Search results for "Free Energy"
showing 10 items of 170 documents
Aggregation Behavior of Halogenated Squaraine Dyes in Buffer, Electrolytes, Organized Media, and DNA
2002
Aggregation properties of bis(3,5-dibromo-2,4,6-trihydroxyphenyl)squaraine (1) and bis(3,5-diiodo-2,4,6-trihydroxyphenyl)squaraine (2) have been examined in buffer and in the presence of electrolytes, β-cyclodextrin, micelles and DNA. These dyes were found to form aggregates in buffer and methanol−water solutions that have absorption bands blue-shifted to those of the monomeric forms. The iodo derivative 2 forms aggregates at much lower concentrations (1.7 × 10-6 M) compared to the bromo derivative 1 (2.35 × 10-6 M) in 20% (vol/vol) methanol−buffer solution. Increase in methanol concentration in methanol−water solutions resulted in the disruption of the aggregates. The intermediate dimer in…
Determination of Individual Gibbs Energies of Anion Transfer and Excess Gibbs Energies Using an Electrochemical Method Based on Insertion Electrochem…
2011
A method is presented to determine, individually and with minimal extra-thermodynamic assumptions, the Gibbs energy for anion transfer between two solvents using solid state electrochemistry of alkynyldiphosphine dinuclear Au(I) complexes (AuC2R)2PPh2C6H4PPh2 (L1, R = Fc; L2, R = C6H4Fc) and the heterometallic Au(I)–Cu(I) [{Au3Cu2(C2R)6}Au3(PPh2C6H4PPh2)3](PF6)2 (L3, R = Fc; L4, R = C6H4Fc) cluster complexes containing ferrocenyl units. These compounds exhibit a well-defined, essentially reversible solid-state oxidation in contact with different electrolytes, based on ferrocenyl-centered oxidation processes involving anion insertion. Voltammetric data can be used for a direct measurement of…
On the exhaust of electromagnetic drive
2016
Recent reports about propulsion without reaction mass have been met on one hand with enthusiasm and on the other hand with some doubts. Namely, closed metal cavities, when fueled with microwaves, have delivered thrust that could eventually maintain satellites on orbits using solar power. However, the measured thrust appears to be without any apparent exhaust. Thus the Law of Action-Reaction seems to have been violated. We consider the possibility that the exhaust is in a form that has so far escaped both experimental detection and theoretical attention. In the thruster's cavity microwaves interfere with each other and invariably some photons will also end up co-propagating with opposite pha…
Are one-step aromatic nucleophilic substitutions of non-activated benzenes concerted processes?
2019
Aromatic nucleophilic substitution (SNAr) reactions of non-electrophilically activated benzenes have been studied within the Molecular Electron Density Theory (MEDT) at the B3LYP/6-311+G(d) computational level. These reactions, taking place through a one-step mechanism, present a high activation Gibbs free energy, ΔG≠ = 31.0 kcal mol-1, which decreases to 22.1 kcal mol-1 in the intramolecular process. A topological analysis of the electron localisation function along the reaction paths permits establishing the non-concerted nature of these SNAr reactions. A series of unstable structures, with similar electronic structures to those of Meisenheimer intermediates, are characterised. The presen…
A molecular electron density theory study of the [3 + 2] cycloaddition reaction of nitrones with strained allenes
2017
Indexación: Scopus. The [3 + 2] cycloaddition (32CA) reaction of C-phenyl-N-tert-butylnitrone with 1,2-cyclohexadiene (CHDE), a strained allene, has been studied within Molecular Electron Density Theory (MEDT) at the DFT B3LYP/6-311G(d,p) computational level. This non-polar 32CA reaction, which takes place through a non-concerted two-stage one-step mechanism, proceeds with a moderate Gibbs free activation energy of 22.7 kcal mol-1, and presents low stereo- and regioselectivities. The reaction begins by the creation of a pseudoradical center at the central carbon of the strained allene with a relatively low energy cost, which immediately promotes the formation the first C-C single bond. This…
Free Energy, Enthalpy and Entropy from Implicit Solvent End-Point Simulations
2018
Free energy is the key quantity to describe the thermodynamics of biological systems. In this perspective we consider the calculation of free energy, enthalpy and entropy from end-point molecular dynamics simulations. Since the enthalpy may be calculated as the ensemble average over equilibrated simulation snapshots the difficulties related to free energy calculation are ultimately related to the calculation of the entropy of the system and in particular of the solvent entropy. In the last two decades implicit solvent models have been used to circumvent the problem and to take into account solvent entropy implicitly in the solvation terms. More recently outstanding advancement in both impli…
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…
Expanding the Active Inference Landscape: More Intrinsic Motivations in the Perception-Action Loop
2018
Active inference is an ambitious theory that treats perception, inference and action selection of autonomous agents under the heading of a single principle. It suggests biologically plausible explanations for many cognitive phenomena, including consciousness. In active inference, action selection is driven by an objective function that evaluates possible future actions with respect to current, inferred beliefs about the world. Active inference at its core is independent from extrinsic rewards, resulting in a high level of robustness across e.g.\ different environments or agent morphologies. In the literature, paradigms that share this independence have been summarised under the notion of in…
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.