Search results for "physical chemistry"
showing 10 items of 1199 documents
Linear and nonlinear optical properties of a series of Ni-dithiolene derivatives
2009
Some linear and nonlinear optical (NLO) properties of Ni(SCH)4 and several of its derivatives have been computed by employing a series of basis sets and a hierarchy of methods (e.g., HF, DFT, coupled cluster, and multiconfigurational techniques). The electronic structure of Ni(SCH)4 has been also analyzed by using CASSCF/CASPT2, ab initio valence bond, and DFT methods. In particular we discuss how the diradicaloid character (DC) of Ni(SCH)4 significantly affects its NLO properties. The quasidegeneracy of the two lowest-energy singlet states 1 mathg and 1 math1u, the clear DC nature of the former, and the very large number of low-lying states enhance the NLO properties values. These particul…
Spin State and Ligand Dissociation in [CpCoL2] Complexes (L = PH3, H2C=CH2): A Computational Study
1999
International audience; The relative energies of [CpCoL] compounds (L = PH3, H2C=CH2) were calculated at the DFT/B3LYP level of theory. The triplet spin state was found to be favored over the singlet by between 33.0 and 21.0 kcal mol−1 for both fixed and optimized geometries. The basis set size was found to be important for the energy calculations, particularly when the energetics of ligand dissociation was examined. The role of the triplet spin state in facilitating the ligand dissociation process is discussed.
Ettringite surface chemistry: Interplay of electrostatic and ion specificity
2011
International audience; This paper presents a detailed experimental study combined with Monte Carlo (MC) simulations within the primitive model of the physical chemistry at the ettringite-water interface over a wide range of pH and bulk conditions for which ettringite exists thanks to its solubility in aqueous solutions. Ettringite, which is an important phase in hydrated cement-based systems, bears a permanent and positive structural charge. In contrast with previous studies, electrokinetic measurements together with the careful chemical analysis of the equilibrium solutions of the dispersions have brought strong support to designate sulfate as being the ion determining the potential. Simu…
Design, assembly and characterization of silicide-based thermoelectric modules
2016
ID: 1143 In: Energy conversion and management, 13-21. Summary: Highlights•Novel silicide-based thermoelectric modules were experimentally investigated.•The modules produced high power of 1.04 W at 405 °C and 3.24 W at 735 °C.•An estimated module efficiency of 5.3% represent the highest reported for silicide systems.AbstractSilicides have attracted considerable attention for use in thermoelectric generators due mainly to low cost, low toxicity and light weight, in contrast to conventional materials such as bismuth and lead telluride. Most reported work has focused on optimizing the materials properties while little has been done on module testing. In this work we have designed and tested mod…
First results of iButton® loggers and infrared camera application inside a greenhouse
2017
Greenhouse microclimate management (temperature, relative humidity) plays a very important role in order to optimize the production process improving pest and disease control, irrigation and energy efficiency. The systems mostly used in Sicily (south Italy) to record the ambient parameters are made up of fixed measuring stations able to give useful information about the climate inside the greenhouse limited to some pre-fixed points. In this study we texted a novel system made up of humidity and temperature data loggers (iButton®) placed inside a greenhouse. The iButton® temperature/humidity logger (DS1923) is a rugged, self-sufficient system that measures temperature and/or humidity and r…
Oxidation of secondary alcohols by duckweed: A biotransformation experiment for undergraduate students
1988
Thermodynamic Interaction Parameters of Tetra-n-undecylcalix[4]resorcinarenes with Selected Solvents Studied by Inverse Gas Chromatography
2004
The basic thermodynamic parameters, characterising intermolecular interactions of tetra-n-undecylcalix[4]resorcinarene and its octaacetate derivative with simple organic solutes, were calculated by using the inverse gas chromatography method. Free energy, enthalpy and entropy of sorption were determined.
Quantitative description of temperature induced self-aggregation thermograms determined by differential scanning calorimetry
2012
A novel thermodynamic approach for the description of differential scanning calorimetry (DSC) experiments on self-aggregating systems is derived and presented. The method is based on a mass action model where temperature dependence of aggregation numbers is considered. The validity of the model was confirmed by describing the aggregation behavior of poly(ethylene oxide)-poly(propylene oxide) block copolymers, which are well-known to exhibit a strong temperature dependence. The quantitative description of the thermograms could be performed without any discrepancy between calorimetric and van 't Hoff enthalpies, and moreover, the aggregation numbers obtained from the best fit of the DSC exper…
Experimental IR study and ab initio modelling of ethylene adsorption in a MFI - type host zeolite.
2009
International audience; Different ab initio methods and experimental results are used to investigate the effect of the adsorption of one ethylene molecule on silicalite-1, a MFI type zeolite. We used simplified models to simulate a portion of a straight or sinusoidal channel of silicalite-1 at a quantum level. The calculated absorption spectra of the models are qualitatively in good agreement with the experimental FTIR spectrum of silicalite-1. Additionally we simulate the FTIR spectrum of the isolated ethylene molecule and that of an ethylene molecule in interaction with the above-mentioned zeolite models. Results are discussed depending on the method and specific basis set and compared wi…
The photophysics and photochemistry of cofacial free base and metallated bisporphyrins held together by covalent architectures
2007
Abstract This review focuses on the photophysical properties of bisporphyrin systems held in a face-to-face configuration by covalent bonds via flexible or rigid spacers and metal–metal bonds. The cofacial arrangement induces intramolecular bismacrocycle interactions promoting basic photophysical events such as excitonic interactions and energy and electron transfers. These events are relevant to mimic light harvesting and reactor devices known for photosynthesis in plants, and can be monitored by luminescence and flash photolysis methods.