Search results for " free energy"
showing 10 items of 137 documents
A molecular electron density theory study of the insertion of CO into frustrated Lewis pair boron-amidines: a [4 + 1] cycloaddition reaction
2019
The insertion of CO into hydrogenated boron-amidine 1 yielding five-membered diazaborolone (5DAB) 3 has been studied within the molecular electron density theory (MEDT) at the DFT ωB97X-D/6-311G(d,p) level. This is a domino process comprised of two consecutive reactions: (i) the dehydrogenation of 1 yielding the frustrated Lewis pair (FLP) boron-amidine 4, which quickly equilibrates with four-membered diazaborolone (4DAB) 2; and (ii) the addition of CO into FLP 4, yielding the final 5DAB 3. Analysis of the Gibbs free energies indicates that the extrusion of H2 demands a high ΔG≠ of 28.6 kcal·mol-1, being endergonic by 6.7 kcal·mol-1. The subsequent addition of CO into FLP 4 presents a low Δ…
Unveiling the Intramolecular Ionic Diels–Alder Reactions within Molecular Electron Density Theory
2021
The intramolecular ionic Diels–Alder (IIDA) reactions of two dieniminiums were studied within the Molecular Electron Density Theory (MEDT) at the ωB97XD/6-311G(d,p) computational level. Topological analysis of the electron localization function (ELF) of dieniminiums showed that their electronic structures can been seen as the sum of those of butadiene and ethaniminium. The superelectrophilic character of dieniminiums accounts for the high intramolecular global electron density transfer taking place from the diene framework to the iminium one at the transition state structures (TSs) of these IIDA reactions, which are classified as the forward electro density flux. The activation enthalpy ass…
Stability of hydrodynamical relativistic planar jets
2004
The effects of relativistic dynamics and thermodynamics in the development of Kelvin-Helmholtz instabilities in planar, relativistic jets along the early phases (namely linear and saturation phases) of evolution has been studied by a combination of linear stability analysis and high-resolution numerical simulations for the most unstable first reflection modes in the temporal approach. Three different values of the jet Lorentz factor (5, 10 and 20) and a few different values of specific internal energy of the jet matter (from 0.08 to $60.0 c^2$) have been considered. Figures illustrating the evolution of the perturbations are also shown.
The effect of vertical ground movement on masonry walls simulated through an elastic–plastic interphase meso-model: a case study
2019
The present paper proposes an interphase model for the simulation of damage propagation in masonry walls in the framework of a mesoscopic approach. The model is thermodynamically consistent, with constitutive relations derived from a Helmholtz free potential energy. With respect to classic interface elements, the internal stress contribute is added to the contact stresses. It is considered that damage, in the form of loss of adhesion or cohesion, can potentially take place at each of the two blocks–mortar physical interfaces. Flow rules are obtained in the framework of the Theory of Plasticity, considering bilinear domains of ‘Coulomb with tension cut-off’ type. The model aims to be a first…
Salinity gradient energy
2016
Abstract Beyond the most common renewable energy sources today exploited for the production of clean energy, salinity gradients power (SGP) has been attracting the increasing interest of scientists and companies involved in the field. This chapter provides an introduction to SGP, reporting a brief history of the technological developments throughout the years, from the beginning to present. A number of different SGP technologies have been developed in the last decades, all based on the concept of harvesting the energy from the controlled mixing of two solutions at different salinities. A theoretical analysis of the energy potential for SGP places this renewable source of energy among those …
Monotonicity and local uniqueness for the Helmholtz equation
2017
This work extends monotonicity-based methods in inverse problems to the case of the Helmholtz (or stationary Schr\"odinger) equation $(\Delta + k^2 q) u = 0$ in a bounded domain for fixed non-resonance frequency $k>0$ and real-valued scattering coefficient function $q$. We show a monotonicity relation between the scattering coefficient $q$ and the local Neumann-Dirichlet operator that holds up to finitely many eigenvalues. Combining this with the method of localized potentials, or Runge approximation, adapted to the case where finitely many constraints are present, we derive a constructive monotonicity-based characterization of scatterers from partial boundary data. We also obtain the local…
Electron-density critical points analysis and catastrophe theory to forecast structure instability in periodic solids
2018
The critical points analysis of electron density,i.e. ρ(x), fromab initiocalculations is used in combination with the catastrophe theory to show a correlation between ρ(x) topology and the appearance of instability that may lead to transformations of crystal structures, as a function of pressure/temperature. In particular, this study focuses on the evolution of coalescing non-degenerate critical points,i.e. such that ∇ρ(xc) = 0 and λ1, λ2, λ3≠ 0 [λ being the eigenvalues of the Hessian of ρ(x) atxc], towards degenerate critical points,i.e. ∇ρ(xc) = 0 and at least one λ equal to zero. The catastrophe theory formalism provides a mathematical tool to model ρ(x) in the neighbourhood ofxcand allo…
Ewald Hering und die Gegenfarbtheorie
1996
Ewald Hering's color-opponent-theory is still considered one of the foundations of the visual sciences. Prior to Hering, Hermann v. Helmholtz introduced a theory of color appearance, which was based primarily on the physical aspects of the stimulus. In contrast to Helmholtz, Hering's theory strongly emphasized the subject's perception of color. As a consequence, Hering considered Helmholtz' theory inadequate. Contrary to some historical accounts, he did not object to Helmholtz's three-receptor explanation for color-mixture. Instead of Helmholtz' fundamental colors red, green, and blue, Hering suggested that the colors possess opponent character: blue-yellow; red-green; and, black-white. Hel…
Metal complex-DNA binding: Insights from molecular dynamics and DFT/MM calculations.
2012
Molecular dynamics (MD) simulations, followed by density functional theory/molecular mechanics (DFT/MM) calculations, provided a detailed structure of the binding site between the cationic metallointercalator (dipyrido [3,2-a:2',3'-c]phenazine)(glycinato)copper(II), [Cu(gly)(dppz)](+), and the two dodeca-deoxynucleotide duplexes [dodeca(dG-dC)]2 and [dodeca(dA-dT)]2. Three simultaneous DNA binding types were detected in the fully optimized DFT/MM structures: 1) metal coordination through exocyclic oxygen atoms of nitrogen bases; 2) intercalation of the dppz chromophore between stacked Watson-Crick AT-AT and GC-GC bases; and 3) hydrogen bonding between the glycinato ligand and amine groups o…
Theoretical study of spiropyran-merocyanine thermal isomerization.
2004
Abstract Quantum mechanical computations at DFT level were carried out on the processes involved in the thermal reaction SP ⇆ ME, where SP is the nitro-substituted spirobenzopyran (1 ′ ,3 ′ -dihydro-1 ′ ,3 ′ ,3 ′ -trimethyl-6-nitro-spiro[2H-1-benzopyran-2,2 ′ - [2H]indole]) in the closed form and ME is the corresponding open form. A detailed theoretical description of the overall reaction is reported along with the thermodynamic parameters for all intermediates and transition states. The obtained activation energy value is in agreement with the available experimental data in solution.