Éditeur(s) : HAL CCSD Elsevier
Résumé : Le titre a été changé Ancien titre: Roles for local crowding and pressure in counteracting density fluctuations at equilibrium
International audience
What is the probability that all the gas in a box accumulates in the same half of this box? Though amusing, this question underlies the fundamental problem of density fluctuations at equilibrium, which has profound implementations in many physical fields. The currently accepted solutions are derived from the studies of Brownian motion by Smoluchowski, but they are not appropriate for the directly colliding particles of gases. Two alternative theories are proposed here using self-regulatory Bernoulli distributions. A discretization of space is first introduced to develop a mechanism of matter congestion holding for high densities. In a second mechanism valid in ordinary conditions, the influence of local pressure on the location of every particle is examined using classical laws of ideal gases. This approach reveals that a negative feedback results from the reciprocal influences between individual particles and the population of particles, which strongly reduces the probability of atypical microstates. Finally, a thermodynamic quantum of time is defined to compare the recurrence times of improbable macrostates predicted through these different approaches.
Physica A: Statistical Mechanics and its Applications

hal-00920985
https://hal-univ-rennes1.archives-ouvertes.fr/hal-00920985
https://hal-univ-rennes1.archives-ouvertes.fr/hal-00920985v2/document
ARXIV : 1404.6223
DOI : 10.1016/j.physa.2014.03.067

Éditeur(s) : HAL CCSD
Résumé : Structure elucidation of unknown compounds has been the task of natural products chemists for a long time and their approach seems to be the most efficient when it comes to identification. Very recently, Kokkotou et al. proposed a work-flow based on an integrative approach for new metabolite identification. This approach, including prediction of 2D NMR HSQC spectra, demonstrated the necessity for implementation of new algorithms leading to the prediction of 2D NMR spectra. Herein we present a method based on both quantum mechanics (QM) and Hierarchical Organisation of Spherical Environments (HOSE) of the prediction 2D NMR spectra.
https://hal.archives-ouvertes.fr/hal-01416667

hal-01416667
https://hal.archives-ouvertes.fr/hal-01416667
https://hal.archives-ouvertes.fr/hal-01416667/document
https://hal.archives-ouvertes.fr/hal-01416667/file/MRC_v1.pdf

Éditeur(s) : HAL CCSD De Gruyter
Résumé : International audience
A comparative study of 9H-pyrido[3,4-b]indole (norharmane) and 1-methyl-9H-pyrido[3,4-b]indole (harmane) as inhibitors for C38 steel corrosion in 1 M HCl solution at 25 °C was carried out. Potentiodynamic polarization and electrochemical impedance spectroscopy (EIS) techniques were applied to study the metal corrosion behavior in the absence and presence of different concentrations of these inhibitors. The OCP as a function of time were also established. Cathodic and anodic polarization curves show that norharmane and harmane are a mixed-type inhibitors. Adsorption of indole derivatives on the C38 steel surface, in 1 M HCl solution, follows the Langmuir adsorption isotherm model. The ΔGads values were calculated and discussed. The potential of zero charge (PZC) of the C38 steel in inhibited solution was studied by the EIS method, and a mechanism for the adsorption process was proposed. Raman spectroscopy confirmed that indole molecules strongly adsorbed onto the steel surface. The electronic properties of indole derivates, obtained using the AM1 semi-empirical quantum chemical approach, were correlated with their experimental efficiencies using the linear resistance model (LR).
ISSN: 0018-3830

hal-01093227
https://hal-agroparistech.archives-ouvertes.fr/hal-01093227
DOI : 10.1515/HF.2010.034