Search results for " function"

First-principles calculations of oxygen interstitials in corundum: a site symmetry approach

2017

The authors are indebted to R. Vila, A. Popov and A. Lushchik for stimulating discussions. This work was carried out within the framework of the EUROfusion Consortium and received funding from the European Union’s Horizon 2020 Research and Innovation Programme under grant agreement 633053. The views and opinions expressed herein do not necessarily reflect those of the European Commission. Support from Latvian National Research Program IMIS2 (2014–2017) is also appreciated. Calculations were carried out using both the Marconi supercomputer system at the Computational Simulation Centre and the Computer Center of St. Petersburg State University.

Assessment of a single-acquisition imaging sequence for oxygen-sensitive (3)He-MRI.

2001

MRI of the lungs using hyperpolarized helium-3 (3He) allows the determination of intrapulmonary oxygen partial pressures (pO2). The need to separate competing processes of signal loss has hitherto required two different imaging series during two different breathing maneuvers. In this work, a new imaging strategy to measure pO2 by a single series of consecutive scans is presented. The feasibility of the method is demonstrated in three healthy human volunteers. Maps and histograms of intrapulmonary pO2 are calculated. Changes in the oxygen concentration of the inhaled gas mixture are well reproduced in the histograms. Monte Carlo (MC) simulations of the temporal evolution of 3He hyperpolariza…

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…

Über die Beziehung zwischen Viskositätszahl und Molekulargewicht bei Polystyrolen im hemikolloiden bis makromolekularen Bereich

1954

An fraktionierten und besonders gereinigten Polystyrolen werden kryoskopische Molekulargewichtsbestimmungen im Molekulargewichtsbereich von 1 000 bis 40 000 duchargefuhrt. Die Mesergebnisse werden durch andere Methoden nachkontrolliert und bestatigt. Von denselben Praparaten wird die Viskositatszahl bestimmt. Es zeigte sich, das diese unabhangig von dem Mechanismus der Polymerisation (Radikalketten oder Ionenketten) ist. Die log Zη-log M-Funktion verlauft entgegen der voraussage der bisher aufgestellten Theorien im untersuchten Bereich flacher als bei hohen Polymerisationsgraden (vgl. Abb.3). Kryoscopic molecular weight determinations are performed on especially purified polystyrene fractio…

Theoretical investigation of paramagnetic group 13 diazabutadiene radicals: insights into the prediction and interpretation of EPR spectroscopy param…

2006

The electronic structures and the spin density distributions of the group 13 1,4-diaza(1,3)butadiene (DAB) radicals [(R-DAB)2M]˙, [(R-DAB)MX2]˙ and {[(R-DAB)MX]2}˙˙ (M = Al, Ga, In; X = F, Cl, Br, I; R = H, Me, tBu, Ph) are studied using density functional theory at both non-relativistic and relativistic levels of theory. The calculations demonstrate that all systems share a qualitatively similar electronic structure and are primarily ligand centred π-radicals. The calculated metal, nitrogen and hydrogen hyperfine couplings are found to be independent of the identity of the R-group and the halogen atom. They are, however, dependent on the geometry and oxidation state of the metal centre. Bo…

Ultrafast Twisting of the Indoline Donor Unit Utilized in Solar Cell Dyes: Experimental and Theoretical Studies

2015

Previous time-resolved measurements on D149, the most-studied dye of the indoline family, had shown a fast time-component of 20–40 ps that had tentatively been attributed to structural relaxation. Using femtosecond transient absorption, we have investigated the isolated indoline donor unit (i.e., without acceptor group) and found an ultrafast decay characterized by two lifetimes of 3.5 and 23 ps. Density functional theory calculations show π-bonding and π*-antibonding character of the central ethylene group for the highest occupied and lowest unoccupied molecular orbitals (HOMO and LUMO), respectively. The LUMO is localized on the flexible vinyl-diphenyl region of the donor unit and a twist…

Solvatochromy and symmetry breaking in two quadrupolar oligophenylenevinylenes

2020

Electrooptical absorption measurements (EOAM), solvatochromic dependences and quantum chemical simulations testify to large dipole moments change of two quadrupolar oligophenylenevinylenes upon transition to Franck-Condon excited state μeFC. The values of the dipole moments μg and μeFC are in the range [(4.2 - 4.9)1030] C m and (30.8 - 47.0)1030C m, respectively. The relations of dipole moments in the ground and excited states determined by EOAM correlate well with results obtained via the solvatochromic method. Calculations carried out by density functional theory (DFT) show that optimized configuration of the ground state of these molecules is not planar. The results from all methods appl…

Decision letter: Structure and mechanism of a phage-encoded SAM lyase revises catalytic function of enzyme family

2020

A statistical study of the additivities of substituent effects in the13C NMR chemical shifts of hydroxy- and chloro-substituted benzenes

1980

The 13C NMR spectra of six hydroxybenzenes, all chlorobenzenes, all chlorophenols and eight chlorocatechols are measured and assigned. The additivity of the substituent effects and the usefulness of some corrective parameters are studied with regression analysis. The order of the chemical shifts is most efficiently predicted by the simplest substituent effect model, containing only the direct effects of the substituents, although the 95% confidence limits of the calculated shifts are as high as 5.6 ppm. If the chemical shifts need to be predicted within the measuring errors (approximately 0.05–0.10 ppm, in the present data), the number of necessary corrections is very impractical. The corre…

Adsorption and activation of O2 at Au chains on MgO/Mo thin films

2010

We have investigated the adsorption of O(2) on Au(n) clusters (n = 1-6) supported by an ultra thin (3ML)MgO(001) film on Mo metal via density functional theory calculations. On thin films, these small clusters have chain like structures and their electronic states resemble 1D quantum well states. The Au(1-3) are charged by one electron whereas the larger Au(4-6) get two electrons from the substrate. This is confirmed both by the symmetries of the HOMO and LUMO states of the clusters and the Bader charge analysis. In contrast to the O(2) adsorption on gas-phase clusters, the adsorption energy of O(2) molecule does not show pronounced oscillations as a function of cluster size. The O(2) is ac…