Search results for "ESA"
showing 10 items of 11914 documents
Electronic, vibrational, and structural properties of a spin-crossover catecholato-iron system in the solid state: theoretical study of the electroni…
2005
As a functional model of the catechol dioxygenases, [(TPA)Fe(Cat)]BPh4 (TPA = tris(2-pyridylmethyl)amine and Cat = catecholate dianion) exhibits the purple-blue coloration indicative of some charge transfer within the ground state. In contrast to a number of high-spin bioinspired systems, it was previously shown that, in the solid state, [(TPA)Fe(Cat)]BPh4 undergoes a two-step S = 1/2 = S = 5/2 spin-crossover. Therefore, the electronic and vibrational characteristics of this compound were investigated in the solid state by UV/Vis absorption and resonance Raman spectroscopies over the temperature range of the transition. This allowed the charge-transfer transitions of the low-spin (LS) form …
Studies of rotational level Λ-doubling by rf-optical double resonance spectroscopy: application to NaK D1Π
1997
Abstract We report here the application of optical-radio frequency double resonance spectroscopy for individual rotational levels of the NaK D 1 Π state. Lambda doubling constant q values for five ν′, J ′ levels are obtained. These data are combined with measurements of dc e - f Stark-mixing-induced changes in optical spectra, and the electric dipole moment d p in the D 1 Π state is determined.
Negative thermal expansion of quartz glass at low temperatures: An ab initio simulation study
2017
Abstract Using a mixed classical Molecular dynamics (MD)/ab initio simulation scheme combined with a quasi-harmonic approximation, we calculate the linear thermal expansion coefficient αL(T) in vitreous silica glasses. The systems are first cooled down by classical MD simulations. Then they are structurally relaxed by ab initio DFT calculations. The vibrational properties are calculated employing the frozen phonon method, and these results are finally used to calculate the Helmholtz free energy as a function of volume. In agreement with experiments, our simulations predict that αL(T) is negative at low temperatures up to T ≈ 150 K. In this low-temperature regime, the simulation results are …
High precision numerical estimates of acoustic phonon frequencies of nonspherical nanoparticles
2006
We introduce an adapted method for calculating the acoustic vibrational frequencies of arbitrarily shaped nanoparticles to high precision. Molecular dynamics simulation results are tested against exact solutions for a free sphere, a hollow sphere and a spheroid. This permits theoretical predictions of the frequencies of peaks in low frequency Raman spectra. Our results demonstrate that vibrational frequencies can be calculated for a wide range of low frequency modes with accuracies on the order of a tenth of a percent.
Raman and theoretical study of the solvent effects on the sizable intramolecular charge transfer in the push-pull 5-(dimethylamino)-5'-nitro-2,2'-bit…
2006
In this paper, we analyze the degree of intramolecular charge transfer in a push-pull π-conjugated system, 5-(dimethylamino)-5'-nitro-2,2'-bithiophene, from changes in frequencies and relative intensities of its strongestRaman scatterings in a bunch of solvents with different polarities. Density functional theory (DFT) was used as a support of the experimental study. Solvent effects on the molecular and electronic structures and on the vibrational properties were estimated by performing B3LYP/6-31G** calculations within the framework of the polarized continuum model (PCM) developed by Tomasi. Calculations reveal that the molecule is highly polarized in the ground state and behaves as a very…
Raman spectroscopy and crystal-field split rotational states of photoproducts CO and H2 after dissociation of formaldehyde in solid argon.
2012
Raman signal is monitored after 248 nm photodissociation of formaldehyde in solid Ar at temperatures of 9-30 K. Rotational transitions J = 2 ← 0 for para-H(2) fragments and J = 3 ← 1 for ortho-H(2) are observed as sharp peaks at 347.2 cm(-1) and 578.3 cm(-1), respectively, which both are accompanied by a broader shoulder band that shows a split structure. The rovibrational spectrum of CO fragments has transitions at 2136.5 cm(-1), 2138.3 cm(-1), 2139.9 cm(-1), and 2149 cm(-1). To explain the observations, we performed adiabatic rotational potential calculations to simulate the Raman spectrum. The simulations indicate that the splitting of rotational transitions is a site effect, where H(2) …
Ion motion in salt water flowing under a transverse magnetic field
2012
The problem of ion motion in an electrolyte solution flowing in a thin rectangular duct with velocity VE in the presence of a transverse magnetic field B0 is studied by means of classical mechanics and electrodynamics. Because of Lorentz force on the ions in the electrolyte solution, a so called Faraday voltage appears at the electrodes orthogonal to both the field B0 and the velocity VE. The dynamics of positive and negative ions (cations and anions, respectively) in this classical system is studied by taking into account the viscosity of the fluid and the process of charge accumulation on the opposite walls of the duct. Hydrogen production is seen to take place at one of the electrodes wh…
Gold catalysts supported on CeO2 and CeO2–Al2O3 for NO reduction by CO
2006
Abstract The reduction of NO x by CO was studied over gold catalyst supported on ceria and ceria–alumina. The mixed supports with different CeO 2 /Al 2 O 3 ratios were prepared by co-precipitation. The catalysts were characterized by means of XRD, TPR, XPS and Raman spectroscopy. The addition of alumina led to a slight enlargement of the gold particles, while the ceria particle size was decreased. Deeper oxygen vacancies formation in the presence of alumina was detected by TPR, XPS and Raman spectroscopy, compared to the pure ceria support. The samples exhibited a high and stable activity and 100% selectivity towards N 2 was reached at 200 °C.
Effect of Ti(IV) loading on CO oxidation activity of gold on TiO2 doped amorphous silica
2006
Abstract Amorphous SiO 2 , doped with various amount of TiO 2 , was used as support for gold nanoparticles. Gold was deposited through the controlled sol formation technique. The effect of the TiO 2 loading on the structural and surface properties was investigated by transmission electron microscopy, X-ray diffraction, Raman and X-ray photoelectron spectroscopy. The catalytic behavior was tested in the oxidation of CO. A significant enhancement in the activity was observed for the gold supported on mixed oxide with low TiO 2 loading. On the basis of characterization data, the positive effect is assigned to the electronic modification of the Ti(IV) of the newly formed Ti O Si bonds.
Structural characterisation of silica supported CoMo catalysts by UV Raman spectroscopy, XPS and X-ray diffraction techniques
2002
The structure of Co-Mo catalysts supported on commercial silica, doped with various amounts of sodium ions, was investigated by means of X-ray diffraction (XRD), UV-Raman spectroscopy and X-ray photoelectron spectroscopy (XPS). Two series of samples were considered. One series was prepared by classic incipient wet impregnation (WI) and the other series by co-impregnation in the presence of nitrilotriacetic acid (NTA). The effect of sodium on the catalyst structure depended on the preparation procedure: in the case of the WI catalysts, sodium promoted the transformation of the polymolybdate species into monomolybdate Na2MoO4; in the case of the NTA prepared samples, sodium induced transforma…