Search results for "THERMODYNAMICS"
showing 10 items of 2774 documents
Experimental-Like Affinity Constants and Enantioselectivity Estimates from Flexible Docking
2012
Experimental-like affinity constants and enantioselectivity estimates, not predicted so far computationally, were obtained using a novel flexible modeling/docking combined strategy. The S- and R-warfarin-human serum albumin (HSA, site I) complexes were used as an interaction model. The process for a verified estimation includes the following: (i) ionized open chain forming at physiological pH (a recent focus); (ii) conformational search (molecular mechanics and Monte Carlo methods); (iii) rigid protein-flexible ligand docking (GlideXP) generating low energy paired S- and R-poses; (iv) graphical comparison against the X-ray crystal structure (unsatisfactory verification step); (v) quantum po…
Heat Pipe-Cooled Microstructured Reactor Concept for Highly Exothermal Ionic Liquid Syntheses
2010
Heat pipes used for cooling of microstructured reactors are a new approach for sustainable processing also in the lab-scale within a temperature range from ambient to more than 180 °C. The main advantage of heat pipe cooling is the dynamic behavior, i.e., the cooling rate depends on the heat released. Heat pipes can also suppress thermal runaways due to their extremely short response times on momentary temperature rises. As an example, the highly exothermal synthesis of 1-ethyl-3-methylimidazolium trifluoromethanesulfonate from the respective reactants 1-ethyl-imidazole and methyltrifluoromethanesulfonate was investigated. By transferring the protocol to continuous-flow conditions in the mi…
Multi-scale theoretical investigation of molecular hydrogen adsorption over graphene: coronene as a case study
2014
The physisorption of molecular hydrogen onto coronene is studied using a multi-scale theoretical approach with Density Functional Theory (DFT) calculations and Molecular Dynamics (MD) simulations. We consider two different kinds of model conformation for the approach of hydrogen towards the coronene i.e., systematic and random. For the systematic attack of hydrogen over coronene, the resulting potential energy profiles from DFT analysis are further found to resemble the Morse potential, and even the highly flexible Murrell–Sorbie (M–S) potential. The resulting M–S fitting also shows a zero-point energy correction of ∼16–17%. On the other hand, the potential energies from the random approach…
On the divide between animate and inanimate
2015
Vitalism was abandoned already for a long time ago, yet the impression that animate beings differ in some fundamental way from inanimate objects continues to thrive. Here, we argue that scale free patterns, found throughout nature, present convincing evidence that this demarcation is only imaginary. Therefore, all systems ought to be regarded alike, i.e., all are consuming free energy in least time. This way evolutionary processes can be understood as a series of changes from one state to another, so that flows of energy themselves naturally select those ways and means, such as species and societies or gadgets and galaxies to consume free energy in the least time in quest of attaining therm…
Ultrafast internal conversion of excited cytosine via the lowest pipi electronic singlet state.
2003
Computational evidence at the CASPT2 level supports that the lowest excited state pipi* contributes to the S1/S0 crossing responsible for the ultrafast decay of singlet excited cytosine. The computed radiative lifetime, 33 ns, is consistent with the experimentally derived value, 40 ns. The nOpi* state does not play a direct role in the rapid repopulation of the ground state; it is involved in a S2/S1 crossing. Alternative mechanisms through excited states pisigma* or nNpi* are not competitive in cytosine.
Modelling the carbon Snoek peak in ferrite: Coupling molecular dynamics and kinetic Monte-Carlo simulations
2008
Abstract Molecular statics, molecular dynamics and kinetic Monte-Carlo are used to model the carbon Snoek peak in ferrite. Using an interatomic EAM potential for the Fe–C system, saddle point energies for the diffusion of carbon have been evaluated under uniaxial stress by molecular statics. These energies have been reintroduced in a kinetic Monte-Carlo scheme to predict the repartition of carbon atoms in different octahedral sites. This repartition leads to an anelastic deformation calculated by molecular dynamics, which causes internal friction (the Snoek peak) for cyclic stress. This approach leads to quantitative predictions of the internal friction, which are in good agreement with exp…
Thermodynamics of computation and linear stability limits of superfluid refrigeration of a model computing array
2019
We analyze the stability of the temperature profile of an array of computing nanodevices refrigerated by flowing superfluid helium, under variations in temperature, computing rate, and barycentric velocity of helium. It turns out that if the variation in dissipated energy per bit with respect to temperature variations is higher than some critical values, proportional to the effective thermal conductivity of the array, then the steady-state temperature profiles become unstable and refrigeration efficiency is lost. Furthermore, a restriction on the maximum rate of variation in the local computation rate is found.
Calcium binding and ionic conduction in single conical nanopores with polyacid chains: model and experiments.
2012
Calcium binding to fixed charge groups confined over nanoscale regions is relevant to ion equilibrium and transport in the ionic channels of the cell membranes and artificial nanopores. We present an experimental and theoretical description of the dissociation equilibrium and transport in a single conical nanopore functionalized with pH-sensitive carboxylic acid groups and phosphonic acid chains. Different phenomena are simultaneously present in this basic problem of physical and biophysical chemistry: (i) the divalent nature of the phosphonic acid groups fixed to the pore walls and the influence of the pH and calcium on the reversible dissociation equilibrium of these groups; (ii) the asym…
Electrochemical properties of crystallized dilithium squarate: insight from dispersion-corrected density functional theory.
2012
International audience; The stacking parameters, lattice constants, and bond lengths of solvent-free dilithium squarate (Li(2)C(4)O(4)) crystals were investigated using density functional theory with and without dispersion corrections. The shortcoming of the GGA (PBE) calculation with respect to the dispersive forces appears in the form of an overestimation of the unit cell volume up to 5.8%. The original Grimme method for dispersion corrections has been tested together with modified versions of this scheme by changing the damping function. One of the modified dispersion-corrected DFT schemes, related to a rescaling of van der Waals radii, provides significant improvements for the descripti…
Dynamical Casimir-Polder force between an excited atom and a conducting wall
2016
We consider the dynamical atom-surface Casimir-Polder force in the non-equilibrium configuration of an atom near a perfectly conducting wall, initially prepared in an excited state with the field in its vacuum state. We evaluate the time-dependent Casimir-Polder force on the atom, and find that it shows an oscillatory behavior from attractive to repulsive both in time and in space. We also investigate the asymptotic behavior in time of the dynamical force and of related local field quantities, showing that the static value of the force, as obtained by a time-independent approach, is recovered for times much larger than the timescale of the atomic self-dressing, but smaller than the atomic d…