Search results for "Quantum"
showing 10 items of 9714 documents
Nonlocal elasticity and related variational principles
2001
Abstract The Eringen model of nonlocal elasticity is considered and its implications in solid mechanics studied. The model is refined by assuming an attenuation function depending on the `geodetical distance' between material particles, such that in the diffusion processes of the nonlocality effects certain obstacles as holes or cracks existing in the domain can be circumvented. A suitable thermodynamic framework with nonlocality is also envisaged as a firm basis of the model. The nonlocal elasticity boundary-value problem for infinitesimal displacements and quasi-static loads is addressed and the conditions for the solution uniqueness are established. Three variational principles, nonlocal…
Gradient elasticity and nonstandard boundary conditions
2003
Abstract Gradient elasticity for a second gradient model is addressed within a suitable thermodynamic framework apt to account for nonlocality. The pertinent thermodynamic restrictions upon the gradient constitutive equations are derived, which are shown to include, besides the field (differential) stress–strain laws, a set of nonstandard boundary conditions. Consistently with the latter thermodynamic requirements, a surface layer with membrane stresses is envisioned in the strained body, which together with the above nonstandard boundary conditions make the body constitutively insulated (i.e. no long distance energy flows out of the boundary surface due to nonlocality). The total strain en…
Development of La3+ Doped CeOthick film humidity sensors
2014
Published version of an article in the journal: Abstract and Applied Analysis. Also available from the publisher at: http://dx.doi.org/10.1155/2014/297632 Open Access The humidity sensitive characteristics of the sensor fabricated from 10 mol% Ladoped CeOnanopowders with particle size 17.26 nm synthesized via hydrothermal method were investigated at different frequencies. It was found that the sensor shows high humidity sensitivity, rapid response-recovery characteristics, and narrow hysteresis loop at 100 Hz in the relative humidity range from 11% to 95%. The impedance of the sensor decreases by about five orders of magnitude as relative humidity increases. The maximum humidity hysteresis …
A new force field including charge directionality for TMAO in aqueous solution
2016
We propose a new force field for trimethylamine N-oxide (TMAO), which is designed to reproduce the long-lived and highly directional hydrogen bond between the TMAO oxygen (OTMAO) atom and surrounding water molecules. Based on the data obtained by ab initio molecular dynamics simulations, we introduce three dummy sites around OTMAO to mimic the OTMAO lone pairs and we migrate the negative charge on the OTMAO to the dummy sites. The force field model developed here improves both structural and dynamical properties of aqueous TMAO solutions. Moreover, it reproduces the experimentally observed dependence of viscosity upon increasing TMAO concentration quantitatively. The simple procedure of the…
Interaction between nitroxyl radicals and CdTe quantum dots: Determination of fluorescence-quenching mechanisms in aqueous solution
2019
Abstract The present work characterizes the optical properties of CdTe quantum dots (CdTe QDs) after interaction with nitroxyl radicals based on steady-state and time-resolved fluorescence spectroscopy studies. QDs of different sizes were exposed to 2 different nitroxyl radicals, i.e., TEMPO and 4-amino-TEMPO radicals. A clear dependence of dynamic and static Stern-Volmer constants values, KD and KS, respectively, was observed as a function of the size of QDs used, with a change from a mostly static mechanism (for smaller QD sizes) to a dynamic mechanism predominating as the nanoparticles increase in size. All observed effects are dependent on both the concentration of the radical and the s…
A quantum mechanics-molecular mechanics study of dissociative electron transfer : The methylchloride radical anion in aqueous solution
2002
The dissociative electron transfer reaction CH3Cl+e−→CH3•+Cl− in aqueous solution is studied by using a QM/MM method. In this work the quantum subsystem (a methylchloride molecule plus an electron) is described using density functional theory while the solvent (300 water molecules) is described using the TIP3P classical potential. By means of molecular dynamics simulations and the thermodynamic integration technique we obtained the potential of mean force (PMF) for the carbon–chlorine bond dissociation of the neutral and radical anion species. Combining these two free energy curves we found a quadratic dependence of the activation free energy on the reaction free energy in agreement with Ma…
Calculation of the relative basicities of methylamines in solution
1990
Abstract The relative basicities in solution of the methylamines have been calculated using the model of Miertus, Scrocco and Tomasi to describe the solvent effect. The surface of the cavity is defined with the GEPOL method. The ab initio calculations have been performed using a 4-31G basis set. The relative order is reproduced using a combination of the gas-phase proton affinities obtained with quantum-mechanical methods by Eades, Weil, Dixon and Douglass and the solvation values obtained by us. The results seem to point out that the irregular order is not due to solvent but to basis-set effects.
Application of SQMFF Vibrational Calculations to Transition States: DFT and ab Initio Study of the Kinetics of Methyl Azide and Ethyl Azide Thermoly…
1998
DFT including nonlocal corrections and ab initio calculations at MP2 and MP4 levels of theory have been performed in order to provide information concerning the mechanism of the rate limiting step of the thermal decomposition of methyl azide and ethyl azide. The chemically interesting points of the ground-state potential energy surface have been fully optimized, and a detailed normal-mode analysis for the reagents and the transition states is presented. The well-established scaled quantum mechanical force field method has been used to obtain reliable vibrational frequencies for these molecular structures. The force fields of transition states have been modified by using the scale factors co…
Modeling of Point Defects in Corundum Crystals
1994
Several different approaches including Hartree-Fock ab initio cluster calculations, semiempirical INDO calculations, and atom-atom potentials were used for modeling of the spatial and electronic structure as well as migration mechanisms of both intrinsic defects (self-trapped and defect-trapped holes, O and Al vacancies) and impurities (transition-metal ions like Co, Fe, Mg, Mn, Ti). The atomic structure of all hole centers is found to be similar to V[sub K] centers in alkali halides (two-site model); their formation is energetically favorable. The energy required for 60[degree] hole reorientations inside the basic oxygen triangles is found to be similar to both the energy for hops between …
Dynamics of spin state conversion processes in the solid state
1989
High spin (HS) ⇌ low spin (LS) conversions in transition metal complexes are nonradiative transitions between spin states. In this contribution, we present a study of the temperature and pressure dependence of the HS ⇌ LS intersystem crossing dynamics. For some iron(II) spin-crossover complexes, the rate constants were determined by line shape analysis of57Fe Mossbauer spectra. Their temperature dependence is described by an Arrhenius equation, their pressure dependence is interpreted within absolute rate theory. HS → LS conversion rates at low temperatures were determined from the relaxation of light-induced formation of HS states, monitored by optical spectroscopy. Deviations from a simpl…