Search results for " free energy"
showing 10 items of 137 documents
A Comparative Ab Initio Thermodynamic Study of Oxygen Vacancies in ZnO and SrTiO3: Emphasis on Phonon Contribution
2013
Using a hybrid Hartree–Fock (HF)-DFT method combined with LCAO basis set and periodic supercell approach, the atomic, electronic structure and phonon properties of oxygen vacancies in ZnO and SrTiO3 were calculated and compared. The important role of a ghost basis function centered at the vacant site and defect spin state for SrTiO3 is discussed. It is shown that the use of hybrid functionals is vital for correct reproduction of defects basic properties. The Gibbs free energy of formation of oxygen vacancies and their considerable temperature dependence has been compared for the two oxides. These calculations were based on the polarizability model for the soft mode temperature behavior in S…
Integration of finite displacement interface element in reference and current configurations
2017
In the present paper the non-linear behaviour of a solid body with embedded cohesive interfaces is examined in a finite displacements context. The principal target is the formulation of a two dimensional interface finite element which is referred to a local reference frame, defined by normal and tangential unit vectors to the interface middle surface. All the geometric operators, such as the interface elongation and the reference frame, are computed as function of the actual nodal displacements. The constitutive cohesive law is defined in terms of Helmholtz free energy for unit undeformed interface surface and, in order to obtain the same nodal force vector and stiffness matrix by the two i…
Novel σ1 antagonists designed for tumor therapy: Structure – activity relationships of aminoethyl substituted cyclohexanes
2021
Abstract Depending on the substitution pattern and stereochemistry, 1,3-dioxanes 1 with an aminoethyl moiety in 4-position represent potent σ1 receptor antagonists. In order to increase the stability, a cyclohexane ring first replaced the acetalic 1, 3-dioxane ring of 1. A large set of aminoethyl substituted cyclohexane derivatives was prepared in a six-step synthesis. All enantiomers and diastereomers were separated by chiral HPLC at the stage of the primary alcohol 7, and their absolute configuration was determined by CD spectroscopy. Neither the relative nor the absolute configuration had a large impact on the σ1 affinity. The highest σ1 affinity was found for cis-configured benzylamines…
Phase equilibria and multiple azeotropy in the associating system methanol + diethylamine
1997
Vapor−liquid equilibrium has been measured for the binary system of methanol (1) + diethylamine (2) at 101.3 and 300 kPa. Both equilibrium isobars show strong deviations from ideal behavior and a single maximum boiling point azeotrope of practically constant composition x1 ≈ 0.76, corresponding to a temperature of 339.8 K at 101.3 kPa and 370.0 K at 300 kPa. The trend of the high-pressure isobar data is consistent with the formation of a second minimum boiling azeotrope, confirming the multiple azeotropic behavior found by others at a higher temperature (398.58 K). Furthermore, the excess Gibbs energy is negative and inflects markedly with composition with increased pressure. The equilibriu…
Damage and plasticity at the interfaces in composite materials and structures
2009
Abstract The structural behavior at the interface between two surfaces of ductile, brittle or quasi-brittle materials is studied by a new analytical elastoplastic damaging model. The model is developed in the framework of a thermodynamically consistent theory. The Helmholtz free energy is written to predict the materials’ hardening or softening. An isotropic damage is considered and the possible effects of dilatancy are taken into account including non-associative flow rules. The interface laws are presented both in a rate and a discrete incremental form. The analytical formulation is then implemented into a finite element code and two structural members are studied to validate the model. T…
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…
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…