Search results for "Theoretical"
showing 10 items of 11439 documents
Coupling between bulk- and surface chemistry in suspensions of charged colloids
2013
The ionic composition and pair correlations in fluid phases of realistically salt-free charged colloidal sphere suspensions are calculated in the primitive model. We obtain the number densities of all ionic species in suspension, including low-molecular weight microions, and colloidal macroions with acidic surface groups, from a self-consistent solution of a coupled physicochemical set of nonlinear algebraic equations and non-mean-field liquid integral equations. Here, we study suspensions of colloidal spheres with sulfonate or silanol surface groups, suspended in demineralized water that is saturated with carbon dioxide under standard atmosphere. The only input required for our theoretical…
Theoretical study of the NH tautomerism in free base porphyrin
1997
Abstract The NH tautomerism of free base porphyrin is investigated at the semiempirical spin-unrestricted AM1 (UAM1) and ab initio RHF/3-21G levels. The UAM1 method provides delocalized geometries for all stationary structures without imposing any symmetry constraint. RHF/3-21G geometry optimizations have to be performed under symmetry restrictions to ensure that realistic delocalized structures are obtained. Both the semiempirical and the ab initio calculations predict that the interconversion between trans tautomers proceeds in an asynchronous two-step process via intermediate cis tautomers. The cis tautomers are characterized as minima in the potential energy surface and are 8–10 kcal m…
Crystal structure of sinhalite MgAlBO4 under high pressure
2015
We report on high-pressure angle-dispersive X-ray diffraction data up to 27 GPa for natural MgAlBO4 sinhalite mineral and ab initio total energy calculations. The experimental bulk modulus of sinhalite is B-0 = 171(3) GPa with a first-pressure derivative of B-0' = 4.2(3). A comparison with other olivine-type compounds shows that the value for B0 is 27% larger than that of Mg2SiO4 forsterite and 29% smaller than that of Al2BeO4 chrysoberyl. These differences are interpreted, on the basis of our ab initio calculations, in terms of the relative incompressibility of Al-O bonds in AlO6 octahedra (with a calculated bulk modulus of 250(1) GPa) as compared to Mg-O bonds in MgO6 octahedra (with a ca…
Ab Initio Study on the Mechanism of the Reactions of the Nitrate Radical with Haloalkenes: 1,2-Dichloroethene, 1,1-Dichloroethene, Trichloroethene, …
2000
A general mechanism for the reactions of the NO3 radical with 1,2-dichloroethene, 1,1-dichloroethene, trichloroethene, and tetrachloroethene is proposed from ab initio DFT calculations. The calculated mechanism shows three main parallel reaction pathways. For the systems where the two carbon atoms are differently substituted, the study includes both the attacks with Markownikoff and contra-Markownikoff orientation. The first reaction pathway leads to the formation of an epoxide along with the NO2 radical, the second one to the formation of carbonyl compounds, and the third one leads, through the cleavage of the C−C bond, to the formation of carbonyl compounds with a lower number of carbon a…
Abel transforms with low regularity with applications to X-ray tomography on spherically symmetric manifolds
2017
We study ray transforms on spherically symmetric manifolds with a piecewise $C^{1,1}$ metric. Assuming the Herglotz condition, the X-ray transform is injective on the space of $L^2$ functions on such manifolds. We also prove injectivity results for broken ray transforms (with and without periodicity) on such manifolds with a $C^{1,1}$ metric. To make these problems tractable in low regularity, we introduce and study a class of generalized Abel transforms and study their properties. This low regularity setting is relevant for geophysical applications.
Automorphisms of hyperelliptic GAG-codes
2009
Abstract We determine the n –automorphism group of generalized algebraic-geometry codes associated with rational, elliptic and hyperelliptic function fields. Such group is, up to isomorphism, a subgroup of the automorphism group of the underlying function field.
Vertical spectrum of ethene: uncontracted versus contracted correlation methods and the role of the adapted molecular orbitals
1998
Abstract Ethylene vertical excitation energies (VEE) below 9.5 eV have been calculated with the complete active-space singles and doubles configuration interaction self-consistent size-consistent dressing (SC) 2 CAS–SDCI. The mean of the absolute deviation from experiment for the calculated VEE are 0.14, 0.05 and 0.03 eV for three different molecular orbital (MO) sets tried. The results show that an uncontracted method and a realistic MO set avoid the difficulties present in the calculation of the strongly mixed Rydberg-valence 1B 1u states.
Utilization of impedance spectroscopy to investigate the self-assembly behavior of amphiphiles soluble in supercritical carbon dioxide: Preliminary r…
2007
Abstract A mixture of CO 2 , water, methyl orange (MO) and Dynol 604 surfactant was analyzed at 309 K and 20 MPa simultaneously by impedance and UV–vis spectroscopy. A plot of the static dielectric constant as a function of the surfactant concentration was obtained using a suitable equivalent circuit to elaborate impedance data. Experimental points can be fitted by two different straight lines whose intersection occurs at about 0.13% (w/w) concentration of Dynol. When the surfactant concentration crossed the aforementioned value, a peak was detectable in the UV–vis spectrum at a wavelength range corresponding to the absorption of MO; absorbance of the peak increased with the surfactant conc…
On the variations of acoustic absorption peak with particle velocity in micro-perforated panels at high level of excitation.
2010
The acoustic behavior of micro-perforated panels (MPP) is studied theoretically and experimentally at high level of pressure excitation. A model based on Forcheimer's regime of flow velocity in the perforations is proposed. This model is valid at relatively high Reynolds numbers and low Mach numbers. The experimental method consists in measuring the acoustical pressure at three different positions in an impedance tube, the two measurement positions usually considered in an impedance tube and one measurement in the vicinity of the rear surface of the MPP. The impedance tube is equipped with a pressure driver instead of the usual loudspeaker and capable of delivering a high sound pressure lev…
A Simple System Based on a Thiourea-Modified Fluorescein for ω-Amino Acid Discrimination
2015
A thiourea-modified fluorescein derivative was synthesized by reaction of fluorescein isothiocyanate with 2-(2-aminoethoxy)ethan-1-ol. UV/Vis absorption and fluorescence emission spectroscopy studies demonstrated that this heteroditopic receptor was able to discriminate among linear aliphatic ω-amino acids with different chain lengths.