmentation of 1 has been found to proceed with activation parameters of ΔH(⧧) = 25.5 kcal/mol and ΔS(⧧) = -2.43 eu and is accompanied by formation of an orange insoluble precipitate. Results from computational studies of the mechanism of HCP generation are in good agreement with experimental data. This high-temperature method of HCP generation has pointed to new reaction chemistry with azide anion to produce the 1,2,3,4-phosphatriazolate anion, HCPN3(-), for which structural data have been obtained in a single-crystal X-ray diffraction study. Negative-ion photoelectron spectroscopy has shown the adiabatic detachment energy for this anion to be 3.555(10) eV. The aromaticity of HCPN3(-) has been assessed using nucleus-independent chemical shift, quantum theory of atoms in molecules, and natural bond orbital methods.
The C̃ (1)B2 state of SO2 has a double-minimum potential in the antisymmetric stretch coordinate, such that the minimum energy geometry has nonequivalent SO bond lengths. However, low-lying levels with odd quanta of antisymmetric stretch (b2 vibrational symmetry) have not previously been observed because transitions into these levels from the zero-point level of the X̃ state are vibronically forbidden. We use IR-UV double resonance to observe the b2 vibrational levels of the C̃ state below 1600 cm(-1) of vibrational excitation. This enables a direct characterization of the vibrational level staggering that results from the double-minimum potential. In addition, it allows us to deperturb the strong c-axis Coriolis interactions between levels of a1 and b2 vibrational symmetry and to determine accurately the vibrational dependence of the rotational constants in the distorted C̃ electronic state.
Hamiltonian in the Fermi-system basis, the vibrational characters of all vibrational levels can be determined unambiguously. It is shown that the bending mode cannot be treated separately from the coupled stretching modes, particularly at vibrational energies of more than 2000 cm −1 . Based on our force field, the structure of the Coriolis interactions in theC state of SO 2 is also discussed.We identify the origin of the alternating patterns in the effective C rotational constants of levels in the vibrational progressions of the symmetry-breaking mode, ν β (which correlates with the antisymmetric stretching mode in our assignment scheme).
Millimeter-wave detected, millimeter-wave optical double resonance (mmODR) spectroscopy is a powerful tool for the analysis of dense, complicated regions in the optical spectra of small molecules. The availability of cavity-free microwave and millimeter wave spectrometers with frequency-agile generation and detection of radiation (required for chirped-pulse Fourier-transform spectroscopy) opens up new schemes for double resonance experiments. We demonstrate a multiplexed population labeling scheme for rapid acquisition of double resonance spectra, probing multiple rotational transitions simultaneously. We also demonstrate a millimeter-wave implementation of the coherenceconverted population transfer scheme for background-free mmODR, which provides a ∼10-fold sensitivity improvement over the population labeling scheme. We analyze perturbations in theC state of SO 2 , and we rotationally assign a b 2 vibrational level at 45 328 cm −1 that borrows intensity via a c-axis Coriolis interaction. We also demonstrate the effectiveness of our multiplexed mmODR scheme for rapid acquisition and assignment of three predissociated vibrational levels of theC state of SO 2 between 46 800 and 47 650 cm −1 . C 2015 AIP Publishing LLC. [http://dx
The dicarbon molecule (C2) is found in flames, comets, stars, and the diffuse interstellar medium. In comets, it is responsible for the green color of the coma, but it is not found in the tail. It has long been held to photodissociate in sunlight with a lifetime precluding observation in the tail, but the mechanism was not known. Here we directly observe photodissociation of C2. From the speed of the recoiling carbon atoms, a bond dissociation energy of 602.804(29) kJ·mol−1 is determined, with an uncertainty comparable to its more experimentally accessible N2 and O2 counterparts. The value is within 0.03 kJ·mol−1 of high-level quantum theory. This work shows that, to break the quadruple bond of C2 using sunlight, the molecule must absorb two photons and undergo two “forbidden” transitions.
The C̃ (1)B2 state of SO2 has a double-minimum potential in the antisymmetric stretch coordinate, such that the minimum energy geometry has nonequivalent SO bond lengths. The asymmetry in the potential energy surface is expressed as a staggering in the energy levels of the ν3(') progression. We have recently made the first observation of low-lying levels with odd quanta of v3('), which allows us-in the current work-to characterize the origins of the level staggering. Our work demonstrates the usefulness of low-lying vibrational level structure, where the character of the wavefunctions can be relatively easily understood, to extract information about dynamically important potential energy surface crossings that occur at much higher energy. The measured staggering pattern is consistent with a vibronic coupling model for the double-minimum, which involves direct coupling to the bound 2 (1)A1 state and indirect coupling with the repulsive 3 (1)A1 state. The degree of staggering in the ν3(') levels increases with quanta of bending excitation, which is consistent with the approach along the C̃ state potential energy surface to a conical intersection with the 2 (1)A1 surface at a bond angle of ∼145°.
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